CA1085995A - Ethylene copolymers - Google Patents
Ethylene copolymersInfo
- Publication number
- CA1085995A CA1085995A CA295,766A CA295766A CA1085995A CA 1085995 A CA1085995 A CA 1085995A CA 295766 A CA295766 A CA 295766A CA 1085995 A CA1085995 A CA 1085995A
- Authority
- CA
- Canada
- Prior art keywords
- copolymer
- methyl
- ethylene
- intrinsic viscosity
- olefin
- 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
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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
Abstract
ABSTRACT OF THE DISCLOSURE
The invention is a copolymer consisting essentially of ethylene and an .alpha.-olefin with 5 to 18 carbon atoms, said copolymer having (i) a density of 0.90 to 0.94 g/cm3, (ii) an intrinsic viscosity (n) of 0.8 to 4.0 dl/g, (iii) a maximum melting point, determined by differential thermal analyis, of 115 to 130°C, and (iv) a gn*(=[n]/[n]?) value of 0.05 to 0.78, in which formula [n] is the intrinsic viscosity of the copolymer and [n]? is the intrinsic viscosity of a linear polyethylene having the same weight average molecular weight determined by the light scattering method as said copolymer.
The copolymer displays improved tear resistance, impact strength, transparency and heat resistance.
The invention is a copolymer consisting essentially of ethylene and an .alpha.-olefin with 5 to 18 carbon atoms, said copolymer having (i) a density of 0.90 to 0.94 g/cm3, (ii) an intrinsic viscosity (n) of 0.8 to 4.0 dl/g, (iii) a maximum melting point, determined by differential thermal analyis, of 115 to 130°C, and (iv) a gn*(=[n]/[n]?) value of 0.05 to 0.78, in which formula [n] is the intrinsic viscosity of the copolymer and [n]? is the intrinsic viscosity of a linear polyethylene having the same weight average molecular weight determined by the light scattering method as said copolymer.
The copolymer displays improved tear resistance, impact strength, transparency and heat resistance.
Description
lV8S9~9S
~ his invention relates to ethylene copolymers having unique structural characteristics not described in the literature an~ superior moldability, and to their melt- -shaped articles such as films or sheets having superior transparency, improved tear resistance and improved impact resistance. The ethylene copolymers of this invention have superior improved properties eliminating the unsatis-factory levels of the various properties, such as tear resistance, impact strength and transparency, of high-pressure polyethylene and the unsatisfactory levels of such properties and heat resistance of conventional ethylene copolymers, and exhibit unique structural characteristics not described in the literatureO
High-pressure polyethylene has been considered to have relatively good transparency, and used in the production of melt-shaped articles such as films, sheets and hollow containersO ~ince, however, the high-pressure polyethylene films have unsatisfactory tear strength or . impact strength, and are difficult to use as thin films,they ; 20 have only limited applications~ ~urthermore, films having superior transparency are difficult to obtain by the infla-tion molding of high-pressure polyethyleneO It has been desired therefore to develop olefinic resins having improved : transparency~
Generally, copolymers of ethylene with a-olefins having at least 3 carbon atoms which are produced by using a Ziegler type catalyst have much the same density as high-pressure polyethylene~ and exhibit relatively good mechanical strengthO When produced by using a vanadium-containing - ` ~08S99S
Ziegler-type catalyst, such copolymers have relatively low melting points, and have unsatisfactory thermal resistanceO
In the presence of a titanium-containing Ziegler-type catalyst, copolymers of ethylene with -olefins having at least 3 carbon atoms are obtained which have poor transparencyO
In the production of such copolymers catalyzed by the titanium-containing Ziegler catalysts, copolymers having much the same transparency as high-pressure polyethylene could be produced by properly modifying the polymerization.
10 conditions or the catalysts (disclosed, for example~ in Canadian Patent 986~250 assigned to Mitsui Petrochemical Industries, Ltdo~ issued on March 23~ 1976; correspondirLg to British Patent 1~355~245 published on October 2 ~ 1974)o It has been impossible in practice, however, to provide .: 15 ethylene copolymers having superior tear resistance and impact resistance which eliminate the unsatisfactory levels of these properties in high-pressure polyethylene films, and exhibit better transparencyO ~he above-cited Canadian Patent does not specifically disclose copolymers of ethylene . 20 with -olefins having 5 to 18 carbon atomsO
We have worked extensively in an attempt to develop ethylene copolymers having the aforesaid improved properties, and consequently found that there exist ethylene copolymers : consisting essentially of ethylene and a-olefins with 5 to 18 carbon atoms which have unique structural characteristics : not described in the literature and which exhibit the afore-said improved propertiesO
It is an object of this invention therefore to provide an ethylene copolymer having unigue structural . - 3 -;
`' - - ~
~08S995 characteristics not described in the literature and -the aforesaid improved propertiesO
~ he above and other objects and advantages of the invention will become more apparent from the following descriptionO
~ he ethylene copolymers of this invention consist-ing essentially of ethylene and -olefins with 5 to 18 carbon atoms have the structural characteristic that as compared with ethylene copolymers described in the litera-ture and being available on the market, they have an exceed-ingly high weight average molecular weight, ~M~ w' (deter-mined by the light scattering method) even when they have the same intrinsic viscosities (~) as the conventional ethylene copolymersO In the present invention, this characteris-tic i.s defined as follows:
(iv) g~ is 0005 - 0078, preferably 0005-00 5 o (~) is the intrinsic viscosity of the copolymer of this invention; and (~)~ is the intrinsic viscosity of a linear polyethylene having the same weight average molecular weight (determined by the light scattering method) as the copolymer of this inventionO
'~ is determined in decalin at 135Co ~he intrinsic viscosity (~)~ of a linear poly-25 ethylene having the same weigh-t average molecular weight ~ w (determined by the light scattering method as that of the copolymer of this invention having the intrinsic viscosity '~) is calculated in accordance with the follow-ing equationO
1~8S995 ,r,)~=5029 x 10 4 x <M~OWo7l3 The g~* values much s~aller than 1 show the structural characteristic that many long-chain branchings e-xist in the copolymer in addition to short-chain branchings derived from the C5-Cl~ a-olefin copolymerized with ethylene (for example, isobutyl branchings when the a-olefin is 4-methyl-l-pentene)O That the ethylene copolymers of this invention have a grl* value of 0005 to Oo789 preferably 0005 to 005 shows that the e-thylene copolymers of this inven-tion are very different in structure from conventionalethylene copolymers having substantially only short-chain branchings and a grl* value of 0080 to 1 n Oo ~he transparency of the conventional ethylene copolymers having a gr* value of 0080 to loO is at best equivalent to that of the high-pressure po]yethylene, and fre~uently inferior to the latter.
