JP3980724B2 - Method for producing (meth) acrylic polymer having hydroxyl group at terminal - Google Patents

Description

【００３２】
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは１〜２０の整数）ＸＣＨ₂Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_m−ＯＨ、Ｈ₃ＣＣ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_m−ＯＨ、（Ｈ₃Ｃ）₂Ｃ（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_m−ＯＨ、ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_m−ＯＨ、
【００３３】
【化２】

【００３４】
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎ、ｍは１〜２０の整数）
ｏ−，ｍ−，ｐ−ＸＣＨ₂−Ｃ₆Ｈ₄−（ＣＨ₂）_n−ＯＨ、ｏ−，ｍ−，ｐ−ＣＨ₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−（ＣＨ₂）_n−ＯＨ、ｏ−，ｍ−，ｐ−ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−（ＣＨ₂）_n−ＯＨ、
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは０〜２０の整数）ｏ−，ｍ−，ｐ−ＸＣＨ₂−Ｃ₆Ｈ₄−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_m−ＯＨ、ｏ−，ｍ−，ｐ−ＣＨ₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_m−ＯＨ、
ｏ−，ｍ−，ｐ−ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_m−ＯＨ、
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは０〜２０の整数、ｍは１〜２０の整数）
ｏ−，ｍ−，ｐ−ＸＣＨ₂−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_m−ＯＨ、ｏ−，ｍ−，ｐ−ＣＨ₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_m−ＯＨ、ｏ−，ｍ−，ｐ−ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_m−ＯＨ、
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎ、ｍは１〜２０の整数）
等が挙げられる。
【００３５】
一般式６に示す化合物の具体例としては、
ＨＯ−ＣＨ₂Ｃ（Ｈ）（Ｘ）−ＣＯ₂Ｒ、ＨＯ−（ＣＨ₂）₂Ｃ（Ｈ）（Ｘ）−ＣＯ₂Ｒ、ＨＯ−（ＣＨ₂）₃Ｃ（Ｈ）（Ｘ）−ＣＯ₂Ｒ、ＨＯ−（ＣＨ₂）₈Ｃ（Ｈ）（Ｘ）−ＣＯ₂Ｒ、
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、Ｒは炭素数１〜２０のアルキル基、アリール基、アラルキル基）
ＨＯ−ＣＨ₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₅、ＨＯ−（ＣＨ₂）₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₅、ＨＯ−（ＣＨ₂）₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₅、
等を挙げることができる。
【００３６】
水酸基を有するハロゲン化スルホニル化合物の具体例を挙げるならば、
ｏ−，ｍ−，ｐ−ＨＯ−（ＣＨ₂）_n−Ｃ₆Ｈ₄−ＳＯ₂Ｘ、
（上式において、Ｘは塩素、臭素、またはヨウ素、ｎは０〜２０の整数）
ｏ−，ｍ−，ｐ−ＨＯ−（ＣＨ₂）_n−Ｏ−Ｃ₆Ｈ₄−ＳＯ₂Ｘ、
（上式において、Ｘは塩素、臭素、またはヨウ素、ｎは１〜２０の整数）
等である。
【００３７】
水酸基を有する有機ハロゲン化物、またはハロゲン化スルホニル化合物を開始剤として（メタ）アクリル系モノマーを重合すると、片末端には水酸基が導入され、他の末端が一般式１で表される末端構造を有する重合体が得られる。この末端のハロゲンを水酸基に変換する方法としては、既に述べた方法をすべて好適に用いることができる。
【００３８】
水酸基を有する有機ハロゲン化物、またはハロゲン化スルホニル化合物を開始剤として用いると、片末端が水酸基、他の末端が式１で示されるハロゲン末端である重合体が得られるが、この重合体の式１のハロゲンを置換できる、同一または異なった官能基を合計２個以上有する化合物を用いて、ハロゲン末端どうしをカップリングさせることによっても、末端に水酸基を有する（メタ）アクリル系重合体を得ることができる。
【００３９】
式１で示される末端ハロゲンを置換できる、同一または異なった官能基を合計２個以上有するものとしては特に制限はないが、ポリオール、ポリアミン、ポリカルボン酸、ポリチオール、およびそれらの塩、アルカリ金属硫化物等が好ましい。これらの化合物を具体的に例示するならば、
エチレングリコール、１，２−プロパンジオール、１，３−プロパンジオール、２−メチル−１，３−プロパンジオール、２，２−ジメチル−１，３−プロパンジオール、１，４−ブタンジオール、１，３−ブタンジオール、１，２−ブタンジオール、２，３−ブタンジオール、ピナコール、１，５−ペンタンジオール、１，４−ペンタンジオール、２，４−ペンタンジオール、１，６−ヘキサンジオール、１，７−ヘプタンジオール、１，８−オクタンジオール、１，９−ノナンジオール、１，１０−デカンジオール、１，１２−ドデカンジオール、１，２−シクロペンタンジオール、１，３−シクロペンタンジオール、１，２−シクロヘキサンジオール、１，３−シクロヘキサンジオール、１，４−シクロヘキサンジオール、グリセロール、１，２，４−ブタントリオール、カテコール、レゾルシノール、ヒドロキノン、１，２−ジヒドロキシナフタレン、１，３−ジヒドロキシナフタレン、１，５−ジヒドロキシナフタレン、２，６−ジヒドロキシナフタレン、２，２’−ビフェノール、４，４’−ビフェノール、ビス（４−ヒドロキシフェニル）メタン、４，４’−イソプロピリデンフェノール、３，３’−（エチレンジオキシ）ジフェノール、α，α’−ジヒドロキシ−ｐ−キシレン、１，１，１−トリス（４−ヒドロキシフェニル）エタン、ピロガロール、１，２，４−ベンゼントリオール、および、上記ポリオール化合物のアルカリ金属塩、
エチレンジアミン、１，３−ジアミノプロパン、１，２−ジアミノプロパン、１，４−ジアミノブタン、１，２−ジアミノ−２−メチルプロパン、１，５−ジアミノペンタン、２，２−ジメチル−１，３−プロパンジアミン、１，６−ヘキサンジアミン、１，７−ヘプタンジアミン、１，８−オクタンジアミン、１，９−ジアミノノナン、１，１０−ジアミノデカン、１，１２−ジアミノドデカン、４，４’−メチレンビス（シクロヘキシルアミン）、１，２−ジアミノシクロヘキサン、１，３−ジアミノシクロヘキサン、１，４−ジアミノシクロヘキサン、１，２−フェニレンジアミン、１，３−フェニレンジアミン、１，４−フェニレンジアミン、α，α’−ジアミノ−ｐ−キシレン、および上記ポリアミン化合物のアルカリ金属塩、
シュウ酸、マロン酸、メチルマロン酸、ジメチルマロン酸、コハク酸、メチルコハク酸、グルタル酸、アジピン酸、１，７−ヘプタンジカルボン酸、１，８−オクタンジカルボン酸、１，９−ノナンジカルボン酸、１，１０−デカンジカルボン酸、１，１１−ウンデカンジカルボン酸、１，１２−ドデカンジカルボン酸、１，２−シクロペンタンジカルボン酸、１，２−シクロヘキサンジカルボン酸、１，３−シクロヘキサンジカルボン酸、１，４−シクロヘキサンジカルボン酸、１，３，５−シクロヘキサントリカルボン酸、フタル酸、イソフタル酸、テレフタル酸、１，２，３−ベンゼントリカルボン酸、１，２，４，５−ベンゼンテトラカルボン酸、および上記ポリカルボン酸のアルカリ金属塩、
１，２−エタンジチオール、１，３−プロパンジチオール、１，４−ブタンジチオール、２，３−ブタンジチオール、１，５−ペンタンジチオール、１，６−ヘキサンジチオール、１，７−ヘプタンジチオール、１，８−オクタンジチオール、１，９−ノナンジチオール、２−メルカプトエチルエーテル、ｐ−キシレン−α，α’−ジチオール、１，２−ベンゼンジチオール、１，３−ベンゼンジチオール、１，４−ベンゼンジチオール、および、上記ポリチオール化合物のアルカリ金属塩、硫化リチウム、硫化ナトリウム、硫化カリウム、等である。
【００４０】
上記のポリオール、ポリアミン、ポリカルボン酸、ポリチオールを用いる際は、置換反応を促進させるために、塩基性化合物が併用され、その具体例としては、リチウム、ナトリウム、カリウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、ナトリウムメトキシド、カリウムメトキシド、ｔｅｒｔ−ブトキシナトリウム、ｔｅｒｔ−ブトキシカリウム、水素化ナトリウム、水素化カリウム等が挙げられる。
【００４１】
上記の各種の方法で得られる、末端に水酸基を有する（メタ）アクリル系重合体より、これを主成分とする硬化性組成物を得ることができる。
この硬化性組成物は以下の２成分：（Ａ）末端に水酸基を有する（メタ）アクリル系重合体、（Ｂ）水酸基と反応しうる官能基を２個以上有する化合物、を必須成分とするものである。
【００４２】
（Ａ）成分の末端に水酸基を有する（メタ）アクリル系重合体は単独で用いても２種類以上を混合して用いてもよい。分子量としては特に制限はないが、５００〜５００００の範囲にあるのが好ましい。５００以下であると（メタ）アクリル系重合体の本来の特性が発現されにくく、５００００以上になると、非常に高粘度あるいは溶解性が低くなり、取り扱いが困難になる。
【００４３】
（Ｂ）成分の水酸基と反応しうる官能基を２個以上有する化合物としては、特に限定はないが、例えば、１分子中に２個以上のイソシアネート基を有する多価イソシアネート化合物、メチロール化メラミンおよびそのアルキルエーテル化物または低縮合化物等のアミノプラスト樹脂、多官能カルボン酸およびそのハロゲン化物等が挙げられる。
【００４４】
１分子中に２個以上のイソシアネート基を有する多価イソシアネート化合物としては従来公知のものを使用することができ、例えば、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、４，４’−ジフェニルメタンジイソシアネート、ヘキサメチレンジイソシアネート、キシリレンジイソシアネート、メタキシリレンジイソシアネート、１，５−ナフタレンジイソシアネート、水素化ジフェニルメタンジイソシアネート、水素化トリレンジイソシアネート、水素化キシリレンジイソシアネート、イソホロンジイソシアネート、一方社油脂製Ｂ−４５のごときトリイソシアネート、等のイソシアネート化合物、スミジュールＮ（住友バイエルウレタン社製）のごときビュレットポリイソシアネート化合物、デスモジュールＩＬ、ＨＬ（バイエルＡ．Ｇ．社製）、コロネートＥＨ（日本ポリウレタン工業社製）のごときイソシアヌレート環を有するポリイソシアネート化合物、スミジュールＬ（住友バイエルウレタン社製）のごときアダクトポリイソシアネート化合物、コロネートＨＬ（日本ポリウレタン社製）のごときアダクトポリイソシアネート化合物等を挙げることができる。また、ブロックイソシアネートを使用しても構わない。これらは単独で使用しても、２種類以上を併用してもよい。
【００４５】
末端に水酸基を有する重合体と２個以上のイソシアネート基を有する化合物との配合比については特に限定されないが、例えば、イソシアネート基と末端に水酸基を有する（メタ）アクリル系重合体の水酸基の比率（ＮＣＯ／ＯＨ（モル比））が０．５〜３．０であることが好ましく、０．８〜２．０であることがより好ましい。
【００４６】
この発明の組成物である末端に水酸基を有する（メタ）アクリル系重合体と２個以上のイソシアネート基を有する化合物の硬化反応を促進させるために、必要に応じて、有機スズ化合物や３級アミン等の公知の触媒を添加してもよい。
有機スズ化合物の具体例としては、オクチル酸スズ、ジブチルスズジアセテート、ジブチルスズジラウレート、ジブチルスズメルカプチド、ジブチルスズチオカルボキシレート、ジブチルスズジマレエート、ジオクチルスズチオカルボキシレート等が挙げられる。また、３級アミン系触媒としては、トリエチルアミン、Ｎ，Ｎ−ジメチルシクロヘキシルアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルプロパン１，３−ジアミン、
Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルヘキサン１，６−ジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’’，Ｎ’’−ペンタメチルジエチレントリアミン、Ｎ，Ｎ，Ｎ’，Ｎ’’，Ｎ’’−ペンタメチルジプロピレントリアミン、テトラメチルグアニジン、トリエチレンジアミン、Ｎ，Ｎ’−ジメチルピペラジン、Ｎ−メチルモルホリン、１，２−ジメチルイミダゾール、ジメチルアミノエタノール、ジメチルアミノエトキシエタノール、Ｎ，Ｎ，Ｎ’−トリメチルアミノエチルエタノールアミン、Ｎ−メチル−Ｎ’−（２−ヒドロキシエチル）ピペラジン、Ｎ−（２−ヒドロキシエチル）モルホリン、ビス（２−ジメチルアミノエチル）エーテル、エチレングリコールビス（３−ジメチル）アミノプロピルエーテル等が例示される。
【００４７】
本発明における硬化性組成物に使用されるアミノプラスト樹脂としては特に限定はなく、メラミンとホルムアルデヒドとの付加反応物（メチロール化合物）、メラミンとホルムアルデヒドの低縮合物、それらのアルキルエーテル化物、ならびに尿素樹脂等が挙げられる。これらは単独で用いても２種以上を併用しても構わない。末端に水酸基を有する（メタ）アクリル系重合体と、アミノプラスト樹脂の硬化反応を促進する目的で、パラトルエンスルホン酸、ベンゼンスルホン酸等の公知の触媒を添加してもよい。
【００４８】
本発明の硬化性組成物に用いられる、１分子中に２個以上のカルボキシル基を有する化合物としては、特に限定されず、例えば、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、フタル酸、無水フタル酸、テレフタル酸、トリメリット酸、ピロメリット酸、マレイン酸、無水マレイン酸、フマル酸、イタコン酸などの多官能カルボン酸またはその無水物、および、これらのハロゲン化物等が挙げられ、これらは単独で用いても２種類以上を併用してもよい。
【００４９】
本発明の２成分（Ａ）、（Ｂ）、および必要に応じて硬化触媒を混合し硬化させれば、深部硬化性に優れた均一な硬化物が得られる。硬化条件については特に制限はないが、一般に０℃〜１００℃、好ましくは２０℃〜８０℃である。
硬化物の性状は用いる（Ａ）成分の重合体および（Ｂ）成分の硬化剤の主鎖骨格や分子量に依存するが、ゴム状のものから樹脂状のものまで幅広く作成することができる。
【００５０】
上記の組成物より得られる硬化物の具体的な用途を挙げるならば、シーリング材、接着剤、粘着材、弾性接着剤、塗料、粉体塗料、発泡体、電気電子用ポッティング材、フィルム、成形材料、人工大理石等である。
次に、本発明の、末端にアルケニル基を有する（メタ）アクリル系重合体は、既に述べた各種の方法により得られる、末端に水酸基を有する（メタ）アクリル系重合体の水酸基をアルケニル基含有置換基に変換することにより製造することができる。
【００５１】
末端の水酸基をアルケニル基含有置換基に変換する方法としては特に制限はなく、各種の方法を用いることができる。例えば、塩化アリルのようなアルケニル基含有ハロゲン化物とナトリウムメトキシドのような塩基を作用させる方法、アリルイソシアネート等のアルケニル基含有イソシアネート化合物を作用させる方法、（メタ）アクリル酸クロリドのようなアルケニル基含有酸ハロゲン化物を反応させる方法、アクリル酸等のアルケニル基含有カルボン酸を酸触媒の存在下に反応させる方法等が挙げられる。
【００５２】
アルケニル基含有ハロゲン化物と塩基を作用させる方法において用いられるアルケニル基含有ハロゲン化物としては、塩化アリル、臭化アリル、ヨウ化アリル、４−クロロ−１−ブテン、４−ブロモ−１−ブテン、４−ヨード−１−ブテン、３−クロロ−２−メチル−１−ブテン、３−ブロモ−２−メチル−１−ブテン、３−ヨード−２−メチル−１−ブテン、等が挙げられ、塩基としては、ナトリウム、カリウム、ナトリウムメトキシド、カリウムメトキシド、ナトリウム−ｔｅｒｔ−ブトキシド、カリウム−ｔｅｒｔ−ブトキシド、水素化ナトリウム、水素化カリウム等が挙げられる。
【００５３】
アルケニル基含有イソシアネート化合物としては、アリルイソシアネート、ブテニルイソシアネート等が挙げられ、これら化合物を反応させる場合、水酸基とイソシアネート基の反応に通常用いられるスズ系、アミン系等の触媒を用いてもよい。
アルケニル基含有酸ハロゲン化物としては（メタ）アクリル酸クロライド、３−ブテン酸クロライド、４−ペンテン酸クロライド、５−ヘキセン酸クロライド、１０−ウンデセン酸クロライド等が挙げられ、実際の反応においては、トリエチルアミンやピリジン等の塩基を併用してもよい。
【００５４】
アルケニル基含有カルボン酸としては、（メタ）アクリル酸、３−ブテン酸、４−ペンテン酸、５−ヘキセン酸、６−ヘプテン酸、７−オクテン酸、１０−ウンデセン酸等が挙げられ、実際の反応においては、ｐ−トルエンスルホン酸等の縮合触媒を用いてもよい。
上記の各種の方法で得られる、末端にアルケニル基を有する（メタ）アクリル系重合体は、これを主成分とする硬化性組成物とすることができる。
【００５５】
この硬化性組成物は以下の２成分： （Ｃ）上記のいずれかの方法により得られる、末端にアルケニル基を有する（メタ）アクリル系重合体、（Ｄ）ヒドロシリル基含有化合物、を必須成分とするものである。
（Ｃ）成分の末端にアルケニル基を有する（メタ）アクリル系重合体は単独で用いても、また、２種類以上を混合して用いても良い。（Ｃ）成分の分子量としては特に制限はないが、５００〜５００００の範囲にあるのが好ましい。５００以下であると、（メタ）アクリル系重合体の本来の特性が発現されにくく、５００００以上であると、非常に高粘度あるいは溶解性が低くなり、取り扱いが困難になる。
【００５６】
（Ｄ）成分のヒドロシリル基含有化合物としては特に制限はなく、各種のものを用いることができる。すなわち、一般式７または８で表される鎖状ポリシロキサン
Ｒ¹⁰ ₃ＳｉＯ−［Ｓｉ（Ｒ¹⁰）₂Ｏ］_a−［Ｓｉ（Ｈ）（Ｒ¹¹）Ｏ］_b−［Ｓｉ（Ｒ¹¹）（Ｒ¹²）Ｏ］_c−ＳｉＲ¹⁰ ₃ （７）
ＨＲ¹⁰ ₂ＳｉＯ−［Ｓｉ（Ｒ¹⁰）₂Ｏ］_a−［Ｓｉ（Ｈ）（Ｒ¹¹）Ｏ］_b−［Ｓｉ（Ｒ¹¹）（Ｒ¹²）Ｏ］_c−ＳｉＲ¹⁰ ₂Ｈ （８）
（式中Ｒ¹⁰およびＲ¹¹は炭素数１〜６のアルキル基、または、フェニル基、Ｒ¹²は炭素数１〜１０のアルキル基またはアラルキル基、ａは０≦ａ≦１００、ｂは２≦ｂ≦１００、ｃは０≦ｃ≦１００の整数を示す）、
一般式９で表される環状シロキサン
【００５７】
【化３】

