JPH09507093A - 懸濁重合によるエチレン重合体の製造方法 - Google Patents
懸濁重合によるエチレン重合体の製造方法Info
- Publication number
- JPH09507093A JPH09507093A JP7517652A JP51765295A JPH09507093A JP H09507093 A JPH09507093 A JP H09507093A JP 7517652 A JP7517652 A JP 7517652A JP 51765295 A JP51765295 A JP 51765295A JP H09507093 A JPH09507093 A JP H09507093A
- Authority
- JP
- Japan
- Prior art keywords
- alkyl
- aryl
- ethylene
- cycloalkyl
- hydrogen
- 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
-
- 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
- C08F10/02—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
- 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
- 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
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/63912—Component covered by group C08F4/62 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
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/63916—Component covered by group C08F4/62 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
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/6392—Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
-
- 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
- Y10S526/943—Polymerization with metallocene catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (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)
Abstract
Description
Claims (1)
- 【特許請求の範囲】 1.エチレンの単独重合体またはエチレンと他のオレフィンもしくはこれらの 混合物との共重合体を、触媒組成物の存在下に懸濁重合により製造する方法であ って、この触媒組成物として、 (A)トリアルキルアルミニウムで処理された微細粉担体、 (B)メタロセン錯体、 (C)開鎖もしくは環式アルモキサン化合物、および (D)アルカリ金属アルキルもしくはアルカリ土類金属アルキルまたはこれら の混合物を有効成分として含有する組成物を使用することを特徴とする方法。 2.組成物(A)として、粒径が1から200μmの範囲内に在る担体を使用 することを特徴とする、請求項1の方法。 3.組成分(A)として、トリメチルアルミニウムで処理されたシリカゲルを 使用することを特徴とする、請求項1または2の方法。 4.組成分(B)として、以下の一般式I で表わされ、式中の Mがチタン、ジルコニウム、ハフニウム、バナジウム、ニオブまたはタンタル を意味し、 Xは弗素、塩素、臭素、沃素、水素、C1−C10アルキル、C6−C15アリール または−OR6を意味し、 R6はC1−C10アルキル、C6−C15アリール、アルキルアリール、アリール アルキル、フルオロアルキルまたはフルオロアリール(それぞれ、アルキル部分 に1から10個の炭素原子、アリール部分に6から20個の炭素原子を有す る)を意味し、 R1からR5はそれぞれ水素、C1−C10アルキル、5から7員のシクロアルキ ル(この置換基がまた置換基としてC1−C10アルキルを持っていてもよい)、 C6−C15アリールまたはアリールアルキルを意味するか、または場合により隣 接する2個の基が合体して炭素原子数4から15の環式基を形成してもよく、R1 からR5はさらにSi(R7)3を意味し、 R7はC1−C10アルキル、C6−C15アリールまたはC3−C10シクロアルキル を意味し、 ZはXの意味を持つか、または を意味し、 この式中のR8からR12は、それぞれ水素、C1−C10アルキル、5から7員の シクロアルキル(これがまた置換基としてC1−C10アルキルを持っていてもよ い)、C6からC15のアリールまたはアリールアルキルを意味するか、または隣 接する2個の基が合体して、4から15個の炭素原子を有する環式基を形成して もよく、R8からR12はさらにSi(R13)3を意味し、 このR13はC1−C10アルキル、C6−C15アリールまたはC3−C10シクロア ルキルを意味し、 あるいはまたR4とZが合体して−[Y(R14)2]n−E−を形成し、 このYは珪素、ゲルマニウム、錫または炭素を意味し、 R14はC1−C10アルキル、C3−C10シクロアルキルまたはC6−C15アリー ルを意味し、 nは1、2、3または4を意味し、 R15はC1−C10アルキル、C6−C15アリニル、C3−C10シクロアルキル、 アルキルアリールまたはSi(R16)3を意味し、 R16はC1−C10アルキル、C6−C15アリール、C3−C10シクロアルキルま たはアルキルアリールを意味する、メタロセン錯体を使用することを特徴とする 、請求項1から3のいずれかの方法。 5.組成分(C)として、以下の一般式IIまたはIII で表わされ、式中のR17がC1−C4アルキルを、mが5から30の整数を意味す る開鎖または環式アルモキサン化合物を使用することを特徴とする、請求項1か ら4のいずれかの方法。 6.組成分(D)として、以下の一般式IVまたはV M1R18 IV M2(R19)2 V で表わされ、式中のM1がリチウム、ナトリウム、カリウム、ルビジウムまたは セシウムを、M2がベリリウム、マグネシウム、カルシウム、ストロンチウム、 バリウム、またはラジウムを、R18、R19がC1−C8アルキルを意味する、アル カリ金属アルキルもしくはアルカリ土類金属アルキルまたはこれらの混合物を使 用することを特徴とする、請求項1から5のいずれかの方法。 7.請求項1から6のいずれかの方法により製造された、エチレンの単独重合 体、またはエチレンと他のオレフィンもしくはこれらの混合物との共重合体。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4344672.8 | 1993-12-27 | ||
DE4344672A DE4344672C1 (de) | 1993-12-27 | 1993-12-27 | Verfahren zur Herstellung von Polymerisaten des Ethylens durch Suspensionspolymerisation |
PCT/EP1994/004125 WO1995018160A1 (de) | 1993-12-27 | 1994-12-13 | Verfahren zur herstellung von polymerisaten des ethylens durch suspensionspolymerisation |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH09507093A true JPH09507093A (ja) | 1997-07-15 |
