CA1138148A - Polyethylene composition and process for producing the same - Google Patents
Polyethylene composition and process for producing the sameInfo
- Publication number
- CA1138148A CA1138148A CA000358085A CA358085A CA1138148A CA 1138148 A CA1138148 A CA 1138148A CA 000358085 A CA000358085 A CA 000358085A CA 358085 A CA358085 A CA 358085A CA 1138148 A CA1138148 A CA 1138148A
- Authority
- CA
- Canada
- Prior art keywords
- molecular weight
- polyethylene
- polymerization
- composition
- average molecular
- 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
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 64
- -1 Polyethylene Polymers 0.000 title claims abstract description 63
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 63
- 239000000203 mixture Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 86
- 239000003054 catalyst Substances 0.000 claims description 18
- 150000002902 organometallic compounds Chemical class 0.000 claims description 5
- 150000003623 transition metal compounds Chemical class 0.000 claims description 3
- 230000000704 physical effect Effects 0.000 abstract description 17
- 239000000155 melt Substances 0.000 abstract description 7
- 229920000642 polymer Polymers 0.000 description 38
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 19
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 14
- 239000005977 Ethylene Substances 0.000 description 14
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 238000009826 distribution Methods 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 238000000071 blow moulding Methods 0.000 description 7
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000011949 solid catalyst Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 230000006353 environmental stress Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 150000002901 organomagnesium compounds Chemical class 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- WPWHSFAFEBZWBB-UHFFFAOYSA-N 1-butyl radical Chemical compound [CH2]CCC WPWHSFAFEBZWBB-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- 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
- C08L23/06—Polyethene
-
- 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
- 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
-
- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A polyethylene composition comprising a mixture of three kinds of polyethylenes (A), (B) and (C) characterized in that:
(i) the viscosity average molecular weight of (A) is 1,000-100,000, the viscosity average molecular weight of (B) is 100,000-1,000,000, the viscosity average molecular weight of (C) is 400,000-6,000,000, the molecular weight ratio of (B) to (A), i.e. B/A, is 2-200 and the molecular weight ratio of (C) to (B), i.e. C/B, is 1.5 or more.
(ii) the mixing ratio of (A) to (B) is 30/70 to 70/30 and the mixing ratio of (C) is 1-10% by weight based on the total composition, and (iii) the melt index of the composition is 0.001-1, and a process for producing said composition. This polyethylene composition is excellent in physical properties in that it has an appropriate die swell, a high melt tension and an excellent moldability and exhibits a high stiffness and a high ESCR.
A polyethylene composition comprising a mixture of three kinds of polyethylenes (A), (B) and (C) characterized in that:
(i) the viscosity average molecular weight of (A) is 1,000-100,000, the viscosity average molecular weight of (B) is 100,000-1,000,000, the viscosity average molecular weight of (C) is 400,000-6,000,000, the molecular weight ratio of (B) to (A), i.e. B/A, is 2-200 and the molecular weight ratio of (C) to (B), i.e. C/B, is 1.5 or more.
(ii) the mixing ratio of (A) to (B) is 30/70 to 70/30 and the mixing ratio of (C) is 1-10% by weight based on the total composition, and (iii) the melt index of the composition is 0.001-1, and a process for producing said composition. This polyethylene composition is excellent in physical properties in that it has an appropriate die swell, a high melt tension and an excellent moldability and exhibits a high stiffness and a high ESCR.
Description
1 This invention relates to a polyethylene resin composition having excellent physical properties and moldability, as well as to an ethylene polymerization process for producing said resin composition with a high productivity.
The characterlstic properties of polyethylene required vary depending on the method of molding and use, and the characteristic properties o~ the polymer are designed so as to ~it ~or them. That is, a polymer having a relatively low molecular weight and a narrow molecular weight distribution is suitable for articles to be molded by injection molding process, while a polymer having a relatively high molecular weight and a broad molecular weight distribution is used for 15 articles to be molded by extrusion, namely blow molding .
or inflation molding process.
As a process ~or producing a polyethylene having a broad molecular weight distribution and used for extrusion molding, a number of processes are proposed.
As one of them, there is proposed a process which comprises melting and mixing together a high molecular weight polyethylene and a low molecular :
weight polyethylene produced elsewhere (Japanese Patent Publication No. 3,215/1970; Japanese Patent Publication .
'~
:' -113Bl~t~
1 No- 22~007/1970).
As another process, the multi-step polymeriza-tion process having two or more steps lnas been attempted (Japanese Patent Publication No. 11,349/1971; Japanese Patent Publication No. 42,716/1973; Japanese Patent Kokai (Laid-Open) No. 47,079/1976; Japanese Patent Kokai (Laid-Open) No. 19,788/1977).
The polymers produced by these processes have very excellent physical properties. That is, the polymers are superior to polymers produced by conventio-nal processes in the balance of stiffness and environ-mental stress cracking resistance (ESCR), so that an article molded from the polymers exhibits sufficient strength and chemical resistance with a low thickness.
Accordingly, a bottle molded by the ~se of this resin is light-weight and can sufficiently compete with conventional products in point of strength, so that its industrial value is quite high from the viewpoints of economizing resources and energies. Further, its high stiffness and good ESCR enable to use it under more severe conditions than ever and to give a product having a higher functionality than ever.
Though a polymer produced by the above-mentioned processes has excellent performances mentioned above, it also has the following faults. That is, it shows a lower die swell than conventional polyethylene, it shows a low melt tension, and it is inferior in moldability. When a molten polymer is extruded from 1138~8 l the die of molding machine, a swelling occurs due to Barus effect. This is called die swell. In the case of blow molding, a bottle is formed from cylindrical molten polymer having a constant length (parison).
Polyethylene molding makers use many kinds of poly-ethylene grades for the sake of manufacturing articles meeting the various requirements of market. Since the polyethylene produced by mixing high molecular weight and low molecular weight polyethylenes or by the multi-step polymerization process is lower than these polymersin die swell, a bottle molded from it has a low wall thickness and product having constant quality is difficult to obtain. Exchange of die is necessary to the control of wall thickness, which decreases produc-tivity and necessitates spare dies. As above, a greatdifference in die swell brings about a great disadvan-tage industrially.
This invention provides a composition having good physical properties and capable of overcoming these faults, as well as a process for producing said composition.
Thus, this invention relates to a polyethylene composition comprising a mixture of three kinds of polyethylenes (A), (B) and (C) wherein:
(i) the viscosity average molecular wegiht of (A) is l,000-lO0,000, the viscosity average molecular weight of (B) is lO0,000-1,000,000, the viscosity average molecular weight of (C) is 400,ooo-6,ooo,ooo, the 1 molecular weight ratio o~ B to A (B/A) is 2-100, and the molecular weight ratio of C to B (C/B) is 1.5 or more, (ii) the mixing ratio (A)/(B) is 30/70 to 70/30 and the mixing ratio of ~C) in the composition is 1-10%
by weight, and (iii) the composition has a melt index of 1 or less, as well as to a process for producing said composition.
According to this invention, there is provided a polyethylene composition having an extensive industrial applicability, having a controlled die swell, a high melt tension and an excellent moldability, exhibiting a high stiffness and a high ESCR, quite excellent in physical properties and suitable for blow molding.
