JP4240209B2 - Modified conjugated diene polymer, production method thereof and composition containing the same - Google Patents

Description

【００４１】
［式中、ＲおよびＲ’はいずれも炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基、Ｒ₃Ｓｉ−で示されるトリオルガノシリル基またはＲ₃ＳｉＯ−で示されるトリオルガノシロキシ基であり、同一でも異なってもよい。ＸおよびＸ’は少なくともＮ原子、Ｏ原子のいずれか１つ以上含む極性基を含有し、同一でも異なってもよい。qは０〜１であり、pおよびｎは０〜２であり、ｍおよびｍ’は０〜１，０００であり、ｌは０〜３の整数を示す。］
【００４２】
上記ヒドロシラン化合物は上式（Ｓ−１）から（Ｓ−６）で表される化合物であれば特に限定されないが、具体例として、式（Ｓ−１）
【００４３】
【化３】

【００４４】
で表される化合物としては、
トリメチルシラン、トリエチルシラン、トリプロピルシラン、トリイソプロピルシラン、トリブチルシラン、トリフェニルシラン、ベンジルジメチルシラン、ｔｅｒｔ−ブチルジメチルシラン、ジ−ｔｅｒｔ−ブチルメチルシラン、ジフェニルメチルシラン、ｎ−オクタデシルジメチルシラン、フェニルジメチルシラン、トリ−ｎ−ヘキシルシラン、トリス（トリメチルシリル）シラン、メトキシジメチルシラン、エトキシジメチルシラン、ジメチルプロポキシシラン、ジメチルイソプロポキシシラン、ブトキシジメチルシラン、ジメチルフェノキシシラン、ジエチルメトキシシラン、エトキシジエチルシラン、ジエチルプロポキシシラン、ジエチルイソプロポキシシラン、ジエチルフェノキシシラン、ジメトキシメチルシラン、エチルジメトキシシラン、ジメトキシプロピルシラン、ジメトキシイソプロピルシラン、ブチルジメトキシシラン、ジメトキシフェニルシラン、ジエトキシメチルシラン、ジエトキシエチルシラン、ジエトキシプロピルシラン、ジエトキシイソプロピルシラン、ブチルジエトキシシラン、ジエトキシフェニルシラン、トリメトキシシラン、トリエトキシシラン、トリプロポキシシラン、トリイソプロポキシシラン、トリブトキシシラン、トリフェノキシシラン、トリペンチルオキシシラン、トリヘキシルシラン、１，２−ビス（ジメチルシリル）ベンゼン、１，４−ビス（ジメチルシリル）ベンゼン、ビス［（ｐ−ジメチルシリル）フェニル］エーテル、（Ｎ，Ｎ−ジメチルアミノ）ジメチルシラン、（Ｎ，Ｎ−ジエチルアミノ）ジメチルシラン、Ｎ，Ｎ−ビス（トリメチルシリル）アミノジメチルシラン、（Ｎ，Ｎ−ジメチルアミノ）ジエチルシラン、（Ｎ，Ｎ−ジエチルアミノ）ジエチルシラン、Ｎ，Ｎ−ビス（トリメチルシリル）アミノジエチルシラン、ジメチルアミノメチルエトキシシラン、ビス（ジメチルアミノ）メチルシラン、ビス（ジメチルアミノ）エチルシラン、ビス（ジメチルアミノ）フェニルシラン、トリス（ジメチルアミノ）シラン、トリス（ジエチルアミノ）シラン、トリス（Ｎ，Ｎ−ビス（トリメチルシリル）アミノ）シラン、ジアセトキシメチルシラン、トリメチルシロキシメチルアセトキシシラン、ジメチルアミノメチルエトキシシラン、１，１，３，３，−テトラメチル−１−メトキシジシロキサン、１，１，３，３−テトラメチル−１−エトキシジシロキサン、１，１，３，３−テトラメチル−１−フェノキシジシロキサン、ペンタメチルジシロキサン、１，１，３，３−テトラメチルジシラザン、１，３，３，５，５，７，７−ヘプタメチル−１，１−ジメトキシテトラシロキサン、１，１，１，３，３，５，５−ヘプタメチルトリシロキサン、ジアセトキシメチルシラン、トリメチルシロキシメチルアセトキシシラン、片末端Ｈポリジメチルシロキサン、フェニルトリス（ジメチルシロキシ）シラン、テトラキス（ジメチルシロキシ）シランなどが挙げられる。
【００４５】
また、式（Ｓ−２）
【００４６】
【化４】

【００４７】
で表される化合物としては、
ジ−ｔｅｒｔ−ブチルシラン、フェニルメチルシラン、ジフェニルシラン、ジメトキシシラン、ジエトキシシラン、ジプロポキシシラン、ジイソプロポキシシラン、ジブトキシシラン、ジフェノキシシラン、メチルフェニルシラン、トリメチルシロキシメチルシランなどが挙げられる。
【００４８】
さらに、式（Ｓ−３）
【００４９】
【化５】

【００５０】
で表される化合物としては、
メチルシラン、エチルシラン、プロピルシラン、イソプロピルシラン、ブチルシラン、フェニルシラン、ヘキシルシラン、メトキシシラン、エトキシシラン、プロポキシシラン、イソプロポキシシラン、ブトキシシラン、フェノキシシラン、ｎ−オクタデシルシラン、ｎ−オクチルシランなどが挙げられる。
【００５１】
さらに、式（Ｓ−４）
【００５２】
【化６】

【００５３】
で表される化合物としては、
１，３−ビス（トリメチルシロキシ）−１，３−ジメチルジシロキサン、ビス（トリメチルシロキシ）メチルシラン、ビス（トリメチルシロキシ）エチルシラン、１，１，１，３，５，５，５−ヘプタメチルトリシロキサン、１，１，１，３，５，７，７，７−オクタメチルテトラシロキサン、トリス（トリメトキシシロキシ）シラン、１，１，３，３−テトラメチルジシロキサン、１，１，３，３−テトライソプロピルジシロキサン、１，１，３，３，５，５−ヘキサメチルトリシロキサン、１，１，３，３，５，５，７，７−オクタメチルテトラシロキサン、１，３−ビス（トリメチルシロキシ）−１，３−ジメチルジシロキサン、メチルＨシロキサン−ジメチルシロキサンコポリマー、Ｈ末端ポリジメチルシロキサン、ポリメチルＨシロキサン、ポリエチルＨシロキサン、ポリフェニル（ジメチルＨシロキシ）シロキサンＨ末端、メチルＨシロキサン−フェニルメチルシロキサンコポリマー、メチルＨシロキサン−オクチルメチルシロキサンコポリマーなどが挙げられる。
【００５４】
さらに、式（Ｓ−５）
【００５５】
【化７】

【００５６】
で表される化合物としては、
１，３，５−トリメチルシクロトリシロキサン、１，３，５，７−テトラメチルシクロテトラシロキサン、１，３，５，７，９−ペンタメチルシクロペンタシラン、１，３，５−トリエチルシクロトリシロキサン、１，３，５，７−テトラエチルシクロテトラシロキサン、１，３，５，７，９−ペンタエチルシクロペンタシラン、１，３，５−トリフェニルシクロトリシロキサン、１，３，５，７−テトラフェニルシクロテトラシロキサン、１，３，５，７，９−ペンタフェニルシクロペンタシランなどが挙げられる。
【００５７】
さらに、式（Ｓ−６）
【００５８】
【化８】

