KR960704943A - 올레핀 중합용 성분 및 촉매(components and catalysts for the polymerization of olefins) - Google Patents
올레핀 중합용 성분 및 촉매(components and catalysts for the polymerization of olefins)Info
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- KR960704943A KR960704943A KR1019960701201A KR19960701201A KR960704943A KR 960704943 A KR960704943 A KR 960704943A KR 1019960701201 A KR1019960701201 A KR 1019960701201A KR 19960701201 A KR19960701201 A KR 19960701201A KR 960704943 A KR960704943 A KR 960704943A
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- Prior art keywords
- mcl
- ind
- compound
- mme
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- 239000003054 catalyst Substances 0.000 title claims abstract 22
- 238000006116 polymerization reaction Methods 0.000 title claims abstract 6
- 150000001336 alkenes Chemical class 0.000 title claims abstract 5
- 150000001875 compounds Chemical class 0.000 claims abstract 30
- 238000000034 method Methods 0.000 claims abstract 16
- 229910052720 vanadium Inorganic materials 0.000 claims abstract 16
- 229910052719 titanium Inorganic materials 0.000 claims abstract 15
- 229910052726 zirconium Inorganic materials 0.000 claims abstract 10
- 229910052735 hafnium Inorganic materials 0.000 claims abstract 9
- -1 magnesium halide Chemical class 0.000 claims abstract 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract 5
- 229910052723 transition metal Inorganic materials 0.000 claims abstract 4
- 150000003624 transition metals Chemical class 0.000 claims abstract 4
- 125000004432 carbon atom Chemical group C* 0.000 claims 11
- 125000000217 alkyl group Chemical group 0.000 claims 8
- 150000004820 halides Chemical class 0.000 claims 8
- 239000007787 solid Substances 0.000 claims 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims 5
- 150000003623 transition metal compounds Chemical class 0.000 claims 5
- 125000003118 aryl group Chemical group 0.000 claims 4
- 150000005840 aryl radicals Chemical class 0.000 claims 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims 3
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims 3
- 229910052739 hydrogen Inorganic materials 0.000 claims 3
- 239000001257 hydrogen Substances 0.000 claims 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims 3
- 229910052753 mercury Inorganic materials 0.000 claims 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 2
- 239000005977 Ethylene Substances 0.000 claims 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 2
- 229910052736 halogen Inorganic materials 0.000 claims 2
- 150000002367 halogens Chemical group 0.000 claims 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 2
- 229910052751 metal Inorganic materials 0.000 claims 2
- 239000002184 metal Substances 0.000 claims 2
- 239000000203 mixture Substances 0.000 claims 2
- 238000002459 porosimetry Methods 0.000 claims 2
- 239000011148 porous material Substances 0.000 claims 2
- 229910052710 silicon Inorganic materials 0.000 claims 2
- 125000001424 substituent group Chemical group 0.000 claims 2
- 101100001475 Aeromonas hydrophila subsp. hydrophila (strain ATCC 7966 / DSM 30187 / BCRC 13018 / CCUG 14551 / JCM 1027 / KCTC 2358 / NCIMB 9240 / NCTC 8049) alr-1 gene Proteins 0.000 claims 1
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 229910018965 MCl2 Inorganic materials 0.000 claims 1
- 239000004793 Polystyrene Substances 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 125000003342 alkenyl group Chemical group 0.000 claims 1
- 150000004703 alkoxides Chemical class 0.000 claims 1
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- 125000002877 alkyl aryl group Chemical group 0.000 claims 1
- 125000003710 aryl alkyl group Chemical group 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 claims 1
- 239000013256 coordination polymer Substances 0.000 claims 1
- 238000004132 cross linking Methods 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 claims 1
- 229910052732 germanium Inorganic materials 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 claims 1
- 239000003446 ligand Substances 0.000 claims 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims 1
- 125000002950 monocyclic group Chemical group 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 125000003367 polycyclic group Chemical group 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- 229920000098 polyolefin Polymers 0.000 claims 1
- 229920002223 polystyrene Polymers 0.000 claims 1
- 150000003254 radicals Chemical class 0.000 claims 1
- 239000012798 spherical particle Substances 0.000 claims 1
- 229910052718 tin Inorganic materials 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 238000012685 gas phase polymerization Methods 0.000 abstract 1
- 229910052749 magnesium Inorganic materials 0.000 abstract 1
- 239000011777 magnesium Substances 0.000 abstract 1
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- 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
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- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- 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
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Abstract
하나 이상의 M-π 결합을 함유하는 Ti, V, Zr 및 Hf, M-π 결합을 함유하지 않는 Ti 또는 Vr의 화합물 및 할로겐화 마그네슘으로 이루어지는 지지체로부터 선택되는 전이 금속 M의 화합물로 이루어지는 올레핀의 중합 반응용 바이메탈성 촉매 성분. 본 발명의 촉매 성분으로부터 수득되는 촉매는 특별히 기체상 중합 반응 방법에 적합하다.
