JPH08509773A - 流動床におけるモノマーの重合プロセス - Google Patents
流動床におけるモノマーの重合プロセスInfo
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- JPH08509773A JPH08509773A JP6524448A JP52444894A JPH08509773A JP H08509773 A JPH08509773 A JP H08509773A JP 6524448 A JP6524448 A JP 6524448A JP 52444894 A JP52444894 A JP 52444894A JP H08509773 A JPH08509773 A JP H08509773A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/1809—Controlling processes
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/1818—Feeding of the fluidising gas
- B01J8/1827—Feeding of the fluidising gas the fluidising gas being a reactant
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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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- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00265—Part of all of the reactants being heated or cooled outside the reactor while recycling
- B01J2208/00274—Part of all of the reactants being heated or cooled outside the reactor while recycling involving reactant vapours
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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
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00584—Controlling the density
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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
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00628—Controlling the composition of the reactive mixture
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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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—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
- C08F210/14—Monomers containing five or more carbon atoms
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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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- 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
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
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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
- C08F4/659—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
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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
- C08F4/659—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
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Abstract
Description
Claims (1)
- 【特許請求の範囲】 1.凝縮モードで運転される気相流動床反応器内で嵩高い配位子遷移金属触媒 を利用して1又はそれ以上のα-オレフィンを重合するための連続式気相重合法 。 2.請求項1記載の方法において、上記反応器内の流動床の中を通過するリサ イクル流が2.0モル%以上、好ましくは5〜60モル%の量の露点上昇成分を 含んでおり、当該露点上昇成分が好ましくは上記リサイクル流中の最も炭素数の 多いα-オレフィン単量体よりも炭素数が1以上少ないものであることを特徴と する方法。 3.請求項2記載の方法において、上記リサイクル流がコモノマーを含んでお り、好ましくは0.2未満Cx/Cy比に維持され(Cx及びCyはそれぞれコモノ マー及びモノマーのモル%である)、好ましくは5〜40モル%の露点上昇成分 を含んでいることを特徴とする方法。 4.請求項3記載の方法において、上記リサイクル流がさらにH2/Cyモル比 0.01未満の水素(H2)を好ましくは10モルppm〜10000モルppmの量 で含んでいることを特徴とする方法。 5.請求項3又は請求項4記載の方法において、上記リサイクル流の組成が( Cx+H2)/Cy比にして0.2未満、好ましくは0.1未満であることを特徴と する方法。 6.請求項1乃至請求項5のいずれか1項記載の方法において、上記リサイク ル流の総重量を基準にした液体の重量%が2.5重量%以上、好ましくは5重量 %〜50重量%、特に20重量%を超えることを特徴とする方法。 7.請求項1乃至請求項6のいずれか1項記載の方法において、上記触媒がメ タロセン、好ましくは約2未満の反応性比を有するメタロセンであることを特徴 とする方法。 8.請求項1乃至請求項7のいずれか1項記載の方法において、上記触媒の生 産性が当該触媒1g当り2000g重合体を超えるものであることを特徴とする 方法。 9.請求項1乃至請求項8のいずれか1項記載の方法において、上記α-オレ フィンモノマーのモル%が10〜90モル%、好ましくは20〜80モル%、特 に25〜75モル%であり、好ましくはそのモノマー分圧が70psia(482. 8kPaa)〜約240psia(1655.2kPaa)であることを特徴とする方法。 10.請求項9記載の方法において、上記リサイクル流がさらに5〜50モル% の量の窒素を含んでいることを特徴とする方法。 11.