CA1198542A - LOW DENSITY ETHYLENE COPOLYMER COMPOSITION OF TWO ETHYLENE-.alpha.-OLEFIN COPOLYMERS - Google Patents
LOW DENSITY ETHYLENE COPOLYMER COMPOSITION OF TWO ETHYLENE-.alpha.-OLEFIN COPOLYMERSInfo
- Publication number
- CA1198542A CA1198542A CA000395280A CA395280A CA1198542A CA 1198542 A CA1198542 A CA 1198542A CA 000395280 A CA000395280 A CA 000395280A CA 395280 A CA395280 A CA 395280A CA 1198542 A CA1198542 A CA 1198542A
- Authority
- CA
- Canada
- Prior art keywords
- copolymer
- ethylene
- molecular weight
- olefin
- alpha
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/24992—Density or compression of components
Abstract
ABSTRACT OF THE DISCLOSURE
An ethylene-.alpha.-olefin copolymer composition comprising two ethylene-.alpha.-olefin copolymers which are different in density, intrinsic viscosity and the number of short chain branching per 1000 carbon atoms. Ex-trusion processed materials, injection molded materials and films obtained from said composition are excellent in strength.
An ethylene-.alpha.-olefin copolymer composition comprising two ethylene-.alpha.-olefin copolymers which are different in density, intrinsic viscosity and the number of short chain branching per 1000 carbon atoms. Ex-trusion processed materials, injection molded materials and films obtained from said composition are excellent in strength.
Description
The present invention relates to an ethylene~-ole~in copolymer compositionO More particularly, the present invention relates to ethylene~a-olefin copolymer composition excellent in processability, impact strenyth, tensile strength, environmental stress cracking resistance, low temperature resistance, creep characteristics, tear strength, transparency, heat-sealing characteristics and chemical characteristics such as chemicals resistance, which is obtained by mixing an ethylene-~-olefin copolymer of a relatively higher molecular weight and an ethylene-a-olefin copolymer of a relatively lower molecular ~eight.
Being excellent in melt rheology characteristics as well as in physical and chemical properties, low density poly-ethylenes manufactured by the high pressure method (hereinafter referred to as "higk pressure polyethylene") have been used for various uses such as films, sheets, pipes, blow bottles, injection molded products, coating materials for steel pipes and foam-molded materials. As mentioned above, high pressure polyethylenes are excellent in melt rheology charactertistics, and therefore, they are excellent in processability. When used for extrusion processing or injection molding, their production efficiency is high, resulting in relatively low electricity consumption. In blown film processing, the above polyethylenes give good bubble stability~ In cast film processing and extrusion lamination processing, there occurs only slight neck-in.
In blow molding, these polye-thylenes give good parison stabilityO
However, when they are processed into molded products, their mechanical strengths, such as tensile strength and impact strength, '.,,,,,,~. , ~.
o are relatively low and accordingly these products can not be used in thin forms.
High pressure polyethylenes have various other problems. They are used in many fields as films. Films of high pressure polyethylenes are re~uired to have the following properties in xecent, highly developed automatic packaging systems.
(1) Good heat-sealing property at low temperatures.
Being excellent in melt rheology characteristics as well as in physical and chemical properties, low density poly-ethylenes manufactured by the high pressure method (hereinafter referred to as "higk pressure polyethylene") have been used for various uses such as films, sheets, pipes, blow bottles, injection molded products, coating materials for steel pipes and foam-molded materials. As mentioned above, high pressure polyethylenes are excellent in melt rheology charactertistics, and therefore, they are excellent in processability. When used for extrusion processing or injection molding, their production efficiency is high, resulting in relatively low electricity consumption. In blown film processing, the above polyethylenes give good bubble stability~ In cast film processing and extrusion lamination processing, there occurs only slight neck-in.
In blow molding, these polye-thylenes give good parison stabilityO
However, when they are processed into molded products, their mechanical strengths, such as tensile strength and impact strength, '.,,,,,,~. , ~.
o are relatively low and accordingly these products can not be used in thin forms.
High pressure polyethylenes have various other problems. They are used in many fields as films. Films of high pressure polyethylenes are re~uired to have the following properties in xecent, highly developed automatic packaging systems.
(1) Good heat-sealing property at low temperatures.
(2) High sealing strength in a condition where heat~sealed portions are not cooled sufficiently and are therefore not solidified yet (this strength is called "hot tack" strength).
Hot tack strength is required because filling of contents and heat sealing are done almost at the same time.
Hot tack strength is required because filling of contents and heat sealing are done almost at the same time.
(3) Sealing strength in a state where heat-sealing portions are contaminated with oils and the like, in packaging of oils and the like. ~This strength is called heat sealing strength in contaminated condition.) However, high pressure polyethylenes are not satisfactory in hot tack and heat sealing strength in cont~m;n~ted condition~ When these polyethylenes are used in blow bottles, pipes and injection molded products, they are inadequate in environmental stress cracking resistance, therefore, cause occasional troubles and are susceptible to attack by chlorine water. Further, they are not ade~uate in creep characteristics, which makes them unusable in pipes of high internal pressure. When high pressure polyethylenes are used as coating materials for steel pipes, their low temperature resistance is not satisfactory, which makes their use in very w~ ~
cold climatic areas improper. In their use as coa-ting materials for electric wires, troub]es occur at times due to inadequate environmental stress cracking resis-tance and water-tree resistance.
(The expression "wa-ter-tree" relates to deterioration of e]ectric insulating materials caused by penetra-tion oE water when said materials are placed under an electric field. This deterioration is referred to as "water~-tree", because the deterioration resembles branches of a tree.) To improve these defects, some attempts have been made.
However, the quality is still not at a satisfactory level.
For improvement of these defects, the following polymer-ization methods have been adopted.
(1) Polymerization of ethylene and other polymerizable monomer such as vinyl acetate.
(2) Method in which ethylene and acrylic acid (or methacrylic acid) are polymerized followed by conversion to a salt with a metal, namely an ionomer.
The former method still has many problems such as (a) re-duction of tear strength, rigidi-ty and heat resistance of films, (b) occurrence of corrosion of extruder and smell in processing due to liberation of acetic acid and (c) occurrence of blocking due to sticky film surface and cold flow. The latter method has problems of reduction of thermal stability and weather resis-tance and of high cost.
Also for improvement of the defec-ts of high pressure polyethylenes, there were made proposals in which a high pressure polyethylene is mixed with another ~-olefin polymer such as high density polyethylene, polypropylene, polybutene, or a rubber.
However, an improvement in one defect causes another problem and no satisfactory answer has been attained.
.
- 3a -. . .
s~
~ s resins which have low densi~ies abou~ equal ~o those of high pressure polyethylenes, there are known resins which are prepared by co-polymerizing ethylene and an ~-olefin under a medium to low pressure using a transition metal catalyst. (Hereinafter, these resins are referred to for brevity as "ethylene-~-olefin copolymers".) The copolymers produced with a vanadium catalyst are low in degree of crystallization, and have problems in hea-t resistance, weather resistance and mechanical strengths. The ethylene-a-olefin copolymers produced under normal polymerization conditions with a titanium catalyst, having generally narrow molecular weight distributions (narrower than those of high pressure polyethylenes~, are relatively excellent in mechanical strengths but poor in melt rheology characteristics and have many problems in processing. In blown film processing, a large quantity of electricity is needed, output is reduced or bubble stability is lost. In high speed processing, "shark skin" appears on film surfaces, thereby reducing product value. Also in blow molding, parison stability is lost, or surfaces oE molded products turn to "shark skin" and product values are lost.
In injection mo~lding, processing temperatures need to be largely raised because of poorer flow property under high pressures as compared with high pressure polyethylenes, which requires more heat energy and moreover causes resin deterioration.
Trials have been made in recen-t years for solving these problems by improving extruders, screws and dies. These approaches require a large amount of expenditure and moreover
cold climatic areas improper. In their use as coa-ting materials for electric wires, troub]es occur at times due to inadequate environmental stress cracking resis-tance and water-tree resistance.
(The expression "wa-ter-tree" relates to deterioration of e]ectric insulating materials caused by penetra-tion oE water when said materials are placed under an electric field. This deterioration is referred to as "water~-tree", because the deterioration resembles branches of a tree.) To improve these defects, some attempts have been made.
However, the quality is still not at a satisfactory level.
For improvement of these defects, the following polymer-ization methods have been adopted.
(1) Polymerization of ethylene and other polymerizable monomer such as vinyl acetate.
(2) Method in which ethylene and acrylic acid (or methacrylic acid) are polymerized followed by conversion to a salt with a metal, namely an ionomer.
The former method still has many problems such as (a) re-duction of tear strength, rigidi-ty and heat resistance of films, (b) occurrence of corrosion of extruder and smell in processing due to liberation of acetic acid and (c) occurrence of blocking due to sticky film surface and cold flow. The latter method has problems of reduction of thermal stability and weather resis-tance and of high cost.
Also for improvement of the defec-ts of high pressure polyethylenes, there were made proposals in which a high pressure polyethylene is mixed with another ~-olefin polymer such as high density polyethylene, polypropylene, polybutene, or a rubber.
However, an improvement in one defect causes another problem and no satisfactory answer has been attained.
.
- 3a -. . .
s~
~ s resins which have low densi~ies abou~ equal ~o those of high pressure polyethylenes, there are known resins which are prepared by co-polymerizing ethylene and an ~-olefin under a medium to low pressure using a transition metal catalyst. (Hereinafter, these resins are referred to for brevity as "ethylene-~-olefin copolymers".) The copolymers produced with a vanadium catalyst are low in degree of crystallization, and have problems in hea-t resistance, weather resistance and mechanical strengths. The ethylene-a-olefin copolymers produced under normal polymerization conditions with a titanium catalyst, having generally narrow molecular weight distributions (narrower than those of high pressure polyethylenes~, are relatively excellent in mechanical strengths but poor in melt rheology characteristics and have many problems in processing. In blown film processing, a large quantity of electricity is needed, output is reduced or bubble stability is lost. In high speed processing, "shark skin" appears on film surfaces, thereby reducing product value. Also in blow molding, parison stability is lost, or surfaces oE molded products turn to "shark skin" and product values are lost.
In injection mo~lding, processing temperatures need to be largely raised because of poorer flow property under high pressures as compared with high pressure polyethylenes, which requires more heat energy and moreover causes resin deterioration.
Trials have been made in recen-t years for solving these problems by improving extruders, screws and dies. These approaches require a large amount of expenditure and moreover
4 --.~,."~
5 ~:
techniques have not been fully developed. Further, various other problems such as the following have been encountered:
(1) with res~ect to mechanical s-trengths of films produced, balancing of machine direc~ion (MD) and transverse direction (TD) is difficult and the tear strength of MD is poorer than that of high pressure polyethylenes, a~d (2) film transparency is inferior to that of high pressure polyethylenes, ~ecause the ethylene-~-olefin copolymer of narrow molecular weight distribution has a faster crystal-ization speed than high pressure polyethylenes and causes melt fracture more easily.
Low density ethylene-~-olefin copolymers are difficult to obtain under normal polymerization condi-tions using a chromium catalyst, because copolymerizability between e-thylene and ~olefin is generally lower with chromium catalysts than with titanium catalysts. When a chromium-titanium ca-talyst is used in order to overcome this problem~ ethylene-~-olefin copolymers obtained have wider molecular weight distributions than copolymers produced with a titanium catalyst and have slightly improved processability. However, their mechanical strengths largely worsen and their physical properties are not much different from those of high pressure polyethylenes and these copolymers provide film sheets and bottles inferior in transparency.
Attempts to improve the transparency of these copolymers have been made by increasing the ~uantity of ~-olefin and reducing the density of the copolymer. This results in a sticky copolymer having much reduced mechanical strength.
According to the knowledge of the present inventors, ethylene-a-olefin copolymers polymerized under a medium to low pressure using a transition metal ca-talyst, have non-uniform component distributions. Namely in these copolymers, the number of short chain branches per 1000 carbon atoms (excluding methyl groups at the ends) (hereinafter referred to as "S.C~B." for brevity~ varies depending upon molecular weight, and generally lower molecular weight components have larger S,C.B. and higher molecular weight components have smaller S.C.B. This phenomenon is considered to be due to tha-t -olefins tend to act as a chain transfer agent or act even to ac-tive sites of catalyst to which molecular weight regulators such as hydrogen tend to act. (cf. Reference .~ ~
1 example l.) Because of the above phenomenon, ethylene-a-olefin copolymers polymerized with the ~olefin con-centratlon increased with an aim ~o reduce to a large extent the density of copolymers produced, only give such products as those having increased S.C.B. in their lower molecular weight components~thereby having in-creased solubiliky in solvents and poor mechanical strengths and causing surface stickiness. This tendency is particularly remarkable in those ethylene-~-olefin copolymers which are polymerized with a catalyst giving wider molecular weight distributions. One of the reasons for poor mechanical strengths of ethylene-~-olefin copolymers havin~ wide molecular weight distributions will be explained by the above fact.
As described above, ethylene-~-olefin copolymers having densities about equal to those of high pressure polyethylenes and synthesized under a medium to low pr sure with a transi~ion metal catalyst, can not satisfy all~of processability, mechanical strengths and trans-parency. For instance, lowering of molecular weight for improvement of processability results in large reduction in mechanical strengths and disappearance of said co-polymer characteristics. Broadening of molecular weight distribution leads to large reduction in mechanical strengths as well (cf. Reference example 2.)~ and more-over transparency worsens and surfaces of molded products get sticky. Thus, both of processability and physical 1 properties are not met together yet, and any low density ethylene-~-olefin copolymer excellent in processability and mechanical strengths have not yet been provided.
As described above, high pressure polyethylenes are excellent in rheology characteristics and processa-bility but relatively poor in mechanical strengths. On the other hand, ethylene-~-olefin copolymers polymerized under a medium to low pressure with a transition metal catalyst and having densities about equal to those of high pressure polyethylenes, have excellent mechanical strengths due to their narrower molecular weight distri-butions but are poor in processability. These property differences are considered to originate from molecular structures of polymers.
High pressure polyethylenes are obtained from radical polymerization under a pressure of about 1500 to 4000 kg/cm at a temperature of about 150 to 350C in an autoclave or a tubular reactor. Their molecular structures are very complicated and, in spite of being homopolymers of ethylene, have short chain branches which are alkyl groups of 1 to 6 carbon atoms. These short chain branches affect crystallinities and therefore densities of polymers. The distribution of short chain branching of high pressure polyethylenes is relatively even, and both lower molecular weight components and higher molecular weight components have almost similar numbers of branches.
Another important feature of high pressure ~1 polyethylenes is that the polyethylenes ~vc ~ ~o long chain branches in complicated structures. Identification of these long chain branches is difficult, but these branches are considered to be alkyl groups of which lengths vary from about lengths of main chains to lengths having carbon atoms of over several thousands. The pre-sence of these long chain branches largely a~fects melt rheology charac~eristics of polymers and this is one of the reasons for/excellent processability of high pressure method polyethylenes.
On the other hand, ethylene-~-olefin copolymers synthesized under a medium to low pressure with a transi-tion metal catalyst and having densities about equal to those of high pressure polyethylenesg are obtained by co polymerizing ethylene and an ~-olefin under a medium to low pressure of about 5 to 150 kg/cm2 and at 0 _ 25GC
nc~mally at a relatively low temperature of 30 to 200C
with a transition metal catalyst in an autoclave or a tubular reactor. Thoir molecular structures are relatively simple. These ethylene-~-olefin copolymers seldom possess long chain branches and have only short chain branches.
These short chain branches are not formed through compli~
cated reaction processes as so in hi~h pressure poly-ethylenes, but are controlled by the kind of an ~-olefin to be used in the copolymerization. As an example, in a copolymerization bet~een ethylene and butene~l, short chain branches formed are normally ethyl branches. These branches could be hexyl branches as a result of dimeriza-_ 9 _ s~
1 tion of butene-l. Short chain branches formed control crystallinities and densities of polymers.
Distribution of short chain branches is also affected by the nature of a transition metal catalyst used in the copolymerization, the type of polymerization and the temperature of polymerization. ~ifferent from the case of high pressure polyethylenes, the distribu-tion is wide. Namely, as a general tr~nd, lower molecular weight components have larger S.C.~. and higher molecular weight components have smaller S.C.B. (cf. Reference . OE~,~
p~ C 1 . ) Ethylene-~-olefin copolymers obtained by copoly merizing ethylene and an ~-olefin under a medium to low pressure with a transition metal catalyst and having densities about equal to those of high pressure poly-ethylenes, have come to be practically used. Therefore, the conventional classification that polyethylene resins having densitles of Oo910 to 0.935 g/cm3 fall in a ca-tegory of high pressure polyethylenes, is improper and a new classification should be developed~mainly based on whether or not a polymer or resin has long chain branches.
As low density polyethylenes substantially not having long chain branches, there are resins which are obtained by polymerization using a transition metal catalyst under a same high pressure and temperature as employed in the manufacture of high pressure method polyethylenes. These resins are also included in "ethylene-~-olefin copolymers"
as defined by the present invention.
s'~
Presence or ahsence of long chain branches is clarified to a considerable extent by a theory of solution~ As an example t the presence of long chain branches in an ethylene polymer can be known by using ~/cn~Q namely g*~ Herein, [n] is the intrinsic viscosity of the ethylene polymer, and r~ ~Q is the intrinsic viscosity of a reference linear polyethylene (high density polyethylene produced from homopolymerization of ethylene under a medium to low pressure with a Zlegler catalyst) having the same weight average molecular weight of the light scattering method. Molecules having more long chain branches have less spread in a solution, and -therefore, their gn is smal:l~
Normally, g* of high pressure polyethylenes is 0O6 or less.
This method is useful, but practically presence of long chain branches can be known more easily and clearly by a correlation between melt index and intrinsic viscosity of polymer. This correlation was shown in Reference example 3.
In there, the intrinsic viscosity of high pressure polyethylene is far lower than that of the ethylene-~-olefin copolymer accord-ing to medium to low pressure method having the same melt lndex, because the former polyethylene has long chain branches.
Due to the difference caused by the presence or absence of long chain branches~ high pressure polyethylenes and ethylene-~-olefin copolymers give largely different properties in melt rheology characteristics, crystallinity, solid mechanical properties and optical properties~
z l The present inventors made strenuous efforts with an aim to obtain polyethylenes which will solve the above-mentioned de~ects o~ polyethylenes~ will have processability equal to or better than that o~ hlgh 5 pressure polyethylenes~ and will be excellent in tear strength, impact strength, environmental stress cracking resistance, low temperature resistance, creep character-istics~ chemicals resistance, transparency and heat-sealing characteristics. As a result, the prese~t in-ventors have found that, by mixing (a) an ethylene-~-olefin copolymer having a relatively higher molecular weight and of which density, intrinsic ~iscosity, S.C.B., kind of ~-olefin and (weight average molecular weight)/
(number average molecular weight~ are specified and (b) another ethylene-~-olefin copolymer having a relatively lower molecular weight and of which density, intrinsic viscosity, S.C.B., kind of ~ olefin and (weight average molecular weight)/(number average molecular weight) are specified, in such a way that the ratio of S.C.B. of the former copolymer over S.C.B. o~ the latter copolymer is in a specified range, ethylene copolymer compositions can be obtained which oempoc~tion h~c extremely good processa-bility compared with the conventional polyethylenes~as well as very excellent physical and chemical properties such as tear strength, impact strength, environmental stress cracking resistance, low temperature resistance, creep characteristics, chemicals resistance, transparency, and heat-sealing characteristics. The present inventors _ 12 -have also found that ekhylene-a oleEin copolymer compositions substantially not having long chain branches and having a specific disbtribution of S.C.B. provide extremely good properties such as tensile strength, impact strength, environmen~al stress cracking resistance, low temperature resistance, creep characteristics, chemicals resistance, transparency and heat sealing character-istics, compared with the conventional polyethylenes, and therefore, with such ethylene-a-olefin copolymer compositions, improvement of processability by broadening of molecular weight distribution can be attained without deterioration of properties described aboveO Thus, the present invention has been achievedO
According to the presenk invention, there is provided an ethylene-~-olefin copolymer composition excellent in transparency and strength and having a density of 0.915 to 0.929 g/cm3, a melt index of OoO2 to 50 g/10 min. and a melt flow ratio of 35 to 250, which comprises lO to 70% by weight of an ethylene ~-olefin copolymer A and 90 to 30~ by weigh-t of an ethylene-~olefin copolymer B; said copolymer A having a higher molecular weight than copolymer B and being a copolymer of ethylene and an ~-olefin of 3 to 18 carbon a-toms and having a density of 0.895 to 0.935 g/cm3, an intrinsic viscosity of 1.2 to 6.0 dl/gl and a n~ber of short chain branches per 1000 carbon atoms (S.C.B.) of 7 to 40 and a (weight average molecular weight)/~umber average molecular weight) value of 2 to 10; said copolymer B being a copolymer of ethylene and an ~-olefin of 3 to 18 carbon atoms and having a density of 0.910 to 0O955 g/cm3, an intrinsic viscosity of 0.3 to 1.5 dl/g and S.C.B. of 5 to 35 and a (weight average molecular weight)/
(number average molecular weight) value of 2 to 10; said copolymer s~
A and said copo].ymer B being selected in order to satisfy a condition that (S oC~B~ of said copolymer A)/(S.C.B. of said copolymer B~ ls 0.6 to 1.7.
The present invention also provides a composition of copolymers of ethylene and an ~-olefin of 3 to 18 carbon atoms, having the following properties:
(1) density of 0.915 to 0.929 g/cm3, (2) intrinsic viscosity ~ of 0,7 to 4.0 dl/g, (3) melt index of 0.02 to 50 g/10 min, (4) the number of short chain branches per 1000 carbon atoms (SoC~B~) being 5 to 45~
(5) rn~ ~ Q namely gn being at least 0.8, where ~ ~ is an intrinsic viscosity of a linear polyethylene having the same weight average molecular wei.ght measured by a light scattering method,
techniques have not been fully developed. Further, various other problems such as the following have been encountered:
(1) with res~ect to mechanical s-trengths of films produced, balancing of machine direc~ion (MD) and transverse direction (TD) is difficult and the tear strength of MD is poorer than that of high pressure polyethylenes, a~d (2) film transparency is inferior to that of high pressure polyethylenes, ~ecause the ethylene-~-olefin copolymer of narrow molecular weight distribution has a faster crystal-ization speed than high pressure polyethylenes and causes melt fracture more easily.
Low density ethylene-~-olefin copolymers are difficult to obtain under normal polymerization condi-tions using a chromium catalyst, because copolymerizability between e-thylene and ~olefin is generally lower with chromium catalysts than with titanium catalysts. When a chromium-titanium ca-talyst is used in order to overcome this problem~ ethylene-~-olefin copolymers obtained have wider molecular weight distributions than copolymers produced with a titanium catalyst and have slightly improved processability. However, their mechanical strengths largely worsen and their physical properties are not much different from those of high pressure polyethylenes and these copolymers provide film sheets and bottles inferior in transparency.
Attempts to improve the transparency of these copolymers have been made by increasing the ~uantity of ~-olefin and reducing the density of the copolymer. This results in a sticky copolymer having much reduced mechanical strength.
According to the knowledge of the present inventors, ethylene-a-olefin copolymers polymerized under a medium to low pressure using a transition metal ca-talyst, have non-uniform component distributions. Namely in these copolymers, the number of short chain branches per 1000 carbon atoms (excluding methyl groups at the ends) (hereinafter referred to as "S.C~B." for brevity~ varies depending upon molecular weight, and generally lower molecular weight components have larger S,C.B. and higher molecular weight components have smaller S.C.B. This phenomenon is considered to be due to tha-t -olefins tend to act as a chain transfer agent or act even to ac-tive sites of catalyst to which molecular weight regulators such as hydrogen tend to act. (cf. Reference .~ ~
1 example l.) Because of the above phenomenon, ethylene-a-olefin copolymers polymerized with the ~olefin con-centratlon increased with an aim ~o reduce to a large extent the density of copolymers produced, only give such products as those having increased S.C.B. in their lower molecular weight components~thereby having in-creased solubiliky in solvents and poor mechanical strengths and causing surface stickiness. This tendency is particularly remarkable in those ethylene-~-olefin copolymers which are polymerized with a catalyst giving wider molecular weight distributions. One of the reasons for poor mechanical strengths of ethylene-~-olefin copolymers havin~ wide molecular weight distributions will be explained by the above fact.
As described above, ethylene-~-olefin copolymers having densities about equal to those of high pressure polyethylenes and synthesized under a medium to low pr sure with a transi~ion metal catalyst, can not satisfy all~of processability, mechanical strengths and trans-parency. For instance, lowering of molecular weight for improvement of processability results in large reduction in mechanical strengths and disappearance of said co-polymer characteristics. Broadening of molecular weight distribution leads to large reduction in mechanical strengths as well (cf. Reference example 2.)~ and more-over transparency worsens and surfaces of molded products get sticky. Thus, both of processability and physical 1 properties are not met together yet, and any low density ethylene-~-olefin copolymer excellent in processability and mechanical strengths have not yet been provided.
As described above, high pressure polyethylenes are excellent in rheology characteristics and processa-bility but relatively poor in mechanical strengths. On the other hand, ethylene-~-olefin copolymers polymerized under a medium to low pressure with a transition metal catalyst and having densities about equal to those of high pressure polyethylenes, have excellent mechanical strengths due to their narrower molecular weight distri-butions but are poor in processability. These property differences are considered to originate from molecular structures of polymers.
High pressure polyethylenes are obtained from radical polymerization under a pressure of about 1500 to 4000 kg/cm at a temperature of about 150 to 350C in an autoclave or a tubular reactor. Their molecular structures are very complicated and, in spite of being homopolymers of ethylene, have short chain branches which are alkyl groups of 1 to 6 carbon atoms. These short chain branches affect crystallinities and therefore densities of polymers. The distribution of short chain branching of high pressure polyethylenes is relatively even, and both lower molecular weight components and higher molecular weight components have almost similar numbers of branches.
Another important feature of high pressure ~1 polyethylenes is that the polyethylenes ~vc ~ ~o long chain branches in complicated structures. Identification of these long chain branches is difficult, but these branches are considered to be alkyl groups of which lengths vary from about lengths of main chains to lengths having carbon atoms of over several thousands. The pre-sence of these long chain branches largely a~fects melt rheology charac~eristics of polymers and this is one of the reasons for/excellent processability of high pressure method polyethylenes.
On the other hand, ethylene-~-olefin copolymers synthesized under a medium to low pressure with a transi-tion metal catalyst and having densities about equal to those of high pressure polyethylenesg are obtained by co polymerizing ethylene and an ~-olefin under a medium to low pressure of about 5 to 150 kg/cm2 and at 0 _ 25GC
nc~mally at a relatively low temperature of 30 to 200C
with a transition metal catalyst in an autoclave or a tubular reactor. Thoir molecular structures are relatively simple. These ethylene-~-olefin copolymers seldom possess long chain branches and have only short chain branches.
These short chain branches are not formed through compli~
cated reaction processes as so in hi~h pressure poly-ethylenes, but are controlled by the kind of an ~-olefin to be used in the copolymerization. As an example, in a copolymerization bet~een ethylene and butene~l, short chain branches formed are normally ethyl branches. These branches could be hexyl branches as a result of dimeriza-_ 9 _ s~
1 tion of butene-l. Short chain branches formed control crystallinities and densities of polymers.
Distribution of short chain branches is also affected by the nature of a transition metal catalyst used in the copolymerization, the type of polymerization and the temperature of polymerization. ~ifferent from the case of high pressure polyethylenes, the distribu-tion is wide. Namely, as a general tr~nd, lower molecular weight components have larger S.C.~. and higher molecular weight components have smaller S.C.B. (cf. Reference . OE~,~
p~ C 1 . ) Ethylene-~-olefin copolymers obtained by copoly merizing ethylene and an ~-olefin under a medium to low pressure with a transition metal catalyst and having densities about equal to those of high pressure poly-ethylenes, have come to be practically used. Therefore, the conventional classification that polyethylene resins having densitles of Oo910 to 0.935 g/cm3 fall in a ca-tegory of high pressure polyethylenes, is improper and a new classification should be developed~mainly based on whether or not a polymer or resin has long chain branches.
As low density polyethylenes substantially not having long chain branches, there are resins which are obtained by polymerization using a transition metal catalyst under a same high pressure and temperature as employed in the manufacture of high pressure method polyethylenes. These resins are also included in "ethylene-~-olefin copolymers"
as defined by the present invention.
s'~
Presence or ahsence of long chain branches is clarified to a considerable extent by a theory of solution~ As an example t the presence of long chain branches in an ethylene polymer can be known by using ~/cn~Q namely g*~ Herein, [n] is the intrinsic viscosity of the ethylene polymer, and r~ ~Q is the intrinsic viscosity of a reference linear polyethylene (high density polyethylene produced from homopolymerization of ethylene under a medium to low pressure with a Zlegler catalyst) having the same weight average molecular weight of the light scattering method. Molecules having more long chain branches have less spread in a solution, and -therefore, their gn is smal:l~
Normally, g* of high pressure polyethylenes is 0O6 or less.
This method is useful, but practically presence of long chain branches can be known more easily and clearly by a correlation between melt index and intrinsic viscosity of polymer. This correlation was shown in Reference example 3.
In there, the intrinsic viscosity of high pressure polyethylene is far lower than that of the ethylene-~-olefin copolymer accord-ing to medium to low pressure method having the same melt lndex, because the former polyethylene has long chain branches.
Due to the difference caused by the presence or absence of long chain branches~ high pressure polyethylenes and ethylene-~-olefin copolymers give largely different properties in melt rheology characteristics, crystallinity, solid mechanical properties and optical properties~
z l The present inventors made strenuous efforts with an aim to obtain polyethylenes which will solve the above-mentioned de~ects o~ polyethylenes~ will have processability equal to or better than that o~ hlgh 5 pressure polyethylenes~ and will be excellent in tear strength, impact strength, environmental stress cracking resistance, low temperature resistance, creep character-istics~ chemicals resistance, transparency and heat-sealing characteristics. As a result, the prese~t in-ventors have found that, by mixing (a) an ethylene-~-olefin copolymer having a relatively higher molecular weight and of which density, intrinsic ~iscosity, S.C.B., kind of ~-olefin and (weight average molecular weight)/
(number average molecular weight~ are specified and (b) another ethylene-~-olefin copolymer having a relatively lower molecular weight and of which density, intrinsic viscosity, S.C.B., kind of ~ olefin and (weight average molecular weight)/(number average molecular weight) are specified, in such a way that the ratio of S.C.B. of the former copolymer over S.C.B. o~ the latter copolymer is in a specified range, ethylene copolymer compositions can be obtained which oempoc~tion h~c extremely good processa-bility compared with the conventional polyethylenes~as well as very excellent physical and chemical properties such as tear strength, impact strength, environmental stress cracking resistance, low temperature resistance, creep characteristics, chemicals resistance, transparency, and heat-sealing characteristics. The present inventors _ 12 -have also found that ekhylene-a oleEin copolymer compositions substantially not having long chain branches and having a specific disbtribution of S.C.B. provide extremely good properties such as tensile strength, impact strength, environmen~al stress cracking resistance, low temperature resistance, creep characteristics, chemicals resistance, transparency and heat sealing character-istics, compared with the conventional polyethylenes, and therefore, with such ethylene-a-olefin copolymer compositions, improvement of processability by broadening of molecular weight distribution can be attained without deterioration of properties described aboveO Thus, the present invention has been achievedO
According to the presenk invention, there is provided an ethylene-~-olefin copolymer composition excellent in transparency and strength and having a density of 0.915 to 0.929 g/cm3, a melt index of OoO2 to 50 g/10 min. and a melt flow ratio of 35 to 250, which comprises lO to 70% by weight of an ethylene ~-olefin copolymer A and 90 to 30~ by weigh-t of an ethylene-~olefin copolymer B; said copolymer A having a higher molecular weight than copolymer B and being a copolymer of ethylene and an ~-olefin of 3 to 18 carbon a-toms and having a density of 0.895 to 0.935 g/cm3, an intrinsic viscosity of 1.2 to 6.0 dl/gl and a n~ber of short chain branches per 1000 carbon atoms (S.C.B.) of 7 to 40 and a (weight average molecular weight)/~umber average molecular weight) value of 2 to 10; said copolymer B being a copolymer of ethylene and an ~-olefin of 3 to 18 carbon atoms and having a density of 0.910 to 0O955 g/cm3, an intrinsic viscosity of 0.3 to 1.5 dl/g and S.C.B. of 5 to 35 and a (weight average molecular weight)/
(number average molecular weight) value of 2 to 10; said copolymer s~
A and said copo].ymer B being selected in order to satisfy a condition that (S oC~B~ of said copolymer A)/(S.C.B. of said copolymer B~ ls 0.6 to 1.7.
The present invention also provides a composition of copolymers of ethylene and an ~-olefin of 3 to 18 carbon atoms, having the following properties:
(1) density of 0.915 to 0.929 g/cm3, (2) intrinsic viscosity ~ of 0,7 to 4.0 dl/g, (3) melt index of 0.02 to 50 g/10 min, (4) the number of short chain branches per 1000 carbon atoms (SoC~B~) being 5 to 45~
(5) rn~ ~ Q namely gn being at least 0.8, where ~ ~ is an intrinsic viscosity of a linear polyethylene having the same weight average molecular wei.ght measured by a light scattering method,
(6) (S.C.B. of the first component group)/(S.C.B. of the second component group) being 0.6 to 0.8 where the two component groups are prepared by consolidating fractions obtained by column fractionation in two portions of lower and higher molecular weight components, said portions being selected so that the weight ratio of the two portions corresponds to the weight ratio of lower and higher molecular weight components calculated from the gel permea-tion chromatography curve,
(7) the second components have a density of 0.910 to 0.955 g/cm , an intrinsic viscosity of 0.3 to ].~5 dl/g and S.C~B. of 5 to 35,
(8) the first componerlts have a density of 0~895 to 0~935 g/cm3, an intrinsic viscosity of 1.~ to 6.0 dl/g and S.C.B. of 7 to 40, and . ,~ .
,. ~
,. ~
(9) the second components are 30 to 90% by weight and the first components are 70 to 10% by weight.
The ~irst feature of this invention is to provide an ethylene copolymer composition of which processabiltiy is about equal to or ~etter than that of high pressure polyethylenes and of which physical and chemical properties such as tensile s-trenth, impact strength, envlronmental stress crackiny resistance, creep chara~teristics, tear strength, transparency, heat-sealing charactertistics and chemicals resis-tance are very excellent.
-14a -~a .
J~ ~`: t `. ,. ~
1 The second feature of this invention is ~hat, because the product o~ this invention i.s excellent in mechanical strengths~ has a rigidity higher than those of high pressure polyethylenes and has a transparency about equal to that o~ high pressure polyethylenes, material saving can be expected with the product of this inven'Gion; for instance~ when this product is used for films, the same per~ormance can be obtained with the thickness 10 to 20% thinner than that of high pressure polyethylenes.
The third feature of this invention is that, because the product of this invention has extrusion processability superior to that of relatively low densi-ty ethylene-~-olefin copolymers by the conventional technique, conventional extruders being used for high pressure polyethylenes can be utilized for the present product without any modification.
The fourth feature of this invention is that, ~ OS ~Sr, ,~7 because the present p~oduct, even if p^~C~S~ ga melt index lower than t~ e of low density ethylene-~-olefin copolymers by the conventional technique~ shows satis-factory flow properties in actual processing, i'G gives excellent bubble stability and mechanical strengths of machine and transverse directions can be easily balanced, whereby molded products can have a uniform quality.
The fifth feature of this invention is that, because a resin composition less sticky than low density ethylene-a~-olefin copolymers by the conventional 1 technlque is ob~ained even when the density of the com-position is lowered, the composition can be applied even for the usages where transparency, flexibility and impact characteristics are required.
In the attached drawings, Figs. 1 to 6 show curves of molecular weight distrib~tions obtained from gel permeation chromatography. Broken lines in these ~igures are for diYiding lower molecular weight components and hlgher molecular weight components into two respective territories.
Fig. 7 is a typical example showing "distribu-tion of S.C.B. against molecular weight" of an ethylene-a-olefin copolymer of the conventional technique.
Fig. 8 shows correlations between melt indices (MI) and tensile impact strengths of ethylene~-olefin copolymers of the conventional technique, with their melt ~low ratios (MFR) used as a parameter.
~ ig. 9 shows correlations between MI and in-trinsic viscosities [n~ of a high pressure polyethylene and a linear polyethylene of the medium to low pressure method as a ~lethod for distinguishing these two polymers.
In the figure, a broken line is drawn to separate two territories, the left side territory is for the high pressure polyethylene of the conventional technique and the right side territory is for the linear polyethylene of the medium to low pressure method.
The present invention will be explained in more detail below.
An ethylene-~-olefin copolymer of a relatively high molecular weight (hereinafter referred to as "copolymer A") which is used in the present invention as one mixing compo~ent, is a copolymer of ethylene and an ~-olefin o~ 3 to 18 carbon atoms.
This a-olefin is one represented by the yeneral formula R-CH=CH2 wherein R is an alkyl group of l to 16 carbon atoms. Examples of the ~-olefin include propylene, butene-l, pentene-l, hexene-l, heptene-l, octene-l, nonene-l, decene-l, 4-methyl-pentene-1, 4-methyl-hexene l and 4, 4-dimethyl-pentene~l. ~nong these o]efins, a~ole~ins of at least 4 carbon atoms are preferred. Particularly, butene-l, pentene-l, hexene-l, octene~l and 4-methyl-pentene-l are preferred from the standpoints of monomer availability, copolymer-izability and quality of polymer obtained. These a-olefins can be used alone or in combinations of two or more. The density of the copolymer A is influenced ~y the kind of an ~-olefin used, the content of the olefin and the in~rinsic viscosity of the copolymer.
For the object o this invention, the density is required to be 0.895 to 0.935 g/cm3 and more preferably 0.895 to 0.930 g/cm3. At a density smaller than 0.895 g/cm3, copolymers stick to the reactor walls causing polymerization difficult, or, the density of the relatively lower molecular weight copolymer (namely "copolymer B" which is described later and used as ano-ther mixing component in the present invention) is required to be raised, resulting in formation of polymer compositions of undesirable quali-ties such as films of poor transparency.
In the density higher than 0.930 g/cm3, the content of the ~-olefin in the copolymer A becomes very low, and the copoly-mer A of such a high density does no-t give satisfactory mechan-ical strengths. For instance, in films, balancing of MD and TD strengths becomes difficult and heat-sealing characteris-tics get worse. S.C.B. in the copolymer A is 7 to 40 and preferable 10 to 40. (~hen R in the above ~-olefin formula is a linear alkyl group, the number of methyl groups a-t branch ends per lO00 carbon atoms is S.C.B. When R is an alkyl group with a branch or branches, for instance, the ~-olefin is ~-methyl-pentene l, the branch is isobutyl group and the half nurr~er of methyl groups at the branch ends is S.C.B ) Short chain branching in ethylene-~-olefin copolymers occurs due to ~-olefins and it hinders crystallization mainly of ethylene sequences and lowers densities. These effects vary depending upon the kind of ~-olefin. Short chain branching is considered to also make some contribution to formation of interlamella molecules, and ultimately affects mechanical s-trengths and thermal properties of copolymers obtained. I'herefore, when S.C.B. is below ~, mechanical strengths and heat-sealing prop-erties of the composition become poor. For instance, in films, balancing of MD and TD strengths is difficult. When S.C.B. is over 40, where occur problems in polymerization of the copoly-mer A. Also the transparency of polymer compositions obtained frorr. the copolymer becomes poor.
~ . ~
5~
The molecular weight of the copolymer A i~ ~enerally 1.2 to 6.0 dl/g in terms of intrinsic viscosity and preferably 1.2 -to 4.5 dl/g. When the intrinsic viscosity is below 1.2 ~1/g, th~ mechanical strength ofthe polymer compositions of -the present invention are reduced. When it is over 6.0 ~l/g, mix-ing with the copolymer s becomes difficult, and the polymer compositions obtained have fish eyes and further their flow properties become worse, as well as their transparency is re-duced. Where the comp~sition is to be used for injec-tion mold-ing, the intrinslc viscosity is preferably 1.2 to 4.0 dl/g and more preferably 1.2 to 3.0 dl/g. If it is less than 1.2 dl/g, mechanical strengths of compositions are lowered. If it is over 4.0 dl/g, mi~ing with the copolymer B becomes insuffi-cient, and polymer composi-tions obtained have fish eyes, deter-iorated flow properties (tend to cause flow marks) and reduced transparency.
The (weight average molecular weigh-t)/(number average molecular weight) ratio of the copolymer A, which is a measure for the molecular weight distribution of the copolymer obtained from gel permeation chromatography (hereinaf-ter abbreviated as "GPC"), should be 2 to 10 and preferably 3 to 8. If it is less than 2, such a copolymer A is difficult to produce. If it is over 10, the polymer compositions have lower mechanical stren~th and, when processed into films, cause blocking.