【００５９】
で表される化合物が挙げられる。
【００６０】
以上の式で表される化合物のほかに、RSiO_1.5で表されるポリセルセスキオキサンまたはＴレジン（例えば、チッソ社製、ＳＳＴ−Ｒ８Ｃ５１）を用いることも可能である。
【００６１】
上記ヒドロシラン化合物の付加率は、共役ジエン系重合体および／またはその水添物の炭素−炭素不飽和二重結合単位に対し、０．０００１〜１００％、好ましくは０．０１〜５０％で、さらに改良効果とコストのバランスから好ましいのは０．０１〜２０％である。０．０００１％未満では、耐衝撃性、接着性、摺動性などの改質効果が殆ど現れない。耐候性、耐熱性および耐オゾン性を改良するためには、ヒドロシリレーションおよび水添により、共役ジエン系重合体の炭素−炭素不飽和二重結合の割合を少なくすることが好ましい。
【００６２】
上記の製造方法で変性共役ジエン系重合体溶液からは、触媒の残渣を除去することが好ましい。触媒を除去する方法としては、反応後の溶液をシリカ、シリカゲル、アルミナ、イオン交換樹脂などで処理するか、変性共役ジエン重合体を製造する際に使用した触媒の種類に応じｐＨをコントロールした水溶液で洗浄する方法などがある。また、反応終了後、残触媒と反応する化合物を添加しても良い。このときの溶液中のポリマー濃度は５０重量％以下にしておくことが好ましい。５０重量％を超える高濃度のポリマーからの除去も可能であるが、多量の触媒を取り除くのに時間化がかかるため好ましくない。物性面の点から触媒残渣の除去が必要ない場合は実施しなくとも良い。
【００６３】
変性共役ジエン系重合体の単離は、例えば重合体溶液に、アセトンまたはアルコールなどを加えて沈殿させる方法、重合体溶液を熱湯中に撹拌下、投入し溶媒を蒸留除去する方法などで行うことができる。
【００６４】
以上の本発明の変性共役ジエン系重合体には、慣用の補助添加成分、例えば可塑剤、酸化防止剤、熱安定剤、光劣化防止剤などの安定剤、滑剤、難燃剤、帯電防止剤、造核剤、金属塩、有機金属化合物、金属不活性剤、防菌・防黴剤、分散剤、軟化剤、架橋剤、共架橋剤、着色剤、熱酸発生剤、光酸発生剤、加硫剤、加硫助剤、発泡剤、発泡助剤などを添加することができる。
【００６５】
上記可塑剤としてはポリマーの分子間に浸透しポリマーの分子間力を弱め、ポリマーの分子運動をし易くするものであればよく、それらの具体例としては、例えばフタル酸ジブチル、フタル酸ジヘプチル、フタル酸２エチルヘキシル、フタル酸ジイソノニル、フタル酸ジイソデシルなどのフタル酸エステル系可塑剤、アジピン酸ジ２エチルヘキシル、アジピン酸ジイソノニル、アジピン酸ジイソデシル、アゼライン酸ジ２エチルヘキシルなどの脂肪族二塩基酸エステル系可塑剤、ポリエステル系可塑剤、エポキシ化大豆油、エポキシ化アマニ油、エポキシ化ステアリン酸オクチル、エポキシ化脂肪酸ブチル、エポキシ化アマニ油脂肪酸ブチルなどのエポキシ系可塑剤、トリクレジルホスフェート、トリフェニルホスフェート、トリ２エチルヘキシルホスフェート、トリキシレニルホスフェート、トリエチルホスフェートなどのリン酸エステル系可塑剤、トリ２エチルヘキシルトリメリレート、トリイソデシルトリメリテートなどのトリメリット酸エステル系可塑剤などが挙げられる。これらは、１種あるいは２種以上を混合して使用することができる。
【００６６】
上記安定剤の具体例としては、例えば、２，６−ジ−ｔ−ブチル−４−メチルフェノール、ｎ−オクタデシル−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート、トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）イソシアネレート、４，４’−ブチリデンビス−（３−メチル−６−ｔ−ブチルフェノール）、トリエチレングリコール−ビス［３−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオネート］などのフェノール系酸化防止剤、ジラウリル−３，３’−チオジプロピオネート、ジミリスチル−３，３’−チオジプロピオネート、ジステアリル−３，３’−チオジプロピオネート、ペンタエリスリトールテトラキス（３−ラウリルチオプロピオネート）などのイオウ系酸化防止剤、トリスノニルフェニルホスファイト、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト、ジステアリルペンタエリスリトールジホスファイト、ビス（２，４−ジ−ｔ−ブチルフェニル）ペンタエリスリトールホスファイト、ビス（２，６−ジ−ｔ−ブチル−４−メチルフェニル）ペンタエリスリトールホスファイト、２，２−メチレンビス（４，６−ジ−ｔ−ブチルフェニル）オクチルホスファイト、テトラキス（２，４−ジ−ｔ−ブチルフェニル）−４，４’−ビフェニレン―ジ―ホスホナイトなどのリン系酸化防止剤、ラクトン系酸化防止剤、ヒドロキシアミン系酸化防止剤などが挙げられる。
また、上記熱安定剤の具体例としては、Ｍｇ、Ｃａ、Ｂａ、Ｚｎ、Ｐｂなどの金属イオンと２−エチルヘキサン酸、ラウリン酸、ステアリン酸、オレイン酸、リシノール酸、イソデカン酸、ネオ酸などの脂肪酸との金属塩、ジメチルスズビス−２−エチルヘキシルチオグリコール、モノメチルスズテアロキシエチルメルカプタイド、ジメチルスズテアロキシエチルメルカプタイド、ジブチルスズマレエート、ジブチルスズビスブチルマレエート、ジブチルスズジラウレート、ジメチルスズビス−２−エチルヘキシルチオグリコレート、ジブチルスズβ−メルカプトプロピオネートなどの有機スズ系安定剤などの熱安定化剤などが挙げられる。
上記光劣化防止剤の具体例としては、例えば、２−（２’−ヒドロキシ−５’−メチルフェニル）ベンゾトリアゾール、２−［２’−ヒドロキシ−３’，５’−ビス（α，α−ジメチルベンジル）フェニル］ベンゾトリアゾール、２−（２’−ヒドロキシ−３’，５’−ジ−ｔ−ブチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−３’，５’−ジ−ｔ−ブチルフェニル）−５−クロロベンゾトリアゾール、２−（２’−ヒドロキシ−３’，５’−ジ−ｔ−アミル）ベンゾトリアゾール、２−（２’−ヒドロキシ−５’−ｔ−オクチルフェニル）ベンゾトリアゾールなどのベンゾトリアゾール系光安定剤、２，４−ジヒドロキシベンゾフェノン、２−ヒドロキシ−４−メトキシベンゾフェノン、２−ヒドロキシ−４−メトキシベンゾフェノン−５−スルフォニックアシッド、２−ヒドロキシ−４−ｎ−オクチルベンゾフェノン、２−ヒドロキシ−４−ｎ−ドデシロキシベンゾフェノンなどのベンゾフェノン系光安定剤、フェニルサリシレート、４−ｔ−ブチルフェニルサリシレートなどのサリシレート系光安定剤、エチル−２−シアノ−３，３−ジフェニルアクリレートなどのシアノアクリレート系光安定剤、２−エトキシ−２’−エチルオキザリックアシッドビスアニリドなどのオキサゾリックアシッドアニリド系光安定剤、ビス−（２，２，６，６−テトラメチル−４−ピペリジエニル）セバケート、ビス−（Ｎ−メチル−２，２，６，６−テトラメチル−４−ピペリジエニル）セバケート、ビス−（１，２，２，６，６−ペンタメチル−４−ピペリジエニル）−２−（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）−２−ｎ−ブチルマロネート、テトラキス（２，２，６，６−テトラメチル−４−ピペリジル）−１，２，３，４−ブタンテトラカルボキシレート、テトラキス（１，２，２，６，６−ペンタメチル−４−ピペリジル）−１，２，３，４−ブタンテトラカルボキシレートなどのヒンダードアミン系光安定剤などが挙げられる。
これらの安定剤は、１種あるいは２種以上を混合して使用することができる。
これらの添加量は、ポリマー成分に対し０．０１〜１重量％であることが好ましく、さらに好ましくは０．０１〜０．５重量％である。
【００６７】
上記滑剤の具体例としては、例えば、流動パラフィン、パラフィンワックス、ポリエチレンワックスなどの炭化水素系滑剤、ステアリルアルコール、ステアリン酸、１２−ヒドロキシステアリン酸などの脂肪酸系および脂肪族アルコール系滑剤、ステアリン酸アミド、オレイン酸アミド、エルカ酸アミド、メチレンビスステアリン酸アミド、エチレンビスステアリン酸アミドなどの脂肪族アマイド系滑剤、ステアリン酸カルシウム、ステアリン酸亜鉛、ステアリン酸マグネシウム、ステアリン酸鉛などの金属石鹸系滑剤、硬化油、ステアリン酸モノグリセライド、ステアリン酸ブチル、ペンタエリスリトールテトラステアレート、ステアリルステアレートなどのエステル系滑剤などを挙げることができる。
これらは、１種あるいは２種以上を混合して使用することができる。
【００６８】
上記難燃剤の具体例としては、例えば、テトラブロモビスフェノールＡ、デカブロモジフェニルエーテル、ヘキサブロモシクロデカンなどのハロゲン系難燃剤、塩素化ポリエチレン、塩素化パラフィン、パークロロシクロペンタデカンなどの塩素系難燃剤、トリクレジルホスフェート、トリフェニルホスフェート、トリスクロロエチルホスフェート、ポリリン酸アンモン、赤燐などのリン系難燃剤、水酸化マグネシウム、水酸化アルミニウム、水酸化ジルコニウム、水酸化カルシウム、水酸化バリウム、塩基性炭酸マグネシウム、三酸化アンチモン、ホウ酸亜鉛、酸化スズ、五酸化リン、ジルコニウム、窒素化グアニジン、ドロマイト、ハイドロタルサイト、酸化錫などが挙げられる。これらのうち、水酸化マグネシウム、水酸化アルミニウム、水酸化カルシウムが有用であると共に工業的に入手し易く好ましい。水酸化マグネシウムは、難燃効果が高く特に好ましい。
また、上記無機難燃剤を用いる場合、難燃効果を高めるために、シリコーン化合物、石英硝子などや、難燃助剤として水ガラス、フリット、ドリップ防止のための窒化珪素短繊維などを併用することもできる。
これらは、１種あるいは２種以上を混合して使用することができる。
【００６９】
上記金属塩、有機金属化合物の具体例としては、例えば、シス−ビス（アセトニトリル）ジクロロ白金（II）、テトラシアノ白金(II)酸カリウム、ヘキサシアノ白金（IV）酸カリウム、シアン化白金(II)、ヘキサクロロ白金(IV)酸六水和物、塩化第二白金酸カリウム、酸化第二白金（一水和物）、シス−ビス（ベンゾニトリル）ジクロロ白金（II）、白金ヘキサフルオロペンタジオネート、白金２，４−ペンタジオネート、パラジウム−炭酸カルシウム、ビス（ベンゾニトリル）ジクロロパラジウム(II)、ビス（アセトニトリル）ジクロロパラジウム(II)、テトラシアノパラジウム(II)酸カリウム三水和物、テトラフルオロほう酸テトラキス（アセトニトリル）パラジウム(II)、ビス（ベンゾニトリル）パラジウム(II)塩化物、パラジウムヘキサフルオロペンタンジオネート、パラジウム２，４−ペンタンジオネート、臭化フェニルマグネシウム、臭化エチルマグネシウム、塩化シクロヘキシルマグネシウム、塩化フェニルマグネシウム、臭化アリルマグネシウム、塩化アリルマグネシウム、ヨウ化メチルマグネシウム、臭化４−フルオロフェニルマグネシウム、ステアリン酸マグネシウム、マグネシウム２，４−ペンタンジオネート、マグネシウムヘキサフルオロペンタンジオネート、マグネシウムトリフルオロペンタンジオネート、塩化マンガン（II）四水和物、酸化マンガン（IV）、過マンガン酸カリ、マンガン酸バリウム、硫酸マンガン(II)一水和物、マンガン(II)アセチルアセトナート、シクロペンタジエニルトリカルボニルマンガン、マンガン(II)ジフルオリド、マンガン(II)２，４−ペンタンジオネート、ヘキサシアノコバルト(II)鉄(II)酸カリウム、塩化コバルト（六水和物）、硝酸コバルト(II)六水和物、ヘキサアンミンコバルト(III)クロリド、ジカルボニルシクロペンタジエニルコバルト、コバルト(III)セパルクレートトリクロリド、ジクロロビス（トリフェニルホスフィン）コバルト(II)、ビス（サリチルアルデヒド）コバルト(II)、コバルト(II)フタロシアニン、臭化コバルト(II)水和物、ホウ化コバルト、ビス（シクロペンタジエニル）コバルト、ヨウ化コバルト(II)、炭酸コバルト(II)水和物、酢酸コバルト(II)、過塩素酸コバルト(II)六水和物、ナフテン酸コバルト、テトラフルオロほう酸ビス（１，５−シクロオクタジエン）ロジウム(Ｉ)水和物、（ビシクロ［２．２．１］ヘプタ−２，５−ジエン）［１，４−ビス（ジフェニルホスフィノ）ブタン］ロジウム（Ｉ）テトラフルオロ硼酸塩、テトラフルオロほう酸［１，４−ビス（ジフェニルホスフィノ）ブタン］（１，５−シクロオクタジエン）ロジウム（Ｉ）、（１，５−シクロオクタジエン）ロジウム(Ｉ)テトラフルオロボレート、ヘキサシアノルテニウム（II）酸カリウム水和物、ルテニウム(III)２，４−ペンタンジオネート、五塩化モリブデン、モリブデン酸アンモニウム、トリス（アセトニトリル）トリカルボニルモリブデン、トリカルボニルトリアミンモリブデン、ベンゼンクロムトリカルボニル、クロロクロム酸ピリジニウム、塩化クロム(III)、重クロム酸カリ、クロム(III)アセチルアセトナート、二クロム酸ビス（テトラブチルアンモニウム）、クロムヘキサカルボニル、トリカルボニル（メチルベンゾエート）クロム、トリカルボニル（シクロヘプタトリエン）クロム、ホウ化クロム、ヘキサシアノクロム酸(III)カリウム、リチウムビス（トリメチルシリル）アミド、リチウムジフェニルホスフィド、リチウム２，４−ペンタンジオネートなどが挙げられる。
これらは、１種あるいは２種以上を混合して使用することができる。
【００７０】
上記熱酸発生剤、光酸発生剤を添加し反応させることで、ポリマー鎖が架橋する場合は適度に架橋させることも好ましい。熱酸発生剤は、通常、５０〜４５０℃、好ましくは２００〜３５０℃に加熱することにより酸を発生する化合物であり、スルホニウム塩、ベンゾチアゾリウム塩、アンモニウム塩、ホスホニウム塩などのオニウム塩が用いられる。
また、光酸発生剤は、通常、１〜１００ｍＪ、好ましくは１０〜５０ｍＪの紫外光照射により酸を発生する化合物である。これら酸発生剤の添加量は、架橋性ポリマー成分に対し０．０１〜３０重量％であることが好ましく、より好ましくは０．０１〜１０重量％である。
これらは、１種あるいは２種以上を混合して使用することができる。
【００７１】
また、本発明の変性共役ジエン系重合体は、溶液中または押し出し機などの混練り機中、変性共役ジエン系重合体と反応し得る化合物と接触させてもよい。
【００７２】
本発明の変性共役ジエン系重合体は、各種重合体などと配合されることにより、優れた物性を有する変性共役ジエン系重合体組成物を与えることができる。
本発明の変性共役ジエン系重合体組成物は、上記変性共役ジエン系重合体（以下、「成分(I)」という）と、非極性重合体（以下、「成分（II−１）」という）、極性重合体（以下、「成分（II−２）」という）および充填剤（以下、「成分(III)」という）から選ばれる少なくとも１種と、を含有する。上記非極性重合体および極性重合体は、樹脂でもゴムでもよい。
【００７３】
上記成分（II−１）（非極性重合体）としては、ポリオレフィン系重合体および芳香族ビニル系重合体から選ばれる少なくとも１種が好ましい。上記ポリオレフィン系重合体としては、超低密度ポリエチレン（ＶＬＤＰＥ）、線状低密度ポリエチレン（ＬＬＤＰＥ）、低密度ポリエチレン（ＬＤＰＥ）、中密度ポリエチレン（ＭＤＰＥ）、高密度ポリエチレン（ＨＤＰＥ）などのポリエチレン樹脂、ランダムタイプまたはブロックタイプまたはホモタイプなどのポリプロピレン樹脂（ＰＰ）、ポリブタジエン（ＰＢＤ）、ポリ１−ブテン（ＰＢ）、ポリメチルペンテン（ＰＭＰ）、エチレン・プロピレン共重合体（ＥＰＭ）、エチレン・１−ブテン共重合体（ＥＢＭ）、エチレン・ヘキセン共重合体（ＥＨＭ）、エチレン・オクテン共重合体（ＥＯＭ）、エチレン・プロピレン・１−ブテン共重合体（ＥＰＢＭ）、エチレン・プロピレン・ジエン共重合体（ＥＰＤＭ）、エチレン・１−ブテン・ジエン共重合体（ＥＢＤＭ）、プロピレン・１−ブテン共重合体（ＰＢＭ）などのプロピレンと炭素数４〜２０のα−オレフィンとの共重合体などが挙げられる。これらは１種単独であるいは２種以上を組み合わせて用いることができる。
【００７４】
また、上記芳香族ビニル系重合体としては、一般ポリスチレン（ＧＰＰＳ）、耐衝撃性ポリスチレン（ＨＩＰＳ）、アイソタクチックポリスチレン（ｉＰＳ）、シンジオタクチックポリスチレン（ｓＰＳ）、ポリα−メチルスチレン（ＰαＭＳ）などが挙げられる。これらは、１種単独であるいは２種以上を組み合わせて用いることができる。
【００７５】
また、上記成分（II−２）（極性重合体）としては、カルボキシル基（酸無水物、金属塩となっているカルボキシル基も含む。）、ヒドロキシル基、ハロゲン基、エポキシ基、オキサゾリン基、スルホン酸基、イソシアネート基、チオ−ル基、エステル結合、カーボネート結合、アミド結合、エーテル結合から選ばれる少なくとも１種を有する重合体が好ましい。これらを有する重合体としては、エチレン・アクリル酸共重合体（ＥＡＡ）、エチレン・メタクリル酸共重合体（ＥＭＡ）、エチレン・メタクリル酸グリシジル共重合体（ＥＧＭＡ）、エチレン・無水マレイン酸・アクリル酸共重合体、（メタ）アクリル酸含有量７〜１５ｍｏｌ％であるエチレンと（メタ）アクリル酸共重合体で、かつＮａ、Ｚｎ、Ｍｇなどの金属イオンにより中和度が２０％以上であるアイオノマー（ＩＯ）、ポリ酢酸ビニル（ＰＶＡｃ）や、ナイロン４，６（ＰＡ４６）、ナイロン６（ＰＡ６）、ナイロン６，６（ＰＡ６６）、ナイロン６，１０（ＰＡ６１０）、ナイロン６，１２（ＰＡ６１２）、ナイロン１２（ＰＡ１２）、ナイロン６，Ｔ（ＰＡ６Ｔ）、ナイロン９，Ｔ（ＰＡ９Ｔ）、強化ポリアミド、ヘキサメチレンジアミンとテレフタル酸からつくられた変性ポリアミドなどのポリアミド樹脂（ＰＡ）、ポリエチレンテレフタレート（ＰＥＴ）、ポリブチレンテレフタレート（ＰＢＴ）、ポリエチレンナフタレート（ＰＥＮ）、ポリラクトンなどのポリエステル樹脂、液晶性ポリエステル（ＬＣＰ）、ポリ−２，２−ビス（ヒドロキシフェニル）プロパンカーボネートなどのポリカーボネート（ＰＣ）、エチレン・アクリル酸エチル共重合体（ＥＥＡ）、エチレン・アクリル酸メチル共重合体（ＥＭＡ）、エチレン・メタクリル酸ヒドロキシエチル共重合体（ＨＥＭＡ）、エチレン・メタクリル酸２−ヒドロキシプロピル共重合体、エチレン・メタクリル酸アミノアルキル共重合体、エチレン・メタクリル酸ブチル共重合体、ポリメタクリル酸メチル（ＰＭＭＡ）、ポリメタクリル酸エチル（ＰＥＭＡ）、メタクリル−スチレン共重合体（ＭＳ Ｒｅｓｉｎ）などのアクリル系重合体、ポリアセタール（ＰＯＭ）、ＡＢＳ樹脂、ＡＥＳ樹脂、ＡＳＡ樹脂、ジアリルフタレート樹脂（ＤＡＰ）、ＥＶＡ樹脂、ＥＥＡ樹脂、フェノール樹脂（ＰＦ）、ポリビニルアルコール（ＰＶＡ）、エチレン−ビニルアルコール共重合体（ＥＶＯＨ）、ポリアリレート（ＰＡＲ）、ノルボルネン樹脂、ポリ（２，６−ジメチル−１，４−フェニレンエーテル）、ポリ（２−メチル−６−エチル−１，４−フェニレンエーテル）、ポリ（２−メチル−６−フェニル−１，４−フェニレンエーテル）、ポリ（２，６−ジクロロ−１，４−フェニレンエーテル）などのポリフェニレンエーテル（ＰＰＥ）、変性ポリフェニレンエーテル（変性ＰＰＥ）、ポリエチレンオキサイド、ポリフェニレンスルフィド（ＰＰＳ）、ポリスルホン（ＰＳＵ）、ポリエーテルスルホン（ＰＥＳ）、熱可塑性ポリエステルエラストマー、熱可塑性ポリウレタンエラストマー、熱可塑性ポリアミドエラストマー、α，β−不飽和ニトリル−アクリル酸エステル−不飽和ジエン共重合ゴム、ウレタンゴム、塩素化ブチルゴム、臭素化ブチルゴム、アクリルゴム、エチレン・アクリルゴム、エピクロルヒドリンゴム、エピクロルヒドリン・エチレンオキシドゴム、クロロプレンゴム、クロロスルフォン化ポリエチレン、塩素化ポリエチレン、塩素化ポリプロピレン、オキサゾリン変性ポリスチレン、オキサゾリン変性スチレン・アクリロニトリル共重合体などが挙げられる。これらは１、種単独であるいは２種以上を組み合わせて用いることができる。
【００７６】
上記成分（II−１）および（II−２）として例示した重合体のうち、上記成分(Ｉ)の分子鎖構造に起因して、エチレンを構造単位として含有するポリエチレン樹脂や、プロピレンを構造単位として含有するポリプロピレン樹脂および芳香族ビニルを構造単位とするポリスチレン系樹脂、更にはポリエチレンテレフタレートなどのポリエステルが物性改良効果に優れ、使用用途を広範なものとすることができるので特に好ましい。また、上記成分（Ｉ）中に極性基を有する際はその極性基と反応する官能基を揺する化合物を添加することも好ましい。
【００７７】
本発明の変性共役ジエン系重合体組成物が、上記成分（Ｉ）および上記成分（II−１）を含有する場合、あるいは上記成分（Ｉ）および上記成分（II−２）を含有する場合、いずれも以下のような含有割合とすることができる。すなわち、上記成分（II−１）および上記成分（II−２）を「成分（II）」として表すと、上記成分（Ｉ）および上記成分（II）の合計を１００重量％とした場合、（Ｉ）／（II）は、好ましくは１〜９９重量％／９９〜１重量％、より好ましくは５〜９５重量％／９５〜５重量％、更に好ましくは１０〜９０重量％／９０〜１０重量％、特に好ましくは２０〜８０重量％／８０〜２０重量％である。上記のような含有割合とすることにより、要求される性能を満足することができる。
【００７８】
また、本発明の変性共役ジエン系重合体組成物が上記成分（Ｉ）、上記成分（II−１）および上記成分（II−２）を含有する場合、以下のような含有割合とすることができる。すなわち、上記成分（II−１）および上記成分（II−２）は、（II−１）／（II−２）が好ましくは１〜９９重量％／９９〜１重量％、より好ましくは５〜９５重量％／９５〜５重量％、更に好ましくは１０〜９０重量％／９０〜１０重量％であり、上記成分（Ｉ）の含有量は、上記成分（II−１）および上記成分（II−２）の含有量の少ない方を１００重量％として、好ましくは１〜１００重量％、より好ましくは５〜５０重量％、更に好ましくは１０〜４０重量％である。上記のような含有割合とすることにより、要求される性能を満足することができる。
【００７９】
上記成分(III)は、特に限定しないが、具体例としては、水酸化マグネシウムのほか、水酸化アルミニウム、水酸化ジルコニウム、水酸化カルシウム、水酸化バリウム、塩基性炭酸マグネシウム、ドロマイト、ハイドロタルサイト、酸化錫、酸化チタン、酸化亜鉛、酸化鉄、酸化マグネシウム、アルミナ、硫酸バリウム、硫酸カルシウム、硫酸ナトリウム、亜硫酸カルシウム、ケイ酸カルシウム、炭酸カルシウム、炭酸マグネシウム、リン酸塩化合物、カーボン、ガラスビーズ、ガラスパウダー、アスベスト、マイカ、タルク、シリカ、ゼオライト、カオリン、ケイ砂、ケイ石、石英粉、シラス、金属繊維などの無機繊維、およびチタン酸カリウムウィスカーなどの無機ウィスカーなどが挙げられる。そして、これらのうちの１種または２種以上を用いることができる。また、上記成分(III)の充填剤は、無処理のまま用いてもよいが、各重合体との親和性や界面結合力を高めるなどの目的で、脂肪酸（ステアリン酸、オレイン酸、パルミチン酸など）またはその金属塩、パラフィン、ワックス、ポリエチレンワックスまたはそれらの変性物、有機ボラン、有機チタネート、シランカップリング剤、アルミカップリング剤などで表面処理を施したものを用いることもできる。
【００８０】
本発明の変性共役ジエン系重合体組成物が、▲１▼上記成分（Ｉ）および成分(III)を含有する場合、▲２▼上記成分（Ｉ）、成分（II−１）および成分(III)を含有する場合、▲３▼上記成分（Ｉ）、成分（II−２）および成分(III)を含有する場合、▲４▼上記成分（Ｉ）、成分（II−１）、成分（II−２）および成分(III)を含有する場合、以下のような含有割合とすることができる。すなわち、上記成分(III)（充填剤）の含有量は、上記成分（Ｉ）などの重合体成分の合計を１００重量％とした場合、好ましくは１〜２００重量％、より好ましくは２〜１５０重量％、特に好ましくは５〜１００重量％である。かかる範囲とすることにより、上記成分（Ｉ）、成分（II−１）、および成分（II−２）による効果を阻害することなく、難燃性や強度などの性質を付与することができる。
【００８１】
本発明の変性共役ジエン系重合体組成物の製造には、押出機、加圧ニーダー、バンバリーミキサーなどの従来公知の混練り機、およびそれらを組み合わせた混練り機を使用することができる。混練りするにあたり、各成分を一括混練りしてもよく、また任意の成分を混練りした後、残りの成分を添加し混練りする多段分割混練り法を採用することができる。また、このようにして得られた重合体組成物は射出成形、押出成形、回転成形、プレス成形、中空成形などの公知の方法で成形することが可能である。
【００８２】
本発明の変性共役ジエン系重合体組成物は、上記構成を備えることにより、引張強度、離型性、摺動性、柔軟性などの改質効果に優れた成形品を与える。これらの改質効果は、いずれかもしくは複数でも良い。
【００８３】
【実施例】
以下、実施例を挙げ、本発明を説明するが、本発明の主旨を越えない限り、実施例に限定されるものではない。また、実施例中の各種の測定は下記の方法に拠った。
（１）共重合体のミクロ構造は、赤外吸収スペクトル法（モレロ法）によって求めた。
（２）結合スチレン含量は、赤外吸収スペクトル法により、検量線を作成し求めた。
（３）重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）（ＴＯＳＯＨ社製、ＨＬＣ−８１２０）を用いてポリスチレン換算で求めた。
（４）カップリング効率は、カップリング剤添加前後の分子量変化から求められ、カップリングされた重合体が全重合体のうちどれだけ含まれているかを表わす。
（５）共役ジエン系重合体のヒドロシラン化合物の付加率および水添率は、２７０ＭＨｚの¹Ｈ−ＮＭＲ測定から算出した。
【００８４】
（６）メルトフローレート（ＭＦＲ）は、ＡＳＴＭ Ｄ１２３８に準拠して、２３０℃、荷重２．１６ｋｇで測定し、成形加工性の指標とした。
（７）引張破断強度および伸びは、ＡＳＴＭ Ｄ６３８に従って、２３℃の温度条件下で試験片（Ｔｙｐｅ１）の引張試験を行い測定した。
（８）成形加工性は、試験片作成時の離型性を評価した。
○：金型から容易に剥がせる。
△：力を入れ金型から引き剥がす必要がある。
（９）硬度
ＪＩＳ Ｋ７２１５に従い測定した。
（１０）摺動性は、ＪＩＳ Ｋ６２６４に従いテーバー摩耗試験により評価した。
◎：摩耗量０〜０．３ｍｇ／１，０００回未満
○：摩耗量０．３〜０．６ｍｇ／１，０００回未満
×：摩耗量０．６ｍｇ／１，０００回以上
（１１）耐ブロッキング性は、55mmφ一軸押出機とペレタイザーを用いてペレットを作成した。作成したペレットを６０℃の恒温槽内で荷重３０ｋｇ／ｃｍ²、７２時間後のペレットの固まりかたより、以下のようにランク分けした。
◎：全く固まらない。
○：殆ど固まらず、容易にバラバラになる。
△：やや固まるが、比較的簡単のほぐすことが出来る。
×：固まり、ほぐすのが困難である。
【００８５】
（１）水添触媒の製造
以下の方法により、実施例および比較例で使用する水添触媒（触媒ＡおよびＢ）を製造した。
［水添触媒合成例］
＜製造例１＞触媒Ａ［ビス（η⁵−シクロペンタジエニル）チタニウム（テトラヒドロフルフリルオキシ）クロリド］の合成
撹拌機、滴下漏斗を備えた１Ｌ容量の三つ口フラスコに無水テトラヒドロフラン２００ｍｌ、テトラヒドロフルフリルアルコール０．２ｍｏｌを加えた。装置を乾燥窒素で乾燥し、ｎ−ブチルリチウム／シクロヘキサン溶液（０．２モル）をフラスコ中に１５℃にて滴下した。反応終了後、テトラヒドロフルフリルオキシリチウム溶液を得た。
【００８６】
乾燥窒素で乾燥した撹拌機、滴下漏斗を備えた１Ｌ容量の三つ口フラスコにビス（η⁵−シクロペンタジエニル）チタニウムジクロリド４９．８ｇ（０．２モル）および無水テトラヒドロフラン２５０ｍｌを加えた。先に合成したテトラフルフリルオキシリチウムのテトラヒドロフラン溶液を室温撹拌下にて約１時間で滴下した。
約２時間後、赤褐色液を濾過し、不溶部をジクロロメタンで洗浄後、ろ液および洗浄液を合わせて減圧下にて溶媒を除去することにより、触媒Ａ［ビス（η⁵−シクロペンタジエニル）チタニウム（テトラヒドロフルフリルオキシ）クロライド］（「［クロロビス（２，４−シクロペンタジエニル）チタン（ＩＶ）テトラヒドロフルフリルアルコキシド］」ともいう。）を得た。なお、収率は９５％であった。
【００８７】
＜製造例２＞触媒Ｂ［ビス（η⁵−シクロペンタジエニル）チタニウム（フルフリルオキシ）クロライド］の合成
撹拌機、滴下漏斗を備えた１Ｌ容量の三つ口フラスコに無水テトラヒドロフラン２００ｍｌ、フルフリルアルコール０．２ｍｏｌを加えた。装置を乾燥窒素で乾燥し、ｎ−ブチルリチウム／シクロヘキサン溶液（０．２モル）をフラスコ中に１５℃にて滴下した。反応終了後、フルフリルオキシリチウム溶液を得た。
【００８８】
乾燥窒素で乾燥した撹拌機、滴下漏斗を備えた１Ｌ容量の三つ口フラスコにビス（η⁵−シクロペンタジエニル）チタニウムジクロリド４９．８ｇ（０．２モル）および無水テトラヒドロフラン２５０ｍｌを加えた。先に合成したフルフリルオキシリチウムのテトラヒドロフラン溶液を室温撹拌下にて約１時間で滴下した。約２時間後、赤褐色液を濾過し、不溶部をジクロロメタンで洗浄後、ろ液および洗浄液を合わせて減圧下にて溶媒を除去することにより、触媒Ｂ［ビス（η⁵−シクロペンタジエニル）チタニウム（フルフリルオキシ）クロライド］（「［クロロビス（２，４−シクロペンタジエニル）チタン（ＩＶ）フルフリルアルコキシド］」ともいう。）を得た。なお、収率は９７％であった。
【００８９】
（２）変性共役ジエン系重合体の製造
以下に記載の方法により、変性共役ジエン系重合体を製造した。なお、スチレンモノマーからなるブロックをＳ、ブタジエンモノマーからなり、かつ（Ｃ）ブロックの特徴を有するブロックをＣ、ブタジエンモノマーからなり、かつ（Ｄ）ブロックの特徴を有するブロックをＢ、スチレンおよびブタジエンからなり、かつ（Ｅ）ブロックの特徴を有するブロックをＳＢおよびメチルメタクリレートからなり（Ｆ）ブロックの特徴を有するブロックをＭと略す。また、変性共役ジエン系重合体の各種性質の測定は下記の方法に拠った。その結果を以下の表１に示す。
【００９０】
［共役ジエン化合物系重合体の製造例］
＜製造例３＞ＣＢＣ共重合体の製造（ａ−１）
窒素置換された、内容積１０リットルの反応容器に、シクロヘキサン５，０００ｇ、１，３ーブタジエン３００ｇ、テトラヒドロフラン０．２５ｇ、ｎ−ブチルリチウム０．７７ｇを加え、重合温度７０℃にて重合させた。反応完結後、ポリマー溶液の一部を取り出し、ミクロ構造を分析したところ、１，２−結合含量が１３重量％であるポリブタジエンであった。引き続き、反応溶液の温度を２０℃としてテトラヒドロフラン７５ｇ、ブタジエン７００ｇを加え、断熱重合させた。３０分間反応後、メチルジクロロシラン０．５５ｇを添加しさらに３０分間反応させた。一部取り出したポリマーを分析したところ、中間ブタジエンブロックの１，２−結合含量は８０重量％であり、ＧＰＣで測定した重量平均分子量は約３０万でおよびカップリング率は８３％であった。
【００９１】
＜製造例４＞ランダムＳＢ共重合体の製造（ａ−２）
窒素置換された、内容積１０リットルの反応容器に、シクロヘキサン５，０００ｇ、１，３ーブタジエン７００ｇ、スチレン３００ｇ、テトラヒドロフラン２０ｇ、ｎ−ブチルリチウム０．６５ｇを加え、重合開始温度４０℃にて断熱重合した。３０分後、系内に水素を導入しポリマーリビングを失活させた。一部取り出したポリマーを分析したところ、１，２−結合含量が４７重量％、スチレン含量は３０．０重量％、ＧＰＣで測定した重量平均分子量は約１６万であった。
【００９２】
＜製造例５＞ＳＢＳ共重合体の製造（ａ−３）
窒素置換された、内容積１０リットルの反応容器に、シクロヘキサン５，０００ｇ、スチレン７５ｇ、テトラヒドロフラン１４０ｇ、ｎ−ブチルリチウム０．９ｇを加え重合開始温度５０℃にて重合し反応完結後、温度を１０℃として１，３−ブタジエン８５０ｇを添加し断熱重合した。３０分後、スチレン７５ｇを添加し、さらに重合をさせた。３０分後、系内に水素を導入しポリマーリビングを失活させた。一部取り出したポリマーを分析したところ、１，２−ビニル結合を７８重量％含有し、スチレン含量は１４．８重量％、ＧＰＣで測定した重量平均分子量は約１３万であった。
【００９３】
＜製造例６＞Ｓ−Ｂ−Ｃ共重合体の製造（ａ―４）
窒素置換された、内容積１０リットルの反応容器に、シクロヘキサン５，０００ｇ、１，３−ブタジエン３００ｇ、テトラヒドロフラン０．２５ｇ、ｎ−ブチルリチウム０．９ｇを加え重合開始温度７０℃にて重合した。反応完結後、ポリマー溶液の一部を取り出し、ミクロ構造を分析したところ、１．２−結合含量が１３％であるポリブタジエンであった。次に、この反応溶液の温度を３０℃としてテトラヒドロフラン１７．５ｇを添加し、１，３−ブタジエン５００ｇを添加し断熱重合させた。３０分間反応後、スチレン２００ｇを添加し３０分間反応させた。一部取り出したポリマーを分析したところ、ポリマーは中間ブタジエンブロックの１，２−ビニル結合が５０重量％、スチレン含量は１９．９重量％、ＧＰＣで測定した重量平均分子量は約１３万であった。
【００９４】
＜製造例７＞Ｓ−Ｂ−Ｍ共重合体の製造（ａ−５）
窒素置換された、内容積１５リットルの反応容器に、メチルシクロヘキサン５，０００ｇ、テトラヒドロフラン２７．５ｇ、スチレン３００ｇ、ｎ−ブチルリチウム１．０ｇを加え、重合開始温度４０℃にて重合させた。反応完結後、温度を１０℃として１，３−ブタジエン６００ｇを添加し断熱重合した。反応完了後、１，１−ジフェニルエチレン２．５ｇ添加し温度を０℃まで冷却した。反応溶液の一部を取り出し、ミクロ構造を分析したところ、１，２−結合含量が６０重量％、スチレン含量が３３．２％であるＳ−Ｂジブロックポリマーであることがわかった。次いで、テトラヒドロフラン４００ｇ添加し温度をさらに−３０℃まで冷却し、メチルメタクリレート１００ｇを添加し反応させた。反応完結後、メタノールを０．４ｇ添加し重合を終了させた。一部取り出したポリマーを分析したところ、ポリマーのＧＰＣで測定した重量平均分子量は約１０万であった。
【００９５】
＜製造例８＞Ｓ−Ｂ−ポリシロキサン共重合体の製造（ａ−６）
窒素置換された、内容積１５リットルの反応容器に、シクロヘキサン５，０００ｇ、テトラヒドロフラン２７．５ｇ、スチレン１５０ｇ、ｎ−ブチルリチウム０．７ｇを加え重合開始温度５０℃にて重合し反応完結後、温度を２０℃として１，３−ブタジエン６００ｇを添加し断熱重合した。反応完結後、反応溶液の一部を取り出し、ミクロ構造を分析したところ、１，２−結合含量が６０重量％、スチレン含量が２０．０重量％であるＳ−Ｂジブロックポリマーであることがわかった。次いで、反応容器温度を６０℃に保温し、１０重量％トルエン溶液のジメチルシクロトリシロキサン１０ｇを添加し３０分反応させた。その後、ジメチルシクロトリシロキサンの総量が２５０ｇとなるようにジメチルシクロトリシロキサンのトルエン溶液をゆっくり添加した。反応終了後、トリメチルシリルクロライドを添加し反応を停止させた。一部取り出したポリマーを分析したところ、ポリマーのＧＰＣで測定した重量平均分子量は約１５万であった。
【００９６】
次に、変性共役ジエン系重合体の実施例を示す。
［変性共役ジエン化合物系重合体の製造例］
＜実施例１＞水添１，１，３，３，−テトラメチル−１−フェノキシジシラン変性ＣＥＢＣ共重合体の製造（Ｉ−１）
製造例３に示した（ａ−１）のポリマー溶液に、ジメチルアルミニウムクロライド１．１ｇと触媒Ａ ２．０ｇおよびｎ−ＢｕＬｉ ０．６ｇの反応物を添加した後、１，１，３，３，−テトラメチル−１−フェノキシジシラン１０．０ｇを添加し、温度１００℃でヒドロシリレーションを１時間行った。そのまま反応容器内に水素を導入し、水素圧１．０ＭＰａで水添反応およびヒドロシリレーションを１時間行った。得られたポリマーは精製後、（Ｉ―１）に対するヒドロシリル化合物の付加率および水添率をＮＭＲ測定より求めた。１，１，３，３，−テトラメチル−１−フェノキシジシランの付加率はフェノキシ基由来の７ｐｐｍ付近のピークより求めた。結果を表１に示す。
【００９７】
＜実施例２＞水添片末端Ｈポリジメチルシロキサン変性ランダムＳＢ共重合体の製造（Ｉ−２）
製造例４に示した（ａ−２）のポリマー溶液に、ジメチルアルミニウムクロライド０．８ｇと触媒Ｂ １．４ｇおよびｎ−ＢｕＬｉ ０．４ｇの反応物を添加した後、片末端Ｈポリジメチルシロキサン（信越化学工業（株）社製、Ｘ−２１−３１２６）１０．０ｇを添加し、温度１００℃でヒドロシリレーションを１時間行った。そのまま反応容器内に水素を導入し、水素圧１．０ＭＰａで水添反応およびヒドロシリレーションを１時間行った。得られたポリマーは精製後、（Ｉ―２）に対するヒドロシリル化合物の付加率および水添率をＮＭＲ測定より求めた。片末端Ｈポリジメチルシロキサンの付加率はメチルシリル基由来の０ｐｐｍ付近のピークより求めた。結果を表１に示す。
【００９８】
＜実施例３＞水添ジエトキシメチルシラン変性ＳＥＢＳ共重合体の製造（Ｉ―３）
製造例５に示した（ａ−３）のポリマー溶液に、ジメチルアルミニウムクロライド１．０ｇと触媒Ａ １．７ｇおよびｎ−ＢｕＬｉ ０．５ｇの反応物を添加した後、ジエトキシメチルシラン１０．０ｇを添加してすぐに水素を導入し、水素圧１．０ＭＰａ、温度１００℃でヒドロシリレーションおよび水添反応を１時間行った。得られたポリマーは精製後、（Ｉ―３）に対するヒドロシリル化合物の付加率および水添率をＮＭＲ測定より求めた。ジエトキシメチルシランの付加率はメチルシリル基由来の０ｐｐｍ付近のピークより求めた。結果を表１に示す。
【００９９】
＜実施例４＞水添１，３，５−トリメチルシクロトリシロキサン変性ＳＥＢＣ共重合体の製造（Ｉ―４）
製造例６に示した（ａ−４）のポリマー溶液に、ジメチルアルミニウムクロライド１．０ｇと触媒Ａ １．６ｇおよびｎ−ＢｕＬｉ ０．５ｇの反応物を添加した後、１，３，５−トリメチルシクロトリシロキサン１０．０ｇを添加し、温度１００℃でヒドロシリレーションを１時間行った。そのまま反応容器内に水素を導入し、水素圧１．０ＭＰａで水添反応およびヒドロシリレーションを１時間行った。得られたポリマーは精製後、（Ｉ―４）に対するヒドロシリル化合物の付加率および水添率をＮＭＲ測定より求めた。１，３，５−トリメチルシクロトリシロキサンの付加率はメチルシリル基由来の０ｐｐｍ付近のピークより求めた。結果を表１に示す。
【０１００】
＜実施例５＞水添片末端Ｈポリジメチルシロキサン変性ＳＥＢＭ共重合体の製造（Ｉ−５）
製造例７に示した（ａ−５）のポリマー溶液に、ジメチルアルミニウムクロライド１．２ｇと（Ｉｎｄ）ＲｕＣｌ（ＰＰｈ₃）₃触媒４．９ｇおよびｎ−ＢｕＬｉ ０．６ｇの反応物を添加した後、片末端Ｈポリジメチルシロキサン（信越化学工業（株）社製、Ｘ−２１−３１２６）１０．０ｇを添加し、温度１００℃でヒドロシリレーションを１時間行った。そのまま反応容器内に水素を導入し、水素圧２．０ＭＰａで水添反応およびヒドロシリレーションを２時間行った。得られたポリマーは精製後、（Ｉ―５）に対するヒドロシリル化合物の付加率および水添率をＮＭＲ測定より求めた。片末端Ｈポリジメチルシロキサンの付加率はメチルシリル基由来の０ｐｐｍ付近のピークより求めた。結果を表１に示す。
【０１０１】
＜実施例６＞水添１，１，３，３，−テトラメチル−１−フェノキシジシラン変性Ｓ−ＥＢ−ポリシロキサン共重合体の製造（Ｉ−６）
製造例８に示した（ａ−６）のポリマー溶液に、ジメチルアルミニウムクロライド０．７ｇと触媒Ａ １．２ｇおよびｎ−ＢｕＬｉ ０．４ｇの反応物を添加した後、１，１，３，３，−テトラメチル−１−フェノキシジシラン １０．０ｇを添加し、温度１００℃でヒドロシリレーションを１時間行った。そのまま反応容器内に水素を導入し、水素圧１．０ＭＰａで水添反応およびヒドロシリレーションを１時間行った。得られたポリマーは精製後、（Ｉ―６）に対するヒドロシリル化合物の付加率および水添率をＮＭＲ測定より求めた。１，１，３，３−テトラメチル−１−フェノキシジシランの付加率はフェノキシ基由来の７ｐｐｍ付近のピークより求めた。結果を表１に示す。
【０１０２】
【表１】

