JPH09504051A - オレフィンの重合用成分と触媒 - Google Patents
オレフィンの重合用成分と触媒Info
- Publication number
- JPH09504051A JPH09504051A JP8500260A JP50026096A JPH09504051A JP H09504051 A JPH09504051 A JP H09504051A JP 8500260 A JP8500260 A JP 8500260A JP 50026096 A JP50026096 A JP 50026096A JP H09504051 A JPH09504051 A JP H09504051A
- Authority
- JP
- Japan
- Prior art keywords
- porosity
- catalyst
- compound
- alkyl
- carbon atoms
- 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 104
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 29
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 81
- 238000000034 method Methods 0.000 claims abstract description 42
- -1 magnesium halide Chemical class 0.000 claims abstract description 36
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical group [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 38
- 150000004820 halides Chemical class 0.000 claims description 32
- 238000004519 manufacturing process Methods 0.000 claims description 30
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 229920000642 polymer Polymers 0.000 claims description 18
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 17
- 239000005977 Ethylene Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000004615 ingredient Substances 0.000 claims description 11
- 229910052726 zirconium Inorganic materials 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 229910052735 hafnium Inorganic materials 0.000 claims description 8
- 150000003623 transition metal compounds Chemical class 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 239000002685 polymerization catalyst Substances 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000012798 spherical particle Substances 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims 1
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- 125000003710 aryl alkyl group Chemical group 0.000 claims 1
- 239000003610 charcoal Substances 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 239000011777 magnesium Substances 0.000 abstract description 44
- 229910052749 magnesium Inorganic materials 0.000 abstract description 11
- 238000004438 BET method Methods 0.000 abstract description 6
- 239000004711 α-olefin Substances 0.000 abstract description 4
- 239000012808 vapor phase Substances 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 64
- 229920001577 copolymer Polymers 0.000 description 27
- 239000002904 solvent Substances 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 16
- 239000004698 Polyethylene Substances 0.000 description 15
- 229920000573 polyethylene Polymers 0.000 description 14
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 14
- 229910007928 ZrCl2 Inorganic materials 0.000 description 12
- 229920000092 linear low density polyethylene Polymers 0.000 description 12
- 239000004707 linear low-density polyethylene Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 11
- 239000012299 nitrogen atmosphere Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000008096 xylene Substances 0.000 description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- 229920001903 high density polyethylene Polymers 0.000 description 6
- 239000004700 high-density polyethylene Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 5
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 4
- 241000282326 Felis catus Species 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- AQZGPSLYZOOYQP-UHFFFAOYSA-N Diisoamyl ether Chemical compound CC(C)CCOCCC(C)C AQZGPSLYZOOYQP-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910010068 TiCl2 Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000012685 gas phase polymerization Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000013081 microcrystal Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- VCOKPLHNHKEXIO-UHFFFAOYSA-L [Cl-].[Cl-].CC1=CC=C(C)C2=C1C=CC2[Zr+2] Chemical compound [Cl-].[Cl-].CC1=CC=C(C)C2=C1C=CC2[Zr+2] VCOKPLHNHKEXIO-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 238000009835 boiling Methods 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- NRQNMMBQPIGPTB-UHFFFAOYSA-N methylaluminum Chemical compound [CH3].[Al] NRQNMMBQPIGPTB-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
- C08F4/74—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals
- C08F4/76—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from refractory metals selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum
-
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08F4/6392—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
-
- 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
- C08F4/65916—Component covered by group C08F4/64 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
- C08F4/64—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
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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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—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.表面積(BET)が約50m2/g以上、多孔度(BET)が0.15cm3/g以上 かつ多孔度(Hg)が0.3cm3/g以上であり、ただし表面積が約150m2/g以下 のとき多孔度(Hg)は約1.5cm3/g以下であることを特徴とする、少なくとも 1つのM−π結合を含有するTi、V、ZrとHfから選択された遷移金属Mの 化合物からなるオレフィン重合用触媒の成分。 2.表面積が150m2/g以上で多孔度(BET)が0.2cm3/g以上を有する請求 項1による成分。 3.表面積が150m2/g以下で多孔度(Hg)が0.5〜1.2cm3/gを有する請求項 1による成分。 4.多孔度(BET)の40%以上が300Å以上の半径を有する細孔による前記請 求項1またはそれ以上による成分。 5.多孔度(BET)の50%以上が600Å〜1000Åの半径の細孔による請求項1 〜3の何れか1つによる成分。 6.150ミクロンより小さい大きさの球状粒子の形である前記請求項の何れか1 つによる成分。 7.少なくとも1つのM−π結合を含有するTi、V、ZrとHfから選択した 遷移金属Mの化合物を200〜800m2/gの表面積、0.3cm3/g以上の多孔度(Hg )を有するMgのハライドまたはそれを含有する支持体に、支持されることによ って得られた前記請求項の何れか1つによる成分。 8.Mgのハライドが150ミクロン以下の大きさの球状粒子の 形である請求項7による成分。 9.Mgのハライドが、300〜600m2/gの表面積と0.5cm3/g以上の多孔度(B ET)を有するシリカ、アルミナ、シリカ−アルミナ及び100〜500m2/gの表面 積と0.5cm3/g以上の多孔度(BET)を有する部分架橋ポリスチレンから選択 された不活性支持体に支持されている請求項7による成分。 10.Mgのハライドが、球状化MgX2アルコール付加物をアルキルAl化合 物と反応させ、次いでアルコールを除去して得られる請求項8による成分。 11.Mgハライドが、MgCl2、3ROH付加物(Rは1〜8の炭素原子の アルキル基)から、これを部分脱アルコール化し、次いでアルキルAl化合物と 反応させて得られる請求項10による成分。 12.遷移金属化合物の金属Mに配位した少なくとも1つのリガンドを含み、共 役π電子を含有する単または多環状構造を有するものである請求項1〜11の何 れか1つによる成分。 13.遷移金属化合物が、構造 〔式中MはTi、V、ZrまたはHf;Cp1とCp11は、同一または異なって 、置換されたものを含むシクロペンタジエニル基で、そのシクロペンタジエニル 環上の2以上の置換分は4〜6の炭素原子を有する1以上の環を形成できる、R1 、R2 とR3は同一または異なって、水素原子、ハロゲン原子、1〜20の炭素原子を有 するアルキルもしくはアルコキシ基、6〜20の炭素原子を有するアノール、アル カリールまたはアラルキル基、1〜20の炭素原子を有するアシル基、アリル基、 ケイ素を含有する置換素;Aは を有する化合物から選択される請求項12による成分。 14.遷移金属化合物が、次の構造: を有する化合物から選択される請求項12による成分。 15.遷移金属化合物が、次の構造: を有する化合物から選択される請求項12による成分。 16.遷移金属化合物が、次の構造: を有する化合物から選択される請求項12による成分。 17.遷移金属化合物が、金属換算重量で0.1〜0.5%の量で存在する前記請求項 の何れか1つによる成分。 18.前記請求項の何れか1つによる成分を、トリアルキルAl(アルキル基は 1〜12の炭素原子を有する)と繰り返し単位−R4AlO−(R4は1〜6の炭 素原子を有するアルキル基または6〜10の炭素原子を有するシクロアルキルも しくはアリール基)を含有しかつ2〜50の繰り返し単位を含有する線状もしく は環状アルモキサン化合物とから選択されたアルキル−Al化合物と反応させた 生成物からなるオレフィン重合用触媒。 19.アルキルAl化合物が、トリアルキル−Alとアルモキサンの混合物であ る請求項18による触媒。 20.アルモキザンが、ポリメチルアルモキサンである請求項18または19に よる触媒。 21.トリアルキルAl化合物が、トリアルキルAlのモル当り0.5〜0.01モル の水と反応させられ、かつ遷移金属Mの化合物が、次の構造: から選択される請求項18または19による触媒。 22.請求項18〜21の何れか1つによる触媒を用いてなる、オレフィンCH2 =CHR(Rは水素または1〜10の炭素原子を有するアルキル、シクロアル キルもしくはアリール基またはアリール基)の重合方法。 23.使用される触媒が、請求項16による成分から得られたものであるオレフ ィンCH2=CHR(Rは1〜10の炭素原子を真するアルキル、シクロアルキ ルもしくはアリール基)の重合方法。 24.使用される触媒が、請求項16による成分から得られたものであるエチレ ンおよびエチレンとCH2=CHR(Rは1〜10の炭素原子を有するアルキル 、シクロアルキルもしくはアリール基)のオレフィンとの混合物の重合方法。 25.請求項22〜24の方法で得ることができるポリオレフィン。 26.請求項25によるポリマーから得ることができる製造物。
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ITMI941065A IT1269837B (it) | 1994-05-26 | 1994-05-26 | Componenti e catalizzatori per la polimerizzazione delle olefine |
IT94A001065 | 1994-05-26 | ||
PCT/EP1995/001949 WO1995032995A1 (en) | 1994-05-26 | 1995-05-23 | Components and catalysts for the polymerization of olefins |
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- 1995-05-23 CA CA002168210A patent/CA2168210A1/en not_active Abandoned
- 1995-05-23 JP JP50026096A patent/JP4275727B2/ja not_active Expired - Fee Related
- 1995-05-23 DE DE69510890T patent/DE69510890T2/de not_active Expired - Fee Related
- 1995-05-23 HU HU9600459A patent/HU216913B/hu not_active IP Right Cessation
- 1995-05-23 AU AU27357/95A patent/AU695548B2/en not_active Ceased
- 1995-05-23 BR BR9506023A patent/BR9506023A/pt not_active IP Right Cessation
- 1995-05-23 RU RU96104254/04A patent/RU2161161C2/ru active
- 1995-05-23 PL PL95312834A patent/PL312834A1/xx unknown
- 1995-05-23 AT AT95922473T patent/ATE182338T1/de not_active IP Right Cessation
- 1995-05-23 KR KR1019960700417A patent/KR960703948A/ko active IP Right Grant
- 1995-05-23 WO PCT/EP1995/001949 patent/WO1995032995A1/en active IP Right Grant
- 1995-05-23 EP EP95922473A patent/EP0712416B1/en not_active Expired - Lifetime
- 1995-05-23 ES ES95922473T patent/ES2135071T3/es not_active Expired - Lifetime
- 1995-05-23 CN CN95190648A patent/CN1092669C/zh not_active Expired - Fee Related
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- 1995-05-25 IL IL11385395A patent/IL113853A/xx not_active IP Right Cessation
- 1995-06-06 TW TW084105655A patent/TW424098B/zh not_active IP Right Cessation
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1996
- 1996-01-25 FI FI960343A patent/FI960343A/fi not_active Application Discontinuation
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003518168A (ja) * | 1999-12-21 | 2003-06-03 | バーゼル、ポリプロピレン、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツング | オレフィン重合用固体触媒の製造方法 |
JP2007522300A (ja) * | 2004-02-16 | 2007-08-09 | スティッチング ダッチ ポリマー インスティテュート | チタノセン−ベースの触媒システム |
Also Published As
Publication number | Publication date |
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ATE182338T1 (de) | 1999-08-15 |
IT1269837B (it) | 1997-04-15 |
BR9506023A (pt) | 1997-10-14 |
US5698487A (en) | 1997-12-16 |
AU695548B2 (en) | 1998-08-13 |
ES2135071T3 (es) | 1999-10-16 |
ZA954216B (en) | 1996-01-22 |
CA2168210A1 (en) | 1995-12-07 |
EP0712416A1 (en) | 1996-05-22 |
HU216913B (hu) | 1999-10-28 |
IL113853A0 (en) | 1995-08-31 |
CN1130914A (zh) | 1996-09-11 |
RU2161161C2 (ru) | 2000-12-27 |
TW424098B (en) | 2001-03-01 |
WO1995032995A1 (en) | 1995-12-07 |
FI960343A0 (fi) | 1996-01-25 |
AU2735795A (en) | 1995-12-21 |
EP0712416B1 (en) | 1999-07-21 |
PL312834A1 (en) | 1996-05-13 |
KR960703948A (ko) | 1996-08-31 |
ITMI941065A0 (it) | 1994-05-26 |
HUT74773A (en) | 1997-02-28 |
NO960310L (no) | 1996-02-23 |
DE69510890D1 (de) | 1999-08-26 |
ITMI941065A1 (it) | 1995-11-26 |
DE69510890T2 (de) | 1999-12-23 |
IL113853A (en) | 1999-10-28 |
JP4275727B2 (ja) | 2009-06-10 |
CN1092669C (zh) | 2002-10-16 |
FI960343A (fi) | 1996-03-25 |
HU9600459D0 (en) | 1996-04-29 |
NO960310D0 (no) | 1996-01-25 |
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