The ethylene-~-olefin copolymer of a relatively low molecular weight (hereinafter abbreviated as "copolymer B") `
which is used in the present invention as another mixiny com-ponent, is a copolymer of ethylene and an ~-olefin of 3 to 18 carbon atoms. As ~-olefins, there may be selected the ~-olefins used in the copolymer A. The density of copolymer B is normally Oo910 to 0.955 g/cm3. Pre~erably, it i5 O. 915 to 0~953 g/cm3.
When the densit~ is below 0.910 g/cm3, the mechanical strength of the copolymer compositions decreases and blocking is caused due to bleeding of lower molecular weight components of low den-sity on film surfaces. When the density is over 0.955 g/cm3 it is too high and, the transparency of the copolymer compositions becomes worse. Where the composi-tion is to be used for injec-tion molding, the density of the copolymer B should be 0.910 to 0.950 g/cm3 and preferably 0.915 to 0.948 g/cm3. When the den-sity is below 0.910 g/cm3, the mechanical strength ofthe compo-sitions is reduced and surface tackiness occurs. When the den~
sity is over 0.950 g/cm3, compositions have too high densities.
S.C.B. of the copolymer B is 5 to 35 and preferably 7 to 30.
When S.C.B. is below 5, the copolymer B has a lower molecular weight as a whole and its crystallization speed is too fast, resulting in poor transparency of the compositions. When S.C.B.
is over 35, reduction in mechanical strength aswell as blocking in films occurs.
The molecular weight of the copolymer B in terms of intrinsic viscosi-ty is 0.3 to 1.5 dl/y, preferably 0.4 to 1.5 dl/g. When the intrinsic viscosity is less than 0.3 dl/g, the mechanical strength and the transparency of the composi-tions .`~'. ' are reduced. When it is over 1.5 ~l/g, the fluidity of the com-positions is poor. Where the composition is to be used for in-jection molding, -the molecular weight of the copolymer s in terms of intrinsic viscosity should be 0.3 to 1.2 dl/g, pref-errably 0.4 to 1.2 dl/g. When the intrinsic viscosity is below 0.3 dl/g, the mechanical strength and the transparency of the composi-tions are reduced. When it is over 1.2 dl/g, the fluidi-ty of the compositions is poor.
The value of (weight average molecular weight)/(number average mulecular weight), namely, Mw/Mn of the copolymer B
determined by gel permeation chromatography (GPC) is 2 to 10, preferably 3 to 8. When Mw/Mn is below 2, the copolymer B is difficult -to produce. When it is over 10, the mechanical strength of the compositions are reduced and surface tackiness of films occurs.
The copolymer A and the copolymer B as mentioned above can be obtained by copolymerizing ethylene and an ~-olefin of 4 to 18 carbon atoms under a medium to low pressure using a transition metal catalyst. For instance, catalysts such as Ziegler type catalyst and Phillips type catalyst as well as polymerization methods such a~ slurry polymerization, gas phase polymerization and solution polymerization are used. As cata-lysts, a Ziegler type catalyst system using a carrier~supported Ziegler catalyst component is .~
z 1 convenient in this invention from i~s activi~y and co-polymeri~abilit~. Specific examples of an effec~ive carrier of ~his carrier-supported Ziegler catalyst component include oxides, hydroxides, chlorides and carbonates of metals and silicon and their mixtures as ~ell as inorganic complexes. More specifically, they are magnesium oxides, titanium oxides, silica~ aluminag magnesium carbonates, divalent metal hydroxychlorides, magnesium hydroxides, magnesium chlorides, magnesium alkoxides, magnesium haloalkoxides, double oxides of magnesium and aluminum and double oxides of magnesium and calcium. Among these compounds, magnesium com-pounds are particularly preferred. The following magne-sium compounds are particularly preferred. The following magnesium compound carrier is most preferred in the production of the low density polyethylene type resin composition of this invention, because it gives a satis~
factory slurry wi~h no abnormal tackiness and there occurs no sticking of polymers to the reactor wall.
(Reference is made to Japanese Patent Publication No.
23561/1980.) Namely, it is the carrier obtained by (a) reacting in a sol~ent an aluminum halide represented by the general formula RnAlX3 n (R is an alkyl, aryl or alkenyl group of 1 to 20 carbon atoms and X is a halogen atom and n is an integer of 0 to 3) and/or a silicon halide represented by the general formula R'SiX4 m (R' is an alkyl, aryl or alkenyl group of 1 to 20 carbon atoms and X is a halogen at;om and m is an integer of 0 to 4) with an organomagnesium compound represen-ted by the general formulas R"MgX and/or R2Mg (R" i5 an alkyl, aryl or alkenyl group of 1 to 20 carhon atoms and X is a halogen atom), and (~) isolat-ing the solid product formed.
As a transition metal catalyst component supported on carriers, there are, for instance, titanium compounds, vanadium compounds and zirconium compounds. Specific axamples include titanium tetrachloride, titanium tetrahromide, titanium -tetra-iodide, titanium trichloride, titanium alkoxy halides or titanium aryloxy halides represented by the general formula Ti(oRl)~ pXp (where Rl is a hydrocarbon group, X is a halogen atom and p is an integer of 0 < p < 4), vanadium tetrachloride, vanadium oxy trichloride, zirconium tetrachloride and zirconium alkoxy halides or zirconium aryloxy halides represented by the general formula Zr(OR2)4 qXq (where R2 is a hydrocarbon group, X is a halogen atom and q is an integer of 0 < q < 4). Among these compounds, titanium compounds and/or vanadium compounds are particularly preferred in the production of -the low density polyethylene type resin composition of this invention, because they give satisfactory slurries with no abnormal tackiness and there occurs almost no sticking of polymers to the reactor wall. (Reference is made to Japanese Patent Publication No. 23561/1980.) Titanium compounds are most preferred from the standpoints of weather resistance and heat resistance.
1 As a component o~ carrier-supported Ziegler catalysts used in this invention, there are also reaction products between an organomagnesium compound and a transition metal compound. Here, the transition metal compound is represented by ~he general formula Ti(oR3)4 rXr (where ~3 is a hydrocarbon group, X is a halogen a~om and r ls an integer o~ 0 _ r < 4, and includes titanium tetrahalides, titanium alkoxides, titanium aryloxides~ titanium alkoxy halides and titanium aryloxy haIides.
As an organometal compound component which forms the catalyst system of this in~ention together with the carrier-supported Ziegler catalyst component, there are organoaluminum compounds such as trialkyl aluminums (triethyl aluminum, tri-n-propyl aluminum, tri-i-butyl alminum, tri-n-butyl aluminum, tri-n-hexyl aluminum, e~;c.), dialkyl aluminum monohalides (diethyl aluminum monochloride~ di-n-propyl aluminum monochloride, di-i-butyl aluminum monochloride, di n-butyl aluminum mono-chloride, di-n-hexyl aluminum monochloride, etc.), alkyl aluminum dihalides (ethyl aluminum dichloride, n-propyl aluminum dichloride, i-butyl aluminum dichloride~ n-butyl aluminum dichloride~ n-hexyl aluminum dichloride, etc.), ethyl aluminum sesquichloride, i-propyl aluminum sesqui-chloride, i-butyl aluminum sesquichloride, n-butyl aluminum sesquichloride and n-hexyl aluminum sesqui-chloride as well as other organometal compounds such as organozinc compounds. These organometal compounds may - 2~ -be used alo~e or in combin~tion of tw~ or more.
In compounding the composition of this invention using the ethylene-~-olefin copolymer A of relatively higher molecular weight and the ethylene-a-olefin copolymer B of relatively lower molecular weight both oE which are obtained with the above catalyst system under a normal medium -to low pressure polymerization method, the following ma~ters must be obeyed.
(l) From -the standpoint of mechanlcal streng-ths, the co-polymers A and B must be selected in order tha-t (S.C.B. of co-polymer A)/(S.C.B. of copolymer B) becomes at least 0.6, pref-erably at least 0.8 and more preferable at least l.O. Mean-while, from the standpoint of transparency, it is necessary that (S.~.B. of copolymer A)/(S.C.B. of copolymer B) is 0.6 to 1.7.
When this ratio is below 0.6, mechanical strengths of the co-polymer composition obtained are reduced. In films, for in-stance, balancing of MD and TD strengths is difficult, heat-sealing characteristics worsen and tackiness is seen. In case of over 1.7, transparency of the copolymer composi-tion is re-duced.
(2) The densi-ty of the copolymer composition is 0.915 to 0.929 g/cm . When the density is below the above lower limi-t, mechanical strengths of the composition is reduced and, ln case of films, tackiness is seen. I~hen the density is above -the upper limit, transparency of the composition worsens.
~1 ~
Where the composition is to be used for extrusion processing, and the density is below the lower limit, the mech-anical strength of the composition is reduced and the products have tackiness. When the density is above the upper limit, the transparency worsens.
Where the composition is -to be used for film pro-cessing and the density is below the lower limit, the mechani-cal strength of the composition is reduced and the fi]ms possess tackiness. When the density is above the upper limit, the transparency worsens.
Where the composition is -to be used, for injection molding and the density is below the lower limit, the mechani-cal strength of the composition is reduced and the molded pro-ducts have tackiness. When the density is above the upper limit, transparency worsens.
(3) The melt index of the copolymer composition is nor-mally preferred to be 0.02 to 50 g/10 min. and more preferred to be 0.05 to 40 g/10 min. and most preferred to be 0.1 to 30 g/10 min. In addition, the melt flow ratio is preferred to be ~5 to 250 and more preferred to be 35 to 200 and most preferred to be 35 to 150. Furthermore, the product of the melt index and the ,,' 1,:
1 melt flow ratio is preferred to be at leas~ 4 and more preferred to be at least 7. When the melt :index and the melt flow ratio are below the lower limits, extrusion processabili~y ~orsens. When they are above the upper limlits~ bubble stability in blown film proces-sing is lost and mechanical strengths are reduced.
In the field of extrusion processing, the MI
of the copolymer composition is preferred to be 0.02 to 2.0 g/10 min. and more preferred to be 0.05 to 2.0 g/
The ~irst feature of this invention is to provide an ethylene copolymer composition of which processabiltiy is about equal to or ~etter than that of high pressure polyethylenes and of which physical and chemical properties such as tensile s-trenth, impact strength, envlronmental stress crackiny resistance, creep chara~teristics, tear strength, transparency, heat-sealing charactertistics and chemicals resis-tance are very excellent.
-14a -~a .
J~ ~`: t `. ,. ~
1 The second feature of this invention is ~hat, because the product o~ this invention i.s excellent in mechanical strengths~ has a rigidity higher than those of high pressure polyethylenes and has a transparency about equal to that o~ high pressure polyethylenes, material saving can be expected with the product of this inven'Gion; for instance~ when this product is used for films, the same per~ormance can be obtained with the thickness 10 to 20% thinner than that of high pressure polyethylenes.
The third feature of this invention is that, because the product of this invention has extrusion processability superior to that of relatively low densi-ty ethylene-~-olefin copolymers by the conventional technique, conventional extruders being used for high pressure polyethylenes can be utilized for the present product without any modification.
The fourth feature of this invention is that, ~ OS ~Sr, ,~7 because the present p~oduct, even if p^~C~S~ ga melt index lower than t~ e of low density ethylene-~-olefin copolymers by the conventional technique~ shows satis-factory flow properties in actual processing, i'G gives excellent bubble stability and mechanical strengths of machine and transverse directions can be easily balanced, whereby molded products can have a uniform quality.
The fifth feature of this invention is that, because a resin composition less sticky than low density ethylene-a~-olefin copolymers by the conventional 1 technlque is ob~ained even when the density of the com-position is lowered, the composition can be applied even for the usages where transparency, flexibility and impact characteristics are required.
In the attached drawings, Figs. 1 to 6 show curves of molecular weight distrib~tions obtained from gel permeation chromatography. Broken lines in these ~igures are for diYiding lower molecular weight components and hlgher molecular weight components into two respective territories.
Fig. 7 is a typical example showing "distribu-tion of S.C.B. against molecular weight" of an ethylene-a-olefin copolymer of the conventional technique.
Fig. 8 shows correlations between melt indices (MI) and tensile impact strengths of ethylene~-olefin copolymers of the conventional technique, with their melt ~low ratios (MFR) used as a parameter.
~ ig. 9 shows correlations between MI and in-trinsic viscosities [n~ of a high pressure polyethylene and a linear polyethylene of the medium to low pressure method as a ~lethod for distinguishing these two polymers.
In the figure, a broken line is drawn to separate two territories, the left side territory is for the high pressure polyethylene of the conventional technique and the right side territory is for the linear polyethylene of the medium to low pressure method.
The present invention will be explained in more detail below.
An ethylene-~-olefin copolymer of a relatively high molecular weight (hereinafter referred to as "copolymer A") which is used in the present invention as one mixing compo~ent, is a copolymer of ethylene and an ~-olefin o~ 3 to 18 carbon atoms.
This a-olefin is one represented by the yeneral formula R-CH=CH2 wherein R is an alkyl group of l to 16 carbon atoms. Examples of the ~-olefin include propylene, butene-l, pentene-l, hexene-l, heptene-l, octene-l, nonene-l, decene-l, 4-methyl-pentene-1, 4-methyl-hexene l and 4, 4-dimethyl-pentene~l. ~nong these o]efins, a~ole~ins of at least 4 carbon atoms are preferred. Particularly, butene-l, pentene-l, hexene-l, octene~l and 4-methyl-pentene-l are preferred from the standpoints of monomer availability, copolymer-izability and quality of polymer obtained. These a-olefins can be used alone or in combinations of two or more. The density of the copolymer A is influenced ~y the kind of an ~-olefin used, the content of the olefin and the in~rinsic viscosity of the copolymer.
For the object o this invention, the density is required to be 0.895 to 0.935 g/cm3 and more preferably 0.895 to 0.930 g/cm3. At a density smaller than 0.895 g/cm3, copolymers stick to the reactor walls causing polymerization difficult, or, the density of the relatively lower molecular weight copolymer (namely "copolymer B" which is described later and used as ano-ther mixing component in the present invention) is required to be raised, resulting in formation of polymer compositions of undesirable quali-ties such as films of poor transparency.
In the density higher than 0.930 g/cm3, the content of the ~-olefin in the copolymer A becomes very low, and the copoly-mer A of such a high density does no-t give satisfactory mechan-ical strengths. For instance, in films, balancing of MD and TD strengths becomes difficult and heat-sealing characteris-tics get worse. S.C.B. in the copolymer A is 7 to 40 and preferable 10 to 40. (~hen R in the above ~-olefin formula is a linear alkyl group, the number of methyl groups a-t branch ends per lO00 carbon atoms is S.C.B. When R is an alkyl group with a branch or branches, for instance, the ~-olefin is ~-methyl-pentene l, the branch is isobutyl group and the half nurr~er of methyl groups at the branch ends is S.C.B ) Short chain branching in ethylene-~-olefin copolymers occurs due to ~-olefins and it hinders crystallization mainly of ethylene sequences and lowers densities. These effects vary depending upon the kind of ~-olefin. Short chain branching is considered to also make some contribution to formation of interlamella molecules, and ultimately affects mechanical s-trengths and thermal properties of copolymers obtained. I'herefore, when S.C.B. is below ~, mechanical strengths and heat-sealing prop-erties of the composition become poor. For instance, in films, balancing of MD and TD strengths is difficult. When S.C.B. is over 40, where occur problems in polymerization of the copoly-mer A. Also the transparency of polymer compositions obtained frorr. the copolymer becomes poor.
~ . ~
5~
The molecular weight of the copolymer A i~ ~enerally 1.2 to 6.0 dl/g in terms of intrinsic viscosity and preferably 1.2 -to 4.5 dl/g. When the intrinsic viscosity is below 1.2 ~1/g, th~ mechanical strength ofthe polymer compositions of -the present invention are reduced. When it is over 6.0 ~l/g, mix-ing with the copolymer s becomes difficult, and the polymer compositions obtained have fish eyes and further their flow properties become worse, as well as their transparency is re-duced. Where the comp~sition is to be used for injec-tion mold-ing, the intrinslc viscosity is preferably 1.2 to 4.0 dl/g and more preferably 1.2 to 3.0 dl/g. If it is less than 1.2 dl/g, mechanical strengths of compositions are lowered. If it is over 4.0 dl/g, mi~ing with the copolymer B becomes insuffi-cient, and polymer composi-tions obtained have fish eyes, deter-iorated flow properties (tend to cause flow marks) and reduced transparency.
The (weight average molecular weigh-t)/(number average molecular weight) ratio of the copolymer A, which is a measure for the molecular weight distribution of the copolymer obtained from gel permeation chromatography (hereinaf-ter abbreviated as "GPC"), should be 2 to 10 and preferably 3 to 8. If it is less than 2, such a copolymer A is difficult to produce. If it is over 10, the polymer compositions have lower mechanical stren~th and, when processed into films, cause blocking.
The ethylene-~-olefin copolymer of a relatively low molecular weight (hereinafter abbreviated as "copolymer B") `
which is used in the present invention as another mixiny com-ponent, is a copolymer of ethylene and an ~-olefin of 3 to 18 carbon atoms. As ~-olefins, there may be selected the ~-olefins used in the copolymer A. The density of copolymer B is normally Oo910 to 0.955 g/cm3. Pre~erably, it i5 O. 915 to 0~953 g/cm3.
When the densit~ is below 0.910 g/cm3, the mechanical strength of the copolymer compositions decreases and blocking is caused due to bleeding of lower molecular weight components of low den-sity on film surfaces. When the density is over 0.955 g/cm3 it is too high and, the transparency of the copolymer compositions becomes worse. Where the composi-tion is to be used for injec-tion molding, the density of the copolymer B should be 0.910 to 0.950 g/cm3 and preferably 0.915 to 0.948 g/cm3. When the den-sity is below 0.910 g/cm3, the mechanical strength ofthe compo-sitions is reduced and surface tackiness occurs. When the den~
sity is over 0.950 g/cm3, compositions have too high densities.
S.C.B. of the copolymer B is 5 to 35 and preferably 7 to 30.
When S.C.B. is below 5, the copolymer B has a lower molecular weight as a whole and its crystallization speed is too fast, resulting in poor transparency of the compositions. When S.C.B.
is over 35, reduction in mechanical strength aswell as blocking in films occurs.
The molecular weight of the copolymer B in terms of intrinsic viscosi-ty is 0.3 to 1.5 dl/y, preferably 0.4 to 1.5 dl/g. When the intrinsic viscosity is less than 0.3 dl/g, the mechanical strength and the transparency of the composi-tions .`~'. ' are reduced. When it is over 1.5 ~l/g, the fluidity of the com-positions is poor. Where the composition is to be used for in-jection molding, -the molecular weight of the copolymer s in terms of intrinsic viscosity should be 0.3 to 1.2 dl/g, pref-errably 0.4 to 1.2 dl/g. When the intrinsic viscosity is below 0.3 dl/g, the mechanical strength and the transparency of the composi-tions are reduced. When it is over 1.2 dl/g, the fluidi-ty of the compositions is poor.
The value of (weight average molecular weight)/(number average mulecular weight), namely, Mw/Mn of the copolymer B
determined by gel permeation chromatography (GPC) is 2 to 10, preferably 3 to 8. When Mw/Mn is below 2, the copolymer B is difficult -to produce. When it is over 10, the mechanical strength of the compositions are reduced and surface tackiness of films occurs.
The copolymer A and the copolymer B as mentioned above can be obtained by copolymerizing ethylene and an ~-olefin of 4 to 18 carbon atoms under a medium to low pressure using a transition metal catalyst. For instance, catalysts such as Ziegler type catalyst and Phillips type catalyst as well as polymerization methods such a~ slurry polymerization, gas phase polymerization and solution polymerization are used. As cata-lysts, a Ziegler type catalyst system using a carrier~supported Ziegler catalyst component is .~
z 1 convenient in this invention from i~s activi~y and co-polymeri~abilit~. Specific examples of an effec~ive carrier of ~his carrier-supported Ziegler catalyst component include oxides, hydroxides, chlorides and carbonates of metals and silicon and their mixtures as ~ell as inorganic complexes. More specifically, they are magnesium oxides, titanium oxides, silica~ aluminag magnesium carbonates, divalent metal hydroxychlorides, magnesium hydroxides, magnesium chlorides, magnesium alkoxides, magnesium haloalkoxides, double oxides of magnesium and aluminum and double oxides of magnesium and calcium. Among these compounds, magnesium com-pounds are particularly preferred. The following magne-sium compounds are particularly preferred. The following magnesium compound carrier is most preferred in the production of the low density polyethylene type resin composition of this invention, because it gives a satis~
factory slurry wi~h no abnormal tackiness and there occurs no sticking of polymers to the reactor wall.
(Reference is made to Japanese Patent Publication No.
23561/1980.) Namely, it is the carrier obtained by (a) reacting in a sol~ent an aluminum halide represented by the general formula RnAlX3 n (R is an alkyl, aryl or alkenyl group of 1 to 20 carbon atoms and X is a halogen atom and n is an integer of 0 to 3) and/or a silicon halide represented by the general formula R'SiX4 m (R' is an alkyl, aryl or alkenyl group of 1 to 20 carbon atoms and X is a halogen at;om and m is an integer of 0 to 4) with an organomagnesium compound represen-ted by the general formulas R"MgX and/or R2Mg (R" i5 an alkyl, aryl or alkenyl group of 1 to 20 carhon atoms and X is a halogen atom), and (~) isolat-ing the solid product formed.
As a transition metal catalyst component supported on carriers, there are, for instance, titanium compounds, vanadium compounds and zirconium compounds. Specific axamples include titanium tetrachloride, titanium tetrahromide, titanium -tetra-iodide, titanium trichloride, titanium alkoxy halides or titanium aryloxy halides represented by the general formula Ti(oRl)~ pXp (where Rl is a hydrocarbon group, X is a halogen atom and p is an integer of 0 < p < 4), vanadium tetrachloride, vanadium oxy trichloride, zirconium tetrachloride and zirconium alkoxy halides or zirconium aryloxy halides represented by the general formula Zr(OR2)4 qXq (where R2 is a hydrocarbon group, X is a halogen atom and q is an integer of 0 < q < 4). Among these compounds, titanium compounds and/or vanadium compounds are particularly preferred in the production of -the low density polyethylene type resin composition of this invention, because they give satisfactory slurries with no abnormal tackiness and there occurs almost no sticking of polymers to the reactor wall. (Reference is made to Japanese Patent Publication No. 23561/1980.) Titanium compounds are most preferred from the standpoints of weather resistance and heat resistance.
1 As a component o~ carrier-supported Ziegler catalysts used in this invention, there are also reaction products between an organomagnesium compound and a transition metal compound. Here, the transition metal compound is represented by ~he general formula Ti(oR3)4 rXr (where ~3 is a hydrocarbon group, X is a halogen a~om and r ls an integer o~ 0 _ r < 4, and includes titanium tetrahalides, titanium alkoxides, titanium aryloxides~ titanium alkoxy halides and titanium aryloxy haIides.
As an organometal compound component which forms the catalyst system of this in~ention together with the carrier-supported Ziegler catalyst component, there are organoaluminum compounds such as trialkyl aluminums (triethyl aluminum, tri-n-propyl aluminum, tri-i-butyl alminum, tri-n-butyl aluminum, tri-n-hexyl aluminum, e~;c.), dialkyl aluminum monohalides (diethyl aluminum monochloride~ di-n-propyl aluminum monochloride, di-i-butyl aluminum monochloride, di n-butyl aluminum mono-chloride, di-n-hexyl aluminum monochloride, etc.), alkyl aluminum dihalides (ethyl aluminum dichloride, n-propyl aluminum dichloride, i-butyl aluminum dichloride~ n-butyl aluminum dichloride~ n-hexyl aluminum dichloride, etc.), ethyl aluminum sesquichloride, i-propyl aluminum sesqui-chloride, i-butyl aluminum sesquichloride, n-butyl aluminum sesquichloride and n-hexyl aluminum sesqui-chloride as well as other organometal compounds such as organozinc compounds. These organometal compounds may - 2~ -be used alo~e or in combin~tion of tw~ or more.
In compounding the composition of this invention using the ethylene-~-olefin copolymer A of relatively higher molecular weight and the ethylene-a-olefin copolymer B of relatively lower molecular weight both oE which are obtained with the above catalyst system under a normal medium -to low pressure polymerization method, the following ma~ters must be obeyed.
(l) From -the standpoint of mechanlcal streng-ths, the co-polymers A and B must be selected in order tha-t (S.C.B. of co-polymer A)/(S.C.B. of copolymer B) becomes at least 0.6, pref-erably at least 0.8 and more preferable at least l.O. Mean-while, from the standpoint of transparency, it is necessary that (S.~.B. of copolymer A)/(S.C.B. of copolymer B) is 0.6 to 1.7.
When this ratio is below 0.6, mechanical strengths of the co-polymer composition obtained are reduced. In films, for in-stance, balancing of MD and TD strengths is difficult, heat-sealing characteristics worsen and tackiness is seen. In case of over 1.7, transparency of the copolymer composi-tion is re-duced.
(2) The densi-ty of the copolymer composition is 0.915 to 0.929 g/cm . When the density is below the above lower limi-t, mechanical strengths of the composition is reduced and, ln case of films, tackiness is seen. I~hen the density is above -the upper limit, transparency of the composition worsens.
~1 ~
Where the composition is to be used for extrusion processing, and the density is below the lower limit, the mech-anical strength of the composition is reduced and the products have tackiness. When the density is above the upper limit, the transparency worsens.
Where the composition is -to be used for film pro-cessing and the density is below the lower limit, the mechani-cal strength of the composition is reduced and the fi]ms possess tackiness. When the density is above the upper limit, the transparency worsens.
Where the composition is -to be used, for injection molding and the density is below the lower limit, the mechani-cal strength of the composition is reduced and the molded pro-ducts have tackiness. When the density is above the upper limit, transparency worsens.
(3) The melt index of the copolymer composition is nor-mally preferred to be 0.02 to 50 g/10 min. and more preferred to be 0.05 to 40 g/10 min. and most preferred to be 0.1 to 30 g/10 min. In addition, the melt flow ratio is preferred to be ~5 to 250 and more preferred to be 35 to 200 and most preferred to be 35 to 150. Furthermore, the product of the melt index and the ,,' 1,:
1 melt flow ratio is preferred to be at leas~ 4 and more preferred to be at least 7. When the melt :index and the melt flow ratio are below the lower limits, extrusion processabili~y ~orsens. When they are above the upper limlits~ bubble stability in blown film proces-sing is lost and mechanical strengths are reduced.
In the field of extrusion processing, the MI
of the copolymer composition is preferred to be 0.02 to 2.0 g/10 min. and more preferred to be 0.05 to 2.0 g/
10 min. and most preferred to be 0.10 to 2.0 g/10 min.
Further, the MFR is preferred to be 35 to 250 and more preferred to be 35 to 200 and most preferred to be 35 to 150. Furthermore, the product of MI and MFR is preferred to be at least 4 and more preferred to be at least 7.
When the MI and the MFR are below the lower limits, extrusion processability worsens. When they are above the upper limits, mechanical strengths are reduced.
In the field of film processing, the MI of the composition is preferred to be 0.02 to 5 g/10 min. and more preferred to be 0.05 to 4 g/10 min. and most pre-ferred to be 0.1 to 3 g/10 min. Further, its MFR is preferred to be 35 to 250 and more preferred to be 35 to 200 and most preferred to be 35 to 150. Furthermore, the product of the MI and the MFR is preferred to be at least 4 and more preferred to be at least 7. When the MI and the MFR are below the lower limits, extrusion processability worsens. When they are above the upper limits, bubble stability in blown film processing is 1 insufficient and mechanical strengths are reduced.
Inthe ~ield o~ injec~ion molding, the MI o~
the composit~on is preferred ~o be 2.0 to 50 g/10 min.
and more preferred to be 2.0 to 30 g/10 min. ~urther~
the MFR is preferred to be 35 to 80 and more pre~erred to be 35 to 70. When the MI is below the lower limit~
moldability worsens and flow marks are produced.
When it is above the upper limit, mechanical strengths are reduced.
In order to provide the composition of this invention excellent in processability and mechanical strengths, it is also important to adequately balance its MI and MFR. A lower MI requires a higher MFR. This requirement is expressed by ~he product of MI and MFR.
For instance, a composition having a MI of about 1 g/
10 min, even if its MFR is as low as 50 to 60, has processability about equal to that of a high pressure polyethylene having the same MI. On the other hand, a composition having a MI of about 0.05 g/10 min.
and a MFR of 50 possesses extremely poor processability and, in order to have satisfactory processability, a MFR of at least 80 is required. The product of MI and MFR of a composition is designed appropriately to meet the requirement of its final application. The designed value of the product o~ MI and MFR can be achieved in the composition by using (a) intrinsic viscosities of the copolymer A of relatively higher molecular weight and the copolymer B of relatively lower molecular weight~
1 (b) values of (weight average molecular weight)/(number average molecular weight) of these copolymers an~ (c) their mixing ratio. If intrinsic viscosities of the copolymer A and the copolymer B are put as ~n ]A (dl/g) and [~]B (dl/g), respectively, and their ratios by weight basis are put as WA and WB (WA + WB = 1), respectively the intrinsic viscosity of the composition obtained by mixing the two copolymers namely [~]T (dl/g) is approxi-mately given by the following formula.
[~1] -. [n]AwA .+ [n~BWB
MI is governed by [n]T unequivocally. Meanwhile, MFR is generally larger when [n ]A/[n]B is larger, and depends upon WA and WB. Therefore, it is difficult to express MF~ unequivocally and, based on preliminary tests, [n ]A~
[n]B, WA and WB are determined to give an intended MFR.
,s~
(L,) In order to obtain a composition which S_~i3Ly the above (1) to (3) conditions, the copolymer A and the copolymer B are preferred to be mixed at a ratio of 10 to 70% by weight (copolymer A) to 90 to 30% by weight (copolymer B). The ratio of 20 to 65% by weight to 80 to 35% by weight is more preferred and the ratio of 30 to 60% by weight to 70 to 40% by weight is most preferred.
The mixing ratio of the two copolymers must be adequately selected by considering S.C.B., densities, intrinsic viscosities and molecular weight distributions of the copolymers A and B as well as the density, MI and MFR
5 ~;~
of an intended composition. I~hen the ratio of the copolymer A
is below its lower limit and the ratio of ~he copolymer B is above its upper limit, the ESC~, impact strenyth, tear strength and low temperature resistance of the composition obtained are poor, and the high strength of the composition of this invention which is obtained when the value oE (S.C.B. of copolymer ~)/-(S.C.B. of copolymer B) is selected to be at least 0.6 as well as the good transparency of the composition of this invention which is obtained when the value of (S.C.~. of copolymer A)/-(S.C.B. of copolymer B) is selected to be 0.6 to 1.7, are not achieved. When the ratio of the copolymer A i5 above its upper limit and the ratio of the copolymer s is below its lower limit, the processability of the compositlon obtained worsens.
As long as the scope of this invention is obeyed, mixing of the ethylene-~ olefin copolymer A of relatively higher molecular weight and the ethylene-~olefin copolymer s of relatively lower molecular weight is not necessarily limited to mixing one of each kind. The mixing may be also done by using two or more kinds of each of the copolymer A and the copolymer B.
There is no particular limitation -to mixing me~hods of the copolymers A and B, and known methods can be used in mixing of these two polymers. Commonly used are a batch type melt kneading method which employs a twin roll or a sanbury mixer af~er separate produc~ion of the copolymers A and B, a continuous melt kneading ~'`''~
1 method employing a twin rotor mixer such as CIM (rnanu-factured by the Japan Steel Works) or FCM (manufactured by Kobe Steel) or a single screw extruder and a solution m~xing method in which a mixture is obtained by dissolv-ing the copolymers A and B in a solvent separately ortogether, blending and finally removing the solvent.
When the copolymers A and B are produced by a high temperature solution polymerization method, it is ad-vantageous from the process standpoint that their composition is obtained by mixing A and B in a solution state at high temperatures and removing the solvent.
Mixing by a two- or multi-stage polymerization method is also possible. In this method, in the first stage, the copo]ymer A is polymerized for a certain length of time and, successively in the second stage, the copolymer B is polymerized using the same catalyst but changing other polymerization conditions until the composition containing the copolymers A and ~ at an intended ratio is obtained~ In this case, the order of polymerization of A and B is not restricted.
The above two- or multi-stage polymerization method is an ideal mixing method, because the copolymers A and B undergo molecular dispersion.
The most effective mixing method can be se-lected from above various mixing methods, in order toobtain a uniform composition, which meets inten~ed requirements.
The intrinsic viscosity [rl] of the ethylene-~-l olefin copolymer composition of this inv~ntion is pre~er-red to be 0.7 to 4 dl/g and more preferred to be 0.8 to 3.5 dl/g and most preferred to be 0.9 to 3 dl/g. When the intrinsic viscosity is below the lower limit, 5 mechanical strengths are reduced and, in blown film processing, bubble stability is insufficient. In case of above the upper limit, extrus~on processability worsens.
S.C.B. of thè composition is preferred to be 5 to 45 and more preferred to be 7 to 40 and most preferred to be 10 to 40. When S.C.B. is below its lower limit, transparency worsens. When S.C.B. is above its upper limit, mechanical strengths are reduced and molded products have tackiness.
Next, the "index of long chain branching" of the copolymer composition of this invention is described.
When the intrinsic viscosity of a copolymer composition o~ this invention is put as [ n] and the intrinsic viscosity of a linear polyethylene having the same Mw measured by light scattering method (a high density polyethylene obtained by homopolymerization of eth~lene under a medium to low pressure using a Ziegler catalyst) is put as [n]Q, [n]/[n]Q namely ~* is called the "index of long chain branching" of the composition and indicates the extent o~ presence of long chain branching ~n the composition.
Now, intrinsic viscosities of two polymers are compared.
One polymer X is a polyethylene having long chain branches of which index of branching is unknown (~or - 3~ -l instance, a high pressure polyethylene) an~ the otherpolymer is a linear polyethylene containing no long chain branches but having the same M~ measured by light sca~tering method. When these two polymers are made into respective very dilute solutions with one same solvent, the polymer X gives a less-viscous solution because thc-spread of its molecular chain is smaller than that of the linear polyethylene. Accordingly, by measuring the intrinsic viscosities of the two polymers and calculating their ratio namely g*, the index of long chain branching can be known. When a polymer has no long chain branches, its gn is almost l within the range of experimental errors. When the polymer has long chain branches, g* is smaller than 1. In most cases, high pressure polyethylenes show gn of below 0.6 and have considerable quantities of long chain branches.
The ethylene-~-olefin copolymer composition of this invention is preferred to have g* of at least o.8 and more preferably at least 0.9 and practically has no long chain branches. When g* is below 0.8 and contain a large quantity o~ long chain branches, the copolymer is poor in tensile strength, impact strength, environ-mental stress cracking resistance, low temperature resistance and chemicals resistance.
(S.C.B. of higher molecular weight components)/
(S.C.B. of lower molecular weight components) of the copolymer composition of this invention is preferred to be at least 0.6 and more preferred to be at least o.8 l and most preferred to be at least lØ In applications where transparency is required, o.6 to 0.8 is preferred.
Here, these S.C.B. are obtained by dividing the compo-sition o~ this invention into two groups of lower mole-cular weight components and higher molecular weightcomponents using molecular weight fractionation and then measuring S.C.B. of each group. When the ratio is below o.6, mechanical strengths of the composition are poor, and when the composition is subJected to extrusion proces-sing and injection molding, balancing of MD and TDstrengths is di~ficult and molded products have sticky surfaces, and in films~ heat-sealing characteristics worsen. When the ratio is o~er o.8, transparency worsens and therefore such a polymer is not suitable for appli-cations where transparency is required. The above mole-cular weight fractionation of the ethylene-~-olefin copolymer into two groups of lower and higher molecular weight components refers to the following method.
(l) A curve of molecular welght distribution is obtained by gel permeation chromatography.
In this case, the abscissa is the logarithm of chain length (unit A) calibrated with a standard poly-styrene sample, and the ordinate is rela'cive weight ~raction. The standard measurement method is described later.
(2) ~n example of cases where curves of ~olecular weight distributions have one peak was shown in Fig. l.
This pattern is seen most 'cypically in ethylene-~-olefin 1 copol~mers. In this case~ a lower molecular weight components side and a higher molecular weight cornponents side are divided by a line drawn between the peak of the curve and the midpoint of' a line drawn be~ween the end o~ lower molecular weight components in the curve and the end o~ higher molecular weight components; and the ratio of areas of these two sides is the weight ratio of lower and higher molecular weight components. Separately, fractions of the same sample are prepared by column fractionation. These fractions are consolidated into two portions o~ lower and higher molecular weight com-ponents~ in order that the weight ratio of these two portions become closest to the weight ratio obtained above.
(3) An example of cases where curves of rnolecular weight distributions have two peaks was shown in Fig. 2.
Also, an e~a~ple having one peak but showing a shoulder at higher molecular weight components side was shown in F~g. 3. Examples havlng three or more peaks are handled as modifications of two peaks and are treated similarly to two peaks. In the case of two or more peaks including shoulders~ a tangent line is drawn between main two peaks of the higher molecular weight components side or between one peak and a shoulder of' the same side, and then a perpendicular is drawn from a point where the dlstance between the GPC curve and the tangent line becomes largest.
This perpendicular splits the lower molecular weight components side and the higher molecular weight components .~j l side, and the ratio of areas of these two sides becomes the ~eight ratio of these two components portions. When peaks are continuous and can not be detected (case of somewhat square curve), the technique of' one peak distrlbution is applied. Separately, fraction of the same sample are prepared by column ~ractionation. These fractlons are consolidated into two portions of lower and higher molecular weight components, in order that the weight ratio of these two portions becomes closest to the weight ratio thus obtained.
Molecular weight fractionation is conducted by the known column fractionation method. Its detailed explanation is made in "Polymer Fractionation" (compiled by M.J.R. Cantow, Academic Press, published in 1967), and therefore, only the outline of the method is described below.
About 5 g of a sample is adsorbed on a carrier~
Celite 745 ~ in xylene and the carrier is charged into a column. The column ls heated to 130C and a mixed solvent of butyl cellosolve and xylene is passed through the column with their mixing ratio being gradually changed (namely with the solvenc of the mixed solvent being e gradually changed). ~ lower molecular weight fractions to higher molecular weight fractions are successively fractionated. To each eluate is added methanol to cause precipitation. After recovery of each polymer, they are dried under reduced pressure to be used as each fraction.
To prevent the decomposition of polymers during ~ 36 -a t-~
~' t~
1 fractionation, 100 ppm of Ir~anox ~ 1076 is added to the original sample as a stabilizer, and also nitrogen is passed through the column to shut off oxygen. The polymer fractions obtained are divided into two groups of lower and higher molecular weight componen-ts so that the weight ratio of these two groups become the above-mentioned weight ratio. Each group is made into a press sheet of about 100 to 300~ thickness and these sheets are sub~ected to Fourier~transform infra-red absorption 10 spectroSCOPY
Further, it is preferable that the character-istic values of the sample obtained by dividing the ethylene-a-olefin copolymer of this invention into two fractions such as a higher molecular weight component and a lower molecular weight component are same to the characteristic values of copolymer A and copolymer B, respectively, as previously defined.
~ When compar~ed with low density ethylene-~olefin copolymers obtained from the conventional medium 'co low pressure method (normally called "linear low density polyethylene or LLDPE"), the polyethylene type resin composition of this invention has the following advantages.
In the field of extrusion processing, the com position of this invention is largely excellent in processability (about equal even to high pressure poly-ethylenes) and moreover has excellent mechanical strengths (ESCR, tensile strength, impact strength and - 37 ~
1 tear stren~th) as well as excellent low temperature ~es~stance. Therefore, reduction in thicknesses of molded products becomes possible. The composition of this invention has wide applications and can be usec1 even in the appliea'cion where transparency is required~
In case o~ filmsg the present composition is far superior in processability (about equal even to high pressure polyethylenes). Further, the composition has exeellent mechanieal strengths sueh as tensile strength, impact strength and tear strength, by which reduction in thicknesses of films becomes possible. Moreover, the present composition has e~cellent transparency and heat~
sealing characteristics, by which it is used as a high quality ~ilm in wide applications including high speed bag manu~aeturing.
In the field o~ inJeetion molding, the present eomposition is largely exeellent in processability (about equal even to high pressure polyethylenes). ~oreover, there occurs no ~low marks, there is no warpage wi'ch molded products, and transparency, low temperature resistanee and meehanical strengths such as environmental stress cracking resistance, tensile strength and impact strength are excellent. Thereby, reduction in thicknesses of molded products is possible and the present composition has wide applications including the case where transparency is required.
To the composition of this invention~ can be added if necessary various additives being common]y used 1 in the industries such as oxidation inhibitors, lubricants, an~i-blocking agents, anti-static agents, photostabilizers, and coloring pigments. Also, other polymers can be added in small quantities as long as the scope of this invention is kept.
Next, the definitions of physical and chemical properties used in this invention are explained below.
(1) Intrinsic viscosity This implies [ n] in tetralin of 135C.
