KR960705853A - 에틸렌의 중합 또는 공중합 방법(process for the polymerization or copolymerization of ethylene) - Google Patents

에틸렌의 중합 또는 공중합 방법(process for the polymerization or copolymerization of ethylene)

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Publication number
KR960705853A
KR960705853A KR1019960702363A KR19960702363A KR960705853A KR 960705853 A KR960705853 A KR 960705853A KR 1019960702363 A KR1019960702363 A KR 1019960702363A KR 19960702363 A KR19960702363 A KR 19960702363A KR 960705853 A KR960705853 A KR 960705853A
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ethylene
silica
bis
catalyst
group
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KR1019960702363A
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English (en)
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KR100325898B1 (ko
Inventor
체루부 서브라마냠
입-콰이 로 프레드릭
크리스틴 옹 시메이
Original Assignee
데니스 피. 산티니
모빌 오일 코오포레이숀
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Priority claimed from US08/148,309 external-priority patent/US5608019A/en
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Publication of KR960705853A publication Critical patent/KR960705853A/ko
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Publication of KR100325898B1 publication Critical patent/KR100325898B1/ko

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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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—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
    • 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
    • C08F4/64—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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

본 발명은 에틸렌의 가스상 중합 및 공중합 방법에 관한 것으로서, 이때 온도에 따라, 수지 생성물의 MI(MI는 ASTM D-1238 조건 E에 따라 측정)로 표현된 분자량이 조절되는데, 중합 온도를 상승시키면 MI가 감소하는 한편, 중합 온도를 저하시키면 MI가 증가한다.

Description

에틸렌의 중합 또는 공중합 방법(PROCESS FOR THE POLYMERIZATION OR COPOLYMERIZATION OF ETHYLENE)
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음
제1도는 본 발명의 방법에 유용한, 올레핀 중합 또는 공중합 반응용 가스상 유체층 반응기의 개요도이다.

Claims (12)

