JP4665270B2 - Polymer radical polymerization initiator, process for producing the same, and graft polymer obtained using the same - Google Patents

Description

……（１）
（式中、Ｒ ^１ はフェニレン基、Ｒ ^２ は水素、ｔ−ブチル基またはＲ ^９ ＯＣ（Ｏ）−基であり、ここでＲ ^９ は炭素数２〜８の直鎖もしくは分岐のアルキル基、炭素数２〜８の直鎖もしくは分岐のアルコキシアルキル基、シクロヘキシル基、またはｔ−ブチルシクロヘキシル基を表わす。Ｒ ^４ はメチル基、Ｒ ^５ はメチル基、Ｒ ^７ はメチル基、Ｒ ^８ はメチル基である。Ｒ ^３ およびＲ ^６ はそれぞれメチル基、またはＲ ^３ およびＲ ^６ が連結した環式構造であって、Ｒ ^３ とＲ ^６ が連結した環式構造の場合には、メチル基、ヒドロキシ基、アセトキシ基、ベンゾイルオキシ基、もしくはメトキシ基の何れかにより置換されていてもよく、環式構造の、置換基、Ｒ ^４ 、Ｒ ^５ 、Ｒ ^７ およびＲ ^８ を除く部分はピペリジン、ピロリジンおよびイソインドリンから選ばれる窒素含有環である。）で表されるアルコキシアミン基が懸垂している高分子ラジカル重合開始剤である。
【００２６】
本出願における第２の発明は、同一分子内にラジカル重合性ビニル基およびアルコキシアミン基の両基を有する下記一般式（２）
【化４】

