JP2017160412A - ホウ素基を含有する官能化エラストマー - Google Patents
ホウ素基を含有する官能化エラストマー Download PDFInfo
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Abstract
Description
立体規則ジエンポリマーは、タイヤコンパウンドの重要な成分として工業的に大規模に製造及び使用されている。高レベルの立体規則性を有するジエンポリマーは、ほぼ例外なく配位重合触媒を用いて製造されるが、配位重合触媒は一般に極性官能基によって害されやすい。この有害作用のために、配位触媒と適合可能なモノマーの種類は通常、単純な炭化水素に限定される。タイヤ業界では周知のことであるが、たとえ低レベルの官能性でも、ある種のタイヤポリマー(アニオン重合又は乳化重合により製造)に組み込まれると、そのようなポリマーを含有するタイヤの性能が著しく改良される。残念なことに、この官能化技術を立体規則ジエンポリマーに適用するための確かな方法は現在のところない。しかしながら、そのようなポリマーがあれば、おそらく公知の非官能化ポリマーに優る優れたタイヤ特性を示すであろう。
国際公開第2004/007602号には、1,4−ジエン、スチレンの重合用及び二つのモノマーの共重合用の触媒が開示されている。この発明の触媒の特徴は、高度の立体選択性、触媒活性、及び極性不純物の存在に対する耐性を含む。前記触媒は、Niベースのジエン重合触媒に特有の特徴(高立体選択性及び触媒活性)と、極性物質の存在に対する明確に定義された特性及び耐性とを兼ね備えている。
本発明はさらに、そのようなコポリマーの製造法にも向けられる。
さらに、そのようなコポリマーの製造法も開示する。
一態様において、非官能化ジエンモノマーは、1,3−ブタジエン又はイソプレンである。
コポリマーは高度の立体規則性を有している。一態様において、コポリマーは、コポリマーのポリブタジエン含量を基にして80重量パーセントを超えるシス1,4ミクロ構造含量を有している。一態様において、コポリマーは、コポリマーのポリブタジエン含量を基にして95重量パーセントを超えるシス1,4ミクロ構造含量を有している。
(アリル)(アレーン)Ni(II)触媒を用いる重合は、O’Connorら(Journal of Applied Polymer Science,Part A:Polymer Chemistry,Vol.48,1901−1912(2010))に記載の方法に従って実施することができる。共重合は、0〜60℃の範囲の温度で溶液重合によって実施することができる。溶液重合のための適切な溶媒は、トルエン、塩化メチレン、及びヘプタンなどである。
ゴム組成物は、官能化コポリマーに加えて、任意にオレフィン性不飽和を含有する一つ又は複数のゴム又はエラストマーを含んでいてもよい。“オレフィン性不飽和を含有するゴム又はエラストマー”又は“ジエン系エラストマー”という語句は、天然ゴム及びその各種未加工形及び再生形、ならびに各種合成ゴムのどちらも含むものとする。本発明の記載において、“ゴム”及び“エラストマー”という用語は、別段の規定のない限り互換的に使用されうる。“ゴム組成物”、“配合ゴム”及び“ゴムコンパウンド”という用語は、各種成分及び材料とブレンド又は混合されているゴムのことを言うのに互換的に使用され、そのような用語はゴム混合又はゴム配合分野の当業者には周知である。代表的な合成ポリマーは、ブタジエン及びその同族体及び誘導体、例えばメチルブタジエン、ジメチルブタジエン及びペンタジエンのホモ重合生成物、ならびにブタジエン又はその同族体もしくは誘導体とその他の不飽和モノマーとから形成されるようなコポリマーである。後者に含まれるものとしては、アセチレン、例えばビニルアセチレン;オレフィン、例えばイソブチレン(イソプレンと共重合してブチルゴムを形成する);ビニル化合物、例えばアクリル酸、アクリロニトリル(ブタジエンと重合してNBRを形成する)、メタクリル酸及びスチレン(後者の化合物はブタジエンと重合してSBRを形成する)のほか、ビニルエステル及び各種不飽和アルデヒド、ケトン及びエーテル、例えばアクロレイン、メチルイソプロペニルケトン及びビニルエチルエーテルなどが挙げられる。合成ゴムの具体例は、ネオプレン(ポリクロロプレン)、ポリブタジエン(シス−1,4−ポリブタジエンを含む)、ポリイソプレン(シス−1,4−ポリイソプレンを含む)、ブチルゴム、ハロブチルゴム、例えばクロロブチルゴム又はブロモブチルゴム、スチレン/イソプレン/ブタジエンゴム、1,3−ブタジエン又はイソプレンとスチレン、アクリロニトリル及びメチルメタクリレートなどのモノマーとのコポリマー、ならびにエチレン/プロピレンターポリマー(エチレン/プロピレン/ジエンモノマー(EPDM)としても知られる)、特にエチレン/プロピレン/ジシクロペンタジエンターポリマーなどである。使用できるゴムの追加例は、アルコキシ−シリル末端官能化溶液重合ポリマー(SBR、PBR、IBR及びSIBR)、ケイ素結合及びスズ結合星状枝分れポリマーなどである。好適なゴム又はエラストマーはポリイソプレン(天然又は合成)、ポリブタジエン及びSBRである。
