JP2014507546A - 環状ジエンと非環状ジエンとの共重合体の製造方法、及びゴム組成物 - Google Patents
環状ジエンと非環状ジエンとの共重合体の製造方法、及びゴム組成物 Download PDFInfo
- Publication number
- JP2014507546A JP2014507546A JP2013557669A JP2013557669A JP2014507546A JP 2014507546 A JP2014507546 A JP 2014507546A JP 2013557669 A JP2013557669 A JP 2013557669A JP 2013557669 A JP2013557669 A JP 2013557669A JP 2014507546 A JP2014507546 A JP 2014507546A
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- neodymium
- copolymer
- compound
- group
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
- C08F4/80—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from iron group metals or platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
-
- 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
-
- 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
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/02—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings
- C08F232/06—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings having two or more carbon-to-carbon double bonds
-
- 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
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
-
- 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
-
- 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
- C08F4/52—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 selected from boron, aluminium, gallium, indium, thallium or rare earths
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/057—Metal alcoholates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T152/00—Resilient tires and wheels
- Y10T152/10—Tires, resilient
- Y10T152/10495—Pneumatic tire or inner tube
Landscapes
- Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerization Catalysts (AREA)
Abstract
Description
窒素でパージした乾燥瓶に、ヘキサン及び1,3−ブタジエン(Bd)/へキサンブレンドを加え、15.0(重量)%Bdのヘキサン溶液300gを得た。この溶液に、トリイソブチルアルミニウム(TIBA)溶液(0.68M、1.35mL)、オクタン酸ニッケル(Ni[EHA]2)溶液(0.050M、0.61mL)及び三フッ化ホウ素ヘキサノエート(BF3*C6H13OH)溶液(1.0M、1.10mL)を加えた。この瓶を80℃の水浴に設置し、1時間回転させた。その後、触媒を不活化し、ポリマーを凝固及び安定化させるため、反応混合物を2,6−ジ−tert−ブチル−4−メチルフェノール(BHT)を含むイソプロパノールで処理した。次いで、ポリブタジエンをドラム乾燥機にて120℃で乾燥した。その特性を表1に示す。
実施例1と同様の手順を用いてコントロールポリマー2を調製した。重合条件及び生成したポリマーの特性を表1に示す。
窒素でパージした乾燥瓶に、ヘキサン(103.6g)、1,3−ブタジエン(Bd)/へキサンブレンド(22.2%、194.6g)及び1,3−シクロヘキサジエン(1.8g)を加え、モノマー15.0%のヘキサン溶液300gを得た。この溶液に、Bdブレンド(1.1g)、TIBA溶液(0.68M、0.99mL)、Ni[EHA]2溶液(0.050M、0.45mL)及びBF3*C6H13OH溶液(1.0M、0.81mL)の順序で作成した予備形成触媒を加えた。この瓶を65℃の水浴に設置し、2.5時間回転させた。その後、触媒を不活化し、ポリマーを凝固及び安定化させるため、反応混合物を2,6−ジ−tert−ブチル−4−メチルフェノール(BHT)を含むイソプロパノールで処理した。次いで、生成したポリマー(ポリマー3)をドラム乾燥機にて120℃で乾燥した。その特性を表1に示す。
実施例3と同様の手順を用いて共重合体を調製した。重合条件及び生成したポリマー(ポリマー4)の特性を表1に示す。
実施例3と同様の手順を用いて共重合体を調製した。重合条件及び生成したポリマー(ポリマー5)の特性を表1に示す。
実施例1〜5で得たポリマーを、表2に示す処方に従ったブラックサイドウォールタイプの配合物を用いて300グラムミキサーにて混ぜ合わせた。
ポリマー3(2.3重量%のCHDを含む)を表2の「ジエンポリマー試料」として用いた。ムーニー粘度測定をASTM D−1646−89に準拠して実施した。混合したゴムストックを145℃で33分間加硫した。Dc/Dn(サイクル当たりの亀裂長さ)及び引裂エネルギーを、MTS810エラストマーテストシステムを用いることにより10%歪(40Hzのパルス変形)の条件で250×103サイクル(5サイクル/秒)にわたり測定した。得られた特性を表3にまとめた。
実施例Aと同様の試験を、ポリマー3に代えてポリマー4(3.5重量%のCHDを含む)を用いて行った。得られた特性を表3にまとめた。
実施例Aと同様の試験を、ポリマー3に代えてポリマー5(5.4重量%のCHDを含む)を用いて行った。得られた特性を表3にまとめた。
実施例Aと同様の試験を、ポリマー3に代えてポリマー1を用いて行った。得られた特性を表3にまとめた。
実施例Aと同様の試験を、ポリマー3に代えてポリマー2を用いて行った。得られた特性を表3にまとめた。