The polyethylenes (A), (~) and (C) which are the constituents of this invention are homopolymers of ethylene or copolymers of ethylene and other olefins or dienes. As said other olefins and dienes used in the copolymerization, ~-olefins such as propylene, butene, pentene, 4-methylpentene-1, hexene, octene, decene and the like, diolefins such as butadiene, isoprene and the like, and cycloolefins such as cyclopentene, cyclohexene, cyclopentadiene, norbornene and the like can be referred to.
Polyethylene (A) is the so-called high density polyethylene having an average molecular weight of 1,000-100,000 and preferably 5,000-70,000 and a density of 0.94-0.98.
113~3148 1 Polyethylene (B) has an average molecular weight of 100,000-1,000,000 and preferable 300,000-800,000 and a density of 0.90-0.97.
The molecular weight ratio of (A) to (B) is
The characterlstic properties of polyethylene required vary depending on the method of molding and use, and the characteristic properties o~ the polymer are designed so as to ~it ~or them. That is, a polymer having a relatively low molecular weight and a narrow molecular weight distribution is suitable for articles to be molded by injection molding process, while a polymer having a relatively high molecular weight and a broad molecular weight distribution is used for 15 articles to be molded by extrusion, namely blow molding .
or inflation molding process.
As a process ~or producing a polyethylene having a broad molecular weight distribution and used for extrusion molding, a number of processes are proposed.
As one of them, there is proposed a process which comprises melting and mixing together a high molecular weight polyethylene and a low molecular :
weight polyethylene produced elsewhere (Japanese Patent Publication No. 3,215/1970; Japanese Patent Publication .
'~
:' -113Bl~t~
1 No- 22~007/1970).
As another process, the multi-step polymeriza-tion process having two or more steps lnas been attempted (Japanese Patent Publication No. 11,349/1971; Japanese Patent Publication No. 42,716/1973; Japanese Patent Kokai (Laid-Open) No. 47,079/1976; Japanese Patent Kokai (Laid-Open) No. 19,788/1977).
The polymers produced by these processes have very excellent physical properties. That is, the polymers are superior to polymers produced by conventio-nal processes in the balance of stiffness and environ-mental stress cracking resistance (ESCR), so that an article molded from the polymers exhibits sufficient strength and chemical resistance with a low thickness.
Accordingly, a bottle molded by the ~se of this resin is light-weight and can sufficiently compete with conventional products in point of strength, so that its industrial value is quite high from the viewpoints of economizing resources and energies. Further, its high stiffness and good ESCR enable to use it under more severe conditions than ever and to give a product having a higher functionality than ever.
Though a polymer produced by the above-mentioned processes has excellent performances mentioned above, it also has the following faults. That is, it shows a lower die swell than conventional polyethylene, it shows a low melt tension, and it is inferior in moldability. When a molten polymer is extruded from 1138~8 l the die of molding machine, a swelling occurs due to Barus effect. This is called die swell. In the case of blow molding, a bottle is formed from cylindrical molten polymer having a constant length (parison).
Polyethylene molding makers use many kinds of poly-ethylene grades for the sake of manufacturing articles meeting the various requirements of market. Since the polyethylene produced by mixing high molecular weight and low molecular weight polyethylenes or by the multi-step polymerization process is lower than these polymersin die swell, a bottle molded from it has a low wall thickness and product having constant quality is difficult to obtain. Exchange of die is necessary to the control of wall thickness, which decreases produc-tivity and necessitates spare dies. As above, a greatdifference in die swell brings about a great disadvan-tage industrially.
This invention provides a composition having good physical properties and capable of overcoming these faults, as well as a process for producing said composition.
Thus, this invention relates to a polyethylene composition comprising a mixture of three kinds of polyethylenes (A), (B) and (C) wherein:
(i) the viscosity average molecular wegiht of (A) is l,000-lO0,000, the viscosity average molecular weight of (B) is lO0,000-1,000,000, the viscosity average molecular weight of (C) is 400,ooo-6,ooo,ooo, the 1 molecular weight ratio o~ B to A (B/A) is 2-100, and the molecular weight ratio of C to B (C/B) is 1.5 or more, (ii) the mixing ratio (A)/(B) is 30/70 to 70/30 and the mixing ratio of ~C) in the composition is 1-10%
by weight, and (iii) the composition has a melt index of 1 or less, as well as to a process for producing said composition.
According to this invention, there is provided a polyethylene composition having an extensive industrial applicability, having a controlled die swell, a high melt tension and an excellent moldability, exhibiting a high stiffness and a high ESCR, quite excellent in physical properties and suitable for blow molding.
The polyethylenes (A), (~) and (C) which are the constituents of this invention are homopolymers of ethylene or copolymers of ethylene and other olefins or dienes. As said other olefins and dienes used in the copolymerization, ~-olefins such as propylene, butene, pentene, 4-methylpentene-1, hexene, octene, decene and the like, diolefins such as butadiene, isoprene and the like, and cycloolefins such as cyclopentene, cyclohexene, cyclopentadiene, norbornene and the like can be referred to.
Polyethylene (A) is the so-called high density polyethylene having an average molecular weight of 1,000-100,000 and preferably 5,000-70,000 and a density of 0.94-0.98.
113~3148 1 Polyethylene (B) has an average molecular weight of 100,000-1,000,000 and preferable 300,000-800,000 and a density of 0.90-0.97.
The molecular weight ratio of (A) to (B) is
2-200 and preferably 5-100. If the molecular weight ratio is lower than 2, the excellent physical properties of this invention are difficult to obtain and the molecular weight distribution cannot be broad sufficient-ly so that the moldability becomes poor. On the other hand, if the molecular weight ratio exceeds 200, there is no advantage in improving physical properties and moldability and there is a disadvantage from the viewpoint of manufacture of the polymer.
Polyethylene (C) has an average molecular weight of 40o,000-6,000,000 and preferably 600,000-4,000,000 and a density of 3.88-0.96.
The molecular weight ratio of (C) to (B) ((C)/(Bj) is 1.5 or more and preferably 2 or more. If the molecular weight ratio is lower than 1.5 or the molecular weight of (C) is less than 400,000, the excellent physical properties of this invention are difficult to obtain and particularly the effect of enhancing the die swell and the effect of enhancing the melt tension and thereby improving the moldability, which are both the characteristic features of this invention, cannot be obtained. On the other hand, if the molecular weight of (C) exceeds 6,ooo,ooo, the uniformity of the composition is injured.
~138~48 1 Next, the mixing ratios between constituents (A), (B) and (C) will be explained. The ratio of (A) to CB) is in the range of 30/70 to 70/30 and preferably 40/60 to 60/40. If the proportion of (A) or (B) exceeds 70%, excellent physical properties and molda-bility cannot be obtained.
The mixing ratio of constituent (C) in the composition is 1-10% by weight and preferably 3-8% by weight. By mixing it within this range, the die swell and the melt tension can be improved and a compo-sition having good physical properties and moldability can be obtained. If the amount of component (C) mixed is small, no effect is obtained. If it exceeds 10%, the melt index of the final composition becomes too low so that the composition becomes poor in moldability and uniformity.
In mixing the three components (A~, (B) and ~C), (A), (B) and (C) may be mixed and kneaded simul-taneously, or it is also allowable to previously mix any two of the three components and then mix and knead the third component therewith. Any of these two mixing methods may be employed. The mixing of these components is carried out under usual conditions in a molten state by using usual extruder or kneader. As said extruder, any of single screw type and double screw type may be used. As that of double screw type, CIM ~anufactured by, for example, The Japan Steel Works, Ltd., as well - . :
.
