KR910016776A - 올레핀 중합에 사용되는 촉매및 예비 중합체, 및 그로 부터 수득 가능한 에틸렌(공)중합체 - Google Patents

올레핀 중합에 사용되는 촉매및 예비 중합체, 및 그로 부터 수득 가능한 에틸렌(공)중합체 Download PDF

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KR910016776A
KR910016776A KR1019910003942A KR910003942A KR910016776A KR 910016776 A KR910016776 A KR 910016776A KR 1019910003942 A KR1019910003942 A KR 1019910003942A KR 910003942 A KR910003942 A KR 910003942A KR 910016776 A KR910016776 A KR 910016776A
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ethylene
particles
solid catalyst
average diameter
zirconium
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끌로드 앙드레 벨리 쟝
쟉끌린 샤브랑 크리스틴
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케이트 와아윅 덴바이
비피 케미칼스 리미티드
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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
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
    • C08F4/10—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of alkaline earth metals, zinc, cadmium, mercury, copper or silver
    • 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
    • C08F110/02—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
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/06—Catalyst characterized by its size
    • 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
    • C08F4/65904—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with another component of C08F4/64
    • 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

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  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Polymerization Catalysts (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

내용 없음

Description

올레핀 중합에 사용되는 촉매및 예비 중합체, 및 그로부터 수득가능한 에틸렌(공)중합체
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음

Claims (10)

  1. -이염화 마그네슘 90~99.9몰%, 및 불안정한 수소가 없는 1종 이상의 유기전자 - 공여 화합물 D0.1~10몰%를 함유하는 지지체, -지르코늄 메탈로센, -티탄 또는 바나듐으로 부터 선택된 전이금속(TM)의 할라이드 1종 이상, -및 임의로 유기 알루미늄 화합물, 바람직하게는 알루미녹산을 함유하며, 질량 평균 직경 Dm이 10~100미크론이고, 입자의 수평균 직경 Dn에 대한 Dm의 비율이 3이하가 되는 입자 크기 분포를 갖는 회전 타원형 입자로 구성된, 1종 이상의 올레핀의 불균질 중합 공정에 적합한 고체 촉매.
  2. 제1항에 있어서, 이염화 마그네슘, 지르코늄 메탈로센, 전이금속(TM)할라이드 및 유기알루미늄 화합물이 0.001~0.2 범위의 Zr/Mg 원자비, 0.01~100범위의 Zr/TM 원자비 및 0~2범위의 Al/Mg 원자비로 촉매 중에 존재함을 특징으로 하는 촉매.
  3. (1) 질량 평균 직경 Dm이 10~100 미크론이고 입자의 수평균 직경 Dn에 대한 Dm의 비율이 3이하인 입자크기 분포를 갖는 회전 타원형 입자의 형태이며, 80~99.5몰%의 염화 마그네슘 및 0.5~20몰%의 불안정한 수소가 없는 1종 이상의 유기 전자 공여 화합물 D를 함유하는 고체 지지체(A)를 (2) 지르코늄 메탈로센(B), 및 티탄 또는 바나듐에서 선택된 전이금속(TM)의 할라이드(C)1종 이상, 및 임의로 유기 알루미늄 화합물(E), 바람직하게는 알루미녹산과 접촉시키는 것을 특징으로 하는, 제1항에 따르는 고체 촉매의 제조방법.
  4. (ⅰ) 폴리에틸렌, 또는 에틸렌과 10중량% 이하의 C3~C8α-올레핀 1종 이상과의 공중합체, 및 (ⅱ)마그네슘, 염소, 알루미늄, 지르코늄, 티탄 및/또는 바나듐 원자를 주성분으로 함유하는 올레핀(공)중합용 활성 촉매를, 지르코늄 및 전이금속(TM)1밀리몰 당 0.1~500g의 폴리에틸렌 또는 에틸렌 공중합체의 양으로 함유하며, Al/(Zr+TM)의 원자비가 10~1000인 예비 중합체 입자.
  5. 제4항에 있어서, 질량 평균 직경 Dm이 10~500미크론이고, 입자의 수평균 직경 Dn에 대한 Dm의 비율이 3이하인 입자 크기 분포를 갖는 회전 타원형 입자로 구성되는 것을 특징으로 하는 예비 중합체 입자.
  6. 제1항에 따르는 고체 촉매 또는 제3항에 따르는 방법에 의해 제조된 고체 촉매를 A1/(Zr+TM)원자비가 10~1000이 되는 양의 유기 알루미늄 화합물, 바람직하게는 알루미녹산의 존재하에 0.1~5MPa의 전체 압력, 0~100℃의 온도에서 액체 탄화수소 중 또는 기체 상에서, 에틸렌, 또는 에틸렌 및 1종 이상의 C3~C8α-올레핀의 혼합물과 접촉시키는 것을 특징으로 하는, 제4항에 따르는 예비 중합체 입자의 제조방법.
  7. 제1항에 따르는 고체 촉매 또는 제3항에 따라 제조된 고체 촉매, 또는 제4항에 따르는 예비 중합체 입자 또는 제6항에 따른 방법에 의해 제조된 예비 중합체 입자를, Al/(Zr+TM) 원자비가 10~1000이 되는 양의 유기 알루미늄 화합물, 바람직하게는 알루미녹산의 존재하에 0.1~5MPa의 전체 압력, 10~110℃의 온도에서 에틸렌, 또는 에틸렌 및 1종 이상의 C3~C8α-올레핀의 혼합물과 접촉시키는 것을 특징으로 하는, 에틸렌의 중합 또는 에틸렌과 1종 이상의 C3~C8α-올레핀과의 공중합 방법.
  8. 제7항에 있어서, 중합 또는 공중합 반응이 액체 탄화수소 슬러리, 또는 바람직하게는 기체상에서 수행되는 것을 특징으로 하는 방법.
  9. (i) 0.89~0.965g/㎤의 밀도, 0.01~100g/10분의 융용 지수(ASTM-D-1238 조건 F), 5~15의 분자량 분포 및 탄소원자 1000개당 0.6개 이하의 에틸렌 불포화도를 갖는 폴리에틸렌, 또는 에틸렌, 또는 에틸렌과 30중량% 이하의 C3~C8α-올레핀 1종 이상과의 공중합체, 및 (ii) 마그네슘, 염소, 알루미늄, 지르코늄, 티탄 및/또는 바나듐 원자를 주성분으로 하고, 지르코늄의 양이 0.5~20중량 ppm인 촉매 잔사를 함유하며, 벌크 밀도가 0.3~0.55g/㎤인, 제7항에 따르는 방법에 의해 수득 가능한 중합체 또는 공중합체 분말.
  10. 제9항에 있어서, 질량 평균 직경 Dm이 150~1500미크론이고, 입자의 수평균 직경 Dn에 대한 Dm의 비율이 3.5이하가 되는 입자 크기 분포를 갖는 회전 타원형 입자로 구성되는 것을 특징으로 하는 중합체 또는 공중합체 분말.
    ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
KR1019910003942A 1990-03-12 1991-03-12 올레핀 중합에 사용되는 촉매및 예비 중합체, 및 그로 부터 수득 가능한 에틸렌(공)중합체 KR910016776A (ko)

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FR9003367 1990-03-12
FR9003367A FR2659336B1 (fr) 1990-03-12 1990-03-12 Catalyseur a base de zirconium, de titane et/ou de vanadium, supporte sur un chlorure de magnesium, procede de preparation et utilisation du catalyseur dans la polymerisation des olefines.

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Publication number Priority date Publication date Assignee Title
CA1268754A (en) * 1985-06-21 1990-05-08 Howard Curtis Welborn, Jr. Supported polymerization catalyst
US4659685A (en) * 1986-03-17 1987-04-21 The Dow Chemical Company Heterogeneous organometallic catalysts containing a supported titanium compound and at least one other supported organometallic compound
IT1221654B (it) * 1987-11-27 1990-07-12 Ausimont Spa Catalizzatori per la polimerizzazione delle olefine
FR2656315B1 (fr) * 1989-12-22 1992-04-17 Bp Chemicals Snc Procede de preparation d'un catalyseur a base de zirconium supporte sur du chlorure de magnesium, et utilisation du catalyseur dans la polymerisation des olefines.
FR2656314B1 (fr) * 1989-12-22 1992-04-17 Bp Chemicals Snc Catalyseur a base de zirconium supporte sur du chlorure de magnesium, procede de preparation et utilisation du catalyseur dans la polymerisation des olefines.
FR2659337B1 (fr) * 1990-03-12 1992-06-05 Bp Chemicals Snc Procede de preparation d'un catalyseur a base de zirconium, de titane et/ou de vanadium supporte sur du chlorure de magnesium, et utilisation du catalyseur dans la polymerisation des olefines.

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EP0447071A1 (en) 1991-09-18
JPH04220405A (ja) 1992-08-11
NO177719C (no) 1995-11-08
DE69123164T2 (de) 1997-03-13
AU645540B2 (en) 1994-01-20
ES2093677T3 (es) 1997-01-01
ZA911289B (en) 1992-10-28
FR2659336B1 (fr) 1993-05-07
DE69123164D1 (de) 1997-01-02
FR2659336A1 (fr) 1991-09-13
FI911214A0 (fi) 1991-03-12
PL289377A1 (en) 1992-03-09
NO910953D0 (no) 1991-03-11
PT97006B (pt) 1998-07-31
ATE145410T1 (de) 1996-12-15
NO910953L (no) 1991-09-13
SG44343A1 (en) 1997-12-19
CS63191A2 (en) 1991-10-15
HUT60297A (en) 1992-08-28
EP0447071B1 (en) 1996-11-20
HU910793D0 (en) 1991-09-30
NO177719B (no) 1995-07-31
PT97006A (pt) 1991-10-31
CN1054775A (zh) 1991-09-25
CA2036766A1 (en) 1991-09-13
FI911214A (fi) 1991-09-13
AU7134491A (en) 1991-09-12

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