JP2004155861A - (meta)acrylic polymer having good oil resistance and its curable composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a material which has heat resistance and oil resistance while securing flexibility by solving the problematical long-term heat resistance of a urethane (meth)acrylate resin known as a material having excellent oil resistance due to the use of a polyether or a polyester in the principal chain. <P>SOLUTION: A (meth)acrylic polymer is produced by the atom transfer radical polymerization, and has at least one hydroxy group at the terminal, and the oil resistance of its molded product is higher than the molded product of a polymer whose repeating unit in the principal chain is changed to butyl acrylate alone by any one item of the immersion test of JIS K 6258 for the lubricating oil of Class 3, No.5 for Land stipulated by JIS K 2215. <P>COPYRIGHT: (C)2004,JPO

Description

【００６１】
（上記式中、Ｘは塩素、臭素、またはヨウ素、ｎは１〜２０の整数）
ＸＣＨ_２Ｃ（Ｏ）Ｏ（ＣＨ_２）_ｎＯ（ＣＨ_２）_ｍ−ＯＨ、Ｈ_３ＣＣ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ_２）_ｎＯ（ＣＨ_２）_ｍ−ＯＨ、（Ｈ_３Ｃ）_２Ｃ（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ_２）_ｎＯ（ＣＨ_２）_ｍ−ＯＨ、ＣＨ_３ＣＨ_２Ｃ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ_２）_ｎＯ（ＣＨ_２）_ｍ−ＯＨ、
【００６２】
【化２】

【００６３】
（上記式中、Ｘは塩素、臭素、またはヨウ素、ｎ、ｍは１〜２０の整数）
ｏ−，ｍ−，ｐ−ＸＣＨ_２−Ｃ_６Ｈ_４−（ＣＨ_２）_ｎ−ＯＨ、ｏ−，ｍ−，ｐ−ＣＨ_３Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−（ＣＨ_２）_ｎ−ＯＨ、ｏ−，ｍ−，ｐ−ＣＨ_３ＣＨ_２Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−（ＣＨ_２）_ｎ−ＯＨ、
（上記式中、Ｘは塩素、臭素、またはヨウ素、ｎは０〜２０の整数）
ｏ−，ｍ−，ｐ−ＸＣＨ_２−Ｃ_６Ｈ_４−（ＣＨ_２）_ｎ−Ｏ−（ＣＨ_２）_ｍ−ＯＨ、ｏ−，ｍ−，ｐ−ＣＨ_３Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−（ＣＨ_２）_ｎ−Ｏ−（ＣＨ_２）_ｍ−ＯＨ、ｏ−，ｍ−，ｐ−ＣＨ_３ＣＨ_２Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−（ＣＨ_２）_ｎ−Ｏ−（ＣＨ_２）_ｍ−ＯＨ、
（上記式中、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−ＸＣＨ_２−Ｃ_６Ｈ_４−Ｏ−（ＣＨ_２）_ｎ−Ｏ−（ＣＨ_２）_ｍ−ＯＨ、ｏ−，ｍ−，ｐ−ＣＨ_３Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−Ｏ−（ＣＨ_２）_ｎ−Ｏ−（ＣＨ_２）_ｍ−ＯＨ、ｏ−，ｍ−，ｐ−ＣＨ_３ＣＨ_２Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−Ｏ−（ＣＨ_２）_ｎ−Ｏ−（ＣＨ_２）_ｍ−ＯＨ、
（上記式中、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。
【００６４】
一般式（７）に示す化合物の具体例としては、
ＨＯ−ＣＨ_２Ｃ（Ｈ）（Ｘ）−ＣＯ_２Ｒ、ＨＯ−（ＣＨ_２）_２Ｃ（Ｈ）（Ｘ）−ＣＯ_２Ｒ、ＨＯ−（ＣＨ_２）_３Ｃ（Ｈ）（Ｘ）−ＣＯ_２Ｒ、ＨＯ−（ＣＨ_２）_８Ｃ（Ｈ）（Ｘ）−ＣＯ_２Ｒ、
（上記式中、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、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基）
ＨＯ−ＣＨ_２Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_５、ＨＯ−（ＣＨ_２）_２Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_５、ＨＯ−（ＣＨ_２）_３Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_５、
（上記式中、Ｘは塩素、臭素、またはヨウ素）
等を挙げることができる。
【００６５】
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−（ＣＨ_２）_ｎ−Ｃ_６Ｈ_４−ＳＯ_２Ｘ、
（上記式中、Ｘは塩素、臭素、またはヨウ素、ｎは０〜２０の整数）
ｏ−，ｍ−，ｐ−ＨＯ−（ＣＨ_２）_ｎ−Ｏ−Ｃ_６Ｈ_４−ＳＯ_２Ｘ、
（上記式中、Ｘは塩素、臭素、またはヨウ素、ｎは１〜２０の整数）
等である。
【００６６】
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。
【００６７】
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。
【００６８】
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個以上有する化合物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、アルカリ金属硫化物（硫化リチウム、硫化ナトリウム、硫化カリウム等）等が挙げられる。
なお、上記におけるアルカリ金属塩としては、リチウム塩、ナトリウム塩、カリウム塩等が挙げられる。
上記開始剤の使用量としては、モノマー１００重量部に対して、好ましくは０．０３〜１００重量部、より好ましくは０．１〜５０重量部である。
【００６９】
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。
【００７０】
ここで、上記のようにして得られた本発明の（メタ）アクリル系重合体は、
末端に水酸基を少なくとも１個有し、その硬化物の耐油性が、ＪＩＳ Ｋ ２２１５に規定される陸用３種５号の潤滑油に対するＪＩＳ Ｋ ６２５８の浸漬試験のいずれか一項目で、その主鎖の繰り返し単位をアクリル酸ブチル単独に変えた重合体の硬化物の耐油性を上回るもの；
末端に水酸基を少なくとも１個有し、その硬化物の耐油性が、ＪＩＳ Ｋ ２２１５に規定される陸用３種５号の潤滑油に対するＪＩＳ Ｋ ６２５８の浸漬試験において、浸漬した前後での質量変化率が５０％以下であるもの；
ＪＩＳ Ｋ ２２１５に規定される陸用３種５号の潤滑油に対するＪＩＳ Ｋ ６２５８の浸漬試験において、潤滑油に浸漬した前後での質量変化が、その主鎖の繰り返し単位をアクリル酸ブチル単独に変えた重合体の硬化物よりも少ないという耐油性を有するもの；
ＪＩＳ Ｋ ２２１５に規定される陸用３種５号の潤滑油に対するＪＩＳ Ｋ ６２５８の浸漬試験において、潤滑油に浸漬した前後での体積変化が、その主鎖の繰り返し単位をアクリル酸ブチル単独に変えた重合体の硬化物よりも少ないという耐油性を有するものである。
【００７１】
本発明における「主鎖の繰り返し単位をアクリル酸ブチル単独に変えた重合体」とは、その架橋構造が本発明における（メタ）アクリル系重合体の架橋構造と本質的に同一であり、その分子量および分子量分布が、本発明における（メタ）アクリル系重合体の分子量および分子量分布のそれぞれ０．５〜１．５倍である、アクリル酸ブチルの単独重合体を意味する。
【００７２】
（メタ）アクリル系重合体の水酸基の数は、特に限定されないが、より架橋性の高い硬化物を得るためには、平均して１個以上、好ましくは１．２個以上、より好ましくは１．５個以上である。
（メタ）アクリル系重合体の水酸基の位置は、少なくとも１個の水酸基が末端にあれば、特に限定はされない。その他に主鎖内部に水酸基を有しても構わないが、架橋させた硬化物にゴム弾性を求める場合等には、末端のみに水酸基を有することが好ましい。
【００７３】
本発明における「ＪＩＳ Ｋ ２２１５に規定される陸用３種５号の潤滑油」とは、酸化防止剤及び清浄剤を添加した陸用内燃機関用潤滑油であり、引火点２００℃以上、動粘度１６．３ｍｍ^２／ｓ以上２１．９ｍｍ^２／ｓ未満、粘度指数８５以上、流動点−５℃以下等の性質を有するものである。
本発明における「ＪＩＳ Ｋ ６２５８の浸漬試験」とは、上記潤滑油に対して、上記（メタ）アクリル系重合体の硬化物の全面を浸漬し、浸漬前と浸漬後の寸法、質量、体積、表面積および引張強さ等の機械的性質の変化を測定するものである。
【００７４】
「耐油性が上回る」とは、浸漬前後での質量変化率、体積変化率、機械的性質の変化率等がより少ないことを意味する。
上記浸漬試験において、浸漬前後での質量変化率は、好ましくは５０％以下、より好ましくは４０％以下、さらに好ましくは３０％以下である。
また、浸漬前後での体積変化率、機械的性質の変化率は、それぞれ好ましくは５０％以下、より好ましくは４０％以下、さらに好ましくは３０％以下である。
このように、上記性質を有する本発明の（メタ）アクリル系重合体は、特に耐油性に優れるものである。
【００７５】
＜＜硬化性組成物＞＞
上記の各種の方法で得られる、末端に少なくとも１個の水酸基を有する（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。本発明の硬化性組成物は、以下の２成分：（Ａ）末端に水酸基を少なくとも１個有する、原子移動ラジカル重合により製造された（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。
【００７６】
（Ａ）成分の、末端に水酸基を少なくとも１個有する（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、５００〜１，０００，０００の範囲にあるのが好ましい。５００未満であると（メタ）アクリル系重合体の本来の特性が発現されにくくなる傾向があり、１，０００，０００を超えると、高粘度となるかあるいは溶解性が低くなり、作業性が低下し易くなる傾向がある。
【００７７】
（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、アミノプラスト樹脂、１分子中に２個以上のカルボキシル基を有する化合物等が挙げられる。好ましくは、多価イソシアネート化合物である。
【００７８】
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）、コロネートＨＬ（日本ポリウレタン工業社製）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。
【００７９】
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。
【００８０】
本発明の硬化性組成物である、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。
【００８１】
有機スズ化合物しては、例えば、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。
【００８２】
３級アミン系触媒としては、例えば、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挙げられる。
【００８３】
本発明の硬化性組成物において（Ｂ）成分として用いら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。また、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。
【００８４】
本発明の硬化性組成物において（Ｂ）成分として用いられる、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、イタコン酸等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る。これらは単独で用いても２種類以上を併用してもよい。
