JP4098890B2 - Polymers and applications - Google Patents

Description

【００２６】
【化２】

【００２７】
等があげられる。
この重合において用いられるビニル系モノマーとしては特に制約はなく、既に例示したものをすべて好適に用いることができる。
この重合は無溶媒又は各種の溶媒中で行うことができる。上記溶媒としては、例えば、ベンゼン、トルエン等の炭化水素系溶媒；ジエチルエーテル、テトラヒドロフラン、ジフェニルエーテル、アニソール、ジメトキシベンゼン等のエーテル系溶媒；塩化メチレン、クロロホルム、クロロベンゼン等のハロゲン化炭化水素系溶媒；アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン系溶媒；メタノール、エタノール、プロパノール、イソプロパノール、ｎ−ブチルアルコール、ｔｅｒｔ−ブチルアルコール等のアルコール系溶媒；アセトニトリル、プロピオニトリル、ベンゾニトリル等のニトリル系溶媒；酢酸エチル、酢酸ブチル等のエステル系溶媒；エチレンカーボネート、プロピレンカーボネート等のカーボネート系溶媒等が挙げられる。これらは、単独又は２種以上を混合して用いることができる。また、エマルジョン系もしくは超臨界流体ＣＯ２を媒体とする系においても重合を行うことができる。
【００２８】
この重合は、室温〜２００℃の範囲で行うことができ、好ましくは、５０〜１５０℃の範囲である。
末端官能基の導入
重合体の末端に架橋性シリル基、あるいは、アルケニル基、あるいは、水酸基を導入する方法としては、限定はされないが、原子移動ラジカル重合の開始剤として重合を開始する官能基以外の官能基を有する有機ハロゲン化物又はハロゲン化スルホニル化合物を用いる方法、又は、重合体の末端のハロゲン基等の官能基を変換する方法、そして、これらの方法の組み合わせが挙げられる。
【００２９】
原子移動ラジカル重合において、重合を開始する官能基以外の官能基を有する有機ハロゲン化物又はハロゲン化スルホニル化合物を開始剤として用いれば、片末端に官能基を有し、他の末端にハロゲン基を有するビニル系重合体が得られる。このようにして得られる重合体の停止末端のハロゲン基を必要な官能基に変換すれば、両末端に官能基を有するビニル系重合体を得ることができる。その変換方法としては、後に記述する方法を使用することができる。また、重合体の停止末端のハロゲン基を置換できる、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、両末端に官能基を有するビニル系重合体を得ることができる。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、アルカリ金属硫化物等が好ましい。
【００３０】
上記の官能基を有する有機ハロゲン化物又はハロゲン化スルホニル化合物に関して、その官能基としては、アルケニル基、架橋性シリル基、ヒドロキシル基、エポキシ基、アミノ基、アミド基等が挙げられる。
アルケニル基を有する有機ハロゲン化物としては限定されず、例えば、一般式１３に示す構造を有するものが例示される。
Ｒ¹⁰Ｒ¹¹Ｃ（Ｘ）−Ｒ¹²−Ｒ¹³−Ｃ（Ｒ³）＝ＣＨ₂ （１３）
（式中、Ｒ³は水素、またはメチル基、Ｒ¹⁰、Ｒ¹¹は水素、または、炭素数１〜２０の１価のアルキル基、アリール基、またはアラルキル、または他端において相互に連結したもの、Ｒ¹²は、−Ｃ（Ｏ）Ｏ−（エステル基）、−Ｃ（Ｏ）−（ケト基）、またはｏ−，ｍ−，ｐ−フェニレン基、Ｒ¹³は直接結合、または炭素数１〜２０の２価の有機基で１個以上のエーテル結合を含んでいても良い、Ｘは塩素、臭素、またはヨウ素）
置換基Ｒ¹⁰、Ｒ¹¹の具体例としては、水素、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ブチル基、ペンチル基、ヘキシル基等が挙げられる。Ｒ¹⁰とＲ¹¹は他端において連結して環状骨格を形成していてもよい。
【００３１】
一般式１３で示される、アルケニル基を有する有機ハロゲン化物の具体例としては、
ＸＣＨ₂Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＣＨ＝ＣＨ₂、Ｈ₃ＣＣ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＣＨ＝ＣＨ₂、（Ｈ₃Ｃ）₂Ｃ（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＣＨ＝ＣＨ₂、ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＣＨ＝ＣＨ₂、
【００３２】
【化３】

【００３３】
（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）ＸＣＨ₂Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_mＣＨ＝ＣＨ₂、Ｈ₃ＣＣ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_mＣＨ＝ＣＨ₂、（Ｈ₃Ｃ）₂Ｃ（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_mＣＨ＝ＣＨ₂、ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_mＣＨ＝ＣＨ₂、
【００３４】
【化４】

【００３５】
（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、ｍは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ₂−Ｃ₆Ｈ₄−（ＣＨ₂）_n−ＣＨ＝ＣＨ₂、ｏ，ｍ，ｐ−ＣＨ₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−（ＣＨ₂）_n−ＣＨ＝ＣＨ₂、ｏ，ｍ，ｐ−ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−（ＣＨ₂）_n−ＣＨ＝ＣＨ₂、
（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−ＣＨ＝ＣＨ₂、ｏ，ｍ，ｐ−ＣＨ₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_m−ＣＨ＝ＣＨ₂、ｏ，ｍ，ｐ−ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_mＣＨ＝ＣＨ₂、
（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、ｍは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ₂−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）_n−ＣＨ＝ＣＨ₂、ｏ，ｍ，ｐ−ＣＨ₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）_n−ＣＨ＝ＣＨ₂、ｏ，ｍ，ｐ−ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）_n−ＣＨ＝ＣＨ₂、
（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−Ｏ−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_m−ＣＨ＝ＣＨ₂、ｏ，ｍ，ｐ−ＣＨ₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_m−ＣＨ＝ＣＨ₂、ｏ，ｍ，ｐ−ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_m−ＣＨ＝ＣＨ₂、
（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、ｍは０〜２０の整数）
アルケニル基を有する有機ハロゲン化物としてはさらに一般式１４で示される化合物が挙げられる。
Ｈ₂Ｃ＝Ｃ（Ｒ₃）−Ｒ¹³−Ｃ（Ｒ¹⁰）（Ｘ）−Ｒ¹⁴−Ｒ¹¹ （１４）
（式中、Ｒ³、Ｒ¹⁰、Ｒ¹¹、Ｒ¹³、Ｘは上記に同じ、Ｒ¹⁴は、直接結合、−Ｃ（Ｏ）Ｏ−（エステル基）、−Ｃ（Ｏ）−（ケト基）、または、ｏ−，ｍ−，ｐ−フェニレン基を表す）
Ｒ¹³は直接結合、または炭素数１〜２０の２価の有機基（１個以上のエーテル結合を含んでいても良い）であるが、直接結合である場合は、ハロゲンの結合している炭素にビニル基が結合しており、ハロゲン化アリル化物である。この場合は、隣接ビニル基によって炭素−ハロゲン結合が活性化されているので、Ｒ¹⁴としてＣ（Ｏ）Ｏ基やフェニレン基等を有する必要は必ずしもなく、直接結合であってもよい。Ｒ¹³が直接結合でない場合は、炭素−ハロゲン結合を活性化するために、Ｒ¹⁴としてはＣ（Ｏ）Ｏ基、Ｃ（Ｏ）基、フェニレン基が好ましい。
【００３６】
一般式１４の化合物を具体的に例示するならば、
ＣＨ₂＝ＣＨＣＨ₂Ｘ、ＣＨ₂＝Ｃ（ＣＨ₃）ＣＨ₂Ｘ、ＣＨ₂＝ＣＨＣ（Ｈ）（Ｘ）ＣＨ₃、ＣＨ₂＝Ｃ（ＣＨ₃）Ｃ（Ｈ）（Ｘ）ＣＨ₃、ＣＨ₂＝ＣＨＣ（Ｘ）（ＣＨ₃）₂、ＣＨ₂＝ＣＨＣ（Ｈ）（Ｘ）Ｃ₂Ｈ₅、ＣＨ₂＝ＣＨＣ（Ｈ）（Ｘ）ＣＨ（ＣＨ₃）₂、ＣＨ₂＝ＣＨＣ（Ｈ）（Ｘ）Ｃ₆Ｈ₅、ＣＨ₂＝ＣＨＣ（Ｈ）（Ｘ）ＣＨ₂Ｃ₆Ｈ₅、ＣＨ₂＝ＣＨＣＨ₂Ｃ（Ｈ）（Ｘ）−ＣＯ₂Ｒ、ＣＨ₂＝ＣＨ（ＣＨ₂）₂Ｃ（Ｈ）（Ｘ）−ＣＯ₂Ｒ、ＣＨ₂＝ＣＨ（ＣＨ₂）₃Ｃ（Ｈ）（Ｘ）−ＣＯ₂Ｒ、ＣＨ₂＝ＣＨ（ＣＨ₂）₈Ｃ（Ｈ）（Ｘ）−ＣＯ₂Ｒ、ＣＨ₂＝ＣＨＣＨ₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₅、ＣＨ₂＝ＣＨ（ＣＨ₂）₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₅、ＣＨ₂＝ＣＨ（ＣＨ₂）₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₅、
（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）
等を挙げることができる。
【００３７】
アルケニル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−ＣＨ₂＝ＣＨ−（ＣＨ₂）_n−Ｃ₆Ｈ₄−ＳＯ₂Ｘ、ｏ−，ｍ−，ｐ−ＣＨ₂＝ＣＨ−（ＣＨ₂）_n−Ｏ−Ｃ₆Ｈ₄−ＳＯ₂Ｘ、
（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）等である。
【００３８】
架橋性シリル基を有する有機ハロゲン化物としては特に限定されず、例えば一般式１５に示す構造を有するものが例示される。
Ｒ¹⁰Ｒ¹¹Ｃ（Ｘ）−Ｒ¹²−Ｒ¹³−Ｃ（Ｈ）（Ｒ³）ＣＨ₂−［Ｓｉ（Ｒ¹⁵）_2-b（Ｙ）_bＯ］_m−Ｓｉ（Ｒ¹⁶）_3-a（Ｙ）_a （１５）
（式中、Ｒ³、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｘは上記に同じ、Ｒ¹⁵、Ｒ¹⁶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、Ｒ⁹またはＲ¹⁰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）
一般式１５の化合物を具体的に例示するならば、
ＸＣＨ₂Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＳｉ（ＯＣＨ₃）₃、ＣＨ₃Ｃ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＳｉ（ＯＣＨ₃）₃、（ＣＨ₃）₂Ｃ（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＳｉ（ＯＣＨ₃）₃、ＸＣＨ₂Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＳｉ（ＣＨ₃）（ＯＣＨ₃）₂、ＣＨ₃Ｃ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＳｉ（ＣＨ₃）（ＯＣＨ₃）₂、（ＣＨ₃）₂Ｃ（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＳｉ（ＣＨ₃）（ＯＣＨ₃）₂、
（上記の各式において、Ｘは塩素、臭素、ヨウ素、ｎは０〜２０の整数、）
ＸＣＨ₂Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_mＳｉ（ＯＣＨ₃）₃、Ｈ₃ＣＣ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_mＳｉ（ＯＣＨ₃）₃、（Ｈ₃Ｃ）₂Ｃ（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_mＳｉ（ＯＣＨ₃）₃、ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_mＳｉ（ＯＣＨ₃）₃、ＸＣＨ₂Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_mＳｉ（ＣＨ₃）（ＯＣＨ₃）₂、Ｈ₃ＣＣ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_m−Ｓｉ（ＣＨ₃）（ＯＣＨ₃）₂、（Ｈ₃Ｃ）₂Ｃ（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_m−Ｓｉ（ＣＨ₃）（ＯＣＨ₃）₂、ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_m−Ｓｉ（ＣＨ₃）（ＯＣＨ₃）₂、
（上記の各式において、Ｘは塩素、臭素、ヨウ素、ｎは１〜２０の整数、ｍは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ₂−Ｃ₆Ｈ₄−（ＣＨ₂）₂Ｓｉ（ＯＣＨ₃）₃、ｏ，ｍ，ｐ−ＣＨ₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−（ＣＨ₂）₂Ｓｉ（ＯＣＨ₃）₃、ｏ，ｍ，ｐ−ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−（ＣＨ₂）₂Ｓｉ（ＯＣＨ₃）₃、ｏ，ｍ，ｐ−ＸＣＨ₂−Ｃ₆Ｈ₄−（ＣＨ₂）₃Ｓｉ（ＯＣＨ₃）₃、ｏ，ｍ，ｐ−ＣＨ₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−（ＣＨ₂）₃Ｓｉ（ＯＣＨ₃）₃、ｏ，ｍ，ｐ−ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−（ＣＨ₂）₃Ｓｉ（ＯＣＨ₃）₃、ｏ，ｍ，ｐ−ＸＣＨ₂−Ｃ₆Ｈ₄−（ＣＨ₂）₂−Ｏ−（ＣＨ₂）₃Ｓｉ（ＯＣＨ₃）₃、ｏ，ｍ，ｐ−ＣＨ₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−（ＣＨ₂）₂−Ｏ−（ＣＨ₂）₃Ｓｉ（ＯＣＨ₃）₃、ｏ，ｍ，ｐ−ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−（ＣＨ₂）₂−Ｏ−（ＣＨ₂）₃Ｓｉ（ＯＣＨ₃）₃、ｏ，ｍ，ｐ−ＸＣＨ₂−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）₃Ｓｉ（ＯＣＨ₃）₃、ｏ，ｍ，ｐ−ＣＨ₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）₃Ｓｉ（ＯＣＨ₃）₃、ｏ，ｍ，ｐ−ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）₃−Ｓｉ（ＯＣＨ₃）₃、ｏ，ｍ，ｐ−ＸＣＨ₂−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）₂−Ｏ−（ＣＨ₂）₃−Ｓｉ（ＯＣＨ₃）₃、ｏ，ｍ，ｐ−ＣＨ₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）₂−Ｏ−（ＣＨ₂）₃Ｓｉ（ＯＣＨ₃）₃、ｏ，ｍ，ｐ−ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）₂−Ｏ−（ＣＨ₂）₃Ｓｉ（ＯＣＨ₃）₃、
（上記の各式において、Ｘは塩素、臭素、またはヨウ素）
等が挙げられる。
【００３９】
上記架橋性シリル基を有する有機ハロゲン化物としてはさらに、一般式１６で示される構造を有するものが例示される。
（Ｒ¹⁶）_3-a（Ｙ）_aＳｉ−［ＯＳｉ（Ｒ¹⁵）_2-b（Ｙ）_b］_m−ＣＨ₂−Ｃ（Ｈ）（Ｒ³）−Ｒ¹³−Ｃ（Ｒ¹⁰）（Ｘ）−Ｒ¹⁴−Ｒ¹¹ （１６）
（式中、Ｒ³、Ｒ¹⁰、Ｒ¹¹、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶、ａ、ｂ、ｍ、Ｘ、Ｙは上記に同じ）
このような化合物を具体的に例示するならば、
（ＣＨ₃Ｏ）₃ＳｉＣＨ₂ＣＨ₂Ｃ（Ｈ）（Ｘ）Ｃ₆Ｈ₅、（ＣＨ₃Ｏ）₂（ＣＨ₃）ＳｉＣＨ₂ＣＨ₂Ｃ（Ｈ）（Ｘ）Ｃ₆Ｈ₅、（ＣＨ₃Ｏ）₃Ｓｉ（ＣＨ₂）₂Ｃ（Ｈ）（Ｘ）−ＣＯ₂Ｒ、（ＣＨ₃Ｏ）₂（ＣＨ₃）Ｓｉ（ＣＨ₂）₂Ｃ（Ｈ）（Ｘ）−ＣＯ₂Ｒ、（ＣＨ₃Ｏ）₃Ｓｉ（ＣＨ₂）₃Ｃ（Ｈ）（Ｘ）−ＣＯ₂Ｒ、（ＣＨ₃Ｏ）₂（ＣＨ₃）Ｓｉ（ＣＨ₂）₃Ｃ（Ｈ）（Ｘ）−ＣＯ₂Ｒ、（ＣＨ₃Ｏ）₃Ｓｉ（ＣＨ₂）₄Ｃ（Ｈ）（Ｘ）−ＣＯ₂Ｒ、（ＣＨ₃Ｏ）₂（ＣＨ３）Ｓｉ（ＣＨ₂）₄Ｃ（Ｈ）（Ｘ）−ＣＯ₂Ｒ、（ＣＨ₃Ｏ）₃Ｓｉ（ＣＨ₂）₉Ｃ（Ｈ）（Ｘ）−ＣＯ₂Ｒ、（ＣＨ₃Ｏ）₂（ＣＨ₃）Ｓｉ（ＣＨ₂）₉Ｃ（Ｈ）（Ｘ）−ＣＯ₂Ｒ、（ＣＨ₃Ｏ）₃Ｓｉ（ＣＨ₂）₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₅、（ＣＨ₃Ｏ）₂（ＣＨ₃）Ｓｉ（ＣＨ₂）₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₅、（ＣＨ₃Ｏ）₃Ｓｉ（ＣＨ₂）₄Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₅、（ＣＨ₃Ｏ）₂（ＣＨ₃）Ｓｉ（ＣＨ₂）₄Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₅、
（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）
等が挙げられる。
【００４０】
上記ヒドロキシル基を持つ有機ハロゲン化物、またはハロゲン化スルホニル化合物としては特に限定されず、下記のようなものが例示される。
ＨＯ−（ＣＨ２）ｎ−ＯＣ（Ｏ）Ｃ（Ｈ）（Ｒ）（Ｘ）
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、Ｒは水素原子または炭素数１〜２０のアルキル基、アリール基、アラルキル基、ｎは１〜２０の整数）上記アミノ基を持つ有機ハロゲン化物、またはハロゲン化スルホニル化合物としては特に限定されず、下記のようなものが例示される。
Ｈ２Ｎ−（ＣＨ２）ｎ−ＯＣ（Ｏ）Ｃ（Ｈ）（Ｒ）（Ｘ）
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、Ｒは水素原子または炭素数１〜２０のアルキル基、アリール基、アラルキル基、ｎは１〜２０の整数）
上記エポキシ基を持つ有機ハロゲン化物、またはハロゲン化スルホニル化合物としては特に限定されず、下記のようなものが例示される。
【００４１】
【化５】

