KR960705626A - 에틸렌의 중합 및 공중합에 사용하기 위한 촉매 조성물(catalyst composition for use in the polymerization and copolymerization of ethylene) - Google Patents

에틸렌의 중합 및 공중합에 사용하기 위한 촉매 조성물(catalyst composition for use in the polymerization and copolymerization of ethylene) Download PDF

Info

Publication number
KR960705626A
KR960705626A KR1019960702431A KR19960702431A KR960705626A KR 960705626 A KR960705626 A KR 960705626A KR 1019960702431 A KR1019960702431 A KR 1019960702431A KR 19960702431 A KR19960702431 A KR 19960702431A KR 960705626 A KR960705626 A KR 960705626A
Authority
KR
South Korea
Prior art keywords
catalyst composition
ethylene
group
transition metal
alkyl
Prior art date
Application number
KR1019960702431A
Other languages
English (en)
Other versions
KR100355623B1 (ko
Inventor
입-콰이 로 프레데릭
에드워드 나우린 토마스
데니스 슈레겐버거 샌드라
팬듀랭 쉬로드카 프래딮
온키 치엔 그레이스
Original Assignee
데니스 피. 산티니
모빌 오일 코오포레이숀
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 데니스 피. 산티니, 모빌 오일 코오포레이숀 filed Critical 데니스 피. 산티니
Publication of KR960705626A publication Critical patent/KR960705626A/ko
Application granted granted Critical
Publication of KR100355623B1 publication Critical patent/KR100355623B1/ko

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/128—Mixtures of organometallic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • 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
    • 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
    • C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/652—Pretreating with metals or metal-containing compounds
    • C08F4/658—Pretreating with metals or metal-containing compounds with metals or metal-containing compounds, not provided for in a single group of groups C08F4/653 - C08F4/657
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/48—Zirconium
    • 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
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61904—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with another component of C08F4/60
    • 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
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61912—Component covered by group C08F4/60 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
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61916—Component covered by group C08F4/60 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
    • C08F4/65904—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
    • 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
    • C08F4/65925—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 non-bridged
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

본 발명은 지지체상에 2개의 전이 금속 성분을 갖는, 이중 하나의 성분은 메탈로센 형태인 에틸렌 중합 촉매에 관한 것으로서, 상기 지지체는 (i) 마그네슘 알킬이 혼입된 실라놀-함유 실리카와 (ii) 알코올을 반응시킴으로써 제로되는 무수성 물질이다. 상기 촉매는 또한 비-메탈로센 전이 금속 화합물도 포함하며, 단일 반응기내에서, 2가지 형태의 분자량 분포를 갖는 에틸렌 공중합체를 생성시킨다.

Description

에틸렌의 중합 및 공중합에 사용하기 위한 촉매 조성물 (CATALYST COMPOSITION FOR USE IN THE POLYMERIZATION AND COPOLYMERIZATION OF ETHYLENE)
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음
제4도는 기체상 중합 (및 공중합을 위한) 유체층 반응기의 개략도이다.

Claims (16)

