JP2022537911A - 液状ゴムの製造方法およびそれから製造された液状ゴム - Google Patents
液状ゴムの製造方法およびそれから製造された液状ゴム Download PDFInfo
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- JP2022537911A JP2022537911A JP2021571694A JP2021571694A JP2022537911A JP 2022537911 A JP2022537911 A JP 2022537911A JP 2021571694 A JP2021571694 A JP 2021571694A JP 2021571694 A JP2021571694 A JP 2021571694A JP 2022537911 A JP2022537911 A JP 2022537911A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate 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
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- 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
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Abstract
Description
グローブボックスにて、100mgの[H(Et2O)2][B(C6F5)4](旭硝子)をマグネティックバーとともにバイアルに入れ、ジクロロメタン2mLに溶解させた後、3当量のジブチルエーテル(Aldrich購買)を投入して30分間真空条件で撹拌することで、触媒組成物を製造した。
[実施例1-1~1-5]
グローブボックスにて乾燥された0.5Lの反応フラスコにマグネティックバーを入れ、下記表1に記載の含量で溶媒を投入し、次いで下記表1に記載の含量でイソプレンをシリンジを用いて投入した後、10分間撹拌した。次いで、前記製造例で製造された触媒組成物を前記反応フラスコに投入し、23℃で30分間重合反応を行った後、メタノール1gを投入して反応を終了し、溶媒を除去して液状ゴムを得た。投入された単量体の含量に対する、得られた液状ゴムの含量から収率を計算した。
グローブボックスにて乾燥された0.5Lの反応フラスコにマグネティックバーを入れ、下記表2に記載の含量で溶媒を投入し、次いで下記表2に記載の含量でイソプレンをシリンジを用いて投入した後、10分間撹拌した。次いで、触媒としてn-ブチルリチウムを、前記投入された溶媒と同一の溶媒に溶解させて前記反応フラスコに投入し、重合反応を1時間行った後、メタノール1gを投入して反応を終了し、溶媒を除去して液状ゴムを得た。投入された単量体の含量に対する、得られた液状ゴムの含量から収率を計算した。
グローブボックスにて乾燥された0.5Lのアンドリューフラスコにマグネティックバーを入れ、下記表3に記載の含量で1,3-ブタジエンを投入し、-20℃で凝縮させた。その後、下記表3に記載の含量で溶媒をシリンジを用いてアンドリューフラスコに投入し、23℃に昇温しながら撹拌した。次いで、前記製造例で製造された触媒組成物を前記アンドリューフラスコに投入し、23℃で60分間重合反応を行った後、メタノール1gを投入して反応を終了し、溶媒を除去して液状ゴムを得た。投入された単量体の含量に対する、得られた液状ゴムの含量から収率を計算した。
グローブボックスにて乾燥された0.5Lの反応フラスコにマグネティックバーを入れ、下記表4に記載の含量で溶媒を投入し、次いで下記表4に記載の含量でスチレンおよびイソプレンをシリンジを用いて投入した後、10分間撹拌した。次いで、前記製造例で製造された触媒組成物を前記反応フラスコに投入し、23℃で10分間重合反応を行った後、メタノール1gを投入して反応を終了し、溶媒を除去して液状ゴムを得た。投入された単量体の含量に対する、得られた液状ゴムの含量から収率を計算した。
グローブボックスにて乾燥された0.5Lの反応フラスコにマグネティックバーを入れ、下記表4に記載の含量で溶媒を投入し、次いで下記表4に記載の含量でスチレンをシリンジを用いて投入した後、10分間撹拌した。次いで、前記製造例で製造された触媒組成物を前記反応フラスコに投入し、23℃で10分間重合反応を行った後、下記表4に記載の含量でイソプレンをシリンジを用いて投入した後、10分間撹拌した。その後、メタノール1gを投入して反応を終了し、溶媒を除去して液状ゴムを得た。投入された単量体の含量に対する、得られた液状ゴムの含量から収率を計算した。
[実験例1]
前記実施例1-1~1-5および比較例1-1~1-3で得られた液状ゴムに対して、数平均分子量、重量平均分子量、分子量分布、およびトランス-1,4結合の含量を下記の方法により測定し、下記表5および6に示した。
下記のゲル浸透クロマトグラフィ(GPC)分析条件下で測定することで、数平均分子量(Mn)、重量平均分子量(Mw)、ピーク分子量(Mp)を測定し、(重量平均分子量)/(数平均分子量)値により分子量分布を計算した。
-カラム:PL MiniMixed B X 2
-溶媒:THF
-流速:0.3ml/min
-試料濃度:2.0mg/ml
-注入量:10μL
-カラム温度:40℃
-Detector:Agilent RI detector
-Standard:Polystyrene(三次関数で補正)
-Data processing:ChemStation