【０１０３】
表１から明らかにように炭素−炭素二重結合を有する重合体に対するヒドロシリル化は水添反応と同一触媒で、水添反応と同時平行して、水添反応前または水添反応を開始した後に行うことが可能であった。製造例３〜８と同様の製造法で得られる重合体と比較して、実施例１〜６で得られた重合体は、炭素−炭素二重結合がヒドロシリル化および高度に水素化されているため、耐熱性・耐候性の優れた重合体であった。
【０１０４】
変性共役ジエン系重合体の配合評価するにあたり、比較のため、以下のように未変性の水添重合体を製造した。
【０１０５】
＜比較例１＞ＣＥＢＣ共重合体（ｂ−１）
製造例３と同様に重合体を製造した。得られたポリマーを分析したところ、１，２−結合含量は一段目ブタジエンブロックで１３重量％、中間ブタジエンブロックで８０重量％、重量平均分子量は約３０万で（ａ―１）と同様のポリマーを得た。反応容器内に水素を導入し、水素圧１．０ＭＰａした後、触媒Ａ ０．７ｇ、ｎ−ＢｕＬｉ ０．１ｇ添加して水添反応を１時間行った。得られたポリマーの水添率は９９．０％であった。
【０１０６】
＜比較例２＞水添ランダムＳＢ共重合体の製造（ｂ−２）
製造例４と同様に重合体を製造した。得られたポリマーを分析したところ、１，２−結合含量が４７重量％、スチレン含量２９．９重量％、重量平均分子量約１６万で、（ａ―２）と同様のポリマーを得た。反応容器内に水素を導入し、水素圧１．０ＭＰａした後、触媒Ｂ ０．５ｇ、ｎ−ＢｕＬｉ ０．１ｇ添加して水添反応を１時間行った。得られたポリマーの水添率は９８．８％であった。
【０１０７】
＜比較例３＞ＳＥＢＳ共重合体の製造（ｂ−３）
製造例５と同様に重合体を製造した。得られたポリマーを分析したところ、１，２−結合含量は７８重量％、スチレン含量は１５．０重量％、重量平均分子量は約１３万で、（ａ―３）と同様のポリマーを得た。反応容器内に水素を導入し、水素圧１．０ＭＰａした後、触媒Ａ ０．３ｇ、ｎ−ＢｕＬｉ ０．１ｇ添加して水添反応を１時間行った。得られたポリマーの水添率は９９．０％であった。
【０１０８】
＜比較例４＞ＳＥＢＣ共重合体の製造（ｂ−４）
製造例６と同様に重合体を製造した。得られたポリマーを分析したところ、１，２−結合含量は一段目ブタジエンブロックで１３重量％、中間ブタジエンブロックで５０重量％、スチレン含量１９．９重量％、重量平均分子量は約１３万で（ａ―４）と同様のポリマーを得た。反応容器内に水素を導入し、水素圧１．０ＭＰａした後、触媒Ａ ０．５ｇ、ｎ−ＢｕＬｉ ０．１ｇ添加して水添反応を１時間行った。得られたポリマーの水添率は９９．３％であった。
【０１０９】
＜比較例５＞ＳＥＢＭ共重合体の製造（ｂ−５）
製造例７と同様に重合体を製造した。得られたポリマーを分析したところ、１，２−結合含量は６０重量％、スチレン含量３０．０重量％、重量平均分子量は約１０万で、（ａ―５）と同様のポリマーを得た。反応容器内に水素を導入し、水素圧２．０ＭＰａした後、（Ｉｎｄ）ＲｕＣｌ（ＰＰｈ₃）₃触媒１．２ｇ、ｎ−ＢｕＬｉ０．１ｇ添加して水添反応を２時間行った。得られたポリマーの水添率は９７．３％であった。
【０１１０】
＜比較例６＞ＳＥＢ−ポリシロキサン共重合体の製造（ｂ−６）
製造例８と同様に重合体を製造した。得られたポリマーを分析したところ、１，２−結合含量は６０重量％、スチレン含量１５．１重量％、重量平均分子量は約１５万で、（ａ―６）と同様のポリマーを得た。反応容器内に水素を導入し、水素圧１．０ＭＰａした後、触媒Ａ ０．５ｇ、ｎ−ＢｕＬｉ ０．１ｇ添加して水添反応を１時間行った。得られたポリマーの水添率は９８．９％であった。
【０１１１】
実施例２および実施例５で作成した（Ｉ−２）および（Ｉ−５）、また比較例２および比較例５で作成した（ｂ−２）および（ｂ−５）を、55mmφ一軸押出機とペレタイザーを用いてペレットを作成した。作成したペレットを６０℃の恒温槽内で荷重３０ｋｇ／ｃｍ²、７２時間後のペレットの固まりかたの結果を以下に示す。
【０１１２】
【表２】

【０１１３】
表２に示すように、片末端Ｈポリジメチルシロキサンを用いて変性した（Ｉ−２）及び（Ｉ−５）は、未変性のポリマーと比較して耐ブロッキング性が改良されている。
【０１１４】
［物性評価］
上記方法により得られた水添変性共役ジエン系重合体を用いて、表３に示す配合処方で混合した。成分（II−１）としてポリプロピレン［チッソ製Ｋ８０１７］、成分(III)として水酸化マグネシウム［協和化学キスマ］を用いた。表３に示す配合物を２２０℃に温度調整した単軸押出機を用いて混合・ペレット化し、射出成形により物性評価用の試験片を作成した。物性評価の結果を表３に示す。比較例として表３に示す配合処方で混合し、同様に試験片を作成した。表３の結果から本発明の樹脂組成物、実施例７〜９は、比較例７〜９に比べて特に破断強度が優れ物性のバランスの取れた組成物が得られることが分かる。
【０１１５】
【表３】

【０１１６】
上記方法により得られた水添変性共役ジエン系重合体を用いて、表４に示す配合処方で混合した。成分（II−１）としてポリプロピレン［チッソ社製、Ｋ８０１７］を用いた。表４に示す配合物を２２０℃に温度調整した単軸押出機を用いて混合・ペレット化し、射出成形により物性評価用の試験片を作成した。物性評価の結果を同じく表４に示す。比較例として同じく表４に示す配合処方で混合し、同様に試験片を作成した。表４の結果から本発明の樹脂組成物である実施例１０および１１は、比較例１０〜１２に比べて、離型性および柔軟性が良好で、特に耐摩耗性の優れる組成物であることがわかる。
【０１１７】
【表４】

