CA2281559A1 - Method and catalyst for producing polyolefins of medium to ultra-high molecular weight - Google Patents
Method and catalyst for producing polyolefins of medium to ultra-high molecular weight Download PDFInfo
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- CA2281559A1 CA2281559A1 CA002281559A CA2281559A CA2281559A1 CA 2281559 A1 CA2281559 A1 CA 2281559A1 CA 002281559 A CA002281559 A CA 002281559A CA 2281559 A CA2281559 A CA 2281559A CA 2281559 A1 CA2281559 A1 CA 2281559A1
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- Prior art keywords
- organic polymer
- polymer material
- compound
- supported
- catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 5
- 238000000034 method Methods 0.000 title claims description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 52
- 229920000620 organic polymer Polymers 0.000 claims abstract description 50
- 239000002861 polymer material Substances 0.000 claims abstract description 26
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 20
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims abstract description 14
- 150000003624 transition metals Chemical class 0.000 claims abstract description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000005977 Ethylene Substances 0.000 claims abstract description 12
- 229920001577 copolymer Polymers 0.000 claims abstract description 12
- 150000001336 alkenes Chemical class 0.000 claims abstract description 9
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 9
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims description 35
- 238000006116 polymerization reaction Methods 0.000 claims description 28
- -1 fluoroenyl Natural products 0.000 claims description 21
- 229910052736 halogen Inorganic materials 0.000 claims description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 20
- 125000003118 aryl group Chemical group 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 125000003545 alkoxy group Chemical group 0.000 claims description 14
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 14
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 230000000737 periodic effect Effects 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 13
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 12
- 125000003342 alkenyl group Chemical group 0.000 claims description 12
- 229910052726 zirconium Inorganic materials 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 8
- 238000003801 milling Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 150000003623 transition metal compounds Chemical class 0.000 claims description 8
- 239000012190 activator Substances 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- MYRTYDVEIRVNKP-UHFFFAOYSA-N divinylbenzene Substances C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 5
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical group CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 5
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 4
- 150000004292 cyclic ethers Chemical class 0.000 claims description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 4
- 230000009477 glass transition Effects 0.000 claims description 4
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 4
- 150000003568 thioethers Chemical class 0.000 claims description 4
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 claims description 4
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 claims description 3
- 125000004772 dichloromethyl group Chemical group [H]C(Cl)(Cl)* 0.000 claims description 3
- 229940126062 Compound A Drugs 0.000 claims description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 2
- KSFCHHFBQJDGFF-UHFFFAOYSA-L cyclopenta-1,3-diene;dichlorotitanium Chemical compound Cl[Ti]Cl.C1C=CC=C1.C1C=CC=C1 KSFCHHFBQJDGFF-UHFFFAOYSA-L 0.000 claims description 2
- QRUYYSPCOGSZGQ-UHFFFAOYSA-L cyclopentane;dichlorozirconium Chemical compound Cl[Zr]Cl.[CH]1[CH][CH][CH][CH]1.[CH]1[CH][CH][CH][CH]1 QRUYYSPCOGSZGQ-UHFFFAOYSA-L 0.000 claims description 2
- IVTQDRJBWSBJQM-UHFFFAOYSA-L dichlorozirconium;indene Chemical compound C1=CC2=CC=CC=C2C1[Zr](Cl)(Cl)C1C2=CC=CC=C2C=C1 IVTQDRJBWSBJQM-UHFFFAOYSA-L 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 125000005024 alkenyl aryl group Chemical group 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 229910052749 magnesium Inorganic materials 0.000 abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 abstract description 4
- 238000001125 extrusion Methods 0.000 abstract description 4
- 238000010096 film blowing Methods 0.000 abstract description 2
- 238000003825 pressing Methods 0.000 abstract description 2
- 238000001746 injection moulding Methods 0.000 abstract 1
- 150000002894 organic compounds Chemical class 0.000 abstract 1
- 239000004711 α-olefin Substances 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 45
- 239000000725 suspension Substances 0.000 description 19
- 239000004698 Polyethylene Substances 0.000 description 17
- 229920000573 polyethylene Polymers 0.000 description 13
- 238000009835 boiling Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000011514 reflex Effects 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 3
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical group Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 2
- JAMNSIXSLVPNLC-UHFFFAOYSA-N (4-ethenylphenyl) acetate Chemical compound CC(=O)OC1=CC=C(C=C)C=C1 JAMNSIXSLVPNLC-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- 241000274177 Juniperus sabina Species 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910001504 inorganic chloride Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000008774 maternal effect Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000003260 vortexing Methods 0.000 description 1
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/65925—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to a method for producing polyolefins of medium to ultra-high molecular weight by homo- or copolymerization of olefins, specifically ethylene, with other alpha-olefins in the presence of a metallocene-type mixed Ziegler-Natta-catalyst placed onto an organic polymer material for producing shaped bodies, for example by extrusion, injection moulding, film blowing, sinter pressing or ram extrusion. According to the invention the catalyst contains as organic polymer material a partly chloromethylated styrene-divinyl benzene copolymer, a complex compound placed onto same containing Mg, Al and transition metals of the fourth subgroup, as well as reaction products of the latter with other organic compounds and transition metals of the fourth subgroup.
Description
S .
Method of and Catatysf for Production of Medium to Ultra-High Molecular Polyolefins The invention covers a production method for medium to ulfira-high molecular poiyolef~ns by way of homopofymeriza#ion or copolymedzation of olefins, and ethylene in particular, with other a olefins in ifie presence of an organic polymer material-supported mixed metallocene Ziegler Natta catalyst for the production of moulded parts through extrusion, in~ectlon moulding, film blowing, 'sinter pressing or ram extrusion etc.
This invenfilon also refers to an organic polymer material-supported mixed rnetallocene Ziegler-Natta catalyst and a production method for a mixed metallocene Z~egiert Natta catalyst supported by an org~ic polymer material.
Homopolymerization and copolymerization of olefins in the presence of soluble homogeneous catalyst systems based on transifion metal complexes, such as titanium or zirconium wifih substituted and unsubsfiifiuted cyclopenfiadienyl ligands and aluminium-organic compounds as cocatalysts, have been known (e.g. US 4404344).
Despite various advantages of said catalysfis such systems are very difficult to handle in polymerization other than solution processes, such as suspension or gas polymerizafion, and then Lead to an insufficient morphology of #tte polymer produced.
In order to avoid such disadvantages catatyst systems have been proposed fixing at least one component on an insoluble firm supporting material to make these catalysts heterogeneous. In most applications said supporting materials are inorganic oxidic compounds, such as silicon or aluminium, often in combination with inorganic chlorides.
Catalyst systems using such supports have fihe disadvantage, however, that fihey have to undergo a high-temperature treatment when being prepared in order to remove excessive moisture and catalyst poisons which remained in the supporting material, and for catalyst conditioning. Other disaduanfiages are corrosion of the polymer finishing machinery due to a residual chlorine content in the polymers produced, and undesired processing phenomena, such as specks, caused by the inorganic supporting material remaining in the polymer.
Much fewer catalyst systems have been proposed which are based on organic polymeric supporting material.
Such supports can be used as porous polymers, such as polyethylene, polypropylene, polystyrene or copolymers as those of styrene or divinyl benzene both uncross-linked and cross-linked as non-functiona(ized substrates. Cafialyst components can be applied on the non-functionalized polymer material by combining the catalyst components with the support in solution and a subsequent removal of the solvent (e.g.
US 5498582, US 5139985, US 5118b48, EP 131832) or embedding the catalyst in the polymer by softening and stirring the polymeric support (EP 131832).
Method of and Catatysf for Production of Medium to Ultra-High Molecular Polyolefins The invention covers a production method for medium to ulfira-high molecular poiyolef~ns by way of homopofymeriza#ion or copolymedzation of olefins, and ethylene in particular, with other a olefins in ifie presence of an organic polymer material-supported mixed metallocene Ziegler Natta catalyst for the production of moulded parts through extrusion, in~ectlon moulding, film blowing, 'sinter pressing or ram extrusion etc.
This invenfilon also refers to an organic polymer material-supported mixed rnetallocene Ziegler-Natta catalyst and a production method for a mixed metallocene Z~egiert Natta catalyst supported by an org~ic polymer material.
Homopolymerization and copolymerization of olefins in the presence of soluble homogeneous catalyst systems based on transifion metal complexes, such as titanium or zirconium wifih substituted and unsubsfiifiuted cyclopenfiadienyl ligands and aluminium-organic compounds as cocatalysts, have been known (e.g. US 4404344).
Despite various advantages of said catalysfis such systems are very difficult to handle in polymerization other than solution processes, such as suspension or gas polymerizafion, and then Lead to an insufficient morphology of #tte polymer produced.
In order to avoid such disadvantages catatyst systems have been proposed fixing at least one component on an insoluble firm supporting material to make these catalysts heterogeneous. In most applications said supporting materials are inorganic oxidic compounds, such as silicon or aluminium, often in combination with inorganic chlorides.