0 [n] = 11.65 x log R
R = t/to t : Seconds of dropping in a concentration of 0.2 dl/g to: Seconds of dropping of tekralin itself 15 (2) Density According to the specification in JIS-K-6750.
With respect to the copolymer B of lower mole-cular weight, when it has a large S.C.B., it is regarded as a low dens~ty product, and according to the specifi cation, it must be subjected to annealing of 100C and 1 hourO However, the copolymer B was conformed in all cases to the specification for high density products and was not subjected to the above annealing.
(3) S.C.B.
Using the C14 labelled product described in the followin~ literature, the subject property was calcu~
lated by employing the FT-IR spectrum substraction method.
5 ~2 1 "Characterization and Properties of Polymers"
Published by KAGAKU DOJIN
Compiled by Mitsuru Nagasawa et al.
Issued on July 10~ 1970 Pages 131 to 146 Determination formulas for various branches are given below.
_ ~0 -j Branch Determina~ion ~ormula Methyl Branches/1000 C = o.49-K 7.25 Ethyl ll = O. 70-K 7.25 If = 0.80 K 7.25 n-Butyl " = 0.78 K 7.25 n-Decyl Other linear chains " = O.80 K 7.25 ~ ~ær -Bu~yl " = 0 45 K 1. 23 u 1 K7 25~ (absorptivi~y) was obtained by using as a reference a linear ethylene homopolymer having the almost same molecular weight and molecular weight distri~
bution and the same ~ n] as those o~ a given sample and employing the spectrum substraction method. Therefore, effects of methyl groups at the ends were cleared.
When R of an ~-ole~in R-CH=CH2 is a linear alkyl, (the number of methyl groups at the branch ends)/
lOOOC is S.C.B. When R is a branched alkyl group, for instance, an ~-olefin is 4-methyl-pentene-1, the branch is the i-butyl group and half number of methyl groups at the branch ends per 1000 carbon atoms is S.C.B.
(4) Weight average molecular weight by ligh-t scattering method This item was measured at 125C by the normal method, with ~-chloronaphthalin used as a solvent and employing a photoelectric type light scattering photo-meter (manufactured by SHIMAZU SEISAKUSH0).
(5) Melt index (MI) According to the condition E of ASTM D 1238.
(6) Melt flow ra~io (MFR) Firstly, MI21 6 (grams per 10 min. under a load of 21.6 kg at 190C) is measured according to ASTM D 1238 condition F. Then, MFR is calculated using the follol~ing formula~
(7) Rigidity (expressed by Olsen's flexural modulus) According to ASTM D 7L~7.
1 Press condition: ASTM D 1898 method C
Test piece: 25 x 70 x 1 mm thickness Span: 25 mm Measurement temperature: 20C
5 (8) Tensile impact strength: According to ASTM D 1822 Press condition: ASTM D 1898 method C
Test piece: S type dumbbell, 1 mm thickness Annealing: 1 hour in boiling water Measurement temperature: 20C
.o (9) Molecular weight distribution (Mw/Mn) GPC method (gel permeation chromatography method) HLC~811 (manufactured by TOYO SODA) Column: TSK-GF.L (GMSP + G7000H4 + GMHx2) Solvent: 1,2,4-trichlorobenzene (TCB) Temperature: 145C
Detector: Differential refractometer Flow quantity: 1 ml/min.
Concentration: 15 mg/10 ml TCB
Measurement data on standard polystyrenes are shown below.
Nominal value Measured value Polystyrene _ _ _ _ _ _ _ _ Mw Mn Mw/Mn Rw An Aw/An #41955 9.82x104 9.62x104 1.02 2083 1744 1.19 (TOYO SODA's) 5 9 l.Q4 140 112 1.25 ~, . --~
; fl ~
1 (10) Environmental stress cracking resistance (ESCR) According to ASTM D 1693.
Expressed in F50 (hr).
The following exceptions were adopted.
~ Concentration of Antaro~-C0630 10% by weight Sample: 3 mm thickness, 0.5 mm notch
Further, the MFR is preferred to be 35 to 250 and more preferred to be 35 to 200 and most preferred to be 35 to 150. Furthermore, the product of MI and MFR is preferred to be at least 4 and more preferred to be at least 7.
When the MI and the MFR are below the lower limits, extrusion processability worsens. When they are above the upper limits, mechanical strengths are reduced.
In the field of film processing, the MI of the composition is preferred to be 0.02 to 5 g/10 min. and more preferred to be 0.05 to 4 g/10 min. and most pre-ferred to be 0.1 to 3 g/10 min. Further, its MFR is preferred to be 35 to 250 and more preferred to be 35 to 200 and most preferred to be 35 to 150. Furthermore, the product of the MI and the MFR is preferred to be at least 4 and more preferred to be at least 7. When the MI and the MFR are below the lower limits, extrusion processability worsens. When they are above the upper limits, bubble stability in blown film processing is 1 insufficient and mechanical strengths are reduced.
Inthe ~ield o~ injec~ion molding, the MI o~
the composit~on is preferred ~o be 2.0 to 50 g/10 min.
and more preferred to be 2.0 to 30 g/10 min. ~urther~
the MFR is preferred to be 35 to 80 and more pre~erred to be 35 to 70. When the MI is below the lower limit~
moldability worsens and flow marks are produced.
When it is above the upper limit, mechanical strengths are reduced.
In order to provide the composition of this invention excellent in processability and mechanical strengths, it is also important to adequately balance its MI and MFR. A lower MI requires a higher MFR. This requirement is expressed by ~he product of MI and MFR.
For instance, a composition having a MI of about 1 g/
10 min, even if its MFR is as low as 50 to 60, has processability about equal to that of a high pressure polyethylene having the same MI. On the other hand, a composition having a MI of about 0.05 g/10 min.
and a MFR of 50 possesses extremely poor processability and, in order to have satisfactory processability, a MFR of at least 80 is required. The product of MI and MFR of a composition is designed appropriately to meet the requirement of its final application. The designed value of the product o~ MI and MFR can be achieved in the composition by using (a) intrinsic viscosities of the copolymer A of relatively higher molecular weight and the copolymer B of relatively lower molecular weight~
1 (b) values of (weight average molecular weight)/(number average molecular weight) of these copolymers an~ (c) their mixing ratio. If intrinsic viscosities of the copolymer A and the copolymer B are put as ~n ]A (dl/g) and [~]B (dl/g), respectively, and their ratios by weight basis are put as WA and WB (WA + WB = 1), respectively the intrinsic viscosity of the composition obtained by mixing the two copolymers namely [~]T (dl/g) is approxi-mately given by the following formula.
[~1] -. [n]AwA .+ [n~BWB
MI is governed by [n]T unequivocally. Meanwhile, MFR is generally larger when [n ]A/[n]B is larger, and depends upon WA and WB. Therefore, it is difficult to express MF~ unequivocally and, based on preliminary tests, [n ]A~
[n]B, WA and WB are determined to give an intended MFR.
,s~
(L,) In order to obtain a composition which S_~i3Ly the above (1) to (3) conditions, the copolymer A and the copolymer B are preferred to be mixed at a ratio of 10 to 70% by weight (copolymer A) to 90 to 30% by weight (copolymer B). The ratio of 20 to 65% by weight to 80 to 35% by weight is more preferred and the ratio of 30 to 60% by weight to 70 to 40% by weight is most preferred.
The mixing ratio of the two copolymers must be adequately selected by considering S.C.B., densities, intrinsic viscosities and molecular weight distributions of the copolymers A and B as well as the density, MI and MFR
5 ~;~
of an intended composition. I~hen the ratio of the copolymer A
is below its lower limit and the ratio of ~he copolymer B is above its upper limit, the ESC~, impact strenyth, tear strength and low temperature resistance of the composition obtained are poor, and the high strength of the composition of this invention which is obtained when the value oE (S.C.B. of copolymer ~)/-(S.C.B. of copolymer B) is selected to be at least 0.6 as well as the good transparency of the composition of this invention which is obtained when the value of (S.C.~. of copolymer A)/-(S.C.B. of copolymer B) is selected to be 0.6 to 1.7, are not achieved. When the ratio of the copolymer A i5 above its upper limit and the ratio of the copolymer s is below its lower limit, the processability of the compositlon obtained worsens.
As long as the scope of this invention is obeyed, mixing of the ethylene-~ olefin copolymer A of relatively higher molecular weight and the ethylene-~olefin copolymer s of relatively lower molecular weight is not necessarily limited to mixing one of each kind. The mixing may be also done by using two or more kinds of each of the copolymer A and the copolymer B.
There is no particular limitation -to mixing me~hods of the copolymers A and B, and known methods can be used in mixing of these two polymers. Commonly used are a batch type melt kneading method which employs a twin roll or a sanbury mixer af~er separate produc~ion of the copolymers A and B, a continuous melt kneading ~'`''~
1 method employing a twin rotor mixer such as CIM (rnanu-factured by the Japan Steel Works) or FCM (manufactured by Kobe Steel) or a single screw extruder and a solution m~xing method in which a mixture is obtained by dissolv-ing the copolymers A and B in a solvent separately ortogether, blending and finally removing the solvent.
When the copolymers A and B are produced by a high temperature solution polymerization method, it is ad-vantageous from the process standpoint that their composition is obtained by mixing A and B in a solution state at high temperatures and removing the solvent.
Mixing by a two- or multi-stage polymerization method is also possible. In this method, in the first stage, the copo]ymer A is polymerized for a certain length of time and, successively in the second stage, the copolymer B is polymerized using the same catalyst but changing other polymerization conditions until the composition containing the copolymers A and ~ at an intended ratio is obtained~ In this case, the order of polymerization of A and B is not restricted.
The above two- or multi-stage polymerization method is an ideal mixing method, because the copolymers A and B undergo molecular dispersion.
The most effective mixing method can be se-lected from above various mixing methods, in order toobtain a uniform composition, which meets inten~ed requirements.
The intrinsic viscosity [rl] of the ethylene-~-l olefin copolymer composition of this inv~ntion is pre~er-red to be 0.7 to 4 dl/g and more preferred to be 0.8 to 3.5 dl/g and most preferred to be 0.9 to 3 dl/g. When the intrinsic viscosity is below the lower limit, 5 mechanical strengths are reduced and, in blown film processing, bubble stability is insufficient. In case of above the upper limit, extrus~on processability worsens.
S.C.B. of thè composition is preferred to be 5 to 45 and more preferred to be 7 to 40 and most preferred to be 10 to 40. When S.C.B. is below its lower limit, transparency worsens. When S.C.B. is above its upper limit, mechanical strengths are reduced and molded products have tackiness.
Next, the "index of long chain branching" of the copolymer composition of this invention is described.
When the intrinsic viscosity of a copolymer composition o~ this invention is put as [ n] and the intrinsic viscosity of a linear polyethylene having the same Mw measured by light scattering method (a high density polyethylene obtained by homopolymerization of eth~lene under a medium to low pressure using a Ziegler catalyst) is put as [n]Q, [n]/[n]Q namely ~* is called the "index of long chain branching" of the composition and indicates the extent o~ presence of long chain branching ~n the composition.
Now, intrinsic viscosities of two polymers are compared.
One polymer X is a polyethylene having long chain branches of which index of branching is unknown (~or - 3~ -l instance, a high pressure polyethylene) an~ the otherpolymer is a linear polyethylene containing no long chain branches but having the same M~ measured by light sca~tering method. When these two polymers are made into respective very dilute solutions with one same solvent, the polymer X gives a less-viscous solution because thc-spread of its molecular chain is smaller than that of the linear polyethylene. Accordingly, by measuring the intrinsic viscosities of the two polymers and calculating their ratio namely g*, the index of long chain branching can be known. When a polymer has no long chain branches, its gn is almost l within the range of experimental errors. When the polymer has long chain branches, g* is smaller than 1. In most cases, high pressure polyethylenes show gn of below 0.6 and have considerable quantities of long chain branches.
The ethylene-~-olefin copolymer composition of this invention is preferred to have g* of at least o.8 and more preferably at least 0.9 and practically has no long chain branches. When g* is below 0.8 and contain a large quantity o~ long chain branches, the copolymer is poor in tensile strength, impact strength, environ-mental stress cracking resistance, low temperature resistance and chemicals resistance.
(S.C.B. of higher molecular weight components)/
(S.C.B. of lower molecular weight components) of the copolymer composition of this invention is preferred to be at least 0.6 and more preferred to be at least o.8 l and most preferred to be at least lØ In applications where transparency is required, o.6 to 0.8 is preferred.
Here, these S.C.B. are obtained by dividing the compo-sition o~ this invention into two groups of lower mole-cular weight components and higher molecular weightcomponents using molecular weight fractionation and then measuring S.C.B. of each group. When the ratio is below o.6, mechanical strengths of the composition are poor, and when the composition is subJected to extrusion proces-sing and injection molding, balancing of MD and TDstrengths is di~ficult and molded products have sticky surfaces, and in films~ heat-sealing characteristics worsen. When the ratio is o~er o.8, transparency worsens and therefore such a polymer is not suitable for appli-cations where transparency is required. The above mole-cular weight fractionation of the ethylene-~-olefin copolymer into two groups of lower and higher molecular weight components refers to the following method.
(l) A curve of molecular welght distribution is obtained by gel permeation chromatography.
In this case, the abscissa is the logarithm of chain length (unit A) calibrated with a standard poly-styrene sample, and the ordinate is rela'cive weight ~raction. The standard measurement method is described later.
(2) ~n example of cases where curves of ~olecular weight distributions have one peak was shown in Fig. l.
This pattern is seen most 'cypically in ethylene-~-olefin 1 copol~mers. In this case~ a lower molecular weight components side and a higher molecular weight cornponents side are divided by a line drawn between the peak of the curve and the midpoint of' a line drawn be~ween the end o~ lower molecular weight components in the curve and the end o~ higher molecular weight components; and the ratio of areas of these two sides is the weight ratio of lower and higher molecular weight components. Separately, fractions of the same sample are prepared by column fractionation. These fractions are consolidated into two portions o~ lower and higher molecular weight com-ponents~ in order that the weight ratio of these two portions become closest to the weight ratio obtained above.
(3) An example of cases where curves of rnolecular weight distributions have two peaks was shown in Fig. 2.
Also, an e~a~ple having one peak but showing a shoulder at higher molecular weight components side was shown in F~g. 3. Examples havlng three or more peaks are handled as modifications of two peaks and are treated similarly to two peaks. In the case of two or more peaks including shoulders~ a tangent line is drawn between main two peaks of the higher molecular weight components side or between one peak and a shoulder of' the same side, and then a perpendicular is drawn from a point where the dlstance between the GPC curve and the tangent line becomes largest.
This perpendicular splits the lower molecular weight components side and the higher molecular weight components .~j l side, and the ratio of areas of these two sides becomes the ~eight ratio of these two components portions. When peaks are continuous and can not be detected (case of somewhat square curve), the technique of' one peak distrlbution is applied. Separately, fraction of the same sample are prepared by column ~ractionation. These fractlons are consolidated into two portions of lower and higher molecular weight components, in order that the weight ratio of these two portions becomes closest to the weight ratio thus obtained.
Molecular weight fractionation is conducted by the known column fractionation method. Its detailed explanation is made in "Polymer Fractionation" (compiled by M.J.R. Cantow, Academic Press, published in 1967), and therefore, only the outline of the method is described below.
About 5 g of a sample is adsorbed on a carrier~
Celite 745 ~ in xylene and the carrier is charged into a column. The column ls heated to 130C and a mixed solvent of butyl cellosolve and xylene is passed through the column with their mixing ratio being gradually changed (namely with the solvenc of the mixed solvent being e gradually changed). ~ lower molecular weight fractions to higher molecular weight fractions are successively fractionated. To each eluate is added methanol to cause precipitation. After recovery of each polymer, they are dried under reduced pressure to be used as each fraction.
To prevent the decomposition of polymers during ~ 36 -a t-~
~' t~
1 fractionation, 100 ppm of Ir~anox ~ 1076 is added to the original sample as a stabilizer, and also nitrogen is passed through the column to shut off oxygen. The polymer fractions obtained are divided into two groups of lower and higher molecular weight componen-ts so that the weight ratio of these two groups become the above-mentioned weight ratio. Each group is made into a press sheet of about 100 to 300~ thickness and these sheets are sub~ected to Fourier~transform infra-red absorption 10 spectroSCOPY
Further, it is preferable that the character-istic values of the sample obtained by dividing the ethylene-a-olefin copolymer of this invention into two fractions such as a higher molecular weight component and a lower molecular weight component are same to the characteristic values of copolymer A and copolymer B, respectively, as previously defined.
~ When compar~ed with low density ethylene-~olefin copolymers obtained from the conventional medium 'co low pressure method (normally called "linear low density polyethylene or LLDPE"), the polyethylene type resin composition of this invention has the following advantages.
In the field of extrusion processing, the com position of this invention is largely excellent in processability (about equal even to high pressure poly-ethylenes) and moreover has excellent mechanical strengths (ESCR, tensile strength, impact strength and - 37 ~
1 tear stren~th) as well as excellent low temperature ~es~stance. Therefore, reduction in thicknesses of molded products becomes possible. The composition of this invention has wide applications and can be usec1 even in the appliea'cion where transparency is required~
In case o~ filmsg the present composition is far superior in processability (about equal even to high pressure polyethylenes). Further, the composition has exeellent mechanieal strengths sueh as tensile strength, impact strength and tear strength, by which reduction in thicknesses of films becomes possible. Moreover, the present composition has e~cellent transparency and heat~
sealing characteristics, by which it is used as a high quality ~ilm in wide applications including high speed bag manu~aeturing.
In the field o~ inJeetion molding, the present eomposition is largely exeellent in processability (about equal even to high pressure polyethylenes). ~oreover, there occurs no ~low marks, there is no warpage wi'ch molded products, and transparency, low temperature resistanee and meehanical strengths such as environmental stress cracking resistance, tensile strength and impact strength are excellent. Thereby, reduction in thicknesses of molded products is possible and the present composition has wide applications including the case where transparency is required.
To the composition of this invention~ can be added if necessary various additives being common]y used 1 in the industries such as oxidation inhibitors, lubricants, an~i-blocking agents, anti-static agents, photostabilizers, and coloring pigments. Also, other polymers can be added in small quantities as long as the scope of this invention is kept.
Next, the definitions of physical and chemical properties used in this invention are explained below.
(1) Intrinsic viscosity This implies [ n] in tetralin of 135C.
0 [n] = 11.65 x log R
R = t/to t : Seconds of dropping in a concentration of 0.2 dl/g to: Seconds of dropping of tekralin itself 15 (2) Density According to the specification in JIS-K-6750.
With respect to the copolymer B of lower mole-cular weight, when it has a large S.C.B., it is regarded as a low dens~ty product, and according to the specifi cation, it must be subjected to annealing of 100C and 1 hourO However, the copolymer B was conformed in all cases to the specification for high density products and was not subjected to the above annealing.
(3) S.C.B.
Using the C14 labelled product described in the followin~ literature, the subject property was calcu~
lated by employing the FT-IR spectrum substraction method.
5 ~2 1 "Characterization and Properties of Polymers"
Published by KAGAKU DOJIN
Compiled by Mitsuru Nagasawa et al.
Issued on July 10~ 1970 Pages 131 to 146 Determination formulas for various branches are given below.
_ ~0 -j Branch Determina~ion ~ormula Methyl Branches/1000 C = o.49-K 7.25 Ethyl ll = O. 70-K 7.25 If = 0.80 K 7.25 n-Butyl " = 0.78 K 7.25 n-Decyl Other linear chains " = O.80 K 7.25 ~ ~ær -Bu~yl " = 0 45 K 1. 23 u 1 K7 25~ (absorptivi~y) was obtained by using as a reference a linear ethylene homopolymer having the almost same molecular weight and molecular weight distri~
bution and the same ~ n] as those o~ a given sample and employing the spectrum substraction method. Therefore, effects of methyl groups at the ends were cleared.
When R of an ~-ole~in R-CH=CH2 is a linear alkyl, (the number of methyl groups at the branch ends)/
lOOOC is S.C.B. When R is a branched alkyl group, for instance, an ~-olefin is 4-methyl-pentene-1, the branch is the i-butyl group and half number of methyl groups at the branch ends per 1000 carbon atoms is S.C.B.
(4) Weight average molecular weight by ligh-t scattering method This item was measured at 125C by the normal method, with ~-chloronaphthalin used as a solvent and employing a photoelectric type light scattering photo-meter (manufactured by SHIMAZU SEISAKUSH0).
(5) Melt index (MI) According to the condition E of ASTM D 1238.
(6) Melt flow ra~io (MFR) Firstly, MI21 6 (grams per 10 min. under a load of 21.6 kg at 190C) is measured according to ASTM D 1238 condition F. Then, MFR is calculated using the follol~ing formula~
(7) Rigidity (expressed by Olsen's flexural modulus) According to ASTM D 7L~7.
1 Press condition: ASTM D 1898 method C
Test piece: 25 x 70 x 1 mm thickness Span: 25 mm Measurement temperature: 20C
5 (8) Tensile impact strength: According to ASTM D 1822 Press condition: ASTM D 1898 method C
Test piece: S type dumbbell, 1 mm thickness Annealing: 1 hour in boiling water Measurement temperature: 20C
.o (9) Molecular weight distribution (Mw/Mn) GPC method (gel permeation chromatography method) HLC~811 (manufactured by TOYO SODA) Column: TSK-GF.L (GMSP + G7000H4 + GMHx2) Solvent: 1,2,4-trichlorobenzene (TCB) Temperature: 145C
Detector: Differential refractometer Flow quantity: 1 ml/min.
Concentration: 15 mg/10 ml TCB
Measurement data on standard polystyrenes are shown below.
Nominal value Measured value Polystyrene _ _ _ _ _ _ _ _ Mw Mn Mw/Mn Rw An Aw/An #41955 9.82x104 9.62x104 1.02 2083 1744 1.19 (TOYO SODA's) 5 9 l.Q4 140 112 1.25 ~, . --~
; fl ~
1 (10) Environmental stress cracking resistance (ESCR) According to ASTM D 1693.
Expressed in F50 (hr).
The following exceptions were adopted.
~ Concentration of Antaro~-C0630 10% by weight Sample: 3 mm thickness, 0.5 mm notch
(11) Tensile strength According to ASTM D 638.
(12) Res~stance to chlorine water Test solution: 0.2% chlorine water Solution quantity: A quantity which gives 1.2 ml/cm against a pressed sample. The solution is replaced daily.
Temperature: 40C
Evaluation: 10 stage evaluation on a sample after 72 hours.
1: Excellent, 10: Overall surface like "foam"
20 (13) Transparency (haze value) Press condition: 180C x 10 min, rapid cooling in ice water Sample: 100~ thickness Haze measurement: Internal haza 25 (14) Brabender torque Brabender6~plastograph ~ was used.
Jacket: W 50 model, 45 g filled Temperature: 190C
1 Rotor revolution: 60 rpm A torque after 30 min. is expressed in kg-m.
(15) Spiral flow length Injection molding machine: 5 ounce injection rnolding machine manufac'Gured by the Japan Steel Works, Ltd.
Mold: Spiral mold (7.5 mm~ semiclrcle~ 2000 mm length~
Molding condition: Resin temperature 250C
Mold temperature 40C
Injec~ion pressure 840 k~/cm2 Injection molding is carried out w~th this mold-ing condition and spiral flow length is measured.
~ The present invention is explained below in more ~3~
by the ~ollowing examples, but it is not restricted by these examples.
Example 1 (1) Synthesis of Organomagnesium Compound In a 500 ml ~our~necked flask equipped with a stirrer, a reflux condenser, and a dropping funnel was placed 16.0 g of flake-shaped magnesium to be used for the production of Grignard reagents. The air and mois-ture inside the ~lask were completely replaced by nitrogen. Into the dropping funnel were charged 68 ml (o.65 mol) of n-butyl chloride and 30 ml of n butyl ether. About 30 ml of this solution was dropped into - 46 ~
~3~
l the ~lask to initiate a reaction~ an~ therea~ter the rest of the solution was dropped in 4 hours a~ 50C. After the completion o~ dropping, the reac~ion was continued for further 1.5 hours at 60C. Then, the reaction system was cooled to room temperature and the unreacted magnesium was filkered off by the use of a glass filter.
n-Butyl magnesium chloride in the n-butyl ether was measured for its concentraticn by hydrolyzing with l N
sulfuric acid and back-titratlng with l N sodium hydroxide using phenolphthalein as an indicator. The concentration was 1.96 mol/l.
(2) Synthesis of Solid Catalyst Component The air and moisture inside a 500 ml four-necked flask equipped with a stirrer, a dropping funnel and a thermometer was completely replaced by nitrogen.
In the flask was placed 130- ml of the n-butyl ether solution containing 0.26 mol of n-butyl magnesium chloride synthesized in the abo~e step (1). From the dropping funnel was dropped 30 ml (0.26 mol) of silicon tetra-chloride o~er 2 hours at 50C. The reaction was con-C~!tinued for~further l hour at 60C. The formed white solid was separated, washed with n-heptane and dried under reduced pressure to obtain 31.5 g of a white solid.
Ten grams of this white solid was placed in a lO0 ml four-necked flask and 50 ml of titanium tetrachloride was added. They were allowed to react with stirring for l hour at 100C. After the completion of the reaction~
n-heptan washing was applied until the washings became 5 ~
1 free from titanium tetrachloride. After drying under reduced pressure, 7.9 g of a solid catalyst component was obtained. ~ach 1 g of this solid catalyst component supported 14 mg of titanium~
Example 2 Ethylene~-olefin copolymers A were polymerized, using the ca~alyst produced in Example 1 and organoalminum compounds (co-catalyst) and employing various ~-olefins and other pclymerization conditions as shown in Table 1.
Densities~ intrinsic viscosities, S.C.B. and (weight average molecular weight/number average molecular weight) of these polymers obtained were also shown in Table 1.
These copolymers are used in the following examples as mixing components.
Example 3 Ethylene u-olefin copolymers B were polymerized, using the catalyst produced in Example 1 and organoalumi-num compounds (co-catalyst) and employing various a-olefins and other polymerization conditions as shown in Table 2.
Densities, intrinsic viscosities, S.C.B. and (weight average molecular weight/number average molecular weight) of these ethylene-a-olefin copolymers were also shown in Table 2.
These copolymers are used in following examples as mixing componentsO
~ 48 -Table 1 Polymeri- Polymeri- Catalyst H2 partial N zationzation quantity Co-catalyst Solvent ~-olefin pressure methodvessel capacity 2 (Q~ (mg) (mmol) (kg) (kg) (kg/cm ) Al-lSlurry 65 134 TEA 100C4 6.o C4~ 6.14 o.84 Al-2Solution 1 25.3 DEAC 2.5C7 0.25 4-MP-1 0.110 Q.l Al-3Slurry 65 130 TEA 50C4 6.Q - C4 6.14 0.25 Al-4 " 65 310 TEA 100 It 11 0.86 Al-5 65 102 TEA 50 " It O.059 Al-6Solution 1 26.0 DEAC 2.5C7 0.30 c6~ 0.Q60 0.1 Al-7 " 1 327 TEA 100 " .l 1.8 Al-8 '~ 1 24.5 DEAC 2.5 " 4-MP-1 0.050 0.15 Al-9Slurry 65 33 TEA 100C4 6.o C4' 6.14 1.1 Al-10 " 65 309 TEA 100 " ll 1. 2 Al-11 ll 65 121 TEA 50 ll 'l o . 98 Al-12 " 65 320 TEA 100 " '~ 3.o Al-13Solution 1 25.0 DEAC 2.5C7 0.25 Cg 0.140 0.1 - Cont'd -/
- Table 1 (Cont'd) C '- Polymeri- Properties partial zation pressure ~empera- Density [~3 _ _ 2 ture S.iC.B. Mw/Mn (kg/cm ) (C) (g/cm3) (dl/g) Note 5.650 0.900 2.2 38 5.9 TEA = Triethyl aluminum 20 140 94 2.5 23 3.6 DEAC = Diethyl aluminum chloride 6.o50 0.905 3.2 30 5,8 4-MP-1: 4-Methylpentene-l 9.550 0.915 2.5 19 5.5 C2' = Ethylene o 4-5 50 o.go8. 4~4 25 6.o C4 = n~Butane 20 140 93 2.5 25 3.7 C4' = Butene~
12.Q140 0.922 2.2 13 5.3 C6' = Hexene-l ~9 20. 140 0.920 2.5 10 3.7 C8' = Octene-112.Q50 0.921 2.5 13 5.5 C7 = n-Heptane 8.o50 0.911 2.2 25 5.7 6.550 0.907 2.2 30 5.7 0.928 2.2 8 5.3 20 140 0.~03 2.5 24 3-9 Table 2 Polymeri- Polymeri- Catalyst H2 partial zationzation quantity Co-catalyst Solvent ~-olefinpressure No.method vessel capacity (Q) (mg) (mmol) (kg) (kg)(kg/cm2) Bl-l Slurry65 345 TEA 100 C4 15 2 C4 1. 211. 5 Bl-2 Solution 1 25.5 DEAC 2 . 5 C7 0.28 4-MP-1 0.030 3.0 Bl-3 Slur~y65 415 TEA 50 C4 15 2 C4 1.6 11.0 Bl-4 65 425 " " c4~ 2.0 10.5 Bl-5 " 65 286 " C4 6.o C4 6.14 9.4 Bl-6 " 65 410 TEA 100 C4 12.0 C4~ 3.0 11.0 Bl-7 Solution 1 25.7 DEAC 2.5 C7 0.254-MP-1 0.050 2.5 Bl-8 Slurry65 250 TEA 100 C4 15- 2 C4~ 0.413.5 ~1-9 .l 65 47 " I~ C4 1 0 . 513 . O
Bl-10 " 65 422 TEA 50 ' C4' 1.8 11.0 Bl-ll " 65 405 " c4~ 1.411.0 Bl-12 Solution 1 26 DEAC 2 . 5 C7 0 25C8' 0.040 3 . O
- Cont'd -~able 2 (Cont'd) C2'- Polymeri- Properties pressure zation (kg~cm2) tempera- Density [n] _ _ ture S.C.B. Mw/Mn ~C) (g~cm3) (dl/g) Note 5.0 70 0. 943 0. 63 15 5.5 TEA - Triethyl aluminum 140 0. 938 0.5~ 13 3. 5 DEAC = Dietnyl aluminum chloride 5.o 70 0.936 0.62 20 5.6 4-MP-1 = 4-Methylpentene-l 5.0 70 0.929 o .65 25 5.7 C2' = Ethylene 8.5 50 0.927 1.1 25 5 O 8 C4 = n-Butane 3.0 50 0 - 91o 0.60 35 5 - 9 c4 ' = Butene-l 61 140 0. 912 0.52 22 3.6 C6' = Hexane-l 1.5 50 0.930 0.28 25 5.7 C8 ' = Octene-l 5. o 70 o . g54 0.62 8 5.2 c7 = n-Heptane 5.0 70 0.934 0.61 22 5.6 5- 70 0.939 0.62 18 5.5 o l 40 0.937 o .49 14 3.6 s~
1 Example 4 Ethylene-~-olefin copolymers A were polymerized, using the catalyst produced in Example 1 and organo-aluminum compounds (co-catalyst) and employing various ~-olefins and other polymerization conditions sho~n in Table 3. Densities, intrinsic viscosities~ S.C.B. and (weight average molecular weight/number average molecular weight) of these ethylene/~-olefin copolymers were also shown in Table 3.
These copolymers are used in the following examples as mlxing components.
Example 5 Ethylene-~-olefin copolymers B were polymerized, using the catalyst produced in ~xample 1 and organoalmi-15 num compounds (co-catalyst) and employing various ~-olefins and other polymerization conditions as shown in Table 4~ Denslties, intrinsic viscosities, S~C.B. and (weight average molecular weight/number average molecular weight) of these ethylene/~-olefin copolymers were also shown ln Table 4.
These copolymers are used in the following examples as mixing components.
- ~3 -Table 3 Polymeri- Polymeri- Catalyst H2 partial N zation zation quantity Co-catalyst Solvent a-olefln pressure method vessel capacity 2 (Q) ~mg) (mmol) (kg) (kg) (kg/cm ) A2-1 Slurry 65 145 TEA 100 C4 6.o C4 ! 6.14 1.38 A2-2 Solution 1 25.5 DEAC 2.5 C7 0.25 4-MP-1 0.11 0.5 A2-3 Slurry 65 141 TEA 50 C4 6.o C4 6.14 0.59 A2-4 ll 65 307 TEA 100 " " 2.3 A2-5 65 311 " " " 1.84 A2-6 ll 65 321 " " " 3.2 C~
A2-7 Solution 1 26.5 DEAC 2.5 C7 0.3 4-MP-1 0.05 0.9 A2-8 Slurry 65 315 TEA 100 C4 6.o C4 6.14 2.6 A2-9 " 65 118 " " " 4.6 A2-10 Solutior.1 24.5 DEAC 2.5 C7 0.3 C6f 0.025 0.9 - Cont'd -Table 3 (Contld) C2'- Polymeri- Properties partial zation pressure tempera- Density [~] _ _ ture S.C.B. Mw/Mn (kg~cm2) (C) (g/cm3) (dl/g) Note 6.o 50 0.902 1. 8 38 5.9 TEA = Triethyl aluminum 140 0.908 1. 8 23 3. 8 DEAC = Diethyl aluminum chloride 6.5 50 0.907 2.5 3 5. 8 4-MP-1 = 4-Methylpentene=l 11 50 0.918 1. 8 17 5.4 c2' = Ethylene 8. 4 50 0.914 1.8 25 5.7 c~ = n-Butane ! 14 50 0.925 1. 8 13 5.3 c4~ = Butene-l ~E
140 o.923 1.8 lo 3.6 C6l = Hexene-l 8.5 50 0.914 1.6 25 5.5 c7 = n-Heptane 17 50 0.929 1.5 lo 5.3 140 0.918 1~ 8 13 3. 8 Table 4 Polymeri- Polymeri- Catalyst H2 partial No. zationzation quantity Co-catalyst Solvent ~-olefinpressure methodvessel capacity 2 (Q~ (mg) (mmol) tkg) (kg) (kg/cm ) B2-1 Slurry6~ 348 TEA100 C415. 2 C4 ~ 1.0 12 B2-2 Solution 1 26.5 DEAC 2. 5 C7O. 28 4-MP-1 0.03 3.0 B2-3 Slurry65 405 TEA50 Cl,15.2 C4~ 1. 68.8 B2-4 " 65 421 " " " 12 B2-5 " 65 407 TEA100 C412. C4 l 2.5 12 B2-6 Solution 1 25.7 DEAC 2.5 C70.25 4-MP-1 0.05 2.5 B2-7 Slurry65 245 " C415 - 2 C4 ~ 0.3 12 B2-8 J' 65 420 TEA50 C4 l 1 ~ 212 B2-9 Solution 1 23.9 DEAC 2.5 C7 3 C6 ' O .017 3.0 - Cont'd -Table 4 ~Contld) C2l- Polymeri- Properties partial zation pressure tempera- Density [~
2 ture 3 S.C.B. Mw/Mn (kg/cm ) (C) (g/cm ) (dl/g) Note 3.0 70 0.943 0.51 15 5.9 TEA = Triethyl aluminum 140 0.938 o.50 13 3.5 DEAC = Diethyl aluminum chloride 5.0 70 Q .935 0.73 20 5.9 4-MP-1 = 4-methylpentene-1 3.0 70 0.929 o .54 25 5 .9 C2l = Ethylene 3.0 50 0.910 0.51 35 6. o C4 = n-Butane o 140 0.912 0.52 22 3.6 c4 r = Butene-l 1.0 50 0.931 0.25 25 5.9 c61 = Hexene-l ~n 3.0 70 o . g38 o .50 18 5.4 c7 = n-Heptane 140 0. 937 0.52 18 3.4 S ~2 1 Example 6 A composition of ethylene-~-olefin copolymers was prepared in two stage polymerization.
The first stage polymerization was carried out for 90 min. by using the catalyst produced in Example 1 and trie~hyl aluminum (co-catalyst) and employing other polymerization conditions as shown in Table 5.
Successively, the second stage polymerization was con-ducted for 123 min. by changing only the hydrogen partial pressure and the ethylene partial pressure as shown in Table 5. In both polymerization stages3 the liquid phase molar ratio o~ ethylene/butene-l/hydrogen was maintained at respecti~e fixed levels. The polymer-~zed ~uantities in each stage were examined from the quantities of fed ethylene. The result indicated that the total polymer consisted of abou-t 45% by weight of higher molecular weight components and about 55% by weight of lower molecular weight components. The sample polymer of the former stage was taXen out immediately be~ore the completion o~ the polymerization and was measured for its density, intrinsic viscosity, S.C.B.
and (weight average molecular weight/number average molecular weight). Also~ similar measurements were made for the whole polymer obtained after the two-stage poly-merization. Using the values of the former stage polymerand the whole polymer, the intrinsic viscosity and S.C.B.
for the polymer ~ormed in the latter stage a]one were calculated. These calculated values are also shown in - 58 ~
1 Table ~. The whole polymer gave: density 0.920 g/cm3, melt index 0.7 g/10 min~ melt flow ratio 65, intrinsic viscosity 1.6 dl/g, S.C.B. 25. The whole polymer was measured for its fluidity and solid physical properties.
Results are shown in Table 9.
The be]ow-described are mixing methods of an ethylene-a-olefin copolymer A having a relatively higher molecular weight and an ethylene-~-olefin copolymer B
having a relatively lower molecular weight.
(a) Mixing with a Banbury mixer (hereinafter refer-red ko as Banbury mixlng) A copolymer A and a copolymer B are mixed in a fi~ed ratio and in order to give a total quantity of 1.0 kg. The mixture is kneaded in a Banbury mixer for 5 min.
with a Pe~a~ revolution of 150 to 230 rpm. At that time, nitrogen replacement should be made sufficiently and the polymer temperature must not exceed ~50C.
(b) Mixing in a solution state (hereinafter referred to as solution mixing) A copolymer A and a copolymer B are mixed ln a fixed ratio and in order to give a total quantity of 100 g.
This mixture is charged into a 3 liter autoclave. Two li.ters of xylene is added as a solvent. With stirring, the mixture is heated up to 200C and is subjected to 1 hour o~ solution mixing. Then, it is cooled below theboiling point, and is added into 10 liters of methanol to cause precipitation. The precipitate is dried for Ll8 hours in a vacuum drier of ~0C to obtain an intended 1 polymer composition.
Example 7 A composition of ethylene-~-olefin copolymers was prepared in two stage polymerization.
The first stage polymerization was carried out ~or 100 min. by using the catalyst produced in Example 1 and triethyl aluminum (co-catalyst) and employing other polymerization conditions as shown in Table 6. Succes-sively~the second stage polymerization was conducted for 150 min. by changing only the hydrogen partial pressure and the ethylene partial pressure as shown in Table 6.
In both polymerization stages 3 the liquid phase molar ratîo of ethylene/butene-l/hydrogen was maintained at respective fixed levels. The polymerized quantitites in each stage were examined from the quantities of fed ethylene. The result indicated that the total polymer consisted of about 50% by weight of higher molecular weight components and about 50% by weight of lower molecular weight components. The sample polymer of the :~ormer stage was taken out immediately before the comple-tion of the polymerization and was measured for its density, intrinsic viscosity, S~C~B~ and (weight average molecular weight / number average molecular weight).
Similar measurements were made also for the whole polymer obtained after the two stage polymerization. Using the values of the former stage polymer and the whole polymer, the intrinsic viscosity and SoC~B~ for the polymer formed _ 60 -1 in the latter stage alone were calculated. These cal-culated values are also shown in Table 6. The whole polymer gave: density 0.923 g/cm3~ melt index 6 g/10 min., melt flow ratio 55, intrinsic viscosity 1.10 dl/g~ S.C.B.
25. The whole polymer was subjected to injection molding and the molded composition was measured for its physical properti.es. Results are shown in Table 10.
~ 61 -\
Table 5 Polymeri- Polymeri- Catalyst H2 partial N zatlon zation quantity Co-catalyst Solvent a-ole~ln pressure method vessel TEA
capacity 2 (Q) (mg) (mg) (~) (g) ~kg/cm ) tage Slurry 0.3 18.5 5 C4 1000 C4' 250 stage Slurry 1.7 - Cont~d -Note C4 = n-Butane C4' = Butene-l C2' = Ethylene TEA = Triethyl aluminum Values ir parenthesis are calculated vales.
Table 5 (Cont'd) C2'- Polymeri- Polymeri-Properties partial zation zation pressure tempera- timeDensity [~]
ture - S.C.B. Mw/Mn ~kg/cm2) ~C)(min) (g/cm3) (dl/g) 3 90 0.902 2.8 35 6.1 8 123 - ~0.~2) (15) -Table 6 Polymeri- Polymeri- Catalyst Co-catalyst H2 partial N zation zationquantity TEA Solvent a-olefinpressure ' method vessel capaçity ~Q)~mg) (mmol~ (g) (g)(kg/cm2) lstStage Slurry 0.45 - 5 25 5 C4 1000 C4' 120 stage Slurry 16 ~9 Note C4 = n-Butane - Cont'd -C4' = Butene-l C2 t = Ethylene TEA = Triethyl aluminum Values in parenthesis are calculated values.