【００５８】
（式中Ｒ¹³およびＲ¹⁴は炭素数１〜６のアルキル基、または、フェニル基、Ｒ¹⁵は炭素数１〜１０のアルキル基またはアラルキル基、ｄは０≦ｄ≦８、ｅは２≦ｅ≦１０、ｆは０≦ｆ≦８の整数を示し、かつ３≦ｄ＋ｅ＋ｆ≦１０である）を用いることができる。
これらは単独で用いても２種以上を混合して用いてもかまわない。これらのシロキサンの中でも（メタ）アクリル系重合体との相溶性の観点から、フェニル基を有する、一般式１０、１１で示される鎖状シロキサンや、一般式１２、１３で示される環状シロキサンが好ましい。
（ＣＨ₃）₃ＳｉＯ−［Ｓｉ（Ｈ）（ＣＨ₃）Ｏ］_g−［Ｓｉ（Ｃ₆Ｈ₅）₂Ｏ］_h−Ｓｉ（ＣＨ₃）₃ （１０）
（ＣＨ₃）₃ＳｉＯ−［Ｓｉ（Ｈ）（ＣＨ₃）Ｏ］_g−［Ｓｉ（ＣＨ₃）｛ＣＨ₂Ｃ（Ｈ）（Ｒ¹⁶）Ｃ₆Ｈ₅｝Ｏ］_h−Ｓｉ（ＣＨ₃）₃ （１１）
（式中、Ｒ¹⁶は水素またはメチル基、ｇは２≦ｇ≦１００、ｈは０≦ｈ≦１００の整数、Ｃ₆Ｈ₅はフェニル基を示す）
【００５９】
【化４】

【００６０】
（式中、Ｒ¹⁶は水素、またはメチル基、ｉは２≦ｉ≦１０、ｊは０≦ｊ≦８、かつ３≦ｉ＋ｊ≦１０である整数、Ｃ₆Ｈ₅はフェニル基）
（Ｄ）成分の少なくとも２個以上のヒドロシリル基を有する硬化剤としてはさらに、分子中に２個以上のアルケニル基を有する低分子化合物に対し、式７〜１３に示したヒドロシリル基含有化合物を、反応後にも一部のヒドロシリル基が残るようにして付加反応させて得られる化合物を用いることもできる。分子中に２個以上のアルケニル基を有する化合物としては、各種のものを用いることができる。例示するならば、１，４−ペンタジエン、１，５−ヘキサジエン、１，６−ヘプタジエン、１，７−オクタジエン、１，８−ノナジエン、１，９−デカジエン等の炭化水素系化合物、Ｏ，Ｏ’−ジアリルビスフェノールＡ、３，３’−ジアリルビスフェノールＡ等のエーテル系化合物、ジアリルフタレート、ジアリルイソフタレート、トリアリルトリメリテート、テトラアリルピロメリテート等のエステル系化合物、ジエチレングリコールジアリルカーボネート等のカーボネート系化合物が挙げられる。
【００６１】
式７〜１３に示した過剰量のヒドロシリル基含有化合物に対し、ヒドロシリル化触媒の存在下、上に挙げたアルケニル基含有化合物をゆっくり滴下することにより該化合物を得ることができる。このような化合物のうち、原料の入手容易性、過剰に用いたシロキサンの除去のしやすさ、さらには（Ｃ）成分の重合体への相溶性を考慮して、下記のものが好ましい。
【００６２】
【化５】

【００６３】
重合体（Ｃ）と硬化剤（Ｄ）は任意の割合で混合することができるが、硬化性の面から、アルケニル基とヒドロシリル基のモル比が５〜０．２の範囲にあることが好ましく、さらに、２．５〜０．４であることが特に好ましい。モル比が５以上になると硬化が不十分でべとつきのある強度の小さい硬化物しか得られず、また、０．２より小さいと、硬化後も硬化物中に活性なヒドロシリル基が大量に残るので、クラック、ボイドが発生し、均一で強度のある硬化物が得られない。
【００６４】
重合体（Ｃ）と硬化剤（Ｄ）との硬化反応は、２成分を混合して加熱することにより進行するが、反応をより迅速に進めるために、ヒドロシリル化触媒が添加される。このようなヒドロシリル化触媒としては、有機過酸化物やアゾ化合物等のラジカル開始剤、および遷移金属触媒が挙げられる。
ラジカル開始剤としては特に制限はなく各種のものを用いることができる。例示するならば、ジ−ｔ−ブチルペルオキシド、２，５−ジメチル−２，５−ジ（ｔ−ブチルペルオキシ）ヘキサン、２，５−ジメチル−２，５−ジ（ｔ−ブチルペルオキシ）−３−ヘキシン、ジクミルペルオキシド、ｔ−ブチルクミルペルオキシド、α，α’−ビス（ｔ−ブチルペルオキシ）イソプロピルベンゼンのようなジアルキルペルオキシド、ベンゾイルペルオキシド、ｐ−クロロベンゾイルペルオキシド、ｍ−クロロベンゾイルペルオキシド、２，４−ジクロロベンゾイルペルオキシド、ラウロイルペルオキシドのようなジアシルペルオキシド、過安息香酸−ｔ−ブチルのような過酸エステル、過ジ炭酸ジイソプロピル、過ジ炭酸ジ−２−エチルヘキシルのようなペルオキシジカーボネート、１，１−ジ（ｔ−ブチルペルオキシ）シクロヘキサン、１，１−ジ（ｔ−ブチルペルオキシ）−３，３，５−トリメチルシクロヘキサンのようなペルオキシケタール等が挙げられる。
【００６５】
また、遷移金属触媒としては、例えば、白金単体、アルミナ、シリカ、カーボンブラック等の担体に白金固体を分散させたもの、塩化白金酸、塩化白金酸とアルコール、アルデヒド、ケトン等との錯体、白金−オレフィン錯体、白金（０）−ジビニルテトラメチルジシロキサン錯体が挙げられる。白金化合物以外の触媒の例としては、ＲｈＣｌ（ＰＰｈ₃）₃， ＲｈＣｌ₃， ＲｕＣｌ₃， ＩｒＣｌ₃，ＦｅＣｌ₃， ＡｌＣｌ₃， ＰｄＣｌ₂・Ｈ₂Ｏ， ＮｉＣｌ₂， ＴｉＣｌ₄等が挙げられる。これらの触媒は単独で用いてもよく、２種類以上を併用してもかまわない。触媒量としては特に制限はないが、（Ａ）成分のアルケニル基１ｍｏｌに対し、１０^-1〜１０^-8ｍｏｌの範囲で用いるのが良く、好ましくは１０^-3〜１０^-6 ｍｏｌの範囲で用いるのがよい。１０^-8ｍｏｌより少ないと硬化が十分に進行しない。またヒドロシリル化触媒は高価であるので１０^-1ｍｏｌ以上用いないのが好ましい。
【００６６】
本発明の２成分（Ｃ）、（Ｄ）、および必要に応じてヒドロシリル化触媒を混合し硬化させれば、深部硬化性に優れた均一な硬化物が得られる。硬化条件については特に制限はないが、一般に０℃〜２００℃、好ましくは３０℃〜１５０℃で１０秒〜２４時間硬化するのがよい。特に８０℃〜１５０℃の高温では１０秒〜１時間程度の短時間で硬化するものも得られる。硬化物の性状は用いる（Ｃ）成分の重合体および（Ｄ）成分の硬化剤の主鎖骨格や分子量に依存するが、ゴム状のものから樹脂状のものまで幅広く作成することができる。本組成物から得られる硬化物の具体的な用途を挙げるならば、シーリング材、接着剤、粘着材、弾性接着剤、塗料、粉体塗料、発泡体、電気電子用ポッティング材、フィルム、ガスケット、各種成形材料、人工大理石等である。 本発明における、末端に架橋性シリル基を有する（メタ）アクリル系重合体は、上記の種々の方法により得られる末端にアルケニル基を有する（メタ）アクリル系重合体に、架橋性シリル基を有するヒドロシラン化合物を付加させることにより製造することができる。末端にアルケニル基を有する（メタ）アクリル系重合体としては、既に説明した方法により得られるものをすべて好適に用いることができる。
【００６７】
ヒドロシラン化合物としては特に制限はないが、代表的なものを示すと、一般式１４
Ｈ−［Ｓｉ（Ｒ¹⁷）_2-b（Ｙ）_bＯ］_m−Ｓｉ（Ｒ¹⁸）_3-a（Ｙ）_a （１４）
（式中、Ｒ¹⁷およびＲ¹⁸は、いずれも炭素数１〜２０のアルキル基、アリール基、アラルキル基、または（Ｒ’）₃ＳｉＯ−（Ｒ’は炭素数１〜２０の１価の炭化水素基であって、３個のＲ’は同一であってもよく、異なっていてもよい）で示されるトリオルガノシロキシ基を示し、Ｒ¹⁷またはＲ¹⁸が２個以上存在するとき、それらは同一であってもよく、異なっていてもよい。Ｙは水酸基または加水分解性基を示し、Ｙが２個以上存在するときそれらは同一であってもよく、異なっていてもよい。ａは０， １， ２， または３ を、また、ｂは０，１，または２を示す。ｍは０〜１９の整数である。ただし、ａ＋ｍｂ≧１であることを満足するものとする。）
で表される化合物が例示される。
【００６８】
上記Ｙで示される加水分解性基としては、特に限定されず、従来公知のものを用いることができ、具体的には、水素、ハロゲン原子、アルコキシ基、アシルオキシ基、ケトキシメート基、アミノ基、アミド基、酸アミド基、アミノオキシ基、メルカプト基、アルケニルオキシ基等が挙げられ、加水分解性がマイルドで取り扱いやすいという点から、アルコキシ基が特に好ましい。該加水分解性基や水酸基は１個のケイ素原子に１〜３個の範囲で結合することができ、ａ＋ｍｂ、すなわち、加水分解性基の総和は、１〜５の範囲が好ましい。加水分解性基や水酸基が反応性ケイ素基中に２個以上結合するときは、それらは同一であっても、異なっていてもよい。架橋性ケイ素化合物を構成するケイ素原子は、１個でもよく、２個以上であってもよいが、シロキサン結合により連結されたケイ素原子の場合には２０個程度まであってもよい。
【００６９】
一般式１４におけるＲ¹⁷やＲ¹⁸の具体例としては、例えば、メチル基やエチル基などのアルキル基、シクロヘキシル基等のシクロアルキル基、フェニル基などのアリール基、ベンジル基などのアラルキル基、Ｒ’がメチル基やフェニル基等である（Ｒ’）₃ＳｉＯ−で示されるトリオルガノシリル基等が挙げられる。
これらヒドロシラン化合物の中でも、特に一般式１５
Ｈ−Ｓｉ（Ｒ¹⁸）_3-a（Ｙ）_a （１５）
（式中、Ｒ¹⁸、Ｙ、ａは前記と同じ。）で表される架橋性基を有するヒドロシラン化合物が、入手容易な点から好ましい。一般式１４または１５で示される架橋性基を有するヒドロシラン化合物の具体例としては、
ＨＳｉＣｌ₃、ＨＳｉ（ＣＨ₃）Ｃｌ₂、ＨＳｉ（ＣＨ₃）₂Ｃｌ、ＨＳｉ（ＯＣＨ₃）₃、ＨＳｉ（ＣＨ₃）（ＯＣＨ₃）₂、ＨＳｉ（ＣＨ₃）₂ＯＣＨ₃、ＨＳｉ（ＯＣ₂Ｈ₅）₃、ＨＳｉ（ＣＨ₃）（ＯＣ₂Ｈ₅）₂、ＨＳｉ（ＣＨ₃）₂ＯＣ₂Ｈ₅、ＨＳｉ（ＯＣ₃Ｈ₇）₃、ＨＳｉ（Ｃ₂Ｈ₅）（ＯＣＨ₃）₂、ＨＳｉ（Ｃ₂Ｈ₅）₂ＯＣＨ₃、
ＨＳｉ（Ｃ₆Ｈ₅）（ＯＣＨ₃）₂、ＨＳｉ（Ｃ₆Ｈ₅）₂（ＯＣＨ₃）、ＨＳｉ（ＣＨ₃）（ＯＣ（Ｏ）ＣＨ₃）₂、ＨＳｉ（ＣＨ₃）₂Ｏ−［Ｓｉ（ＣＨ₃）₂Ｏ］₂−Ｓｉ（ＣＨ₃）（ＯＣＨ₃）₂、ＨＳｉ（ＣＨ₃）［Ｏ−Ｎ＝Ｃ（ＣＨ₃）₂］₂
（但し、上記化学式中、Ｃ₆Ｈ₅はフェニル基を示す）
等が挙げられる。
【００７０】
このような架橋性シリル基を有するヒドロシラン化合物を、末端にアルケニル基を有する（メタ）アクリル系重合体に付加させる際には、ヒドロシリル化触媒を使用することが可能で、上述のヒドロシリル化触媒をすべて用いることができる。
末端に架橋性シリル基を有する（メタ）アクリル系重合体は、末端に水酸基を有する（メタ）アクリル系重合体に、架橋性シリル基および水酸基と反応する官能基を併せ有する化合物を反応させることによっても得ることができる。水酸基と反応する官能基としては、例えばハロゲン原子を有する基、カルボン酸ハライド、カルボン酸、イソシアネート基等が挙げられるが、化合物の入手容易性や、水酸基と反応させる際の反応条件がマイルドで、架橋性シリル基の分解が起こりにくい点で、イソシアネート基が好ましい。
【００７１】
このような、架橋性シリル基を有するイソシアネート系化合物としては特に制限はなく、公知のものを使用することができる。具体例を示すならば、
（ＣＨ₃Ｏ）₃Ｓｉ−（ＣＨ₂）_n−ＮＣＯ、（ＣＨ₃Ｏ）₂（ＣＨ₃）Ｓｉ−（ＣＨ₂）_n−ＮＣＯ、（Ｃ₂Ｈ₅Ｏ）₃Ｓｉ−（ＣＨ₂）_n−ＮＣＯ、（Ｃ₂Ｈ₅Ｏ）₂（ＣＨ₃）Ｓｉ−（ＣＨ₂）_n−ＮＣＯ、（ｉ−Ｃ₃Ｈ₇Ｏ）₃Ｓｉ−（ＣＨ₂）_n−ＮＣＯ、（ｉ−Ｃ₃Ｈ₇Ｏ）₂（ＣＨ₃）Ｓｉ−（ＣＨ₂）_n−ＮＣＯ、（ＣＨ₃Ｏ）₃Ｓｉ−（ＣＨ₂）_n−ＮＨ−（ＣＨ₂）_m−ＮＣＯ、（ＣＨ₃Ｏ）₂（ＣＨ₃）Ｓｉ−（ＣＨ₂）_n−ＮＨ−（ＣＨ₂）_m−ＮＣＯ、（Ｃ₂Ｈ₅Ｏ）₃Ｓｉ−（ＣＨ₂）_n−ＮＨ−（ＣＨ₂）_m−ＮＣＯ、（Ｃ₂Ｈ₅Ｏ）₂（ＣＨ₃）Ｓｉ−（ＣＨ₂）_n−ＮＨ−（ＣＨ₂）_m−ＮＣＯ、
（ｉ−Ｃ₃Ｈ₇Ｏ）₃Ｓｉ−（ＣＨ₂）_n−ＮＨ−（ＣＨ₂）_m−ＮＣＯ、（ｉ−Ｃ₃Ｈ₇Ｏ）₂（ＣＨ₃）Ｓｉ−（ＣＨ₂）_n−ＮＨ−（ＣＨ₂）_m−ＮＣＯ、
（上記式中、ｎ、ｍは１〜２０の整数）
等が挙げられる。
【００７２】
末端に水酸基を有する（メタ）アクリル系重合体と、架橋性シリル基を有するイソシアネート化合物の反応は、無溶媒、または各種の溶媒中で行うことができ、反応温度は、０℃〜１００℃、好ましくは、２０℃〜５０℃である。この際、水酸基とイソシアネート基の反応を促進するために既に例示したスズ系触媒、３級アミン系触媒を使用することができる。
【００７３】
上記の各方法で得られた、末端に架橋性シリル基を有する（メタ）アクリル系重合体は、これを主成分とする硬化性組成物にすることができる。
主成分である（メタ）アクリル系重合体は、単独で用いても、また、２種類以上を混合して用いてもよい。また、その分子量については特に制限はないが、
５００〜５００００の範囲にあるのが好ましい。分子量が５００以下であると、（メタ）アクリル系重合体の本来の特性が発現されにくく、また、５００００以上であると、ハンドリングが困難になる。
【００７４】
末端に加水分解性シリル基を有する（メタ）アクリル系重合体は、水分と接触すると縮合反応による網目を形成し、３次元網目構造を有する硬化物（架橋体）を与える。加水分解速度は温度、湿度、加水分解性基の種類により異なるので、使用条件に応じて適切な加水分解性基を選択しなければならない。また、加水分解性シリル基を末端に有する（メタ）アクリル系重合体を保存する時には、水分との接触を可能な限り断つ必要がある。
【００７５】
硬化反応を促進するために硬化触媒を添加してもよい。縮合触媒としてはテトラブチルチタネート、テトラプロピルチタネート等のチタン酸エステル；ジブチル錫ジラウレート、ジブチル錫マレエート、ジブチル錫ジアセテート、オクチル酸錫、ナフテン酸錫等の有機錫化合物；オクチル酸鉛、ブチルアミン、オクチルアミン、ジブチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、ジエチレントリアミン、トリエチレンテトラミン、オレイルアミン、オクチルアミン、シクロヘキシルアミン、ベンジルアミン、ジエチルアミノプロピルアミン、キシリレンジアミン、トリエチレンジアミン、グアニジン、ジフェニルグアニジン、２，４，６−トリス（ジメチルアミノメチル）フェノール、モルホリン、Ｎ−メチルモルホリン、１，３−ジアザビシクロ（５，４，６）ウンデセン−７等のアミン系化合物あるいはそれらのカルボン酸塩；過剰のポリアミンと多塩基酸から得られる低分子量ポリアミド樹脂；過剰のポリアミンとエポキシ化合物の反応生成物；アミノ基を有するシランカップリング剤、例えば、γ−アミノプロピルトリメトキシシラン、Ｎ−（β−アミノエチル）アミノプロピルメチルジメトキシシラン等の公知のシラノール触媒１種または２種以上を必要に応じて用いればよい。硬化触媒の使用量は末端に架橋性シリル基を有する（メタ）アクリル系重合体に対し、０〜１０重量％で使用するのが好ましい。加水分解性基Ｙがアルコキシ基である場合は、この重合体のみでは硬化速度が遅いので、硬化触媒を使用することが好ましい。
【００７６】
主成分である末端に架橋性シリル基を有する（メタ）アクリル系重合体に、必要に応じて硬化触媒を混合し硬化させれば、均一な硬化物を得ることができる。硬化条件としては特に制限はないが、一般に０〜１００℃、好ましくは１０〜５０℃で１時間〜１週間程度である。硬化物の性状は用いる重合体の主鎖骨格や分子量に依存するが、ゴム状のものから樹脂状のものまで幅広く作成することができる。
【００７７】
上記の組成物より得られる硬化物の具体的な用途としては、シーリング材、接着剤、粘着材、弾性接着剤、塗料、粉体塗料、発泡体、電気電子用ポッティング材、フィルム、成形材料、人工大理石等を挙げることができる。
【００７８】
【実施例】
以下に、この発明の具体的な実施例を示すが、この発明は、下記実施例に限定されるものではない。
実施例１
３０ｍＬの耐圧反応容器に、アクリル酸−ｎ−ブチル（５ｍＬ、４．４７ｇ、３４．９ｍｍｏｌ）、α，α’−ジブロモ−ｐ−キシレン（１８５ｍｇ、０．７０ｍｍｏｌ）、臭化第一銅（１００ｍｇ、０．７０ｍｍｏｌ）、２，２’−ビピリジル（３２６ｍｇ、２．１０ｍｍｏｌ）、酢酸エチル（４ｍＬ）、アセトニトリル（１ｍＬ）を仕込み、窒素バブリングを１０分間行って溶存酸素を除去した後、封管した。混合物を１３０℃に加熱し、３時間反応させた。反応容器を室温にもどし、メタクリル酸−２−ヒドロキシエチル（０．３５２ｍＬ、３６４ｍｇ、２．８０ｍｍｏｌ）を加えて封管し、８０℃で２時間反応させた。混合物を酢酸エチル（２０ｍＬ）で希釈し、１０％塩酸で３回、ブラインで１回洗浄した。有機層をＮａ₂ＳＯ₄で乾燥した後、溶媒を減圧下留去し、下式に示す末端に水酸基を有するポリ（アクリル酸−ｎ−ブチル）を４．１１ｇ得た（８２％）。重合体の数平均分子量はＧＰＣ測定（ポリスチレン換算）により５９００、分子量分布は１．４５であった。また、¹Ｈ−ＮＭＲ分析より、重合体１分子あたりの水酸基は平均３．２個であった。
【００７９】
【化６】