, . ' ' ~13~ 8 1 as FCM, DSM and the like manufactured by Farrel Co. may be used. As said kneader, Banbury mixer may be used, for example.
The composition thus produced has a melt index of 0.001-1 and preferably 0.005-0.5, a density of
Polyethylene (C) has an average molecular weight of 40o,000-6,000,000 and preferably 600,000-4,000,000 and a density of 3.88-0.96.
The molecular weight ratio of (C) to (B) ((C)/(Bj) is 1.5 or more and preferably 2 or more. If the molecular weight ratio is lower than 1.5 or the molecular weight of (C) is less than 400,000, the excellent physical properties of this invention are difficult to obtain and particularly the effect of enhancing the die swell and the effect of enhancing the melt tension and thereby improving the moldability, which are both the characteristic features of this invention, cannot be obtained. On the other hand, if the molecular weight of (C) exceeds 6,ooo,ooo, the uniformity of the composition is injured.
~138~48 1 Next, the mixing ratios between constituents (A), (B) and (C) will be explained. The ratio of (A) to CB) is in the range of 30/70 to 70/30 and preferably 40/60 to 60/40. If the proportion of (A) or (B) exceeds 70%, excellent physical properties and molda-bility cannot be obtained.
The mixing ratio of constituent (C) in the composition is 1-10% by weight and preferably 3-8% by weight. By mixing it within this range, the die swell and the melt tension can be improved and a compo-sition having good physical properties and moldability can be obtained. If the amount of component (C) mixed is small, no effect is obtained. If it exceeds 10%, the melt index of the final composition becomes too low so that the composition becomes poor in moldability and uniformity.
In mixing the three components (A~, (B) and ~C), (A), (B) and (C) may be mixed and kneaded simul-taneously, or it is also allowable to previously mix any two of the three components and then mix and knead the third component therewith. Any of these two mixing methods may be employed. The mixing of these components is carried out under usual conditions in a molten state by using usual extruder or kneader. As said extruder, any of single screw type and double screw type may be used. As that of double screw type, CIM ~anufactured by, for example, The Japan Steel Works, Ltd., as well - . :
.
, . ' ' ~13~ 8 1 as FCM, DSM and the like manufactured by Farrel Co. may be used. As said kneader, Banbury mixer may be used, for example.
The composition thus produced has a melt index of 0.001-1 and preferably 0.005-0.5, a density of
3.967-0.935 and a molecular weight distribution of 60 or more and preferably 75 or more in terms of MIR, and it is a polymer suitable for extrusion molding.
The polyethylenes (A), (B) and (C) can be produced by the usual suspension polymerization, gas phase polymerization or solution polymerization using the low-pressure or medium pressure process. The catalyst used in the polymerization may be any catalyst, so far as it can produce the polyethylenes (A), (B) and (C). Industrially, however, such a high-activity catalyst comprising transition metal compound and organometallic compound as mentioned later and claimed in this application is preferable, because a step for removing the catalyst may be omitted in case using this catalyst.
In producing the composition of this invention, it is allowable to produce polyethylenes CA~, CB) and (C) separately by the usual polymerization process and then mix them together as mentioned above. In order to more enhance the uniformity of the composition, however, it is preferable to produce the composition by a multi-step continuous polymerization comprising three or more steps.
~13B~48 1 Next, the production process by multi-step polymerization will be explained.
As the polymerization catalyst, catalysts comprising a transition metal compound and an organo-5 metallic compound are used, and those invented by thepresent inventors and mentioned in Japanese Patent Publication Nos. 36,788/1977, 36,790/1977, 36,791/1977, 36,792/1977, 50,070/1977, 36,794/1977, 36,795/1977, 36,796/1977, 36,915/1977, 36,917/1977 and 6, olg/1978 and Japanese Patent Kokai (Laid-Open) Nos. 21,876/1975, 31,835/1975, 72,044/1975, 78,619/1975 and 40,696/1978 are effective. They comprise a solid catalyst component (A) and an organometallic compound (B), wherein said solid catalyst component (A) is obtainable by reacting the following (i) and (ii) or ~i), (ii) and (iiij:
(i) an organomagnesium compound represented ~y the following general formula:
M~Mg~RlpR2qxrys wherein ~ is a number equal to or greater than O; ~ is a number greater than O; p, q, r and s are numbers eaual to or greater than O and having the following relation:
p + q + r + s = m~ + 2~;
(m is the balence of M mentioned below) M is metallic element belonging to the I-III group of the periodic table; Rl and R2 are hydrocarbon groups having identical or different number of carbon atoms; ~ and Y, identical ~138~48 l or dif erent, represent halogen, oR3, oSiR4R5R6, NR7R8 or SR9 wherein R3, R4, R5, R5, R7 and R8 represent hydrogen atom or hydrocarbon group and R9 represents hydrocarbon group;
(ii) a titanium compound or a vanadium compound having at least one halogen atom;
(iii) a halide compound of Al, B, Si, Ge, Sn, Te or Sb. As said organometallic compound (B) compounds of the metals belonging to the I-III groups of the periodic table are used, among which complexes comprising organoaluminum compound and organomagnesium compound are particularly preferable.
The reaction between the catalyst component (A) and the organometallic compound component ~B) can be carried out by adding both the components into the polymerization system and making it progress under the polymerization conditions with the progress of the polymerization, though it may also be carried out prior to the polymerization. The proportion of the cataiyst components reacted is preferably in the range of 1-3,000 mmoles of (B) component per 1 g of CA? component.
In place of catalyst component CA), a titanium compound supported on an inorganic magnesium compound may also be used.
The polymerization is carried out in a saturated hydrocarbon having 4-10 carbon atoms. The step for obtaining the high molecular weight polyethylene (C) having an average molecular weight of 400,000 or 1 more may be any step of the multi-step polymerization.
In order to obtain a high molecular weight, however, it is necessary that the concentration of molecular weight regulator (for example, hydrogen) is very low. Accor-dingly, it is advantageous to produce (C) in the firstor last step of the polymerization as shown by the following scheme (a) or (b):
(a) (C)-(B)-(A) or (C)-(A)-(B) (b) (A)-(B)-(C) Hereunder, the procedure will be explained with reference to the case of first of all polymerizing (C), for the sake of simplifying the description.
For obtaining a high molecular weight polyethylene (C), the polymerization is carried out at a pressure of 0.5-20 kg/cm2 G, preferably 0.5-10 kg/cm2 G, and at a polymerization temperature of 30-110, preferably 40-80C, to obtain a polyethylene ~C) satis-fying the above-mentioned conditions. This polymerization for obtaining (C) may also be carried out by a batch process.
The polymerizations of the second and later steps are carried out at a polymerization temperature of 110C or below, referably in the range of 60-90C, and at a polymerization pressure ranging from 1 to 30 kg/cm G.
`~ With reference to the drawing, a typical flow of this invention will be explained below in detail.
, 1 From line (2), ethylene, hexane, catalyst and the like are fed into polymerization apparatus (1) of the first step where the polymerization is carried out to give a high molecular weight polymer (C) having an average molecular weight of 400,000 or more. The slurry containing the high molecular weight polyethylene thus formed is introduced into the polymerization apparatus
The polyethylenes (A), (B) and (C) can be produced by the usual suspension polymerization, gas phase polymerization or solution polymerization using the low-pressure or medium pressure process. The catalyst used in the polymerization may be any catalyst, so far as it can produce the polyethylenes (A), (B) and (C). Industrially, however, such a high-activity catalyst comprising transition metal compound and organometallic compound as mentioned later and claimed in this application is preferable, because a step for removing the catalyst may be omitted in case using this catalyst.