Table 6 (Cont'd) C2'- Polymeri- Polymeri- Properties partial zat~on zation pressure tempera- tiJne Density ~3S.C.B. Mw~Fn (kg/cm2) (C) (min) (g/cm3) (dl/g) 2~ 100 0.910 1.75 30 5.8 4.~ 150 (0.5) ~20) _ 1 Example ~
The ethylene-~-olefin copolymer A1-1 obtained in Example 2 and the ethylene-~-olefin copolymer Bl-l obtained in Example 3 were mixed at a 50/50 weight ratio and kneaded in a Banbury mixer. A composition having a density, MI and MFR shown in Table 7 was prepared.
., c~
Physical properties of the composition w~ also shown in Table 7. For the purpose of comparison, in Table 7 ~Pe also shown Comparative example 1 using a high pressure polyethylene based on the conventional technique (com-mercial product: Sumikathene ~ F101-1 manufactured by Sumitomo Chemical Co., Ltd.) as well as Comparative example 2 using a low density ethylene-~-olefin copolymer of the conventional technique.
As is obvious from Table 7, the polymer compo-sition of this invention is excellent, compared with the high pressure polyethylene~ with its lower Brabender torque (excellent in processability) and higher tensile impact strength~ ESCR, rigidity and tensile strength.
It is also obvious from Table 7 that, ~ompared with the low density ethylene-~-olefin copolymer of the conventional technique, the polymer composition of this invention has a much lower Brabender torque (very excel-lent in processability) and a much higher tensile impact 25 strength and tensile strength.
Table 7 Copolymer A Copolymer B Properties of composition Mixing Desig- % by Desig- % by Density MIDistribu-method na~ion weight nation weight (g/cm3) (g/ MFR tion index 10 min) of S.C.B.*
~xample 8Banbury Al-l 50 Bl-l 50 0.921 1.1 65 2.5 Comparative _ 0.922 0.3 65 Example 1 Comparative 0.920 1.0 30 Example 2 - Cont'd - ~g * Distribution index of S.C.B. = (S.C.B. of copolymer A)/(S.C.B. of ~opolymer B) ~n ~s ~able 7 (Cont'd) Physical properties of composition Tensile impact Olsen's flexural ESCR Tensile Brabender Chlorine strength modulus F50 strength torque water (kg-cm/cm2) ~kg/cm2) (hr) (kg/cm2) (kg.m) resistance 340 2600 1000 290 1~9 200 ~200 3 1~0 2.2 5 230 3200 1000 250 2.9 2 o~
s~
l Example 9 The ethylene-a~ole~in copolymer A2-1 o~tained in Example 4 and ~he ethylene-a-olefin copolymer B2-1 obtained in Example 5 were mixed at a 50/50 weight ratio and kneaded in a 3anbury mixer. A composi~ion having a density3 melt index and melt flow ra~io shown in Table 8 was prepared. Physical properties of the composition ~e~ also shown in Table 8. For the purpose o~ compari-.. , ~ r~son, in Table 8 ~e also shown Comparative example 3 using a high pressure method polyet,hylene based on the conventional technique (commercial product: Sumikathene ~ G
701 manufactured by Sumitomo Chemical Co., Ltd.) as well as Comparative example 4 using a low density ethylene-~-olefin copolymer of the conventional technique. As is obvious from Table 8, the polymer composition o~ this invention has a better fluidity at injection molding than the high pressure polyethylene and, moreover, has a much higher tensile impact strength, rigidity~ ESCR and tensile strength. Also, the polymer composition of the present invention is largely excellent in fluidity at in~ection molding, compared with the low density ethylene-a-olefin copolymer of the conventional technique, and further has a much higher tensile impact strength and ESCR.
Examples lO to 14 Ethylene-a-olefin copolymers A obtained in Example 2 and ethylene~-a-olefin copolymers B obtained in \
S~
1 Example 3 were mixed in various ratios and the composi-tions having densities, MIs and r~Rs shown in Table 9 ~e were obtained. Their physical properties w~ also shown in Table 9.
In Table 9 ~a~ also s~own a similar composition obtained f'rom two stage polymeri2ation (Example 6). For the purpose of comparison, in Table 9 were also shown Comaprative examples 5, 6 and 7 as examples of low density ethylene-~-olefin copolymers of the conventional technique of which moleGular weight distributions are made wider and of which lower molecular weight components have larger S.C.~. and of which higher molecular weight com-ponents have smaller S.C.B.
As is obvious from Table 9, in the compositions of this invention, S.C.B. in higher molecular weight components is more than or about equal to that in lower molecular weight components as seen in distribution index of S.C.B. (compare Examples 6, 10 and 14 with Com-parative examples 5 and ~, and ~xample 13 with Compara-tive example 7). ~herefore, the compositions of thisinvention have much higher tensile impact strengths and tensile strengths than the comparative compositions of the conventional technique do. By comparison of Com-parative example 2 in Table 7 with Comparative example 5 in Table 9, it is seen that widening of' molecular weight distribution in the manufacture of a low densi~y ethylene-~-olefin copolymer of the conventional technique maintain~
ing density and MI (larger MFR gives wider di.stribl1tion) - 70 ~
l results in lar~e reduction in tensile impact strength and tensile strength.
/
Table 8 Copolymer A Copolymer B Properties of composition Mixing method Desig- % by Desig- % by Density MI Distribu-nation weight nat1on weight (g/cm3) (g/ MFR tion index 10 mi~) of S.C.B.
Example 9Banbury A2-1 50 B2-1 50 0.924 5 502O5 Comparative o.g20 6 35 Example 3 Gomparative _ 0.924 5 30 -Example 4 - Cont'd -* Distribution index of S.C.B. = (S.C.B. of copolymer A)/(S.C.B. of copolymer B) p~
Table 8 (Cont~d) Tensile impact Olsenls flexural ESCR Tensile Spinal blow strength modulus F~o strength length (kg-cm~cm2) (kg/cm2)(fir) (kg/cm2) (mm) 190 290~lO0 220 130 l20 21002 150 120 llO 3500 .30 180 80 P~
Table 9 Mixing Copolymer A Copolymer B Properties of composition method Desig- % by Desig- % by ~ensity MI MFR Distribu-nation weight nation wei~ht (g/cm3)(~/ tion index 10 min) of S.C.B.
Example 6 - Two slage polymer1zation - 0.920 0 7 65 (2.3) Example 10Solution Al-2 60 Bl-2 40 0.920 0.5 70 1.8 Example 11Banbury Al-3 50 Bl-3 50 0.920 0.25 80 1.5 Example 12 " Al-4 50 Bl-4 50 0.920 0.8 50 0.7 Example 13 " Al-ll 50 Bl-9 50 0.929 1.2 70 3.8 Example 14Solution Al-13 60 Bl-12 40 0.919 0.5 70 1.7 G~
~1 Example 5an ury Al-7 50 Bl-6 50 0.920 1.1 65 0.37 ComparativeSolution Al-8 60 Bl-7 40 0.919 0.5 70 0.50 Examlple 6 Example 7anbury Al-12 50 Bl-10 50 0.930 1.2 7~ o.36 (S.C.B. of copolymer A) - Con~'d -* Distribut~on index _ of S.G.B. (S.C.B. of copolymer B) Table 9 (Cont'd) Physical properties of composition Tens~le impact Olsen's flexural Tensile strength modulus s~rength Tackiness (kg-cm/cm2) (kg/cm2) (kg/cm2) 370 2700 300 o 480 260Q 320 o 480 2700 320 o 30Q 2900 260 o 250 . 3700 25~ o ~n 500 2500 31~ o 110 3200 180 x 200 3100 200 x 4500 200 o 5~;~
1 Examples 15 to 17 Ethylene-~-olefin copolymers A obtained in Example 4 and ethylene-~olefin copolymers B obtained in Example 5 were mixed in various ratios and the composi-tions having densities, melt indices and melt flow ratiosshown in Table 10 were obtained. Their physical proper-ties ~ also shown in Table 10.
~s In Table 10 w~ also shown a similar composi-tion obtained from two stage polymerization (Example 7).
For the purpose of comparison, in Table 10 were also shown Comparative examples 8, 9 and 10 as examples of low density ethylene-~-olefin copolymers of the conven-tional technique of whiGh molecular weight distributions are made wider~ and of whîch lower molecular weight components have larger S.C.B. and of which higher molecular weight components have smaller S.C.B.
As is obvious from Table 10, in the compositions of this invention, the higher molecular weight components have larger S.C.B. than the lower molecular weight com-ponents do~ as seen in distribution index of S.C.B.(compare Examples 7, 15, 16 with Comparative examples 8 and 9, and Example 17 with Comparative example 10).
Therefore, the compositions of this invention have much higher tensile impact strengths ESCRs and tensile strengths than.the comparative compositions of the con-ventional technique do. By comparison of Comparative example 4 in Table 8 with Comparative example 9 in Table 10, it is seen that widening of molecular weight 1 distribution in the manufacture of a low density ethylene-~-olefin copolymer o~ the conventional technique maintein-ing density and MI (larger M~R gives wider distribution) results in large reduction in tensile impact strength, 5 ESCR and tensile strength.
Exa~.ples 18 to 20 Ethylene-~ olefin copolymers A obtained in Example 2 and ethylene-~olefin copolymers B obtained in Exmaple 3 were mixed in various ratios and the composi-tions having densities, MIs and MFRs shown in Table 11w~ obtained. Their physical properties were also shown in Table 11.
~ or the purpose of comparison~ in Table 11 c~
~e~ also shown an example (Comparative example 1) of high pressure polyethylenes of the conventional techni-que; an example (Comparative example 11) of low density ethylene~~-olefin copolymers of the conventional techni-que of which molecular weight distributions are made wider~ and of which lower molecular weight components have larger S.C.B. and of which higher molecular weight components have smaller S.C.B.; and an example (Compa,ra-tive example 12, to be compared with Example 19) of ethylene-~-olefin copolymers compositions of which distribution indices of S.C.B. meet the object of this invention but of which lower molecular weight components have a too low intrinsic viscosity.
It is clearly seen from Table 11 that proper S~2 1 selection of distribution index of S.C.B. gives good transparency about equal to that of high pressure poly~
ethylenes as well as a much more excellent tensile impact s~rength and tensile strength than those of high pressure polyethylenes.
It is learned from comparison of Example 19 with Comparative example 12 tha~ a too low intrinsic viscosity of lower molecular weight components badly affects the tensile impact strength and transparency of the copolymer composition.
Table 10 Mixing Copolymer A Copolymer B Properties of composition method Desig- % by Desig- % by Density MIDistribu-nation weight nation weight (g/cm3) (g/ MFR tion index 10 min~ of S.C.B.*
Example 7 - Two slage polymerization - 0.923 6 55 (1.5) Example 15Solution A2-2 50 B2-2 50 0.923 5 50 1.8 Example 16 " Q2-3 30 B2-3 70 0.924 3 60 1.5 Example 17Banbury A2-8 45 B2-8 55 0.929 10 45 1.4 Comparative Solution A2-7 50 B2-6 50 0.922 5 50 0.45 Example 8 Example 9anbury A2_4 50 B2-5 50 0.920 5 50 0.49 ~1 Comparative. " A2_9 45 B2-4 55 0.930 10 45 0.40Example 10 \
- Cont'd -* . . . . (S.C.B. of copolymer A) Dlstrlbutlon lndex _ of S.C.B. ~S.C.B. of copolymer B) Table lQ (Cont'd) Phy~ical properties of composition Tensile impact Olsen's flexural ESCR Tensile strength modulus F~o strengh Tackiness (kg-cm~cm2) (kg/cm2)(~r) (kg/cm2) 170 3000 50 22~ o 240 3000100 ~50 o 190 3000 30 230 o 120 4000 5 200 o o 100 3600 15 150 x 320Q 13 130 x 4500 1 110 o Table 11 Copolymer A Copolymer B Properties of composition Mixing method Desig- % by Desig- % by Density MI Distribu-nation weight nation weight (g/cm3) (g/ MFR tion index Example 18 Solution Al-5 30 Bl-5 70 0.920 0.15 100 1.0 Example 19 " Al-6 50 Bl-11 50 0.920 0.8 50 1.0 Example 20 Banbury Al-l 50 Bl-4. 50 0.916 1.1 65 1.6 Comparative 0.9220.3 65 ~ Example 1 o~
Compa ative Banbury Al-9 50 Bl-6 50 0.920 0.8 50 0.4 Comparative " Al-10 65 Bl-8 35 o.920 0.8 50 1.0 Example 12 - Cont'd -~Distribution index of S.C.B. = (SOC~B. of copolymer A)/(S.C.B. of copolymer B) ~able 11 (Cont'd) Physical properties of composition Tensile impact Olsen's flexural Tensile strengthmodulus strength Tackiness Haze (kg-cm/cm2)(kg/cm2). (kg/cm2) (%) 4802~0~ 320 o 5 4002800 250 o 4202l00 250 o 5 , 2002200 180 o 5 co ~
~h 1503300 200 x 12 1302800 220 o 15 1 ExamPles 21, 22, 23 Ethylene-~-olefin copolymers A obtained in Example 4 and ethylene-~-olefin copolymers B obtained in Example 5 were mixed at various ratios, and the composi-5 tions having densities, MIs and MFRs shown in Table 12were obtained. Their physical properties T~e~e also shown in Table 12. For the purpose o~ comparison, in c~e Table 12 we~e also shown Comparative example 3 using a high pressure polyethylene of the conventional technique;
Comparative example 13 using a composition of low density eth~Jlene-~-olefin copolymers of the conventional techni-que of which molecular weight distribution is made wider and of whlch lower molecular weight components have more S.C.B. and of which higher molecular weight components have less S.C.B.; and Comparative example 14 (to be com-pared with Example 22) using a composition of ethylene-~-olefin copolymers of which distribution index of S.C.B.
meets the scope of the present invention but of which lower molecular weight components have a too low intrinsic viscosity. It is obvious from Taole 12 that proper se~
lection of distribution index of S.C~B. gives good transparency about equal to that of high pressure poly~
ethylenes and much more excellent tensile impact strength, tensile strength and ESCR than those of high 2~ pressure polyethylenes. From comparison of Example 22 with Comparative example 14, it is learned that a ~oo low intrinsic viscosity of lower molecular weight com-ponents badly affects tensile impact strength and transparency.
Table 12 Copolymer A Copolymer B Properties of composition Mix ng Desig- % by Desig- % by Density MI Distribu-me o nation weight nation weight (g/cm3) (g/ MFR tion index - lO min) of S.C.B.
Example 21 Solution A2-lO 50 B2-9 50 0.923 5 50 0.72 Example 22 Banbury A2-5 50 B2-4 50 0.922 5 50 l.0 Example 23 " A2-1 50 B2-4 50 0.920 5 50 1.6 Comparative " A2-6 50 B2-5 50 0.923 5 50 0.37 omparlatl4e ;, A2-8 65 B2-7 35 0.922 5 5Q l.0 Comparative 0.920 6 35 -Example 3 - Cont'd -* Distribution index of S.C.B. = ~S.C.B. of copolymer A)/(S.C.B. of copolymer B) Table 12 (Ccnt'd) Physical properties of composition Tensile impact Olsen's flexural E~CR Tensile Tacki- Haze strength modulus ~ F~o strength ness (%) (kg-cm/crn2) (kg~cm~) (~r) ~k~/cm2) 200 3100 20 250 o 7 17~ 2900 3G 220 o 7 5 3600 10 130 x 12 c '~ 80 3200 30 190 0 12 ~1 120 2100 2 150 o 7 ~
1 Comparative Example 1 A commercial high pressure polyethylene (Sumikathene ~ F101-1 manufactured by Sumitomo Chemical Co.~ Ltcl.) was measured for its physical properties and sub~ected to blow molding.
Results wefe shown in Table 7 and 11.
Comparative Example 2 An ethylene-a-ole~in copolymer o~ the conven-tional technique was synthesized employing polymerization conditions as shown in Table 13 in which the catalyst prepared in Example 1 and triethyl aluminum (co-catalyst) were used. The copolymer gave: density 0.920 g/cm3, MI
1.0 g/10 min.~ MFR 30. Its physical properties ~e shown in Table 7~
Table 13 Poly- Poly Catalyst Co- Sol- ~~ H2 C2s Polymeri- Polymeri-meri- meri- quan~ity catalyst vent olefin partial partial zation zation zation zation TEA pressure pressure tempera- time method vessel ture capacity (Q) (mg) (mmol) (kg) (kg) (kg/cm2) (kg/cm2) (C) (min) Slurry 65 197 1 7.0 c74l6 4.2 10 50 100 ,~
Note TEA = Triethyl aluminum C4 = n-Butane C2' = Ethylene c4 r = Bu~ene-l _ 1 Comparative Example 3 A commercial high pressure polyethylene (Sumikathene ~G701 manufactured by Sumitomo Chemical Co., Ltd.) was measured for its physical properties and sub-jected to injection molding.
re Results w~e shown in Table 8 and 12.
~' Comparative Example 4 A low density ethylene-a-olefin copolymer of the conventional technique was synthesized employing polymerization conditions shown in Table 14 in which the catalyst prepared in Example 1 and triethyl aluminum (co-catalyst) were used. The copolymer gave: density 0.924 g/cm3, melt index 5 g/]0 min.~ melt flow ratio 30.
~e Its physical properties w~ shown in Table 8.
Table 14 Poly- Poly- Cataly~t Co- Sol- a~ H2 C2~ Polymeri- Polymeri-meri- meri- quantity catalyst vent olefin partial partlal zation zation zation zation TEA pressure pressure temper~- time method vessel ture capacity (Q) ~mg)(mmol) (kg)(~g) (kg/cm2) (kg~c~2) (C) (min) I
~ Slurry 65 19925 6C4~ 6.14 10.2 11.3 50 gO
Note~ TEA = Triethyl aluminum C2' = Ethylene C4 = n-ButaneC4' = Butene-l 1 Comparative Examples 5, 6, 7 and 11 Compositions of ethylene-~-olefin copolymers of the conventional technique were prepared by blending ethylene-~-olefin copolymers A obtained in Example 2 and 5 ethylene-~-olefin copolymers B obtained in Example 3 at rakios shown in Table 9 or 11. However in these copoly-mer compositions, molecular weight distributions are made wider and lower molecular wei~ht components have larger S.C.B. and higher molecular weight components have smaller S.C.B. Densities, MIs, MFRs and physical pro-perties of these compositions w~e shown in Table 9 or 11.
Comparative Exampie 12 By blendin~ an ethylene-~ ole.fin copolymer A
obtained in ~xample 2 and an ethylene-~-olefin copolymer B obtained in Example 3 at a mixing ratio shown in Table 11, a composition of ethylene-~-olefin copolymers was prepared of which distribution index of S.C.B. meets the scope of the present invention but of which lower mole~
cular weight components have a too low inkrinsic viscosi-ty. Its density, MI, MFR and physical properkiesshown in Table 11.
Comparative Examples 8, 9, 10 and 13 Compositions of' ethylene-~-olefin copolymers of the conventional techn~que were prepared by blending ethylene ~-olefin copolymers A obtained in Example 4 and ethylene-~-olefin copolymers B obtained in Example 5 at ~ 9O -1 mixing ratios shown in Table 10 or 12. However in these compositions, molecular weight di.stributions are made wider and lower molecular weight components have larger S.C.B. and higher molecular weight components have smaller S.C.B. Densities, MIs, MFRs and physical properties of these compositions we~e shown in Table lO or 12.
Comparative Example 14 By blending an ethylene-a-olefin copolymer A
obtained in Example 4 and an ethylene--a-olefin copolymer B obtained in Example 5 at a mixing ratio shown in Table 12, a composition of ethylene-~-olefin copolymers was prepared of which distribution index of S.C.B. meets the scope of this invention but of which lower molecular weight components have too low an intrinsic viscosity.
Its density, MI, MFR and physical properties we~e shown in Table 12.
Example 24 Ethylene~~-olefin copolymers A were polymerized using the catalyst produced in Example l and organoalumi-num compounds (co-catalyst) and employing a-olefins and other polymerization conditions as shown in Table 15.
2Q Their densities, intrinsic viscosities, S.C.B. and (weight average molecular weight/number average molecular weight) G' ~
~e shown in Table 15.
These polymers are used in the following examples as mixing components.
~able 15 Polymeri- Polymeri- Catalyst H2 partial zationzation quantity Co-catalyst Solvent ~-olefin pressure No.method vessel capacity (~ (mg) (mmol) (kg) (kg~ ~kg/cm2) A3-1 Slurry65 131 TEA 100 C4 6.0 c4 6.14 0.45 A3-2 Solution 1 25.1DEAC 2.5 C7 G.22 4-MP-1 0.130 0.10 A3-3 1 24.8 " C7 0.30 C6' O.Q55 0.10 A3-4 Slurry65 307 TEA 100 C4 5~ C4 6.14 0.9 A3-5 " 65 130 TEA 50 " " 0.22 A3-6 " 65 125 11 l t~ 1. 8 A3-7 65 3Ql TEA 100 11 ,l 1 . 2 A3-8 " 65 318 " " " 2.0 A3-9 i~ 65 308 " " " 1.4 Note TEQ = triethyl aluminum DEAC = Diethyl aluminum chloride - Cont'd -4-MP-1 = 4-Methylpentene-1 C2' = Ethylene C4 = n-Butane C4' = Butene-l C6l = Hexene-l C7 = n-Heptane Table 15 (Cont'd) C2'- Polymeri- Properties partial zation pressure tempera- Density [n]
ture S.G.B. Mw/Mn (kg/cm2) (C) (g/cm3) (dl/g) 5.0 ~0 o.899 2.6 3~ 5.9 140 0.899 2.6 27 3.5 2Q 140 0.902 2.6 24 3.7 9.0 50 0.914 2.4 22 6.o 5.5 50 o.go6 3.2 28 5.8 b~
~ Z~
18 50 0.923 2.6 9 5.5 ~1 12 50 0.919 2.4 16 5.8 0.928 2.4 8 5.4 9.0 50 0.914 2.2 22 5.7 l Example 25 Ethylene-~-olefin copolymers B were polymerized using the catalyst produced in Example l and organoalumi-num compounds (co-catalyst) and employing a~ole~ins and other polymerization conditions shown in Table 16. Their densitiesg intrinsic viscosities, S.C.B. and (weight average molecular weight/number average molecular weight) c7re ,~ W~4 shown in Table 16.
These copolymers are used in the following examples as mixing components.
Table 16 Polymeri- Polymeri- Catalyst H2 partial N zationzation quantity Co-catalyst Solvent a-olefinpressure me~hodvessel capa~ity (Q) (nlg~~mmol) (kg) (kg)(k~/cm ) B3-1 Slurry65 405TEA 50 C4 12.0 C4~ 2.0 10.8 B3-2 Solution 1 25.5 DEAC 2.5 C7 0.30 4-MP-1 0.025 2.4 B3-3 i 1 24.2 " C7 0.32 C6' 0.0132.4 B3-4 Slurry65 330TEA lG0 C4 15-2 C4' 0.7 7.5 B3-5 65 391 i' " C4~ 1.8 7,2 B3 6 ll 65 408 " C4 12.0 C4' 4-Q ~
B3-7 65 350 C4 15-2 C4 1.3 7.5 ~9 B3-8 " 65 45 TEA 50 " C4' 1.6 8.8 B3-9 '~ 65 390TEA 100 " C4' 0.2015.0 - Cont'd -Note TEA = triethyl aluminum DEAC = Diethyl aluminum chloride 4-MP-1 = 4-Methylpentene-1 C2' = Ethylene C4 = n-Butane C4' = Butene-l C6' = Hexene-l C7 = n-Heptane Table 16 (Cont~d) C2'- Polymeri- Properties partial zation pressure tempera- Density [n ~ s C.B. Mw/Mn ture (kg/cm2) (C~ (g/cm3) (dl/g) ~.3 70 o.942 o.83 15 ~.5 140 0.943 0.81 10 3.7 140 0.940 0.82 12 3.8 5.0 70 0.949 0.~5 11 5.3 0 8.0 70 0.941 0.~2 14 5.4 4.0 50 0.910 0.82 35 5.9 -~7 5.0 70 00942 0.75 16 5 P~
5.~ - 70 0.935 0.74 20 5.9 1.5 7~ 0.949 0.27 11 5.6 1 Example 26 A composition of ethylene-~-olefin copolymers was prepared from a two stage polymerization. The first stage polymeri~ation was carried out for 90 min. using the catalyst obtained in Example 1 and triethyl aluminum (co-catalyst) and employing other polymerization condi~
tions shown in Table 17.
Successively the second stage polymerization was condu~ted for 150 min. by changing only the hydrogen partial pressure and the ethylene partial pressure as shown in table 17. In both stages~ the liquid phase molar ratio of ethylene, butene-1 and hydrogen were kept at respective fixed levels. Polymerized quantities in each stage were calculated ~rom quantities of fed ethylene.
The total polymer consisted of about 50% by weight of lower molecular weight components. Immediately before the completion of the first stage polymerization, a part of the polymer formed was taken out as a polymer sample of the first stage and measured for its density, intrinsic viscosity~ S.C.B. and (weight average molecular weight/
number average molecular weight). Similar measurements were also made for the whole polymer of this two stage poly-merization. From the values o-~ the first stage polymer and the whole polymer, the intrinsic viscosity and S.C.B.
of the polymer formed in the second stage along were calculated, and they ~ shown in Table 17. The whol~
polymer gave: density 0.919 g/cm , melt index 0.5 g/10 min,, melt flow ratio 70, intrinsic visco$ity 1.70 dl/g~
- 97 ~
5 ~2 S.C.B. 27. The flow characteristics and the solid physical properties of the whole polymer are shown in Table 19.
Example 27 By mixing the ethylene-~-olefin copolymer A3-1 obtained in Example 24 and the ethylene ~-olefin copolymer B3-1 obtained in Example 25 at a 50/50 weight ratio and kneading the mixture in a Banbury mixer, a composition having the density, MI and MFR
as shown in Table 18 was prepared. The physical properties of this composition are also shown in Tahle 18.
For the purpose of comparison, in Table 18 are also shown Comparative examples 15 and 16 using high pressure poly-ethylenes of the conventional technique (commercial produc-ts Sumikathene ~ F208-1, F101-1 manufactured by Sumitomo Chemical Co., Ltd.) as well as Comparative example 17 using a low density ethylene-~ olefin copolymer of the conventional technique.
It is obvious from Table 18 that the copolymer composition of this invention has a ~rabender torque about equal to those of high pressure polyethylenes (good in processability) and is quite excellent in tensile impact strength, rigidity, ESCR and tensile strength, compared with these polyethylenes.
When compared with the low density ethylene-~-olefin copolymer of the conventional technique, this composi-tion has a much smaller Brabender torque 5~
1 (proGessability is much better), a superior tensile impact strength and tensile strength.
_ 99 _ T~ble 17 Polymeri- Polymeri- Catalyst H2 partial N zation zation quantity Co-catalyst Solvent ~-olefin pressure method ~essel TEA
capacity (Q) (mg~ (mmol) (g~ (g) (kg/cm2) ge Slurry 4 24.3 5 ~4 1000 C4' 250 stage Slurry 14 o - Cont~d -Note C4 = n-Butane TEA = Triethyl aluminum en C4 r = Butene-l ( ) = Calculated values C2' = ~thylene Table 17 (Cont'd) C2'- Polymeri- Polymer~- Properties partial zation zation pressure tempera- time Density [n ] _ _ ture S.C.B. Mw/Mn (kg/cm2) (C) (min) (g/cm3~ (dl/g) 3 90 0.900 2.6 37 5.8 5o 8 150 _ ~o.8) (17) -Il ~
C~
Table 18 Copolymer A Copolymer B Properties of composition Mixing - .
method Desig- % by Desig- % by Density MI Distribu-nation weight nation weight (g/cm ) (og/ i ) M~R of S.C B.*
Example 27 Banbury A3-1 50 B3-l 50 0.920 0.5 70 2.5 Comparative 0.923 l 4 50 Example 15 ompalatl~e _ _ _ _ _ 0.922 0.3 65 -Comparative Example 17 ~ ~ ~ ~ ~ 0~920 0.5 30 - G~
- Cont'd -* Distribution index (S.C.B. of copolymer A) of S.C.B. ~S.C.B. of copolymer B) j /
Table 18 ~Cont'd) Physical properties of composition Tensile impact Olsen's flexural ESCR Tensile Brabonder strengthmodulus F50 strength torque (kg-cm/cm2)(kg~cm2) (hr) (kg/cm2) (kg-m) 450 2600 >1000 320 2.0 130 2400 0.3 160 1.9 200 2200 30 180 2.2 I
~ 280 3200 >1000 260 3.5 ~
s~
1 Examples 28 to 31 ~.
Compositions having densities, MIs and MFRs shown in Table 19 were obtained, by blending ethylene-N -~
-olefin copolymers A obtained in Example 24 and ethylene~
~-olefin copolymers B obtained in Example 25 at mixing ratios as shown in Table 19. The physical properties of these compositions w~e shown in Table l9.
-~ In Table 19 ~e also shown a composition of similar ethylene-~-olefin copolymers synthesized in two l~ stage polymerization (Example 26) as well as, for com-parison5 ethylene-a-olefin copolymers compositions (Com-parative examples 18, 19, 20) of which higher molecular weight components have smaller S.C.B. than lower molecular weight components do or have relatively few S.C.B. Also as shown in Table 19 an ethylene-~-olefin copolymers com-position (Comparative example 21, to be compare~ with Examples 30 and 31) of which di~tribution index of S.C.~.
meets the scope of the presetn invention but of which lower molecular weight components have too low an intrinsic viscosity.
As is obvious from Table 19, in the compositions of this invention, higher molecular weight components have larger S~C.~. than lower molecular weight components do. (Comparison should be made between Examples 26, 28 and 29 and Comparative example 18, and also between Example 30 and 31 and Comparative examples l9 and 20.) The compositlons cf this invention are also far superior in tensile impact strength and tensile strength to the Comparative examples.
Table 19 Copolymer A Copolymer B Properties of composltion Mixin~
method Desig- % by Desig- % by Density MIDistri~u-nation weight nation weight (g/cm3) (g/ MFR tion index 10 min) of S.C.B.*
Example 26 - - - - - 0.919 0.5 70 (2.2) Example 28 Solution A3-2 50 B3-2 50 0.920 0.5 7 2.7 Example 29 " A3-3 5 B3-3 50 0.92Q 0.5 70 2.0 Example 30 Banbury A3-4 5 B3-4 50 0.929 0.8 50 2.0 Example 31 Solution A3-5 30 B3-5 7 0.929 0.8 50 2.0 Comparat ve Banbury A3-6 50 B3-~ 50 0.920 0.5 70 0.26 r~A
Comparative llA3-7 5 B3 7 50 Q.929 0.8 50 1.0 Comparative "A3-8 5Q B3-8 50 0.929 o.8 50 0.4 Example 20 Example 21 A3-9 65 B3-9 35 0.929 o.8 50 2.0 - Cont'd -*Distribution index = (S C B. of copolymer A~/(S.C-B- of copolymer B) Table 19 (Cont'd).
Tensile ~mpact Olsen's flexural ~ensile strength modulus strength Tackiness (kg~cm/cm2) ~kg/cm2) ~kg/cm2) 470 2500 320 o 550 2600 3~0 o 520 2600 320 o 300 ~000 300 o 280 400~ 290 o 150 3300 210 x o~ .~
C; 3 200 4200 240 o ~1 4500 200 o 120 4000 230 o 1 Example 32 The composition prepared in Fxample 27 and the low density ethylene-~ olefin copolymer of the convention-al technique used in Compara~ive example 17 were subjected to film processing under the f'ollowing conditions.
Processing conditions Extruder: Tanabe 30 mm~ extruder Screw: Full flight L/D Y 28, C.R. = 2.5 Die: Diameter 50 rnm, die gap 2.0 mm Temperature control: Cl 170g C~ 220, C3 220, Screw revolution: 35 rpm Output: 3.2 kg/hr Blow up ratio: 2.5 Frost line height: 180 mm Take-of'f speed: 5 m/min Film thickness: 35 ~
Also, the cornmercial high pressure polyethylenes used in Comparative examples 15 and 16 were subjected to film processlng under the following conditions.
Die gap: 1.0 mm ~emperature control: Cl 140, C2 160, C3 160, ~o~ f~o"s (Other c~nidtions were same as those applied above.) In the case of the low density ethylene-~-olefin copolyrne-r of the conventional technique used in Comparative example 17, a satisfactory film was not obtained with too much load put on the motor and with 1 shark skin formed on the film surface.
In the cases of the composition prepared in Example 27 and the commercial high pressure polyethylenes used in Comparative examples 15 and 16, satisfactory films were obtained with no excessive motor loads. The physical properties of these films were shown in Table 20. The film of the composition prepared in Example 27 is far superior to those of the high pressure poly-ethylenes, in dart impact strength, Elmendorf tear strengths (absolute value and MD/TD balance), tensile strengthg heat-sealing characteristics, hot tack property and heat sealing strength in contaminated condition.
In the film of the composition prepared in Example 27, heat-sealing strength and heat sealing strength in contaminated condition had about same values, while, in khe films of Comparative examples 15 and 16, heat sealing strength in contaminated condition were slightly lower than heat-sealing strength.
The measurement methods of the physical proper-ties shown in table 20 are described below.
Dart impact strengkh: In accordance with ASTM D 1709A.
Elmendorf tear strength: In accordance with JIS Z
1702.
Tensile strength: In accordance with JIS K 6732 62 Heat-sealing characteristics: Heat-sealing strength of a film heat-sealed with a heat sealer of bar type. The maximum heat-sealing strength was obtained when pulled under conditions S~2 l of film thi~kness of 35~, width of 15 mm and pulling speed of 200 rnm/min. after heat-sealing under sealing pressure of 1 kg/cm , 0.5 sec~ and each incremental 5C.
Hot tack property: A test sample (25 mm wide and 400 mm long) was folded into two~ and the one end was fixed to the upper clamp and a stripping weight was placed on the other end.
The area near the crease was inserted between heating bars and heat-sealed under a sealing pressure of l kg/cm2 for 0.5 sec., and then the length of the stripped surface was measured.
Heat Sealing strength in contaminated condition:
This is a test method for evaluating the heat-sealing characteristics in the condition that the heat-sealed surface is soiled with contents such as mayonaise, edible oils and flours.
Specifically, a test film sample was folded in such a way that the surface soiled with an edible oil came inside, and was heat-sealed under the same conditions as used in heat-sealing characteristics. Then, its heat~
sealing strength was measured.
Comparative E~ample 15 A comrnercial high pressure polyethylerle (Sumikathene ~ F208-l manufactured by Sumitomo Chemical Co., Ltd.) was su~jected to measurernents of physical 1 properties and film processing. Results ~e shown in Tables 18 and 20.
Comparative Example 16 A commercial high pressure polyethylene (Sumikathene ~ F 101-1 manufactured by Sumitomo Chemical Co., Ltd.) was subjected to measurements of physical c~e properties and film processing. Results ~ePe shown in Tables 18 and 20.
Comparative Example 17 A low density ethylene-~-olefin copolymer of the conventional technique was synthesized, using the catalyst produced in Example 1 and triethyl aluminum (co-catalyst) and employing the other polymerization conditions shown in Table 21. The copolymer gave:
5 dens~ty 0.920 g/cm3, MI 0.5 g/10 min., MFR 30. The C?~
physical properties of this polymer w~ shown in Table 18.
Comparative Examples 18, 19, 20 Compositions of ethylene-~-olefin copolymers of the conventional technique were prepared, by mixing ethylene-~-olefin copolymers A obtained in Example 24 and ethylene ~-olefin copolymers B obtained in Example 25 at ratios shown in Table 19. In these compositions~
molecular weight distributions are made wider and lower molecular weight components have larger S.C.B. and higher 1 molecular weight components have smaller S.C.B. Densi~
ties, MIs, MFRs and physical properties of these compo-CJ~
sitions ~e shown in Table 1~.
Comparative Example 21 By mixing an ethylene-~ olefin copolymer A
obtained in Example 24 and an ethylene-a olefin copolymer B obtained in Example 25 at a ratio as shown in Table 19, a composition of ethylene-~-olefin copolymers were pre-pared of which distribution index of S~C~B~g meets the scope of this invention but of which lower molecular weight weight components have a too low intrinsic viscosity.
Its density, MI, MFR and physical properties were shown in Table 19.
Table 20 I
Dart Elmenderf Tensile Heat- Hot tack Heat sealing impact tear strength sealing property strength in strength strength MDiTDstrength contaminated (kg-cm/mm) MD/TD (kg/15mm condition.
(kg/cm) (kg/cm2~width) (mrn) Example 27 700 120/150 45Q/410 1.5 1.0 o Comparative 270 80/50 250/210 0.7 4.0 a p Comparative 250 70/70 280/250 0.7 3.0 a I\) ~ff Table 21 Poly- Poly- Catalyst Co- Sol- a- H2 C2~ Polymeri- Polymeri-mer1- meri- quantity catalyst vent olefin partial partial zation zation zation zation TEA pressure pressure tempera- time method vessel ture capacity 2 2 (Q) (mg) (mmol) (kg) (kg) (kg/cm ) (kg~cm ) (C~ (min) Slurry 65 202 7~ C4~ 3 0 10 50 90 ~J ~
Note TEA = Triethyl aluminum C~
æ~
C4 = n-Butane p~
C4' - Butene-l C2' = Ethylene 1 Example 33 Ethylene-a-olefin copolymers A were synthesized using the catalyst produced in ~xample 1 and organo-aluminum compounds (co-catalyst) and employing ~-olefins and other polymerization conditions as shown in Table 22.
Densities~ intrinsic viscosities, S.C.B. and (weight average molecular weight/number average molecular weight) of these copolymers w~e shown in Table 22.
These copolymers are used in the following examples as mixing components.
Example 34 Ethylene-~ olefin copolymers B were synthesized using the cataly~t produced in Example 1 and organo-aluminum compounds (co-catalyst) and employing ~-olefins and other polymerization conditions as shown in Table 23. Densities, intrinsic viscosities, S.C.B. and (weight average molecular weight/number a~erage molecular weight) of these copolymers we~ shown in Table 23.
These copolymers are used in the following examples as mixing components.
Table 22 Polymeri- Polymeri- Catalyst H2 partial zationzation quantity Co-catalyst Solvent ~-olefin pressure No.method vessel capacity 2 (Q~ (mg) (m~ol) (kg) (kg) (kg/cm ) A4-1 Slurry65 310 TEA 100 C4 6.o C4 7 6.14 0.70 A4-2 Solution 1 24.3DEAC 2.5 C7 0.27 4-MP-1 0.090 0.15 A4-3 Slurry65 83 TEA 50 C4 6.o C4t 6.14 -9 A4-4 " 65 39 TEA 100 " " 1.2 A4-5 ll 65 145 TEA 50 " " 59 Q~
A4-6 Solution i 25.2DEAC 2.5 C7 0.30 C6' O.035 0.2 A4-7 Slurry65 33 TEA 100 C4 6.o c4 6.14 o.36 A4-8 " 65 125 " " " 1.8 A4-9 Solutlon 1 24.5DEAC 2.5 C7 0.40 4-MP-1 0.040 0.25 A4-10 Slurry65 121 TEA 100 C4 6.o C4' 3.7 1.2 A4-11 " 65 302 ~ " C4l 6.14 1.4 - Cont'd /
Table 22 (Cont'd) C2'- Polymeri- Properties partial zatlon pressure tempera- Den~ity [n] _ _ Note ture S.C.B. Mw/Mn (kg/cm2) (C) (g~cm3) (dl/g) TEA = Triethyl aluminum 7.8 50 0.912 2.6 24 5.6 DEAC = ~iethyl aluminum chloride 140 0.912 2.5 17 3.4 4-MP-1 = 4-Methylpentene-l 7.0 5Q 0.912 4.4 20 5.8 C4 = n-Butane 3.Q 50 0.9ll 2.2 25 5.7 C4' = Bu~ene-l 6.7 50 0.906 2.6 29 5,8 C6' = Hexene-l 140 o.gog 2.2 18 3.4 C7 = n-Heptane 9.0 50 0.917 3.3 16 5.6 18 50 0.923 2.6 9 5.5 140 0.923 2.5 8 3.3 0.925 3.3 6 5.5 8.5 ~0 0.913 2.1 23 5.4 Table 23 Polymeri- Folymeri- Catalyst H2 partial No zation zation quantity Co-catalyst Solvent ~-olefin pressure method vessel capacity ' 2 (Q) ~mg) (mmol) (kg) (kg)(kg/cm ) B4-1 Slurry 65 402 TEA50 C4 12. a C4l 3.2 7.8 B4-2 Solution1 24O2 DEAC 2.5 C7 0.804-MP-1 0.045 2.2 B4-3 Slurry b5 405 TEA 5 C4 12.0 C4' 3.2 7.0 B4-4 " 65 425 C4 15.2 c4 2,010.5 B4-5 65 411 " " c47 1.6 6.5 B4-6 Solution1 25.1 DEAC 2.5 C7 0.82 C6~ 0,017 2.7 B4-7 Slurry 65 346TEA 100 C4 15.2 C4 1.1 12 ~4-8 " 65 408 ll C~ 12.0 C4' 4 5.2 B4-9 Solution~ 24.9 DEAC 2.5 C7 0.284 MP-1 0.055 2.0 B4-10 Slurry 65 250TEA lOQ C4 15.2 C4 t o.413.5 B4-11 " 65 410TEA 50 c4l 1.4 12 ~4-12 " 65 290 " C4 6.0 C4 6.14 8.1 - Cont'd /
Table 23 (Cont'd) C2~- Polymeri- Properties partial zation pres~ure tempera- Density [~]
ture S.C.B. Mw/Mn (kg/cm2) (C) (g/cm3) (dl/g) Note 6 70 0.929 o .85 24 5.8 TEA = Triethyl aluminum 140 0.929 0.81 17 3.6 DEAC = Diethyl aluminum chloride 6 70 0.928 o . go 24 5.7 4-MP-1 = 4-Methylpenten-l 0.929 o .65 25 5.7 C4 = n-Butane 0.935 0.83 20 5-5 C4~ = Butene-l ~g 140 0 O 926 0.63 18 3.5 C6' = Hexene-l ~n 3 70 0.941 0.52 16 5.4 C7 = n-Heptane ~a 4 50 0.910 0.82 35 5 - 9 lo 140 0. g~ 2 o .85 22 3.7 1.5 50 0.930 0.28 2~ 5.7 3 70 o .g34 o.53 22 5.8 9 50 0.927 1.2 23 5.7 85~
1 Example 35 A composition of ekhylene-~-olefin copolymers was prepared in two stage polymerization. The first stage polymerization was carried out for 70 min. using the catalyst produced in Example 1 and triethyl alminum (co-catalyst) and other polymerization conditions as shown in Table 24. Successively~the second stage poly-<
merization was conducted for 180 min. by changing onlythe hydrogen partial pressure and the ethylene partial pressure as shown in Table 24. In both stages, the liquid phase molar ratio of ethylene, butene-l and hydrogen was kept at respective fixed levels. The polymerized quanti-ties in each stage were calculated from the quantities - of fed ethylene. The copolymers consisted of about 50%
by weight of higher molecular weight componenks and about 50% by weight of lower molecular weight components.