【００８０】
製造例１（水酸基含有開始剤の製造）
窒素雰囲気下、エチレングリコール（１０．９ｍＬ、１９５ｍｍｏｌ）とピリジン（３ｇ、３９ｍｍｏｌ）のＴＨＦ溶液（１０ｍＬ）に２−ブロモプロピオン酸クロライド（２ｍＬ、３．３５ｇ、１９．５ｍｍｏｌ）を０℃でゆっくり滴下した。そのままの温度で溶液を２時間攪拌した。希塩酸（２０ｍＬ）と酢酸エチル（３０ｍＬ）を加え、２層を分離した。有機層を希塩酸、およびブラインで洗浄し、Ｎａ₂ＳＯ₄で乾燥した後、揮発分を減圧下留去し、粗成生物を得た（３．０７ｇ）。この粗生成物を減圧蒸留することにより（７０〜７３℃、０．５ｍｍＨｇ）、下式に示す、ヒドロキシエチル−２−ブロモプロピオネートを得た（２．１４ｇ、５６％）。
Ｈ₃ＣＣ（Ｈ）（Ｂｒ）Ｃ（Ｏ）Ｏ（ＣＨ₂）₂−ＯＨ
実施例２
３０ｍＬの耐圧反応容器に、アクリル酸−ｎ−ブチル（５ｍＬ、４．４７ｇ、３４．９ｍｍｏｌ）、製造例１で得られた水酸基含有開始剤（１３８ｍｇ、０．６９８ｍｍｏｌ）、臭化第一銅（１００ｍｇ、０．６９８ｍｍｏｌ）、２，２’−ビピリジル（２１８ｍｇ、１．４０ｍｍｏｌ）、酢酸エチル（４ｍＬ）、アセトニトリル（１ｍＬ）を仕込み、窒素バブリングを行って溶存酸素を除去した後、封管した。混合物を１３０℃に加熱し、２時間反応させた。反応容器を室温にもどし、メタクリル酸−２−ヒドロキシエチル（０．１７６ｍＬ、１８２ｍｇ、１．４０ｍｍｏｌ）を加え、１００℃で２時間反応させた。混合物を酢酸エチル（２０ｍＬ）で希釈し、不溶分を濾別した後、濾液を１０％塩酸で２回、ブラインで１回洗浄した。有機層をＮａ₂ＳＯ₄で乾燥した後、溶媒を減圧下留去し、下式に示す末端に水酸基を有するポリ（アクリル酸−ｎ−ブチル）を４．４４ｇ得た（収率９３％）。重合体の数平均分子量はＧＰＣ測定（ポリスチレン換算）により、６１００、分子量分布は１．３２であった。また、¹Ｈ−ＮＭＲ測定により、重合体１分子当たりの水酸基は、平均３．３個であった。
【００８１】
【化７】

【００８２】
実施例３
実施例２において、アクリル酸−ｎ−ブチルを１０ｍＬ使用する以外は全く同様にして、化７に示すポリ（アクリル酸−ｎ−ブチル）を６．９６ｇ得た（収率７５％）。重合体の数平均分子量はＧＰＣ測定（ポリスチレン換算）により、８３００、分子量分布は１．３２であった。また、¹Ｈ−ＮＭＲ測定により、重合体１分子当たりの水酸基は、平均２．２個であった。
実施例４
実施例２において、アクリル酸−ｎ−ブチルを７．５ｍＬ使用する以外は全く同様にして、化７に示すポリ（アクリル酸−ｎ−ブチル）を５．７５ｇ得た（収率８２％）。重合体の数平均分子量はＧＰＣ測定（ポリスチレン換算）により、７５００、分子量分布は１．３６であった。また、¹Ｈ−ＮＭＲ測定により、重合体１分子当たりの水酸基は、平均２．１個であった。
実施例５
５０ｍＬの耐圧反応容器に、アクリル酸−ｎ−ブチル（１０．９４ｍＬ、９．７８ｇ、７６．３ｍｍｏｌ）、製造例１で得られた水酸基含有開始剤（３０１ｍｇ、１．５３ｍｍｏｌ）、臭化第一銅（２１９ｍｇ、１．５３ｍｍｏｌ）、２，２’−ビピリジル（４７６ｍｇ、３．０５ｍｍｏｌ）、酢酸エチル（８．８ｍＬ）、アセトニトリル（２．２ｍＬ）を仕込み、窒素バブリングを行って溶存酸素を除去した後、封管した。混合物を１３０℃に加熱し、１．３時間反応させた。混合物を酢酸エチル（２０ｍＬ）で希釈し、１０％塩酸で３回、ブラインで１回洗浄した。有機層をＮａ₂ＳＯ₄で乾燥した後、溶媒を減圧下留去し、片末端に水酸基を有するポリ（アクリル酸−ｎ−ブチル）を５．２３ｇ得た（５３％）。重合体の数平均分子量はＧＰＣ測定（ポリスチレン換算）により３４００、分子量分布は１．３１であった。また、¹Ｈ−ＮＭＲ分析より、重合体１分子あたりの水酸基は平均１．０９個であった。
【００８３】
次に、攪拌子、還流冷却管を備えた５０ｍＬの３つ口フラスコに、上で得られた片末端に水酸基を有するポリ（アクリル酸−ｎ−ブチル）（２．１５ｇ）、Ｎａ₂Ｓ・９Ｈ₂Ｏ（７６．３ｍｇ、０．３１８ｍｍｏｌ）、およびエタノール（３ｍＬ）を仕込み、還流温度で３時間攪拌した。室温に冷却した後、酢酸エチル（５ｍＬ）、１０％塩酸（５ｍＬ）を加え、２層を分離した。有機層を１０％塩酸とブラインで洗浄し、Ｎａ₂ＳＯ₄で乾燥した後、揮発分を減圧下留去することにより、下式に示す両末端に水酸基を有するポリ（アクリル酸−ｎ−ブチル）を１．９３ｇ得た。重合体の数平均分子量はＧＰＣ測定（ポリスチレン換算）により、５７００、分子量分布は１．３９であった。
【００８４】
【化８】

【００８５】
実施例６〜１０（硬化物の作成）
実施例１〜５で得られた両末端に水酸基を有するポリ（アクリル酸−ｎ−ブチル）と、下式に示す３官能イソシアネート化合物（一方社油脂製Ｂ−４５）、およびスズ系触媒（株式会社日東化成製、Ｕ−２２０、ジブチルスズジアセチルアセトネート）をよく混合した。なお、混合割合は、（メタ）アクリル系重合体の水酸基と、イソシアネート化合物のイソシアネート基がモル比で１／１となる量、また、スズ系触媒は、重合体１００重量部に対し、０．１重量部とした。
【００８６】
上記混合物を減圧下に脱泡し、型枠に流し込んで８０℃で１５時間加熱硬化させた。得られた硬化物をトルエンに２４時間浸漬し、前後の重量変化から、ゲル分率を算出した。結果を表１に示した。
【００８７】
【化９】

【００８８】
【表１】

【００８９】
実施例１１
１Ｌのオートクレーブを用い、実施例２の２０倍のスケール（アクリル−ｎ−酸ブチル１００ｇ使用）にて、末端に水酸基を有するポリ（アクリル酸−ｎ−ブチル）を８２ｇ得た（７５％）。得られた重合体の数平均分子量はＧＰＣ測定（ポリスチレン換算）により５１００、分子量分布は１．２９であった。
【００９０】
次に、上記のようにして得られた末端に水酸基を有するポリ（アクリル酸−ｎ−ブチル）（５０ｇ）およびピリジン（１０ｍＬ）のトルエン溶液（１００ｍＬ）に、窒素雰囲気下、６０℃で、１０−ウンデセン酸クロリド（７．２２ｍＬ、６．８１ｇ、３３．６ｍｍｏｌ）をゆっくりと滴下し、６０℃で３時間攪拌した。生成した白色固体を濾過し、有機層を希塩酸およびブラインで洗浄した。有機層をＮａ₂ＳＯ₄で乾燥し、減圧下に濃縮することにより、下式に示す末端にアルケニル基を有するポリ（アクリル酸−ｎ−ブチル）（４３ｇ）を得た。得られた重合体の数平均分子量はＧＰＣ測定（ポリスチレン換算）により５４００、分子量分布は１．３であった。また、¹Ｈ−ＮＭＲ分析により、重合体１分子当たりのアルケニル基の個数は平均２．２８個であった。
【００９１】
【化１０】