【０１１８】
＊）信越化学工業（株）社製、ＫＦ９６Ｈ−１万
なお、本発明では、前記具体的実施例に示すものに限られず、目的、用途に応じて種々変更した実施例とすることができる。
【０１１９】
【発明の効果】
本発明は、炭素−炭素二重結合を有する重合体を、少なくとも１つのケイ素−水素結合を有する化合物で共役ジエン系重合体中の不飽和結合にヒドロシリレーションを行って得られた変性共役ジエン系重合体およびその水添物の製造する方法であり、得られる変性共役ジエン系重合体組成物は、従来、特に加工性、摺動性、引張強度など十分な物性の得られなかった配合において良好な物性バランスを示す優れた組成物を提供することができる。また、官能基を有する重合体を当て得ることが可能であるため、充填剤を高分散させることが可能であり、極性樹脂との相溶性向上も可能である。ヒドロシリレーションにより種々の官能基を有する変性共役ジエン系重合体を製造することが可能であり、それら変性共役ジエン系重合体の組成物は耐熱性、耐候性、耐衝撃性、耐油性、成形加工性、摺動性、耐ブロッキング性、着色性、耐脱色性、低クリープ性、柔軟性、引張強度などの物性の改質において容易に良好な物性を与えることが可能である。従って、これら組成物の利用分野としては、食品包装容器、各種トレー、シート、チューブ、フィルム、繊維、積層物、コーティングやプリント基板の電気・電子部品、コンピュータなどのＯＡ機器や家電の筺体、自動車内外装材、タイヤ、外板部品、精密部品、建材などの各種工業部品が挙げられ、また、これらの利用分野では、本発明の変性共役ジエン系重合体組成物を発泡しても好ましく使用できる。[0001]
BACKGROUND OF THE INVENTION
  The present inventionProcess for producing modified conjugated diene polymerMore specifically, heat resistance, weather resistance, impact resistance, oil resistance, moldability, slidability, blocking resistance, colorability, decoloration resistance, low creep resistance, flexibility, and tensile strength modification Modified Conjugated Diene Polymer Obtaining Excellent Molded ArticleManufacturing methodAbout.
[0002]
[Prior art]
Conventionally, hydrosilylation to carbon-carbon double bonds using transition metal compounds such as platinum and rhodium is known not only in olefin monomers but also in polymers such as high molecular weight polybutadiene ( Non-patent document 1, Patent document 1).
In recent years, hydrosilylation of olefin monomers using a metallocene transition metal compound as a catalyst is also known (Non-Patent Documents 2 to 3).
Various methods for hydrosilylating a polymer having a carbon-carbon double bond using a transition metal catalyst have been reported. Specifically, hydrosilylation of an isobutylene polymer having a carbon-carbon double bond at the molecular end (Patent Document 2), hydrosilylation to hydrogenated polybutadiene and hydrogenated polyisoprene (Patent Document 3), and molecules Hydrosilylation for polybutadiene and polyisoprene having an epoxy group and a double bond in the chain has been reported (Patent Document 4). However, the former has few remaining double bonds and cannot be modified by an arbitrary amount of hydrosilylation, and it has been difficult to obtain the desired property-modifying effect arbitrarily. The latter can be hydrosilylated at a relatively arbitrary value, but is a curable substance, and therefore, it is difficult to impart impact resistance, weather resistance, and flexibility, and applications that can be used are limited.
On the other hand, it is already known that a hydrogenated polymer can be obtained by hydrogenating a polymer having a carbon-carbon double bond using various metal catalysts. Various methods are used for other modification methods of the hydrogenated polymer. For example, after anionic polymerization, a method in which a terminal anion and a polar group are reacted and then hydrogenated, after producing a hydrogenated polymer There is a method of grafting polar groups using peroxide. However, the former can only modify molecular ends, and the effect of improving mechanical properties and the like is low. The latter can add an arbitrary amount of functional groups, but there is a problem of unreacted modifier treatment and polymer molecular cleavage. Therefore, the weather resistance and heat resistance may be reduced.
[0003]
[Non-Patent Document 1]
Appl. Polym. Symp. 26, 73 (1975)
[Patent Document 1]
JP-A-53-119831
[Non-Patent Document 2]
J. et al. Am. Chem. Soc. 113, 8564 (1991)
[Non-Patent Document 3]
Organometallics 11, 1095 (1992)
[Patent Document 2]
JP-A 63-6041
[Patent Document 3]
JP-A-7-165817
[Patent Document 4]
JP-A-9-263607
[0004]
[Problems to be solved by the invention]
  The present invention has a carbon-carbon double bondWhen producing a hydrogenated conjugated diene polymer,By hydrosilylating a hydrosilane compound having at least one hydrogen-silicon bond, excellent modification properties such as tensile strength, releasability, slidability, flexibility, and blocking resistance are excellent.PolymerThere is to get.
[0005]
[Means for Solving the Problems]
  The present invention has a polystyrene equivalent weight average molecular weight of 10,000 to 2,000,000 obtained by (co) polymerizing a conjugated diene compound or a monomer component comprising a conjugated diene compound and another monomer copolymerizable with the conjugated diene compound. To the conjugated diene polymer ofProduction of modified conjugated diene polymer using hydrosilylation and hydrogenation using hydrosilane compound having at least one silicon-hydrogen bond, and hydrosilylation and hydrogenation to the conjugated diene polymer using the same catalyst Regarding the method.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in detail below.
As the conjugated diene polymer having a carbon-carbon double bond used in the present invention, a polymer having a carbon-carbon double bond at a side chain or a molecular end with a small steric hindrance is suitable for hydrosilylation and hydrogenation. It is mentioned in terms of high reactivity. Polymers useful for hydrosilylation and hydrogenation are not particularly limited and include, for example, natural rubber, polyisoprene, polybutadiene, polycyclohexadiene, butadiene-isoprene copolymer, propylene-butadiene copolymer, styrene- Butadiene copolymer, styrene-isoprene copolymer, styrene-butadiene-isoprene copolymer, chloroprene rubber, acrylonitrile-butadiene copolymer, acrylonitrile-isoprene copolymer, styrene-butadiene-methyl methacrylate copolymer, styrene- Isoprene-methyl methacrylate copolymer, styrene-butadiene-lactone copolymer, styrene-isoprene-lactone copolymer, styrene-butadiene-siloxane copolymer, styrene-isoprene-siloxane Polymer, isobutylene - isoprene copolymers, ethylene - propylene - diene copolymers and the like and derivatives thereof.
[0007]
The method for producing the conjugated diene polymer is not particularly limited, but the organic monomer, transition metal catalyst, radical generator, acid generator in a solvent such as a solvent-free or organic solvent, water, or inert gas. It is obtained by contacting or irradiating light with an initiator mainly composed of a compound such as an agent.
In the present invention, the conjugated diene polymer having a carbon-carbon double bond is a polymer composed of a conjugated diene compound or a copolymer composed of an aromatic vinyl compound or a (meth) acrylate compound copolymerizable with the conjugated diene compound. A preferred method for producing them is to produce these conjugated diene polymers using an initiator composed of an organometallic catalyst or a transition metal catalyst in an inert organic solvent. Moreover, a modified conjugated diene polymer can be produced by hydrosilylation and hydrogenation of the produced conjugated diene polymer.
[0008]
Specific examples of the method for producing the conjugated diene polymer include, in an inert organic solvent, an organic alkali metal catalyst or a transition metal catalyst as a polymerization initiator, and if necessary, in the presence of a Lewis base, and / or Alternatively, an aromatic vinyl compound and / or a (meth) acrylate compound is polymerized to produce a conjugated diene polymer solution.
[0009]
The composition ratio of the conjugated diene compound, the aromatic vinyl compound, and the (meth) acrylate compound is not particularly limited, but the conjugated diene compound is 5 to 100% by weight, the aromatic vinyl compound is 0 to 95% by weight, and the (meth) acrylate compound 0. -95% by weight, preferably in the range of 5 to 95% by weight, 95 to 5% by weight, and 0 to 50% by weight [however, conjugated diene compound + aromatic vinyl compound + (meth) acrylate compound = 100% by weight] Can be made. If the content of the monomer (conjugated diene compound) for introducing a carbon-carbon double bond in the conjugated diene polymer is less than 5% by weight, hydrosilylation is insufficient, and the modification effect intended by the present invention is sufficiently achieved. I can't get it.
[0010]
Examples of the conjugated diene compound used in the method of the present invention include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-octadiene, 1, 3-hexadiene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,3-cyclooctadiene, 4,5-diethyl-1,3-octadiene, 3-butyl- 1,3-octadiene, myrcene, chloroprene, 2-trimethoxysilyl-1,3-butadiene, 2-triisopropoxysilyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1-phenyl-1 , 3-butadiene, 1,4-diphenyl-1,3-butadiene, 1-cyano-1,3-butadiene, and the like. , 1,3-butadiene, isoprene, 1,3-cyclohexadiene high polymerization reactivity, preferred from the viewpoint of easy availability in the industry. Moreover, these can be used individually by 1 type or in combination of 2 or more types.
[0011]
Examples of the aromatic vinyl compound used in the method of the present invention include styrene, tert-butylstyrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene, p-isopropylstyrene, p-tert. -Butylstyrene, pn-butylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, divinylbenzene, 1,1-diphenylstyrene, 1-vinylnaphthalene, 2-vinyl Naphthalene, 2-vinylanthracene, 9-vinylanthracene, p-vinylbenzylpropyl ether, p-vinylbenzylbutyl ether, p-vinylbenzylhexyl ether, p-vinylbenzylpentyl ether, m-N, N-diethylaminoethylstyrene, p -N, N-di Tylaminoethylstyrene, pN, N-dimethylaminoethylstyrene, o-vinylbenzyldimethylamine, p-vinylbenzyldimethylamine, p-vinylbenzyldiethylamine, p-vinylbenzyldi (n-propyl) amine, p- Vinylbenzyldi (n-butyl) amine, p-2-trimethylethenylstyrene, vinylpyridine, 2-vinylbiphenyl, 4-vinylbiphenyl, o-methoxystyrene, p-methoxystyrene, p- (tert-butyldimethylsiloxy) ) Styrene and the like. Among these, styrene, tert-butyl styrene, α-methyl styrene and vinyl pyridine are preferable because of high polymerization reactivity. Furthermore, styrene and tert-butyl styrene are most preferable because they are easily available industrially. Moreover, these can be used individually by 1 type or in combination of 2 or more types.
[0012]
Examples of the (meth) acrylate compound used in the present invention include methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, Acrylate compounds such as pentyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, propyl methacrylate, hexyl methacrylate Rate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, myristyl methacrylate, palmityl methacrylate, stearyl methacrylate, behenyl methacrylate, methacrylate compounds such as octyl dodecyl methacrylate. Furthermore, methyl acrylate, tert-butyl acrylate, methyl methacrylate, and tert-butyl methacrylate are most preferred because of their high reactivity and industrial availability. Moreover, these can be used individually by 1 type or in combination of 2 or more types. The polymer containing the (meth) acrylate compound is preferably produced by a prescription in which a monomer such as a conjugated diene compound and an aromatic vinyl compound is first polymerized and then the (meth) acrylate compound is added.
[0013]
Regarding the production of a conjugated diene polymer according to the present invention, a conjugated diene compound as an essential component and an aromatic vinyl compound and a (meth) acrylate compound can be copolymerized, but a compound copolymerizable with a conjugated diene compound If so, it may be similarly copolymerized. Examples of such compounds include cyclic siloxane compounds, maleimide compounds, macromonomers, and the like.
[0014]
  Cyclic siloxaneCompoundIs not particularly limited, for example, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, 1,3,5-tris (3,3,3-trifluoropropyl) -1,3,5-trimethylcyclotrisiloxane, Hexaethylcyclotrisiloxane, hexaphenylcyclotrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetraethoxy-1,3,5,7-tetramethylcyclotetrasiloxane 1,3,5,7-tetrakis (3,3,3-trifluoropropyl) -1,3,5,5-tetramethylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3 , 5,7-tetrapropoxycyclotetrasiloxane, 1,3,5,7-tetraisopropoxy-1,3,5,7-tetrame Rucyclotetrasiloxane, 1,3,5,7-tetrabutoxy-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetra Phenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5,7,9-pentaethoxy-1,3,5,7,9- Examples include pentamethylcyclopentasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. Among these, hexamethylcyclotrisiloxane and octamethylcyclotetrasiloxane are preferable because they have high polymerization reactivity, easily control the molecular weight distribution, and are easily available industrially.
[0015]
Examples of the maleimide compound include N-ethylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, N-iso-butylmaleimide, N-tert-butylmaleimide, Nn-octylmaleimide, and N-cyclohexylmaleimide. , N-benzylmaleimide, N-phenylmaleimide and the like. In addition, 1,1-diphenylethylene, stilbene, trimethylsilylethylene, ethyleneamide, and the like can also be used.
[0016]
Regarding the production of the conjugated diene polymer according to the present invention, ethylene oxide, propylene oxide, epichlorohydrin, butylene oxide, 1,2-epoxy-3-is added to the active terminal of the conjugated diene polymer produced using an organic antari compound as a polymerization initiator. Oxirane compounds such as methylbutane and glycerol or aldehyde compounds such as benzaldehyde, acetaldehyde, decanal, formaldehyde, 2,3-epoxycyclohexanecarboxaldehyde or ketones or epoxy ketones such as acetone, acetophenone, benzophenone, acetylcyclohexane, 2-butanone Ε-caprolactone, δ-valerolactone, β-propionlactone, methylated caprolactone, butanoic acid capro Lactone may also be obtained lactone heptanoic acid, a lactone-based compound is reacted conjugated diene polymer such as octanoic acid lactone.
[0017]
The inert solvent used in the present invention is not particularly limited as long as it is an inert solvent that does not react with the organic alkali metal catalyst or the transition metal catalyst. Examples of the inert solvent include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, and octane, alicyclic hydrocarbon solvents such as cyclopentane, methylcyclopentane, cyclohexane, and methylcyclohexane, benzene, xylene, Aromatic hydrocarbon solvents such as toluene and ethylbenzene can be mentioned, and they can be used alone or in combination of two or more according to the purpose.
[0018]
Examples of the organic alkali metal compound that is a polymerization initiator used in the present invention include an organic lithium compound and an organic sodium compound, and an organic lithium compound is particularly preferable. As the organic lithium compound, for example, an organic monolithium compound, an organic dilithium compound, or an organic polylithium compound is used. Specific examples thereof include ethyl lithium, n-propyl lithium, iso-propyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, pentyl lithium, hexyl lithium, cyclohexyl lithium, phenyl lithium, hexamethylene di Lithium, cyclopentadienyl lithium, indenyl lithium, 1,1-diphenyl-n-hexyl lithium, 1,1-diphenyl-3-methylpentyl lithium, lithium naphthalene, butadienyl dilithium, isopropenyl dilithium, m -Diisoprenyl dilithium, polybutadienyl lithium, polyisoprenyl lithium, polystyrene-butadienyl lithium, polystyrenyl lithium, polyethylenyl lithium, poly-1,3-cyclohexadi Nyllithium, polystyrene-1,3-cyclohexadienyl lithium, polybutadiene-1,3-cyclohexadienyl lithium, 1,3-phenylene-bis- (3-methyl-1-phenylpentylidene) bislithium, 1,3 -Phenylene-bis- (3-methyl-1, [4-methylphenyl] pentylidene) bislithium, 1,3-phenylene-bis- (3-methyl-1, [4-dodecylphenyl] pentylidene) bislithium, , 1,4,4-tetraphenyl-1,4-dilithiobutane, 1,3-bis (1-lithio-1,3-dimethylpentyl) benzene, 1,4-bis (1-lithio-1,3-dimethyl) Pentyl) benzene, 1,3-bis (1-lithio-1-ethyl-3-methylpentyl) benzene, 1,4-bis (1-lithio-) -Ethyl-3-methylpentyl) benzene, 3-lithio-1- [N, N-bis (trimethylsilyl)] aminopropane, 2-lithio-1- [N, N-bis (trimethylsilyl)] aminoethane, 3-lithio -2,2-dimethyl-1- [N, N-bis (trimethylsilyl)] aminopropane, 2,2,5,5-tetramethyl-1- (3-lithiopropyl) -1-aza-2,5- Disilacyclopentane, 2,2,5,5-tetramethyl-1- (3-lithio-2,2-dimethyl-propyl) -1-aza-2,5-disilacyclopentane, 2,2,5 , 5-tetramethyl-1- (2-lithioethyl) -1-aza-2,5-disilacyclopentane, 3-lithio-1- [N- (tert-butyl-dimethylsilyl) -N-trimethylsilyl] aminoprop 3-lithio-1- [N- {di (tert-butyl) -methylsilyl} -N-trimethylsilyl] aminopropane, 3-lithio-1- [N- (tert-butyl-dimethylsilyl) -N-trimethylsilyl Aminoethane, 3-lithio-1- [N- {di (tert-butyl) -methylsilyl} -N-trimethylsilyl] aminoethane, 3-lithio-2,2-dimethyl-1- [N- (tert-butyl-dimethyl) Silyl) -N-trimethylsilyl] aminopropane, 3-lithio-2,2-dimethyl-1- [N- {di (tert-butyl) -methylsilyl} -N-trimethylsilyl] aminopropane, 3-lithio-1- ( N-methyl-N-trimethylsilyl) aminopropane, 3-lithio-1- (N-ethyl-N-trimethylsilyl) aminop Pan, 2-lithio-1- (N-methyl-N-trimethylsilyl) aminoethane, 2-lithio-1- (N-ethyl-N-trimethylsilyl) aminoethane, 3-lithio-1- [N-methyl-N- ( tert-butyl-dimethylsilyl)] aminopropane, 3-lithio-1- [N-methyl-N- {di (tert-butyl) -methylsilyl}] aminopropane, 3-lithio-1- [N-ethyl-N -(Tert-butyl-dimethylsilyl)] aminopropane, 3-lithio-1- [N-ethyl-N- {di (tert-butyl) -methylsilyl}] aminopropane, 3-lithio-1- [N-methyl -N- (tert-butyl-dimethylsilyl)] aminoethane, 3-lithio-1- [N-methyl-N- {di (tert-butyl) -methylsilyl}] amino Ethane, 3-lithio-1- [N-ethyl-N- (tert-butyl-dimethylsilyl)] aminoethane, 3-lithio-1- [N-ethyl-N- {di (tert-butyl) -methylsilyl}] Examples include aminoethane. Among these, preferable organic lithium compounds include ethyl lithium, n-propyl lithium, iso-propyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, cyclohexyl lithium, butadienyl lithium, isopropenyl dilithium. , Polybutadienyl lithium, polyisoprenyl lithium, polystyrene-butadienyl lithium, polystyryl lithium, poly-1,3-cyclohexadienyl lithium, polystyrene-1,3-cyclohexadienyl lithium, polybutadiene-1, 3-cyclohexadienyl lithium, 1,3-phenylene-bis- (3-methyl-1-phenylpentylidene) bislithium, 1,3-phenylene-bis- (3-methyl-1, [4-methylphenyl] Penchili Emissions) bislithium, 1,3-bis (1-lithio-1,3-dimethylpentyl) benzene, 1,4-bis (1-lithio-1,3-dimethylpentyl) include benzene. More preferable organic lithium compounds include n-butyllithium, sec-butyllithium, tert-butyllithium, 1,3-bis (1-lithio-1,3-dimethylpentyl) benzene, 1,3-phenylene- Bis- (3-methyl-1-phenylpentylidene) bislithium is mentioned.
The amount of the organic alkali metal catalyst used is not particularly limited, and various amounts can be used as necessary. Usually, the amount is 0.02 to 15% by weight per 100% by weight of the monomer, preferably 0. Used in an amount of 0.03 to 5% by weight.
[0019]
The organic alkali metal catalyst as the initiator can be used as a reaction product with a secondary amine compound or a tertiary amine compound. As the organic alkali metal catalyst to be reacted with the secondary amine compound or the tertiary amine compound, an organic lithium compound is preferable. More preferably, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, 1,3-bis (1-lithio-1,3-dimethylpentyl) benzene, 1,3-phenylene-bis- (3-methyl -1-Phenylpentylidene) bislithium is used.
[0020]
Examples of secondary amine compounds to be reacted with the organic alkali metal catalyst include dimethylamine, diethylamine, dipropylamine, di-n-butylamine, di-sec-butylamine, dipentylamine, dihexylamine, and di-n-octyl. Amine, di- (2-ethylhexyl) amine, dicyclohexylamine, N-methylbenzylamine, diallylamine, morpholine, piperazine, 2,6-dimethylmorpholine, 2,6-dimethylpiperazine, 1-ethylpiperazine, 2-methylpiperazine, 1-benzylpiperazine, piperidine, 3,3-dimethylpiperidine, 2,6-dimethylpiperidine, 1-methyl-4- (methylamino) piperidine, 2,2,6,6-tetramethylpiperidine, pyrrolidine, 2,5 -Dimethylpyrrolidine, Zechijin, hexamethyleneimine, heptamethyleneimine, 5-benzyloxyindole, 3-azaspiro [5,5] undecane, 3-azabicyclo [3.2.2] nonane, carbazole and the like.
[0021]
Examples of the tertiary amine compound to be reacted with the organoalkali metal catalyst include N, N-dimethyl-o-toluidine, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, α-picoline, β-picoline, γ-picoline, benzyldimethylamine, benzyldiethylamine, benzyldipropylamine, benzyldibutylamine, (o-methylbenzyl) dimethylamine, (m-methylbenzyl) dimethylamine, (p-methyl) Benzyl) dimethylamine, N, N-tetramethylene-o-toluidine, N, N-heptamethylene-o-toluidine, N, N-hexamethylene-o-toluidine, N, N-trimethylenebenzylamine, N, N -Tetramethylenebenzylamine, N, N-hexamethylenebenzylamine, N, N Tetramethylene (o-methylbenzyl) amine, N, N-tetramethylene (p-methylbenzyl) amine, N, N-hexamethylene (o-methylbenzyl) amine, N, N-hexamethylene (p-methylbenzyl) An amine etc. are mentioned.
[0022]
  The organic alkali metal catalyst includes organic alkali metal salts, organic alkaline earth salts, crown ethers, CH₃(OCH₂CH₂)_zAlkali metal alcoholate represented by OLi (z = 1 to 3), alkylsiloxylithium, organicaluminumA compound or the like can also be added and used as a polymerization initiator. These compounds are compounds having a coordination ability to the organic alkali metal catalyst, and serve as a stabilizer for controlling the reactivity of the organic alkali metal catalyst.
[0023]
  Specific examples of the stabilizer include lithium chloride, lithium bromide, lithium iodide, lithium fluoride, potassium chloride, potassium bromide, potassium iodide, potassium fluoride, barium chloride, barium bromide, barium iodide. Organic alkali metal salts and organic alkaline earth salts such as barium fluoride, magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride, magnesium nitrate, 12-crown-4, 15-crown-5, 18-crown -6, 1,4,7,10,13,16-hexathiacyclooctadecane, 1,4,7,10-tetrathiacyclohexadecane, 1,4,8,11-tetrathiacyclotetradecane, 4,7, Crowns such as 13,16,21,24-hexaoxa-1,10-diazobicyclo [8.8.8] hexacosane Ether, methoxylithium, ethoxylithium, tert-butoxylithium, lithium methoxyethanolate, lithium methoxyethoxyethanolate, 2- [N- (2-dimethylamino) -N-methylamino] ethylate, lithium 2- (dimethylamino) Organics such as alkali metal alcoholates such as ethylate, alkylsiloxylithiums such as sec-butyldimethylsiloxylithium, ethylaluminum dichloride, diisopropylaluminum-1,3-di-tert-butylphenoxidealuminumCompound etc. are mentioned. These can be used in the range of 0.5 times to 10 times mol of the organic alkali metal catalyst as necessary.
[0024]