Catalyst systems using such supports have fihe disadvantage, however, that fihey have to undergo a high-temperature treatment when being prepared in order to remove excessive moisture and catalyst poisons which remained in the supporting material, and for catalyst conditioning. Other disaduanfiages are corrosion of the polymer finishing machinery due to a residual chlorine content in the polymers produced, and undesired processing phenomena, such as specks, caused by the inorganic supporting material remaining in the polymer.
Much fewer catalyst systems have been proposed which are based on organic polymeric supporting material.
Such supports can be used as porous polymers, such as polyethylene, polypropylene, polystyrene or copolymers as those of styrene or divinyl benzene both uncross-linked and cross-linked as non-functiona(ized substrates. Cafialyst components can be applied on the non-functionalized polymer material by combining the catalyst components with the support in solution and a subsequent removal of the solvent (e.g.
US 5498582, US 5139985, US 5118b48, EP 131832) or embedding the catalyst in the polymer by softening and stirring the polymeric support (EP 131832).
Such procedures have turned out to be disadvantageous in so far that the catalysts not firmly fixed on the polymeric support, are exposed, especially during polymerization, to constant abrasion from the surface by fihe suspending agent, the monomers or vortexing in the gas-phase process, for example. and the embedding of the catalyst in the polymeric supports makes them partially inaccessible for polymerization reactions. This leads, among other things, to a less active catalyst system and a high proportion of undesired very fine polymer particles.
On the other hand, procedures are known which overcome such disadvantages. by a firm fixation of the catalyst components on the polymer surface by forming chemical bonds through functional groups of the supporting maternal.
Known solutions for that purpose are catalysts composed of bis-cyclopentadienyl zirconium compounds and methyl alumoxanes on styrene divinyl benzene polymers containing p-acetoxystyrene {US 5461017}. if applied on industrial scale said catalysts have the disadvanfiage tfiat they need cocafialysts which are very costly and insuf~cienfily available.
In addition to that supported catalysts are known to reach a firm fixation of the catalyst components on the organic polymer materials by chemical reaction of chlorine, for example, being present in the supporfiing materials as it is the case with polyvinyl chloride or chlorine-methylated styrene divinyl benzene polymers, and using as transition metal compounds those of titanium (US 44.77639, DD 282013).
Particular disadvantages here are that even if the amount of residual catalyst in the polymer is very tow the polymers produced by such catalyst systems always have a markedly poorer self colour compared to other catalyst systems based on zirconium. The use of a special transition metal for the catalyst system has also a negative impact on the range of product properties achievable for the polymers produced with such system.
Other disadvantages of the known solutions for a firm fixation of the catalyst components on the polymer surface by forming chemical bonds through functional groups of the supporting material are polymerization activities of the catalyst systems which are frequently insufficient for industrial applications, too costly a manufacture of the supported catalysts in multi-stage processes requiring a repeated addition and separation of solvents, a necessary separation of inert reaction media prior to catalyst feeding and too low a flexibility when it comes to adjusting the product properties, particularly the flow behaviour and molecular mass parameters respectively, which excludes the production of poiyolefcns using ultra-high molecular weights, for example (e.g. DD 257431, DD 275b93).
On the other hand, procedures are known which overcome such disadvantages. by a firm fixation of the catalyst components on the polymer surface by forming chemical bonds through functional groups of the supporting maternal.
Known solutions for that purpose are catalysts composed of bis-cyclopentadienyl zirconium compounds and methyl alumoxanes on styrene divinyl benzene polymers containing p-acetoxystyrene {US 5461017}. if applied on industrial scale said catalysts have the disadvanfiage tfiat they need cocafialysts which are very costly and insuf~cienfily available.
In addition to that supported catalysts are known to reach a firm fixation of the catalyst components on the organic polymer materials by chemical reaction of chlorine, for example, being present in the supporfiing materials as it is the case with polyvinyl chloride or chlorine-methylated styrene divinyl benzene polymers, and using as transition metal compounds those of titanium (US 44.77639, DD 282013).
Particular disadvantages here are that even if the amount of residual catalyst in the polymer is very tow the polymers produced by such catalyst systems always have a markedly poorer self colour compared to other catalyst systems based on zirconium. The use of a special transition metal for the catalyst system has also a negative impact on the range of product properties achievable for the polymers produced with such system.
Other disadvantages of the known solutions for a firm fixation of the catalyst components on the polymer surface by forming chemical bonds through functional groups of the supporting material are polymerization activities of the catalyst systems which are frequently insufficient for industrial applications, too costly a manufacture of the supported catalysts in multi-stage processes requiring a repeated addition and separation of solvents, a necessary separation of inert reaction media prior to catalyst feeding and too low a flexibility when it comes to adjusting the product properties, particularly the flow behaviour and molecular mass parameters respectively, which excludes the production of poiyolefcns using ultra-high molecular weights, for example (e.g. DD 257431, DD 275b93).
So, it has been the task of said invention to develop a production method for medium to ultra-high molecular polyethylene by way of homopolymerization or copoiymerization of ethylene using o~-oieflns in the presence of an organic polymer-supported mixed metaflocene Ziegler-Natta cataiyst and to develop an organic polymer-supported mixed metalfocene Zieg~er Natfa catalyst which do not have the disadvantages mentioned above and feature a high polymerization activity, a low residual catalyst content and an excellent colour of the polymer as well as a tow-cost production of the same.
According to the invention the polymerization for the production of medium to ultra-high molecular polyethylene by way of homopoiymerization and copolymerization of ethylene using a olefins in the presence of an organic polymer material-supported mixed metailocene Ziegler-Natta catalyst is initiated by 1. an organic polymer material-supported mixed metaliocene ~egier-Natta catalyst confiaining a) as organic polymer material a partially chlorine-methylated styrene divinyi benzene copolymer with a - divinyf benzene content between 1 and 45 ~ wt.
- chlorine content between 5 and 23 ~ wt.
- specific surface area between 5 and I,OOg m2lg. and a - grain size between 5d and 3,000 Vim.
b} a complex compound supported by the said organic polymer material with the general formula (i~r"MgX2-ire) {i~nAiY3.r,~, {Z,4Me'Xa.q} EDr where R - alkyl, cycloaikyl, aryl, aralkyl, aikaryi, alkenyi X - halogen Y - hydrogen, halogen, alkaxy Z - cyclopentadienyl, fluoroenyi, indenyi and their substitutes or hydrogenated compounds Me' - transition metal of fV~" subgroup of periodic system ED - organic compounds acting as electron donator, e. g. linear or cyclic ethers, thioethers and others;
m - 1 or 2 ':.
..
' 4 n - numeric value between 1 and 3 p - numeric value between O.l and 1 q - 1,2,3or4 -r - numeric value between 1 and 2 c) the reaction product of the organic polymer material-supported complex compound of b) with a mixture of A) a compound of the genera! formula XnMe2 Ya-r"
where X, Y - halogen, alkyl, alkenyl, aryl, alkaryi. araikyi, alkoxy, aroxy Mez = transifiion metal of IVt" subgroup of periodic sysfiern m - i,23or4, and B) a compound of the general formula RnCXa-n where R - hydrogen, alkyl, aryl, alkaryl, aralkyl, chloromethyl, dichloromethyl, trichloromethyl or part(atty hafogenated alkyl X - halogen, alkyl, alkenyl, aryl, alkaryl, aralkyl, alkoxy, aroxy n-0, l,2or3 at a molar ratio of compounds A) and B) ranging between 1 : 0. ~ to 1 : 2, with - the parent substance for the organic polymer material supported compound under b) being obtained by intensive milling of the organic polymer material with the transition metal compound below the glass-transition temperature of fihe polymer under anaerobic conditions;
- the transition metals of ifie IV'" subgroup of fhe periodic system of the organic polymer material-supported complex compound under b) Me' and the compound of the general formula under A) of fine reaction product under c) Me2 being of a different nature, and 2. a compound serving as an activator and not condensed as alumoxane of the general formula l~",AIYa.,n where R - altcyl, cyeioalkyt, aryl, atkaryt, araftcyl, alkenyt Y - hydrogen, halogen, atkoxy m - numeric value between 1 and 3.
According to the invention the organic polymer material can be a partially chEorine-methylated styrene-divinyi benzene copolymer with a - dhrinyi benzene content between 2 and 25 ~ wt.
- chiadne content between 15 and 22.5 96 wt.
- specfic surface area between 10 and 30Q mZlg, and a - grain size between 80 and 2,tM70 ~. m.
According to the invention transition metals of the tV'n subgroup of ifie pertodic system Me' and Me2 can be those of zirconium and titanium.
Contained in the organic polymer material-supported compound Mel as transition metal of tV'" subgroup of the periodic system can be that of zirconium and in the compound A) of the reacfiion mixture Mez that of fitanium.
b According to the invention the compound acting as an activator and not condensed as alumoxane can be tn'isobutyi aluminium.
According to the invention a bis(cycloperytadienylrtitanium dichloride can serve as a transition rneinl compound for the parsnt substrate formed through intensive milting with fhe organic polymer material for the organic polymer material-supported compound. The transition metal compound for the parent substrate formed through intensive milting with the organic polymer material for the organic polymer material-supported compound can also be a bis(cyclopentadienyt}-zirconium dichloride, a bis(indenyl~
zirconium dichloride or a bis(fluoroenylrzirconium dichloride.