JP3785423B2 JP3785423B2 (ja) | 2006-06-14 |
Family
ID=6506364
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP51765295A Expired - Fee Related JP3785423B2 (ja) | 1993-12-27 | 1994-12-13 | 懸濁重合によるエチレン重合体の製造方法 |
Country Status (11)
Country | Link |
---|---|
US (1) | US5756607A (ja) |
EP (1) | EP0737213B1 (ja) |
JP (1) | JP3785423B2 (ja) |
KR (1) | KR100354725B1 (ja) |
CN (1) | CN1051321C (ja) |
AT (1) | ATE159956T1 (ja) |
DE (2) | DE4344672C1 (ja) |
ES (1) | ES2108563T3 (ja) |
FI (1) | FI114712B (ja) |
NO (1) | NO309193B1 (ja) |
WO (1) | WO1995018160A1 (ja) |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1994021691A1 (en) * | 1993-03-25 | 1994-09-29 | Mobil Oil Corporation | Process for forming a granular resin |
DE4431838A1 (de) * | 1994-09-07 | 1996-03-14 | Basf Ag | Geträgerte Metallocen-Katalysatorsysteme |
US6506866B2 (en) * | 1994-11-17 | 2003-01-14 | Dow Global Technologies Inc. | Ethylene copolymer compositions |
US7153909B2 (en) | 1994-11-17 | 2006-12-26 | Dow Global Technologies Inc. | High density ethylene homopolymers and blend compositions |
CA2186696A1 (en) * | 1995-09-29 | 1997-03-30 | Takashi Seki | Catalyst component and catalyst |
DE19606166A1 (de) * | 1996-02-20 | 1997-08-21 | Basf Ag | Verfahren zur Herstellung von Polymerisaten von Alkenen durch Suspensionspolymerisation |
JPH09309926A (ja) * | 1996-05-17 | 1997-12-02 | Dow Chem Co:The | エチレン共重合体の製造方法 |
DE19621969A1 (de) * | 1996-05-31 | 1997-12-04 | Basf Ag | Verfahren zur Herstellung von kristallinen Polymerisaten durch Dispersionspolymerisation in Gegenwart von Metallocenkatalysatorsystemen |
DE69831819T2 (de) * | 1997-01-30 | 2006-07-06 | Total Petrochemicals Research Feluy, Seneffe | Selektive Wirkung von Metallocen-Katalysatoren für die Herstellung von isotaktischen Polyolefinen |
US6441116B1 (en) | 1997-09-03 | 2002-08-27 | Idemitsu Kosan Co., Ltd. | Ethylenic copolymer, composition containing said copolymer, and ethylenic copolymer film |
US20030236365A1 (en) * | 2002-06-24 | 2003-12-25 | Fina Technology, Inc. | Polyolefin production with a high performance support for a metallocene catalyst system |
EP2440564A4 (en) | 2009-06-11 | 2014-07-09 | Grace W R & Co | PROCESS FOR PRODUCING ALUMINOXANE AND CATALYSTS COMPRISING ALUMINOXANE THUS PREPARED |
US9127096B2 (en) * | 2010-10-18 | 2015-09-08 | California Institute Of Technology | Methods and systems for synthesis of an ultra high molecular weight polymer |
US11028192B2 (en) | 2017-03-27 | 2021-06-08 | Exxonmobil Chemical Patents Inc. | Solution process to make ethylene copolymers |
Family Cites Families (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3242150A (en) * | 1960-03-31 | 1966-03-22 | Phillips Petroleum Co | Method and apparatus for the recovery of solid olefin polymer from a continuous path reaction zone |
US3248179A (en) * | 1962-02-26 | 1966-04-26 | Phillips Petroleum Co | Method and apparatus for the production of solid polymers of olefins |
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 |
US5077255A (en) * | 1986-09-09 | 1991-12-31 | Exxon Chemical Patents Inc. | New supported polymerization catalyst |
JPH072794B2 (ja) * | 1986-12-29 | 1995-01-18 | 昭和電工株式会社 | ポリオレフインの製造方法 |
JP2538595B2 (ja) * | 1987-05-13 | 1996-09-25 | 三井石油化学工業株式会社 | オレフイン重合用固体触媒 |
US4925821A (en) * | 1987-12-17 | 1990-05-15 | Exxon Chemical Patents Inc. | Method for utilizing triethyaluminum to prepare an alumoxane support for an active metallocene catalyst |
DD267986A1 (de) * | 1988-01-06 | 1989-05-17 | Tech Hochschule C Schorlemmer | Verfahren zur katalytischen homo- und copolymerisation von ethylen |
