KR950703595A - 장쇄 분지된 중합체 및 그의 제조방법(long chain branched polymers and a process to make long chain branched polymers) - Google Patents

장쇄 분지된 중합체 및 그의 제조방법(long chain branched polymers and a process to make long chain branched polymers) Download PDF

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KR950703595A
KR950703595A KR1019950701185A KR19950701185A KR950703595A KR 950703595 A KR950703595 A KR 950703595A KR 1019950701185 A KR1019950701185 A KR 1019950701185A KR 19950701185 A KR19950701185 A KR 19950701185A KR 950703595 A KR950703595 A KR 950703595A
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polymer
branched
carbon atoms
side chain
branched polyolefin
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패트릭 브랜트
조 안 마리 캐니츠
안토니 레이 다이아스
로버트 리 뱀버거
게리 프레드릭 리시아르디
폴 마크 헨릭스
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벤셔 카펜헤르
엑손 케미칼 패턴츠 인코포레이티드
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Publication of KR950703595A publication Critical patent/KR950703595A/ko

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    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F
    • C08F290/042—Polymers of hydrocarbons as defined in group C08F10/00
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    • C08F10/02—Ethene
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    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • 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
    • C08F2/00—Processes of polymerisation
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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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/08—Butenes
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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
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
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    • 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
    • C08F4/65927—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 two cyclopentadienyl rings being mutually bridged
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    • 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
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/09—Long chain branches
    • C—CHEMISTRY; METALLURGY
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    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/06—Metallocene or single site catalysts
    • 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
    • Y10S526/943—Polymerization with metallocene catalysts

Abstract

신규 중합체 및 선형 긴 측쇄 분지를 혼입시켜 이 중합체를 제조하는 방법이 제공된다. 장쇄 선형 분지는 중합체의 엉킴을 위한 임계 분자량보다 더 큰 분자량을 가지는 최소한 몇몇 분지를 가지는 중합체 주쇄의 탄소원자 1000개당 5.0분지 이하의 빈도로 형성된다. 선형 장쇄 분지 중합체는 액상 및 슬러리 공정에서 연결된 메탈로센 촉매 중합동안에 알파-올레핀 거대분자 혼입에 의하여 생산된다. 중합체는 고상 중합체의 우수한 기계적 특성과 중합체 용융물의 우수한 가공 특성을 가짐을 특징으로 한다. 이 중합체는 기존의 제조 기술로 매우 광범위한 제품을 제조하는 데 유용하다.

Description

장쇄 분지된 중합체 및 그의 제조방법(LONG CHAIN BRANCHED POLYMERS AND A PROCESS TO MAKE LONG CHAIN BRANCHED POLYMERS)
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음

Claims (17)