In producing the composition of this invention, it is allowable to produce polyethylenes CA~, CB) and (C) separately by the usual polymerization process and then mix them together as mentioned above. In order to more enhance the uniformity of the composition, however, it is preferable to produce the composition by a multi-step continuous polymerization comprising three or more steps.
~13B~48 1 Next, the production process by multi-step polymerization will be explained.
As the polymerization catalyst, catalysts comprising a transition metal compound and an organo-5 metallic compound are used, and those invented by thepresent inventors and mentioned in Japanese Patent Publication Nos. 36,788/1977, 36,790/1977, 36,791/1977, 36,792/1977, 50,070/1977, 36,794/1977, 36,795/1977, 36,796/1977, 36,915/1977, 36,917/1977 and 6, olg/1978 and Japanese Patent Kokai (Laid-Open) Nos. 21,876/1975, 31,835/1975, 72,044/1975, 78,619/1975 and 40,696/1978 are effective. They comprise a solid catalyst component (A) and an organometallic compound (B), wherein said solid catalyst component (A) is obtainable by reacting the following (i) and (ii) or ~i), (ii) and (iiij:
(i) an organomagnesium compound represented ~y the following general formula:
M~Mg~RlpR2qxrys wherein ~ is a number equal to or greater than O; ~ is a number greater than O; p, q, r and s are numbers eaual to or greater than O and having the following relation:
p + q + r + s = m~ + 2~;
(m is the balence of M mentioned below) M is metallic element belonging to the I-III group of the periodic table; Rl and R2 are hydrocarbon groups having identical or different number of carbon atoms; ~ and Y, identical ~138~48 l or dif erent, represent halogen, oR3, oSiR4R5R6, NR7R8 or SR9 wherein R3, R4, R5, R5, R7 and R8 represent hydrogen atom or hydrocarbon group and R9 represents hydrocarbon group;
(ii) a titanium compound or a vanadium compound having at least one halogen atom;
(iii) a halide compound of Al, B, Si, Ge, Sn, Te or Sb. As said organometallic compound (B) compounds of the metals belonging to the I-III groups of the periodic table are used, among which complexes comprising organoaluminum compound and organomagnesium compound are particularly preferable.
The reaction between the catalyst component (A) and the organometallic compound component ~B) can be carried out by adding both the components into the polymerization system and making it progress under the polymerization conditions with the progress of the polymerization, though it may also be carried out prior to the polymerization. The proportion of the cataiyst components reacted is preferably in the range of 1-3,000 mmoles of (B) component per 1 g of CA? component.
In place of catalyst component CA), a titanium compound supported on an inorganic magnesium compound may also be used.
The polymerization is carried out in a saturated hydrocarbon having 4-10 carbon atoms. The step for obtaining the high molecular weight polyethylene (C) having an average molecular weight of 400,000 or 1 more may be any step of the multi-step polymerization.
In order to obtain a high molecular weight, however, it is necessary that the concentration of molecular weight regulator (for example, hydrogen) is very low. Accor-dingly, it is advantageous to produce (C) in the firstor last step of the polymerization as shown by the following scheme (a) or (b):
(a) (C)-(B)-(A) or (C)-(A)-(B) (b) (A)-(B)-(C) Hereunder, the procedure will be explained with reference to the case of first of all polymerizing (C), for the sake of simplifying the description.
For obtaining a high molecular weight polyethylene (C), the polymerization is carried out at a pressure of 0.5-20 kg/cm2 G, preferably 0.5-10 kg/cm2 G, and at a polymerization temperature of 30-110, preferably 40-80C, to obtain a polyethylene ~C) satis-fying the above-mentioned conditions. This polymerization for obtaining (C) may also be carried out by a batch process.
The polymerizations of the second and later steps are carried out at a polymerization temperature of 110C or below, referably in the range of 60-90C, and at a polymerization pressure ranging from 1 to 30 kg/cm G.
`~ With reference to the drawing, a typical flow of this invention will be explained below in detail.
, 1 From line (2), ethylene, hexane, catalyst and the like are fed into polymerization apparatus (1) of the first step where the polymerization is carried out to give a high molecular weight polymer (C) having an average molecular weight of 400,000 or more. The slurry containing the high molecular weight polyethylene thus formed is introduced into the polymerization apparatus
(4) of the second step by means of pump (3).
In the polymerization apparatus (4), ethylene, hexane, hydrogen, catalyst components etc. are fed from line (5) and polymerized to give low molecular weight polyethylene (A). The slurry in the polymerization apparatus (4) is led into flash drum (6) where the unreacted ethylene and hydrogen are removed. The ethylene and hydrogen removed are brought into a state of higher pressure by compressor (7) and returned to the polymerization apparatus (4). On the other hand, the slurry in the flash drum is introduced into polymerization apparatus (9) of the third step by pump (8).
In polymerization apparatus C9), ethylene, hexane, catalyst components etc. are fed ~rom line Clo) and polymerized to give high molecular weight poly-ethylene CB), whereby the molecular weight of the polymer is adjusted to the intended ultimate value.
The polymer in the polymerization apparatus (9) is after-treated and then withdrawn as a product.
The flow explained above is one of the ~ypical : , 1138~48 1 examples of this invention, and it is also allowable, if necessary, to produce high molecular weight poly-ethylene (B) in polymerization apparatus (4) and low molecular weight polyethylene (A) in polymerization apparatus (9). In this case flash drum (o) can be omitted. It is also allowable to circulate the content of the polymerization apparatus of later step, i.e.
(9), into the preceding polymerization apparatus, i.e.
(4).
According to such a flow sheet, the polymeri-zation is carried out continuously and a polymer having good physical properties can be obtained.
The polymerization of this invention is not limited to homopolymerization of ethylene but it may also be a copolymerization of ethylene and 0.5-20% by mole of other olefin such as propylene, butene, 4-methylpentene-l, hexene, octene, butadiene, isoprene or the like. By these copolymerizations, polymers having respective characteristic features in physical properties can be obtained.
As is apparent from the description given above and the examples mentioned later, the characteristic feature of this invention consists in the following points. Thus, in the first place, this invention gives a polyethylene composition having an extensive industrial applicability, a controlled die swell, a broad molecular weight distribution and a high stiffness, exhibiting a high ESCR, quite excellent in physical properties and :
1 suitable for blow molding. In ,,he second place, such a composition can be obtained with a high productivity by a continuous polymerization. In the third place, this invention provides a method for controlling the die swell of polymer for blow molding by means of a continuous polymerization and a method for enhancing melt tension and thereby improving moldability.
Hereunder, this invention will be illustrated in more detail by way of examples, but the invention is by no means limited by these examples.
The meanings of the symbols used in the examples and comparative examples and the conditions of the measurements therefor are as follows:
(i) MI: It expresses melt index. It was measured according to ASTM D-1238 at a temperature of 190C under a load of 2.16 kg.
(ii~ MIR: It means the quotient obtainable by dividing the value of MI measured under the conditions of MI measurement under a high load of 21.6 kg with the value of MI of the above-mentioned paragraph (i). It is a measure of molecular weight distribution. Its higher value means a broader molecular weight distribu-tion.