請求項9記載の方法において、重合体生成物が50%を超えるCDBI及 び/又は0.850g/cm3〜0.970g/cm3の範囲内の密度及び/又は0.01dg/ min以上で1000dg/min未満のメルトインデックスを有することを特徴とする 方法。 12.請求項3乃至請求項11のいずれか1項記載の方法において、上記少なく とも2種類のα-オレフィン単量体が0.001〜0.2の比率のC4及びC2α-オ レフィンであるか、或いは上記少なくとも2種類のα-オレフィン単量体が0.0 01〜0.15の比率のC5及びC2α-オレフィンであるか、或いは上記少なくと も2種類のα-オレフィン単量体が0.001〜0.1の比率のC6及びC2α-オレ フィンであるか、或いは上記少なくとも2種類のα-オレフィン単量体が0.00 1〜0.05の比率のC8及びC2α-オレフィンであることを特徴とする方法。 13.凝縮モードで運転される気相流動床反応器内でエチレンと少なくとも1種 類の共重合可能な好ましくは炭素数3〜15のα-オレフィンコモノマーを重合 するための連続法にして、当該方法が次の諸段階: a)上記反応器内の流動床を通してリサイクル流を流通する段階、ただし、 当該リサイクル流は、0.2未満、好ましくは0.1未満の比率のCx/C2、2.0 モル%以上の量の露点上昇成分、及び任意成分として当該リサイクル流の残余を なす非凝縮性不活性成分を含んでなる(Cx及びC2はそれぞれコモノマー及びエ チレンのモル%である); b)上記反応器の中に反応性条件下で触媒を導入して上記リサイクル流を重 合体生成物に重合させる段階; c)未反応単量体を含んだ上記リサイクル流を反応器から回収する段階; d)上記リサイクル流の上記比率が維持されるように、重合した単量体の代 わりに上記リサイクル流に追加単量体を導入する段階; e)上記リサイクル流を上記反応器に再度導入する段階;及び f)上記反応器から上記重合体生成物を取り出す段階 を含んでなることを特徴とする方法。 14.請求項13記載の方法において、上記触媒がメタロセンであり、適宜アル モキサン又はイオン性活性化錯体と共に使用することを特徴とする方法。 15.請求項13又は請求項14記載の方法において、上記コモノマーがヘキセ ン-1であって反応性比が2未満であり、しかも上記重合体生成物の密度が0. 88g/cm3〜0.970g/cm3の範囲内でメルトインデックスが0.1dg/min〜1 000dg/minであるか、或いは上記コモノマーがオクテン-1であって反応性比 が1未満であり、しかも上記重合体生成物の密度が0.88g/cm3〜0.970g/c m3の範囲内でメルトインデックスが0.1dg/min〜1000dg/minであることを 特徴とする方法。 16.請求項13乃至請求項15のいずれか1項記載の方法において、H2/C2 のモル比が約0.01未満であることを特徴とする方法。 17.気相流動床反応器内でエチレンと少なくとも1種類の共重合可能な好まし くは炭素数3〜15のα-オレフィンコモノマーを重合するための連続法にして 、当該方法が次の諸段階: a)上記反応器を通してリサイクル流を流通する段階、ただし、当該リサイ クル流は、0.2未満の比率の(Cx+H2)/C2、2.0モル%以上の量の露点上 昇成分及び当該リサイクル流の残余をなす非凝縮性不活性成分を含んでなる(Cx 、H2及びC2はそれぞれコモノマー、水素及びエチレンのモル%である); b)上記反応器の中に反応性条件下で一般式(Cp)mMRnR′pで表される 触媒系とアルモキサン又はイオン性活性化剤を導入して上記リサイクル流を重合 体生成物に重合させる段階(式中、Cpは置換又は未置換シクロペンタジエニル 環であり、Mは第IV族、第V族又は第VI族遷移金属であり、R及びR′は各々独 立にハロゲン、ヒドロカルビル基又は炭素数1〜20 のヒドロカルビルオキシ基から選択されるものであり、m=1〜3、n=0〜3 、p=0〜3であってm+n+pの合計はMの酸化状態に等しい); c)未反応単量体を含んだ上記リサイクル流を反応器から回収する段階; d)上記リサイクル流を圧縮及び冷却して、リサイクル流の総重量を基準に した液体の重量%が10重量%を超えるように液相及び気相を生じさせて、当該 リサイクル流を反応器に再度導入する段階; e)上記リサイクル流の上記比率が維持されるように、重合した単量体の代 わりに上記リサイクル流に追加単量体を導入する段階;及び f)上記反応器から上記重合体生成物を取り出す段階 を含んでなることを特徴とする方法。 18.請求項17記載の方法において、上記の液相と気相を別々に反応器に導入 することを特徴とする方法。 19.請求項17又は請求項18記載の方法において、上記重合体生成物が0. 910g/cm3未満の密度及び/又は3dg/minを超えるメルトインデックスを有す ることを特徴とする方法。
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US1993/003946 WO1994025495A1 (en) | 1993-05-20 | 1993-04-26 | Process for polymerizing monomers in fluidized beds |
US6525093A | 1993-05-20 | 1993-05-20 | |
US93/03946 | 1993-05-20 | ||
US08/065,250 | 1993-05-20 | ||
PCT/US1994/004513 WO1994025497A1 (en) | 1993-04-26 | 1994-04-25 | Process for polymerizing monomers in fluidized beds |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
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JP2006126464A Division JP4191748B2 (ja) | 1993-04-26 | 2006-04-28 | 流動床におけるモノマーの重合プロセス |
Publications (1)
Publication Number | Publication Date |
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JPH08509773A true JPH08509773A (ja) | 1996-10-15 |
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ID=26745385
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
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JP6524448A Pending JPH08509773A (ja) | 1993-04-26 | 1994-04-25 | 流動床におけるモノマーの重合プロセス |
JP2006126464A Expired - Lifetime JP4191748B2 (ja) | 1993-04-26 | 2006-04-28 | 流動床におけるモノマーの重合プロセス |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
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JP2006126464A Expired - Lifetime JP4191748B2 (ja) | 1993-04-26 | 2006-04-28 | 流動床におけるモノマーの重合プロセス |
Country Status (12)
Country | Link |
---|---|
EP (1) | EP0696293B2 (ja) |