……（２）
（式中、Ｒ ^１ はフェニレン基、Ｒ ^２ は水素、ｔ−ブチル基またはＲ ^９ ＯＣ（Ｏ）−基であり、ここでＲ ^９ は炭素数２〜８の直鎖もしくは分岐のアルキル基、炭素数２〜８の直鎖もしくは分岐のアルコキシアルキル基、シクロヘキシル基、またはｔ−ブチルシクロヘキシル基を表わす。Ｒ ^４ はメチル基、Ｒ ^５ はメチル基、Ｒ ^７ はメチル基、Ｒ ^８ はメチル基である。Ｒ ^３ およびＲ ^６ はそれぞれメチル基、またはＲ ^３ およびＲ ^６ が連結した環式構造であって、Ｒ ^３ とＲ ^６ が連結した環式構造の場合には、メチル基、ヒドロキシ基、アセトキシ基、ベンゾイルオキシ基、もしくはメトキシ基の何れかにより置換されていてもよく、環式構造の、置換基、Ｒ ^４ 、Ｒ ^５ 、Ｒ ^７ およびＲ ^８ を除く部分はピペリジン、ピロリジンおよびイソインドリンから選ばれる窒素含有環である。また、Ｒ^１０は水素またはメチル基を示す。）で表される化合物（Ａ）と、ラジカル重合性単量体（Ｂ１）と、ラジカル重合開始剤（Ｃ）とを含む混合物を、前記ラジカル重合開始剤（Ｃ）が分解し、かつ前記化合物（Ａ）が分解しない温度領域で加熱することを特徴とする、請求項１に記載の高分子ラジカル重合開始剤の製造方法である。
【００２７】
本出願における第３の発明は、第１の発明に記載の高分子ラジカル重合開始剤およびラジカル重合性単量体（Ｂ２）を１００〜１８０℃の範囲において加熱することにより得られるグラフトポリマーである。
【００２８】
【発明の実施の形態】
以下に、この発明の実施の形態について詳細に説明する。
【００２９】
本発明の高分子ラジカル重合開始剤は、一般式（１）で示されるアルコキシアミン基が分子主鎖に懸垂した高分子化合物である。
一般式（１）において、Ｒ ^１ はフェニレン基、Ｒ ^２ は水素、ｔ−ブチル基またはＲ ^９ ＯＣ（Ｏ）−基であり、ここでＲ ^９ は炭素数２〜８の直鎖もしくは分岐のアルキル基、炭素数２〜８の直鎖もしくは分岐のアルコキシアルキル基、シクロヘキシル基、またはｔ−ブチルシクロヘキシル基を表わす。Ｒ ^４ はメチル基、Ｒ ^５ はメチル基、Ｒ ^７ はメチル基、Ｒ ^８ はメチル基である。Ｒ ^３ およびＲ ^６ はそれぞれメチル基、またはＲ ^３ およびＲ ^６ が連結した環式構造であって、Ｒ ^３ とＲ ^６ が連結した環式構造の場合には、メチル基、ヒドロキシ基、アセトキシ基、ベンゾイルオキシ基、もしくはメトキシ基の何れかにより置換されていてもよく、環式構造の、置換基、Ｒ ^４ 、Ｒ ^５ 、Ｒ ^７ およびＲ ^８ を除く部分はピペリジン、ピロリジンおよびイソインドリンから選ばれる窒素含有環である。
【００３０】
本発明において、高分子ラジカル重合開始剤の分子量は、グラフトポリマーに対する要求特性に応じて適宜決定することができるが、ゲルパーミエーションクロマトグラフィ（以下ＧＰＣという）により測定されるスチレン換算分子量において、数平均分子量が３０００〜５０万の範囲であることが好ましく、さらに５０００から４０万の範囲であることがより好ましい。高分子ラジカル重合開始剤の分子量が３０００未満であると、グラフトポリマーにした場合に幹ポリマーの物性が十分発現できなくなる傾向にあり、一方、分子量が５０万を越えると溶融状態あるいは溶液状態での高分子ラジカル重合開始剤の粘度が高くなり、この開始剤製造時およびグラフトポリマー製造時の作業性が悪くなる傾向にあるので好ましくない。
【００３１】
さらに、本発明の高分子ラジカル重合開始剤一分子当たりに懸垂したアルコキシアミンペンダント基の平均個数は、３〜２００個の範囲内であることが好ましく、さらに５〜１００個の範囲にあることが好ましい。アルコキシアミン基の個数が1個または2個の場合であっても、枝ポリマーの分子量を十分に大きくすることによって、グラフトポリマーとしての効果発現は可能であるが、アルコキシアミン基の平均個数が３より少ない場合には、アルコキシアミン基を分子内に有さない高分子量体が生成しやすくなるうえ、グラフトポリマーにした場合に枝ポリマーの物性が十分発現できなくなる傾向にあるので好ましくない。一方、平均個数が２００個よりも多いと、幹ポリマーの物性が十分発現できなくなる傾向にあるので好ましくない。
【００３２】
上記のような高分子ラジカル重合開始剤は、次のようにして得ることができる。
即ち、同一分子内にラジカル重合性ビニル基とアルコキシアミン基の両基を有する一般式（２）で示される化合物（Ａ）（以下、化合物Ａと記す）とラジカル重合性単量体（Ｂ１）とラジカル重合開始剤（Ｃ）からなる混合物を、ラジカル重合開始剤（Ｃ）が分解し前記化合物（Ａ）が分解しない温度領域で加熱する（以下、第一段目重合と記す）。
一般式（２）においては、Ｒ ^１ はフェニレン基、Ｒ ^２ は水素、ｔ−ブチル基またはＲ ^９ ＯＣ（Ｏ）−基であり、ここでＲ ^９ は炭素数２〜８の直鎖もしくは分岐のアルキル基、炭素数２〜８の直鎖もしくは分岐のアルコキシアルキル基、シクロヘキシル基、またはｔ−ブチルシクロヘキシル基を表わす。Ｒ ^４ はメチル基、Ｒ ^５ はメチル基、Ｒ ^７ はメチル基、Ｒ ^８ はメチル基である。Ｒ ^３ およびＲ ^６ はそれぞれメチル基、またはＲ ^３ およびＲ ^６ が連結した環式構造であって、Ｒ ^３ とＲ ^６ が連結した環式構造の場合には、メチル基、ヒドロキシ基、アセトキシ基、ベンゾイルオキシ基、もしくはメトキシ基の何れかにより置換されていてもよく、環式構造の、置換基、Ｒ ^４ 、Ｒ ^５ 、Ｒ ^７ およびＲ ^８ を除く部分はピペリジン、ピロリジンおよびイソインドリンから選ばれる窒素含有環である。また、Ｒ^１０は水素またはメチル基である。
【００３３】
一般式（２）で示される化合物（Ａ）の具体的な例としては、２−（２'，２'，６'，６'−テトラメチル−１'−ピペリジニルオキシ）−２−（４'−ビニルフェニル）エタノール、２−（４'−ヒドロキシ−２'，２'，６'，６'−テトラメチル−１'−ピペリジニルオキシ）−２−（３'−ビニルフェニル）エタノール、２−ｔ−ブトキシ−１−（２'，２'，６'，６'−テトラメチル−１'−ピペリジニルオキシ）−１−（４'−ビニルフェニル）エタン、２−ｔ−ブトキシ−１−（４'−ヒドロキシ−２'，２'，６'，６'−テトラメチル−１'−ピペリジニルオキシ）−１−（３'−ビニルフェニル）エタン、２−ｔ−ブトキシ−１−（４'−アセトキシ−２'，２'，６'，６'−テトラメチル−１'−ピペリジニルオキシ）−１−（３'−ビニルフェニル）エタン、２−ｔ−ブトキシ−１−（１'，１'，３'，３'−テトラメチル−２'，３'−ジヒドロ−１'Ｈ−２−イソインドリルオキシ）−１−（４'−イソプロペニルフェニル）エタン、２−イソプロピルオキシカルボニルオキシ−１−（２'，２'，６'，６'−テトラメチル−１'−ピペリジニルオキシ）−１−（４'−ビニルフェニル）エタン、２−イソプロピルオキシカルボニルオキシ−１−（４'−ヒドロキシ−２'，２'，６'，６'−テトラメチル−１'−ピペリジニルオキシ）−１−（３'−ビニルフェニル）エタン、２−（２'−エトキシエチルオキシカルボニルオキシ）−１−（４'−メトキシ−２'，２'，６'，６'−テトラメチル−１'−ピペリジニルオキシ）−１−（４'−ビニルフェニル）エタン、２−シクロヘキシルオキシカルボニルオキシ−１−（４'−メチル−２'，２'，６'，６'−テトラメチル−１'−ピペリジニルオキシ）−１−（４'−ビニルフェニル）エタン、２−（２'−エチルヘキシルオキシカルボニルオキシ）−１−（２'，２'，６'，６'−テトラメチル−１'−ピペリジニルオキシ）−１−（４'−ビニルフェニル）エタン、２−（４'−ｔ−ブチルシクロヘキシルオキシカルボニルオキシ）−１−（２'，２'，６'，６'−テトラメチル−１'−ピペリジニルオキシ）−１−（４'−ビニルフェニル）エタン、２−イソプロピルオキシカルボニルオキシ−１−（４'−ベンゾイルオキシ−２'，２'，６'，６'−テトラメチル−１'−ピペリジニルオキシ）−１−（４'−ビニルフェニル）エタン、２−イソプロピルオキシカルボニルオキシ−１−（２'，２'，６'，６'−テトラメチル−１'−ピペリジニルオキシ）−１−（４'−イソプロペニルフェニル）エタン、２−イソプロピルオキシカルボニルオキシ−１−（２'，２'，５'，５'−テトラメチル−１'−ピロリジニルオキシ）−１−（４'−ビニルフェニル）エタン、２−イソプロピルオキシカルボニルオキシ−１−（ジ−ｔ−ブチルニトロキシル）−１−（４'−ビニルフェニル）エタンなどが挙げられる。
【００３４】
本発明において、第一段目重合に用いられるラジカル重合性単量体（Ｂ１）は、化合物（Ａ）と共重合体可能なビニル単量体であって、目的とするグラフトポリマーの幹ポリマーを構成するのに適したものの中から適宜選択することができる。化合物（Ａ）と共重合可能なラジカル重合性単量体（Ｂ１）の具体的な例としては、スチレン、ｐ−メチルスチレン、クロルメチルスチレン、α−メチルスチレンなどのスチレン系単量体、アクリル酸、メタクリル酸、クロトン酸、イタコン酸、マレイン酸、フマル酸などのカルボキシル基含有ビニル単量体、無水マレイン酸、無水イタコン酸などの酸無水基含有ビニル単量体、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸デシル、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、３−ヒドロキシプロピル（メタ）アクリレート、ヒドロキシブチル（メタ）アクリレート、グリシジル（メタ）アクリレート、フマル酸ジメチル、フマル酸ジエチル、フマル酸ジブチルなどのエステル基含有ビニル単量体、（メタ）アクリル酸２−イソシアネートエチル、ｍ−イソプロペニル−α，α−ジメチルベンジルイソシアネートなどのイソシアネート基含有ビニル単量体、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート、Ｎ−ｔ−ブチルアミノエチル（メタ）アクリレートなどの窒素含有アルキル（メタ）アクリレート、アクリルアミド、メタクリルアミド、Ｎ−メチル（メタ）アクリルアミド、Ｎ−エチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリルアミドなどのアミド基含有ビニル単量体、２−ビニルピリジン、４−ビニルピリジンなどの芳香族含窒素ビニル単量体、アクリロニトリル、メタクリロニトリルなどのニトリル基含有ビニル単量体などが挙げられる。
【００３５】
これらラジカル重合性単量体のうち特に好ましいものとしては、分子内に酸素原子または窒素原子を含むラジカル重合性単量体であり、具体的にはカルボキシル基含有ビニル単量体、酸無水基含有ビニル単量体、エステル基含有ビニル単量体、イソシアネート基含有ビニル単量体、窒素含有アルキル(メタ)アクリレート、アミド基含有ビニル単量体、芳香族含窒素ビニル単量体、ニトリル基含有ビニル単量体などが挙げられる。
【００３６】
これらラジカル重合性単量体はそれぞれ単独で、または２種以上を混合して用いることができる。グラフトポリマーとした場合に枝ポリマーとは異なる物性を幹ポリマーに導入することが望ましい場合には、第一段目重合にスチレン系以外のラジカル重合性単量体のみを用いても良いが、少なくとも１種以上のスチレン系以外のラジカル重合性単量体を含む単量体混合物を用いることが、より好ましい。なぜならば、本発明の高分子ラジカル重合開始剤を用いたグラフトポリマーの製造に際し、より高度に分子量が制御された枝ポリマーを得るには、スチレン系単量体を含む単量体を用いることがより好ましいからである。
【００３７】
本発明において、第一段目重合において用いられる上記の化合物（Ａ）とラジカル重合性単量体（Ｂ１）の使用量は、得られる高分子ラジカル重合開始剤中に所望されるアルコキシアミン基の個数に依存して適宜選択することができるが、通常、（Ａ）に対する（Ｂ１）のモル比が１０〜５００倍の範囲であることが好ましい。ラジカル重合性単量体（Ｂ１）の使用モル比が１０倍より少ないと、グラフトポリマーにした場合、枝ポリマーと枝ポリマーの間の幹ポリマーの鎖長が短くなりすぎて幹ポリマーの物性が十分発現できなくなる傾向にあり、一方、５００倍を超えて大きくなると、枝ポリマー間の幹ポリマーの鎖長が長くなりすぎて枝ポリマーの物性が十分発現できなくなる傾向にあるので好ましくない。
【００３８】
本発明において、第一段目重合は、上記の化合物（Ａ）とラジカル重合性単量体（Ｂ１）とラジカル重合開始剤（Ｃ）からなる混合物を、ラジカル重合開始剤（Ｃ）が分解し化合物（Ａ）が分解しない温度領域で行われる。