【００４２】
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、Ｒは水素原子または炭素数１〜２０のアルキル基、アリール基、アラルキル基、ｎは１〜２０の整数）以下に末端官能基変換により架橋性シリル基、アルケニル基、水酸基を導入する方法について記述する。これらの官能基はお互いに前駆体となりうるので、架橋性シリル基から溯る順序で記述していく。
【００４３】
架橋性シリル基を少なくとも１個有するビニル系重合体の合成方法としては、（Ａ）アルケニル基を少なくとも１個有するビニ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、ヒドロシリル化触媒存在下に付加させる方法（Ｂ）水酸基を少なくとも１個有するビニル系重合体に一分子中に架橋性シリル基とイソシアネート基のような水酸基と反応し得る基を有する化合物を反応させる方法（Ｃ）ラジカル重合によりビニル系重合体を合成する際に、１分子中に重合性のアルケニル基と架橋性シリル基を併せ持つ化合物を反応させる方法（Ｄ）ラジカル重合によりビニル系重合体を合成する際に、架橋性シリル基を有する連鎖移動剤を用いる方法（Ｅ）反応性の高い炭素−ハロゲン結合を少なくとも１個有するビニル系重合体に１分子中に架橋性シリル基と安定なカルバニオンを有する化合物を反応させる方法；などがあげられる。
【００４４】
（Ａ）の方法で用いるアルケニル基を少なくとも１個有するビニル系重合体は種々の方法で得られる。以下に合成方法を例示するが、これらに限定されるわけではない。
（Ａ−ａ）ラジカル重合によりビニル系重合体を合成する際に、例えば下記の一般式１７に挙げられるような一分子中に重合性のアルケニル基と重合性の低いアルケニル基を併せ持つ化合物を第２のモノマーとして反応させる方法。
【００４５】
Ｈ₂Ｃ＝Ｃ（Ｒ²³）−Ｒ²⁴−Ｒ²⁵−Ｃ（Ｒ²⁶）＝ＣＨ₂ （１７）
（式中、Ｒ²³は水素またはメチル基を示し、Ｒ²⁴は−Ｃ（Ｏ）Ｏ−、またはｏ−，ｍ−，ｐ−フェニレン基を示し、Ｒ２５は直接結合、または炭素数１〜２０の２価の有機基を示し、１個以上のエーテル結合を含んでいてもよい。Ｒ²⁶は水素、または炭素数１〜１０のアルキル基、炭素数６〜１０のアリール基または炭素数７〜１０のアラルキル基を示す）
なお、一分子中に重合性のアルケニル基と重合性の低いアルケニル基を併せ持つ化合物を反応させる時期に制限はないが、特にリビングラジカル重合で、ゴム的な性質を期待する場合には重合反応の終期あるいは所定のモノマーの反応終了後に、第２のモノマーとして反応させるのが好ましい。
【００４６】
（Ａ−ｂ）リビングラジカル重合によりビニル系重合体を合成する際に、重合反応の終期あるいは所定のモノマーの反応終了後に、例えば１，５−ヘキサジエン、１，７−オクタジエン、１，９−デカジエンなどのような重合性の低いアルケニル基を少なくとも２個有する化合物を反応させる方法。
（Ａ−ｃ）反応性の高い炭素−ハロゲン結合を少なくとも１個有するビニル系重合体に、例えばアリルトリブチル錫、アリルトリオクチル錫などの有機錫のようなアルケニル基を有する各種の有機金属化合物を反応させてハロゲンを置換する方法。
【００４７】
（Ａ−ｄ）反応性の高い炭素−ハロゲン結合を少なくとも１個有するビニル系重合体に、一般式１８に挙げられるようなアルケニル基を有する安定化カルバニオンを反応させてハロゲンを置換する方法。
Ｍ⁺Ｃ^-（Ｒ²⁷）（Ｒ²⁸）−Ｒ²⁹−Ｃ（Ｒ²⁶）＝ＣＨ₂ （１８）
（式中、Ｒ²⁶は上記に同じ、Ｒ²⁷、Ｒ²⁸はともにカルバニオンＣ^-を安定化する電子吸引基であるか、または一方が前記電子吸引基で他方が水素または炭素数１〜１０のアルキル基、またはフェニル基を示す。Ｒ²⁹は直接結合、または炭素数１〜１０の２価の有機基を示し、１個以上のエーテル結合を含んでいてもよい。Ｍ＋はアルカリ金属イオン、または４級アンモニウムイオンを示す）
Ｒ²⁷、Ｒ²⁸の電子吸引基としては、−ＣＯ₂Ｒ、−Ｃ（Ｏ）Ｒおよび−ＣＮの構造を有するものが特に好ましい。
【００４８】
（Ａ−ｅ）反応性の高い炭素−ハロゲン結合を少なくとも１個有するビニル系重合体に、例えば亜鉛のような金属単体あるいは有機金属化合物を作用させてエノレートアニオンを調製し、しかる後にハロゲンやアセチル基のような脱離基を有するアルケニル基含有化合物、アルケニル基を有するカルボニル化合物、アルケニル基を有するイソシアネート化合物、アルケニル基を有する酸ハロゲン化物等の、アルケニル基を有する求電子化合物と反応させる方法。
【００４９】
（Ａ−ｆ）反応性の高い炭素−ハロゲン結合を少なくとも１個有するビニル系重合体に、例えば一般式（１９）あるいは（２０）に示されるようなアルケニル基を有するオキシアニオンあるいはカルボキシレートアニオンを反応させてハロゲンを置換する方法。
Ｈ₂Ｃ＝Ｃ（Ｒ²⁶）−Ｒ³⁰−Ｏ^-Ｍ⁺ （１９）
（式中、Ｒ²⁶、Ｍ⁺は上記に同じ。Ｒ³⁰は炭素数１〜２０の２価の有機基で１個以上のエーテル結合を含んでいてもよい）
Ｈ₂Ｃ＝Ｃ（Ｒ²⁶）−Ｒ³¹−Ｃ（Ｏ）Ｏ^-Ｍ⁺ （２０）
（式中、Ｒ²⁶、Ｍ⁺は上記に同じ。Ｒ³¹は直接結合、または炭素数１〜２０の２価の有機基で１個以上のエーテル結合を含んでいてもよい）
などが挙げられる。
【００５０】
上述の反応性の高い炭素−ハロゲン結合を少なくとも１個有するビニル系重合体の合成法は、前述のような有機ハロゲン化物等を開始剤とし、遷移金属錯体を触媒とする原子移動ラジカル重合法が挙げられるがこれらに限定されるわけではない。
またアルケニル基を少なくとも１個有するビニル系重合体は、水酸基を少なくとも１個有するビニル系重合体から得ることも可能であり、以下に例示する方法が利用できるがこれらに限定されるわけではない。水酸基を少なくとも１個有するビニル系重合体の水酸基に、
（Ａ−ｇ）ナトリウムメトキシドのような塩基を作用させ、塩化アリルのようなアルケニル基含有ハロゲン化物と反応させる方法。
【００５１】
（Ａ−ｈ）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反応させる方法。
（Ａ−ｉ）（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ピリジン等の塩基存在下に反応させる方法。
（Ａ−ｊ）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】
本発明では（Ａ−ａ）（Ａ−ｂ）のようなアルケニル基を導入する方法にハロゲンが直接関与しない場合には、リビングラジカル重合法を用いてビニル系重合体を合成することが好ましい。制御がより容易である点から（Ａ−ｂ）の方法がさらに好ましい。
反応性の高い炭素−ハロゲン結合を少なくとも１個有するビニル系重合体のハロゲンを変換することによりアルケニル基を導入する場合は、反応性の高い炭素−ハロゲン結合を少なくとも１個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、遷移金属錯体を触媒としてビニル系モノマーをラジカル重合すること（原子移動ラジカル重合法）により得る、末端に反応性の高い炭素−ハロゲン結合を少なくとも１個有するビニル系重合体を用いるのが好ましい。制御がより容易である点から（Ａ−ｆ）の方法がさらに好ましい。
【００５３】
また、架橋性シリル基を有する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２１で示される化合物が例示される。
Ｈ−［Ｓｉ（Ｒ²¹）_2-b（Ｙ）_bＯ］_m−Ｓｉ（Ｒ₂₂）_3-a（Ｙ）_a （２１）
（式中、Ｒ²¹、Ｒ²²、ａ、ｂ、ｍ、Ｙは前記に同じ。）
これらヒドロシラン化合物の中でも、特に一般式（２２）
Ｈ−Ｓｉ（Ｒ²²）_3-a（Ｙ）_a （２２）
（式中、Ｒ²²、Ｙ、ａは前記に同じ）
で示される架橋性基を有する化合物が入手容易な点から好ましい。
【００５４】
上記の架橋性シリル基を有するヒドロシラン化合物をアルケニル基に付加させる際には、遷移金属触媒が通常用いられる。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。
【００５５】
（Ｂ）および（Ａ−ｇ）〜（Ａ−ｊ）の方法で用いる水酸基を少なくとも１個有するビニル系重合体の製造方法は以下のような方法が例示されるが、これらの方法に限定されるものではない。
（Ｂ−ａ）ラジカル重合によりビニル系重合体を合成する際に、例えば下記の一般式（２３）に挙げられるような一分子中に重合性のアルケニル基と水酸基を併せ持つ化合物を第２のモノマーとして反応させる方法。
Ｈ₂Ｃ＝Ｃ（Ｒ²³）−Ｒ²⁴−Ｒ²⁵−ＯＨ （２３）
（式中、Ｒ²³、Ｒ²⁴、Ｒ²⁵は上記に同じ）
なお、一分子中に重合性のアルケニル基と水酸基を併せ持つ化合物を反応させる時期に制限はないが、特にリビングラジカル重合で、ゴム的な性質を期待する場合には重合反応の終期あるいは所定のモノマーの反応終了後に、第２のモノマーとして反応させるのが好ましい。
【００５６】
（Ｂ−ｂ）リビングラジカル重合によりビニル系重合体を合成する際に、重合反応の終期あるいは所定のモノマーの反応終了後に、例えば１０−ウンデセノール、５−ヘキセノール、アリルアルコールのようなアルケニルアルコールを反応させる方法。
（Ｂ−ｃ）例えば特開平５−２６２８０８に示される水酸基含有ポリスルフィドのような水酸基含有連鎖移動剤を多量に用いてビニル系モノマーをラジカル重合させる方法。
（Ｂ−ｄ）例えば特開平６−２３９９１２、特開平８−２８３３１０に示されるような過酸化水素あるいは水酸基含有開始剤を用いてビニル系モノマーをラジカル重合させる方法。
（Ｂ−ｅ）例えば特開平６−１１６３１２に示されるようなアルコール類を過剰に用いてビニル系モノマーをラジカル重合させる方法。
（Ｂ−ｆ）例えば特開平４−１３２７０６などに示されるような方法で、反応性の高い炭素−ハロゲン結合を少なくとも１個に有するビニル系重合体のハロゲンを加水分解あるいは水酸基含有化合物と反応させることにより、末端に水酸基を導入する方法。
（Ｂ−ｇ）反応性の高い炭素−ハロゲン結合を少なくとも１個有するビニル系重合体に、一般式（２４）に挙げられるような水酸基を有する安定化カルバニオンを反応させてハロゲンを置換する方法。
Ｍ＋Ｃ−（Ｒ²⁷）（Ｒ²⁸）−Ｒ²⁹−ＯＨ （２４）
（式中、Ｒ²⁷、Ｒ²⁸、Ｒ²⁹、は上記に同じ）
Ｒ²⁷、Ｒ²⁸の電子吸引基としては、−ＣＯ₂Ｒ、−Ｃ（Ｏ）Ｒおよび−ＣＮの構造を有するものが特に好ましい。
【００５７】
（Ｂ−ｈ）反応性の高い炭素−ハロゲン結合を少なくとも１個有するビニル系重合体に、例えば亜鉛のような金属単体あるいは有機金属化合物を作用させてエノレートアニオンを調製し、しかる後にアルデヒド類、又はケトン類を反応させる方法。
（Ｂ−ｉ）反応性の高い炭素−ハロゲン結合を少なくとも１個有するビニル系重合体に、例えば一般式２５あるいは２６に示されるような水酸基を有するオキシアニオンあるいはカルボキシレートアニオンを反応させてハロゲンを置換する方法。
ＨＯ−Ｒ³⁰−Ｏ^-Ｍ⁺ （２５）
（式中、Ｒ³⁰およびＭ⁺は前記に同じ）
ＨＯ−Ｒ³¹−Ｃ（Ｏ）Ｏ^-Ｍ⁺ （２６）
（式中、Ｒ³¹およびＭ⁺は前記に同じ）
等が挙げられる。
【００５８】
本発明では（Ｂ−ａ）〜（Ｂ−ｅ）のような水酸基を導入する方法にハロゲンが直接関与しない場合には、リビングラジカル重合法を用いてビニル系重合体を合成することが好ましい。制御がより容易である点から（Ｂ−ｂ）の方法がさらに好ましい。
反応性の高い炭素−ハロゲン結合を少なくとも１個有するビニル系重合体のハロゲンを変換することにより水酸基を導入する場合は、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、遷移金属錯体を触媒としてビニル系モノマーをラジカル重合すること（原子移動ラジカル重合法）により得る、末端に反応性の高い炭素−ハロゲン結合を少なくとも１個有するビニル系重合体を用いるのが好ましい。制御がより容易である点から（Ｂ−ｉ）の方法がさらに好ましい。
【００５９】
また、一分子中に架橋性シリル基とイソシアネート基のような水酸基と反応し得る基を有する化合物としては、例えばγ−イソシアナートプロピルトリメトキシシラン、γ−イソシアナートプロピルメチルジメトキシシラン、γ−イソシアナートプロピルトリエトキシシラン等が挙げられ、必要により一般に知られているウレタン化反応の触媒を使用できる。
【００６０】
（Ｃ）の方法で用いる一分子中に重合性のアルケニル基と架橋性シリル基を併せ持つ化合物としては、例えばトリメトキシシリルプロピル（メタ）アクリレート、メチルジメトキシシリルプロピル（メタ）アクリレートなどのような、下記一般式２７で示すものが挙げられる。
Ｈ₂Ｃ＝Ｃ（Ｒ²³）−Ｒ²⁴−Ｒ³²−［Ｓｉ（Ｒ²¹）_2-b（Ｙ）_bＯ］_m−Ｓｉ（Ｒ²²）_3-a（Ｙ）_a （２７）
（式中、Ｒ²¹、Ｒ²²、Ｒ²³、Ｒ²⁴、Ｙ、ａ、ｂ、ｍは上記に同じ。Ｒ³²は、直接結合、または炭素数１〜２０の２価の有機基で１個以上のエーテル結合を含んでいてもよい。）
一分子中に重合性のアルケニル基と架橋性シリル基を併せ持つ化合物を反応させる時期に特に制限はないが、特にリビングラジカル重合で、ゴム的な性質を期待する場合には重合反応の終期あるいは所定のモノマーの反応終了後に、第２のモノマーとして反応させるのが好ましい。
（Ｄ）の連鎖移動剤法で用いられる、架橋性シリル基を有する連鎖移動剤としては例えば特公平３−１４０６８、特公平４−５５４４４に示される、架橋性シリル基を有するメルカプタン、架橋性シリル基を有するヒドロシランなどが挙げられる。
【００６１】
（Ｅ）の方法で用いられる、上述の反応性の高い炭素−ハロゲン結合を少なくとも１個有するビニル系重合体の合成法は、前述のような有機ハロゲン化物等を開始剤とし、遷移金属錯体を触媒とする原子移動ラジカル重合法が挙げられるがこれらに限定されるわけではない。一分子中に架橋性シリル基と安定化カルバニオンを併せ持つ化合物としては一般式２８で示すものが挙げられる。
【００６２】
Ｍ⁺Ｃ^-（Ｒ²⁷）（Ｒ²⁸）−Ｒ³³−Ｃ（Ｈ）（Ｒ³⁴）−ＣＨ₂−［Ｓｉ（Ｒ²¹）_2-b（Ｙ）_bＯ］_m−Ｓｉ（Ｒ²²）_3-a（Ｙ）_a （２８）
（式中、Ｒ²¹、Ｒ²²、Ｒ²⁷、Ｒ²⁸、Ｙ、ａ、ｂ、ｍ、は前記に同じ。Ｒ³³は直接結合、または炭素数１〜１０の２価の有機基で１個以上のエーテル結合を含んでいてもよい、Ｒ³⁴は水素、または炭素数１〜１０のアルキル基、炭素数６〜１０のアリール基または炭素数７〜１０のアラルキル基を示す。）
Ｒ²⁷、Ｒ²⁸の電子吸引基としては、−ＣＯ₂Ｒ、−Ｃ（Ｏ）Ｒおよび−ＣＮの構造を有するものが特に好ましい。
上述のような方法により合成される重合体は、分子量分布の狭いビニル系重合体である。従って、数平均分子量が等しく分子量分布の広い重合体に比べて粘度が低いために、硬化性組成物として用いる際に、取扱いが容易である。
用途
以下に本発明の重合体について、その末端の官能基別に用途について説明するが、本発明の重合体の用途はこれに限定されるものではない。
【００６３】
本発明の末端に架橋性シリル基を有するビニル系重合体は、従来公知の各種縮合触媒の存在下、あるいは非存在下にシロキサン結合を形成することにより架橋、硬化する。硬化物の性状としては、重合体の分子量と主鎖骨格に応じて、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。従ってこの重合体はシーリング材や接着剤、弾性接着剤、粘着剤、塗料、粉体塗料、発泡体、電気電子用ポッティング剤、フィルム、ガスケット、各種成形材料等に利用することができる。
【００６４】
本発明の末端にアルケニル基を有するビニル系重合体は、そのもの単独、あるいは適当な架橋剤を用いることにより、硬化物を与える。
中でも末端に（メタ）アクリロイル基を有するビニル系重合体は、各種重合開始剤の存在下、あるいは非存在下に加熱することにより硬化物を与える。また、各種の光重合開始剤の存在下、光照射により架橋硬化する。
【００６５】
末端にアルケニル基を有するビニル系重合体の硬化剤としては、各種の多価ハイドロジェンシリコン化合物を用いることができる。この際、硬化反応の触媒として従来公知のヒドロシリル化触媒を用いることができる。
本発明の末端にアルケニル基を有するビニル系重合体を硬化させると、その分子量と主鎖骨格に応じて、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。硬化物の具体的な用途としては、シーリング材、接着剤、粘着剤、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剤、フィルム、ガスケット、各種成形材料、人工大理石等である。
【００６６】
本発明の末端に水酸基を有するビニル系重合体は、水酸基と反応し得る官能基を２個以上有する化合物を硬化剤として用いることにより、均一に硬化する。硬化剤の具体例としては、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。これらの硬化剤を使用して硬化物を作成する際には、それぞれ適当な硬化触媒を使用することができる。
【００６７】
本発明の末端に水酸基を有するビニル系重合体を硬化させると、その分子量と主鎖骨格に応じて、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。硬化物の具体的な用途としては、シーリング材、接着剤、粘着剤、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剤、フィルム、ガスケット、各種成形材料、人工大理石等である。
【００６８】
【実施例】
以下にこの発明のビニル系重合体を実施例に基づき説明するが、この発明は、下記実施例に限定されるものではない。
【００６９】
【製造例１】
２―アリロキシエチルメタクリレートの製造例
撹拌機、温度計、還流冷却管、ディーンスターク管を取り付けた三つ口フラスコに、メタクリル酸（１３７．７ｇ、１．６ｍｏｌ）、エチレングリコールモノアリルエーテル（８０．７ｇ、０．８ｍｏｌ）、ｐ−トルエンスルホン酸（０．７６ｇ、４．０ｍｍｏｌ）、およびトルエン（６５０ｍＬ）を仕込んだ。１２０℃で５時間反応させた後、ｐ−トルエンスルホン酸を０．１２ｇ追加し、さらに同じ温度で６時間反応させ、ｐ−トルエンスルホン酸を０．１ｇ追加した。同じ温度でさらに９時間反応させて反応を終了した。この間、液体クロマトグラフィーでメタクリル酸とエチレングリコールモノアリルエーテルを追跡し、転化率は最終的に９８％に達した。ＮａＨＣＯ₃水溶液を加えて中和し、２層を分離した。水層をトルエンで１回抽出し、有機層をＣａＣｌ₂で乾燥した後、揮発分を減圧下留去した。粗生成物を減圧蒸留する（６０℃、２ｍｍＨｇ）ことにより、下式に示す２−アリロキシエチルメタクリレートを９８．７ｇ得た（収率７３％）。
Ｈ₂Ｃ＝Ｃ（ＣＨ₃）ＣＯ₂（ＣＨ₂）₂ＯＣＨ₂ＣＨ＝ＣＨ₂
【００７０】
【製造例２】
アルケニル基を有するカルボン酸塩の製造（１）
水酸化カリウムの１／２Ｎエタノ−ル溶液（２００ｍＬ）にウンデシレン酸（１８．８ｇ、０．１０２ｍｏｌ）を撹拌しながら０℃でゆっくり滴下した。揮発分を減圧下留去することにより粗生成物を得た。粗生成物をアセトンで洗浄後、減圧下加熱することにより下式に示すウンデシレン酸のカリウム塩の白色固体を得た（８．８８ｇ、収率８８％）。
ＣＨ₂＝ＣＨ−（ＣＨ₂）₈−ＣＯ₂ ^-Ｋ⁺
【００７１】
【製造例３】
アルケニル基を有するカルボン酸塩の製造例（２）
メタノ−ル（２４５ｍＬ）に４−ペンテン酸（４９ｇ、０．４８９ｍｏｌ）、カリウム−ｔｅｒｔ−ブトキシド（５４．９ｇ、０．４８９ｍｏｌ）を仕込み、０℃で撹拌した。揮発分を減圧下留去することにより下式に示すペンテン酸カリウム塩を得た。
ＣＨ₂＝ＣＨ−（ＣＨ₂）₂−ＣＯ₂ ^-Ｋ⁺
【００７２】
【製造例４】
水酸基を有する開始剤の製造例
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時間撹拌した。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
【００７３】
【製造例５】
アルケニル基を有する開始剤の製造例（１）
５０ｍＬの２口フラスコを窒素置換し、２−アリルオキシエタノール（２．５ｍＬ、２３．４ｍｍｏｌ）、ピリジン（３ｍＬ）、およびＴＨＦ（１０ｍＬ）を仕込んだ。溶液を０℃に冷却し、２−ブロモプロピオン酸クロライド（２ｍＬ、１９．５２ｍｍｏｌ）をゆっくり滴下した。そのままの温度で１時間撹拌を続けた後、酢酸エチル（１０ｍＬ）を加え、生成したピリジンの塩酸塩を濾過により除去した。濾液を希塩酸（１０ｍＬ）、ＮａＨＣＯ₃水溶液（１０ｍＬ）、さらにブライン（１０ｍＬ）で洗浄した。有機層をＮａ₂ＳＯ₄で乾燥し、揮発分を減圧化留去した。得られた粗生成物を減圧蒸留することにより、下式に示すアリルオキシエチル−２−ブロモプロピオネートを得た。（７８．５〜８１℃（１．３ｍｍＨｇ）、２．９８６ｇ）。
ＣＨ₃Ｃ（Ｈ）（Ｂｒ）Ｃ（Ｏ）Ｏ−ＣＨ₂ＣＨ₂−Ｏ−ＣＨ₂ＣＨ＝ＣＨ₂
【００７４】
【実施例１】
１Ｌの耐圧反応容器に、アクリル酸−ｎ−ブチル（１１２ｍＬ、１００ｇ、０．７８ｍｏｌ）、製造例４で得られた水酸基含有開始剤（３．０７ｇ、１５．６ｍｍｏｌ）、臭化第一銅（２．２４ｇ、１５．６ｍｍｏｌ）、２，２'−ビピリジル（４．８７ｇ、３１．２ｍｍｏｌ）、酢酸エチル（９０ｍＬ）、アセトニトリル（２２ｍＬ）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（３．９２ｍＬ、４．０６ｇ、３１．２ｍｍｏｌ）を加え、１１０℃で２時間反応させた。混合物を酢酸エチル（２００ｍＬ）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、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。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。
【００７５】
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、７５℃で、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、７５℃で３時間撹拌した。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、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。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１．３０であった。また、オリゴマー１分子当たりに導入されたアルケニル基は、¹Ｈ ＮＭＲ分析より、２．２８個であった。
【００７６】
次に、３０ｍＬの耐圧反応容器に、上で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^-4当量）を仕込み、１００℃で１時間撹拌した。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。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１．３７であった。また、オリゴマー１分子当たりに導入されたシリル基は、¹Ｈ ＮＭＲ分析より、２．２４個であった。
【００７７】
次に、上記のようにして得られた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−ｎ−酸ブチル）（１ｇ）と硬化触媒（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。
【００７８】
【実施例２】
末端に水酸基を有するポリ（アクリル酸−ｎ−ブチル）の合成
１Ｌの耐圧反応容器に、アクリル酸−ｎ−ブチル（１１２ｍＬ、１００ｇ、０．７８ｍｏｌ）、参考例１で得られた水酸基含有開始剤（３．０７ｇ、１５．６ｍｍｏｌ）、臭化第一銅（２．２４ｇ、１５．６ｍｍｏｌ）、２，２'−ビピリジル（４．８７ｇ、３１．２ｍｍｏｌ）、酢酸エチル（９０ｍＬ）、アセトニトリル（２２ｍＬ）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（３．９２ｍＬ、４．０６ｇ、３１．２ｍｍｏｌ）を加え、１１０℃で２時間反応させた。混合物を酢酸エチル（２００ｍＬ）で希釈し、不溶分を濾別した後、濾液を１０％塩酸とブラインで洗浄、有機層をＮａ₂ＳＯ₄で乾燥した。溶媒を減圧下留去し、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。この重合体の粘度は２５Ｐａ・ｓであり、数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）により、５１００、分子量分布は１．２９であった。また、¹Ｈ−ＮＭＲ分析より求めた重合体１分子あたりの平均の水酸基の個数は２．３９個であった。
末端にアルケニル基を有するポリ（アクリル酸−ｎ−ブチル）の合成
上で得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、７５℃で、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、７５℃で３時間撹拌した。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、有機層をＮａ₂ＳＯ₄で乾燥した。減圧下で濃縮することにより、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。重合体の数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）により、５４００、分子量分布は１．３０であった。また、¹Ｈ−ＮＭＲ分析より求めた重合体１分子当たりに導入されたアルケニル基は、２．２８個であった。
末端に架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）の合成
３０ｍＬの耐圧反応容器に、上記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）、白金ビス（ジビニルテトラメチルジシロキサン）（８．３×１０^-8ｍｏｌ／Ｌキシレン溶液、アルケニル基に対し、１０−４当量）を仕込み、１００℃で１時間撹拌した。揮発分を減圧下留去することにより、架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）を２ｇ得た。重合体の数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）により５９００、分子量分布は１．３７であった。また、¹Ｈ−ＮＭＲ分析より求めた重合体１分子当たりに導入されたシリル基は、２．２４個であった。
【００７９】
【参考例１】
実施例２の架橋性シリル基末端重合体（１ｇ）と硬化触媒（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、減圧乾燥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。トルエン抽出により求めたゲル分率は７８％であった。
【００８０】
【参考例２】
実施例２の末端に架橋性シリル基を有する重合体１００重量部、水１重量部、ジブチルスズジメトキサイド１重量部をよく混合し、型枠に流し込んで、減圧乾操器を用いて室温で脱泡した。５０℃で２０時間加熱硬化させることにより、均一なゴム状硬化物シートが得られた。トルエン抽出により求めたゲル分率は８８％であった。ゴム状硬化物シートから２（１／３）号形ダンベル試験片を打ち抜き、オートグラフを用いて引っ張り試験を行った（２００ｍｍ／ｍｉｎ）。破断強度は０．３２ＭＰａ、破断伸びは３４％であった。
【００８１】
【実施例３】
末端にハロゲンを有するポリ（アクリル酸−ｎ−ブチル）の合成
５００ｍｌの耐圧反応容器に、アクリル酸−ｎ−ブチル（１１２ｍＬ、１００ｇ、０．７８ｍｏｌ）、ジブロモキシレン（４．１２ｇ、１５．６ｍｍｏｌ）、臭化第一銅（２．２４ｇ、１５．６ｍｍｏｌ）、２，２'−ビピリジル（４．８７ｇ、３１．２ｍｍｏｌ）、酢酸エチル（９０ｍＬ）、アセトニトリル（２０ｍＬ）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（３．９２ｍＬ、４．０６ｇ、３１．２ｍｍｏｌ）を加え、１１０℃で２時間反応させた。混合物を酢酸エチル（２００ｍＬ）で希釈し、活性アルミナのカラムを通して銅触媒を除去精製することにより末端にＢｒ基を有する重合体を得た。得られた重合体の数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）で５７００、分子量分布１．３７であった。
末端にアルケニル基を有するポリ（アクリル酸−ｎ−ブチル）の合成
窒素雰囲気下、５００ｍｌフラスコに上記で得た末端にハロゲンを有するポリ（アクリル酸−ｎ−ブチル）８４ｇ、ペンテン酸カリウム７．７ｇ（５６ｍｍｏｌ）、ＤＭＡｃ８０ｍｌを仕込み、７０℃で４時間反応させた。反応混合液中の未反応のペンテン酸カリウムおよび生成した臭化カリウムを水抽出精製により除去し、末端にアルケニル基を有する重合体を得た。この重合体７０ｇとこれと等重量の珪酸アルミ（協和化学製：キョ−ワ−ド７００ＰＥＬ）をトルエンに混合し、１００℃で撹拌した。４時間後、珪酸アルミを濾過し、濾液の揮発分を減圧下加熱して留去することによって重合体を精製した。得られた重合体の数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）で４７６０、分子量分布１．７３であった。また¹Ｈ−ＮＭＲ分析より求めた重合体１分子あたりのアルケニル基の個数は１．７８個であった。
末端に架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）の合成
２００ｍｌ耐圧反応管に上記で得た末端にアルケニル基を有する重合体６０ｇ、メチルジメトキシシラン８．４ｍＬ（６８．１ｍｍｏｌ）、オルトギ酸メチル２．５ｍＬ（２２．９ｍｍｏｌ）、白金ビス（ジビニルテトラメチルジシロキサン）５×１０^-3ｍｍｏｌを仕込み、１００℃で４時間反応させ、架橋性ケイ素基含有重合体を得た。得られた重合体の数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）で６０００、分子量分布１．４４であった。また¹Ｈ−ＮＭＲ分析より求めた重合体１分子あたりの架橋性シリル基の個数は１．５９個であった。
【００８２】
【参考例３】
実施例３で得た末端に架橋性シリル基を有する重合体１００重量部に水１重量部、ジブチル錫ジメトキサイド１重量部を混合攪拌し、厚さ２ｍｍの型枠に流し込んだ。減圧乾燥器を用いて室温で脱泡し、５０℃で２日間加熱硬化させることにより、均一なゴム状硬化物シートが得られた。トルエン抽出により求めたゲル分率は９３％であった。ゴム状硬化物シートから２（１／３）号形ダンベル試験片を打ち抜き、オートグラフを用いて引っ張り試験を行った（２００ｍｍ／ｍｉｎ）。破断強度は０．２６ＭＰａ、破断伸びは７５％であった。
【００８３】
【実施例４】
末端にハロゲンを有するポリ（アクリル酸−ｎ−ブチル）の合成
５０ｍｌフラスコに臭化第一銅０．６３ｇ（４．４ｍｍｏｌ）、ペンタメチルジエチレントリアミン０．７６ｇ（４．４ｍｍｏｌ）、アセトニトリル５ｍｌ、２，５−ジブロモアジピン酸ジエチル１．６ｇ（４．４ｍｍｏｌ）、アクリル酸ブチル４４．７ｇ（３４９ｍｍｏｌ）を仕込み、凍結脱気をおこなった後、窒素雰囲気下で７０℃７時間反応させた。活性アルミナのカラムを通して銅触媒を除去精製することにより末端にＢｒ基を有する重合体を得た。得られた重合体の数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）で１０７００、分子量分布１．１５であった。
末端にアルケニル基を有するポリ（アクリル酸−ｎ−ブチル）の合成
窒素雰囲気下、２００ｍｌフラスコに上記で得た末端にハロゲンを有するポリ（アクリル酸−ｎ−ブチル）３５ｇ、ペンテン酸カリウム２．２ｇ（１６．１ｍｍｏｌ）、ＤＭＡｃ３５ｍＬを仕込み、７０℃で４時間反応させた。反応混合液中の未反応のペンテン酸カリウムおよび生成した臭化カリウムを水抽出精製により除去し、末端にアルケニル基を有する重合体を得た。得られた重合体の数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）で１１３００、分子量分布１．１２であった。また¹Ｈ−ＮＭＲ分析より求めた重合体１分子あたりのアルケニル基の個数は１．８２個であった。
末端に架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）の合成
２００ｍＬ耐圧反応管に上記で得た末端にアルケニル基を有する重合体１５ｇ、メチルジメトキシシラン１．８ｍＬ（１４．５ｍｍｏｌ）オルトギ酸メチル０．２６ｍＬ（２．４ｍｍｏｌ）、白金ビス（ジビニルテトラメチルジシロキサン）１０^-4ｍｍｏｌを仕込み、１００℃で４時間反応させ、末端に架橋性シリル基を有する重合体を得た。得られた重合体の粘度は４４Ｐａ・ｓであり、数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）で１１９００、分子量分布１．１２であった。また¹Ｈ−ＮＭＲ分析により重合体１分子あたりの架橋性ケイ素基の個数は１．４６個であった。
【００８４】
【参考例４】
実施例４で得た末端に架橋性シリル基を有する重合体１００重量部に水１重量部、ジブチルスズジメトキサイド１重量部を混合攪拌し、厚さ２ｍｍの型枠に流し込んだ。減圧乾操器を用いて室温で脱泡し、５０℃で１０日間加熱硬化させることにより、均一なゴム状硬化物シートが得られた。トルエンン抽出により求めたゲル分率は９８％であった。ゴム状硬化物シートから２（１／３）号形ダンベル試験片を打ち抜き、オートグラフを用いて引っ張り試験を行った（２００ｍｍ／ｍｉｎ）。破断強度は０．３５ＭＰａ、破断伸びは７７％であった。
【００８５】
【実施例５】
末端にアルケニル基を有するポリ（アクリル酸−ｎ−ブチル）の合成
１００ｍＬのガラス反応容器に、アクリル酸ブチル（５０．０ｍＬ、４４．７ｇ、０．３４９ｍｏｌ）、臭化第一銅（１．２５ｇ、８．７２ｍｍｏｌ）、ペンタメチルジエチレントリアミン（１．８２ｍＬ、１．５１ｇ、８．７２ｍｍｏｌ）、およびアセトニトリル（５ｍＬ）を仕込み、冷却後減圧脱気したのち窒素ガスで置換した。よく撹拌した後、ジエチル２，５−ジブロモアジペート（１．５７ｇ、４．３６ｍｍｏｌ）を添加し、７０℃で加熱撹拌した。６０分後に１，７−オクタジエン（６．４４ｍＬ、４．８０ｇ、４３．６ｍｍｏｌ）を添加し、７０℃で加熱撹拌を２時間継続した。混合物を活性アルミナで処理した後、揮発分を減圧下加熱して留去した。生成物を酢酸エチルに溶解させ、２％塩酸、ブラインで洗浄した。有機層をＮａ₂ＳＯ₄で乾燥し、揮発分を減圧下加熱して留去することにより、末端にアルケニル基を有する重合体を得た。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１３１００、分子量分布は１．２２であった。また¹Ｈ−ＮＭＲ分析より求めた重合体１分子あたりのアルケニル基の個数は２．０１個であった。
末端に架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）の合成
上記で得られた、末端にアルケニル基を有するポリ（アクリル酸−ｎ−ブチル）（３０．５ｇ）、重合体と等重量の珪酸アルミ（協和化学製：キョ−ワ−ド７００ＰＥＬ）をトルエンに混合し、１００℃で撹拌した。４時間後、珪酸アルミを濾過し、濾液の揮発分を減圧下加熱して留去することによって重合体を精製した。
２００ｍＬの耐圧ガラス反応容器に、精製した上記重合体（２３．３ｇ）、ジメトキシメチルシラン（２．５５ｍＬ、２０．７ｍｍｏｌ）、オルトぎ酸ジメチル（０．３８ｍＬ、３．４５ｍｍｏｌ）、および白金触媒を仕込んだ。ただし、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２×１０^-4当量とした。反応混合物を１００℃で３時間加熱した。混合物の揮発分を減圧留去することにより、末端に架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）を得た。得られた重合体の数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）で１３９００、分子量分布１．２５であった。また¹Ｈ−ＮＭＲ分析より求めた重合体１分子あたりの架橋性ケイ素基の個数は１．５８個であった。
【００８６】
【参考例５】
実施例５で得た末端に架橋性シリル基を有する重合体１００重量部に水１重量部、ジブチル錫ジメトキサイド１重量部を混合攪拌し、厚さ２ｍｍの型枠に流し込んだ。減圧乾燥器を用いて室温で脱泡し、５０℃で１０日間加熱硬化させることにより、均一なゴム状硬化物シートが得られた。トルエン抽出により求めたゲル分率は８５％であった。ゴム状硬化物シートから２（１／３）号形ダンベル試験片を打ち抜き、オートグラフを用いて引っ張り試験を行った（２００ｍｍ／ｍｉｎ）。破断強度は０．３４ＭＰａ、破断伸びは８６％であった。
【００８７】
【実施例６】
末端にハロゲンを有するポリ（アクリル酸−ｎ−ブチル）の合成
５０ｍＬフラスコに臭化第一銅０．６３ｇ（４．４ｍｍｏｌ）、ペンタメチルジエチレントリアミン０．７６ｇ（４．４ｍｍｏｌ）、アセトニトリル５ｍＬ、２，５−ジブロモアジピン酸ジエチル０．７８ｇ（２．２ｍｍｏｌ）、アクリル酸ブチル４４．７ｇ（３４９ｍｍｏｌ）を仕込み、凍結脱気をおこなった後、窒素雰囲気下で７０℃６時間反応させた。活性アルミナのカラムを通して銅触媒を除去精製することにより末端にＢｒ基を有する重合体を得た。得られた重合体の数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）で２３６００、分子量分布１．１４であった。
末端にアルケニル基を有するポリ（アクリル酸−ｎ−ブチル）の合成
窒素雰囲気下、２００ｍＬフラスコに上記で得た末端にＢｒ基を有する重合体３４ｇ、ペンテン酸カリウム１．０ｇ（７．６ｍｍｏｌ）、ＤＭＡｃ３４ｍＬを仕込み、７０℃で４時間反応させた。反応混合液中の未反応のペンテン酸カリウムおよび生成した臭化カリウムを水抽出精製により除去し、末端にアルケニル基を有する重合体を得た。この末端にアルケニル基を有する重合体と等重量（３０．５ｇ）の珪酸アルミ（協和化学製：キョ−ワ−ド７００ＰＥＬ）とをトルエンに混合し、１００℃で撹拌した。４時間後、珪酸アルミを濾過し、濾液の揮発分を減圧下加熱して留去することによって重合体を精製した。得られた重合体の数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）で２４８００、分子量分布１．１４であった。また¹Ｈ−ＮＭＲ分析より求めた重合体１分子あたりのアルケニル基の個数は１．４６個であった。
末端に架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）の合成
２００ｍｌ耐圧反応管に上記で得た末端にアルケニル基を有する重合体２１ｇ、メチルジメトキシシラン０．９４ｍｌ（７．６ｍｍｏｌ）オルトギ酸メチル０．１３ｍｌ（１．３ｍｍｏｌ）、白金ビス（ジビニルテトラメチルジシロキサン）２×１０^-4ｍｍｏｌを仕込み、１００℃で４時間反応させ、末端に架橋性シリル基を有する重合体を得た。得られた重合体の粘度は１００Ｐａ・ｓであり、数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）で２５４００、分子量分布１．１６であった。また¹Ｈ−ＮＭＲ分析より求めた重合体１分子あたりの架橋性シリル基の個数は１．４８個であった。
【００８８】
【参考例６】
実施例６で得た末端に架橋性シリル基を有する重合体１００重量部に水１重量部、ジブチル錫ジメトキサイド１重量部を混合攪拌し、厚さ２ｍｍの型枠に流し込んだ。減圧乾操器を用いて室温で脱泡し、５０℃で２日間加熱硬化させることにより、均一なゴム状硬化物シートが得られた。トルエン抽出により求めたゲル分率は９４％であった。ゴム状硬化物シートから２（１／３）号形ダンベル試験片を打ち抜き、オートグラフを用いて引っ張り試験を行った（２００ｍｍ／ｍｉｎ）。破断強度は０．４０ＭＰａ、破断伸びは３２３％であった。
【００８９】
【比較例１】
架橋性ケイ素基含有モノマーを用いた架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）の合成
トルエン４００ｇ、アクリル酸ブチル３８５ｇ、メタクリル酸メチルジメトキシシリルプロピル１５ｇ、アゾビスイソブチロニトリル６ｇを１Ｌフラスコ中で窒素バブリングしながら１０５℃で７時間重合した。トルエンを留去することにより架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）が得られた。この重合体の粘度は７４Ｐａ・ｓであり、数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）により、８５００、分子量分布は２．４７であった。また¹Ｈ−ＮＭＲ分析より求めた重合体１分子あたりの平均の水酸基の個数は１．４０個であった。
【００９０】
【比較参考例１】
比較例１の架橋性シリル基を有する重合体１００重量部に水１重量部、ジブチル錫ジメトキサイド１重量部を混合攪拌し、厚さ２ｍｍの型枠に流し込んだ。減圧乾操器を用いて室温で脱泡し、５０℃で１０日間加熱硬化させることにより、均一なゴム状硬化物シートが得られた。トルエン抽出により求めたゲル分率は７８％であった。ゴム状硬化物シートから２（１／３）号形ダンベル試験片を打ち抜き、オートグラフを用いて引っ張り試験を行った（２００ｍｍ／ｍｉｎ）。破断強度は０．１４ＭＰａ、破断伸びは６９％であった。
【００９１】
【比較例２】
架橋性ケイ素基含有モノマーを用いた架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）の合成
トルエン２１０ｇ、アクリル酸ブチル２９３ｇ、メタクリル酸メチルジメトキシシリルプロピル７．２ｇ、アゾビスイソバレロニトリル１．８ｇを１Ｌフラスコ中で窒素バブリングしながら１０５℃で７時間重合した。トルエンを留去することにより架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）が得られた。この重合体の粘度は１１０Ｐａ・ｓであり、数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）により９６００、分子量分布は２．８６であった。
実施例２から６と比較例１、２の結果を表１にまとめた。
【００９２】
【表１】