Ciii~ Molecular weight (Mw): Mw was determined from intrinsic viscosity [n~ measured in decalin at 135C and according to the following equation:
~n~ = 6.8 x 10-4MW0 67 l which is mentioned in Journal of Polymer Science, 36, 91 (1957).
(iv) Density: Real density measured according to ASTM D-1505.
In the polymerization apparatus (4), ethylene, hexane, hydrogen, catalyst components etc. are fed from line (5) and polymerized to give low molecular weight polyethylene (A). The slurry in the polymerization apparatus (4) is led into flash drum (6) where the unreacted ethylene and hydrogen are removed. The ethylene and hydrogen removed are brought into a state of higher pressure by compressor (7) and returned to the polymerization apparatus (4). On the other hand, the slurry in the flash drum is introduced into polymerization apparatus (9) of the third step by pump (8).
In polymerization apparatus C9), ethylene, hexane, catalyst components etc. are fed ~rom line Clo) and polymerized to give high molecular weight poly-ethylene CB), whereby the molecular weight of the polymer is adjusted to the intended ultimate value.
The polymer in the polymerization apparatus (9) is after-treated and then withdrawn as a product.
The flow explained above is one of the ~ypical : , 1138~48 1 examples of this invention, and it is also allowable, if necessary, to produce high molecular weight poly-ethylene (B) in polymerization apparatus (4) and low molecular weight polyethylene (A) in polymerization apparatus (9). In this case flash drum (o) can be omitted. It is also allowable to circulate the content of the polymerization apparatus of later step, i.e.
(9), into the preceding polymerization apparatus, i.e.
(4).
According to such a flow sheet, the polymeri-zation is carried out continuously and a polymer having good physical properties can be obtained.
The polymerization of this invention is not limited to homopolymerization of ethylene but it may also be a copolymerization of ethylene and 0.5-20% by mole of other olefin such as propylene, butene, 4-methylpentene-l, hexene, octene, butadiene, isoprene or the like. By these copolymerizations, polymers having respective characteristic features in physical properties can be obtained.
As is apparent from the description given above and the examples mentioned later, the characteristic feature of this invention consists in the following points. Thus, in the first place, this invention gives a polyethylene composition having an extensive industrial applicability, a controlled die swell, a broad molecular weight distribution and a high stiffness, exhibiting a high ESCR, quite excellent in physical properties and :
1 suitable for blow molding. In ,,he second place, such a composition can be obtained with a high productivity by a continuous polymerization. In the third place, this invention provides a method for controlling the die swell of polymer for blow molding by means of a continuous polymerization and a method for enhancing melt tension and thereby improving moldability.
Hereunder, this invention will be illustrated in more detail by way of examples, but the invention is by no means limited by these examples.
The meanings of the symbols used in the examples and comparative examples and the conditions of the measurements therefor are as follows:
(i) MI: It expresses melt index. It was measured according to ASTM D-1238 at a temperature of 190C under a load of 2.16 kg.
(ii~ MIR: It means the quotient obtainable by dividing the value of MI measured under the conditions of MI measurement under a high load of 21.6 kg with the value of MI of the above-mentioned paragraph (i). It is a measure of molecular weight distribution. Its higher value means a broader molecular weight distribu-tion.
Ciii~ Molecular weight (Mw): Mw was determined from intrinsic viscosity [n~ measured in decalin at 135C and according to the following equation:
~n~ = 6.8 x 10-4MW0 67 l which is mentioned in Journal of Polymer Science, 36, 91 (1957).
(iv) Density: Real density measured according to ASTM D-1505.
5 (v) ESCR: It indicates environmental stress cracking resistance. It is measured by introducing a nonionic surfactant into a 500 ml bottle (weight 42 g, wall thickness o.8 mm) molded by means of a 50~ blow molding machine at a cylinder temperature of 160C and a die temperature of 40C so as to fill up 10% of the inner volume, placing the bottle in an oven kept at 60C and applying a constant inner pressure. ESCR is expressed by the length of time required for breaking 50% of the tested bottles.
(vi) Die swell: It is expressed by the weight of parison, per 20 cm, extruded at a temperature of 170C
by the use of a blow molding die having an outer diameter of 16 mm and an inner diameter of 10 mm.
Example l (a) Synthesis of catalyst An organoaluminum-magnesium complex having ' Al~g6(C2H5)3(n-C4H9~l2 was Synthesized by introducing 138 g of di-n-butylmagnesium and 19 g of triethylaluminum together with 2 liters of n-heptane into a stirring tank having a capacity of 4 liters and allowing to react at 80C for 2 hours. After moisture and oxygen had been removed by substitution with dry : , .:
. .
. ~ . ,,, :
1 nitrogen, 800 ml of a n-heptane solution containing 400 mmoles (54 g) of this com~lex was reacted with 800 ml of a n-heptane solution containing 400 mmoles of titanium tetrachloride at -20C ~or 4 hours with stirr-ing. The resulting hydrocarbon-insoluble solid was isolated and washed with n-heptane to obtain 106 g of a solid.
The solid thus obtained was diluted with n-hexane and used for polymerization.
(b) Production of polyethylene By using a stainless made polymerization apparatus (9) having a reaction volume of 200 liters, polyethylene was produced by continuous polymerization.
The polymerization was controlled at a polymerization temperature of 86C and a polymerization pressure of 12 kg/cm G. As catalyst, triethylaluminum was introduced at a concentration of 0.5 mmole/liter. A
solid catalyst was also introduced at a rate of about 3.5 g/hour together with hexane at a rate of 30 liters/
hour so as to give a polymer formation of 8 kg/hour.
Hydrogen, having a concentration of about 75%, was used as a molecular weight regulator. Thus, polyethylene ~A) having a molecular weight of 25,000 was obtained.
The catalytic effect was 110,000 g polymer/g-Ti.
Polyethylene (B) was produced under the same conditions as in polyethylene (A), except that concen-tration of hydrogen was about 15% and solid catalyst was fed at a rate of about 0.5 g/hour. As the result, , :
1 polyethylene (B) having a molecular weight of 320,000 was obtained. The catalytic e~fect was 780,000 g polymer/g-Ti.
Polyethylene (C) was produced under the same conditions as in polyethylene (A), except that concen-tration of hydrogen was about 2%, the pressure was 8 kg/cm2 G, the polymerization temperature was 73C and the solid catalyst was fed at a rate of about 0.4 g/
hour. As the result, polyethylene (C) having a molecular weight of 1,000,000 was obtained. The catalytic effect was 970,000 g polymer/g-Ti.
(c) Production of polyethylene composition The polyethylenes (A) and (B) produced in (b) were mixed together at a ratio of 50 : 50, to which was added 5% by weight of polyethylene (C). The mixture was kneaded together with 1,000 ppm of Irganox 1076 and 1,000 ppm of calcium stearate and extruded at 190C by means of an extruder of 40 mm~ to give pellets.
Characteristic properties of this composition are shown in Table 1. The composition exhibits good physical properties in that ESCR and stiffness are well balanced and die swell is also high.
Example 2 A composition was produced by multi-step continuous polymerization using the same catalyst as in Example 1.