具体的な重合温度としては、０〜１２０℃が好ましく、２０〜１００℃がより好ましい。重合温度が０℃以下では、重合速度が遅いため重合完結までに長時間を要するので経済的に不利である。一方、重合温度が１２０℃以上では、上記化合物（Ａ）の分解が顕著になり、結果として最終的に得られるグラフトポリマーの構造の制御が困難になりゲルが発生したり、グラフトポリマーの純度が低下するので好ましくない。
【００３９】
本発明において、第一段目重合に用いられるラジカル重合開始剤（Ｃ）は、通常の有機過酸化物あるいはアゾ化合物を用いることができるが、上記の重合温度条件下で有効にラジカルを発生しうるものが好ましく、したがって、重合温度に依存して適宜選択すると良い。通常、用いられるラジカル重合開始剤（Ｃ）の具体的な例としては、ｔ−ブチルペルオキシネオデカノエート、ｔ−オクチルペルオキシネオデカノエート、ｔ−ブチルペルオキシピバレート、ｔ−ヘキシルペルオキシピバレート、ｔ−ブチルペルオキシ２−エチルヘキサノエート、ｔ−オクチルペルオキシイソブチレート、ｔ−ブチルペルオキシイソプロピルカーボネート、ｔ−ブチルペルオキシラウレート、ｔ−ブチルペルオキシベンゾエートなどのペルオキシエステル類、イソブチリルペルオキシド、３，５，５−トリメチルヘキサノイルペルオキシド、ラウロイルペルオキシド、ベンゾイルペルオキシドなどのジアシルペルオキシド類、ジプロピルペルオキシジカーボネート、ジイソプロピルペルオキシジカーボネート、ジ（２−エチルヘキシル）ペルオキシジカーボネートなどのペルオキシジカーボネート類、１，１−ビス（ｔ−ブチルペルオキシ）−２−メチルシクロヘキサン、１，１−ビス（ｔ−ブチルペルオキシ）シクロヘキサン、１，１−ビス（ｔ−ブチルペルオキシ）−３，３，５−トリメチルシクロヘキサン、１，１−ビス（ｔ−ヘキシルペルオキシ）−３，３，５−トリメチルシクロヘキサン、２，２−ビス（４，４−ジ−ｔ−ブチルペルオキシシクロヘキシル）などのペルオキシケタール類、２，２’−アゾビス（イソブチロニトリル）、２，２’−アゾビス（２，４−ジメチルバレロニトリル）、２，２’−アゾビス（シクロヘキサンニトリル）、２，２’−アゾビス（２−メチルブチロニトリル）、２，２’−アゾビス（２，４−ジメチル−４−メトキシバレロニトリル）などのアゾ化合物が挙げられる。また、ｔ−ブチルヒドロペルオキシド、クメンヒドロペルオキシドなどを硫酸第一鉄、硫酸第一銅、アスコルビン酸ナトリウムなどの還元剤を用いて還元してラジカルを発生させる方法、または光重合開始剤に光照射してラジカルを発生させる方法によって、重合を開始することもできる。
【００４０】
本発明において、第一段目重合は、塊状重合、懸濁重合、溶液重合および乳化重合など公知の重合方法によって行うことができ、単量体の種類、重合温度、所望される高分子ラジカル重合開始剤の分子量などによって適宜選択することができる。
【００４１】
本発明において、第一段目重合に懸濁重合を採用した場合、分散剤として水溶性高分子の保護コロイド剤、難溶性無機物を重合系に添加することができる。水溶性高分子保護コロイド剤としては、ポリビニルアルコール、ポリビニルピロリドン、メチルセルロース等があり、これらのうちポリビニルアルコールが好ましい。また、難溶性無機物としては、第三燐酸カルシウム、燐酸マグネシウム、ピロ燐酸カルシウム、ベントナイト等が挙げられる。難溶性無機物を分散剤とした場合には、ドデシルベンゼンスルホン酸ソーダ、α−オレフィンスルフォン酸ソーダなどのアニオン界面活性剤を少量使用することが好ましい。
【００４２】
本発明において、第一段目重合に溶液重合を採用した場合、溶媒の具体的な例としては、トルエン、キシレン、エチルベンゼンなどの芳香族炭化水素系溶媒、メチルエチルケトン、メチルイソブチルケトンなどのケトン系溶媒、酢酸エチル、酢酸ブチル、酢酸イソブチルなどのエステル系溶媒、メタノール、イソプロピルアルコール、ｎ−ブチルアルコールなどのアルコール系溶媒、エチレングリコール、エチレングリコールジアセテート、エチレングリコールモノメチルエーテル、エチレングリコールジエチルエーテル、エチレングリコールメチルエーテルアセテートなどのエチレングリコール系溶媒、ジエチレングリコール、ジエチレングリコールジメチルエーテル、ジエチレングリコールモノブチルエーテルなどのジエチレングリコール系溶媒、プロピレングリコール、プロピレングリコールメチルエーテルアセテートなどのプロピレングリコール系溶媒が挙げられ、これらを単独で、あるいは混合物として用いることができる。
【００４３】
本発明においては、必要に応じてα−メチルスチレンダイマー（２，４−ジフェニル−４−メチル−１−ペンテン）、ターピノーレン、ｎ−オクチルメルカプタン、ｔ−ドデシルメルカプタン、２−メルカプトエタノール、チオフェノールなどの公知の連鎖移動剤を使用できる。
【００４４】
本発明においては、第一段目重合が完結した後、高分子ラジカル重合開始剤は、そのままで、あるいは溶媒留去または再沈殿などの精製工程を経た後に、グラフトポリマーを得るための重合（以下、第二段目重合と記す）に供される。
【００４５】
本発明において第二段目重合は、前記一般式（１）で示される高分子ラジカル重合開始剤およびラジカル重合性単量体（Ｂ２）を含む混合物を加熱することにより実施される。
【００４６】
即ち、一般式（１）で示される高分子ラジカル重合開始剤が熱的作用によって、幹ポリマー側に結合した炭素ラジカルと、安定なニトロキシドラジカルに開裂する。炭素ラジカルは系中に存在するラジカル重合性単量体（Ｂ２）との付加重合を開始する。一方、ニトロキシドラジカルは重合を開始することなく、炭素ラジカルからの生長ポリマーラジカルとの間で、再結合と再開裂を繰り返しながら重合反応が進行する、いわゆるリビング的なラジカル重合により第二段目重合が行われる。
【００４７】
本発明において、第二段目重合は、上記第一段目重合と同様に塊状重合、懸濁重合、溶液重合および乳化重合など公知の重合方法によって行うことができ、単量体の種類、重合温度、所望される高分子ラジカル重合開始剤の分子量などによって適宜選択することができる。
【００４８】
本発明において、第二段目重合に用いられるラジカル重合性単量体（Ｂ２）としては、前記第一段目重合に用いることが可能なラジカル重合性単量体（Ｂ１）の中から、得られるグラフトポリマーの要求される物性に応じて選択したものを適宜用いることができるが、第二段目重合で得られるグラフトポリマーの枝ポリマーの分子量を効果的に大きくする目的あるいはより高度に制御する目的で、スチレン系単量体単独物あるいは少なくとも一種以上のスチレン系単量体を含むラジカル重合性単量体混合物を用いることが好ましい。
【００４９】
本発明において、第二段目重合で得られるグラフトポリマーの枝ポリマーの分子量は、幹ポリマーの分子量との関係および目的とするグラフトポリマーの分子量によって適宜決定することができる。高分子ラジカル重合開始剤（Ａ）中に懸垂したアルコキシアミンペンダント基の個数（即ち、最終的に得られる枝ポリマーの個数）に依存するが、通常、枝ポリマーは、ＧＰＣによるスチレン換算分子量が１０００〜１５万の範囲であることが好ましく、２０００〜１０万の範囲であることがより好ましい。分子量が１０００より小さいと、グラフトポリマーにした場合、枝ポリマーの物性が十分発現できなくなる傾向にあり、一方、１５万を超えると、幹ポリマーの物性が十分発現できなくなる傾向にあるので好ましくない。
【００５０】
本発明において、第二段目重合の重合温度は１００〜１８０℃の範囲が好ましく、１１０〜１６０℃の範囲がより好ましい。重合の温度が１００℃以下では、高分子ラジカル重合開始剤の分解速度が遅くなり、結果として重合時間が長くなる傾向にあるので好ましくない。一方、重合温度が１８０℃よりも高くなると重合速度の制御が困難になる上、熱重合により第二段目重合時に添加されたラジカル重合性（Ｂ２）のホモポリマーが生成しやすくなり、結果としてグラフトポリマーの純度が低下するので好ましくない。
【００５１】
【実施例】
以下、本発明をより詳細に説明するため、実施例を用いて説明を行うが、本発明の要旨を越えない限り、実施例によって本発明が限定されるものではない。
なお、本発明の実施においては、予め特願平１０−２０６１４６号公報に記載の方法に準じて、以下のように本発明の高分子ラジカル重合開始剤を得るための化合物（Ａ）を合成した。
【００５２】
＜化合物（Ａ）の合成＞
攪拌機、コンデンサーおよび窒素ガス導入管を備えた１００ｍｌの４つ口フラスコに、ジビニルベンゼン（新日鐵化学社製「ＤＶＢ−９６０」、ｍ−およびｐ−ジビニルベンゼンの異性体混合物、純度９６％）５０ｇと４−ヒドロキシ− ２，２，６，６−テトラメチルピペリジン−１−オキシル（ＨＯ−ＴＥＭＰＯ）８．６１ｇ（５０ｍｍｏｌ）の混合物を投入し内容物を窒素置換した。ついで内容物を５０℃に加熱し、ジーイソプロピルペルオキシジカーボネート（ＩＰＰ）１１．６ｇ（５５．６ｍｍｏｌ）を２０分かけて分割添加した。その後、５０℃で５時間反応をした後、ジビニルベンゼンの大部分を減圧下に留去した。得られた組成物をシリカゲルクロマトグラフィで精製し、淡黄色油状物１２．８ｇを得た。
これを高速液体クロマトグラフィ（ＨＰＬＣ）、質量分析、^１Ｈ−ＮＭＲおよび^１３Ｃ−ＮＭＲにより構造確認を行った結果、２−イソプロピルオキシカルボニルオキシ−１−（４’−ヒドロキシ−２’，２’，６’，６’−テトラメチル−１’−ピペリジニルオキシ）−１−（３’−ビニルフェニル）エタンと２−イソプロピルオキシカルボニルオキシ−１−（４’−ヒドロキシ−２’，２’，６’，６’−テトラメチル−１’−ピペリジニルオキシ）−１−（４’−ビニルフェニル）エタンの混合物（以下、Ａ−１）であることを確認した。ＨＰＬＣおよびＧＰＣ分析から求めた純度は９８％であった。
【００５３】
同様にして、以下の本発明の化合物（Ａ２〜Ａ４）を合成した。
２−ｔ−ブトキシ−１−（４’−ヒドロキシ−２’，２’，６’，６’−テトラメチル−１’−ピペリジニルオキシ）−１−（３’−ビニルフェニル）エタンと２−ｔ−ブトキシ−１−（４’−ヒドロキシ−２’，２’，６’，６’−テトラメチル−１’−ピペリジニルオキシ）−１−（４’−ビニルフェニル）エタンの混合物（純度９８％、Ａ−２）
２−（４’−ヒドロキシ−２’，２’，６’，６’−テトラメチル−１’−ピペリジニルオキシ）−２−（３’−ビニルフェニル）エタノールと２−（４’−ヒドロキシ−２’，２’，６’，６’−テトラメチル−１’−ピペリジニルオキシ）−２−（４’−ビニルフェニル）エタノールの混合物（純度９９％、Ａ−３）２−イソプロピルオキシカルボニルオキシ−１−（２’，２’，６’，６’−テトラメチル−１’−ピペリジニルオキシ）−１−（４’−ビニルフェニル）エタン（純度９８％、Ａ−４）
【００５４】
＜実施例１＞
参考例で得た化合物Ａ−１を０．６２ｇ（１．５ｍｍｏｌ）、メチルメタクリレート（ＭＭＡ）４．４１ｇ（４４．０ｍｍｏｌ）、重合開始剤としてｔ−ヘキシルパーオキシピバレート（ＨＰＶ）０．０１０ｇ（０．０４９ｍｍｏｌ）、分子量調節剤としてｎ−オクチルメルカプタン０．０５ｇの混合物に窒素を吹込み、酸素を除去した上で、内容量１０ｍｌのガラスアンプル中に注入したのち封管し、反応温度６０℃にて６時間重合を行った。その後、内容物を５０ｍｌのテトラヒドロフラン（ＴＨＦ）に溶解させ、その溶液をメタノール３００ｍｌに滴下して高分子量体の再沈殿を行った。この精製操作を再度繰り返して行い、未反応の化合物Ａ−１、ＭＭＡおよびＨＰＶを完全に取り除いた後、生成物を３０℃で２４時間減圧下に放置し乾燥させた。
【００５５】
上記の操作により得られた高分子量体の重量は２．９１ｇであり、収率は５８．２％であった。ＧＰＣで分子量を測定したところ、スチレン換算で数平均分子量２．０万、重量平均分子量３．４万のポリＭＭＡであることを確認した。
この化合物の^１Ｈ−ＮＭＲスペクトル（テトラメチルシラン（ＴＭＳ）／重クロロホルム（ＣＤＣｌ_３））を、図１に示す。それぞれのプロトンの帰属は次のとおりである。（δ（ｐｐｍ））
０．６５〜１．５５；メチルおよびメチレンプロトン
１．６５〜２．１５；メチルプロトン
３．６０ ；エステルメチルプロトン
６．８〜７．３ ；ベンゼン環プロトン
^１Ｈ−ＮＭＲ分析結果より、化合物Ａ−１に由来するベンゼン環プロトンと、ポリＭＭＡのエステルメチル基に由来するプロトンとの比から、高分子量体１分子あたりに平均して６．８個のアルコキシアミン基が導入されていることがわかった。
以上のことから、この化合物が次式（化５）で示される本発明の高分子ラジカル重合開始剤（以下、ＬＲＰＩ−１とする）であることを確認した。
【００５６】
【化５】