実施例および比較例で得られた液状ゴムを、NMR測定のための溶媒であるCDCl3に溶解させ、Varian社の500MHz NMRを用いて1H NMRを測定し、結合の位置によってトランス-1,4結合およびシス-1,4結合の形態を確認し、下記数学式1によりトランス-1,4結合の含量(モル%)を計算した。比較例のシス-1,4結合の含量と1,2-単位結合の含量も同様の方法により計算した。
前記実施例2で得られた液状ゴムに対して、数平均分子量、重量平均分子量、分子量分布、トランス-1,4結合の含量、および1,2-単位結合の含量を前記実験例1と同様の方法により測定し、下記表7に示した。ここで、1,2-単位結合の含量は、生成された共役ジエン結合の総含量から、トランス-1,4結合の含量およびシス-1,4結合の含量を除いた残部の含量から計算した。
前記実施例3-1~3-3で得られた液状ゴムに対して、数平均分子量、重量平均分子量、分子量分布、およびトランス-1,4結合の含量を前記実験例1と同様の方法により測定し、下記表8に示した。
Claims (12)
- R1~R4は、それぞれ独立して、水素、ハロゲン基、またはハロゲン基で置換された炭素数1~12のアルキル基である、請求項1に記載の液状ゴムの製造方法。
- 前記化学式1で表される化合物のうち有機ボレートは、テトラキス(フェニル)ボレート、テトラキス(ペンタフルオロフェニル)ボレート、テトラキス[3,5-ビス(トリフルオロメチル)フェニル]ボレート、およびその誘導体からなる群から選択される1つ以上である、請求項1に記載の液状ゴムの製造方法。
- 前記触媒組成物は、アルミニウム系助触媒を含む、請求項1に記載の液状ゴムの製造方法。
- 前記アルミニウム系助触媒は、メチルアルミノキサン、変性メチルアルミノキサン、トリメチルアルミニウム、トリエチルアルミニウム、トリ-n-プロピルアルミニウム、トリイソプロピルアルミニウム、トリ-n-ブチルアルミニウム、トリイソブチルアルミニウム、トリ-t-ブチルアルミニウム、トリペンチルアルミニウム、トリヘキシルアルミニウム、トリシクロヘキシルアルミニウム、トリオクチルアルミニウム、トリ-2-エチルヘキシルアルミニウム、ジメチルアルミニウムクロリド、ジエチルアルミニウムクロリド、ジイソプロピルアルミニウムクロリド、ジイソブチルアルミニウムクロリド、ジメチルアルミニウムブロミド、メチルアルミニウムジクロリド、エチルアルミニウムジクロリド、イソプロピルアルミニウムジクロリド、アルミニウムクロリド、およびエチルアルミニウムジブロミドからなる群から選択される1つ以上である、請求項4に記載の液状ゴムの製造方法。
- 前記化学式1で表される化合物を含む触媒および前記アルミニウム系助触媒の重量比が1:0.1~1:50である、請求項4に記載の液状ゴムの製造方法。
- 前記触媒組成物は、前記有機溶媒および前記共役ジエン系単量体の100重量部に対して0.1重量部以下で含まれる、請求項1に記載の液状ゴムの製造方法。
- 前記(S10)ステップにおける重合は、芳香族ビニル系単量体を含んで行われる、請求項1に記載の液状ゴムの製造方法。
- 前記(S10)ステップの前に、有機溶媒および触媒組成物の存在下で、芳香族ビニル系単量体を重合反応させるステップ(S1)を含む、請求項1に記載の液状ゴムの製造方法。
- 共役ジエン系単量体単位を単独で含むか、共役ジエン系単量体単位および芳香族ビニル系単量体単位を含み、
数平均分子量が100,000g/mol未満であり、
常温(23℃±3℃)で液体状態で存在し、
前記共役ジエン系単量体単位を単独で含む場合、前記共役ジエン系単量体単位のトランス-1,4結合の割合が75%以上であり、シス-1,4結合の割合が1%以下であって、それ以外の結合は1,2-結合である、液状ゴム。 - 重量平均分子量が1,000g/mol~20,000g/molであり、数平均分子量が1,000g/mol~6,000g/molであるジエン系重合体を含む、請求項11に記載の液状ゴム。
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Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61136507A (ja) * | 1984-12-07 | 1986-06-24 | Kuraray Co Ltd | トランス共役ジエンオリゴマ−の製造方法 |
JP2000344814A (ja) * | 1999-06-01 | 2000-12-12 | Nippon Shokubai Co Ltd | カチオン重合方法及びそれに用いる触媒 |
US20080249267A1 (en) * | 2005-11-21 | 2008-10-09 | Basf Se | Method for Producing Highly Reactive Isobutylene Homo-or Copolymers Using Boron-Containing Catalyst Complexes |
WO2010119708A1 (ja) * | 2009-04-16 | 2010-10-21 | 株式会社ブリヂストン | チオール含有液状ゴム組成物 |
CN103059368A (zh) * | 2011-10-21 | 2013-04-24 | 黄宝琛 | 低分子反式-1,4-聚异戊二烯蜡的应用 |
CN103204973A (zh) * | 2012-01-12 | 2013-07-17 | 青岛科技大学 | 一种低分子量反式-1,4-聚二烯烃共聚物及其制备方法和用途 |