Description
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음
Claims (30)
- (a) M-π 결합을 함유하지 않는 Ti 또는 V 화합물 및 선택적으로 Mg 할로겐화물상에 지지된 전자 공여 화합물을 함유하는 고체 성분과, 하나 이상의 M-π 결합을 함유하는 Ti, V, Zr 및 Hf 중에서 선택된 전이금속 M의 화합물을 접촉시키거나, 또는 (b) Mg 할로겐화물 상에 지지된 하나 이상의 M-π 결합을 함유하는 Ti, V, Zr 및 Hf의 화합물을 함유하는 고체 성분과 M-π 결합을 함유하는 않는 Ti 또는 V 화합물을 접촉시키거나, 또는 (c) M-π 결합을 함유하지 않는 Ti 또는 V의 화합물 및 하나 이상의 M-π 결합을 갖는 V, Ti, Zr 도는 Hf의 화합물과 Mg 할로겐화물을 함유하는 지지체를 접촉시켜 수득되는 산물을 함유하는 올레핀 중합용 촉매 성분에 있어서, 상기 (a) 및 (b) 에서의 성분 및 (c) 에서의 지지체는 0.3㎤/g 초과의 다공성 (수은 다공성 측정계로 측정한, 반경 10000Å 이하의 구멍에 기인)을 갖는 것을 특징으로 하는 촉매 성분.
- 제1항에 있어서, 다공성이 0.4 내지 1.5㎤/g인 촉매 성분.
- 제1항에 있어서, 전체 다공성이 0.6 내지 4㎤/g (수은 다공성측정계로 측정)인 촉매 성분.
- 제1항에 있어서, 고체 성분(b) 및 (c)에서 사용되는 지지체의 다공성(BET)은 0.3 내지 1㎤/g이고, 표면적(BET)는 40㎡/g 보다 큰 촉매 성분.
- 제1항에 있어서, 고체성분 (a)는 0.2㎤/g 미만의 다공성 (BET)을 가지며, 표면적(BET)는 20 내지 40㎡/g인 촉매 성분.
- 제1항에 있어서, 성분 (a) 및 (b) 및 (c)에 사용되는 지지체는 10 내지 150㎛의 평균 직경을 갖는 구형의 입자 형태인 촉매 성분.
- 제1항에 있어서, Mg 할로겐화물은 고체 성분 (a) 및 (b)에 존재하거나, 또는 (c)에 사용되는 지지체의 형성은 300 내지 600㎡/g의 표면적(BET) 값 및 0.5㎤/g 초과의 다공성(BET)을 갖는 실리카, 알루미나 및 실리카-알루미나, 및 100 내지 500㎡/g의 표면적(BET) 및 0.5㎤/g 초과의 다공성(BET)의 값을 갖는 부분적으로 가교된 폴리스티렌 중에서 선택된 불활성 지지체 상에 지지되는 촉매 성분.