【００５７】
＜実施例２〜４＞
実施例１において、化合物Ａおよび単量体の種類と使用量、並びに重合温度と時間をかえた以外は、実施例１に準じて高分子ラジカル重合開始剤の合成を行った。合成における諸条件と併せて、合成物の分析結果を表１に示す。
【００５８】
【表１】

尚、上記表１および下記において、各記号はそれぞれ以下のものを表す。
単量体
ＣＭＳ：クロロメチルスチレン（ｍ体およびｐ体の混合物）
重合開始剤
ＨＰＶ：ｔ−ヘキシルパーオキシピバレート（日本油脂株式会社製「パーヘキシルＰＶ」）
ＢＰＶ：ｔ−ブチルパーオキシピバレート（日本油脂株式会社製「パーブチルＰＶ」）
添加剤
ＭＳＤ：α−メチルスチレンダイマー（日本油脂株式会社製「ノフマーＭＳＤ」）
ＯＭ：ｎ−オクチルメルカプタン
【００５９】
【化６】

【００６０】
【化７】

【００６１】
【化８】

【００６２】
＜実施例５＞
攪拌機、コンデンサー、温度計、窒素ガス導入管を備えた３００ｍｌの４つ口フラスコに溶媒としてジエチレングリコールジメチルエーテル３０ｇを入れ、溶媒および容器内の空間部を窒素ガスで十分に置換した。溶媒を６５℃に加熱し、窒素気流下攪拌しながら１．５７ｇ（３．８ｍｍｏｌ）の化合物Ａ−１、Ｎ，Ｎ−ジメチルアクリルアミド（ＤＭＡＡ）１５．０ｇ（０．１５２ｍｏｌ）、ジエチレングリコールジメチルエーテル９．０９ｇおよび重合開始剤としてＢＰＶ０．１６７ｇの混合物を１５分毎に８回に分けて添加した。添加終了後さらに６５℃で３時間、さらに８５℃で１時間重合を行った。
【００６３】
ガスクロマトグラフィおよびＧＰＣ分析の結果、ＤＭＡＡの転化率は１００％であり、得られた溶液は３０％（１６．７ｇ）の高分子量体を含んでいることがわかった。
また、高分子量体の数平均分子量は６．０万、重量平均分子量は１３．４万であった。溶液の一部から再沈により取り出した高分子量体の^１Ｈ−ＮＭＲ（ＴＭＳ／ＣＤＣｌ_３）分析結果は次のとおりである。（δ（ｐｐｍ））
０．６〜１．６；メチルおよびメチレンプロトン
１．７〜２．２；メチルプロトン
３．０ ；−Ｎ（ＣＨ_３）_２
６．８〜７．３；ベンゼン環プロトン
^１Ｈ−ＮＭＲ分析結果より、化合物Ａ−１に由来するベンゼン環プロトンと、窒素原子に結合したメチルに由来するプロトンとの比から、高分子量体１分子あたりに平均して１５．５個のアルコキシアミン基が導入されていることがわかった。
以上のことから、この化合物が式（化９）で示される本発明の高分子ラジカル重合開始剤（以下、ＬＲＰＩ−５とする）であることを確認した。
【００６４】
【化９】

【００６５】
＜実施例６＞
内容量２０ｍｌのガラスアンプルに、実施例１で得られたＬＲＰＩ−１を２ｇ、スチレン１０ｇを注入し窒素置換したうえで封管し、１２５℃で５時間重合を行った。内容物を５０ｍｌのＴＨＦに溶解し、その溶液をメタノール５００ｍｌに滴下して高分子量体の再沈殿を行った。この精製操作を再度繰り返して行い未反応のスチレン単量体を完全に取り除いた後、高分子量体を３０℃で２４時間減圧下に放置し乾燥させた。
【００６６】
得られた高分子量体の重量は７．０ｇであり、スチレンの転化率は５０．０％であった。得られた高分子量体の分子量は、ＧＰＣ測定によればスチレン換算で数平均分子量が６．６万、重量平均分子量が９．７万であった。さらにソックスレー管を用いた分別抽出により、得られた高分子量体の組成は、スチレンとＭＭＡのグラフト共重合体が９７％、ポリスチレンホモポリマーが３％であり、ポリＭＭＡホモポリマーおよびゲル分をほとんど含まないことが確認された。さらに、グラフト体の組成比を^１Ｈ−ＮＭＲにより分析した結果、枝ポリマー部分は平均で６８．５個のスチレン単量体から構成されていることがわかった。
【００６７】
＜実施例７〜１０＞
実施例２〜５で合成された本発明の高分子ラジカル重合開始剤を用いて、以下の表２に示す重合条件に従い実施例６と同様にして本発明のグラフトポリマーの合成を行った。これらの分析結果を、表２に併せて示す。尚、表２において、ＢＡはアクリル酸ブチルを示す。
【００６８】
【表２】