【００９３】
ゴム的な性質が要求される用途の場合、モジュラス／破断時強度／破断時伸びのバランスを向上させるため、重合体分子量の高分子量化が望まれる。特に本発明の様な架橋性官能基を有する重合体においては、分子量がゴム設計の重要な指標となる架橋点間分子量と密接に関連しているため、その傾向が強い。 数平均分子量は架橋点間分子量を左右する重要なパラメーターの一つであり、上記物性バランスの向上のためにはこれを大きくできることが望ましい。
【００９４】
本発明の架橋性シリル基を有するビニル系重合体は分子量分布を狭く制御できるので、ほぼ同じ数平均分子量の重合体で比較した場合の粘度は非常に低くなり、その結果取扱い性に優れた原料となる（実施例４の粘度は比較例２の半分以下）。また粘度に制限がある場合は、ほぼ同じ粘度ではより数平均分子量の高い重合体が合成可能なため、よりモジュラス／強度／伸びバランスの優れた硬化物が得られる（実施例７）。またリビングラジカル重合法により架橋性シリル基を有するビニル系重合体を得ているため、一分子当たりの平均の架橋性シリル基の量がほぼ同じであっても、架橋性シリル基を含有しない重合体の量が少なくなり、ゲル分の高い硬化物を得ることができる（実施例４と比較例１）。
【００９５】
【参考例７】
硬化物の耐熱性
参考例４で得た架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）の硬化物シートの一部を１５０℃のオーブンに入れ、２４時間後に取り出し、表面状態を観察した。表面状態に異常はなかった。
【００９６】
【比較例３】
末端に架橋性シリル基を有するポリジメチルシロキサン（シリコーン）の合成
２００ｍｌフラスコに分子量１７，２００の末端ビニルポリジメチルシロキサン（アヅマックス製ＤＭＳ−Ｖ２５：不飽和基当量０．１１ｅｑ／ｋｇ）９７ｇ、メチルジメトキシシラン２．３ｇ（２１．４ｍｍｏｌ）、白金ビス（ジビニルテトラメチルジシロキサン）１０^-3ｍｍｏｌを加え、７０℃で６時間反応した。得られた架橋性シリル基末端ポリジメチルシロキサンの数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）で１１９００、分子量分布２．５２であった。¹ＨＮＭＲ（３００ＭＨｚ）で不飽和基由来のピークは消失し、ポリマ−主鎖由来のケイ素原子に結合したメチルプロトンとメトキシシリル基のプロトンの強度比から求めたポリジメチルシロキサンポリマー１分子当たりの架橋性ケイ素基の個数は２であった。粘度は６ポイズであった。
【００９７】
【比較参考例２】
硬化物の耐熱性
比較例３の架橋性シリル基を有する重合体１００重量部に水１重量部、ジブチルスズジメトキサイド１重量部を混合攪拌し、厚さ２ｍｍの型枠に流し込んだ。減圧脱泡し、５０℃で１０日間加熱硬化させた。得られた硬化物シートの一部を１５０℃のオーブンに入れ、２４時間後に取り出し、表面状態を観察した。表面に異常はなかった。
【００９８】
【比較例４】
末端にアリル基を有するポリイソブチレンの合成
窒素置換した２Ｌの耐圧ガラス製重合容器に、モレキュラーシーブスで乾燥させたエチルシクロヘキサン２０５ｍｌおよびトルエン８１９ｍｌ、ｐ−ジクミルクロライド２．８９ｇ（１２．５ｍｍｏｌ）を加えた。
イソブチレンモノマー３３２ｍｌ（３．９１ｍｏｌ）を重合容器に導入し、次に２−メチルピリジン０．４５４ｇ（４．８８ｍｍｏｌ）と四塩化チタン６．６９ｍｌ（６１．０ｍｍｏｌ）加えて重合を開始した。反応時間７０分後に、アリルトリメチルシラン６．８６ｇ（６０．０ｍｍｏｌ）を加えてポリマー末端にアリル基の導入反応を行った。反応時間１２０分後に、反応溶液を水で洗浄したあと、溶剤を留去することにより末端にアリル基を有するポリイソブチレンを得た。
末端に架橋性シリル基を有するポリイソブチレンの合成
上記で得られた末端にアリル基を有する重合体２００ｇを約７５℃まで昇温した後、メチルジメトキシシラン１．５［eq／ビニル基］、白金（ビニルシロキサン）錯体５×１０^-5［eq／ビニル基］を添加し、ヒドロシリル化反応を行った。ＦＴ−ＩＲにより反応追跡を行い、約２０時間で１６４０cm^-1のオレフィン吸収が消失した。
得られた末端に架橋性シリル基を有するポリイソブチレンの粘度は３６０Ｐａ・ｓであり、数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）で４８００、分子量分布１．５２であった。また¹Ｈ−ＮＭＲ分析より求めた重合体１分子あたりの架橋性シリル基の個数は１．６６個であった。
【００９９】
【比較参考例３】
硬化物の耐熱性
比較例４の末端に架橋性シリル基を有する重合体１００重量部に水１重量部、ジブチル錫ジメトキシド１重量部を混合攪拌し、厚さ２ｍｍの型枠に流し込んだ。減圧脱泡し、５０℃で１０日間加熱硬化させた。得られた硬化物シートの一部を１５０℃のオーブンに入れ、２４時間後に取り出し、表面状態を観察した。表面は溶解しており、一部液状物が流れ出していた。
【０１００】
参考例７および比較参考例２、３の結果を表２に示した。
【０１０１】
【表２】