【００９２】
実施例１２
還流冷却管と攪拌子を備え付けた５０ｍＬの３つ口フラスコに、実施例５で得られた両末端に水酸基を有するポリ（アクリル酸−ｎ−ブチル）（７８０ｍｇ）、ピリジン（０．３ｍＬ）およびトルエン（２ｍＬ）を仕込んだ。窒素雰囲気下、１０−ウンデセン酸クロリド（０．０７０５ｍＬ、０．３２８ｍｍｏｌ）を６０℃で滴下し、そのままの温度で３時間攪拌した。酢酸エチル（５ｍＬ）、１０％塩酸（５ｍＬ）を加え、２層を分離した。有機層を１０％塩酸およびブラインで洗浄し、Ｎａ₂ＳＯ₄で乾燥した後、揮発分を減圧下留去することにより、下式に示す、両末端にアルケニル基を有するポリ（アクリル酸−ｎ−ブチル）を得た（５６０ｍｇ）。得られた重合体の数平均分子量はＧＰＣ測定（ポリスチレン換算）により、６５００、分子量分布は１．３１であった。
【００９３】
【化１１】

【００９４】
実施例１３〜１４
実施例１１、１２で得られた両末端にアルケニル基を有するポリ（アクリル酸ブチル）、下式に示したヒドロシリル基含有化合物、および０価白金の１，１，３，３−テトラメチル−１，３−ジビニルジシロキサン錯体（８．３×１０^-8ｍｏｌ／Ｌキシレン溶液）をよく混合した。ヒドロシリル基含有化合物の使用量は、重合体のアルケニル基とヒドロシリル基含有化合物のヒドロシリル基がモル比で１／１．２となる量、また、白金触媒の使用量は、重合体のアルケニル基に対して、モル比で１０^-4〜１０^-3当量とした。
【００９５】
このようにして得られた組成物の一部を１３０℃のホットプレート上にて硬化試験を行い、ゲル化時間を測定した。また、残りの組成物を減圧下に脱気し、型枠に流し込んで加熱硬化させ、ゴム状の硬化物を得た。硬化物をトルエンに２４時間浸漬し、前後の重量変化からそのゲル分率を測定した。結果を表２に示した
【００９６】
。
【化１２】

【００９７】
【表２】

【００９８】
実施例１５
３０ｍＬの耐圧反応容器に、実施例１１で得られた両末端にアルケニル基を有するポリ（アクリル酸ブチル）（２ｇ）、メチルジメトキシシラン（０．３２ｍＬ）、オルトギ酸メチル（０．０９ｍＬ、アルケニル基に対し３当量）、０価白金の１，１，３，３−テトラメチル−１，３−ジビニルジシロキサン錯体（８．３×１０^-8ｍｏｌ／Ｌキシレン溶液、アルケニル基に対し、１０^ー4当量）を仕込み、１００℃で１時間攪拌した。揮発分を減圧下留去することにより、下式に示す、両末端にメチルジメトキシシリル基を有するポリ（アクリル酸−ｎ−ブチル）を２ｇ得た。
【００９９】
【化１３】

【０１００】
次に、上記のようにして得られた両末端に架橋性シリル基を有するポリ（アクリル−ｎ−酸ブチル）（１ｇ）と硬化触媒（株式会社日東化成製、Ｕ−２２０、ジブチルスズジアセチルアセトナート、３０ｍｇ）をよく混合し、型枠に流し込んで、減圧乾操器を用いて室温で脱泡した。室温に７日間放置することにより、均一なゴム状硬化物が得られた。ゲル分率は７８％であった。
製造例２
１００ｍＬの反応器に、アクリル酸−ｎ−ブチル（２０ｍＬ、１７．９ｇ、０．１４０ｍｍｏｌ）、２，５−ジブロモアジピン酸ジエチル（０．６２８ｇ、１．７４ｍｍｏｌ）、臭化第一銅（２２５ｍｇ、１．５７ｍｍｏｌ）、ペンタメチルジエチレントリアミン（０．３２８ｍＬ、０．２７２ｇ、１．５７ｍｍｏｌ）、トルエン（２．０ｍＬ）を仕込み、凍結脱気を行った後、窒素置換した。混合物を７０℃に加熱し、４５分間反応させた。この時点で、モノマーの反応率は８２％であった。反応混合物を酢酸エチルで希釈し、活性アルミナのカラムを通し、銅触媒を除き、下式に示す末端に臭素基を持つポリ（アクリル酸−ｎ−ブチル）を得た。生成したポリマーの数平均分子量は１０２００、分子量分布は１．１４であった。
【０１０１】
【化１４】

【０１０２】
実施例１６
製造例２で得られたポリ（アクリル酸−ｎ−ブチル）（５．００ｇ）、４−ヒドロキシブチル酸ナトリウム塩（０．２４８ｇ、１．９６７ｍｍｏｌ）をＮ，Ｎ−ジメチルアセトアミド（１０ｍＬ）中で混合し、７０℃で３時間攪拌した。反応溶液を酢酸エチルで希釈し、水で洗浄後、有機層の揮発分を減圧留去することにより下式に示す両末端に水酸基を有する重合体を得た。¹Ｈ ＮＭＲ測定により、重合体１分子あたりの水酸基数は、平均１．６６個であった。
【０１０３】
【化１５】

【０１０４】
実施例１７
実施例１６で得られた両末端に水酸基を有するポリ（アクリル酸−ｎ−ブチル）と下式に示す３官能イソシアネート化合物（一方社油脂製Ｂ−４５）をよく混合した。なお、混合割合は重合体の水酸基とイソシアネート化合物のイソシアネート基がモル比で１／３となる量とした。
【０１０５】
【化１６】