Claims (20)
- 重合触媒システムを用いて非環状共役ジエンと環状共役ジエンとの共重合体を製造するに当たり、
(a)遷移金属化合物またはランタニド金属化合物と、
(b)アルキル化剤と、
(c)無機ハロゲン化アルコラートと
を含む重合触媒システムを利用して少なくとも一種の非環状共役ジエンモノマーを少なくとも一種の環状共役ジエンモノマーと重合する工程を備え、
該共重合体が少なくとも90%の非環状共役ジエンモノマーを含み、40,000〜300,000の数平均分子量と、少なくとも92%のシス結合量を有することを特徴とする共重合体の製造方法。 - 前記共重合体が、50,000〜150,000の数平均分子量を有する請求項1に記載の方法。
- 前記少なくとも一種の非環状共役ジエンが、1,3−ブタジエン、イソプレン、1,3−ペンタジエン、1,3−ヘキサジエン、2,3−ジメチル−1,3−ブタジエン、2−エチル−1,3−ブタジエン、2−メチル−1,3−ペンタジエン、3−メチル−1,3−ペンタジエン、4−メチル−1,3−ペンタジエン及び2,4−ヘキサジエンからなる群より選択される請求項1に記載の方法。
- 前記少なくとも一種の環状共役ジエンが、1,3−シクロペンタンジエン、1,3−シクロヘキサジエン、1,3−シクロヘプタジエン、1,3-シクロオクタジエン並びにこれらの誘導体からなる群より選択される請求項1に記載の方法。
- 前記重合触媒システムが、
(a)ニッケル化合物、コバルト化合物及びパラジウム化合物からなる群より選択される遷移金属化合物と、
(b)アルキル化剤と、
(c)無機ハロゲン化アルコラートと
を含む請求項1に記載の方法。 - 前記重合触媒システムが、
(a)ランタン化合物、サマリウム化合物及びネオジム化合物からなる群より選択されるランタニド金属化合物と、
(b)アルキル化剤と、
(c)無機ハロゲン化アルコラートと
を含む請求項1に記載の方法。 - 前記遷移金属化合物が、安息香酸ニッケル、酢酸ニッケル、ナフテン酸ニッケル、オクタン酸ニッケル、ネオデカン酸ニッケル、ビス(α−フリルジオキシム)ニッケル、パルミチン酸ニッケル、ステアリン酸ニッケル、ニッケルアセチルアセトネート、ニッケルサリチルアルデヒド、ビス(シクロペンタジエン)ニッケル、ビス(サリチルアルデヒド)エチレンジイミンニッケル、シクロペンタジエニル−ニッケルニトロシル、ビス(η3−アリル)ニッケル、ビス(π−シクロオクタ−1,5−ジエン)ニッケル、ビス(η3−アリルトリフルオロ酢酸ニッケル)、ニッケルテトラカルボニル、ニッケルボロアシレート、ネオデカン酸ホウ酸ニッケル、ヘキサン酸ホウ酸ニッケル、ナフテン酸ホウ酸ニッケル、ステアリン酸ホウ酸ニッケル、オクタン酸ホウ酸ニッケル、2−エチルへキサン酸ホウ酸ニッケル及びこれらの混合物からなる群より選択される請求項5に記載の方法。
- 前記無機ハロゲン化アルコラートのアルコラート部分が4〜20の炭素原子を含む請求項1に記載の方法。
- 前記無機ハロゲン化アルコラートが三フッ化ホウ素アルコラートである請求項1に記載の方法。
- 前記アルキル化剤が、式AlRnX3−n(式中の各Rは同一でも異なってもよく、炭素原子を介してアルミニウム原子に結合する一価の有機基であり、各Xは同一でも異なってもよく、水素原子、カルボキシル基、アルコキシド基またはアリールオキシド基であり、nは1〜3の整数である)を有する有機アルミニウム化合物である請求項1に記載の方法。
- 前記重合触媒システムの少なくとも一部を、モノマーに加える前に遷移金属化合物またはランタニド金属化合物をアルキル化剤と混合し、その後無機ハロゲン化アルコラートと混合する工程を備えた方法により予備形成する請求項1に記載の方法。
- 前記共重合体が2〜5の多分散性指数を有する請求項1に記載の方法。
- 前記共重合体が少なくとも95%のシス−1,4−結合量を有する請求項1に記載の方法。
- 前記少なくとも一種の非環状共役ジエンが1,3−ブタジエンであり、前記少なくとも一種の環状共役ジエンが1,3−シクロヘキサジエンであり、前記金属含有化合物がオクタン酸ニッケルであり、前記無機ハロゲン化アルコラートが三フッ化ホウ素アルコラートであり、前記アルキル化剤がトリイソブチルアルミニウムであり、前記共重合体が2〜5の多分散性指数及び少なくとも95%のシス−1,4−結合量を有する請求項1に記載の方法。
- 少なくとも一種の環状共役ジエンモノマー及び少なくとも一種の非環状共役ジエンモノマーを含む少なくとも一種の共重合体と、
少なくとも一種のゴムコンパウンドとを含み、
該少なくとも一種の共重合体が少なくとも90%の非環状共役ジエンモノマーを含み、50,000〜150,000の数平均分子量及び少なくとも92%のシス結合量を有することを特徴とするゴム組成物。 - 前記少なくとも一種の共重合体を40〜60phr含む請求項15に記載のゴム組成物。
- 前記少なくとも一種のゴムコンパウンドが天然ゴム、ポリイソプレン、ポリブタジエン及びスチレン−ブタジエン共重合体ゴムからなる群より選択される請求項15に記載のゴム組成物。
- 請求項1に記載の方法によって作製した少なくとも30phrの少なくとも一種の共重合体と、
70phr未満の少なくとも一種のゴムコンパウンドとを含み、
該少なくとも一種のゴムコンパウンドが天然ゴム、ポリイソプレン、ポリブタジエン及びスチレン−ブタジエン共重合体ゴムからなる群より選択されることを特徴とするゴム組成物。 - 請求項14に記載の方法によって作製した少なくとも30phrの少なくとも一種の共重合体と、
70phr未満の少なくとも一種のゴムコンパウンドとを含み、
該少なくとも一種のゴムコンパウンドが天然ゴム、ポリイソプレン、ポリブタジエン及びスチレン−ブタジエン共重合体ゴムからなる群より選択されることを特徴とするゴム組成物。 - トレッド構成材と、内側及び外側のサイドウォール構成材と、ケーシング構成材とを備え、
前記内側及び外側のサイドウォール構成材並びにケーシング構成材からなる群より選択した構成材の少なくとも一つが請求項1に記載の方法によって調製した共重合体を含むことを特徴とする空気入りタイヤ。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US25148709P | 2009-10-14 | 2009-10-14 | |
US61/251,487 | 2009-10-14 | ||
PCT/US2010/052473 WO2011047021A1 (en) | 2009-10-14 | 2010-10-13 | Processes for preparation of cyclic acyclic diene copolymer and rubber composition |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2015187152A Division JP6062517B2 (ja) | 2009-10-14 | 2015-09-24 | 環状ジエンと非環状ジエンとの共重合体の製造方法、及びゴム組成物 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2014507546A true JP2014507546A (ja) | 2014-03-27 |
