JPH10511706A - 重合触媒系、それらの製造及び使用 - Google Patents
重合触媒系、それらの製造及び使用Info
- Publication number
- JPH10511706A JPH10511706A JP8513296A JP51329696A JPH10511706A JP H10511706 A JPH10511706 A JP H10511706A JP 8513296 A JP8513296 A JP 8513296A JP 51329696 A JP51329696 A JP 51329696A JP H10511706 A JPH10511706 A JP H10511706A
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Classifications
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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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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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
- 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
- C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound
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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
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/02—Anti-static agent incorporated into the catalyst
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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
- 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
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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
- 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
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
- C08F4/6192—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/61922—Component covered by group C08F4/60 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
- C08F4/61927—Component covered by group C08F4/60 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 bridged
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
Claims (1)
- 【特許請求の範囲】 1.アルモキサン、表面改質剤、多孔質担体及び式、 [式中、M1は、周期表の4、5又は6族の金属であり、 R1及びR2は同一か又は異なり、水素原子、C1−C10アルキル基、C1−C10 アルコキシ基、C6−C10アリール基、C6−C10アリールオキシ基、C2−C1 0 アルケニル基、C7−C40アリールアルキル基、C7−C40アルキルアリール基 、C8−C40アリールアルケニル基又はハロゲン原子のうちの1つであり、 R3及びR4は水素原子であり、 R5及びR6は同一か又は異なり、好ましくは同一であり、ハロゲン原子、ハ ロゲン化されていてもよいC1−C10アルキル基、ハロゲン化されていてもよい C6−C10アリール基、C2−C10アルケニル基、C7−C40アリールアルキル基 、C7−C40アルキルアリール基、C8−C40アリールアルケニル基、−NR15 2 、−SR15、−OR15、−OSiR15 3又は−PR15 2基(式中、R15はハロゲン原 子、C1−C10アルキル基又はC6−C10アリール基の1つである)の1つであり 、 R7は、 =BR11、=AlR11、−Ge−、−Sn−、−O−、−S−、=SO、=SO2 、=NR11、=CO、PR11又は=P(O)R11 (式中、R11、R12及びR13は、同一か又は異なり、水素原子、ハロゲン原 子、C1−C20アルキル基、C1−C20フルオロアルキル基、C6−C30アリール 基、C6−C30フルオロアリール基、C1−C20アルコキシ基、C2−C20アルケ ニル基、C7−C40アリールアルキル基、C8−C40アリールアルケニル基、C7 −C40アルキルアリール基の1つであるか又は、R11とR12又はR11及びR13は それらを結合する原子とともに環状系を形成し、 M2は、珪素、ゲルマニウム又は錫である) であり、 R8は及びR9は同一か又は異なり、R11について記載した意味を有し、 m及びnは同一か又は異なり、0、1又は2であり、m+nは0、1又は2 であり、 基R10は同一か又は異なり、さらに2つの隣接するR10基はともに結合して 環状系を形成し得る、R11、R12及びR13について記載した意味を有する] により表わされるメタロセン触媒成分を溶媒中で化合させ、溶液を生成する工 程を含む、メタロセン触媒成分、アルモキサン及び多孔質担体を含む、担持され た触媒系を製造する方法。 