【０１０２】
本発明の架橋性シリル基を有するビニル系重合体の硬化物は、シリコーン系重合体と同レベルの耐熱性を有し、ポリイソブリレン系よりも耐熱性に優れているので、耐熱性の要求される用途に用いることができる。
【０１０３】
【参考例８】
促進耐候性
参考例４で得た架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）の硬化物シートの一部をサンシャイン・ウエザオ・メーターを用いて促進耐候性試験をおこない、表面状態の観察をおこなった。１０００時間経過後も表面の溶解や変色は起こっていなかった。
【０１０４】
【比較参考例４、５】
参考例４で得た架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）の硬化物の代わりに、比較参考例４では比較例３で得たシリコーン系重合体を、比較参考例５では比較例４で得たポリイソブチレン系重合体を用いて参考例８と同様に促進耐候性試験をおこなった。比較参考例４は１０００時間経過後も表面の溶解や変色は起こっていなかった。一方比較参考例５では５００時間経過後に表面の溶解が始まっていた。
【０１０５】
本発明の架橋性シリル基を有するビニル系重合体を用いた組成物は、シリコーン系重合体組成物と同レベルの耐候性を有しており、ポリイソブリレン系よりもはるかに優れているので、耐候性の要求される用途に用いることができる。
【０１０６】
【参考例９】
一液深部硬化性
実施例５で得た架橋性シリル基を有する重合体１００重量部をトルエンで共沸脱水した。窒素雰囲気下でメチルトリメトキシシラン１重量部、ジブチルスズジアセチルアセトナート１重量部を順次添加し、サンプル瓶に密栓保存することにより一液配合物を作製した。恒温恒湿室（２３℃６０％ＲＨ）で１週間保存後、サンプルチューブに払い出した。払い出し２４時間後に硬化部分を取り出し、その深さ方向の厚みを測定した結果、３ｍｍであった。
【０１０７】
【比較参考例６、７】
一液深部硬化性
実施例５で得た重合体の代わりに、比較参考例６では比較例３で得たシリコーン系重合体を、比較参考例７では比較例４で得たポリイソブチレン系重合体を用いて参考例９と同様に深部硬化性を測定した。比較参考例６の深部硬化性は３ｍｍであった。比較参考例７では、表面に薄皮が張っただけで内部は硬化していなかった。
本発明の架橋性シリル基を有するビニル系重合体組成物は、シリコーン系組成物と同レベルの一液深部硬化性を有しており、ポリイソブリレン系組成物よりもはるかに優れているため、一液型のシーラントなどの組成物として用いることができる。
【０１０８】
【参考例１０】
接着性
実施例５で得た架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）１００重量部に、膠質炭酸カルシウム１２０重量部、ジオクチルフタレート５０重竜部、アミノ基を有する架橋性シリル基含有化合物Ａ−１１２０（日本ユニカー製）２重量部、ジブチルスズジアセチルアセトナート１重量部を加えてよく混合し、ガラス基材上にビード状に施工した。室温で７日放置後、界面に切り込みを入れて引き剥がすことにより、接着性を評価した。破壊状況は配合硬化物の凝集破壊であった。
本発明の架橋性シリル基を有するビニル系重合体の組成物は、十分な接着性を有しており、接着性のある硬化性組成物として充分用いることができる。
【０１０９】
【参考例１１】
塗装性
実施例５で得た架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）１００重量部に、酸化チタン１０重量部、膠質炭酸カルシウム１００重量部、重質炭酸カルシウム４０重量部、オクチル酸スズ３重量部とラウリルアミン０．７５重量部の反応物を加えてよく混合し、シートを作製した。シート作製の翌日に、１０％の水で希釈したアクリルエマルジョン塗料（水性トップ、日本ペイント製）を塗布した。問題なく塗布できた。
【０１１０】
【比較参考例８】
塗装性
参考例１１において実施例５で得た架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）の代わりに比較例３で得た架橋性ケイ素基を有するポリジメチルシロキサンを用いて同様の実験をおこなった。塗料を塗ってもすぐにはじいてしまった。
本発明の架橋性シリル基を有するビニル系重合体を用いた組成物は、シリコーン系重合体を用いた組成物と異なり、十分な塗装性を有していた。したがって塗装可能なシーラントなどの硬化性組成物として用いることが可能である。
【０１１１】
【参考例１２】
汚染性
実施例５で得た架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）１００重量部に、酸化チタン１０重量部、膠質炭酸カルシウム１００重量部、重質炭酸カルシウム４０重量部、オクチル酸スズ３重量部とラウリルアミン０．７５重量部の反応物を加えてよく混合し、プライマー（Ｎｏ．４０、横浜ゴム製）を塗布した御影石の目地に充填し、屋外に暴露した。８カ月を経過しても目地周りはきれいであった。
【０１１２】
【比較参考例９】
参考例１２において実施例５で得た架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）の代わりに比較例３で得た架橋性シリル基を有するポリジメチルシロキサンを用いて同様の実験をおこなった。８ヶ月経過すると目地の周辺が薄黒く汚れていた。
本発明の架橋性シリル基を有するビニル系重合体を用いた組成物は、シリコーン系重合体を用いた組成物と異なり、御影石の汚染がなかった。従って汚染のないシーラントなどの硬化性組成物として用いることが可能である。
【０１１３】
【参考例１３】
粘着剤
実施例４と同様の処方で得た架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）１００重量部に、特殊ロジンエステル（スーパーエステルＡ−１００、荒川化学製）の４０％トルエン溶液１７５重量部（ロジンエステルとして７０重量部）、＃９１８（スズ触媒、三共有機製）２重量部を混合し、ＰＥＴフィルム上に１００μｍのコーターを用いて塗布した。室温で１日放置後、５０℃で１日加熱した。ＪＩＳ Ｚ ０２３７に従って、１８０度引き剥がし粘着力をおこなった結果、４．５Ｎ／２５ｍｍであった。
本発明の架橋性シリル基を有するビニル系重合体は、粘着剤として使用可能である。
【０１１４】
【実施例７】
３０ｍＬの耐圧ガラス反応容器に、アクリル酸ブチル（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（２１７ｍｇ、１．４０ｍｍｏｌ）、酢酸エチル（４ｍＬ）、およびアセトニトリル（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、２時間反応させた。混合物を冷却した後、メチルジメトキシシリルプロピルメタクリレート（６５０ｍｇ、２．８ｍｍｏｌ）を添加し、１００℃で２時間反応させた。混合物を冷却後、酢酸エチル（２０ｍＬ）で希釈し、生成した不溶固体をろ過した後、濾液を塩化アンモニウム水溶液で２回、ブラインで１回洗浄した。有機層をＮａ₂ＳＯ₄で乾燥し、揮発分を減圧下留去し、末端にメチルジメトキシシリル基を有するポリ（アクリル酸ブチル）を４．７８ｇ得た（９０％）。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７１００、分子量分布は１．７４であった。また、¹Ｈ ＮＭＲ分析により、１分子あたりに導入されたシリル基は３．２個であった。
【０１１５】
【実施例８】
１Ｌの耐圧反応容器に、アクリル酸−ｎ−ブチル（１１２ｍＬ、１００ｇ、０．７８ｍｏｌ）、製造例１で合成された水酸基含有開始剤（３．０７ｇ、１５．６ｍｍｏｌ）、臭化第一銅（２．２４ｇ、１５．６ｍｍｏｌ）、２，２'−ビピリジル（４．８７ｇ、３１．２ｍｍｏｌ）、酢酸エチル（９０ｍＬ）、アセトニトリル（２２ｍＬ）を仕込み、窒素ガスを１０分間吹き込んで溶存酸素を除去した後、封管した。混合物を１３０℃に加熱し、１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（３．９２ｍＬ、４．０６ｇ、３１．２ｍｍｏｌ）を加え、１００℃で１時間反応させた。混合物を酢酸エチルで希釈し、不溶分を濾別した後、濾液を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、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。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１．３５であった。
【０１１６】
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）（６８ｇ）およびピリジン（１４ｍＬ）のトルエン溶液（１００ｍＬ）に、窒素雰囲気下、７５℃で、ウンデセン酸クロリド（７．１ｍＬ、３３．０ｍｍｏｌ）をゆっくりと滴下し、６０℃で反応させた。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、末端にアルケニル基を有するポリ（アクリル酸−ｎ−ブチル）（６４ｇ）を得た。重合体のトルエン溶液に珪酸アルミ（協和化学製：キョ−ワ−ド７００ＰＥＬ）を添加して還流温度で撹拌し、重合体中の微量不純物を除去した。オリゴマ−１分子当たりに導入されたアルケニル基は、¹ＨＮＭＲ分析より、２．８個であった。
【０１１７】
次に、１００ｍＬの耐圧ガラス反応容器に、上記重合体（２５．３ｇ）、ジメトキシメチルヒドロシラン（４．８ｍＬ、３８．７ｍｍｏｌ）、オルトぎ酸ジメチル（１．４ｍＬ、１２．９ｍｍｏｌ）、及び、白金触媒を仕込んだ。ただし、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当量とした。反応混合物を１００℃で３時間加熱した。混合物の揮発分を減圧留去することにより、末端にシリル基を有するポリ（アクリル酸−ｎ−ブチル）を得た。オリゴマ−１分子当たりに導入されたシリル基は、¹Ｈ ＮＭＲ分析より、２．２個であった。
【０１１８】
【参考例１４】
実施例７で合成された末端に架橋性シリル基を有するポリ（アクリル酸ブチル）（２．５ｇ）と硬化触媒（日東化成製、Ｕ−２２０、７５ｍｇ）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５４％であった。
【０１１９】
【参考例１５】
実施例８で合成された末端にシリル基を有するポリ（アクリル酸ブチル）に、ジブチルスズジメトキシド及び水を加えてよく混合した。スズ触媒及び水の使用量は、それぞれ重合体に対して１重量部とした。
このようにして得られた組成物を型枠に流し込んで、減圧脱気し、５０℃で２０時間加熱硬化させ、ゴム弾性を有するシート状硬化物を得た。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すると、８８％であった。
【０１２０】
シート状硬化物から２（１／３）号形ダンベル試験片を打ち抜き、島津製オートグラフを用いて、引っ張り試験を行った（測定条件：２３℃、２００ｍｍ／ｍｉｎ）。破断強度は０．３２ＭＰａ、破断伸びは３４％であった。
【０１２１】
【実施例９】
次に、３０ｍＬの耐圧ガラス反応容器に、アクリル酸ブチル（２．５ｍＬ、２．２４ｇ、１７．４５ｍｍｏｌ）、α，α'−ジブロモ−ｐ−キシレン（９２．５ｍｇ、０．３５ｍｍｏｌ）、臭化第一銅（５０ｍｇ、０．３５ｍｍｏｌ）、２，２'−ビピリジル（１６３ｍｇ、１．０５ｍｍｏｌ）、および酢酸エチル（２ｍＬ）、アセトニトリル（０．５ｍＬ）を仕込み、窒素ガスを１０分間吹き込んで溶存酸素を除去した後、封管した。混合物を１３０℃に加熱し、１時間反応させた。室温に冷却した後、製造例１で得られたアリロキシエチルメタクリレート（６００ｍｇ、３．５ｍｍｏｌ）を窒素ガス雰囲気下で添加して封管した。混合物を８０℃に加熱し、１時間反応させた。混合物を酢酸エチル（２０ｍＬ）で希釈し、生成した不溶固体をろ過した後、濾液を希塩酸で２回、ブラインで１回洗浄した。有機層をＮａ₂ＳＯ₄で乾燥し、揮発分を減圧下留去し、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ブチルを１．９７ｇ得た（重合収率８８％）。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６７００、分子量分布は１．６０であった。また、オリゴマー１分子当たりに導入されたアルケニル基は、¹ＨＮＭＲ分析より、５．４個であった。
【０１２２】
【化６】

【０１２３】
【実施例１０】
３０ｍＬの耐圧ガラス反応容器に、アクリル酸ブチル（５ｍＬ、４．４７ｇ、３４．９ｍｍｏｌ）、α，α'−ジブロモ−ｐ−キシレン（１８０ｍｇ、０．６９ｍｍｏｌ）、臭化第一銅（９８ｍｇ、０．６９ｍｍｏｌ）、２，２'−ビピリジル（３１９ｇ、２．０６ｍｍｏｌ）、および酢酸エチル（４ｍＬ）、アセトニトリル（１ｍｌ）を仕込み、窒素ガスを１０分間吹き込んで溶存酸素を除去した後、封管した。混合物を１３０℃に加熱し、１時間反応させた。混合物を冷却後、窒素雰囲気下でアリルトリブチル錫（０．５１ｍＬ、１．６４ｍｍｏｌ）を添加し、１００℃で１時間反応させた。混合物を酢酸エチル（２０ｍＬ）で希釈し、生成した不溶固体をろ過した後、濾液を希塩酸で２回、ブラインで１回洗浄した。有機層をＮａ₂ＳＯ₄で乾燥し、揮発分を減圧下留去し、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ブチルとブロモトリブチル錫の混合物を得た（収量４．４８ｇ）。重合体の数平均分子量はＧＰＣ測定により（ポリスチレン換算）により６３００、分子量分布は１．５７であった。また、オリゴマー１分子当たりに導入されたアルケニル基は、¹Ｈ ＮＭＲ分析より、２．２個であった。
【０１２４】
【化７】

【０１２５】
【実施例１１】
５０ｍＬの２口フラスコを窒素置換し、２−アリルオキシエタノール（２．５ｍＬ、２３．４ｍｍｏｌ）、ピリジン（３ｍＬ）、およびＴＨＦ（１０ｍＬ）を仕込んだ。溶液を０℃に冷却し、２−ブロモプロピオン酸クロライド（２ｍＬ、１９．５２ｍｍｏｌ）をゆっくり滴下した。そのままの温度で１時間撹拌を続けた後、酢酸エチル（１０ｍＬ）を加え、生成したピリジンの塩酸塩を濾過により除去した。濾液を希塩酸（１０ｍＬ）、ＮａＨＣＯ₃水溶液（１０ｍＬ）、さらにブライン（１０ｍＬ）で洗浄した。有機層をＮａ₂ＳＯ₄で乾燥し、揮発分を減圧化留去した。得られた粗生成物を減圧蒸留することにより、下式に示すアリルオキシエチル−２−ブロモプロピオネートを得た。（７８．５〜８１℃（１．３ｍｍＨｇ）、２．９８６ｇ）。
【０１２６】
ＣＨ₃Ｃ（Ｈ）（Ｂｒ）Ｃ（Ｏ）Ｏ−ＣＨ₂ＣＨ₂−Ｏ−ＣＨ₂ＣＨ＝ＣＨ₂
次に、３０ｍＬの耐圧ガラス反応容器に、アクリル酸ブチル（２．５ｍＬ、２．２４ｇ、１７．４５ｍｍｏｌ）、上で得られたアルケニル基を有する開始剤（１６５ｍｇ、０．６９８ｍｍｏｌ）、臭化第一銅（１００ｍｇ、０．６９８ｍｍｏｌ）、２，２'−ビピリジル（２１８ｍｇ、１．４０ｍｍｏｌ）、アセトニトリル（０．５ｍＬ）、酢酸エチル（２ｍＬ）を仕込み、窒素ガスを１０分間吹き込んで溶存酸素を除去した後、封管した。混合物を１３０℃に加熱し、５０分反応させた。室温に冷却した後、混合物を酢酸エチル（２０ｍＬ）で希釈し、生成した不溶固体をろ過した後、濾液を希塩酸で２回、ブラインで１回洗浄した。有機層をＮａ₂ＳＯ₄で乾燥し、揮発分を減圧下留去して、片末端にアルケニル基、他の末端には臭素を有するポリ（アクリル酸ブチル）を１．９０ｇ得た（７９％）。重合体の数平均分子量はＧＰＣ測定により（ポリスチレン換算）により３６００、分子量分布は１．５１であった。また、オリゴマー１分子当たりに導入されたアルケニル基は、¹Ｈ ＮＭＲ分析より、０．７５個であった。
【０１２７】
次に、撹拌子、還流冷却管を備えた５０ｍＬの３つ口フラスコに、上記のようにして得られた重合体（１．９０ｇ）、Ｎａ₂Ｓ・９Ｈ₂Ｏ（７０．２ｍｇ、０．２９３ｍｍｏｌ）、およびエタノール（３ｍＬ）を仕込み、還流温度で３時間撹拌した。室温に冷却した後、酢酸エチル（１０ｍＬ）、希塩酸（１０ｍＬ）を加え、２層を分離した。有機層を希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アルケニル基を有するポリ（アクリル酸）ブチルを１．６９ｇ得た。重合体の数平均分子量はＧＰＣ測定により（ポリスチレン換算）により５１００、分子量分布は１．７３であった。
【０１２８】
【化８】

【０１２９】
【実施例１２】
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時間撹拌した。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
１Ｌの耐圧反応容器に、アクリル酸−ｎ−ブチル（１１２ｍＬ、１００ｇ、０．７８ｍｏｌ）、上で得られた水酸基含有開始剤（３．０７ｇ、１５．６ｍｍｏｌ）、臭化第一銅（２．２４ｇ、１５．６ｍｍｏｌ）、２，２'−ビピリジル（４．８７ｇ、３１．２ｍｍｏｌ）、酢酸エチル（９０ｍＬ）、アセトニトリル（２２ｍＬ）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（３．９２ｍＬ、４．０６ｇ、３１．２ｍｍｏｌ）を加え、１１０℃で２時間反応させた。混合物を酢酸エチル（２００ｍＬ）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、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。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。
【０１３０】
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、７５℃で、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、７５℃で３時間撹拌した。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。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１．３０であった。また、オリゴマー１分子当たりに導入されたアルケニル基は、¹ＨＮＭＲ分析より、２．２８個であった。
【０１３１】
【化９】

【０１３２】
【比較例５】
特開平６−２１１９２２の製造例３に従って、両末端に水酸基を有するポリ（アクリル酸−ｎ−ブチル）を合成した。すなわち、撹拌子と滴下ロートを備え付けた１００ｍＬの３つ口フラスコに、２−ヒドロキシエチルジスルフィド（３０．８ｇ、２４．４ｍＬ、０．２ｍｏｌ）を加えた。フラスコを１００℃に加熱し、アクリル酸−ｎ−ブチル（１２．８ｇ、１４．３２ｍＬ、０．１ｍｏｌ）とＡＩＢＮ（０．３２８ｇ、０．００２ｍｏｌ）の混合物を３０分かけて滴下した。混合物をさらに１時間、１００℃にて撹拌した。トルエン（２０ｍＬ）を加え、混合物を分液ロートに静置し、下層を分離した。上層を水で３回洗浄し、Ｎａ₂ＳＯ₄で乾燥した後、減圧下、揮発分を留去することにより、両末端に水酸基を有するポリ（アクリル酸−ｎ−ブチル）を得た（１２．１８ｇ、９５％）。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、４３００、分子量分布は４．２２であった。
【０１３３】
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）（１０．５１ｇ）およびピリジン（２ｍＬ）のトルエン溶液（１５ｍＬ）に、窒素雰囲気下、６０℃で、ウンデセン酸クロリド（０．８９８ｍＬ、８４８ｍｇ、４．１８ｍｍｏｌ）をゆっくりと滴下し、６０℃で３時間撹拌した。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）（７．４５ｇ）を得た。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、４４００、分子量分布は４．３１であった。
【０１３４】
【参考例１６〜１９および比較参考例１０】
硬化物の作成
実施例９〜１２、および比較例５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）をトルエンに溶解し、重合体と等量の珪酸アルミ（協和化学製：キョーワード７００ＰＥＬ）を添加して１時間撹拌し、重合体中の微量不純物を除去した。
【０１３５】
次に、精製されたそれぞれのポリ（アクリル酸ブチル）と、下式に示す多価ハイドロジェンシリコン化合物、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。多価ハイドロジェンシリコン化合物の使用量は、重合体のアルケニル基とハイドロジェンシリコン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。
【０１３６】
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３に示した。
【０１３７】
【化１０】

【０１３８】
【表３】

【０１３９】
【実施例１３】
実施例９において、アクリル酸−ｎ−ブチルのかわりにアクリル酸メチルを使用する以外は同様にして、末端にアルケニル基を有するポリ（アクリル酸メチル）を得た（収率９３％）。重合体の数平均分子量はＧＰＣ測定により（ポリスチレン換算）により７９００、分子量分布は２．０であった。また、オリゴマー１分子当たりに導入されたアルケニル基は、１Ｈ ＮＭＲ分析より平均３．３個であった。
【０１４０】
【実施例１４】
還流管付き５００ｍＬ三つ口フラスコで、触媒として臭化第一銅（１．５０ｇ、１０．５ｍｍｏｌ）、配位子としてペンタメチルジエチレントリアミン（１．６５ｍＬ）、開始剤としてジエチル−２，５−ジブロモアジペート（９．４２ｇ、２６．２ｍｏｌ）、溶媒としてアセトニトリル（３０ｍＬ）を用いて、アクリル酸−ｎ−ブチル（３００ｍＬ）を窒素雰囲気下７０℃で重合し、アクリル酸−ｎ−ブチルの重合率が９３％の時点で、１，７−オクタジエン（３８．６ｍＬ，０．２６１ｍｏｌ）を添加し、同温度で加熱した。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て触媒を除き、揮発分を減圧留去することにより、末端にアルケニル基を有する重合体を得た。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１３８００、分子量分布は１．２８であった。オリゴマ−１分子当たりに導入されたアルケニル基は、¹Ｈ ＮＭＲ分析より、１．８４個であった。
【０１４１】
【実施例１５】
３０ｍＬの耐圧ガラス反応容器に、アクリル酸−ｎ−ブチル（７．５ｍＬ、６．７２ｇ、５１．３ｍｍｏｌ）、α，α' −ジブロモ−ｐ−キシレン（２７０ｍｇ、１．０３ｍｍｏｌ）、臭化第一銅（１５０ｍｇ、１．０３ｍｍｏｌ）、２，２' −ビピリジル（３２２ｍｇ、２．０６ｍｍｏｌ）、酢酸エチル（６ｍＬ）、及び、アセトニトリル（１．５ｍＬ）を仕込み、窒素ガスを１０分間吹き込んで溶存酸素を除去した後、封管した。混合物を１３０℃に加熱し、１．５時間反応させた。混合物を酢酸エチル（２０ｍＬ）で希釈し、生成した不溶固体をろ過した後、濾液を希塩酸で２回、ブラインで１回洗浄した。有機層をＮａ₂ＳＯ₄で乾燥し、揮発分を減圧下留去し、末端にハロゲンを有するポリ（アクリル酸−ｎ−ブチル）を５．０ｇ得た（重合収率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５６００、分子量分布は１．３２であった。
【０１４２】
上記重合体（５．００ｇ）、製造例２で合成されたウンデシレン酸カリウム塩（４７６ｍｇ、２．１４ｍｍｏｌ）、及び、ジメチルアセトアミド（１０ｍＬ）を仕込み、窒素雰囲気下、７０℃で６時間反応させた。混合物の揮発分を減圧留去した後、酢酸エチルを加えて不溶分を濾別した。濾液の揮発分を減圧留去することにより、末端にアルケニル基を有するポリ（アクリル酸−ｎ−ブチル）４．７７ｇを得た。オリゴマ−１分子当たりに導入されたアルケニル基は、¹Ｈ ＮＭＲ分析より、１．７０個であった。
【０１４３】
【実施例１６】
実施例１５と同様にして、触媒として臭化第一銅（１．５０ｇ、１０．５ｍｍｏｌ）、配位子としてペンタメチルジエチレントリアミン（０．６９ｍＬ）、開始剤としてジエチル−２，５−ジブロモアジペート（９．４２ｇ、２６．２ｍｏｌ）、溶媒としてアセトニトリル（３０ｍＬ）を用いて、アクリル酸−ｎ−ブチル（３００ｍＬ）を窒素雰囲気下７０℃で重合し、末端にハロゲンを有するポリ（アクリル酸−ｎ−ブチル）を得た。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１１３００、分子量分布は１．１６であった。
【０１４４】
次に、カルボン酸塩として製造例３で製造されたペンテン酸カリウム塩を用いて実施例１５と同様の操作により、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。オリゴマ−１分子当たりに導入されたアルケニル基は、¹Ｈ ＮＭＲ分析より、１．８４個であった。
【０１４５】
【実施例１７】
３０ｍＬの耐圧ガラス反応容器に、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（１８０ｍｇ、０．６９ｍｍｏｌ）、臭化第一銅（９８ｍｇ、０．６９ｍｍｏｌ）、２，２'−ビピリジル（３１９ｇ、２．０６ｍｍｏｌ）、および酢酸エチル（４ｍＬ）、アセトニトリル（１ｍｌ）を仕込み、窒素ガスを１０分間吹き込んで溶存酸素を除去した後、封管した。混合物を１３０℃に加熱し、１時間反応させた。混合物を冷却後、窒素雰囲気下でアリルトリブチル錫（０．５１ｍＬ、１．６４ｍｍｏｌ）を添加し、１００℃で１時間反応させた。混合物を酢酸エチル（２０ｍＬ）で希釈し、生成した不溶固体をろ過した後、濾液を希塩酸で２回、ブラインで１回洗浄した。有機層をＮａ₂ＳＯ₄で乾燥し、揮発分を減圧下留去し、末端にアルケニル基を有するポリアクリル酸−ｎ−ブチルとブロモトリブチル錫の混合物を得た（収量４．４８ｇ）。重合体の数平均分子量はＧＰＣ測定により（ポリスチレン換算）により６３００、分子量分布は１．５７であった。また、オリゴマー１分子当たりに導入されたアルケニル基は、¹Ｈ ＮＭＲ分析より、２．２個であった。
【０１４６】
【実施例１８】
３０ｍＬの耐圧ガラス反応容器に、アクリル酸メチル（５ｍＬ、４．７８ｇ、５５．５ｍｍｏｌ）、２−メチル−２−ブロモプロピオン酸アリル（０．３５４ｍＬ、４６０ｍｇ、２．２２ｍｍｏｌ）、臭化第一銅（３１８ｍｇ、２．２２ｍｍｏｌｍｍｏｌ）、２，２'−ビピリジル（１．０４ｇ、６．６６ｍｍｏｌ）、アセトニトリル（１ｍＬ）、酢酸エチル（４ｍＬ）を仕込み、真空脱気を３回行って溶存酸素を除去した後、封管した。混合物を８０℃に加熱し、３時間反応させた。室温に冷却した後、混合物を酢酸エチル（２０ｍＬ）で希釈し、生成した不溶固体をろ過した後、濾液を希塩酸で２回、ブラインで１回洗浄した。有機層をＮａ₂ＳＯ₄で乾燥し、揮発分を減圧下留去して、片末端にアルケニル基、他の末端には臭素を有するポリ（アクリル酸メチル）を３．９３ｇ得た（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２７００、分子量分布は１．４８であった。また、オリゴマー１分子当たりに導入されたアルケニル基は、¹Ｈ ＮＭＲ分析より、０．８１個であった。
【０１４７】
次に、撹拌子、還流冷却管を備えた５０ｍＬの３つ口フラスコに、上記のようにして得られた重合体（１．１７ｇ）、Ｎａ₂Ｓ・９Ｈ₂Ｏ（５７．６ｍｇ、０．２４０ｍｍｏｌ）、およびエタノール（２ｍＬ）を仕込み、還流温度で３時間撹拌した。室温に冷却した後、酢酸エチル（１０ｍＬ）、希塩酸（１０ｍＬ）を加え、２層を分離した。有機層を希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、末端にアルケニル基を有するポリ（アクリル酸メチル）を１．１１ｇ得た。重合体の数平均分子量はＧＰＣ測定により（ポリスチレン換算）により４２００、分子量分布は１．７１であった。
【０１４８】
【実施例１９】
１Ｌの耐圧反応容器に、アクリル酸−ｎ−ブチル（１１２ｍＬ、１００ｇ、０．７８ｍｏｌ）、製造例３で得られた水酸基含有開始剤（３．０７ｇ、１５．６ｍｍｏｌ）、臭化第一銅（２．２４ｇ、１５．６ｍｍｏｌ）、２，２'−ビピリジル（４．８７ｇ、３１．２ｍｍｏｌ）、酢酸エチル（９０ｍＬ）、アセトニトリル（２２ｍＬ）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（３．９２ｍＬ、４．０６ｇ、３１．２ｍｍｏｌ）を加え、１１０℃で２時間反応させた。混合物を酢酸エチル（２００ｍＬ）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、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。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。
【０１４９】
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、７５℃で、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、７５℃で３時間撹拌した。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、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。
【０１５０】
【参考例２０〜２９】
硬化物の作成
製造例１３〜１９で得られた末端にアルケニル基を有する重合体を珪酸アルミ（協和化学製、キョーワード７００ＰＥＬ）で処理し、重合体中の微量不純物を除去した。
【０１５１】
次に、精製されたポリ（アクリル酸エステル）と、多価ハイドロジェンシリコン化合物、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。多価ハイドロジェンシリコン化合物として、下記に示す化合物（Ｓ−１、Ｓ−２）、もしくはα−メチルスチレンで一部変性したメチルハイドロジェンシロキサン（Ｓ−３：ＳｉＨ価７．６９ｍｍｏｌ／ｇ）を用いた。多価ハイドロジェンシリコン化合物の使用量は、重合体のアルケニル基とハイドロジェンシリコン化合物のＳｉＨ基がモル比で１／１．２〜１／１．５となる量とした。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、所定量添加した。
【０１５２】
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、１００℃に加熱し、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４に示した。
【０１５３】
【化１１】