JP5815758B2 JP5815758B2 (ja) | 2015-11-17 |
Family
ID=43416601
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2013557669A Expired - Fee Related JP5815758B2 (ja) | 2009-10-14 | 2010-10-13 | 環状ジエンと非環状ジエンとの共重合体の製造方法、及びゴム組成物 |
JP2015187152A Expired - Fee Related JP6062517B2 (ja) | 2009-10-14 | 2015-09-24 | 環状ジエンと非環状ジエンとの共重合体の製造方法、及びゴム組成物 |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2015187152A Expired - Fee Related JP6062517B2 (ja) | 2009-10-14 | 2015-09-24 | 環状ジエンと非環状ジエンとの共重合体の製造方法、及びゴム組成物 |
Country Status (8)
Country | Link |
---|---|
US (2) | US8701728B2 (ja) |
EP (1) | EP2488556B1 (ja) |
JP (2) | JP5815758B2 (ja) |
KR (1) | KR101762461B1 (ja) |
CN (1) | CN102666596B (ja) |
BR (1) | BR112012008797A2 (ja) |
RU (1) | RU2543376C2 (ja) |
WO (1) | WO2011047021A1 (ja) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
RU2543376C2 (ru) * | 2009-10-14 | 2015-02-27 | Бриджстоун Корпорейшн | Способы получения сополимера циклического и ациклического диена и резиновой смеси |
US8598286B1 (en) | 2012-11-05 | 2013-12-03 | The Goodyear Tire & Rubber Company | High cis diene/phenylbutadiene copolymers prepared using a Ziegler/Natta neodymium catalyst |
US8816032B1 (en) | 2013-05-24 | 2014-08-26 | The Goodyear Tire & Rubber Company | Copolymer of conjugated diene and 1-vinylcycloalkene |
KR101656126B1 (ko) * | 2013-09-30 | 2016-09-08 | 주식회사 엘지화학 | 신규한 네오디뮴 화합물 및 이를 포함하는 디엔 중합용 촉매 |
EP3156639A1 (en) | 2015-10-15 | 2017-04-19 | Continental Automotive GmbH | Fuel injection valve with a weld ring and method for producing the same |
US10066035B2 (en) * | 2015-12-07 | 2018-09-04 | Bridgestone Corporation | Catalyst systems and methods for preparation of 1,4-polybutadiene rubber |
US10919989B2 (en) * | 2017-10-20 | 2021-02-16 | Iowa State University Research Foundation, Inc. | End group functionalization agents for polydiene |
KR102193437B1 (ko) * | 2017-10-30 | 2020-12-21 | 주식회사 엘지화학 | 공액디엔 중합용 촉매의 제조방법, 촉매 및 이를 이용한 공액디엔계 중합체의 제조방법 |
CN108002970A (zh) * | 2017-12-26 | 2018-05-08 | 濮阳盛华德化工有限公司 | 一种1,5-环辛二烯的制备方法 |
CN110256618A (zh) * | 2019-05-31 | 2019-09-20 | 宁波金海晨光化学股份有限公司 | 一种顺式-1,4结构的聚间戊二烯及其制备方法和应用 |
CN115109189B (zh) * | 2022-06-15 | 2024-01-30 | 宁夏清研高分子新材料有限公司 | 一种环烯烃共聚物材料的制备方法、催化剂体系及其应用 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55104306A (en) * | 1979-02-06 | 1980-08-09 | Sumitomo Chem Co Ltd | Production of cyclopentadiene copolymer resin |
JPS55104307A (en) * | 1979-02-06 | 1980-08-09 | Sumitomo Chem Co Ltd | Production of cyclopentadiene resin and copolymer resin |
JP2000026581A (ja) * | 1998-05-08 | 2000-01-25 | Toyota Central Res & Dev Lab Inc | 環状共役ジエン系重合体及びその重合方法 |
JP2001302704A (ja) * | 2000-04-20 | 2001-10-31 | Ube Ind Ltd | 変性ポリブタジエンの製造方法、変性ポリブタジエン、およびゴム組成物 |
JP2009013420A (ja) * | 2001-02-28 | 2009-01-22 | Bridgestone Corp | 狭い分子量分布を示す共役ジエン重合体の連続製造方法およびそれから製造された製品 |
Family Cites Families (95)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL289530A (ja) * | 1962-03-03 | |||
US3297667A (en) | 1963-02-28 | 1967-01-10 | Union Carbide Corp | Production of cis-1, 4-polydienes by polymerization of 1, 3-dienes |