本明細書中で使用され、従来の慣例に従う用語“phr”は、“100重量部のゴム、又はエラストマーあたりの各材料の重量部”を意味する。
ゴム組成物は、約1〜約150phrのシリカを含みうる。別の態様においては、10〜100phrのシリカが使用されうる。
従来型シリカは、電子顕微鏡による測定で例えば0.01〜0.05ミクロンの範囲の平均極限粒径を有すると予測されうるが、シリカ粒子は、それよりさらに小さい、又はおそらくは大きいサイズであってもよい。
他のフィラーもゴム組成物に使用できる。例えば、超高分子量ポリエチレン(UHMWPE)などの粒子状フィラー、米国特許第6,242,534号;6,207,757号;6,133,364号;6,372,857号;5,395,891号;又は6,127,488号に開示されているような架橋粒子状ポリマーゲル、及び米国特許第5,672,639号に開示されているような可塑化デンプン複合フィラーなどであるが、これらに限定されない。そのようなその他のフィラーは1〜30phrの範囲の量で使用されうる。
Ni触媒IIの合成は文献に記載されている(O’Connorら,Organometallics 2009,28 2372−2384)。あるいは、この錯体のMg塩と過剰のNaBArF 4の混合物を実施例2で概要を示した手順に従って製造することもできる。
本実施例では、Ni(II)配位触媒の合成について説明する。式IIIの化合物は以下のようにして式IIの化合物に変換された。化合物III(8mmol)をNaBArF 4(8mmol)及びメシチレン(20mmol)と、100mlシュレンクチューブ内の40mlジエチルエーテル中で混合し、−78℃に冷却した。5分後、ジエチルエーテル中1Mのアリルマグネシウムブロミド8mlを撹拌下で滴加し、アリルマグネシウムブロミドの添加完了後、冷却浴の交換により、温度を−20℃に上げた。−20℃で60分後、冷却浴を取り除き、混合物を25℃に温めた。この温度でエーテルは蒸留除去され、粗固体が残った。次に、塩化メチレン(30ml)を加え、混合物を撹拌した後、固体をろ過した。ヘプタン(10mL)を塩化メチレン溶液に加え、得られた混合物を高真空下で濃縮乾固し、約50%の収率のNiベースの触媒IIを含有する6.85gの固体を得た。
以下の実施例において、1,3-ブタジエンと、(E)−4,4,5,5−テトラメチル−2−(3−メチルブタ−1,3−ジエン−1−イル)−1,3,2−ジオキサボロラン(式IV)との共重合について説明する。
(E)−4,4,5,5−テトラメチル−2−(3−メチルブタ−1,3−ジエン−1−イル)−1,3,2−ジオキサボロランの合成
13C NMR (400 MHz, 25℃, C6D6): δ = 152.7 (C3), 143.4 (C2), 120.0 (C1), 117.2 (b, C4), 83.1 (C5), 24.9 (C6), 17.7 (C7)。
本実施例では、1,3−ブタジエンと式IVのモノマーとの共重合を示す。重合を実施して表1に示されているような4個のコポリマーサンプルを製造した。
式IVのモノマーを、火炎乾燥シュレンクフラスコにトルエン溶液として加え(トルエンの全体積は、サンプル1〜3が15mL、サンプル4が35mL)、次いでフラスコをゴムセプタムで密封した。ブタジエンを、−78℃でトルエン中に凝縮させるか(サンプル1〜3)又は反応温度でトルエンの飽和(サンプル4)によって加えた。重合は、示された反応温度でトルエン(5mL)中触媒を添加することにより開始された。重合は、示された時間、その温度で行わせた。0.5mLのNEt3を加えて重合を終了させた。残留ブタジエンを減圧下で注意深く除去し、ポリマーを、BHTの存在下(約100mg/100mL)、MeOH中に沈殿させた。形成されたポリマーを減圧下50℃で一晩乾燥させ、示された収量gのポリ(ブタジエン−コ−(E)−4,4,5,5−テトラメチル−2−(3−メチルブタ−1,3−ジエン−1−イル)−1,3,2−ジオキサボロラン)を得た。サンプルを分析し、結果を表1に示した。分子量Mn及び多分散性(PDI)は、THF中でのGPCを用い、ポリスチレン標準に対して測定した。ガラス転移温度TgはDSCを用いて測定した。ポリマーのミクロ構造は、NMR分析(1H及び13C)により決定した。
[発明の態様]
1.1,3−ブタジエン及びイソプレンからなる群から選ばれるモノマーと、式I又はV:
3.少なくとも95重量パーセントのシス1,4ミクロ構造含量を含む、1記載のコポリマー。
5.0.5〜20重量パーセントの、式I又はVのモノマーから誘導された単位を含む、1記載のコポリマー。
7.式Iのモノマーが、(E)−4,4,5,5−テトラメチル−2−(3−メチルブタ−1,3−ジエン−1−イル)−1,3,2−ジオキサボロランである、1記載のコポリマー。
9.1記載のコポリマーを含むゴム組成物。
10.8記載のゴム組成物を含む空気入りタイヤ。
14.重合触媒が、式II:
15.芳香族架橋基が、下記構造:
Claims (5)
- 80重量パーセントを超えるシス1,4ミクロ構造含量を特徴とする、請求項1に記載のコポリマー。
- 請求項1に記載のコポリマーを含むゴム組成物を特徴とする空気入りタイヤ。
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