Immediately before the completion of the first stage polymerization, a part of the polymer was taken out and measured for its density, intrinsic viscosity, S.C.B.
and (weight average molecular weight/number average molecular weight). The whole polymer obtained after the second stage was also measured for the same test items.
From the values of the first stage polymer and the whole polymer~ the intrinsic viscosity and S.C.B. of the poly-mer formed in the second stage alone were calculatedThese values were shown in Table 24~ The whole polymer gave: density O.g21 g/cm3, MI 0.5 g/10 min., MFR 70, intrinsic viscosity 1.7 dl/g, S.C.B. 24. Flow \
l charac~eristics and solid physical properties of the whole polymer were shown in Table 26.
Example 36 By mixing the ethylene-~-olefin copolymer A4 l obtained in Example 33 and the ethylene-~-olefin copolymer B4-l obtained in Example 34 at a S0/50 weight ratio and kneading the mixture in a Banbury mixer, a composition of ethylene-~-olefin copolymers having the density, MI
and MFR shown in Table 25 was prepared. Physical pro-perties of this composition were also shown in Table 25.For comparison, in Table 25 were also shown Comparative examples 15 and 16 using high pressure polyethylenes of the conventional technique ~commercial product Sumikathene ~ F 208-1, F lOl-l manufactured by Sumitomo Chemical Co., Ltd.) as well as Comparative e~ample 17 using a low density ethylene-~-olefin copolymer of the conventional technique.
As is obvious from Table 25, the polymer com-position of' the present in~ention, when compared T~ith high preF,sure polyethylenes, has about an equal Brabender torque (satisfactory in processability)~ and is much superior in tensile impact strength, rigidity, ESCR and tensile strengthg and further is about equally satis-factory in transparency.
Compared with the low density ethylene-~-olefin copolymer of the conventional technique, this polymer composition has a much lower Brabender torque (far s~
l excellent in processability) and a higher tensile impact strength and tensile s~rength.
Examples 38, 39, 40, 41, 42, 43 By mixing the ethylene-a~olefin copolymers A
obtained in Example 33 and the ethylene-a-olefin copoly~
mers B obtained in Example 34 at -ratios as shown in Table 26, compositions having densities~ MIs and MFRs shown in Table 26 were obtained. Physical properties of e these compositions w~ also shown in Table 26.
In Table 26 ~e also shown a similar composi-.
tion prepared by two stage polymeri~ation (Example 35) and, for the purpose of comparison, compositions of low density ethylene-a-ole~in copolymers of the conventional technique (Comparative examples 22, 23, 25) of which molecular weight distributions are made wlder and of which lower molecular weight components have larger S.C.B.
and of which higher molecular weight components have smaller S.C.B. In Table 26 ~*~ also show~ a composition of ethylene-~-olefin copolymers (Comparative example 24, to be compared with Examples 40 and 42) of which distri-bution index of S.C.B. meets the scope of this invention but of which lower molecular weight components have a too low intrinsic viscosity.
As seen in Table 26, in the compositions of this invention, S.C.B. of higher molecular weight components are more than or about equal to those of lower molecular weight components. (Compare Examples 35, 38 and 41 with s~
1 Comparative examples 22 and 23, and Example 43 with Com-parative example 25.) Therefore, compared with the compositions of the conventional technique, the composi-tions of this invention are far excellent in tensile impact strength and tensile strengthg and are superior in transparency.
From the comparison between Comparative example 17 of Table 25 and Comparative example 22 of Table 26, it is learned that widening of molecular weight distri~
bution (higher MFR gives wider distribution) in the manufacture of a low density ethylene-~-olefin copolymer of the conventional technique with its density and M-~kept constant results in large reduction in tensile impact strength and tensile strength.
From the comparison of Examples 40 and L~2 with Comparative example 24, it is learned that a too low intrinsic viscosity of lower molecular weight components badly affects its tensile impact strength, tensile strength and transparency.
- 122 ~
Table 24 Polymeri- Polymeri- Catalyst Co~catalyst H2 partia N zation zation quantity TEA Solvent a-olefin pressure method vessel capacity (mg) (mmol) (g) (g~ (kg/cm2) 1st Slurry o.6 stage 24.3 5 C4 1000 C4' 250 stnage Slurry 10 ~1 - Cont'd -Note C4 = n-Butane TEA = Triethyl aluminum C4 t = Butene-l ( ) = Calculated values C2' - Ethylene Table 24 (Cont'd) C2'- Polymeri- Polymeri- Properties partial zatlon zation pressure tempera- time Density [n]
2 ture (min).~g/cm3) (dl/g) S-C-B~ Mw/Mn 4 700.912 2.6 24 5.7 180 - ~0.8~ (23) ~ e~
Table 25 Copolymer A Copolymer B Properties of composition Mixing method Desig- % by Desig- % by Density MI Distribu-nati.on weight nation weight ~g/cm3) (g/ MFR tion index 10 min.) of S.C.B.
Example 36Banbury A4-1 50 B4-1 50 0.920 0.5 70 1.0 Example 37 " B4-11 50 B4-12 50 0.921 0.7 40 1.0 Comparative Xi~h pressure Example 15 polyethylene (Sumikathene ~ F208-1) 9 3 1.4 ~0 Example 16 i~ (Sumikathene ~ F101-1) o.g22 0.3 65 ~
Comparative Low density ethylene/a-olefin Exan~ple 17 copolymer of the conventional 0.920 0.5 30 -technique - Cont'd -(S.C.B. of copolymer A) Distribution index o~ S.C.B. (S.C.B. of copolymer B) ~) Table 25 (Cont'd) Phisical properties of composition Tensile inpact Olsen's flexual ESCR Tensile Brabender strength modulus F~o strengkh Ha~e torque (kg-cm/cm2) (kg/cm2) (~r) (kg/cm') (%) (kg-m) 350 28~0 >1000 280 5 2.0 370 3000 >1000 290 5 2~6 130 2400 0.3 160 4 1.9 200 2200 30 180 6 2.2 ~g ~n 280 3200 >1000 260 5 3-5 ~
Table 26 Copolymer A Copolymer B Properties of composition Mixing method Desig- % by Desig- % by Dens~ty MIDistribu-nation we-'ght nation weight (g~cm3) ~g/ MFR tion index 10 min.) of S.C.B.*
Example 35 - Two ~tage polymerization - 0.921 0.570 (1.0) Example 38Solution A4-2 50 B4-2 500.920 o.6 70 1.0 Example 39 " A4-3 30 B4-3 70 0.921 0.390 o.8 Example 40Banbury A4-4 50 B4-4 50 0.920 1.165 1.0 Example 41tt A4-5 50 B4-5 50 0.920 0.5 7 1.5 Example 42Solution A4-6 50 B4-6 50Q.920 1.1 65 1.0 Example 43Banbury A4-7 50 B4-7 50 0.929 0.2lQ0 1.0 _.
Comparative " A4-8 50 B4-8 500.920 0.5 70 0.26 Compa ative Solution A4-9 50 B4_9 500.920 0.6 65 o.36 Example 24Banbury A4 4 65 B4-10 35 0.920 o.850 1.0 Comparative " A4-10 50 B4-11 500.930 0.2 100 0.27 Example 25 - Cont'd -Distribution index of 3.C.B. = (S.C.B. of copolymer A)/~S.C.B. of copolymer B) /
Table 26 (Cont'd) Physical properties of composition Tensile impact Olsen's flexural -Tensile strength modulus strength Haze Tackiness (kg-cm/cm2) (kg/cm2) (kg/cm2) (%) 340 28Qo 28Q ~ o 37~ 2800 300 7 o 2~0 2800 250 6 o 400 2700 300 ~ o ~ 36Q 2800 310 5 o 3~0 4200 . 300 8 o 150 3300 210 12 x 130 2800 220 15 o 170 4800 230 20 o sl~
1 Example 44 The compositions prepared in Examples 36 and 37 as well as the low density ethylene-~-olefin copolymer of the conventional technique used in Comparative example 17 were subjected to film processing in the same condi-tions as used in Example 32.
The comrnercial high pressure polyethylenes used in Comparative examples 15 and 16 were also subjected to film processing in the same conditions. A satisfactory film was not obtained from the low density ethylene-~-olefin copolymer of the conventional technique used in Comparative example 17, with too much load put on the motor and with shark skin formed on the film surface.
Satisfactory films having good transparency were obtained from the compositions prepared in Examples 36 and 37 and the commercial high pressure polyethylenes used in Comparative examples 15 and 16, with no problem of` motor load. Physical properties of these films ~ e shown in Table 27. Compared with the films of the high pressure method polyethylenes, the films of the composi-tions prepared in Examples 36 and 37 had about same trans _S-Gj~ O r parency but were l&rgcly _~^^l'_n' in dart impact strength, Elmendorf tear strength (absolute value property and MD/TD balance), heat-sealing properties, tensile strength, hot tack and heat sealing strength in contami-nated condition. In case of the films of the compositions prepared in Examples 36 and 37, heat~sealing strengths and heat sealing strength in contaminated condition were at _ 129 --l about same levels, but in the films of the high pressure polyethylenes of Comparative example 16, heat sealing strength in contaminated condition were lower than heat-sealing strengths.
Comparative Examples 22, 23, 25 By mixing ethylene-~-olefin copolymers A
obtained in Example 33 and ethylene-a-olefin copolymers B obtained in Example 34 at ratios as shown in Table 263 compositlons of low density ethylene-~-olefin copolymers of the conventional technique were prepared of which molecular weight distribution are made wider and of which lower molecular weight components have larger S.C.B. and of which higher molecular weight components have smaller S.C.B. Densities, MIs, MFRs and physical properties of .~ ~ 15 these compositions ~e*e shown in ~able 26.
Comparative Example 24 By mixing an ethylene ~ olefin copolymer A
obtained in Example 33 and an ethylene-~-olefin copolymer B obtained in Example 34 at a ratio shown in Table 26, a composition of ethylen-~-olefin copolymers was prepared of which distribution index Or S.C.B. meets the scope of this invention but of which lower molecular weight com~
ponents have a too low intrinsic viscosity. Its density, MI, MFR and physical properties w~ shown in Table 26.
Table 27 Haze Dart Elmendorf Tensile Heat- Hot tack Heat sealing impact tear strength sealing property strength in strength strength MD/TD strength contaminated (%) (kg-cm/mm) MD/TD (kg/15mm condition ~kg/cm) (kg/cm2) width) (mm) Example 36 5 5O 90~120 410/380 1.2 2.0 o Example 37 5 450 60/120 420/370 1.3 2.0 o Comparative 4 270 80/50 250/210 0.7 4.0 Example 15 Example 16 250 70/70 280/250 0.7 3.0 ~1 1 Example 45 Ethylene-a-olefin copolymers were synthesized using the catalyst produced in Example 1 and organo-aluminum compounds (co-catalyst) and employing ~-ole~ins and other pol.ymerization conditions as shown in Table 28.
Densities, intrinsic viscosities~ and S.C.B~ of these copolymers w~ shown in Table 28.
These copolymers are used in the ~ollowing examples as higher molecular weight components.
Example 46 Ethylene-a~ole~in copolymers were synthesized using the catalyst produced in Example 1 and organoalumi-num compounds (co-catalyst) and employing a-ole~ins and other polymerization conditions as shown in Table 29.
5 Densities~ intrinsic viscosities and S.C.B. of these c~e copolymers ~e~ shown in Table 29.
These copolymers are used in the following examples as lower molecular weight components.
Table 28 Polymeri- Polymeri- Catalyst H2 partial Nozation zation quantit~T Co-catalyst Solvent a-olefin pressure method vessel capacity (Q~ ~.g) (mmol) (kg) (kg) (kg) A-l Slurry 65 131 TEA 100 C4 6.o c4 6.14 0.45 A-2 " 65 145 TEA 5 A-3 65 310 TEA 100 " " 0.70 A-4 " 65 125 l " , 1.8 A-5SQlution 1 25.3 DEAC 2.5 G7 0.25 4-MP-l 0.11 0.1 A-6 " 1 24.5 " C7 0.30 4-MP-1 0.05 0.15 A-7 Slurry 65 121 TEA 5 C4 6.o c4l 6.14 0.98 A-8 .11 65 320 TEA 100 " " 3.0 - Cont'd -Note TEA = Triethyl aluminum C4 = n-Butane DEAC = Diethyl aluminum chloride C4' = Butene-1 4-MP-1 = 4-Methylpentene-1 C7 = n-Heptane Table 28 (Cont'd) C2'- Polymeri- Properties partial zation pressure tempera- Density ~rl~
ture S.C.B.
~kg/cm2) (C) (g/cm3) (dl/g) 5.0 50 0.899 2.6 38 6.7 50 0.906 2.6 29 7.8 50 0.912 2.6 24 18 50 0.923 2.6 ~ 20 140 94 2.5 23 140 0.920 2.5 lO
6.5 50 ~.907 2.2 30 5~ 0.928 2.2 8 Table 29 Polymeri- Polymeri- Catalyst H2 partial Nozation zation quantity Co-catalyæt Solvent a-ole~inpressure method vessel capacity (Q)(mg) (mmol) (kg~ (kg~ (kg~cm2) B-l Slurry 65405 TEA 50 C4 5~ c4~ 2.0 10.8 B-2 " 65411 " C4 15.2 C4' 1.6 6.5 B-3 " 65402 l~ C4 12.0 C4 3.2 7.8 B-4 65408 TEA 100 c4 400 5.2 B-5Solution 126.5 DEAC 2.5 C7 0.28 4-MP-1 0.03 3.0 B-6 ' 125.7 c7 0.25 4-MP-1 5 2.5 ~A
Ç~
B-7 Slurry 65407 TEA 100 C4 15.4 C4~ 0.5 13.0 ~1 B-8 " 65422 TEA 50 C4 15-2 C4' 1.8 11.0 - Cont'd -Note TEA = Triethyl aluminum C4 = n-Butane DEAC = Die~hyl aluminum chloride C4' = Butene-l 4-MP-1 = 4-Methylpentene-1 C7 = n-Heptane ) Table 29 ~Cont'd) c2~- Polymer~i- Properties partial zation pressure tempera- Density [n]
ture S.C.B.
(kg/cm23 (C) (g/cm3) ~dl/g) 8.3 70 0.912 '~3 15 7 0.935 0.83 20 6 70 0.929 0.85 24 4 50 0.910 0.82 35 140 o.938 5 13 140 0.912 0.52 22 ~8 7 953 0.62 9 0~934 0.61 22 ~J
l Example 47 A composition of ethylene-a-olefin copolymers was prepared in two stage polymerization. The first stage polymerization was carried out for 70 min. using the cataly~t produced in Example 1 and triethyl aluminum (co-catalyst) and other polymerization condit-ions as shown in Table 30. Successively, the second stage poly-merization was conducted for 180 min. by changing only the hydrogen partial pressure and the ethylene partial pressure as shown in Table 30. In both stages, the liquid phase molar ratio of ethylene, butene-l and hydrogen was kept constant at respective fixed levels~
The polymerized quantities in each stage were calculated from the quantities of fed ethylene. The copolymer com-position consisted of about 50% by weight of highermolecular weight components and about 50% by welght of lower molecular weight components. Immediately before the completion of the first stage polymerization, a part of the polymer was taken out and measured for its density, intrinsic viscosity and S.C.B. The whole polymer obtained after the second stage was also measured ~or the same test items. From the values of the first stage polymer and the whole polymer, the intrinsic viscosity and the number of branched short chains of the polymer formed in the second stage alone were calcula~ed. These values were shown in Table 30. The whole polymer gave: density 0.921 g/cm3, MI 0.5 g/10 min., MFR 70, intrinsic viscosity 1.7 dl/g, S.C.B. 24, gn 93 The whoel polymer was subjected 5~
1 to gel permeation chromatography an~ a curve of molecular weight distribution shown in ~ig. 4 was obtained.
Because of bimodal distribution which has two peaks 3 the curve was divided into two parts usin~ broken lines. The areas of each part were calculated, and the lower molecular weight components and the higher molecular weight components were determined to be 48 and 52% by weight 7 respectively.
The whole polymer was divided into 30 fractions using column chromatography. These fractîons were divid~
ed into two parts (the lower molecular weight components and the higher molecular weight components) so that the former became 48% by weight and the latter 52% by weight.
S.C.B., densities and intrinsic viscosities of each com-ponent w~ shown in Table 32.
Flow characteristics and solid physical proper-~ eties of the whole polymer ~r~ shown in ~able 33.
In the following examples~ ethylene-~-olefin copolymers as higher molecular weight components and ethylene-a-olefin copolymers as lower molecular weight components were mixed at respective fixed ratios (total quantity 1 kg) and kneaded for 5 min. with a Ba~bury mixer (150 ko 230 rpm). At that time, replacement by nitrogen was conducted completely and the polymer temperatures were controlled not to exceed 250C.
When sample quantities were small, mixing was made in xylene. After mixing, the whole solution was added into methanol to cause precipitation. After 5`~ `
filtration, the precipitate was completely dried in a vacuum drier and used as a copolymers composition sample.
Examples 48, 49, 50 Ethylene-~-olefin copolymers obtained in Example 45 and ethylene-a~olefin copolymers obtained in Example 46 were kneaded with a sanbury mixer at ratios as shown in Table 31.
Tllus, compositions of copolymers having densities, ~Is, MFRs, intrinsic viscosities, S.C.B. and g* shown in Table 32 were obtained. These compositions had molecular weight distribution curves about equal to Figure 4. With the same technique as used in Example 47, quantities of lower molecular weight components and higher molecular weiyht components were calculated, and they were both approximately 50% by weight as shown in Table 32~ Physical proper-ties of these compositions are shown in Table 33 With the same technique as used in Example 47, column fractlonation was applied in order to divide into higher molecular weight components and lower molecular weigh-t components.
Characteristics of the components are shown in Table 32.
In Tables 32 and 33 are also shown Example 47 using a composition of ethylene-~-oleEin copolymers prepared in two stage polymerization and, for comparison, Comparative example 26 using a high pressure method polyethylene of the conventional technique (commercial product Sumikathene ~ F 101-1 manufactured by Sumitomo
Temperature: 40C
Evaluation: 10 stage evaluation on a sample after 72 hours.
1: Excellent, 10: Overall surface like "foam"
20 (13) Transparency (haze value) Press condition: 180C x 10 min, rapid cooling in ice water Sample: 100~ thickness Haze measurement: Internal haza 25 (14) Brabender torque Brabender6~plastograph ~ was used.
Jacket: W 50 model, 45 g filled Temperature: 190C
1 Rotor revolution: 60 rpm A torque after 30 min. is expressed in kg-m.
(15) Spiral flow length Injection molding machine: 5 ounce injection rnolding machine manufac'Gured by the Japan Steel Works, Ltd.
Mold: Spiral mold (7.5 mm~ semiclrcle~ 2000 mm length~
Molding condition: Resin temperature 250C
Mold temperature 40C
Injec~ion pressure 840 k~/cm2 Injection molding is carried out w~th this mold-ing condition and spiral flow length is measured.
~ The present invention is explained below in more ~3~
by the ~ollowing examples, but it is not restricted by these examples.
Example 1 (1) Synthesis of Organomagnesium Compound In a 500 ml ~our~necked flask equipped with a stirrer, a reflux condenser, and a dropping funnel was placed 16.0 g of flake-shaped magnesium to be used for the production of Grignard reagents. The air and mois-ture inside the ~lask were completely replaced by nitrogen. Into the dropping funnel were charged 68 ml (o.65 mol) of n-butyl chloride and 30 ml of n butyl ether. About 30 ml of this solution was dropped into - 46 ~
~3~
l the ~lask to initiate a reaction~ an~ therea~ter the rest of the solution was dropped in 4 hours a~ 50C. After the completion o~ dropping, the reac~ion was continued for further 1.5 hours at 60C. Then, the reaction system was cooled to room temperature and the unreacted magnesium was filkered off by the use of a glass filter.
n-Butyl magnesium chloride in the n-butyl ether was measured for its concentraticn by hydrolyzing with l N
sulfuric acid and back-titratlng with l N sodium hydroxide using phenolphthalein as an indicator. The concentration was 1.96 mol/l.
(2) Synthesis of Solid Catalyst Component The air and moisture inside a 500 ml four-necked flask equipped with a stirrer, a dropping funnel and a thermometer was completely replaced by nitrogen.
In the flask was placed 130- ml of the n-butyl ether solution containing 0.26 mol of n-butyl magnesium chloride synthesized in the abo~e step (1). From the dropping funnel was dropped 30 ml (0.26 mol) of silicon tetra-chloride o~er 2 hours at 50C. The reaction was con-C~!tinued for~further l hour at 60C. The formed white solid was separated, washed with n-heptane and dried under reduced pressure to obtain 31.5 g of a white solid.
Ten grams of this white solid was placed in a lO0 ml four-necked flask and 50 ml of titanium tetrachloride was added. They were allowed to react with stirring for l hour at 100C. After the completion of the reaction~
n-heptan washing was applied until the washings became 5 ~
1 free from titanium tetrachloride. After drying under reduced pressure, 7.9 g of a solid catalyst component was obtained. ~ach 1 g of this solid catalyst component supported 14 mg of titanium~
Example 2 Ethylene~-olefin copolymers A were polymerized, using the ca~alyst produced in Example 1 and organoalminum compounds (co-catalyst) and employing various ~-olefins and other pclymerization conditions as shown in Table 1.
Densities~ intrinsic viscosities, S.C.B. and (weight average molecular weight/number average molecular weight) of these polymers obtained were also shown in Table 1.
These copolymers are used in the following examples as mixing components.
Example 3 Ethylene u-olefin copolymers B were polymerized, using the catalyst produced in Example 1 and organoalumi-num compounds (co-catalyst) and employing various a-olefins and other polymerization conditions as shown in Table 2.
Densities, intrinsic viscosities, S.C.B. and (weight average molecular weight/number average molecular weight) of these ethylene-a-olefin copolymers were also shown in Table 2.
These copolymers are used in following examples as mixing componentsO
~ 48 -Table 1 Polymeri- Polymeri- Catalyst H2 partial N zationzation quantity Co-catalyst Solvent ~-olefin pressure methodvessel capacity 2 (Q~ (mg) (mmol) (kg) (kg) (kg/cm ) Al-lSlurry 65 134 TEA 100C4 6.o C4~ 6.14 o.84 Al-2Solution 1 25.3 DEAC 2.5C7 0.25 4-MP-1 0.110 Q.l Al-3Slurry 65 130 TEA 50C4 6.Q - C4 6.14 0.25 Al-4 " 65 310 TEA 100 It 11 0.86 Al-5 65 102 TEA 50 " It O.059 Al-6Solution 1 26.0 DEAC 2.5C7 0.30 c6~ 0.Q60 0.1 Al-7 " 1 327 TEA 100 " .l 1.8 Al-8 '~ 1 24.5 DEAC 2.5 " 4-MP-1 0.050 0.15 Al-9Slurry 65 33 TEA 100C4 6.o C4' 6.14 1.1 Al-10 " 65 309 TEA 100 " ll 1. 2 Al-11 ll 65 121 TEA 50 ll 'l o . 98 Al-12 " 65 320 TEA 100 " '~ 3.o Al-13Solution 1 25.0 DEAC 2.5C7 0.25 Cg 0.140 0.1 - Cont'd -/
- Table 1 (Cont'd) C '- Polymeri- Properties partial zation pressure ~empera- Density [~3 _ _ 2 ture S.iC.B. Mw/Mn (kg/cm ) (C) (g/cm3) (dl/g) Note 5.650 0.900 2.2 38 5.9 TEA = Triethyl aluminum 20 140 94 2.5 23 3.6 DEAC = Diethyl aluminum chloride 6.o50 0.905 3.2 30 5,8 4-MP-1: 4-Methylpentene-l 9.550 0.915 2.5 19 5.5 C2' = Ethylene o 4-5 50 o.go8. 4~4 25 6.o C4 = n~Butane 20 140 93 2.5 25 3.7 C4' = Butene~
12.Q140 0.922 2.2 13 5.3 C6' = Hexene-l ~9 20. 140 0.920 2.5 10 3.7 C8' = Octene-112.Q50 0.921 2.5 13 5.5 C7 = n-Heptane 8.o50 0.911 2.2 25 5.7 6.550 0.907 2.2 30 5.7 0.928 2.2 8 5.3 20 140 0.~03 2.5 24 3-9 Table 2 Polymeri- Polymeri- Catalyst H2 partial zationzation quantity Co-catalyst Solvent ~-olefinpressure No.method vessel capacity (Q) (mg) (mmol) (kg) (kg)(kg/cm2) Bl-l Slurry65 345 TEA 100 C4 15 2 C4 1. 211. 5 Bl-2 Solution 1 25.5 DEAC 2 . 5 C7 0.28 4-MP-1 0.030 3.0 Bl-3 Slur~y65 415 TEA 50 C4 15 2 C4 1.6 11.0 Bl-4 65 425 " " c4~ 2.0 10.5 Bl-5 " 65 286 " C4 6.o C4 6.14 9.4 Bl-6 " 65 410 TEA 100 C4 12.0 C4~ 3.0 11.0 Bl-7 Solution 1 25.7 DEAC 2.5 C7 0.254-MP-1 0.050 2.5 Bl-8 Slurry65 250 TEA 100 C4 15- 2 C4~ 0.413.5 ~1-9 .l 65 47 " I~ C4 1 0 . 513 . O
Bl-10 " 65 422 TEA 50 ' C4' 1.8 11.0 Bl-ll " 65 405 " c4~ 1.411.0 Bl-12 Solution 1 26 DEAC 2 . 5 C7 0 25C8' 0.040 3 . O
- Cont'd -~able 2 (Cont'd) C2'- Polymeri- Properties pressure zation (kg~cm2) tempera- Density [n] _ _ ture S.C.B. Mw/Mn ~C) (g~cm3) (dl/g) Note 5.0 70 0. 943 0. 63 15 5.5 TEA - Triethyl aluminum 140 0. 938 0.5~ 13 3. 5 DEAC = Dietnyl aluminum chloride 5.o 70 0.936 0.62 20 5.6 4-MP-1 = 4-Methylpentene-l 5.0 70 0.929 o .65 25 5.7 C2' = Ethylene 8.5 50 0.927 1.1 25 5 O 8 C4 = n-Butane 3.0 50 0 - 91o 0.60 35 5 - 9 c4 ' = Butene-l 61 140 0. 912 0.52 22 3.6 C6' = Hexane-l 1.5 50 0.930 0.28 25 5.7 C8 ' = Octene-l 5. o 70 o . g54 0.62 8 5.2 c7 = n-Heptane 5.0 70 0.934 0.61 22 5.6 5- 70 0.939 0.62 18 5.5 o l 40 0.937 o .49 14 3.6 s~
1 Example 4 Ethylene-~-olefin copolymers A were polymerized, using the catalyst produced in Example 1 and organo-aluminum compounds (co-catalyst) and employing various ~-olefins and other polymerization conditions sho~n in Table 3. Densities, intrinsic viscosities~ S.C.B. and (weight average molecular weight/number average molecular weight) of these ethylene/~-olefin copolymers were also shown in Table 3.
These copolymers are used in the following examples as mlxing components.
Example 5 Ethylene-~-olefin copolymers B were polymerized, using the catalyst produced in ~xample 1 and organoalmi-15 num compounds (co-catalyst) and employing various ~-olefins and other polymerization conditions as shown in Table 4~ Denslties, intrinsic viscosities, S~C.B. and (weight average molecular weight/number average molecular weight) of these ethylene/~-olefin copolymers were also shown ln Table 4.
These copolymers are used in the following examples as mixing components.
- ~3 -Table 3 Polymeri- Polymeri- Catalyst H2 partial N zation zation quantity Co-catalyst Solvent a-olefln pressure method vessel capacity 2 (Q) ~mg) (mmol) (kg) (kg) (kg/cm ) A2-1 Slurry 65 145 TEA 100 C4 6.o C4 ! 6.14 1.38 A2-2 Solution 1 25.5 DEAC 2.5 C7 0.25 4-MP-1 0.11 0.5 A2-3 Slurry 65 141 TEA 50 C4 6.o C4 6.14 0.59 A2-4 ll 65 307 TEA 100 " " 2.3 A2-5 65 311 " " " 1.84 A2-6 ll 65 321 " " " 3.2 C~
A2-7 Solution 1 26.5 DEAC 2.5 C7 0.3 4-MP-1 0.05 0.9 A2-8 Slurry 65 315 TEA 100 C4 6.o C4 6.14 2.6 A2-9 " 65 118 " " " 4.6 A2-10 Solutior.1 24.5 DEAC 2.5 C7 0.3 C6f 0.025 0.9 - Cont'd -Table 3 (Contld) C2'- Polymeri- Properties partial zation pressure tempera- Density [~] _ _ ture S.C.B. Mw/Mn (kg~cm2) (C) (g/cm3) (dl/g) Note 6.o 50 0.902 1. 8 38 5.9 TEA = Triethyl aluminum 140 0.908 1. 8 23 3. 8 DEAC = Diethyl aluminum chloride 6.5 50 0.907 2.5 3 5. 8 4-MP-1 = 4-Methylpentene=l 11 50 0.918 1. 8 17 5.4 c2' = Ethylene 8. 4 50 0.914 1.8 25 5.7 c~ = n-Butane ! 14 50 0.925 1. 8 13 5.3 c4~ = Butene-l ~E
140 o.923 1.8 lo 3.6 C6l = Hexene-l 8.5 50 0.914 1.6 25 5.5 c7 = n-Heptane 17 50 0.929 1.5 lo 5.3 140 0.918 1~ 8 13 3. 8 Table 4 Polymeri- Polymeri- Catalyst H2 partial No. zationzation quantity Co-catalyst Solvent ~-olefinpressure methodvessel capacity 2 (Q~ (mg) (mmol) tkg) (kg) (kg/cm ) B2-1 Slurry6~ 348 TEA100 C415. 2 C4 ~ 1.0 12 B2-2 Solution 1 26.5 DEAC 2. 5 C7O. 28 4-MP-1 0.03 3.0 B2-3 Slurry65 405 TEA50 Cl,15.2 C4~ 1. 68.8 B2-4 " 65 421 " " " 12 B2-5 " 65 407 TEA100 C412. C4 l 2.5 12 B2-6 Solution 1 25.7 DEAC 2.5 C70.25 4-MP-1 0.05 2.5 B2-7 Slurry65 245 " C415 - 2 C4 ~ 0.3 12 B2-8 J' 65 420 TEA50 C4 l 1 ~ 212 B2-9 Solution 1 23.9 DEAC 2.5 C7 3 C6 ' O .017 3.0 - Cont'd -Table 4 ~Contld) C2l- Polymeri- Properties partial zation pressure tempera- Density [~
2 ture 3 S.C.B. Mw/Mn (kg/cm ) (C) (g/cm ) (dl/g) Note 3.0 70 0.943 0.51 15 5.9 TEA = Triethyl aluminum 140 0.938 o.50 13 3.5 DEAC = Diethyl aluminum chloride 5.0 70 Q .935 0.73 20 5.9 4-MP-1 = 4-methylpentene-1 3.0 70 0.929 o .54 25 5 .9 C2l = Ethylene 3.0 50 0.910 0.51 35 6. o C4 = n-Butane o 140 0.912 0.52 22 3.6 c4 r = Butene-l 1.0 50 0.931 0.25 25 5.9 c61 = Hexene-l ~n 3.0 70 o . g38 o .50 18 5.4 c7 = n-Heptane 140 0. 937 0.52 18 3.4 S ~2 1 Example 6 A composition of ethylene-~-olefin copolymers was prepared in two stage polymerization.
The first stage polymerization was carried out for 90 min. by using the catalyst produced in Example 1 and trie~hyl aluminum (co-catalyst) and employing other polymerization conditions as shown in Table 5.
Successively, the second stage polymerization was con-ducted for 123 min. by changing only the hydrogen partial pressure and the ethylene partial pressure as shown in Table 5. In both polymerization stages3 the liquid phase molar ratio o~ ethylene/butene-l/hydrogen was maintained at respecti~e fixed levels. The polymer-~zed ~uantities in each stage were examined from the quantities of fed ethylene. The result indicated that the total polymer consisted of abou-t 45% by weight of higher molecular weight components and about 55% by weight of lower molecular weight components. The sample polymer of the former stage was taXen out immediately be~ore the completion o~ the polymerization and was measured for its density, intrinsic viscosity, S.C.B.
and (weight average molecular weight/number average molecular weight). Also~ similar measurements were made for the whole polymer obtained after the two-stage poly-merization. Using the values of the former stage polymerand the whole polymer, the intrinsic viscosity and S.C.B.
for the polymer ~ormed in the latter stage a]one were calculated. These calculated values are also shown in - 58 ~
1 Table ~. The whole polymer gave: density 0.920 g/cm3, melt index 0.7 g/10 min~ melt flow ratio 65, intrinsic viscosity 1.6 dl/g, S.C.B. 25. The whole polymer was measured for its fluidity and solid physical properties.
Results are shown in Table 9.
The be]ow-described are mixing methods of an ethylene-a-olefin copolymer A having a relatively higher molecular weight and an ethylene-~-olefin copolymer B
having a relatively lower molecular weight.
(a) Mixing with a Banbury mixer (hereinafter refer-red ko as Banbury mixlng) A copolymer A and a copolymer B are mixed in a fi~ed ratio and in order to give a total quantity of 1.0 kg. The mixture is kneaded in a Banbury mixer for 5 min.
with a Pe~a~ revolution of 150 to 230 rpm. At that time, nitrogen replacement should be made sufficiently and the polymer temperature must not exceed ~50C.
(b) Mixing in a solution state (hereinafter referred to as solution mixing) A copolymer A and a copolymer B are mixed ln a fixed ratio and in order to give a total quantity of 100 g.
This mixture is charged into a 3 liter autoclave. Two li.ters of xylene is added as a solvent. With stirring, the mixture is heated up to 200C and is subjected to 1 hour o~ solution mixing. Then, it is cooled below theboiling point, and is added into 10 liters of methanol to cause precipitation. The precipitate is dried for Ll8 hours in a vacuum drier of ~0C to obtain an intended 1 polymer composition.
Example 7 A composition of ethylene-~-olefin copolymers was prepared in two stage polymerization.
The first stage polymerization was carried out ~or 100 min. by using the catalyst produced in Example 1 and triethyl aluminum (co-catalyst) and employing other polymerization conditions as shown in Table 6. Succes-sively~the second stage polymerization was conducted for 150 min. by changing only the hydrogen partial pressure and the ethylene partial pressure as shown in Table 6.
In both polymerization stages 3 the liquid phase molar ratîo of ethylene/butene-l/hydrogen was maintained at respective fixed levels. The polymerized quantitites in each stage were examined from the quantities of fed ethylene. The result indicated that the total polymer consisted of about 50% by weight of higher molecular weight components and about 50% by weight of lower molecular weight components. The sample polymer of the :~ormer stage was taken out immediately before the comple-tion of the polymerization and was measured for its density, intrinsic viscosity, S~C~B~ and (weight average molecular weight / number average molecular weight).
Similar measurements were made also for the whole polymer obtained after the two stage polymerization. Using the values of the former stage polymer and the whole polymer, the intrinsic viscosity and SoC~B~ for the polymer formed _ 60 -1 in the latter stage alone were calculated. These cal-culated values are also shown in Table 6. The whole polymer gave: density 0.923 g/cm3~ melt index 6 g/10 min., melt flow ratio 55, intrinsic viscosity 1.10 dl/g~ S.C.B.
25. The whole polymer was subjected to injection molding and the molded composition was measured for its physical properti.es. Results are shown in Table 10.
~ 61 -\
Table 5 Polymeri- Polymeri- Catalyst H2 partial N zatlon zation quantity Co-catalyst Solvent a-ole~ln pressure method vessel TEA
capacity 2 (Q) (mg) (mg) (~) (g) ~kg/cm ) tage Slurry 0.3 18.5 5 C4 1000 C4' 250 stage Slurry 1.7 - Cont~d -Note C4 = n-Butane C4' = Butene-l C2' = Ethylene TEA = Triethyl aluminum Values ir parenthesis are calculated vales.
Table 5 (Cont'd) C2'- Polymeri- Polymeri-Properties partial zation zation pressure tempera- timeDensity [~]
ture - S.C.B. Mw/Mn ~kg/cm2) ~C)(min) (g/cm3) (dl/g) 3 90 0.902 2.8 35 6.1 8 123 - ~0.~2) (15) -Table 6 Polymeri- Polymeri- Catalyst Co-catalyst H2 partial N zation zationquantity TEA Solvent a-olefinpressure ' method vessel capaçity ~Q)~mg) (mmol~ (g) (g)(kg/cm2) lstStage Slurry 0.45 - 5 25 5 C4 1000 C4' 120 stage Slurry 16 ~9 Note C4 = n-Butane - Cont'd -C4' = Butene-l C2 t = Ethylene TEA = Triethyl aluminum Values in parenthesis are calculated values.
Table 6 (Cont'd) C2'- Polymeri- Polymeri- Properties partial zat~on zation pressure tempera- tiJne Density ~3S.C.B. Mw~Fn (kg/cm2) (C) (min) (g/cm3) (dl/g) 2~ 100 0.910 1.75 30 5.8 4.~ 150 (0.5) ~20) _ 1 Example ~
The ethylene-~-olefin copolymer A1-1 obtained in Example 2 and the ethylene-~-olefin copolymer Bl-l obtained in Example 3 were mixed at a 50/50 weight ratio and kneaded in a Banbury mixer. A composition having a density, MI and MFR shown in Table 7 was prepared.
., c~
Physical properties of the composition w~ also shown in Table 7. For the purpose of comparison, in Table 7 ~Pe also shown Comparative example 1 using a high pressure polyethylene based on the conventional technique (com-mercial product: Sumikathene ~ F101-1 manufactured by Sumitomo Chemical Co., Ltd.) as well as Comparative example 2 using a low density ethylene-~-olefin copolymer of the conventional technique.
As is obvious from Table 7, the polymer compo-sition of this invention is excellent, compared with the high pressure polyethylene~ with its lower Brabender torque (excellent in processability) and higher tensile impact strength~ ESCR, rigidity and tensile strength.
It is also obvious from Table 7 that, ~ompared with the low density ethylene-~-olefin copolymer of the conventional technique, the polymer composition of this invention has a much lower Brabender torque (very excel-lent in processability) and a much higher tensile impact 25 strength and tensile strength.