2.前記溶液の総容量が多孔質支持体の総孔隙量の0.8 倍乃至3.0 倍である、請 求項1に記載の方法。 3.メタロセン触媒成分が2つ以上のメタロセン触媒成分を含む、請求項1又は 請求項2に記載の方法。 4.担持された触媒系をオレフィンモノマーで予備重合する工程をさらに含む、 請求項1乃至3のいずれか1請求項に記載の方法。 5.m及びnが0であり、M2が珪素である、請求項1乃至4のいずれか1請求 項に記載の方法。 6.R5及びR6がC1-10アルキルである、請求項1乃至5のいずれか1請求項に 記載の方法。 7.3つのR10基が水素であり、1つがC6-30アリール基である、請求項1乃至 6のいずれか1請求項に記載の方法。 8.少なくとも1つのR10基がC1-10アルキルである、請求項1乃至7のいずれ か1請求項に記載の方法。 9.メタロセン成分が、 rac-ジメチルシランジイルビス(2-メチル-4,5- ベンゾインデニル)ジルコニ ウムジクロリド、 rac-ジメチルシランジイルビス(2-メチルインデニル)ジルコニウムジクロリ ド、 rac-ジメチルシランジイルビス(2-メチル-4,6- ジイソプロピルインデニル) ジルコニウムジクロリド、 rac-ジメチルシランジイルビス(2-メチル-4- フェニルインデニル)ジルコニ ウムジクロリド及び rac-ジメチルシランジイルビス(2-エチル-4- フェニルインデニル)ジルコニ ウムジクロリド から成る群から選ばれる、請求項1乃至8のいずれか1請求項に記載の方法。 10.表面改質剤が、担持された触媒系の総重量の0.2 重量%から5重量%より少 ない範囲の量で存在する、請求項1乃至9のいずれか1請求項に記載の方法。 11.表面改質剤が、式、 [式中、R1は水素又は、1乃至50の炭素原子を有する線状あるいは分枝状ア ルキル基であり、R2は(CH2)x(式中、xは1乃至50の整数である)のヒ ドロキシ基である] により表わされる、請求項1乃至10のいずれか1請求項に記載の方法。 12.表面改質剤が、化学式、C18H37N(CH2CH2OH)2、C12H25N(C H2CH2OH)2及びCH3(CH2)7(CH)2(CH2)7OCOCH2(CHO H)4CH2OHにより表わされる化合物の群から選ばれる少なくとも1つの化合 物である、請求項1乃至11のいずれか1請求項に記載の方法。 13.a)キラルの4族遷移金属で架橋された置換されたビスインデニルメタロセ ン触媒及び第一溶媒を含む第一成分並びに、アルモキサン及び第二溶媒を含む第 二成分を化合させ、反応生成物溶液を生成する工程、 b)その反応生成物と多孔質支持体を、担持された触媒系の生成中のいずれの 時点においても多孔質支持体に添加される反応生成物の総容量が多孔質支持体の 総孔隙量の4倍未満であるように化合させる工程及び c)表面改質剤を導入する工程 を含む、第一成分、第二成分及び多孔質支持体を含む、担持された触媒系を製 造する方法。 14.メタロセン触媒成分が、一般式、 [式中、M1は、周期表の4、5又は6族の金属であり、 R1及びR2は同一か又は異なり、水素原子、C1−C10アルキル基、C1−C10 アルコキシ基、C6−C10アリール基、C6−C10アリールオキシ基、C2−C1 0 アルケニル基、C7−C40アリールアルキル基、C7−C40アルキルアリール基 、C8−C40アリールアルケニル基又はハロゲン原子のうちの1つであり、 R3及びR4は水素原子であり、 R5及びR6は同一か又は異なり、好ましくは同一であり、ハロゲン原子、ハ ロゲン化されていてもよいC1−C10アルキル基、ハロゲン化されていてもよい C6−C10アリール基、C2−C10アルケニル基、C7−C40アリールアルキル基 、C7−C40アルキルアリール基、C8−C40アリールアルケニル基、−NR15 2 、−SR15、−OR15、−OSiR15 3又は−PR15 2基(式中、R15はハロゲン原 子、C1−C10アルキル基又はC6−C10アリール基の1つである)の1つであり 、 R7は、 =BR11、=AlR11、−Ge−、−Sn−、−O−、−S−、=SO、=SO2 、=NR11、=CO、PR11又は=P(O)R11 (式中、R11、R12及びR13は、同一か又は異なり、水素原子、ハロゲン原子 、C1−C20アルキル基、C1−C20フルオロアルキル基、C6−C30アリール 基、C6−C30フルオロアリール基、C1−C20アルコキシ基、C2−C20アルケ ニル基、C7−C40アリールアルキル基、C8−C40アリールアルケニル基、C7 −C40アルキルアリール基の1つであるか又は、R11とR12又 はR11及びR13 はそれらを結合する原子とともに環状系を形成し、 M2は、珪素、ゲルマニウム又は錫である) であり、 R8は及びR9は同一か又は異なり、R11について記載した意味を有し、 m及びnは同一か又は異なり、0、1又は2であり、m+nは0、1又は2 であり、 基R10は同一か又は異なり、さらに2つの隣接するR10基はともに結合して 環状系を形成し得る、R11、R12及びR13について記載した意味を有する] により表わされる、請求項13に記載の方法。 15.請求項1乃至14のいずれかの方法により製造された担持された触媒系の存在 下で、プロピレンを単独で又は1種以上の他のオレフィンと組み合わせて重合す る方法。 16.請求項1又は請求項12に記載の方法により製造される担持された触媒系。
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US32267594A | 1994-10-13 | 1994-10-13 | |
US08/322,675 | 1994-10-13 | ||
US08/502,231 US6124230A (en) | 1995-07-13 | 1995-07-13 | Polymerization catalyst systems, their production and use |