【０１０６】
上記混合物を減圧下に脱泡し、１００℃で２４時間加熱硬化させた。得られた硬化物をトルエンに２４時間浸漬し、前後の重量変化から、ゲル分率を算出すると９７％であった。
【０１０７】
【発明の効果】
本発明によれば、これまで製造することが困難であった、末端に水酸基を高い比率で有する（メタ）アクリル系重合体を簡便に得ることができ、硬化特性の優れた硬化性組成物を得ることができる。また、該水酸基の反応性を利用して末端にアルケニル基あるいは架橋性シリル基を有する（メタ）アクリル系重合体を簡便に得ることができ、それぞれの末端官能性（メタ）アクリル系重合体から硬化特性の優れた硬化性組成物を得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a (meth) acrylic polymer having a hydroxyl group at the terminal, a curable composition using the polymer, and an alkenyl group or a crosslinkable silyl group derived from the polymer. The present invention relates to a method for producing a polymer having a group, and a curable composition containing them as a main component.
[0002]
[Prior art]
It is known that a polymer having a hydroxyl group at a terminal is crosslinked by using a compound having a functional group that reacts with a hydroxyl group, such as an isocyanate compound, as a curing agent, and gives a cured product having excellent heat resistance and durability. It has been.
Examples of the main chain skeleton of the polymer having a hydroxyl group at the end include polyether polymers such as polyethylene oxide, polypropylene oxide, and polytetramethylene oxide, polybutadiene, polyisoprene, polychloroprene, polyisobutylene, and hydrogens thereof. Examples include hydrocarbon polymers such as additives, and polyester polymers such as polyethylene terephthalate, polybutylene terephthalate, and polycaprolactone, which are used for various applications based on the main chain skeleton and the crosslinking type.
[0003]
[Problems to be solved by the invention]
Among the polymers obtained by ionic polymerization or condensation polymerization exemplified above, vinyl polymers obtained by radical polymerization and having a hydroxyl group at the terminal have not been practically used yet. Among vinyl polymers, (meth) acrylic polymers have characteristics that cannot be obtained with the above polyether polymers, hydrocarbon polymers, or polyester polymers, such as high weather resistance and transparency. Those having a hydroxyl group in the side chain are used for weather-resistant paints and the like.
[0004]
If a (meth) acrylic polymer having a hydroxyl group at the molecular chain end can be obtained by a simple method, a cured product having excellent cured properties such as elasticity can be obtained as compared with those having a hydroxyl group in the side chain. . Therefore, the manufacturing method has been studied by many researchers so far, but it is not easy to manufacture them industrially.
Japanese Patent Laid-Open No. 5-262808 discloses a method of synthesizing a (meth) acrylic polymer having hydroxyl groups at both ends using a disulfide having hydroxyl groups as a chain transfer agent. In order to reliably introduce an alkenyl group, a chain transfer agent must be used in a large amount relative to the initiator, which is a problem in the production process. Japanese Patent Publication No. 1-19402 discloses a method for producing a (meth) acrylic polymer having a hydroxyl group at the terminal using hydrogen peroxide as an initiator. In this method, hydroxyl groups are surely attached to both terminals. Introducing a vinyl monomer having a hydroxyl group (for example, 2-hydroxyethyl methacrylate) is actually employed. Furthermore, in JP-A-4-132706, a (meth) acrylic polymer having a halogen at the terminal is obtained by polymerization of a (meth) acrylic monomer using telogen such as carbon tetrachloride, and the terminal halogen is converted to a diol compound, a hydroxyl group. A method for producing a vinyl polymer having a hydroxyl group at the terminal, characterized by reacting and replacing a nucleophilic agent such as a carboxylic acid and a hydroxyl group-containing amine, is disclosed. Also in this method, since the chain transfer of telogen is not sufficient, it is difficult to introduce functional groups at both ends at a high ratio.
[0005]
Therefore, in the present invention, it is an object to provide a method for producing a (meth) acrylic polymer having a hydroxyl group at a terminal at a high ratio as compared with a conventional method, and a curable composition containing them as a main component. To do. It is another object of the present invention to provide a curable composition using another functional group (alkenyl group, crosslinkable silyl group) by using the reactivity of the terminal hydroxyl group and introducing them. .
[0006]
[Means for Solving the Problems]
Among the above-mentioned problems, the (meth) acrylic polymer having a hydroxyl group at the terminal contains an organic halide or a sulfonyl halide compound as an initiator, an element of Group 8, 9, 10, or 11 of the periodic table. Converting a halogen of a (meth) acrylic polymer having a terminal structure represented by the general formula 1 obtained by polymerizing a (meth) acrylic monomer using a metal complex as a central metal as a catalyst to a hydroxyl group-containing substituent Can be manufactured.
-CH₂-C (R¹) (CO₂R²(X) (1)
(Wherein R¹Is hydrogen or methyl, R²Is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, X is chlorine, bromine, or iodine)
As a specific example of such a production method, for example, a metal complex having an organic halide as an initiator and an element of Group 8, 9, 10, or 11 of the periodic table as a central metal is used as a catalyst (meth). A method of producing a (meth) acrylic polymer having a terminal structure represented by general formula 1 by polymerizing an acrylic monomer, and further reacting a compound having both a polymerizable alkenyl group and a hydroxyl group, or a general formula A method in which an enolate anion is prepared by allowing a metal simple substance or an organometallic compound to act on the (meth) acrylic polymer having the terminal structure shown in 1, and then reacting with an aldehyde or a ketone, a hydroxyl-containing oxyanion or hydroxyl group And the like.
[0007]
In addition, the polymer is prepared by using a halide having a hydroxyl group or a sulfonyl halide as an initiator, and a metal complex having a group 8 element, a group 9, a group 10, or a group 11 element as a central metal as a catalyst ( By polymerizing a (meth) acrylic monomer, a (meth) acrylic polymer having a structure represented by general formula 1 at one end and a hydroxyl group at the other end is produced, and further, halogen is converted into a hydroxyl group-containing substituent. It can also be manufactured. Furthermore, using a halide having a hydroxyl group or a halogenated sulfonyl compound as an initiator, a (meth) acrylic polymer having a structure represented by general formula 1 at one end and a hydroxyl group at the other end, and The polymer can also be produced by coupling halogen ends to each other using a compound having two or more functional groups which can be substituted for the halogen of formula 1 and having the same or different functional groups.
[0008]
The curable composition of the present invention comprises the following two components: (A) a (meth) acrylic polymer having a hydroxyl group at the terminal, and (B) a compound having at least two functional groups capable of reacting with a hydroxyl group. It is what.
In the present invention, the (meth) acrylic polymer having an alkenyl group at the terminal can be produced by converting the terminal hydroxyl group of the (meth) acrylic polymer having a hydroxyl group at the terminal into an alkenyl group-containing substituent. it can. The curable composition mainly composed of a (meth) acrylic polymer having an alkenyl group at the terminal, obtained by such a method, has the following two components: (C) (meth) acrylic having an alkenyl group at the terminal A system polymer and (D) a hydrosilyl group-containing compound are essential components.
[0009]
Furthermore, the (meth) acrylic polymer having a crosslinkable silyl group at the terminal in the present invention is obtained by adding a hydrosilane compound having a crosslinkable silyl group to the (meth) acrylic polymer having an alkenyl group at the terminal. Moreover, it can manufacture by making the compound which has a crosslinkable silyl group and the functional group which reacts with a hydroxyl group react with the (meth) acrylic-type polymer which has a hydroxyl group at the terminal. A curable composition can be obtained using as a main component a (meth) acrylic polymer having a crosslinkable silyl group at the terminal, obtained by such a method.
[0010]
In addition, the (meth) acrylic polymer having various functional groups at the terminal obtained by the present invention also has a feature that the molecular weight distribution is narrow.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
In the production of a (meth) acrylic polymer having a hydroxyl group at the terminal, the present invention can employ an organic halide or a sulfonyl halide as an initiator, Group 8, Group 9, Group 11, or Group 11 of the periodic table. The halogen of the (meth) acrylic polymer having a terminal structure represented by the general formula 1 produced by polymerizing a (meth) acrylic monomer using a metal complex having a group element as a central metal as a catalyst is substituted with a hydroxyl group-containing substituent. It is characterized by converting into.
-CH₂-C (R¹) (CO₂R²(X) (1)
(Wherein R¹Is hydrogen or methyl, R²Is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, X is chlorine, bromine, or iodine)
As a method for producing a (meth) acrylic polymer having halogen at the terminal, for example, in polymerization using a halide as a chain transfer agent (telogen), carbon tetrachloride, carbon tetrabromide, methylene chloride, methylene bromide, etc. The method used has been used. However, with this method, it is difficult to reliably introduce halogen at both ends.
[0012]
For this method, when living radical polymerization, which has been studied energetically recently, halogen is introduced at a high ratio at the terminal (for example, Matyjazewski et al., J. Am. Chem. Soc. 1995, 117, 5614, Macromolecules, 1995, 28, 7901, Science 1996, 272, 866. Or see Sawamoto et al., Macromolecules 1995, 28, 1721). Although these methods are radical polymerization, the polymerization proceeds in a living manner, and a polymer having a narrow molecular weight distribution (Mw / Mn = 1.1 to 1.5) is obtained. The molecular weight depends on the charging ratio of the monomer and the initiator. It can be controlled freely.
[0013]
In this living radical polymerization, an organic halide as an initiator, particularly an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having a halogen at the α-position or a compound having a halogen at the benzyl-position), or Halogenated sulfonyl compounds are used.
In order to obtain a crosslinkable (meth) acrylic polymer using this polymerization method, an organic halide having two or more starting points or a sulfonyl halide compound is used as an initiator. Specific examples are:
o-, m-, p-XCH₂-C₆H_Four-CH₂X, o-, m-, p-CH_ThreeC (H) (X) -C₆H_Four-C (H) (X) CH_Three, O-, m-, p- (CH_Three)₂C (X) -C₆H_Four-C (X) (CH_Three)₂,
(However, in the above chemical formula,₆H_FourIs a phenylene group, X is chlorine, bromine, or iodine)
RO₂C-C (H) (X)-(CH₂)_n-C (H) (X) -CO₂R, RO₂CC (CH_Three) (X)-(CH₂)_n-C (CH_Three) (X) -CO₂R, RC (O) -C (H) (X)-(CH₂)_n-C (H) (X) -C (O) R, RC (O) -C (CH_Three) (X)-(CH₂)_n-C (CH_Three) (X) -C (O) R,
(In the formula, R is an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, n is an integer of 0 to 20, and X is chlorine, bromine, or iodine)
XCH₂C (O) CH₂X, CH_ThreeC (H) (X) C (O) C (H) (X) CH_Three, (CH_Three)₂C (X) C (O) C (X) (CH_Three)₂, C₆H_FiveC (H) (X)-(CH₂)_n-C (H) (X) C₆H_Five,
(In the above formula, X is chlorine, bromine, or iodine, and n is an integer of 0 to 20)
XCH₂CO₂-(CH₂)_n-OCOCH₂X, CH_ThreeC (H) (X) CO₂-(CH₂)_n-OCOC (H) (X) CH_Three, (CH_Three)₂C (X) CO₂-(CH₂)_n-OCOC (X) (CH_Three)₂,
(In the above formula, X is chlorine, bromine, iodine, n is an integer of 1-20)
XCH₂C (O) C (O) CH₂X, CH_ThreeC (H) (X) C (O) C (O) C (H) (X) CH_Three, (CH_Three)₂C (X) C (O) C (O) C (X) (CH_Three)₂, O-, m-, p-XCH₂CO₂-C₆H_Four-OCOCH₂X, o-, m-, p-CH_ThreeC (H) (X) CO₂-C₆H_Four-OCOC (H) (X) CH_Three, O-, m-, p- (CH_Three)₂C (X) CO₂-C₆H_Four-OCOC (X) (CH_Three)₂, O-, m-, p-XSO₂-C₆H_Four-SO₂X,
(Where X is chlorine, bromine or iodine)
Etc.
[0014]
As the catalyst, a metal complex having a central metal of Group 8, 9, 10, or 11 of the periodic table is used. As the metal species, monovalent copper, divalent ruthenium, divalent iron, and divalent nickel are particularly preferable. Specifically, cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous acetate, cuprous perchlorate, etc. . In the case of using a copper compound, it is effective to add a ligand such as 2,2'-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives in order to enhance the catalytic activity. In addition, tristriphenylphosphine complex of divalent ruthenium chloride (RuCl₂(PPh_Three)_Three) Is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, it is effective to add aluminum alkoxides as an activator. Furthermore, divalent iron bistriphenylphosphine complex (FeCl₂(PPh_Three)₂), Divalent nickel bistriphenylphosphine complex (NiCl)₂(PPh_Three)₂) Is also suitable as a catalyst.
[0015]
There is no restriction | limiting in particular as a (meth) acrylic-type monomer used in the superposition | polymerization of this invention, Various things can be used. For example, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate-n-propyl, isopropyl (meth) acrylate, (meth) acrylate-n-butyl, (meth) acryl Isobutyl acid, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid n-heptyl, (Meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl, (meth) acrylic acid phenyl, (meta ) Toluyl acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, (meth) acrylic acid 3-methoxybutyl (meth) -2-hydroxyethyl acrylate, and (meth) acrylic acid-2-hydroxypropyl and the like. These may be used alone or in combination of two or more. Further, if necessary, other vinyl monomers such as styrene, α-methylstyrene, acrylonitrile and the like can be copolymerized.
[0016]
The polymerization of the present invention can be carried out without solvent or in various solvents. Moreover, superposition | polymerization can be performed in the range of room temperature-200 degreeC, Preferably it is 50-150 degreeC.
The (meth) acrylic polymer having a hydroxyl group at the terminal can be obtained by carrying out a halogen conversion reaction of the (meth) acrylic polymer having a halogen at the terminal obtained by the above polymerization.
[0017]
As such a method, first, a (meth) acrylic polymer having a terminal structure represented by the general formula 1 is produced by the above polymerization, and a compound having both a polymerizable alkenyl group and a hydroxyl group is prepared as the second monomer. The method of making it react is mentioned. In the above polymerization, the polymerization terminal retains the polymerization activity, and the polymerization proceeds again when a vinyl monomer is newly added. Therefore, if a vinyl monomer having both a polymerizable alkenyl group and a hydroxyl group is added, a radical addition reaction occurs in the polymerization active alkenyl group portion, and the hydroxyl group remains as it is. Therefore, a (meth) acrylic polymer having a hydroxyl group at the terminal Can be obtained. Such a second monomer may be added together with the catalyst after the first polymerization is completed and the polymer is isolated, or may be reacted again, or added in-situ during the polymerization. May be reacted. In the latter case, the higher the monomer conversion in the first polymerization, the better, and preferably 80% or more. If it is 80% or less, the hydroxyl groups are distributed not on the molecular ends but on the side chains, which impairs the mechanical properties of the cured product.
[0018]
In this case, the compound having both a polymerizable alkenyl group and a hydroxyl group can be theoretically added by adding an amount equal to the number of polymerization terminals (since it is living polymerization, it is almost equal to the number of initiator starting points). One hydroxyl group is introduced to every terminal, but in order to reliably introduce hydroxyl groups to all terminals, an excess amount, specifically, 1 to 5 times the number of terminals. It is good to use. If it is used more than 5 times, hydroxyl groups are introduced at high density at the end of the polymer, and the expected cured product properties are often not obtained.
[0019]
The compound having both a polymerizable alkenyl group and a hydroxyl group is not particularly limited.
H₂C = C (R^Three-R^Four-R^Five-OH (2)
(Wherein R^ThreeIs hydrogen or methyl group, R^FourIs —C (O) O— (ester group), or o-, m-, p-phenylene group, R^FiveIs a direct bond or a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds)
The compound shown by these is mentioned. R^FourIs an (meth) acrylate compound, R^FourThose having a phenylene group are styrenic compounds. R in general formula 2^FiveAs alkylene groups such as methylene, ethylene and propylene, phenylene groups such as o-, m- and p-phenylene groups, aralkyl groups such as benzyl groups, -CH₂CH₂-O-CH₂CH₂-Or -OCH₂CH₂An alkylene group containing an ether bond such as-is exemplified.
[0020]
Among these, because it is easy to obtain,
H₂C = C (H) C (O) O (CH₂)_n-OH, H₂C = C (CH_Three) C (O) O (CH₂)_n-OH,
(In the above formulas, n is an integer of 1 to 20)
H₂C = C (H) C (O) O (CH₂)_n-O- (CH₂)_mOH, H₂C = C (CH_Three) C (O) O (CH₂)_n-O- (CH₂)_m-OH,
(In the above formulas, n and m are integers of 1 to 20)
o-, m-, pH₂C = CH-C₆H_Four-(CH₂)_n-OH, o-, m-, pH₂C = C (CH_Three-C₆H_Four-(CH₂)_n-OH,
(In the above formula, n is an integer of 0 to 20)
o-, m-, pH₂C = CH-C₆H_Four-O (CH₂)_n-OH, o-, m-, pH₂C = C (CH_Three-C₆H_Four-O (CH₂)_n-OH,
(In the above formula, n is an integer of 1 to 20)
Is preferred.
[0021]
As a method for converting a terminal halogen to a hydroxyl group-containing substituent, an enolate anion is prepared by reacting a halogen or a (meth) acrylic polymer having a terminal with a metal or an organometallic compound, and then an aldehyde. It is also possible to use a method of reacting alcohols or ketones.
Examples of the metal simple substance include alkali metals such as lithium, sodium and potassium, alkaline earth metals such as magnesium and calcium, aluminum and zinc. Of these, zinc is particularly preferred because the generated enolate anion does not easily cause side reactions such as attacking or transferring other ester groups. Specific examples of the organometallic compound include organic lithium, organic sodium, organic potassium, organic magnesium such as Grignard reagent, organic aluminum, and organic zinc. In order to efficiently metallize halogen, it is preferable to use organic lithium or organic magnesium.
[0022]
The aldehydes and ketones are not particularly limited, and various types can be used. To illustrate,
Formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and the like.
[0023]
The method for introducing a hydroxyl group-containing substituent using zinc and aldehydes or ketones is a so-called Reformatsky reaction, which is a particularly preferred embodiment. Various solvents can be used in this reaction, but aprotic solvents are preferable, and ether solvents such as tetrahydrofuran and diethyl ether are particularly preferable among them. The reaction can be carried out in the range of room temperature to 100 ° C.
[0024]
As another method for producing a (meth) acrylic polymer having a hydroxyl group at the terminal, a (meth) acrylic polymer having a terminal structure represented by general formula 1 is reacted with a hydroxyl group-containing oxyanion represented by general formula 3. A method is mentioned.
M⁺O^--R⁶-OH (3)
(Wherein R⁶Is a divalent alkyl group having 1 to 20 carbon atoms, a divalent aryl group having 6 to 20 carbon atoms, or a divalent aralkyl group having 7 to 20 carbon atoms, and may contain one or more ether bonds. , M⁺Is an alkali metal ion or quaternary ammonium ion) M⁺Is a counter ion of oxyanion, alkali metal ion such as lithium ion, sodium ion, potassium ion, tetramethylammonium ion, tetraethylammonium ion, trimethylbenzylammonium ion, trimethyldodecylammonium ion, tetrabutylammonium ion, dimethylpiperidin Quaternary ammonium ions such as um ions are exemplified.
[0025]
The oxyanion of the general formula 3 can be obtained by allowing a suitable base to act on the precursor diol compound. Such precursors include the following compounds:
HO- (CH₂)_n-OH (n is an integer of 2 to 20), HO-CH (CH_Three) CH₂OH, HO-CH (CH_Three) CH₂CH₂OH, HO-CH₂CH (CH_Three) CH₂-OH, HO-CH₂C (CH_Three)₂CH₂-OH, HO-CH₂C (CH_Three) (C₂H_Five) CH₂-OH, HO-CH₂C (C₂H_Five)₂CH₂-OH, CH_ThreeCH₂CH (OH) CH₂-OH, CH_ThreeCH (OH) CH (OH) CH_Three, HO- (CH₂O)_n-H (n is an integer of 1 to 20), HO- (CH₂CH₂O)_n-H (n is an integer of 1 to 10), HO- (CH₂CH (CH_ThreeO)_n-H (n is an integer of 1 to 6), o-, m-, p-HO-C₆H_Four-OH, o-, m-, p-HO-C₆H_Four-(CH₂)_nOH (n is an integer of 1 to 14), o-, m-, p-HO- (CH₂)_n-C₆H_Four-(CH₂)_mOH (n and m are integers of 1 to 13 and n + m ≦ 14), 3-methylcatechol, 4-methylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2,5-dimethylresorcinol, methylhydroquinone, 2,3 -Dimethylhydroquinone, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,2'-biphenol, 4,4'-biphenol, 4,4 ' -Isopropylidenediphenol, and the like. Among these, o-, m-, p-HO-C is preferable because the reactivity of the oxyanion is mild, and the terminal halogen of the general formula 1 is selectively substituted and is easily available.₆H_Four-OH, o-, m-, p-HO-C₆H_Four-(CH₂)_nOH (n is an integer of 1 to 14) is preferable. These diol compounds may be used in a molar ratio of 1 equivalent to the terminal of formula 1, but are preferably 1 to 5 equivalents.
[0026]
Various bases are used to extract protons from the above compounds to form carbanions of formula 3. These bases include:
Sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, lithium ethoxide, sodium-tert-butoxide, potassium-tert-butoxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate, hydrogen Examples include sodium hydride, potassium hydride, methyllithium, ethyllithium, n-butyllithium, tert-butyllithium, lithium diisopropylamide, lithium hexamethyldisilazide and the like. Although the usage-amount of the base with respect to the diol which is a precursor is 0.5-3.0 equivalent normally, Preferably it is 0.8-1.5 equivalent. Solvents used in preparing the carbanion of formula 3 by reaction of the above precursor with a base include, for example, tetrahydrofuran, dioxane, diethyl ether, dimethylformamide, hexamethylphosphoric triamide, ethanol, methanol, isopropyl alcohol, tert- Butyl alcohol or the like is used.
[0027]
A (meth) acrylic polymer having a hydroxyl group at the terminal can also be obtained by allowing the hydroxyl group-containing carboxylate anion represented by the general formula 4 to act on the (meth) acrylic polymer having the terminal structure of Formula 1. Can do.
M⁺OC^-(O) -R⁶-OH (4)
(Wherein R⁶, M⁺Is the same as above)
The carboxylate anion of Formula 4 can be prepared by allowing a suitable base to act on the hydroxyl group-containing carboxylic acid that is the precursor. Such precursors include the following compounds:
HO₂C- (CH₂)_n-OH (n is an integer of 1 to 20), HO₂C-CH (OH) CH_Three, HO₂C-CH₂CH (OH) CH_Three, O-, m-, p-HO₂CC₆H_Four-OH, o-, m-, p-HO₂C- (CH₂)_n-C₆H_Four-OH, o-, m-, p-HO₂CC₆H_Four-(CH₂)_n-OH (n is an integer of 1 to 14), o-, m-, p-HO₂C- (CH₂)_n-C₆H_Four-(CH₂)_m-OH,
(N and m are integers of 1 to 13, n + m ≦ 14)
Is exemplified.
[0028]
In order to extract a proton from the above compound to obtain a carboxylate anion of the formula 4, the base exemplified in the preparation of the oxyanion of the formula 3 can be suitably used. When a base is allowed to act on the hydroxyl group-containing carboxylic acid, the proton of the carboxylic acid having higher acidity is extracted, and the carboxylate anion of formula 4 is selectively obtained. Although the usage-amount of a base is 0.5-3.0 equivalent normally with respect to a hydroxyl-containing carboxylic acid, Preferably it is 0.8-1.5 equivalent.
[0029]
In polymerization of (meth) acrylic monomers using an organic halide or a sulfonyl halide as an initiator and a metal complex having a group 8 element, group 9, group 10, or group 11 element as a central metal as a catalyst When a halide having a hydroxyl group is used as an initiator, a (meth) acrylic polymer having a hydroxyl group at one end and a halogen represented by Formula 1 at the other end can be obtained. If the halogen at the terminal of the polymer thus obtained is converted into a hydroxyl group-containing substituent, a (meth) acrylic polymer having hydroxyl groups at both ends can be produced.
[0030]
Although there is no restriction | limiting in particular as the halide which has a hydroxyl group, What has the structure shown in General formula 5 or 6 is preferable.
R⁷R⁸C (X) -R⁹-R^Five-OH (5)
(Wherein R^FiveIs the same as above, R⁷, R⁸Is hydrogen, a monovalent alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, or those connected to each other at the other end, R⁹Is -C (O) O- (ester group), -C (O)-(keto group), or o-, m-, p-phenylene group, X is chlorine, bromine, or iodine)
HO-R^Five-C (R⁷) (X) -R⁹-R⁸  (6)
(Wherein R^Five, R⁷, R⁸, R⁹, X is the same as above)
Specific examples of the compound represented by the general formula 5 include
XCH₂C (O) O (CH₂)_n-OH, H_ThreeCC (H) (X) C (O) O (CH₂)_n-OH, (H_ThreeC)₂C (X) C (O) O (CH₂)_n-OH, CH_ThreeCH₂C (H) (X) C (O) O (CH₂)_n-OH,
[0031]
[Chemical 1]

[0032]
(In each of the above formulas, X is chlorine, bromine, or iodine, and n is an integer of 1 to 20) XCH₂C (O) O (CH₂)_nO (CH₂)_m-OH, H_ThreeCC (H) (X) C (O) O (CH₂)_nO (CH₂)_m-OH, (H_ThreeC)₂C (X) C (O) O (CH₂)_nO (CH₂)_m-OH, CH_ThreeCH₂C (H) (X) C (O) O (CH₂)_nO (CH₂)_m-OH,
[0033]
[Chemical 2]