The transition metal catalyst that is a polymerization initiator used in the present invention includes Nd, Ni, Co, Ti, V, Cr, Cu, Fe, Mn, Ru, and Rh as a central metal, and a Cp ring (cyclopenta Dienyl ring), a compound in which hydrogen on the Cp ring is optionally substituted with an alkyl chain, at least one ligand selected from Cl, CO, octanoic acid, naphthenic acid, versatic acid, acetylacetone, and alkoxy groups Transition metal compounds are preferred. Specific examples of these include versatic acid Nd, (C_FiveH₉Cp)₂NdCl, TiCl_Four, CoBr₂Ti (On-Bu)_FourTi (On-Pr)_Four, CpTiCl_Three, Cp₂Ni, Cp₂VCl, CpVCl₂(PEt_Three)₂, CpRuCl_Three, CpTiCl₂-1,3-diisopropylphenoxide, naphthenic acid Ni, Ni (acac)₂, Co (acac)_Three, Cr (acac)_Three, V (acac)_Three, Fe (acac)_Three, Mn (acac)_Three, C₈H₁₂(C_FiveH₁₁) NRhCl. These compounds include triisobutylaluminum, triethylaluminum, trimethylaluminum, diethylaluminum chloride, ethylaluminum dichloride, MAO and other Al compounds, trihydroborane, triethylborane, trifluoroborane, 9-borabicyclo [3.3.1]. It is preferable to add a promoter such as a boron compound such as nonane dimer.
[0025]
The polymerization temperature of the conjugated diene polymer according to the present invention is generally -10 ° C to 150 ° C, preferably 0 ° C to 120 ° C. Further, it is desirable to replace the polymerization atmosphere with an inert gas such as nitrogen gas. The polymerization pressure is not particularly limited as long as the polymerization pressure is within a range sufficient to maintain the monomer and solvent in a liquid phase within the above polymerization range. Furthermore, care must be taken not to mix impurities, such as water and oxygen, that inactivate the polymerization initiator, catalyst and living polymer in the polymerization system. In addition, when the solvent or monomer is polymerized using a sufficiently purified impurity having a small amount of impurities, a monodispersed living polymer having a narrow molecular weight distribution can be obtained.
[0026]
In the production of the conjugated diene polymer according to the present invention, the microstructure of the conjugated diene compound unit, that is, the vinyl bond content such as 1, 2 or 3, 4 bonds can be controlled by using a Lewis base together with the above inert solvent. Can be controlled. Examples of such Lewis bases include ethers and amines. Specifically,
(1) Diethyl ether, tetrahydrofuran, propyl ether, butyl ether, higher ether, tetrahydrofurfuryl methyl ether, tetrahydrofurfuryl ethyl ether, 1,4-dioxane, bis (tetrahydrofurfuryl) formal, 2,2-bis (2- Tetrahydrofurfuryl) propane, and ether derivatives of polyalkylene glycols such as ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, propylene glycol diethyl ether, and propylene glycol ethyl propyl ether, and the like, and
(2) N, N, N, N-tetramethylethylenediamine, N, N, N, N-tetramethylmethylenediamine, N, N, N, N-tetraethylethylenediamine, N, N, N, N-tetramethyl- 1,3-propanediamine, pyridine, and tertiary amines such as tributylamine and sparteine
Etc.
The said Lewis base can be used individually by 1 type or in combination of 2 or more type according to the objective.
[0027]
In the production of the conjugated diene polymer in the present invention, when the conjugated diene compound and the aromatic vinyl compound are randomly copolymerized, the chain number of the aromatic vinyl compound can be controlled by adding a potassium compound. . Examples of the potassium compound added together with such a polymerization initiator include potassium alkoxides such as potassium isopropoxide, potassium t-butoxide, potassium t-amyloxide, potassium n-heptaoxide, potassium benzyl oxide, potassium phenoxide and the like. , Potassium phenoxide, isovaleric acid, caprylic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linolenic acid, benzoic acid, phthalic acid, 2-ethylhexanoic acid, dodecylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, hexa Potassium salts of organic sulfonic acids such as decylbenzenesulfonic acid and octadecylbenzenesulfonic acid; diethyl phosphite, diisopropyl phosphite, diphenyl phosphite, dibutyl phosphite, dilauryl phosphite Such as how potassium salt is used. These potassium compounds are added within a range not causing a problem in production because the polymerization activity of the polymerization initiator is lowered.
[0028]
  The above-described inert organic solvent, Lewis acid, monomer such as conjugated diene compound, polymerization initiator and other compounds added as necessary are mixed in a temperature-controllable reactor so that the conjugated diene system according to the present invention is used. PolymerManufacturebe able to. The molecular weight of the polymer thus produced is in the range of 10,000 to 2,000,000, preferably 40,000 to 1,000,000, more preferably 50,000 to 500,000 in terms of polystyrene weight average molecular weight.
[0029]
From the viewpoint of physical properties and molding processability of the resulting composition, the structure of the conjugated diene polymer is, as shown above, a random copolymer composed of a conjugated diene compound and an aromatic vinyl compound, and the following ( A block copolymer containing two or more polymer blocks selected from the polymer blocks of A) to (F) is preferred.
(A) Aromatic vinyl compound polymer block containing 80% by weight or more of aromatic vinyl compound
(B) Conjugated diene compound polymer block containing 80% by weight or more of conjugated diene compound
(C) Conjugated diene compound polymer block having a total of 1,2 bonds and 3,4 bonds of less than 25% by weight
(D) Conjugated diene compound polymer block having a total of 1,2 bonds and 3,4 bonds of 25 wt% to 90 wt%
(E) A random copolymer block of an aromatic vinyl compound and a conjugated diene compound.
(F) (meth) acrylate compound polymer block in which (meth) acrylate compound is 80% by weight or more
[0030]
The chain of the aromatic vinyl compound of the random copolymer comprising the conjugated diene compound and the aromatic vinyl compound is not particularly limited, but a single chain having one polymerization unit of the aromatic vinyl compound is 40% by weight. The long chain of 8 or more polymerized units of the aromatic vinyl compound is preferably 10% by weight or less of the total bonded aromatic vinyl compound. Here, the aromatic vinyl compound chain in the copolymer is analyzed by gel permeation chromatogram after decomposing the copolymer with ozone [Tanaka et al., Polymer,22, 1721 (1981)].
[0031]
The random copolymer block (E) may include a so-called taper type in which the aromatic vinyl compound content continuously changes in one molecule, and the chain of the aromatic vinyl compound is not particularly limited.
In addition, the conjugated diene polymer in the present invention is not particularly limited as long as it is a block copolymer including two or more polymer blocks selected from the polymer blocks (A) to (F). Specifically, (A)-(B), (A)-(C), (A)-(D), (A)-(E), (B)-(E), (B)-( F), (C)-(D), (C)-(E), [(A)-(B)] xY, [(A)-(C)] xY, [(A)- (D)] x-Y, [(A)-(E)] x-Y, [(B)-(E)] x-Y, [(C)-(A)] x-Y, [(C )-(D)] x-Y, [(C)-(E)] x-Y, [(F)-(A)] x-Y, [(F)-(B)] x-Y, [ (F)-(C)] x-Y, [(F)-(D)] x-Y, [(F)-(E)] x-Y, (A)-(B)-(C), ( )-(B)-(E), (A)-(B)-(F), (A)-(B)-(A), (A)-(C)-(A), (A)- (C)-(B), (A)-(C)-(E), (A)-(C)-(F), (A)-(D)-(A), (A)-(D )-(B), (A)-(D)-(E), (A)-(D)-(F), (A)-(E)-(A), (A)-(E)- (B), (A)-(E)-(C), (A)-(E)-(D), (A)-(E)-(F), (B)-(A)-(C ), (B)-(A)-(D), (B)-(A)-(E), (B)-(A)-(F), (C)-(A)-(C), (F)-(B)-(F), (F)-(C)-(F), (F)-(D)-(F), (F)-(E)-(F), [( A)-(B)-(C)] xY, [(A)-(B)-(D)] xY, (A)-(B)-(E)] xY, [(A)-(B)-(A)] xY, [(A)-(C)-(A)] xY, [(A)-(C)-(B)] xY, [(A)-(C)-(D)] xY, [(A)-(C)-(E)] xY , [(A)-(D)-(A)] xY, [(A)-(D)-(B)] xY, [(A)-(D)-(E)] x- Y, [(A)-(E)-(A)] x-Y, [(A)-(E)-(B)] x-Y, [(A)-(E)-(C)] x -Y, [(A)-(E)-(D)] x-Y, (A)-(B)-(A)-(B), (A)-(B)-(A)-(F ), (B)-(A)-(B)-(A), (A)-(C)-(A)-(C), (C)-(A)-(C)-(A), [(A)-(B)-(A)-(B)] x-Y, (A)-(B)-(A)- (B)-(A), [(A)-(B)-(A)-(B)-(A)] xY, etc. [where x ≧ 2 and Y is a coupling agent Is a residue].
[0032]
In addition, a block copolymerized with a compound copolymerizable with a conjugated diene compound, that is, a compound such as the above cyclic siloxane compound, maleimide compound, or macromonomer, can be contained in the conjugated diene polymer.
[0033]
Examples of the coupling agent include halogen compounds, epoxy compounds, carbonyl compounds, polyvinyl compounds, alkoxysilanes, and the like. Specific examples of the coupling agent include halogenated silane compounds such as methyldichlorosilane, methyltrichlorosilane, butyltrichlorosilane, and tetrachlorosilane, dibromoethane, epoxidized soybean oil, tetrachlorogermanium, and bis (trichlorosilyl) ethane. , Hexachlorodisiloxane, diethyl adipate, dimethyl adipate, dimethyl terephthalate, diethyl terephthalate, polyisocyanate, tetrachlorotin, tetrabromotin, trichlorobutyltin, trichloromethyltin, trichlorooctyltin, dibromodimethyltin, dichlorodimethyl Tin, dichlorodibutyltin, dichlorodioctyltin, 1,2-bis (trichlorostannyl) ethane, 1,2-bis (methyldichlorostannylethane), 1,4 Bis (trichlorostannyl) butane, 1,4-bis (methyldichlorostannyl) butane, ethyltin tristearate, butyltin trisoctanoate, butyltin tristearate, butyltin trislaurate, dibutyltin bisoctanoate, dibutyltin Tin compounds such as bis-stearate and dibutyltin bislaurate, tetraethoxysilane, tetramethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, methylpropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, Ethyltributoxysilane, ethyltripentyloxysilane, ethyltrineopentyloxysilane, ethyltrihexyloxysilane, phenyltrimethoxysilane, phenyltrie Xysilane, phenyltributoxysilane, 2- (chloromethyl) allyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldibutoxysilane, diphenyldimethoxysilane, Aliphatic hydrocarbon alkoxysilane compounds such as diphenyldiethoxysilane, diphenyldibutoxysilane, methyldimethoxyamyloxysilane, and methyldiethoxyamyloxysilane, methyltriphenoxysilane, ethyltriphenoxysilane, phenyltriphenoxysilane, dimethyl Aromatic hydrocarbon alkoxysilane compounds such as diphenoxysilane, diethyldiphenoxysilane, and diphenyldiphenoxysilane. Γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxy Silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3 4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, and β- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane, γ-glycidoxypropylene Functional groups such as triphenoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylmethylphenoxyethoxysilane, γ-glycidoxypropyldiethoxyphenoxysilane, γ-methacryloxypropylmethyldiphenoxysilane N, N-bis (trimethylsilyl) aminopropyltrimethoxysilane, N, N-bis (trimethylsilyl) aminopropyltriethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane, N , N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane, N, N-bis (trimethylsilyl) aminoethyltrimethoxysilane, N, N-bis (trimethylsilyl) aminoethyltriethoxysilane N, N-bis (trimethylsilyl) aminoethylmethyldiethoxysilane, N, N-bis (trimethylsilyl) aminoethylmethyldimethoxysilane, etc., a compound that becomes a primary amine when the protective group is removed by hydrolysis, etc., N -Methyl-N-trimethylsilylaminopropyltrimethoxysilane, N-methyl-N-trimethylsilylaminopropyltriethoxysilane, N-methyl-N-trimethylsilylaminopropylmethyldiethoxysilane, N-methyl-N-trimethylsilylaminopropylmethyldimethoxy Silane, N-methyl-N-trimethylsilylaminoethyltrimethoxysilane, N-methyl-N-trimethylsilylaminoethyltriethoxysilane, N-methyl-N-trimethylsilylaminoethylmethyldiethoxy Silane, N-methyl-N-trimethylsilylaminoethylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, dimethoxymethyl-3-piperazinopropylsilane, And a compound that becomes a secondary amine when the protective group is removed by hydrolysis of 3-piperazinopropyltrimethoxysilane or the like, N, N-dimethylaminopropyltrimethoxysilane, N, N-dimethylaminopropyltriethoxysilane, N, N-dimethylaminopropylmethyldiethoxysilane, N, N-dimethylaminopropylmethyldimethoxysilane, N, N-dimethylaminoethyltrimethoxysilane, N, N-dimethylaminoethyltriethoxysilane, N, N-bis Methylaminoe Tertiary amine compounds such as rumethyldiethoxysilane, N, N-bismethylaminoethylmethyldimethoxysilane, dimethoxymethyl-2-piperidinoethylsilane, and 2-piperidinoethyltrimethoxysilane, trimethylsiloxytriphenoxy Examples thereof include alkoxysilane compounds such as silane, trimethylsiloxytrimethoxysilane, trimethylsiloxytriethoxysilane, and trimethylsiloxytributoxysilane, divinylbenzene, dibenzoylpyridine, diacetylpyridine, and divinylpyridine. These can be used alone or in combination of two or more. In particular, methyldichlorosilane, methyltrichlorosilane, butyltrichlorosilane, and tetrachlorosilane are preferable because they can be strictly coupled.
[0034]
In the present invention, when the conjugated diene polymer obtained by the various methods described above has an active site, the active site is usually deactivated by using a polymerization terminator. Specific examples of the polymerization terminator include, for example, hydrogen, carbon monoxide, carbon dioxide, methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, heptanol, octanol and other alcohols, methyl chloride, chloride. Ethyl, propyl chloride, butyl chloride, benzyl chloride, 3-bromo-1- [N, N-bis (trimethylsilyl)] aminopropane, 2-bromo-1- [N, N-bis (trimethylsilyl)] aminoethane, 3- Bromo-2,2-dimethyl-1- [N, N-bis (trimethylsilyl)] aminopropane, 2,2,5,5-tetramethyl-1- (3-bromopropyl) -1-aza-2,5 -Disilacyclopentane, 2,2,5,5-tetramethyl-1- (3-bromo-2,2-dimethyl-propyl Pill) -1-aza-2,5-disilacyclopentane, 2,2,5,5-tetramethyl-1- (2-bromoethyl) -1-aza-2,5-disilacyclopentane, 3- Bromo-1- [N- (tert-butyl-dimethylsilyl) -N-trimethylsilyl] aminopropane, 3-bromo-1- [N- {di (tert-butyl) -methylsilyl} -N-trimethylsilyl] aminopropane, 3-bromo-1- [N- (tert-butyl-dimethylsilyl) -N-trimethylsilyl] aminoethane, 3-bromo-1- [N- {di (tert-butyl) -methylsilyl} -N-trimethylsilyl] aminoethane, 3-bromo-2,2-dimethyl-1- [N- (tert-butyl-dimethylsilyl) -N-trimethylsilyl] aminopropane, 3-bromide -2,2-dimethyl-1- [N- {di (tert-butyl) -methylsilyl} -N-trimethylsilyl] aminopropane, 3-bromo-1- (N-methyl-N-trimethylsilyl) aminopropane, 3- Bromo-1- (N-ethyl-N-trimethylsilyl) aminopropane, 2-bromo-1- (N-methyl-N-trimethylsilyl) aminoethane, 2-bromo-1- (N-ethyl-N-trimethylsilyl) aminoethane, 3-bromo-1- [N-methyl-N- (tert-butyl-dimethylsilyl)] aminopropane, 3-bromo-1- [N-methyl-N- {di (tert-butyl) -methylsilyl}] amino Propane, 3-bromo-1- [N-ethyl-N- (tert-butyl-dimethylsilyl)] aminopropane, 3-bromo-1- [N -Ethyl-N- {di (tert-butyl) -methylsilyl}] aminopropane, 3-bromo-1- [N-methyl-N- (tert-butyl-dimethylsilyl)] aminoethane, 3-bromo-1- [ N-methyl-N- {di (tert-butyl) -methylsilyl}] aminoethane, 3-bromo-1- [N-ethyl-N- (tert-butyl-dimethylsilyl)] aminoethane, 3-bromo-1- [ N-ethyl-N- {di (tert-butyl) -methylsilyl}] aminoethane, 3-chloro-1- [N, N-bis (trimethylsilyl)] aminopropane, 2-chloro-1- [N, N-bis (Trimethylsilyl)] aminoethane, 3-chloro-2,2-dimethyl-1- [N, N-bis (trimethylsilyl)] aminopropane, 2,2,5,5-tetra Tyl-1- (3-chloropropyl) -1-aza-2,5-disilacyclopentane, 2,2,5,5-tetramethyl-1- (3-chloro-2,2-dimethyl-propyl) -1-aza-2,5-disilacyclopentane, 2,2,5,5-tetramethyl-1- (2-chloroethyl) -1-aza-2,5-disilacyclopentane, 3-chloro- 1- [N- (tert-butyl-dimethylsilyl) -N-trimethylsilyl] aminopropane, 3-chloro-1- [N- {di (tert-butyl) -methylsilyl} -N-trimethylsilyl] aminopropane, 3- Chloro-1- [N- (tert-butyl-dimethylsilyl) -N-trimethylsilyl] aminoethane, 3-chloro-1- [N- {di (tert-butyl) -methylsilyl} -N-trimethylsilane L] aminoethane, 3-chloro-2,2-dimethyl-1- [N- (tert-butyl-dimethylsilyl) -N-trimethylsilyl] aminopropane, 3-chloro-2,2-dimethyl-1- [N- {Di (tert-butyl) -methylsilyl} -N-trimethylsilyl] aminopropane, 3-chloro-1- (N-methyl-N-trimethylsilyl) aminopropane, 3-chloro-1- (N-ethyl-N-trimethylsilyl) ) Aminopropane, 2-chloro-1- (N-methyl-N-trimethylsilyl) aminoethane, 2-chloro-1- (N-ethyl-N-trimethylsilyl) aminoethane, 3-chloro-1- [N-methyl-N -(Tert-butyl-dimethylsilyl)] aminopropane, 3-chloro-1- [N-methyl-N- {di (tert-butyl) ) -Methylsilyl}] aminopropane, 3-chloro-1- [N-ethyl-N- (tert-butyl-dimethylsilyl)] aminopropane, 3-chloro-1- [N-ethyl-N- {di (tert -Butyl) -methylsilyl}] aminopropane, 3-chloro-1- [N-methyl-N- (tert-butyl-dimethylsilyl)] aminoethane, 3-chloro-1- [N-methyl-N- {di ( tert-butyl) -methylsilyl}] aminoethane, 3-chloro-1- [N-ethyl-N- (tert-butyl-dimethylsilyl)] aminoethane, 3-chloro-1- [N-ethyl-N- {di ( tert-butyl) -methylsilyl}] aminoethane, methyl bromide, ethyl bromide, propyl bromide, butyl bromide, methyl iodide, ethyl iodide, propyl iodide, iodine Butyl, 2,2,5,5-tetramethyl-1- (3-propyl iodide) -1-alkyl halide or a derivative thereof, such as aza-2,5-disilacyclopentane and the like. Moreover, these can be used individually by 1 type or in combination of 2 or more types.
[0035]
In the present invention, a compound having a polar group can be reacted in addition to the method of deactivating the active site of the conjugated diene polymer by using the above-mentioned polymerization terminator.
Specific examples of the compound having a polar group include N, N-bis (trimethylsilyl) aminopropyldimethylethoxysilane, N, N-bis (trimethylsilyl) aminopropyldimethylmethoxysilane, and N, N. -Bis (trimethylsilyl) aminoethyldimethylethoxysilane, N, N-bis (trimethylsilyl) aminoethyldimethylmethoxysilane, 1-trimethylsilyl-2-dimethoxy-1-aza-2-silacyclopentane, 1-trimethylsilyl-2-diethoxy -1-aza-2-silacyclopentane, N-methyl-N-trimethylsilylaminopropyldimethylethoxysilane, N-methyl-N-trimethylsilylaminopropyldimethylmethoxysilane, N-methyl-N-trimethylsilylaminoethyl Methylethoxysilane, N-methyl-N-trimethylsilylaminoethyldimethylmethoxysilane, N, N-dimethylaminopropyldimethylethoxysilane, N, N-dimethylaminopropyldimethylmethoxysilane, N, N-bismethylaminoethyldimethylethoxysilane N, N-bismethylaminoethyldimethylmethoxysilane, 1,1,3,3-tetramethyl-1-phenoxydisiloxane, N-benzylidenemethylamine, N-benzylideneethylamine, N-benzylidenebutylamine, N-benzylideneaniline N-benzylidenebenzylamine, N-benzylidenetoluidine, N- (α-phenylbenzylidene) benzylamine, N- (α-phenylbenzylidene) amine, N-butylidenebenzenesulfenamide N-isopropylidenebenzenesulfenamide, N-benzylidenebenzenesulfenamide, N- (α-phenylbenzylidene) benzenesulfenamide, N-trimethylsilylbenzaldoimine, N-triphenylsilylbenzaldoimine, N-trimethylsilyl ( 1-phenylpentylidene) amine, N-trimethylsilylethylideneamine, N- (tert-butyl-dimethyl) silyl (1-phenylpentylidene) amine, N- (tert-butyl-dimethyl) silylethylideneamine, N- [di (Tert-Butyl) -methyl] silyl (1-phenylpentylidene) amine, N- [di (tert-butyl) -methyl] silylethylideneamine and the like.
[0036]
The catalyst used in hydrosilylation and hydrogenation of the conjugated diene polymer obtained by the above production method is a compound containing any one of group Ib, IVb, Vb, VIb, VIIb, and Group VIII metals. For example, a compound containing Ti, V, Co, Ni, Zr, Ru, Rh, Pd, Hf, Re, and Pt atoms. Specific compounds include metallocene compounds such as Ti, Zr, Hf, Co, Ni, Rh, and Ru, metals such as Pd, Ni, Pt, Rh, and Ru, carbon, silica, alumina, diatomaceous earth, basic Examples thereof include a supported heterogeneous catalyst supported on a support such as activated carbon.
Specific examples of metallocene compounds include Kaminsky catalyst, ansa metallocene catalyst, non-crosslinked half, having two ligands in which Cp ring or hydrogen on Cp ring is substituted with alkyl group. A metallocene catalyst, a bridge | crosslinking half metallocene catalyst, etc. can be mentioned.
In addition, a homogeneous Ziegler catalyst in which an organic salt or acetylacetone salt of a metal element such as Ni or Co and a reducing agent such as organoaluminum are combined, or an organometallic compound such as Ru or Rh may be used. As the catalyst for the hydrosilylation and hydrogenation reaction, separate catalysts may be used for each reaction, but it is preferable to use the same catalyst. It is necessary to select a catalyst that is active for hydrosilylation and hydrogenation as the catalyst to be used is a simple process for production because the same catalyst is used.
Such a catalyst is preferably a metallocene compound containing any of Ti, Zr, Hf, Ni, Co, Ru, and Rh, more preferably a metallocene compound containing any of Ti, Zr, and Hf. It is. Among these, a catalyst obtained by reacting a titanocene compound and alkoxylithium is an inexpensive and industrially particularly useful catalyst.
Specific examples include JP-A-1-275605, JP-A-5-271326, JP-A-5-271325, JP-A-5-222115, JP-A-11-292924, and JP-A-11-292924. JP 2000-37632 A, JP 59-133203 A, JP 63-5401 A, JP 62-218403 A, JP 7-90017 A, JP 43-19960 A, It is a catalyst described in Japanese Patent Publication No. 47-40473. Moreover, these various catalysts may use only 1 type, and can also use 2 or more types together.
[0037]
In the hydrosilylation and hydrogenation, a conjugated diene polymer solution obtained by production of a conjugated diene polymer is preferably used as it is, and the reaction temperature is in the range of 20 ° C to 150 ° C, preferably 50 ° C to 150 ° C. In the presence of the above catalyst in the range of ° C., it can be carried out by introducing a hydrosilane compound into the system during hydrosilylation and hydrogen into the system during hydrogenation.
[0038]
In the present invention, the modified conjugated diene polymer can be partially or selectively hydrogenated by hydrogenation. The hydrogenation rate can be arbitrarily selected, and is 10%, preferably 50% or more, of the aliphatic double bond based on the conjugated diene compound which is an unsaturated part, in order to improve heat resistance, weather resistance and ozone resistance. It is desirable to hydrogenate 90% or more, more preferably 95% or more. Particularly preferred is hydrogenation of 99% or more.
It is also preferable to hydrogenate a double bond on an aromatic ring based on an aromatic vinyl compound. The hydrogenation rate of the double bond on the aromatic ring can be arbitrarily selected from 0 to 100% depending on the application. The hydrogenated modified conjugated diene polymer can be obtained by reacting in the presence of a hydrogenation catalyst under hydrogen pressure of 0.1 to 10 MPa. Under the above reaction conditions, the target polymer can be obtained by adding the hydrosilane compound to the carbon-carbon double bond in the polymer before hydrogenation and / or during hydrogenation and / or in the latter half of hydrogenation. it can.
[0039]
The hydrosilane compound may be a compound in which at least one hydrogen atom is bonded to a silicon atom. Further, it may be a dihydrosilane compound in which two hydrogen atoms are bonded or a trihydrosilane compound in which three hydrogen atoms are bonded, and is a compound selected from compounds represented by the following formulas (S-1) to (S-6).
[0040]
[Chemical formula 2]