【００６９】
【発明の効果】
本発明によれば、簡便な方法によって、安定な炭素−炭素に結合により分子主鎖に特定構造のアルコキシアミンのペンダント基が懸垂した高分子重合開始剤を得ることができる。また、得られた高分子ラジカル重合開始剤を用いて、幹ポリマーと枝ポリマーが安定な炭素−炭素に結合により結合し、イオン反応およびラジカル反応に対して安定なグラフトポリマーを高純度で得ることができる。
本発明によって得られるグラフトポリマーは、例えば、少なくとも２種以上の互いに相溶性のない高分子量体同士を均一に混合するための相溶化剤、界面活性剤、顔料分散剤、接着性改良剤などとしての用途に対し優れた効果を有する。
【図面の簡単な説明】
【図１】本発明による実施例１の化合物の^１Ｈ−ＮＭＲスペクトル[0001]
BACKGROUND OF THE INVENTION
The present invention is a high molecular weight polymer obtained by polymerizing a radical polymerizable monomer, and a polymer radical polymerization initiator in which an alkoxyamine group having a specific structure is suspended (pendant) in the molecular main chain of the polymer And a production method thereof, and further, a graft polymer obtained using the polymer radical polymerization initiator.
[0002]
[Prior art]
A method for obtaining a graft polymer by radical polymerization in which a stable free radical is involved using a polymer radical polymerization initiator having an alkoxyamine group in the molecule has already been known, for example, JP-A-60-89452, JP-A-10-60064, JP-A-11-171946, Angew. Chem. Int. Ed. Engl.,34, 1456 (1995), Angew. Chem. Int. Ed. Engl.,36, 270 (1997) and Macromolecules,31, 4396 (1998) disclose the technology.
[0003]
In these prior arts, methods for obtaining a polymer radical polymerization initiator having an alkoxyamine group in the molecule can be roughly classified into two types. One of these methods is a method in which a high molecular weight compound is synthesized in advance and then an alkoxyamine group is introduced into the molecule by radical reaction or ionic reaction to obtain a polymer radical polymerization initiator (hereinafter referred to as “Method I”). ”). Another method is to obtain a compound having both radical polymerizable vinyl group and alkoxyamine group in the same molecule (hereinafter referred to as “alkoxyamine having vinyl group”) by synthesis, This is a method of polymerizing a monomer by copolymerizing it with another monomer to obtain a polymer radical polymerization initiator having an alkoxyamine group in the molecule (hereinafter referred to as “Method II”).
In the prior art, after obtaining the polymer radical polymerization initiator by any one of the above-mentioned two methods, a graft polymer is synthesized using this.
[0004]
JP-A-60-89452, JP-A-10-60064, JP-A-11-171946 and Angew. Chem. Int. Ed. Engl.,36, 270 (1997), a polymer radical polymerization initiator is obtained by the above-mentioned “Method I”.
[0005]
That is, in the method described in JP-A-60-89452, a high molecular weight body (polybutadiene or polyisobutyl methacrylate) having a general structure is synthesized in advance, and a hydrogen atom is extracted in the presence of nitroxide into the high molecular weight body. By reacting the generated radical with nitroxide present in the system, a polymer radical polymerization initiator having an alkoxyamine pendant group in the molecule is obtained.
[0006]
In addition, in the method described in JP-A-10-60064, a radical generated in a high molecular weight molecule by light irradiation and a nitroxide present in the system are reacted to form an alkoxyamine group in the molecule. The polymer radical polymerization initiator which has is obtained.
[0007]
In the method described in JP-A-11-171946, a high molecular weight product is obtained by treating polyethylene with ozone or copolymerizing a monomer having a peroxide group in the molecule with another monomer. After the peroxide group is introduced into the molecule, the peroxide group is thermally cleaved, and the generated radical, the monomer present in the system, and the nitroxide are reacted with each other, thereby increasing the number of alkoxyamine pendant groups in the molecule. A molecular radical polymerization initiator has been obtained.
[0008]
Angew. Chem. Int. Ed. Engl.,36, 270 (1997), by reacting a benzyl chloride group present in a high molecular weight product obtained by copolymerizing styrene and chloromethylstyrene with an alkoxyamine having a hydroxyl group in the molecule, A polymer radical polymerization initiator having an alkoxyamine pendant group in the body molecule is obtained.
[0009]
On the other hand, the above-mentioned JP-A-60-89452, Angew. Chem. Int. Ed. Engl.,34, 1456 (1995), and Macromolecules,31, 4396 (1998), a polymer radical polymerization initiator is obtained by the above-mentioned “Method II”.
[0010]
That is, in the method described in JP-A-60-89452, a hydroxyl group is once obtained by reacting a carbon center radical generated by thermal decomposition of an azo compound having a hydroxyl group in the molecule with nitroxide. An alkoxyamine is obtained. Thereafter, the hydroxyl group is esterified with (meth) acrylic acid chloride to obtain an alkoxyamine having a vinyl group, and this is copolymerized with other monomers to form an oligomer (with a low molecular weight of 5000 or less). There is a radical polymerization initiator.
[0011]
Angew. Chem. Int. Ed. Engl.,34, 1456 (1995), a chloromethylstyrene and a hydroxyl group-containing alkoxyamine were previously reacted to obtain an alkoxyamine having a vinyl group, and then copolymerized with styrene to give a polymer radical having polystyrene as the main chain. A polymerization initiator is obtained.
[0012]
In addition, Macromolecules,31, 4396 (1998), a compound having a non-conjugated vinyl group and an alkoxyamine having a hydroxyl group are reacted to obtain an alkoxyamine having a non-conjugated vinyl group, and then propylene or 2-methylpentene is used as a metallocene catalyst. The polymer radical polymerization initiator having polystyrene as the main chain is obtained by copolymerization.
[0013]
The above Angew. Chem. Int. Ed. Engl.,34, 1456 (1995) and Macromolecules,31, 4396 (1998) are obtained by thermally decomposing benzoyl peroxide in the presence of a nitroxide compound and a styrene monomer and hydrolyzing the resulting product.
[0014]
[Problems to be solved by the invention]
However, the polymer radical polymerization initiators disclosed in the prior art and the graft polymers synthesized using these have the following problems.
[0015]
That is, a hydrogen abstraction reaction from a high molecular weight substance described in JP-A-60-89452, a photoreaction to a high molecular weight substance described in JP-A-10-60064, and JP-A-11-171946. Cleavage of the peroxide group in the described high molecular weight, and Angew. Chem. Int. Ed. Engl.,36, 270 (1997), a method for obtaining a polymer radical polymerization initiator by a reaction using a high molecular weight substance classified as “Method I” as a starting material, such as a reaction with an active site in a high molecular weight substance, The high molecular weight materials used in the reaction must be high molecular weight materials having hydrogen atoms that can be selectively and easily extracted, and must be high molecular weight materials that can be cleaved by light irradiation or heat treatment to generate radicals. It was not practical because it was necessary to satisfy certain conditions, such as a high molecular weight compound having an active site that reacts with a hydroxyl group.
[0016]
In addition, in order to efficiently introduce nitroxide into the high molecular weight substance in the above method, it is necessary to make an excess of nitroxide exist in the system with respect to the radical generated on the high molecular weight molecule, which is economically disadvantageous. At the same time, a process for removing excess nitroxide that was not involved in the reaction from the polymer radical polymerization initiator is required. Furthermore, since the high molecular weight material is used as a starting material for the reaction, the reaction is not easy to control, requires special equipment such as a light irradiation device, requires the use of a solvent, etc. There were many points, and from this point, it was not a practical method.
[0017]
On the other hand, “Method II” is relatively excellent as a method for obtaining a polymer radical polymerization initiator. However, the conventional technique has the following problems.
[0018]
That is, in the method described in JP-A-60-89452, as described above, an oligomeric radical polymerization initiator and further a graft oligomer are obtained using an alkoxyamine having a vinyl group synthesized by an esterification reaction. ing. Therefore, the graft polymer has a structure in which the backbone polymer and the branch polymer are bonded by an ester bond. As a matter of course, since this bond is weak against ionic reaction, the alkoxyamine group is easily released from the oligomeric radical polymerization initiator, and even if a graft polymer is obtained, the branch polymer is easily released. Therefore, there has been a problem that physical properties as a graft polymer cannot be expressed. In addition, due to this structural defect, the coating film obtained from the graft polymer is expected to have poor water resistance, acid rain resistance, weather resistance, and the like.
[0019]
Further, the invention described in Japanese Patent Application Laid-Open No. 60-89452 is aimed at obtaining an oligomer, and only a graft polymer having a very low molecular weight, particularly a molecular weight of a branch polymer, is obtained. Was not fully expressed. That is, when the obtained graft polymer is used as a compatibilizer, an emulsifier, a separation stabilizer, etc. of a mixture comprising two or more kinds of high molecular weight substances, there is a problem that it does not have a sufficient effect. .
[0020]
Similarly, Angew. Chem. Int. Ed. Engl.,34, 1456 (1995), the resulting graft polymer has a benzylic hydrogen bonded to a highly active oxygen atom for radical reactions in the portion bonded to the backbone polymer and the branch polymer, For example, there is a potential structural defect in which the benzylic hydrogen is gradually extracted by oxygen radicals in the air and decomposes and deteriorates, and the branch polymer is likely to be detached from the trunk polymer. In addition, regarding the graft polymer obtained using the polymer radical polymerization initiator, there is a description regarding the reaction to obtain a branched styrene homopolymer, but regarding the synthesis of a graft copolymer composed of two or more monomers. There is no specific description. Branched homopolystyrene has no effect as a compatibilizer, an emulsifier, a separation stabilizer and the like.
[0021]
Macromolecules,31, 4396 (1998), is a compound having a non-conjugated vinyl group derived from an aliphatic terminal olefin compound, and thus is a polymer by radical copolymerization that is industrially easy to implement. When it was going to obtain a radical polymerization initiator, there were restrictions on the kind of monomer which can be copolymerized. That is, there is a problem that it is difficult to obtain a polymer radical polymerization initiator having a polymer main chain composed of a monomer having a conjugated vinyl group such as a (meth) acrylic acid derivative monomer and styrene. .
[0022]
In addition, the above Angew. Chem. Int. Ed. Engl.,34, 1456 (1995) and Macromolecules,31, 4396 (1998) are very complicated in that all of them require at least three stages of reaction in order to obtain an alkoxyamine having a vinyl group for synthesizing a polymer radical polymerization initiator. Therefore, it was extremely disadvantageous in terms of cost and was not practical.
[0023]
In view of the circumstances as described above, the present invention is a method for obtaining a polymer radical polymerization initiator useful for graft polymer synthesis and having a molecular main chain and an alkoxyamine group bonded by a carbon-carbon bond by a simple reaction. And a polymer radical polymerization initiator thereof, and using the polymer radical polymerization initiator, is stable against ionic reactions and radical reactions, and substantially homopolymers of monomers constituting a branched polymer. An object of the present invention is to provide a high-purity graft polymer that does not involve polymer formation.
[0024]
[Means for Solving the Problems]
As a result of intensive studies to solve the problems of the conventional method, the present inventors have used a commercially available and inexpensive raw material, and a specific vinyl group obtained by a simple one-step method. It was found that a polymer radical polymerization initiator can be obtained by using an alkoxyamine having a bond between the molecular main chain of the polymer radical polymerization initiator and an alkoxyamine group, and the polymer radical polymerization initiator is used. As a result of the polymerization, the trunk polymer and the branch polymer are bonded by a stable carbon-carbon bond, the molecular weight of the branch polymer is uniform, narrow polydispersity, and a highly pure graft polymer with a very low homopolymer content is obtained. The present invention was completed with the knowledge that it was obtained.
[0025]
  That is, the first invention in the present application is a high molecular weight product obtained by polymerizing a radical polymerizable monomer, and from the main chain, the following general formula (1)
[Chemical 3]

                            ...... (1)
(WhereR ¹ Is a phenylene group, R ² Is hydrogen, t-butyl group or R ⁹ OC (O) — group, where R ⁹ Represents a linear or branched alkyl group having 2 to 8 carbon atoms, a linear or branched alkoxyalkyl group having 2 to 8 carbon atoms, a cyclohexyl group, or a t-butylcyclohexyl group. R ⁴ Is a methyl group, R ⁵ Is a methyl group, R ⁷ Is a methyl group, R ⁸ Is a methyl group. R ³ And R ⁶ Are each a methyl group or R ³ And R ⁶ Are linked cyclic structures, R ³ And R ⁶ In the case of a cyclic structure in which is bonded, it may be substituted with any of a methyl group, a hydroxy group, an acetoxy group, a benzoyloxy group, or a methoxy group. ⁴ , R ⁵ , R ⁷ And R ⁸ The portion other than is a nitrogen-containing ring selected from piperidine, pyrrolidine and isoindoline.) Is a polymer radical polymerization initiator in which an alkoxyamine group represented by
[0026]
  The second invention in this application is the following general formula (2) having both radically polymerizable vinyl group and alkoxyamine group in the same molecule.
[Formula 4]