- 제6항에 있어서, Mg 할로겐화물은 MgX2·알콜 부가물 X는 할로겐이다)을 구형화하고, 알킬-Al 화합물과 반응 시켜 알콜을 제거함으로 수득되는 촉매 성분.
- 제8항에 있어서, Mg 할로겐화물은 MgCl2·3ROH 부가물 (R은 탄소수 1 내지 8의 알킬 라디칼이다)을 부분적으로 탈알콜화하고, 알킬-Al 화합물과 반응시킴으로 수득되는 Mg 염화물인 촉매 성분.
- 제1항에 있어서, 전이 금속 화합물은 금속 M 상에 배위된, 공액된 π 전자를 함유하는 모노-또는 폴리시클릭 구조를 갖는 하나 이상의 리간드 L을 함유하는 촉매 성분.
- 제10항에 있어서, 전이 금속 화합물은 하기 구조를 갖는 화합물로부터 선택되는 촉매 성분 :CpⅠMR1 aR2 bR3 c(Ⅰ)CpⅠCpⅡMR1 aR2 b(Ⅱ)(CpⅠ-Ae-CpⅡMR1 aR2 b(Ⅲ)[식중, M은 Ti, V, Zr 또는 Hf 이고 ; CpⅠCpⅡ는 동일하거나, 상이하고, 시클로펜타디에닐기 또는 치환된 시클로펜타디에닐기이며; 상기 시클로펜타디에닐기 상의 둘 이상의 치환체는 탄소수 4 내지 6의 하나 이상의 고리를 형성할 수 있으며; R1, R2, R3은 동일하거나 상이하며, 수소 또는 할로겐원자, 탄소수 1 내지 20의 알킬 또는 알콕시기, 탄소수 6 내지 20의 아릴, 알크아릴 또는 아르알킬, 탄소수 1 내지 20의 아실옥시기, 아릴기, 또는 규소 원자를 함유하는 치환체이고; A는 알케닐 가교 또는 하기 구조로부터 선택되는 구조이며 : =BR1, =AlR1, -Ge-, -Sn-, -O-, -S-, =SO, =SO2, =NR1, =PR1및 =P(O)R1(M1은 Si, Ge 또는 Sn 이고; R1및 R2는 동일하거나 상이하며, 탄소수 1 내지 4의 알킬기 또는 탄소수 6 내지 10의 아릴기이다); a, b, 및 c는 개별적으로 0 내지 4의 정수이며; e는 0 내지 6의 정수이며, 둘이상의 라디칼 R1, R2및 R3은 고리를 형성할 수 있다.]
- 제10항에 있어서, 전이 금속 화합물은 하기 구조를 갖는 화합물로부터 선택되는 촉매 성분 : (Me5Cp) MMe3, (Me5Cp) M (OMe)3, (Me5Cp) MCl3, (CP) MCl3, (Cp) MMe3, (MeCp) MMe3, (Me3Cp) MMe3, (Me4Cp) MCl3, (Ind) MBenz3, (Cp) MBu3.
- 제10항에 있어서, 전이 금속 화합물은 하기 구조를 갖는 화합물로부터 선택되는 촉매 성분 : (Cp)2MMe2, (CP)2MPh2, (Cp)2MEt|2, (Cp)2MCl2, (Cp)2M (OMe)2, (Cp)2M (OMe)Cl, (MeCp)2MCl2, (Me5Cp)2MCl2, (Me5Cp)2MMe2, (Me5Cp)2MMeCl, (Cp)(Me5Cp)MCl2, (1-MeFlu)2MCl2, (BuCp)2MCl2, (Me3Cp)2MCl2, (Me4Cp)2MCl2, (Me5Cp)2M(OMe)2, (Me5Cp)2M(OH)Cl, (Me5Cp)|2M(OH)2, (Me5Cp)2M(C6H5)2, (Me5Cp)2M(CH3)Cl, (EtMe4Cp)2MCl2[(C|6H5)Me4Cp]2MCl2, (Et5Cp)2MCl|2, (Me5Cp)2M(C6H5)Cl, (Ind)2MCl2, (Ind)2MMe2, (H4Ind)2MCl|2, (H4Ind)2MMe2, (Me4Cp)(Me5Cp)MCl|2, (Me5Cp)MCl2, {[Si (CH3)3]Cp}2MCl2, {[Si(CH3)3]2Cp}2MCl2.
- 제10항에 있어서, 전이 금속 화합물은 하기 구조를 갖는 화합물로부터 선택되는 촉매 성분 : C2H4(Ind)2MCl2, C2H4(Ind)|2MMe2, C2H4(H4Ind)MCl2, C2H|4(H4Ind)2MMe2, Me2Si (Me4Cp)3MCl2, Me2Si(Me4Cp)2MMe2, ME2SICP2MCL2, Me2SiCp2MMe|2, Me2Si(Me4Cp)2MMeOMe, Me2Si(Flu)2MCl2, Me2Si(2-Et-5-iPrCp)2MCl2, Me2Si(H4Ind)2MCl|2, Me2Si(H4FLu)2MCl2, Me2SiCH2(Ind)2MCl2, Me2Si(2-Me-H4Ind)2MCl2, Me2Si(2-MeInd)2MCl2, Me2Si(2-Et-5-iPr-Cp)2MCl2, Me2Si(2-Me-5-EtCp)2MCl|2, Me2Si(2-Me-5-Me-Cp)2MCl2, Me2Si(2-Me-4, 5-벤조인데닐)2MCl2, Me2Si(4, 5-벤조인데닐)|2MCl2, Me2Si(2-EtInd)2MCl2, Me2Si(2-iPr-Ind)2MCl2, Me2Si(2-T-부틸-Ind)MCl|2, Me2Si-(3-t-부틸-5-MeCp)2MCl2, Me2Si(3-t-부틸-5-MECP)2MMe2, Me2Si(2-MeInd)2MCl2, C2H4(2-Me-4, 5-벤조인데닐)2MCl2, Me2C(Flu)CpMCl2, Ph2Si(Ind)2MCl2, Ph(Me)SiInd)2MCl2, C2H4(H4Ind)M(NMe2)OMe, 이소프로필리덴-(3-t-부틸-Cp)(Flu)MCl|2, Me2C(Me4Cp)(MeCp)MCl2, MeSi(Ind)2MCl2, MeSi(Ind)|2MMe2, Me2Si(Me4Cp)2MCl(OEt), C2H4(Ind)2-M(NMe2)2, C2H4(Me|4Cp)2MCl2, C2Me4(Ind)2-M(NMe2)2, C2H4(Me5Cp)2MCl2, C2Me4(Ind)2MCl2, Me2Si(3-Me-Ind)2MCl|2, C2H4(2-Me-Ind)2MCl2, C2H4(3-Me-Ind)|2MCl2, C2H4(4, 7-Me2-Ind)2MCl2, C2H4(5,6-Me2-Ind)2MCl2, C2H4(2,4,7-Me3Ind)2MCl2, C2H4(3,4,7-Me3Ind)2MCl2, C2H4(2-Me-H4Ind)2MCl2, C2H4(4,7-Me2-H|4Ind)2MCl2, C2H4(2,4,7-Me3-H4Ind)2MCl2, Me2Si(4, 7-Me2-Ind)|2MCl2, Me2Si(5, 6-Me2-Ind)2MCl2, Me2Si(2,4,7-Me3-H4Ind)2MCl2.
- 제1항에 있어서, 전이 금속 M의 화합물은 금속으로 표현된 0.1 내지 5중량%의 양으로 존재하는 촉매성분.
- 제1항에 있어서, 성분(a)에 존재하는 또는 (b) 에서의 성분 또는 (c) 에서의 지지체와의 반응에 사용되는 M-π 결합을 함유하지 않는 Ti 화합물은 Ti의 할로겐화물 또는 할로 알콕시화물, 또는 VCl3또는 VOCl3으로 부터 선택된 V의 화합물인 촉매 성분.
- 제16항에 있어서, Ti 화합물은 TiCl4, TiCl3및 식 Ti(OR)mXn(식중, R은 탄소수 1 내지 12의 탄화수소 라디칼 또는 -COR 기이고, X는 할로겐이며, m+n은 Ti의 원자가이다.)로부터 선택되는 촉매 성분.
- 제16항 또는 제17항에 있어서, Ti 또는 V의 화합물은 금속으로 표현된 15중량% 이하의 양으로 존재하는 촉매 성분.
- 제1항에 따른 성분과, 트리알킬-Al(알킬기는 탄소수 1 내지 12를 갖는다.) 및 반복 단위 -(R4)AlO-(식중, R4는 탄소수 1 내지 8의 알킬기 또는 시클로알킬기이다) 또는 탄소수 6 내지 10의 아릴기 및 1 내지 50개의 반복 단위를 포함하는 직쇄 또는 고리형 알루미녹산 화합물로부터 선택되는 알킬-Al 화합물과의 반응산물로 이루어지는 올레핀 중합 반응용 촉매.
- 제19항에 있어서, 알킬-Al 화합물이 트리알킬-Al 및 알루미녹산의 혼합물인 촉매.
- 제19항 또는 제20항에 있어서, 알루미녹산은 폴리(메틸 알루미녹산)인 촉매.
- 제19항에 있어서, 트리알킬-Al이 트리메틸-Al, 트리에틸-Al, 트리-n-부틸-Al, 트리이소부틸-Al, 트리핵실-Al, 트리이소헥실-Al 및 트리옥틸-Al로부터 선택되는 촉매.
- 제19항 또는 제20항에 있어서, 트리알킬-Al 화합물이 트리알킬-Al 화합물 1몰당 0.5 내지 0.01몰의 물과반응되고, 전이 금속 M의 화합물은 하기로부터 선택되는 촉매 : C2H4(Ind)2MCl2, C2H4(Ind)|2MMe2, C2H4(H4Ind)MCl2, C2H|4(H4Ind)2MMe2, Me2Si (Me4Cp)3MCl2, Me2Si(Me4Cp)2MMe2, ME2SICP2MCL2, Me2SiCp2MMe2, Me2Si(Me4Cp)2MMeOMe, Me2Si(Flu)2MCl2, Me2Si(2-Et-5-iPrCp)2MCl2, Me|2Si(H4Ind)2MCl2, Me2Si(H4FLu)2MCl2, Me2SiCH2(Ind)2MCl2, Me2Si(2-Me-H4Ind)2MCl2, Me2Si(2-MeInd)2MCl2, Me2Si(2-Et-5-iPr-Cp)2MCl2, Me2Si(2-Me-5-EtCp)2MCl2, Me2Si(2-Me-5-Me-Cp)|2MCl2, Me2Si(2-Me-4, 5-벤조인데닐)2MCl2, Me2Si(4, 5-벤조인데닐)2MCl2, Me|2Si(2-EtInd)2MCl2, Me2Si(2-iPr-Ind)2MCl2, Me2Si(2-T-부틸-Ind)MCl2, Me2Si-(3-t-부틸-5-MeCp)|2MCl2, Me2Si(3-t-부틸-5-MECP)2MMe2, Me2Si(2-MeInd)2MCl|2, C2H4(2-Me-4, 5-벤조인데닐)2MCl2, Me2C(Flu)CpMCl2, Ph2Si(Ind)2MCl2, Ph(Me)SiInd)2MCl2, C2H4(H|4Ind)M(NMe2)OMe, 이소프로필리덴-(3-t-부틸-Cp)(Flu)MCl2,Me2C(Me4Cp)(MeCp)MCl2,MeSi(Ind)|2MCl2, MeSi(Ind)2MMe2,Me2Si(Me4Cp)2MCl(OEt),C2H|4(Ind)2-M(NMe2)2, C2H4(Me4Cp)|2MCl2, C2Me4(Ind)2-M(NMe2)2, C2H4(Me|5Cp)2MCl2, C2Me4(Ind)2MCl2, Me2Si(3-Me-Ind)2MCl2, C2H4(2-Me-Ind)2MCl2, C2H4(3-Me-Ind)2MCl|2, C2H4(4, 7-Me2-Ind)2MCl2, C2H4(5,6-Me2-Ind)2MCl2, C2H4(2,4,7-Me3Ind)2MCl|2, C2H4(3,4,7-Me3Ind)2MCl2, C2H4(2-Me-H4Ind)2MCl2, C2H4(4,7-Me2-H4Ind)2MCl2, C2H|4(2,4,7-Me3-H4Ind)2MCl2, Me2Si(4, 7-Me2-Ind)2MCl2, Me2Si(5, 6-Me2-Ind)2MCl2, Me2Si(2,4,7-Me3-H4Ind)2MCl2.
- 제19항에 따른 촉매가 사용되는 올레핀 CH2=CHR (식중, R은 수소 또는 탄소수 1 내지 10의 알킬, 시클로알킬, 또는 아릴 라디칼이다)의 중합 방법.
- 제13항에 따른 성분으로부터 수득되는 촉매가 사용되는, 올레핀 CH2=CHR (식중, R은 탄소수 1 내지 10의 알킬, 시클로알킬, 또는 아릴 라디칼이다)의 중합 방법.
- 제13항에 따른 성분으로부터 수득되는 촉매가 사용되는, 에틸렌, 및 에틸렌과 올레핀 CH2=CHR (식중, R은 탄소수 1 내지 10의 알킬, 시클로알킬, 또는 아릴 라디칼이다)과의 혼합물의 중합 방법.
- 제24항의 방법에 따라 수득될 수 있는 폴리올레핀.
- 제26항의 방법에 따라 수득될 수 있는 에틸렌 중합체.
- 하기로 이루어지는 촉매의 존재하에서 수해되는 올레핀 CH2=CHR (식중, R은 수소 또는 탄소수 1 내지 10의 알킬, 시클로알킬, 또는 아릴 라디칼이다)의 중합 방법 : (A) 하기 (a) 및 (b) 에서의 성분 및 (c)에서의 지지체는 0.3㎤/g 초과의 다공성 (수은 다공성측정계로 측정한, 반경 10000Å 이하의 구멍에 기인)을 가짐을 특징으로 하며, (a) M-π 결합을 함유하지 않는 Ti 도는 V 화합물 및 선택적으로 Mg 할로겐화물상에 지지된 전자 공여 화합물을 함유하는 고체 성분과, 하나 이상의 M-π 결합을 함유하는, Ti, V, Zr 및 Hf 중에서 된 전자 공여 화합물을 함유하는 고체 성분과, 하나 이상의 M-π 결합을 함유하는, Ti, V, Zr 및 Hf 중에서 선택된 전이 금속 M의 화합물을 접촉시키거나, 또는 (b) Mg 할로겐화물 상에 지지된 하나 이상의 M-π 결합을 함유하지 않는 V, Ti, Zr 또는 Hf의 화합물을 함유하는 고체 성분과 M-π 결합을 함유하지 않는 Ti 또는 V 화합물을 접촉시키거나, 또는 (c) M-π 결합을 함유하지 않는 Ti 또는 V의 화합물 및 하나 이상의 M-π 결합을 갖는, V, Ti, Zr 또는 Hf의 화합물과 Mg 할로겐화물을 함유하는 지지체를 접촉시켜 수득되는 산물을 함유하는 고체 성분; 및 (B) 트리알킬-Al 화합물.
- 제27항 또는 제28항에 따른 중합체로부터 수득되는 성형 제품.※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
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-
1994
- 1994-07-08 IT ITMI941421A patent/IT1270070B/it active IP Right Grant
-
1995
- 1995-06-06 US US08/470,624 patent/US5691264A/en not_active Expired - Lifetime
- 1995-07-04 PL PL95313412A patent/PL313412A1/xx unknown
- 1995-07-04 BR BR9506294A patent/BR9506294A/pt not_active Application Discontinuation
- 1995-07-04 CA CA002171296A patent/CA2171296A1/en not_active Abandoned
- 1995-07-04 WO PCT/EP1995/002587 patent/WO1996001855A1/en active IP Right Grant
- 1995-07-04 KR KR1019960701201A patent/KR960704943A/ko not_active Application Discontinuation
- 1995-07-04 JP JP8504103A patent/JPH09502764A/ja not_active Withdrawn
- 1995-07-04 DK DK95925823T patent/DK0717755T3/da active
- 1995-07-04 EP EP95925823A patent/EP0717755B1/en not_active Expired - Lifetime
- 1995-07-04 AT AT95925823T patent/ATE176788T1/de not_active IP Right Cessation
- 1995-07-04 DE DE69507873T patent/DE69507873T2/de not_active Expired - Fee Related
- 1995-07-04 HU HU9600907A patent/HU217575B/hu not_active IP Right Cessation
- 1995-07-04 ES ES95925823T patent/ES2129836T3/es not_active Expired - Lifetime
- 1995-07-04 AU AU29811/95A patent/AU694974B2/en not_active Ceased
- 1995-07-04 CN CN95190808A patent/CN1134710A/zh active Pending
- 1995-07-05 ZA ZA955602A patent/ZA955602B/xx unknown
- 1995-07-06 IL IL11449195A patent/IL114491A/xx not_active IP Right Cessation
- 1995-07-07 TR TR95/00834A patent/TR199500834A2/xx unknown
-
1996
- 1996-03-06 FI FI961036A patent/FI961036A/fi unknown
- 1996-03-07 NO NO960929A patent/NO960929L/no not_active Application Discontinuation
-
1997
- 1997-06-27 US US08/883,750 patent/US6291607B1/en not_active Expired - Fee Related
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HUT75172A (en) | 1997-04-28 |
CA2171296A1 (en) | 1996-01-25 |
IT1270070B (it) | 1997-04-28 |
FI961036A (fi) | 1996-05-06 |
ES2129836T3 (es) | 1999-06-16 |
ITMI941421A1 (it) | 1996-01-08 |
NO960929L (no) | 1996-04-25 |
AU694974B2 (en) | 1998-08-06 |
EP0717755B1 (en) | 1999-02-17 |
MX9600901A (es) | 1997-12-31 |
US6291607B1 (en) | 2001-09-18 |
HU217575B (hu) | 2000-02-28 |
EP0717755A1 (en) | 1996-06-26 |
NO960929D0 (no) | 1996-03-07 |
DK0717755T3 (da) | 1999-05-10 |
ZA955602B (en) | 1996-06-05 |
FI961036A0 (fi) | 1996-03-06 |
IL114491A0 (en) | 1995-11-27 |
WO1996001855A1 (en) | 1996-01-25 |
US5691264A (en) | 1997-11-25 |
JPH09502764A (ja) | 1997-03-18 |
HU9600907D0 (en) | 1996-05-28 |
DE69507873T2 (de) | 1999-08-26 |
TR199500834A2 (tr) | 1996-06-21 |
ATE176788T1 (de) | 1999-03-15 |
AU2981195A (en) | 1996-02-09 |
CN1134710A (zh) | 1996-10-30 |
PL313412A1 (en) | 1996-06-24 |
DE69507873D1 (de) | 1999-03-25 |
US20010018501A1 (en) | 2001-08-30 |
ITMI941421A0 (it) | 1994-07-08 |
IL114491A (en) | 2000-06-01 |
BR9506294A (pt) | 1997-08-12 |
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