US08/502,231 | 1995-07-13 | ||
PCT/US1995/012789 WO1996011961A1 (en) | 1994-10-13 | 1995-10-12 | Polymerization catalyst systems, their production and use |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH10511706A true JPH10511706A (ja) | 1998-11-10 |
Family
ID=26983548
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8513296A Pending JPH10511706A (ja) | 1994-10-13 | 1995-10-12 | 重合触媒系、それらの製造及び使用 |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0785956B1 (ja) |
JP (1) | JPH10511706A (ja) |
KR (1) | KR100367964B1 (ja) |
CN (1) | CN1096470C (ja) |
DE (1) | DE69509403T2 (ja) |
ES (1) | ES2132744T3 (ja) |
WO (1) | WO1996011961A1 (ja) |
Cited By (1)
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JP2007077228A (ja) * | 2005-09-13 | 2007-03-29 | Mitsui Chemicals Inc | オレフィン重合触媒用担体、オレフィン重合触媒およびオレフィン系重合体粒子 |
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US5057475A (en) * | 1989-09-13 | 1991-10-15 | Exxon Chemical Patents Inc. | Mono-Cp heteroatom containing group IVB transition metal complexes with MAO: supported catalyst for olefin polymerization |
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. |
TW294669B (ja) * | 1992-06-27 | 1997-01-01 | Hoechst Ag | |
DE4242486A1 (de) * | 1992-12-16 | 1994-06-23 | Basf Ag | Propylen-Homopolymere |
CA2129794A1 (en) * | 1993-08-10 | 1995-02-11 | Toshiyuki Tsutsui | Olefin polymerization catalysts and methods of olefin polymerization |
-
1995
- 1995-10-12 ES ES95938716T patent/ES2132744T3/es not_active Expired - Lifetime
- 1995-10-12 KR KR1019970702394A patent/KR100367964B1/ko not_active IP Right Cessation
- 1995-10-12 DE DE69509403T patent/DE69509403T2/de not_active Expired - Lifetime
- 1995-10-12 EP EP95938716A patent/EP0785956B1/en not_active Expired - Lifetime
- 1995-10-12 CN CN95195652A patent/CN1096470C/zh not_active Expired - Lifetime
- 1995-10-12 JP JP8513296A patent/JPH10511706A/ja active Pending
- 1995-10-12 WO PCT/US1995/012789 patent/WO1996011961A1/en active IP Right Grant
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007077228A (ja) * | 2005-09-13 | 2007-03-29 | Mitsui Chemicals Inc | オレフィン重合触媒用担体、オレフィン重合触媒およびオレフィン系重合体粒子 |
JP4732087B2 (ja) * | 2005-09-13 | 2011-07-27 | 三井化学株式会社 | オレフィン重合触媒用担体、オレフィン重合触媒およびオレフィン系重合体粒子 |
Also Published As
Publication number | Publication date |
---|---|
CN1096470C (zh) | 2002-12-18 |
DE69509403D1 (de) | 1999-06-02 |
CN1164861A (zh) | 1997-11-12 |
KR100367964B1 (ko) | 2003-04-26 |
WO1996011961A1 (en) | 1996-04-25 |
DE69509403T2 (de) | 1999-10-07 |
EP0785956A1 (en) | 1997-07-30 |
EP0785956B1 (en) | 1999-04-28 |
KR970706317A (ko) | 1997-11-03 |
ES2132744T3 (es) | 1999-08-16 |
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