JPH09505342A - エチレン共重合用触媒組成物 - Google Patents
エチレン共重合用触媒組成物Info
- Publication number
- JPH09505342A JPH09505342A JP7514526A JP51452695A JPH09505342A JP H09505342 A JPH09505342 A JP H09505342A JP 7514526 A JP7514526 A JP 7514526A JP 51452695 A JP51452695 A JP 51452695A JP H09505342 A JPH09505342 A JP H09505342A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- magnesium
- silica
- compound
- molar ratio
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
Classifications
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- 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
-
- 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
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
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- 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
- B01J31/122—Metal aryl or alkyl 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
- B01J31/128—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
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- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- 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
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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
- 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
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- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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
Description
Claims (1)
- 【特許請求の範囲】 1. 触媒先駆体、およびこの触媒先駆体を活性化するトリアルキルアルミニウ ム助触媒を含んでなる、エチレと炭素原子3〜10個のアルファオレフィンとを 共重合するための触媒組成物であって、先駆体が、 (i) シリカ1g当たり0.4〜0.9ミリモルのOH基を有するシリカ ; (ii) Mg:OHのモル比が1.0〜1.8となる量で存在する、式Rm MgR′n(式中、各RおよびR′は炭素原子2〜10個のアルキル基であり、 m+nはマグネシウムの原子価に等しい)のジアルキルマグネシウム化合物; (iii) テトラアルキルオルトシリケート:Mgのモル比が0.4〜1.0 となる量のテトラアルキルオルトシリケート(アルキル基は2〜6個の炭素原子 を含む);並びに (iv) Ti:Mgのモル比が0.7〜1.4となる量のTiCl4を含んで 成ることを改良点とし、そして触媒先駆体のK値が0.4未満であり、KはK= [Ti]/([Mg]+4[Si])として定義され、式中、[Ti]はTiC l4によってもたらされるチタン金属濃度であり、[Mg]は上記ジアルキルマ グネシウム化合物によってもたらされるマグネシウム金属濃度であり、[Si] は上記テトラアルキルオルトシリケートによってもたらされる濃度である、 上記の触媒組成物。 2. ジアルキルマグネシウム化合物がジブチルマグネシウムである、請求項1 に記載の触媒。 3. テトラアルキルオルトシリケートがテトラエチルオルトシリケートまたは テトラブチルオルトシリケートである、請求項1または2に記載の触媒。 4. 助触媒がトリエチルアルミニウムである、請求項1、2または3に記載の 触媒。 5. K値が0.23〜0.31である、上記請求項のいずれか1項に記載の触 媒。 6. テトラアルキルオルトシリケート:Mgのモル比が0.5〜0.8である 、上記請求項のいずれか1項に記載の触媒。 7. 触媒先駆体を形成する方法であって、 (a) 非極性溶媒中のシリカのスラリーを与えること、ここでシリカは、シリ カ1g当たり0.4〜0.9ミリモルのOH基を有するものであり; (b) 上記シリカを、式RmMgR′n(式中、各RおよびR′は炭素原子4〜 10個のアルキル基であり、m+nはマグネシウムの原子価に等しい)のジアル キルマグネシウム化合物と、Mg:OHのモル比が1.0〜1.8となる量で接 触させて、上記シリカを含浸させ、そして工程(b)の生成物を形成すること; (c) 上記工程(b)の生成物に、テトラアルキルオルトシリケート(アルキ ル基は2〜6個の炭素原子を有する)を、テトラアルキルオルトシリケート:M gのモル比が0.4〜1.0となる量で加えて、工程(c)の生成物を形成する こと;並びに (d) 上記工程(c)の生成物をTiCl4と、Ti:Mgのモル比が0.7 〜1.4となる量で接触させて、K値が0.4未満の上記触媒先駆体を形成する こと、ここで、KはK=[Ti]/([Mg]+4[Si])として定義され、 式中、[Ti]はTiCl4によってもたらされるチタン金属濃度であり、[M g]は上記ジアルキルマグネシウム化合物によってもたらされるマグネシウム金 属濃度であり、[Si]は上記テトラアルキルオルトシリケートによってもたら される濃度である を含んでなる上記の方法。 