  1. (a) 알루미늄 알킬 비-산소 함유 활성화제; 및 (b) 상기 알루미늄 알킬 활성화제에 의해 활성화되는 전이 금속 및 비-메탈로센전이 금속의 활성화된 메탈로센 화합물을 포함하는 조성물을 함유하는 고형의 무수성 지지체를 포함하고, 상기 지지체는, (1) RmMgR′n(식 중 Rm및 Rn은 C1-12의 알킬기이며, m 및 n은 각각 0.1 또는 2이되, 단, m＋n은 Mg의 원자가와 같고, RmMgR′n은 이것과 OH간의 물비가 0.5 : 1 내지 4 : 1이 되도록 하는 양으로 존재함)이 혼입된, OH 기를 갖는 실리카와; (2) 일반식 R″O-(식 중, R″는 C1-12의 알킬기임)를 가지며 상기 RmMgR′n중의 Rm및 R′n을 치환시키는데 효과적인 알콕시기를 제공하고, 알코올 대 Mg의 볼비가 0.5 내지 2.0이 되도록 하기에 효과적인 양으로 사용되는 유기 알코올 시약의 반응 생성물인, 고밀도 및 선형 저밀도의 2가지 형태의 분자량 분포를 갖는 에틸렌 중합체 및 공중합체를 제조하는데 사용하기 위한 촉매 조성물.
  2. 제1항에 있어서, 상기 각각의 Rm및 R′n이 C4-10알킬기인 촉매 조성물.
  3. 제2항에 있어서, 상기 각각의 Rm및 R′n이 부틸기인 촉매 조성물.
  4. 제2항에 있어서, 상기 각각의 Rm및 R′n이 n－부틸인 촉매 조성물.
  5. 제1항 내지 제4항 중 어느 한 항에 있어서, 상기 R″가 C1-8알킬기인 촉매 조성물.
  6. 제1항 내지 제5항중 어느 한 항에 있어서, 상기 R″O－가 알코올로서 제공되는 촉매 조성물.
  7. 제1항 내지 제6항중 어느 한 항에 있어서, 상기 반응 생성물이, (i) －OH기를 갖는 고형의 다공성 실리카와 비극성 용매로 이루어진 슬러리를 제공하는 단계; (ii) 상기 실리카에 상기 비극성 용매에 가용성인 상기 RmMgR′n을 혼입시켜 중간체(ii)를 형성시키는 단계(이때, 상기 Mg : －OH기는 2 이하임); 및 (iii) 상기 단계(ii)의 중간체를 R″OH : RmMgR′n의 몰비가 0.5 내지 2.0이 되도록 하기에 효과적인 양의 상기 R″OH로 처리하는 단계에 의해 형성되는 촉매 조성물.
  8. 제7항에 있어서, 상기 단계(iii) 후에, (iv) 상기 단계(iii)의 생성물을 TiCl4로 처리하여 티타늄－함유 중간체를 형성시키는 단계; 및 (v) 상기 티타늄－함유 중간체를 상기 활성화제와 결합시키는 단계를 추가로 포함하는 촉매 조성물.
  9. 제1항 내지 제8항 중 어느 한 항에 있어서, 상기 비-메탈로센 전이 금속이 티타늄인 촉매 조성물.
  10. 제9항에 있어서, 상기 비-메탈로센 전이 금속이 티타늄 테트라클로라이드인 촉매 조성물.
  11. 제1항 내지 제10항 중 어느 한 항에 있어서, 상기 활성화제가 트리메틸알루미늄인 촉매 조성물.
  12. 제1항 내지 제11항 중 어느 한 항에 있어서, 상기 메탈로센 전이 금속이 하기 일반식을 갖는 화합물로서 제공되는 촉매 조성물 :
    CpxMAyBz
    상기 식중에서, Cp는 비치환 또는 C1-6의 알킬 또는 알킬렌에 의해 치환되는 시클로펜타디에닐이고, x는 1 이상이며, 각각의 A 및 B는 할로겐 또는 C1-8의 알킬이고, y＋z는 3 이하이되, 단, x＋y＋z는 M의 원자가와 같아야 하며, M은 티타늄 지르코늄 또는 하프늄으로 구성되는 군에서 선택된다.
  13. 제12항에 있어서, 상기 메탈로센 화합물이 비스-(시클로펜타디에닐) 지르코늄 디클로라이드 및 비스-(n-부틸시클로펜타디에닐) 지르코늄 디클로라이드로 구성되는 군에서 선택되는 촉매 조성물.
  14. 제1항 내지 제13항 중 어느 한 항에 있어서, 상기 메틸로센 화합물이 메틸알루목산 용액에 의해 활성화되고, 상기 실리카는 기공용적이 1.0 내지 4.0㎤/g이며, 상기 용액은 부피가 상기 기공의 전체 용적과 동일한 촉매 조성물.
  15. 단일 반응기내에서, 제1항 내지 제14항 중 어느 한 항에 의해 촉매 존해하에 에틸렌을 중합시켜, 고밀도 및 선형 저밀도의 2가지 형태의 분자량 분포를 갖는 에킬렌 중합체를 형성시키는 것을 포함하는, 고밀도 및 선형 저밀도의 2가지 형태의 분자량 분포를 갖는 상기 에틸렌 중합체 및 공중합체를 제조 방법.
  16. 제15항에 있어서, 상기 에틸렌을 C3-8알파 올레핀과 공중합시켜, 고밀도 및 선형 저밀도의 2가지 형태의 분자량 분포를 갖는 상기 에틸렌 공중합체를 형성시키는 방법.
    ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
KR1019960702431A 1993-11-15 1994-11-15 촉매조성물을사용한에틸렌중합체및공중합체의제조방법 KR100355623B1 (ko)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US15166493A 1993-11-15 1993-11-15
US08/151,664 1993-11-15