US3541063A (en) | 1967-12-29 | 1970-11-17 | Goodyear Tire & Rubber | Process for the polymerization of diolefins with a catalyst comprising alkylaluminum compounds,group iii-b organo metal compounds and organoaluminum fluoride compounds |
US3740382A (en) | 1969-12-31 | 1973-06-19 | S Beilin | Stereospecific synthetic rubber based on 1,3-butadiene and method of producing same |
US3723400A (en) * | 1969-12-31 | 1973-03-27 | I Garmonov | Method of producing 1,4-cis-polybutadiene and cis-copolymers of butadiene |
GB1294167A (en) * | 1970-08-07 | 1972-10-25 | Inst Neftechimicheskogo Sintez | Stereospecific synthetic rubber based on 1,3-butadiene and method of producing same |
US3873489A (en) | 1971-08-17 | 1975-03-25 | Degussa | Rubber compositions containing silica and an organosilane |
BE787691A (fr) | 1971-08-17 | 1973-02-19 | Degussa | Composes organosiliciques contenant du soufre |
US3978103A (en) | 1971-08-17 | 1976-08-31 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler | Sulfur containing organosilicon compounds |
US3794604A (en) | 1971-09-24 | 1974-02-26 | Goodyear Tire & Rubber | Diolefin polymerization catalyst composition |
SU580840A3 (ru) | 1974-02-07 | 1977-11-15 | Дегусса (Фирма) | Способ получени серосодержащих кремнийорганических соединений |
US4020251A (en) | 1974-02-27 | 1977-04-26 | Phillips Petroleum Company | 1,3-Cyclodiene-acyclic conjugated diene copolymers |
US4127710A (en) | 1974-10-02 | 1978-11-28 | Phillips Petroleum Company | Copolymerization of a 1,3-cyclodiene and a linear conjugated diene |
US4002594A (en) | 1975-07-08 | 1977-01-11 | Ppg Industries, Inc. | Scorch retardants for rubber reinforced with siliceous pigment and mercapto-type coupling agent |
US4223116A (en) | 1976-06-17 | 1980-09-16 | Phillips Petroleum Company | Conjugated diene polymerization process and catalyst |
US4113930A (en) | 1976-08-02 | 1978-09-12 | Phillips Petroleum Company | Hydrogenated 1,3-cyclohexadiene/1,3-butadiene copolymers |
US4138536A (en) | 1976-12-20 | 1979-02-06 | Phillips Petroleum Company | Polymerization of 1,3-cyclodiene with vinylaromatic hydrocarbon |
US4107081A (en) | 1977-06-24 | 1978-08-15 | The Firestone Tire & Rubber Company | Catalyst system and process for polymerization of conjugated dienes therewith |
US4174431A (en) | 1977-11-07 | 1979-11-13 | The Firestone Tire & Rubber Company | Process for polymerizing conjugated dienes |
DE3006001A1 (de) * | 1979-02-19 | 1980-09-04 | Sumitomo Chemical Co | Verfahren zur herstellung von cyclopentadienmischpolymerisaten, ein solches mischpolymerisat enthaltende kautschukmassen und deren vulkanisationsprodukte |
US4264753A (en) | 1979-10-18 | 1981-04-28 | The Firestone Tire & Rubber Company | Process for polymerizing conjugated dienes |
US4248988A (en) | 1979-10-18 | 1981-02-03 | The Firestone Tire & Rubber Company | Process for the preparation of cyclized polymeric dienes |
CA1223396A (en) | 1981-06-29 | 1987-06-23 | Tooru Shibata | Process for producing conjugated diene polymer |
IT1140452B (it) | 1981-09-25 | 1986-09-24 | Anic Spa | Procedimento per la polimerizzazione di diolefine coniugate e mezzi adatti allo scopo |
US4522988A (en) | 1984-06-04 | 1985-06-11 | The Firestone Tire & Rubber Company | Method of preparing high cis-1,4 diene polymers having good green strength and tack |