Thus, into polymerization apparatus (1) having 11~38148 1 an inner volume of 20 liters, the same solid catalyst as in Example 1 was fed at a rate of 1.3 mmoles (based on Ti atom)/hour and triethylaluminum was fed at a rate of 20 mmoles (based on metallic atom)/hour. ~lso, purified hexane was fed at a rate of 40 liters/hour and ethylene was fed into polymerization apparatus (1) at a rate of about 1.0 NM3/hour. Polymerization was carried out by adjusting the conditions o~ polymerization apparatus (1) to a polymerization temperature of 60C and a pressure of 3 kg/cm2 G, whereby polyethylene (C) was obtained. The polymer slurry formed by this polymeriza-tion was brought into a state of elevated pressure with slurry pump (3) and introduced into polymerization apparatus (4) having an inner volume of 300 liters at a pressure of 15 kg/cm G and a temperature of 85C.
Into the polymerization apparatus (4), ethylene was introduced at a rate of 7 NM3/hour and hydrogen was introduced at a rate of 0.25 NM3/hour, and polymeriza-tion was carried out to give polyethylene (A). The polymer slurry in the polymerization apparatus (4) was led to flash drum (6) having a pressure of 1 kg/cm2 G
and a temperature of 75C where unreacted ethylene and hydrogen were separated. Then the slurry was brought into a state of elevated pressure and introduced into polymerization apparatus (9) by means of slurry pump (8). Polymerization apparatus (9) was kept at a temperature of 73C and a pressure of 8 kg/cm2 G, to which purified n-hexane, triethylaluminum, ethylene, 113B~48 1 hydrogen and butene were fed at rates of, respectively, 40 liters/hour, 20 mmoles/hour, 7.2 NM3/hour, 0.02 NM3/hour and 17 mmoles/hour to produce polyethylene (B).
The capacity of polymerization apparatus (9) was 200 liters.
After the three steps of polymerization were carried out as above, the polymer taken out from polymerization apparatus (9) had a melt index of 0.3, and other physical properties of this polymer were good similarly to Example 1, as shown in Table 1. The surface of the molded bottle was better than that obtained in Example 1 and more improved in uniformity.
The polyethylene formed in polymerization apparatus (1) had an average molecular wei~ht of about 2,000,000 and the proportion of its formation to the total formation (the sum of formation in polymerization apparatuses (1), (~) and (9)) was 6%.
The molecular weight of polymer (A) polymerized in the polymerization apparatus of the second step and the molecular weight of polymer (B) polymerized in the polymerization apparatus of the third step were determined by measuring MI of the polymers leaving respective poly-merization apparatuses, estimating the MI values of the polymers formed in respective polymerization ~pparatuses from the following relation:
MI -0.175 = xMI -0.175 + yMIy x + y = 1 l (Journal of Polymer Science, Part A, 2, 2977-3007 (1964)) and determining their molecular weights from the actually measured relationship between MI and n, wherein:
x, y: weight fractions of polymer formation velocity in respective polymerization apparatuses, MIt: melt index of the final polymer which has passed the two polymerization apparatuses, MIX: melt index in the polymerization apparatus x, and MIy: melt index in the polymerization apparatus y.
A That is, ~ is determined from the observed values of MIt and MIX.
Molecular weights of the polymers of the second and third steps were 21,000 and 260,000, respec-tively, as determined by the above-mentioned procedure.
Example 3 Polymerization was carried out in the same manner as in Example 2 with the same catalyst as in Example l, provided that the polymerization conditions of the third step for making polyethylene (B) were the same as in Example 2 except that the temperature was 65C and hydrogen was fed at a rate of 0.01 NM3/hour.
The polymer obtained by this polymerization had a MI of 0.04. Other physical properties of this polymer are shown in Table 1.
: -1~3B~4B
1 Example 4 In the same manner as in Example 1, the polyethylenes (A) and (B) obtained in Example 1 were mixed together at a ratio of 45 : 55, to which was added 3% of the polyethylene (C) obtained in Example 1.
Together with additives, the mixture was kneaded and extruded to give pellets. Characteristic properties of this composition are shown in Table 1.
Comparative Example 1 A polyethylene having a MI value of 0.3 was produced by one step polymerization by using the same catalyst as in Example 1. Characteristic properties of this polyethylene are shown in Table 1. It has a low MIR and is very poor in moldability. Further, it exhibits a low ESCR and a low die swell.
Comparative Example 2 Polyethylenes (A) and (B) were produced by repeating the procedure of Example 1, provided that the polyethylene (B) had a molecular weight of 400,000.
The two components (A) and (B) were mixed together at a ratio of 50 : 50. The same additives as in Example 1 were added to the mixture, from which pellets were made.
The results are shown in Table 1. Though the composition has a high ESCR and a high MIR, it has a low die swell.
1~38~41~
l Comparative Example 3 3y using the same catalyst as in Example l, polymerizations corresponding to the second and third steps of Example 2 were practised without practising the super-high molecular weight polymerization of t'ne first step of Example 2.
A polymerization corresponding to the second step of the polymerization of Example 2 was practised in the first step and a polymerization corresponding to the third step of the polymerization of Example 2 was practised in the second step. The polymerization conditions in the first step were nearly the same as in the second step of Example 2, and the polymer obtained had a molecular weight of 21,000. The polymerization conditions in the second step were nearly ~he same as in the third step of Example 2, except that the feed of hydrogen was approximately zero. The polymer obtained had MI of 0.31. Its physical properties are shown in Table 1. As seen, it exhibits a low die swell though it shows a good balance between ESCR and stiffness.
Comparative Example 4 Polyethylenes CA), (B~ and (C) were produced in the same manner as in Example l, except that poly-ethylene (C) had a molecular weight of 430,000, components (A) and (B) were mixed together at a ratio of 50 : 50 and (C) was added thereto in a proportion of 6% based on the total composition. The same 1 additives as in Example 1 were added to the mixture, from which pellets were made. The results are shown in Table 1. Though ESCR and MIR are both high, the rise in die swell is ver~ small.
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~ o =r u~ o oc H ~ ~ O
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o ~ ~ ~ ~ ~ ~ h ~ a~ ~ ~
Z '~ ~ ~ ~
~ ~ ~ L'~ '~ ~1 0~1 V~ 0~
(vi) Die swell: It is expressed by the weight of parison, per 20 cm, extruded at a temperature of 170C
by the use of a blow molding die having an outer diameter of 16 mm and an inner diameter of 10 mm.
Example l (a) Synthesis of catalyst An organoaluminum-magnesium complex having ' Al~g6(C2H5)3(n-C4H9~l2 was Synthesized by introducing 138 g of di-n-butylmagnesium and 19 g of triethylaluminum together with 2 liters of n-heptane into a stirring tank having a capacity of 4 liters and allowing to react at 80C for 2 hours. After moisture and oxygen had been removed by substitution with dry : , .:
. .
. ~ . ,,, :
1 nitrogen, 800 ml of a n-heptane solution containing 400 mmoles (54 g) of this com~lex was reacted with 800 ml of a n-heptane solution containing 400 mmoles of titanium tetrachloride at -20C ~or 4 hours with stirr-ing. The resulting hydrocarbon-insoluble solid was isolated and washed with n-heptane to obtain 106 g of a solid.
The solid thus obtained was diluted with n-hexane and used for polymerization.
(b) Production of polyethylene By using a stainless made polymerization apparatus (9) having a reaction volume of 200 liters, polyethylene was produced by continuous polymerization.
The polymerization was controlled at a polymerization temperature of 86C and a polymerization pressure of 12 kg/cm G. As catalyst, triethylaluminum was introduced at a concentration of 0.5 mmole/liter. A
solid catalyst was also introduced at a rate of about 3.5 g/hour together with hexane at a rate of 30 liters/
hour so as to give a polymer formation of 8 kg/hour.