Publications (2)

Publication Number Publication Date
KR960705626A true KR960705626A (ko) 1996-11-08
KR100355623B1 KR100355623B1 (ko) 2003-02-11

Family

ID=22539742

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1019960702431A KR100355623B1 (ko) 1993-11-15 1994-11-15 촉매조성물을사용한에틸렌중합체및공중합체의제조방법

Country Status (11)

Country Link
EP (1) EP0729387B1 (ko)
JP (1) JP3771579B2 (ko)
KR (1) KR100355623B1 (ko)
CN (1) CN1049897C (ko)
AU (1) AU687943B2 (ko)
DE (1) DE69420737T2 (ko)
ES (1) ES2135689T3 (ko)
SG (1) SG43850A1 (ko)
TW (1) TW299336B (ko)
WO (1) WO1995013871A1 (ko)
ZA (1) ZA948934B (ko)

Families Citing this family (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5643846A (en) * 1993-04-28 1997-07-01 Fina Technology, Inc. Process for a isotactic/syndiotactic polymer blend in a single reactor
US5804524A (en) * 1993-04-28 1998-09-08 Fina Technology, Inc. Process for a isotactic/syndiotactic polymer blend in a single reactor
US5614456A (en) * 1993-11-15 1997-03-25 Mobil Oil Corporation Catalyst for bimodal molecular weight distribution ethylene polymers and copolymers
US5882750A (en) * 1995-07-03 1999-03-16 Mobil Oil Corporation Single reactor bimodal HMW-HDPE film resin with improved bubble stability
US6486089B1 (en) * 1995-11-09 2002-11-26 Exxonmobil Oil Corporation Bimetallic catalyst for ethylene polymerization reactions with uniform component distribution
US6417130B1 (en) * 1996-03-25 2002-07-09 Exxonmobil Oil Corporation One pot preparation of bimetallic catalysts for ethylene 1-olefin copolymerization
WO1999002570A1 (en) * 1997-07-08 1999-01-21 Bp Chemicals Limited Supported polymerisation catalyst
US6001766A (en) * 1997-12-24 1999-12-14 Mobil Oil Corporation Bimetallic catalysts for ethylene polymerization reactions activated with paraffin-soluble alkylalumoxanes
DE19828271A1 (de) 1998-06-25 1999-12-30 Elenac Gmbh Verfahren zur Herstellung eines geträgerten Katalysatorsystems
US6420298B1 (en) * 1999-08-31 2002-07-16 Exxonmobil Oil Corporation Metallocene catalyst compositions, processes for making polyolefin resins using such catalyst compositions, and products produced thereby
US6444605B1 (en) 1999-12-28 2002-09-03 Union Carbide Chemicals & Plastics Technology Corporation Mixed metal alkoxide and cycloalkadienyl catalysts for the production of polyolefins
US6399531B1 (en) 1999-12-28 2002-06-04 Union Carbide Chemicals & Plastics Technology Corporation Hybrid ziegler-natta and cycloalkadienyl catalysts for the production of polyolefins
KR20050033541A (ko) 2001-11-30 2005-04-12 엑손모빌 케미칼 패턴츠 인코포레이티드 고활성 이금속 촉매
BR0309539A (pt) 2002-05-06 2005-03-01 Union Carbide Chem Plastic Composições de catalisadores misturados para a produção de poliolefinas e seu uso
US8202940B2 (en) 2004-08-19 2012-06-19 Univation Technologies, Llc Bimodal polyethylene compositions for blow molding applications
