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KR960037706A - 에틸렌 중합체와 이를 얻는 방법 - Google Patents

에틸렌 중합체와 이를 얻는 방법 Download PDF

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KR960037706A
KR960037706A KR1019960012921A KR19960012921A KR960037706A KR 960037706 A KR960037706 A KR 960037706A KR 1019960012921 A KR1019960012921 A KR 1019960012921A KR 19960012921 A KR19960012921 A KR 19960012921A KR 960037706 A KR960037706 A KR 960037706A
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ethylene
reactor
catalyst
hybrid
weight percent
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KR100430198B1 (ko
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브로우 레트 잭케스
프로멜 미첼
로스트 올리비어
코치 베노이트
비안 지앙
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피. 안토인
솔베이 소시에테 아노님
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/06Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
    • C08F297/08Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02Ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00Polymerisation catalysts
    • C08F4/42Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44Metals; 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
    • C08F4/60Metals; 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
    • C08F4/62Refractory metals or compounds thereof
    • C08F4/64Titanium, zirconium, hafnium or compounds thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02Ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/04Dual catalyst, i.e. use of two different catalysts, where none of the catalysts is a metallocene

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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

최소한 1.4의 팽창율(RB), 최소한 55h의 응력하의 내균열성(ESCR)과 최소한 0.2g/10분의 용융지수(MI5)를 갖는 에틸렌 중합체.
첫째는 두 반응기에서의 중합에 사용되는 티타늄과 지르코늄을 주성분으로하고, 둘째는 두 반응기에서의 중합에 사용된는 티타늄 촉매와 티타늄 및 지르코늄 촉매의 혼합물로 이루어지고 ; 셋째는 단일 또는 두 반응기에서의 중합에 사용되는, 실리카, 알루미나와 인산 알루미늄에서 선택한 최소한 둘의 구성성분으로 이루어지는 지지체에서 크롬을 주성하는 다른 촉매계를 사용하여 에틸렌 중합체를 얻는 방법.

Description

에틸렌 중합체와 이를 얻는 방법
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음

Claims (13)

  1. 최소한 1.4의 팽창율(RB), 최소한 55h의 응력하의 내균열성(ESCR)과 최소한 0.2g/10분의 용융지수(MI5)를 갖는 에틸렌 중합체.
  2. 제1항에 있어서, 다음 관계식에 해당하는 g/10분으로 표시되는 용융지수(MI5)와, dPAS로 표시되고 190℃에서 100S-1의 속도기울기로 측정되는 동적 점도 n을 갖는 에틸렌 중합체 ;
  3. 제1항 또는 제2항에 있어서, 952∼958㎞/㎥의 표준밀도를 갖는 에틸렌 중합체.
  4. 제1항 내지 제3항 중 어느 한 항에 있어서, 부텐, 헥산과 이들의 혼합물에서 선택한 0.1∼10중량%의 혼성단량체로 이루어지는 에틸렌 중합체.
  5. 최소한 2의 Zr/Ti몰비로 티타늄과 지르코늄을 함유하는 촉매 고체와 혼성-촉매의 존재하에 일련이 두 반응기에서 에틸렌을 하나 또는 그 이상의 혼성-단량체와 임의로 중합하고, 제일 반응기에 에틸렌, 임의의 혼성단량체와/또는 수소, 촉매 고체와 혼성 촉매를 공급하고, 제일 반응기와 반응 매체를 제어 반응기에 옮기고, 제이 반응기에 에틸렌, 임의의 혼성-단량체와/또는 수소를 공급하는 것으로 이루어지는 제1항 내지 제4항 중 어느 한 항에 따른 에틸렌 중합체의 제조방법.
  6. 제5항에 있어서, 촉매고체가 주로 0.5∼10중량%의 티타늄, 5∼40중량%의 지르코늄, 20∼80중량%의 할로겐, 1∼30중량%의 마그네슘과 0.5∼10중량%의 알루미늄으로 이루어지는 제조방법.
  7. 유일한 활성요소로서 티타늄을 함유하는 제일 촉매고체 및 활성 요소로서 티타늄과 지르코늄을 함유하는 제이 촉매 고체와 혼성-촉매의 존재하에 일련의 두 반응기에서 에틸렌을 임의의 하나 또는 그 이상의 혼성-단량체와 중합시키고, 제일 반응기에 에틸렌, 임의의 혼성-단량체와/또는 수소, 제일 및 제이 촉매고체와 혼성-촉매를 공급하고, 제일 반응기의 반응 매체를 제이 반응기로 옮기고, 제이 반응기에 에틸렌과 임의의 혼성-단량체와/또는 수소를 공급하는 것으로 이루어지는 제1항 내지 제4항 중 어느 한 항에 따른 에틸렌 중합체의 제조방법.
  8. 제7항에 있어서, 제일 촉매고체가 주로 10∼30중량%의 티타늄, 20∼60중량%의 할로겐, 0.5∼20중량%의 마그네슘과 0.1∼10중량%의 알루미늄으로 이루어지고 제이 촉매 고체가 주로 0.5∼10중량%의 티타늄, 5∼40중량%의 지르코늄, 20∼80중량%의 할로겐, 1∼30중량%의 마그네슘과 0.5∼10중량%의 알루미늄으로 이루어지는 제조방법.
  9. 제5항 내지 제8항 주 어느 한 항에 있어서, 제일 단계에서 액체 착물을 얻을때까지 산소-함유 유기마그네슘 화합물을 산소-함유 유기티나튬 화합물과 적합하기로는 산소-함유 유기지르코늄 화합물과 반응시키고, 제이 단계에서 이 책체착물을 일반식 A1Rn X 3-n(여기서 R은 탄화수소기이고 x는 할로겐이고 n은 3 이하이다)의 할로겐화 유기 알루미늄 화합물로 처리하여 촉매 고체 착물로서 액체착물을 침전시켜서 제조한 촉매 고체를 사용하는 제조방법.
  10. 제1항 내지 제4항 중 어느 한 항에 있어서, 실리카, 알루미나와 인산 알루미늄에서 선택한 최소한 둘의 구성성분을 함유하는 지지체에 크롬을 함유하는 촉매 고체의 존재하에 임의로 혼성-촉매와/또는 수소의 존재하에 단일 반응기에서 에틸렌을 임의의 하나 또는 그 이상의 혼성-단량체와 중합시키는 에틸렌 중합체의 제조방법.
  11. 제1항 내지 제4항 중 어느 한 항에 있어서, 실리카, 알루미나와 인산 알루미늄에서 선택한 최소한 둘의 구성성분을 함유하는 지지체에 크롬을 함유하는 촉매 고체와, 혼성-촉매의 존재하에 연속적으로 정열된 두 반응기에서 에틸렌을 임의의 하나 또는 그 이상이 혼성-단량체와 중합시키고, 제일 반응기에 에틸렌, 임의의 혼성-단량체와/또는 수소, 촉매 고체를 공급하고, 제일 반응기의 반응 매체를 제이 반응기에 옮기고, 제이 반응기에 에틸렌과 임의의 혼성-단량체와/또는 수소를 공급하고, 두 반응기중 최소한 하나에 혼성-단량체를 존재시키는, 에틸렌 중합체의 제조방법.
  12. 제10항 또는 제11항에 있어서, 촉매고체가 0.05∼10중량%의 크롬을 함유하고 지지체가 실리카(X), 알루미나(Y)와 인산알루미늄(Z)을 (X) : (Y) : (Z)몰비, (10∼95) : (1∼80) : (1∼85)로 함유하는 제조방법.
  13. 제10항 내지 제12항 중 어느 한 항에 있어서 혼성-촉매가 20개 이하의 탄소원자를 함유하는 알킬기를 갖는 트리알킬붕소인 제조방법.
    ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
KR1019960012921A 1995-04-28 1996-04-25 에틸렌중합체와이를얻는방법 KR100430198B1 (ko)