【００８５】
本発明の硬化性組成物の上記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。
硬化触媒としては、例えば、硫酸、メタンスルホン酸、ｐ−トルエンスルホン酸等の酸性触媒；スカンジウム、イットリウム、ジルコニウム、ハフニウム、バナジウム、チタン金属のハライド類、硝酸塩類、カルボン酸塩類、アルコラート類およびアセチルアセトン型錯体等の金属触媒等が挙げられる。
各成分の配合量としては、（Ａ）成分１００重量部に対して、好ましくは（Ｂ）成分１０〜２００重量部、硬化触媒０〜１０重量部であり、より好ましくは（Ｂ）成分８０〜１２０重量部、硬化触媒０．１〜５重量部である。
【００８６】
硬化条件については特に制限はないが、硬化温度は、一般に０℃〜１５０℃、好ましくは２０℃〜１００℃である。硬化時間は、０．５時間〜１週間、好ましくは１〜２４時間である。
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。
【００８７】
上記の組成物より得られる硬化物は限定されないが、具体的な用途を挙げるならば、建築用弾性シーリング材や複層ガラス用シーリング材等のシーリング材、太陽電池裏面封止材等の電気・電子部品材料、電線・ケーブル用絶縁被覆材等の電気絶縁材料、粘着剤、接着剤、弾性接着剤、塗料、粉体塗料、コーティング材、発泡体、電気電子用ポッティング剤、フィルム、ガスケット、注型材料、各種成形材料、および、網入りガラスや合わせガラス端面（切断部）の防錆・防水用封止材等の様々な用途に利用可能である。
【００８８】
【実施例】
以下に、本発明の具体的な実施例を比較例と併せて説明するが、本発明は、下記実施例に限定されるものではない。
なお、下記実施例および比較例中、「部」および「％」は、それぞれ「重量部」および「重量％」を表す。
また、下記実施例中、「数平均分子量」および「分子量分布（重量平均分子量と数平均分子量の比）」は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いた標準ポリスチレン換算法により算出した。ただし、ＧＰＣカラムとしてポリスチレン架橋ゲルを充填したもの（ｓｈｏｄｅｘ ＧＰＣ Ｋ−８０４；昭和電工（株）製）、ＧＰＣ溶媒としてクロロホルムを用いた。
【００８９】
（製造例１）
還流管および攪拌機付きの３００ｍＬのフラスコに、ＣｕＢｒ（１．０１ｇ、７ｍｍｏｌ）を仕込み、反応容器内を窒素置換した。アセトニトリル（１１．５ｍＬ）を加え、オイルバス中７０℃で１５分間攪拌した。これにアクリル酸ブチル（３３．６ｍＬ、２３４ｍｍｏｌ）、アクリル酸エチル（４６．７ｍＬ、４３１ｍｍｏｌ）、アクリル酸２−メトキシエチル（３４．９ｍＬ、２７２ｍｍｏｌ）、２，５−ジブロモアジピン酸ジエチル（２．８１ｇ、７．８ｍｍｏｌ）、ペンタメチルジエチレントリアミン（０．０５ｍＬ、０．０４ｇ、０．２ｍｍｏｌ）（これ以降トリアミンと表す）を加え、反応を開始した。７０℃で加熱攪拌しながら、途中でトリアミン（０．２０ｍＬ、０．１６ｇ、０．９ｍｍｏｌ）を追加した。反応開始より１８０分経過時、モノマー転化率９８％で、５−ヘキセン−１−オール（１４．１ｍＬ、１１．７ｇ、１１７ｍｍｏｌ）、トリアミン（０．４９ｍＬ、０．４１ｇ、２．３ｍｍｏｌ）を加え、引き続き８０℃で４８０分加熱攪拌した。
【００９０】
反応混合物の揮発分を減圧留去した後、トルエン（５００ｇ）で希釈し、濾過により固形物を除去した。引き続き、酸性珪酸アルミ（５ｇ、協和化学製、キョーワード７００ＳＬ）、塩基性珪酸アルミ（５ｇ、協和化学製、キョーワード５００ＳＨ）を仕込み、窒素気流下１００℃で４時間加熱攪拌した。珪酸アルミを濾過により除去した後、ろ液のトルエンを減圧留去することにより、水酸基末端共重合体｛水酸基末端ポリ（アクリル酸ブチル、アクリル酸エチル、アクリル酸メトキシエチル）の共重合体：重合体［１］｝を得た。得られた共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１７８００、分子量分布は１．１６であった。共重合体１分子当たりに導入された平均の水酸基の数を^１Ｈ−ＮＭＲ分析により求めたところ、約２．５個であった。
【００９１】
（製造例２）
アクリル酸モノマーとしてアクリル酸ブチルのみを用い、アクリル酸エチルとアクリル酸２−メトキシエチルを添加しなかった以外は製造例１と同様にして、水酸基末端アクリル酸ブチル重合体（重合体［２］）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２５９００、分子量分布は１．２３であった。重合体１分子当たりに導入された平均の水酸基の数を^１Ｈ−ＮＭＲ分析により求めたところ、２．７個であった。
【００９２】
（実施例１）
製造例１で得られた重合体［１］１００部に対して、イソホロンジイソシアネート１２部、１，４−ブタンジオール２．８部、トリメチロールプロパン０．８部混合し、４価Ｓｎ触媒（ジブチル錫ジラウレート０．１部）を用いて、５０℃で１２時間、その後９０℃で６時間硬化養生させ、シート状の硬化物を得た。
【００９３】
（比較例１）
実施例１で用いた重合体［１］の代わりに、製造例２で得られた重合体［２］を用いた以外は実施例１と同様にして、シート状の硬化物を作製した。
【００９４】
（評価１）耐油性
実施例１と比較例１についてそれぞれ、硬化後の硬化物をＪＩＳ Ｋ ６２５８に規定される浸漬試験に基づき耐油性の評価を行った。ＪＩＳ Ｋ ２２１５に規定される陸用３種５号の潤滑油としては、市販のエンジンオイル（商品名ＧＥＯＭＡ、ＳＪグレード、５Ｗ−３０：ＪＯＭＯ製）を使用し、これに、上記硬化物を１５０℃で７２時間浸漬させた。その結果、質量変化率は、比較例１で得られた重合体［２］の硬化物では２６％であったのに対し、実施例１で得られた重合体［１］の硬化物は６％であり、水酸基末端ポリ（アクリル酸ブチル、アクリル酸エチル、アクリル酸メトキシエチル）の共重合体の方が、アクリル酸ブチル単独重合体の硬化物より良好な耐油性を示した。
【００９５】
【発明の効果】
本発明は、末端に水酸基を少なくとも１個有し、その硬化物の耐油性が、ＪＩＳＫ ２２１５に規定される陸用３種５号の潤滑油に対するＪＩＳ Ｋ ６２５８の浸漬試験のいずれか一項目で、その主鎖の繰り返し単位をアクリル酸ブチル単独に変えた重合体の硬化物の耐油性を上回り、原子移動ラジカル重合により製造された（メタ）アクリル系重合体、ならびに、その重合体を含有する硬化性組成物からなり、耐油性が改善され、耐熱性、柔軟性にも優れる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention is characterized by having at least one hydroxyl group at a terminal, and having an oil resistance of a cured product exceeding an oil resistance of a cured product of a polymer obtained by changing a repeating unit of the main chain to butyl acrylate alone. The present invention relates to a (meth) acrylic polymer produced by atom transfer radical polymerization, and a curable composition containing the polymer.
[0002]
[Prior art]
It is known that a polymer having a hydroxyl group at a terminal is cross-linked by using a compound having a functional group that reacts with a hydroxyl group, for example, an isocyanate compound as a curing agent, to give a cured product having excellent heat resistance and durability. Have been.
[0003]
Examples of such a main chain skeleton of a polymer having a hydroxyl group at its terminal include polyether polymers such as polyethylene oxide, polypropylene oxide and polytetramethylene oxide, polybutadiene, polyisoprene, polychloroprene, polyisobutylene and hydrogens thereof. Examples thereof include hydrocarbon polymers such as additives, and polyester polymers such as polyethylene terephthalate, polybutylene terephthalate, and polycaprolactone, and are used for various purposes based on the main chain skeleton and the crosslinking method.
[0004]
Among the polymers obtained by ionic polymerization or polycondensation as exemplified above, vinyl polymers obtained by radical polymerization and having a hydroxyl group at a terminal have not yet been practically used. Among vinyl polymers, (meth) acrylic polymers cannot be obtained with the above polyether-based polymers, hydrocarbon-based polymers, or polyester-based polymers because of their high heat resistance, weather resistance, transparency, etc. Those having characteristics and having a hydroxyl group in a side chain are used for weather-resistant paints and the like.
[0005]
If a (meth) acrylic polymer having a hydroxyl group at a 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 one having a hydroxyl group in a side chain. . Therefore, the production method has been studied by many researchers, but it is not easy to produce them industrially.
[0006]
A method for synthesizing a (meth) acrylic polymer having a hydroxyl group at both ends using a disulfide having a hydroxyl group as a chain transfer agent has been disclosed. However, a large amount of the chain transfer agent must be used for the initiator, which is a problem in the production process (for example, see Patent Document 1). Further, a method for producing a (meth) acrylic polymer having a hydroxyl group at a terminal using hydrogen peroxide as an initiator is disclosed, but it is difficult to reliably introduce hydroxyl groups at both terminals in this method, In practice, a method of copolymerizing a vinyl monomer having a hydroxyl group (for example, 2-hydroxyethyl methacrylate) is employed (for example, see Patent Document 2).