  1. 에틸렌을 중합시키거나, 또는 3 내지 10개의 탄소원자를 가진 알파-올레핀과 에틸렌을 공중합시켜 MI(g/10분)값이 0.0001 내지 500인 수지를 제조하는 방법으로서, 하기 (a) 내지 (e) 단계를 포함하는 방법; (a) 입상의 활성 지지된 메탈로센 촉매를 유체층 가스상 반응기에서 액화시키는 단계로서 그 촉매는 지지체, 전이금속(MTr) 및 Al을 포함하고, MTr의 양(원소 기준)은 0.001 내지 10 중량％이고, Al의 양은(원소 기준) 1 내지 40 중량％이며, Al:MTr의 비(원소 기준)는 25 내지 10000인 단계; (b) 상기 촉매를, (1) 에틸렌, (2) 에틸렌과 수소의 혼합물, (3) 에틸렌과 C3-C10의 알파 올레핀의 혼합물, 및 (4) 에틸렌과 수소 및 C3-C10의 알파 올레핀의 혼합물로 구성된 군중에서 선택된 공급 원료와 접촉시킴으로써 중합 생성물을 제조하는 단계; (c) 중합 압력은 1000psi(6.9MPa) 미만, 중합 온도는 55℃ 내지 115℃로 유지시키는 단계; (d) 액화된 촉매를 시약과 접촉시킴으로써 중합된 중합 생성물의 MI를 증가시키거나 또는 저하시키는 단계; 및 (e) 중합 생성물을 회수하는 단계.
  2. 제1항에 있어서, 시약으로서 이소펜탄 및/또는 전자 공여 화합물을 사용하면 중합된 생성물이 MI가 저하되는 방법.
  3. 제2항에 있어서, 이소펜탄을 2 내지 80 psi(14 내지 550 KPa)의 부분 압력하에서 사용하는 방법.
  4. 제2항에 있어서, 에틸렌에 대해 0.01 내지 500ppm의 몰비를 이루는 양으로 전자 공여 화합물을 사용하는 방법.
  5. 제2항에 있어서, 전자 공여 화합물이 산소, 일산화 탄소 및 이산화 탄소로 구성된 군중에서 선택되는 방법.
  6. 제2항에 있어서, 이소펜탄올, 산소, 일산화 탄소 및 이산화 탄소로 구성된 군중에서 선택된 전자 공여 화합물과 함께 공급하는 방법.
  7. 제1항에 있어서, 시약으로서 물 또는 전자 인출 화합물을 사용하면 중합된 생성물의 MI가 상승하는 방법.
  8. 제1항에 있어서, 지지체가 실리카, 알루미나 또는 실리카/알루미나인 방법.
  9. 제8항에 있어서, 촉매의, 입자크기가 1 내지 500 미크론이고 실리카, MTr및 Al을 포함하는 다공성 무정형 입자 형태로서, 이때 Al:MTr의 비는 70 내지 350이고; 상기 실리카의 기공 부피는 0.1 내지 5㎠/g이고, 히드록실 기의 농도는 실리카의 0 내지 2.5 ㎜ole/g이며; 상기 촉매는, 상기 실리카를 메탈로센 및 알룸옥산으로 구성된 일정 부피의 혼합물과 접촉시킴으로써 활성 형태로 제조하며, 이때 상기 혼합물의 부피는 상기 탈수된 실리카의 총 기공 부피보다 작고; 상기 메탈로센은 일반식 CpmMAnBp을 가지는데, 식중 Cp는 치환된 시클로펜타디에닐 기이고, m은 1 또는 2이고, M은 지르코늄 또는 하프늄이며, A 및 B는 각각 할로겐 원자, 수소 원자, 알콕시기 및 알킬기로 구성된 군중에서 선택되나, 단 m+n+p는 금속의 M의 원자가와 동일하며; 상기 알룸옥산은, 선형 알룸옥산 소중합체의 경우에는 일반식 R-(Al(R)-O)m-AlR2를 가지거나, 또는 환형 알룸옥산 소중합체의 경우에는 일반식 (Al(R)-O)m을 가지며, 식중 n은 1 내지 40이고, m은 3 내지 40이며, R은 C1-C8의 알킬기인 방법.
  10. 제9항에 있어서, 메탈로센이 비스(n-부틸시클로펜타디에닐)금속 디할라이드, 비스(n-부틸시클로펜타디에닐)금속 히드리도할라이드, 비스(n-부틸시클로펜타디에
    닐)금속 모노알킬 모노할라이드, 비스(n-부틸시클로펜타디에닐)금속 디알킬 및 비스(인데닐)금속 디할라이드로 구성된 군중에서 선택되는 방법.
  11. 제10항에 있어서, 메탈로센이 비스(이소부틸시클로펜타디에닐)지르코늄 디클로라이드인 방법.
  12. 제1항에 있어서, 상기 중합 압력을 400psi(2.8MPa) 미만으로 유지하는 방법.
    ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
KR1019960702363A 1993-11-08 1994-11-03 에틸렌의중합또는공중합방법 KR100325898B1 (ko)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US08/148,309 US5608019A (en) 1992-12-28 1993-11-08 Temperature control of MW in olefin polymerization using supported metallocene catalyst
US148,309 1993-11-08
US15406993A 1993-11-18 1993-11-18
US154,069 1993-11-18
PCT/US1994/012586 WO1995013305A1 (en) 1993-11-08 1994-11-03 Process for the polymerization or copolymerization of ethylene

Publications (2)

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KR960705853A true KR960705853A (ko) 1996-11-08
KR100325898B1 KR100325898B1 (ko) 2002-06-29

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Country Link
EP (1) EP0728151B1 (ko)
JP (1) JPH09504825A (ko)
KR (1) KR100325898B1 (ko)
CN (1) CN1078213C (ko)
AU (1) AU690169B2 (ko)
CA (1) CA2174430A1 (ko)
DE (1) DE69426938T2 (ko)
ES (1) ES2157312T3 (ko)
TW (1) TW344745B (ko)
WO (1) WO1995013305A1 (ko)

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Publication number Publication date
EP0728151A4 (en) 1997-03-26
CN1078213C (zh) 2002-01-23
KR100325898B1 (ko) 2002-06-29
EP0728151B1 (en) 2001-03-21
JPH09504825A (ja) 1997-05-13
TW344745B (en) 1998-11-11
AU1087195A (en) 1995-05-29
EP0728151A1 (en) 1996-08-28
WO1995013305A1 (en) 1995-05-18
AU690169B2 (en) 1998-04-23
CN1134708A (zh) 1996-10-30
DE69426938T2 (de) 2001-11-08
DE69426938D1 (de) 2001-04-26
ES2157312T3 (es) 2001-08-16
CA2174430A1 (en) 1995-05-18

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