【０１５４】
【表４】

【０１５５】
【実施例２０】
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４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、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。この重合体の粘度をＥ型粘度系により測定したところ（剪断速度：１０ｓｅｃ^-1、２３℃）、３８８ポイズであった。
【０１５６】
【化１２】

【０１５７】
【比較例６】
特開平５−２６２８０８の実施例１に従い、両末端に水酸基を有するポリ（アクリル酸−ｎ−ブチル）を合成した。すなわち、撹拌子と滴下ロートを備え付けた１００ｍＬの３つ口フラスコに、２−ヒドロキシエチルジスルフィド（３０．８ｇ、２４．４ｍＬ、０．２ｍｏｌ）を加えた。フラスコを１００℃に加熱し、アクリル酸−ｎ−ブチル（１２．８ｇ、１４．３２ｍＬ、０．１ｍｏｌ）とＡＩＢＮ（０．３２８ｇ、０．００２ｍｏｌ）の混合物を３０分かけて滴下した。混合物をさらに１時間、１００℃にて撹拌した。トルエン（２０ｍＬ）を加え、混合物を分液ロートに静置し、下層を分離した。上層を水で３回洗浄し、Ｎａ₂ＳＯ₄で乾燥した後、減圧下、揮発分を留去することにより、両末端に水酸基を有するポリ（アクリル酸−ｎ−ブチル）を得た（１２．１８ｇ、９５％）。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、４３００、分子量分布は４．２２であった。この重合体の粘度をＥ型粘度系により測定したところ（剪断速度：１０ｓｅｃ^-1、２３℃）、４９０ポイズであった。また、¹Ｈ−ＮＭＲ分析より求めた重合体１分子あたりの平均の水酸基の個数は１．４２個であった。
【０１５８】
実施例２０および比較例６で得られた重合体の性状を表５にまとめた。
【０１５９】
【表５】

【０１６０】
実施例２０の重合体は比較例６の重合体よりも、数平均分子量がかなり高いにも関わらず、粘度は低い。ここにおいて、本発明の重合体の分子量分布が狭いことの優位性が明らかである。
【０１６１】
【参考例３０および比較参考例１１】
ウレタン硬化物の作成
実施例２０、および比較例６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）を、それぞれ、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（日東化成製、Ｕ−２２０、ジブチルスズジアセチルアセトネート）と、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。
【０１６２】
上記各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。得られたシート状硬化物の一部をトルエンに２４時間浸漬し、前後の重量変化から、ゲル分率を算出した。また、シート状硬化物からＪＩＳＫ６３０１に準拠した３号ダンベルを打ち抜き、引張速度２００ｍｍ／ｍｉｎで引張試験を行なった。結果を表６に示した。
【０１６３】
【化１３】

【０１６４】
【表６】

【０１６５】
参考例３０の方が、比較参考例１１よりも破断強度、伸び、ゲル分率のすべてにおいて上回る。本発明の重合体の進歩性が明らかである。
【０１６６】
【実施例２１】
末端に水酸基を有するポリ（アクリル酸−ｎ−ブチル）の合成
１Ｌの耐圧反応容器に、アクリル酸−ｎ−ブチル（１１２ｍＬ、１００ｇ、０．７８ｍｏｌ）、製造例４で得られた水酸基含有開始剤（３．０７ｇ、１５．６ｍｍｏｌ）、臭化第一銅（２．２４ｇ、１５．６ｍｍｏｌ）、２，２'−ビピリジル（４．８７ｇ、３１．２ｍｍｏｌ）、酢酸エチル（９０ｍＬ）、アセトニトリル（２０ｍＬ）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（３．９２ｍＬ、４．０６ｇ、３１．２ｍｍｏｌ）を加え、１１０℃で２時間反応させた。混合物を酢酸エチル（２００ｍＬ）で希釈し、不溶分を濾別した後、濾液を１０％塩酸とブラインで洗浄、有機層をＮａ₂ＳＯ₄で乾燥した。溶媒を減圧下留去し、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。この重合体の粘度は２５Ｐａ・ｓであり、数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）により、５１００、分子量分布は１．２９であった。また、¹Ｈ−ＮＭＲ分析より求めた重合体１分子あたりの平均の水酸基の個数は２．３９個であった。
末端に架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）の合成
上記で合成した末端に水酸基を有するポリ（アクリル酸−ｎ−ブチル）（４．９４ｇ、ＯＨ＝２．３０ｍｍｏｌ）をトルエン存在下５０℃で共沸脱水を行なった。ここへオクチル酸スズ（４．９ｍｇ）およびトルエン（６ｍＬ）を加え、５０℃でメチルジメトキシシリルプロピルイソシアネート（０．５２４ｇ、２．７７ｍｍｏｌ）を滴下した。、滴下終了後、７０℃に反応温度を上げ４時間反応を継続した。１Ｈ−ＮＭＲで水酸基の結合したメチレン基のシグナル（３．８ｐｐｍ）が消失したことにより、未反応の水酸基はないものと判断した。揮発分を減圧により留去し、末端に架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）を得た。この重合体の粘度は２２Ｐａ・ｓであり、数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）により、４９００、分子量分布は１．６０であった。
【０１６７】
【参考例３１】
実施例２１で得た末端に架橋性シリル基を有する重合体１００重量部に対し、ジブチルスズジアセチルアセトナート１重量部を混合し、型枠に流し込んで、減圧乾燥器を用いて室温で脱泡した。５０℃で２０時間加熱硬化させることにより、均一なゴム状硬化物シートが得られた。トルエン抽出により求めたゲル分率は９３％であった。
ゴム状硬化物シートから２（１／３）号形ダンベル試験片を打ち抜き、オートグラフを用いて引っ張り試験を行った（２００ｍｍ／ｍｉｎ）ところ破断強度は０．３１ＭＰａ、破断伸びは３５％であった。
【０１６８】
【比較例７】
水酸基含有ジスルフィドを用いた末端に架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）の合成
比較例６で合成した末端に水酸基を有するポリ（アクリル酸−ｎ−ブチル）（４．５２ｇ、ＯＨ＝１．８５ｍｍｏｌ）をトルエン存在下５０℃で共沸脱水を行なった。ここへオクチル酸スズ（４．５２ｍｇ）およびトルエン（６ｍＬ）を加え、５０℃でメチルジメトキシシリルプロピルイソシアネート（０．４２１ｇ、２．２２ｍｍｏｌ）を滴下した。、滴下終了後、７０℃に反応温度を上げ４時間反応を継続した。１Ｈ−ＮＭＲで水酸基の結合したメチレン基のシグナル（３．８ｐｐｍ）が消失したことにより、未反応の水酸基はないものと判断した。揮発分を減圧により留去し、末端に架橋性シリル基を有するポリ（アクリル酸−ｎ−ブチル）を得た。この重合体の粘度は５３Ｐａ・ｓであり、数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）により、４７００、分子量分布は３．７１であった。
【０１６９】
【比較参考例１２】
比較例７の末端に架橋性シリル基を有する重合体１００重量部に対し、ジブチルスズジアセチルアセトナート１重量部を混合し、型枠に流し込んで、減圧乾操器を用いて室温で脱泡した。５０℃で２０時間加熱硬化させることにより、均一なゴム状硬化物シートが得られた。トルエン抽出により求めたゲル分率は８２％であった。抽出分を濃縮して¹Ｈ−ＮＭＲを測定したが、その中には架橋性シリル基は存在していなかった。
【０１７０】
ゴム状硬化物シートから２（１／３）号形ダンベル試験片を打ち抜き、オートグラフを用いて引っ張り試験を行った（２００ｍｍ／ｍｉｎ）ところ破断強度は０．２１ＭＰａ、破断伸びは９３％であった。
【０１７１】
【実施例２２】
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。
【０１７２】
【化１４】

【０１７３】
【実施例２３】
実施例２０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。
【０１７４】
【実施例２４】
実施例２０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。
【０１７５】
【実施例２５】
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４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。
【０１７６】
次に、撹拌子、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時間撹拌した。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。
【０１７７】
【化１５】

【０１７８】
【参考例３２〜３５】
硬化物の作成
実施例２２〜２５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（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。
【０１７９】
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７に示した。
【０１８０】
【化１６】

【０１８１】
【表７】

【０１８２】
【実施例２６】
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。
【０１８３】
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。
【０１８４】
【参考例３６】
実施例２６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。この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。
【０１８５】
【発明の効果】
本発明の、末端に架橋性シリル基、あるいは、アルケニル基、あるいは、水酸基を有するビニル系重合体は、リビングラジカル重合を利用することにより製造されるので、分子量分布が狭い。従って通常のラジカル重合により製造される、同等の分子量を有する重合体に比較して粘度が低く、硬化性組成物として用いる際に、取扱いが容易であると期待される。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a vinyl polymer having a crosslinkable silyl group, an alkenyl group, or a hydroxyl group at a terminal. More particularly, the present invention relates to a vinyl polymer having a narrow molecular weight distribution and thus easy handling.
[0002]
[Prior art]
Vinyl polymers having a crosslinkable silyl group in the molecule, particularly (meth) acrylic polymers, are utilized as highly weather resistant paints by utilizing the weather resistance of the main chain and the crosslinking point. These (meth) acrylic polymers are usually produced by a method in which a (meth) acrylic monomer having a crosslinkable silyl group is copolymerized with other monomers, so that the crosslinkable silyl group is an arbitrary component in the molecular chain. Therefore, it is difficult to use for rubber applications. On the other hand, there is an attempt to produce a (meth) acrylic polymer having a crosslinkable silyl group at a molecular end and use it for a sealing material or an adhesive. As a method for producing a (meth) acrylic polymer having a crosslinkable silyl group at the molecular terminal, for example, in JP-B-3-14068, a (meth) acrylic monomer is used as a crosslinkable silyl group-containing mercaptan, a crosslinkable silyl group. And a method of polymerizing in the presence of a radical polymerization initiator having a crosslinkable silyl group. In JP-B-4-55444, an acrylic monomer is converted into a crosslinkable silyl group-containing hydrosilane compound or a tetrahalosilane. A method of polymerizing in the presence is disclosed. JP-A-6-221922 is characterized by first synthesizing an acrylic polymer having a hydroxyl group at a terminal by using a large amount of a hydroxyl group-containing polysulfide with respect to the initiator, and further converting the hydroxyl group. A method for producing a (meth) acrylic polymer having a crosslinkable silyl group at the terminal is described.
[0003]
On the other hand, a polymer having an alkenyl group at the end of the molecular chain is known to be crosslinked by itself or using a curing agent such as a hydrosilyl group-containing compound to give a cured product having excellent heat resistance and durability. ing. Examples of the main chain skeleton of such a polymer include polyether polymers such as polyethylene oxide, polypropylene oxide, and polytetramethylene oxide, hydrocarbons such as polybutadiene, polyisoprene, polychloroprene, polyisobutylene, and hydrogenated products thereof. Polymers, polyester polymers such as polyethylene terephthalate, polybutylene terephthalate, polycaprolactone, polysiloxane polymers such as polydimethylsiloxane, etc., and are used in various applications depending on the properties of the main chain skeleton. Yes.
[0004]
Among the polymers obtained by ionic polymerization or condensation polymerization exemplified above, vinyl polymers obtained by radical polymerization and having a functional group at the terminal are hardly practically used. Among vinyl polymers, vinyl polymers have characteristics that cannot be obtained with the above-described polyether polymers or polyester polymers, such as high weather resistance and transparency. For example, alkenyl groups In the side chain, those having high weather resistance are used.
[0005]
If a vinyl polymer having an alkenyl group at the molecular end can be obtained by a simple method, a cured product having excellent cured product properties can be obtained as compared with those having an alkenyl group in the side chain. Therefore, many researchers have studied the production method so far, but it is not easy to produce them industrially.
JP-A-1-247403 discloses a method for synthesizing a vinyl polymer having an alkenyl group at both ends using an alkenyl group-containing disulfide as a chain transfer agent, and JP-A-6-219922 discloses a disulfide having a hydroxyl group. Used to synthesize vinyl polymers having hydroxyl groups at both ends, and further disclosed methods for synthesizing vinyl polymers having alkenyl groups at both ends by utilizing the reactivity of hydroxyl groups. In this method, it is difficult to reliably introduce alkenyl groups at both ends, and a cured product having satisfactory characteristics cannot be obtained. In order to reliably introduce an alkenyl group at both ends, a large amount of chain transfer agent must be used, which is a problem in the production process. In these methods, since ordinary radical polymerization is used, it is difficult to control the molecular weight and molecular weight distribution (ratio of number average molecular weight to number average molecular weight) of the obtained polymer.
[0006]
In addition, 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 known.
As the main chain skeleton of the polymer having a hydroxyl group at the end, as with the alkenyl-terminated polymer, a polyether polymer such as polyethylene oxide, polypropylene oxide, polytetramethylene oxide, polybutadiene, polyisoprene, Examples include hydrocarbon polymers such as polychloroprene, polyisobutylene or hydrogenated products thereof, and polyester polymers such as polyethylene terephthalate, polybutylene terephthalate, polycaprolactone, etc. Used for applications.
[0007]
Vinyl polymers, especially (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.
If a vinyl polymer having a hydroxyl group at the molecular chain terminal 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, many methods have been studied by many researchers until now, but it is not easy to manufacture them industrially.
[0008]
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, by polymerization of a (meth) acrylic monomer using a telogen such as methylene dibromide, a (meth) acrylic polymer having halogen at the terminal is obtained, and the terminal halogen is converted to a diol compound, 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 hydroxyl group-containing carboxylic acid or 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 hydroxyl groups at both ends at a high ratio.
[0009]
In addition, since any of the above methods uses normal radical polymerization, the resulting polymer has a wide molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) (usually 2 or more), and therefore has a high viscosity. There is. When the viscosity is high, for example, when it is used as a sealing material or an adhesive, there are problems that handling at the time of construction becomes difficult and a filler for reinforcement cannot be blended in a large amount.
[0010]
[Problems to be solved by the invention]
In the above method for producing a vinyl polymer, since ordinary radical polymerization is used, the resulting polymer has a wide molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) (generally 2 or more), Therefore, there is a problem that the viscosity is high. When the viscosity is high, for example, when it is used as a sealing material or an adhesive, there are problems that handling at the time of construction becomes difficult and a filler for reinforcement cannot be blended in a large amount.
The present invention solves these problems and provides a vinyl polymer that is easy to handle because of its narrow molecular weight distribution.
[0011]
Recently, research on living radical polymerization has been actively conducted (for example, Matyjazewski et al., J. Am. Chem. Soc. 1995, 117, 5614, Macromolecules, 1995, 28, 7901, Science 1996, 272, 866. (See Sawamoto et al., Macromolecules 1995, 28, 1721), and by using these polymerization methods, vinyl polymers having a halogen at the terminal and having a narrow molecular weight distribution can be obtained. The present inventor has found that a vinyl polymer having a narrow molecular weight distribution and having a crosslinkable silyl group, alkenyl group or hydroxyl group at the end of the molecule can be obtained by using this novel living radical polymerization method. The invention has been reached.
[0012]
[Means for Solving the Problems]
The present invention has at least one cross-linkable silyl group represented by the general formula 1, or an alkenyl group represented by the general formula 2 or a hydroxyl group at the molecular end, and measured by gel permeation chromatography. The vinyl polymer having a ratio of the weight average molecular weight to the number average molecular weight of less than 1.8.
-[Si (R¹)_2-b(Y)_bO]_m-Si (R²)_3-a(Y)_a(1)
(Wherein R¹And R²Are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or aralkyl groups having 7 to 20 carbon atoms, or (R ′)._ThreeA triorganosiloxy group represented by Si— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different). , R1 or R2 may be the same or different when two or more are present. 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. )
H₂C = C (R^Three-(2)
(Wherein R^ThreeIs hydrogen or methyl group)
[0013]
DETAILED DESCRIPTION OF THE INVENTION
The present invention has at least one cross-linkable silyl group represented by the general formula 1, or an alkenyl group represented by the general formula 2 or a hydroxyl group at the molecular end, and measured by gel permeation chromatography. The vinyl polymer having a ratio of the weight average molecular weight to the number average molecular weight of less than 1.8.
-[Si (R¹)_2-b(Y)_bO]_m-Si (R²)_3-a(Y)_a(1)
(Wherein R¹And R²Are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or aralkyl groups having 7 to 20 carbon atoms, or (R ′)._ThreeA triorganosiloxy group represented by Si— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different). , R¹Or R²When 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. )
H₂C = C (R^Three-(2)
(Wherein R^ThreeIs hydrogen or methyl group)
The number of the crosslinkable silyl group of the general formula 1 or the alkenyl group or the hydroxyl group represented by the general formula 2 is at least 1 per molecule, preferably 1.2 to 4. If it is less than 1, problems such as poor curability when used as a curable composition may occur.
[0014]
The vinyl polymer of the present invention is characterized in that the molecular weight distribution, that is, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is narrow. Have. The value of the molecular weight distribution is less than 1.8, preferably 1.7 or less, more preferably 1.6 or less, particularly preferably 1.5 or less, particularly preferably 1.4 or less. Yes, most preferably 1.3 or less. The GPC measurement in the present invention is not particularly limited, but usually, chloroform is used as the mobile phase, and the measurement is performed with a polystyrene gel column. The number average molecular weight and the like can be determined in terms of polystyrene.
[0015]
Although the number average molecular weight of the vinyl polymer of the present invention is not particularly limited, a range of 500 to 100,000 is preferable, and a range of 3000 to 50,000 is more preferable. When the molecular weight is 500 or less, the original characteristics of the vinyl polymer are hardly expressed, and when it is 100,000 or more, handling becomes difficult.
It does not specifically limit as a vinyl-type monomer used for manufacture of the principal chain of the vinyl-type polymer of this invention, A various thing can be used. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n- Butyl, isobutyl (meth) acrylate, (tert-butyl) (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acryl 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) Phenyl acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate (Meth) acrylic acid-3-methoxybutyl, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid stearyl, (meth) acrylic acid glycidyl, (meth) 2-aminoethyl acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate , 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate , (Perfluoromethylmethyl) (meth) acrylate, (me T) 2-perfluoromethyl-2-perfluoroethylmethyl acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluoro (meth) acrylate (Meth) acrylic acid monomers such as hexadecylethyl; styrene monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and their salts; perfluoroethylene, perfluoropropylene, vinylidene fluoride, etc. Fluorine-containing vinyl monomers; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters of fumaric acid and Dialkyl esters; maleimide monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; nitrile groups such as acrylonitrile and methacrylonitrile Vinyl monomers; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; butadiene And conjugated dienes such as isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like. These may be used alone or a plurality of these may be copolymerized. Of these, a styrene monomer and a (meth) acrylic acid monomer are preferable from the physical properties of the product. More preferred are acrylic ester monomers and methacrylic ester monomers, and even more preferred is butyl acrylate. In the present invention, these preferable monomers may be copolymerized with other monomers, and in this case, it is preferable that these preferable monomers are contained in a weight ratio of 40%. In the above expression format, for example, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.
[0016]
In the polymer having a crosslinkable silyl group at the terminal, the hydrolyzable group represented by Y in the general formula 1 is not particularly limited, and any conventionally known hydrolyzable group can be used. An atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminooxy group, a mercapto group, an alkenyloxy group and the like can be mentioned, and an alkoxy group is particularly preferable because it is 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 a + mb, that is, the total sum of hydrolyzable groups is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the crosslinkable 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. In the case of silicon atoms linked by a siloxane bond, up to about 20 silicon atoms may be used.
[0017]
In the polymer having an alkenyl group at the terminal, the alkenyl group represented by the general formula 2 will be described in more detail. First, an alkenyl group represented by the general formula 3 and bonded to the main chain via a hydrocarbon group may be mentioned.
H₂C = C (R^Four-R^Five-(3)
(Wherein R^FourIs the same as above, R^FiveIs a direct bond, or an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an aralkylene group having 7 to 20 carbon atoms, and may contain one or more ether bonds)
R other than direct bond^FiveAs a specific example, for example,-(CH₂)_n-(N is an integer from 1 to 20), -CH (CH_Three) CH₂-, -CH (CH_Three) (CH₂)₂-, -CH₂CH (CH_Three)-, -C (CH_Three)₂-,-(CH₂)_n-O- (CH₂)_m-(N and m are integers of 1 to 20, where n + m≤20), o-, m-, p-C₆H_Four-, O-, m-, p- (CH₂)_n-C₆H_Four-(CH₂)_m-(N and m are integers of 0 to 14, where n + m ≤ 14) and the like, but are not limited thereto.
[0018]
In addition to this, the alkenyl group represented by the general formula 2 is bonded to the main chain via an ether bond represented by the general formula 4 and the ester bond represented by the general formulas 5 and 6 as represented by the general formula 4. And an alkenyl group bonded to the main chain via a carbonate group represented by the general formula 7.
H₂C = C (R^Four-R^Five-O- (4)
H₂C = C (R^Four-R^Five-OC (O)-(5)
H₂C = C (R^Four-R^Five-C (O) O- (6)
H₂C = C (R^Four-R^Five-OC (O) O- (7)
(In the above formulas, R^Four, R^FiveIs the same as above)
R^FiveAs specific examples, all of those already exemplified can be preferably used.
[0019]
Such hydroxyl group will be described in more detail. First, the hydroxyl group bonded to the main chain by a hydrocarbon group represented by the general formula 8 can be mentioned.
HO-R⁶-(8)
(Wherein R⁶Is a direct bond, or an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an aralkylene group having 7 to 20 carbon atoms, and may contain one or more ether bonds)
R other than direct bond⁶As a specific example, for example,-(CH₂)_n-(N is an integer from 1 to 20), -CH (CH_Three) CH₂-, -CH (CH_Three) (CH₂)₂-, -CH₂CH (CH3)-, -C (CH_Three)₂-,-(CH₂)_n-O- (CH₂)_m-(N and m are integers of 1 to 20, where n + m≤20), -CH (C₆H_Five)-, -C (CH_Three) (C₆H_Five)-, O-, m-, p-C₆H_Four-, O-, m-, p- (CH₂)_n-C₆H_Four-(CH₂)_m-(N and m are integers of 0 to 14, where n + m ≤ 14) and the like, but are not limited thereto.
[0020]
In addition to this, as a terminal hydroxyl group, a hydroxyl group bonded to the main chain via an ether bond represented by general formula 9, a hydroxyl group bonded to the main chain via an ester bond represented by general formulas 10 and 11, Furthermore, the hydroxyl group couple | bonded with a principal chain through the carbonate group shown by General formula 12 is mentioned.
HO-R⁷-O- (9)
HO-R⁷-OC (O)-(10)
HO-R⁷-C (O) O- (11)
HO-R⁷-OC (O) O- (12)
(R⁷May be an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an aralkylene group having 7 to 20 carbon atoms, and may contain one or more ether bonds) R⁷As a specific example, R⁶All of the groups shown as specific examples (except for a direct bond) can be preferably used.
Synthesis of polymer backbone
The main chain of the polymer of the present invention is not limited, but is preferably produced by a living radical polymerization method.
[0021]
Living radical polymerization is radical polymerization in which the activity at the polymerization terminal is maintained without loss. In the narrow sense, living polymerization refers to polymerization in which the terminal always has activity, but generally includes pseudo-living polymerization in which the terminal is inactivated and the terminal is in equilibrium. . The definition in the present invention is also the latter. In recent years, living radical polymerization has been actively researched by various groups. Examples include cobalt porphyrin complexes (J. Am. Chem. Soc. 1994, 116, 7943), those using radical scavengers such as nitroxide compounds (Macromolecules, 1994, 27, 7228), organic halides, etc. And atom transfer radical polymerization using a transition metal complex as a catalyst. In the present invention, there is no particular limitation as to which of these methods is used, but atom transfer radical polymerization is preferred from the viewpoint of ease of control. In atom transfer radical polymerization, polymerization is performed using an organic halide or a sulfonyl halide compound as an initiator and a metal complex having a transition metal as a central metal as a catalyst. (For example, Matyjaszewski et al., J. Am. Chem. Soc. 1995, 117, 5614, Macromolecules 1995, 28, 7901, Science 1996, 272, 866, International Publications WO 96/30421 and WO 97/18247, or Sawamoto et al. 1995, 28, 1721). According to these methods, in general, the polymerization rate is very high and radical polymerization such as coupling between radicals is likely to occur, but the polymerization proceeds like a living and the molecular weight distribution is narrow (that is, Mw / Mn). A polymer having a value of about 1.1 to 1.5 is obtained, and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.
[0022]
In this atom transfer radical polymerization, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, an ester compound having a halogen at the α-position or a compound having a halogen at the benzyl-position), or a halogen It is preferable to use a sulfonyl chloride compound or the like as an initiator. The transition metal complex used as the catalyst for the living radical polymerization is not particularly limited, and preferable transition metal complexes of groups 7, 8, 9, 10, and 11 are more preferably zero-valent copper, 1 And a complex of divalent copper, divalent ruthenium, divalent iron, or divalent nickel. Of these, a copper complex is preferable. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, etc. is there. When a copper compound is used, 2,2′-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine, etc. in order to increase the catalytic activity A ligand such as a polyamine is added. 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, an aluminum alkoxide is added as an activator. Furthermore, a divalent iron bistriphenylphosphine complex (FeCl₂(PPh_Three)₂) Bivalent nickel bistriphenylphosphine complex (NiCl)₂(PPh_Three)₂), And a bivalent nickel bistributylphosphine complex (NiBr)₂(PBu_Three)₂) Is also suitable as a catalyst.
[0023]
In this polymerization method, an organic halide or a sulfonyl halide compound is usually used as an initiator. For example,
C₆H_Five-CH₂X, C₆H_Five-C (H) (X) CH_Three, C₆H_Five-C (X) (CH_Three)₂(However, in the above chemical formula, C6H5 is a phenyl group, X is chlorine, bromine, or iodine)
R⁸-C (H) (X) -CO₂R⁹, R⁸-C (CH_Three) (X) -CO₂R⁹, R⁸-C (H) (X) -C (O) R⁹, R⁸-C (CH_Three) (X) -C (O) R⁹,
(Wherein R⁸And R⁹Are the same or different, are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, and X is chlorine, bromine, or iodine)
R⁸-C₆H_Four-SO₂X
(In each of the above formulas, R⁸Is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, X is chlorine, bromine, or iodine)
Etc.
[0024]
In order to obtain a polymer having two or more terminal structures of the present invention in one molecule, an organic halide having two or more starting points or a sulfonyl halide compound is preferably used as an initiator. For example,
[0025]
[Chemical 1]