US4591624A (en) | 1984-07-02 | 1986-05-27 | The Firestone Tire & Rubber Company | Catalyst system and process for polymerizing conjugated dienes |
US4520123A (en) | 1984-07-02 | 1985-05-28 | The Firestone Tire & Rubber Company | Catalyst system and process for polymerizing conjugated dienes |
IT1186747B (it) | 1985-07-01 | 1987-12-16 | Enichem Elastomers | Procedimento migliorato per la polimerizzazione o copolimerizzazione del butadiene |
US5064910A (en) | 1986-09-05 | 1991-11-12 | Japan Synthetic Rubber Co., Ltd. | Preparation of conjugated diene polymers modified with an organo-tin or germanium halide |
GB8830007D0 (en) | 1988-12-22 | 1989-02-15 | Enichem Elastomers | Polymerization of butadiene |
SU1705305A1 (ru) * | 1989-07-03 | 1992-01-15 | Ярославский Научно-Исследовательский Институт Мономеров Для Синтетического Каучука | Способ получени полимеров на основе циклопентадиена |
US5260370A (en) | 1990-09-21 | 1993-11-09 | Bridgestone Corporation | Oil extended ultra high molecular weight elastomers |
US5231152A (en) | 1990-12-18 | 1993-07-27 | Bridgestone Corporation | Continuous process for preparing copolymers of conjugated dienes and aromatic vinyl compounds |
FR2673187B1 (fr) | 1991-02-25 | 1994-07-01 | Michelin & Cie | Composition de caoutchouc et enveloppes de pneumatiques a base de ladite composition. |
CA2077370C (en) | 1991-09-03 | 1998-12-15 | James E. Hall | Dispersion copolymers in linear aliphatic solvents |
JP3207502B2 (ja) | 1992-04-20 | 2001-09-10 | 株式会社ブリヂストン | 共重合体の製造方法 |
US5248722A (en) | 1992-06-02 | 1993-09-28 | Bridgestone Corporation | Tire tread composition |
WO1994028038A1 (fr) * | 1993-05-21 | 1994-12-08 | Asahi Kasei Kogyo Kabushiki Kaisha | Polymere diene conjugue cyclique |
JP3141190B2 (ja) | 1993-05-21 | 2001-03-05 | 旭化成株式会社 | 環状共役ジエン系共重合体 |
JP3101151B2 (ja) | 1993-05-21 | 2000-10-23 | 旭化成工業株式会社 | 環状共役ジエン系重合体及びその重合方法 |
JP3441015B2 (ja) | 1993-06-16 | 2003-08-25 | 旭化成株式会社 | 飽和環状分子構造単位を含有する新規重合体 |
WO1995004090A1 (fr) | 1993-07-30 | 1995-02-09 | Nippon Zeon Co., Ltd. | Copolymere de diene conjugue modifie, son procede de production et composition le contenant |
US5428119A (en) | 1993-11-09 | 1995-06-27 | Polysar Rubber Corporation | Process for polybutadiene production using catalyst with high activity |
US5508336A (en) | 1993-12-29 | 1996-04-16 | Bridgestone Corporation | Rubber composition |
US6300451B1 (en) | 1994-10-24 | 2001-10-09 | Exxon Chemical Patents Inc. | Long-chain branched polymers and their production |
US5580919A (en) | 1995-03-14 | 1996-12-03 | The Goodyear Tire & Rubber Company | Silica reinforced rubber composition and use in tires |
US5674932A (en) | 1995-03-14 | 1997-10-07 | The Goodyear Tire & Rubber Company | Silica reinforced rubber composition and use in tires |
JP3555809B2 (ja) | 1995-06-19 | 2004-08-18 | 株式会社ブリヂストン | ラジアルタイヤ |
AT405285B (de) | 1995-09-07 | 1999-06-25 | Semperit Ag | Kautschukmischung |
US5583245A (en) | 1996-03-06 | 1996-12-10 | The Goodyear Tire & Rubber Company | Preparation of sulfur-containing organosilicon compounds |