US4935397A (en) * | 1988-09-28 | 1990-06-19 | Exxon Chemical Patents Inc. | Supported metallocene-alumoxane catalyst for high pressure polymerization of olefins and a method of preparing and using the same |
US5086135A (en) * | 1989-12-26 | 1992-02-04 | Mobil Oil Corporation | Zirconium-based catalyst composition for polymerizing olefins and polymerization therewith |
US5032562A (en) * | 1989-12-27 | 1991-07-16 | Mobil Oil Corporation | Catalyst composition and process for polymerizing polymers having multimodal molecular weight distribution |
US5145818A (en) * | 1989-12-29 | 1992-09-08 | Mitsui Petrochemical Industries, Ltd. | Olefin polymerization catalyst and process for the polymerization of olefins |
JP2826362B2 (ja) * | 1990-02-13 | 1998-11-18 | 三井化学株式会社 | オレフィン重合用固体触媒の製造方法、オレフィン重合用固体触媒およびオレフィンの重合方法 |
DE4024421A1 (de) * | 1990-08-01 | 1992-02-06 | Basf Ag | Ziegler-natta-katalysatorsysteme mit metallorganischen verbindungen |
EP0474391B1 (en) * | 1990-08-21 | 1995-10-25 | Nippon Oil Co. Ltd. | Polyolefins |
EP0490269B1 (en) * | 1990-12-10 | 1996-02-28 | Idemitsu Kosan Company Limited | Graft copolymer and process for producing the same |
DE69219206T2 (de) * | 1991-05-31 | 1997-08-28 | Mitsui Petrochemical Ind | Fester Katalysatorbestandteil, Katalysator und Verfahren für Olefinpolymerisation |
DE4139262A1 (de) * | 1991-11-29 | 1993-06-03 | Basf Ag | Getraegerte katalysatorsysteme zur polymerisation von c(pfeil abwaerts)2(pfeil abwaerts)- bis c(pfeil abwaerts)1(pfeil abwaerts)(pfeil abwaerts)0(pfeil abwaerts)-alkenen |
US5391660A (en) * | 1992-01-14 | 1995-02-21 | Nippon Oil Company, Limited | Process for preparing polyolefines |
FI112233B (fi) * | 1992-04-01 | 2003-11-14 | Basell Polyolefine Gmbh | Katalyytti olefiinipolymerointia varten, menetelmä sen valmistamiseksi ja sen käyttö |
US5459217A (en) * | 1993-04-09 | 1995-10-17 | Mitsui Petrochemical Industries, Ltd. | Ethylene/alpha-olefin copolymer |
US5525678A (en) * | 1994-09-22 | 1996-06-11 | Mobil Oil Corporation | Process for controlling the MWD of a broad/bimodal resin produced in a single reactor |
-
1993
- 1993-12-27 DE DE4344672A patent/DE4344672C1/de not_active Expired - Lifetime
-
1994
- 1994-12-13 CN CN94194653A patent/CN1051321C/zh not_active Expired - Fee Related
- 1994-12-13 KR KR1019960703455A patent/KR100354725B1/ko not_active IP Right Cessation
- 1994-12-13 EP EP95904458A patent/EP0737213B1/de not_active Expired - Lifetime
- 1994-12-13 WO PCT/EP1994/004125 patent/WO1995018160A1/de active IP Right Grant
- 1994-12-13 JP JP51765295A patent/JP3785423B2/ja not_active Expired - Fee Related
- 1994-12-13 AT AT95904458T patent/ATE159956T1/de not_active IP Right Cessation
- 1994-12-13 ES ES95904458T patent/ES2108563T3/es not_active Expired - Lifetime
- 1994-12-13 US US08/666,409 patent/US5756607A/en not_active Expired - Fee Related
- 1994-12-13 DE DE59404553T patent/DE59404553D1/de not_active Expired - Fee Related
-
1996
- 1996-06-25 FI FI962620A patent/FI114712B/fi active
- 1996-06-26 NO NO962696A patent/NO309193B1/no not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
FI962620A (fi) | 1996-06-25 |
KR100354725B1 (ko) | 2003-01-06 |
CN1051321C (zh) | 2000-04-12 |
DE59404553D1 (de) | 1997-12-11 |
ES2108563T3 (es) | 1997-12-16 |
FI114712B (fi) | 2004-12-15 |
EP0737213A1 (de) | 1996-10-16 |
DE4344672C1 (de) | 1995-06-14 |
CN1139439A (zh) | 1997-01-01 |
JP3785423B2 (ja) | 2006-06-14 |
FI962620A0 (fi) | 1996-06-25 |
NO309193B1 (no) | 2000-12-27 |
EP0737213B1 (de) | 1997-11-05 |
NO962696L (no) | 1996-06-26 |
NO962696D0 (no) | 1996-06-26 |
WO1995018160A1 (de) | 1995-07-06 |
US5756607A (en) | 1998-05-26 |
ATE159956T1 (de) | 1997-11-15 |
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