According to ifie invention the polymer produced by way of homopoiymerization or copolymerization of ethylene using a-olefins in the presence of an organic potymer material-supported mixed metallocene Ziegier-Natta catalyst can have viscoslties befween 200 and 3.f700 ml/g.
According to the ir~venfion the organic polymer material-supported mixed metallocene Ziegier-Natty catalyst may contain:
a} as an organic polymer material a partially chlorine-methylated styrene divinyl benzene copafymer wiifi a - divinyl benzene content between 1 and 45 °~ wt.
- chlorine content between 5 and 23 ~ wfi.
- specific surface area of 5 to 1,000 m2(g, and a - grain size befinreen 50 and 3,000 ~.m, b) a complex compound supported by the above polymer mafierial the general formula being RmMgX2.m} . (RnAfY3.a}p . (ZqMe~Xa-~ . EDr where R - alkyl, cycloalkyl, aryl. aralkyl, alkaryl, atkenyl X - halogen Y - hydrogen, halogen. alkoxy Z - cyciopentadienyl, fluoroenyl, indenyl and their substituted and hydrogenated compounds respectively ~S . ' L
Me' - firansifiion metal of iVm subgroup of periodic system ED - organic compounds acting as electron donoior such as linear or cyclic ethers, thioethers and others m -1 or2 n - numeric value between 1 and 3 p - numeric value between 0.1 and 1 q -1,7,3,or4 r - numeric value befiween 1 and 2 c) reaction product of the organic polymer material-supported comptex compound of b) with a mixfiure of A) _ a compound of the general formula XrnMe2 Y4-m where X, Y -halogen, alkyl, alkenyl, aryl, aikaryl, araikyl, alkoxy, aroxy;
Me2- transition metal of iV'" subgroup of periodic system m -1,2,3or4, and g) a compound of the general formula RnCXa-n where R - hydrogen, alkyl, aryl, alkaryl, aralkyi, chloromethyi, dichloromethyf, trichloromethyl or partially halogenated alkyl;
X - halogen, alkyl, alkenyl, aryl, alkaryl, aralkyt, alkoxy. aroxy;
n -0, 1, 2or3 at a molar ratio of the compounds A) and B) between 1 : 0.1 and 1 : 2 with - the parent substrate for the organic polymer material-supported compound under b) being obtained by intensive milling of organic polymer material wim me transition metal compound below tfie glass-transition temperature of the polymer under anaerobic condfions;
- the transition metals of iV"~ subgroup of periodic system of the organic polymer material-supported complex com-pound under (b) Me° and the compound of the general formula under A) of the reaction product under c) Mea being of a different nature. and - the organic polymer material-supported mixed rnetallocene Zegler-Natta catalyst being activated by a compound not condensed as alumoxane of the general formula R~,AIYa-", where R - alkyl, cycloalkyl, aryl, alkaryi, aralkyi, alkenyl Y - hydrogen, halogen, alkoxy m - numerical value between 1 and 3.
According to the invention the organic polymer material-supported mixed metailocene Ziegler-Natta catalyst can be made by causing the a. m. components to react with each other in the given order.
- _ CA 02281559 1999-08-19 According to the invention, an organic polymer materiel-supported mired metaliocene Zlegler Natta catalyst as described above can be used as the catalyst system and a compound not condensed as alumoxane with the given general formula can be used as an activator for the manufacture of txxnopotymers and multipotymers of C2 to C,2alkenes.
The homopolymers and copolymers of olefins developed and prepared using such catalysts feature an excellent morphology wifih no major part of very fine polymer particles caused by abrasion of the catalyst fixed on the polymer surface, and very good optical properties. A very high flexibility can be actveved when it comes to adjusting the product properties, !. e. stow behaviaur and molecular weight parameters when using the same catalyst system, which permits, for example, the production of polyoletins of uitra-high molecular weight. No corrosion appears on the polymer finishing machines and also no undesired processing phenomena, such as specks.
-fhe supported mixed metaltocene T~egler-Natty catalyst shows a good handling in the different polymerization processes for the production of polyolefins, a high polymerization actrvity and an easy accessibltrty obviating the need of using insufficiently available cacatalysts without high-temperature treatment and without multiple separation of inert reaction media.
The following describes several selected appiicafiions in deta~7.
Example I
a) Preparation of a supported mixed metailocene T~egler Natty catalyst In a mixture of 32.1 ml dried hexane and 3 .77 mi dried tetrahydrofurane 0.394 g magnesium chips were dispersed under anaerobic conditions, and caused to react through boiling, 'rf necessary, with a trace of iodine at the reflex by stirring with 2.22 ml distilled n-butyl chloride being added dropwise over a period of approx. 10 minutes. After another 4.5 hours of boiling at the reflex ifie magnesium chips were totally dissolved and the formation of the magnesium-organic compound completed.
Then, over a period of 25 minutes a quantity of 15.47 mi triisobutyl aluminium in the form of a 5 ~ solution in hexane was added dropwise to a boiling suspension and heated for another hour while being stirred at the reflex. At room temperature 3.10 g of a mixture of 25 ~ wt. bis(indenyl)-zirconium dichloride and 75 ~b wt.
partially chlorine-methyiated styrene-divinyl benzene copolymer formed through anaerobic intensive milling in a Syalon cup using a. planetary micromill, with a - divinyi benzene content of 5.5 96 wt.
- chlorine content of 21.b 9o wt.
- specific surface area of 55 mzig, and a - grain size between 300 and 1,200 tun is added to this 5uspenStOn. After that while being cooled down a mixture of 0.44 rnl l .2-dichloroethane, i2 ml hexane and 0.40 ml titanium tetrachloride was added dropwise and left in the boiling heat for another two hours.
The resulting light brown suspension of the mixed catalyst contained about 1.3 mg titanium per ml of suspension and approx. O.b2 mg zirconium per ml of suspension.
b) Polymerization using the supported mixed metallocene Ziegler-Naita catalyst According to the figures of Table I hexane containing trlisobufyl aluminium as an activator was filled Into a secured and ethylene-flushed agitated autoclave, the relevant amount of the mixed catalyst suspension made as given under a) was added in the form of diluted hexane and ethylene was applied at a pressure of two bar. After rapid heating up of the mixture to the polymerization temperature of 85 °C while being intensively agitated, the ethylene pressure was finally set according to the value of Table 1 and kept constant by continuously replenishing tfie used up monomer over the polymerization period of two hours. Replenishing was then interrupted to finish the test, the reactor content cooled down, expanded and polyethylene ~Ifiered off and dried.
The results of polymerization and the properties of the formed polyethylene can be seen in Table 2. The test shows that it is possible to obtain a polymer of excellent morphology, such as a high bulk density, a very high viscosity number and hence, a very high malecuiar weight by using an organic polymer material-supported mixed metallocene Ziegler-Natta catalyst according to ifie invention. The product also features an excellent self colour, which can be seen from the high colour index C~ and can be produced with a very high catalyst yield. The mixed catalyst proper can be made and used applying a simple method without high-temperature treatment and without multiple separation of Inert reacfion media in the form of a suspension or their dilutes and obviates the need of using insufficiently available cocatalysts.
~,xamoie 2 Cfor comparison) a) Preparation of a supported metaliocene Zegler-Natta catalyst When making this catalyst the procedure of Example 1 Was applied but titanium tetrachloride was substituted by zirconium tetrachloride. Thus, 32.6 ml hexane, 1.8 mi tetrahydrofurane and 0.40 g magnesium chips reacted with 2.25 ml n-buiylchloride and 15.4 ml triisobutyl aluminium as a solution added dropwise and 3.147 g of the ground material of bls(indenyi)-zirconium dichloride and the partially chlorine-methylated styrene-divinyi benzene copolymer of Example l introduced at fhe mass ratio indicated there. After further reaction with 0.45 ml 1.2-dichloroethane, 12.2 ml hexane and 0.65 ml zirconium tetrachloride a catalyst suspension containing approx.
1.4 mg zirconium per rnl of suspension was formed.
b) Polymerization using the supported metaflocene Z~egfer-Natty catalyst Polymerization using the Ziegier-Natty catalyst made under a) based on zirconium as a transition metal was carried out similarly to the polymerization in Example i and the figures are given in 'table 1. Since no ethylene decrease was found after one hour of reaction, catalyst suspension containing 0.212 mg zirconium was again added, and the test stopped after another 10 minutes because no ethylene was consumed.
With this kind of polymerlzafiion only traces of non-separable polyethylene could be obtained i,~ the form of a wail encrustation difficult to remove. , This example shows that no medium to ultra-high molecular polyethylenes with the desired properties can be obtained if other than the procedure described in the invention is applied.