[0034]
(In the above formulas, X is chlorine, bromine, or iodine, and n and m are integers of 1 to 20)
o-, m-, p-XCH₂-C₆H_Four-(CH₂)_n-OH, o-, m-, p-CH_ThreeC (H) (X) -C₆H_Four-(CH₂)_n-OH, o-, m-, p-CH_ThreeCH₂C (H) (X) -C₆H_Four-(CH₂)_n-OH,
(In each of the above formulas, X is chlorine, bromine, or iodine, and n is an integer of 0 to 20) o-, m-, p-XCH₂-C₆H_Four-(CH₂)_n-O- (CH₂)_m-OH, o-, m-, p-CH_ThreeC (H) (X) -C₆H_Four-(CH₂)_n-O- (CH₂)_m-OH,
o-, m-, p-CH_ThreeCH₂C (H) (X) -C₆H_Four-(CH₂)_n-O- (CH₂)_m-OH,
(In each of the above formulas, X is chlorine, bromine, or iodine, n is an integer of 0-20, m is an integer of 1-20)
o-, m-, p-XCH₂-C₆H_Four-O- (CH₂)_n-O- (CH₂)_m-OH, o-, m-, p-CH_ThreeC (H) (X) -C₆H_Four-O- (CH₂)_n-O- (CH₂)_m-OH, o-, m-, p-CH_ThreeCH₂C (H) (X) -C₆H_Four-O- (CH₂)_n-O- (CH₂)_m-OH,
(In the above formulas, X is chlorine, bromine, or iodine, and n and m are integers of 1 to 20)
Etc.
[0035]
Specific examples of the compound represented by the general formula 6 include
HO-CH₂C (H) (X) -CO₂R, HO- (CH₂)₂C (H) (X) -CO₂R, HO- (CH₂)_ThreeC (H) (X) -CO₂R, HO- (CH₂)₈C (H) (X) -CO₂R,
(In the above formulas, X is chlorine, bromine, or iodine, R is an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group)
HO-CH₂C (H) (X) -C₆H_Five, HO- (CH₂)₂C (H) (X) -C₆H_Five, HO- (CH₂)_ThreeC (H) (X) -C₆H_Five,
Etc.
[0036]
If the specific example of the halogenated sulfonyl compound which has a hydroxyl group is given,
o-, m-, p-HO- (CH₂)_n-C₆H_Four-SO₂X,
(In the above formula, X is chlorine, bromine, or iodine, and n is an integer of 0 to 20)
o-, m-, p-HO- (CH₂)_n-OC₆H_Four-SO₂X,
(In the above formula, X is chlorine, bromine, or iodine, and n is an integer of 1 to 20)
Etc.
[0037]
When a (meth) acrylic monomer is polymerized using an organic halide having a hydroxyl group or a sulfonyl halide compound as an initiator, a hydroxyl group is introduced at one end and the other end has a terminal structure represented by the general formula 1. A polymer is obtained. As a method for converting the terminal halogen to a hydroxyl group, all the methods described above can be preferably used.
[0038]
When an organic halide having a hydroxyl group or a halogenated sulfonyl compound is used as an initiator, a polymer in which one terminal is a hydroxyl group and the other terminal is a halogen terminal represented by Formula 1 is obtained. It is possible to obtain a (meth) acrylic polymer having a hydroxyl group at the terminal end by coupling the halogen ends to each other using a compound having a total of two or more functional groups that can substitute the halogen of the same or different. it can.
[0039]
There are no particular restrictions on those having a total of two or more of the same or different functional groups capable of substituting the terminal halogen represented by Formula 1, but polyols, polyamines, polycarboxylic acids, polythiols, and salts thereof, alkali metal sulfides A thing etc. are preferable. If these compounds are specifically exemplified,
Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1, 3-butanediol, 1,2-butanediol, 2,3-butanediol, pinacol, 1,5-pentanediol, 1,4-pentanediol, 2,4-pentanediol, 1,6-hexanediol, 1 , 7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, glycero 1,2,4-butanetriol, catechol, resorcinol, hydroquinone, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,2′-biphenol 4,4′-biphenol, bis (4-hydroxyphenyl) methane, 4,4′-isopropylidenephenol, 3,3 ′-(ethylenedioxy) diphenol, α, α′-dihydroxy-p-xylene, 1,1,1-tris (4-hydroxyphenyl) ethane, pyrogallol, 1,2,4-benzenetriol, and an alkali metal salt of the polyol compound,
Ethylenediamine, 1,3-diaminopropane, 1,2-diaminopropane, 1,4-diaminobutane, 1,2-diamino-2-methylpropane, 1,5-diaminopentane, 2,2-dimethyl-1,3 -Propanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-diaminononane, 1,10-diaminodecane, 1,12-diaminododecane, 4,4'- Methylenebis (cyclohexylamine), 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, α, α′-diamino-p-xylene, and an alkali metal salt of the polyamine compound,
Oxalic acid, malonic acid, methylmalonic acid, dimethylmalonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, 1,7-heptanedicarboxylic acid, 1,8-octanedicarboxylic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1 , 4-cyclohexanedicarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2,3-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, and An alkali metal salt of the polycarboxylic acid,
1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,7-heptanedithiol, 1 , 8-octanedithiol, 1,9-nonanedithiol, 2-mercaptoethyl ether, p-xylene-α, α'-dithiol, 1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol And alkali metal salts of the above polythiol compounds, lithium sulfide, sodium sulfide, potassium sulfide, and the like.
[0040]
When using the above polyol, polyamine, polycarboxylic acid, polythiol, a basic compound is used in combination to promote the substitution reaction. Specific examples thereof include lithium, sodium, potassium, sodium carbonate, potassium carbonate, carbonic acid. Examples thereof include sodium hydride, sodium methoxide, potassium methoxide, tert-butoxy sodium, tert-butoxy potassium, sodium hydride, potassium hydride and the like.
[0041]
From the (meth) acrylic polymer having a hydroxyl group at the terminal obtained by the various methods described above, a curable composition containing this as a main component can be obtained.
This curable composition comprises the following two components: (A) a (meth) acrylic polymer having a hydroxyl group at the terminal, and (B) a compound having two or more functional groups capable of reacting with a hydroxyl group. It is.
[0042]
The (meth) acrylic polymer having a hydroxyl group at the terminal of the component (A) may be used alone or in combination of two or more. Although there is no restriction | limiting in particular as molecular weight, It is preferable to exist in the range of 500-50000. When it is 500 or less, the original characteristics of the (meth) acrylic polymer are hardly expressed, and when it is 50000 or more, the viscosity or solubility becomes very low and handling becomes difficult.
[0043]
(B) Although it does not specifically limit as a compound which has 2 or more of functional groups which can react with the hydroxyl group of a component, For example, the polyvalent isocyanate compound which has 2 or more isocyanate groups in 1 molecule, methylolated melamine, and Examples thereof include aminoplast resins such as alkyl etherified products or low-condensed products, polyfunctional carboxylic acids, and halides thereof.
[0044]
As the polyvalent isocyanate compound having two or more isocyanate groups in one molecule, conventionally known ones can be used. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4 '-Diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, metaxylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate -Isocyanate compound such as triisocyanate such as -45, Buret polyisocyanate compound such as Sumidur N (manufactured by Sumitomo Bayer Urethane Co., Ltd.), Desmodur A polyisocyanate compound having an isocyanurate ring such as IL, HL (manufactured by Bayer AG), coronate EH (manufactured by Nippon Polyurethane Industry Co., Ltd.), an adduct polyisocyanate compound such as Sumidur L (manufactured by Sumitomo Bayer Urethane Co., Ltd.), Examples thereof include adduct polyisocyanate compounds such as Coronate HL (manufactured by Nippon Polyurethane Co., Ltd.). Moreover, you may use block isocyanate. These may be used alone or in combination of two or more.
[0045]
The compounding ratio of the polymer having a hydroxyl group at the terminal and the compound having two or more isocyanate groups is not particularly limited. For example, the ratio of the hydroxyl group of the (meth) acrylic polymer having a hydroxyl group at the isocyanate group and the terminal ( NCO / OH (molar ratio)) is preferably 0.5 to 3.0, more preferably 0.8 to 2.0.
[0046]
In order to accelerate the curing reaction of the (meth) acrylic polymer having a hydroxyl group at the terminal and the compound having two or more isocyanate groups as the composition of the present invention, an organic tin compound or a tertiary amine is used as necessary. You may add well-known catalysts, such as.
Specific examples of the organic tin compound include tin octylate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, dibutyltin dimaleate, and dioctyltin thiocarboxylate. Further, as the tertiary amine catalyst, triethylamine, N, N-dimethylcyclohexylamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropane 1,3 A diamine,
N, N, N ′, N′-tetramethylhexane 1,6-diamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N ′, N ″, N '' -Pentamethyldipropylenetriamine, tetramethylguanidine, triethylenediamine, N, N'-dimethylpiperazine, N-methylmorpholine, 1,2-dimethylimidazole, dimethylaminoethanol, dimethylaminoethoxyethanol, N, N, N '-Trimethylaminoethylethanolamine, N-methyl-N'-(2-hydroxyethyl) piperazine, N- (2-hydroxyethyl) morpholine, bis (2-dimethylaminoethyl) ether, ethylene glycol bis (3-dimethyl) ) Aminopropyl ether and the like are exemplified.
[0047]
The aminoplast resin used in the curable composition in the present invention is not particularly limited, and is an addition reaction product (methylol compound) of melamine and formaldehyde, a low condensate of melamine and formaldehyde, an alkyl etherified product thereof, and urea. Examples thereof include resins. These may be used alone or in combination of two or more. For the purpose of promoting the curing reaction between the (meth) acrylic polymer having a hydroxyl group at the terminal and the aminoplast resin, a known catalyst such as paratoluenesulfonic acid or benzenesulfonic acid may be added.
[0048]
The compound having two or more carboxyl groups in one molecule used in the curable composition of the present invention is not particularly limited. For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, phthalate Examples thereof include polyfunctional carboxylic acids such as acid, phthalic anhydride, terephthalic acid, trimellitic acid, pyromellitic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid or their anhydrides, and halides thereof. These may be used alone or in combination of two or more.
[0049]
If the two components (A) and (B) of the present invention and, if necessary, a curing catalyst are mixed and cured, a uniform cured product excellent in deep part curability can be obtained. Although there is no restriction | limiting in particular about hardening conditions, Generally 0 to 100 degreeC, Preferably it is 20 to 80 degreeC.
The properties of the cured product depend on the main chain skeleton and molecular weight of the polymer of component (A) and the curing agent of component (B) to be used, but can be widely prepared from rubbery to resinous.
[0050]
Specific examples of cured products obtained from the above composition include sealing materials, adhesives, adhesives, elastic adhesives, paints, powder paints, foams, potting materials for electric and electronic devices, films, and molding. Materials, artificial marble, etc.
Next, the (meth) acrylic polymer having an alkenyl group at the terminal of the present invention is obtained by the various methods described above, and the hydroxyl group of the (meth) acrylic polymer having a hydroxyl group at the terminal contains an alkenyl group. It can manufacture by converting into a substituent.
[0051]
The method for converting the terminal hydroxyl group into an alkenyl group-containing substituent is not particularly limited, and various methods can be used. For example, a method of reacting an alkenyl group-containing halide such as allyl chloride with a base such as sodium methoxide, a method of reacting an alkenyl group-containing isocyanate compound such as allyl isocyanate, an alkenyl group such as (meth) acrylic acid chloride Examples thereof include a method of reacting a contained acid halide and a method of reacting an alkenyl group-containing carboxylic acid such as acrylic acid in the presence of an acid catalyst.
[0052]
Examples of the alkenyl group-containing halide used in the method of reacting an alkenyl group-containing halide with a base include allyl chloride, allyl bromide, allyl iodide, 4-chloro-1-butene, 4-bromo-1-butene, 4 -Iodo-1-butene, 3-chloro-2-methyl-1-butene, 3-bromo-2-methyl-1-butene, 3-iodo-2-methyl-1-butene, etc. Examples thereof include sodium, potassium, sodium methoxide, potassium methoxide, sodium tert-butoxide, potassium tert-butoxide, sodium hydride, potassium hydride and the like.
[0053]
Examples of the alkenyl group-containing isocyanate compound include allyl isocyanate and butenyl isocyanate. When these compounds are reacted, a tin-based or amine-based catalyst usually used for the reaction between a hydroxyl group and an isocyanate group may be used.
Examples of the alkenyl group-containing acid halide include (meth) acrylic acid chloride, 3-butenoic acid chloride, 4-pentenoic acid chloride, 5-hexenoic acid chloride, 10-undecenoic acid chloride and the like. In the actual reaction, triethylamine is used. Or a base such as pyridine may be used in combination.
[0054]
Examples of the alkenyl group-containing carboxylic acid include (meth) acrylic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 10-undecenoic acid, and the like. In the reaction, a condensation catalyst such as p-toluenesulfonic acid may be used.
The (meth) acrylic polymer having an alkenyl group at the terminal, obtained by the various methods described above, can be a curable composition containing this as a main component.
[0055]
This curable composition comprises the following two components: (C) a (meth) acrylic polymer having an alkenyl group at the terminal, (D) a hydrosilyl group-containing compound, obtained by any of the above methods, as an essential component To do.
The (meth) acrylic polymer having an alkenyl group at the terminal of the component (C) may be used alone or in combination of two or more. Although there is no restriction | limiting in particular as molecular weight of (C) component, It is preferable to exist in the range of 500-50000. When it is 500 or less, the original characteristics of the (meth) acrylic polymer are hardly expressed, and when it is 50000 or more, the viscosity or solubility is very low and handling becomes difficult.
[0056]
There is no restriction | limiting in particular as a hydrosilyl group containing compound of (D) component, Various things can be used. That is, a linear polysiloxane represented by the general formula 7 or 8
R^Ten _ThreeSiO- [Si (R^Ten)₂O]_a-[Si (H) (R¹¹) O]_b-[Si (R¹¹) (R¹²) O]_c-SiR^Ten _Three  (7)
HR^Ten ₂SiO- [Si (R^Ten)₂O]_a-[Si (H) (R¹¹) O]_b-[Si (R¹¹) (R¹²) O]_c-SiR^Ten ₂H (8)
(Where R^TenAnd R¹¹Is an alkyl group having 1 to 6 carbon atoms, or a phenyl group, R¹²Is an alkyl group or aralkyl group having 1 to 10 carbon atoms, a is 0 ≦ a ≦ 100, b is 2 ≦ b ≦ 100, and c is an integer of 0 ≦ c ≦ 100),
Cyclic siloxane represented by general formula 9
[0057]
[Chemical 3]

[0058]
(Where R¹³And R¹⁴Is an alkyl group having 1 to 6 carbon atoms, or a phenyl group, R¹⁵Is an alkyl group or aralkyl group having 1 to 10 carbon atoms, d is 0 ≦ d ≦ 8, e is an integer of 2 ≦ e ≦ 10, f is an integer of 0 ≦ f ≦ 8, and 3 ≦ d + e + f ≦ 10) Can be used.
These may be used alone or in combination of two or more. Among these siloxanes, chain siloxanes represented by general formulas 10 and 11 and cyclic siloxanes represented by general formulas 12 and 13 having a phenyl group are preferable from the viewpoint of compatibility with (meth) acrylic polymers. .
(CH_Three)_ThreeSiO- [Si (H) (CH_Three) O]_g-[Si (C₆H_Five)₂O]_h-Si (CH_Three)_Three  (10)
(CH_Three)_ThreeSiO- [Si (H) (CH_Three) O]_g-[Si (CH_Three) {CH₂C (H) (R¹⁶) C₆H_Five} O]_h-Si (CH_Three)_Three  (11)
(Wherein R¹⁶Is hydrogen or a methyl group, g is 2 ≦ g ≦ 100, h is an integer of 0 ≦ h ≦ 100, C₆H_FiveRepresents a phenyl group)
[0059]
[Formula 4]

[0060]
(Wherein R¹⁶Is hydrogen or a methyl group, i is 2 ≦ i ≦ 10, j is an integer satisfying 0 ≦ j ≦ 8 and 3 ≦ i + j ≦ 10, C₆H_FiveIs a phenyl group)
As the curing agent having at least two or more hydrosilyl groups as the component (D), the hydrosilyl group-containing compound represented by the formulas 7 to 13 with respect to the low molecular compound having two or more alkenyl groups in the molecule, A compound obtained by addition reaction such that a part of the hydrosilyl group remains after the reaction can also be used. Various compounds can be used as the compound having two or more alkenyl groups in the molecule. For example, hydrocarbon compounds such as 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, O, O Ether compounds such as' -diallyl bisphenol A, 3,3'-diallyl bisphenol A, ester compounds such as diallyl phthalate, diallyl isophthalate, triallyl trimellitate, tetraallyl pyromellitate, carbonates such as diethylene glycol diallyl carbonate System compounds.
[0061]
The compound can be obtained by slowly dropping the above-mentioned alkenyl group-containing compound in the presence of a hydrosilylation catalyst with respect to an excessive amount of the hydrosilyl group-containing compound represented by Formulas 7 to 13. Of these compounds, the following are preferred in view of the availability of raw materials, the ease of removal of the excessively used siloxane, and the compatibility of the component (C) with the polymer.
[0062]
[Chemical formula 5]