  1. C2-C30알파 올레핀의 단일중합체 또는 공중합체의 주쇄(b); 및 C2-C30알파 올레핀의 단일중합체 또는 공중합체를 포함하는 탄소 원자수 250 이상의 측쇄 (a)를 포함하고, 측쇄는 1000개의 주쇄 탄소원자당 0.1 내지 5의 평균 측쇄 빈도로 중합체 주쇄에 분포되고; 30,000 이상의 중량 평균 분자량 및 6이하의 Mw/Mn을 가지는 분지된 폴리올레핀.
  2. 제1항에 있어서, 상기 측쇄(a)가 탄소원자수 300 내지 3000의 탄소원자 길이를 가지는 분지된 폴리올레핀.
  3. 제1항 또는 제2항에 있어서, 30,000 내지 1,000,000의 Mw을 가지는 분지된 폴리올레핀.
  4. 제1항 내지 제3항 중 어느 한 항에 있어서, 1 내지 4의 Mw/Mn을 가지는 분지된 폴리올레핀.
  5. 제1항 내지 제4항 중 어느 한 항에 있어서, 1000개의 주쇄 탄소원자당 0.2 내지 3의 평균 측쇄빈도로 측쇄가 존재하는 분지된 폴리올레핀.
  6. 제1항 내지 제5항 중 어느 한 항에 있어서, 측쇄 (a)가 에틸렌 및 C3내지 C30의 알파 올레핀으로부터 유도되고, 이와는 별도로 주쇄가 에틸렌 및 C3내지 C30의 알파 올레핀으로부터 유도되는 분지된 폴리올레핀.
  7. 제1항 내지 제6항 중 어느 한 항에 있어서, 0.85 내지 0.95 g/㎤의 밀도를 가짐을 특징으로 하는 분지된 폴리올레핀.
  8. 제1항 내지 제7항 중 어느 한 항에 있어서, 측쇄 (a)가 에틸렌과 프로필렌의 블럭 공중합체를 포함하는 분지된 폴리올레핀.
  9. 제1항 내지 제8항 중 어느 한 항에 있어서, 측쇄 (a)가 주쇄를 따라 삽입점에 존재하는 에틸렌 블럭과 C3내지 C30의 알파 올레핀의 중합체를 포함하는 분지된 폴리올레핀.
  10. 조성물 중량을 기준으로 5중량% 이상의 제1항 내지 제9항 중 어느 한 항의 분지된 폴리올레핀을 함유하는 중합체 블랜드 조성물.
  11. 제1항 내지 제9항 중 어느 한 항의 분지된 폴리올레핀 중합체를 포함하는 필름 또는 제품.
  12. 1)중합반응 조건하에서, 하나 이상의 알파 올레핀 단량체를 촉매 시스템과 접촉반응시켜 탄소원자수 250 이상이 길이를 가지는 비닐 종결된 거대단량체를 형성하는 단계; 2)연속적으로 중합반응 조건하에서, 상기 비닐 종결된 거대 단량체를 하나 이상의 알파 올레핀 단량체 및 사이클로펜타디에닐 전이 금속 촉매와 조촉매 또는 활성제를 포함하는 촉매 시스템과 접촉반응시키는 단계를 포함하는, 제1항 내지 제6항 중 어느 한 항의 폴리올레핀을 제조하는 방법.
  13. 제12항에 있어서, 전이 금속이 Zr, Hf 또는 Ti인 방법.
  14. 제12항 또는 제13항에 있어서, 조촉매 활성제가 알룸옥산 또는 루이스산 활성제인 방법.
  15. 제12항 내지 제14항 중 어느 한 항에 있어서, 단계 2)을 위한 중합반응 조건이 액상, 가스상, 벌크상, 또는 초임계상 중합반응 조건인 방법.
  16. 제1항에 있어서, 약 9kcal/몰 이상의 활성화 에너지 또는 0.75×0.0115중합체의 Mw-325)의 점도 및 1.3×((7.68×10-5)×Mw-4.32)의 용융 강도를 가지는 분지된 폴리올레핀.
  17. 제12항 내지 제15항 중 어느 한 항에 있어서, 사이클로펜타디에닐 전이 금속 촉매가 단일 사이클로펜타디에닐 그룹 및 각각이 전이금속에 결합된 이형원자 함유 그룹을 포함하는 전이금속 화합물(이때 사이클로펜타디에닐 그룹 및 이형원자 함유 그룹은 이가 잔기를 통하여 임의로 연결된다)인 방법.
    ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
KR1019950701185A 1992-09-29 1993-09-17 장쇄 분지된 중합체 및 그의 제조방법(long chain branched polymers and a process to make long chain branched polymers) KR950703595A (ko)

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US95453992A 1992-09-29 1992-09-29
US07/954539 1992-09-29
PCT/US1993/008833 WO1994007930A1 (en) 1992-09-29 1993-09-17 Long chain branched polymers and a process to make long chain branched polymers

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EP (1) EP0662980A1 (ko)
JP (1) JPH08502303A (ko)
KR (1) KR950703595A (ko)
AU (1) AU4928993A (ko)
CA (1) CA2145635A1 (ko)
RU (1) RU95110681A (ko)
WO (1) WO1994007930A1 (ko)

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