[0026]
[Chemical formula 2]

[0027]
Etc.
There is no restriction | limiting in particular as a vinyl-type monomer used in this superposition | polymerization, All already illustrated can be used suitably.
This polymerization can be carried out without solvent or in various solvents. Examples of the solvent include hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether, tetrahydrofuran, diphenyl ether, anisole and dimethoxybenzene; halogenated hydrocarbon solvents such as methylene chloride, chloroform and chlorobenzene; acetone Ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol and tert-butyl alcohol; nitrile solvents such as acetonitrile, propionitrile and benzonitrile; acetic acid Examples thereof include ester solvents such as ethyl and butyl acetate; carbonate solvents such as ethylene carbonate and propylene carbonate. These can be used individually or in mixture of 2 or more types. Polymerization can also be carried out in an emulsion system or a system using supercritical fluid CO2 as a medium.
[0028]
This polymerization can be performed in the range of room temperature to 200 ° C, and preferably in the range of 50 to 150 ° C.
Introduction of terminal functional groups
The method of introducing a crosslinkable silyl group, alkenyl group, or hydroxyl group at the end of the polymer is not limited, but has a functional group other than the functional group that initiates polymerization as an initiator of atom transfer radical polymerization. Examples thereof include a method using an organic halide or a sulfonyl halide compound, a method for converting a functional group such as a halogen group at the terminal of a polymer, and a combination of these methods.
[0029]
In atom transfer radical polymerization, if an organic halide or sulfonyl halide compound having a functional group other than the functional group that initiates polymerization is used as an initiator, it has a functional group at one end and a halogen group at the other end. A vinyl polymer is obtained. A vinyl polymer having functional groups at both ends can be obtained by converting the halogen group at the terminal end of the polymer thus obtained into a necessary functional group. As the conversion method, a method described later can be used. A vinyl having functional groups at both ends can also be obtained by coupling halogen ends to each other using a compound having two or more of the same or different functional groups in total that can replace the halogen group at the terminal end of the polymer. A polymer can be obtained. There are no particular restrictions on the compound having two or more of the same or different functional groups that can replace the terminal halogen, but polyols, polyamines, polycarboxylic acids, polythiols, and salts thereof, alkali metal sulfides, and the like are preferable.
[0030]
Regarding the organic halide or sulfonyl halide compound having the above functional group, examples of the functional group include an alkenyl group, a crosslinkable silyl group, a hydroxyl group, an epoxy group, an amino group, and an amide group.
The organic halide having an alkenyl group is not limited, and examples thereof include those having a structure represented by the general formula 13.
R^TenR¹¹C (X) -R¹²-R¹³-C (R^Three) = CH₂(13)
(Wherein R^ThreeIs hydrogen or a methyl group, R^Ten, R¹¹Is hydrogen, or a monovalent alkyl group having 1 to 20 carbon atoms, an aryl group, or aralkyl, or those interconnected at the other end, R¹²-C (O) O- (ester group), -C (O)-(keto group), or o-, m-, p-phenylene group, R¹³Is a direct bond, or a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds, X is chlorine, bromine, or iodine)
Substituent R^Ten, R¹¹Specific examples thereof include hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, pentyl group, hexyl group and the like. R^TenAnd R¹¹May be linked at the other end to form a cyclic skeleton.
[0031]
Specific examples of the organic halide having an alkenyl group represented by the general formula 13 include
XCH₂C (O) O (CH₂)_nCH = CH₂, H_ThreeCC (H) (X) C (O) O (CH₂)_nCH = CH₂, (H_ThreeC)₂C (X) C (O) O (CH₂)_nCH = CH₂, CH_ThreeCH₂C (H) (X) C (O) O (CH₂)_nCH = CH₂,
[0032]
[Chemical Formula 3]

[0033]
(In each of the above formulas, X is chlorine, bromine, or iodine, n is an integer of 0 to 20) XCH₂C (O) O (CH₂)_nO (CH₂)_mCH = CH₂, H_ThreeCC (H) (X) C (O) O (CH₂)_nO (CH₂)_mCH = CH₂, (H_ThreeC)₂C (X) C (O) O (CH₂)_nO (CH₂)_mCH = CH₂, CH_ThreeCH₂C (H) (X) C (O) O (CH₂)_nO (CH₂)_mCH = CH₂,
[0034]
[Formula 4]

[0035]
(In each of the above formulas, X is chlorine, bromine, or iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20)
o, m, p-XCH₂-C₆H_Four-(CH₂)_n-CH = CH₂, O, m, p-CH_ThreeC (H) (X) -C₆H_Four-(CH₂)_n-CH = CH₂, O, m, p-CH_ThreeCH₂C (H) (X) -C₆H_Four-(CH₂)_n-CH = CH₂,
(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-CH = CH₂, O, m, p-CH_ThreeC (H) (X) -C₆H_Four-(CH₂)_n-O- (CH₂)_m-CH = CH₂, O, m, p-CH_ThreeCH₂C (H) (X) -C₆H_Four-(CH₂)_n-O- (CH₂)_mCH = CH₂,
(In each of the above formulas, X is chlorine, bromine, or iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20)
o, m, p-XCH₂-C₆H_Four-O- (CH₂)_n-CH = CH₂, O, m, p-CH_ThreeC (H) (X) -C₆H_Four-O- (CH₂)_n-CH = CH₂, O, m, p-CH_ThreeCH₂C (H) (X) -C₆H_Four-O- (CH₂)_n-CH = CH₂,
(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-O- (CH₂)_n-O- (CH₂)_m-CH = CH₂, O, m, p-CH_ThreeC (H) (X) -C₆H_Four-O- (CH₂)_n-O- (CH₂)_m-CH = CH₂, O, m, p-CH_ThreeCH₂C (H) (X) -C₆H_Four-O- (CH₂)_n-O- (CH₂)_m-CH = CH₂,
(In each of the above formulas, X is chlorine, bromine, or iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20)
Examples of the organic halide having an alkenyl group further include compounds represented by the general formula 14.
H₂C = C (R_Three-R¹³-C (R^Ten) (X) -R¹⁴-R¹¹  (14)
(Wherein R^Three, R^Ten, R¹¹, R¹³, X is the same as above, R¹⁴Represents a direct bond, —C (O) O— (ester group), —C (O) — (keto group), or o-, m-, p-phenylene group)
R¹³Is a direct bond or a divalent organic group having 1 to 20 carbon atoms (which may contain one or more ether bonds). The groups are bonded and are allylic halides. In this case, since the carbon-halogen bond is activated by the adjacent vinyl group, R¹⁴It is not always necessary to have a C (O) O group or a phenylene group, and a direct bond may be used. R¹³In order to activate the carbon-halogen bond,¹⁴Is preferably a C (O) O group, a C (O) group, or a phenylene group.
[0036]
If the compound of the general formula 14 is specifically illustrated,
CH₂= CHCH₂X, CH₂= C (CH_Three) CH₂X, CH₂= CHC (H) (X) CH_Three, CH₂= C (CH_Three) C (H) (X) CH_Three, CH₂= CHC (X) (CH_Three)₂, CH₂= CHC (H) (X) C₂H_Five, CH₂= CHC (H) (X) CH (CH_Three)₂, CH₂= CHC (H) (X) C₆H_Five, CH₂= CHC (H) (X) CH₂C₆H_Five, CH₂= CHCH₂C (H) (X) -CO₂R, CH₂= CH (CH₂)₂C (H) (X) -CO₂R, CH₂= CH (CH₂)_ThreeC (H) (X) -CO₂R, CH₂= CH (CH₂)₈C (H) (X) -CO₂R, CH₂= CHCH₂C (H) (X) -C₆H_Five, CH₂= CH (CH₂)₂C (H) (X) -C₆H_Five, CH₂= CH (CH₂)_ThreeC (H) (X) -C₆H_Five,
(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)
Etc.
[0037]
Specific examples of halogenated sulfonyl compounds having an alkenyl group include o-, m-, and p-CH.₂= CH- (CH₂)_n-C₆H_Four-SO₂X, o-, m-, p-CH₂= CH- (CH₂)_n-OC₆H_Four-SO₂X,
(In the above formulas, X is chlorine, bromine, or iodine, and n is an integer of 0 to 20).
[0038]
It does not specifically limit as an organic halide which has a crosslinkable silyl group, For example, what has the structure shown in General formula 15 is illustrated.
R^TenR¹¹C (X) -R¹²-R¹³-C (H) (R^Three) CH₂-[Si (R¹⁵)_2-b(Y)_bO]_m-Si (R¹⁶)_3-a(Y)_a(15)
(Wherein R^Three, R^Ten, R¹¹, R¹², R¹³, X is the same as above, R¹⁵, R¹⁶Are 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). , R⁹Or R^TenWhen 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 exist, 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)
If the compound of the general formula 15 is specifically illustrated,
XCH₂C (O) O (CH₂)_nSi (OCH_Three)_Three, CH_ThreeC (H) (X) C (O) O (CH₂)_nSi (OCH_Three)_Three, (CH_Three)₂C (X) C (O) O (CH₂)_nSi (OCH_Three)_Three, XCH₂C (O) O (CH₂)_nSi (CH_Three) (OCH_Three)₂, CH_ThreeC (H) (X) C (O) O (CH₂)_nSi (CH_Three) (OCH_Three)₂, (CH_Three)₂C (X) C (O) O (CH₂)_nSi (CH_Three) (OCH_Three)₂,
(In the above formulas, X is chlorine, bromine, iodine, n is an integer of 0-20)
XCH₂C (O) O (CH₂)_nO (CH₂)_mSi (OCH_Three)_Three, H_ThreeCC (H) (X) C (O) O (CH₂)_nO (CH₂)_mSi (OCH_Three)_Three, (H_ThreeC)₂C (X) C (O) O (CH₂)_nO (CH₂)_mSi (OCH_Three)_Three, CH_ThreeCH₂C (H) (X) C (O) O (CH₂)_nO (CH₂)_mSi (OCH_Three)_Three, XCH₂C (O) O (CH₂)_nO (CH₂)_mSi (CH_Three) (OCH_Three)₂, H_ThreeCC (H) (X) C (O) O (CH₂)_nO (CH₂)_m-Si (CH_Three) (OCH_Three)₂, (H_ThreeC)₂C (X) C (O) O (CH₂)_nO (CH₂)_m-Si (CH_Three) (OCH_Three)₂, CH_ThreeCH₂C (H) (X) C (O) O (CH₂)_nO (CH₂)_m-Si (CH_Three) (OCH_Three)₂,
(In the above formulas, X is chlorine, bromine, iodine, n is an integer of 1-20, m is an integer of 0-20)
o, m, p-XCH₂-C₆H_Four-(CH₂)₂Si (OCH_Three)_Three, O, m, p-CH_ThreeC (H) (X) -C₆H_Four-(CH₂)₂Si (OCH_Three)_Three, O, m, p-CH_ThreeCH₂C (H) (X) -C₆H_Four-(CH₂)₂Si (OCH_Three)_Three, O, m, p-XCH₂-C₆H_Four-(CH₂)_ThreeSi (OCH_Three)_Three, O, m, p-CH_ThreeC (H) (X) -C₆H_Four-(CH₂)_ThreeSi (OCH_Three)_Three, O, m, p-CH_ThreeCH₂C (H) (X) -C₆H_Four-(CH₂)_ThreeSi (OCH_Three)_Three, O, m, p-XCH₂-C₆H_Four-(CH₂)₂-O- (CH₂)_ThreeSi (OCH_Three)_Three, O, m, p-CH_ThreeC (H) (X) -C₆H_Four-(CH₂)₂-O- (CH₂)_ThreeSi (OCH_Three)_Three, O, m, p-CH_ThreeCH₂C (H) (X) -C₆H_Four-(CH₂)₂-O- (CH₂)_ThreeSi (OCH_Three)_Three, O, m, p-XCH₂-C₆H_Four-O- (CH₂)_ThreeSi (OCH_Three)_Three, O, m, p-CH_ThreeC (H) (X) -C₆H_Four-O- (CH₂)_ThreeSi (OCH_Three)_Three, O, m, p-CH_ThreeCH₂C (H) (X) -C₆H_Four-O- (CH₂)_Three-Si (OCH_Three)_Three, O, m, p-XCH₂-C₆H_Four-O- (CH₂)₂-O- (CH₂)_Three-Si (OCH_Three)_Three, O, m, p-CH_ThreeC (H) (X) -C₆H_Four-O- (CH₂)₂-O- (CH₂)_ThreeSi (OCH_Three)_Three, O, m, p-CH_ThreeCH₂C (H) (X) -C₆H_Four-O- (CH₂)₂-O- (CH₂)_ThreeSi (OCH_Three)_Three,
(In the above formulas, X is chlorine, bromine, or iodine)
Etc.
[0039]
Examples of the organic halide having a crosslinkable silyl group further include those having a structure represented by general formula 16.
(R¹⁶)_3-a(Y)_aSi- [OSi (R¹⁵)_2-b(Y)_b]_m-CH₂-C (H) (R^Three-R¹³-C (R^Ten) (X) -R¹⁴-R¹¹  (16)
(Wherein R^Three, R^Ten, R¹¹, R¹³, R¹⁴, R¹⁵, R¹⁶, A, b, m, X, Y are the same as above)
If such a compound is specifically illustrated,
(CH_ThreeO)_ThreeSiCH₂CH₂C (H) (X) C₆H_Five, (CH_ThreeO)₂(CH_Three) SiCH₂CH₂C (H) (X) C₆H_Five, (CH_ThreeO)_ThreeSi (CH₂)₂C (H) (X) -CO₂R, (CH_ThreeO)₂(CH_Three) Si (CH₂)₂C (H) (X) -CO₂R, (CH_ThreeO)_ThreeSi (CH₂)_ThreeC (H) (X) -CO₂R, (CH_ThreeO)₂(CH_Three) Si (CH₂)_ThreeC (H) (X) -CO₂R, (CH_ThreeO)_ThreeSi (CH₂)_FourC (H) (X) -CO₂R, (CH_ThreeO)₂(CH3) Si (CH₂)_FourC (H) (X) -CO₂R, (CH_ThreeO)_ThreeSi (CH₂)₉C (H) (X) -CO₂R, (CH_ThreeO)₂(CH_Three) Si (CH₂)₉C (H) (X) -CO₂R, (CH_ThreeO)_ThreeSi (CH₂)_ThreeC (H) (X) -C₆H_Five, (CH_ThreeO)₂(CH_Three) Si (CH₂)_ThreeC (H) (X) -C₆H_Five, (CH_ThreeO)_ThreeSi (CH₂)_FourC (H) (X) -C₆H_Five, (CH_ThreeO)₂(CH_Three) Si (CH₂)_FourC (H) (X) -C₆H_Five,
(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)
Etc.
[0040]
The organic halide having a hydroxyl group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.
HO- (CH2) n-OC (O) C (H) (R) (X)
(In the above formulas, X is chlorine, bromine, or iodine, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20) Organic having the amino group It does not specifically limit as a halide or a sulfonyl halide compound, The following are illustrated.
H2N- (CH2) n-OC (O) C (H) (R) (X)
(In the above formulas, X is chlorine, bromine, or iodine, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)
The organic halide having the epoxy group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.
[0041]
[Chemical formula 5]