US7892466B2 (en) 2004-08-19 2011-02-22 Univation Technologies, Llc Oxygen tailoring of polyethylene resins
US7285617B2 (en) 2004-10-08 2007-10-23 Exxonmobil Chemical Patents Inc. Oxygen tailoring of polyethylene blow molding resins
US8835577B2 (en) 2007-11-15 2014-09-16 Univation Technologies, Llc Catalyst systems having a tailored hydrogen response
RU2542104C2 (ru) 2009-05-14 2015-02-20 Юнивейшн Текнолоджиз, Ллк Смешанные металлические каталитические системы со специально адаптированным откликом на водород
SG10201710894QA (en) * 2013-06-29 2018-02-27 Dow Global Technologies Llc A polyethylene composition and process for polymerizing the same
WO2016171810A1 (en) 2015-04-20 2016-10-27 Exxonmobil Chemical Patents Inc. Supported catalyst systems and processes for use thereof
US10723819B2 (en) 2017-02-20 2020-07-28 Exxonmobil Chemical Patents, Inc. Supported catalyst systems and processes for use thereof
WO2018151903A1 (en) 2017-02-20 2018-08-23 Exxonmobil Chemical Patents Inc. Supported catalyst systems and processes for use thereof
CN111108130B (zh) 2017-08-04 2022-06-28 埃克森美孚化学专利公司 具有含-CH2-SiMe3部分的非桥连二茂铪的混合催化剂
US10844150B2 (en) 2017-08-04 2020-11-24 Exxonmobil Chemical Patents Inc. Mixed catalysts with 2,6-bis(imino)pyridyl iron complexes and bridged hafnocenes
US10703838B2 (en) 2017-10-31 2020-07-07 Exxonmobil Chemical Patents Inc. Mixed catalyst systems with four metallocenes on a single support
US10926250B2 (en) 2017-12-01 2021-02-23 Exxonmobil Chemical Patents Inc. Catalyst systems and polymerization processes for using the same
KR102405495B1 (ko) 2017-12-01 2022-06-08 엑손모빌 케미칼 패턴츠 인코포레이티드 촉매계 및 이를 사용하기 위한 중합 방법
US10865258B2 (en) 2018-01-31 2020-12-15 Exxonmobil Chemical Patents Inc. Mixed catalyst systems containing bridged metallocenes with a pendant group 13 element, processes for making a polymer product using same, and products made from same
US10851187B2 (en) 2018-01-31 2020-12-01 Exxonmobil Chemical Patents Inc. Bridged metallocene catalysts with a pendant group 13 element, catalyst systems containing same, processes for making a polymer product using same, and products made from same
CN110964143A (zh) * 2018-09-30 2020-04-07 中国石油天然气股份有限公司 饮料瓶盖用聚乙烯基础树脂及其制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4530914A (en) * 1983-06-06 1985-07-23 Exxon Research & Engineering Co. Process and catalyst for producing polyethylene having a broad molecular weight distribution
US4578373A (en) * 1984-09-04 1986-03-25 Exxon Research & Engineering Co. Polymerization catalyst system
US5032562A (en) * 1989-12-27 1991-07-16 Mobil Oil Corporation Catalyst composition and process for polymerizing polymers having multimodal molecular weight distribution
US5332706A (en) * 1992-12-28 1994-07-26 Mobil Oil Corporation Process and a catalyst for preventing reactor fouling