[0041]
[Wherein, R and R ′ are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, R_ThreeTriorganosilyl group represented by Si- or R_ThreeA triorganosiloxy group represented by SiO-, which may be the same or different. X and X ′ each contain a polar group containing at least one of N and O atoms, and may be the same or different. q is 0 to 1, p and n are 0 to 2, m and m 'are 0 to 1,000, and l is an integer of 0 to 3. ]
[0042]
  The hydrosilane compound is represented by the above formulas (S-1) to (S-6).Represented byAlthough it will not specifically limit if it is a compound, As a specific example, Formula (S-1)
[0043]
[Chemical 3]

[0044]
  As a compound represented by
Trimethylsilane, triethylsilane, tripropylsilane, triisopropylsilane, tributylsilane, triphenylsilane, benzyldimethylsilane, tert-butyldimethylsilane, di-tert-butylmethylsilane, diphenylmethylsilane, n-octadecyldimethylsilane, phenyl Dimethylsilane, tri-n-hexylsilane, tris (trimethylsilyl) silane, methoxydimethylsilane, ethoxydimethylsilane, dimethylpropoxysilane, dimethylisopropoxysilane, butoxydimethylsilane, dimethylphenoxysilane, diethylmethoxysilane, ethoxydiethylsilane, diethyl Propoxysilane, diethylisopropoxysilane, diethylphenoxysilane, dimethoxymethylsilane, ethyldimethyl Xisilane, Dimethoxypropylsilane, Dimethoxyisopropylsilane, Butyldimethoxysilane, Dimethoxyphenylsilane, Diethoxymethylsilane, Diethoxyethylsilane, Diethoxypropylsilane, Diethoxyisopropylsilane, Butyldiethoxysilane, Diethoxyphenylsilane, Trimethoxy Silane, triethoxysilane, tripropoxysilane, triisopropoxysilane, tributoxysilane, triphenoxysilane, tripentyloxysilane, trihexylsilane, 1,2-bis (dimethylsilyl) benzene, 1,4-bis (dimethyl) Silyl) benzene, bis [(p-dimethylsilyl) phenyl] ether, (N, N-dimethylamino) dimethylsilane, (N, N-diethylamino) dimethylsilane, N, -Bis (trimethylsilyl) aminodimethylsilane, (N, N-dimethylamino) diethylsilane, (N, N-diethylamino) diethylsilane, N, N-bis (trimethylsilyl) aminodiethylsilane, dimethylaminomethylethoxysilane, bis ( Dimethylamino) methylsilane, bis (dimethylamino) ethylsilane, bis (dimethylamino) phenylsilane, tris (dimethylamino) silane, tris (diethylamino) silane, tris (N, N-bis (trimethylsilyl) amino) silane, diacetoxymethyl Silane, trimethylsiloxymethylacetoxysilane, dimethylaminomethylethoxysilane, 1,1,3,3-tetramethyl-1-methoxydisiloxane, 1,1,3,3-tetramethyl-1-ethoxydisiloxa 1,1,3,3-tetramethyl-1-phenoxydisiloxane, pentamethyldisiloxane, 1,1,3,3-tetramethyldisilazane, 1,3,3,5,5,7,7 -Heptamethyl-1,1-dimethoxytetrasiloxane, 1,1,1,3,3,5,5-heptaExamples thereof include methyltrisiloxane, diacetoxymethylsilane, trimethylsiloxymethylacetoxysilane, one-end H polydimethylsiloxane, phenyltris (dimethylsiloxy) silane, and tetrakis (dimethylsiloxy) silane.
[0045]
Moreover, Formula (S-2)
[0046]
[Formula 4]

[0047]
As a compound represented by
Di-tert-butylsilane, phenylmethylsilane, diphenylsilane, dimethoxysilane, diethoxysilane, dipropoxysilane, diisopropoxysilane, dibutoxysilane,Diphenoxysilane, Methylphenylsilane, trimethylsiloxymethylsilane, and the like.
[0048]
Furthermore, Formula (S-3)
[0049]
[Chemical formula 5]

[0050]
As a compound represented by
Examples include methylsilane, ethylsilane, propylsilane, isopropylsilane, butylsilane, phenylsilane, hexylsilane, methoxysilane, ethoxysilane, propoxysilane, isopropoxysilane, butoxysilane, phenoxysilane, n-octadecylsilane, and n-octylsilane. .
[0051]
Furthermore, Formula (S-4)
[0052]
[Chemical 6]

[0053]
As a compound represented by
1,3-bis (trimethylsiloxy) -1,3-dimethyldisiloxane, bis (trimethylsiloxy) methylsilane, bis (trimethylsiloxy) ethylsilane, 1,1,1,3,5,5,5-heptamethyltrisiloxane 1,1,1,3,5,7,7-octamethyltetrasiloxane, tris (trimethoxysiloxy) silane, 1,1,3,3-tetramethyldisiloxane, 1,1,3,3 -Tetraisopropyldisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1,3-bis ( Trimethylsiloxy) -1,3-dimethyldisiloxane, methyl H siloxane-dimethyl siloxane copolymer, H-terminated polydimethyl siloxane, polymethyl H Hexane, polyethyl H siloxane, polyphenyl (dimethyl H siloxy) siloxane H end, methyl H siloxane - phenyl methyl siloxane copolymer, methyl H siloxane - like octylmethylsiloxane copolymer.
[0054]
Furthermore, Formula (S-5)
[0055]
[Chemical 7]

[0056]
As a compound represented by
1,3,5-trimethylcyclotrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasilane, 1,3,5-triethylcyclotri Siloxane, 1,3,5,7-tetraethylcyclotetrasiloxane, 1,3,5,7,9-pentaethylcyclopentasilane, 1,3,5-triphenylcyclotrisiloxane, 1,3,5,7 -Tetraphenylcyclotetrasiloxane, 1,3,5,7,9-pentaphenylcyclopentasilane and the like.
[0057]
Furthermore, Formula (S-6)
[0058]
[Chemical 8]