CN107915797A (zh) * | 2017-11-22 | 2018-04-17 | 山东玉皇化工有限公司 | 液体聚丁二烯橡胶、环氧化液体聚丁二烯橡胶及其制备方法 |
JP2022519216A (ja) * | 2019-08-26 | 2022-03-22 | エルジー・ケム・リミテッド | 触媒組成物およびこれを用いた炭化水素樹脂の製造方法 |
JP2022531425A (ja) * | 2019-12-06 | 2022-07-06 | エルジー・ケム・リミテッド | 触媒組成物およびそれを用いたポリイソブテンの製造方法 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3746339B2 (ja) * | 1996-11-07 | 2006-02-15 | 三井化学株式会社 | 液状ゴム、その液状ゴム組成物およびその組成物からなる加硫ゴム |
WO2003064484A1 (en) * | 2002-01-28 | 2003-08-07 | Dow Global Technologies Inc. | Metal complex compositions based on cobalt and their use as polymerization catalyst for olefins and dienes |
JP5237565B2 (ja) * | 2007-02-09 | 2013-07-17 | 株式会社ブリヂストン | 光硬化性液状ゴム組成物 |
CN101812151A (zh) * | 2010-05-26 | 2010-08-25 | 中国科学院长春应用化学研究所 | 一种聚丁二烯的制备方法 |
CN102887966B (zh) * | 2012-10-30 | 2014-09-03 | 中国科学院长春应用化学研究所 | 一种稀土催化体系及在制备共轭二烯液体橡胶上的应用 |
US10507692B2 (en) | 2014-10-06 | 2019-12-17 | Sumitomo Rubber Industries, Ltd. | Rubber compound for tires, pneumatic tire, and an airless tire |
CN107805288A (zh) * | 2017-11-06 | 2018-03-16 | 山东玉皇化工有限公司 | 一种低分子量液体聚二烯烃的制备方法 |
CN108440698B (zh) * | 2018-04-28 | 2020-10-16 | 中国科学院青岛生物能源与过程研究所 | 一种高反式-1,4-聚异戊二烯的制备方法 |
CN108690156A (zh) * | 2018-04-28 | 2018-10-23 | 青岛科技大学 | 一种高单体转化率合成反式-1,4-聚异戊二烯的新方法 |
CN110563861B (zh) * | 2018-06-05 | 2022-02-01 | 中国石油天然气股份有限公司 | 一种端环氧基聚二烯烃液体橡胶及其制备方法 |
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Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61136507A (ja) * | 1984-12-07 | 1986-06-24 | Kuraray Co Ltd | トランス共役ジエンオリゴマ−の製造方法 |
JP2000344814A (ja) * | 1999-06-01 | 2000-12-12 | Nippon Shokubai Co Ltd | カチオン重合方法及びそれに用いる触媒 |
US20080249267A1 (en) * | 2005-11-21 | 2008-10-09 | Basf Se | Method for Producing Highly Reactive Isobutylene Homo-or Copolymers Using Boron-Containing Catalyst Complexes |
WO2010119708A1 (ja) * | 2009-04-16 | 2010-10-21 | 株式会社ブリヂストン | チオール含有液状ゴム組成物 |
CN103059368A (zh) * | 2011-10-21 | 2013-04-24 | 黄宝琛 | 低分子反式-1,4-聚异戊二烯蜡的应用 |
CN103204973A (zh) * | 2012-01-12 | 2013-07-17 | 青岛科技大学 | 一种低分子量反式-1,4-聚二烯烃共聚物及其制备方法和用途 |
CN107915797A (zh) * | 2017-11-22 | 2018-04-17 | 山东玉皇化工有限公司 | 液体聚丁二烯橡胶、环氧化液体聚丁二烯橡胶及其制备方法 |
JP2022519216A (ja) * | 2019-08-26 | 2022-03-22 | エルジー・ケム・リミテッド | 触媒組成物およびこれを用いた炭化水素樹脂の製造方法 |
JP2022531425A (ja) * | 2019-12-06 | 2022-07-06 | エルジー・ケム・リミテッド | 触媒組成物およびそれを用いたポリイソブテンの製造方法 |
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WO2021235678A1 (ko) | 2021-11-25 |
EP3981803A1 (en) | 2022-04-13 |
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