[0007]
Further, by polymerization of a (meth) acrylic monomer using a telogen such as carbon tetrachloride, a (meth) acrylic polymer having a terminal halogen is obtained, and the terminal halogen is converted to a diol compound, a hydroxyl group-containing carboxylic acid, a hydroxyl group-containing amine. There is a method for producing a vinyl polymer having a hydroxyl group at a terminal, characterized by reacting with a nucleophile such as described above (see, for example, Patent Document 3). Also in this method, since the chain transfer of telogen is not sufficient, it is difficult to introduce a high ratio of functional groups at both ends.
[0008]
On the other hand, as a material having excellent oil resistance, an anaerobic resin containing a urethane (meth) acrylate resin as a main component (for example, see Patent Documents 4 to 7) can be mentioned. There is a problem in long-term heat resistance to use.
[0009]
[Patent Document 1]
JP-A-5-262808
[Patent Document 2]
Japanese Patent Publication No. 1-19402
[Patent Document 3]
JP-A-4-132706
[Patent Document 4]
JP-A-58-187481
[Patent Document 5]
JP-A-64-112
[Patent Document 6]
Japanese Patent Publication No. 3-32593
[Patent Document 7]
JP-A-61-2719
[0010]
[Problems to be solved by the invention]
Therefore, provision of a material having oil resistance while securing heat resistance and flexibility has been an issue. Accordingly, an object of the present invention is to provide a (meth) acrylic polymer having at least one hydroxyl group at a terminal and having good oil resistance, and a curable composition containing the polymer. .
[0011]
[Means for Solving the Problems]
As a result of intensive studies in view of the above situation, the present invention has found that the above problems can be solved by using a specific (meth) acrylic polymer having at least one hydroxyl group at a terminal, and arrived at the present invention. .
[0012]
That is, the present invention has at least one hydroxyl group at the end, and the oil resistance of the cured product is one of the immersion tests of JIS K 6258 for land type No. 5 lubricating oil specified in JIS K 2215. One item relates to a (meth) acrylic polymer produced by atom transfer radical polymerization, characterized by exceeding the oil resistance of a cured product of a polymer in which the main chain repeating unit is changed to butyl acrylate alone. .
Further, the present invention has at least one hydroxyl group at the terminal, and the oil resistance of the cured product is determined by immersion test in JIS K 6258 immersion test for land type 3 lubricating oil specified in JIS K 2215. The present invention relates to a (meth) acrylic polymer produced by atom transfer radical polymerization, wherein a mass change rate before and after the polymerization is 50% or less.
Furthermore, the present invention relates to a curable composition comprising (A) the above (meth) acrylic polymer and (B) a compound having at least two functional groups capable of reacting with a hydroxyl group as essential components.
[0013]
Hereinafter, the (meth) acrylic polymer and the curable composition of the present invention will be described in detail.
[0014]
BEST MODE FOR CARRYING OUT THE INVENTION
<< (meth) acrylic polymer >>
<Main chain>
The (meth) acrylic monomer constituting the main chain of the (meth) acrylic polymer of the present invention is not particularly limited, and various types can be used. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, ( Isobutyl meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (n) -methacrylate -Heptyl, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate , Toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl acrylate, 4-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, stearyl (meth) acrylate, (meth) Glycidyl acrylate, 2-aminoethyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, (meth) acryl 2-trifluoromethylethyl acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, Perfluoromethyl (meth) acrylate, di (meth) acrylate Perfluoromethylmethyl, 2-perfluoromethyl-2-perfluoroethylmethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, (meth) 2-perfluorohexadecylethyl acrylate and the like. These may be used alone or a plurality of them may be copolymerized.
The (meth) acrylic polymer of the present invention does not include a homopolymer of butyl acrylate.
[0015]
Above all, acrylic monomers are preferred, and acrylic ester monomers are more preferred, in view of the physical properties of the product. Further, a polymer containing at least one of ethyl acrylate and alkoxyalkyl acrylate as an essential structural unit, that is, a copolymer containing any of ethyl acrylate, 2-methoxyethyl acrylate, and 2-ethoxyethyl acrylate And the like are more preferable from the viewpoint of oil resistance. Further, a copolymer of ethyl acrylate, 2-methoxyethyl acrylate, and butyl acrylate is most preferable, and its ratio can be changed in consideration of physical properties such as oil resistance and low-temperature characteristics. In the present invention, these preferred monomers may be copolymerized with other monomers, or may be further subjected to block copolymerization, in which case the preferred monomers should be present in a total weight ratio of at least 40%. Is preferred.
In the above expression format, for example, (meth) acrylic acid means acrylic acid and / or methacrylic acid.
[0016]
The molecular weight distribution of the (meth) acrylic polymer of the present invention, that is, the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is as follows: Although not particularly limited, it is preferably less than 1.8, more preferably 1.7 or less, further preferably 1.6 or less, still more preferably 1.5 or less, and particularly preferably 1.4. Or less, and most preferably 1.3 or less. In the GPC measurement in the present invention, chloroform is usually used as a mobile phase, the measurement is performed using a polystyrene gel column, and the number average molecular weight and the like can be determined in terms of polystyrene.
[0017]
The number average molecular weight of the (meth) acrylic polymer in the present invention is not particularly limited, but is preferably in the range of 500 to 1,000,000, and more preferably 1,000 to 100,000, as measured by gel permeation chromatography. Is more preferable, and 5,000 to 50,000 is still more preferable.
[0018]
<Main chain synthesis method>
In the present invention, the (meth) acrylic polymer is produced by atom transfer radical polymerization. This will be described below.
Among the "living radical polymerization methods", the "atom transfer radical polymerization method" in which an organic halide or a sulfonyl halide compound or the like is used as an initiator and a vinyl monomer is polymerized using a transition metal complex as a catalyst is the "living radical polymerization method". In addition to its features, it has a halogen or the like which is relatively advantageous for a functional group conversion reaction at its terminal, and has a high degree of freedom in designing initiators and catalysts. preferable.
Further, in this method, the polymerization proceeds in a living manner while being a radical polymerization, a polymer having a narrow molecular weight distribution (Mw / Mn = 1.1 to 1.5) is obtained, and the molecular weight is determined by charging a monomer and an initiator. It can be freely controlled by the ratio.
[0019]
The atom transfer radical polymerization method is described in, for example, Matyjaszewski et al., Journal of American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614; Macromolecules 1995 28, 7901; Science, 1996, 272, 866; WO96 / 30421; WO97 / 18247; WO98 / 01480; WO98 / 40415; Sawamoto et al., Macromolecules. (Macromolecules) 1995, Vol. 28, p. 1721; JP-A-9-208616; JP-A-8-41117.
[0020]
In this atom transfer radical polymerization method, as an initiator, an organic halide, 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 a sulfonyl halide compound.
[0021]
In order to obtain a (meth) acrylic polymer having at least one hydroxyl group at a terminal by using this polymerization method, an organic halide or a sulfonyl halide compound having two or more starting points is used as an initiator. As specific examples of them,
o-, m-, p-XCH ₂ -C ₆ H ₄ -CH ₂ X, o-, m-, p-CH ₃ C (H) (X) -C ₆ H ₄ -C (H) (X) CH ₃ , O-, m-, p- (CH ₃ ) ₂ C (X) -C ₆ H ₄ -C (X) (CH ₃ ) ₂ ,
(In the above formula, C ₆ H ₄ Is a phenylene group, X is chlorine, bromine or iodine)
RO ₂ CC (H) (X)-(CH ₂ ) _n -C (H) (X) -CO ₂ R, RO ₂ CC (CH ₃ ) (X)-(CH ₂ ) _n -C (CH ₃ ) (X) -CO ₂ R, RC (O) -C (H) (X)-(CH ₂ ) _n -C (H) (X) -C (O) R, RC (O) -C (CH ₃ ) (X)-(CH ₂ ) _n -C (CH ₃ ) (X) —C (O) R, wherein R 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, and n is 0 to An integer of 20, and X is chlorine, bromine, or iodine)
XCH ₂ C (O) CH ₂ X, CH ₃ C (H) (X) C (O) C (H) (X) CH ₃ , (CH ₃ ) ₂ C (X) C (O) C (X) (CH ₃ ) ₂ , C ₆ H ₅ C (H) (X)-(CH ₂ ) _n -C (H) (X) C ₆ H ₅ ,
(Where X is chlorine, bromine or iodine, and n is an integer of 0 to 20)
XCH ₂ CO ₂ − (CH ₂ ) _n -OCOCH ₂ X, CH ₃ C (H) (X) CO ₂ − (CH ₂ ) _n -OCOC (H) (X) CH ₃ , (CH ₃ ) ₂ C (X) CO ₂ − (CH ₂ ) _n -OCOC (X) (CH ₃ ) ₂ ,
(Where X is chlorine, bromine or iodine, and n is an integer of 1 to 20)
XCH ₂ C (O) C (O) CH ₂ X, CH ₃ C (H) (X) C (O) C (O) C (H) (X) CH ₃ , (CH ₃ ) ₂ C (X) C (O) C (O) C (X) (CH ₃ ) ₂ , O-, m-, p-XCH ₂ CO ₂ -C ₆ H ₄ -OCOCH ₂ X, o-, m-, p-CH ₃ C (H) (X) CO ₂ -C ₆ H ₄ -OCOC (H) (X) CH ₃ , O-, m-, p- (CH ₃ ) ₂ C (X) CO ₂ -C ₆ H ₄ -OCOC (X) (CH ₃ ) ₂ , O-, m-, p-XSO ₂ -C ₆ H ₄ -SO ₂ X,
(Where X is chlorine, bromine, or iodine)
And the like.