Example 3 a) Preparation of supported mixed metallocene Ziegier-Natty catalyst In a mixture of 27.0 ml dried hexane and 1.49 m! dried tetrahydrofurane 0.33 g magnesium chips were dispersed under anaerobic conditions and caused to react while boiling, if necessary with a trace of iodine at the reflux, stirring the same with 1.86 mi distilled n-butyl chloride added dropwise over a period of approx. 10 minutes, After another 11 hours of boiling at the reflex the magnesium chips were completely dissolved and the formation of the magnesium-organic compound completed. Then, over a period of 30 minutes a quantity of I 1.Q ml triisobutyl aluminium was dropped into the boiling suspension in the form of 5 ~ solution in hexane and heated up for another hour sfirring it at the reflex.
At room temperature 2.b05 g of a mixture of 25 96 wt. bis(cyclopentadienyl)-zirconium dichloride and 75 96 wt. partially chlorine-methylated styrene-divinyl benzene copolymer obtained by anaerobic intensive milling in a Syalon cup using a planetary micromill, with a - divinyi benzene content of 5.5 96 wt.
-chlorine content of 21.6 ~ wt.
specil9c surface area of 55 m2/g, and a - grain size between 300 and 1.200 ~.m were fed to this suspension.
After that while cooling the suspension a mixture of 0.37 ml 1.2-dichioroethane. 10.1 mi hexane and 0.34 ml titanium tetrachloride were added dropwise and left in the boiling heat for another two hours.
The resulting light brown suspension of the mixed catalyst contained approx.
1.1 n,g titanium per ml suspension and approx. 0.91 mg zirconium per ml suspension.
b) Polymerization using the supported mixed metallocene Ziegier-Natty catalyst For the polymerization using the supported mixed metaifocene Ziegler Naita catalyst formed according to a) on the basis of zirconium and titanium as transition metals the procedure described in Example 1 was chosen. The used quantities of catalyst suspension and activator as well as soiVents and the sefi partial pressure of ethylene can be gathered from Table 1.
i2 Table 3 gives the polymerization results and properties of the polyethylene produced. it can be seen that the mixed catalyst according to the invention has a high pvlymerizatton activity. This cafnlyst; too, ccrn be easily produced obviating the need of t,igi,-temperature treatment and multiple separafiion of inert reaction media and can be used without insuf~cientfy avallabe cocatalysts.
The polymer proper features a very high moleCUlar weight. a high bulk density and an excellent self-colour. Excellent is also the law proportion of very fine polymer particles caused by abrasion of the catalyst fixed on the polymer surtace, which results from the low proportion of polymer with a grain size below 250 ~m in the entire grain size range.
The polymer also shows a low ash and a low residual catalyst content as well as a sufficiently high temperature of the oxidation maximum.
~xamnle 4 Cfor comparison a) Preparation of supported metallocene Ziegler-Natta catalyst The Said Catalyst was Synthesized similarly to Example 3 but ifie.bis(cyclopentadienyl)-zirconium dichloride was replaced by bis(cyctopentadienyl}-titanium dichloride.
Consequently, 36.3 mi hexane, 2 ml tetrahydrofurane and 0.445 g magnesium chips were caused fio react with 2.5 mi n-butyl chloride and 16.5 ml triisobutyl aluminium as a solution in hexane were added and 3.064 g of a ground substance consisting of one part by weight of bis(cyclopentadienyl)-titanium dichloride and three parts by weight of the partially chlorine-methytated styrene divinyl benzene copolymer described in Example 3 were injected. Then, the reaction with 0.5 ml 7 .2 dichloroethane, i3.b mi hexane and 0.35 ml titanium tetrachloride took place. The obtained cocoa-brown catalyst suspension contained approx. 1.7 mg titanium per mi of suspension.
b) Polymerization using ifie supported metallocene Ziegier-Natta catalyst In tfils example polymerization Was carried out with the catalyst produced under a) on the basis of titanium as transition metal only following the data of Example 3 and Table 1. The properties of the polyethylene thus obtained and the results of polymerization are compared with Example 3 and can be gathered, from Table 3.
it can be clearly seen that if the procedure Is other than according to the invention polymers with a comparable molecular weight can be produced but have not the desired properties. Polymers produced otherwise than according to the invenfiion.
have a lower bulk density, a considerably poorer colour index, a very large quantity of a grain size below 250 Vim, a markedly worse ash and residual catalyst content, a lower temperature of the oxidation maximum and a lower molecular catalyst output, Example 5 a) Preparation of supported mixed metallocene Tiegler-fVatta catalyst The supported mixed metallocene Ziegler-Natta catalysfi on the basis of t~is<cycSopentadienyl)-zirconium dichloride and tifianium tetrachloride was prepared in the same way as described in Example 3.
b) Polymerization using supported mixed metallacene Ziegler-Natta catalyst Polymerization was carried out as given in F-xample 3 and Table I. But in this example the process took place in the presence of hydrogen the partial pressure of which was adjusted after the firsfi partial quantity of ethylene had been applied at room temperature. Table 4 gives the polymerization results and the properties of the resulting polyethylene. The lower polymer viscosity number achieved because of the use of hydrogen shows the high flexibility of the mixed catalyst when It comes to the adjustment of the product features and the flow behaviour and the molecular weight parameters in particular, when using the same catalyst system as given in Example 3.
The producfi also features, despite a relatively low viscosity number, an excellent colour index confirming the outstanding optics of the polymer produced according to the 'snventian.
Examt~le b a) Preparation of supported mixed metallocene Ziegler-Nafita catalyst The supported mixed metallocene Ziegler-Natta catalyst using the components bis<cyclopenfiadlenylrzirconium dichloride and titanium tetrachloride was prepared as described in Example 3.
b) Polymerization using supported mixed metallocene Ziegler-Nafita catalyst The polymer was made as given.in Example 5 and Table I. in addition to Example butene was used as comonomer and as a solution In hexane at a concentration of 111.3 ml butenelml added after the reaction temperature had been reached and the pressure adjusted.
A summary of results of polymerization and properties of fihe polyethylene formed is given in Table 4. Here too, the advantages of the method according to the invention are clearly visible even if butane was added as a comonomer.
Examales 7 and B
a) Preparation of supported mixed metailacene Ziegier-hlatta catalyst The supported mixed metallocene Ziegler-Natta catalyst was made according to Example 3 based on bis(cyciopenfiadfenyl)-zirconium dichloride and titanium tetrachloride.
b) Polymerization using supported mixed metallocene Zlegler-Natta catalyst Pofymerizafion took place as described in Example ~ and under consideration of the f(gures given In Table 1. instead of butene as a comonomer hexene also dissolved in hexane was used but with a hexene content of 25.2 9b wt. It was added to the reaction mixture in ten equidisfiant time steps over the entire period of polymerizafion and at equal partial amounts.
Table 4 gives 1fie polymerization results and the polyethylene properties reflecting the advantages of the method according to the invention and the high flexibility of the mixed catalyst even if hexene fs used as a comonomer.
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Table 2 Polymerfzatfon results and polyethylene propsrtles of Example 1 Properties Unit Value Pot mertzatton rest~Its Po1 mer field 225.3 Catal st field kg PE/g (Zr+Ti) 1 656.5 Catalyst yield kg PE/mmol (Lr f Ti) 102.3 Pot eth tone ro erttes BuIK densi DIN 53468 /I 334 Densi 1S01183 /cm3 0.939 Yscosity number SO 7191 crn3/ 1 310 Colour index Cv Hunter Lab 115.6 Table 3 Polymerization results and polyettrylene properties of Examples 3 and Pro erties Unit Exam Exam le to Pol merization _ results Pof mar field 168.7 i fi7.4 Catal st field k PE/ Me 827 88T
Catat st field k PE mmol 50.7 42.2 Me Poi ~th lane ro erHes Bulk density g/I 292 27fi DIN 534b8 Densi SO 7 T /cm3 ~ 0.938 0.937 Viscosity number SO T 19 T cm3l T 594 1 722 Colour index Cv Hunter Lab ' T T7.0 112.0 Grain size distribution Medium rain size 549 295 Proportion up to 250 m ~ 21.6 45.3 Residual catai st in of mars Ti m wt 0.8 1.8 Zr m wt 2. T
_ _ AI m wt 88 Ash m wt 230 490 Temperature of C . 209.8 2117.3 oxidation maximum DTA
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According to the invention the polymerization for the production of medium to ultra-high molecular polyethylene by way of homopoiymerization and copolymerization of ethylene using a olefins in the presence of an organic polymer material-supported mixed metailocene Ziegler-Natta catalyst is initiated by 1. an organic polymer material-supported mixed metaliocene ~egier-Natta catalyst confiaining a) as organic polymer material a partially chlorine-methylated styrene divinyi benzene copolymer with a - divinyf benzene content between 1 and 45 ~ wt.
- chlorine content between 5 and 23 ~ wt.
- specific surface area between 5 and I,OOg m2lg. and a - grain size between 5d and 3,000 Vim.
b} a complex compound supported by the said organic polymer material with the general formula (i~r"MgX2-ire) {i~nAiY3.r,~, {Z,4Me'Xa.q} EDr where R - alkyl, cycloaikyl, aryl, aralkyl, aikaryi, alkenyi X - halogen Y - hydrogen, halogen, alkaxy Z - cyclopentadienyl, fluoroenyi, indenyi and their substitutes or hydrogenated compounds Me' - transition metal of fV~" subgroup of periodic system ED - organic compounds acting as electron donator, e. g. linear or cyclic ethers, thioethers and others;
m - 1 or 2 ':.