JP (2) | JPH08509773A (ja) |
CN (1) | CN1130913A (ja) |
AT (1) | ATE260305T1 (ja) |
AU (1) | AU681147B2 (ja) |
CA (1) | CA2161448C (ja) |
DE (1) | DE69433579T3 (ja) |
DK (1) | DK0970971T3 (ja) |
ES (2) | ES2148327T5 (ja) |
GR (1) | GR3034220T3 (ja) |
RU (1) | RU2125063C1 (ja) |
WO (1) | WO1994025497A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002510720A (ja) * | 1998-04-07 | 2002-04-09 | エクソンモービル・ケミカル・パテンツ・インク | 重合方法 |
JP2018514628A (ja) * | 2015-05-08 | 2018-06-07 | エクソンモービル ケミカル パテンツ インコーポレイテッド | 重合方法 |
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US5462999A (en) * | 1993-04-26 | 1995-10-31 | Exxon Chemical Patents Inc. | Process for polymerizing monomers in fluidized beds |
US5763543A (en) * | 1994-09-14 | 1998-06-09 | Exxon Chemical Patents Inc. | Olefin polymerization process with little or no scavenger present |
US5712353A (en) * | 1994-10-31 | 1998-01-27 | Exxon Chemical Patents Inc. | Gas phase polymerization process |
US5693727A (en) * | 1996-06-06 | 1997-12-02 | Union Carbide Chemicals & Plastics Technology Corporation | Method for feeding a liquid catalyst to a fluidized bed polymerization reactor |
US5990250A (en) * | 1997-05-30 | 1999-11-23 | Union Carbide Chemicals & Plastics Technology Corporation | Method of fluidized bed temperature control |
WO1999002573A1 (en) * | 1997-07-08 | 1999-01-21 | Union Carbide Chemicals & Plastics Technology Cor Poration | Method for reducing sheeting during olefin polymerization |
DE19801859A1 (de) | 1998-01-20 | 1999-07-22 | Bayer Ag | Verfahren zur Vermeidung von Instabilitäten bei der Gasphasenpolymerisation von Kautschuk |
MXPA01004337A (es) | 1998-11-02 | 2002-04-24 | Pont Dow Elastomers L L C Du | Interpolimeros de alfa-olefina/etileno que disminuyen el esfuerzo cortante. |
US6127441A (en) * | 1998-11-05 | 2000-10-03 | Nippon Unicar Company Limited | Expandable resin composition |
US6258903B1 (en) * | 1998-12-18 | 2001-07-10 | Univation Technologies | Mixed catalyst system |
US6218484B1 (en) * | 1999-01-29 | 2001-04-17 | Union Carbide Chemicals & Plastics Technology Corporation | Fluidized bed reactor and polymerization process |
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- 1994-04-25 JP JP6524448A patent/JPH08509773A/ja active Pending
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- 1994-04-25 EP EP94914901A patent/EP0696293B2/en not_active Expired - Lifetime
- 1994-04-25 DK DK99118595T patent/DK0970971T3/da active
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2002510720A (ja) * | 1998-04-07 | 2002-04-09 | エクソンモービル・ケミカル・パテンツ・インク | 重合方法 |
JP2018514628A (ja) * | 2015-05-08 | 2018-06-07 | エクソンモービル ケミカル パテンツ インコーポレイテッド | 重合方法 |
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EP0696293A1 (en) | 1996-02-14 |
CN1130913A (zh) | 1996-09-11 |
WO1994025497A1 (en) | 1994-11-10 |
DE69433579T3 (de) | 2009-11-05 |
ATE260305T1 (de) | 2004-03-15 |
DE69433579D1 (de) | 2004-04-01 |
RU2125063C1 (ru) | 1999-01-20 |
ES2212443T3 (es) | 2004-07-16 |
CA2161448C (en) | 2003-10-14 |
AU6712794A (en) | 1994-11-21 |
ES2148327T5 (es) | 2009-11-17 |
EP0696293B1 (en) | 2000-05-24 |
EP0696293B2 (en) | 2009-06-17 |
DE69433579T2 (de) | 2004-12-16 |
GR3034220T3 (en) | 2000-12-29 |
ES2212443T5 (es) | 2009-11-13 |
JP4191748B2 (ja) | 2008-12-03 |
JP2006241467A (ja) | 2006-09-14 |
ES2148327T3 (es) | 2000-10-16 |
DK0970971T3 (da) | 2004-03-29 |
CA2161448A1 (en) | 1994-11-10 |
AU681147B2 (en) | 1997-08-21 |
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