[0059]
The compound represented by these is mentioned.
[0060]
In addition to the compounds represented by the above formula, RSiO_1.5It is also possible to use polycelsesquioxane or T-resin (for example, SST-R8C51, manufactured by Chisso).
[0061]
The addition rate of the hydrosilane compound is 0.0001 to 100%, preferably 0.01 to 50%, based on the carbon-carbon unsaturated double bond unit of the conjugated diene polymer and / or hydrogenated product thereof. Furthermore, 0.01 to 20% is preferable from the balance between the improvement effect and the cost. If it is less than 0.0001%, the modification effects such as impact resistance, adhesiveness, and slidability hardly appear. In order to improve weather resistance, heat resistance and ozone resistance, it is preferable to reduce the proportion of carbon-carbon unsaturated double bonds in the conjugated diene polymer by hydrosilylation and hydrogenation.
[0062]
The catalyst residue is preferably removed from the modified conjugated diene polymer solution by the above production method. As a method for removing the catalyst, the solution after the reaction is treated with silica, silica gel, alumina, ion exchange resin or the like, or an aqueous solution whose pH is controlled according to the type of catalyst used when producing the modified conjugated diene polymer. There is a method of washing with. Further, a compound that reacts with the remaining catalyst may be added after completion of the reaction. The polymer concentration in the solution at this time is preferably 50% by weight or less. Although removal from a polymer having a high concentration exceeding 50% by weight is possible, it takes time to remove a large amount of catalyst, which is not preferable. If it is not necessary to remove the catalyst residue from the standpoint of physical properties, it may not be performed.
[0063]
Isolation of the modified conjugated diene polymer is performed by, for example, a method in which acetone or alcohol is added to the polymer solution to precipitate, a method in which the polymer solution is stirred in hot water, and the solvent is distilled off. Can do.
[0064]
The modified conjugated diene polymer of the present invention includes conventional auxiliary additive components such as plasticizers, antioxidants, heat stabilizers, stabilizers such as photodegradants, lubricants, flame retardants, antistatic agents, Nucleating agent, metal salt, organometallic compound, metal deactivator, antibacterial / antifungal agent, dispersant, softener, crosslinking agent, co-crosslinking agent, colorant, thermal acid generator, photoacid generator, additive Sulfur agents, vulcanization aids, foaming agents, foaming aids and the like can be added.
[0065]
Any plasticizer may be used as long as it penetrates between the molecules of the polymer to weaken the intermolecular force of the polymer and facilitates the molecular movement of the polymer. Specific examples thereof include, for example, dibutyl phthalate, diheptyl phthalate, Phthalic acid ester plasticizers such as diethylhexyl phthalate, diisononyl phthalate and diisodecyl phthalate, Aliphatic dibasic acid plastics such as di-2-ethylhexyl adipate, diisononyl adipate, diisodecyl adipate, and di-2-ethylhexyl azelate Agents, polyester plasticizers, epoxidized soybean oil, epoxidized linseed oil, epoxidized octyl stearate, epoxidized fatty acid butyl, epoxidized linseed oil fatty acid butyl, etc., tricresyl phosphate, triphenyl phosphate, Tri 2 ethyl f Shiruhosufeto, trixylenyl phosphate, phosphoric acid ester plasticizers such as triethyl phosphate, tri 2-ethylhexyl trimellitate rate, trimellitic acid ester plasticizers such as tri-isodecyl trimellitate and the like. These can be used alone or in combination of two or more.
[0066]
Specific examples of the stabilizer include, for example, 2,6-di-t-butyl-4-methylphenol, n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl). ) Propionate, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanate, 4,4'-butylidenebis- (3-methyl-6-t-butylphenol), triethylene glycol-bis [3 -(3-t-butyl-4-hydroxy-5-methylphenyl) propionate] and the like, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate , Distearyl-3,3′-thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate), etc. Antioxidant, trisnonylphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol phosphite Phyto, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, tetrakis (2,4 Phosphorus antioxidants such as -di-t-butylphenyl) -4,4'-biphenylene-di-phosphonite, lactone antioxidants, hydroxyamine antioxidants and the like.
Specific examples of the heat stabilizer include metal ions such as Mg, Ca, Ba, Zn, and Pb, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, ricinoleic acid, isodecanoic acid, and neoic acid. Metal salts with fatty acids, dimethyltin bis-2-ethylhexyl thioglycol, monomethyltin tearoxyethyl mercaptide, dimethyltin tearoxyethyl mercaptaide, dibutyltin maleate, dibutyltin bisbutylmaleate, dibutyltin dilaurate, dimethyltin Examples thereof include heat stabilizers such as organotin stabilizers such as bis-2-ethylhexyl thioglycolate and dibutyltin β-mercaptopropionate.
Specific examples of the photodegradation inhibitor include, for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α- Dimethylbenzyl) phenyl] benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t- Butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-amyl) benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzo Benzotriazole light stabilizers such as triazole, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxyben Benzophenone light stabilizers such as zophenone-5-sulfonic acid, 2-hydroxy-4-n-octylbenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, phenyl salicylate, 4-t-butylphenyl salicylate, etc. Salicylate-based light stabilizers, cyanoacrylate-based light stabilizers such as ethyl-2-cyano-3,3-diphenyl acrylate, and oxazolic acid anilide-based compounds such as 2-ethoxy-2′-ethyl oxalic acid bisanilide Light stabilizer, bis- (2,2,6,6-tetramethyl-4-piperidienyl) sebacate, bis- (N-methyl-2,2,6,6-tetramethyl-4-piperidienyl) sebacate, bis- (1,2,2,6,6-pentamethyl-4-piperidienyl) -2 (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4 Examples include hindered amine light stabilizers such as -butanetetracarboxylate and tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate.
These stabilizers can be used alone or in combination of two or more.
The amount of addition is preferably 0.01 to 1% by weight, more preferably 0.01 to 0.5% by weight, based on the polymer component.
[0067]
Specific examples of the lubricant include, for example, hydrocarbon-based lubricants such as liquid paraffin, paraffin wax, and polyethylene wax, fatty acid-based and aliphatic alcohol-based lubricants such as stearyl alcohol, stearic acid, and 12-hydroxystearic acid, and stearamide. , Aliphatic amide lubricants such as oleic acid amide, erucic acid amide, methylene bis stearic acid amide, ethylene bis stearic acid amide, metal soap based lubricants such as calcium stearate, zinc stearate, magnesium stearate, lead stearate, hardening Examples thereof include ester lubricants such as oil, stearic acid monoglyceride, butyl stearate, pentaerythritol tetrastearate and stearyl stearate.
These can be used alone or in combination of two or more.
[0068]
Specific examples of the flame retardant include, for example, halogen flame retardants such as tetrabromobisphenol A, decabromodiphenyl ether, hexabromocyclodecane, chlorinated flame retardants such as chlorinated polyethylene, chlorinated paraffin, and perchlorocyclopentadecane. Phosphoric flame retardants such as tricresyl phosphate, triphenyl phosphate, trischloroethyl phosphate, ammonium polyphosphate, red phosphorus, magnesium hydroxide, aluminum hydroxide, zirconium hydroxide, calcium hydroxide, barium hydroxide, basic carbonate Examples include magnesium, antimony trioxide, zinc borate, tin oxide, phosphorus pentoxide, zirconium, nitrogenated guanidine, dolomite, hydrotalcite, and tin oxide. Of these, magnesium hydroxide, aluminum hydroxide, and calcium hydroxide are useful and preferred because they are easily available industrially. Magnesium hydroxide is particularly preferable because of its high flame retardant effect.
In addition, when using the above inorganic flame retardants, in order to enhance the flame retardant effect, silicone compounds, quartz glass, etc., and water glass, frit, silicon nitride short fibers for preventing drip, etc. as flame retardant aids should be used in combination. You can also.
These can be used alone or in combination of two or more.
[0069]
Specific examples of the metal salt and organometallic compound include, for example, cis-bis (acetonitrile) dichloroplatinum (II), potassium tetracyanoplatinate (II), potassium hexacyanoplatinate (IV), platinum (II) cyanide, Hexachloroplatinic (IV) acid hexahydrate, potassium diplatinate, diplatinum oxide (monohydrate), cis-bis (benzonitrile) dichloroplatinum (II), platinum hexafluoropentadionate, platinum 2,4-pentadionate, palladium-calcium carbonate, bis (benzonitrile) dichloropalladium (II), bis (acetonitrile) dichloropalladium (II), potassium tetracyanopalladium (II) trihydrate, tetrafluoroboric acid Tetrakis (acetonitrile) palladium (II), bis (benzonitrile) palladium (II) chloride, palladium hexafluoro Nandionate, palladium 2,4-pentanedionate, phenyl magnesium bromide, ethyl magnesium bromide, cyclohexyl magnesium chloride, phenyl magnesium chloride, allyl magnesium bromide, allyl magnesium chloride, methyl magnesium iodide, 4-fluorophenyl magnesium bromide , Magnesium stearate, magnesium 2,4-pentanedionate, magnesium hexafluoropentanedionate, magnesium trifluoropentanedionate, manganese (II) chloride tetrahydrate, manganese (IV) oxide, potassium permanganate, manganese Barium acid, manganese (II) sulfate monohydrate, manganese (II) acetylacetonate, cyclopentadienyl tricarbonyl manganese, manganese (II) difluoride, manganese (II) 2,4-pen Ndionate, potassium hexacyanocobalt (II) iron (II), cobalt chloride (hexahydrate), cobalt nitrate (II) hexahydrate, hexaamminecobalt (III) chloride, dicarbonylcyclopentadienyl cobalt, cobalt (III) Sepallate trichloride, dichlorobis (triphenylphosphine) cobalt (II), bis (salicylaldehyde) cobalt (II), cobalt (II) phthalocyanine, cobalt (II) bromide hydrate, cobalt boride, bis (Cyclopentadienyl) cobalt, cobalt (II) iodide, cobalt (II) carbonate hydrate, cobalt (II) acetate, cobalt (II) perchlorate hexahydrate, cobalt naphthenate, bis (tetrafluoroborate) (1,5-cyclooctadiene) rhodium (I) hydrate, (bicyclo [2.2.1] hepta-2,5-diene) [1,4-bis (dipheni Ruphosphino) butane] rhodium (I) tetrafluoroborate, tetrafluoroborate [1,4-bis (diphenylphosphino) butane] (1,5-cyclooctadiene) rhodium (I), (1,5-cycloocta Diene) rhodium (I) tetrafluoroborate, hexacyanoruthenium (II) potassium hydrate, ruthenium (III) 2,4-pentandionate, molybdenum pentachloride, ammonium molybdate, tris (acetonitrile) tricarbonylmolybdenum, tri Carbonyl triamine molybdenum, benzene chromium tricarbonyl, pyridinium chlorochromate, chromium (III) chloride, potassium dichromate, chromium (III) acetylacetonate, bis (tetrabutylammonium dichromate), chromium hexacarbonyl, tricarbonyl ( Methylben Zoate) chromium, tricarbonyl (cycloheptatriene) chromium, chromium boride, potassium hexacyanochromate (III), lithium bis (trimethylsilyl) amide, lithium diphenylphosphide, lithium 2,4-pentandionate and the like.
These can be used alone or in combination of two or more.
[0070]
When the polymer chain is crosslinked by adding and reacting the thermal acid generator and the photoacid generator, it is also preferable to moderately crosslink. The thermal acid generator is a compound that generates an acid by heating to 50 to 450 ° C., preferably 200 to 350 ° C., and is an onium salt such as a sulfonium salt, a benzothiazolium salt, an ammonium salt, or a phosphonium salt. Is used.
Moreover, a photo-acid generator is a compound which generate | occur | produces an acid by ultraviolet light irradiation of 1-100 mJ normally, Preferably 10-50 mJ. The amount of these acid generators added is preferably 0.01 to 30% by weight, more preferably 0.01 to 10% by weight, based on the crosslinkable polymer component.
These can be used alone or in combination of two or more.
[0071]
Further, the modified conjugated diene polymer of the present invention may be brought into contact with a compound that can react with the modified conjugated diene polymer in a solution or in a kneader such as an extruder.
[0072]
The modified conjugated diene polymer of the present invention can be blended with various polymers to give a modified conjugated diene polymer composition having excellent physical properties.
The modified conjugated diene polymer composition of the present invention includes the modified conjugated diene polymer (hereinafter referred to as “component (I)”) and a nonpolar polymer (hereinafter referred to as “component (II-1)”). And at least one selected from a polar polymer (hereinafter referred to as “component (II-2)”) and a filler (hereinafter referred to as “component (III)”). The nonpolar polymer and the polar polymer may be a resin or a rubber.
[0073]
As said component (II-1) (nonpolar polymer), at least 1 sort (s) chosen from a polyolefin-type polymer and an aromatic vinyl-type polymer is preferable. Examples of the polyolefin polymer include polyethylene resins such as very low density polyethylene (VLDPE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), medium density polyethylene (MDPE), and high density polyethylene (HDPE), Random type, block type or homo type polypropylene resin (PP), polybutadiene (PBD), poly 1-butene (PB), polymethylpentene (PMP), ethylene / propylene copolymer (EPM), ethylene 1-butene Copolymer (EBM), ethylene / hexene copolymer (EHM), ethylene / octene copolymer (EOM), ethylene / propylene / 1-butene copolymer (EPBM), ethylene / propylene / diene copolymer ( EPDM), ethylene 1- Ten-diene copolymer (EBDM), propylene-1-butene copolymer (PBM) propylene and copolymers of α- olefin having 4 to 20 carbon atoms, and the like. These can be used alone or in combination of two or more.
[0074]
Examples of the aromatic vinyl polymer include general polystyrene (GPPS), high impact polystyrene (HIPS), isotactic polystyrene (iPS), syndiotactic polystyrene (sPS), and poly α-methylstyrene (PαMS). Etc. These can be used alone or in combination of two or more.
[0075]
Moreover, as said component (II-2) (polar polymer), a carboxyl group (an acid anhydride and the carboxyl group used as a metal salt are also included), a hydroxyl group, a halogen group, an epoxy group, an oxazoline group, sulfone. A polymer having at least one selected from an acid group, an isocyanate group, a thiol group, an ester bond, a carbonate bond, an amide bond, and an ether bond is preferable. Polymers having these include ethylene / acrylic acid copolymer (EAA), ethylene / methacrylic acid copolymer (EMA), ethylene / glycidyl methacrylate copolymer (EGMA), ethylene / maleic anhydride / acrylic acid. Copolymer, an ionomer having a (meth) acrylic acid content of 7 to 15 mol% and a copolymer of ethylene and (meth) acrylic acid, and having a neutralization degree of 20% or more with metal ions such as Na, Zn, Mg, etc. (IO), polyvinyl acetate (PVAc), nylon 4,6 (PA46), nylon 6 (PA6), nylon 6,6 (PA66), nylon 6,10 (PA610), nylon 6,12 (PA612), Nylon 12 (PA12), nylon 6, T (PA6T), nylon 9, T (PA9T), reinforced polyamide, hexamethyl Polyamide resins (PA) such as modified polyamide made from diamine and terephthalic acid, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polyester resins such as polylactone, liquid crystalline polyester (LCP) Polycarbonate (PC) such as poly-2,2-bis (hydroxyphenyl) propane carbonate, ethylene / ethyl acrylate copolymer (EEA), ethylene / methyl acrylate copolymer (EMA), ethylene / hydroxy methacrylate Ethyl copolymer (HEMA), ethylene / methacrylic acid 2-hydroxypropyl copolymer, ethylene / aminoalkyl methacrylate copolymer, ethylene / butyl methacrylate copolymer, polymethyl methacrylate PMMA), polyethyl methacrylate (PEMA), acrylic polymers such as methacryl-styrene copolymer (MS Resin), polyacetal (POM), ABS resin, AES resin, ASA resin, diallyl phthalate resin (DAP), EVA Resin, EEA resin, phenol resin (PF), polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOH), polyarylate (PAR), norbornene resin, poly (2,6-dimethyl-1,4-phenylene) Ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4) -Phenylene ether (PPE) such as phenylene ether), modified poly Nylene ether (modified PPE), polyethylene oxide, polyphenylene sulfide (PPS), polysulfone (PSU), polyethersulfone (PES), thermoplastic polyester elastomer, thermoplastic polyurethane elastomer, thermoplastic polyamide elastomer, α, β-unsaturated nitrile -Acrylic acid ester-Unsaturated diene copolymer rubber, urethane rubber, chlorinated butyl rubber, brominated butyl rubber, acrylic rubber, ethylene / acrylic rubber, epichlorohydrin rubber, epichlorohydrin / ethylene oxide rubber, chloroprene rubber, chlorosulfonated polyethylene, chlorinated polyethylene Chlorinated polypropylene, oxazoline-modified polystyrene, oxazoline-modified styrene / acrylonitrile copolymer, and the like. These can be used singly or in combination of two or more.
[0076]
Among the polymers exemplified as the components (II-1) and (II-2), a polyethylene resin containing ethylene as a structural unit due to the molecular chain structure of the component (I), and propylene as a structural unit Polypropylene resins containing aromatic vinyl as a structural unit, and polyesters such as polyethylene terephthalate are particularly preferable because they have an excellent effect of improving physical properties and can be used in a wide range of applications. Moreover, when the said component (I) has a polar group, it is also preferable to add the compound which shakes the functional group which reacts with the polar group.
[0077]
When the modified conjugated diene polymer composition of the present invention contains the component (I) and the component (II-1), or the component (I) and the component (II-2), In any case, the content can be as follows. That is, when the component (II-1) and the component (II-2) are expressed as “component (II)”, when the total of the component (I) and the component (II) is 100% by weight, I) / (II) is preferably 1 to 99% by weight / 99 to 1% by weight, more preferably 5 to 95% by weight / 95 to 5% by weight, and still more preferably 10 to 90% by weight / 90 to 10% by weight. %, Particularly preferably 20 to 80% by weight / 80 to 20% by weight. By setting the content ratio as described above, the required performance can be satisfied.
[0078]
Moreover, when the modified conjugated diene polymer composition of the present invention contains the above component (I), the above component (II-1) and the above component (II-2), the content ratio may be as follows. it can. That is, in the component (II-1) and the component (II-2), (II-1) / (II-2) is preferably 1 to 99% by weight / 99 to 1% by weight, more preferably 5 to 5%. 95% by weight / 95 to 5% by weight, more preferably 10 to 90% by weight / 90 to 10% by weight. The content of the component (I) is the above component (II-1) and the component (II- The lower content of 2) is 100% by weight, preferably 1 to 100% by weight, more preferably 5 to 50% by weight, and still more preferably 10 to 40% by weight. By setting the content ratio as described above, the required performance can be satisfied.
[0079]
The component (III) is not particularly limited, but specific examples include magnesium hydroxide, aluminum hydroxide, zirconium hydroxide, calcium hydroxide, barium hydroxide, basic magnesium carbonate, dolomite, hydrotalcite, Tin oxide, titanium oxide, zinc oxide, iron oxide, magnesium oxide, alumina, barium sulfate, calcium sulfate, sodium sulfate, calcium sulfite, calcium silicate, calcium carbonate, magnesium carbonate, phosphate compound, carbon, glass beads, glass Examples thereof include inorganic fibers such as powder, asbestos, mica, talc, silica, zeolite, kaolin, silica sand, quartzite, quartz powder, shirasu, and metal fibers, and inorganic whiskers such as potassium titanate whiskers. And 1 type, or 2 or more types of these can be used. Further, the filler of the above component (III) may be used as it is, but for the purpose of increasing affinity with each polymer and interfacial binding force, fatty acids (stearic acid, oleic acid, palmitic acid) Or a metal salt thereof, paraffin, wax, polyethylene wax or a modified product thereof, an organic borane, an organic titanate, a silane coupling agent, an aluminum coupling agent, or the like may be used.
[0080]
When the modified conjugated diene polymer composition of the present invention contains (1) the component (I) and the component (III), (2) the component (I), the component (II-1) and the component (III (3) When the above component (I), component (II-2) and component (III) are contained, (4) The above component (I), component (II-1), component (II) -2) and the component (III), the content can be as follows. That is, the content of the component (III) (filler) is preferably 1 to 200% by weight, more preferably 2 to 150% when the total of the polymer components such as the component (I) is 100% by weight. % By weight, particularly preferably 5 to 100% by weight. By setting it as this range, properties, such as a flame retardance and intensity | strength, can be provided, without inhibiting the effect by the said component (I), component (II-1), and component (II-2).
[0081]
For the production of the modified conjugated diene polymer composition of the present invention, a conventionally known kneader such as an extruder, a pressure kneader, a Banbury mixer, or a kneader combining them can be used. In kneading, each component may be kneaded at once, or a multistage divided kneading method may be employed in which any components are kneaded and then the remaining components are added and kneaded. The polymer composition thus obtained can be molded by a known method such as injection molding, extrusion molding, rotational molding, press molding, or hollow molding.
[0082]
The modified conjugated diene polymer composition of the present invention is provided with the above-described configuration, thereby giving a molded product excellent in reforming effects such as tensile strength, releasability, slidability, and flexibility. Any or more of these reforming effects may be used.
[0083]
【Example】
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, unless it exceeds the main point of this invention, it is not limited to an Example. Various measurements in the examples were based on the following methods.
(1) The microstructure of the copolymer was determined by an infrared absorption spectrum method (Morero method).
(2) The bound styrene content was determined by preparing a calibration curve by infrared absorption spectroscopy.
(3) The weight average molecular weight was calculated in terms of polystyrene using gel permeation chromatography (GPC) (manufactured by TOSOH, HLC-8120).
(4) Coupling efficiency is determined from the change in molecular weight before and after the addition of the coupling agent, and represents how much of the coupled polymer is included in the total polymer.
(5) Addition rate and hydrogenation rate of hydrosilane compound of conjugated diene polymer are 270 MHz.¹Calculated from 1 H-NMR measurement.
[0084]
(6) The melt flow rate (MFR) was measured at 230 ° C. under a load of 2.16 kg in accordance with ASTM D1238, and used as an index of molding processability.
(7) Tensile breaking strength and elongation were measured by performing a tensile test of a test piece (Type 1) under a temperature condition of 23 ° C. according to ASTM D638.
(8) The moldability was evaluated by the releasability at the time of preparing the test piece.
○: Can be easily removed from the mold.
Δ: It is necessary to apply force and peel off from the mold.
(9) Hardness
It measured according to JIS K7215.
(10) The slidability was evaluated by a Taber abrasion test according to JIS K6264.
A: Wear amount 0 to 0.3 mg / less than 1,000 times
○: Abrasion amount 0.3 to 0.6 mg / less than 1,000 times
X: Amount of wear 0.6 mg / 1,000 times or more
(11) For blocking resistance, pellets were prepared using a 55 mmφ single screw extruder and a pelletizer. Load the prepared pellets in a constant temperature bath at 60 ° C. at 30 kg / cm²Based on how the pellets agglomerate after 72 hours, they were ranked as follows.
A: Not hardened at all.
○: Almost no solidification and easily fall apart.
Δ: Slightly solidified, but can be loosened relatively easily.
X: It is hard to loosen and loosen.
[0085]
(1) Production of hydrogenation catalyst
Hydrogenation catalysts (Catalysts A and B) used in Examples and Comparative Examples were produced by the following method.
[Example of hydrogenation catalyst synthesis]
<Production Example 1> Catalyst A [Bis (η^Five-Cyclopentadienyl) titanium (tetrahydrofurfuryloxy) chloride]
200 ml of anhydrous tetrahydrofuran and 0.2 mol of tetrahydrofurfuryl alcohol were added to a 1 L three-necked flask equipped with a stirrer and a dropping funnel. The apparatus was dried with dry nitrogen, and an n-butyllithium / cyclohexane solution (0.2 mol) was dropped into the flask at 15 ° C. After completion of the reaction, a tetrahydrofurfuryloxylithium solution was obtained.
[0086]
A 1 L three-necked flask equipped with a stirrer and a dropping funnel dried with dry nitrogen was bis (η^Five-Cyclopentadienyl) titanium dichloride 49.8 g (0.2 mol) and 250 ml of anhydrous tetrahydrofuran were added. The tetrahydrofuran solution of tetrafurfuryloxylithium synthesized previously was added dropwise over about 1 hour with stirring at room temperature.
After about 2 hours, the reddish brown liquid was filtered, the insoluble part was washed with dichloromethane, the filtrate and the washing liquid were combined, and the solvent was removed under reduced pressure, whereby catalyst A [bis (η^Five-Cyclopentadienyl) titanium (tetrahydrofurfuryloxy) chloride] (also referred to as “[chlorobis (2,4-cyclopentadienyl) titanium (IV) tetrahydrofurfurylalkoxide]”)). The yield was 95%.
[0087]
<Production Example 2> Catalyst B [Bis (η^Five-Cyclopentadienyl) titanium (furfuryloxy) chloride]
200 ml of anhydrous tetrahydrofuran and 0.2 mol of furfuryl alcohol were added to a 1 L three-necked flask equipped with a stirrer and a dropping funnel. The apparatus was dried with dry nitrogen, and an n-butyllithium / cyclohexane solution (0.2 mol) was dropped into the flask at 15 ° C. After completion of the reaction, a furfuryloxylithium solution was obtained.
[0088]
A 1 L three-necked flask equipped with a stirrer and a dropping funnel dried with dry nitrogen was bis (η^Five-Cyclopentadienyl) titanium dichloride 49.8 g (0.2 mol) and 250 ml of anhydrous tetrahydrofuran were added. The tetrahydrofuran solution of furfuryloxylithium synthesized previously was added dropwise over about 1 hour with stirring at room temperature. After about 2 hours, the reddish brown liquid was filtered, the insoluble part was washed with dichloromethane, the filtrate and the washing liquid were combined, and the solvent was removed under reduced pressure, whereby catalyst B [bis (η^Five-Cyclopentadienyl) titanium (furfuryloxy) chloride] (also referred to as “[chlorobis (2,4-cyclopentadienyl) titanium (IV) furfurylalkoxide]”)). The yield was 97%.
[0089]
(2) Production of modified conjugated diene polymer
A modified conjugated diene polymer was produced by the method described below. A block composed of styrene monomer is composed of S, a butadiene monomer, and a block having the characteristics of (C) block is composed of C, a block composed of butadiene monomer, and a block having the characteristics of (D) block is composed of B, styrene and butadiene. And (E) a block having the feature of the block is made of SB and methyl methacrylate, and (F) a block having the feature of the block is abbreviated as M. The various properties of the modified conjugated diene polymer were measured according to the following methods. The results are shown in Table 1 below.
[0090]
[Production Example of Conjugated Diene Compound Polymer]
<Production Example 3> Production of CBC copolymer (a-1)
5,000 g of cyclohexane, 300 g of 1,3-butadiene, 0.25 g of tetrahydrofuran, and 0.77 g of n-butyllithium were added to a reaction vessel having an internal volume of 10 liters purged with nitrogen, and polymerized at a polymerization temperature of 70 ° C. After completion of the reaction, a part of the polymer solution was taken out and analyzed for the microstructure. As a result, it was polybutadiene having a 1,2-bond content of 13% by weight. Subsequently, the temperature of the reaction solution was set to 20 ° C., 75 g of tetrahydrofuran and 700 g of butadiene were added, and adiabatic polymerization was performed. After reacting for 30 minutes, 0.55 g of methyldichlorosilane was added and reacted for another 30 minutes. When a partly taken out polymer was analyzed, the 1,2-bond content of the intermediate butadiene block was 80% by weight, the weight average molecular weight measured by GPC was about 300,000, and the coupling rate was 83%.
[0091]
<Production Example 4> Production of random SB copolymer (a-2)
Into a reaction vessel with an internal volume of 10 liters substituted with nitrogen, 5,000 g of cyclohexane, 700 g of 1,3-butadiene, 300 g of styrene, 20 g of tetrahydrofuran, and 0.65 g of n-butyllithium are added, and adiabatic polymerization at a polymerization start temperature of 40 ° C. did. After 30 minutes, hydrogen was introduced into the system to deactivate the polymer living. When a part of the polymer taken out was analyzed, the 1,2-bond content was 47% by weight, the styrene content was 30.0% by weight, and the weight average molecular weight measured by GPC was about 160,000.
[0092]
<Production Example 5> Production of SBS copolymer (a-3)
Into a reaction vessel with an internal volume of 10 liters purged with nitrogen, 5,000 g of cyclohexane, 75 g of styrene, 140 g of tetrahydrofuran and 0.9 g of n-butyllithium are added and polymerized at a polymerization start temperature of 50 ° C. As a temperature, 1,850 butadiene of 1,3-butadiene was added and subjected to adiabatic polymerization. After 30 minutes, 75 g of styrene was added for further polymerization. After 30 minutes, hydrogen was introduced into the system to deactivate the polymer living. When a part of the polymer taken out was analyzed, it contained 78% by weight of 1,2-vinyl bond, the styrene content was 14.8% by weight, and the weight average molecular weight measured by GPC was about 130,000.
[0093]
<Production Example 6> Production of S—B—C copolymer (a-4)
Into a reaction vessel purged with nitrogen and having an internal volume of 10 liters, 5,000 g of cyclohexane, 300 g of 1,3-butadiene, 0.25 g of tetrahydrofuran, and 0.9 g of n-butyllithium were added, and polymerization was performed at a polymerization start temperature of 70 ° C. After completion of the reaction, a part of the polymer solution was taken out and analyzed for the microstructure. As a result, it was polybutadiene having a 1.2-bond content of 13%. Next, the temperature of this reaction solution was set to 30 ° C., 17.5 g of tetrahydrofuran was added, and 500 g of 1,3-butadiene was added for adiabatic polymerization. After reacting for 30 minutes, 200 g of styrene was added and reacted for 30 minutes. As a result of analyzing a partially extracted polymer, the polymer had 50% by weight of 1,2-vinyl bond in the intermediate butadiene block, 19.9% by weight of styrene, and the weight average molecular weight measured by GPC was about 130,000. .
[0094]
<Production Example 7> Production of SBM copolymer (a-5)
5,000 g of methylcyclohexane, 27.5 g of tetrahydrofuran, 300 g of styrene, and 1.0 g of n-butyllithium were added to a reaction vessel purged with nitrogen and having an internal volume of 15 liters, and polymerized at a polymerization initiation temperature of 40 ° C. After completion of the reaction, the temperature was set to 10 ° C., 600 g of 1,3-butadiene was added, and adiabatic polymerization was performed. After completion of the reaction, 2.5 g of 1,1-diphenylethylene was added and the temperature was cooled to 0 ° C. When a part of the reaction solution was taken out and the microstructure was analyzed, it was found to be an SB diblock polymer having a 1,2-bond content of 60% by weight and a styrene content of 33.2%. Next, 400 g of tetrahydrofuran was added and the temperature was further cooled to −30 ° C., and 100 g of methyl methacrylate was added and reacted. After completion of the reaction, 0.4 g of methanol was added to complete the polymerization. When a partially extracted polymer was analyzed, the weight average molecular weight measured by GPC of the polymer was about 100,000.
[0095]
<Production Example 8> Production of SB-polysiloxane copolymer (a-6)
Into a reaction vessel purged with nitrogen and having an internal volume of 15 liters, 5,000 g of cyclohexane, 27.5 g of tetrahydrofuran, 150 g of styrene and 0.7 g of n-butyllithium were added and polymerized at a polymerization initiation temperature of 50 ° C. Was adiabatic polymerization by adding 600 g of 1,3-butadiene. After completion of the reaction, a part of the reaction solution was taken out and analyzed for microstructure. As a result, it was found to be an SB diblock polymer having a 1,2-bond content of 60% by weight and a styrene content of 20.0% by weight. all right. Next, the reaction vessel temperature was kept at 60 ° C., 10 g of 10% by weight toluene solution of dimethylcyclotrisiloxane was added, and the mixture was reacted for 30 minutes. Thereafter, a toluene solution of dimethylcyclotrisiloxane was slowly added so that the total amount of dimethylcyclotrisiloxane was 250 g. After completion of the reaction, trimethylsilyl chloride was added to stop the reaction. When a partially extracted polymer was analyzed, the weight average molecular weight measured by GPC of the polymer was about 150,000.
[0096]
Next, examples of the modified conjugated diene polymer will be shown.
[Production Example of Modified Conjugated Diene Compound Polymer]
<Example 1> Production of hydrogenated 1,1,3,3, -tetramethyl-1-phenoxydisilane-modified CEBC copolymer (I-1)
To the polymer solution of (a-1) shown in Production Example 3, 1.1 g of dimethylaluminum chloride, 2.0 g of catalyst A and 0.6 g of n-BuLi were added, and then 1,1,3,3 , -Tetramethyl-1-phenoxydisilane (10.0 g) was added, and hydrosilylation was performed at a temperature of 100 ° C. for 1 hour. Hydrogen was introduced into the reaction vessel as it was, and hydrogenation reaction and hydrosilylation were performed for 1 hour at a hydrogen pressure of 1.0 MPa. The obtained polymer was purified, and the addition rate and hydrogenation rate of the hydrosilyl compound relative to (I-1) were determined by NMR measurement. The addition rate of 1,1,3,3-tetramethyl-1-phenoxydisilane was determined from a peak around 7 ppm derived from a phenoxy group. The results are shown in Table 1.
[0097]
<Example 2> Production of hydrogenated piece-terminated H polydimethylsiloxane-modified random SB copolymer (I-2)
To the polymer solution of (a-2) shown in Production Example 4, 0.8 g of dimethylaluminum chloride, 1.4 g of catalyst B and 0.4 g of n-BuLi were added, and then one-end H polydimethylsiloxane ( 10.0 g of Shin-Etsu Chemical Co., Ltd., X-21-3126) was added, and hydrosilylation was performed at a temperature of 100 ° C. for 1 hour. Hydrogen was introduced into the reaction vessel as it was, and hydrogenation reaction and hydrosilylation were performed for 1 hour at a hydrogen pressure of 1.0 MPa. After purification of the obtained polymer, the addition rate and hydrogenation rate of the hydrosilyl compound relative to (I-2) were determined by NMR measurement. The addition rate of one-terminal H polydimethylsiloxane was determined from a peak near 0 ppm derived from a methylsilyl group. The results are shown in Table 1.
[0098]
<Example 3> Production of hydrogenated diethoxymethylsilane-modified SEBS copolymer (I-3)
To the polymer solution of (a-3) shown in Production Example 5, 1.0 g of dimethylaluminum chloride, 1.7 g of catalyst A and 0.5 g of n-BuLi were added, and then 10.0 g of diethoxymethylsilane. Immediately after addition of hydrogen, hydrogen was introduced, and hydrosilylation and hydrogenation reaction were performed for 1 hour at a hydrogen pressure of 1.0 MPa and a temperature of 100 ° C. The obtained polymer was purified, and the addition rate and hydrogenation rate of the hydrosilyl compound relative to (I-3) were determined by NMR measurement. The addition rate of diethoxymethylsilane was determined from a peak near 0 ppm derived from a methylsilyl group. The results are shown in Table 1.
[0099]
<Example 4> Production of hydrogenated 1,3,5-trimethylcyclotrisiloxane-modified SEBC copolymer (I-4)
To the polymer solution of (a-4) shown in Production Example 6, 1.0 g of dimethylaluminum chloride, 1.6 g of catalyst A and 0.5 g of n-BuLi were added, and then 1,3,5-trimethyl. 10.0 g of cyclotrisiloxane was added, and hydrosilylation was performed at a temperature of 100 ° C. for 1 hour. Hydrogen was introduced into the reaction vessel as it was, and hydrogenation reaction and hydrosilylation were performed for 1 hour at a hydrogen pressure of 1.0 MPa. The obtained polymer was purified, and the addition rate and hydrogenation rate of the hydrosilyl compound relative to (I-4) were determined by NMR measurement. The addition rate of 1,3,5-trimethylcyclotrisiloxane was determined from a peak near 0 ppm derived from a methylsilyl group. The results are shown in Table 1.
[0100]
<Example 5> Production of hydrogenated piece-terminated H polydimethylsiloxane-modified SEBM copolymer (I-5)
To the polymer solution of (a-5) shown in Production Example 7, 1.2 g of dimethylaluminum chloride and (Ind) RuCl (PPh_Three)_ThreeAfter adding 4.9 g of the catalyst and 0.6 g of n-BuLi, 10.0 g of one-terminal H polydimethylsiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., X-21-3126) was added, and the temperature was 100. Hydrosilylation was carried out for 1 hour at 0 ° C. Hydrogen was introduced into the reaction vessel as it was, and hydrogenation reaction and hydrosilylation were performed at a hydrogen pressure of 2.0 MPa for 2 hours. The obtained polymer was purified, and the addition rate and hydrogenation rate of the hydrosilyl compound relative to (I-5) were determined by NMR measurement. The addition rate of one-terminal H polydimethylsiloxane was determined from a peak near 0 ppm derived from a methylsilyl group. The results are shown in Table 1.
[0101]
<Example 6> Production of hydrogenated 1,1,3,3-tetramethyl-1-phenoxydisilane-modified S-EB-polysiloxane copolymer (I-6)
To the polymer solution of (a-6) shown in Production Example 8, 0.7 g of dimethylaluminum chloride, 1.2 g of catalyst A and 0.4 g of n-BuLi were added, and then 1,1,3,3 , -Tetramethyl-1-phenoxydisilane (10.0 g) was added, and hydrosilylation was performed at a temperature of 100 ° C. for 1 hour. Hydrogen was introduced into the reaction vessel as it was, and hydrogenation reaction and hydrosilylation were performed for 1 hour at a hydrogen pressure of 1.0 MPa. After purification of the obtained polymer, the addition rate and hydrogenation rate of the hydrosilyl compound relative to (I-6) were determined by NMR measurement. The addition rate of 1,1,3,3-tetramethyl-1-phenoxydisilane was determined from a peak around 7 ppm derived from a phenoxy group. The results are shown in Table 1.
[0102]
[Table 1]