[0022]
As the catalyst, a metal complex having a Group 8 element, a Group 9, a Group 10, or a Group 11 element as a central metal is used. As the metal species, particularly, monovalent copper, divalent ruthenium, divalent iron, divalent nickel, and the like are preferable, and monovalent copper is more preferable.
To be more specific, as the monovalent copper compound, cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous acetate, peroxide Cuprous chlorate and the like can be mentioned. When a copper compound is used, it is effective to add a ligand such as 2,2′-bipyridyl and its derivative, and 1,10-phenanthroline and its derivative in order to enhance the catalytic activity. Also, tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) Are also suitable as catalysts. When a ruthenium compound is used as a catalyst, it is effective to add an aluminum alkoxide as an activator. Further, bistriphenylphosphine complex of divalent iron (FeCl ₂ (PPh ₃ ) ₂ ), Bistriphenylphosphine complex of divalent nickel (NiCl ₂ (PPh ₃ ) ₂ ) Are also suitable as catalysts.
[0023]
The amount of the initiator to be used is preferably 0.03 to 100 parts by weight, more preferably 0.1 to 50 parts by weight, based on 100 parts by weight of the monomer.
The amount of the catalyst used is preferably 0.01 to 100 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the monomer.
The polymerization in the present invention can be performed without a solvent or in various solvents. Examples of the solvent include hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether and tetrahydrofuran; halogenated hydrocarbon solvents such as methylene chloride and chloroform; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone. Solvents: alcoholic solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol and tert-butyl alcohol; nitrile solvents such as acetonitrile, propionitrile and benzonitrile; ester solvents such as ethyl acetate and butyl acetate; Examples thereof include carbonate solvents such as ethylene carbonate and propylene carbonate, and these can be used alone or in combination of two or more. In addition, an emulsion or supercritical fluid CO ₂ Polymerization can also be carried out in a system using as a medium. Among these, a nitrile solvent is preferable, and acetonitrile is more preferable, from the viewpoint of the effect of improving the catalyst stability.
Further, the polymerization can be carried out in a range of room temperature to 200 ° C, preferably 50 to 150 ° C. The polymerization time is 0.5 to 24 hours, preferably 1 to 12 hours.
[0024]
<< Introduction of hydroxyl group to terminal >>
The (meth) acrylic polymer having at least one hydroxyl group at the terminal is obtained by substituting the halogen of the (meth) acrylic polymer having a terminal structure represented by the general formula (1) obtained by the above polymerization with a hydroxyl group-containing substituent It can be obtained by converting to a group.
-CH ₂ -C (R ¹ ) (CO ₂ R ² ) (X) (1)
(Where R ¹ Is a hydrogen atom or a methyl group, 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, and X is chlorine, bromine, or iodine.
[0025]
R ² Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, and the like. Is mentioned.
Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, and an anthracenyl group.
Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group and a phenylethyl group.
The description of the above group also applies to the description of the group for R described above.
[0026]
<Method of reacting a compound having both a polymerizable alkenyl group and a hydroxyl group>
As a method for introducing a hydroxyl group into the terminal described above, first, a (meth) acrylic polymer having a terminal structure represented by the general formula (1) is produced by the above polymerization, and a polymerizable alkenyl group and a hydroxyl group are further added. A method of reacting a compound having the same as the second monomer is given.
[0027]
In the above-mentioned polymerization, the polymerization terminal retains the polymerization activity, and the polymerization proceeds again when a new vinyl monomer is added. Therefore, if a vinyl monomer having both a polymerizable alkenyl group and a hydroxyl group is added, a radical addition reaction occurs at the polymerization active alkenyl group portion, and the hydroxyl group remains as it is, so that a (meth) acrylic polymer having a hydroxyl group at a terminal is obtained. Can be obtained. Such a second monomer may be added together with a catalyst to cause a new reaction after the first polymerization is completed and the polymer is isolated, or may be added in the middle of the polymerization (in-situ). Reaction. In the latter case, the higher the monomer conversion of the first polymerization, the better, preferably 80% or more. If it is less than 80%, the hydroxyl group tends to be distributed not in the molecular terminal but in the molecular chain, and the mechanical properties of the cured product tend to deteriorate.
[0028]
At this time, a compound having both a polymerizable alkenyl group and a hydroxyl group can be added in an amount equal to the number of polymerization terminals (substantially equal to the number of starting points of the initiator because it is living polymerization). In each case, one hydroxyl group is introduced into all terminals, but in order to surely introduce hydroxyl groups into all terminals, an excess amount, specifically, 1 to 5 times the number of terminals is used. Preferably, it is used. If it is used more than 5 times, a hydroxyl group tends to be easily introduced into the terminal of the polymer at a high density, and it becomes difficult to obtain cured physical properties as expected.
[0029]
The compound having both a polymerizable alkenyl group and a hydroxyl group is not particularly limited. For example, the compound having the general formula (2)
H ₂ C = C (R ³ ) -R ⁴ -R ⁵ -OH (2)
(Where R ³ Is a hydrogen atom 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 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.
[0030]
In the general formula (2), R ⁴ Is an ester group, a (meth) acrylate compound, R ⁴ However, those having a phenylene group are styrene compounds.
R ⁵ As an alkylene group such as methylene, ethylene and propylene; a phenylene group such as o-, m- and p-phenylene group; an aralkylene group such as benzylene group; ₂ CH ₂ -O-CH ₂ CH ₂ -Or -OCH ₂ CH ₂ And an alkylene group containing an ether bond.
[0031]
Among these, from the point of being easily available,
H ₂ C = C (H) C (O) O (CH ₂ ) _n -OH, H ₂ C = C (CH ₃ ) C (O) O (CH ₂ ) _n -OH,
(In the above formula, n is an integer of 1 to 20)
H ₂ C = C (H) C (O) O (CH ₂ ) _n -O- (CH ₂ ) _m OH, H ₂ C = C (CH ₃ ) C (O) O (CH ₂ ) _n -O- (CH ₂ ) _m -OH,
(Where n and m are integers of 1 to 20)
o-, m-, pH ₂ C = CH-C ₆ H ₄ − (CH ₂ ) _n -OH, o-, m-, pH ₂ C = C (CH ₃ ) -C ₆ H ₄ − (CH ₂ ) _n -OH,
(In the above formula, n is an integer of 0 to 20)
o-, m-, pH ₂ C = CH-C ₆ H ₄ -O (CH ₂ ) _n -OH, o-, m-, pH ₂ C = C (CH ₃ ) -C ₆ H ₄ -O (CH ₂ ) _n -OH,
(In the above formula, n is an integer of 1 to 20)
Is preferred.
[0032]
The solvent used in the reaction is not particularly limited, but may be, for example, a hydrocarbon solvent such as benzene or toluene; an ether solvent such as diethyl ether or tetrahydrofuran; which can be used during polymerization; methylene chloride, chloroform or the like. Halogenated hydrocarbon solvents; Ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol; acetonitrile, propionitrile, benzo Nitrile solvents such as nitrile; ester solvents such as ethyl acetate and butyl acetate; carbonate solvents such as ethylene carbonate and propylene carbonate; and the like, alone or in combination of two or more. Kill. In addition, an emulsion or supercritical fluid CO ₂ Polymerization can also be carried out in a system using as a medium. These solvents may be the same as or different from the solvents used during the polymerization. Among these, a nitrile solvent is preferable, and acetonitrile is more preferable, from the viewpoint of the effect of improving the catalyst stability. The reaction temperature is from room temperature to 200 ° C, preferably from 50 to 150 ° C. The reaction time is 10 minutes to 24 hours, preferably 0.5 to 12 hours.
[0033]
<Method of reacting aldehydes and ketones after reacting metal compound>
As a method for converting a terminal halogen into a hydroxyl group-containing substituent, an enolate anion is prepared by reacting a (meth) acrylic polymer having a terminal structure represented by the general formula (1) with a simple metal or an organometallic compound. Thereafter, a method of reacting aldehydes or ketones can also be used.
[0034]
Examples of the simple metal include alkali metals such as lithium, sodium and potassium, alkaline earth metals such as magnesium and calcium, aluminum and zinc. Among them, zinc is particularly preferable because the generated enolate anion hardly causes side reactions such as attacking or transferring other ester groups.
Specific examples of the organic metal compound include organic lithium, organic sodium, organic potassium, organic magnesium such as Grignard reagent, organic aluminum, organic zinc, and the like. In order to efficiently metallize halogen, it is preferable to use organic lithium and organic magnesium.
The amount of the metal simple substance or the organometallic compound to be used is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the (meth) acrylic polymer.
[0035]
The aldehydes and ketones are not particularly limited, and various types can be used. Aldehydes include, for example, formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and the like. Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, and benzophenone.
The amount of the aldehydes or ketones to be used is preferably 0.1 to 100 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the (meth) acrylic polymer.
[0036]
The method for introducing a hydroxyl-containing substituent using zinc and an aldehyde or ketone is a so-called Reformatsky reaction, which is a particularly preferred embodiment.
In this reaction, various solvents can be used, but an aprotic solvent (for example, tetrahydrofuran, diethyl ether, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, etc.) is preferable, and among them, tetrahydrofuran, diethyl ether, etc. Ether solvents are particularly preferred.
The reaction can be performed in the range of 0 to 100 ° C. The reaction time is 0.5 to 24 hours, preferably 1 to 12 hours.
[0037]
<Method of reacting a hydroxyl group-containing oxyanion>
As another method for producing a (meth) acrylic polymer having a hydroxyl group at a terminal, a (meth) acrylic polymer having a terminal structure represented by the general formula (1) is prepared by converting a hydroxyl group-containing oxy polymer represented by the general formula (3) to A method of reacting with an anion is exemplified.
M ⁺ O ⁻ -R ⁶ -OH (3)
(Where R ⁶ Is a divalent alkylene group having 1 to 20 carbon atoms, a divalent arylene group having 6 to 20 carbon atoms, or a divalent aralkylene group having 7 to 20 carbon atoms, even if it contains one or more ether bonds. Good, M ⁺ Is an alkali metal ion or a quaternary ammonium ion)
[0038]
M ⁺ Is a counter ion of an oxyanion, for example, an alkali metal ion such as a lithium ion, a sodium ion, or a potassium ion; tetramethylammonium ion, tetraethylammonium ion, trimethylbenzylammonium ion, trimethyldodecylammonium ion, tetrabutylammonium ion, And quaternary ammonium ions such as lydinium ions.
[0039]
R ⁶ Wherein the divalent alkylene group having 1 to 20 carbon atoms, the divalent arylene group having 6 to 20 carbon atoms, and the divalent aralkylene group having 7 to 20 carbon atoms each have at least one ether bond. More specifically, examples include those used in diol compounds that are precursors of the oxyanion of the following general formula (3).
[0040]
The oxyanion of the general formula (3) can be obtained by allowing a suitable base to act on a diol compound as a precursor thereof.
Examples of the precursor diol compound include, for example,
HO- (CH ₂ ) _n -OH (n is an integer of 2 to 20), HO-CH (CH ₃ ) CH ₂ OH, HO-CH (CH ₃ ) CH ₂ CH ₂ OH, HO-CH ₂ CH (CH ₃ ) CH ₂ -OH, HO-CH ₂ C (CH ₃ ) ₂ CH ₂ -OH, HO-CH ₂ C (CH ₃ ) (C ₂ H ₅ ) CH ₂ -OH, HO-CH ₂ C (C ₂ H ₅ ) ₂ CH ₂ -OH, CH ₃ CH ₂ CH (OH) CH ₂ -OH, CH ₃ CH (OH) CH (OH) CH ₃ , HO- (CH ₂ O) _n -H (n is an integer of 1 to 20), HO- (CH ₂ CH ₂ O) _n -H (n is an integer of 1 to 10), HO- (CH ₂ CH (CH ₃ ) O) _n -H (n is an integer of 1 to 6), o-, m-, p-HO-C ₆ H ₄ -OH, o-, m-, p-HO-C ₆ H ₄ − (CH ₂ ) _n OH (n is an integer of 1 to 14), o-, m-, p-HO- (CH ₂ ) _n -C ₆ H ₄ − (CH ₂ ) _m OH (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 ′ -Isopropylidene diphenol and the like.
[0041]
Of these, o-, m-, p-HO-C is preferred because it has a mild reactivity of the oxyanion, selectively substitutes the terminal halogen of the general formula (1), and is easily available. ₆ H ₄ -OH, o-, m-, p-HO-C ₆ H ₄ − (CH ₂ ) _n OH (n is an integer of 1 to 14) is preferred.
These diol compounds may be used in a molar ratio of 1 equivalent to the terminal of formula (1), but preferably 1 to 5 equivalents.
[0042]
Various bases are used to extract a proton from the above compound to obtain an oxyanion of the formula (3).
Examples of the base include sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, lithium ethoxide, sodium-tert-butoxide, potassium-tert-butoxide, sodium carbonate, potassium carbonate, and lithium carbonate. , Sodium hydrogencarbonate, sodium hydride, potassium hydride, methyllithium, ethyllithium, n-butyllithium, tert-butyllithium, lithium diisopropylamide, lithium hexamethyldisilazide and the like.
The amount of the base to be used is usually 0.5 to 3.0 equivalents, preferably 0.8 to 1.5 equivalents, based on the precursor diol compound.
[0043]
Examples of the solvent used when preparing the oxyanion of the formula (3) by the reaction between the above precursor and a base include tetrahydrofuran, dioxane, diethyl ether, dimethylformamide, hexamethylphosphoric triamide, ethanol, methanol, and isopropyl alcohol. , Tert-butyl alcohol and the like are used.
The reaction temperature is from -30 to 50C, preferably from 0C to room temperature. The reaction time is 0.5 to 12 hours, preferably 1 to 6 hours.
[0044]
Further, the solvent used in the method of reacting a hydroxyl group-containing oxyanion with the terminal of the (meth) acrylic polymer is not particularly limited, and examples thereof include polar aprotic solvents such as dimethyl sulfoxide, dimethylformamide, and dimethylacetamide. No.
The reaction temperature is from room temperature to 150 ° C, preferably 50 to 100 ° C. The reaction time is 0.5 to 24 hours, preferably 1 to 12 hours.
[0045]
<Method for reacting hydroxyl group-containing carboxylate anion>
The (meth) acrylic polymer having a terminal hydroxyl group can also be reacted with the (meth) acrylic polymer having a terminal structure of the formula (1) by the hydroxyl group-containing carboxylate anion represented by the general formula (4). Coalescence can be obtained.
M ⁺ OC ⁻ (O) -R ⁶ -OH (4)
(Where R ⁶ , M ⁺ Is the same as above)
[0046]
The carboxylate anion of the formula (4) can be prepared by allowing a suitable base to act on a hydroxyl group-containing carboxylic acid as a precursor thereof.
As the hydroxyl group-containing carboxylic acid as a precursor, for example,
HO ₂ C- (CH ₂ ) _n -OH (n is an integer of 1 to 20), HO ₂ C-CH (OH) CH ₃ , HO ₂ C-CH ₂ CH (OH) CH ₃ , O-, m-, p-HO ₂ CC ₆ H ₄ -OH, o-, m-, p-HO ₂ C- (CH ₂ ) _n -C ₆ H ₄ -OH, o-, m-, p-HO ₂ CC ₆ H ₄ − (CH ₂ ) _n -OH (n is an integer of 1 to 14), o-, m-, p-HO ₂ C- (CH ₂ ) _n -C ₆ H ₄ − (CH ₂ ) _m -OH (n and m are integers of 1 to 13 and n + m ≦ 14)
And the like.
[0047]
In order to extract a proton from the above compound to obtain a carboxylate anion of the formula (4), the bases and solvents exemplified in the preparation of the oxyanion of the formula (3) can be suitably used. The temperature and time are the same as in the preparation of the oxyanion. When a base acts on the above-mentioned hydroxyl group-containing carboxylic acid, protons of the carboxylic acid having higher acidity are extracted, and a carboxylate anion of the formula (4) is selectively obtained.
The amount of the base to be used is generally 0.5 to 3.0 equivalents, preferably 0.8 to 1.5 equivalents, relative to the hydroxyl group-containing carboxylic acid.
[0048]
The solvent used in the method of reacting the hydroxyl group-containing carboxylate anion with the terminal of the (meth) acrylic polymer is not particularly limited, and examples thereof include polar aprotic solvents such as dimethylsulfoxide, dimethylformamide, and dimethylacetamide. Can be
The reaction temperature is from room temperature to 150 ° C, preferably 50 to 100 ° C. The reaction time is 0.5 to 24 hours, preferably 1 to 12 hours.
[0049]
<Method of reacting a low polymerizable olefin compound having a hydroxyl group>
The (meth) acrylic polymer having a terminal structure represented by the formula (1) is reacted with a low-polymerizable olefin compound having a hydroxyl group represented by the general formula (5) to give a terminal having a hydroxyl group (meth). ) An acrylic polymer can be obtained.
[0050]
During and at the end of the atom transfer radical polymerization, when a low-polymerizable olefin compound having a hydroxyl group is added, almost one terminal is added to the terminal. As a result, the hydroxyl group of the olefin compound is introduced to the terminal of the polymer. Is done. The end point of the polymerization is a point when preferably 80% or more of the monomer has reacted, more preferably 90% or more, still more preferably 95% or more, and particularly preferably 99% or more.
[0051]
The low polymerizable olefin compound having a hydroxyl group is selected from the compounds represented by the general formula (5).
H ₂ C = C (R ⁸ ) -R ⁷ -OH (5)
(Where R ⁷ Is a divalent organic group having 1 to 20 carbon atoms, which may contain one or more ether bonds; ⁸ Is a hydrogen atom or a methyl group)
[0052]
In the general formula (5), R ⁷ As a specific example,
− (CH ₂ ) _n -(N is an integer of 1 to 20),
-CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, -C (CH ₃ ) ₂ -, -C (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) ₂ -, -CH ₂ CH (CH ₃ )-,
− (CH ₂ ) _n -O-CH ₂ -(N is an integer of 1 to 19),
-CH (CH ₃ ) -O-CH ₂ -, -CH (CH ₂ CH ₃ ) -O-CH ₂ -, -C (CH ₃ ) ₂ -O-CH ₂ -, -C (CH ₃ ) (CH ₂ CH ₃ ) -O-CH ₂ -, -C (CH ₂ CH ₃ ) ₂ -O-CH ₂ −,
− (CH ₂ ) _n -O- (CH ₂ ) _m -(M and n are integers from 1 to 19, provided that 2 ≦ m + n ≦ 20),
− (CH ₂ ) _n -C (O) O- (CH ₂ ) _m -(M and n are integers from 1 to 19, provided that 2 ≦ m + n ≦ 20),
− (CH ₂ ) _n -OC (O)-(CH ₂ ) _m -C (O) O- (CH ₂ ) _l -(L is an integer of 0 to 18, m and n are integers of 1 to 17, provided that 2 ≦ l + m + n ≦ 18),
− (CH ₂ ) _n -O-, m-, pC ₆ H ₄ −,
− (CH ₂ ) _n -O-, m-, pC ₆ H ₄ − (CH ₂ ) _m -(M is an integer of 0 to 13, n is an integer of 1 to 14, provided that 1 ≦ m + n ≦ 14),
− (CH ₂ ) _n -O-, m-, pC ₆ H ₄ -O- (CH ₂ ) _m -(M is an integer of 0 to 13, n is an integer of 1 to 14, provided that 1 ≦ m + n ≦ 14),
− (CH ₂ ) _n -O-, m-, pC ₆ H ₄ -O-CH (CH ₃ )-(N is an integer of 1 to 12),
− (CH ₂ ) _n -O-, m-, pC ₆ H ₄ -OC (CH ₃ ) ₂ -(N is an integer of 1 to 11),
− (CH ₂ ) _n -O-, m-, pC ₆ H ₄ -C (O) O- (CH ₂ ) _m -(M and n are integers of 1 to 12, provided that 2 ≦ m + n ≦ 13),
− (CH ₂ ) _n -OC (O) -o-, m-, pC ₆ H ₄ -C (O) O- (CH ₂ ) _m -(M and n are integers of 1 to 11, provided that 2 ≦ m + n ≦ 12),
− (CH ₂ ) _n -O-, m-, pC ₆ H ₄ -OC (O)-(CH ₂ ) _m -(M and n are integers of 1 to 12, provided that 2 ≦ m + n ≦ 13),
− (CH ₂ ) _n -C (O) O-o-, m-, pC ₆ H ₄ − (CH ₂ ) _m -(M and n are integers of 1 to 11, provided that 2 ≦ m + n ≦ 12),
And the like.
[0053]
In the general formula (5), R ⁸ Is a hydrogen atom or a methyl group, preferably a hydrogen atom.
[0054]
When a low polymerizable olefin compound having a hydroxyl group is allowed to react with the polymerization terminal, the reaction may be performed as it is. The attached compound may be used. Examples of the protecting group include an acetyl group, a silyl group, and an alkoxy group.
The amount of the low-polymerizable olefin compound having a hydroxyl group to be added is not particularly limited. Since these compounds do not have very high reactivity of the alkenyl group, it is preferable to increase the addition amount in order to increase the reaction rate. On the other hand, in order to reduce the cost, the addition amount is equal to the growth terminal. Closer is preferable, and it is necessary to optimize according to the situation.
[0055]
The solvent used in the reaction is not particularly limited, but may be, for example, a hydrocarbon solvent such as benzene or toluene; an ether solvent such as diethyl ether or tetrahydrofuran; which can be used during polymerization; methylene chloride, chloroform or the like. Halogenated hydrocarbon solvents; Ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol; acetonitrile, propionitrile, benzo Nitrile solvents such as nitrile; ester solvents such as ethyl acetate and butyl acetate; carbonate solvents such as ethylene carbonate and propylene carbonate; and the like, alone or in combination of two or more. Kill. In addition, an emulsion or supercritical fluid CO ₂ Polymerization can also be carried out in a system using as a medium. These solvents may be the same as or different from the solvents used during the polymerization. Among these, a nitrile solvent is preferable, and acetonitrile is more preferable, from the viewpoint of the effect of improving the catalyst stability. The reaction temperature is from room temperature to 200 ° C, preferably from 50 to 150 ° C. The reaction time is 10 minutes to 24 hours, preferably 0.5 to 12 hours.
[0056]
<Method of using an initiator having a hydroxyl group>
In the polymerization of (meth) acrylic monomers using an organic halide or a sulfonyl halide compound as an initiator and a metal complex having a central metal of Group 8, 9, 10, or 11 of the periodic table as a catalyst. When an organic halide or a sulfonyl halide compound 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 the formula (1) at another end can be obtained. . By converting the terminal halogen of the polymer thus obtained into a hydroxyl group-containing substituent, a (meth) acrylic polymer having hydroxyl groups at both ends can be produced.
[0057]
The organic halide having a hydroxyl group is not particularly limited, but preferably has a structure represented by the general formula (6) or (7).
R ⁹ R ¹⁰ C (X) -R ¹¹ -R ⁵ -OH (6)
(Where R ⁵ Is the same as above, R ⁹ , R ¹⁰ Is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a compound connected to each other at the other end; ¹¹ Is -C (O) O- (ester group), -C (O)-(keto group), or o-, m-, p-phenylene group, and X is chlorine, bromine or iodine.
HO-R ⁵ -C (R ⁹ ) (X) -R ¹¹ -R ¹⁰ (7)
(Where R ⁵ , R ⁹ , R ¹⁰ , R ¹¹ , X is the same as above)
[0058]
R ⁹ , R ¹⁰ The alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 20 carbon atoms, and the aralkyl group having 7 to 20 carbon atoms in ² And the same ones as described in the above. Further, what is mutually connected at the other end is R ⁹ And R ¹⁰ Represents a cycloalkyl group together with an adjacent carbon atom, and examples of the cycloalkyl group include cyclobutyl, cyclopentyl, and cyclohexyl.
[0059]
Specific examples of the compound represented by the general formula (6) include:
XCH ₂ C (O) O (CH ₂ ) _n -OH, H ₃ CC (H) (X) C (O) O (CH ₂ ) _n -OH, (H ₃ C) ₂ C (X) C (O) O (CH ₂ ) _n -OH, CH ₃ CH ₂ C (H) (X) C (O) O (CH ₂ ) _n -OH,
[0060]
Embedded image

[0061]
(Where X is chlorine, bromine or iodine, and n is an integer of 1 to 20)
XCH ₂ C (O) O (CH ₂ ) _n O (CH ₂ ) _m -OH, H ₃ CC (H) (X) C (O) O (CH ₂ ) _n O (CH ₂ ) _m -OH, (H ₃ C) ₂ C (X) C (O) O (CH ₂ ) _n O (CH ₂ ) _m -OH, CH ₃ CH ₂ C (H) (X) C (O) O (CH ₂ ) _n O (CH ₂ ) _m -OH,
[0062]
Embedded image

[0063]
(In the above formula, X is chlorine, bromine, or iodine, and n and m are integers of 1 to 20.)
o-, m-, p-XCH ₂ -C ₆ H ₄ − (CH ₂ ) _n -OH, o-, m-, p-CH ₃ C (H) (X) -C ₆ H ₄ − (CH ₂ ) _n -OH, o-, m-, p-CH ₃ CH ₂ C (H) (X) -C ₆ H ₄ − (CH ₂ ) _n -OH,
(Where X is chlorine, bromine or iodine, and n is an integer of 0 to 20)
o-, m-, p-XCH ₂ -C ₆ H ₄ − (CH ₂ ) _n -O- (CH ₂ ) _m -OH, o-, m-, p-CH ₃ C (H) (X) -C ₆ H ₄ − (CH ₂ ) _n -O- (CH ₂ ) _m -OH, o-, m-, p-CH ₃ CH ₂ C (H) (X) -C ₆ H ₄ − (CH ₂ ) _n -O- (CH ₂ ) _m -OH,
(In the above formula, X is chlorine, bromine, or iodine, n is an integer of 0 to 20, and m is an integer of 1 to 20.)
o-, m-, p-XCH ₂ -C ₆ H ₄ -O- (CH ₂ ) _n -O- (CH ₂ ) _m -OH, o-, m-, p-CH ₃ C (H) (X) -C ₆ H ₄ -O- (CH ₂ ) _n -O- (CH ₂ ) _m -OH, o-, m-, p-CH ₃ CH ₂ C (H) (X) -C ₆ H ₄ -O- (CH ₂ ) _n -O- (CH ₂ ) _m -OH,
(In the above formula, X is chlorine, bromine, or iodine, and n and m are integers of 1 to 20.)
And the like.
[0064]
Specific examples of the compound represented by the general formula (7) include:
HO-CH ₂ C (H) (X) -CO ₂ R, HO- (CH ₂ ) ₂ C (H) (X) -CO ₂ R, HO- (CH ₂ ) ₃ C (H) (X) -CO ₂ R, HO- (CH ₂ ) ₈ C (H) (X) -CO ₂ R,
(Where X is chlorine, bromine or iodine, R is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms)
HO-CH ₂ C (H) (X) -C ₆ H ₅ , HO- (CH ₂ ) ₂ C (H) (X) -C ₆ H ₅ , HO- (CH ₂ ) ₃ C (H) (X) -C ₆ H ₅ ,
(Where X is chlorine, bromine, or iodine)
And the like.
[0065]
If specific examples of the halogenated sulfonyl compound having a hydroxyl group,
o-, m-, p-HO- (CH ₂ ) _n -C ₆ H ₄ -SO ₂ X,
(Where X is chlorine, bromine or iodine, and n is an integer of 0 to 20)
o-, m-, p-HO- (CH ₂ ) _n -OC ₆ H ₄ -SO ₂ X,
(Where X is chlorine, bromine or iodine, and n is an integer of 1 to 20)
And so on.
[0066]
When a (meth) acrylic monomer is polymerized using an organic halide or a sulfonyl halide compound having a hydroxyl group 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). Is obtained. As a method of converting the terminal halogen into a hydroxyl group, any of the methods described above can be suitably used.
[0067]
When an organic halide or a sulfonyl halide compound having a hydroxyl group is used as an initiator, a polymer having one end having a hydroxyl group and the other end having a halogen end represented by the formula (1) is obtained. The (meth) acrylic polymer having a hydroxyl group at a terminal can also be obtained by coupling halogen terminals with a compound having a total of two or more identical or different functional groups capable of substituting a halogen of (1). Obtainable.
[0068]
The compound having two or more identical or different functional groups capable of substituting the terminal halogen represented by the formula (1) is not particularly limited, and examples thereof include polyols, polyamines, polycarboxylic acids, polythiols, and salts thereof. 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, glycerol, 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 alkali metal salts of the above polyol compounds; ethylenediamine, 1,3-diaminopropane , 1,2-diaminopropane, 1,4-di Minobutane, 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, 4,4-diaminocyclohexane, 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, α, α′-diamino-p-xylene, and alkali metal salts of the above polyamine compounds; oxalic acid , Malonic acid, methyl malonic acid, dimethyl malonic acid, succinic acid, methyl succinic acid, gluta Sulfonic 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 alkali metal salts of the above polycarboxylic acids; 1,2-ethanedithiol, 1,3 -Propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,5-pen Dithiol, 1,6-hexanedithiol, 1,7-heptanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 2-mercaptoethylether, p-xylene-α, α′-dithiol, 1,2 -Benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, and alkali metal salts and alkali metal sulfides (such as lithium sulfide, sodium sulfide, and potassium sulfide) of the polythiol compound.
In addition, as an alkali metal salt in the above, a lithium salt, a sodium salt, a potassium salt, etc. are mentioned.
The amount of the initiator to be used is preferably 0.03 to 100 parts by weight, more preferably 0.1 to 50 parts by weight, based on 100 parts by weight of the monomer.
[0069]
When using the above polyols, polyamines, polycarboxylic acids, and polythiols, a basic compound is used in combination to promote the substitution reaction. Specific examples thereof include lithium, sodium, potassium, sodium carbonate, potassium carbonate, and carbonate. Examples include sodium hydrogen, sodium methoxide, potassium methoxide, sodium tert-butoxide, potassium tert-butoxide, sodium hydride, potassium hydride and the like.
[0070]
Here, the (meth) acrylic polymer of the present invention obtained as described above is
It has at least one hydroxyl group at the terminal, and the oil resistance of the cured product is one of the main items of the immersion test of JIS K 6258 for land type No. 5 lubricating oil specified in JIS K 2215. More than the oil resistance of a cured product of a polymer in which the chain repeating unit is changed to butyl acrylate alone;
In the immersion test of JIS K 6258 for land type No. 5 lubricating oil specified in JIS K 2215, the mass change before and after immersion has at least one hydroxyl group at the terminal and the cured product has oil resistance. Having a rate of 50% or less;
In the immersion test of JIS K 6258 for lubricating oil of land type 3, No. 5 specified in JIS K 2215, the change in mass before and after immersion in the lubricating oil changed the main chain repeating unit to butyl acrylate alone. Less oil-hardened than cured polymer;
In the immersion test of JIS K 6258 for lubricating oil of land type 3 No. 5 specified in JIS K 2215, the change in volume before and after immersion in the lubricating oil changed the main chain repeating unit to butyl acrylate alone. It has oil resistance that it is less than the cured product of the polymer.
[0071]
The “polymer in which the main chain repeating unit is changed to butyl acrylate alone” in the present invention means that the crosslinked structure is essentially the same as the crosslinked structure of the (meth) acrylic polymer in the present invention, and its molecular weight is And a butyl acrylate homopolymer having a molecular weight distribution of 0.5 to 1.5 times the molecular weight and the molecular weight distribution of the (meth) acrylic polymer in the present invention, respectively.
[0072]
The number of hydroxyl groups of the (meth) acrylic polymer is not particularly limited, but in order to obtain a cured product having higher crosslinkability, it is one or more, preferably 1.2 or more, more preferably one or more on average. .5 or more.
The position of the hydroxyl group of the (meth) acrylic polymer is not particularly limited as long as at least one hydroxyl group is at the terminal. In addition, a hydroxyl group may be present in the main chain, but when a crosslinked cured product requires rubber elasticity, it is preferable to have a hydroxyl group only at the terminal.
[0073]
The term “land type No. 3 lubricating oil specified by JIS K 2215” in the present invention is a lubricating oil for a land internal combustion engine to which an antioxidant and a detergent are added, and has a flash point of 200 ° C. or higher and an Viscosity 16.3mm ² / S or more and 21.9 mm ² / S, a viscosity index of 85 or more, and a pour point of -5 ° C or less.
The “immersion test of JIS K 6258” in the present invention means that the entire surface of the cured product of the (meth) acrylic polymer is immersed in the lubricating oil, and the dimensions, mass, volume before and after immersion, It measures changes in mechanical properties such as surface area and tensile strength.
[0074]
The phrase “excellent in oil resistance” means that the rate of change in mass, the rate of change in volume, the rate of change in mechanical properties, etc. before and after immersion are smaller.
In the immersion test, the rate of change in mass before and after immersion is preferably 50% or less, more preferably 40% or less, and even more preferably 30% or less.
The rate of change in volume and the rate of change in mechanical properties before and after immersion are each preferably 50% or less, more preferably 40% or less, and even more preferably 30% or less.
As described above, the (meth) acrylic polymer of the present invention having the above properties is particularly excellent in oil resistance.
[0075]
<< Curable composition >>
From the (meth) acrylic polymer having at least one hydroxyl group at the terminal obtained by the above-mentioned various methods, a curable composition containing this as a main component can be obtained. The curable composition of the present invention comprises the following two components: (A) a (meth) acrylic polymer having at least one hydroxyl group at a terminal, produced by atom transfer radical polymerization, and (B) a hydroxyl group. A compound having two or more functional groups is an essential component.
[0076]
The (meth) acrylic polymer having at least one terminal hydroxyl group of the component (A) may be used alone or in combination of two or more.
The molecular weight is not particularly limited, but is preferably in the range of 500 to 1,000,000. If it is less than 500, the intrinsic properties of the (meth) acrylic polymer tend to be hardly exhibited, and if it exceeds 1,000,000, the viscosity becomes high or the solubility becomes low, and the workability decreases. It tends to be easier.
[0077]
The compound having two or more functional groups capable of reacting with a hydroxyl group as the component (B) is not particularly limited. For example, a polyvalent isocyanate compound having two or more isocyanate groups in one molecule, an aminoplast resin And compounds having two or more carboxyl groups in one molecule. Preferably, it is a polyvalent isocyanate compound.
[0078]
As the polyvalent isocyanate compound having two or more isocyanate groups in one molecule, conventionally known polyvalent isocyanate compounds, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4 '-Diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, meta-xylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, and B An isocyanate compound such as -45; a bullet polyisocyanate compound such as Sumidur N (manufactured by Sumitomo Bayer Urethane Co.); Desmodur I L, HL (manufactured by Bayer AG) and Coronate EH (manufactured by Nippon Polyurethane Industry Co., Ltd.); polyisocyanate compounds having an isocyanurate ring; Adduct polyisocyanate compound and the like. Further, a blocked isocyanate may be used. These may be used alone or in combination of two or more.
[0079]
The mixing ratio of the polymer having a terminal hydroxyl group to the compound having two or more isocyanate groups is not particularly limited. For example, the isocyanate group and the hydroxyl group of the (meth) acrylic polymer having a terminal hydroxyl group may be used. The ratio (NCO / OH (molar ratio)) is preferably 0.5 to 3.0, and more preferably 0.8 to 2.0.
[0080]
In order to accelerate the curing reaction between the (meth) acrylic polymer having a hydroxyl group at a terminal and a compound having two or more isocyanate groups, which is a curable composition of the present invention, an organic tin compound or A known catalyst such as a tertiary amine may be added.
[0081]
Examples of the organotin compound include tin octylate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, dibutyltin dimaleate, and dioctyltin thiocarboxylate.
[0082]
Examples of the tertiary amine catalyst include triethylamine, N, N-dimethylcyclohexylamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropane1,3 -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.
[0083]
The aminoplast resin used as the component (B) in the curable composition of the present invention is not particularly limited, and is an addition reaction product of melamine and formaldehyde (a methylol compound), a low-condensation product of melamine and formaldehyde, and an alkyl thereof. Examples include etherified products, urea resins, and the like. These may be used alone or in combination of two or more. A known catalyst such as paratoluenesulfonic acid and benzenesulfonic acid may be added for the purpose of accelerating the curing reaction of the aminoplast resin with the (meth) acrylic polymer having a hydroxyl group at the terminal.
[0084]
The compound having two or more carboxyl groups in one molecule used as the component (B) in the curable composition of the present invention is not particularly limited, and examples thereof include oxalic acid, malonic acid, succinic acid, and glutaric acid. Polyfunctional carboxylic acids such as adipic acid, phthalic acid, phthalic anhydride, terephthalic acid, trimellitic acid, pyromellitic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid or anhydrides thereof, and halogens thereof And the like. These may be used alone or in combination of two or more.
[0085]
By mixing and curing the two components (A) and (B) of the curable composition of the present invention and, if necessary, a curing catalyst, a uniform cured product having excellent deep curability can be obtained.
Examples of the curing catalyst include acidic catalysts such as sulfuric acid, methanesulfonic acid, and p-toluenesulfonic acid; scandium, yttrium, zirconium, hafnium, vanadium, titanium metal halides, nitrates, carboxylate salts, alcoholates, and acetylacetone. And a metal catalyst such as a type complex.
The amount of each component is preferably 10 to 200 parts by weight of the component (B) and 0 to 10 parts by weight of the curing catalyst with respect to 100 parts by weight of the component (A), and more preferably 80 to 100 parts by weight of the component (B). 120 parts by weight and 0.1 to 5 parts by weight of the curing catalyst.
[0086]
The curing conditions are not particularly limited, but the curing temperature is generally 0 ° C to 150 ° C, preferably 20 ° C to 100 ° C. The curing time is 0.5 hour to 1 week, preferably 1 to 24 hours.
The properties of the cured product depend on the main chain skeleton and molecular weight of the polymer of the component (A) and the curing agent of the component (B), but can be widely prepared from rubber to resin.
[0087]
The cured product obtained from the above composition is not limited, but specific applications include sealing materials such as an elastic sealing material for buildings and a sealing material for double-layered glass, and electric / electrical materials such as a solar cell back surface sealing material. Electronic component materials, electrical insulating materials such as insulating coating materials for electric wires and cables, adhesives, adhesives, elastic adhesives, paints, powder coatings, coating materials, foams, potting agents for electric and electronic devices, films, gaskets, and notes It can be used for various purposes such as a mold material, various molding materials, a netted glass, a rustproof / waterproof sealing material for an end face (cut portion) of a laminated glass, and the like.
[0088]
【Example】
Hereinafter, specific examples of the present invention will be described together with comparative examples, but the present invention is not limited to the following examples.
In the following Examples and Comparative Examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.
In the following examples, “number average molecular weight” and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)” were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, a GPC column filled with a crosslinked polystyrene gel (shodex GPC K-804; manufactured by Showa Denko KK) was used, and chloroform was used as a GPC solvent.
[0089]
(Production Example 1)
CuBr (1.01 g, 7 mmol) was charged into a 300 mL flask equipped with a reflux tube and a stirrer, and the inside of the reaction vessel was purged with nitrogen. Acetonitrile (11.5 mL) was added, and the mixture was stirred at 70 ° C. for 15 minutes in an oil bath. To this, butyl acrylate (33.6 mL, 234 mmol), ethyl acrylate (46.7 mL, 431 mmol), 2-methoxyethyl acrylate (34.9 mL, 272 mmol), diethyl 2,5-dibromoadipate (2.81 g) 7.8 mmol) and pentamethyldiethylenetriamine (0.05 mL, 0.04 g, 0.2 mmol) (hereinafter referred to as triamine) were added to initiate the reaction. While heating and stirring at 70 ° C., triamine (0.20 mL, 0.16 g, 0.9 mmol) was added on the way. 180 minutes after the start of the reaction, 5-hexen-1-ol (14.1 mL, 11.7 g, 117 mmol) and triamine (0.49 mL, 0.41 g, 2.3 mmol) were added at a monomer conversion of 98%. Subsequently, the mixture was heated and stirred at 80 ° C. for 480 minutes.
[0090]
After evaporating the volatile components of the reaction mixture under reduced pressure, the reaction mixture was diluted with toluene (500 g), and the solid substance was removed by filtration. Subsequently, acidic aluminum silicate (5 g, manufactured by Kyowa Chemical Co., Ltd., Kyoward 700SL) and basic aluminum silicate (5 g, manufactured by Kyowa Chemical Co., Ltd., Kyoward 500SH) were charged, and heated and stirred at 100 ° C. for 4 hours under a nitrogen stream. After the aluminum silicate was removed by filtration, the toluene in the filtrate was distilled off under reduced pressure to obtain a copolymer of hydroxyl-terminated copolymer / hydroxy-terminated poly (butyl acrylate, ethyl acrylate, methoxyethyl acrylate): heavy Merged [1]｝ was obtained. The number average molecular weight of the obtained copolymer was 17,800 by GPC measurement (in terms of polystyrene), and the molecular weight distribution was 1.16. The average number of hydroxyl groups introduced per copolymer molecule ¹ It was about 2.5 as determined by 1 H-NMR analysis.
[0091]
(Production Example 2)
Hydroxyl-terminated butyl acrylate polymer (Polymer [2]) in the same manner as in Production Example 1 except that only butyl acrylate was used as the acrylic acid monomer, and ethyl acrylate and 2-methoxyethyl acrylate were not added. Got. The number average molecular weight of the obtained polymer was 25,900 by GPC measurement (in terms of polystyrene), and the molecular weight distribution was 1.23. The average number of hydroxyl groups introduced per polymer molecule ¹ It was 2.7 as determined by 1 H-NMR analysis.
[0092]
(Example 1)
To 100 parts of the polymer [1] obtained in Production Example 1, 12 parts of isophorone diisocyanate, 2.8 parts of 1,4-butanediol and 0.8 part of trimethylolpropane were mixed, and a tetravalent Sn catalyst (dibutyl Using 0.1 part of tin dilaurate), the composition was cured and cured at 50 ° C. for 12 hours and then at 90 ° C. for 6 hours to obtain a sheet-shaped cured product.
[0093]
(Comparative Example 1)
A sheet-like cured product was produced in the same manner as in Example 1 except that the polymer [2] obtained in Production Example 2 was used instead of the polymer [1] used in Example 1.
[0094]
(Evaluation 1) Oil resistance
For each of Example 1 and Comparative Example 1, the cured product after curing was evaluated for oil resistance based on an immersion test specified in JIS K6258. Commercially available engine oil (trade name: GEOMA, SJ grade, 5W-30: manufactured by JOMO) is used as the lubricating oil for land type 3 and 5 specified in JIS K 2215. C. for 72 hours. As a result, the mass change was 26% in the cured product of the polymer [2] obtained in Comparative Example 1, whereas the cured product of the polymer [1] obtained in Example 1 was 6%. %, And the copolymer of hydroxyl group-terminated poly (butyl acrylate, ethyl acrylate, methoxyethyl acrylate) showed better oil resistance than the cured product of butyl acrylate homopolymer.
[0095]
【The invention's effect】
The present invention has at least one hydroxyl group at the terminal, and the oil resistance of the cured product is determined by any one of the immersion tests of JIS K 6258 for land type 3 lubricating oil specified in JIS K 2215. A (meth) acrylic polymer produced by atom transfer radical polymerization, which exceeds the oil resistance of a cured product of a polymer in which the repeating unit of the main chain is changed to butyl acrylate alone, and contains the polymer It is made of a curable composition, has improved oil resistance, and has excellent heat resistance and flexibility.

Claims (16)

It has at least one hydroxyl group at the terminal, and the oil resistance of the cured product is one of the items of the immersion test of JIS K 6258 for lubricating oil of land type 3 No. 5 specified in JIS K 2215. A (meth) acrylic polymer produced by atom transfer radical polymerization, characterized by exceeding the oil resistance of a cured product of a polymer in which the chain repeating unit is changed to butyl acrylate alone. In the immersion test of JIS K 6258 for land type No. 5 lubricating oil specified in JIS K 2215, the mass change before and after immersion has at least one hydroxyl group at the terminal and the cured product has oil resistance. A (meth) acrylic polymer produced by atom transfer radical polymerization, wherein the ratio is 50% or less. In the immersion test of JIS K 6258 for land type 3 lubricating oil specified in JIS K 2215, the change in mass before and after immersion in lubricating oil changed the main chain repeating unit to butyl acrylate alone. The (meth) acrylic polymer according to claim 1 or 2, which has less oil resistance than a cured product of the polymer. In the immersion test of JIS K 6258 for land type No. 5 lubricating oil specified in JIS K 2215, the change in volume before and after immersion in lubricating oil changed the main chain repeating unit to butyl acrylate alone. The (meth) acrylic polymer according to any one of claims 1 to 3, which has less oil resistance than a cured product of the polymer. The (meth) acrylic polymer according to any one of claims 1 to 4, having a molecular weight distribution of less than 1.8. The (meth) acrylic polymer according to any one of claims 1 to 5, wherein the main chain is an acrylic polymer. The (meth) acrylic polymer according to claim 6, wherein the main chain is an acrylic ester polymer. The (meth) acrylic polymer according to claim 6, wherein at least one of ethyl acrylate and alkoxyalkyl acrylate is used as an essential constituent unit of the acrylic polymer. The (meth) acrylic polymer according to claim 8, wherein the alkoxyalkyl acrylate is 2-methoxyethyl acrylate and / or 2-ethoxyethyl acrylate. An atom transfer radical polymerization method using an organic halide or a sulfonyl halide compound as an initiator and a metal complex having a central metal of Group 8, 9, 10, or 11 of the periodic table as a catalyst (meth) Claims characterized by being obtained by converting a halogen of a (meth) acrylic polymer having a terminal structure represented by the general formula (1) obtained by polymerizing an acrylic monomer into a hydroxyl group-containing substituent. Item 10. The (meth) acrylic polymer according to any one of Items 1 to 9.
—CH ₂ —C (R ¹ ) (CO ₂ R ² ) (X) (1)
(Wherein, R ¹ is a hydrogen atom or a methyl group, 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 atom transfer radical polymerization method using an organic halide or a sulfonyl halide compound as an initiator and a metal complex having a central metal of Group 8, 9, 10, or 11 of the periodic table as a catalyst (meth) A (meth) acrylic polymer having a terminal structure represented by the general formula (1) is produced by polymerizing an acrylic monomer, and further a compound having both a polymerizable alkenyl group and a hydroxyl group represented by the general formula (2) The (meth) acrylic polymer according to claim 10, which is obtained by reacting with (A).
^{_{H 2 C = C (R 3}} ) -R 4 -R 5 -OH (2)
(Wherein, R ³ is a hydrogen atom 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 a group having 1 carbon atom. ~ 20 divalent organic groups which may contain one or more ether linkages) A metal (meth) acrylic polymer having a terminal structure represented by the general formula (1) is reacted with a metal simple substance or an organometallic compound to prepare an enolate anion, and then reacted with an aldehyde or a ketone. The (meth) acrylic polymer according to claim 10, characterized in that: A (meth) acrylic polymer having a terminal structure represented by the general formula (1) is obtained by reacting with a hydroxyl group-containing oxyanion represented by the general formula (3) or a hydroxyl group-containing carboxylate anion represented by the formula (4). The (meth) acrylic polymer according to claim 10, characterized in that:
^{M + O - -R 6 -OH (} 3)
(Wherein, R ⁶ is a divalent alkylene group having 1 to 20 carbon atoms, a divalent arylene group having 6 to 20 carbon atoms, or a divalent aralkylene group having 7 to 20 carbon atoms, and one or more ethers M ⁺ is an alkali metal ion or a quaternary ammonium ion, which may contain a bond)
^{M + O - C (O)} -R 6 -OH (4)
(Wherein R ⁶ and M ⁺ are the same as above) It is obtained by reacting a (meth) acrylic polymer having a terminal structure represented by the general formula (1) with a low polymerizable olefin compound having a hydroxyl group represented by the general formula (5). 11. The (meth) acrylic polymer according to 10.
^{_{H 2 C = C (R 8}} ) -R 7 -OH (5)
(Wherein, R ⁷ is a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds, and R ⁸ is a hydrogen atom or a methyl group) The following two components: (A) a (meth) acrylic polymer according to any one of claims 1 to 14, which has at least one hydroxyl group at a terminal and is produced by atom transfer radical polymerization, and (B) a hydroxyl group. A curable composition comprising, as an essential component, a compound having at least two reactive functional groups. The curable composition according to claim 15, wherein the compound (B) having at least two functional groups capable of reacting with a hydroxyl group is a polyvalent isocyanate compound.