JP2000507635A - ポリオレフィンエラストマーを製造するための重合方法、メタロセンプロ触媒を活性化するためのカチオン生成性助触媒、特有の性質を併せ有するポリオレフィンエラストマーおよびそれから造られた製品 - Google Patents
ポリオレフィンエラストマーを製造するための重合方法、メタロセンプロ触媒を活性化するためのカチオン生成性助触媒、特有の性質を併せ有するポリオレフィンエラストマーおよびそれから造られた製品Info
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Abstract
Description
Claims (1)
- 【特許請求の範囲】 1. エチレン、少なくとも1のその他のα−オレフィン及び所望により少なく とも1のジエンモノマーを液相重合してエラストマーを得る方法であって、上記 モノマーを液相重合条件下、メタロセンプロ触媒(このメタロセンプロ触媒は、 一般式(I)及び/又は(II)、 (Cp1R1 m)R3 n(Cp2R2 p)MXq (I) (Cp1R1 m)R3 nYrMXs (II) 〔式中、配位子(Cp1R1 m)のCp1及び配位子(Cp2R2 p)のCp2は同一又 は異なるシクロペンタジエニル環であり、R1及びR2はそれぞれ独立にハロゲン 又は約20までの炭素原子を含むヒドロカルビル、ハロカルビル、ヒドロカルビ ル置換有機メタロイド又はハロカルビル置換有機メタロイド基であり、mは0〜 5であり、pは0〜5であり、会合した上記シクロペンタジエニル環の隣接する 炭素原子上の2つのR1及び/又はR2置換基は結合して一体となって4〜約20 の炭素原子を含む環を形成することもでき、R3は架橋基であり、nは0又は1 であり、YはMに配位するヘテロ原子含有配位子であり、Mは3〜6の原子価を 有する遷移金属であり、各Xは非シクロペンタジエニル配位子であって、独立に ハロゲン又は約20までの炭素原子を含むヒドロカルビル、オキシヒドロカルビ ル、ハロカルビル、ヒドロカルビル置換有機メタロイド、オキシヒドロカルビル 置換有機メタロイド又はハロカルビル置換有機メタロイド基であり、qはMの原 子価マイナス2に等しく、rはnの値を有し、sはrが0のときMの原子価マイ ナス1に等しく、rが1のときMの原子価マイナス2に等しい、〕 の少なくとも1の化合物である)と助触媒(この助触媒は、アルミノキサン又は メタロセンプロ触媒中の少なくとも1のX配位子をその全数まで独立に水素原子 、又は約20までの炭素原子を含むカルボヒドリル基又は約20までの炭素原子 を含むオキシカルボヒドリル基によって交換することのできる金属及び/又はメ タロイド含有第1成分、少なくとも1の電子吸引性置換基を有する少なくとも1 のアリール基を有する、中性金属及び/又はメタロイド含有第2成分、及び少な くとも1の電子吸引性置換基を有する少なくとも1のアリール基を有する、アニ オ ン性金属及び/又はメタロイド含有第3成分を含むカチオン生成性助触媒である が、ただし、メタロセンプロ触媒が式(I)の一つであり助触媒が全くアルミノ キサンであるとき、配位子(CP1R1 m)は配位子(Cp2R2 p)とは異なり、架 橋基R3は少なくとも2の嵩高基を有し、nは1であり、当該プロ触媒が全く式 (II)の一つであるとき、助触媒はカチオン生成性助触媒を含む)を組み合わ せることによって得られた生成物を含む、触媒的に有効量の触媒の存在下で重合 することを含む、上記方法。 2. メタロセンプロ触媒(I)中において、架橋基R3が構造、 〔式中、嵩高基R4及びR5はそれぞれ独立に約20までの炭素原子及び0〜3の ヘテロ原子を含むシクロヒドロカルビル基であるか、同基を含む、〕 を有する、請求項1の方法。 3. 前記シクロヒドロカルビル基が、シクロアルキル、ヘテロシクロアルキル 、シクロアルケニル、ヘテロシクロアルケニル、アリール、ヘテロアリール、ア ルカリール、アルキルヘテロアリール、アラルキル又はヘテロアラルキル基であ る、請求項2の方法。 4. 重合触媒として、その遷移金属に配位した少なくとも1の非シクロペンタ ジエニル配位子Xを有するメタロセンプロ触媒をアルミノオキサン助触媒と組み 合わせることによって得られる生成物を用いて、少なくとも1のオレフィンを重 合してポリオレフィンを得る方法において、該アルミノオキサン助触媒の一部又 は全部を、1以上のX配位子をその全数まで独立に水素原子、約20までの炭素 原子を含むカルボヒドリル基又は約20までの炭素原子を含むオキシカルボヒド リル基によって交換することのできる金属及び/又はメタロイド含有第1成分、 少なくとも1の電子吸引性置換基を有する少なくとも1のアリール基を有する、 中性金属及び/又はメタロイド含有第2成分、及び少なくとも1の電子吸引性置 換基を有する少なくとも1のアリール基を有する、アニオン性金属及び/又はメ タロイド含有第3成分を含むカチオン生成性助触媒に置換することを特徴とする 前記方法。 5. メタロセンプロ触媒(このメタロセンプロ触媒は、一般式(I)及び/又 は(11)、 (Cp1R1 m)R3 n(Cp2R2 p)MXq (I) (Cp1R1 m)R3 nYrMXs (II) 〔式中、配位子(Cp1R1 m)のCp1及び配位子(Cp2R2 p)のCp2は同一又 は異なるシクロペンタジエニル環であり、R1及びR2はそれぞれ独立にハロゲン 又は約20までの炭素原子を含むヒドロカルビル、ハロカルビル、ヒドロカルビ ル置換有機メタロイド又はハロカルビル置換有機メタロイド基であり、mは0〜 5であり、pは0〜5であり、会合した上記シクロペンタジエニル環の隣接する 炭素原子上の2つのR1及び/又はR2置換基は結合して一体となって4〜約20 の炭素原子を含む環を形成することもでき、R3は架橋基であり、nは0又は1 であり、YはMに配位するヘテロ原子含有配位子であり、Mは3〜6の原子価を 有する遷移金属であり、各Xは非シクロペンタジエニル配位子であって、独立に ハロゲン又は約20までの炭素原子を含むヒドロカルビル、オキシヒドロカルビ ル、ハロカルビル、ヒドロカルビル置換有機メタロイド、オキシヒドロカルビル 置換有機メタロイド又はハロカルビル置換有機メタロイド基であり、qはMの原 子価マイナス2に等しく、rはnの値を有し、sはrが0のときMの原子価マイ ナス1に等しく、rが1のときMの原子価マイナス2に等しい、〕 の1又はそれ以上の化合物である)とカチオン生成性助触媒(この助触媒は、上 記メタロセンプロ触媒中の少なくとも1のX配位子をその全数まで独立に水素原 子、又は約20までの炭素原子を含むカルボヒドリル基又は約20までの炭素原 子を含むオキシカルボヒドリル基によって交換することのできる金属及び/又は メタロイド含有第1成分、少なくとも1の電子吸引性置換基を有する少なくとも 1のアリール基を有する、中性金属及び/又はメタロイド含有第2成分、及び少 なくとも1の電子吸引性置換基を有する少なくとも1のアリール基を有する、ア ニオン性金属及び/又はメタロイド含有第3成分を含む)とを組み合わせて得ら れる生成物を含む、触媒。 6. メタロセンプロ触媒(I)において、架橋基R3が構造、 〔式中、嵩高基R4及びR5はそれぞれ独立に約20までの炭素原子及び0〜3の ヘテロ原子を含むシクロヒドロカルビル基であるか、同基を含む、〕 を有する、請求項5の触媒。 7. 上記シクロヒドロカルビル基が、シクロアルキル、ヘテロシクロアルキル 、シクロアルケニル、ヘテロシクロアルケニル、アリール、ヘテロアリール、ア ルカリール、アルキルヘテロアリール、アラルキル又はヘテロアラルキル基であ る、請求項6の触媒。 8. 配位子(Cp1R1 m)が無置換シクロペンタジエニルであり、配位子(C p2R2 p)がインデニル又はフルオレニルであり、Mがジルコニウムであり、R4 及びR5のそれぞれ配位子がフェニルであり、Xがそれぞれ塩素である、請求項 7の触媒。 9. メタロセンプロ触媒(II)において、n及びrがともに1であり、Mの 原子価が4であり、配位子Xがハロゲンであり、sが2である、請求項5の触媒 。 10.上記カチオン生成性助触媒において、第1成分がアルミニウム化合物であ り、第2成分がボラン化合物であり、第3成分が金属ボレート化合物である、請 求項5の触媒。 11.上記アルミニウム化合物がトリアルキルアルミニウム又はジアルキルアル ミニウムハイドライドであり、上記ボラン化合物がトリス(ハロアリール)ボラ ンであり、上記金属ボレート化合物がアルカリ金属−、アルカリ土類金属−、遷 移金属−又はメタロイドテトラキス(ハロアリール)ボレートである、請求項1 0の触媒。 12.上記アルミニウム化合物がトリアルキルアルミニウムであり、上記ボラン 化合物がトリス(ハロフェニル)ボランであり、上記金属ボレート化合物がアル カリ金属テトラキス(ハロフェニル)ボレートである、請求項11の触媒。 13.メタロセンプロ触媒活性化用カチオン生成性助触媒(この助触媒は、上記 メタロセンの遷移金属へ配位した1又はそれ以上の非シクロペンタジエニル配位 子を存在する配位子の全数まで独立に水素原子、約20までの炭素原子を含むカ ルボヒドリル基又は約20までの炭素原子を含むオキシヒドロカルビル基によっ て交換することのできる金属及び/又はメタロイド含有第1成分、少なくとも1 の電子吸引性置換基を有する少なくとも1のアリール基を有する、中性金属及び /又はメタロイド含有第2成分、及び少なくとも1の電子吸引性置換基を有する 少なくとも1のアリール基を有する、アニオン性金属及び/又はメタロイド含有 第3成分を含む)。 14.