KR960000928A - 올레핀 중합을 위한 촉매 시스템내 유용한 중합체-결합 리간드, 및 중합체-결합 메탈로센 - Google Patents
올레핀 중합을 위한 촉매 시스템내 유용한 중합체-결합 리간드, 및 중합체-결합 메탈로센 Download PDFInfo
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- KR960000928A KR960000928A KR1019950019332A KR19950019332A KR960000928A KR 960000928 A KR960000928 A KR 960000928A KR 1019950019332 A KR1019950019332 A KR 1019950019332A KR 19950019332 A KR19950019332 A KR 19950019332A KR 960000928 A KR960000928 A KR 960000928A
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- cyclopentadienyl
- polymer
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- fluorenyl
- carbon atoms
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- 229920000642 polymer Polymers 0.000 title claims abstract 20
- 239000003446 ligand Substances 0.000 title claims abstract 13
- 238000006116 polymerization reaction Methods 0.000 title claims abstract 7
- 239000003054 catalyst Substances 0.000 title claims abstract 5
- 150000001336 alkenes Chemical class 0.000 title claims 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims 3
- 238000000034 method Methods 0.000 claims abstract 18
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims abstract 16
- -1 cyclopentadienyl compound Chemical group 0.000 claims abstract 12
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract 11
- 150000004820 halides Chemical class 0.000 claims abstract 10
- 239000004793 Polystyrene Substances 0.000 claims abstract 8
- 229920002223 polystyrene Polymers 0.000 claims abstract 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract 6
- 229910052732 germanium Inorganic materials 0.000 claims abstract 4
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract 4
- 229910052710 silicon Inorganic materials 0.000 claims abstract 4
- 229910052718 tin Inorganic materials 0.000 claims abstract 4
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract 2
- 150000001340 alkali metals Chemical class 0.000 claims abstract 2
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract 2
- 239000001257 hydrogen Substances 0.000 claims abstract 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 16
- 229910000077 silane Inorganic materials 0.000 claims 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 7
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 7
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims 5
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims 5
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims 5
- 150000001875 compounds Chemical class 0.000 claims 4
- 229910001507 metal halide Inorganic materials 0.000 claims 4
- 150000005309 metal halides Chemical class 0.000 claims 4
- 125000003545 alkoxy group Chemical group 0.000 claims 3
- 125000000217 alkyl group Chemical group 0.000 claims 3
- 125000003118 aryl group Chemical group 0.000 claims 3
- 235000010290 biphenyl Nutrition 0.000 claims 3
- 239000004305 biphenyl Substances 0.000 claims 3
- 125000006267 biphenyl group Chemical group 0.000 claims 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims 3
- WFSPUOYRSOLZIS-UHFFFAOYSA-N silane zirconium Chemical compound [SiH4].[Zr] WFSPUOYRSOLZIS-UHFFFAOYSA-N 0.000 claims 3
- 125000001424 substituent group Chemical group 0.000 claims 3
- 229910052726 zirconium Inorganic materials 0.000 claims 3
- XJONFIGVOQMBIP-UHFFFAOYSA-L Cl[Zr](Cl)C1C=CC=C1 Chemical compound Cl[Zr](Cl)C1C=CC=C1 XJONFIGVOQMBIP-UHFFFAOYSA-L 0.000 claims 2
- 229910052735 hafnium Inorganic materials 0.000 claims 2
- 239000002685 polymerization catalyst Substances 0.000 claims 2
- 229910052719 titanium Inorganic materials 0.000 claims 2
- 229910052720 vanadium Inorganic materials 0.000 claims 2
- 239000005046 Chlorosilane Substances 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 150000001339 alkali metal compounds Chemical class 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- QUYDSKYNFIMLFU-UHFFFAOYSA-N chloro-(9h-fluoren-9-yl)-diphenylsilane Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1[Si](Cl)(C=1C=CC=CC=1)C1=CC=CC=C1 QUYDSKYNFIMLFU-UHFFFAOYSA-N 0.000 claims 1
- ASKXKLKPJMASHF-UHFFFAOYSA-N chloro-cyclopenta-2,4-dien-1-yl-(9H-fluoren-9-yl)-methylsilane Chemical compound Cl[Si](C)(C1C2=CC=CC=C2C=2C=CC=CC1=2)C1C=CC=C1 ASKXKLKPJMASHF-UHFFFAOYSA-N 0.000 claims 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 claims 1
- BMTKGBCFRKGOOZ-UHFFFAOYSA-K cyclopenta-1,3-diene;zirconium(4+);trichloride Chemical group [Cl-].[Cl-].[Cl-].[Zr+4].C=1C=C[CH-]C=1 BMTKGBCFRKGOOZ-UHFFFAOYSA-K 0.000 claims 1
- 239000010977 jade Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 239000012968 metallocene catalyst Substances 0.000 claims 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical group C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 229910052723 transition metal Inorganic materials 0.000 abstract 1
- 150000003624 transition metals Chemical class 0.000 abstract 1
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- 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
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
- C08F4/6192—Component covered by group C08F4/60 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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- C08F8/00—Chemical modification by after-treatment
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- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- 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
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon 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
- 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
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
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- 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
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
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- C08F4/61922—Component covered by group C08F4/60 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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Abstract
일반식 QM(R)m에 의해 표현되는 중합체 결합 리간드 및 그를 제조하는 방법이 제공되는데, 상기식에서, Q는 폴리스티렌이고, M은 Si, C, Ge, Sn,P, 또는 N이고, 각 R은 적어도 하나의 R이 시클로펜타디에닐형 화합물인 것이며,m은 2 또는 3이고, 상기 방법은 폴리스티렌이 알칼리금속으로 금속화된 플리스티렌 및 유기할로겐화물 화합물이 일반식 XM(R)m(여기서, X는 할로겐화물)에 의해 표현되는 유기할로겐화물 화합물을 반응시키는 것으로 구성된다. 본 발명의 다른 면은 일반식 QM(R)mZYn에 의해 표현되는 중합체 결합 메탈로센 및 그를 제조하는 방법을 포함하는데, 상기식에서, Z는 전이금속이고,Y는 할로겐화물, 메틸, 수소, 또는 시클로펜타디에닐형 기이며, n은 2 또는 3이다. 본 발명의 또 다른면은 유기알루미녹산 및 중합체 결합 메탈로센을 포함하는 촉매 시스템, 그를 제조하는 방법, 및 상기 촉매 시스템을 사용하는 중합 방법을 포함한다.
Description
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음
Claims (33)
- 메탈로센 촉매 성분으로서 유용한 중합체-결합 리간드를 제조하는 방법으로서, 금속화된 플리스티렌 및 유기할로겐화물 화합물을 반응시키고; 상기 폴리스티렌이 알칼리금속과 금속화되고; 상기 유기할로겐화물 화합물이 일반식 XM(R)m에 의해 표현되는데, 여기서, X는 할로겐화물이고, M은 Si,C,Ge,Sn,P,또는 N이고, 각 R은 알킬, 시클로알킬, 아릴, 및 1-36 탄소원자를 함유하는 시클로펜타디에닐형 기로 구성되는 군으로부터 각각 선택되는 히드로카르빌기이고, 단, 적어도 한 R니는 시클로펜타디에닐, 치환 시클로펜타디에닐, 인데닐, 치환 인데닐, 플루오레닐, 또는 치환 플루오레닐인 시클로펜타디에닐형기이고, 이때 치환체는 1-12탄소원자를 함유하는 히드로카르빌기, 1-12탄소원자를 함유하는 알콕시키, 또는 할로겐화물이며,m은 2 또는 3인 것으로 구성되는 방법.
- 제1항에 있어서, 상기 유기할로겐화물 화합물이 클로로실란인 방법.
- 제2항에 이어서, 상기 유기할로겐화물 화합물이 (클로로)(디페닐)(9-플루오레닐)실란인 방법.
- 제2항에 있어서, 상기 유기할로겐화물 화합물이 (클로로)(시클로펜타디에닐)(9-플루오레닐)(메틸)실란인 방법.
- 제1-4항중 어느 한 항에 있어서, 상기 금속화된 폴리스티렌이 리튬첨가된 플리스티렌인 방법.
- 제1-4항 중 어느 한 항에 있어서, 상기 금속화된 폴리스티렌이 리튬첨가된 메틸폴리스티릴시클로펜타디엔인 방법.
- 제1-4항중 어느 한 항에 있어서, 상기 중합체-결합 리간드 및 1-12 탄소원자를 함유하는 알칼리 금속화합물을 반응시켜 금속화된 중합체-결합 리간드를 형성하고나서, 상기 금속화된 중합체-결합 리간드 및 금속 할로겐화물을 반응시켜 중합체-결합 메탈로센을 형성하고; 상기 금속 할로겐화물이 일반식 ZY4에 의해 표현되고; 상기식에서, Z는 Zr,Hf,Ti 또는 V이고; 각 Y는 할로겐화물, 메티 및 5-36 탄소원자를 함유하는 시클로펜타디에닐형 기로 구성되는 군으로부터 각각 선택되며, 단 적어도 세 Y기는 할로겐화물로 부터 선택되는 것을 포함하는 방법.
- 제7항에 있어서, 상기 금속 할로겐화물이 시할로겐화지르코늄, 예컨대 사염화지르코늄인 방법.
- 제7항에 있어서, 상기 금속 할로겐화물이 시클로펜타디에닐삼염화지르코늄인 방법.
- 제7-9항 중 어느 한 항에 있어서, 알루미녹산 조촉매와 상기 중합체-결합 메탈로센을 반응시켜 촉매 시스템을 형성하는 것을 포함하는 방법.
- 제10항에 있어서, 상기 알루미녹산 조촉매가 메틸알루미녹산인 방법.
- 제10항에 있어서, 상기 알루미녹산 조촉매가 상기 메탈로센내 금속의 몰당 알루미늄 약 0.5몰-약10,000몰 범위의 양으로 제공되는 방법.
- 일반식 QM(R)m에 의해 표현되는 중합체-결합 리간드; 여기서, Q는 폴리스티렌이고 ;M은 Si,C,Ge,Sn,P,또는 N이고; 각 R은 1-20탄소원자를 함유하는 알킬 및 시클로알킬기, 6-20탄소원자를 함유하는 아릴기, 및 시클로펜타디에닐형기로 구성되는 군으로부터 각각 선택되는 히드로카르빌기옥, 단, 적어도 한 R기는 시클로펜타디에닐형기이고, M이 C일때 적어도 두R기는 시클로펜타디에닐, 치환된 시클로펜타디에닐, 인데닐, 치환된 인데닐, 플루오레닐, 또는 치환된 플루오레닐인 시클로펜타디에닐형기이고, 이때 치환체는 1-12 탄소원자를 함유하는 히드로카르빌기, 1-12탄소원자를 함유하는 알콕시기, 또는 할로겐화물을 포함하며; m은 2 또는 3이다.
- 제13항에 있어서, M이 Si인 중합체-결합 리간드.
- 제14항에 있어서, (디페닐)(9-플루오레닐)((폴리스티릴)시클로펜타디에닐)실란 중합체-결합 리간드.
- 제14항에 있어서, (시클로펜타디에닐)(9-플루오레닐)(메틸)(폴리스티릴)실란인 중합체-결합 리간드.
- 제14항에 있어서, (디페닐)(9-플루오레닐)(폴리스티릴)실란인 중합체-결합 리간드.
- 제14항에 있어서, (시클로펜타디에닐)(9-플루오레닐)(메틸)(폴리스티릴)메틸)실란인 중합체-결합 리간드.
- 제14항에 있어서, (디페닐)(9-플루오레닐)(폴리스티릴)메틸)실란인 중합체-결합 리간드.
- 일반식 QM(R)mZYn에 의해 표현되는 중합체-결합 메탈로센: 여기서, Q는 폴리스트렌이고; M은 Si,C,Ge,Sn,P,또는 N이고;각 R은 1-20탄소원자를 함유하는 알킬 및 시클로알킬기, 6-20 탄소원자를 함유하는 아릴기, 및 시클로펜타디에닐형기로 구성되는 군으로부터 각각 선택되는 히드로카르빌기이고,단, 적어도 한 R기는 시클로펜타디에닐형기이고 ,M이 C일때 적어도 두 R기는 시클로펜타디에닐, 치환된 시클로펜타디에닐, 인데닐, 치환된 인데닐, 플루오레닐, 또는 치환된 플루오레닐인 시클로펜타디에닐형 기이고, 이때 치환체는 1-12탄소원자를 함유하는 히드로카르빌기, 1-12탄소원자를 함유하는 알콕시기, 또는 할로겐화물을 포함하며; m은 2 또는 3이고; Z는 Zr,Hf,Ti 또는 V이고; 각 Y는 할로겐화물, 메틸, 수소, 및 5-36 탄소원자를 함유하는 시클로펜타디에닐형기로 구성되는 군으로부터 각각 선택되며; n은 2 또는 3이다.
- 제20항에 있어서, Z이 Zr인 중합체-결합 메탈로센.
- 제21항에 있어서, (디페닐)(9-플로오레닐)(폴리스티릴)시클로펜타디에닐)실란 지르코늄 이염화물인 중합체-결합 메탈로센.
- 제21항에 있어서, (시클로펜타디에닐)(9-플루오레닐)(메틸)(폴리스티릴)실란 지르코늄 이염화물인 중합체-결합 메탈로센.
- 제21항에 있어서, (디페닐)(9-플로오레닐)(폴리스티릴)실란 시클로펜타디에닐)실란 시클로펜타디에닐지르코늄 이염화물인 중합체-결합 메탈로센.
- 제21항에 있어서, (시클로펜타디에닐)(9-플루오레닐)(메틸)((폴리스티릴)메틸)실란 지르코늄 이염화물인 중합체-결합 메탈로센.
- 제21항에 있어서, (디페닐)(9-플로오레닐)((폴리스티릴)메틸)실란 시클로펜타디에닐지르코늄 이염화물인 중합체-결합 메탈로센.
- 제20-26항 중 어느 한 항에 따른 중합체-결합 메탈로센 및 하기 일반식의 반복 단위 @(여기서, R1은 1-8탄소원자를 함유하는 히드로카르빌기이고, x는 2-50임)을 함유하는 알루미녹산 조촉매로 구성되는 중합 촉매 시스템.
- 제27항에 있어서, 각 Y가 각각 할로겐화물 또는 5-36 탄소원자를 함유하는 시클로펜타디에닐형 기인 중합 촉매 시스템.
- 중합 조건하에서, 제27항에 따른 촉매 시스템과 적어도 한 올레핀을 저복 시키는 것으로 구성된 중합방법.
- 제29항에 있어서, 상기 중합 조건이 약 20℃-약 200℃ 범위의 온도를 포함하는 방법.
- 제29항에 있어서, 상기 중합이 입자 형태 조건하에서 수행되는 방법.
- 제31항에 있어서, 상기 중합 조건이 약 50℃-약 110℃ 범위의 온도를 포함하는 방법.
- 제29항에 있어서, 상기 적어도 한 올레핀이 에틸렌으로 구성되는 방법.※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/268,425 US5473020A (en) | 1994-06-30 | 1994-06-30 | Polymer bound ligands, polymer bound metallocenes, catalyst systems, preparation, and use |
| US8/268425 | 1994-06-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR960000928A true KR960000928A (ko) | 1996-01-25 |
Family
ID=23022944
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019950019332A KR960000928A (ko) | 1994-06-30 | 1995-06-29 | 올레핀 중합을 위한 촉매 시스템내 유용한 중합체-결합 리간드, 및 중합체-결합 메탈로센 |
Country Status (17)
| Country | Link |
|---|---|
| US (6) | US5473020A (ko) |
| EP (1) | EP0690076A1 (ko) |
| JP (1) | JPH08188611A (ko) |
| KR (1) | KR960000928A (ko) |
| CN (1) | CN1127759A (ko) |
| AU (1) | AU669317B2 (ko) |
| BG (1) | BG99755A (ko) |
| BR (1) | BR9503059A (ko) |
| CA (1) | CA2152192A1 (ko) |
| CZ (1) | CZ171595A3 (ko) |
| FI (1) | FI953234A (ko) |
| HU (1) | HUT73199A (ko) |
| NO (1) | NO952620L (ko) |
| PL (1) | PL309453A1 (ko) |
| SK (1) | SK85395A3 (ko) |
| TR (1) | TR199500786A2 (ko) |
| ZA (1) | ZA955323B (ko) |
Families Citing this family (58)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0705810A3 (en) * | 1994-09-22 | 1997-04-09 | Shell Int Research | Process for cleaning starting materials for metal-catalyzed reactions and cleaning agents that can be used therefor |
| US5770755A (en) * | 1994-11-15 | 1998-06-23 | Phillips Petroleum Company | Process to prepare polymeric metallocenes |
| DE19506553A1 (de) * | 1995-02-24 | 1996-08-29 | Basf Ag | Polymere enthaltende Katalysatorsysteme |
| US5587439A (en) * | 1995-05-12 | 1996-12-24 | Quantum Chemical Corporation | Polymer supported catalyst for olefin polymerization |
| US5885924A (en) | 1995-06-07 | 1999-03-23 | W. R. Grace & Co.-Conn. | Halogenated supports and supported activators |
| US5610115A (en) * | 1995-07-20 | 1997-03-11 | Samsung General Chemicals Co., Ltd. | Organic carrier supported metallocene catalyst for olefin polymerization |
| US5670680A (en) * | 1996-04-26 | 1997-09-23 | The Dow Chemical Company | Method for producing octahydrofluorenyl metal complexes |
| US5747404A (en) * | 1996-05-28 | 1998-05-05 | Lyondell Petrochemical Company | Polysiloxane supported metallocene catalysts |
| EP0856524A1 (en) * | 1997-02-01 | 1998-08-05 | Repsol Quimica S.A. | Heterogeneous catalyst components for olefins polymerization, preparation process and use thereof |
| DE19706409A1 (de) * | 1997-02-19 | 1998-08-20 | Buna Sow Leuna Olefinverb Gmbh | Verfahren und Katalysator zur Herstellung von mittel- bis ultrahochmolekularen Polyolefinen |
| US6239235B1 (en) | 1997-07-15 | 2001-05-29 | Phillips Petroleum Company | High solids slurry polymerization |
| US6551955B1 (en) | 1997-12-08 | 2003-04-22 | Albemarle Corporation | Particulate group 4 metallocene-aluminoxane catalyst compositions devoid of preformed support, and their preparation and their use |
| US6677265B1 (en) | 1997-12-08 | 2004-01-13 | Albemarle Corporation | Process of producing self-supported catalysts |
| EP1037931B1 (en) | 1997-12-08 | 2004-02-04 | Albemarle Corporation | Catalyst compositions of enhanced productivity |
| US20020111441A1 (en) | 1998-03-20 | 2002-08-15 | Kendrick James Austin | Continuous slurry polymerization volatile removal |
| US6281300B1 (en) * | 1998-03-20 | 2001-08-28 | Exxon Chemical Patents, Inc. | Continuous slurry polymerization volatile removal |
| US7268194B2 (en) * | 1998-03-20 | 2007-09-11 | Exxonmobil Chemical Patents Inc. | Continuous slurry polymerization process and apparatus |
| KR100531628B1 (ko) * | 1998-03-20 | 2005-11-29 | 엑손모빌 케미칼 패턴츠 인코포레이티드 | 연속적인 슬러리 중합반응의 휘발물질 제거 |
| US6977283B1 (en) | 1998-04-07 | 2005-12-20 | Exxonmobil Chemical Patents Inc. | Polymerization process |
| US6245868B1 (en) | 1998-05-29 | 2001-06-12 | Univation Technologies | Catalyst delivery method, a catalyst feeder and their use in a polymerization process |
| US7354880B2 (en) * | 1998-07-10 | 2008-04-08 | Univation Technologies, Llc | Catalyst composition and methods for its preparation and use in a polymerization process |
| KR100430438B1 (ko) | 1998-10-22 | 2004-07-19 | 대림산업 주식회사 | 담지메탈로센촉매,그제조방법및이를이용한폴리올레핀의중합방법 |
| US6087290A (en) * | 1999-01-19 | 2000-07-11 | Hughes Electronics Corporation | Si-N-Si-bridged metallocenes, their production and use |
| US6197714B1 (en) * | 1999-03-23 | 2001-03-06 | Cryovac, Inc. | Supported catalysts and olefin polymerization processes utilizing same |
| US6197715B1 (en) * | 1999-03-23 | 2001-03-06 | Cryovac, Inc. | Supported catalysts and olefin polymerization processes utilizing same |
| EP1203030A4 (en) * | 1999-07-15 | 2003-08-13 | Conocophillips Co | SLUDGE DRAINAGE BY FURSCH |
| US6346586B1 (en) * | 1999-10-22 | 2002-02-12 | Univation Technologies, Llc | Method for preparing a supported catalyst system and its use in a polymerization process |
| US6281155B1 (en) | 1999-11-19 | 2001-08-28 | Equistar Chemicals, L.P. | Supported olefin polymerization catalysts |
| KR100416471B1 (ko) * | 1999-12-30 | 2004-01-31 | 삼성아토피나주식회사 | 폴리머 중합용 신규 메탈로센 담지촉매 |
| US6573412B1 (en) * | 2000-05-12 | 2003-06-03 | Bridgestone Corporation | Chain-coupled polymeric alkoxide compounds having controlled viscosity |
| US7220804B1 (en) * | 2000-10-13 | 2007-05-22 | Univation Technologies, Llc | Method for preparing a catalyst system and its use in a polymerization process |
| US6593267B2 (en) | 2000-12-18 | 2003-07-15 | Univation Technologies, Llc | Method for preparing a supported catalyst system and its use in a polymerization process |
| US6933258B2 (en) | 2000-12-19 | 2005-08-23 | Univation Technologies, L.L.C. | Catalyst composition and methods for its preparation and use in a polymerization process |
| US7084220B2 (en) * | 2003-02-05 | 2006-08-01 | Lg Chem, Ltd. | Catalyst system for preparing styrene polymer and method for preparing of styrene polymer using the same |
| JP4742221B2 (ja) * | 2003-03-21 | 2011-08-10 | ダウ グローバル テクノロジーズ エルエルシー | モルホロジー制御オレフィン重合プロセス |
| US6930156B2 (en) * | 2003-10-22 | 2005-08-16 | Equistar Chemicals, Lp | Polymer bound single-site catalysts |
| US20070073012A1 (en) * | 2005-09-28 | 2007-03-29 | Pannell Richard B | Method for seed bed treatment before a polymerization reaction |
| US7985811B2 (en) * | 2004-01-02 | 2011-07-26 | Univation Technologies, Llc | Method for controlling sheeting in gas phase reactors |
| US20050148742A1 (en) * | 2004-01-02 | 2005-07-07 | Hagerty Robert O. | Method for controlling sheeting in gas phase reactors |
| BRPI0514170B1 (pt) | 2004-08-27 | 2017-04-25 | Chevron Phillips Chemical Co Lp | sistema de fabricação para produzir poliolefina e método para operar um processo de fabricação de poliolefina |
| US7125939B2 (en) * | 2004-08-30 | 2006-10-24 | Equistar Chemicals, Lp | Olefin polymerization with polymer bound single-site catalysts |
| US7629421B2 (en) * | 2005-12-21 | 2009-12-08 | Chevron Phillips Chemical Company Lp | Monomer recovery by returning column overhead liquid to the reactor |
| EP2183286B1 (en) * | 2007-08-16 | 2012-12-12 | Univation Technologies, LLC | Continuity additives and their use in polymerization processes |
| US8012900B2 (en) * | 2007-12-28 | 2011-09-06 | Chevron Phillips Chemical Company, L.P. | Nano-linked metallocene catalyst compositions and their polymer products |
| US8080681B2 (en) | 2007-12-28 | 2011-12-20 | Chevron Phillips Chemical Company Lp | Nano-linked metallocene catalyst compositions and their polymer products |
| US7863210B2 (en) | 2007-12-28 | 2011-01-04 | Chevron Phillips Chemical Company Lp | Nano-linked metallocene catalyst compositions and their polymer products |
| MX2010007480A (es) | 2008-01-07 | 2010-10-11 | Univation Tech Llc | Sistemas de alimentacion de catalizador y metodos para usarlos. |
| EP2376540B1 (en) | 2009-01-08 | 2013-04-03 | Univation Technologies, LLC | Additive for polyolefin polymerization processes |
| WO2010080871A1 (en) | 2009-01-08 | 2010-07-15 | Univation Technologies, Llc | Additive for gas phase polymerization processes |
| US8205815B2 (en) * | 2009-05-15 | 2012-06-26 | Fellowes, Inc. | Paper alignment sensor arrangement |
| US7919639B2 (en) * | 2009-06-23 | 2011-04-05 | Chevron Phillips Chemical Company Lp | Nano-linked heteronuclear metallocene catalyst compositions and their polymer products |
| MY158186A (en) | 2009-07-28 | 2016-09-15 | Univation Tech Llc | Polymerization process using a supported constrained geometry catalyst |
| RU2577324C2 (ru) | 2010-12-22 | 2016-03-20 | Юнивейшн Текнолоджиз, Ллк | Добавка для способов полимеризации полиолефина |
| EP2610269A1 (en) | 2011-12-28 | 2013-07-03 | Saudi Basic Industries Corporation | Catalyst composition and method for preparing the same |
| EP3080200B1 (en) | 2013-12-09 | 2018-11-14 | Univation Technologies, LLC | Feeding polymerization additives to polymerization processes |
| GB2533770B (en) | 2014-12-22 | 2021-02-10 | Norner Verdandi As | Polyethylene for pipes |
| US10029230B1 (en) | 2017-01-24 | 2018-07-24 | Chevron Phillips Chemical Company Lp | Flow in a slurry loop reactor |
| KR102513518B1 (ko) | 2020-12-23 | 2023-03-22 | 디엘케미칼 주식회사 | 메탈로센 올레핀 중합 공정용 대전방지제를 이용한 올레핀 중합 방법 |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1268754A (en) * | 1985-06-21 | 1990-05-08 | Howard Curtis Welborn, Jr. | Supported polymerization catalyst |
| US5084534A (en) * | 1987-06-04 | 1992-01-28 | Exxon Chemical Patents, Inc. | High pressure, high temperature polymerization of ethylene |
| US5153157A (en) * | 1987-01-30 | 1992-10-06 | Exxon Chemical Patents Inc. | Catalyst system of enhanced productivity |
| US4882384A (en) * | 1988-02-01 | 1989-11-21 | Shell Oil Company | Modified block copolymers |
| US5155080A (en) | 1988-07-15 | 1992-10-13 | Fina Technology, Inc. | Process and catalyst for producing syndiotactic polyolefins |
| DE3844282A1 (de) * | 1988-12-30 | 1990-07-05 | Hoechst Ag | Bisindenyl-derivat und verfahren zu seiner herstellung |
| IT8919252A0 (it) * | 1989-01-31 | 1989-01-31 | Ilano | Catalizzatori per la polimerizzazione di olefine. |
| ES2071888T3 (es) * | 1990-11-12 | 1995-07-01 | Hoechst Ag | Bisindenilmetalocenos sustituidos en posicion 2, procedimiento para su preparacion y su utilizacion como catalizadores en la polimerizacion de olefinas. |
| JP3036852B2 (ja) * | 1990-12-28 | 2000-04-24 | 三井化学株式会社 | オレフィン重合用触媒 |
| US5362824A (en) * | 1991-12-13 | 1994-11-08 | Mobil Oil Corporation | Olefin polymerization catalysts |
-
1994
- 1994-06-30 US US08/268,425 patent/US5473020A/en not_active Expired - Fee Related
-
1995
- 1995-05-31 US US08/454,764 patent/US5492973A/en not_active Expired - Fee Related
- 1995-05-31 US US08/455,306 patent/US5492985A/en not_active Expired - Fee Related
- 1995-05-31 US US08/455,488 patent/US5492978A/en not_active Expired - Fee Related
- 1995-05-31 US US08/455,382 patent/US5492975A/en not_active Expired - Fee Related
- 1995-05-31 US US08/455,380 patent/US5492974A/en not_active Expired - Fee Related
- 1995-06-20 CA CA002152192A patent/CA2152192A1/en not_active Abandoned
- 1995-06-27 ZA ZA955323A patent/ZA955323B/xx unknown
- 1995-06-27 AU AU23277/95A patent/AU669317B2/en not_active Expired - Fee Related
- 1995-06-29 SK SK853-95A patent/SK85395A3/sk unknown
- 1995-06-29 EP EP95110160A patent/EP0690076A1/en not_active Withdrawn
- 1995-06-29 CZ CZ951715A patent/CZ171595A3/cs unknown
- 1995-06-29 CN CN95108178A patent/CN1127759A/zh active Pending
- 1995-06-29 BG BG99755A patent/BG99755A/bg unknown
- 1995-06-29 FI FI953234A patent/FI953234A/fi not_active Application Discontinuation
- 1995-06-29 KR KR1019950019332A patent/KR960000928A/ko not_active Application Discontinuation
- 1995-06-29 TR TR95/00786A patent/TR199500786A2/xx unknown
- 1995-06-29 HU HU9501916A patent/HUT73199A/hu unknown
- 1995-06-29 NO NO952620A patent/NO952620L/no unknown
- 1995-06-30 PL PL95309453A patent/PL309453A1/xx unknown
- 1995-06-30 JP JP7198988A patent/JPH08188611A/ja active Pending
- 1995-06-30 BR BR9503059A patent/BR9503059A/pt not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| NO952620D0 (no) | 1995-06-29 |
| EP0690076A1 (en) | 1996-01-03 |
| NO952620L (no) | 1996-01-02 |
| CZ171595A3 (en) | 1996-01-17 |
| FI953234A (fi) | 1995-12-31 |
| HUT73199A (en) | 1996-06-28 |
| FI953234A0 (fi) | 1995-06-29 |
| BR9503059A (pt) | 1996-04-23 |
| US5492975A (en) | 1996-02-20 |
| SK85395A3 (en) | 1996-12-04 |
| CN1127759A (zh) | 1996-07-31 |
| US5492978A (en) | 1996-02-20 |
| JPH08188611A (ja) | 1996-07-23 |
| HU9501916D0 (en) | 1995-08-28 |
| ZA955323B (en) | 1996-02-13 |
| TR199500786A2 (tr) | 1996-10-21 |
| US5473020A (en) | 1995-12-05 |
| US5492985A (en) | 1996-02-20 |
| PL309453A1 (en) | 1996-01-08 |
| US5492973A (en) | 1996-02-20 |
| US5492974A (en) | 1996-02-20 |
| AU2327795A (en) | 1996-01-25 |
| BG99755A (bg) | 1996-06-28 |
| CA2152192A1 (en) | 1995-12-31 |
| AU669317B2 (en) | 1996-05-30 |
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