..
' 4 n - numeric value between 1 and 3 p - numeric value between O.l and 1 q - 1,2,3or4 -r - numeric value between 1 and 2 c) the reaction product of the organic polymer material-supported complex compound of b) with a mixture of A) a compound of the genera! formula XnMe2 Ya-r"
where X, Y - halogen, alkyl, alkenyl, aryl, alkaryi. araikyi, alkoxy, aroxy Mez = transifiion metal of IVt" subgroup of periodic sysfiern m - i,23or4, and B) a compound of the general formula RnCXa-n where R - hydrogen, alkyl, aryl, alkaryl, aralkyl, chloromethyl, dichloromethyl, trichloromethyl or part(atty hafogenated alkyl X - halogen, alkyl, alkenyl, aryl, alkaryl, aralkyl, alkoxy, aroxy n-0, l,2or3 at a molar ratio of compounds A) and B) ranging between 1 : 0. ~ to 1 : 2, with - the parent substance for the organic polymer material supported compound under b) being obtained by intensive milling of the organic polymer material with the transition metal compound below the glass-transition temperature of fihe polymer under anaerobic conditions;
- the transition metals of ifie IV'" subgroup of fhe periodic system of the organic polymer material-supported complex compound under b) Me' and the compound of the general formula under A) of fine reaction product under c) Me2 being of a different nature, and 2. a compound serving as an activator and not condensed as alumoxane of the general formula l~",AIYa.,n where R - altcyl, cyeioalkyt, aryl, atkaryt, araftcyl, alkenyt Y - hydrogen, halogen, atkoxy m - numeric value between 1 and 3.
According to the invention the organic polymer material can be a partially chEorine-methylated styrene-divinyi benzene copolymer with a - dhrinyi benzene content between 2 and 25 ~ wt.
- chiadne content between 15 and 22.5 96 wt.
- specfic surface area between 10 and 30Q mZlg, and a - grain size between 80 and 2,tM70 ~. m.
According to the invention transition metals of the tV'n subgroup of ifie pertodic system Me' and Me2 can be those of zirconium and titanium.
Contained in the organic polymer material-supported compound Mel as transition metal of tV'" subgroup of the periodic system can be that of zirconium and in the compound A) of the reacfiion mixture Mez that of fitanium.
b According to the invention the compound acting as an activator and not condensed as alumoxane can be tn'isobutyi aluminium.
According to the invention a bis(cycloperytadienylrtitanium dichloride can serve as a transition rneinl compound for the parsnt substrate formed through intensive milting with fhe organic polymer material for the organic polymer material-supported compound. The transition metal compound for the parent substrate formed through intensive milting with the organic polymer material for the organic polymer material-supported compound can also be a bis(cyclopentadienyt}-zirconium dichloride, a bis(indenyl~
zirconium dichloride or a bis(fluoroenylrzirconium dichloride.
According to ifie invention the polymer produced by way of homopoiymerization or copolymerization of ethylene using a-olefins in the presence of an organic potymer material-supported mixed metallocene Ziegier-Natta catalyst can have viscoslties befween 200 and 3.f700 ml/g.
According to the ir~venfion the organic polymer material-supported mixed metallocene Ziegier-Natty catalyst may contain:
a} as an organic polymer material a partially chlorine-methylated styrene divinyl benzene copafymer wiifi a - divinyl benzene content between 1 and 45 °~ wt.
- chlorine content between 5 and 23 ~ wfi.
- specific surface area of 5 to 1,000 m2(g, and a - grain size befinreen 50 and 3,000 ~.m, b) a complex compound supported by the above polymer mafierial the general formula being RmMgX2.m} . (RnAfY3.a}p . (ZqMe~Xa-~ . EDr where R - alkyl, cycloalkyl, aryl. aralkyl, alkaryl, atkenyl X - halogen Y - hydrogen, halogen. alkoxy Z - cyciopentadienyl, fluoroenyl, indenyl and their substituted and hydrogenated compounds respectively ~S . ' L
Me' - firansifiion metal of iVm subgroup of periodic system ED - organic compounds acting as electron donoior such as linear or cyclic ethers, thioethers and others m -1 or2 n - numeric value between 1 and 3 p - numeric value between 0.1 and 1 q -1,7,3,or4 r - numeric value befiween 1 and 2 c) reaction product of the organic polymer material-supported comptex compound of b) with a mixfiure of A) _ a compound of the general formula XrnMe2 Y4-m where X, Y -halogen, alkyl, alkenyl, aryl, aikaryl, araikyl, alkoxy, aroxy;
Me2- transition metal of iV'" subgroup of periodic system m -1,2,3or4, and g) a compound of the general formula RnCXa-n where R - hydrogen, alkyl, aryl, alkaryl, aralkyi, chloromethyi, dichloromethyf, trichloromethyl or partially halogenated alkyl;
X - halogen, alkyl, alkenyl, aryl, alkaryl, aralkyt, alkoxy. aroxy;
n -0, 1, 2or3 at a molar ratio of the compounds A) and B) between 1 : 0.1 and 1 : 2 with - the parent substrate for the organic polymer material-supported compound under b) being obtained by intensive milling of organic polymer material wim me transition metal compound below tfie glass-transition temperature of the polymer under anaerobic condfions;
- the transition metals of iV"~ subgroup of periodic system of the organic polymer material-supported complex com-pound under (b) Me° and the compound of the general formula under A) of the reaction product under c) Mea being of a different nature. and - the organic polymer material-supported mixed rnetallocene Zegler-Natta catalyst being activated by a compound not condensed as alumoxane of the general formula R~,AIYa-", where R - alkyl, cycloalkyl, aryl, alkaryi, aralkyi, alkenyl Y - hydrogen, halogen, alkoxy m - numerical value between 1 and 3.
According to the invention the organic polymer material-supported mixed metailocene Ziegler-Natta catalyst can be made by causing the a. m. components to react with each other in the given order.
- _ CA 02281559 1999-08-19 According to the invention, an organic polymer materiel-supported mired metaliocene Zlegler Natta catalyst as described above can be used as the catalyst system and a compound not condensed as alumoxane with the given general formula can be used as an activator for the manufacture of txxnopotymers and multipotymers of C2 to C,2alkenes.
The homopolymers and copolymers of olefins developed and prepared using such catalysts feature an excellent morphology wifih no major part of very fine polymer particles caused by abrasion of the catalyst fixed on the polymer surface, and very good optical properties. A very high flexibility can be actveved when it comes to adjusting the product properties, !. e. stow behaviaur and molecular weight parameters when using the same catalyst system, which permits, for example, the production of polyoletins of uitra-high molecular weight. No corrosion appears on the polymer finishing machines and also no undesired processing phenomena, such as specks.
-fhe supported mixed metaltocene T~egler-Natty catalyst shows a good handling in the different polymerization processes for the production of polyolefins, a high polymerization actrvity and an easy accessibltrty obviating the need of using insufficiently available cacatalysts without high-temperature treatment and without multiple separation of inert reaction media.
The following describes several selected appiicafiions in deta~7.
Example I
a) Preparation of a supported mixed metailocene T~egler Natty catalyst In a mixture of 32.1 ml dried hexane and 3 .77 mi dried tetrahydrofurane 0.394 g magnesium chips were dispersed under anaerobic conditions, and caused to react through boiling, 'rf necessary, with a trace of iodine at the reflex by stirring with 2.22 ml distilled n-butyl chloride being added dropwise over a period of approx. 10 minutes. After another 4.5 hours of boiling at the reflex ifie magnesium chips were totally dissolved and the formation of the magnesium-organic compound completed.
Then, over a period of 25 minutes a quantity of 15.47 mi triisobutyl aluminium in the form of a 5 ~ solution in hexane was added dropwise to a boiling suspension and heated for another hour while being stirred at the reflex. At room temperature 3.10 g of a mixture of 25 ~ wt. bis(indenyl)-zirconium dichloride and 75 ~b wt.
partially chlorine-methyiated styrene-divinyl benzene copolymer formed through anaerobic intensive milling in a Syalon cup using a. planetary micromill, with a - divinyi benzene content of 5.5 96 wt.
- chlorine content of 21.b 9o wt.
- specific surface area of 55 mzig, and a - grain size between 300 and 1,200 tun is added to this 5uspenStOn. After that while being cooled down a mixture of 0.44 rnl l .2-dichloroethane, i2 ml hexane and 0.40 ml titanium tetrachloride was added dropwise and left in the boiling heat for another two hours.
The resulting light brown suspension of the mixed catalyst contained about 1.3 mg titanium per ml of suspension and approx. O.b2 mg zirconium per ml of suspension.
b) Polymerization using the supported mixed metallocene Ziegler-Naita catalyst According to the figures of Table I hexane containing trlisobufyl aluminium as an activator was filled Into a secured and ethylene-flushed agitated autoclave, the relevant amount of the mixed catalyst suspension made as given under a) was added in the form of diluted hexane and ethylene was applied at a pressure of two bar. After rapid heating up of the mixture to the polymerization temperature of 85 °C while being intensively agitated, the ethylene pressure was finally set according to the value of Table 1 and kept constant by continuously replenishing tfie used up monomer over the polymerization period of two hours. Replenishing was then interrupted to finish the test, the reactor content cooled down, expanded and polyethylene ~Ifiered off and dried.
The results of polymerization and the properties of the formed polyethylene can be seen in Table 2. The test shows that it is possible to obtain a polymer of excellent morphology, such as a high bulk density, a very high viscosity number and hence, a very high malecuiar weight by using an organic polymer material-supported mixed metallocene Ziegler-Natta catalyst according to ifie invention. The product also features an excellent self colour, which can be seen from the high colour index C~ and can be produced with a very high catalyst yield. The mixed catalyst proper can be made and used applying a simple method without high-temperature treatment and without multiple separation of Inert reacfion media in the form of a suspension or their dilutes and obviates the need of using insufficiently available cocatalysts.
~,xamoie 2 Cfor comparison) a) Preparation of a supported metaliocene Zegler-Natta catalyst When making this catalyst the procedure of Example 1 Was applied but titanium tetrachloride was substituted by zirconium tetrachloride. Thus, 32.6 ml hexane, 1.8 mi tetrahydrofurane and 0.40 g magnesium chips reacted with 2.25 ml n-buiylchloride and 15.4 ml triisobutyl aluminium as a solution added dropwise and 3.147 g of the ground material of bls(indenyi)-zirconium dichloride and the partially chlorine-methylated styrene-divinyi benzene copolymer of Example l introduced at fhe mass ratio indicated there. After further reaction with 0.45 ml 1.2-dichloroethane, 12.2 ml hexane and 0.65 ml zirconium tetrachloride a catalyst suspension containing approx.
1.4 mg zirconium per rnl of suspension was formed.
b) Polymerization using the supported metaflocene Z~egfer-Natty catalyst Polymerization using the Ziegier-Natty catalyst made under a) based on zirconium as a transition metal was carried out similarly to the polymerization in Example i and the figures are given in 'table 1. Since no ethylene decrease was found after one hour of reaction, catalyst suspension containing 0.212 mg zirconium was again added, and the test stopped after another 10 minutes because no ethylene was consumed.
With this kind of polymerlzafiion only traces of non-separable polyethylene could be obtained i,~ the form of a wail encrustation difficult to remove. , This example shows that no medium to ultra-high molecular polyethylenes with the desired properties can be obtained if other than the procedure described in the invention is applied.
Example 3 a) Preparation of supported mixed metallocene Ziegier-Natty catalyst In a mixture of 27.0 ml dried hexane and 1.49 m! dried tetrahydrofurane 0.33 g magnesium chips were dispersed under anaerobic conditions and caused to react while boiling, if necessary with a trace of iodine at the reflux, stirring the same with 1.86 mi distilled n-butyl chloride added dropwise over a period of approx. 10 minutes, After another 11 hours of boiling at the reflex the magnesium chips were completely dissolved and the formation of the magnesium-organic compound completed. Then, over a period of 30 minutes a quantity of I 1.Q ml triisobutyl aluminium was dropped into the boiling suspension in the form of 5 ~ solution in hexane and heated up for another hour sfirring it at the reflex.
At room temperature 2.b05 g of a mixture of 25 96 wt. bis(cyclopentadienyl)-zirconium dichloride and 75 96 wt. partially chlorine-methylated styrene-divinyl benzene copolymer obtained by anaerobic intensive milling in a Syalon cup using a planetary micromill, with a - divinyi benzene content of 5.5 96 wt.
-chlorine content of 21.6 ~ wt.
specil9c surface area of 55 m2/g, and a - grain size between 300 and 1.200 ~.m were fed to this suspension.
After that while cooling the suspension a mixture of 0.37 ml 1.2-dichioroethane. 10.1 mi hexane and 0.34 ml titanium tetrachloride were added dropwise and left in the boiling heat for another two hours.
The resulting light brown suspension of the mixed catalyst contained approx.
1.1 n,g titanium per ml suspension and approx. 0.91 mg zirconium per ml suspension.
b) Polymerization using the supported mixed metallocene Ziegier-Natty catalyst For the polymerization using the supported mixed metaifocene Ziegler Naita catalyst formed according to a) on the basis of zirconium and titanium as transition metals the procedure described in Example 1 was chosen. The used quantities of catalyst suspension and activator as well as soiVents and the sefi partial pressure of ethylene can be gathered from Table 1.
i2 Table 3 gives the polymerization results and properties of the polyethylene produced. it can be seen that the mixed catalyst according to the invention has a high pvlymerizatton activity. This cafnlyst; too, ccrn be easily produced obviating the need of t,igi,-temperature treatment and multiple separafiion of inert reaction media and can be used without insuf~cientfy avallabe cocatalysts.
The polymer proper features a very high moleCUlar weight. a high bulk density and an excellent self-colour. Excellent is also the law proportion of very fine polymer particles caused by abrasion of the catalyst fixed on the polymer surtace, which results from the low proportion of polymer with a grain size below 250 ~m in the entire grain size range.
The polymer also shows a low ash and a low residual catalyst content as well as a sufficiently high temperature of the oxidation maximum.
~xamnle 4 Cfor comparison a) Preparation of supported metallocene Ziegler-Natta catalyst The Said Catalyst was Synthesized similarly to Example 3 but ifie.bis(cyclopentadienyl)-zirconium dichloride was replaced by bis(cyctopentadienyl}-titanium dichloride.
Consequently, 36.3 mi hexane, 2 ml tetrahydrofurane and 0.445 g magnesium chips were caused fio react with 2.5 mi n-butyl chloride and 16.5 ml triisobutyl aluminium as a solution in hexane were added and 3.064 g of a ground substance consisting of one part by weight of bis(cyclopentadienyl)-titanium dichloride and three parts by weight of the partially chlorine-methytated styrene divinyl benzene copolymer described in Example 3 were injected. Then, the reaction with 0.5 ml 7 .2 dichloroethane, i3.b mi hexane and 0.35 ml titanium tetrachloride took place. The obtained cocoa-brown catalyst suspension contained approx. 1.7 mg titanium per mi of suspension.
b) Polymerization using ifie supported metallocene Ziegier-Natta catalyst In tfils example polymerization Was carried out with the catalyst produced under a) on the basis of titanium as transition metal only following the data of Example 3 and Table 1. The properties of the polyethylene thus obtained and the results of polymerization are compared with Example 3 and can be gathered, from Table 3.
it can be clearly seen that if the procedure Is other than according to the invention polymers with a comparable molecular weight can be produced but have not the desired properties. Polymers produced otherwise than according to the invenfiion.
have a lower bulk density, a considerably poorer colour index, a very large quantity of a grain size below 250 Vim, a markedly worse ash and residual catalyst content, a lower temperature of the oxidation maximum and a lower molecular catalyst output, Example 5 a) Preparation of supported mixed metallocene Tiegler-fVatta catalyst The supported mixed metallocene Ziegler-Natta catalysfi on the basis of t~is<cycSopentadienyl)-zirconium dichloride and tifianium tetrachloride was prepared in the same way as described in Example 3.
b) Polymerization using supported mixed metallacene Ziegler-Natta catalyst Polymerization was carried out as given in F-xample 3 and Table I. But in this example the process took place in the presence of hydrogen the partial pressure of which was adjusted after the firsfi partial quantity of ethylene had been applied at room temperature. Table 4 gives the polymerization results and the properties of the resulting polyethylene. The lower polymer viscosity number achieved because of the use of hydrogen shows the high flexibility of the mixed catalyst when It comes to the adjustment of the product features and the flow behaviour and the molecular weight parameters in particular, when using the same catalyst system as given in Example 3.
The producfi also features, despite a relatively low viscosity number, an excellent colour index confirming the outstanding optics of the polymer produced according to the 'snventian.
Examt~le b a) Preparation of supported mixed metallocene Ziegler-Nafita catalyst The supported mixed metallocene Ziegler-Natta catalyst using the components bis<cyclopenfiadlenylrzirconium dichloride and titanium tetrachloride was prepared as described in Example 3.
b) Polymerization using supported mixed metallocene Ziegler-Nafita catalyst The polymer was made as given.in Example 5 and Table I. in addition to Example butene was used as comonomer and as a solution In hexane at a concentration of 111.3 ml butenelml added after the reaction temperature had been reached and the pressure adjusted.
A summary of results of polymerization and properties of fihe polyethylene formed is given in Table 4. Here too, the advantages of the method according to the invention are clearly visible even if butane was added as a comonomer.
Examales 7 and B
a) Preparation of supported mixed metailacene Ziegier-hlatta catalyst The supported mixed metallocene Ziegler-Natta catalyst was made according to Example 3 based on bis(cyciopenfiadfenyl)-zirconium dichloride and titanium tetrachloride.
b) Polymerization using supported mixed metallocene Zlegler-Natta catalyst Pofymerizafion took place as described in Example ~ and under consideration of the f(gures given In Table 1. instead of butene as a comonomer hexene also dissolved in hexane was used but with a hexene content of 25.2 9b wt. It was added to the reaction mixture in ten equidisfiant time steps over the entire period of polymerizafion and at equal partial amounts.
Table 4 gives 1fie polymerization results and the polyethylene properties reflecting the advantages of the method according to the invention and the high flexibility of the mixed catalyst even if hexene fs used as a comonomer.
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Catat st field k PE mmol 50.7 42.2 Me Poi ~th lane ro erHes Bulk density g/I 292 27fi DIN 534b8 Densi SO 7 T /cm3 ~ 0.938 0.937 Viscosity number SO T 19 T cm3l T 594 1 722 Colour index Cv Hunter Lab ' T T7.0 112.0 Grain size distribution Medium rain size 549 295 Proportion up to 250 m ~ 21.6 45.3 Residual catai st in of mars Ti m wt 0.8 1.8 Zr m wt 2. T
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Claims (10)
1. an organic polymer material-supported mixed metallocene Ziegler-Natta catalyst containing a) as organic polymer material a partially chlorine-methylated styrene-divinyl benzene copolymer with a - divinyl benzene content between 1 and 45 % wt.
- chlorine content between 5 and 23 % wt.
- specific surface area between 5 and 1,000 m2/g, and a - grain size between 50 and 3,000 µm, b) a complex compound supported by said organic polymer material with the general formula (RmMgX2-m)~(RnAlY3-n)p~(ZqMe1X4-q)~EDr where R - alkyl, cycloalkyl, aryl, aralkyl, alkaryl, alkenyl X - halogen Y - hydrogen, halogen, alkoxy Z - cyclopentadienyl, fluoroenyl, indenyl and their substitutes or hydrogenated compounds Me1 - transition metal of IV th subgroup of periodic system ED - organic compounds acting as an electron donator, e. g, linear or cyclic ethers, thioethers and others m - 1 or 2 n - numeric value between 1 and 3 p - numeric value between 0.1 and 7 4 - 1, 2, 3 or 4 r - numeric value between 1 and 2 c) the reaction product of the organic polymer material-supported complex compound of b) with a mixture of A) a compound of the general formula XmMe2Y4-m where X, Y - halogen, alkyl, alkenyl, aryl, alkaryl, aralkyl, alkoxy, aroxy Me2 - transition metal of IV th subgroup of periodic system m - 1. 2, 3 or 4, and B) a compound of the general formula RnCX4-n where R - hydrogen, alkyl, aryl, alkaryl, aralkyl, chloromethyl, dichloromethyl, trichloromethyl or partially halogenated alkyl X - halogen, alkyl, alkenyl, aryl, alkaryl, aralkyl, alkoxy, aroxy n-0, 1, 2 or 3 at a molar ratio of compounds A) and B) ranging between 1:0.1 and 1:2, with - the parent substance for the organic polymer material supported compound under b) being prepared by intensive milling of the organic polymer material with the transition metal compound below the glass-transition temperature of the polymer under anaerobic conditions;
- the transition metals of the IV th subgroup of the periodic system of the organic polymer material-supported complex compound under b) Me1 and the compound of the general formula under A) of the reaction product under c) Me2 being of different nature, and 2. a compound being effective as an activator and not condensed as alumoxane of the general formula RmAlY3-m where R - alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkenyl Y - hydrogen, halogen, alkoxy m - numeric value between 1 and 3.
- chlorine content between 5 and 23 % wt.
- specific surface area between 5 and 1,000 m2/g, and a - grain size between 50 and 3,000 µm, b) a complex compound supported by said organic polymer material with the general formula (RmMgX2-m)~(RnAlY3-n)p~(ZqMe1X4-q)~EDr where R - alkyl, cycloalkyl, aryl, aralkyl, alkaryl, alkenyl X - halogen Y - hydrogen, halogen, alkoxy Z - cyclopentadienyl, fluoroenyl, indenyl and their substitutes or hydrogenated compounds Me1 - transition metal of IV th subgroup of periodic system ED - organic compounds acting as an electron donator, e. g, linear or cyclic ethers, thioethers and others m - 1 or 2 n - numeric value between 1 and 3 p - numeric value between 0.1 and 7 4 - 1, 2, 3 or 4 r - numeric value between 1 and 2 c) the reaction product of the organic polymer material-supported complex compound of b) with a mixture of A) a compound of the general formula XmMe2Y4-m where X, Y - halogen, alkyl, alkenyl, aryl, alkaryl, aralkyl, alkoxy, aroxy Me2 - transition metal of IV th subgroup of periodic system m - 1. 2, 3 or 4, and B) a compound of the general formula RnCX4-n where R - hydrogen, alkyl, aryl, alkaryl, aralkyl, chloromethyl, dichloromethyl, trichloromethyl or partially halogenated alkyl X - halogen, alkyl, alkenyl, aryl, alkaryl, aralkyl, alkoxy, aroxy n-0, 1, 2 or 3 at a molar ratio of compounds A) and B) ranging between 1:0.1 and 1:2, with - the parent substance for the organic polymer material supported compound under b) being prepared by intensive milling of the organic polymer material with the transition metal compound below the glass-transition temperature of the polymer under anaerobic conditions;
- the transition metals of the IV th subgroup of the periodic system of the organic polymer material-supported complex compound under b) Me1 and the compound of the general formula under A) of the reaction product under c) Me2 being of different nature, and 2. a compound being effective as an activator and not condensed as alumoxane of the general formula RmAlY3-m where R - alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkenyl Y - hydrogen, halogen, alkoxy m - numeric value between 1 and 3.
2. Process according to claim 1 whereby a partially chlorine-methylated styrene-divenyl benzene copolymer is used as organic polymer material, which has a - divinyl content between 2 and 25 % wt.
- chlorine content between 15 and 22.5 9% wt.
- specific surface area between 10 and 300 m2/g, and a - grain size between 80 and 2000 µm.
- chlorine content between 15 and 22.5 9% wt.
- specific surface area between 10 and 300 m2/g, and a - grain size between 80 and 2000 µm.
3. Process as claimed in claims 1 and 2 whereby as transition metals of the µm subgroup of the periodic system Me1 and Me2 those of zirconium and titanium are used.
4. Process as claimed in claims 1 through 3 whereby as transition metal of the µm subgroup of the period system in the organic polymer material-supported compound Me1 that of zirconium and in the compound A) of the reaction mixture Me2 that of titanium is contained.
5. Process as claimed in claims 1 through 4 whereby the compound acting as an activator and not condensed, as alumoxane is triisobutyl aluminium.
6. Process as claimed in claims 1 through 5 whereby a bis(cyclopentadienyl)-titanium dichloride serves as a transition metal compound for the parent substance formed through intensive milling with the organic polymer material, for the organic polymer material-supported compound.
7. Process as claimed in claims 7 through 5 whereby a bis(cyclopentadienyl)-zirconium dichloride, a bis(indenyl)-zirconium dichloride or a bis(fluoroenyl)-zirconium dichloride is used as a transition metal compound for the parent substance formed through intensive milling with the organic polymer material, for the organic polymer-material supported compound.
8. Process as claimed in claims 1 through 7 whereby ethylene is used as olefin.
9. An organic polymer material-supported mixed metallocene Ziegler-Natta catalyst containing 21~
a) as organic polymer material a partially chlorine-methylated styrene-divinyl benzene copolymer with a - divinyl benzene content between 1 and 45 % wt.
- chlorine content between 5 and 23 % wt.
- specific surface area between 5 and 1.000 m2/g, and a - grain size between 50 and 3,000µm b) a complex compound supported by the said organic polymer material with the general formula (RmMgX2-m) (RnAlY3-n)p (ZqMe1X4-q)EDr where R - alkyl, cycloalkyl, aryl, aralkyl, alkaryl, alkenyl X - halogen Y - hydrogen, halogen, alkoxy Z - cyclopentadienyl, fluoroenyl, indenyl and their substitutes or hydrogenated compounds Me1 - transition metal of IV th subgroup of periodic system ED - organic compounds acting as electron donator, e. g, linear or cyclic ethers, thioethers and others;
m - 1 or 2 n - numerical value between 1 and 3 p - numerical value between 0,1 and 1 q - 1, 2, 3 or 4 r - numerical value between 1 and 2, c) the reaction product of the organic polymer material-supported complex compound of b) with a mixture of A) a compound of the general formula XmMe2Y4-m where X,Y - halogen, alkyl, alkenyl, aryl, alkaryl, aralkyl, alkoxy, aroxy Me2 - transition metal of IV th subgroup of periodic system m - 1, 2, 3 or 4, and B) a compound of the general formula RnCX4-n where R - hydrogen, alkyl, aryl, alkaryl, aralkyl, chloromethyl, dichloromethyl, trichloromethyl or partially halogenated alkyl X - halogen, alkyl, alkenyl aryl, alkary, aralkyl, alkoxy, aroxy n - 0, 1, 2 or 3 at a molar ratio of the compounds A) and B) ranging between 1:0.1 and 1:2, with - the parent substance for the organic polymer material supported compound under b) formed by intensive milling of the organic polymer material with the transition metal compound below the glass-transition temperature of the polymer under anaerobic conditions;
- the transition metals of the IV th subgroup of the periodic system of the organic polymer material-supported complex compound under b) Me1 and the compound of the general formula under A) of the reaction product under c) Me2 being of a different nature, and - the organic polymer material-supported mixed metallocene Ziegler-Natta catalyst being activated by a compound not condensed as alumoxane of the general formula RmAlY3-n, where R - alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkenyl Y - hydrogen, halogen, alkoxy m - numeric value between 1 and 3.
a) as organic polymer material a partially chlorine-methylated styrene-divinyl benzene copolymer with a - divinyl benzene content between 1 and 45 % wt.