[0103]
As apparent from Table 1, the hydrosilylation of the polymer having a carbon-carbon double bond is the same catalyst as the hydrogenation reaction, and simultaneously with the hydrogenation reaction, before the hydrogenation reaction or after the hydrogenation reaction is started. It was possible to do. Compared to the polymers obtained by the same production method as in Production Examples 3 to 8, the polymers obtained in Examples 1 to 6 have hydrosilylated and highly hydrogenated carbon-carbon double bonds. Therefore, the polymer was excellent in heat resistance and weather resistance.
[0104]
In evaluating the blending of the modified conjugated diene polymer, an unmodified hydrogenated polymer was produced as follows for comparison.
[0105]
<Comparative example 1> CEBC copolymer (b-1)
A polymer was produced in the same manner as in Production Example 3. When the obtained polymer was analyzed, the 1,2-bond content was 13% by weight for the first butadiene block, 80% by weight for the intermediate butadiene block, and the weight average molecular weight was about 300,000, which was the same polymer as in (a-1). Got. After hydrogen was introduced into the reaction vessel and the hydrogen pressure was 1.0 MPa, 0.7 g of catalyst A and 0.1 g of n-BuLi were added, and a hydrogenation reaction was performed for 1 hour. The hydrogenation rate of the obtained polymer was 99.0%.
[0106]
<Comparative Example 2> Production of hydrogenated random SB copolymer (b-2)
A polymer was produced in the same manner as in Production Example 4. When the obtained polymer was analyzed, a polymer similar to (a-2) having a 1,2-bond content of 47% by weight, a styrene content of 29.9% by weight and a weight average molecular weight of about 160,000 was obtained. Hydrogen was introduced into the reaction vessel, the hydrogen pressure was 1.0 MPa, 0.5 g of catalyst B and 0.1 g of n-BuLi were added, and hydrogenation reaction was performed for 1 hour. The hydrogenation rate of the obtained polymer was 98.8%.
[0107]
<Comparative Example 3> Production of SEBS copolymer (b-3)
A polymer was produced in the same manner as in Production Example 5. When the obtained polymer was analyzed, the 1,2-bond content was 78% by weight, the styrene content was 15.0% by weight, the weight average molecular weight was about 130,000, and a polymer similar to (a-3) was obtained. . Hydrogen was introduced into the reaction vessel, the hydrogen pressure was 1.0 MPa, 0.3 g of catalyst A and 0.1 g of n-BuLi were added, and hydrogenation reaction was performed for 1 hour. The hydrogenation rate of the obtained polymer was 99.0%.
[0108]
<Comparative Example 4> Production of SEBC copolymer (b-4)
A polymer was produced in the same manner as in Production Example 6. When the obtained polymer was analyzed, the 1,2-bond content was 13% by weight for the first butadiene block, 50% by weight for the intermediate butadiene block, 19.9% by weight for styrene, and the weight average molecular weight was about 130,000 ( A polymer similar to a-4) was obtained. Hydrogen was introduced into the reaction vessel, the hydrogen pressure was 1.0 MPa, 0.5 g of catalyst A and 0.1 g of n-BuLi were added, and hydrogenation reaction was performed for 1 hour. The hydrogenation rate of the obtained polymer was 99.3%.
[0109]
<Comparative Example 5> Production of SEBM copolymer (b-5)
A polymer was produced in the same manner as in Production Example 7. When the obtained polymer was analyzed, the 1,2-bond content was 60% by weight, the styrene content was 30.0% by weight, the weight average molecular weight was about 100,000, and the same polymer as (a-5) was obtained. Hydrogen was introduced into the reaction vessel, and after a hydrogen pressure of 2.0 MPa, (Ind) RuCl (PPh_Three)_ThreeHydrogenation reaction was performed for 2 hours by adding 1.2 g of catalyst and 0.1 g of n-BuLi. The hydrogenation rate of the obtained polymer was 97.3%.
[0110]
<Comparative Example 6> Production of SEB-polysiloxane copolymer (b-6)
A polymer was produced in the same manner as in Production Example 8. When the obtained polymer was analyzed, the 1,2-bond content was 60% by weight, the styrene content was 15.1% by weight, the weight average molecular weight was about 150,000, and the same polymer as (a-6) was obtained. Hydrogen was introduced into the reaction vessel, the hydrogen pressure was 1.0 MPa, 0.5 g of catalyst A and 0.1 g of n-BuLi were added, and hydrogenation reaction was performed for 1 hour. The hydrogenation rate of the obtained polymer was 98.9%.
[0111]
(I-2) and (I-5) prepared in Example 2 and Example 5, and (b-2) and (b-5) prepared in Comparative Example 2 and Comparative Example 5 were converted into a 55 mmφ single screw extruder. And pelletizer was prepared using a pelletizer. Load the prepared pellets in a constant temperature bath at 60 ° C. at 30 kg / cm²The results of how the pellets are agglomerated after 72 hours are shown below.
[0112]
[Table 2]

[0113]
As shown in Table 2, the blocking resistance of (I-2) and (I-5) modified with one-end H polydimethylsiloxane is improved as compared with the unmodified polymer.
[0114]
[Evaluation of the physical properties]
Using the hydrogenated modified conjugated diene polymer obtained by the above method, mixing was performed according to the formulation shown in Table 3. Polypropylene [K8017 manufactured by Chisso] was used as the component (II-1), and magnesium hydroxide [Kyowa Chemical Kisuma] was used as the component (III). The compounds shown in Table 3 were mixed and pelletized using a single screw extruder whose temperature was adjusted to 220 ° C., and test pieces for physical property evaluation were prepared by injection molding. The results of physical property evaluation are shown in Table 3. As a comparative example, mixing was performed according to the formulation shown in Table 3, and test pieces were similarly prepared. From the results of Table 3, it can be seen that the resin compositions of the present invention, Examples 7 to 9, are excellent in breaking strength and have a balanced physical property as compared with Comparative Examples 7 to 9.
[0115]
[Table 3]

[0116]
Using the hydrogenated modified conjugated diene polymer obtained by the above method, mixing was performed according to the formulation shown in Table 4. Polypropylene [manufactured by Chisso Corporation, K8017] was used as the component (II-1). The compounds shown in Table 4 were mixed and pelletized using a single screw extruder whose temperature was adjusted to 220 ° C., and test pieces for evaluating physical properties were prepared by injection molding. The results of physical property evaluation are also shown in Table 4. As a comparative example, they were mixed in the same formulation as shown in Table 4, and test pieces were similarly prepared. From the results of Table 4, Examples 10 and 11, which are resin compositions of the present invention, are compositions having good release properties and flexibility, and particularly excellent wear resistance, as compared with Comparative Examples 10-12. I understand.
[0117]
[Table 4]

[0118]
*) KF96H-10,000, manufactured by Shin-Etsu Chemical Co., Ltd.
Note that the present invention is not limited to the specific examples described above, and can be variously modified examples according to the purpose and application.
[0119]
【The invention's effect】
The present invention relates to a modified conjugated diene obtained by hydrosilating a polymer having a carbon-carbon double bond with an unsaturated bond in a conjugated diene polymer with a compound having at least one silicon-hydrogen bond. The modified conjugated diene polymer composition obtained is a method for producing a polymer and a hydrogenated product thereof, and the conventional conjugated diene polymer composition has been conventionally used in a formulation in which sufficient physical properties such as workability, slidability and tensile strength have not been obtained. An excellent composition exhibiting a good balance of physical properties can be provided. In addition, since a polymer having a functional group can be applied, the filler can be highly dispersed, and compatibility with the polar resin can be improved. It is possible to produce modified conjugated diene polymers having various functional groups by hydrosilylation, and the composition of these modified conjugated diene polymers is heat resistance, weather resistance, impact resistance, oil resistance, molding It is possible to easily give good physical properties in the modification of physical properties such as workability, slidability, blocking resistance, coloring property, decoloration resistance, low creep property, flexibility and tensile strength. Therefore, the application fields of these compositions include food packaging containers, various trays, sheets, tubes, films, fibers, laminates, electrical and electronic parts for coatings and printed boards, OA equipment such as computers, housings for home appliances, automobiles, etc. Various industrial parts such as inner / outer materials, tires, outer plate parts, precision parts, building materials can be mentioned. In these fields of use, the modified conjugated diene polymer composition of the present invention can be preferably used even when foamed. .

Claims (13)

  Conjugated diene compounds having a polystyrene equivalent weight average molecular weight of 10,000 to 2,000,000 obtained by (co) polymerizing a conjugated diene compound or a monomer component comprising a conjugated diene compound and another monomer copolymerizable with the conjugated diene compound The polymer is hydrosilated and hydrogenated using a hydrosilane compound having at least one silicon-hydrogen bond, and the hydrosilylation and hydrogenation of the conjugated diene polymer is performed with the same catalyst. A method for producing a modified conjugated diene polymer.   The monomer component is 5 to 100% by weight of a conjugated diene compound, 0 to 95% by weight of an aromatic vinyl compound, and 0 to 95% by weight of a (meth) acrylate compound [provided that the conjugated diene compound + aromatic vinyl compound + (meth) acrylate The method for producing a modified conjugated diene polymer according to claim 1, wherein the compound is 100% by weight.   The method for producing a modified conjugated diene polymer according to claim 1 or 2, wherein the conjugated diene polymer is a random copolymer comprising a conjugated diene compound and an aromatic vinyl compound. The modified conjugated diene heavy polymer according to claim 1 or 2 , wherein the conjugated diene polymer is a block polymer containing two or more polymer blocks selected from the following blocks (A) to (F). Manufacturing method of coalescence.
(A) Aromatic vinyl compound polymer block in which aromatic vinyl compound is 80% by weight or more (B) Conjugated diene compound polymer block in which conjugated diene compound is 80% by weight or more (C) 1, 2 bond and 3, Conjugated diene compound polymer block having a total of 4 bond contents of less than 25% by weight (D) Conjugated diene compound polymer block having a total of 1,2 and 3,4 bond contents of 25% by weight to 90% by weight (E ) Random copolymer block of aromatic vinyl compound and conjugated diene compound (F) (Meth) acrylate compound polymer block with 80% by weight or more of (meth) acrylate compound   The method for producing a modified conjugated diene polymer according to any one of claims 1 to 4, wherein the conjugated diene compound is at least one selected from the group of butadiene, isoprene, and cyclohexadiene.   The modified conjugated diene polymer according to any one of claims 2 to 5, wherein the aromatic vinyl compound is styrene.   The method for producing a modified conjugated diene polymer according to any one of claims 2 to 5, wherein the (meth) acrylate compound is at least one selected from the group consisting of methyl methacrylate, tert-butyl methacrylate, and ethyl acrylate. The modified conjugated diene polymer according to any one of claims 1 to 7, wherein the hydrosilane compound used in hydrosilylation is at least one compound selected from the group of the following formulas (S-1) to (S-6). Manufacturing method.

[Wherein, R and R ′ are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, triorganosilyl groups represented by R ₃ Si— A triorganosiloxy group represented by R ₃ SiO—, which may be the same or different. X and X ′ contain a polar group containing at least one of N and O atoms, and may be the same or different. q is 0 to 1, p and n are 0 to 2, m and m ′ are 0 to 1000, and l is an integer of 0 to 3. ] The method for producing a modified conjugated diene polymer according to any one of claims 1 to 8, wherein the conjugated diene polymer is produced by living anion polymerization. The method for producing a modified conjugated diene polymer according to any one of claims 1 to 9 , wherein a hydrogenation ratio of the conjugated diene polymer to the unsaturated bond is 10 to 100%. Hydrosilane compound having at least one silicon-hydrogen bond in an unsaturated bond of the conjugated diene polymer at any time before hydrogenation, during hydrogenation, or after hydrogenation is completed The method for producing a modified conjugated diene polymer according to any one of claims 1 to 10 , wherein hydrosilylation is carried out. Hydrogenation catalyst is Ti, Zr, Hf, Co, Ni, Pd, Pt, Ru, Rh, and Re according to claim 1-11 which is a compound containing at least one atom selected from the group consisting of A method for producing a modified conjugated diene polymer. The modified conjugated diene polymer according to any one of claims 1 to 11 , wherein the hydrogenation catalyst is a metallocene compound containing at least one atom selected from the group consisting of Ti, Zr, Hf, Co, Ru, and Rh. Manufacturing method.