KR930023376A - 올레핀 중합용 촉매계, 이의 중합법과 얻은 중합체 - Google Patents

올레핀 중합용 촉매계, 이의 중합법과 얻은 중합체 Download PDF

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KR930023376A
KR930023376A KR1019930007629A KR930007629A KR930023376A KR 930023376 A KR930023376 A KR 930023376A KR 1019930007629 A KR1019930007629 A KR 1019930007629A KR 930007629 A KR930007629 A KR 930007629A KR 930023376 A KR930023376 A KR 930023376A
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catalyst system
propylene
cocatalyst
carbon atoms
hydrocarbon group
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진-루이스-코스타
파마아트 사빈
할로트 궤탄
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더블유. 니첼스
솔베이 (소시에떼 아노님)
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Publication of KR930023376A publication Critical patent/KR930023376A/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
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/06—Macromolecular 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
    • C08F297/08—Macromolecular 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
    • C08F297/083—Macromolecular 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 the monomers being ethylene or propylene
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • 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
    • 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
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • 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
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • 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
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/06—Macromolecular 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
    • 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
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/06—Macromolecular 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
    • C08F297/08—Macromolecular 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
    • 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
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/01—High molecular weight, e.g. >800,000 Da.
    • 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
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/15—Isotactic
    • 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
    • Y10S526/901—Monomer polymerized in vapor state in presence of transition metal containing catalyst

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Abstract

촉매계가 한편으로는 착화된 삼염화 티타늄, 다른 한편으로는 비할로겐화 유기알루미늄 활성화제로 이루어진다.
이들 촉매계를 기체상 올레핀 중합법에 사용했을 때, 높은 혼성단량체 함량을 갖는 공중합체의 경우에 까지 매우 낮은 값으로 조절될 수 있는 이 소택틱성 지수를 갖고 우수한 주입도를 갖는 광범위한 동종중합체와 공중합체(랜덤과 블록)를 제조할 수 있다.
또한 전이제 없이 촉매계는 증가된 활성도를 갖는 고분자량의 중합체를 합성하는 것이 가능하다.
특히, 이들 중합법은 프로필렌의 경우에 특히 유리한 결과를 가져온다.

Description

올레핀 중합용 촉매계, 이의 중합법과 얻은 중합체
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음

Claims (17)