Hydrogen, having a concentration of about 75%, was used as a molecular weight regulator. Thus, polyethylene ~A) having a molecular weight of 25,000 was obtained.
The catalytic effect was 110,000 g polymer/g-Ti.
Polyethylene (B) was produced under the same conditions as in polyethylene (A), except that concen-tration of hydrogen was about 15% and solid catalyst was fed at a rate of about 0.5 g/hour. As the result, , :
1 polyethylene (B) having a molecular weight of 320,000 was obtained. The catalytic e~fect was 780,000 g polymer/g-Ti.
Polyethylene (C) was produced under the same conditions as in polyethylene (A), except that concen-tration of hydrogen was about 2%, the pressure was 8 kg/cm2 G, the polymerization temperature was 73C and the solid catalyst was fed at a rate of about 0.4 g/
hour. As the result, polyethylene (C) having a molecular weight of 1,000,000 was obtained. The catalytic effect was 970,000 g polymer/g-Ti.
(c) Production of polyethylene composition The polyethylenes (A) and (B) produced in (b) were mixed together at a ratio of 50 : 50, to which was added 5% by weight of polyethylene (C). The mixture was kneaded together with 1,000 ppm of Irganox 1076 and 1,000 ppm of calcium stearate and extruded at 190C by means of an extruder of 40 mm~ to give pellets.
Characteristic properties of this composition are shown in Table 1. The composition exhibits good physical properties in that ESCR and stiffness are well balanced and die swell is also high.
Example 2 A composition was produced by multi-step continuous polymerization using the same catalyst as in Example 1.
Thus, into polymerization apparatus (1) having 11~38148 1 an inner volume of 20 liters, the same solid catalyst as in Example 1 was fed at a rate of 1.3 mmoles (based on Ti atom)/hour and triethylaluminum was fed at a rate of 20 mmoles (based on metallic atom)/hour. ~lso, purified hexane was fed at a rate of 40 liters/hour and ethylene was fed into polymerization apparatus (1) at a rate of about 1.0 NM3/hour. Polymerization was carried out by adjusting the conditions o~ polymerization apparatus (1) to a polymerization temperature of 60C and a pressure of 3 kg/cm2 G, whereby polyethylene (C) was obtained. The polymer slurry formed by this polymeriza-tion was brought into a state of elevated pressure with slurry pump (3) and introduced into polymerization apparatus (4) having an inner volume of 300 liters at a pressure of 15 kg/cm G and a temperature of 85C.
Into the polymerization apparatus (4), ethylene was introduced at a rate of 7 NM3/hour and hydrogen was introduced at a rate of 0.25 NM3/hour, and polymeriza-tion was carried out to give polyethylene (A). The polymer slurry in the polymerization apparatus (4) was led to flash drum (6) having a pressure of 1 kg/cm2 G
and a temperature of 75C where unreacted ethylene and hydrogen were separated. Then the slurry was brought into a state of elevated pressure and introduced into polymerization apparatus (9) by means of slurry pump (8). Polymerization apparatus (9) was kept at a temperature of 73C and a pressure of 8 kg/cm2 G, to which purified n-hexane, triethylaluminum, ethylene, 113B~48 1 hydrogen and butene were fed at rates of, respectively, 40 liters/hour, 20 mmoles/hour, 7.2 NM3/hour, 0.02 NM3/hour and 17 mmoles/hour to produce polyethylene (B).
The capacity of polymerization apparatus (9) was 200 liters.
After the three steps of polymerization were carried out as above, the polymer taken out from polymerization apparatus (9) had a melt index of 0.3, and other physical properties of this polymer were good similarly to Example 1, as shown in Table 1. The surface of the molded bottle was better than that obtained in Example 1 and more improved in uniformity.
The polyethylene formed in polymerization apparatus (1) had an average molecular wei~ht of about 2,000,000 and the proportion of its formation to the total formation (the sum of formation in polymerization apparatuses (1), (~) and (9)) was 6%.
The molecular weight of polymer (A) polymerized in the polymerization apparatus of the second step and the molecular weight of polymer (B) polymerized in the polymerization apparatus of the third step were determined by measuring MI of the polymers leaving respective poly-merization apparatuses, estimating the MI values of the polymers formed in respective polymerization ~pparatuses from the following relation:
MI -0.175 = xMI -0.175 + yMIy x + y = 1 l (Journal of Polymer Science, Part A, 2, 2977-3007 (1964)) and determining their molecular weights from the actually measured relationship between MI and n, wherein:
x, y: weight fractions of polymer formation velocity in respective polymerization apparatuses, MIt: melt index of the final polymer which has passed the two polymerization apparatuses, MIX: melt index in the polymerization apparatus x, and MIy: melt index in the polymerization apparatus y.
A That is, ~ is determined from the observed values of MIt and MIX.
Molecular weights of the polymers of the second and third steps were 21,000 and 260,000, respec-tively, as determined by the above-mentioned procedure.
Example 3 Polymerization was carried out in the same manner as in Example 2 with the same catalyst as in Example l, provided that the polymerization conditions of the third step for making polyethylene (B) were the same as in Example 2 except that the temperature was 65C and hydrogen was fed at a rate of 0.01 NM3/hour.
The polymer obtained by this polymerization had a MI of 0.04. Other physical properties of this polymer are shown in Table 1.
: -1~3B~4B
1 Example 4 In the same manner as in Example 1, the polyethylenes (A) and (B) obtained in Example 1 were mixed together at a ratio of 45 : 55, to which was added 3% of the polyethylene (C) obtained in Example 1.
Together with additives, the mixture was kneaded and extruded to give pellets. Characteristic properties of this composition are shown in Table 1.
Comparative Example 1 A polyethylene having a MI value of 0.3 was produced by one step polymerization by using the same catalyst as in Example 1. Characteristic properties of this polyethylene are shown in Table 1. It has a low MIR and is very poor in moldability. Further, it exhibits a low ESCR and a low die swell.
Comparative Example 2 Polyethylenes (A) and (B) were produced by repeating the procedure of Example 1, provided that the polyethylene (B) had a molecular weight of 400,000.
The two components (A) and (B) were mixed together at a ratio of 50 : 50. The same additives as in Example 1 were added to the mixture, from which pellets were made.
The results are shown in Table 1. Though the composition has a high ESCR and a high MIR, it has a low die swell.
1~38~41~
l Comparative Example 3 3y using the same catalyst as in Example l, polymerizations corresponding to the second and third steps of Example 2 were practised without practising the super-high molecular weight polymerization of t'ne first step of Example 2.
A polymerization corresponding to the second step of the polymerization of Example 2 was practised in the first step and a polymerization corresponding to the third step of the polymerization of Example 2 was practised in the second step. The polymerization conditions in the first step were nearly the same as in the second step of Example 2, and the polymer obtained had a molecular weight of 21,000. The polymerization conditions in the second step were nearly ~he same as in the third step of Example 2, except that the feed of hydrogen was approximately zero. The polymer obtained had MI of 0.31. Its physical properties are shown in Table 1. As seen, it exhibits a low die swell though it shows a good balance between ESCR and stiffness.