Table 7 Copolymer A Copolymer B Properties of composition Mixing Desig- % by Desig- % by Density MIDistribu-method na~ion weight nation weight (g/cm3) (g/ MFR tion index 10 min) of S.C.B.*
~xample 8Banbury Al-l 50 Bl-l 50 0.921 1.1 65 2.5 Comparative _ 0.922 0.3 65 Example 1 Comparative 0.920 1.0 30 Example 2 - Cont'd - ~g * Distribution index of S.C.B. = (S.C.B. of copolymer A)/(S.C.B. of ~opolymer B) ~n ~s ~able 7 (Cont'd) Physical properties of composition Tensile impact Olsen's flexural ESCR Tensile Brabender Chlorine strength modulus F50 strength torque water (kg-cm/cm2) ~kg/cm2) (hr) (kg/cm2) (kg.m) resistance 340 2600 1000 290 1~9 200 ~200 3 1~0 2.2 5 230 3200 1000 250 2.9 2 o~
s~
l Example 9 The ethylene-a~ole~in copolymer A2-1 o~tained in Example 4 and ~he ethylene-a-olefin copolymer B2-1 obtained in Example 5 were mixed at a 50/50 weight ratio and kneaded in a 3anbury mixer. A composi~ion having a density3 melt index and melt flow ra~io shown in Table 8 was prepared. Physical properties of the composition ~e~ also shown in Table 8. For the purpose o~ compari-.. , ~ r~son, in Table 8 ~e also shown Comparative example 3 using a high pressure method polyet,hylene based on the conventional technique (commercial product: Sumikathene ~ G
701 manufactured by Sumitomo Chemical Co., Ltd.) as well as Comparative example 4 using a low density ethylene-~-olefin copolymer of the conventional technique. As is obvious from Table 8, the polymer composition o~ this invention has a better fluidity at injection molding than the high pressure polyethylene and, moreover, has a much higher tensile impact strength, rigidity~ ESCR and tensile strength. Also, the polymer composition of the present invention is largely excellent in fluidity at in~ection molding, compared with the low density ethylene-a-olefin copolymer of the conventional technique, and further has a much higher tensile impact strength and ESCR.
Examples lO to 14 Ethylene-a-olefin copolymers A obtained in Example 2 and ethylene~-a-olefin copolymers B obtained in \
S~
1 Example 3 were mixed in various ratios and the composi-tions having densities, MIs and r~Rs shown in Table 9 ~e were obtained. Their physical properties w~ also shown in Table 9.
In Table 9 ~a~ also s~own a similar composition obtained f'rom two stage polymeri2ation (Example 6). For the purpose of comparison, in Table 9 were also shown Comaprative examples 5, 6 and 7 as examples of low density ethylene-~-olefin copolymers of the conventional technique of which moleGular weight distributions are made wider and of which lower molecular weight components have larger S.C.~. and of which higher molecular weight com-ponents have smaller S.C.B.
As is obvious from Table 9, in the compositions of this invention, S.C.B. in higher molecular weight components is more than or about equal to that in lower molecular weight components as seen in distribution index of S.C.B. (compare Examples 6, 10 and 14 with Com-parative examples 5 and ~, and ~xample 13 with Compara-tive example 7). ~herefore, the compositions of thisinvention have much higher tensile impact strengths and tensile strengths than the comparative compositions of the conventional technique do. By comparison of Com-parative example 2 in Table 7 with Comparative example 5 in Table 9, it is seen that widening of' molecular weight distribution in the manufacture of a low densi~y ethylene-~-olefin copolymer of the conventional technique maintain~
ing density and MI (larger MFR gives wider di.stribl1tion) - 70 ~
l results in lar~e reduction in tensile impact strength and tensile strength.
/
Table 8 Copolymer A Copolymer B Properties of composition Mixing method Desig- % by Desig- % by Density MI Distribu-nation weight nat1on weight (g/cm3) (g/ MFR tion index 10 mi~) of S.C.B.
Example 9Banbury A2-1 50 B2-1 50 0.924 5 502O5 Comparative o.g20 6 35 Example 3 Gomparative _ 0.924 5 30 -Example 4 - Cont'd -* Distribution index of S.C.B. = (S.C.B. of copolymer A)/(S.C.B. of copolymer B) p~
Table 8 (Cont~d) Tensile impact Olsenls flexural ESCR Tensile Spinal blow strength modulus F~o strength length (kg-cm~cm2) (kg/cm2)(fir) (kg/cm2) (mm) 190 290~lO0 220 130 l20 21002 150 120 llO 3500 .30 180 80 P~
Table 9 Mixing Copolymer A Copolymer B Properties of composition method Desig- % by Desig- % by ~ensity MI MFR Distribu-nation weight nation wei~ht (g/cm3)(~/ tion index 10 min) of S.C.B.
Example 6 - Two slage polymer1zation - 0.920 0 7 65 (2.3) Example 10Solution Al-2 60 Bl-2 40 0.920 0.5 70 1.8 Example 11Banbury Al-3 50 Bl-3 50 0.920 0.25 80 1.5 Example 12 " Al-4 50 Bl-4 50 0.920 0.8 50 0.7 Example 13 " Al-ll 50 Bl-9 50 0.929 1.2 70 3.8 Example 14Solution Al-13 60 Bl-12 40 0.919 0.5 70 1.7 G~
~1 Example 5an ury Al-7 50 Bl-6 50 0.920 1.1 65 0.37 ComparativeSolution Al-8 60 Bl-7 40 0.919 0.5 70 0.50 Examlple 6 Example 7anbury Al-12 50 Bl-10 50 0.930 1.2 7~ o.36 (S.C.B. of copolymer A) - Con~'d -* Distribut~on index _ of S.G.B. (S.C.B. of copolymer B) Table 9 (Cont'd) Physical properties of composition Tens~le impact Olsen's flexural Tensile strength modulus s~rength Tackiness (kg-cm/cm2) (kg/cm2) (kg/cm2) 370 2700 300 o 480 260Q 320 o 480 2700 320 o 30Q 2900 260 o 250 . 3700 25~ o ~n 500 2500 31~ o 110 3200 180 x 200 3100 200 x 4500 200 o 5~;~
1 Examples 15 to 17 Ethylene-~-olefin copolymers A obtained in Example 4 and ethylene-~olefin copolymers B obtained in Example 5 were mixed in various ratios and the composi-tions having densities, melt indices and melt flow ratiosshown in Table 10 were obtained. Their physical proper-ties ~ also shown in Table 10.
~s In Table 10 w~ also shown a similar composi-tion obtained from two stage polymerization (Example 7).
For the purpose of comparison, in Table 10 were also shown Comparative examples 8, 9 and 10 as examples of low density ethylene-~-olefin copolymers of the conven-tional technique of whiGh molecular weight distributions are made wider~ and of whîch lower molecular weight components have larger S.C.B. and of which higher molecular weight components have smaller S.C.B.
As is obvious from Table 10, in the compositions of this invention, the higher molecular weight components have larger S.C.B. than the lower molecular weight com-ponents do~ as seen in distribution index of S.C.B.(compare Examples 7, 15, 16 with Comparative examples 8 and 9, and Example 17 with Comparative example 10).
Therefore, the compositions of this invention have much higher tensile impact strengths ESCRs and tensile strengths than.the comparative compositions of the con-ventional technique do. By comparison of Comparative example 4 in Table 8 with Comparative example 9 in Table 10, it is seen that widening of molecular weight 1 distribution in the manufacture of a low density ethylene-~-olefin copolymer o~ the conventional technique maintein-ing density and MI (larger M~R gives wider distribution) results in large reduction in tensile impact strength, 5 ESCR and tensile strength.
Exa~.ples 18 to 20 Ethylene-~ olefin copolymers A obtained in Example 2 and ethylene-~olefin copolymers B obtained in Exmaple 3 were mixed in various ratios and the composi-tions having densities, MIs and MFRs shown in Table 11w~ obtained. Their physical properties were also shown in Table 11.
~ or the purpose of comparison~ in Table 11 c~
~e~ also shown an example (Comparative example 1) of high pressure polyethylenes of the conventional techni-que; an example (Comparative example 11) of low density ethylene~~-olefin copolymers of the conventional techni-que of which molecular weight distributions are made wider~ and of which lower molecular weight components have larger S.C.B. and of which higher molecular weight components have smaller S.C.B.; and an example (Compa,ra-tive example 12, to be compared with Example 19) of ethylene-~-olefin copolymers compositions of which distribution indices of S.C.B. meet the object of this invention but of which lower molecular weight components have a too low intrinsic viscosity.
It is clearly seen from Table 11 that proper S~2 1 selection of distribution index of S.C.B. gives good transparency about equal to that of high pressure poly~
ethylenes as well as a much more excellent tensile impact s~rength and tensile strength than those of high pressure polyethylenes.
It is learned from comparison of Example 19 with Comparative example 12 tha~ a too low intrinsic viscosity of lower molecular weight components badly affects the tensile impact strength and transparency of the copolymer composition.
Table 10 Mixing Copolymer A Copolymer B Properties of composition method Desig- % by Desig- % by Density MIDistribu-nation weight nation weight (g/cm3) (g/ MFR tion index 10 min~ of S.C.B.*
Example 7 - Two slage polymerization - 0.923 6 55 (1.5) Example 15Solution A2-2 50 B2-2 50 0.923 5 50 1.8 Example 16 " Q2-3 30 B2-3 70 0.924 3 60 1.5 Example 17Banbury A2-8 45 B2-8 55 0.929 10 45 1.4 Comparative Solution A2-7 50 B2-6 50 0.922 5 50 0.45 Example 8 Example 9anbury A2_4 50 B2-5 50 0.920 5 50 0.49 ~1 Comparative. " A2_9 45 B2-4 55 0.930 10 45 0.40Example 10 \
- Cont'd -* . . . . (S.C.B. of copolymer A) Dlstrlbutlon lndex _ of S.C.B. ~S.C.B. of copolymer B) Table lQ (Cont'd) Phy~ical properties of composition Tensile impact Olsen's flexural ESCR Tensile strength modulus F~o strengh Tackiness (kg-cm~cm2) (kg/cm2)(~r) (kg/cm2) 170 3000 50 22~ o 240 3000100 ~50 o 190 3000 30 230 o 120 4000 5 200 o o 100 3600 15 150 x 320Q 13 130 x 4500 1 110 o Table 11 Copolymer A Copolymer B Properties of composition Mixing method Desig- % by Desig- % by Density MI Distribu-nation weight nation weight (g/cm3) (g/ MFR tion index Example 18 Solution Al-5 30 Bl-5 70 0.920 0.15 100 1.0 Example 19 " Al-6 50 Bl-11 50 0.920 0.8 50 1.0 Example 20 Banbury Al-l 50 Bl-4. 50 0.916 1.1 65 1.6 Comparative 0.9220.3 65 ~ Example 1 o~
Compa ative Banbury Al-9 50 Bl-6 50 0.920 0.8 50 0.4 Comparative " Al-10 65 Bl-8 35 o.920 0.8 50 1.0 Example 12 - Cont'd -~Distribution index of S.C.B. = (SOC~B. of copolymer A)/(S.C.B. of copolymer B) ~able 11 (Cont'd) Physical properties of composition Tensile impact Olsen's flexural Tensile strengthmodulus strength Tackiness Haze (kg-cm/cm2)(kg/cm2). (kg/cm2) (%) 4802~0~ 320 o 5 4002800 250 o 4202l00 250 o 5 , 2002200 180 o 5 co ~
~h 1503300 200 x 12 1302800 220 o 15 1 ExamPles 21, 22, 23 Ethylene-~-olefin copolymers A obtained in Example 4 and ethylene-~-olefin copolymers B obtained in Example 5 were mixed at various ratios, and the composi-5 tions having densities, MIs and MFRs shown in Table 12were obtained. Their physical properties T~e~e also shown in Table 12. For the purpose o~ comparison, in c~e Table 12 we~e also shown Comparative example 3 using a high pressure polyethylene of the conventional technique;
Comparative example 13 using a composition of low density eth~Jlene-~-olefin copolymers of the conventional techni-que of which molecular weight distribution is made wider and of whlch lower molecular weight components have more S.C.B. and of which higher molecular weight components have less S.C.B.; and Comparative example 14 (to be com-pared with Example 22) using a composition of ethylene-~-olefin copolymers of which distribution index of S.C.B.
meets the scope of the present invention but of which lower molecular weight components have a too low intrinsic viscosity. It is obvious from Taole 12 that proper se~
lection of distribution index of S.C~B. gives good transparency about equal to that of high pressure poly~
ethylenes and much more excellent tensile impact strength, tensile strength and ESCR than those of high 2~ pressure polyethylenes. From comparison of Example 22 with Comparative example 14, it is learned that a ~oo low intrinsic viscosity of lower molecular weight com-ponents badly affects tensile impact strength and transparency.
Table 12 Copolymer A Copolymer B Properties of composition Mix ng Desig- % by Desig- % by Density MI Distribu-me o nation weight nation weight (g/cm3) (g/ MFR tion index - lO min) of S.C.B.
Example 21 Solution A2-lO 50 B2-9 50 0.923 5 50 0.72 Example 22 Banbury A2-5 50 B2-4 50 0.922 5 50 l.0 Example 23 " A2-1 50 B2-4 50 0.920 5 50 1.6 Comparative " A2-6 50 B2-5 50 0.923 5 50 0.37 omparlatl4e ;, A2-8 65 B2-7 35 0.922 5 5Q l.0 Comparative 0.920 6 35 -Example 3 - Cont'd -* Distribution index of S.C.B. = ~S.C.B. of copolymer A)/(S.C.B. of copolymer B) Table 12 (Ccnt'd) Physical properties of composition Tensile impact Olsen's flexural E~CR Tensile Tacki- Haze strength modulus ~ F~o strength ness (%) (kg-cm/crn2) (kg~cm~) (~r) ~k~/cm2) 200 3100 20 250 o 7 17~ 2900 3G 220 o 7 5 3600 10 130 x 12 c '~ 80 3200 30 190 0 12 ~1 120 2100 2 150 o 7 ~
1 Comparative Example 1 A commercial high pressure polyethylene (Sumikathene ~ F101-1 manufactured by Sumitomo Chemical Co.~ Ltcl.) was measured for its physical properties and sub~ected to blow molding.
Results wefe shown in Table 7 and 11.
Comparative Example 2 An ethylene-a-ole~in copolymer o~ the conven-tional technique was synthesized employing polymerization conditions as shown in Table 13 in which the catalyst prepared in Example 1 and triethyl aluminum (co-catalyst) were used. The copolymer gave: density 0.920 g/cm3, MI
1.0 g/10 min.~ MFR 30. Its physical properties ~e shown in Table 7~
Table 13 Poly- Poly Catalyst Co- Sol- ~~ H2 C2s Polymeri- Polymeri-meri- meri- quan~ity catalyst vent olefin partial partial zation zation zation zation TEA pressure pressure tempera- time method vessel ture capacity (Q) (mg) (mmol) (kg) (kg) (kg/cm2) (kg/cm2) (C) (min) Slurry 65 197 1 7.0 c74l6 4.2 10 50 100 ,~
Note TEA = Triethyl aluminum C4 = n-Butane C2' = Ethylene c4 r = Bu~ene-l _ 1 Comparative Example 3 A commercial high pressure polyethylene (Sumikathene ~G701 manufactured by Sumitomo Chemical Co., Ltd.) was measured for its physical properties and sub-jected to injection molding.
re Results w~e shown in Table 8 and 12.
~' Comparative Example 4 A low density ethylene-a-olefin copolymer of the conventional technique was synthesized employing polymerization conditions shown in Table 14 in which the catalyst prepared in Example 1 and triethyl aluminum (co-catalyst) were used. The copolymer gave: density 0.924 g/cm3, melt index 5 g/]0 min.~ melt flow ratio 30.
~e Its physical properties w~ shown in Table 8.
Table 14 Poly- Poly- Cataly~t Co- Sol- a~ H2 C2~ Polymeri- Polymeri-meri- meri- quantity catalyst vent olefin partial partlal zation zation zation zation TEA pressure pressure temper~- time method vessel ture capacity (Q) ~mg)(mmol) (kg)(~g) (kg/cm2) (kg~c~2) (C) (min) I
~ Slurry 65 19925 6C4~ 6.14 10.2 11.3 50 gO
Note~ TEA = Triethyl aluminum C2' = Ethylene C4 = n-ButaneC4' = Butene-l 1 Comparative Examples 5, 6, 7 and 11 Compositions of ethylene-~-olefin copolymers of the conventional technique were prepared by blending ethylene-~-olefin copolymers A obtained in Example 2 and 5 ethylene-~-olefin copolymers B obtained in Example 3 at rakios shown in Table 9 or 11. However in these copoly-mer compositions, molecular weight distributions are made wider and lower molecular wei~ht components have larger S.C.B. and higher molecular weight components have smaller S.C.B. Densities, MIs, MFRs and physical pro-perties of these compositions w~e shown in Table 9 or 11.
Comparative Exampie 12 By blendin~ an ethylene-~ ole.fin copolymer A
obtained in ~xample 2 and an ethylene-~-olefin copolymer B obtained in Example 3 at a mixing ratio shown in Table 11, a composition of ethylene-~-olefin copolymers was prepared of which distribution index of S.C.B. meets the scope of the present invention but of which lower mole~
cular weight components have a too low inkrinsic viscosi-ty. Its density, MI, MFR and physical properkiesshown in Table 11.
Comparative Examples 8, 9, 10 and 13 Compositions of' ethylene-~-olefin copolymers of the conventional techn~que were prepared by blending ethylene ~-olefin copolymers A obtained in Example 4 and ethylene-~-olefin copolymers B obtained in Example 5 at ~ 9O -1 mixing ratios shown in Table 10 or 12. However in these compositions, molecular weight di.stributions are made wider and lower molecular weight components have larger S.C.B. and higher molecular weight components have smaller S.C.B. Densities, MIs, MFRs and physical properties of these compositions we~e shown in Table lO or 12.
Comparative Example 14 By blending an ethylene-a-olefin copolymer A
obtained in Example 4 and an ethylene--a-olefin copolymer B obtained in Example 5 at a mixing ratio shown in Table 12, a composition of ethylene-~-olefin copolymers was prepared of which distribution index of S.C.B. meets the scope of this invention but of which lower molecular weight components have too low an intrinsic viscosity.
Its density, MI, MFR and physical properties we~e shown in Table 12.
Example 24 Ethylene~~-olefin copolymers A were polymerized using the catalyst produced in Example l and organoalumi-num compounds (co-catalyst) and employing a-olefins and other polymerization conditions as shown in Table 15.
2Q Their densities, intrinsic viscosities, S.C.B. and (weight average molecular weight/number average molecular weight) G' ~
~e shown in Table 15.
These polymers are used in the following examples as mixing components.
~able 15 Polymeri- Polymeri- Catalyst H2 partial zationzation quantity Co-catalyst Solvent ~-olefin pressure No.method vessel capacity (~ (mg) (mmol) (kg) (kg~ ~kg/cm2) A3-1 Slurry65 131 TEA 100 C4 6.0 c4 6.14 0.45 A3-2 Solution 1 25.1DEAC 2.5 C7 G.22 4-MP-1 0.130 0.10 A3-3 1 24.8 " C7 0.30 C6' O.Q55 0.10 A3-4 Slurry65 307 TEA 100 C4 5~ C4 6.14 0.9 A3-5 " 65 130 TEA 50 " " 0.22 A3-6 " 65 125 11 l t~ 1. 8 A3-7 65 3Ql TEA 100 11 ,l 1 . 2 A3-8 " 65 318 " " " 2.0 A3-9 i~ 65 308 " " " 1.4 Note TEQ = triethyl aluminum DEAC = Diethyl aluminum chloride - Cont'd -4-MP-1 = 4-Methylpentene-1 C2' = Ethylene C4 = n-Butane C4' = Butene-l C6l = Hexene-l C7 = n-Heptane Table 15 (Cont'd) C2'- Polymeri- Properties partial zation pressure tempera- Density [n]
ture S.G.B. Mw/Mn (kg/cm2) (C) (g/cm3) (dl/g) 5.0 ~0 o.899 2.6 3~ 5.9 140 0.899 2.6 27 3.5 2Q 140 0.902 2.6 24 3.7 9.0 50 0.914 2.4 22 6.o 5.5 50 o.go6 3.2 28 5.8 b~
~ Z~
18 50 0.923 2.6 9 5.5 ~1 12 50 0.919 2.4 16 5.8 0.928 2.4 8 5.4 9.0 50 0.914 2.2 22 5.7 l Example 25 Ethylene-~-olefin copolymers B were polymerized using the catalyst produced in Example l and organoalumi-num compounds (co-catalyst) and employing a~ole~ins and other polymerization conditions shown in Table 16. Their densitiesg intrinsic viscosities, S.C.B. and (weight average molecular weight/number average molecular weight) c7re ,~ W~4 shown in Table 16.
These copolymers are used in the following examples as mixing components.
Table 16 Polymeri- Polymeri- Catalyst H2 partial N zationzation quantity Co-catalyst Solvent a-olefinpressure me~hodvessel capa~ity (Q) (nlg~~mmol) (kg) (kg)(k~/cm ) B3-1 Slurry65 405TEA 50 C4 12.0 C4~ 2.0 10.8 B3-2 Solution 1 25.5 DEAC 2.5 C7 0.30 4-MP-1 0.025 2.4 B3-3 i 1 24.2 " C7 0.32 C6' 0.0132.4 B3-4 Slurry65 330TEA lG0 C4 15-2 C4' 0.7 7.5 B3-5 65 391 i' " C4~ 1.8 7,2 B3 6 ll 65 408 " C4 12.0 C4' 4-Q ~
B3-7 65 350 C4 15-2 C4 1.3 7.5 ~9 B3-8 " 65 45 TEA 50 " C4' 1.6 8.8 B3-9 '~ 65 390TEA 100 " C4' 0.2015.0 - Cont'd -Note TEA = triethyl aluminum DEAC = Diethyl aluminum chloride 4-MP-1 = 4-Methylpentene-1 C2' = Ethylene C4 = n-Butane C4' = Butene-l C6' = Hexene-l C7 = n-Heptane Table 16 (Cont~d) C2'- Polymeri- Properties partial zation pressure tempera- Density [n ~ s C.B. Mw/Mn ture (kg/cm2) (C~ (g/cm3) (dl/g) ~.3 70 o.942 o.83 15 ~.5 140 0.943 0.81 10 3.7 140 0.940 0.82 12 3.8 5.0 70 0.949 0.~5 11 5.3 0 8.0 70 0.941 0.~2 14 5.4 4.0 50 0.910 0.82 35 5.9 -~7 5.0 70 00942 0.75 16 5 P~
5.~ - 70 0.935 0.74 20 5.9 1.5 7~ 0.949 0.27 11 5.6 1 Example 26 A composition of ethylene-~-olefin copolymers was prepared from a two stage polymerization. The first stage polymeri~ation was carried out for 90 min. using the catalyst obtained in Example 1 and triethyl aluminum (co-catalyst) and employing other polymerization condi~
tions shown in Table 17.
Successively the second stage polymerization was condu~ted for 150 min. by changing only the hydrogen partial pressure and the ethylene partial pressure as shown in table 17. In both stages~ the liquid phase molar ratio of ethylene, butene-1 and hydrogen were kept at respective fixed levels. Polymerized quantities in each stage were calculated ~rom quantities of fed ethylene.
The total polymer consisted of about 50% by weight of lower molecular weight components. Immediately before the completion of the first stage polymerization, a part of the polymer formed was taken out as a polymer sample of the first stage and measured for its density, intrinsic viscosity~ S.C.B. and (weight average molecular weight/
number average molecular weight). Similar measurements were also made for the whole polymer of this two stage poly-merization. From the values o-~ the first stage polymer and the whole polymer, the intrinsic viscosity and S.C.B.
of the polymer formed in the second stage along were calculated, and they ~ shown in Table 17. The whol~
polymer gave: density 0.919 g/cm , melt index 0.5 g/10 min,, melt flow ratio 70, intrinsic visco$ity 1.70 dl/g~
- 97 ~
5 ~2 S.C.B. 27. The flow characteristics and the solid physical properties of the whole polymer are shown in Table 19.
Example 27 By mixing the ethylene-~-olefin copolymer A3-1 obtained in Example 24 and the ethylene ~-olefin copolymer B3-1 obtained in Example 25 at a 50/50 weight ratio and kneading the mixture in a Banbury mixer, a composition having the density, MI and MFR
as shown in Table 18 was prepared. The physical properties of this composition are also shown in Tahle 18.
For the purpose of comparison, in Table 18 are also shown Comparative examples 15 and 16 using high pressure poly-ethylenes of the conventional technique (commercial produc-ts Sumikathene ~ F208-1, F101-1 manufactured by Sumitomo Chemical Co., Ltd.) as well as Comparative example 17 using a low density ethylene-~ olefin copolymer of the conventional technique.
It is obvious from Table 18 that the copolymer composition of this invention has a ~rabender torque about equal to those of high pressure polyethylenes (good in processability) and is quite excellent in tensile impact strength, rigidity, ESCR and tensile strength, compared with these polyethylenes.
When compared with the low density ethylene-~-olefin copolymer of the conventional technique, this composi-tion has a much smaller Brabender torque 5~
1 (proGessability is much better), a superior tensile impact strength and tensile strength.
_ 99 _ T~ble 17 Polymeri- Polymeri- Catalyst H2 partial N zation zation quantity Co-catalyst Solvent ~-olefin pressure method ~essel TEA
capacity (Q) (mg~ (mmol) (g~ (g) (kg/cm2) ge Slurry 4 24.3 5 ~4 1000 C4' 250 stage Slurry 14 o - Cont~d -Note C4 = n-Butane TEA = Triethyl aluminum en C4 r = Butene-l ( ) = Calculated values C2' = ~thylene Table 17 (Cont'd) C2'- Polymeri- Polymer~- Properties partial zation zation pressure tempera- time Density [n ] _ _ ture S.C.B. Mw/Mn (kg/cm2) (C) (min) (g/cm3~ (dl/g) 3 90 0.900 2.6 37 5.8 5o 8 150 _ ~o.8) (17) -Il ~
C~
Table 18 Copolymer A Copolymer B Properties of composition Mixing - .
method Desig- % by Desig- % by Density MI Distribu-nation weight nation weight (g/cm ) (og/ i ) M~R of S.C B.*
Example 27 Banbury A3-1 50 B3-l 50 0.920 0.5 70 2.5 Comparative 0.923 l 4 50 Example 15 ompalatl~e _ _ _ _ _ 0.922 0.3 65 -Comparative Example 17 ~ ~ ~ ~ ~ 0~920 0.5 30 - G~
- Cont'd -* Distribution index (S.C.B. of copolymer A) of S.C.B. ~S.C.B. of copolymer B) j /
Table 18 ~Cont'd) Physical properties of composition Tensile impact Olsen's flexural ESCR Tensile Brabonder strengthmodulus F50 strength torque (kg-cm/cm2)(kg~cm2) (hr) (kg/cm2) (kg-m) 450 2600 >1000 320 2.0 130 2400 0.3 160 1.9 200 2200 30 180 2.2 I
~ 280 3200 >1000 260 3.5 ~
s~
1 Examples 28 to 31 ~.
Compositions having densities, MIs and MFRs shown in Table 19 were obtained, by blending ethylene-N -~
-olefin copolymers A obtained in Example 24 and ethylene~
~-olefin copolymers B obtained in Example 25 at mixing ratios as shown in Table 19. The physical properties of these compositions w~e shown in Table l9.
-~ In Table 19 ~e also shown a composition of similar ethylene-~-olefin copolymers synthesized in two l~ stage polymerization (Example 26) as well as, for com-parison5 ethylene-a-olefin copolymers compositions (Com-parative examples 18, 19, 20) of which higher molecular weight components have smaller S.C.B. than lower molecular weight components do or have relatively few S.C.B. Also as shown in Table 19 an ethylene-~-olefin copolymers com-position (Comparative example 21, to be compare~ with Examples 30 and 31) of which di~tribution index of S.C.~.
meets the scope of the presetn invention but of which lower molecular weight components have too low an intrinsic viscosity.
As is obvious from Table 19, in the compositions of this invention, higher molecular weight components have larger S~C.~. than lower molecular weight components do. (Comparison should be made between Examples 26, 28 and 29 and Comparative example 18, and also between Example 30 and 31 and Comparative examples l9 and 20.) The compositlons cf this invention are also far superior in tensile impact strength and tensile strength to the Comparative examples.
Table 19 Copolymer A Copolymer B Properties of composltion Mixin~
method Desig- % by Desig- % by Density MIDistri~u-nation weight nation weight (g/cm3) (g/ MFR tion index 10 min) of S.C.B.*
Example 26 - - - - - 0.919 0.5 70 (2.2) Example 28 Solution A3-2 50 B3-2 50 0.920 0.5 7 2.7 Example 29 " A3-3 5 B3-3 50 0.92Q 0.5 70 2.0 Example 30 Banbury A3-4 5 B3-4 50 0.929 0.8 50 2.0 Example 31 Solution A3-5 30 B3-5 7 0.929 0.8 50 2.0 Comparat ve Banbury A3-6 50 B3-~ 50 0.920 0.5 70 0.26 r~A
Comparative llA3-7 5 B3 7 50 Q.929 0.8 50 1.0 Comparative "A3-8 5Q B3-8 50 0.929 o.8 50 0.4 Example 20 Example 21 A3-9 65 B3-9 35 0.929 o.8 50 2.0 - Cont'd -*Distribution index = (S C B. of copolymer A~/(S.C-B- of copolymer B) Table 19 (Cont'd).
Tensile ~mpact Olsen's flexural ~ensile strength modulus strength Tackiness (kg~cm/cm2) ~kg/cm2) ~kg/cm2) 470 2500 320 o 550 2600 3~0 o 520 2600 320 o 300 ~000 300 o 280 400~ 290 o 150 3300 210 x o~ .~
C; 3 200 4200 240 o ~1 4500 200 o 120 4000 230 o 1 Example 32 The composition prepared in Fxample 27 and the low density ethylene-~ olefin copolymer of the convention-al technique used in Compara~ive example 17 were subjected to film processing under the f'ollowing conditions.
Processing conditions Extruder: Tanabe 30 mm~ extruder Screw: Full flight L/D Y 28, C.R. = 2.5 Die: Diameter 50 rnm, die gap 2.0 mm Temperature control: Cl 170g C~ 220, C3 220, Screw revolution: 35 rpm Output: 3.2 kg/hr Blow up ratio: 2.5 Frost line height: 180 mm Take-of'f speed: 5 m/min Film thickness: 35 ~
Also, the cornmercial high pressure polyethylenes used in Comparative examples 15 and 16 were subjected to film processlng under the following conditions.
Die gap: 1.0 mm ~emperature control: Cl 140, C2 160, C3 160, ~o~ f~o"s (Other c~nidtions were same as those applied above.) In the case of the low density ethylene-~-olefin copolyrne-r of the conventional technique used in Comparative example 17, a satisfactory film was not obtained with too much load put on the motor and with 1 shark skin formed on the film surface.
In the cases of the composition prepared in Example 27 and the commercial high pressure polyethylenes used in Comparative examples 15 and 16, satisfactory films were obtained with no excessive motor loads. The physical properties of these films were shown in Table 20. The film of the composition prepared in Example 27 is far superior to those of the high pressure poly-ethylenes, in dart impact strength, Elmendorf tear strengths (absolute value and MD/TD balance), tensile strengthg heat-sealing characteristics, hot tack property and heat sealing strength in contaminated condition.
In the film of the composition prepared in Example 27, heat-sealing strength and heat sealing strength in contaminated condition had about same values, while, in khe films of Comparative examples 15 and 16, heat sealing strength in contaminated condition were slightly lower than heat-sealing strength.
The measurement methods of the physical proper-ties shown in table 20 are described below.
Dart impact strengkh: In accordance with ASTM D 1709A.
Elmendorf tear strength: In accordance with JIS Z
1702.
Tensile strength: In accordance with JIS K 6732 62 Heat-sealing characteristics: Heat-sealing strength of a film heat-sealed with a heat sealer of bar type. The maximum heat-sealing strength was obtained when pulled under conditions S~2 l of film thi~kness of 35~, width of 15 mm and pulling speed of 200 rnm/min. after heat-sealing under sealing pressure of 1 kg/cm , 0.5 sec~ and each incremental 5C.
Hot tack property: A test sample (25 mm wide and 400 mm long) was folded into two~ and the one end was fixed to the upper clamp and a stripping weight was placed on the other end.
The area near the crease was inserted between heating bars and heat-sealed under a sealing pressure of l kg/cm2 for 0.5 sec., and then the length of the stripped surface was measured.
Heat Sealing strength in contaminated condition:
This is a test method for evaluating the heat-sealing characteristics in the condition that the heat-sealed surface is soiled with contents such as mayonaise, edible oils and flours.
Specifically, a test film sample was folded in such a way that the surface soiled with an edible oil came inside, and was heat-sealed under the same conditions as used in heat-sealing characteristics. Then, its heat~
sealing strength was measured.
Comparative E~ample 15 A comrnercial high pressure polyethylerle (Sumikathene ~ F208-l manufactured by Sumitomo Chemical Co., Ltd.) was su~jected to measurernents of physical 1 properties and film processing. Results ~e shown in Tables 18 and 20.
Comparative Example 16 A commercial high pressure polyethylene (Sumikathene ~ F 101-1 manufactured by Sumitomo Chemical Co., Ltd.) was subjected to measurements of physical c~e properties and film processing. Results ~ePe shown in Tables 18 and 20.
Comparative Example 17 A low density ethylene-~-olefin copolymer of the conventional technique was synthesized, using the catalyst produced in Example 1 and triethyl aluminum (co-catalyst) and employing the other polymerization conditions shown in Table 21. The copolymer gave:
5 dens~ty 0.920 g/cm3, MI 0.5 g/10 min., MFR 30. The C?~
physical properties of this polymer w~ shown in Table 18.
Comparative Examples 18, 19, 20 Compositions of ethylene-~-olefin copolymers of the conventional technique were prepared, by mixing ethylene-~-olefin copolymers A obtained in Example 24 and ethylene ~-olefin copolymers B obtained in Example 25 at ratios shown in Table 19. In these compositions~
molecular weight distributions are made wider and lower molecular weight components have larger S.C.B. and higher 1 molecular weight components have smaller S.C.B. Densi~
ties, MIs, MFRs and physical properties of these compo-CJ~
sitions ~e shown in Table 1~.
Comparative Example 21 By mixing an ethylene-~ olefin copolymer A
obtained in Example 24 and an ethylene-a olefin copolymer B obtained in Example 25 at a ratio as shown in Table 19, a composition of ethylene-~-olefin copolymers were pre-pared of which distribution index of S~C~B~g meets the scope of this invention but of which lower molecular weight weight components have a too low intrinsic viscosity.
Its density, MI, MFR and physical properties were shown in Table 19.
Table 20 I
Dart Elmenderf Tensile Heat- Hot tack Heat sealing impact tear strength sealing property strength in strength strength MDiTDstrength contaminated (kg-cm/mm) MD/TD (kg/15mm condition.
(kg/cm) (kg/cm2~width) (mrn) Example 27 700 120/150 45Q/410 1.5 1.0 o Comparative 270 80/50 250/210 0.7 4.0 a p Comparative 250 70/70 280/250 0.7 3.0 a I\) ~ff Table 21 Poly- Poly- Catalyst Co- Sol- a- H2 C2~ Polymeri- Polymeri-mer1- meri- quantity catalyst vent olefin partial partial zation zation zation zation TEA pressure pressure tempera- time method vessel ture capacity 2 2 (Q) (mg) (mmol) (kg) (kg) (kg/cm ) (kg~cm ) (C~ (min) Slurry 65 202 7~ C4~ 3 0 10 50 90 ~J ~
Note TEA = Triethyl aluminum C~
æ~
C4 = n-Butane p~
C4' - Butene-l C2' = Ethylene 1 Example 33 Ethylene-a-olefin copolymers A were synthesized using the catalyst produced in ~xample 1 and organo-aluminum compounds (co-catalyst) and employing ~-olefins and other polymerization conditions as shown in Table 22.
Densities~ intrinsic viscosities, S.C.B. and (weight average molecular weight/number average molecular weight) of these copolymers w~e shown in Table 22.
These copolymers are used in the following examples as mixing components.
Example 34 Ethylene-~ olefin copolymers B were synthesized using the cataly~t produced in Example 1 and organo-aluminum compounds (co-catalyst) and employing ~-olefins and other polymerization conditions as shown in Table 23. Densities, intrinsic viscosities, S.C.B. and (weight average molecular weight/number a~erage molecular weight) of these copolymers we~ shown in Table 23.
These copolymers are used in the following examples as mixing components.
Table 22 Polymeri- Polymeri- Catalyst H2 partial zationzation quantity Co-catalyst Solvent ~-olefin pressure No.method vessel capacity 2 (Q~ (mg) (m~ol) (kg) (kg) (kg/cm ) A4-1 Slurry65 310 TEA 100 C4 6.o C4 7 6.14 0.70 A4-2 Solution 1 24.3DEAC 2.5 C7 0.27 4-MP-1 0.090 0.15 A4-3 Slurry65 83 TEA 50 C4 6.o C4t 6.14 -9 A4-4 " 65 39 TEA 100 " " 1.2 A4-5 ll 65 145 TEA 50 " " 59 Q~
A4-6 Solution i 25.2DEAC 2.5 C7 0.30 C6' O.035 0.2 A4-7 Slurry65 33 TEA 100 C4 6.o c4 6.14 o.36 A4-8 " 65 125 " " " 1.8 A4-9 Solutlon 1 24.5DEAC 2.5 C7 0.40 4-MP-1 0.040 0.25 A4-10 Slurry65 121 TEA 100 C4 6.o C4' 3.7 1.2 A4-11 " 65 302 ~ " C4l 6.14 1.4 - Cont'd /
Table 22 (Cont'd) C2'- Polymeri- Properties partial zatlon pressure tempera- Den~ity [n] _ _ Note ture S.C.B. Mw/Mn (kg/cm2) (C) (g~cm3) (dl/g) TEA = Triethyl aluminum 7.8 50 0.912 2.6 24 5.6 DEAC = ~iethyl aluminum chloride 140 0.912 2.5 17 3.4 4-MP-1 = 4-Methylpentene-l 7.0 5Q 0.912 4.4 20 5.8 C4 = n-Butane 3.Q 50 0.9ll 2.2 25 5.7 C4' = Bu~ene-l 6.7 50 0.906 2.6 29 5,8 C6' = Hexene-l 140 o.gog 2.2 18 3.4 C7 = n-Heptane 9.0 50 0.917 3.3 16 5.6 18 50 0.923 2.6 9 5.5 140 0.923 2.5 8 3.3 0.925 3.3 6 5.5 8.5 ~0 0.913 2.1 23 5.4 Table 23 Polymeri- Folymeri- Catalyst H2 partial No zation zation quantity Co-catalyst Solvent ~-olefin pressure method vessel capacity ' 2 (Q) ~mg) (mmol) (kg) (kg)(kg/cm ) B4-1 Slurry 65 402 TEA50 C4 12. a C4l 3.2 7.8 B4-2 Solution1 24O2 DEAC 2.5 C7 0.804-MP-1 0.045 2.2 B4-3 Slurry b5 405 TEA 5 C4 12.0 C4' 3.2 7.0 B4-4 " 65 425 C4 15.2 c4 2,010.5 B4-5 65 411 " " c47 1.6 6.5 B4-6 Solution1 25.1 DEAC 2.5 C7 0.82 C6~ 0,017 2.7 B4-7 Slurry 65 346TEA 100 C4 15.2 C4 1.1 12 ~4-8 " 65 408 ll C~ 12.0 C4' 4 5.2 B4-9 Solution~ 24.9 DEAC 2.5 C7 0.284 MP-1 0.055 2.0 B4-10 Slurry 65 250TEA lOQ C4 15.2 C4 t o.413.5 B4-11 " 65 410TEA 50 c4l 1.4 12 ~4-12 " 65 290 " C4 6.0 C4 6.14 8.1 - Cont'd /
Table 23 (Cont'd) C2~- Polymeri- Properties partial zation pres~ure tempera- Density [~]
ture S.C.B. Mw/Mn (kg/cm2) (C) (g/cm3) (dl/g) Note 6 70 0.929 o .85 24 5.8 TEA = Triethyl aluminum 140 0.929 0.81 17 3.6 DEAC = Diethyl aluminum chloride 6 70 0.928 o . go 24 5.7 4-MP-1 = 4-Methylpenten-l 0.929 o .65 25 5.7 C4 = n-Butane 0.935 0.83 20 5-5 C4~ = Butene-l ~g 140 0 O 926 0.63 18 3.5 C6' = Hexene-l ~n 3 70 0.941 0.52 16 5.4 C7 = n-Heptane ~a 4 50 0.910 0.82 35 5 - 9 lo 140 0. g~ 2 o .85 22 3.7 1.5 50 0.930 0.28 2~ 5.7 3 70 o .g34 o.53 22 5.8 9 50 0.927 1.2 23 5.7 85~
1 Example 35 A composition of ekhylene-~-olefin copolymers was prepared in two stage polymerization. The first stage polymerization was carried out for 70 min. using the catalyst produced in Example 1 and triethyl alminum (co-catalyst) and other polymerization conditions as shown in Table 24. Successively~the second stage poly-<
merization was conducted for 180 min. by changing onlythe hydrogen partial pressure and the ethylene partial pressure as shown in Table 24. In both stages, the liquid phase molar ratio of ethylene, butene-l and hydrogen was kept at respective fixed levels. The polymerized quanti-ties in each stage were calculated from the quantities - of fed ethylene. The copolymers consisted of about 50%
by weight of higher molecular weight componenks and about 50% by weight of lower molecular weight components.