  1. 보조촉매는 비할로겐화 유기알루미늄 화합물이고, 촉매고체는 전자-공여 화합물로 전처리된 TiCl4를 다음 일반식(Ⅰ)으로 표시되는 조성물(C)과 접촉시켜서 나온 액체물질을 할로겐화 활성화제의 존재하에 열처리하여 얻은 착화된 삼염화 티타늄임을 특징으로 하는 TiCl3를 주성분으로 한 촉매고체와 유기금속 보조촉매로 이루어지는 촉매계 :
    AlRP(Y)qX3-(p+q)
    상기 식에서 -R은 탄화수소기이고, -Y는 R'와 R〃가 각각 탄화수소기 또는 수소원자를 나타내는 -OR', -SR'와 -NR'R〃에서 선택한 기를 나타내고, -X는 할로겐을 나타내고, -P는 0＜p＜3와 같은 수이고, -q는 0＜p＜3와 같은 수이고, p+q 총합은 0＜p+q≤3이다.
  2. 제 1항에 있어서, 유기알루미늄 보조촉매가 다음 것들 중 하나에서 선택한 최소한 하나의 화합물을 함유함을 특징으로 하는 촉매계 :
    a) 다음 일반식으로 표시되는 유기알루미늄 화합물 :
    AlRrY3-r
    상기 식에서 -R은 알킬, 아릴알킬, 알킬아릴과 시클로알킬기에서 선택한 1-18개의 탄소원자를 함유하는 탄화수소기를 나타내, -Y는 R'와 R〃가 각각 수소원자 또는 탄화수소기를 나타내는 -OR,-SR'와 -NR'R〃에서 선택한 기를 나타내고, -r는 0＜r≤3와 같은 수이다.
    b)다음 일반식으로 나타낼 수 있는 고리형 과/또는 선형인 알루민옥산형의 올리고머 :
    [Al(R)-O]n'+2또는 (R)2Al-O-[Al(R)-O]n'-Al(R2)
    상기 식에서 R은 탄화수소기이고 n'는 2-50의 정수이다.
  3. 제 2항에 있어서, 보조촉매를 실 AlR3(여기서 R은 2-6개의 탄소원자를 함유하는 알킬기이다.)에서 선택함을 특징으로 하는 촉매계.
  4. 제 3항에 있어서, 보조촉매가 트리에틸 알루미늄 또는 트리-n-부틸알루미늄임을 특징으로 하는 촉메계.
  5. 제 1항 내지 제 4항 어느 한 항에 있어서, 상기 일반식(Ⅰ)에서 -R은 2-8개의 탄소원자를 함유하는 선형 또는 분지형 알킬기를 나타내고, -Y는 R'가 1-12개의 탄소원자를 함유하는 선형 또는 분지형 알킬기와 6-35개의 탄소원자를 함유하는 아릴기인 -OR'를 나타내고, -X는 염소를 나타내고, -P는 1≤p≤2와 같은 수이고, -q는 0.1≤p≤2와 같은 수임을 특징으로 하는 촉매계.
  6. 제 1항 내지 제 5항중 어느 한 항에 있어서, 전자-공여 화합물을 지방족 에테르에서 선택하고 할로겐화 활성화제를 무기 할로겐 화합물에서 선택함을 특징으로 하는 촉매계.
  7. 제 1항 내지 제 6항중 어느 한 항에 따른 촉매계를 사용하여 2-18개의 탄소원자를 함유하는 말단 불포화를 갖는 올레핀을 기체상 중합함을 특징으로 하는 중합법.
  8. 제 7항에 있어서, 프로필렌 동종중합체 또는 공중합체의 제조에 사용함을 특징으로하는 중합법.
  9. 제 7항 또는 제 8항에 있어서, 보조촉매에서 알루미늄과 촉매계에서 티타늄의 몰비가 약 0.5-100이고 이 비율을 원하는 이소택틱도의 함수로서 선택함을 특징으로 하는 중합법.
  10. 수소 또는 다른 전이제 없이 행함을 특징으로 하는 제 1항 내지 제 9항중 어느 한 항에 의하여 고분자량의 중합체를 제조함을 특징으로 하는 제조방법.
  11. 약 87% 내지 약 60%내의 이소택틱성 지수와 1s이하의 주입도를 가짐을 특징으로 하는 프로필렌 동종중합체.
  12. 1s 이하의 주입도와 약 25-65J/g의 용융 엔탈피를 가짐을 특징으로 하는 93중량% 이상의 프로필렌을 함유하는 프로필렌과 에틸렌의 랜덤 공중합체.
  13. 약 10-70%의 랜덤공중합체의 블록의 함량, 1s 이하의 주입도와 약 100-600MPa의 굽힘계수를 가짐을 특징으로 하는 프로필렌과 에필렌의 블록공중합체.
  14. 제 13항에 있어서, 첫번째 블로깅 약 87% 내지 약 60% 범위내에서 이소택틱성 지수를 갖는 프로필렌 동종중합체 임을 특징으로 하는 블록공중합체.
  15. 제 11항 내지 제 14항중 어느 한 항에 있어서, 108g/몰 이상의 분자량과 약 8-12의 Mw/Mn 비율을 가짐을 특징으로 하는 프로필렌 중합체.
  16. 제 11항 내지 제 15항중 어느 한 항에 따른 하나 또는 그 이상의 중합체로 이루어짐을 특징으로 하는 조성물.
  17. 제 16항에 따른 조성물로 전체적 또는 부분적으로 이루어짐을 특징으로 하는 성형물.
    ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
KR1019930007629A 1992-05-04 1993-05-04 올레핀 중합용 촉매계, 이의 중합법과 얻은 중합체 KR930023376A (ko)

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BE9200412A BE1006840A5 (fr) 1992-05-04 1992-05-04 Systeme catalytique pour la polymerisation d'olefines; procede pour cette polymerisation et polymeres ainsi obtenus.
BE09200412 1992-05-04

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EP (2) EP0570045B1 (ko)
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CN (2) CN1037847C (ko)
AT (2) ATE163945T1 (ko)
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EP0808858B1 (fr) 2002-01-09
DE69317324T2 (de) 1998-09-10
EP0570045A2 (fr) 1993-11-18
FI932010A0 (fi) 1993-05-04
NO931604D0 (no) 1993-05-03
EP0808858A2 (fr) 1997-11-26
BR9301734A (pt) 1993-11-09
DE69317324D1 (de) 1998-04-16
NO970860D0 (no) 1997-02-26
EP0808858A3 (fr) 1998-04-29
ATE211746T1 (de) 2002-01-15
EP0570045A3 (ko) 1994-02-23
CN1166500A (zh) 1997-12-03
DE69331445D1 (de) 2002-02-14
US5922813A (en) 1999-07-13
CN1080641A (zh) 1994-01-12
MX9302547A (es) 1994-07-29
CA2095385A1 (fr) 1993-11-05
NO301171B1 (no) 1997-09-22
JP3352754B2 (ja) 2002-12-03
DE69331445T2 (de) 2003-01-16
US5891976A (en) 1999-04-06
FI932010A (fi) 1993-11-05
JPH0632829A (ja) 1994-02-08
NO970860L (no) 1993-11-05
US5902764A (en) 1999-05-11
NO931604L (no) 1993-11-05
EP0570045B1 (fr) 1998-03-11
CN1037847C (zh) 1998-03-25
ATE163945T1 (de) 1998-03-15
TW298594B (ko) 1997-02-21
ES2115717T3 (es) 1998-07-01
BE1006840A5 (fr) 1995-01-03

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