[0063]
The polymer (C) and the curing agent (D) can be mixed at an arbitrary ratio, but from the viewpoint of curability, the molar ratio of the alkenyl group to the hydrosilyl group is preferably in the range of 5 to 0.2. Furthermore, it is particularly preferably 2.5 to 0.4. When the molar ratio is 5 or more, curing is insufficient and only a cured product having low tackiness and a low strength can be obtained. When the molar ratio is less than 0.2, a large amount of active hydrosilyl groups remain in the cured product even after curing. Cracks and voids are generated, and a uniform and strong cured product cannot be obtained.
[0064]
The curing reaction between the polymer (C) and the curing agent (D) proceeds by mixing and heating the two components, but a hydrosilylation catalyst is added to advance the reaction more rapidly. Such hydrosilylation catalysts include radical initiators such as organic peroxides and azo compounds, and transition metal catalysts.
There is no restriction | limiting in particular as a radical initiator, Various things can be used. Illustratively, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) -3 Hexyne, dicumyl peroxide, t-butylcumyl peroxide, dialkyl peroxides such as α, α′-bis (t-butylperoxy) isopropylbenzene, benzoyl peroxide, p-chlorobenzoyl peroxide, m-chlorobenzoyl peroxide, 2 , 4-dichlorobenzoyl peroxide, diacyl peroxides such as lauroyl peroxide, peracid esters such as perbenzoic acid-tert-butyl, peroxydicarbonates such as diisopropyl percarbonate, di-2-ethylhexyl percarbonate, , 1-Di (t-butylperoxy) si And peroxyketals such as chlorohexane and 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane.
[0065]
Examples of the transition metal catalyst include platinum alone, alumina, silica, carbon black and the like in which a platinum solid is dispersed, chloroplatinic acid, a complex of chloroplatinic acid and alcohol, aldehyde, ketone, etc., platinum -An olefin complex and a platinum (0) -divinyltetramethyldisiloxane complex are mentioned. Examples of catalysts other than platinum compounds include RhCl (PPh_Three)_Three, RhCl_Three, RuCl_Three, IrCl_Three, FeCl_Three, AlCl_Three, PdCl₂・ H₂O, NiCl₂, TiCl_FourEtc. These catalysts may be used alone or in combination of two or more. Although there is no restriction | limiting in particular as a catalyst amount, It is 10 with respect to 1 mol of alkenyl groups of (A) component.^-1-10^-8It should be used in the range of mol, preferably 10^-3-10^-6 It is good to use in the range of mol. 10^-8If it is less than mol, curing does not proceed sufficiently. Also, since hydrosilylation catalysts are expensive, 10^-1It is preferable not to use more than mol.
[0066]
If the two components (C) and (D) of the present invention and, if necessary, the hydrosilylation catalyst are mixed and cured, a uniform cured product excellent in deep part curability can be obtained. Although there is no restriction | limiting in particular about hardening conditions, Generally it is good to harden at 10 degreeC-200 degreeC, Preferably it is 30 degreeC-150 degreeC for 10 second-24 hours. In particular, at a high temperature of 80 ° C. to 150 ° C., a material that cures in a short time of about 10 seconds to 1 hour can be obtained. The properties of the cured product depend on the main chain skeleton and molecular weight of the polymer of component (C) and the curing agent of component (D) to be used, but can be widely prepared from rubbery to resinous. If the specific use of the hardened | cured material obtained from this composition is given, a sealing material, an adhesive agent, an adhesive material, an elastic adhesive agent, a coating material, a powder coating material, a foam, a potting material for electric and electronics, a film, a gasket, Various molding materials, artificial marble, etc. The (meth) acrylic polymer having a crosslinkable silyl group at the terminal in the present invention has a crosslinkable silyl group in the (meth) acrylic polymer having an alkenyl group at the terminal obtained by the various methods described above. It can be produced by adding a hydrosilane compound. As the (meth) acrylic polymer having an alkenyl group at the terminal, all those obtained by the method described above can be suitably used.
[0067]
Although there is no restriction | limiting in particular as a hydrosilane compound, When a typical thing is shown, it is General formula 14
H- [Si (R¹⁷)_2-b(Y)_bO]_m-Si (R¹⁸)_3-a(Y)_a  (14)
(Wherein R¹⁷And R¹⁸Are all alkyl groups having 1 to 20 carbon atoms, aryl groups, aralkyl groups, or (R ')._ThreeA triorganosiloxy group represented by SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different). , R¹⁷Or R¹⁸When two or more are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y are present, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer of 0-19. However, it shall be satisfied that a + mb ≧ 1. )
The compound represented by these is illustrated.
[0068]
The hydrolyzable group represented by Y is not particularly limited, and conventionally known hydrolyzable groups can be used. Specifically, hydrogen, halogen atom, alkoxy group, acyloxy group, ketoximate group, amino group, amide can be used. Groups, acid amide groups, aminooxy groups, mercapto groups, alkenyloxy groups and the like, and alkoxy groups are particularly preferred from the viewpoint that they are mild and easy to handle. The hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3, and the sum of a + mb, that is, the hydrolyzable group is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the reactive silicon group, they may be the same or different. The number of silicon atoms constituting the crosslinkable silicon compound may be one or two or more, but in the case of silicon atoms linked by a siloxane bond, it may be up to about 20.
[0069]
R in general formula 14¹⁷Or R¹⁸Specific examples of these include, for example, an alkyl group such as a methyl group or an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, and R ′ is a methyl group or a phenyl group. Yes (R ')_ThreeExamples include triorganosilyl groups represented by SiO-.
Among these hydrosilane compounds, in particular, the general formula 15
H-Si (R¹⁸)_3-a(Y)_a  (15)
(Wherein R¹⁸, Y and a are the same as described above. The hydrosilane compound having a crosslinkable group represented by (2) is preferred from the viewpoint of easy availability. Specific examples of the hydrosilane compound having a crosslinkable group represented by the general formula 14 or 15 include
HSiCl_Three, HSi (CH_Three) Cl₂, HSi (CH_Three)₂Cl, HSi (OCH_Three)_Three, HSi (CH_Three) (OCH_Three)₂, HSi (CH_Three)₂OCH_Three, HSi (OC₂H_Five)_Three, HSi (CH_Three) (OC₂H_Five)₂, HSi (CH_Three)₂OC₂H_Five, HSi (OC_ThreeH₇)_Three, HSi (C₂H_Five) (OCH_Three)₂, HSi (C₂H_Five)₂OCH_Three,
HSi (C₆H_Five) (OCH_Three)₂, HSi (C₆H_Five)₂(OCH_Three), HSi (CH_Three) (OC (O) CH_Three)₂, HSi (CH_Three)₂O- [Si (CH_Three)₂O]₂-Si (CH_Three) (OCH_Three)₂, HSi (CH_Three) [O-N = C (CH_Three)₂]₂
(However, in the above chemical formula, C₆H_FiveRepresents a phenyl group)
Etc.
[0070]
When such a hydrosilane compound having a crosslinkable silyl group is added to a (meth) acrylic polymer having an alkenyl group at the terminal, a hydrosilylation catalyst can be used. All can be used.
A (meth) acrylic polymer having a crosslinkable silyl group at the terminal is prepared by reacting a compound having both a crosslinkable silyl group and a functional group that reacts with a hydroxyl group with a (meth) acrylic polymer having a hydroxyl group at the terminal. Can also be obtained. Examples of the functional group that reacts with a hydroxyl group include a group having a halogen atom, a carboxylic acid halide, a carboxylic acid, an isocyanate group, etc., but the availability of the compound and the reaction conditions when reacting with a hydroxyl group are mild, An isocyanate group is preferable in that the decomposition of the crosslinkable silyl group hardly occurs.
[0071]
There is no restriction | limiting in particular as such an isocyanate type compound which has a crosslinkable silyl group, A well-known thing can be used. For example,
(CH_ThreeO)_ThreeSi- (CH₂)_n-NCO, (CH_ThreeO)₂(CH_Three) Si- (CH₂)_n-NCO, (C₂H_FiveO)_ThreeSi- (CH₂)_n-NCO, (C₂H_FiveO)₂(CH_Three) Si- (CH₂)_n-NCO, (i-C_ThreeH₇O)_ThreeSi- (CH₂)_n-NCO, (i-C_ThreeH₇O)₂(CH_Three) Si- (CH₂)_n-NCO, (CH_ThreeO)_ThreeSi- (CH₂)_n-NH- (CH₂)_m-NCO, (CH_ThreeO)₂(CH_Three) Si- (CH₂)_n-NH- (CH₂)_m-NCO, (C₂H_FiveO)_ThreeSi- (CH₂)_n-NH- (CH₂)_m-NCO, (C₂H_FiveO)₂(CH_Three) Si- (CH₂)_n-NH- (CH₂)_m-NCO,
(I-C_ThreeH₇O)_ThreeSi- (CH₂)_n-NH- (CH₂)_m-NCO, (i-C_ThreeH₇O)₂(CH_Three) Si- (CH₂)_n-NH- (CH₂)_m-NCO,
(In the above formula, n and m are integers of 1 to 20)
Etc.
[0072]
The reaction of the (meth) acrylic polymer having a hydroxyl group at the terminal and the isocyanate compound having a crosslinkable silyl group can be carried out in the absence of a solvent or in various solvents, and the reaction temperature is 0 ° C. to 100 ° C., Preferably, it is 20 to 50 ° C. At this time, the tin-based catalyst and the tertiary amine-based catalyst already exemplified for promoting the reaction between the hydroxyl group and the isocyanate group can be used.
[0073]
The (meth) acrylic polymer having a crosslinkable silyl group at the terminal obtained by each of the above methods can be made into a curable composition containing this as a main component.
The main component (meth) acrylic polymer may be used alone or in combination of two or more. There is no particular limitation on the molecular weight,
It is preferably in the range of 500-50000. When the molecular weight is 500 or less, the original characteristics of the (meth) acrylic polymer are hardly expressed, and when it is 50000 or more, handling becomes difficult.
[0074]
A (meth) acrylic polymer having a hydrolyzable silyl group at the terminal forms a network by a condensation reaction when it comes into contact with moisture, and gives a cured product (crosslinked product) having a three-dimensional network structure. Since the hydrolysis rate varies depending on the temperature, humidity, and type of hydrolyzable group, an appropriate hydrolyzable group must be selected according to the use conditions. Further, when storing a (meth) acrylic polymer having a hydrolyzable silyl group at the end, it is necessary to cut off contact with moisture as much as possible.
[0075]
A curing catalyst may be added to accelerate the curing reaction. Condensation catalysts include titanic acid esters such as tetrabutyl titanate and tetrapropyl titanate; organotin compounds such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate and tin naphthenate; lead octylate, butylamine and octyl Amine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, octylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2, 4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 1,3-diazabicyclo (5,4, ) Amine compounds such as undecene-7 or their carboxylates; low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; reaction products of excess polyamines and epoxy compounds; silane coupling agents having amino groups For example, one or more known silanol catalysts such as γ-aminopropyltrimethoxysilane and N- (β-aminoethyl) aminopropylmethyldimethoxysilane may be used as necessary. The curing catalyst is preferably used in an amount of 0 to 10% by weight based on the (meth) acrylic polymer having a crosslinkable silyl group at the terminal. When the hydrolyzable group Y is an alkoxy group, it is preferable to use a curing catalyst because the curing rate is slow only with this polymer.
[0076]
A uniform cured product can be obtained by mixing a curing catalyst with a (meth) acrylic polymer having a crosslinkable silyl group at the terminal, which is the main component, if necessary, and curing. Although there is no restriction | limiting in particular as hardening conditions, Generally 0-100 degreeC, Preferably it is about 10-50 degreeC for about 1 hour-1 week. The properties of the cured product depend on the main chain skeleton and molecular weight of the polymer to be used, but can be widely prepared from rubbery to resinous.
[0077]
Specific uses of the cured product obtained from the above composition include sealing materials, adhesives, adhesives, elastic adhesives, paints, powder paints, foams, potting materials for electric and electronic materials, films, molding materials, Artificial marble can be mentioned.
[0078]
【Example】
Specific examples of the present invention are shown below, but the present invention is not limited to the following examples.
Example 1
In a 30 mL pressure-resistant reaction vessel, acrylic acid-n-butyl (5 mL, 4.47 g, 34.9 mmol), α, α′-dibromo-p-xylene (185 mg, 0.70 mmol), cuprous bromide (100 mg) , 0.70 mmol), 2,2′-bipyridyl (326 mg, 2.10 mmol), ethyl acetate (4 mL) and acetonitrile (1 mL) were added, nitrogen bubbling was performed for 10 minutes to remove dissolved oxygen, and the tube was sealed. . The mixture was heated to 130 ° C. and reacted for 3 hours. The reaction vessel was returned to room temperature, 2-hydroxyethyl methacrylate (0.352 mL, 364 mg, 2.80 mmol) was added and sealed, and reacted at 80 ° C. for 2 hours. The mixture was diluted with ethyl acetate (20 mL) and washed 3 times with 10% hydrochloric acid and once with brine. The organic layer is Na₂SO_FourAfter drying, the solvent was distilled off under reduced pressure to obtain 4.11 g of poly (acrylic acid-n-butyl) having a hydroxyl group at the terminal end represented by the following formula (82%). The number average molecular weight of the polymer was 5900 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.45. Also,¹From 1 H-NMR analysis, the average number of hydroxyl groups per molecule of the polymer was 3.2.
[0079]
[Chemical 6]

[0080]
Production Example 1 (Production of hydroxyl group-containing initiator)
2-Bromopropionic acid chloride (2 mL, 3.35 g, 19.5 mmol) was slowly added dropwise at 0 ° C. to a THF solution (10 mL) of ethylene glycol (10.9 mL, 195 mmol) and pyridine (3 g, 39 mmol) in a nitrogen atmosphere. did. The solution was stirred at that temperature for 2 hours. Dilute hydrochloric acid (20 mL) and ethyl acetate (30 mL) were added, and the two layers were separated. The organic layer is washed with dilute hydrochloric acid and brine, and Na₂SO_FourAfter drying, the volatile matter was distilled off under reduced pressure to obtain a crude product (3.07 g). The crude product was distilled under reduced pressure (70 to 73 ° C., 0.5 mmHg) to obtain hydroxyethyl-2-bromopropionate represented by the following formula (2.14 g, 56%).
H_ThreeCC (H) (Br) C (O) O (CH₂)₂-OH
Example 2
In a 30 mL pressure-resistant reaction vessel, acrylic acid-n-butyl (5 mL, 4.47 g, 34.9 mmol), the hydroxyl group-containing initiator obtained in Production Example 1 (138 mg, 0.698 mmol), cuprous bromide ( 100 mg, 0.698 mmol), 2,2′-bipyridyl (218 mg, 1.40 mmol), ethyl acetate (4 mL), and acetonitrile (1 mL) were charged, and dissolved oxygen was removed by nitrogen bubbling, and then sealed. The mixture was heated to 130 ° C. and reacted for 2 hours. The reaction vessel was returned to room temperature, 2-hydroxyethyl methacrylate (0.176 mL, 182 mg, 1.40 mmol) was added, and the mixture was reacted at 100 ° C. for 2 hours. The mixture was diluted with ethyl acetate (20 mL), insolubles were filtered off, and the filtrate was washed twice with 10% hydrochloric acid and once with brine. The organic layer is Na₂SO_FourAfter drying, the solvent was distilled off under reduced pressure to obtain 4.44 g of poly (acrylic acid-n-butyl) having a hydroxyl group at the end represented by the following formula (yield: 93%). The number average molecular weight of the polymer was 6100 according to GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.32. Also,¹According to 1 H-NMR measurement, the average number of hydroxyl groups per molecule of the polymer was 3.3.
[0081]
[Chemical 7]