[0042]
(In the above formulas, X is chlorine, bromine, or iodine, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20). Describes a method for introducing a crosslinkable silyl group, alkenyl group, or hydroxyl group. Since these functional groups can be precursors to each other, they are described in the order from the crosslinkable silyl group.
[0043]
As a method for synthesizing a vinyl polymer having at least one crosslinkable silyl group, (A) a hydrosilane compound having a crosslinkable silyl group is added to a vinyl polymer having at least one alkenyl group in the presence of a hydrosilylation catalyst. Method of adding (B) Method of reacting a vinyl polymer having at least one hydroxyl group with a compound having a group capable of reacting with a hydroxyl group such as a crosslinkable silyl group and an isocyanate group in one molecule (C) By radical polymerization Method of reacting a compound having both a polymerizable alkenyl group and a crosslinkable silyl group in one molecule when synthesizing a vinyl polymer (D) When synthesizing a vinyl polymer by radical polymerization, (E) A method using a chain transfer agent having a group 1 for a vinyl polymer having at least one highly reactive carbon-halogen bond A method of reacting a compound having a stable carbanion and crosslinkable silyl group in the child; and the like.
[0044]
The vinyl polymer having at least one alkenyl group used in the method (A) can be obtained by various methods. Although the synthesis method is illustrated below, it is not necessarily limited to these.
(Aa) When synthesizing a vinyl polymer by radical polymerization, for example, a compound having both a polymerizable alkenyl group and a low polymerizable alkenyl group in one molecule as shown in the following general formula 17 is used. The method of making it react as a monomer of 2.
[0045]
H₂C = C (R^{twenty three}-R^{twenty four}-R^{twenty five}-C (R²⁶) = CH₂(17)
(Wherein R^{twenty three}Represents hydrogen or a methyl group, R^{twenty four}Represents —C (O) O— or o-, m-, p-phenylene group, R25 represents a direct bond or a divalent organic group having 1 to 20 carbon atoms, and has one or more ether bonds. May be included. R²⁶Represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms)
There is no limitation on the timing of reacting a compound having both a polymerizable alkenyl group and a low polymerizable alkenyl group in one molecule. It is preferable to react as the second monomer at the end or after completion of the reaction of the predetermined monomer.
[0046]
(Ab) When synthesizing a vinyl polymer by living radical polymerization, for example, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer. A method of reacting a compound having at least two alkenyl groups having low polymerizability, such as
(Ac) Various organometallic compounds having an alkenyl group such as organotin such as allyltributyltin and allyltrioctyltin on a vinyl polymer having at least one highly reactive carbon-halogen bond A method of replacing halogen by reaction.
[0047]
(Ad) A method in which halogen is substituted by reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with a stabilized carbanion having an alkenyl group as shown in general formula 18.
M⁺C^-(R²⁷) (R²⁸-R²⁹-C (R²⁶) = CH₂(18)
(Wherein R²⁶Is the same as above, R²⁷, R²⁸Are both carbanion C^-Are one of the electron-withdrawing groups and the other is hydrogen, an alkyl group having 1 to 10 carbon atoms, or a phenyl group. R²⁹Represents a direct bond or a divalent organic group having 1 to 10 carbon atoms, and may contain one or more ether bonds. M + represents an alkali metal ion or a quaternary ammonium ion)
R²⁷, R²⁸As an electron withdrawing group,₂Those having the structures of R, -C (O) R and -CN are particularly preferred.
[0048]
(Ae) An enolate anion is prepared by reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with, for example, a single metal such as zinc or an organometallic compound. A method of reacting with an electrophilic compound having an alkenyl group, such as an alkenyl group-containing compound having a leaving group such as an acetyl group, a carbonyl compound having an alkenyl group, an isocyanate compound having an alkenyl group, an acid halide having an alkenyl group .
[0049]
(Af) An oxyanion or carboxylate anion having an alkenyl group as represented by the general formula (19) or (20) is added to a vinyl polymer having at least one highly reactive carbon-halogen bond. A method of replacing halogen by reaction.
H₂C = C (R²⁶-R³⁰-O^-M⁺(19)
(Wherein R²⁶, M⁺Is the same as above. R³⁰Is a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds)
H₂C = C (R²⁶-R³¹-C (O) O^-M⁺(20)
(Wherein R²⁶, M⁺Is the same as above. R³¹May be a direct bond or a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds)
Etc.
[0050]
The above-described method for synthesizing a vinyl polymer having at least one carbon-halogen bond having high reactivity is an atom transfer radical polymerization method using an organic halide as described above as an initiator and a transition metal complex as a catalyst. For example, but not limited to.
Further, the vinyl polymer having at least one alkenyl group can be obtained from a vinyl polymer having at least one hydroxyl group, and the methods exemplified below can be used, but are not limited thereto. In the hydroxyl group of a vinyl polymer having at least one hydroxyl group,
(Ag) A method of reacting a base such as sodium methoxide with an alkenyl group-containing halide such as allyl chloride.
[0051]
(Ah) A method of reacting an alkenyl group-containing isocyanate compound such as allyl isocyanate.
(Ai) A method in which an alkenyl group-containing acid halide such as (meth) acrylic acid chloride is reacted in the presence of a base such as pyridine.
(Aj) A method in which an alkenyl group-containing carboxylic acid such as acrylic acid is reacted in the presence of an acid catalyst;
[0052]
In the present invention, when a halogen is not directly involved in a method for introducing an alkenyl group such as (Aa) and (Ab), it is preferable to synthesize a vinyl polymer using a living radical polymerization method. The method (Ab) is more preferable from the viewpoint of easier control.
When an alkenyl group is introduced by converting the halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond, an organic halide having at least one highly reactive carbon-halogen bond, or A vinyl heavy polymer having at least one highly reactive carbon-halogen bond at the terminal, obtained by radical polymerization of a vinyl monomer using a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst (atom transfer radical polymerization method). It is preferable to use coalescence. In view of easier control, the method (Af) is more preferable.
[0053]
Moreover, there is no restriction | limiting in particular as a hydrosilane compound which has a crosslinkable silyl group, If a typical thing is shown, the compound shown by General formula 21 will be illustrated.
H- [Si (R^{twenty one})_2-b(Y)_bO]_m-Si (R_{twenty two})_3-a(Y)_a  (21)
(Wherein R^{twenty one}, R^{twenty two}, A, b, m and Y are the same as above. )
Among these hydrosilane compounds, in particular, the general formula (22)
H-Si (R^{twenty two})_3-a(Y)_a  (22)
(Wherein R^{twenty two}, Y and a are the same as above)
The compound which has a crosslinkable group shown by is preferable from a point with easy acquisition.
[0054]
When the hydrosilane compound having a crosslinkable silyl group is added to an alkenyl group, a transition metal catalyst is usually used. Examples of the transition metal catalyst include platinum simple substance, 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-olefin. Complex, platinum (0) -divinyltetramethyldisiloxane complex is 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.
[0055]
Examples of the method for producing a vinyl polymer having at least one hydroxyl group used in the methods (B) and (Ag) to (Aj) include the following methods, but are limited to these methods. It is not something.
(Ba) When synthesizing a vinyl polymer by radical polymerization, for example, a compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule as shown in the following general formula (23) is used as the second monomer. How to react as.
H₂C = C (R^{twenty three}-R^{twenty four}-R^{twenty five}-OH (23)
(Wherein R^{twenty three}, R^{twenty four}, R^{twenty five}Is the same as above)
There is no limitation on the timing of reacting the compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule. However, particularly in the case of living radical polymerization, when the rubber-like properties are expected, the end of the polymerization reaction or a predetermined monomer. After completion of the reaction, it is preferable to react as the second monomer.
[0056]
(Bb) When a vinyl polymer is synthesized by living radical polymerization, an alkenyl alcohol such as 10-undecenol, 5-hexenol or allyl alcohol is reacted at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer. How to make.
(Bc) A method in which a vinyl monomer is radically polymerized using a large amount of a hydroxyl group-containing chain transfer agent such as a hydroxyl group-containing polysulfide described in JP-A-5-262808.
(Bd) A method of radical polymerization of a vinyl monomer using hydrogen peroxide or a hydroxyl group-containing initiator as disclosed in, for example, JP-A-6-239912 and JP-A-8-283310.
(Be) A method of radical polymerization of a vinyl monomer by using an excessive amount of alcohol as disclosed in, for example, JP-A-6-116312.
(Bf) Hydrolysis of a vinyl polymer having at least one highly reactive carbon-halogen bond or reaction with a hydroxyl group-containing compound by a method such as disclosed in JP-A-4-132706. To introduce a hydroxyl group into the terminal.
(Bg) A method in which a vinyl polymer having at least one highly reactive carbon-halogen bond is reacted with a stabilized carbanion having a hydroxyl group as listed in the general formula (24) to substitute a halogen.
M + C- (R²⁷) (R²⁸-R²⁹-OH (24)
(Wherein R²⁷, R²⁸, R²⁹Is the same as above)
R²⁷, R²⁸As an electron withdrawing group,₂Those having the structures of R, -C (O) R and -CN are particularly preferred.
[0057]
(Bh) An enolate anion is prepared by allowing a metal polymer such as zinc or an organometallic compound to act on a vinyl polymer having at least one highly reactive carbon-halogen bond, and then aldehydes. Or a method of reacting ketones.
(Bi) By reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with an oxyanion or carboxylate anion having a hydroxyl group as shown in the general formula 25 or 26, for example, How to replace.
HO-R³⁰-O^-M⁺(25)
(Wherein R³⁰And M⁺Is the same as above)
HO-R³¹-C (O) O^-M⁺(26)
(Wherein R³¹And M⁺Is the same as above)
Etc.
[0058]
In the present invention, when halogen is not directly involved in the method of introducing a hydroxyl group such as (Ba) to (Be), it is preferable to synthesize a vinyl polymer using a living radical polymerization method. The method (Bb) is more preferable in terms of easier control.
When introducing a hydroxyl group by converting halogen in a vinyl polymer having at least one highly reactive carbon-halogen bond, an organic halide or a sulfonyl halide compound is used as an initiator, and a transition metal complex is used as a catalyst. It is preferable to use a vinyl polymer having at least one highly reactive carbon-halogen bond at the terminal obtained by radical polymerization of a vinyl monomer (atom transfer radical polymerization method). The method (Bi) is more preferable from the viewpoint of easier control.
[0059]
Examples of the compound having a crosslinkable silyl group and a group capable of reacting with a hydroxyl group such as an isocyanate group in one molecule include γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, and γ-isocyanate. Examples thereof include natopropyltriethoxysilane, and a generally known catalyst for urethanization reaction can be used if necessary.
[0060]
Examples of the compound having both a polymerizable alkenyl group and a crosslinkable silyl group in one molecule used in the method (C) include trimethoxysilylpropyl (meth) acrylate and methyldimethoxysilylpropyl (meth) acrylate. What is shown by the following general formula 27 is mentioned.
H₂C = C (R^{twenty three}-R^{twenty four}-R³²-[Si (R^{twenty one})_2-b(Y)_bO]_m-Si (R^{twenty two})_3-a(Y)_a  (27)
(Wherein R^{twenty one}, R^{twenty two}, R^{twenty three}, R^{twenty four}, Y, a, b, m are the same as above. R³²May contain one or more ether bonds in a direct bond or a divalent organic group having 1 to 20 carbon atoms. )
There is no particular limitation on the timing of reacting the compound having both a polymerizable alkenyl group and a crosslinkable silyl group in one molecule. However, particularly in the case of living radical polymerization, when a rubber-like property is expected, the end of the polymerization reaction or a predetermined value is determined. It is preferable to make it react as a 2nd monomer after completion | finish of reaction of this monomer.
Examples of the chain transfer agent having a crosslinkable silyl group used in the chain transfer agent method of (D) include mercaptans having a crosslinkable silyl group and crosslinkable silyl as shown in, for example, Japanese Patent Publication Nos. 3-14068 and 4-55444. And hydrosilane having a group.
[0061]
The method for synthesizing a vinyl polymer having at least one highly reactive carbon-halogen bond, which is used in the method (E), uses an organic halide as described above as an initiator, and a transition metal complex. Examples thereof include, but are not limited to, an atom transfer radical polymerization method using a catalyst. Examples of the compound having both a crosslinkable silyl group and a stabilized carbanion in one molecule include those represented by the general formula 28.
[0062]
M⁺C^-(R²⁷) (R²⁸-R³³-C (H) (R³⁴) -CH₂-[Si (R^{twenty one})_2-b(Y)_bO]_m-Si (R^{twenty two})_3-a(Y)_a(28)
(Wherein R^{twenty one}, R^{twenty two}, R²⁷, R²⁸, Y, a, b, m are the same as above. R³³Is a direct bond or a divalent organic group having 1 to 10 carbon atoms and may contain one or more ether bonds, R³⁴Represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. )
R²⁷, R²⁸As an electron withdrawing group,₂Those having the structures of R, -C (O) R and -CN are particularly preferred.
The polymer synthesized by the method as described above is a vinyl polymer having a narrow molecular weight distribution. Therefore, since the viscosity is lower than that of a polymer having an equal number average molecular weight and a wide molecular weight distribution, it is easy to handle when used as a curable composition.
Application
The use of the polymer of the present invention will be described below for each terminal functional group, but the use of the polymer of the present invention is not limited thereto.
[0063]
The vinyl polymer having a crosslinkable silyl group at the terminal of the present invention is crosslinked and cured by forming a siloxane bond in the presence or absence of various conventionally known condensation catalysts. The properties of the cured product can be broadly created from rubbery to resinous depending on the molecular weight and main chain skeleton of the polymer. Therefore, this polymer can be used for sealing materials, adhesives, elastic adhesives, pressure-sensitive adhesives, paints, powder paints, foams, potting agents for electric and electronic use, films, gaskets, various molding materials and the like.
[0064]
The vinyl polymer having an alkenyl group at the terminal of the present invention gives a cured product by itself or using an appropriate crosslinking agent.
Among these, a vinyl polymer having a (meth) acryloyl group at the terminal gives a cured product by heating in the presence or absence of various polymerization initiators. Further, it is crosslinked and cured by light irradiation in the presence of various photopolymerization initiators.
[0065]
As the curing agent for the vinyl polymer having an alkenyl group at the terminal, various polyvalent hydrogen silicon compounds can be used. At this time, a conventionally known hydrosilylation catalyst can be used as a catalyst for the curing reaction.
When the vinyl polymer having an alkenyl group at the terminal of the present invention is cured, it can be widely produced from rubbery to resinous depending on its molecular weight and main chain skeleton. Specific applications of cured products include sealing materials, adhesives, adhesives, elastic adhesives, paints, powder paints, foams, electrical and potting agents, films, gaskets, various molding materials, artificial marble, etc. is there.
[0066]
The vinyl polymer having a hydroxyl group at the terminal of the present invention is uniformly cured by using a compound having two or more functional groups capable of reacting with a hydroxyl group as a curing agent. Specific examples of the curing agent include, for example, a polyisocyanate compound having two or more isocyanate groups in one molecule, an aminoplast resin such as methylolated melamine and an alkyl etherified product or a low-condensed product thereof, a polyfunctional carboxylic acid, and Examples thereof include halides thereof. When producing a cured product using these curing agents, an appropriate curing catalyst can be used.
[0067]
When the vinyl polymer having a hydroxyl group at the terminal of the present invention is cured, it can be widely produced from rubbery to resinous depending on the molecular weight and main chain skeleton. Specific applications of cured products include sealing materials, adhesives, adhesives, elastic adhesives, paints, powder paints, foams, electrical and potting agents, films, gaskets, various molding materials, artificial marble, etc. is there.
[0068]
【Example】
Hereinafter, the vinyl polymer of the present invention will be described based on examples, but the present invention is not limited to the following examples.
[0069]
[Production Example 1]
Production example of 2-allyloxyethyl methacrylate
In a three-necked flask equipped with a stirrer, thermometer, reflux condenser, and Dean-Stark tube, methacrylic acid (137.7 g, 1.6 mol), ethylene glycol monoallyl ether (80.7 g, 0.8 mol), p -Toluenesulfonic acid (0.76 g, 4.0 mmol) and toluene (650 mL) were charged. After reacting at 120 ° C. for 5 hours, 0.12 g of p-toluenesulfonic acid was added, and further reacted at the same temperature for 6 hours, and 0.1 g of p-toluenesulfonic acid was added. The reaction was terminated at the same temperature for another 9 hours. During this time, methacrylic acid and ethylene glycol monoallyl ether were traced by liquid chromatography, and the conversion finally reached 98%. NaHCO_ThreeAn aqueous solution was added to neutralize and the two layers were separated. The aqueous layer is extracted once with toluene, and the organic layer is extracted with CaCl.₂After drying, the volatiles were removed under reduced pressure. The crude product was distilled under reduced pressure (60 ° C., 2 mmHg) to obtain 98.7 g of 2-allyloxyethyl methacrylate represented by the following formula (yield 73%).
H₂C = C (CH_ThreeCO₂(CH₂)₂OCH₂CH = CH₂
[0070]
[Production Example 2]
Production of carboxylate having alkenyl group (1)
Undecylenic acid (18.8 g, 0.102 mol) was slowly added dropwise to a 1 / 2N ethanol solution (200 mL) of potassium hydroxide at 0 ° C. with stirring. Volatile components were distilled off under reduced pressure to obtain a crude product. The crude product was washed with acetone and then heated under reduced pressure to obtain a white solid of undecylenic acid potassium salt represented by the following formula (8.88 g, yield 88%).
CH₂= CH- (CH₂)₈-CO₂ ^-K⁺
[0071]
[Production Example 3]
Production example (2) of carboxylate having alkenyl group
4-Pentenoic acid (49 g, 0.489 mol) and potassium tert-butoxide (54.9 g, 0.489 mol) were charged in methanol (245 mL), and the mixture was stirred at 0 ° C. Volatile components were distilled off under reduced pressure to obtain potassium pentenoate represented by the following formula.
CH₂= CH- (CH₂)₂-CO₂ ^-K⁺
[0072]
[Production Example 4]
Production example of an initiator having a hydroxyl group
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
[0073]
[Production Example 5]
Production example (1) of an initiator having an alkenyl group
The 50 mL 2-necked flask was purged with nitrogen, and 2-allyloxyethanol (2.5 mL, 23.4 mmol), pyridine (3 mL), and THF (10 mL) were charged. The solution was cooled to 0 ° C. and 2-bromopropionic acid chloride (2 mL, 19.52 mmol) was slowly added dropwise. After stirring at the same temperature for 1 hour, ethyl acetate (10 mL) was added, and the resulting hydrochloride of pyridine was removed by filtration. The filtrate was diluted with dilute hydrochloric acid (10 mL), NaHCO 3_ThreeWashed with aqueous solution (10 mL) and then brine (10 mL). The organic layer is Na₂SO_FourThe volatile matter was distilled off under reduced pressure. The resulting crude product was distilled under reduced pressure to obtain allyloxyethyl-2-bromopropionate represented by the following formula. (78.5-81 degreeC (1.3mmHg), 2.986g).
CH_ThreeC (H) (Br) C (O) O-CH₂CH₂-O-CH₂CH = CH₂
[0074]
[Example 1]
In a 1 L pressure-resistant reaction vessel, acrylic acid-n-butyl (112 mL, 100 g, 0.78 mol), the hydroxyl group-containing initiator obtained in Production Example 4 (3.07 g, 15.6 mmol), cuprous bromide ( 2.24 g, 15.6 mmol), 2,2′-bipyridyl (4.87 g, 31.2 mmol), ethyl acetate (90 mL), acetonitrile (22 mL) were charged, and nitrogen bubbling was performed to remove dissolved oxygen. Sealed. The mixture was heated to 130 ° C. and reacted for 2 hours. The reaction vessel was returned to room temperature, 2-hydroxyethyl methacrylate (3.92 mL, 4.06 g, 31.2 mmol) was added, and the mixture was reacted at 110 ° C. for 2 hours. The mixture was diluted with ethyl acetate (200 mL), insolubles were filtered off, and the filtrate was washed twice with 10% hydrochloric acid and once with brine. After the organic layer was dried over Na2SO4, the solvent was distilled off under reduced pressure to obtain 82 g of poly (acrylic acid-n-butyl) having a hydroxyl group at the terminal. The number average molecular weight of the polymer was 5100 according to GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.29.
[0075]
Next, poly (acrylic acid-n-butyl) having a hydroxyl group at the terminal obtained as described above (50 g) and a toluene solution (100 mL) of pyridine (10 mL) were added to undecene at 75 ° C. in a nitrogen atmosphere. Acid chloride (7.22 mL, 6.81 g, 33.6 mmol) was slowly added dropwise and stirred at 75 ° 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) having an alkenyl group (43 g). The number average molecular weight of the polymer was 5400 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.30. The alkenyl group introduced per oligomer molecule is¹According to 1 H NMR analysis, the number was 2.28.
[0076]
Next, in a 30 mL pressure-resistant reaction vessel, poly (butyl acrylate) having alkenyl groups at both ends obtained above (2 g), methyldimethoxysilane (0.32 mL), methyl orthoformate (0.09 mL, 3 equivalents to an alkenyl group), 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex of zero-valent platinum (8.3 × 10^-810 mol / L xylene solution, alkenyl group^-FourEquivalent weight) and stirred at 100 ° C. for 1 hour. Volatile components were 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. The number average molecular weight of the polymer was 5900 according to GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.37. In addition, the silyl group introduced per oligomer molecule is¹According to 1 H NMR analysis, it was 2.24.
[0077]
Next, poly (acrylic-n-acid butyl) having methyldimethoxysilyl groups at both ends obtained as described above (1 g) and a curing catalyst (manufactured by Nitto Kasei, U-220, dibutyltin diacetylacetonate, 30 mg) ) Were 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%.
[0078]
[Example 2]
Synthesis of poly (acrylic acid-n-butyl) having a hydroxyl group at the terminal
In a 1 L pressure-resistant reaction vessel, acrylic acid-n-butyl (112 mL, 100 g, 0.78 mol), the hydroxyl group-containing initiator obtained in Reference Example 1 (3.07 g, 15.6 mmol), cuprous bromide ( 2.24 g, 15.6 mmol), 2,2′-bipyridyl (4.87 g, 31.2 mmol), ethyl acetate (90 mL), acetonitrile (22 mL) were charged, and nitrogen bubbling was performed to remove dissolved oxygen. Sealed. The mixture was heated to 130 ° C. and reacted for 2 hours. The reaction vessel was returned to room temperature, 2-hydroxyethyl methacrylate (3.92 mL, 4.06 g, 31.2 mmol) was added, and the mixture was reacted at 110 ° C. for 2 hours. The mixture was diluted with ethyl acetate (200 mL), insolubles were filtered off, the filtrate was washed with 10% hydrochloric acid and brine, and the organic layer was washed with Na.₂SO_FourAnd dried. The solvent was distilled off under reduced pressure to obtain 82 g of poly (acrylic acid-n-butyl) having a hydroxyl group at the terminal. This polymer had a viscosity of 25 Pa · s, a number average molecular weight of 5100 as measured by GPC (mobile phase chloroform, polystyrene conversion), and a molecular weight distribution of 1.29. Also,¹The average number of hydroxyl groups per polymer molecule determined by 1 H-NMR analysis was 2.39.
Synthesis of poly (acrylic acid-n-butyl) having an alkenyl group at the terminal
To a toluene solution (100 mL) of poly (acrylic acid-n-butyl) having a hydroxyl group at the terminal obtained above and pyridine (10 mL) at 75 ° C. under a nitrogen atmosphere, undecenoic acid chloride (7.22 mL, 6.81 g, 33.6 mmol) was slowly added dropwise and stirred at 75 ° C. for 3 hours. The resulting white solid was filtered, the organic layer was washed with dilute hydrochloric acid and brine, and the organic layer was washed with Na₂SO_FourAnd dried. By concentrating under reduced pressure, poly (acrylic acid-n-butyl) (43 g) having an alkenyl group was obtained. The number average molecular weight of the polymer was 5400 according to GPC measurement (mobile phase chloroform, polystyrene conversion), and the molecular weight distribution was 1.30. Also,¹The number of alkenyl groups introduced per molecule of polymer determined by 1 H-NMR analysis was 2.28.
Synthesis of poly (acrylic acid-n-butyl) having a crosslinkable silyl group at the terminal
In a 30 mL pressure-resistant reaction vessel, poly (butyl acrylate) having alkenyl groups at both ends obtained above (2 g), methyldimethoxysilane (0.32 mL), methyl orthoformate (0.09 mL, based on alkenyl groups) 3 equivalents), platinum bis (divinyltetramethyldisiloxane) (8.3 × 10^-8mol / L xylene solution, 10-4 equivalents relative to the alkenyl group), 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 a crosslinkable silyl group. The number average molecular weight of the polymer was 5900 according to GPC measurement (mobile phase chloroform, polystyrene conversion), and the molecular weight distribution was 1.37. Also,¹The number of silyl groups introduced per molecule of polymer determined by 1 H-NMR analysis was 2.24.
[0079]
[Reference Example 1]
The crosslinkable silyl group-terminated polymer (1 g) of Example 2 and a curing catalyst (manufactured by Nitto Kasei, U-220, dibutyltin diacetylacetonate, 30 mg) were mixed well, poured into a mold, and then using a vacuum dryer. Defoamed at room temperature. A uniform rubber-like cured product was obtained by leaving it to stand at room temperature for 7 days. The gel fraction determined by toluene extraction was 78%.
[0080]
[Reference Example 2]
100 parts by weight of the polymer having a crosslinkable silyl group at the end of Example 2, 1 part by weight of water, and 1 part by weight of dibutyltin dimethoxide are mixed well, poured into a mold, and at room temperature using a vacuum dryer. Defoamed. A uniform rubber-like cured product sheet was obtained by heating and curing at 50 ° C. for 20 hours. The gel fraction determined by toluene extraction was 88%. A 2 (1/3) type dumbbell test piece was punched from the rubber-like cured sheet, and a tensile test was performed using an autograph (200 mm / min). The breaking strength was 0.32 MPa and the breaking elongation was 34%.
[0081]
[Example 3]
Synthesis of poly (acrylic acid-n-butyl) having halogen at its terminal
In a 500 ml pressure-resistant reaction vessel, acrylic acid-n-butyl (112 mL, 100 g, 0.78 mol), dibromoxylene (4.12 g, 15.6 mmol), cuprous bromide (2.24 g, 15.6 mmol), 2,2′-bipyridyl (4.87 g, 31.2 mmol), ethyl acetate (90 mL) and acetonitrile (20 mL) were charged, and nitrogen bubbling was performed to remove dissolved oxygen, followed by sealing. The mixture was heated to 130 ° C. and reacted for 2 hours. The reaction vessel was returned to room temperature, 2-hydroxyethyl methacrylate (3.92 mL, 4.06 g, 31.2 mmol) was added, and the mixture was reacted at 110 ° C. for 2 hours. The mixture was diluted with ethyl acetate (200 mL), and purified by removing the copper catalyst through a column of activated alumina to obtain a polymer having a Br group at the end. The number average molecular weight of the obtained polymer was 5700 in GPC measurement (mobile phase chloroform, polystyrene conversion), and the molecular weight distribution was 1.37.
Synthesis of poly (acrylic acid-n-butyl) having an alkenyl group at the terminal
Under a nitrogen atmosphere, 84 g of poly (acrylic acid-n-butyl) having halogen at the terminal obtained above, 7.7 g (56 mmol) of potassium pentenoate, and DMAc 80 ml were charged in a 500 ml flask and reacted at 70 ° C. for 4 hours. Unreacted potassium pentenoate and produced potassium bromide in the reaction mixture were removed by water extraction purification to obtain a polymer having an alkenyl group at the terminal. 70 g of this polymer and an equivalent weight of aluminum silicate (manufactured by Kyowa Chemical: Kyowaard 700PEL) were mixed in toluene and stirred at 100 ° C. After 4 hours, the aluminum silicate was filtered, and the polymer was purified by heating and distilling off the volatiles of the filtrate under reduced pressure. The number average molecular weight of the obtained polymer was 4760 by GPC measurement (mobile phase chloroform, polystyrene conversion), and the molecular weight distribution was 1.73. Also¹The number of alkenyl groups per polymer molecule determined by 1 H-NMR analysis was 1.78.
Synthesis of poly (acrylic acid-n-butyl) having a crosslinkable silyl group at the terminal
In a 200 ml pressure resistant reaction tube, 60 g of the polymer having an alkenyl group at the terminal obtained above, 8.4 mL (68.1 mmol) of methyldimethoxysilane, 2.5 mL (22.9 mmol) of methyl orthoformate, platinum bis (divinyltetramethyldi) Siloxane) 5 × 10^-3mmol was charged and reacted at 100 ° C. for 4 hours to obtain a crosslinkable silicon group-containing polymer. The number average molecular weight of the obtained polymer was 6000 by GPC measurement (mobile phase chloroform, polystyrene conversion), and the molecular weight distribution was 1.44. Also¹The number of crosslinkable silyl groups per molecule of the polymer determined by 1 H-NMR analysis was 1.59.
[0082]
[Reference Example 3]
1 part by weight of water and 1 part by weight of dibutyltin dimethoxide were mixed and stirred in 100 parts by weight of the polymer having a crosslinkable silyl group at the terminal obtained in Example 3, and poured into a 2 mm thick mold. A uniform rubber-like cured product sheet was obtained by defoaming at room temperature using a vacuum dryer and heat-curing at 50 ° C. for 2 days. The gel fraction determined by toluene extraction was 93%. A 2 (1/3) type dumbbell test piece was punched from the rubber-like cured sheet, and a tensile test was performed using an autograph (200 mm / min). The breaking strength was 0.26 MPa and the breaking elongation was 75%.
[0083]
[Example 4]
Synthesis of poly (acrylic acid-n-butyl) having halogen at its terminal
In a 50 ml flask, 0.63 g (4.4 mmol) of cuprous bromide, 0.76 g (4.4 mmol) of pentamethyldiethylenetriamine, 5 ml of acetonitrile, 1.6 g (4.4 mmol) of diethyl 2,5-dibromoadipate, acrylic After charging 44.7 g (349 mmol) of butyl acid and performing freeze degassing, it was reacted at 70 ° C. for 7 hours in a nitrogen atmosphere. The polymer having a Br group at the end was obtained by removing and purifying the copper catalyst through an activated alumina column. The number average molecular weight of the obtained polymer was 10700 in GPC measurement (mobile phase chloroform, polystyrene conversion), and the molecular weight distribution was 1.15.
Synthesis of poly (acrylic acid-n-butyl) having an alkenyl group at the terminal
Under a nitrogen atmosphere, a 200 ml flask was charged with 35 g of poly (acrylic acid-n-butyl) having halogen at the terminal obtained above, 2.2 g (16.1 mmol) of potassium pentenoate and 35 ml of DMAc, and reacted at 70 ° C. for 4 hours. It was. Unreacted potassium pentenoate and produced potassium bromide in the reaction mixture were removed by water extraction purification to obtain a polymer having an alkenyl group at the terminal. The number average molecular weight of the obtained polymer was 11300 in GPC measurement (mobile phase chloroform, polystyrene conversion), and the molecular weight distribution was 1.12. Also¹The number of alkenyl groups per polymer molecule determined by 1 H-NMR analysis was 1.82.
Synthesis of poly (acrylic acid-n-butyl) having a crosslinkable silyl group at the terminal
In a 200 mL pressure-resistant reaction tube, 15 g of the polymer having an alkenyl group at the terminal obtained above, methyldimethoxysilane 1.8 mL (14.5 mmol), methyl orthoformate 0.26 mL (2.4 mmol), platinum bis (divinyltetramethyldisiloxane) ) 10^-Fourmmol was charged and reacted at 100 ° C. for 4 hours to obtain a polymer having a crosslinkable silyl group at the terminal. The viscosity of the obtained polymer was 44 Pa · s, and the number average molecular weight was 11900 in GPC measurement (mobile phase chloroform, polystyrene conversion), and the molecular weight distribution was 1.12. Also¹According to 1 H-NMR analysis, the number of crosslinkable silicon groups per polymer molecule was 1.46.
[0084]
[Reference Example 4]
1 part by weight of water and 1 part by weight of dibutyltin dimethoxide were mixed and stirred in 100 parts by weight of the polymer having a crosslinkable silyl group at the end obtained in Example 4, and poured into a 2 mm thick mold. A uniform rubber-like cured material sheet was obtained by defoaming at room temperature using a vacuum dryer and heating and curing at 50 ° C. for 10 days. The gel fraction determined by toluene extraction was 98%. A 2 (1/3) type dumbbell test piece was punched from the rubber-like cured sheet, and a tensile test was performed using an autograph (200 mm / min). The breaking strength was 0.35 MPa and the breaking elongation was 77%.
[0085]
[Example 5]
Synthesis of poly (acrylic acid-n-butyl) having an alkenyl group at the terminal
In a 100 mL glass reaction vessel, butyl acrylate (50.0 mL, 44.7 g, 0.349 mol), cuprous bromide (1.25 g, 8.72 mmol), pentamethyldiethylenetriamine (1.82 mL, 1.51 g). , 8.72 mmol), and acetonitrile (5 mL) were charged, and after cooling, degassed under reduced pressure, and then replaced with nitrogen gas. After stirring well, diethyl 2,5-dibromoadipate (1.57 g, 4.36 mmol) was added, and the mixture was heated and stirred at 70 ° C. After 60 minutes, 1,7-octadiene (6.44 mL, 4.80 g, 43.6 mmol) was added, and heating and stirring were continued at 70 ° C. for 2 hours. After the mixture was treated with activated alumina, the volatile components were distilled off by heating under reduced pressure. The product was dissolved in ethyl acetate and washed with 2% hydrochloric acid, brine. The organic layer is Na₂SO_FourThe polymer having alkenyl groups at the ends was obtained by heating and evaporating volatile components under reduced pressure. The number average molecular weight of the obtained polymer was 13100 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.22. Also¹The number of alkenyl groups per polymer molecule determined by 1 H-NMR analysis was 2.01.
Synthesis of poly (acrylic acid-n-butyl) having a crosslinkable silyl group at the terminal
Poly (acrylic acid-n-butyl) having an alkenyl group at the terminal (30.5 g) obtained above and aluminum silicate (Kyowa Kagaku: Kyowaard 700PEL) of the same weight as the polymer in toluene. Mix and stir at 100 ° C. After 4 hours, the aluminum silicate was filtered, and the polymer was purified by heating and distilling off the volatiles of the filtrate under reduced pressure.
In a 200 mL pressure-resistant glass reaction vessel, the purified polymer (23.3 g), dimethoxymethylsilane (2.55 mL, 20.7 mmol), dimethyl orthoformate (0.38 mL, 3.45 mmol), and platinum catalyst are added. Prepared. However, the amount of platinum catalyst used is 2 × 10 in molar ratio to the alkenyl group of the polymer.^-FourEquivalent. The reaction mixture was heated at 100 ° C. for 3 hours. The volatile content of the mixture was distilled off under reduced pressure to obtain poly (acrylic acid-n-butyl) having a crosslinkable silyl group at the terminal. The number average molecular weight of the obtained polymer was 13900 in GPC measurement (mobile phase chloroform, polystyrene conversion), and the molecular weight distribution was 1.25. Also¹The number of crosslinkable silicon groups per polymer molecule determined by 1 H-NMR analysis was 1.58.
[0086]
[Reference Example 5]
1 part by weight of water and 1 part by weight of dibutyltin dimethoxide were mixed and stirred into 100 parts by weight of the polymer having a crosslinkable silyl group at the end obtained in Example 5, and poured into a 2 mm thick mold. A uniform rubber-like cured material sheet was obtained by defoaming at room temperature using a vacuum dryer and heat-curing at 50 ° C. for 10 days. The gel fraction determined by toluene extraction was 85%. A 2 (1/3) type dumbbell test piece was punched from the rubber-like cured sheet, and a tensile test was performed using an autograph (200 mm / min). The breaking strength was 0.34 MPa and the breaking elongation was 86%.
[0087]
[Example 6]
Synthesis of poly (acrylic acid-n-butyl) having halogen at its terminal
In a 50 mL flask, cuprous bromide 0.63 g (4.4 mmol), pentamethyldiethylenetriamine 0.76 g (4.4 mmol), acetonitrile 5 mL, diethyl 2,5-dibromoadipate 0.78 g (2.2 mmol), acrylic After charging 44.7 g (349 mmol) of butyl acid and performing freeze degassing, it was reacted at 70 ° C. for 6 hours in a nitrogen atmosphere. The polymer having a Br group at the end was obtained by removing and purifying the copper catalyst through an activated alumina column. The number average molecular weight of the obtained polymer was 23600 in GPC measurement (mobile phase chloroform, polystyrene conversion) and the molecular weight distribution was 1.14.
Synthesis of poly (acrylic acid-n-butyl) having an alkenyl group at the terminal
Under a nitrogen atmosphere, 34 g of the polymer having a Br group at the terminal obtained above, 1.0 g (7.6 mmol) of potassium pentenoate, and 34 mL of DMAc were charged in a 200 mL flask and reacted at 70 ° C. for 4 hours. Unreacted potassium pentenoate and produced potassium bromide in the reaction mixture were removed by water extraction purification to obtain a polymer having an alkenyl group at the terminal. The polymer having an alkenyl group at the terminal and an equal weight (30.5 g) of aluminum silicate (manufactured by Kyowa Chemical Co., Ltd .: Kyowaard 700PEL) were mixed in toluene and stirred at 100 ° C. After 4 hours, the aluminum silicate was filtered, and the polymer was purified by heating and distilling off the volatiles of the filtrate under reduced pressure. The number average molecular weight of the obtained polymer was 24800 and molecular weight distribution 1.14 by GPC measurement (mobile phase chloroform, polystyrene conversion). Also¹The number of alkenyl groups per polymer molecule determined by 1 H-NMR analysis was 1.46.
Synthesis of poly (acrylic acid-n-butyl) having a crosslinkable silyl group at the terminal
21 g of polymer having an alkenyl group at the terminal obtained above in a 200 ml pressure resistant reaction tube, 0.94 ml (7.6 mmol) of methyldimethoxysilane, 0.13 ml (1.3 mmol) of methyl orthoformate, platinum bis (divinyltetramethyldisiloxane) 2x10^-Fourmmol was charged and reacted at 100 ° C. for 4 hours to obtain a polymer having a crosslinkable silyl group at the terminal. The viscosity of the obtained polymer was 100 Pa · s, and the number average molecular weight was 25400 in GPC measurement (mobile phase chloroform, polystyrene conversion), and the molecular weight distribution was 1.16. Also¹The number of crosslinkable silyl groups per polymer molecule determined by 1 H-NMR analysis was 1.48.
[0088]
[Reference Example 6]
1 part by weight of water and 1 part by weight of dibutyltin dimethoxide were mixed and stirred in 100 parts by weight of the polymer having a crosslinkable silyl group at the terminal obtained in Example 6, and poured into a 2 mm thick mold. A uniform rubber-like cured product sheet was obtained by defoaming at room temperature using a vacuum dryer and heating and curing at 50 ° C. for 2 days. The gel fraction determined by toluene extraction was 94%. A 2 (1/3) type dumbbell test piece was punched from the rubber-like cured sheet, and a tensile test was performed using an autograph (200 mm / min). The breaking strength was 0.40 MPa, and the breaking elongation was 323%.
[0089]
[Comparative Example 1]
Synthesis of poly (acrylic acid-n-butyl) having a crosslinkable silyl group using a crosslinkable silicon group-containing monomer
400 g of toluene, 385 g of butyl acrylate, 15 g of methyldimethoxysilylpropyl methacrylate, and 6 g of azobisisobutyronitrile were polymerized at 105 ° C. for 7 hours while bubbling nitrogen in a 1 L flask. By distilling off toluene, poly (acrylic acid-n-butyl) having a crosslinkable silyl group was obtained. This polymer had a viscosity of 74 Pa · s, a number average molecular weight of 8,500, and a molecular weight distribution of 2.47, as measured by GPC (mobile phase chloroform, polystyrene conversion). Also¹The average number of hydroxyl groups per polymer molecule determined by 1 H-NMR analysis was 1.40.
[0090]
[Comparative Reference Example 1]
1 part by weight of water and 1 part by weight of dibutyltin dimethoxide were mixed with 100 parts by weight of the polymer having a crosslinkable silyl group of Comparative Example 1 and poured into a 2 mm thick formwork. A uniform rubber-like cured material sheet was obtained by defoaming at room temperature using a vacuum dryer and heating and curing at 50 ° C. for 10 days. The gel fraction determined by toluene extraction was 78%. A 2 (1/3) type dumbbell test piece was punched from the rubber-like cured sheet, and a tensile test was performed using an autograph (200 mm / min). The breaking strength was 0.14 MPa, and the breaking elongation was 69%.
[0091]
[Comparative Example 2]
Synthesis of poly (acrylic acid-n-butyl) having a crosslinkable silyl group using a crosslinkable silicon group-containing monomer
210 g of toluene, 293 g of butyl acrylate, 7.2 g of methyldimethoxysilylpropyl methacrylate, and 1.8 g of azobisisovaleronitrile were polymerized at 105 ° C. for 7 hours while bubbling nitrogen in a 1 L flask. By distilling off toluene, poly (acrylic acid-n-butyl) having a crosslinkable silyl group was obtained. The polymer had a viscosity of 110 Pa · s, a number average molecular weight of 9600 as measured by GPC (mobile phase chloroform, polystyrene conversion), and a molecular weight distribution of 2.86.
The results of Examples 2 to 6 and Comparative Examples 1 and 2 are summarized in Table 1.
[0092]
[Table 1]