Immediately before the completion of the first stage polymerization, a part of the polymer was taken out and measured for its density, intrinsic viscosity, S.C.B.
and (weight average molecular weight/number average molecular weight). The whole polymer obtained after the second stage was also measured for the same test items.
From the values of the first stage polymer and the whole polymer~ the intrinsic viscosity and S.C.B. of the poly-mer formed in the second stage alone were calculatedThese values were shown in Table 24~ The whole polymer gave: density O.g21 g/cm3, MI 0.5 g/10 min., MFR 70, intrinsic viscosity 1.7 dl/g, S.C.B. 24. Flow \
l charac~eristics and solid physical properties of the whole polymer were shown in Table 26.
Example 36 By mixing the ethylene-~-olefin copolymer A4 l obtained in Example 33 and the ethylene-~-olefin copolymer B4-l obtained in Example 34 at a S0/50 weight ratio and kneading the mixture in a Banbury mixer, a composition of ethylene-~-olefin copolymers having the density, MI
and MFR shown in Table 25 was prepared. Physical pro-perties of this composition were also shown in Table 25.For comparison, in Table 25 were also shown Comparative examples 15 and 16 using high pressure polyethylenes of the conventional technique ~commercial product Sumikathene ~ F 208-1, F lOl-l manufactured by Sumitomo Chemical Co., Ltd.) as well as Comparative e~ample 17 using a low density ethylene-~-olefin copolymer of the conventional technique.
As is obvious from Table 25, the polymer com-position of' the present in~ention, when compared T~ith high preF,sure polyethylenes, has about an equal Brabender torque (satisfactory in processability)~ and is much superior in tensile impact strength, rigidity, ESCR and tensile strengthg and further is about equally satis-factory in transparency.
Compared with the low density ethylene-~-olefin copolymer of the conventional technique, this polymer composition has a much lower Brabender torque (far s~
l excellent in processability) and a higher tensile impact strength and tensile s~rength.
Examples 38, 39, 40, 41, 42, 43 By mixing the ethylene-a~olefin copolymers A
obtained in Example 33 and the ethylene-a-olefin copoly~
mers B obtained in Example 34 at -ratios as shown in Table 26, compositions having densities~ MIs and MFRs shown in Table 26 were obtained. Physical properties of e these compositions w~ also shown in Table 26.
In Table 26 ~e also shown a similar composi-.
tion prepared by two stage polymeri~ation (Example 35) and, for the purpose of comparison, compositions of low density ethylene-a-ole~in copolymers of the conventional technique (Comparative examples 22, 23, 25) of which molecular weight distributions are made wlder and of which lower molecular weight components have larger S.C.B.
and of which higher molecular weight components have smaller S.C.B. In Table 26 ~*~ also show~ a composition of ethylene-~-olefin copolymers (Comparative example 24, to be compared with Examples 40 and 42) of which distri-bution index of S.C.B. meets the scope of this invention but of which lower molecular weight components have a too low intrinsic viscosity.
As seen in Table 26, in the compositions of this invention, S.C.B. of higher molecular weight components are more than or about equal to those of lower molecular weight components. (Compare Examples 35, 38 and 41 with s~
1 Comparative examples 22 and 23, and Example 43 with Com-parative example 25.) Therefore, compared with the compositions of the conventional technique, the composi-tions of this invention are far excellent in tensile impact strength and tensile strengthg and are superior in transparency.
From the comparison between Comparative example 17 of Table 25 and Comparative example 22 of Table 26, it is learned that widening of molecular weight distri~
bution (higher MFR gives wider distribution) in the manufacture of a low density ethylene-~-olefin copolymer of the conventional technique with its density and M-~kept constant results in large reduction in tensile impact strength and tensile strength.
From the comparison of Examples 40 and L~2 with Comparative example 24, it is learned that a too low intrinsic viscosity of lower molecular weight components badly affects its tensile impact strength, tensile strength and transparency.
- 122 ~
Table 24 Polymeri- Polymeri- Catalyst Co~catalyst H2 partia N zation zation quantity TEA Solvent a-olefin pressure method vessel capacity (mg) (mmol) (g) (g~ (kg/cm2) 1st Slurry o.6 stage 24.3 5 C4 1000 C4' 250 stnage Slurry 10 ~1 - Cont'd -Note C4 = n-Butane TEA = Triethyl aluminum C4 t = Butene-l ( ) = Calculated values C2' - Ethylene Table 24 (Cont'd) C2'- Polymeri- Polymeri- Properties partial zatlon zation pressure tempera- time Density [n]
2 ture (min).~g/cm3) (dl/g) S-C-B~ Mw/Mn 4 700.912 2.6 24 5.7 180 - ~0.8~ (23) ~ e~
Table 25 Copolymer A Copolymer B Properties of composition Mixing method Desig- % by Desig- % by Density MI Distribu-nati.on weight nation weight ~g/cm3) (g/ MFR tion index 10 min.) of S.C.B.
Example 36Banbury A4-1 50 B4-1 50 0.920 0.5 70 1.0 Example 37 " B4-11 50 B4-12 50 0.921 0.7 40 1.0 Comparative Xi~h pressure Example 15 polyethylene (Sumikathene ~ F208-1) 9 3 1.4 ~0 Example 16 i~ (Sumikathene ~ F101-1) o.g22 0.3 65 ~
Comparative Low density ethylene/a-olefin Exan~ple 17 copolymer of the conventional 0.920 0.5 30 -technique - Cont'd -(S.C.B. of copolymer A) Distribution index o~ S.C.B. (S.C.B. of copolymer B) ~) Table 25 (Cont'd) Phisical properties of composition Tensile inpact Olsen's flexual ESCR Tensile Brabender strength modulus F~o strengkh Ha~e torque (kg-cm/cm2) (kg/cm2) (~r) (kg/cm') (%) (kg-m) 350 28~0 >1000 280 5 2.0 370 3000 >1000 290 5 2~6 130 2400 0.3 160 4 1.9 200 2200 30 180 6 2.2 ~g ~n 280 3200 >1000 260 5 3-5 ~
Table 26 Copolymer A Copolymer B Properties of composition Mixing method Desig- % by Desig- % by Dens~ty MIDistribu-nation we-'ght nation weight (g~cm3) ~g/ MFR tion index 10 min.) of S.C.B.*
Example 35 - Two ~tage polymerization - 0.921 0.570 (1.0) Example 38Solution A4-2 50 B4-2 500.920 o.6 70 1.0 Example 39 " A4-3 30 B4-3 70 0.921 0.390 o.8 Example 40Banbury A4-4 50 B4-4 50 0.920 1.165 1.0 Example 41tt A4-5 50 B4-5 50 0.920 0.5 7 1.5 Example 42Solution A4-6 50 B4-6 50Q.920 1.1 65 1.0 Example 43Banbury A4-7 50 B4-7 50 0.929 0.2lQ0 1.0 _.
Comparative " A4-8 50 B4-8 500.920 0.5 70 0.26 Compa ative Solution A4-9 50 B4_9 500.920 0.6 65 o.36 Example 24Banbury A4 4 65 B4-10 35 0.920 o.850 1.0 Comparative " A4-10 50 B4-11 500.930 0.2 100 0.27 Example 25 - Cont'd -Distribution index of 3.C.B. = (S.C.B. of copolymer A)/~S.C.B. of copolymer B) /
Table 26 (Cont'd) Physical properties of composition Tensile impact Olsen's flexural -Tensile strength modulus strength Haze Tackiness (kg-cm/cm2) (kg/cm2) (kg/cm2) (%) 340 28Qo 28Q ~ o 37~ 2800 300 7 o 2~0 2800 250 6 o 400 2700 300 ~ o ~ 36Q 2800 310 5 o 3~0 4200 . 300 8 o 150 3300 210 12 x 130 2800 220 15 o 170 4800 230 20 o sl~
1 Example 44 The compositions prepared in Examples 36 and 37 as well as the low density ethylene-~-olefin copolymer of the conventional technique used in Comparative example 17 were subjected to film processing in the same condi-tions as used in Example 32.
The comrnercial high pressure polyethylenes used in Comparative examples 15 and 16 were also subjected to film processing in the same conditions. A satisfactory film was not obtained from the low density ethylene-~-olefin copolymer of the conventional technique used in Comparative example 17, with too much load put on the motor and with shark skin formed on the film surface.
Satisfactory films having good transparency were obtained from the compositions prepared in Examples 36 and 37 and the commercial high pressure polyethylenes used in Comparative examples 15 and 16, with no problem of` motor load. Physical properties of these films ~ e shown in Table 27. Compared with the films of the high pressure method polyethylenes, the films of the composi-tions prepared in Examples 36 and 37 had about same trans _S-Gj~ O r parency but were l&rgcly _~^^l'_n' in dart impact strength, Elmendorf tear strength (absolute value property and MD/TD balance), heat-sealing properties, tensile strength, hot tack and heat sealing strength in contami-nated condition. In case of the films of the compositions prepared in Examples 36 and 37, heat~sealing strengths and heat sealing strength in contaminated condition were at _ 129 --l about same levels, but in the films of the high pressure polyethylenes of Comparative example 16, heat sealing strength in contaminated condition were lower than heat-sealing strengths.
Comparative Examples 22, 23, 25 By mixing ethylene-~-olefin copolymers A
obtained in Example 33 and ethylene-a-olefin copolymers B obtained in Example 34 at ratios as shown in Table 263 compositlons of low density ethylene-~-olefin copolymers of the conventional technique were prepared of which molecular weight distribution are made wider and of which lower molecular weight components have larger S.C.B. and of which higher molecular weight components have smaller S.C.B. Densities, MIs, MFRs and physical properties of .~ ~ 15 these compositions ~e*e shown in ~able 26.
Comparative Example 24 By mixing an ethylene ~ olefin copolymer A
obtained in Example 33 and an ethylene-~-olefin copolymer B obtained in Example 34 at a ratio shown in Table 26, a composition of ethylen-~-olefin copolymers was prepared of which distribution index Or S.C.B. meets the scope of this invention but of which lower molecular weight com~
ponents have a too low intrinsic viscosity. Its density, MI, MFR and physical properties w~ shown in Table 26.
Table 27 Haze Dart Elmendorf Tensile Heat- Hot tack Heat sealing impact tear strength sealing property strength in strength strength MD/TD strength contaminated (%) (kg-cm/mm) MD/TD (kg/15mm condition ~kg/cm) (kg/cm2) width) (mm) Example 36 5 5O 90~120 410/380 1.2 2.0 o Example 37 5 450 60/120 420/370 1.3 2.0 o Comparative 4 270 80/50 250/210 0.7 4.0 Example 15 Example 16 250 70/70 280/250 0.7 3.0 ~1 1 Example 45 Ethylene-a-olefin copolymers were synthesized using the catalyst produced in Example 1 and organo-aluminum compounds (co-catalyst) and employing ~-ole~ins and other pol.ymerization conditions as shown in Table 28.
Densities, intrinsic viscosities~ and S.C.B~ of these copolymers w~ shown in Table 28.
These copolymers are used in the ~ollowing examples as higher molecular weight components.
Example 46 Ethylene-a~ole~in copolymers were synthesized using the catalyst produced in Example 1 and organoalumi-num compounds (co-catalyst) and employing a-ole~ins and other polymerization conditions as shown in Table 29.
5 Densities~ intrinsic viscosities and S.C.B. of these c~e copolymers ~e~ shown in Table 29.
These copolymers are used in the following examples as lower molecular weight components.
Table 28 Polymeri- Polymeri- Catalyst H2 partial Nozation zation quantit~T Co-catalyst Solvent a-olefin pressure method vessel capacity (Q~ ~.g) (mmol) (kg) (kg) (kg) A-l Slurry 65 131 TEA 100 C4 6.o c4 6.14 0.45 A-2 " 65 145 TEA 5 A-3 65 310 TEA 100 " " 0.70 A-4 " 65 125 l " , 1.8 A-5SQlution 1 25.3 DEAC 2.5 G7 0.25 4-MP-l 0.11 0.1 A-6 " 1 24.5 " C7 0.30 4-MP-1 0.05 0.15 A-7 Slurry 65 121 TEA 5 C4 6.o c4l 6.14 0.98 A-8 .11 65 320 TEA 100 " " 3.0 - Cont'd -Note TEA = Triethyl aluminum C4 = n-Butane DEAC = Diethyl aluminum chloride C4' = Butene-1 4-MP-1 = 4-Methylpentene-1 C7 = n-Heptane Table 28 (Cont'd) C2'- Polymeri- Properties partial zation pressure tempera- Density ~rl~
ture S.C.B.
~kg/cm2) (C) (g/cm3) (dl/g) 5.0 50 0.899 2.6 38 6.7 50 0.906 2.6 29 7.8 50 0.912 2.6 24 18 50 0.923 2.6 ~ 20 140 94 2.5 23 140 0.920 2.5 lO
6.5 50 ~.907 2.2 30 5~ 0.928 2.2 8 Table 29 Polymeri- Polymeri- Catalyst H2 partial Nozation zation quantity Co-catalyæt Solvent a-ole~inpressure method vessel capacity (Q)(mg) (mmol) (kg~ (kg~ (kg~cm2) B-l Slurry 65405 TEA 50 C4 5~ c4~ 2.0 10.8 B-2 " 65411 " C4 15.2 C4' 1.6 6.5 B-3 " 65402 l~ C4 12.0 C4 3.2 7.8 B-4 65408 TEA 100 c4 400 5.2 B-5Solution 126.5 DEAC 2.5 C7 0.28 4-MP-1 0.03 3.0 B-6 ' 125.7 c7 0.25 4-MP-1 5 2.5 ~A
Ç~
B-7 Slurry 65407 TEA 100 C4 15.4 C4~ 0.5 13.0 ~1 B-8 " 65422 TEA 50 C4 15-2 C4' 1.8 11.0 - Cont'd -Note TEA = Triethyl aluminum C4 = n-Butane DEAC = Die~hyl aluminum chloride C4' = Butene-l 4-MP-1 = 4-Methylpentene-1 C7 = n-Heptane ) Table 29 ~Cont'd) c2~- Polymer~i- Properties partial zation pressure tempera- Density [n]
ture S.C.B.
(kg/cm23 (C) (g/cm3) ~dl/g) 8.3 70 0.912 '~3 15 7 0.935 0.83 20 6 70 0.929 0.85 24 4 50 0.910 0.82 35 140 o.938 5 13 140 0.912 0.52 22 ~8 7 953 0.62 9 0~934 0.61 22 ~J
l Example 47 A composition of ethylene-a-olefin copolymers was prepared in two stage polymerization. The first stage polymerization was carried out for 70 min. using the cataly~t produced in Example 1 and triethyl aluminum (co-catalyst) and other polymerization condit-ions as shown in Table 30. Successively, the second stage poly-merization was conducted for 180 min. by changing only the hydrogen partial pressure and the ethylene partial pressure as shown in Table 30. In both stages, the liquid phase molar ratio of ethylene, butene-l and hydrogen was kept constant at respective fixed levels~
The polymerized quantities in each stage were calculated from the quantities of fed ethylene. The copolymer com-position consisted of about 50% by weight of highermolecular weight components and about 50% by welght of lower molecular weight components. Immediately before the completion of the first stage polymerization, a part of the polymer was taken out and measured for its density, intrinsic viscosity and S.C.B. The whole polymer obtained after the second stage was also measured ~or the same test items. From the values of the first stage polymer and the whole polymer, the intrinsic viscosity and the number of branched short chains of the polymer formed in the second stage alone were calcula~ed. These values were shown in Table 30. The whole polymer gave: density 0.921 g/cm3, MI 0.5 g/10 min., MFR 70, intrinsic viscosity 1.7 dl/g, S.C.B. 24, gn 93 The whoel polymer was subjected 5~
1 to gel permeation chromatography an~ a curve of molecular weight distribution shown in ~ig. 4 was obtained.
Because of bimodal distribution which has two peaks 3 the curve was divided into two parts usin~ broken lines. The areas of each part were calculated, and the lower molecular weight components and the higher molecular weight components were determined to be 48 and 52% by weight 7 respectively.
The whole polymer was divided into 30 fractions using column chromatography. These fractîons were divid~
ed into two parts (the lower molecular weight components and the higher molecular weight components) so that the former became 48% by weight and the latter 52% by weight.
S.C.B., densities and intrinsic viscosities of each com-ponent w~ shown in Table 32.
Flow characteristics and solid physical proper-~ eties of the whole polymer ~r~ shown in ~able 33.
In the following examples~ ethylene-~-olefin copolymers as higher molecular weight components and ethylene-a-olefin copolymers as lower molecular weight components were mixed at respective fixed ratios (total quantity 1 kg) and kneaded for 5 min. with a Ba~bury mixer (150 ko 230 rpm). At that time, replacement by nitrogen was conducted completely and the polymer temperatures were controlled not to exceed 250C.
When sample quantities were small, mixing was made in xylene. After mixing, the whole solution was added into methanol to cause precipitation. After 5`~ `
filtration, the precipitate was completely dried in a vacuum drier and used as a copolymers composition sample.
Examples 48, 49, 50 Ethylene-~-olefin copolymers obtained in Example 45 and ethylene-a~olefin copolymers obtained in Example 46 were kneaded with a sanbury mixer at ratios as shown in Table 31.
Tllus, compositions of copolymers having densities, ~Is, MFRs, intrinsic viscosities, S.C.B. and g* shown in Table 32 were obtained. These compositions had molecular weight distribution curves about equal to Figure 4. With the same technique as used in Example 47, quantities of lower molecular weight components and higher molecular weiyht components were calculated, and they were both approximately 50% by weight as shown in Table 32~ Physical proper-ties of these compositions are shown in Table 33 With the same technique as used in Example 47, column fractlonation was applied in order to divide into higher molecular weight components and lower molecular weigh-t components.
Characteristics of the components are shown in Table 32.
In Tables 32 and 33 are also shown Example 47 using a composition of ethylene-~-oleEin copolymers prepared in two stage polymerization and, for comparison, Comparative example 26 using a high pressure method polyethylene of the conventional technique (commercial product Sumikathene ~ F 101-1 manufactured by Sumitomo
- 13~ -1 Chemical Co., Ltd.), Comparative example 27 using a com-position of low density ethylene-~-olefin copolymers of the conventional technique and Comparative example 28 using a composition of low density ethylene~~-olefin copolymers of the conventional technique of which moelcular ~ei~h~ d~stribukion is made wider and of which lower molecular weight components have larger S.C.B. and of which higher molecular weight components have smaller S.C.B.
As is obvious from Tables 32 and 33, when com-pared with the high pressure polyethylene, the copolymer compositions of this invention have about equivalent Brabender torques (excellent in processabi]ity), and are largely excellent in tensile impact strength, rigidity, ESCR and tensile strength. Transparency is equally good, because distribution index of S.C.B. is in a certain range as defined by the present invention. When compared with the composition of low density ethylene-~-olefin copoly-mers of the conventional technique, the compositions of this invention have far smaller Brabender torques (much better processability) and higher tensile impact strengths and tensile strengths.
~ 'rom comparison between Comparative examples 27 and 28 in Tables 32 and 33, it is learned that widening of molecular weight distribution (larger MFR gives wider distribution) in the manufacture of a low density ethylene-~-olefin copolymer of the conventional technique with density and MI fixed results in large reduction in tensile impact strength and tensile strength.
Table 30 Polymeri- Polymer- Catalyst Co-catalyst H2 partial No. zation zation quantity TEA Solvent ~-olefinpressure method vessel capacity 2 (Q) (mg) (mmol~ (g) (g~ (kg/cm ) ls~ Slurry 0.6 24O3 5 C4 10~0 C4' 250 stage Slurry 10 ~
- Cont'd -Note C4 = n-Butane TEA = Triethyl aluminum C4' = Butene-l ( ) = Calculated values C2' = Ethylene Table 30 (Cont'd) C2'- Polymeri- Polymeri-Properties partial zation zation pressure tempera- timeDensity [~ S.C.B.
ture tkg/cm2) (C) (min)(g/cm3) (dl/g) 4 7Q 0.912 2.6 24 180 _ (o~8) (23) Table 31 Higher molecular weight Lower molecular weight component component Designation ~ by weight Designation ~ by weight Example 48 A-l 50 B-l 5 Fxample 49 A-2 50 B-2 50 Example 5Q A-3 5Q B-3 50 Comparative Example 28 A-4 50 B-4 50 ~
.
~r, Table 32 Propert1es of copolymer Density MI MFR [n] S~C~Bo gn (g/cm3) ~g/10 min.) (dl/g) Example 47 0.921 0.5 70 1.7 24 o.g6 Example 48 0.920 0~5 7 1.7 26 -97 Example 49 0.920 0.5 70 1.7 25 0.93 Example 50 0.920 0.5 70 1.7 24 0.97 Comparative Example 26 0.922 0-3 65 1.06 23 o.48 Comparative Example 27 0.920 0.5 30 1.7 23 0.95 Comparative Example 28 0.920 0.5 70 1.7 22 o.g5 - Cont'd -Degree of S.C.B. of hig~er Distribution index molecular weight component of S~C~B~ Degree of S.C.B~ of lower molecular weight component Table 32 (Cont'd) GPC
Length of main peak chain ~A~ Ratio (% by weight) Lower Higher Lower Hlgher molecular molecular molecular molecu].ar weight weight weight weight component component component component 1.7 x 103 3O~ x 103 48 52 1.7 x 103 3.4 x 103 48 52 1.6 x 103 3.5 x 103 47 53 1.9 x 103 3.4 x 103 48 ~2 .05 x 103 6.5 x 103 36 64 ~n 2. 8 x 103 5 5 .6 x 103 1 3.6 x 1o3 49 51 - Contld -Table 32 (Cont'd) Characterist1cs of components frac~ionated by column fractionation Lower molecular weight Higher molecular component weight component S.C.B Density [~] S.C.B Density rn] Distribution (g/cm3) (dl/g) (g/cm3)(dl/g) index of 0.920 o.8 18 0.915 2.6 0.6 27 0.924 o.8 25 0.910 2.6 0.9 28 0.923 0.7 20 0.91~ 2.5 0.7 0.920 o.8 18 0.~15 2.5 o.6 27 0 . 916 o . 6 19 0.926 1.4 0.7 38 o.go6 1.1 8 - 0.925 2.4 0.2 37 ~.907 o.8 7 0.926 2.6 0.2 Table 33 Physical properties of copolymer Tensile Olsen's Tensile ESCR
impact Flexural strength Haze Torque F50 Tackiness strength modulus (kg-cm/cm2) (kg/cm2) (kg/cm23 (~) (kg-m) ~hr) Example 47 340 2800 280 5 2.0>1000 o Example 48 450 2600 320 20 2.0>1000 0 Example 49 400 2700 300 ~ 2~0>1000 o Example 50 350 2800 280 5 2.0>1000 o Comparative 200 2200 180 6 2.230 o Example 26 Comparative 280 320Q 260 8 3.5>1000 ~ _ Comparative 150 3300 210 12 Z.O>1000 x Example 28 Examples 51, 52 Compositions of ethylene-~-olefin copolymers were prepared by mixlng ethylene-~olefin copolymers obtained in Example 45 and ethylene-~-olefin copolymers obtained in Example 46 at ratios shown in Tab].e 34. Densities, MIs, MFRs, ~], S.C.B. and g* of these compositions are shown in Table 35. Their physical properties are shown in Table 36.
Molecular weight distributions of Examples 51 and 52 showed "one al-most symmetrical mountain'l curves. The curve in Fig. 5 is that of Example 52.
Column fractionation was applied with the same technique as used in Example 47.
Its results are shown in Table 35.
In Tables 35 and 36 are also shown low density ethylene-~-olefin copolymers of the conventional technique (Comparative examples 29 and 30) of which molecular weight distributions are made wider and of which lower mole-cular weight components have larger S.C.~. and of which higher molecular weight components have smaller S.C.B.
Curves of molecular weight distributions of Comparative examples 29 and 30 were similar to those of Examples 51 and 52. As seen from Tables 35 and 36, in the compositions of this invention, S.C.B. of higher molecular weight components and those of lower molecular weight components are nearly equal (com-pare Example 51 with Comparative example 29, and also Example 52 with Compara-tive example 30), therefore, the compositions .
1 of the present invention are far superior to the copolymers of the conventional technique in tensile impact strength and tensile strength.
Comparative Example 26 A commercial high pressure polyethylene (Sumikathene ~ F 101-1 manufactured by Sumitomo Chemical Co., Ltd.) was subjected to measurements of physical properties and. Results we~e shown in Table 33.
This polyethylene has 10W g* of o.48 and it suggests that this sample has many long chain branches.
Its molecular weight distribution curve was sbown in Fig. 6. Column fractionation was applied with the same technique as used in Example 47. The fractions obtained were divided into two groups so that khe lower molecular weight component group and the higher molecular weight component group became about 36 and 64% by weight, res-pectively. Densities, S.C.B. and intrinsic viscosity of each group were measured and results we~e shown in Table 32.
Comparative Example 27 A low density ethylene-~-olefin copolymer of the conventional technique was synthesized using the catalyst produced in Example 1~ triethyl aluminum (co-catalyst) and other polymerization conditions as shown in Table 37. The copolymer gave: density 0.920 g/cm3 MI 0.5 g/10 min., MFR 30~ intrinslc viscosity 1.7 dl/g~
Z
S.C.B. 23, g* 0.95. Its physical properties are shown in Table 33. Its mole-cular weight distribution showed "one a:Lmost symmetrical mo~tntain" curve, as seen in Fig. 1. From the area ratio, the lower molecular weight components and the higher molecular weight components were determined to be both 50% by weight.
Column fractionation was applied with the same technique as used in Example 47 and results are shown in Table 32.
Comparative Example 28 By mixing the ethylene-~-olefin copolymer ~-~ obtained in Fxample ~5 and the ethylene-~-olefin copolymer B-4 obtained in Example 46 at the ratio as given in Table 31, a composition of low density ethylene-~-olefin copolymers of the conventional technique was prepared of which molecular weight distribution i5 made wider and oE which lower molecular weight components have larger S.C.B.
and of which higher molecular weight components have smaller S.C.~. Its den-sity, MI, MFR, [n], and g* are shown in Table 32. The molecular weight distri-bution curve of this composition was almost equal to that in Fig. 4. With the same technique as used in Example 47, the ratio of the lower and higher mole-cular weight components was determined. Column fractionation was also con-ducted. These results are shown in Table 32. Physical properties of this com-position are shown in Table 33.
1 Comparative Examples 29, 30 By mixing ethylene-a-olefin copolymers obtained in Example 45 and ethylene~-olefin copolymers obtained in Rxample 46 a~, ratios as shown in Table 34, compositions of low density ethylene-~-olefin copolymers of the con-ventional technique were prepared of which molecular weigh weight distributions are made wider and of which lower molecular weight components have larger S~C~Bo and of which higher molecular weight components have smaller S.C.~. Densities, MIs, MFRs, [n], S.C.B. and g* of these compositions were shown in Table 35. Physical properties of the~e compositions were shown in Table 36.
Table 34 Higher molecular weight Lower molecular weight component component Designation % by weight Designation % by weight Example 51 A-5 60 B 5 40 Example 52 A-7 50 B-7 50 Comparati.ve Example 29 A-6 60 B-6 40 Comparative Example 30 A-8 50 B-8 50 ~n Table 35 Properties of copolymer Density MI MFR ~] S~C.B. gn (g/cm3) (g~10 min) (dl/g) Example 51 0.920 0.5 70 1.7 19 0.91 Example 52 0.929 1.2 70 1.4 20 -95 Comparative Example 29 0.919 0.5 70 1.7 17 .96 Comparative Example 30 0.929 1.2 70 1.4 17 0.93 ~ 7 - Cont'd -Degree of S.C.B. of higher Distribution index _ molecular weight component of S.C.B. Degree of S.C.B. of lower molecular we~ght component Tahle 35 (Cont'd) GPC
o Length of main peak chain (A? Ratio (% by weight) Lower Higher Lower Higher molecular molecular molecular molecular weight weightweight weight component component component component Uniform d strLbuti3on (peak) 57 43 Uniform distribution (peak? 48 52 1.6 x 103 ~nUniform d stribution (peak) 58 42 Uniform distribution (peak~ 48 52 1.6 x 103 - Cont'd -/
Table 35 (Conttd) Characteristics of components fractionated by column fractionation Lower molecular weight Higher molecular component weight component Distribution S.C B Density [~]S.c g, Density [~] index o~
(g/cm3) (dl/g)(g/cm ) (dl/g) S.C,B.*
22 0 933 0 5 15 0.920 2.4 0.7 0.935 o.6 20 0.915 2.2 1.0 ~n 24 0.930 0.5 ~ 0.927 2.4 0.3 2~ 0.922 o.6 6 0.930 2.1 0.2 P~
Table 36 Physical properties Gf copolymer Tensile Olsen's Tensile impact Flexural strength ~acki-strength modulus ness (kg-cm/cm2) (kg/cm2) (kg/cm2) :
Example 51 480 2600 320 o Example 52 250 37 250 o I Comparative Example 29 200 3100 200 x O~ Comparative Fxample 30 70 4500 200 G
G~
r~
a~
Table 37 Poly- Poly- Catalyst Co- Sol- ~~ H2 C21 Polymeri- Polymeri-meri- meri- quantity catalyst vent olefin partial partial zation zation zation zation TEA pressure pressure tempera- time method vessel ture capacity (Q) (mg) (mmol) (kg) (kg) (kg/cm2) (kg~cm2) ~C) (min) Slurry 65 202 7.0 7.16 3 10 50 90 Note TEA = Triethyl aluminum C4 = n-Butane ~1 C2' = Ethylene C4' = Butene-l 1 Reference Example 1 An ethylene-~-olefin copolymer was synthesized from ethylene and butene-l, using the catalyst produced in Example 1, die~hyl alminum monochloride (co-catal~st) and other polymerization conditions as shown in Table 38.
Properties of this copolymer we~ shown in Table 39.
3y applying column fractionation~ the copolymer was fractionated into fractions of different molecular weights. Then, distribution of S.C.B. against molecular weight was examined as shown in Fig. 7.
In column fractionation, about 5 g of the sample was placed in a fractionation column after being adsorbed on a carrier (Celite 745) in xylene. Then, the column was heated to 130C, and butyl cellosolve and xylene were passed through the column with the mixing ratio being gradually changed in order to obtain a gradual increase in solvencyO Thus, all the copolymer fractions of lower to higher molecular weight were separated. To the eluates was added methanol to cause precipitation of the copolymers. After recovery, the polymers were dried under reduced pressure and each copolymer fraction was obtained. In the above column fractionation process, in order to prevent the possible decomposition of the copolymers, 100 ppm of Irganox ~ 1076 was added to the original sample and further air inside the column was replaced by nitrogen. Using each copolymer fraction, pressed sheets having about 100 to 300~ thickness were prepared, and S.C.B. of each copolymer fraction were s~
1 calculated by conducting Fourier-transform infrared absorption spectroscopy. Molecular welghts of each copolymer fraction were calculated, using intrinsic viscosities [ n] measured in tetralin of 135C and the following formula.
[ ] 5 1 10-4 M- 0 725 Reference Example 2 With ethylene-~-olefin copolymers of the con-ventional technique~ a relationship between melt index (MI) and tensile impact strength was examined with melt flow ratio (MFR) used as a parameter. Results were shown in Fig. 8. It is revealed that widening of molecular weight distribution results in remarkable reduction in tensile impact strength. (In the figure~ molecular weight distribu~ion was represented by MFR. Larger MFR means wider molecular weight distribution.)O These ethylene-~-ole~in copolymers were subjected to molecular weight fra~tionation with the same technique as used in Reference Example 1. All the copolymers showed trends similar to that of Reference Example 1. The fractions were divided into two groups (lower molecular weight group and higher molecular weight group) in such a way that each group became about 50% by weight~ and (S.C.B.
of higher molecular weight component/~.C.~.,of ~ower f~C~/~f~ G'~
I 25 molecular weight component) was olaou'atcd. It was below 0.5 in all the copolymers.
s~
1 Reference Example 3 With a high pressure method polyethylene of the conventional technique and a linear, high density poly-ethylene of medium to low pressure method, correlations between melt index (MI) and intrinsic viscosity [n] were examined and~shown in Fig. 9. The correlation lines of each sample are clearly divided by a partition line (broken line). It is learned that the high pressure polyethylene has much lower inkrinsic viscosity than that of the linear high density polyethylene of the same melt indexO
A correlation between melt index and intrinsic viscosity was examined with the ethylene-~-olefin copolymers of the present invention. All of the copoly-mers of the present invention fell in the zone of thelinear, high density polyethylene.
Table 38 Polymeri- Polymeri- Catalyst H2 C2' Polymeri- Polymeri-zation zation quantity Solvent a-olefin parkial partial zation zation method vessel pressure pressure kempera- time capacity ture (~) (mg) (g) (g)~kg/cm2) (kg/cm2) (C) (min) Solution 1 25.1 C7 300C4 40 3-5 20 140 90 i--~1 ~3 Table 39 Propert ies Densiby (g/10 min) MFR S . C .B .
0 . 924 4 25 20 G~
As is obvious from Tables 32 and 33, when com-pared with the high pressure polyethylene, the copolymer compositions of this invention have about equivalent Brabender torques (excellent in processabi]ity), and are largely excellent in tensile impact strength, rigidity, ESCR and tensile strength. Transparency is equally good, because distribution index of S.C.B. is in a certain range as defined by the present invention. When compared with the composition of low density ethylene-~-olefin copoly-mers of the conventional technique, the compositions of this invention have far smaller Brabender torques (much better processability) and higher tensile impact strengths and tensile strengths.
~ 'rom comparison between Comparative examples 27 and 28 in Tables 32 and 33, it is learned that widening of molecular weight distribution (larger MFR gives wider distribution) in the manufacture of a low density ethylene-~-olefin copolymer of the conventional technique with density and MI fixed results in large reduction in tensile impact strength and tensile strength.
Table 30 Polymeri- Polymer- Catalyst Co-catalyst H2 partial No. zation zation quantity TEA Solvent ~-olefinpressure method vessel capacity 2 (Q) (mg) (mmol~ (g) (g~ (kg/cm ) ls~ Slurry 0.6 24O3 5 C4 10~0 C4' 250 stage Slurry 10 ~
- Cont'd -Note C4 = n-Butane TEA = Triethyl aluminum C4' = Butene-l ( ) = Calculated values C2' = Ethylene Table 30 (Cont'd) C2'- Polymeri- Polymeri-Properties partial zation zation pressure tempera- timeDensity [~ S.C.B.
ture tkg/cm2) (C) (min)(g/cm3) (dl/g) 4 7Q 0.912 2.6 24 180 _ (o~8) (23) Table 31 Higher molecular weight Lower molecular weight component component Designation ~ by weight Designation ~ by weight Example 48 A-l 50 B-l 5 Fxample 49 A-2 50 B-2 50 Example 5Q A-3 5Q B-3 50 Comparative Example 28 A-4 50 B-4 50 ~
.
~r, Table 32 Propert1es of copolymer Density MI MFR [n] S~C~Bo gn (g/cm3) ~g/10 min.) (dl/g) Example 47 0.921 0.5 70 1.7 24 o.g6 Example 48 0.920 0~5 7 1.7 26 -97 Example 49 0.920 0.5 70 1.7 25 0.93 Example 50 0.920 0.5 70 1.7 24 0.97 Comparative Example 26 0.922 0-3 65 1.06 23 o.48 Comparative Example 27 0.920 0.5 30 1.7 23 0.95 Comparative Example 28 0.920 0.5 70 1.7 22 o.g5 - Cont'd -Degree of S.C.B. of hig~er Distribution index molecular weight component of S~C~B~ Degree of S.C.B~ of lower molecular weight component Table 32 (Cont'd) GPC
Length of main peak chain ~A~ Ratio (% by weight) Lower Higher Lower Hlgher molecular molecular molecular molecu].ar weight weight weight weight component component component component 1.7 x 103 3O~ x 103 48 52 1.7 x 103 3.4 x 103 48 52 1.6 x 103 3.5 x 103 47 53 1.9 x 103 3.4 x 103 48 ~2 .05 x 103 6.5 x 103 36 64 ~n 2. 8 x 103 5 5 .6 x 103 1 3.6 x 1o3 49 51 - Contld -Table 32 (Cont'd) Characterist1cs of components frac~ionated by column fractionation Lower molecular weight Higher molecular component weight component S.C.B Density [~] S.C.B Density rn] Distribution (g/cm3) (dl/g) (g/cm3)(dl/g) index of 0.920 o.8 18 0.915 2.6 0.6 27 0.924 o.8 25 0.910 2.6 0.9 28 0.923 0.7 20 0.91~ 2.5 0.7 0.920 o.8 18 0.~15 2.5 o.6 27 0 . 916 o . 6 19 0.926 1.4 0.7 38 o.go6 1.1 8 - 0.925 2.4 0.2 37 ~.907 o.8 7 0.926 2.6 0.2 Table 33 Physical properties of copolymer Tensile Olsen's Tensile ESCR
impact Flexural strength Haze Torque F50 Tackiness strength modulus (kg-cm/cm2) (kg/cm2) (kg/cm23 (~) (kg-m) ~hr) Example 47 340 2800 280 5 2.0>1000 o Example 48 450 2600 320 20 2.0>1000 0 Example 49 400 2700 300 ~ 2~0>1000 o Example 50 350 2800 280 5 2.0>1000 o Comparative 200 2200 180 6 2.230 o Example 26 Comparative 280 320Q 260 8 3.5>1000 ~ _ Comparative 150 3300 210 12 Z.O>1000 x Example 28 Examples 51, 52 Compositions of ethylene-~-olefin copolymers were prepared by mixlng ethylene-~olefin copolymers obtained in Example 45 and ethylene-~-olefin copolymers obtained in Example 46 at ratios shown in Tab].e 34. Densities, MIs, MFRs, ~], S.C.B. and g* of these compositions are shown in Table 35. Their physical properties are shown in Table 36.
Molecular weight distributions of Examples 51 and 52 showed "one al-most symmetrical mountain'l curves. The curve in Fig. 5 is that of Example 52.
Column fractionation was applied with the same technique as used in Example 47.
Its results are shown in Table 35.
In Tables 35 and 36 are also shown low density ethylene-~-olefin copolymers of the conventional technique (Comparative examples 29 and 30) of which molecular weight distributions are made wider and of which lower mole-cular weight components have larger S.C.~. and of which higher molecular weight components have smaller S.C.B.
Curves of molecular weight distributions of Comparative examples 29 and 30 were similar to those of Examples 51 and 52. As seen from Tables 35 and 36, in the compositions of this invention, S.C.B. of higher molecular weight components and those of lower molecular weight components are nearly equal (com-pare Example 51 with Comparative example 29, and also Example 52 with Compara-tive example 30), therefore, the compositions .
1 of the present invention are far superior to the copolymers of the conventional technique in tensile impact strength and tensile strength.
Comparative Example 26 A commercial high pressure polyethylene (Sumikathene ~ F 101-1 manufactured by Sumitomo Chemical Co., Ltd.) was subjected to measurements of physical properties and. Results we~e shown in Table 33.
This polyethylene has 10W g* of o.48 and it suggests that this sample has many long chain branches.
Its molecular weight distribution curve was sbown in Fig. 6. Column fractionation was applied with the same technique as used in Example 47. The fractions obtained were divided into two groups so that khe lower molecular weight component group and the higher molecular weight component group became about 36 and 64% by weight, res-pectively. Densities, S.C.B. and intrinsic viscosity of each group were measured and results we~e shown in Table 32.
Comparative Example 27 A low density ethylene-~-olefin copolymer of the conventional technique was synthesized using the catalyst produced in Example 1~ triethyl aluminum (co-catalyst) and other polymerization conditions as shown in Table 37. The copolymer gave: density 0.920 g/cm3 MI 0.5 g/10 min., MFR 30~ intrinslc viscosity 1.7 dl/g~
Z
S.C.B. 23, g* 0.95. Its physical properties are shown in Table 33. Its mole-cular weight distribution showed "one a:Lmost symmetrical mo~tntain" curve, as seen in Fig. 1. From the area ratio, the lower molecular weight components and the higher molecular weight components were determined to be both 50% by weight.
Column fractionation was applied with the same technique as used in Example 47 and results are shown in Table 32.
Comparative Example 28 By mixing the ethylene-~-olefin copolymer ~-~ obtained in Fxample ~5 and the ethylene-~-olefin copolymer B-4 obtained in Example 46 at the ratio as given in Table 31, a composition of low density ethylene-~-olefin copolymers of the conventional technique was prepared of which molecular weight distribution i5 made wider and oE which lower molecular weight components have larger S.C.B.
and of which higher molecular weight components have smaller S.C.~. Its den-sity, MI, MFR, [n], and g* are shown in Table 32. The molecular weight distri-bution curve of this composition was almost equal to that in Fig. 4. With the same technique as used in Example 47, the ratio of the lower and higher mole-cular weight components was determined. Column fractionation was also con-ducted. These results are shown in Table 32. Physical properties of this com-position are shown in Table 33.