                                (2)
(WhereR ¹ Is a phenylene group, R ² Is hydrogen, t-butyl group or R ⁹ OC (O) — group, where R ⁹ Represents a linear or branched alkyl group having 2 to 8 carbon atoms, a linear or branched alkoxyalkyl group having 2 to 8 carbon atoms, a cyclohexyl group, or a t-butylcyclohexyl group. R ⁴ Is a methyl group, R ⁵ Is a methyl group, R ⁷ Is a methyl group, R ⁸ Is a methyl group. R ³ And R ⁶ Are each a methyl group or R ³ And R ⁶ Are linked cyclic structures, R ³ And R ⁶ In the case of a cyclic structure in which is bonded, it may be substituted with any of a methyl group, a hydroxy group, an acetoxy group, a benzoyloxy group, or a methoxy group. ⁴ , R ⁵ , R ⁷ And R ⁸ The portion other than is a nitrogen-containing ring selected from piperidine, pyrrolidine and isoindoline.R¹⁰Represents hydrogen or a methyl group. ), The radical polymerization initiator (C) is decomposed into a mixture containing the compound (A), the radical polymerizable monomer (B1), and the radical polymerization initiator (C), and the compound 2. The method for producing a polymer radical polymerization initiator according to claim 1, wherein heating is performed in a temperature range where (A) does not decompose.
[0027]
3rd invention in this application is the graft polymer obtained by heating the polymeric radical polymerization initiator and radical polymerizable monomer (B2) as described in 1st invention in the range of 100-180 degreeC. .
[0028]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail.
[0029]
  The polymer radical polymerization initiator of the present invention is a polymer compound in which an alkoxyamine group represented by the general formula (1) is suspended from a molecular main chain.
   In general formula (1),R ¹ Is a phenylene group, R ² Is hydrogen, t-butyl group or R ⁹ OC (O) — group, where R ⁹ Represents a linear or branched alkyl group having 2 to 8 carbon atoms, a linear or branched alkoxyalkyl group having 2 to 8 carbon atoms, a cyclohexyl group, or a t-butylcyclohexyl group. R ⁴ Is a methyl group, R ⁵ Is a methyl group, R ⁷ Is a methyl group, R ⁸ Is a methyl group. R ³ And R ⁶ Are each a methyl group or R ³ And R ⁶ Are linked cyclic structures, R ³ And R ⁶ In the case of a cyclic structure in which is bonded, it may be substituted with any of a methyl group, a hydroxy group, an acetoxy group, a benzoyloxy group, or a methoxy group. ⁴ , R ⁵ , R ⁷ And R ⁸ The portion other than is a nitrogen-containing ring selected from piperidine, pyrrolidine and isoindoline.
[0030]
In the present invention, the molecular weight of the polymer radical polymerization initiator can be appropriately determined according to the required characteristics for the graft polymer, but the number average in the styrene equivalent molecular weight measured by gel permeation chromatography (hereinafter referred to as GPC). The molecular weight is preferably in the range of 3000 to 500,000, more preferably in the range of 5000 to 400,000. When the molecular weight of the polymer radical polymerization initiator is less than 3000, the physical properties of the trunk polymer tend not to be sufficiently expressed when the graft polymer is used. On the other hand, when the molecular weight exceeds 500,000, it is in a molten state or a solution state. This is not preferable because the viscosity of the polymer radical polymerization initiator becomes high and the workability during the production of the initiator and the graft polymer tends to deteriorate.
[0031]
Furthermore, the average number of alkoxyamine pendant groups suspended per molecule of the polymer radical polymerization initiator of the present invention is preferably in the range of 3 to 200, and more preferably in the range of 5 to 100. preferable. Even if the number of alkoxyamine groups is one or two, the effect as a graft polymer can be realized by sufficiently increasing the molecular weight of the branched polymer, but the average number of alkoxyamine groups is 3 If the amount is less, it is not preferable because a polymer having no alkoxyamine group in the molecule is likely to be formed, and the physical properties of the branched polymer tend not to be sufficiently expressed when a graft polymer is used. On the other hand, when the average number is more than 200, the physical properties of the trunk polymer tend not to be sufficiently exhibited, which is not preferable.
[0032]
  The polymer radical polymerization initiator as described above can be obtained as follows.
That is, the compound (A) represented by the general formula (2) having both radically polymerizable vinyl group and alkoxyamine group in the same molecule (hereinafter referred to as compound A) and the radically polymerizable monomer (B1). And a radical polymerization initiator (C) are heated in a temperature range where the radical polymerization initiator (C) is not decomposed and the compound (A) is not decomposed (hereinafter referred to as first-stage polymerization).
  In general formula (2),R ¹ Is a phenylene group, R ² Is hydrogen, t-butyl group or R ⁹ OC (O) — group, where R ⁹ Represents a linear or branched alkyl group having 2 to 8 carbon atoms, a linear or branched alkoxyalkyl group having 2 to 8 carbon atoms, a cyclohexyl group, or a t-butylcyclohexyl group. R ⁴ Is a methyl group, R ⁵ Is a methyl group, R ⁷ Is a methyl group, R ⁸ Is a methyl group. R ³ And R ⁶ Are each a methyl group or R ³ And R ⁶ Are linked cyclic structures, R ³ And R ⁶ In the case of a cyclic structure in which is bonded, it may be substituted with any of a methyl group, a hydroxy group, an acetoxy group, a benzoyloxy group, or a methoxy group. ⁴ , R ⁵ , R ⁷ And R ⁸ The portion other than is a nitrogen-containing ring selected from piperidine, pyrrolidine and isoindoline.R¹⁰Is hydrogen or a methyl group.
[0033]
  Specific examples of the compound (A) represented by the general formula (2) include 2- (2 ′, 2 ′, 6 ′, 6′-tetramethyl-1′-piperidinyloxy) -2- ( 4′-vinylphenyl) ethanol, 2- (4′-hydroxy-2 ′, 2 ′, 6 ′, 6′-tetramethyl-1′-piperidinyloxy) -2- (3′-vinylphenyl) ethanol 2-t-butoxy-1- (2 ′, 2 ′, 6 ′, 6′-tetramethyl-1′-piperidinyloxy) -1- (4′-vinylphenyl) ethane, 2-t-butoxy -1- (4′-hydroxy-2 ′, 2 ′, 6 ′, 6′-tetramethyl-1′-piperidinyloxy) -1- (3′-vinylphenyl) ethane, 2-t-butoxy- 1- (4′-acetoxy-2 ′, 2 ′, 6 ′, 6′-tetramethyl-1′-piperidinyloxy) -1- (3′-vinylphenyl) ethane 2-t-butoxy-1- (1 ′, 1 ′, 3 ′, 3′-tetramethyl-2 ′, 3′-dihydro-1′H-2-isoindolyloxy) -1- (4′- Isopropenylphenyl) ethane,2-isopropyloxycarbonyloxy-1- (2 ′, 2 ′, 6 ′, 6′-tetramethyl-1′-piperidinyloxy) -1- (4′-vinylphenyl) ethane, 2-isopropyloxycarbonyl Oxy-1- (4′-hydroxy-2 ′, 2 ′, 6 ′, 6′-tetramethyl-1′-piperidinyloxy) -1- (3′-vinylphenyl) ethane, 2- (2 ′ -Ethoxyethyloxycarbonyloxy) -1- (4′-methoxy-2 ′, 2 ′, 6 ′, 6′-tetramethyl-1′-piperidinyloxy) -1- (4′-vinylphenyl) ethane 2-cyclohexyloxycarbonyloxy-1- (4′-methyl-2 ′, 2 ′, 6 ′, 6′-tetramethyl-1′-piperidinyloxy) -1- (4′-vinylphenyl) ethane , 2- (2'-ethylhexyloxycarbonyloxy) 1- (2 ′, 2 ′, 6 ′, 6′-tetramethyl-1′-piperidinyloxy) -1- (4′-vinylphenyl) ethane, 2- (4′-t-butylcyclohexyloxycarbonyl) Oxy) -1- (2 ′, 2 ′, 6 ′, 6′-tetramethyl-1′-piperidinyloxy) -1- (4′-vinylphenyl) ethane, 2-isopropyloxycarbonyloxy-1- (4′-benzoyloxy-2 ′, 2 ′, 6 ′, 6′-tetramethyl-1′-piperidinyloxy) -1- (4′-vinylphenyl) ethane, 2-isopropyloxycarbonyloxy-1 -(2 ', 2', 6 ', 6'-tetramethyl-1'-piperidinyloxy) -1- (4'-isopropenylphenyl) ethane, 2-isopropyloxycarbonyloxy-1- (2' , 2 ′, 5 ′, 5′-tetramethyl-1′-pyrrolidini Oxy) -1- (4'-vinylphenyl) ethane, 2-isopropyl-oxycarbonyl-1- (di -t- butyl nitroxyl) -1- (4'-vinylphenyl) ethane.
[0034]
In the present invention, the radically polymerizable monomer (B1) used in the first stage polymerization is a vinyl monomer that can be copolymerized with the compound (A). It can be appropriately selected from those suitable for configuration. Specific examples of the radical polymerizable monomer (B1) copolymerizable with the compound (A) include styrene monomers such as styrene, p-methylstyrene, chloromethylstyrene, and α-methylstyrene, acrylic Acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid and other carboxyl group-containing vinyl monomers, maleic anhydride, itaconic anhydride and other acid anhydride group-containing vinyl monomers, methyl (meth) acrylate , Ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Propyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate Relate, glycidyl (meth) acrylate, dimethyl fumarate, diethyl fumarate, dibutyl fumarate and other ester group-containing vinyl monomers, (meth) acrylate 2-isocyanate ethyl, m-isopropenyl-α, α-dimethylbenzyl Nitrogen-containing alkyl such as isocyanate group-containing vinyl monomer such as isocyanate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, Nt-butylaminoethyl (meth) acrylate Amides such as (meth) acrylate, acrylamide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide Containing vinyl monomer, 2-vinyl pyridine, aromatic nitrogen-containing vinyl monomers such as 4-vinylpyridine, acrylonitrile, methacrylonitrile and the like nitrile group-containing vinyl monomers such.
[0035]
Among these radically polymerizable monomers, particularly preferred are radically polymerizable monomers containing oxygen or nitrogen atoms in the molecule, specifically carboxyl group-containing vinyl monomers and acid anhydride groups. Vinyl monomer, ester group-containing vinyl monomer, isocyanate group-containing vinyl monomer, nitrogen-containing alkyl (meth) acrylate, amide group-containing vinyl monomer, aromatic nitrogen-containing vinyl monomer, nitrile group-containing vinyl And monomers.
[0036]
These radically polymerizable monomers can be used alone or in admixture of two or more. When it is desirable to introduce a physical property different from the branched polymer into the trunk polymer when the graft polymer is used, only a radically polymerizable monomer other than styrene may be used for the first stage polymerization. It is more preferable to use a monomer mixture containing one or more radical polymerizable monomers other than styrene. This is because in the production of a graft polymer using the polymer radical polymerization initiator of the present invention, in order to obtain a branched polymer with a higher molecular weight controlled, it is necessary to use a monomer containing a styrenic monomer. It is because it is more preferable.
[0037]
In the present invention, the amount of the compound (A) and the radical polymerizable monomer (B1) used in the first stage polymerization is such that the desired alkoxyamine group in the resulting polymer radical polymerization initiator is used. Although it can be appropriately selected depending on the number, it is usually preferred that the molar ratio of (B1) to (A) is in the range of 10 to 500 times. When the molar ratio of the radically polymerizable monomer (B1) is less than 10 times, when the graft polymer is used, the chain length of the trunk polymer between the branch polymer becomes too short, and the physical properties of the trunk polymer are sufficient. On the other hand, if it exceeds 500 times, the chain length of the trunk polymer between the branch polymers becomes too long, and the physical properties of the branch polymer tend not to be sufficiently expressed, which is not preferable.
[0038]
In the present invention, in the first stage polymerization, the radical polymerization initiator (C) decomposes the mixture composed of the compound (A), the radical polymerizable monomer (B1) and the radical polymerization initiator (C). The reaction is performed in a temperature range where the compound (A) does not decompose.
As specific polymerization temperature, 0-120 degreeC is preferable and 20-100 degreeC is more preferable. When the polymerization temperature is 0 ° C. or lower, the polymerization rate is slow, and thus it takes a long time to complete the polymerization, which is economically disadvantageous. On the other hand, when the polymerization temperature is 120 ° C. or higher, the decomposition of the compound (A) becomes remarkable, and as a result, it becomes difficult to control the structure of the graft polymer finally obtained, the gel is generated, and the purity of the graft polymer is low. Since it falls, it is not preferable.