その遷移金属に配位した少なくとも1の非シクロペンタジエニル配位子X を有するメタロセンプロ触媒をアルミノキサン助触媒と組み合わせることによっ て得られる生成物を含有する触媒において、該アルミノキサン助触媒の一部又は 全部を、1又はそれ以上のX配位子をその全数まで独立に水素原子、約20まで の炭素原子を含むカルボヒドリル基又は約20までの炭素原子を含むオキシヒド ロカルビル基によって交換することのできる金属及び/又はメタロイド含有第1 成分、少なくとも1の電子吸引性置換基を有する少なくとも1のアリール基を有 する、中性金属及び/又はメタロイド含有第2成分、及び少なくとも1の電子吸 引性置換基を有する少なくとも1のアリール基を有する、アニオン性金属及び/ 又はメタロイド含有第3成分を含むカチオン生成性助触媒によって置換すること を特徴とする、前記触媒。 15.メタロセンプロ触媒(このメタロセンプロ触媒は、一般式(I)及び/又 は(II)、 (Cp1R1 m)R3 n (Cp2R2 p)MXq (I) (Cp1R1 m)R3 nYrMXs (II) 〔式中、配位子(Cp1R1 m)のCp1及び配位子(Cp2R2 p)のCp2は同一又 は異なるシクロペンタジエニル環であり、R1及びR2はそれぞれ独立にハロゲン 又は約20までの炭素原子を含むヒドロカルビル、ハロカルビル、ヒドロカルビ ル置換有機メタロイド又はハロカルビル置換有機メタロイド基であり、mは0〜 5であり、pは0〜5であり、会合した上記シクロペンタジエニル環の隣接する 炭素原子上の2つのR1及び/又はR2置換基は結合して一体となって4〜約20 の炭素原子を含む環を形成することもでき、R3は架橋基であり、n は0又は1であり、YはMに配位するヘテロ原子含有基であり、Mは3〜6の原 子価を有する遷移金属であり、各Xは非シクロペンタジエニル配位子であって、 独立にハロゲン又は約20までの炭素原子を含むヒドロカルビル、オキシヒドロ カルビル、ハロカルビル、ヒドロカルビル置換有機メタロイド、オキシヒドロカ ルビル置換有機メタロイド又はハロカルビル置換有機メタロイド基であり、qは Mの原子価マイナス2に等しく、rはnの値を有し、sはrが0のときMの原子 価マイナス1に等しく、rがlのときMの原子価マイナス2に等しい、〕 の少なくとも1の化合物である)をカチオン生成性助触媒(このカチオン生成性 助触媒は、上記メタロセンプロ触媒中の少なくとも1のX配位子をその全数まで 独立に水素原子、又は約20までの炭素原子を含むカルボヒドリル基又は約20 までの炭素原子を含むオキシカルボヒドリル基によって交換することのできる金 属及び/又はメタロイド含有第1成分、少なくとも1の電子吸引性置換基を有す る少なくとも1のアリール基を有する、中性金属及び/又はメタロイド含有第2 成分、及び少なくとも1の電子吸引性構成部分を有する少なくともlのアリール 基を有する、アニオン性金属及び/又はメタロイド含有第3成分を含む)によっ て活性化する方法(この方法は上記メタロセンプロ触媒をオレフィンの存在下任 意の組み合わせ又は任意の順番でカチオン生成性助触媒の成分と組み合わせるこ とを含む)。 16.メタロセンプロ触媒をアルミノキサン助触媒によって活性化してメタロセ ン触媒を得る方法において、上記アルミノキサン助触媒の一部又は全部を、上記 メタロセンの遷移金属へ配位した1又はそれ以上の非シクロペンタジエニル配位 子を存在する配位子の全数まで独立に水素原子、約20までの炭素原子を含むカ ルボヒドリル基又は約20までの炭素原子を含むオキシヒドロカルビル基によっ て交換することのできる金属及び/又はメタロイド含有第1成分、少なくとも1 の電子吸引性置換基を有する少なくとも1のアリール基を有する、中性金属及び /又はメタロイド含有第2成分、及び少なくとも1の電子吸引性置換基を有する 少なくとも1のアリール基を有する、アニオン性金属及び/又はメタロイド含有 第3成分を含有するカチオン生成性助触媒によって置換することを特徴とする、 前記方法。 17.請求項1のエチレンの液相重合法から得られるエラストマー。 18.エチレン、少なくとも1のその他のα−オレフィン及び所望により少なく とも1のジエンの液相重合から得られるエラストマー(このエラストマーは、約 200,000〜約2,000,000のMw、約10〜約200の125℃に おけるML1+4、約1.25〜約10のMw/Mn、約−25℃未満のTg及び約 0.3〜約7のtan δを有する)。 19.粘度調整量の請求項18のエラストマーを含有する潤滑油。 20.請求項18のエラストマーを含むゴム製品(このゴム製品は、ホース、動 力伝達ベルト、コンベアベルト、ガスケット、布地コーティング、自動車バンパ ー、エアスプリング、靴中底、靴踵、屋根葺き部材、ワイヤ又はケーブル用ジャ ケッティング又は隙間ふさぎから選択される)。
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US08/630,650 | 1996-04-10 | ||
PCT/US1997/005323 WO1997038019A1 (en) | 1996-04-10 | 1997-04-01 | Polymerization process for producing polyolefin elastomer, cation-generating cocatalyst for activating a metallocene procatalyst, polyolefin elastomer possessing a unique combination of properties and products manufactured therefrom |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006206925A (ja) * | 2000-08-11 | 2006-08-10 | Uniroyal Chemical Co Inc | 液状ポリアルファオレフィンポリマーの製造法、そのためのメタロセン触媒、得られるポリマー及びそれを含有する潤滑剤 |
JP2009518507A (ja) * | 2005-12-06 | 2009-05-07 | エクソンモービル・ケミカル・パテンツ・インク | エチレンエラストマー組成物 |
JP2013144814A (ja) * | 2008-07-18 | 2013-07-25 | Denki Kagaku Kogyo Kk | オレフィン−芳香族ポリエン共重合体 |
EP4043500A1 (en) | 2014-02-13 | 2022-08-17 | Mitsui Chemicals, Inc. | Ethylene·alpha-olefin·non-conjugated polyene copolymer, use thereof, and manufacturing method thereof |
Families Citing this family (85)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6991563B2 (en) * | 2001-03-23 | 2006-01-31 | Acushnet Company | Perimeter weighted golf ball |
US6209227B1 (en) * | 1997-10-31 | 2001-04-03 | Kimberly-Clark Worldwide, Inc. | Shoe cover with slip-resistant sole |
ES2203074T3 (es) | 1998-02-17 | 2004-04-01 | Exxonmobil Chemical Patents Inc. | Procedimiento de copolimerizaci0n de etileno. |
EP1082368B1 (en) * | 1998-04-30 | 2004-10-20 | Uniroyal Chemical Company, Inc. | Roof sheeting |
KR100287955B1 (ko) * | 1998-06-08 | 2001-05-02 | 유현식 | 올레핀계 또는 스티렌계 중합용 신규 메탈로센 촉매 및 이를 이용한 중합방법 |
US6355745B1 (en) * | 1998-06-30 | 2002-03-12 | The Dow Chemical Company | Syndiotactic monovinylidene aromatic polymerization process |
GB9816940D0 (en) * | 1998-08-05 | 1998-09-30 | Bp Chem Int Ltd | Polymerisation catalysts |
US6294631B1 (en) * | 1998-12-15 | 2001-09-25 | Exxonmobil Chemical Patents Inc. | Hyperbranched polymers by coordination polymerization |
KR100662062B1 (ko) | 1999-03-30 | 2006-12-27 | 미쓰이 가가쿠 가부시키가이샤 | 윤활유용 점도 조정제 및 윤활유 조성물 |
BR0002755A (pt) * | 1999-05-19 | 2001-01-30 | Union Carbide Chem Plastic | Método para controlar peso molecular e distribuição de peso molecular em polìmeros produzidos usando um catalisador de sìtio único |
US6291386B1 (en) * | 1999-05-25 | 2001-09-18 | Equistar Chemicals, Lp | Process for the in-situ preparation of single-site transition metal catalysts and polymerization process |
WO2000074934A1 (en) * | 1999-06-07 | 2000-12-14 | Champlain Cable Corporation | Improved battery cable |
US6825295B2 (en) * | 1999-12-10 | 2004-11-30 | Dow Global Technologies Inc. | Alkaryl-substituted group 4 metal complexes, catalysts and olefin polymerization process |
US6497676B1 (en) | 2000-02-10 | 2002-12-24 | Baxter International | Method and apparatus for monitoring and controlling peritoneal dialysis therapy |
US6764985B2 (en) | 2000-05-10 | 2004-07-20 | Mitsui Chemicals, Inc. | Viscosity modifier for lubricating oil and lubricating oil composition |
DE10035091A1 (de) * | 2000-07-17 | 2002-01-31 | Bayer Ag | Verfahren zur Herstellung von EP(D)M |
DE10047772A1 (de) * | 2000-09-27 | 2002-04-18 | Kalle Nalo Gmbh & Co Kg | Polyamidhaltige Kunststoff-Zusammensetzungen und daraus hergestellte Folien |
US6372848B1 (en) | 2000-10-10 | 2002-04-16 | Baxter International Inc. | Blend of ethylene and α-olefin copolymers obtained using a metallocene catalyst for fabricating medical films and tubings |
CN102146031B (zh) * | 2001-03-26 | 2014-08-06 | 陶氏环球技术有限责任公司 | 不饱和脂肪酸酯或不饱和脂肪酸与低级烯烃的置换方法 |
DE50207018D1 (en) * | 2001-06-21 | 2006-07-06 | Habasit Ag | Monolithischer riemen mit ethylen-alpha olefin-copolymeren |
US20030125662A1 (en) | 2002-01-03 | 2003-07-03 | Tuan Bui | Method and apparatus for providing medical treatment therapy based on calculated demand |
US6686419B2 (en) | 2002-02-08 | 2004-02-03 | Exxonmobil Chemical Patents Inc. | Multimodal ethylene, alpha-olefin and diene polymers, processes for making and devices comprising such compositions |
US6833171B2 (en) | 2002-04-03 | 2004-12-21 | Kimberly-Clark Worldwide, Inc. | Low tack slip-resistant shoe cover |
BR0309359B1 (pt) | 2002-04-29 | 2014-03-18 | Dow Global Technologies Inc | Composição de alfa,ômega-poliéster de poliol, composição de alfa,ômega-poliéster poliamina e composição de poliéster poliolefina |
DE60327855D1 (de) | 2002-06-19 | 2009-07-16 | Exxonmobil Chem Patents Inc | Verfahren zur polymerisation von ethylen, höheren alpha-olefin-comonomeren und dienen, insbesondere vinyl norbornen und nach diesem verfahren hergestellte polymere |
US7238164B2 (en) | 2002-07-19 | 2007-07-03 | Baxter International Inc. | Systems, methods and apparatuses for pumping cassette-based therapies |
DE10259243A1 (de) * | 2002-12-17 | 2004-07-01 | Merck Patent Gmbh | Verfahren zur Herstellung von Co- und Terpolymeren aus Olefinen |
JP4414673B2 (ja) | 2003-04-25 | 2010-02-10 | バンドー化学株式会社 | 摩擦伝動ベルト |
EP3112385B1 (en) | 2003-07-09 | 2020-01-08 | Arlanxeo Netherlands B.V. | Process for the production of a polymer comprising monomeric units of ethylene, an -olefin and a vinyl norbornene |
ATE400542T1 (de) * | 2003-10-09 | 2008-07-15 | Dow Global Technologies Inc | Verbessertes verfahren zur synthese ungesättigter alkohole |
US7285608B2 (en) * | 2004-04-21 | 2007-10-23 | Novolen Technology Holdings C.V. | Metallocene ligands, metallocene compounds and metallocene catalysts, their synthesis and their use for the polymerization of olefins |
DE102005061627A1 (de) | 2005-12-21 | 2007-06-28 | Lanxess Deutschland Gmbh | Synthetischer Kautschuk mit enger Molekulargewichtsverteilung, ein Verfahren zu seiner Herstellung und seine Verwendung |
JP5157174B2 (ja) * | 2006-01-18 | 2013-03-06 | 住友化学株式会社 | エチレン−α−オレフィン−ポリエンランダム共重合体の製造方法 |
WO2008010962A2 (en) * | 2006-07-17 | 2008-01-24 | Dow Global Technologies Inc. | Processes for correlating uv-vis spectra of norbornene compound to polymerization processes using the same, and related purification methods and compositions |
US8080699B2 (en) * | 2009-08-28 | 2011-12-20 | Chemtura Corporation | Two-stage process and system for forming high viscosity polyalphaolefins |
US7731689B2 (en) | 2007-02-15 | 2010-06-08 | Baxter International Inc. | Dialysis system having inductive heating |
US7998115B2 (en) | 2007-02-15 | 2011-08-16 | Baxter International Inc. | Dialysis system having optical flowrate detection |
US8558964B2 (en) | 2007-02-15 | 2013-10-15 | Baxter International Inc. | Dialysis system having display with electromagnetic compliance (“EMC”) seal |
US8870812B2 (en) | 2007-02-15 | 2014-10-28 | Baxter International Inc. | Dialysis system having video display with ambient light adjustment |
US8361023B2 (en) | 2007-02-15 | 2013-01-29 | Baxter International Inc. | Dialysis system with efficient battery back-up |
US7943711B2 (en) * | 2007-05-14 | 2011-05-17 | Exxonmobil Chemical Patents Inc. | Ethylene elastomer compositions |
WO2010051268A1 (en) * | 2008-10-31 | 2010-05-06 | Dow Global Technologies Inc. | Olefin metathesis process employing bimetallic ruthenium complex with bridging hydrido ligands |
US8969481B2 (en) | 2008-12-18 | 2015-03-03 | Exxonmobil Chemical Patent Inc. | Peroxide cured TPV |
JP5088330B2 (ja) * | 2009-01-06 | 2012-12-05 | Jsr株式会社 | 熱可塑性エラストマー組成物、並びにこれを用いた発泡体及びその製造方法 |
DE102009013183A1 (de) | 2009-03-17 | 2010-09-23 | Woco Industrietechnik Gmbh | Vulkanisierbare Kautschukmischungen sowie Elastomerformteile, erhältlich aus diesen Kautschukmischungen |
KR101262305B1 (ko) * | 2009-07-01 | 2013-05-08 | 주식회사 엘지화학 | 전이금속 촉매를 이용한 탄성 중합체의 제조방법 |
US9505957B2 (en) | 2012-03-09 | 2016-11-29 | Exxonmobil Chemical Patents Inc. | Polyolefin adhesive compositions comprising nucleating agents for improved set time |
EP2928691B1 (en) | 2012-12-05 | 2021-07-28 | ExxonMobil Chemical Patents Inc. | Ethylene-based polymers and articles made therefrom |
EP2934889A2 (en) | 2012-12-18 | 2015-10-28 | ExxonMobil Chemical Patents Inc. | Polyethylene films and method of making same |
CN105209505B (zh) | 2013-05-14 | 2017-04-19 | 埃克森美孚化学专利公司 | 基于乙烯的聚合物和由其制得的制品 |
EP2818513B1 (en) * | 2013-06-25 | 2015-12-23 | Lanxess Elastomers B.V. | Oil extended ethylene-alpha-olefin-non-conjugated diene copolymer |
EP3060399A1 (en) | 2013-10-16 | 2016-08-31 | ExxonMobil Chemical Patents Inc. | Enhanced stretched cling performance polyolefin films |
WO2015076618A1 (ko) | 2013-11-21 | 2015-05-28 | 주식회사 엘지화학 | 폴리올레핀의 제조 방법 및 이로부터 제조된 폴리올레핀 |
CN107709384B (zh) * | 2015-05-28 | 2020-09-01 | 陶氏环球技术有限责任公司 | 形成乙烯/α-烯烃互聚物的方法 |
CN106366226B (zh) * | 2015-07-23 | 2019-11-12 | 中国石油化工股份有限公司 | 一种过渡金属催化剂组合物及其应用 |
WO2017034680A1 (en) * | 2015-08-25 | 2017-03-02 | Exxonmobil Chemical Patents Inc. | Ethylene copolymer with in-situ oil production |
US10800865B2 (en) | 2015-09-14 | 2020-10-13 | Exxonmobil Chemical Patents Inc. | Process for making branched EPDM and the EPDM therefrom |
EP4257639A3 (en) | 2015-09-17 | 2023-12-06 | ExxonMobil Chemical Patents Inc. | Polyethylene polymers and articles made therefrom |
KR101927460B1 (ko) * | 2016-01-27 | 2018-12-10 | 주식회사 엘지화학 | 혼성 담지 촉매 및 이를 이용하는 올레핀 중합체의 제조 방법 |
EP3414280A1 (en) | 2016-02-10 | 2018-12-19 | ExxonMobil Chemical Patents Inc. | Polyethylene shrink films and processes for making the same |
WO2017184234A1 (en) | 2016-04-22 | 2017-10-26 | Exxonmobil Chemical Patents Inc. | Polyethylene sheets |
WO2018017180A1 (en) | 2016-07-21 | 2018-01-25 | Exxonmobil Chemical Patents Inc. | Rotomolded compositions, articles, and processes for making the same |
WO2018048472A1 (en) | 2016-09-09 | 2018-03-15 | Exxonmobil Chemical Patents Inc. | Pilot plant scale semi-condensing operation |
WO2018102091A1 (en) | 2016-12-02 | 2018-06-07 | Exxonmobil Chemical Patents Inc. | Polyethylene films |
US20200108539A1 (en) | 2017-04-06 | 2020-04-09 | ExxonMobil Chemica Patents Inc. | Cast Films and Processes for Making the Same |
WO2018226311A1 (en) | 2017-06-08 | 2018-12-13 | Exxonmobil Chemical Patents Inc. | Polyethylene blends and extrudates and methods of making the same |
US11179516B2 (en) | 2017-06-22 | 2021-11-23 | Baxter International Inc. | Systems and methods for incorporating patient pressure into medical fluid delivery |
WO2019022801A1 (en) | 2017-07-24 | 2019-01-31 | Exxonmobil Chemical Patents Inc. | POLYETHYLENE FILMS AND METHODS OF PRODUCING THE SAME |
US11302459B2 (en) | 2017-10-06 | 2022-04-12 | Exxonmobil Chemical Patents Inc. | Polyethylene extrudates and methods of making the same |
US11479624B2 (en) | 2017-11-17 | 2022-10-25 | Exxonmobil Chemical Patents Inc. | PE-RT pipes and processes for making the same |
US11441023B2 (en) | 2018-04-27 | 2022-09-13 | Exxonmobil Chemical Patents Inc. | Polyethylene films and methods of making the same |
EP3788081A1 (en) | 2018-05-02 | 2021-03-10 | ExxonMobil Chemical Patents Inc. | Methods for scale-up from a pilot plant to a larger production facility |
US11459408B2 (en) | 2018-05-02 | 2022-10-04 | Exxonmobil Chemical Patents Inc. | Methods for scale-up from a pilot plant to a larger production facility |
CN112154174B (zh) | 2018-05-22 | 2024-02-06 | 埃克森美孚化学专利公司 | 形成膜的方法及其相关的计算装置 |
CN109957057B (zh) * | 2019-04-01 | 2021-03-05 | 厦门大学 | 一种制备poe用茂金属催化剂的活化及进料方法 |
CN114901732A (zh) | 2019-12-09 | 2022-08-12 | 埃克森美孚化学专利公司 | 纵向取向的聚乙烯薄膜 |
US20230024066A1 (en) | 2019-12-09 | 2023-01-26 | Exxonmobil Chemical Patents Inc. | Biaxially Oriented Polyethylene Films |
WO2021119158A1 (en) | 2019-12-09 | 2021-06-17 | Exxonmobil Chemical Patents Inc. | Biaxially oriented polyethylene films and process for production thereof |
WO2021154442A1 (en) | 2020-01-31 | 2021-08-05 | Exxonmobil Research And Engineering Company | Polyethylene films having high tear strength |
US20230159679A1 (en) | 2020-03-18 | 2023-05-25 | Exxonmobil Chemical Patents Inc. | Extrusion Blow Molded Articles and Processes for Making Same |
US20230182366A1 (en) | 2020-05-19 | 2023-06-15 | Exxonmobil Chemical Patents Inc. | Extrusion Blow Molded Containers And Processes For Making Same |
WO2021262838A1 (en) | 2020-06-26 | 2021-12-30 | Exxonmobil Chemical Patents Inc. | Copolymers composed of ethylene, a-olefin, non-conjugated diene, and substituted styrene and articles therefrom |
CN114437273B (zh) * | 2020-10-30 | 2023-07-25 | 中国石油天然气股份有限公司 | 一种丁基橡胶的制备方法 |
CN117980354A (zh) | 2021-10-26 | 2024-05-03 | 埃克森美孚化学专利公司 | 具有卓越加工性和机械性质的高度取向线性低密度聚乙烯膜 |
WO2023244901A1 (en) | 2022-06-15 | 2023-12-21 | Exxonmobil Chemical Patents Inc. | Ethylene-based polymers, articles made therefrom, and processes for making same |
Family Cites Families (88)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5324800A (en) | 1983-06-06 | 1994-06-28 | Exxon Chemical Patents Inc. | Process and catalyst for polyolefin density and molecular weight control |
DE3508887A1 (de) | 1985-03-13 | 1986-09-25 | Hoechst Ag, 6230 Frankfurt | Verfahren zur herstellung von optisch aktiven polyolefinen |
JPH0678501B2 (ja) | 1985-11-21 | 1994-10-05 | 大日本インキ化学工業株式会社 | 水性被覆組成物 |
US4752597A (en) | 1985-12-12 | 1988-06-21 | Exxon Chemical Patents Inc. | New polymerization catalyst |
US5153157A (en) | 1987-01-30 | 1992-10-06 | Exxon Chemical Patents Inc. | Catalyst system of enhanced productivity |
US5055438A (en) | 1989-09-13 | 1991-10-08 | Exxon Chemical Patents, Inc. | Olefin polymerization catalysts |
PL276385A1 (en) | 1987-01-30 | 1989-07-24 | Exxon Chemical Patents Inc | Method for polymerization of olefines,diolefins and acetylene unsaturated compounds |
US5391629A (en) | 1987-01-30 | 1995-02-21 | Exxon Chemical Patents Inc. | Block copolymers from ionic catalysts |
US5241025A (en) | 1987-01-30 | 1993-08-31 | Exxon Chemical Patents Inc. | Catalyst system of enhanced productivity |
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 |
DE3726067A1 (de) | 1987-08-06 | 1989-02-16 | Hoechst Ag | Verfahren zur herstellung von 1-olefinpolymeren |
JP2573613B2 (ja) | 1987-08-14 | 1997-01-22 | 三菱化学株式会社 | エチレンの重合法 |
US4931417A (en) | 1987-11-09 | 1990-06-05 | Chisso Corporation | Transition-metal compound having a bis-substituted-cyclopentadienyl ligand of bridged structure |
US5017714A (en) | 1988-03-21 | 1991-05-21 | Exxon Chemical Patents Inc. | Silicon-bridged transition metal compounds |
US4871705A (en) | 1988-06-16 | 1989-10-03 | Exxon Chemical Patents Inc. | Process for production of a high molecular weight ethylene a-olefin elastomer with a metallocene alumoxane catalyst |
US5001205A (en) | 1988-06-16 | 1991-03-19 | Exxon Chemical Patents Inc. | Process for production of a high molecular weight ethylene α-olefin elastomer with a metallocene alumoxane catalyst |
US5229478A (en) | 1988-06-16 | 1993-07-20 | Exxon Chemical Patents Inc. | Process for production of high molecular weight EPDM elastomers using a metallocene-alumoxane catalyst system |
CA1327673C (en) * | 1988-06-16 | 1994-03-08 | Sigmund Floyd | Process for production of high molecular weight epdm elastomers using a metallocene-alumoxane catalyst system |
US4892851A (en) | 1988-07-15 | 1990-01-09 | Fina Technology, Inc. | Process and catalyst for producing syndiotactic polyolefins |
US5243002A (en) | 1988-07-15 | 1993-09-07 | Fina Technology, Inc. | Process and catalyst for producing syndiotactic polymers |
US5223468A (en) | 1988-07-15 | 1993-06-29 | Fina Technology, Inc. | Process and catalyst for producing syndiotactic polymers |
US5155080A (en) | 1988-07-15 | 1992-10-13 | Fina Technology, Inc. | Process and catalyst for producing syndiotactic polyolefins |
DE3836059A1 (de) | 1988-10-22 | 1990-05-03 | Hoechst Ag | Verfahren zur herstellung eines ethylen-propylen-copolymers |
IT1237398B (it) | 1989-01-31 | 1993-06-01 | Ausimont Srl | Catalizzatori per la polimerizzazione di olefine. |
DE3907965A1 (de) * | 1989-03-11 | 1990-09-13 | Hoechst Ag | Verfahren zur herstellung eines syndiotaktischen polyolefins |
DE3907964A1 (de) | 1989-03-11 | 1990-09-13 | Hoechst Ag | Verfahren zur herstellung eines syndiotaktischen polyolefins |
US5441920A (en) | 1989-03-21 | 1995-08-15 | Exxon Chemical Patents Inc. | Silicon-bridged transition metal compounds |
EP0391655B1 (en) * | 1989-04-04 | 1995-06-14 | Sharp Kabushiki Kaisha | A drive device for driving a matrix-type LCD apparatus |
DE3922546A1 (de) | 1989-07-08 | 1991-01-17 | Hoechst Ag | Verfahren zur herstellung von cycloolefinpolymeren |
US5034549A (en) | 1989-07-28 | 1991-07-23 | Akzo N.V. | Olefin polymerization catalyst |
US5026798A (en) | 1989-09-13 | 1991-06-25 | Exxon Chemical Patents Inc. | Process for producing crystalline poly-α-olefins with a monocyclopentadienyl transition metal catalyst system |
US5064802A (en) | 1989-09-14 | 1991-11-12 | The Dow Chemical Company | Metal complex compounds |
ES2087145T3 (es) * | 1989-10-10 | 1996-07-16 | Fina Technology | Catalizadores metalocenos con acidos de lewis y alkilo-aluminios. |
US5036034A (en) | 1989-10-10 | 1991-07-30 | Fina Technology, Inc. | Catalyst for producing hemiisotactic polypropylene |
US5387568A (en) * | 1989-10-30 | 1995-02-07 | Fina Technology, Inc. | Preparation of metallocene catalysts for polymerization of olefins |
DE4005947A1 (de) | 1990-02-26 | 1991-08-29 | Basf Ag | Loesliche katalysatorsysteme zur polymerisation von c(pfeil abwaerts)2(pfeil abwaerts)- bis c(pfeil abwaerts)1(pfeil abwaerts)(pfeil abwaerts)0(pfeil abwaerts)-alk-1-enen |
US5272236A (en) * | 1991-10-15 | 1993-12-21 | The Dow Chemical Company | Elastic substantially linear olefin polymers |
ES2071888T3 (es) | 1990-11-12 | 1995-07-01 | Hoechst Ag | Bisindenilmetalocenos sustituidos en posicion 2, procedimiento para su preparacion y su utilizacion como catalizadores en la polimerizacion de olefinas. |
US5369196A (en) * | 1990-11-30 | 1994-11-29 | Idemitsu Kosan Co., Ltd. | Production process of olefin based polymers |
JP3048653B2 (ja) | 1991-02-07 | 2000-06-05 | 三菱化学株式会社 | α‐オレフィン重合体の製造 |
JP3117231B2 (ja) | 1991-03-11 | 2000-12-11 | 三井化学株式会社 | 幅広い分子量分布を有するシンジオタクチックポリ−α−オレフィンの製造方法 |
JP3193066B2 (ja) | 1991-05-02 | 2001-07-30 | 三菱化学株式会社 | プロピレンランダム共重合体の製造法 |
US5191132A (en) | 1991-05-09 | 1993-03-02 | Phillips Petroleum Company | Cyclopentadiene type compounds and method for making |
US5401817A (en) | 1991-05-09 | 1995-03-28 | Phillips Petroleum Company | Olefin polymerization using silyl-bridged metallocenes |
US5399636A (en) | 1993-06-11 | 1995-03-21 | Phillips Petroleum Company | Metallocenes and processes therefor and therewith |
US5436305A (en) | 1991-05-09 | 1995-07-25 | Phillips Petroleum Company | Organometallic fluorenyl compounds, preparation, and use |
DE4120009A1 (de) | 1991-06-18 | 1992-12-24 | Basf Ag | Loesliche katalysatorsysteme zur herstellung von polyalk-1-enen mit hohen molmassen |
DE69222700T2 (de) * | 1991-07-11 | 1998-03-26 | Idemitsu Kosan Co | Verfahren zur Herstellung von Polymeren auf Olefinbasis und Olefin-Polymerisationskatalysatoren |
US5391789A (en) | 1991-08-08 | 1995-02-21 | Hoechst Aktiengesellschaft | Bridged, chiral metallocenes, processes for their preparation and their use as catalysts |
US5416228A (en) | 1991-10-07 | 1995-05-16 | Fina Technology, Inc. | Process and catalyst for producing isotactic polyolefins |
ATE286918T1 (de) | 1991-10-15 | 2005-01-15 | Basell Polyolefine Gmbh | Verfahren zur herstellung eines olefinpolymers unter verwendung von metallocenen mit speziell substituierten indenylliganden |
US5281679A (en) | 1991-11-07 | 1994-01-25 | Exxon Chemical Patents Inc. | Catalyst and method of broadening polymer molecular weight distribution and increasing polymer tensile impact strength and products made thereof |
DE69224463T2 (de) | 1991-11-28 | 1998-07-09 | Showa Denko Kk | Neues Metallocen und Verfahren zur Herstellung von Polyolefinen unter Verwendung desselben |
TW318184B (ja) | 1991-11-30 | 1997-10-21 | Hoechst Ag | |
DE59206948D1 (de) | 1991-11-30 | 1996-09-26 | Hoechst Ag | Metallocene mit benzokondensierten Indenylderivaten als Liganden, Verfahren zu ihrer Herstellung und ihre Verwendung als Katalysatoren |
DE69232297T2 (de) | 1992-01-06 | 2002-08-14 | Dow Chemical Co | Katalysatorzusammensetzung |
NL9200059A (nl) * | 1992-01-14 | 1993-08-02 | Biddle F H Bv | Luchtbehandelingsinrichting. |
EP0552946B1 (en) * | 1992-01-23 | 1997-04-16 | Mitsui Petrochemical Industries, Ltd. | Ethylene/alpha-olefin/7-methyl-1,6-octadiene copolymer rubber and composition of the same |
EP0552945B1 (en) | 1992-01-23 | 1997-05-07 | Mitsui Petrochemical Industries, Ltd. | Process for the preparation of polyolefin |
US5331057A (en) | 1992-02-22 | 1994-07-19 | Hoechst Aktiengesellschaft | Cycloolefin block copolymers and a process for their preparation |
US5330948A (en) | 1992-03-31 | 1994-07-19 | Northwestern University | Homogeneous catalysts for stereoregular olefin polymerization |
US5296433A (en) | 1992-04-14 | 1994-03-22 | Minnesota Mining And Manufacturing Company | Tris(pentafluorophenyl)borane complexes and catalysts derived therefrom |
DE69322082T2 (de) * | 1992-04-20 | 1999-06-17 | Exxon Chemical Patents Inc | Copolymere des ethylens mit verzweigten olefinen |
US5308817A (en) | 1992-05-18 | 1994-05-03 | Fina Technology, Inc. | Metallocene catalyst component with good catalyst efficiency after aging |
US5434115A (en) | 1992-05-22 | 1995-07-18 | Tosoh Corporation | Process for producing olefin polymer |
WO1993025591A1 (en) * | 1992-06-18 | 1993-12-23 | Spherilene S.R.L. | Process for preparing an ethylenic polymer |
US5620760A (en) * | 1992-06-30 | 1997-04-15 | Montell Technology Company Bv | Shaped articles for biomedical use |
ATE165832T1 (de) | 1992-08-03 | 1998-05-15 | Targor Gmbh | Verfahren zur herstellung eines olefinpolymers unter verwendung von metallocenen mit speziell substituierten indenylliganden |
JP2936189B2 (ja) | 1992-09-09 | 1999-08-23 | 東ソー株式会社 | 有機遷移金属錯体 |
US5317036A (en) | 1992-10-16 | 1994-05-31 | Union Carbide Chemicals & Plastics Technology Corporation | Gas phase polymerization reactions utilizing soluble unsupported catalysts |
KR100311244B1 (ko) | 1993-02-22 | 2001-12-15 | 가지와라 야스시 | 에틸렌/α-올레핀공중합체의제조방법 |
US5372980A (en) | 1993-06-03 | 1994-12-13 | Polysar | Bimetallic metallocene alumoxane catalyst system and its use in the preparation of ethylene-alpha olefin and ethylene-alpha olefin-non-conjugated diolefin elastomers |
JPH0733812A (ja) * | 1993-07-02 | 1995-02-03 | Idemitsu Kosan Co Ltd | スチレン系重合体製造触媒及びそれを用いたスチレン系重合体の製造方法 |
AU7521794A (en) | 1993-08-06 | 1995-02-28 | Exxon Chemical Patents Inc. | Polymerization catalysts, their production and use |
US5459117A (en) | 1993-08-27 | 1995-10-17 | Ewen; John A. | Doubly-conformationally locked, stereorigid catalysts for the preparation of tactiospecific polymers |
IT1271406B (it) * | 1993-09-13 | 1997-05-28 | Spherilene Srl | Procedimento per la preparazione di polimeri dell'etilene e prodotti ottenuti |
US5466649A (en) | 1993-10-15 | 1995-11-14 | Exxon Chemical Patents Inc. | Polymerization catalyst systems, their production and use |
DE4337233A1 (de) | 1993-10-30 | 1995-05-04 | Basf Ag | Verfahren zur Herstellung von Polymerisaten von C¶2¶- bis C¶1¶¶0¶-Alk-1-enen unter Verwendung von racemischen Metallocenkomplexen als Katalysatoren |
JP3379172B2 (ja) | 1993-11-11 | 2003-02-17 | 東ソー株式会社 | エチレン・α−オレフィン共重合体 |
US5491207A (en) | 1993-12-14 | 1996-02-13 | Exxon Chemical Patents Inc. | Process of producing high molecular weight ethylene-α-olefin elastomers with an indenyl metallocene catalyst system |
WO1995016716A1 (en) | 1993-12-14 | 1995-06-22 | Exxon Chemical Patents Inc. | Process for producing elastomers with an indenyl metallocene catalyst system |
US5674795A (en) * | 1993-12-23 | 1997-10-07 | Union Carbide Chemicals & Plastics Technology Corporation | Spray dried, filled metallocene catalyst composition for use in polyolefin manufacture |
EP0668295B1 (en) | 1994-02-17 | 1998-06-03 | Union Carbide Chemicals & Plastics Technology Corporation | Spray dried, filled metallocene catalyst composition for use in polyolefin manufacture |
DE69500979T2 (de) * | 1994-07-22 | 1998-03-05 | Mitsubishi Chem Corp | Katalysatorbestandteil für alpha-Olefinpolymerisation und Verfahren zur Herstellung von alpha-Olefinpolymeren unter Anwendung desselben |
TW383313B (en) * | 1994-12-20 | 2000-03-01 | Mitsui Petrochemical Ind | Preparation of ethylene-alpha-olefin-nonconjugate polyene random copolymers, the copolymers obtaining which, and the use of the copolymers |
TW383314B (en) * | 1994-12-20 | 2000-03-01 | Mitsui Petrochemical Ind | Ethylene-alpha-olefin-nonconjugated polyene random copolymer, rubber composition, and process for preparing the random copolymer |
US5696213A (en) * | 1995-04-21 | 1997-12-09 | Exxon Chemical Patents Inc. | Ethylene-α-olefin-diolefin elastomers solution polymerization process |
SG64939A1 (en) | 1995-07-17 | 2002-02-19 | Mitsui Chemicals Inc | Olefin polymerization catalyst, process for preparing olefin polymer, and olefin polymer |
-
1996
- 1996-04-10 US US08/630,650 patent/US6225426B1/en not_active Expired - Lifetime
-
1997
- 1997-04-01 CN CNA2007101802372A patent/CN101186658A/zh active Pending
- 1997-04-01 DK DK97917770T patent/DK0892816T3/da active
- 1997-04-01 CN CNB97193715XA patent/CN100436484C/zh not_active Expired - Fee Related
- 1997-04-01 PT PT97917770T patent/PT892816E/pt unknown
- 1997-04-01 RU RU98120351/04A patent/RU2205837C2/ru active
- 1997-04-01 JP JP53627897A patent/JP3274686B2/ja not_active Expired - Fee Related
- 1997-04-01 BR BR9708645-2A patent/BR9708645A/pt not_active IP Right Cessation
- 1997-04-01 CN CNB031277535A patent/CN100389129C/zh not_active Expired - Fee Related
- 1997-04-01 EP EP97917770A patent/EP0892816B1/en not_active Expired - Lifetime
- 1997-04-01 AT AT97917770T patent/ATE229039T1/de not_active IP Right Cessation
- 1997-04-01 DE DE69717614T patent/DE69717614T2/de not_active Expired - Lifetime
- 1997-04-01 WO PCT/US1997/005323 patent/WO1997038019A1/en active IP Right Grant
- 1997-04-01 ES ES97917770T patent/ES2190529T3/es not_active Expired - Lifetime
- 1997-04-01 KR KR10-2004-7014875A patent/KR100505840B1/ko not_active IP Right Cessation
- 1997-12-15 US US08/990,612 patent/US6136744A/en not_active Expired - Lifetime
- 1997-12-15 US US08/990,922 patent/US6147025A/en not_active Expired - Lifetime
- 1997-12-15 US US08/990,364 patent/US6060572A/en not_active Expired - Lifetime
-
1999
- 1999-10-27 HK HK99104796.0A patent/HK1019609A1/xx not_active IP Right Cessation
-
2001
- 2001-03-19 JP JP2001078458A patent/JP2001302731A/ja active Pending
- 2001-11-22 JP JP2001357894A patent/JP2002249521A/ja active Pending
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006206925A (ja) * | 2000-08-11 | 2006-08-10 | Uniroyal Chemical Co Inc | 液状ポリアルファオレフィンポリマーの製造法、そのためのメタロセン触媒、得られるポリマー及びそれを含有する潤滑剤 |
JP2009518507A (ja) * | 2005-12-06 | 2009-05-07 | エクソンモービル・ケミカル・パテンツ・インク | エチレンエラストマー組成物 |
JP2013144814A (ja) * | 2008-07-18 | 2013-07-25 | Denki Kagaku Kogyo Kk | オレフィン−芳香族ポリエン共重合体 |
EP4043500A1 (en) | 2014-02-13 | 2022-08-17 | Mitsui Chemicals, Inc. | Ethylene·alpha-olefin·non-conjugated polyene copolymer, use thereof, and manufacturing method thereof |
Also Published As
Publication number | Publication date |
---|---|
US6060572A (en) | 2000-05-09 |
EP0892816B1 (en) | 2002-12-04 |
CN1215408A (zh) | 1999-04-28 |
CN1544484A (zh) | 2004-11-10 |
PT892816E (pt) | 2003-04-30 |
HK1019609A1 (en) | 2000-02-18 |
DE69717614T2 (de) | 2003-07-24 |
US6136744A (en) | 2000-10-24 |
DE69717614D1 (de) | 2003-01-16 |
US6147025A (en) | 2000-11-14 |
US6225426B1 (en) | 2001-05-01 |
ATE229039T1 (de) | 2002-12-15 |
KR20040091150A (ko) | 2004-10-27 |
ES2190529T3 (es) | 2003-08-01 |
BR9708645A (pt) | 2002-06-04 |
KR100505840B1 (ko) | 2005-08-03 |
DK0892816T3 (da) | 2003-03-31 |
JP3274686B2 (ja) | 2002-04-15 |
WO1997038019A1 (en) | 1997-10-16 |
CN100436484C (zh) | 2008-11-26 |
CN101186658A (zh) | 2008-05-28 |
RU2205837C2 (ru) | 2003-06-10 |
EP0892816A1 (en) | 1999-01-27 |
JP2001302731A (ja) | 2001-10-31 |
JP2002249521A (ja) | 2002-09-06 |
CN100389129C (zh) | 2008-05-21 |
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