Also Published As

Publication number Publication date
SG43850A1 (en) 1997-11-14
CN1136286A (zh) 1996-11-20
EP0729387B1 (en) 1999-09-15
WO1995013871A1 (en) 1995-05-26
AU1097295A (en) 1995-06-06
AU687943B2 (en) 1998-03-05
ZA948934B (en) 1996-05-10
JP3771579B2 (ja) 2006-04-26
EP0729387A4 (en) 1997-06-11
KR100355623B1 (ko) 2003-02-11
EP0729387A1 (en) 1996-09-04
TW299336B (ko) 1997-03-01
ES2135689T3 (es) 1999-11-01
DE69420737T2 (de) 2000-01-05
JPH09505236A (ja) 1997-05-27
CN1049897C (zh) 2000-03-01
DE69420737D1 (de) 1999-10-21

Similar Documents

Publication Publication Date Title
KR960705626A (ko) 에틸렌의 중합 및 공중합에 사용하기 위한 촉매 조성물(catalyst composition for use in the polymerization and copolymerization of ethylene)
CA2387900C (en) A method for preparing a supported catalyst system and its use in a polymerization process
JP3380554B2 (ja) 重合触媒系、その製造及び使用
RU2241717C2 (ru) Каталитические системы и их применение в процессе полимеризации
US4897455A (en) Polymerization process
CA1268754A (en) Supported polymerization catalyst
US4808561A (en) Supported polymerization catalyst
CA1277973C (en) Supported polymerization catalyst
KR100355402B1 (ko) 선형 저밀도 폴리에틸렌중합체의 제조방법
KR970706899A (ko) 이정 분자량 분포를 갖는 에틸렌 중합체 및 공중합체용 촉매(catalyst for bimodal molecular weight distribution ethylene polymers and copolymers)
KR970705437A (ko) 단일 반응기내에서의 분자량 분포가 넓거나 또는 이중 모드인 수지의 촉매적 조절 방법(catalytic control of the mwd of a broad/bimodal resin in a single reactor)
US5763547A (en) Supported catalyst complexes for olefin in polymerization
BRPI0615803B1 (pt) Catalyst composition comprising metallocene compound, process for polymerization of olefins in the presence of the catalyst composition, process for the production of the catalyst composition and metallocene compound
JP2010513651A (ja) オレフィンを重合するためのポリマー担持型メタロセン触媒組成物
EP0729478B1 (en) A catalyst composition for the copolymerization of ethylene
KR20020054318A (ko) 메탈로센 촉매 조성물, 상기 촉매 조성물을 사용한폴리올레핀 수지의 제조 방법 및 그에 의해 제조된 생성물
EP2970535B1 (en) Polymer products and multi-stage polymerization processes for the production thereof
CA2394533A1 (en) Polymerization process
JP3785423B2 (ja) 懸濁重合によるエチレン重合体の製造方法
US20020010076A1 (en) Group 15 containing transition metal catalyst compounds and catalyst systems
US5397757A (en) Cocatalysts for metallocene-based olefin polymerization catalyst systems
MXPA02006935A (es) Proceso de polimerizacion de etileno.
US5977392A (en) Organometallic catalysts for the polymerization and copolymerization of alpha-olefins
EP1222215B1 (en) Supported metallocene catalyst system for olefin polymerization
KR100548104B1 (ko) 알크-1-엔의 (공)중합용 촉매 조성물

Legal Events

Date Code Title Description
A201 Request for examination
E902 Notification of reason for refusal
E902 Notification of reason for refusal
E701 Decision to grant or registration of patent right
GRNT Written decision to grant
FPAY Annual fee payment

Payment date: 20070718

Year of fee payment: 6

LAPS Lapse due to unpaid annual fee