US5719207A (en) | 1996-03-18 | 1998-02-17 | The Goodyear Tire & Rubber Company | Silica reinforced rubber composition and tire with tread |
US5696197A (en) | 1996-06-21 | 1997-12-09 | The Goodyear Tire & Rubber Company | Heterogeneous silica carbon black-filled rubber compound |
JP3606411B2 (ja) | 1996-07-10 | 2005-01-05 | 株式会社ブリヂストン | タイヤ加硫成型用金型およびその製造方法 |
JP3117645B2 (ja) | 1996-09-03 | 2000-12-18 | 株式会社ブリヂストン | 空気入りラジアルタイヤ |
US5663396A (en) | 1996-10-31 | 1997-09-02 | The Goodyear Tire & Rubber Company | Preparation of sulfur-containing organosilicon compounds |
US5684172A (en) | 1997-02-11 | 1997-11-04 | The Goodyear Tire & Rubber Company | Process for the preparation of organosilicon polysulfide compounds |
US5684171A (en) | 1997-02-11 | 1997-11-04 | The Goodyear Tire & Rubber Company | Process for the preparation of organosilicon polysulfide compounds |
US6384117B1 (en) | 1997-07-11 | 2002-05-07 | Bridgestone Corporation | Processability of silica-filled rubber stocks |
US6221943B1 (en) | 1997-07-11 | 2001-04-24 | Bridgestone Corporation | Processability of silica-filled rubber stocks |
US6525118B2 (en) | 1997-07-11 | 2003-02-25 | Bridgestone Corporation | Processability of silica-filled rubber stocks with reduced hysteresis |
CN100376585C (zh) | 1997-08-21 | 2008-03-26 | 通用电气公司 | 用于填充橡胶的封端巯基硅烷偶联剂 |
US5971046A (en) | 1997-09-17 | 1999-10-26 | Bridgestone/Firestone, Inc. | Method and apparatus for bonding an active tag to a patch and a tire |
US6399732B2 (en) | 1998-10-14 | 2002-06-04 | Bridgestone Corporation | Preparation of conjugated diene polymers by using an iron-based catalayst system |
US6211313B1 (en) | 1999-11-12 | 2001-04-03 | Bridgestone Corporation | Iron-based catalyst composition and process for producing conjugated diene polymers |
EP1099711B1 (en) | 1999-11-12 | 2006-03-29 | JSR Corporation | Modified conjugated diene polymer, method of producing it and rubber composition comprising the same |
US6977281B1 (en) | 1999-11-12 | 2005-12-20 | Bridgestone Corporation | Modified polymers prepared with lanthanide-based catalysts |
US6992147B1 (en) | 1999-11-12 | 2006-01-31 | Bridgestone Corporation | Modified polymers prepared with lanthanide-based catalysts |
FR2802542A1 (fr) | 1999-12-20 | 2001-06-22 | Michelin Soc Tech | Composition de caoutchouc vulcanisable pour la fabrication d'un pneumatique et pneumatique dont la bande de roulement comprend une telle composition |
US6288183B1 (en) | 1999-12-30 | 2001-09-11 | Bridgestone Corporation | Catalyst composition and process for controlling the characteristics of conjugated diene polymers |
US6160063A (en) | 1999-12-30 | 2000-12-12 | Bridgestone Corporation | Iron-based catalyst for producing binary cis-1,4-/1,2-polybutadiene |
US6765066B2 (en) | 1999-12-30 | 2004-07-20 | Bridgestone Corporation | Copolymers prepared by using both anionic polymerization techniques and coordination catalysts |
US6348550B1 (en) | 2000-04-13 | 2002-02-19 | Bridgestone Corporation | Molybdenum-based catalyst composition and process for controlling the characteristics of conjugated diene polymers |
US6590017B1 (en) | 2000-05-15 | 2003-07-08 | Bridgestone Corporation | Processability of silica-reinforced rubber containing an amide compound |