[0082]
Example 3
In Example 2, 6.96 g of poly (acrylic acid-n-butyl) shown in Chemical formula 7 was obtained in the same manner except that 10 mL of acrylic acid-n-butyl was used (yield 75%). The number average molecular weight of the polymer was 8300 according to GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.32. Also,¹According to 1 H-NMR measurement, the average number of hydroxyl groups per molecule of the polymer was 2.2.
Example 4
Except that 7.5 mL of acrylic acid-n-butyl was used in Example 2, 5.75 g of poly (acrylic acid-n-butyl) represented by Chemical formula 7 was obtained (yield 82%). The number average molecular weight of the polymer was 7500 according to GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.36. Also,¹The average number of hydroxyl groups per molecule of the polymer was 2.1 by 1 H-NMR measurement.
Example 5
In a 50 mL pressure-resistant reaction vessel, acrylic acid-n-butyl (10.94 mL, 9.78 g, 76.3 mmol), the hydroxyl group-containing initiator obtained in Production Example 1 (301 mg, 1.53 mmol), first bromide Copper (219 mg, 1.53 mmol), 2,2′-bipyridyl (476 mg, 3.05 mmol), ethyl acetate (8.8 mL), acetonitrile (2.2 mL) were charged, and dissolved oxygen was removed by nitrogen bubbling. After that, it was sealed. The mixture was heated to 130 ° C. and reacted for 1.3 hours. The mixture was diluted with ethyl acetate (20 mL) and washed 3 times with 10% hydrochloric acid and once with brine. The organic layer is Na₂SO_FourAfter drying, the solvent was distilled off under reduced pressure to obtain 5.23 g of poly (acrylic acid-n-butyl) having a hydroxyl group at one end (53%). The number average molecular weight of the polymer was 3400 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.31. Also,¹From 1 H-NMR analysis, the average number of hydroxyl groups per polymer molecule was 1.09.
[0083]
Next, in a 50 mL three-necked flask equipped with a stirrer and a reflux condenser, poly (acrylic acid-n-butyl) having a hydroxyl group at one end obtained above (2.15 g), Na₂S • 9H₂O (76.3 mg, 0.318 mmol) and ethanol (3 mL) were charged, and the mixture was stirred at reflux temperature for 3 hours. After cooling to room temperature, ethyl acetate (5 mL) and 10% hydrochloric acid (5 mL) were added, and the two layers were separated. The organic layer was washed with 10% hydrochloric acid and brine, and Na₂SO_FourAfter drying, the volatile matter was distilled off under reduced pressure to obtain 1.93 g of poly (acrylic acid-n-butyl) having hydroxyl groups at both ends represented by the following formula. The number average molecular weight of the polymer was 5700 according to GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.39.
[0084]
[Chemical 8]

[0085]
Examples 6 to 10 (creation of cured product)
Poly (acrylic acid-n-butyl) having hydroxyl groups at both ends obtained in Examples 1 to 5, trifunctional isocyanate compound (B-45 manufactured by Yushi Co., Ltd.) represented by the following formula, and tin-based catalyst (stock) Nitto Kasei Co., Ltd., U-220, dibutyltin diacetylacetonate) was mixed well. The mixing ratio was such that the hydroxyl group of the (meth) acrylic polymer and the isocyanate group of the isocyanate compound had a molar ratio of 1/1, and the tin-based catalyst was 0.1% relative to 100 parts by weight of the polymer. The amount was 1 part by weight.
[0086]
The above mixture was degassed under reduced pressure, poured into a mold and cured by heating at 80 ° C. for 15 hours. The obtained cured product was immersed in toluene for 24 hours, and the gel fraction was calculated from the weight change before and after. The results are shown in Table 1.
[0087]
[Chemical 9]

[0088]
[Table 1]

[0089]
Example 11
Using a 1 L autoclave, 82 g of poly (acrylic acid-n-butyl) having a hydroxyl group at the terminal was obtained (75%) on a scale 20 times that of Example 2 (using 100 g of acryl-n-butyl acid). The number average molecular weight of the obtained polymer was 5100 according to GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.29.
[0090]
Next, to a toluene solution (100 mL) of poly (acrylic acid-n-butyl) (50 g) having a hydroxyl group at the terminal obtained as described above and pyridine (10 mL) at 60 ° C. in a nitrogen atmosphere. -Undecenoic acid chloride (7.22 mL, 6.81 g, 33.6 mmol) was slowly added dropwise and stirred at 60 ° C for 3 hours. The resulting white solid was filtered and the organic layer was washed with dilute hydrochloric acid and brine. The organic layer is Na₂SO_FourAnd concentrated under reduced pressure to obtain poly (acrylic acid-n-butyl) (43 g) having an alkenyl group at the terminal shown in the following formula. The number average molecular weight of the obtained polymer was 5400 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.3. Also,¹According to 1 H-NMR analysis, the average number of alkenyl groups per polymer molecule was 2.28.
[0091]
[Chemical Formula 10]

[0092]
Example 12
In a 50 mL three-necked flask equipped with a reflux condenser and a stirrer, poly (acrylic acid-n-butyl) having a hydroxyl group at both ends obtained in Example 5 (780 mg), pyridine (0.3 mL) and Toluene (2 mL) was charged. Under a nitrogen atmosphere, 10-undecenoic acid chloride (0.0705 mL, 0.328 mmol) was added dropwise at 60 ° C., and the mixture was stirred at the same temperature for 3 hours. Ethyl acetate (5 mL) and 10% hydrochloric acid (5 mL) were added, and the two layers were separated. The organic layer is washed with 10% hydrochloric acid and brine, and Na₂SO_FourAfter drying, the volatile matter was distilled off under reduced pressure to obtain poly (acrylic acid-n-butyl) having an alkenyl group at both ends shown in the following formula (560 mg). The number average molecular weight of the obtained polymer was 6500 according to GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.31.
[0093]
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[0094]
Examples 13-14
Poly (butyl acrylate) having an alkenyl group at both ends obtained in Examples 11 and 12, a hydrosilyl group-containing compound represented by the following formula, and 1,1,3,3-tetramethyl-1 of zerovalent platinum , 3-Divinyldisiloxane complex (8.3 × 10^-8mol / L xylene solution) was mixed well. The amount of the hydrosilyl group-containing compound used is such that the molar ratio of the alkenyl group of the polymer to the hydrosilyl group of the hydrosilyl group-containing compound is 1 / 1.2, and the amount of platinum catalyst used is the amount of the alkenyl group of the polymer. In contrast, the molar ratio is 10^-Four-10^-3Equivalent.
[0095]
A part of the composition thus obtained was subjected to a curing test on a hot plate at 130 ° C., and the gelation time was measured. The remaining composition was degassed under reduced pressure, poured into a mold and heat-cured to obtain a rubber-like cured product. The cured product was immersed in toluene for 24 hours, and the gel fraction was measured from the weight change before and after. The results are shown in Table 2.
[0096]
.
Embedded image

[0097]
[Table 2]

[0098]
Example 15
In a 30 mL pressure-resistant reaction vessel, poly (butyl acrylate) having alkenyl groups at both ends obtained in Example 11 (2 g), methyldimethoxysilane (0.32 mL), methyl orthoformate (0.09 mL, alkenyl group) 3 equivalents), 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex of zero-valent platinum (8.3 × 10^-810 mol / L xylene solution, alkenyl group^-4Equivalent) and stirred at 100 ° C. for 1 hour. The volatile matter was distilled off under reduced pressure to obtain 2 g of poly (acrylic acid-n-butyl) having methyldimethoxysilyl groups at both ends, as shown in the following formula.
[0099]
Embedded image

[0100]
Next, poly (acryl-n-butyl acid) having a crosslinkable silyl group at both ends obtained as described above (1 g) and a curing catalyst (manufactured by Nitto Kasei Co., Ltd., U-220, dibutyltin diacetylacetonate) , 30 mg) was mixed well, poured into a mold, and defoamed at room temperature using a vacuum dryer. A uniform rubber-like cured product was obtained by leaving it to stand at room temperature for 7 days. The gel fraction was 78%.
Production Example 2
To a 100 mL reactor was added n-butyl acrylate (20 mL, 17.9 g, 0.140 mmol), diethyl 2,5-dibromoadipate (0.628 g, 1.74 mmol), cuprous bromide (225 mg, 1.57 mmol), pentamethyldiethylenetriamine (0.328 mL, 0.272 g, 1.57 mmol) and toluene (2.0 mL) were charged, freeze degassed, and then purged with nitrogen. The mixture was heated to 70 ° C. and allowed to react for 45 minutes. At this point, the monomer conversion was 82%. The reaction mixture was diluted with ethyl acetate, passed through an activated alumina column, the copper catalyst was removed, and poly (acrylic acid-n-butyl) having a bromine group at the end shown in the following formula was obtained. The number average molecular weight of the produced polymer was 10200, and the molecular weight distribution was 1.14.
[0101]
Embedded image

[0102]
Example 16
Poly (n-butyl acrylate) (5.00 g) obtained in Production Example 2 and sodium 4-hydroxybutyrate (0.248 g, 1.967 mmol) in N, N-dimethylacetamide (10 mL) Mix and stir at 70 ° C. for 3 hours. The reaction solution was diluted with ethyl acetate, washed with water, and the volatile matter in the organic layer was distilled off under reduced pressure to obtain a polymer having hydroxyl groups at both ends represented by the following formula.¹According to 1 H NMR measurement, the number of hydroxyl groups per polymer molecule was 1.66 on average.
[0103]
Embedded image

[0104]
Example 17
The poly (acrylic acid-n-butyl) having hydroxyl groups at both ends obtained in Example 16 and the trifunctional isocyanate compound represented by the following formula (B-45, manufactured by Yushi Co., Ltd.) were mixed well. The mixing ratio was such that the hydroxyl group of the polymer and the isocyanate group of the isocyanate compound were 1/3 in molar ratio.
[0105]
Embedded image

[0106]
The above mixture was degassed under reduced pressure and cured by heating at 100 ° C. for 24 hours. The obtained cured product was immersed in toluene for 24 hours, and the gel fraction was calculated to be 97% from the weight change before and after.
[0107]
【The invention's effect】
According to the present invention, a (meth) acrylic polymer having a high proportion of hydroxyl groups at the ends, which has been difficult to produce, can be easily obtained, and a curable composition having excellent curing characteristics is obtained. Obtainable. In addition, by utilizing the reactivity of the hydroxyl group, a (meth) acrylic polymer having an alkenyl group or a crosslinkable silyl group at the terminal can be easily obtained. From each terminal functional (meth) acrylic polymer A curable composition having excellent curing characteristics can be obtained.

Claims (13)

Polymerizing a (meth) acrylic monomer using an organic halide or a sulfonyl halide as an initiator and a metal complex having a group 8 element, group 9, group 10, or group 11 element as a central metal in the periodic table as a catalyst. The (meth) acrylic polymer having a terminal hydroxyl group is obtained by converting the halogen of the (meth) acrylic polymer having a terminal structure represented by the general formula 1 into a hydroxyl group-containing substituent obtained by A method,
—CH ₂ —C (R ¹ ) (CO ₂ R ² ) (X) (1)
(Wherein R ¹ is hydrogen or methyl, R ² is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, X is chlorine, bromine, or Iodine)
A (meth) acrylic polymer having a terminal hydroxyl group is reacted with a compound having both a polymerizable alkenyl group and a hydroxyl group as a second monomer to a (meth) acrylic polymer having a terminal structure represented by the general formula 1. Manufacturing method. The process according to claim 1, wherein the compound having both a polymerizable alkenyl group and a hydroxyl group is a compound represented by the general formula 2.
^{_{H 2 C = C (R 3}} ) -R 4 -R 5 -OH (2)
Wherein R ³ is hydrogen or a methyl group, R ⁴ is —C (O) O— (ester group), or o-, m-, p-phenylene group, R ⁵ is a direct bond, or 1 to 20 divalent organic groups may contain one or more ether bonds) Polymerizing a (meth) acrylic monomer using an organic halide or a sulfonyl halide as an initiator and a metal complex having a group 8 element, group 9, group 10, or group 11 element as a central metal in the periodic table as a catalyst. The (meth) acrylic polymer having a terminal hydroxyl group is obtained by converting the halogen of the (meth) acrylic polymer having a terminal structure represented by the general formula 1 into a hydroxyl group-containing substituent obtained by A method,
—CH ₂ —C (R ¹ ) (CO ₂ R ² ) (X) (1)
(Wherein R ¹ is hydrogen or methyl, R ² is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, X is chlorine, bromine, or Iodine)
After converting the terminal structure of the (meth) acrylic polymer into an enolate anion by reacting a metal simple substance or an organometallic compound with the (meth) acrylic polymer having the terminal structure represented by the general formula 1, the enolate anion A method for producing a (meth) acrylic polymer having a hydroxyl group at the terminal, which is converted into a hydroxyl group-containing substituent by reacting with aldehydes or ketones.   The method according to claim 3, wherein the metal simple substance is zinc. Polymerizing a (meth) acrylic monomer using an organic halide or a sulfonyl halide as an initiator and a metal complex having a group 8 element, group 9, group 10, or group 11 element as a central metal in the periodic table as a catalyst. The (meth) acrylic polymer having a terminal hydroxyl group is obtained by converting the halogen of the (meth) acrylic polymer having a terminal structure represented by the general formula 1 into a hydroxyl group-containing substituent obtained by A method,
—CH ₂ —C (R ¹ ) (CO ₂ R ² ) (X) (1)
(Wherein R ¹ is hydrogen or methyl, R ² is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, X is chlorine, bromine, or Iodine)
The (meth) acrylic polymer having a terminal structure represented by general formula 1 is reacted with a hydroxyl group-containing oxyanion represented by general formula 3 or a hydroxyl group-containing carboxylate anion represented by formula 4 to convert halogen to a hydroxyl group-containing substituent. The manufacturing method of the (meth) acrylic-type polymer which has a hydroxyl group at the terminal.
M ⁺ O ⁻ —R ⁶ —OH (3)
(In the formula, R ⁶ is a divalent alkyl group having 1 to 20 carbon atoms, a divalent aryl group having 6 to 20 carbon atoms, or a divalent aralkyl group having 7 to 20 carbon atoms, and one or more ether bonds. M ⁺ is an alkali metal ion or a quaternary ammonium ion)
M ⁺ O ^— C (O) —R ⁶ —OH (4)
(Wherein R ⁶ and M ⁺ are the same as above)   6. The production method according to claim 1, wherein the organic halide which is an initiator or the halogenated sulfonyl compound is a halide having a hydroxyl group. Polymerizing a (meth) acrylic monomer using an organic halide or a sulfonyl halide as an initiator and a metal complex having a group 8 element, group 9, group 10, or group 11 element as a central metal in the periodic table as a catalyst. The (meth) acrylic polymer having a terminal hydroxyl group is obtained by converting the halogen of the (meth) acrylic polymer having a terminal structure represented by the general formula 1 into a hydroxyl group-containing substituent obtained by A method,
—CH ₂ —C (R ¹ ) (CO ₂ R ² ) (X) (1)
(Wherein R ¹ is hydrogen or methyl, R ² is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, X is chlorine, bromine, or Iodine)
An organic halide as an initiator or a halide having a hydroxyl group as a sulfonyl halide compound is used to form a (meth) acrylic polymer having a structure represented by the general formula 1 at one end and a hydroxyl group at the other end. A compound having two or more of the same or different functional groups that can be substituted with the halogen of the general formula 1 is used to couple the halogen terminals together, and has a hydroxyl group at the terminal (meth) A method for producing an acrylic polymer. The production method according to claim 6 or 7, wherein the halide having a hydroxyl group is a compound represented by formula 5 or 6.
R ⁷ R ⁸ C (X) —R ⁹ —R ⁵ —OH (5)
(In the formula, R ⁵ is a direct bond, or a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds. R ⁷ and R ⁸ are hydrogen or 1 to 1 carbon atoms. An alkyl group having 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, or those linked to each other at the other end, R ⁹ is —C (O) O— (ester group), -C (O)-(keto group), or o-, m-, p-phenylene group, X is chlorine, bromine, or iodine)
HO—R ⁵ —C (R ⁷ ) (X) —R ⁹ —R ⁸ (6)
(Wherein R ⁵ , R ⁷ , R ⁸ , R ⁹ and X are the same as above)   8. The halogen-terminated coupling reaction of the general formula 1 is carried out using a compound selected from the group consisting of polyols, polyamines, polycarboxylic acids, polythiols, salts thereof, and alkali metal sulfides. The manufacturing method as described. After obtaining the (meth) acrylic polymer having a hydroxyl group at the terminal by the method according to any one of claims 1 to 9, the terminal hydroxyl group of the (meth) acrylic polymer is converted to an alkenyl group-containing substituent. A process for producing a (meth) acrylic polymer having an alkenyl group at a terminal, characterized by: A hydrosilane compound having a crosslinkable silyl group is added to the (meth) acrylic polymer having an alkenyl group at the terminal after obtaining the (meth) acrylic polymer having an alkenyl group at the terminal by the method according to claim 10. A method for producing a (meth) acrylic polymer having a crosslinkable silyl group at a terminal, which is characterized in that it is added. After obtaining the (meth) acrylic polymer having a hydroxyl group at the terminal by the method according to any one of claims 1 to 9, the (meth) acrylic polymer having a hydroxyl group at the terminal, The manufacturing method of the (meth) acrylic-type polymer which has a crosslinkable silyl group at the terminal characterized by making the compound which has the functional group which reacts react.   The production method according to claim 12, wherein the functional group that reacts with a hydroxyl group is an isocyanate group.