8. ジアルキルマグネシウム化合物がジブチルマグネシウムである、請求項7 に記載の方法。 9. テトラアルキルオルトシリケートがテトラエチルオルトシリケートまたは テトラブチルオルトシリケートである、請求項7または8に記載の方法。 10. 助触媒がトリエチルアルミニウムである、請求項7、8または9に記載 の方法。 11. K値が0.23〜0.31である、請求項7〜10のいずれか1項に記 載の方法。 12. テトラアルキルオルトシリケート:Mgのモル比が0.5〜0.8であ る、請求項7〜11のいずれか1項に記載の方法。 13. 工程(a)〜(d)を40〜65℃の温度で行う、請求項7〜12のい ずれか1項に記載の方法。 14. エチレンと炭素原子3〜10個のアルファ−オレフィンとを、請求項1 〜6のいずれか1項で定義した触媒の存在下で重合することを含んでなる、エチ レンの共重合体を製造する方法。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US151,666 | 1993-11-15 | ||
US08/151,666 US5470812A (en) | 1991-11-06 | 1993-11-15 | High activity polyethylene catalysts prepared with alkoxysilane reagents |
PCT/US1994/013053 WO1995013873A1 (en) | 1993-11-15 | 1994-11-14 | Catalyst composition for copolymerizing ethylene |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH09505342A true JPH09505342A (ja) | 1997-05-27 |
JP3667334B2 JP3667334B2 (ja) | 2005-07-06 |
Family
ID=22539754
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP51452695A Expired - Lifetime JP3667334B2 (ja) | 1993-11-15 | 1994-11-14 | エチレン共重合用触媒組成物 |
Country Status (10)
Country | Link |
---|---|
US (1) | US5470812A (ja) |
EP (1) | EP0729388A4 (ja) |
JP (1) | JP3667334B2 (ja) |
KR (1) | KR100326624B1 (ja) |
CN (1) | CN1066740C (ja) |
AU (1) | AU688821B2 (ja) |
CA (1) | CA2174661C (ja) |
TW (1) | TW287173B (ja) |
WO (1) | WO1995013873A1 (ja) |
ZA (1) | ZA948929B (ja) |
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-
1993
- 1993-11-15 US US08/151,666 patent/US5470812A/en not_active Expired - Lifetime
-
1994
- 1994-11-10 ZA ZA948929A patent/ZA948929B/xx unknown
- 1994-11-14 EP EP95901233A patent/EP0729388A4/en not_active Withdrawn
- 1994-11-14 KR KR1019960702430A patent/KR100326624B1/ko not_active IP Right Cessation
- 1994-11-14 AU AU10553/95A patent/AU688821B2/en not_active Ceased
- 1994-11-14 CN CN94194149A patent/CN1066740C/zh not_active Expired - Lifetime
- 1994-11-14 WO PCT/US1994/013053 patent/WO1995013873A1/en not_active Application Discontinuation
- 1994-11-14 JP JP51452695A patent/JP3667334B2/ja not_active Expired - Lifetime
- 1994-11-14 CA CA002174661A patent/CA2174661C/en not_active Expired - Lifetime
- 1994-12-02 TW TW083111205A patent/TW287173B/zh not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
EP0729388A4 (en) | 1996-10-30 |
JP3667334B2 (ja) | 2005-07-06 |
CN1135191A (zh) | 1996-11-06 |
WO1995013873A1 (en) | 1995-05-26 |
AU1055395A (en) | 1995-06-06 |
EP0729388A1 (en) | 1996-09-04 |
AU688821B2 (en) | 1998-03-19 |
CA2174661A1 (en) | 1995-05-26 |
CN1066740C (zh) | 2001-06-06 |
US5470812A (en) | 1995-11-28 |
ZA948929B (en) | 1996-08-12 |
TW287173B (ja) | 1996-10-01 |
KR100326624B1 (ko) | 2002-08-08 |
CA2174661C (en) | 2009-05-12 |
KR960705627A (ko) | 1996-11-08 |
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