US6608145B1 (en) | 2000-10-13 | 2003-08-19 | Bridgestone Corporation | Silica-reinforced rubber compounded with an organosilane tetrasulfide silica coupling agent at high mixing temperature |
US6627712B2 (en) | 2001-02-19 | 2003-09-30 | Bridgestone Corporation | Manufacture of conjugated diene polymers by using an iron-based catalyst composition |
US6465585B2 (en) | 2001-02-19 | 2002-10-15 | Bridgestone Corporation | Chromium-based catalyst composition for producing conjugated diene polymers |
US6320004B1 (en) | 2001-04-05 | 2001-11-20 | Bridgestone Corporation | Manufacture of conjugated diene polymers by using an iron-based catalyst composition |
US6995228B2 (en) | 2001-08-17 | 2006-02-07 | Asahi Kasei Kabushiki Kaisha | Copolymer of conjugated cyclodiene |
EP1293521B1 (en) | 2001-09-13 | 2008-02-13 | JSR Corporation | Cyclic olefin addition copolymer and process for producing same, crosslinkable composition, crosslinked product and process for producing same, and optically transparent material and application thereof |
US6579949B1 (en) | 2001-10-30 | 2003-06-17 | Bridgestone Corporation | Preparation of low hysteresis rubber by reacting a lithium polymer with a sulfur containing reagent |
US20040242780A1 (en) | 2001-11-05 | 2004-12-02 | Christine Rademacher | Process for producing blends of syndiotactic, 1,2-polybutadiene and rubbery elastomers |
US6699813B2 (en) | 2001-11-07 | 2004-03-02 | Bridgestone Corporation | Lanthanide-based catalyst composition for the manufacture of polydienes |
US6699941B1 (en) | 2002-11-07 | 2004-03-02 | Kraton Polymers U.S. Llc | Block copolymer |
JP4240209B2 (ja) | 2003-05-21 | 2009-03-18 | Jsr株式会社 | 変性共役ジエン系重合体、その製造方法およびそれを含む組成物 |
US7094849B2 (en) | 2003-12-15 | 2006-08-22 | Bridgestone Corporation | Bulk polymerization process for producing polydienes |
BRPI0508379A (pt) | 2004-03-01 | 2007-07-31 | Bridgestone Corp | reator de polimerização contìnua |
ES2588177T3 (es) | 2004-03-02 | 2016-10-31 | Bridgestone Corporation | Proceso de polimerización en masa |
EP1764375B1 (en) | 2004-07-02 | 2015-03-04 | Riken | Polymerization catalyst compositions containing metallocene complexes and polymerisation processes using them |
JP4901101B2 (ja) | 2004-12-28 | 2012-03-21 | 株式会社ブリヂストン | 変性重合体、ゴム組成物及びタイヤ |
US7585805B2 (en) | 2005-11-22 | 2009-09-08 | Bridgestone Corporation | Nickel-based catalyst composition |
US7671138B2 (en) | 2006-05-26 | 2010-03-02 | Bridgestone Corporation | Polymers functionized with hydrobenzamides |
US20080051519A1 (en) | 2006-08-28 | 2008-02-28 | Steven Luo | Polymers functionalized with nitro compounds |
US7732534B2 (en) | 2006-08-28 | 2010-06-08 | Bridgestone Corporation | Polymers functionalized with nitro compounds |
US7820580B2 (en) * | 2007-11-15 | 2010-10-26 | Bridgestone Corporation | Nickel-based catalysts for preparing high cis 1,4-polydienes |
RU2543376C2 (ru) * | 2009-10-14 | 2015-02-27 | Бриджстоун Корпорейшн | Способы получения сополимера циклического и ациклического диена и резиновой смеси |
-
2010
- 2010-10-13 RU RU2012119513/04A patent/RU2543376C2/ru active
- 2010-10-13 EP EP10766476.5A patent/EP2488556B1/en not_active Not-in-force