Comparative Example 4 Polyethylenes CA), (B~ and (C) were produced in the same manner as in Example l, except that poly-ethylene (C) had a molecular weight of 430,000, components (A) and (B) were mixed together at a ratio of 50 : 50 and (C) was added thereto in a proportion of 6% based on the total composition. The same 1 additives as in Example 1 were added to the mixture, from which pellets were made. The results are shown in Table 1. Though ESCR and MIR are both high, the rise in die swell is ver~ small.
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' ' 113814~
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Claims (8)
1. A polyethylene composition comprising a mixture of three kinds of polyethylenes (A), (B) and (C) characterized in that:
(i) the viscosity average molecular weight of (A) is 1,000-100,000, the viscosity average molecular weight of (B) is 100,000-1,000,000, the viscosity average molecular weight of (C) is 400,000-6,000,000, the molecular weight ratio of (B) to (A), (B/A), is 2-200, and the molecular weight ratio of (C) to (B), (C/B), is 1.5 or more, (ii) the mixing ratio of (A) to (B), (A/B), is 30/70 to 70/30 and the mixing ratio of (C) to the total composition is 1-10% by weight, and (iii) melt index of the composition is 0.001-1.
(i) the viscosity average molecular weight of (A) is 1,000-100,000, the viscosity average molecular weight of (B) is 100,000-1,000,000, the viscosity average molecular weight of (C) is 400,000-6,000,000, the molecular weight ratio of (B) to (A), (B/A), is 2-200, and the molecular weight ratio of (C) to (B), (C/B), is 1.5 or more, (ii) the mixing ratio of (A) to (B), (A/B), is 30/70 to 70/30 and the mixing ratio of (C) to the total composition is 1-10% by weight, and (iii) melt index of the composition is 0.001-1.
2. A polyethylene composition according to Claim 1, wherein melt index of the composition is 0.005-0.5.
3. A polyethylene composition according to Claim 1, wherein the viscosity average molecular weight of polyethylene (C) is 600,000-4,000,000.
4. A polyethylene composition according to Claim 1, wherein the viscosity average molecular weight of polyethylene (A) is 5,000-70,000, the viscosity average molecular weight of polyethylene (B) is 300,000-800,000 and the molecular weight ratio of (B) to (A), (B/A), is 5-100.
5. A polyethylene composition according to Claim 1, wherein the molecular weight ratio of (C) to (B), (C/B), is 2 or more.
6. A polyethylene composition according to Claim 1, wherein the mixing ratio of (C) is 3-8% by weight based on the total composition.
7. A multi-step continuous polymerization process for producing the polyethylene composition mentioned in Claim 1 which comprises producing polyethylenes (A), (B) and (C) all different in molecular weight in three or more polymerization apparatuses connected in series by the use of a catalyst comprising a transition metal compound and an organometallic compound.
8. A multi-step continuous polymerization process for producing polyethylene according to Claim 7, wherein the number of the polymerization apparatuses connected in series is 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP107129/79 | 1979-08-24 | ||
| JP54107129A JPS5910724B2 (en) | 1979-08-24 | 1979-08-24 | Continuous polymerization of ethylene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1138148A true CA1138148A (en) | 1982-12-21 |
Family
ID=14451230
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000358085A Expired CA1138148A (en) | 1979-08-24 | 1980-08-12 | Polyethylene composition and process for producing the same |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US4336352A (en) |
| JP (1) | JPS5910724B2 (en) |
| BE (1) | BE884866A (en) |
| BR (1) | BR8005307A (en) |
| CA (1) | CA1138148A (en) |
| DE (1) | DE3031540C2 (en) |
| FR (1) | FR2463791B1 (en) |
| GB (1) | GB2056996B (en) |
| IT (1) | IT1193551B (en) |
| NL (1) | NL186095C (en) |
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| NL91643C (en) * | 1953-12-21 | |||
| GB905668A (en) * | 1959-04-08 | 1962-09-12 | Courtaulds Ltd | Improvements in and relating to filamentary products |
| US3125548A (en) * | 1961-05-19 | 1964-03-17 | Polyethylene blend | |
| NL135766C (en) * | 1961-09-08 | 1900-01-01 | ||
| BE634711A (en) * | 1962-07-10 | |||
| NL6412934A (en) | 1964-07-20 | 1966-01-21 | ||
| GB1233599A (en) | 1966-04-04 | 1971-05-26 | ||
| US3770852A (en) * | 1966-04-12 | 1973-11-06 | Nat Distillers Chem Corp | Polyolefin resin blends |
| DE1720611C3 (en) | 1967-01-28 | 1984-03-01 | Hoechst Ag, 6230 Frankfurt | Process for the polymerization of ethylene or its mixtures with higher alpha-olefins |
| DE1669696A1 (en) * | 1967-05-20 | 1971-08-26 | Basf Ag | Manufacture of moldings from ethylene polymers |
| US3914342A (en) * | 1971-07-13 | 1975-10-21 | Dow Chemical Co | Ethylene polymer blend and polymerization process for preparation thereof |
| US3969470A (en) * | 1975-04-21 | 1976-07-13 | E. I. Du Pont De Nemours And Company | Process for recycling hydrogen when making blends of olefin copolymers |
| FR2312511A1 (en) * | 1975-05-27 | 1976-12-24 | Naphtachimie Sa | DRY POLYMERIZATION OF OLEFINS IN SERIAL REACTORS |
| NL7509292A (en) * | 1975-08-05 | 1977-02-08 | Stamicarbon | PROCESS FOR PREPARING POLYOLEFINS WITH A WIDE MOLECULAR WEIGHT DISTRIBUTION. |
| JPS5516048A (en) * | 1978-07-20 | 1980-02-04 | Sumitomo Chem Co Ltd | Preparation of propylene-ethylene block copolymer |
| JPS5846212B2 (en) * | 1979-05-18 | 1983-10-14 | 旭化成株式会社 | polyethylene composition |
-
1979
- 1979-08-24 JP JP54107129A patent/JPS5910724B2/en not_active Expired
-
1980
- 1980-08-11 US US06/176,739 patent/US4336352A/en not_active Expired - Lifetime
- 1980-08-12 GB GB8026213A patent/GB2056996B/en not_active Expired
- 1980-08-12 CA CA000358085A patent/CA1138148A/en not_active Expired
- 1980-08-21 BR BR8005307A patent/BR8005307A/en unknown
- 1980-08-21 NL NLAANVRAGE8004745,A patent/NL186095C/en not_active IP Right Cessation
- 1980-08-21 BE BE0/201817A patent/BE884866A/en not_active IP Right Cessation
- 1980-08-21 DE DE3031540A patent/DE3031540C2/en not_active Expired
- 1980-08-22 IT IT24262/80A patent/IT1193551B/en active
- 1980-08-22 FR FR8018415A patent/FR2463791B1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| IT1193551B (en) | 1988-07-08 |
| IT8024262A0 (en) | 1980-08-22 |
| BE884866A (en) | 1980-12-16 |
| BR8005307A (en) | 1981-03-04 |
| NL186095C (en) | 1990-09-17 |
| GB2056996A (en) | 1981-03-25 |
| JPS5632506A (en) | 1981-04-02 |
| DE3031540C2 (en) | 1985-06-05 |
| DE3031540A1 (en) | 1981-04-09 |
| JPS5910724B2 (en) | 1984-03-10 |
| FR2463791B1 (en) | 1986-03-28 |
| FR2463791A1 (en) | 1981-02-27 |
| US4336352A (en) | 1982-06-22 |
| NL8004745A (en) | 1981-02-26 |
| GB2056996B (en) | 1983-11-23 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |