JPH08511300A - オレフィン類重合用の成分と触媒 - Google Patents
オレフィン類重合用の成分と触媒Info
- Publication number
- JPH08511300A JPH08511300A JP7524948A JP52494895A JPH08511300A JP H08511300 A JPH08511300 A JP H08511300A JP 7524948 A JP7524948 A JP 7524948A JP 52494895 A JP52494895 A JP 52494895A JP H08511300 A JPH08511300 A JP H08511300A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- compound
- transition metal
- alkyl
- prepolymer
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 158
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 54
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 18
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 70
- -1 magnesium halide Chemical class 0.000 claims abstract description 54
- 239000011777 magnesium Substances 0.000 claims abstract description 49
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 29
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 24
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 16
- 150000003624 transition metals Chemical class 0.000 claims abstract description 16
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 15
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims description 59
- 238000000034 method Methods 0.000 claims description 56
- 239000010936 titanium Substances 0.000 claims description 33
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 26
- 239000005977 Ethylene Substances 0.000 claims description 26
- 229920000642 polymer Polymers 0.000 claims description 26
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 229910052726 zirconium Inorganic materials 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 150000004820 halides Chemical class 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229910052735 hafnium Inorganic materials 0.000 claims description 10
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 10
- 229910052753 mercury Inorganic materials 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000012798 spherical particle Substances 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 150000003623 transition metal compounds Chemical class 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 125000004423 acyloxy group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- 125000002950 monocyclic group Chemical group 0.000 claims description 2
- 125000003367 polycyclic group Chemical group 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims 6
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 claims 1
- 239000013081 microcrystal Substances 0.000 claims 1
- 229920000098 polyolefin Polymers 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- 239000012967 coordination catalyst Substances 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 45
- 239000004698 Polyethylene Substances 0.000 description 32
- 229920000573 polyethylene Polymers 0.000 description 32
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- 239000000969 carrier Substances 0.000 description 18
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 18
- 229920001577 copolymer Polymers 0.000 description 17
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 14
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 12
- 239000008096 xylene Substances 0.000 description 12
- 229910007928 ZrCl2 Inorganic materials 0.000 description 11
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012968 metallocene catalyst Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 102100036301 C-C chemokine receptor type 7 Human genes 0.000 description 2
- 101710149858 C-C chemokine receptor type 7 Proteins 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910010068 TiCl2 Inorganic materials 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 235000008429 bread Nutrition 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000012685 gas phase polymerization Methods 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000004291 polyenes Chemical class 0.000 description 2
- 230000000707 stereoselective effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- ZMZGFLUUZLELNE-UHFFFAOYSA-N 2,3,5-triiodobenzoic acid Chemical group OC(=O)C1=CC(I)=CC(I)=C1I ZMZGFLUUZLELNE-UHFFFAOYSA-N 0.000 description 1
- HTUQMBTYIHSYEI-UHFFFAOYSA-L 4,7-dimethyl-2h-inden-2-ide;zirconium(4+);dichloride Chemical compound [Cl-].[Cl-].[Zr+4].CC1=CC=C(C)C2=C1C=C[CH-]2.CC1=CC=C(C)C2=C1C=C[CH-]2 HTUQMBTYIHSYEI-UHFFFAOYSA-L 0.000 description 1
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910010062 TiCl3 Inorganic materials 0.000 description 1
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- WXCZUWHSJWOTRV-UHFFFAOYSA-N but-1-ene;ethene Chemical compound C=C.CCC=C WXCZUWHSJWOTRV-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003610 charcoal Chemical group 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229940099352 cholate Drugs 0.000 description 1
- BHQCQFFYRZLCQQ-OELDTZBJSA-N cholic acid Chemical compound C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 BHQCQFFYRZLCQQ-OELDTZBJSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical class ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920000576 tactic polymer Polymers 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
- 239000012808 vapor phase Substances 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
- C08F4/63—Pretreating the metal or compound covered by group C08F4/62 before the final contacting with the metal or compound covered by group C08F4/44
- C08F4/632—Pretreating with metals or metal-containing compounds
- C08F4/634—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
-
- 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
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/63904—Component covered by group C08F4/62 containing a transition metal-carbon bond in combination with another component of C08F4/62
-
- 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
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/63912—Component covered by group C08F4/62 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
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/63916—Component covered by group C08F4/62 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
-
- 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
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/6392—Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
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- Y10S526/904—Monomer polymerized in presence of transition metal containing catalyst at least part of which is supported on a polymer, e.g. prepolymerized catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
Description
Claims (1)
- 【特許請求の範囲】 1.1以上のオレフィンCH2=CHR(式中、Rは水素又は炭素原子1〜12 のアルキル、シクロアルキル又はアリール)及び/又は1以上のジ−又はポリエ ンを、Ti、V、Zr又はHfの化合物を300Å以下の微結晶の平均サイズを 有する粒子の形のマグネシウムハライドを接触させて得られた生成物からなる配 位触媒で重合させて得られたプレポリマー(但し、マグネシウムハライドはプレ ポリマー中、50〜50000ppmの量で存在)に、少なくとも1つのM−π 結合をもつTi、V、Zr及びHfから選択される遷移金属Mの化合物を接触さ せて得ることができる生成物からなるオレフィン重合用の触媒の成分。 2.遷移金属Mの化合物が、金属M上に配位した少なくとも1つの配位子Lを含 有し、その配位子Lは共役π電子を含む単環又は多環の構造をもつ請求項1に記 載の触媒の成分。 3.原子比M/Mgが、0.1より大きい請求項1又は2に記載の触媒の成分。 4.比M/Mgが、0.3〜3である請求項3に記載の触媒の成分。 5.Mgハライドの微結晶が、150Å以下のサイズである請求項1〜4の1以 上に記載の成分。 6.Mgハライドが、MgCl2である請求項1〜5の1以上に記載の成分。 7.遷移金属化合物が、以下の構造: 〔式中、MはTi、V、Zr又はHfであり、CpI及びCpIIは互いに同一ま たは異なって、置換されてもよいシクロペンタジエニル基であり、前記シクロペ ンタジエニル基上の2以上の置換基は炭素原子4〜6を有する1以上の環を形成 することができ、R1、R2及びR3は同一または異なって、水素、ハロゲンの原 子、炭素原子1〜20のアルキル又はアルコキシル基、炭素原子6〜20のアリ ール、アルカリル又はアラルキル、炭素原子1〜20のアシロキシ基、アリル基 、又は珪素原子含有の置換基であり、Aはアルケニル橋又は以下; =BR1,=AlR1,−Ge−,−Sn−,−O−,−S−,=SO,=SO2 ,=NR1,=PR1又は=P(O)R1(式中、M1はSi、Ge又はSnであり 、R1及びR2は同一または異なって、炭素原子1〜4のアルキル基又は炭素原子 6〜10のアリール基であり、a、b、cは独立に0〜4の整数であり、eは1 〜6の整数であり、R1、R2及びR3の基の2以上は環を形成することができる )から選択される構造を有する〕 を有する化合物から選択される請求項1〜6の1以上に記載の成分。 8.遷移金属化合物が、以下の化合物; から選択される請求項7に記載の成分。 9.遷移金属化合物が、以下の化合物; から選択される請求項7に記載の成分。 10.遷移金属化合物が、以下の化合物; から選択される請求項7に記載の成分。 11.プレポリマーが、100ミクロン以下のサイズ、0.3cm3/g以上の 窒素多孔度及び200m2/gより大きい表面積を有する球状粒子の形である固 体成分である触媒で得られる請求項1〜10の1以上に記載の成分。 12.プレポリマーが、100ミクロン以下のサイズ、200m2/g以下の表 面積及び0.5〜2cc/gの水銀多孔度を有する球状粒子の形である固体成分 である触媒で得られる請求項1〜11の1以上に記載の成分。 13.プレポリマーが、50,000Å以下の半径を有する細孔に関して、水銀 多孔度が0.3cm3/gより大きい請求項1〜12の1以上に記載の成分。 14.プレポリマーが、50,000Å以下の半径を有する細孔に関して、水銀 多孔度が0.4cm3/gより大きい請求項1〜13の1以上に記載の成分。 15.プレポリマーが、50,000Å以下の半径を有する細孔に関して、水銀 多孔度が0.5cm3/gより大きい請求項1〜14の1以上に記載の成分。 16.固体成分中のチタニウムの含量が、1重量%より大きい請求項11又は1 2に記載の成分。 17.オレフィンプレポリマーを、遷移金属Mの化合物と、Al−トリアルキル とポリアルモキサンから選択したAl−アルキル化合物(Al/遷移金属Mの化 合物のモル比が2以上である)との炭化水素溶媒中での、溶液に接触させること により得ることができる請求項1〜16の1以上に記載の成分。 18.300Å以下の微結晶の平均サイズを有する粒子の形のマグネシウムハラ イドと、少なくとも1つのM−π結合をもつTi、V、Zr及びHfから選択さ れる遷移金属Mの化合物(遷移金属Mの化合物はマグネシウムハライドと少なく とも部分的に結合した形で存在し、原子比M/Mgが0.1より大きい)とを分 散液中に含むオレフィンプレポリマーからなるオレフィン重合用の触媒の成分。 19.Al−トリアルキル(アルキル基が炭素原子1〜12を有する)と反復単 位−(R4)AlO−(式中、R4は炭素原子1〜6のアルキル基又はシクロアル キル又は炭素原子6〜10のアリール基で、2〜50の反復単位を含む)を含む 直鎖又 は環状のアルモキサン化合物から選択されたAl−アルキル化合物と請求項1〜 18の1以上に記載の成分との反応の生成物からなるオレフィン重合用の触媒。 20.Al−アルキル化合物が、Al−トリアルキル及びアルモキサンの混合物 である請求項19に記載の触媒。 21.アルモキサンが、ポリメチルアルモキサンである請求項19又は20に記 載の触媒。 22.Al−トリアルキル化合物が、Al−トリアルキルのモルに対して水0. 5〜0.01モルで反応され、遷移金属Mの化合物が以下; から選択される請求項19又は20に記載の触媒。 23.触媒が請求項19〜22の1以上の記載に従って用いられるオレフィンC H2=CHR(式中、Rは水素又は炭素原子1〜10のアルキル、シクロアルキ ル又はアリール)の重合方法。 24.請求項10に記載の成分から得られる触媒を用いるオレフィンCH2=C HR(式中、Rは炭素原子1〜10のアルキル、シクロアルキル又はアリール基 )の重合方法。 25.請求項10に記載の成分から得られる触媒を用いるエチレン及びオレフィ ンCH2=CHR(式中、RはC1〜10のアルキル、シクロアルキル又はアリ ール基)との混合物の重合方法。 26.請求項23〜25の方法で得られるポリオレフィン。 27.請求項26のポリマーから得られる製品。
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ITMI940596A IT1269931B (it) | 1994-03-29 | 1994-03-29 | Componenti e catalizzatori per la polimerizzazione di olefine |
PCT/EP1995/001066 WO1995026369A1 (en) | 1994-03-29 | 1995-03-22 | Components and catalysts for the polymerization of olefins |
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