- chlorine content between 5 and 23 % wt.
- specific surface area between 5 and 1.000 m2/g, and a - grain size between 50 and 3,000µm b) a complex compound supported by the said organic polymer material with the general formula (RmMgX2-m) (RnAlY3-n)p (ZqMe1X4-q)EDr where R - alkyl, cycloalkyl, aryl, aralkyl, alkaryl, alkenyl X - halogen Y - hydrogen, halogen, alkoxy Z - cyclopentadienyl, fluoroenyl, indenyl and their substitutes or hydrogenated compounds Me1 - transition metal of IV th subgroup of periodic system ED - organic compounds acting as electron donator, e. g, linear or cyclic ethers, thioethers and others;
m - 1 or 2 n - numerical value between 1 and 3 p - numerical value between 0,1 and 1 q - 1, 2, 3 or 4 r - numerical value between 1 and 2, c) the reaction product of the organic polymer material-supported complex compound of b) with a mixture of A) a compound of the general formula XmMe2Y4-m where X,Y - halogen, alkyl, alkenyl, aryl, alkaryl, aralkyl, alkoxy, aroxy Me2 - transition metal of IV th subgroup of periodic system m - 1, 2, 3 or 4, and B) a compound of the general formula RnCX4-n where R - hydrogen, alkyl, aryl, alkaryl, aralkyl, chloromethyl, dichloromethyl, trichloromethyl or partially halogenated alkyl X - halogen, alkyl, alkenyl aryl, alkary, aralkyl, alkoxy, aroxy n - 0, 1, 2 or 3 at a molar ratio of the compounds A) and B) ranging between 1:0.1 and 1:2, with - the parent substance for the organic polymer material supported compound under b) formed by intensive milling of the organic polymer material with the transition metal compound below the glass-transition temperature of the polymer under anaerobic conditions;
- the transition metals of the IV th subgroup of the periodic system of the organic polymer material-supported complex compound under b) Me1 and the compound of the general formula under A) of the reaction product under c) Me2 being of a different nature, and - the organic polymer material-supported mixed metallocene Ziegler-Natta catalyst being activated by a compound not condensed as alumoxane of the general formula RmAlY3-n, where R - alkyl, cycloalkyl, aryl, alkaryl, aralkyl, alkenyl Y - hydrogen, halogen, alkoxy m - numeric value between 1 and 3.
10. Catalyst as claimed in claim 9 whereby the catalyst is made with the components and in the order as described in claim 9.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19706409.4 | 1997-02-19 | ||
| DE19706409A DE19706409A1 (en) | 1997-02-19 | 1997-02-19 | Process and catalyst for the production of medium to ultra high molecular weight polyolefins |
| PCT/DE1998/000420 WO1998037108A1 (en) | 1997-02-19 | 1998-02-13 | Method and catalyst for producing polyolefins of medium to ultra-high molecular weight |
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| CA2281559A1 true CA2281559A1 (en) | 1998-08-27 |
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| CA002281559A Abandoned CA2281559A1 (en) | 1997-02-19 | 1998-02-13 | Method and catalyst for producing polyolefins of medium to ultra-high molecular weight |
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| JP (1) | JP2001511842A (en) |
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| GC0000293A (en) | 2000-10-10 | 2006-11-01 | Saudi Basic Ind Corp | Catalyst composition and process for olfin polymerization and copolymerization using supported metallocene catalyst systems |
| KR100443383B1 (en) * | 2001-07-09 | 2004-08-09 | 한국과학기술원 | Process for Preparing Metallocene Catalyst Supported on Polymer Bead for Highly Active Olefin Polymerization |
| EP1302480B1 (en) * | 2001-10-15 | 2004-08-11 | Saudi Basic Industries Corporation (Sabic) | Catalyst percursor for homo-or copolymerization of olefins and polymerization process using that catalyst precursor |
| ATE296319T1 (en) * | 2002-07-12 | 2005-06-15 | Saudi Basic Ind Corp | SUPPORTED ZIEGLER - METALLOCENE POLYMERIZATION CATALYST AND THE USE THEREOF FOR THE POLYMERIZATION OF OLEFINS |
| US6861487B2 (en) | 2003-04-15 | 2005-03-01 | Saudi Basic Industries Corporation | Catalyst precursor for the polymerization of olefins and polymerization process using the same |
| DE102004035308A1 (en) * | 2004-07-21 | 2006-02-09 | Ticona Gmbh | Process for the preparation of ultra-high molecular weight polymers using unbridged metallocene catalysts |
| US6995235B1 (en) * | 2005-05-02 | 2006-02-07 | Univation Technologies, Llc | Methods of producing polyolefins and films therefrom |
| EP1878755A1 (en) * | 2006-07-14 | 2008-01-16 | Borealis Technology Oy | Ligand-modified ziegler-natta catalyst for olefin (co) polymerisation |
| CN102294233B (en) * | 2011-07-21 | 2013-06-12 | 南京大学 | Method for regulating and controlling structure and performance of nanocomposite adsorbent |
| CN115340619B (en) * | 2021-05-12 | 2023-11-28 | 中国石油天然气股份有限公司 | Low ash content ultra-high molecular weight polyethylene resin and preparation method thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD257431A1 (en) * | 1982-11-26 | 1988-06-15 | Buna Chem Werke Veb | PROCESS FOR THE PRODUCTION OF OLEFIN POLYMERS |
| DD275693A1 (en) * | 1984-08-15 | 1990-01-31 | Buna Chem Werke Veb | PROCESS FOR THE PRODUCTION OF OLEFIN POLYMERS |
| DD254942A1 (en) * | 1986-12-17 | 1988-03-16 | Akad Wissenschaften Ddr | METHOD FOR PRODUCING HIGH-ACTIVE CATALYSTS FOR OLEFIN POLYMERIZATION |
| DD255352A1 (en) * | 1986-12-22 | 1988-03-30 | Buna Chem Werke Veb | METHOD FOR PRODUCING HIGH-ACTIVE CATALYSTS FOR OLEFIN POLYMERIZATION |
| DE3714258A1 (en) * | 1987-04-29 | 1988-11-10 | Bayer Ernst Prof Dr | METHOD FOR PRESENTING MONODISPERSE, CROSSLINKED POLYMER BALLS |
| DD282013A5 (en) * | 1989-02-13 | 1990-08-29 | Buna Chem Werke Veb | METHOD FOR PRODUCING HIGH-ACTIVE CATALYSTS FOR ETHYLENE POLYMERIZATION OF ULTRAHOCHMOLECULAR POLYETHYLENE |
| US5032562A (en) * | 1989-12-27 | 1991-07-16 | Mobil Oil Corporation | Catalyst composition and process for polymerizing polymers having multimodal molecular weight distribution |
| US5473020A (en) * | 1994-06-30 | 1995-12-05 | Phillips Petroleum Company | Polymer bound ligands, polymer bound metallocenes, catalyst systems, preparation, and use |
-
1997
- 1997-02-19 DE DE19706409A patent/DE19706409A1/en not_active Withdrawn
-
1998
- 1998-02-13 DE DE59804058T patent/DE59804058D1/en not_active Expired - Fee Related
- 1998-02-13 BR BR9807844-5A patent/BR9807844A/en unknown
- 1998-02-13 JP JP53614498A patent/JP2001511842A/en active Pending
- 1998-02-13 EP EP98912217A patent/EP0961791B1/en not_active Expired - Lifetime
- 1998-02-13 CN CN98802587A patent/CN1248269A/en active Pending
- 1998-02-13 WO PCT/DE1998/000420 patent/WO1998037108A1/en not_active Ceased
- 1998-02-13 CA CA002281559A patent/CA2281559A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| DE19706409A1 (en) | 1998-08-20 |
| DE59804058D1 (en) | 2002-06-13 |
| CN1248269A (en) | 2000-03-22 |
| BR9807844A (en) | 2000-10-31 |
| EP0961791B1 (en) | 2002-05-08 |
| JP2001511842A (en) | 2001-08-14 |
| EP0961791A1 (en) | 1999-12-08 |
| WO1998037108A1 (en) | 1998-08-27 |
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