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BE09500397 1995-04-28
BE9500397A BE1009308A3 (fr) 1995-04-28 1995-04-28 Polymere d'ethylene et procedes pour son obtention.

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KR960037706A true KR960037706A (ko) 1996-11-19
KR100430198B1 KR100430198B1 (ko) 2004-07-30

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CN (1) CN1127525C (ko)
AR (3) AR025116A1 (ko)
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AU (1) AU697264B2 (ko)
BE (1) BE1009308A3 (ko)
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HUP9601108A3 (en) 2001-01-29
RU2164231C2 (ru) 2001-03-20
BR9602100A (pt) 1998-10-06
DE69603773D1 (de) 1999-09-23
US6291602B1 (en) 2001-09-18
ATE227746T1 (de) 2002-11-15
EP0908474B1 (fr) 2002-11-13
EP0906922B1 (fr) 2003-01-08
JPH08301932A (ja) 1996-11-19
ZA963067B (en) 1996-07-29
NO961697L (no) 1996-10-29
ATE230767T1 (de) 2003-01-15
CN1127525C (zh) 2003-11-12
AU5069896A (en) 1996-11-07
AR025116A1 (es) 2002-11-13
EP0908474A3 (fr) 1999-05-19
EP0906922A2 (fr) 1999-04-07
DE69625711T2 (de) 2003-10-09
DE69624844D1 (de) 2002-12-19
NO961697D0 (no) 1996-04-26
US6201078B1 (en) 2001-03-13
HU9601108D0 (en) 1996-06-28
ATE183524T1 (de) 1999-09-15
EP0739909A1 (fr) 1996-10-30
AR025117A2 (es) 2002-11-13
DE69603773T2 (de) 2000-03-09
EP0908474A2 (fr) 1999-04-14
ES2138286T3 (es) 2000-01-01
JP4091667B2 (ja) 2008-05-28
BE1009308A3 (fr) 1997-02-04
CZ122296A3 (en) 1996-11-13
CN1147521A (zh) 1997-04-16
AU697264B2 (en) 1998-10-01
DE69624844T2 (de) 2003-10-09
US6335411B1 (en) 2002-01-01
HUP9601108A2 (en) 1997-12-29
CA2174400A1 (fr) 1996-10-29
EP0906922A3 (en) 1999-05-19
CZ290626B6 (cs) 2002-09-11
NO315325B1 (no) 2003-08-18
JP2008050614A (ja) 2008-03-06
HU223095B1 (hu) 2004-03-29
CA2174400C (fr) 2008-09-09
KR100430198B1 (ko) 2004-07-30
DE69625711D1 (de) 2003-02-13
AR025118A2 (es) 2002-11-13
EP0739909B1 (fr) 1999-08-18
JP4145951B2 (ja) 2008-09-03

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