In addition to the aforesaid structural character-istic (iv), the ethylene copolymers of this invention have the following structural characteristics (i) to (iii)o (i) They have a density of 0090 to 0094 g/cm39 preferably 0091 to 00935 g/cm30 (ii) They have an intrinsic viscosi-ty (~) of 008 to 400 dl/g9 preferably loO to 300 dl/go (iii) ~hey have a maximum melting point, deter-mined by differen-tial thermal analysis (DSC), of 115 to 130C9 and in many cases 115 to 125Co ~he maximum melting point, as referred to in (iii) above9 denotes the highest melting point among two or more melting points (peaks) which usually exist in the DSC endo-thermic curve of the ethylene copolymer of this inventionO
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1:~85995 In order for the copolymer of this invention to have good transparency~ it should have a density of not more than 0094 g/cm3, preferab1y no-t more than 0~935 g/cm30 On the other hand~ to secure superior mechanical character-istics, and freedom from stickiness1 the copolymer of this invention should have a density of at least 0.90 g/Gm3 and preferably at least Oo91 g/cm3~
~he instrinsic viscosity (~) of the copolymer of this invention is 008 to 4~0 dl/g, preferably loO -to 300 dl/g, and for use as films~ its suitable intrinsic viscosity ~) is loO to 300 dl/g Preferably9 the ethylene copolymers of this invention consisting essentially of ethylene and a-olefins with 5 to 18 carbon atoms should have the following character-istics (v) to (vii) in addition to the characteristics (ij to (ivj~
(v) ~ey have an average spherulite size~ deter-mined by the small angle laser scattering method, of not more than 6u, preferably not more than 4~10 (vi) Ihey have two or more melting points deter-mined by differential thermal analysis (DSC)o (Vii) Ihey have a standard deviation (~) of the distribution of ethylene content of not more than 3%, preferably l 'G0 205 %0 ~he characteristics (v) means that -the ethylene copolymers of this invention have much smalle~ average spherulite sizes than the conventional ethylene copolymers having the same composition of constituent units~
~he average spherulite size (R) is determined by ' the small angle laser scattering method using a 70ll-thick press sheet which is obtained by hea-ting the copolymer to 220C and pressing it with water cooling at a pressure of 100 kg/cm --Go Specificall~, using a small angle laser scattering device 5 an Hv scattering pattern is obtained when the polarizer in -the incident beam is vertical and -the analyser in the scattered beam is horizontalO Ihen, the scattering angle ~m which gives the maximum value in the distribution of the scattering intensity in the scatter-ing pattern is determined~ a~d the spherulite size (R) is obtained from the following equationO
4~* R sin (~)= 400 (R~ So Stein's equation; see J0 Applo l~hys~
VolO 31, NoO 11, 1873 (1960) ) The structural characteristic (vi) means that the ethylene copolymers of this invention include two or more crystal typesO For example, as shown in Figo 1, a copolymer of ethylene with 4-methyl-1-pentene of this invention which has a gT~* of 0013jan (rl) of 1042 dl/g, a density of 00926 g/cm3 and a maximum melting point in DSC of 122C has melt-ing points at 10&C~ 119C and 122C in its DSC endothermic curve. This shows that ir this example, three cry.stal types existO :For comparison~ ~igo 2 shows the DSC endothermic curve of a comparative copolymer of ethylene with 4 methyl-l--pentene having a grl* f 0o83~ an ~rl) of lo 53 dl/g~ a density of Oo927 g/cm3 and a melting point of 125Co In this example~ only one melting point is found at 125C, and this shows that only one crystal t~7pe exists The characte:ristic (vii) shows that the e-thylene ~ 7 --copolymers of this invention have a very naIrow distribution of the content of ethyleneO ~he standard deviation (~) is calculated from the following equationO
_ , _ 5 = /~ (Xi - X-)2~
~' 5 wherein xi is the content of ethylene, x is the average of xi values, and x = ~ixiwi 9 a the proportion by weightO
~or example 9 the copolymer shown in ~igo 1 has a standard deviation (~) of 1035 mole%9 and the copolymer shown in Figo 2 shows a standard deviation (a) of 3072 mole%0 Fractionation of the copolymer of this invention according to chemical composition is performed by fraction-ating it into five fractions by the Soxhlet extraction method~ and the number of shor-t-chain branchings derived ~ 15 from the a-olefin is determined by infrared absorption ; spectroscopy. ~he five fractions are as follows:
.. (1) A fraction soluble in p-xylene at room temper-. ature - (2) A fraction extracted with boiling n-hexane ; 20 (3) ~ fraction extracted with boiling benzene (4) A fraction extracted with boiling n-heptane (5) A fraction extracted with boiling p-xylene Examples of the a-olefin comonomer which constitutes the copolymer of this invention are 1-pentene, l-hexene 9 l-octene, l-decene, l-dodecene, 1-tetradecene1 l-octadecene 9 3-methyl-1-butene~ 3-methyl-1-pentene, 4-methyl-1-pentene, 3-me-thyl-1-hexene, 4-methyl-1-hexene, 5-methyl-1-hexene, 3-methyl-1-heptene, 5-methyl-1-heptene, and mixtures of :, . . . . .
10~5995 theseO Preferred ~-olefins are thos~ containing 6 to 12 carbon atoms 9 above all l-hexene 9 l-octene., l-decene~
3-~nethyl-1-pentene 9 4-methyl-1-pentene 9 5-methyl-l~hexene and 5-methyl-1-hepteneO 4-Methyl-l-pentene is especially preferredO
Ihe proportion of the comonomer to be copolymerized can be varied as desired according -to the type of the co-monomerO To afford a copolymer having the density specified by (i) above 9 the suitable proportion of the comonomer is usually about 1 to about 30 % by weight, preferably about 3 to about 20% by weight, based on the weight of the copolymerO
When an a-olefin having not more than 4 carbon atoms is se-lected as the comonomer1 a copolymer having su~erior mechanical strength and/or transparency specified in the present inven-tion cannot be obtainedO
In the production of the ethylene copolymer of hisinvention, the selection of the catalyst and the polymeriza-tion conditions is importantO
Preferably9 the catalyst to be used is a catalyst composed of a solid titanium catalyst component and an organo-aluminum compoundO The use of a catalyst composed of a solid~
magnesium-containing titanium catalyst component and an : organoaluminum compound is more preferredO Especially preferred catalysts are those in which the solid titanium 2S catalyst component is the one which is obtained by supporting titanium on a compound containing a magnesium halide 5 especially magnesium chloride, and which has a C~/Ti weight ratio of 5 to 150 9 an Mg/Ti mole ratio of 3 to 90, and a surface area of at least 70 m2/g 9 preferably more than 150 l~S9 9S
m /g~ Of these catalysts composed of such preferred solid titanium catal.yst components and organoalminum compounds, especially suitable ones are the catalysts di~closed in British Patent 1,433,537 published on ~ugust 25, 1976 (corresponding to German O~S 2346471 laid open on April 18, 1974) and German OLS 2461677 laid open on July lO, 19750 ~hese p~tents do not give a specific example of copolymer-izing ethylene with an ~-olefin having 5 to 18 carbon atomsO
A solid titanium catalys-t component which is disclosed in the cited British Patent 1~433,537 and has the surface area specified hereinabove can be synthesized, for example~ by adding about 3 to about 7 moles of a lower alcohol such as ethanol to l mole of magnesium chloride, reacting the adduct with an organoaluminum compound in an 5 amount sufficient to react with the alcohol, and then reacting the resulting product with titanium tetrachloride or its solution in an inert hydrocarbon~
~he solid titanium catalyst component disclosed in the German 0~ 2461677 can be prepared by reacting the solid titanium catalys-t component obtained by the method of the British Patent 1,433,537 further with small amounts of titanium tetrachloride and an organoaluminum compoundO
~ he solid titanium catalyst components obtained by these two methods contain titanium, magnesium, halogen 25 and aluminum, and a surface area of at least 70 m2/g, preferably more than 150 m2/g but not exceeding 500 m2/gO
In addition to the selec-tion of the titanium catalyst componen-t~ the selection of -thc- organoaluminum compound as another catalyst component is of importance ~.
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in obtaining the copolymers of this inventionO Preferred organoaluminum compounds are organoaluminum halides of the empirical formula RnA~X3_n wherein R represents a hydro-carbon group such as an alkyl group wi-th l to 12 carbon atoms, X represents a halide such as chloride, bromide, iodide, and l~-n~205, preferably lO~=n<-2DO9 especially prefer-ably lO~=n<1080 A mixture of two or more such organoaluminum halides can also be used if it has an average composition within the above formulaO preferred species are alkylaluminum sesquichlorides and dialkylaluminum chlorideO ~he alkyl-aluminum sesquichloride and mixtures thereof with dialkyl-aluminum chloride are especially preferredO
When a trialkylaluminum, dialkylaluminum hydride, dialkylaluminum alkoxide or alkylaluminum alkoxyhydride~
all of which are frequently used in the poly~erization of ethylene, is used as the organoaluminum compound, the co-polymers obtained usually have a g~* of at least 0080, a standz.rd deviation (~) of atleast 300 mole%, an average spherulite size (R) of not more than 7u9 and one or two melt-ing pointsO
In the production of the ethylene copolymers ofthis invention9 the selection of the copolymerization con-;. ditions is important besides the selection of the catalyst~
Copolymerization should be carried out at a temperature above the melting point of the copolymer prefer-ably in the co-presence of a hydrocarbon solvent, or using - the monomer itself as a solvent, and under such conditions that the solvent and the resulting copolymer form a homogene-ous phaseO Preferably, the polymerization is carried out --_ ~.V~3S995 continuously while maintaining the concentrations of the monomers (ethylene and the comonomer) constantO ~he conditions which will give a homogeneous phase of the solvent and the copolymer vary according, for example, to the type of the solvent, the concentratlons (or pressures) of the monomers (ethylene and the comono~er) or hydrogen, the polymerization temperature and the molecular weight (intrinsic viscosity) of the copolymerO It is advisable therefore to set such conditions by preliminary experimentsO
As an example, Figo 3 shows the precipitation.
point in hexane of an ethylene/4-methyl-l-pentene copolymer having an intrinsic viscosity !~) of 1042 dl/g, a density of 00926 g/cm3, a 4-methyl-l-pentne content of 209 mole%
and melting points of 108C, 119C and 122C~ ~he axis of abscissas represents the total pressure (the total pressure of hexane and ethylene, and optionally 4-methyl-1-pentene, in the case of a gaseous phase), and the axis of ordinates represents the temperature (precipitation temperature) at which the polymerization system becomes a heterogeneous phaseO Curve (l) shows precipitation points in a mixture of hexane and 4-methyl-l-pentene (in a ratio of 85:15) with a copolymer concentration of 150 g/l; curve (2), precipita-tion points in the same mixture with a copolymer concentra-tion of lO0 g/~; and curve (3), precipitation points in the same mixture with a copolymer concentration of 50 g/~0 Curve (4) shows precipitation points in hexane with a co-polymer concentration of 50 g/~0 At temperatures higher than the precipita-tion points, a heterogeneous phase resultsO
It can be seen from Figo 3 that when the copolymer .
10~3S995 ;
concentration is 50 to 150 g/~g the temperature range within which pol~merization c~n be carried out in a homo-geneous phase is broader with higher concentration of the copolymer and higher pressuresO It is also clear from it that the operable temperature range differs according to the amounts of the monomers (ethylene and the comonomer)0 ~ igo 3 represents one model, and in an actual polymerization system, the temperature range for attain-ing a hom~geneous phase is set experimentally prior to actual operationO
.. ~ow concentrations of the copolymer are not . economical, and the operable temperature range is narrow at low concentrationsO If the concentration of the copoly-mer is too high, the viscosity of the solution.rises extreme-.. 15 ly high to inhibit the smooth proceeding of the polymeriza-tion reactionO Hence, it is usually preferred to maintain the concentration of the copolymer at about 50 to about ~: 200 g per liter of the solventO
, ,.~.
Examples of the hydrocarbon solvent are aliphatic ~;; 20 hydrocarbons such as n-hexane, n-heptane, iso-hexane, n-.- pentene, octane, decane and kerosene; alicyclic hydrocarbons ,:: such as cyclohexane or methylcyclohexane, and aromatic hydrocarbons such as benzene, toluene or xyleneO
- ~he suitable amount of the solid titanium catalyst component is 0O0005 to loO millimole, preferably OoOOl to - Ool millimole, calculated as titanium atom, per liter of .
the solvent, and the suitable amount of the organoaluminum ` compound is OoOl to 10 millimoles, preferably 0005 to 1~0 `!,-, millimole, calculated as aluminum, per liter of the solventO
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1~t35995 It is preferred that at this time, the Al/TI mole ratio be ad~usted to at least 1.
The proportion of the -olefin with 5 to lô csrbon atoms to be fed to the polymerization sy6tem, which varies according, for exanple, to the type Or the ~-olefin, the polymerization temperature and the partial pres-sure of ethylene in the polymerization vessel, is O.G5 to 20 moles, prefer-ably 0.10 to 5 moles, per mole of ethylene. Preferably, the polymerization is carried out under elevated pressures of, say, 2 to 100 kg/cm , preferably 15 to 70 kg/cm . The molecular weight of the copolymer is Pdjusted prefer-ably by using hydrogen.
The copolymers of this invention have better transparency, tearresistance and impact resistance than hieh-pressure polyethylene, and are suitable for use as films. ~hese superior properties along with their very good heat-sealability indicate their suitability as packaging films.
Films of these copolymers, whether obtained by a T-aie method or an infla-tion method, have a high level of transparency. The copolymers of this in-vention can also be formed into various shaped articles ~y, for exa~ple, blow molding, in~ection molding, or extrusion molding. Multilayer films can also be prepared by extrusion coating on other films. They can also be used as blends Nith other thermoplastic resins, for example olefin polymers such as polyethylene, polypropylene, poly-l-butene po~y-4-methyl-1-pentene, as ethyl- ~;
ene/Fropylene copolymer, an ethylene/butene copolymer or a prop~lene/l-but-ene copolymer. These other thermoplastic resins can be used in minor amounts, for instance less than 50~ by weight based on the ~eight of the blend, preferably in an amount of less than 40% use of high-pressure poly-ethylene is particularly preferred. ~hey can also be incorporated ~itk pet-roleum resins, waxes, ' - , , , :
" 1085995 -stabilizers, antistatic agents, ultraviolet absorbers, synthetic or natural rubbers, lubricants, inorganic fillers, etcO
~he following examples illustrate the present invention in more detailO
xample 1 Preparation of catalyst:-In a stream of nitrogen, 10 moles of commerciallyavailable anhyd~ous magnesium chloride was suspended in ~0 liters of dehydrated and purified hexane, and with stirring 60 moles of ethanol was added dropwise over the course of 1 hourO The reaction was carried out for 1 hour at room temperatureO To the reaction product was added dropwise 27 moles of diethylalumi.num chloride, and the mixture was stirred for 1 hour at room temperatureO Subsequently., 100 moles of titanium tetrachloride was addedO ~he mixture was heated to 70C, and reacted for 3 hours with stirringO
The resulting solid was separated by decantation, and re-peatedly washed with purified hexane to form a suspension of it in hexaneO The concentration of titanium was determined by titrationO
Polymerisation:-. A 200 liter continuous polymerization reactor ; was charged continuously with 80 liters/hr of dehydrated ` 25 and purified hexane, 32 millimoles/hr of ethylaluminum sesquichloride, and 10 2 millimoles/hr., calculated as titanium, of the carrier-supported catalyst component prepared as aboveO
Into the polymerization reactor, 13 kg/hr of ethylene, 13o 0 kg/hr of 4-methyl-1-pentene, and 100 liters/hr of hydrogen r~
lV85995 were fed simultaneouslyO At a temperature of 145C and a total pressure of 30 kg/cm -G, these monomers were co-polymerized while maintaining the residence ti~e at 1 hou~, and the concentration of the copolymer at 112 g per liter of hexaneO The resulting copolymer had a density of 00922 g/cm3, a melt index of 2024 and a molecular weight <~w Of 2~5607000~ and contained 1302 isobutyl groupsper lO00 carbon atomsO A rapidly cooled press-formed sheet of ; the copolymer having a g~* of 0O09 and a thickness of 70 ;: 10 had an average spherulite size (R) of 1 D 5IID
A film having a width of 350 mm and a thickness of 30~,1. was prepared from the copolymer by a tubular film-forming machine for high-pressure polyethylene (made by .~ Modern Machinery)~ The molding conditions were as follows:
, 15 the resin temperature 180C; the speed of screw rotation " lO0 revolutions per minute; the die diameter 100 mm; and the width of the die slit 0O7 mmO
~he results are shown in ~able 1D
Commercially available high-pressure polyethylenes '`' 20 shown in ~able 4 were molded in the same way as above, and , .
~: the results are shown in ~able 4O (Comparative Examples 7 to ll) D
Example 2 and Comparative Examples 1 to 3 :~ Various ethylene/4-methyl-l-pentene copolymers were prepared under the conditions described in Table l using the titanium catalyst component prepared~in Example 1 D ~he properties of these copolymers are shown in ~able lo ` ~he aluminum catalyst component used in Comparative Example 2 w~s obtained by reacting 005 mole of ethyl alcohol with l mole of triethyl aluminumD
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E~ample 3 Preparation of catalyst:-In a stream of nitrogen,, 10 moles of commercially . available magnesium chloride was suspended in 50 liters of ~' 5 dehydrated and purified hexane, and with stirring, 60 moles of ethanol was added dropwise over the course of 1 hourO The - reaction was then performed for l hour at room temperatureO
;~ To the reaction product was added dropwise 28 moles of diethylaluminum chloride at room temperature~ and the mixture was stirred for 1 hourO Subsequently~ 7 moles of titanium tetrachloride and 7 moles of triethyl aluminum were added~
and the reducing reaction was performed at room temperature ~'. for 4 hours wi-th stirringO ~he solid portion turned light brown which is a color peculiar to trivalent titaniumO ~he ,:.
, 15 titanium concentration of the resulting hexane suspension . ,, ' was determined by titrationO
' Polymerization:-The same continuous polymerization apparatus as used in Example 1 was charged continuously with ~0 Q/hr of hexane, 32 millimoles/hr of ethylaluminum sesquichloride ,. and 102 millimoles/hr~ calculated as titanium, of the supported ,~ catalyst componentO Into the polymerization vessel, 120 5 :. kg/hr of ethylene, lloO kg/hr of 4-methyl-1-pentene and 110 , .
~ Q/hr of hydrogen were continuously fed simultaneouslyO At '' 25 a temperature of 145C and a total pressure of 30 kg/cm2-Gq the monomers were copolymerized while maintaining the ~' residence time at 1 hour~ and the concentration of the co-: polymer at 110 g per liter of the hexaneO me properties ,: of th.e resulting copolymer~ and the properties of its molded " .
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1~85995 products prepared in the same way as in EXample 1 are shown in ~able 20 Ex~mple 4 and Co~ara-tive EYamples 4 and 5 Various ethylene/4-methyl-1-pentene copolymers were prepared under the conditions shown in ~able 2 using the titanium catalyst componen-t prepared in ~xample 30 ~he results are also shown in ~able 20 , ;
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Example 5 _ Ethylene and an a-olefin mixture (~ialene 610, a trademark for a product of Mitsubishi Chemical C01 Ltdo;
mixture of 3509% of l-hexene, 3303% of l-octene and 3008%
of l-decene) were simultaneously fed continuously into a polymerization vessel, and copolymerized under the condi-tions shown in Table 3 using the titanium catalyst component described in EXample 30 The properties of the resulting copolymer and its molded articles prepared in the same way as in Example 1 are shown in Table 30 Example 6 and Comparative Exam~le 6 In the same way as in Example 5, ethylene and an a-olefin mixture (Dialene 124, a trademark for a product ,~, .
of Mitsubishi Chemical CoO, Ltdo; mi~ture consisting of 5606% of l-dodecene and 4304% of l-tetradecene) or l-butene : were continuously polymerizedO The properties of the copoly-mers obtained are shown in Table 30 iO8S995 _ , ~D
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~ his invention relates to ethylene copolymers having unique structural characteristics not described in the literature an~ superior moldability, and to their melt- -shaped articles such as films or sheets having superior transparency, improved tear resistance and improved impact resistance. The ethylene copolymers of this invention have superior improved properties eliminating the unsatis-factory levels of the various properties, such as tear resistance, impact strength and transparency, of high-pressure polyethylene and the unsatisfactory levels of such properties and heat resistance of conventional ethylene copolymers, and exhibit unique structural characteristics not described in the literatureO
High-pressure polyethylene has been considered to have relatively good transparency, and used in the production of melt-shaped articles such as films, sheets and hollow containersO ~ince, however, the high-pressure polyethylene films have unsatisfactory tear strength or . impact strength, and are difficult to use as thin films,they ; 20 have only limited applications~ ~urthermore, films having superior transparency are difficult to obtain by the infla-tion molding of high-pressure polyethyleneO It has been desired therefore to develop olefinic resins having improved : transparency~
Generally, copolymers of ethylene with a-olefins having at least 3 carbon atoms which are produced by using a Ziegler type catalyst have much the same density as high-pressure polyethylene~ and exhibit relatively good mechanical strengthO When produced by using a vanadium-containing - ` ~08S99S
Ziegler-type catalyst, such copolymers have relatively low melting points, and have unsatisfactory thermal resistanceO
In the presence of a titanium-containing Ziegler-type catalyst, copolymers of ethylene with -olefins having at least 3 carbon atoms are obtained which have poor transparencyO
In the production of such copolymers catalyzed by the titanium-containing Ziegler catalysts, copolymers having much the same transparency as high-pressure polyethylene could be produced by properly modifying the polymerization.
10 conditions or the catalysts (disclosed, for example~ in Canadian Patent 986~250 assigned to Mitsui Petrochemical Industries, Ltdo~ issued on March 23~ 1976; correspondirLg to British Patent 1~355~245 published on October 2 ~ 1974)o It has been impossible in practice, however, to provide .: 15 ethylene copolymers having superior tear resistance and impact resistance which eliminate the unsatisfactory levels of these properties in high-pressure polyethylene films, and exhibit better transparencyO ~he above-cited Canadian Patent does not specifically disclose copolymers of ethylene . 20 with -olefins having 5 to 18 carbon atomsO
We have worked extensively in an attempt to develop ethylene copolymers having the aforesaid improved properties, and consequently found that there exist ethylene copolymers : consisting essentially of ethylene and a-olefins with 5 to 18 carbon atoms which have unique structural characteristics : not described in the literature and which exhibit the afore-said improved propertiesO
It is an object of this invention therefore to provide an ethylene copolymer having unigue structural . - 3 -;
`' - - ~
~08S995 characteristics not described in the literature and -the aforesaid improved propertiesO
~ he above and other objects and advantages of the invention will become more apparent from the following descriptionO
~ he ethylene copolymers of this invention consist-ing essentially of ethylene and -olefins with 5 to 18 carbon atoms have the structural characteristic that as compared with ethylene copolymers described in the litera-ture and being available on the market, they have an exceed-ingly high weight average molecular weight, ~M~ w' (deter-mined by the light scattering method) even when they have the same intrinsic viscosities (~) as the conventional ethylene copolymersO In the present invention, this characteris-tic i.s defined as follows:
(iv) g~ is 0005 - 0078, preferably 0005-00 5 o (~) is the intrinsic viscosity of the copolymer of this invention; and (~)~ is the intrinsic viscosity of a linear polyethylene having the same weight average molecular weight (determined by the light scattering method) as the copolymer of this inventionO
'~ is determined in decalin at 135Co ~he intrinsic viscosity (~)~ of a linear poly-25 ethylene having the same weigh-t average molecular weight ~ w (determined by the light scattering method as that of the copolymer of this invention having the intrinsic viscosity '~) is calculated in accordance with the follow-ing equationO
1~8S995 ,r,)~=5029 x 10 4 x <M~OWo7l3 The g~* values much s~aller than 1 show the structural characteristic that many long-chain branchings e-xist in the copolymer in addition to short-chain branchings derived from the C5-Cl~ a-olefin copolymerized with ethylene (for example, isobutyl branchings when the a-olefin is 4-methyl-l-pentene)O That the ethylene copolymers of this invention have a grl* value of 0005 to Oo789 preferably 0005 to 005 shows that the e-thylene copolymers of this inven-tion are very different in structure from conventionalethylene copolymers having substantially only short-chain branchings and a grl* value of 0080 to 1 n Oo ~he transparency of the conventional ethylene copolymers having a gr* value of 0080 to loO is at best equivalent to that of the high-pressure po]yethylene, and fre~uently inferior to the latter.
In addition to the aforesaid structural character-istic (iv), the ethylene copolymers of this invention have the following structural characteristics (i) to (iii)o (i) They have a density of 0090 to 0094 g/cm39 preferably 0091 to 00935 g/cm30 (ii) They have an intrinsic viscosi-ty (~) of 008 to 400 dl/g9 preferably loO to 300 dl/go (iii) ~hey have a maximum melting point, deter-mined by differen-tial thermal analysis (DSC), of 115 to 130C9 and in many cases 115 to 125Co ~he maximum melting point, as referred to in (iii) above9 denotes the highest melting point among two or more melting points (peaks) which usually exist in the DSC endo-thermic curve of the ethylene copolymer of this inventionO
. - 5 -:
- . , .
1:~85995 In order for the copolymer of this invention to have good transparency~ it should have a density of not more than 0094 g/cm3, preferab1y no-t more than 0~935 g/cm30 On the other hand~ to secure superior mechanical character-istics, and freedom from stickiness1 the copolymer of this invention should have a density of at least 0.90 g/Gm3 and preferably at least Oo91 g/cm3~
~he instrinsic viscosity (~) of the copolymer of this invention is 008 to 4~0 dl/g, preferably loO -to 300 dl/g, and for use as films~ its suitable intrinsic viscosity ~) is loO to 300 dl/g Preferably9 the ethylene copolymers of this invention consisting essentially of ethylene and a-olefins with 5 to 18 carbon atoms should have the following character-istics (v) to (vii) in addition to the characteristics (ij to (ivj~
(v) ~ey have an average spherulite size~ deter-mined by the small angle laser scattering method, of not more than 6u, preferably not more than 4~10 (vi) Ihey have two or more melting points deter-mined by differential thermal analysis (DSC)o (Vii) Ihey have a standard deviation (~) of the distribution of ethylene content of not more than 3%, preferably l 'G0 205 %0 ~he characteristics (v) means that -the ethylene copolymers of this invention have much smalle~ average spherulite sizes than the conventional ethylene copolymers having the same composition of constituent units~
~he average spherulite size (R) is determined by ' the small angle laser scattering method using a 70ll-thick press sheet which is obtained by hea-ting the copolymer to 220C and pressing it with water cooling at a pressure of 100 kg/cm --Go Specificall~, using a small angle laser scattering device 5 an Hv scattering pattern is obtained when the polarizer in -the incident beam is vertical and -the analyser in the scattered beam is horizontalO Ihen, the scattering angle ~m which gives the maximum value in the distribution of the scattering intensity in the scatter-ing pattern is determined~ a~d the spherulite size (R) is obtained from the following equationO
4~* R sin (~)= 400 (R~ So Stein's equation; see J0 Applo l~hys~
VolO 31, NoO 11, 1873 (1960) ) The structural characteristic (vi) means that the ethylene copolymers of this invention include two or more crystal typesO For example, as shown in Figo 1, a copolymer of ethylene with 4-methyl-1-pentene of this invention which has a gT~* of 0013jan (rl) of 1042 dl/g, a density of 00926 g/cm3 and a maximum melting point in DSC of 122C has melt-ing points at 10&C~ 119C and 122C in its DSC endothermic curve. This shows that ir this example, three cry.stal types existO :For comparison~ ~igo 2 shows the DSC endothermic curve of a comparative copolymer of ethylene with 4 methyl-l--pentene having a grl* f 0o83~ an ~rl) of lo 53 dl/g~ a density of Oo927 g/cm3 and a melting point of 125Co In this example~ only one melting point is found at 125C, and this shows that only one crystal t~7pe exists The characte:ristic (vii) shows that the e-thylene ~ 7 --copolymers of this invention have a very naIrow distribution of the content of ethyleneO ~he standard deviation (~) is calculated from the following equationO
_ , _ 5 = /~ (Xi - X-)2~
~' 5 wherein xi is the content of ethylene, x is the average of xi values, and x = ~ixiwi 9 a the proportion by weightO
~or example 9 the copolymer shown in ~igo 1 has a standard deviation (~) of 1035 mole%9 and the copolymer shown in Figo 2 shows a standard deviation (a) of 3072 mole%0 Fractionation of the copolymer of this invention according to chemical composition is performed by fraction-ating it into five fractions by the Soxhlet extraction method~ and the number of shor-t-chain branchings derived ~ 15 from the a-olefin is determined by infrared absorption ; spectroscopy. ~he five fractions are as follows:
.. (1) A fraction soluble in p-xylene at room temper-. ature - (2) A fraction extracted with boiling n-hexane ; 20 (3) ~ fraction extracted with boiling benzene (4) A fraction extracted with boiling n-heptane (5) A fraction extracted with boiling p-xylene Examples of the a-olefin comonomer which constitutes the copolymer of this invention are 1-pentene, l-hexene 9 l-octene, l-decene, l-dodecene, 1-tetradecene1 l-octadecene 9 3-methyl-1-butene~ 3-methyl-1-pentene, 4-methyl-1-pentene, 3-me-thyl-1-hexene, 4-methyl-1-hexene, 5-methyl-1-hexene, 3-methyl-1-heptene, 5-methyl-1-heptene, and mixtures of :, . . . . .
10~5995 theseO Preferred ~-olefins are thos~ containing 6 to 12 carbon atoms 9 above all l-hexene 9 l-octene., l-decene~
3-~nethyl-1-pentene 9 4-methyl-1-pentene 9 5-methyl-l~hexene and 5-methyl-1-hepteneO 4-Methyl-l-pentene is especially preferredO
Ihe proportion of the comonomer to be copolymerized can be varied as desired according -to the type of the co-monomerO To afford a copolymer having the density specified by (i) above 9 the suitable proportion of the comonomer is usually about 1 to about 30 % by weight, preferably about 3 to about 20% by weight, based on the weight of the copolymerO
When an a-olefin having not more than 4 carbon atoms is se-lected as the comonomer1 a copolymer having su~erior mechanical strength and/or transparency specified in the present inven-tion cannot be obtainedO
In the production of the ethylene copolymer of hisinvention, the selection of the catalyst and the polymeriza-tion conditions is importantO
Preferably9 the catalyst to be used is a catalyst composed of a solid titanium catalyst component and an organo-aluminum compoundO The use of a catalyst composed of a solid~
magnesium-containing titanium catalyst component and an : organoaluminum compound is more preferredO Especially preferred catalysts are those in which the solid titanium 2S catalyst component is the one which is obtained by supporting titanium on a compound containing a magnesium halide 5 especially magnesium chloride, and which has a C~/Ti weight ratio of 5 to 150 9 an Mg/Ti mole ratio of 3 to 90, and a surface area of at least 70 m2/g 9 preferably more than 150 l~S9 9S
m /g~ Of these catalysts composed of such preferred solid titanium catal.yst components and organoalminum compounds, especially suitable ones are the catalysts di~closed in British Patent 1,433,537 published on ~ugust 25, 1976 (corresponding to German O~S 2346471 laid open on April 18, 1974) and German OLS 2461677 laid open on July lO, 19750 ~hese p~tents do not give a specific example of copolymer-izing ethylene with an ~-olefin having 5 to 18 carbon atomsO
A solid titanium catalys-t component which is disclosed in the cited British Patent 1~433,537 and has the surface area specified hereinabove can be synthesized, for example~ by adding about 3 to about 7 moles of a lower alcohol such as ethanol to l mole of magnesium chloride, reacting the adduct with an organoaluminum compound in an 5 amount sufficient to react with the alcohol, and then reacting the resulting product with titanium tetrachloride or its solution in an inert hydrocarbon~
~he solid titanium catalyst component disclosed in the German 0~ 2461677 can be prepared by reacting the solid titanium catalys-t component obtained by the method of the British Patent 1,433,537 further with small amounts of titanium tetrachloride and an organoaluminum compoundO
~ he solid titanium catalyst components obtained by these two methods contain titanium, magnesium, halogen 25 and aluminum, and a surface area of at least 70 m2/g, preferably more than 150 m2/g but not exceeding 500 m2/gO
In addition to the selec-tion of the titanium catalyst componen-t~ the selection of -thc- organoaluminum compound as another catalyst component is of importance ~.
' - 10 -` - -~08599S
in obtaining the copolymers of this inventionO Preferred organoaluminum compounds are organoaluminum halides of the empirical formula RnA~X3_n wherein R represents a hydro-carbon group such as an alkyl group wi-th l to 12 carbon atoms, X represents a halide such as chloride, bromide, iodide, and l~-n~205, preferably lO~=n<-2DO9 especially prefer-ably lO~=n<1080 A mixture of two or more such organoaluminum halides can also be used if it has an average composition within the above formulaO preferred species are alkylaluminum sesquichlorides and dialkylaluminum chlorideO ~he alkyl-aluminum sesquichloride and mixtures thereof with dialkyl-aluminum chloride are especially preferredO
When a trialkylaluminum, dialkylaluminum hydride, dialkylaluminum alkoxide or alkylaluminum alkoxyhydride~
all of which are frequently used in the poly~erization of ethylene, is used as the organoaluminum compound, the co-polymers obtained usually have a g~* of at least 0080, a standz.rd deviation (~) of atleast 300 mole%, an average spherulite size (R) of not more than 7u9 and one or two melt-ing pointsO
In the production of the ethylene copolymers ofthis invention9 the selection of the copolymerization con-;. ditions is important besides the selection of the catalyst~
Copolymerization should be carried out at a temperature above the melting point of the copolymer prefer-ably in the co-presence of a hydrocarbon solvent, or using - the monomer itself as a solvent, and under such conditions that the solvent and the resulting copolymer form a homogene-ous phaseO Preferably, the polymerization is carried out --_ ~.V~3S995 continuously while maintaining the concentrations of the monomers (ethylene and the comonomer) constantO ~he conditions which will give a homogeneous phase of the solvent and the copolymer vary according, for example, to the type of the solvent, the concentratlons (or pressures) of the monomers (ethylene and the comono~er) or hydrogen, the polymerization temperature and the molecular weight (intrinsic viscosity) of the copolymerO It is advisable therefore to set such conditions by preliminary experimentsO
As an example, Figo 3 shows the precipitation.
point in hexane of an ethylene/4-methyl-l-pentene copolymer having an intrinsic viscosity !~) of 1042 dl/g, a density of 00926 g/cm3, a 4-methyl-l-pentne content of 209 mole%
and melting points of 108C, 119C and 122C~ ~he axis of abscissas represents the total pressure (the total pressure of hexane and ethylene, and optionally 4-methyl-1-pentene, in the case of a gaseous phase), and the axis of ordinates represents the temperature (precipitation temperature) at which the polymerization system becomes a heterogeneous phaseO Curve (l) shows precipitation points in a mixture of hexane and 4-methyl-l-pentene (in a ratio of 85:15) with a copolymer concentration of 150 g/l; curve (2), precipita-tion points in the same mixture with a copolymer concentra-tion of lO0 g/~; and curve (3), precipitation points in the same mixture with a copolymer concentration of 50 g/~0 Curve (4) shows precipitation points in hexane with a co-polymer concentration of 50 g/~0 At temperatures higher than the precipita-tion points, a heterogeneous phase resultsO
It can be seen from Figo 3 that when the copolymer .
10~3S995 ;
concentration is 50 to 150 g/~g the temperature range within which pol~merization c~n be carried out in a homo-geneous phase is broader with higher concentration of the copolymer and higher pressuresO It is also clear from it that the operable temperature range differs according to the amounts of the monomers (ethylene and the comonomer)0 ~ igo 3 represents one model, and in an actual polymerization system, the temperature range for attain-ing a hom~geneous phase is set experimentally prior to actual operationO
.. ~ow concentrations of the copolymer are not . economical, and the operable temperature range is narrow at low concentrationsO If the concentration of the copoly-mer is too high, the viscosity of the solution.rises extreme-.. 15 ly high to inhibit the smooth proceeding of the polymeriza-tion reactionO Hence, it is usually preferred to maintain the concentration of the copolymer at about 50 to about ~: 200 g per liter of the solventO
, ,.~.
Examples of the hydrocarbon solvent are aliphatic ~;; 20 hydrocarbons such as n-hexane, n-heptane, iso-hexane, n-.- pentene, octane, decane and kerosene; alicyclic hydrocarbons ,:: such as cyclohexane or methylcyclohexane, and aromatic hydrocarbons such as benzene, toluene or xyleneO
- ~he suitable amount of the solid titanium catalyst component is 0O0005 to loO millimole, preferably OoOOl to - Ool millimole, calculated as titanium atom, per liter of .
the solvent, and the suitable amount of the organoaluminum ` compound is OoOl to 10 millimoles, preferably 0005 to 1~0 `!,-, millimole, calculated as aluminum, per liter of the solventO
..... .
:;
:
1~t35995 It is preferred that at this time, the Al/TI mole ratio be ad~usted to at least 1.
The proportion of the -olefin with 5 to lô csrbon atoms to be fed to the polymerization sy6tem, which varies according, for exanple, to the type Or the ~-olefin, the polymerization temperature and the partial pres-sure of ethylene in the polymerization vessel, is O.G5 to 20 moles, prefer-ably 0.10 to 5 moles, per mole of ethylene. Preferably, the polymerization is carried out under elevated pressures of, say, 2 to 100 kg/cm , preferably 15 to 70 kg/cm . The molecular weight of the copolymer is Pdjusted prefer-ably by using hydrogen.
The copolymers of this invention have better transparency, tearresistance and impact resistance than hieh-pressure polyethylene, and are suitable for use as films. ~hese superior properties along with their very good heat-sealability indicate their suitability as packaging films.
Films of these copolymers, whether obtained by a T-aie method or an infla-tion method, have a high level of transparency. The copolymers of this in-vention can also be formed into various shaped articles ~y, for exa~ple, blow molding, in~ection molding, or extrusion molding. Multilayer films can also be prepared by extrusion coating on other films. They can also be used as blends Nith other thermoplastic resins, for example olefin polymers such as polyethylene, polypropylene, poly-l-butene po~y-4-methyl-1-pentene, as ethyl- ~;
ene/Fropylene copolymer, an ethylene/butene copolymer or a prop~lene/l-but-ene copolymer. These other thermoplastic resins can be used in minor amounts, for instance less than 50~ by weight based on the ~eight of the blend, preferably in an amount of less than 40% use of high-pressure poly-ethylene is particularly preferred. ~hey can also be incorporated ~itk pet-roleum resins, waxes, ' - , , , :
" 1085995 -stabilizers, antistatic agents, ultraviolet absorbers, synthetic or natural rubbers, lubricants, inorganic fillers, etcO
~he following examples illustrate the present invention in more detailO
xample 1 Preparation of catalyst:-In a stream of nitrogen, 10 moles of commerciallyavailable anhyd~ous magnesium chloride was suspended in ~0 liters of dehydrated and purified hexane, and with stirring 60 moles of ethanol was added dropwise over the course of 1 hourO The reaction was carried out for 1 hour at room temperatureO To the reaction product was added dropwise 27 moles of diethylalumi.num chloride, and the mixture was stirred for 1 hour at room temperatureO Subsequently., 100 moles of titanium tetrachloride was addedO ~he mixture was heated to 70C, and reacted for 3 hours with stirringO
The resulting solid was separated by decantation, and re-peatedly washed with purified hexane to form a suspension of it in hexaneO The concentration of titanium was determined by titrationO
Polymerisation:-. A 200 liter continuous polymerization reactor ; was charged continuously with 80 liters/hr of dehydrated ` 25 and purified hexane, 32 millimoles/hr of ethylaluminum sesquichloride, and 10 2 millimoles/hr., calculated as titanium, of the carrier-supported catalyst component prepared as aboveO
Into the polymerization reactor, 13 kg/hr of ethylene, 13o 0 kg/hr of 4-methyl-1-pentene, and 100 liters/hr of hydrogen r~
lV85995 were fed simultaneouslyO At a temperature of 145C and a total pressure of 30 kg/cm -G, these monomers were co-polymerized while maintaining the residence ti~e at 1 hou~, and the concentration of the copolymer at 112 g per liter of hexaneO The resulting copolymer had a density of 00922 g/cm3, a melt index of 2024 and a molecular weight <~w Of 2~5607000~ and contained 1302 isobutyl groupsper lO00 carbon atomsO A rapidly cooled press-formed sheet of ; the copolymer having a g~* of 0O09 and a thickness of 70 ;: 10 had an average spherulite size (R) of 1 D 5IID
A film having a width of 350 mm and a thickness of 30~,1. was prepared from the copolymer by a tubular film-forming machine for high-pressure polyethylene (made by .~ Modern Machinery)~ The molding conditions were as follows:
, 15 the resin temperature 180C; the speed of screw rotation " lO0 revolutions per minute; the die diameter 100 mm; and the width of the die slit 0O7 mmO
~he results are shown in ~able 1D
Commercially available high-pressure polyethylenes '`' 20 shown in ~able 4 were molded in the same way as above, and , .
~: the results are shown in ~able 4O (Comparative Examples 7 to ll) D
Example 2 and Comparative Examples 1 to 3 :~ Various ethylene/4-methyl-l-pentene copolymers were prepared under the conditions described in Table l using the titanium catalyst component prepared~in Example 1 D ~he properties of these copolymers are shown in ~able lo ` ~he aluminum catalyst component used in Comparative Example 2 w~s obtained by reacting 005 mole of ethyl alcohol with l mole of triethyl aluminumD
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~)8S99S
E~ample 3 Preparation of catalyst:-In a stream of nitrogen,, 10 moles of commercially . available magnesium chloride was suspended in 50 liters of ~' 5 dehydrated and purified hexane, and with stirring, 60 moles of ethanol was added dropwise over the course of 1 hourO The - reaction was then performed for l hour at room temperatureO
;~ To the reaction product was added dropwise 28 moles of diethylaluminum chloride at room temperature~ and the mixture was stirred for 1 hourO Subsequently~ 7 moles of titanium tetrachloride and 7 moles of triethyl aluminum were added~
and the reducing reaction was performed at room temperature ~'. for 4 hours wi-th stirringO ~he solid portion turned light brown which is a color peculiar to trivalent titaniumO ~he ,:.
, 15 titanium concentration of the resulting hexane suspension . ,, ' was determined by titrationO
' Polymerization:-The same continuous polymerization apparatus as used in Example 1 was charged continuously with ~0 Q/hr of hexane, 32 millimoles/hr of ethylaluminum sesquichloride ,. and 102 millimoles/hr~ calculated as titanium, of the supported ,~ catalyst componentO Into the polymerization vessel, 120 5 :. kg/hr of ethylene, lloO kg/hr of 4-methyl-1-pentene and 110 , .
~ Q/hr of hydrogen were continuously fed simultaneouslyO At '' 25 a temperature of 145C and a total pressure of 30 kg/cm2-Gq the monomers were copolymerized while maintaining the ~' residence time at 1 hour~ and the concentration of the co-: polymer at 110 g per liter of the hexaneO me properties ,: of th.e resulting copolymer~ and the properties of its molded " .
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1~85995 products prepared in the same way as in EXample 1 are shown in ~able 20 Ex~mple 4 and Co~ara-tive EYamples 4 and 5 Various ethylene/4-methyl-1-pentene copolymers were prepared under the conditions shown in ~able 2 using the titanium catalyst componen-t prepared in ~xample 30 ~he results are also shown in ~able 20 , ;
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Example 5 _ Ethylene and an a-olefin mixture (~ialene 610, a trademark for a product of Mitsubishi Chemical C01 Ltdo;
mixture of 3509% of l-hexene, 3303% of l-octene and 3008%
of l-decene) were simultaneously fed continuously into a polymerization vessel, and copolymerized under the condi-tions shown in Table 3 using the titanium catalyst component described in EXample 30 The properties of the resulting copolymer and its molded articles prepared in the same way as in Example 1 are shown in Table 30 Example 6 and Comparative Exam~le 6 In the same way as in Example 5, ethylene and an a-olefin mixture (Dialene 124, a trademark for a product ,~, .
of Mitsubishi Chemical CoO, Ltdo; mi~ture consisting of 5606% of l-dodecene and 4304% of l-tetradecene) or l-butene : were continuously polymerizedO The properties of the copoly-mers obtained are shown in Table 30 iO8S995 _ , ~D
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Claims (10)
1. A copolymer consisting essentially of ethylene and an .alpha.-olefin with 5 to 18 carbon atoms, said copolymer having (i) a density of 0.90 to 0.94 g/cm3, (ii) an intrinsic viscosity (n) of 0.8 to 4.0 dl/g, (iii) a maximum melting point, determined by differential thermal analysis, of 115 to 130°C, and (iv) a gn*(=[n]/[n]?) value of 0.05 to 0.78, in which formula [n] is the intrinsic viscosity of the copolymer and [n]? is the intrinsic viscosity of a linear polyethylene having the same weight average molecular weight determined by the light scattering method as said copolymer.
2. The copolymer of claim 1 which has (v) an average spherulite size, determined by the small angle laser scatter-ing method, of not more than 6 µ.
3. The copolymer of claim 1 which has (vi) two or more melting points determined by differential thermal analysis.
4. The copolymer of claim 1 which has (vii) a standard deviation (?) of the distribution of ethylene content of not more than 3 mole%.
5. The copolymer of claim 1 wherein the gn* value is 0.05 to 0.5.
6. The copolymer of claim 1 wherein the .alpha.-olefin has 6 to 12 carbon atoms.
7. The copolymer of claim 1 wherein the .alpha.-olefin is at least one member selected from the group consisting of 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-octadecene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3-methyl-1-hexene, 4-methyl-1-hexene, 5-methyl-1-hexene, 3-methyl-1-heptene and 5-methyl-1-heptene.
8. The copolymer of claim 1 wherein the density is 0.91 to 0.935 g/cm3.
9. The copolymer of claim 1 wherein the intrinisic viscosity is 1.0 to 3.0 dl/g.
10. A blend of the copolymer of claim 1 with polyethylene.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP52007315A JPS5952643B2 (en) | 1977-01-27 | 1977-01-27 | ethylene copolymer |
| JP7315/77 | 1977-01-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1085995A true CA1085995A (en) | 1980-09-16 |
Family
ID=11662552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA295,766A Expired CA1085995A (en) | 1977-01-27 | 1978-01-26 | Ethylene copolymers |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US4205021A (en) |
| JP (1) | JPS5952643B2 (en) |
| AT (1) | AT365210B (en) |
| CA (1) | CA1085995A (en) |
| DE (1) | DE2803598C2 (en) |
| FR (1) | FR2378804A1 (en) |
| GB (1) | GB1586533A (en) |
| IT (1) | IT1093402B (en) |
| NL (1) | NL173755B (en) |
| PT (1) | PT67555B (en) |
| TR (1) | TR19823A (en) |
Families Citing this family (150)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1157617A (en) * | 1977-12-14 | 1983-11-29 | Milton L. Weiner | Oriented polypropylene with linear low density polyethylene copolymer coating |
| JPS5512008A (en) * | 1978-06-29 | 1980-01-28 | Mitsui Petrochemical Ind | Packing laminate sack |
| IT1110494B (en) * | 1978-08-02 | 1985-12-23 | Montedison Spa | ETHYLENE POLYMERS AND PROCEDURE FOR THEIR PREPARATION |
| US4303710A (en) * | 1978-08-16 | 1981-12-01 | Mobil Oil Corporation | Coextruded multi-layer polyethylene film and bag construction |
| US4399180A (en) * | 1978-09-15 | 1983-08-16 | Mobil Oil Corporation | Coextruded thermoplastic stretch-wrap |
| JPS6011925B2 (en) | 1978-10-18 | 1985-03-29 | 三井化学株式会社 | Method for producing ethylene copolymer |
| JPS603323B2 (en) * | 1978-12-11 | 1985-01-28 | 三井化学株式会社 | Polymerization method of olefins |
| JPS56122807A (en) * | 1980-03-04 | 1981-09-26 | Mitsubishi Petrochem Co Ltd | Polymerization of ethylene |
| JPS5628826A (en) * | 1979-08-20 | 1981-03-23 | Kohjin Co Ltd | Thermoshrinking film and manufacturing thereof |
| US4340641A (en) * | 1979-10-05 | 1982-07-20 | Mobil Oil Corporation | Heat sealable packaging film comprising propylene polymer substrate and a surface layer blend of ethylene copolymer and propylene copolymer |
| US4339493A (en) * | 1979-10-05 | 1982-07-13 | Mobil Oil Corporation | Heat sealable packaging film comprising propylene polymer substrate and olefin surface layer blend of polybutene-1 and an ethylene or a propylene copolymer |
| US4339496A (en) * | 1979-10-05 | 1982-07-13 | Mobil Oil Corporation | Heat sealable packaging film comprising propylene polymer substrate and a surface layer blend of ethylene copolymer and propylene copolymer |
| US4340640A (en) * | 1979-10-05 | 1982-07-20 | Mobil Oil Corporation | Heat sealable packaging film comprising propylene polymer substrate and a surface layer blend of ethylene copolymer and propylene copolymer |
| JPS5764551A (en) * | 1980-10-09 | 1982-04-19 | Mitsui Petrochemical Ind | Composite film |
| JPS5778408A (en) * | 1980-11-05 | 1982-05-17 | Mitsui Petrochem Ind Ltd | Production of ethylene copolymer |
| US4346834A (en) * | 1980-11-18 | 1982-08-31 | Mobil Oil Corporation | Thermoplastic carrying bag with polyolefin resin blend |
| JPS57105411A (en) * | 1980-12-23 | 1982-06-30 | Mitsubishi Petrochem Co Ltd | Ethylenic copolymer |
| JPS57123053A (en) * | 1981-01-23 | 1982-07-31 | Mitsui Petrochemical Ind | Composite film |
| JPS6036217B2 (en) * | 1981-04-07 | 1985-08-19 | 東亜燃料工業株式会社 | Modified polyethylene composition |
| CA1174423A (en) * | 1981-04-23 | 1984-09-18 | Ralph C. Golike | Shrink films of ethylene/alpha-olefin copolymers |
| US4597920A (en) * | 1981-04-23 | 1986-07-01 | E. I. Du Pont De Nemours And Company | Shrink films of ethylene/α-olefin copolymers |
| US4367256A (en) * | 1981-05-15 | 1983-01-04 | Union Carbide Corporation | Cling-wrap polyethylene film |
| FR2509742B1 (en) * | 1981-07-15 | 1985-11-15 | Charbonnages Ste Chimique | |
| US4349648A (en) * | 1981-07-31 | 1982-09-14 | Union Carbide Corporation | Catalyst composition for copolymerizing ethylene |
| JPS5863334A (en) * | 1981-10-14 | 1983-04-15 | 三井化学株式会社 | Freely bendable structure for irrigation |
| US4464426A (en) * | 1981-11-03 | 1984-08-07 | Union Carbide Corporation | Multilayer film having a layer of low pressure, low density heterogeneous ethylene copolymers |
| US4513038A (en) * | 1981-11-03 | 1985-04-23 | Union Carbide Corporation | Multilayer film having a layer of low pressure, low density heterogeneous ethylene copolymers |
| FR2519007B1 (en) * | 1981-12-24 | 1985-12-27 | Charbonnages Ste Chimique | MODIFIED COPOLYMERS OF ETHYLENE AND AT LEAST ONE A-OLEFIN AND PROCESS FOR THEIR PREPARATION |
| IT1210855B (en) * | 1982-02-12 | 1989-09-29 | Assoreni Ora Enichem Polimeri | LINEAR STRUCTURE ETHYLENE POLYMERS AND PROCESSES FOR THEIR PREPARATION. |
| US4532189A (en) * | 1982-02-19 | 1985-07-30 | W. R. Grace & Co., Cryovac Div. | Linear polyethylene shrink films |
| US4418114A (en) * | 1982-04-29 | 1983-11-29 | Mobil Oil Corporation | Coextruded thermoplastic stretch-wrap |
| FR2529563B1 (en) * | 1982-06-30 | 1986-01-24 | Charbonnages Ste Chimique | COMPOSITIONS OF POLYPROPYLENE AND ETHYLENE / A-OLEFIN COPOLYMERS AND THEIR APPLICATION IN THE MANUFACTURE OF SINGLE-ORIENTED YARNS |
| FR2532649B1 (en) * | 1982-09-07 | 1986-08-29 | Bp Chimie Sa | COPOLYMERIZATION OF ETHYLENE AND HEXENE-1 IN A FLUIDIZED BED |
| US4588650A (en) * | 1982-09-29 | 1986-05-13 | The Dow Chemical Company | Olefin polymer stretch/cling film |
| JPS5966405A (en) * | 1982-10-07 | 1984-04-14 | Mitsui Petrochem Ind Ltd | Ethylenic copolymer film |
| JPS5975910A (en) * | 1982-10-25 | 1984-04-28 | Mitsui Petrochem Ind Ltd | Ethylene copolymer |
| JPS5975906A (en) * | 1982-10-25 | 1984-04-28 | Mitsui Petrochem Ind Ltd | Ethylene/alpha-olefin copolymer |
| JPS5975909A (en) * | 1982-10-25 | 1984-04-28 | Mitsui Petrochem Ind Ltd | Ethylene/alpha-olefin copolymer resin |
| US4598128A (en) * | 1983-03-14 | 1986-07-01 | Phillips Petroleum Company | Polymer composition and preparation method |
| US4485217A (en) * | 1983-04-13 | 1984-11-27 | Mobil Oil Corporation | Method for reducing shrinkage of injection molded linear low density polyethylene |
| US4792595A (en) * | 1983-06-15 | 1988-12-20 | Exxon Research & Engineering Co. | Narrow MWD alpha-olefin copolymers |
| US4540753A (en) * | 1983-06-15 | 1985-09-10 | Exxon Research & Engineering Co. | Narrow MWD alpha-olefin copolymers |
| US4959436A (en) * | 1983-06-15 | 1990-09-25 | Exxon Research And Engineering Co. | Narrow MWD alpha-olefin copolymers |
| FI68632C (en) * | 1983-06-22 | 1985-10-10 | Neste Oy | FOER FARING FRAMSTAELLNING AV SAMPOLYMER AV ETEN OCH LANGKEDJADE ALFA-OLEFINER |
| JPS6052945U (en) * | 1983-09-16 | 1985-04-13 | 山陽国策パルプ株式会社 | release paper |
| JPS6088016A (en) * | 1983-10-21 | 1985-05-17 | Mitsui Petrochem Ind Ltd | Ethylene copolymer |
| US4617241A (en) * | 1984-01-23 | 1986-10-14 | W. R. Grace & Co., Cryovac Div. | Linear polyethylene stretch/shrink films |
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-
1977
- 1977-01-27 JP JP52007315A patent/JPS5952643B2/en not_active Expired
-
1978
- 1978-01-18 US US05/870,365 patent/US4205021A/en not_active Expired - Lifetime
- 1978-01-20 PT PT67555A patent/PT67555B/en unknown
- 1978-01-25 NL NLAANVRAGE7800906,A patent/NL173755B/en not_active Application Discontinuation
- 1978-01-25 AT AT0054678A patent/AT365210B/en not_active IP Right Cessation
- 1978-01-26 CA CA295,766A patent/CA1085995A/en not_active Expired
- 1978-01-26 GB GB3267/78A patent/GB1586533A/en not_active Expired
- 1978-01-26 FR FR7802181A patent/FR2378804A1/en active Granted
- 1978-01-26 IT IT19674/78A patent/IT1093402B/en active
- 1978-01-27 DE DE2803598A patent/DE2803598C2/en not_active Expired
- 1978-01-27 TR TR19823A patent/TR19823A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| AT365210B (en) | 1981-12-28 |
| PT67555B (en) | 1979-06-18 |
| ATA54678A (en) | 1981-05-15 |
| DE2803598C2 (en) | 1986-10-09 |
| JPS5392887A (en) | 1978-08-15 |
| NL173755B (en) | 1983-10-03 |
| US4205021A (en) | 1980-05-27 |
| FR2378804A1 (en) | 1978-08-25 |
| IT1093402B (en) | 1985-07-19 |
| IT7819674A0 (en) | 1978-01-26 |
| PT67555A (en) | 1978-02-01 |
| FR2378804B1 (en) | 1980-10-17 |
| DE2803598A1 (en) | 1978-08-03 |
| JPS5952643B2 (en) | 1984-12-20 |
| TR19823A (en) | 1980-01-24 |
| GB1586533A (en) | 1981-03-18 |
| NL7800906A (en) | 1978-07-31 |
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