- 2010-10-13 WO PCT/US2010/052473 patent/WO2011047021A1/en active Application Filing
- 2010-10-13 JP JP2013557669A patent/JP5815758B2/ja not_active Expired - Fee Related
- 2010-10-13 CN CN201080053629.2A patent/CN102666596B/zh not_active Expired - Fee Related
- 2010-10-13 KR KR1020127012211A patent/KR101762461B1/ko active IP Right Grant
- 2010-10-13 BR BR112012008797-5A patent/BR112012008797A2/pt active Search and Examination
- 2010-10-13 US US13/501,206 patent/US8701728B2/en not_active Expired - Fee Related
-
2014
- 2014-03-24 US US14/223,413 patent/US9056928B2/en not_active Expired - Fee Related
-
2015
- 2015-09-24 JP JP2015187152A patent/JP6062517B2/ja not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55104306A (en) * | 1979-02-06 | 1980-08-09 | Sumitomo Chem Co Ltd | Production of cyclopentadiene copolymer resin |
JPS55104307A (en) * | 1979-02-06 | 1980-08-09 | Sumitomo Chem Co Ltd | Production of cyclopentadiene resin and copolymer resin |
JP2000026581A (ja) * | 1998-05-08 | 2000-01-25 | Toyota Central Res & Dev Lab Inc | 環状共役ジエン系重合体及びその重合方法 |
JP2001302704A (ja) * | 2000-04-20 | 2001-10-31 | Ube Ind Ltd | 変性ポリブタジエンの製造方法、変性ポリブタジエン、およびゴム組成物 |
JP2009013420A (ja) * | 2001-02-28 | 2009-01-22 | Bridgestone Corp | 狭い分子量分布を示す共役ジエン重合体の連続製造方法およびそれから製造された製品 |
Also Published As
Publication number | Publication date |
---|---|
US20140288250A1 (en) | 2014-09-25 |
KR20120095909A (ko) | 2012-08-29 |
WO2011047021A1 (en) | 2011-04-21 |
US20120255661A1 (en) | 2012-10-11 |
BR112012008797A2 (pt) | 2020-09-15 |
CN102666596A (zh) | 2012-09-12 |
US9056928B2 (en) | 2015-06-16 |
RU2543376C2 (ru) | 2015-02-27 |
KR101762461B1 (ko) | 2017-07-27 |
CN102666596B (zh) | 2014-04-02 |
JP6062517B2 (ja) | 2017-01-18 |
JP2016040372A (ja) | 2016-03-24 |
EP2488556A1 (en) | 2012-08-22 |
US8701728B2 (en) | 2014-04-22 |
EP2488556B1 (en) | 2013-09-11 |
JP5815758B2 (ja) | 2015-11-17 |
RU2012119513A (ru) | 2013-11-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6062517B2 (ja) | 環状ジエンと非環状ジエンとの共重合体の製造方法、及びゴム組成物 | |
US6699813B2 (en) | Lanthanide-based catalyst composition for the manufacture of polydienes | |
JP5016917B2 (ja) | 官能化ポリマー | |
EP2075267B1 (en) | Process for producing polydienes | |
JP6446004B2 (ja) | ニッケル系触媒組成物 | |
JP2013060606A (ja) | ポリジエンを製造するためのバルク重合法 | |
JP5124127B2 (ja) | ニッケル系触媒組成物 | |
JP2018503727A (ja) | 熟成ランタニド系触媒系及びシス−1,4−ポリジエンの調製における同触媒系の使用 | |
US9803032B2 (en) | Processes for the preparation of high-cis polydienes | |
JP6464153B2 (ja) | シアノ基を含むイミン化合物を用いたポリマー官能化 | |
US20070276098A1 (en) | Polymers functionalized with hydrobenzamide | |
CN115461382A (zh) | 用于产生聚二烯的金属基催化剂 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20131003 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20141212 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20141216 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20150205 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20150825 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20150924 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 5815758 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
LAPS | Cancellation because of no payment of annual fees |