[0039]
In the present invention, as the radical polymerization initiator (C) used in the first stage polymerization, a normal organic peroxide or azo compound can be used, but it generates radicals effectively under the above polymerization temperature conditions. Therefore, it may be appropriately selected depending on the polymerization temperature. Specific examples of the radical polymerization initiator (C) usually used include t-butylperoxyneodecanoate, t-octylperoxyneodecanoate, t-butylperoxypivalate, and t-hexylperoxypivalate. Peroxyesters such as t-butylperoxy 2-ethylhexanoate, t-octylperoxyisobutyrate, t-butylperoxyisopropyl carbonate, t-butylperoxylaurate, t-butylperoxybenzoate, isobutyryl peroxide, Diacyl peroxides such as 3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide, benzoyl peroxide, dipropyl peroxydicarbonate, diisopropyl peroxydicarbonate, di (2-ethyl) Hexyl) peroxydicarbonates such as peroxydicarbonate, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t- Butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 2,2-bis (4,4-di-t-butylperoxy) Cyclohexyl) and other peroxyketals, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (cyclohexanenitrile), 2, 2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethyl-4-meth) Shi valeronitrile) an azo compound such. In addition, a method of reducing radicals such as t-butyl hydroperoxide and cumene hydroperoxide using a reducing agent such as ferrous sulfate, cuprous sulfate, sodium ascorbate to generate radicals, or photoirradiation of a photopolymerization initiator Then, the polymerization can be started by a method of generating radicals.
[0040]
In the present invention, the first stage polymerization can be carried out by a known polymerization method such as bulk polymerization, suspension polymerization, solution polymerization and emulsion polymerization, and the type of monomer, polymerization temperature, desired polymer radical polymerization. It can be appropriately selected depending on the molecular weight of the initiator.
[0041]
In the present invention, when suspension polymerization is employed in the first stage polymerization, a protective colloid agent of a water-soluble polymer and a hardly soluble inorganic substance can be added to the polymerization system as a dispersant. Examples of the water-soluble polymer protective colloid agent include polyvinyl alcohol, polyvinyl pyrrolidone, and methyl cellulose. Of these, polyvinyl alcohol is preferable. Examples of the hardly soluble inorganic substance include tricalcium phosphate, magnesium phosphate, calcium pyrophosphate, bentonite and the like. When a hardly soluble inorganic substance is used as a dispersant, it is preferable to use a small amount of an anionic surfactant such as sodium dodecylbenzene sulfonate or sodium α-olefin sulfonate.
[0042]
In the present invention, when solution polymerization is employed in the first stage polymerization, specific examples of the solvent include aromatic hydrocarbon solvents such as toluene, xylene, and ethylbenzene, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. , Ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, alcohol solvents such as methanol, isopropyl alcohol, n-butyl alcohol, ethylene glycol, ethylene glycol diacetate, ethylene glycol monomethyl ether, ethylene glycol diethyl ether, ethylene glycol Ethylene glycol solvents such as methyl ether acetate, diethylene glycol such as diethylene glycol, diethylene glycol dimethyl ether, diethylene glycol monobutyl ether System solvent, propylene glycol, propylene glycol solvents such as propylene glycol methyl ether acetate and the like, can be used as these alone or in mixtures.
[0043]
In the present invention, α-methylstyrene dimer (2,4-diphenyl-4-methyl-1-pentene), terpinolene, n-octyl mercaptan, t-dodecyl mercaptan, 2-mercaptoethanol, thiophenol and the like as necessary. These known chain transfer agents can be used.
[0044]
In the present invention, after the first stage polymerization is completed, the polymer radical polymerization initiator is used as it is or after undergoing a purification step such as solvent distillation or reprecipitation, to obtain a polymerization (hereinafter referred to as a graft polymer). , Described as second-stage polymerization).
[0045]
In the present invention, the second stage polymerization is carried out by heating a mixture containing the polymer radical polymerization initiator represented by the general formula (1) and the radical polymerizable monomer (B2).
[0046]
That is, the polymer radical polymerization initiator represented by the general formula (1) is cleaved into a carbon radical bonded to the trunk polymer side and a stable nitroxide radical by thermal action. The carbon radical starts addition polymerization with the radical polymerizable monomer (B2) present in the system. On the other hand, the nitroxide radical does not start the polymerization, but the polymerization reaction proceeds with the growing polymer radical from the carbon radical while repeating recombination and re-cleavage. Is done.
[0047]
In the present invention, the second stage polymerization can be carried out by a known polymerization method such as bulk polymerization, suspension polymerization, solution polymerization and emulsion polymerization in the same manner as the first stage polymerization. The temperature can be appropriately selected depending on the molecular weight of the desired polymer radical polymerization initiator.
[0048]
In the present invention, the radical polymerizable monomer (B2) used for the second stage polymerization is obtained from the radical polymerizable monomer (B1) that can be used for the first stage polymerization. The graft polymer selected according to the required physical properties of the graft polymer can be used as appropriate, but the purpose is to effectively increase the molecular weight of the graft polymer of the graft polymer obtained by the second stage polymerization or to control it to a higher degree. For the purpose, it is preferable to use a styrene monomer alone or a radical polymerizable monomer mixture containing at least one styrene monomer.
[0049]
In the present invention, the molecular weight of the branch polymer of the graft polymer obtained by the second stage polymerization can be appropriately determined depending on the relationship with the molecular weight of the trunk polymer and the molecular weight of the target graft polymer. Although it depends on the number of alkoxyamine pendant groups suspended in the polymer radical polymerization initiator (A) (that is, the number of finally obtained branch polymers), the branch polymer usually has a styrene equivalent molecular weight of 1000 by GPC. It is preferably in the range of ˜150,000, and more preferably in the range of 2,000 to 100,000. If the molecular weight is less than 1000, when a graft polymer is used, the physical properties of the branch polymer tend not to be sufficiently expressed, whereas if it exceeds 150,000, the physical properties of the trunk polymer tend not to be sufficiently expressed.
[0050]
In the present invention, the polymerization temperature of the second stage polymerization is preferably in the range of 100 to 180 ° C, more preferably in the range of 110 to 160 ° C. When the polymerization temperature is 100 ° C. or lower, the decomposition rate of the polymer radical polymerization initiator is slow, and as a result, the polymerization time tends to be long, which is not preferable. On the other hand, when the polymerization temperature is higher than 180 ° C., it becomes difficult to control the polymerization rate, and it becomes easy to generate a radical polymerizable (B2) homopolymer added at the second stage polymerization by thermal polymerization. This is not preferable because the purity of the graft polymer is lowered.
[0051]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the examples as long as the gist of the present invention is not exceeded.
In carrying out the present invention, the compound (A) for obtaining the polymer radical polymerization initiator of the present invention was synthesized as follows in accordance with the method described in Japanese Patent Application No. 10-206146 in advance. .
[0052]
<Synthesis of Compound (A)>
To a 100 ml four-necked flask equipped with a stirrer, a condenser and a nitrogen gas introduction tube, divinylbenzene (“DVB-960” manufactured by Nippon Steel Chemical Co., Ltd., isomer mixture of m- and p-divinylbenzene, purity 96%) A mixture of 50 g and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (HO-TEMPO) 8.61 g (50 mmol) was added, and the contents were replaced with nitrogen. The contents were then heated to 50 ° C., and 11.6 g (55.6 mmol) of diisopropyl peroxydicarbonate (IPP) was added in portions over 20 minutes. Then, after reacting at 50 degreeC for 5 hours, most divinylbenzene was distilled off under pressure reduction. The resulting composition was purified by silica gel chromatography to obtain 12.8 g of a pale yellow oil.
This is high performance liquid chromatography (HPLC), mass spectrometry,¹H-NMR and¹³As a result of confirming the structure by C-NMR, 2-isopropyloxycarbonyloxy-1- (4′-hydroxy-2 ′, 2 ′, 6 ′, 6′-tetramethyl-1′-piperidinyloxy)- 1- (3′-vinylphenyl) ethane and 2-isopropyloxycarbonyloxy-1- (4′-hydroxy-2 ′, 2 ′, 6 ′, 6′-tetramethyl-1′-piperidinyloxy)- It was confirmed that it was a mixture of 1- (4′-vinylphenyl) ethane (hereinafter referred to as A-1). The purity determined from HPLC and GPC analysis was 98%.
[0053]
Similarly, the following compounds (A2 to A4) of the present invention were synthesized.
2-t-butoxy-1- (4′-hydroxy-2 ′, 2 ′, 6 ′, 6′-tetramethyl-1′-piperidinyloxy) -1- (3′-vinylphenyl) ethane and 2 A mixture of t-butoxy-1- (4′-hydroxy-2 ′, 2 ′, 6 ′, 6′-tetramethyl-1′-piperidinyloxy) -1- (4′-vinylphenyl) ethane ( Purity 98%, A-2)
2- (4′-hydroxy-2 ′, 2 ′, 6 ′, 6′-tetramethyl-1′-piperidinyloxy) -2- (3′-vinylphenyl) ethanol and 2- (4′-hydroxy -2 ′, 2 ′, 6 ′, 6′-tetramethyl-1′-piperidinyloxy) -2- (4′-vinylphenyl) ethanol mixture (purity 99%, A-3) 2-isopropyloxy Carbonyloxy-1- (2 ′, 2 ′, 6 ′, 6′-tetramethyl-1′-piperidinyloxy) -1- (4′-vinylphenyl) ethane (purity 98%, A-4)
[0054]
<Example 1>
0.62 g (1.5 mmol) of Compound A-1 obtained in Reference Example, 4.41 g (44.0 mmol) of methyl methacrylate (MMA), 0.010 g of t-hexylperoxypivalate (HPV) as a polymerization initiator (0.049 mmol), nitrogen was blown into a mixture of 0.05 g of n-octyl mercaptan as a molecular weight regulator to remove oxygen, and after pouring into a glass ampoule having an internal volume of 10 ml, the reaction tube was sealed. Polymerization was performed at 6 ° C. for 6 hours. Thereafter, the content was dissolved in 50 ml of tetrahydrofuran (THF), and the solution was dropped into 300 ml of methanol to reprecipitate the high molecular weight product. This purification operation was repeated again to completely remove unreacted compounds A-1, MMA and HPV, and then the product was left to dry under reduced pressure at 30 ° C. for 24 hours.
[0055]
The weight of the high molecular weight product obtained by the above operation was 2.91 g, and the yield was 58.2%. When the molecular weight was measured by GPC, it was confirmed to be a polyMMA having a number average molecular weight of 20,000 and a weight average molecular weight of 34,000 in terms of styrene.
Of this compound¹H-NMR spectrum (tetramethylsilane (TMS) / deuterated chloroform (CDCl₃)) Is shown in FIG. The assignment of each proton is as follows. (Δ (ppm))
0.65 to 1.55; methyl and methylene protons
1.65 to 2.15; methyl proton
3.60; ester methyl proton
6.8-7.3; benzene ring proton
¹From the H-NMR analysis results, an average of 6.8 alkoxy molecules per molecule of high molecular weight was determined based on the ratio of the benzene ring proton derived from Compound A-1 to the proton derived from the ester methyl group of polyMMA. It was found that an amine group was introduced.
From the above, it was confirmed that this compound was a polymer radical polymerization initiator of the present invention represented by the following formula (Formula 5) (hereinafter referred to as LRPI-1).
[0056]
[Chemical formula 5]

[0057]
<Examples 2 to 4>
In Example 1, a polymer radical polymerization initiator was synthesized according to Example 1 except that the type and amount of compound A and the monomer used, and the polymerization temperature and time were changed. Table 1 shows the analysis results of the synthesized product together with various conditions in the synthesis.
[0058]
[Table 1]

In Table 1 and below, each symbol represents the following.
Monomer
CMS: Chloromethylstyrene (mixture of m-form and p-form)
Polymerization initiator
HPV: t-hexyl peroxypivalate ("Perhexyl PV" manufactured by NOF Corporation)
BPV: t-butyl peroxypivalate (Nippon Yushi Co., Ltd. “Perbutyl PV”)
Additive
MSD: α-methylstyrene dimer (“NOFMER MSD” manufactured by NOF Corporation)
OM: n-octyl mercaptan
[0059]
[Chemical 6]

[0060]
[Chemical 7]

[0061]
[Chemical 8]

[0062]
<Example 5>
A 300 ml four-necked flask equipped with a stirrer, a condenser, a thermometer, and a nitrogen gas inlet tube was charged with 30 g of diethylene glycol dimethyl ether as a solvent, and the solvent and the space in the container were sufficiently replaced with nitrogen gas. While heating the solvent to 65 ° C. and stirring under a nitrogen stream, 1.57 g (3.8 mmol) of compound A-1, 15.0 g (0.152 mol) of N, N-dimethylacrylamide (DMAA), diethylene glycol dimethyl ether 9. A mixture of 09 g and 0.167 g of BPV as a polymerization initiator was added in 8 portions every 15 minutes. After the addition, polymerization was further performed at 65 ° C. for 3 hours and further at 85 ° C. for 1 hour.
[0063]
As a result of gas chromatography and GPC analysis, it was found that the conversion of DMAA was 100%, and the obtained solution contained 30% (16.7 g) of a high molecular weight product.
The number average molecular weight of the high molecular weight product was 60,000 and the weight average molecular weight was 1340. Of high molecular weight polymer extracted from a part of the solution by reprecipitation¹H-NMR (TMS / CDCl₃) The analysis results are as follows. (Δ (ppm))
0.6-1.6; methyl and methylene protons
1.7-2.2; methyl proton
3.0; -N (CH₃)₂
6.8-7.3; benzene ring proton
¹From the result of 1 H-NMR analysis, the ratio of the benzene ring proton derived from compound A-1 to the proton derived from methyl bonded to the nitrogen atom averaged 15.5 alkoxy molecules per molecule. It was found that an amine group was introduced.
From the above, it was confirmed that this compound was a polymer radical polymerization initiator of the present invention represented by the formula (Formula 9) (hereinafter referred to as LRPI-5).
[0064]
[Chemical 9]

[0065]
<Example 6>
2 g of LRPI-1 obtained in Example 1 and 10 g of styrene were injected into a glass ampoule having an internal volume of 20 ml and purged with nitrogen, and the tube was sealed and polymerized at 125 ° C. for 5 hours. The contents were dissolved in 50 ml of THF, and the solution was dropped into 500 ml of methanol to reprecipitate the high molecular weight product. This purification operation was repeated again to completely remove the unreacted styrene monomer, and then the high molecular weight product was left to dry under reduced pressure at 30 ° C. for 24 hours.
[0066]
The weight of the obtained high molecular weight product was 7.0 g, and the conversion of styrene was 50.0%. According to GPC measurement, the obtained high molecular weight product had a number average molecular weight of 66,000 and a weight average molecular weight of 97,000 in terms of styrene. Furthermore, the composition of the high molecular weight obtained by fractional extraction using a Soxhlet tube was 97% for the graft copolymer of styrene and MMA and 3% for the polystyrene homopolymer. It was confirmed not to include. Furthermore, the composition ratio of the graft body¹As a result of analysis by 1 H-NMR, it was found that the branched polymer portion was composed of 68.5 styrene monomers on average.
[0067]
<Examples 7 to 10>
Using the polymer radical polymerization initiator of the present invention synthesized in Examples 2 to 5, the graft polymer of the present invention was synthesized in the same manner as in Example 6 according to the polymerization conditions shown in Table 2 below. These analysis results are also shown in Table 2. In Table 2, BA represents butyl acrylate.
[0068]
[Table 2]

[0069]
【The invention's effect】
According to the present invention, it is possible to obtain a polymer polymerization initiator in which a pendant group of an alkoxyamine having a specific structure is suspended in a molecular main chain by bonding to stable carbon-carbon by a simple method. In addition, using the obtained polymer radical polymerization initiator, the trunk polymer and the branch polymer are bonded to a stable carbon-carbon bond to obtain a graft polymer that is stable against ionic and radical reactions with high purity. Can do.
The graft polymer obtained by the present invention can be used, for example, as a compatibilizer, surfactant, pigment dispersant, adhesion improver, etc. for uniformly mixing at least two kinds of high molecular weight polymers that are not compatible with each other. It has an excellent effect for the use.
[Brief description of the drawings]
FIG. 1 shows the compound of Example 1 according to the present invention.¹H-NMR spectrum

Claims (3)

A high molecular weight product obtained by polymerizing a radically polymerizable monomer, which has the following general formula (1)

...... (1)
Wherein R ¹ is a phenylene group, R ² is hydrogen, a t-butyl group or an R ⁹ OC (O) — group, wherein R ⁹ is a linear or branched alkyl group having 2 to 8 carbon atoms, Represents a straight or branched alkoxyalkyl group having 2 to 8 carbon atoms, a cyclohexyl group, or a t-butylcyclohexyl group, wherein R ⁴ is a methyl group, R ⁵ is a methyl group, R ⁷ is a methyl group, and R ⁸ is a methyl group. in a .R ³ and R ⁶ are each methyl or a cyclic structure R ³ and R ⁶ are linked, in the case of cyclic structures R ³ and R ⁶ are linked, the methyl group, hydroxy group , An acetoxy group, a benzoyloxy group, or a methoxy group, and the portion of the cyclic structure excluding the substituents R ⁴ , R ⁵ , R ⁷ and R ⁸ is piperidine, pyrrolidine and isoin It is a nitrogen-containing ring selected from drin. A polymer radical polymerization initiator in which an alkoxyamine group represented by) is suspended. The following general formula (2) having both radically polymerizable vinyl group and alkoxyamine group in the same molecule

(2)

Wherein R ¹ is a phenylene group, R ² is hydrogen, a t-butyl group or an R ⁹ OC (O) — group, wherein R ⁹ is a linear or branched alkyl group having 2 to 8 carbon atoms, Represents a straight or branched alkoxyalkyl group having 2 to 8 carbon atoms, a cyclohexyl group, or a t-butylcyclohexyl group, wherein R ⁴ is a methyl group, R ⁵ is a methyl group, R ⁷ is a methyl group, and R ⁸ is a methyl group. in a .R ³ and R ⁶ are each methyl or a cyclic structure R ³ and R ⁶ are linked, in the case of cyclic structures R ³ and R ⁶ are linked, the methyl group, hydroxy group , An acetoxy group, a benzoyloxy group, or a methoxy group, and the portion of the cyclic structure excluding the substituents R ⁴ , R ⁵ , R ⁷ and R ⁸ is piperidine, pyrrolidine and isoin A nitrogen-containing ring selected from drin , and R ¹⁰ represents hydrogen or a methyl group), a radical polymerizable monomer (B1), a radical polymerization initiator (C The radical polymerization initiator according to claim 1, wherein the mixture is heated in a temperature range in which the radical polymerization initiator (C) is decomposed and the compound (A) is not decomposed. Manufacturing method.   A graft polymer obtained by heating the polymer radical polymerization initiator and the radical polymerizable monomer (B2) according to claim 1 in a range of 100 to 180 ° C.

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