1 Comparative Examples 29, 30 By mixing ethylene-a-olefin copolymers obtained in Example 45 and ethylene~-olefin copolymers obtained in Rxample 46 a~, ratios as shown in Table 34, compositions of low density ethylene-~-olefin copolymers of the con-ventional technique were prepared of which molecular weigh weight distributions are made wider and of which lower molecular weight components have larger S~C~Bo and of which higher molecular weight components have smaller S.C.~. Densities, MIs, MFRs, [n], S.C.B. and g* of these compositions were shown in Table 35. Physical properties of the~e compositions were shown in Table 36.
Table 34 Higher molecular weight Lower molecular weight component component Designation % by weight Designation % by weight Example 51 A-5 60 B 5 40 Example 52 A-7 50 B-7 50 Comparati.ve Example 29 A-6 60 B-6 40 Comparative Example 30 A-8 50 B-8 50 ~n Table 35 Properties of copolymer Density MI MFR ~] S~C.B. gn (g/cm3) (g~10 min) (dl/g) Example 51 0.920 0.5 70 1.7 19 0.91 Example 52 0.929 1.2 70 1.4 20 -95 Comparative Example 29 0.919 0.5 70 1.7 17 .96 Comparative Example 30 0.929 1.2 70 1.4 17 0.93 ~ 7 - Cont'd -Degree of S.C.B. of higher Distribution index _ molecular weight component of S.C.B. Degree of S.C.B. of lower molecular we~ght component Tahle 35 (Cont'd) GPC
o Length of main peak chain (A? Ratio (% by weight) Lower Higher Lower Higher molecular molecular molecular molecular weight weightweight weight component component component component Uniform d strLbuti3on (peak) 57 43 Uniform distribution (peak? 48 52 1.6 x 103 ~nUniform d stribution (peak) 58 42 Uniform distribution (peak~ 48 52 1.6 x 103 - Cont'd -/
Table 35 (Conttd) Characteristics of components fractionated by column fractionation Lower molecular weight Higher molecular component weight component Distribution S.C B Density [~]S.c g, Density [~] index o~
(g/cm3) (dl/g)(g/cm ) (dl/g) S.C,B.*
22 0 933 0 5 15 0.920 2.4 0.7 0.935 o.6 20 0.915 2.2 1.0 ~n 24 0.930 0.5 ~ 0.927 2.4 0.3 2~ 0.922 o.6 6 0.930 2.1 0.2 P~
Table 36 Physical properties Gf copolymer Tensile Olsen's Tensile impact Flexural strength ~acki-strength modulus ness (kg-cm/cm2) (kg/cm2) (kg/cm2) :
Example 51 480 2600 320 o Example 52 250 37 250 o I Comparative Example 29 200 3100 200 x O~ Comparative Fxample 30 70 4500 200 G
G~
r~
a~
Table 37 Poly- Poly- Catalyst Co- Sol- ~~ H2 C21 Polymeri- Polymeri-meri- meri- quantity catalyst vent olefin partial partial zation zation zation zation TEA pressure pressure tempera- time method vessel ture capacity (Q) (mg) (mmol) (kg) (kg) (kg/cm2) (kg~cm2) ~C) (min) Slurry 65 202 7.0 7.16 3 10 50 90 Note TEA = Triethyl aluminum C4 = n-Butane ~1 C2' = Ethylene C4' = Butene-l 1 Reference Example 1 An ethylene-~-olefin copolymer was synthesized from ethylene and butene-l, using the catalyst produced in Example 1, die~hyl alminum monochloride (co-catal~st) and other polymerization conditions as shown in Table 38.
Properties of this copolymer we~ shown in Table 39.
3y applying column fractionation~ the copolymer was fractionated into fractions of different molecular weights. Then, distribution of S.C.B. against molecular weight was examined as shown in Fig. 7.
In column fractionation, about 5 g of the sample was placed in a fractionation column after being adsorbed on a carrier (Celite 745) in xylene. Then, the column was heated to 130C, and butyl cellosolve and xylene were passed through the column with the mixing ratio being gradually changed in order to obtain a gradual increase in solvencyO Thus, all the copolymer fractions of lower to higher molecular weight were separated. To the eluates was added methanol to cause precipitation of the copolymers. After recovery, the polymers were dried under reduced pressure and each copolymer fraction was obtained. In the above column fractionation process, in order to prevent the possible decomposition of the copolymers, 100 ppm of Irganox ~ 1076 was added to the original sample and further air inside the column was replaced by nitrogen. Using each copolymer fraction, pressed sheets having about 100 to 300~ thickness were prepared, and S.C.B. of each copolymer fraction were s~
1 calculated by conducting Fourier-transform infrared absorption spectroscopy. Molecular welghts of each copolymer fraction were calculated, using intrinsic viscosities [ n] measured in tetralin of 135C and the following formula.
[ ] 5 1 10-4 M- 0 725 Reference Example 2 With ethylene-~-olefin copolymers of the con-ventional technique~ a relationship between melt index (MI) and tensile impact strength was examined with melt flow ratio (MFR) used as a parameter. Results were shown in Fig. 8. It is revealed that widening of molecular weight distribution results in remarkable reduction in tensile impact strength. (In the figure~ molecular weight distribu~ion was represented by MFR. Larger MFR means wider molecular weight distribution.)O These ethylene-~-ole~in copolymers were subjected to molecular weight fra~tionation with the same technique as used in Reference Example 1. All the copolymers showed trends similar to that of Reference Example 1. The fractions were divided into two groups (lower molecular weight group and higher molecular weight group) in such a way that each group became about 50% by weight~ and (S.C.B.
of higher molecular weight component/~.C.~.,of ~ower f~C~/~f~ G'~
I 25 molecular weight component) was olaou'atcd. It was below 0.5 in all the copolymers.
s~
1 Reference Example 3 With a high pressure method polyethylene of the conventional technique and a linear, high density poly-ethylene of medium to low pressure method, correlations between melt index (MI) and intrinsic viscosity [n] were examined and~shown in Fig. 9. The correlation lines of each sample are clearly divided by a partition line (broken line). It is learned that the high pressure polyethylene has much lower inkrinsic viscosity than that of the linear high density polyethylene of the same melt indexO
A correlation between melt index and intrinsic viscosity was examined with the ethylene-~-olefin copolymers of the present invention. All of the copoly-mers of the present invention fell in the zone of thelinear, high density polyethylene.
Table 38 Polymeri- Polymeri- Catalyst H2 C2' Polymeri- Polymeri-zation zation quantity Solvent a-olefin parkial partial zation zation method vessel pressure pressure kempera- time capacity ture (~) (mg) (g) (g)~kg/cm2) (kg/cm2) (C) (min) Solution 1 25.1 C7 300C4 40 3-5 20 140 90 i--~1 ~3 Table 39 Propert ies Densiby (g/10 min) MFR S . C .B .
0 . 924 4 25 20 G~
Claims (23)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An ethylene-.alpha.-olefin copolymer composition excellent in transparency and strength and having a density of 0.915 to 0.929 g/cm3, a melt index of 0.02 to 50 g/10 min. and a melt flow ratio of 35 to 250, which comprises 1.0 to 70% by weight of an ethylene-.alpha.-olefin copolymer A and 90 to 30% by weight of an ethylene-.alpha.-olefin copolymer B; said copolymer A having a higher molecular weight than copolymer B and being a copolymer of ethylene and an .alpha.-olefin of 3 to 18 carbon atoms and having a density of 0.895 to 0.935 g/cm3, an intrinsic viscosity of 1.2 to 6.0 dl/g, a number of short chain branches per 1000 carbon atoms (hereinafter abbreviated as "S.C.B.") of 7 to 40 and a (weight average molecular weight)/(number average molecular weight) value of 2 to 10; said copolymer B being a copolymer of ethylene and an .alpha.-olefin of 3 to 18 carbon atoms and having a density of 0.910 to 0.955 g/cm3, an intrinsic viscosity of 0.3 to 1.5 dl/g, an S.C.B. of 5 to 35 and a (weight average molecular weight)/(number average molecular weight) value of 2 to 10; said copolymer A and said copolymer B being selected in order to satisfy a condition that (S.C.B. of said copolymer A)/(S.C.B. of said copolymer B) is 0.6 to 1.7.
2. An ethylene-.alpha.-olefin copolymer composition according to claim 1, wherein at least one of said copolymer A and said copolymer B is an ethylene-butene-1 copolymer.
3. An ethylene-.alpha.,-olefin copolymer composition according to claim 1, wherein at least one of said copolymer A and said copolymer B is an ethylene-4-methyl-pentene-1 copolymer.
4. An ethylene-.alpha.-olefin copolymer composition according to claim 1, wherein at least one of said copolymer A and said copolymer B is an ethylene-hexene-1 copolymer.
5. An ethylene-.alpha.-olefin copolymer composition according to claim 1, wherein at least one of said copolymer A and said copolymer B is an ethylene-octene-1 copolymer.
6. An extrusion processed material excellent in transparency and strength, obtained from an ethylene-.alpha.-olefin copolymer composition having a den-sity of 0.915 to 0.929 g/cm3 and a melt index of 0.02 to 2.0 g/10 min. accord-ing to claim 1.
7. A film excellent in transparency and strength, obtained from an ethylene-.alpha.-olefin copolymer composition having a density of 0.915 to 0.929 g/cm3 and a melt index of 0.02 to 5 g/10 min. according to claim 1.
8. An injection molded material excellent in transparency and strength, obtained from an ethylene-.alpha.-olefin copolymer composition having a density of 0.915 to 0.929 g/cm3, a melt index of 2.0 to 50 g/10 min. and a melt flow ratio of 35 to 80 according to claim 1, which is obtained by mixing a copolymer A hav-ing an intrinsic viscosity of 1.2 to 4.0 dl/g and a copolymer B having a den-sity of 0.910 to 0.950 g/cm and an intrinsic viscosity of 0.3 to 1.2 dl/g.
9. An ethylene-.alpha.-olefin copolymer composition according to claim 1, 3 or 4, wherein said copolymer composition is prepared by a multi-stage polymerization.
10. An ethylene-.alpha.-olefin copolymer composition according to claim 1, characterized in that said copolymer components are mixed as a result of a two stage polymerization wherein, in the first stage, said copolymer A is polymerized under certain polymerization conditions for a certain length of time and successively, in the second stage, said copolymer B is polymer-ized with the first stage polymerization conditions changed other than catalysts until an intended weight ratio of copolymers A and B is obtained.
11. An extrusion processed material according to claim 6, characterized in that said ethylene-.alpha.-olefin copolymer composi-tion is obtained as a result of a multi-stage polymerization.
12. A film according to claim 7, characterized in that said ethylene-.alpha.-olefin copolymer composition is obtained as a result of a multi stage polymerization.
13. An injection molded material according to claim 8, characterized in that said ethylene-a-olefin copolymer composi-tion is obtained as a result of a multi-stage polymerization.
14. A composition of copolymers of ethylene and an .alpha.-olefin of 3 to 18 carbon atoms, having first and second copolymer component groups, said first component group having a higher molecular weight than said second component group, having the following properties:
(1) density of 0.915 to 0.929 g/cm3, (2) intrinsic viscosity [?] of 0.7 to 4.0 dl/g, (3) melt index of 0.02 to 50 g/10 min., (4) S.C.B. being 5 to 45, (5) [n]/[n]? namely g? being at least 0.8, where [n]?
is an intrinsic viscosity of a linear polyethylene having the same weight average molecular weight measured by a light scatter-ing method, (6) (S.C.B. of the first component group)/(S.C.B. of the second component group) being 0.6 to 0.8 where the two component groups are prepared by consolidating fractions obtained by column fractionation in two portions of lower and higher molecular weight components, said portions being selected so that the weight ratio of the two portions corresponds to the weight ratio of lower and higher molecular weight components calculated from the gel permeation chromatography curve, (7) the second components have a density of 0.910 to 0.955 g/cm3, an intrinsic viscosity of 0.3 to 1.5 dl/g and S.C.B.
of 5 to 35, (8) the first components have a density of 0.895 to 0.935 g/cm3, an intrinsic viscosity of 1.2 to 6.0 dl/g and S.C.B.
of 7 to 40, and (9) the second components are 30 to 90% by weight and the first components are 70 to 10% by weight.
(1) density of 0.915 to 0.929 g/cm3, (2) intrinsic viscosity [?] of 0.7 to 4.0 dl/g, (3) melt index of 0.02 to 50 g/10 min., (4) S.C.B. being 5 to 45, (5) [n]/[n]? namely g? being at least 0.8, where [n]?
is an intrinsic viscosity of a linear polyethylene having the same weight average molecular weight measured by a light scatter-ing method, (6) (S.C.B. of the first component group)/(S.C.B. of the second component group) being 0.6 to 0.8 where the two component groups are prepared by consolidating fractions obtained by column fractionation in two portions of lower and higher molecular weight components, said portions being selected so that the weight ratio of the two portions corresponds to the weight ratio of lower and higher molecular weight components calculated from the gel permeation chromatography curve, (7) the second components have a density of 0.910 to 0.955 g/cm3, an intrinsic viscosity of 0.3 to 1.5 dl/g and S.C.B.
of 5 to 35, (8) the first components have a density of 0.895 to 0.935 g/cm3, an intrinsic viscosity of 1.2 to 6.0 dl/g and S.C.B.
of 7 to 40, and (9) the second components are 30 to 90% by weight and the first components are 70 to 10% by weight.
15. A copolymer composition according to claim 14 which gives at least a two-peak molecular weight distribution curve when subjected to gel permeation chromatography, in which curve the second component group contains at least one component having a peak chain length of 2 x 102 to 3.0 x 103 ? and the first component group contains at least one component having a peak chain length of 1 x 103 to 6 x 104 .ANG..
16. A copolymer composition according to claim 14, wherein said second components have S.C.B. of 7 to 30 and said first components have S.C.B. of 10 to 40.
17. A copolymer composition according to claim 14 which has a melt index of 0.04 to 10 g/10 min.
18. A copolymer composition according to claim 14, which has a melt flow ratio of 35 to 250.
19. A copolymer composition according to claim 18, wherein the .alpha.-olefin is butene-1.
20. A copolymer composition according to claim 18, wherein the .alpha.-olefin is 4-methyl-pentene-1.
21. A copolymer composition according to claim 18, wherein the .alpha.-olefin is hexene-1.
22. A copolymer composition according to claim 18, wherein the .alpha.-olefin is octene-1.
23. A copolymer composition according to claim 18, which is obtained from a multi-stage polymerization using a carrier-supported Ziegler catalyst.
Applications Claiming Priority (14)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14038/81 | 1981-01-30 | ||
| JP1403881A JPS57126809A (en) | 1981-01-30 | 1981-01-30 | Ethylene/alpha-olefin copolymer |
| JP14042/81 | 1981-01-30 | ||
| JP14044/81 | 1981-01-30 | ||
| JP1404381A JPS57126838A (en) | 1981-01-30 | 1981-01-30 | Improved ethylenic resin composition |
| JP1404481A JPS57126839A (en) | 1981-01-30 | 1981-01-30 | Improved polyethylene resin composition |
| JP14040/81 | 1981-01-30 | ||
| JP1404081A JPS57126835A (en) | 1981-01-30 | 1981-01-30 | Ethylenic resin composition |
| JP14043/81 | 1981-01-30 | ||
| JP56014042A JPS57126837A (en) | 1981-01-30 | 1981-01-30 | High-quality ethylenic resin composition |
| JP14041/81 | 1981-01-30 | ||
| JP56014039A JPS57126834A (en) | 1981-01-30 | 1981-01-30 | Ethylene-alpha-olefin copolymer resin composition |
| JP1404181A JPS57126836A (en) | 1981-01-30 | 1981-01-30 | High-quality polyethylene resin composition |
| JP14039/81 | 1981-01-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1198542A true CA1198542A (en) | 1985-12-24 |
Family
ID=27563669
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000395280A Expired CA1198542A (en) | 1981-01-30 | 1982-02-01 | LOW DENSITY ETHYLENE COPOLYMER COMPOSITION OF TWO ETHYLENE-.alpha.-OLEFIN COPOLYMERS |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4438238A (en) |
| EP (1) | EP0057891B2 (en) |
| CA (1) | CA1198542A (en) |
| DE (1) | DE3276704D1 (en) |
| GB (1) | GB2093044B (en) |
Families Citing this family (131)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4576993A (en) * | 1978-09-20 | 1986-03-18 | Raychem Limited | Low density polyethylene polymeric compositions |
| US4532189A (en) * | 1982-02-19 | 1985-07-30 | W. R. Grace & Co., Cryovac Div. | Linear polyethylene shrink films |
| JPS6088016A (en) * | 1983-10-21 | 1985-05-17 | Mitsui Petrochem Ind Ltd | Ethylene copolymer |
| US4590124A (en) * | 1984-05-10 | 1986-05-20 | W. R. Grace & Co., Cryovac Div. | Storm window film |
| US4643943A (en) * | 1984-05-30 | 1987-02-17 | W. R. Grace & Co., Cryovac Div. | Multi-layer polyolefin shrink film |
| US4514465A (en) * | 1984-05-30 | 1985-04-30 | W. R. Grace & Co., Cryovac Div. | Storm window film comprising at least five layers |
| JPS6154934A (en) * | 1984-08-27 | 1986-03-19 | 富士写真フイルム株式会社 | Film for packaging photographic photosensitive material |
| US4847164A (en) * | 1984-10-18 | 1989-07-11 | The Dow Chemical Company | Ethylene copolymers reacted with metal oxides |
| US4614764A (en) * | 1985-03-06 | 1986-09-30 | Mobil Oil Corporation | Linear low density ethylene polymers blended with modified linear low density ethylene polymers |
| US4976898A (en) * | 1985-06-17 | 1990-12-11 | Viskase Corporation | Process for making puncture resistant, heat-shrinkable films containing very low density polyethylene |
| US5059481A (en) * | 1985-06-17 | 1991-10-22 | Viskase Corporation | Biaxially stretched, heat shrinkable VLDPE film |
| CA1340037C (en) * | 1985-06-17 | 1998-09-08 | Stanley Lustig | Puncture resistant, heat-shrinkable films containing very low density polyethylene copolymer |
| US5256351A (en) * | 1985-06-17 | 1993-10-26 | Viskase Corporation | Process for making biaxially stretched, heat shrinkable VLDPE films |
| USRE35285E (en) * | 1985-09-30 | 1996-06-25 | W. R. Grace & Co.-Conn. | Thermoplastic multi-layer packaging film and bags made therefrom |
| DE3689520T2 (en) * | 1985-11-07 | 1994-04-28 | Showa Denko Kk | TRANSPARENT, HIGH DENSITY POLYETHYLENE FILM AND THEIR PRODUCTION. |
| US4705829A (en) * | 1986-04-11 | 1987-11-10 | Mobil Oil Corporation | Low density polyethylene resin compositions and thermoplastic films thereof |
| US5066724A (en) * | 1986-04-25 | 1991-11-19 | Rexene Products Company | Novel film compositions |
| JPH0737547B2 (en) * | 1986-09-05 | 1995-04-26 | 三井石油化学工業株式会社 | Agricultural coating film |
| US4824912A (en) * | 1987-08-31 | 1989-04-25 | Mobil Oil Corporation | Terblends and films of LLDPE, LMW-HDPE and HMW-HDPE |
| US5112686A (en) * | 1987-10-27 | 1992-05-12 | The Dow Chemical Company | Linear ethylene polymer staple fibers |
| US4990204A (en) * | 1987-10-27 | 1991-02-05 | The Dow Chemical Company | Improved spunbonding of linear polyethylenes |
| AU619785B2 (en) * | 1987-10-27 | 1992-02-06 | Dow Chemical Company, The | Spunbonded unshaped polyethylene blend |
| US4842922A (en) * | 1987-10-27 | 1989-06-27 | The Dow Chemical Company | Polyethylene fibers and spunbonded fabric or web |
| US4804714A (en) * | 1987-11-20 | 1989-02-14 | Union Carbide Corporation | Polyolefin blends |
| KR900701870A (en) * | 1988-05-06 | 1990-12-04 | 리챠드 지·워터맨 | Super low density linear low density polyethylene |
| FI893348A (en) * | 1988-07-11 | 1990-01-12 | Sumitomo Chemical Co | ETYLEN-A-OLEFINKOPOLYMER OCH FILMER FRAMSTAELLDA AV DENNA. |
| US5032463A (en) * | 1988-07-18 | 1991-07-16 | Viskase Corporation | Very low density polyethylene film from blends |
| US5082902A (en) * | 1988-07-22 | 1992-01-21 | Mobil Oil Corporation | Method for reducing cycle time and improving molded part impact energy and ESCR of linear high density polyethylene using a blend of two linear polyethylenes of different densities |
| US5382631A (en) * | 1988-09-30 | 1995-01-17 | Exxon Chemical Patents Inc. | Linear ethylene interpolymer blends of interpolymers having narrow molecular weight and composition distributions |
| US5382630A (en) * | 1988-09-30 | 1995-01-17 | Exxon Chemical Patents Inc. | Linear ethylene interpolymer blends of interpolymers having narrow molecular weight and composition distribution |
| WO1990003414A1 (en) * | 1988-09-30 | 1990-04-05 | Exxon Chemical Patents Inc. | Linear ethylene interpolymer blends of interpolymers having narrow molecular weight and composition distributions |
| DE68929006T2 (en) † | 1988-12-26 | 1999-10-07 | Mitsui Chemicals Inc | Olefin copolymers and process for making them |
| US5237013A (en) * | 1989-08-30 | 1993-08-17 | Idemitsu Petrochemical Company Limited | Composition of polybutene-1 and a process for preparing same |
| US5548014A (en) * | 1989-09-13 | 1996-08-20 | Exxon Chemical Patents Inc. | Blends of ethylene copolymers for hot melt adhesives |
| DD300443A5 (en) * | 1989-09-13 | 1992-06-11 | Exxon Chemical Patents Inc | HOT MELT GLUE |
| JPH03115445A (en) * | 1989-09-29 | 1991-05-16 | Nippon Petrochem Co Ltd | Ethylenic polymer composition |
| US5102955A (en) * | 1989-12-29 | 1992-04-07 | Mobil Oil Corporation | Broad distribution, high molecular weight low density polyethylene and method of making thereof |
| CA2033486A1 (en) * | 1990-01-03 | 1991-07-04 | David T. Raske | Extended-life polyethylene gas distribution pipe |
| FI112252B (en) * | 1990-02-05 | 2003-11-14 | Fibervisions L P | High temperature resistant fiber bindings |
| US5519091A (en) * | 1990-02-13 | 1996-05-21 | Mitsui Petrochemical Industries, Ltd. | Method for the preparation of ethylene polymer compositions |
| TW206240B (en) * | 1990-02-13 | 1993-05-21 | Mitsui Petroleum Chemicals Ind | |
| US6006745A (en) * | 1990-12-21 | 1999-12-28 | Minnesota Mining And Manufacturing Company | Device for delivering an aerosol |
| JP3045548B2 (en) * | 1990-12-28 | 2000-05-29 | 日本石油化学株式会社 | Polyethylene composition |
| US6747113B1 (en) | 1991-01-18 | 2004-06-08 | The Dow Chemical Company | Silica supported transition metal catalyst |
| US6172173B1 (en) | 1991-01-18 | 2001-01-09 | The Dow Chemical Company | Silica supported transition metal catalyst |
| AU660043B2 (en) * | 1991-07-18 | 1995-06-08 | Exxon Chemical Patents Inc. | Heat sealed article |
| JPH0565373A (en) * | 1991-09-06 | 1993-03-19 | Nippon Petrochem Co Ltd | Polyethylene composition |
| JPH05194796A (en) * | 1991-09-18 | 1993-08-03 | Phillips Petroleum Co | Polyethylene blend |
| US5250612A (en) * | 1991-10-07 | 1993-10-05 | The Dow Chemical Company | Polyethylene films exhibiting low blocking force |
| US5395471A (en) * | 1991-10-15 | 1995-03-07 | The Dow Chemical Company | High drawdown extrusion process with greater resistance to draw resonance |
| US5847053A (en) * | 1991-10-15 | 1998-12-08 | The Dow Chemical Company | Ethylene polymer film made from ethylene polymer blends |
| US5582923A (en) * | 1991-10-15 | 1996-12-10 | The Dow Chemical Company | Extrusion compositions having high drawdown and substantially reduced neck-in |
| US5674342A (en) * | 1991-10-15 | 1997-10-07 | The Dow Chemical Company | High drawdown extrusion composition and process |
| US6316549B1 (en) | 1991-10-15 | 2001-11-13 | The Dow Chemical Company | Ethylene polymer fiber made from ethylene polymer blends |
| US5677383A (en) * | 1991-10-15 | 1997-10-14 | The Dow Chemical Company | Fabricated articles made from ethylene polymer blends |
| US5530065A (en) * | 1992-01-07 | 1996-06-25 | Exxon Chemical Patents Inc. | Heat sealable films and articles made therefrom |
| DE69324280T2 (en) * | 1992-01-13 | 1999-08-12 | Hercules Inc | Heat-bondable fibers for resistant nonwovens |
| EP0641362B1 (en) * | 1992-04-20 | 1998-11-11 | Exxon Chemical Patents Inc. | Ethylene/branched olefin copolymers |
| CA2148353C (en) * | 1992-11-02 | 2002-05-21 | Exxon Chemical Patents Inc. | Blends of ethylene copolymers for hot melt adhesives |
| ATE291059T1 (en) | 1992-11-13 | 2005-04-15 | Cryovac Inc | HEAT SHRINKABLE FILMS CONTAINING COPOLYMERS PRODUCED BY SINGLE SITE CATALYSIS. |
| GB9224876D0 (en) † | 1992-11-27 | 1993-01-13 | Exxon Chemical Patents Inc | Improved processing polyolefin blends |
| BE1006439A3 (en) * | 1992-12-21 | 1994-08-30 | Solvay Societe Annonyme | Method for preparing a composition of polymers of ethylene, polymer composition and use of ethylene. |
| US5420220A (en) * | 1993-03-25 | 1995-05-30 | Mobil Oil Corporation | LLDPE films |
| SG50447A1 (en) * | 1993-06-24 | 1998-07-20 | Hercules Inc | Skin-core high thermal bond strength fiber on melt spin system |
| US5631069A (en) * | 1994-05-09 | 1997-05-20 | The Dow Chemical Company | Medium modulus molded material comprising substantially linear polyethlene and fabrication method |
| EP0759047A1 (en) * | 1994-05-09 | 1997-02-26 | The Dow Chemical Company | Medium modulus film and fabrication method |
| US5455303A (en) * | 1994-06-20 | 1995-10-03 | Montell North America Inc. | Linear low density polyethylene based compositions with improved optics |
| CA2152239C (en) * | 1994-06-28 | 1998-09-22 | Hermann Van Laak | Polyethylene molding compositions |
| US5514455A (en) * | 1994-07-08 | 1996-05-07 | Union Carbide Chemicals & Plastics Technology Corporation | Film extruded from an in situ blend of ethylene copolymers |
| US5503914A (en) * | 1994-07-08 | 1996-04-02 | Union Carbide Chemicals & Plastics Technology Corporation | Film extruded from an in situ blend of ethylene copolymers |
| US5792534A (en) * | 1994-10-21 | 1998-08-11 | The Dow Chemical Company | Polyolefin film exhibiting heat resistivity, low hexane extractives and controlled modulus |
| US7153909B2 (en) * | 1994-11-17 | 2006-12-26 | Dow Global Technologies Inc. | High density ethylene homopolymers and blend compositions |
| US6506866B2 (en) | 1994-11-17 | 2003-01-14 | Dow Global Technologies Inc. | Ethylene copolymer compositions |
| DK0719879T3 (en) * | 1994-12-19 | 2000-09-18 | Fibervisions L P | Process for producing fibers for high strength nonwoven materials and the resulting fibers and nonwoven fabrics |
| DE69614695T2 (en) | 1995-07-10 | 2002-06-20 | Borealis Tech Oy | COATING COMPOSITION |
| US5795941A (en) * | 1995-10-03 | 1998-08-18 | The Dow Chemical Company | Crosslinkable bimodal polyolefin compositions |
| US5925448A (en) † | 1995-11-07 | 1999-07-20 | Union Carbide Chemicals & Plastics Technology Corporation | Film extruded from a blend of ethylene copolymers |
| JP3840499B2 (en) * | 1996-01-22 | 2006-11-01 | ザ・ダウ・ケミカル・カンパニー | Polyolefin elastomer blends with improved properties |
| JPH09309926A (en) * | 1996-05-17 | 1997-12-02 | Dow Chem Co:The | Production of ethylene copolymer |
| US5849823A (en) * | 1996-09-04 | 1998-12-15 | The Dow Chemical Company | Homogeneously branched ethylene α-olefin interpolymer compositions for use in gasket applications |
| JP3724129B2 (en) | 1996-09-30 | 2005-12-07 | 三井化学株式会社 | Rubber modifier |
| JPH10259279A (en) * | 1997-03-19 | 1998-09-29 | Sumitomo Chem Co Ltd | Polyethylene-based resin composition and its film |
| US5919565A (en) * | 1997-03-20 | 1999-07-06 | Union Carbide Chemicals & Plastics Technology Corporation | Tree resistant cable |
| US6153551A (en) * | 1997-07-14 | 2000-11-28 | Mobil Oil Corporation | Preparation of supported catalyst using trialkylaluminum-metallocene contact products |
| DE19849426A1 (en) * | 1998-10-27 | 2000-05-04 | Elenac Gmbh | Bimodal polyethylene blends with high mixing quality |
| CN100453566C (en) * | 1999-06-17 | 2009-01-21 | 三井化学株式会社 | Ethylene (co) polymers and use thereof |
| US6497676B1 (en) | 2000-02-10 | 2002-12-24 | Baxter International | Method and apparatus for monitoring and controlling peritoneal dialysis therapy |
| US6455638B2 (en) | 2000-05-11 | 2002-09-24 | Dupont Dow Elastomers L.L.C. | Ethylene/α-olefin polymer blends comprising components with differing ethylene contents |
| US6388051B1 (en) | 2000-12-20 | 2002-05-14 | Union Carbide Chemicals & Plastics Technology Corporation | Process for selecting a polyethylene having improved processability |
| MY137183A (en) * | 2001-03-16 | 2009-01-30 | Dow Global Technologies Inc | Method of making interpolymers and products made therefrom |
| WO2003020821A1 (en) * | 2001-08-31 | 2003-03-13 | Dow Global Technologies Inc. | Multimodal polyethylene material |
| US20030125662A1 (en) * | 2002-01-03 | 2003-07-03 | Tuan Bui | Method and apparatus for providing medical treatment therapy based on calculated demand |
| US7238164B2 (en) * | 2002-07-19 | 2007-07-03 | Baxter International Inc. | Systems, methods and apparatuses for pumping cassette-based therapies |
| US7396881B2 (en) * | 2002-10-01 | 2008-07-08 | Exxonmobil Chemical Patents Inc. | Polyethylene compositions for rotational molding |
| DE60331562D1 (en) * | 2002-10-01 | 2010-04-15 | Exxonmobil Chem Patents Inc | |
| US7943700B2 (en) * | 2002-10-01 | 2011-05-17 | Exxonmobil Chemical Patents Inc. | Enhanced ESCR of HDPE resins |
| US7396878B2 (en) * | 2002-10-01 | 2008-07-08 | Exxonmobil Chemical Patents Inc. | Polyethylene compositions for injection molding |
| JP4084209B2 (en) * | 2003-02-21 | 2008-04-30 | 株式会社ジェイエスピー | Foam molded body and method for producing the same |
| TW200504093A (en) * | 2003-05-12 | 2005-02-01 | Dow Global Technologies Inc | Polymer composition and process to manufacture high molecular weight-high density polyethylene and film therefrom |
| US6870010B1 (en) * | 2003-12-01 | 2005-03-22 | Univation Technologies, Llc | Low haze high strength polyethylene compositions |
| US20050209563A1 (en) * | 2004-03-19 | 2005-09-22 | Peter Hopping | Cassette-based dialysis medical fluid therapy systems, apparatuses and methods |
| DE102004020524A1 (en) * | 2004-04-26 | 2005-11-10 | Basell Polyolefine Gmbh | Polyethylene for film, e.g. stretch film, used in carrier bags, contains ethylene homopolymers and/or copolymers of ethylene with 1-alkenes |
| US7696280B2 (en) * | 2004-04-30 | 2010-04-13 | Chevron Phillips Chemical Company, Lp | HDPE resins for use in pressure pipe and related applications |
| US8022142B2 (en) * | 2008-12-15 | 2011-09-20 | Exxonmobil Chemical Patents Inc. | Thermoplastic olefin compositions |
| DE102006001959A1 (en) | 2006-01-13 | 2007-07-19 | Basell Polyolefine Gmbh | Preparation of monoimine compound, useful in the polymerization of olefin, comprises reacting dicarbonyl compound with an aniline compound in presence of an aliphatic, non-aromatic solvent |
| JP5575470B2 (en) * | 2006-05-02 | 2014-08-20 | ダウ グローバル テクノロジーズ エルエルシー | High density polyethylene composition, method of making it, wire and cable jacket made therefrom, and method of making such wire and cable jacket |
| US8080699B2 (en) * | 2009-08-28 | 2011-12-20 | Chemtura Corporation | Two-stage process and system for forming high viscosity polyalphaolefins |
| US8870812B2 (en) * | 2007-02-15 | 2014-10-28 | Baxter International Inc. | Dialysis system having video display with ambient light adjustment |
| US7731689B2 (en) | 2007-02-15 | 2010-06-08 | Baxter International Inc. | Dialysis system having inductive heating |
| US8558964B2 (en) | 2007-02-15 | 2013-10-15 | Baxter International Inc. | Dialysis system having display with electromagnetic compliance (“EMC”) seal |
| US7998115B2 (en) * | 2007-02-15 | 2011-08-16 | Baxter International Inc. | Dialysis system having optical flowrate detection |
| US8361023B2 (en) * | 2007-02-15 | 2013-01-29 | Baxter International Inc. | Dialysis system with efficient battery back-up |
| DE102007017903A1 (en) * | 2007-04-13 | 2008-10-16 | Basell Polyolefine Gmbh | Polyethylene and catalyst composition and process for its preparation |
| US8193284B2 (en) * | 2007-07-26 | 2012-06-05 | Sumitomo Chemical Company, Limited | Process for producing polyolefin resin composition |
| CN101981110B (en) * | 2007-12-18 | 2013-03-27 | 巴塞尔聚烯烃股份有限公司 | PE moulding composition for producing injection-molded screw cap closures and high-strenght screw cap closure for carbonated beverages produced therewith |
| MX2010010020A (en) * | 2008-03-12 | 2010-09-30 | Dow Global Technologies Inc | Clarified polypropylene and ethylene alpha olefin blend. |
| US8410217B2 (en) * | 2008-12-15 | 2013-04-02 | Exxonmobil Chemical Patents Inc. | Thermoplastic polyolefin blends |
| US8497325B2 (en) | 2008-12-15 | 2013-07-30 | Exxonmobil Chemical Patents Inc. | Thermoplastic polyolefin blends and films therefrom |
| US8101685B2 (en) * | 2008-12-15 | 2012-01-24 | Exxonmobil Chemical Patents Inc. | Thermoplastic elastomer polyolefin in-reactor blends and molded articles therefrom |
| US8772411B2 (en) * | 2009-05-22 | 2014-07-08 | Equistar Chemicals, Lp | Preparation of polyolefin-based adhesives |
| US8993693B2 (en) | 2012-03-23 | 2015-03-31 | Formosa Plastics Corporation | Ethylene copolymers with a novel composition distribution and processes for making the same |
| BR112014030664A2 (en) * | 2012-06-28 | 2017-06-27 | Dow Global Technologies Llc | foamable formulation composition, process for preparing a foamed composition and foamed composition |
| WO2014190039A1 (en) * | 2013-05-22 | 2014-11-27 | Dow Global Technologies Llc | Low density ethylene-based compositions with improved melt strength, output, and mechanical properties |
| JP6688217B2 (en) * | 2013-05-22 | 2020-04-28 | ダウ グローバル テクノロジーズ エルエルシー | Low density ethylene polymer composition with high melt strength and medium to high density control |
| US20150322184A1 (en) * | 2014-05-07 | 2015-11-12 | Chevron Phillips Chemical Company Lp | High Performance Moisture Barrier Films at Lower Densities |
| US11760851B2 (en) | 2014-06-30 | 2023-09-19 | Formosa Plastics Corporation, U.S.A. | Cast film component layer exhibiting an outstanding cling property |
| US11352451B2 (en) * | 2016-07-13 | 2022-06-07 | Exxonmobil Chemical Patents Inc. | Dual metallocene catalyst copolymer compositions |
| CN109641990B (en) * | 2016-07-13 | 2022-08-19 | 埃克森美孚化学专利公司 | Dual metallocene catalyst copolymer compositions |
| US11299567B2 (en) * | 2016-07-14 | 2022-04-12 | Exxonmobil Chemical Patents Inc. | Lubricating oil compositions comprising dual metallocene-catalyzed bimodal copolymer compositions useful as viscosity modifiers |
| CN111032772B (en) * | 2017-06-14 | 2022-07-15 | 埃克森美孚化学专利公司 | Ethylene copolymer blends for crosslinking applications |
| US11179516B2 (en) | 2017-06-22 | 2021-11-23 | Baxter International Inc. | Systems and methods for incorporating patient pressure into medical fluid delivery |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE626817A (en) * | 1962-01-15 | |||
| BE721676A (en) * | 1967-10-02 | 1969-04-01 | ||
| CA984087A (en) * | 1971-06-30 | 1976-02-17 | Robert J. Turbett | High density ethylene copolymer blend as cable jacketing |
| US3914342A (en) | 1971-07-13 | 1975-10-21 | Dow Chemical Co | Ethylene polymer blend and polymerization process for preparation thereof |
| US4390677A (en) * | 1978-03-31 | 1983-06-28 | Karol Frederick J | Article molded from ethylene hydrocarbon copolymer |
| JPS5610506A (en) | 1979-07-09 | 1981-02-03 | Mitsui Petrochem Ind Ltd | Production of ethylene polymer composition |
| JPS5692937A (en) | 1979-12-26 | 1981-07-28 | Nippon Oil Co Ltd | Resin composition for molding polyethylene film |
| JPS56120741A (en) | 1980-02-29 | 1981-09-22 | Nippon Oil Co Ltd | Polyethylene resin composition |
-
1982
- 1982-01-25 US US06/342,428 patent/US4438238A/en not_active Expired - Lifetime
- 1982-02-01 EP EP82100690A patent/EP0057891B2/en not_active Expired - Lifetime
- 1982-02-01 GB GB8202753A patent/GB2093044B/en not_active Expired
- 1982-02-01 DE DE8282100690T patent/DE3276704D1/en not_active Expired
- 1982-02-01 CA CA000395280A patent/CA1198542A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE3276704D1 (en) | 1987-08-13 |
| EP0057891B1 (en) | 1987-07-08 |
| EP0057891B2 (en) | 1997-08-27 |
| US4438238A (en) | 1984-03-20 |
| GB2093044A (en) | 1982-08-25 |
| EP0057891A3 (en) | 1982-09-01 |
| EP0057891A2 (en) | 1982-08-18 |
| GB2093044B (en) | 1984-12-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1198542A (en) | LOW DENSITY ETHYLENE COPOLYMER COMPOSITION OF TWO ETHYLENE-.alpha.-OLEFIN COPOLYMERS | |
| CA2629576C (en) | Closures for bottles | |
| CA2217165C (en) | Thermoplastic olefin articles having high surface gloss and mar resistance | |
| CA2052402C (en) | Olefin polymer films | |
| US4205021A (en) | Ethylene copolymers | |
| CA2172941C (en) | Polyethylene resin composition for heavy-duty packaging bag and polyethylene resin film produced from the same | |
| US5189106A (en) | Polyethylene composition | |
| CN1697764B (en) | Screw cap composition | |
| JP4216185B2 (en) | Ethylene polymer composition | |
| CA2176387A1 (en) | Heat sealable films and articles made therefrom | |
| CA2222076C (en) | Polypropylene resin compositions | |
| AU612271B2 (en) | Linear low density polyethylene of ultra low density | |
| EP1187876A1 (en) | Injection moulding | |
| HUT54722A (en) | Linear ethylene interpolymer mixtures | |
| AU3151199A (en) | High density polyethylene compositions, a process for the production thereof and films prepared thereof | |
| HU209701B (en) | A polypropilene multilayer film | |
| CA2033396A1 (en) | Broad distribution, high molecular weight low density polyethylene and method of making thereof | |
| EP1646668A1 (en) | Injection moulding polymer | |
| FI75581B (en) | HETEROGENA COPYYMER AVYLEN FOER FRAMSTAELLNING AV FILMER. | |
| CN104769031A (en) | Ethylene-based polymers and articles made therefrom | |
| EP0146968A2 (en) | A Laminated polypropylene film | |
| EP0191990A2 (en) | Crosslinked resin compositions | |
| EP0719829B1 (en) | Polypropylene composition and laminated and oriented film therefrom | |
| JPS647096B2 (en) | ||
| JPH0373582B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |