KR100549770B1 - 저분자량 올레핀 (공)중합체의 제조 방법 - Google Patents
저분자량 올레핀 (공)중합체의 제조 방법 Download PDFInfo
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- KR100549770B1 KR100549770B1 KR1020030075832A KR20030075832A KR100549770B1 KR 100549770 B1 KR100549770 B1 KR 100549770B1 KR 1020030075832 A KR1020030075832 A KR 1020030075832A KR 20030075832 A KR20030075832 A KR 20030075832A KR 100549770 B1 KR100549770 B1 KR 100549770B1
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- 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
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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
- C08F4/62—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
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Abstract
Description
Claims (12)
- (A) 하기 화학식 1로 표시되는 제4족 전이 금속 화합물, 및(B) (B-1) 유기 금속 화합물,(B-2) 유기 알루미늄 화합물,(B-3) 유기 알루미늄옥시 화합물,(B-4) 상기 제4족 전이 금속 화합물 (A)와 반응하여 이온쌍을 형성하는 루이스산, 하기 화학식 2의 이온성 화합물, 보란 화합물, 카르보란 화합물 또는 이들의 조합에서 선택되는 1종 이상의 화합물을 포함하는 올레핀 중합용 촉매의 존재하에, 에틸렌을 주단량체로 하는 올레핀을 100 내지 250 ℃ 범위에서 단독 중합 또는 공중합시킴으로써, 저분자량 올레핀 (공)중합체를 제조하는 방법.<화학식 1>[식 중, R1, R2, R3 및 R4는 각각 동일 또는 상이할 수도 있으며, 수소, C1-6 알킬기, C1-3 알킬로 치환될 수 있는 C5-12 시클로알킬기, C5-12 시클로알킬-C1-3 알킬렌기, C5-10 방향족기 또는 C1-3 알킬로 치환될 수 있는 Si1-3 규소함유기이고;R5, R6, R7, R8, R9, R10, R11 및 R12는 각각 동일 또는 상이할 수도 있으며, 수소, C1-4 알킬기, 페닐로 치환된 C1-6 알킬기 또는 C1-3 알킬로 치환될 수 있는 C5-10 방향족기이고;-(Y(R13)(R14))-는 각각 동일 또는 상이할 수 있으며,Y는 C 또는 Si이고,R13 및 R14는 각각 동일 또는 상이할 수도 있으며, 수소, C1-3 알킬기 또는 C5-10 방향족기이고,R1 내지 R14의 인접한 치환기는 서로 결합하여 C1-3 알킬기로 치환될 수 있는 C5-10 시클로알킬 또는 C5-10 방향족 환을 형성할 수도 있으며,MQj는 ZrCl2, ZrBr2, ZrMe2, ZrEt2, Zr(n-Pr)2, ZrMeEt, ZrClMe, ZrBrMe, Zr(s-트랜스-η4-1,3-부타디엔), Zr(s-트랜스-η4-1,4-Ph2-1,3-부타디엔), Zr(s-트랜스-η4-3-Me-1,3-펜타디엔), Zr(s-트랜스-η4-1,4-(CH2Ph)2-1,3-부타디엔), Zr(s-트랜스-η4-2,4-헥사디엔), Zr(s-트랜스-η4-1,3-펜타디엔), Zr(s-트랜스-η4-1,4-(p-tol)2-1,3-부타디엔), Zr(s-트랜스-η4-1,4-(SiMe3)2-1,3-부타디엔), Zr(s-시스-η4-1,3-부타디엔), Zr(s-시스-η4-1,4-Ph2-1,3-부타디엔), Zr(s-시스-η4-3-Me-1,3-펜타디엔), Zr(s-시스-η4-1,4-(CH2Ph)2-1,3-부타디엔), Zr(s-시스-η4-2,4-헥사디엔), Zr(s-시스-η4-1,3-펜타디엔), Zr(s-시스-η4-1,4-(p-tol)2-1,3-부타디엔), Zr(s-시스-η4-1,4-(SiMe3)2-1,3-부타디엔), Zr(OTs)2, Zr(OMs)2, Zr(OTf)2 및 이들 전이 금속을 지르코늄에서 티탄 또는 하프늄으로 바꾼 것들로부터 선택되고,n은 2 내지 4의 정수이다.]<화학식 2>[식 중, Re+로서는 H+, 카르베늄 양이온, 옥소늄 양이온, 암모늄 양이온, 포스포늄 양이온, 시클로헵틸트리에닐 양이온, 전이 금속을 갖는 페로세늄 양이온이고, Rf 내지 Ri는 서로 동일 또는 상이할 수 있고, 아릴기 또는 치환 아릴기이다.]
- 제1항에 있어서, 저분자량 올레핀 (공)중합체의 135 ℃ 데칼린 중에서 측정한 극한 점도 [η]가 0.6 dl/g 이하인 저분자량 올레핀 (공)중합체의 제조 방법.
- 제1항에 있어서, 에틸렌을 주단량체로 하는 탄소 원자수 2 내지 20의 올레핀을 단독 중합 또는 임의의 조합으로 공중합시켜 저분자량 올레핀 (공)중합체를 얻는 저분자량 올레핀 (공)중합체의 제조 방법.
- 제3항에 있어서, 올레핀의 하나 이상이 에틸렌, 프로필렌, 1-옥텐, 1-데센, 1-도데센 또는 테트라데센인 방법.
- 제1항에 있어서, 상기 화학식 1로 표시되는 제4족 전이 금속 화합물이, 하기 화학식 1a로 표시되는 제4족 전이 금속 화합물인 것을 특징으로 하는 저분자량 올레핀 (공)중합체의 제조 방법.<화학식 1a>[식 중, R1, R2, R3 및 R4는 각각 동일 또는 상이할 수도 있으며, 수소, C1-6 알킬기, C1-3 알킬로 치환될 수 있는C5-12 시클로알킬기, C5-12 시클로알킬-C1-3 알킬렌기, C5-10 방향족기 또는 C1-3 알킬로 치환될 수 있는 Si1-3 규소함유기이고;R5, R6, R7, R8, R9, R10, R11 및 R12는 각각 동일 또는 상이할 수도 있으며, 수소, C1-4 알킬기, 페닐로 치환된 C1-6 알킬기 또는 C1-3 알킬로 치환될 수 있는 C5-10 방향족기이고;Y1 및 Y2는 C 또는 Si이고, 서로 동일 또는 상이할 수 있으며,R13, R14, R15 및 R16은 각각 동일 또는 상이할 수도 있으며, 수소, C1-3 알킬기 또는 C5-10 방향족기이고,n은 1 내지 3의 정수이고, n=1일 때는 상기 R1 내지 R16은 동시에 수소 원자가 아니고, 각각 동일 또는 상이할 수 있고,R5 내지 R12의 인접한 치환기는 서로 결합하여 C1-3 알킬기로 치환될 수 있는 C5-10 시클로알킬 또는 C5-10 방향족 환을 형성할 수도 있으며,R13과 R15는 서로 결합하여 C1-3 알킬기로 치환될 수 있는 C5-10 시클로알킬 또는 C5-10 방향족 환을 형성할 수도 있고, 또한 R13과 R15가 서로 결합하여 C1-3 알킬기로 치환될 수 있는 C5-10 시클로알킬 또는 C5-10 방향족 환을 형성함과 동시에 R14와 R16이 서로 결합하여 C1-3 알킬기로 치환될 수 있는 C5-10 시클로알킬 또는 C5-10 방향족 환을 형성할 수도 있고,MQj는 ZrCl2, ZrBr2, ZrMe2, ZrEt2, Zr(n-Pr)2, ZrMeEt, ZrClMe, ZrBrMe, Zr(s-트랜스-η4-1,3-부타디엔), Zr(s-트랜스-η4-1,4-Ph2-1,3-부타디엔), Zr(s-트랜스-η4-3-Me-1,3-펜타디엔), Zr(s-트랜스-η4-1,4-(CH2Ph)2-1,3-부타디엔), Zr(s-트랜스-η4-2,4-헥사디엔), Zr(s-트랜스-η4-1,3-펜타디엔), Zr(s-트랜스-η4-1,4-(p-tol)2-1,3-부타디엔), Zr(s-트랜스-η4-1,4-(SiMe3)2-1,3-부타디엔), Zr(s-시스-η4-1,3-부타디엔), Zr(s-시스-η4-1,4-Ph2-1,3-부타디엔), Zr(s-시스-η4-3-Me-1,3-펜타디엔), Zr(s-시스-η4-1,4-(CH2Ph)2-1,3-부타디엔), Zr(s-시스-η4-2,4-헥사디엔), Zr(s-시스-η4-1,3-펜타디엔), Zr(s-시스-η4-1,4-(p-tol)2-1,3-부타디엔), Zr(s-시스-η4-1,4-(SiMe3)2-1,3-부타디엔), Zr(OTs)2, Zr(OMs)2, Zr(OTf)2 및 이들 전이 금속을 지르코늄에서 티탄 또는 하프늄으로 바꾼 것들로부터 선택된다.]
- 제1항 내지 제5항 중 어느 한 항에 있어서, 상기 중합의 평균 체류 시간이 2 시간 이하인 저분자량 올레핀 (공)중합체의 제조 방법.
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JP2002316579A JP2004149673A (ja) | 2002-10-30 | 2002-10-30 | エチレン系ワックスの製造方法 |
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KR1020050100232A KR100551147B1 (ko) | 2002-10-30 | 2005-10-24 | 저분자량 올레핀 (공)중합체의 제조에 사용되는 중합 촉매 |
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KR (2) | KR100549770B1 (ko) |
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US7214749B2 (en) * | 2004-07-09 | 2007-05-08 | The Texas A&M University Systems | Catalyst system for high activity and stereoselectivity in the homopolymerization and copolymerization of olefins |
CN100390256C (zh) | 2004-11-26 | 2008-05-28 | 三井化学株式会社 | 合成润滑油和润滑油组合物 |
US7026494B1 (en) | 2005-01-10 | 2006-04-11 | Chevron Phillips Chemical Company, Lp | Polymerization catalysts for producing high melt index polymers without the use of hydrogen |
US7834204B2 (en) * | 2005-05-25 | 2010-11-16 | Mitsui Chemicals, Inc. | Fluorene derivative, transition metal compound, catalyst for olefin polymerization, and process for producing olefin polymer |
WO2007002585A1 (en) * | 2005-06-28 | 2007-01-04 | Shell Internationale Research Maatschappij B.V. | Copolymers of c10+ alpha olefins with other alpha olefins and method for copolymerization |
KR100978260B1 (ko) * | 2005-12-27 | 2010-08-26 | 엘지디스플레이 주식회사 | 액정표시장치 및 그 제조방법 |
EP2097424A1 (de) * | 2006-11-17 | 2009-09-09 | Chemetall GmbH | Koordinationsverbindungen der borgruppe |
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TWI304413B (en) | 2008-12-21 |
KR100551147B1 (ko) | 2006-02-13 |
CN1498905A (zh) | 2004-05-26 |
EP1416000B1 (en) | 2011-12-21 |
US20080171651A1 (en) | 2008-07-17 |
US20050131171A1 (en) | 2005-06-16 |
CN1807469B (zh) | 2010-09-08 |
CN1807469A (zh) | 2006-07-26 |
CN1261463C (zh) | 2006-06-28 |
TW200415161A (en) | 2004-08-16 |
KR20040038781A (ko) | 2004-05-08 |
EP1416000A1 (en) | 2004-05-06 |
US7241848B2 (en) | 2007-07-10 |
EP1640385A2 (en) | 2006-03-29 |
KR20050115449A (ko) | 2005-12-07 |
JP2004149673A (ja) | 2004-05-27 |
TW200617042A (en) | 2006-06-01 |
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