[0093]
For applications that require rubber-like properties, it is desired to increase the molecular weight of the polymer in order to improve the balance of modulus / strength at break / elongation at break. Particularly in a polymer having a crosslinkable functional group as in the present invention, the tendency is strong because the molecular weight is closely related to the molecular weight between crosslinking points, which is an important index for rubber design. The number average molecular weight is one of the important parameters that influence the molecular weight between cross-linking points, and it is desirable that the number average molecular weight can be increased in order to improve the physical property balance.
[0094]
Since the vinyl polymer having a crosslinkable silyl group of the present invention can narrowly control the molecular weight distribution, the viscosity when compared with a polymer having almost the same number average molecular weight is extremely low, and as a result, a raw material excellent in handleability. (The viscosity of Example 4 is less than half that of Comparative Example 2). Further, when the viscosity is limited, a polymer having a higher number average molecular weight can be synthesized at substantially the same viscosity, so that a cured product having a better modulus / strength / elongation balance can be obtained (Example 7). In addition, since a vinyl polymer having a crosslinkable silyl group has been obtained by the living radical polymerization method, even if the average amount of the crosslinkable silyl group per molecule is almost the same, a polymer containing no crosslinkable silyl group is used. The amount of coalescence is reduced, and a cured product having a high gel content can be obtained (Example 4 and Comparative Example 1).
[0095]
[Reference Example 7]
Heat resistance of cured product
A part of the cured product sheet of poly (acrylic acid-n-butyl) having a crosslinkable silyl group obtained in Reference Example 4 was placed in an oven at 150 ° C., taken out after 24 hours, and the surface state was observed. There was no abnormality in the surface condition.
[0096]
[Comparative Example 3]
Synthesis of polydimethylsiloxane (silicone) having a terminal silyl group
In a 200-ml flask, 97 g of terminal vinyl polydimethylsiloxane having a molecular weight of 17,200 (Amax DMS-V25: unsaturated group equivalent 0.11 eq / kg), 2.3 g (21.4 mmol) of methyldimethoxysilane, platinum bis (divinyltetramethyl) Disiloxane) 10^-3mmol was added and reacted at 70 ° C. for 6 hours. The number average molecular weight of the obtained crosslinkable silyl group-terminated polydimethylsiloxane was 11900 in GPC measurement (mobile phase chloroform, polystyrene conversion), and the molecular weight distribution was 2.52.¹The peak derived from the unsaturated group disappears in HNMR (300 MHz), and the crosslinkability per molecule of the polydimethylsiloxane polymer determined from the intensity ratio of the methyl proton bonded to the silicon atom derived from the polymer main chain and the proton of the methoxysilyl group. The number of silicon groups was 2. The viscosity was 6 poise.
[0097]
[Comparative Reference Example 2]
Heat resistance of cured product
1 part by weight of water and 1 part by weight of dibutyltin dimethoxide were mixed and stirred in 100 parts by weight of the polymer having a crosslinkable silyl group of Comparative Example 3, and poured into a 2 mm thick mold. Degassed under reduced pressure and cured by heating at 50 ° C. for 10 days. A part of the obtained cured sheet was put in an oven at 150 ° C., taken out after 24 hours, and the surface state was observed. There was no abnormality on the surface.
[0098]
[Comparative Example 4]
Synthesis of polyisobutylene having an allyl group at the end
Into a 2 L pressure-resistant glass polymerization vessel purged with nitrogen, 205 ml of ethylcyclohexane dried with molecular sieves, 819 ml of toluene and 2.89 g (12.5 mmol) of p-dicumulyl chloride were added.
332 ml (3.91 mol) of isobutylene monomer was introduced into the polymerization vessel, and then 0.454 g (4.88 mmol) of 2-methylpyridine and 6.69 ml (61.0 mmol) of titanium tetrachloride were added to initiate the polymerization. After 70 minutes of reaction time, 6.86 g (60.0 mmol) of allyltrimethylsilane was added to carry out an allyl group introduction reaction at the polymer end. After 120 minutes of reaction time, the reaction solution was washed with water, and then the solvent was distilled off to obtain polyisobutylene having an allyl group at the terminal.
Synthesis of polyisobutylene having a crosslinkable silyl group at the end
After 200 g of the polymer having an allyl group at the terminal obtained above was heated to about 75 ° C., methyldimethoxysilane 1.5 [eq / vinyl group], platinum (vinylsiloxane) complex 5 × 10^-Five[Eq / vinyl group] was added to carry out a hydrosilylation reaction. Follow up the reaction by FT-IR, about 1640cm in about 20 hours^-1Olefin absorption disappeared.
The viscosity of the polyisobutylene having a crosslinkable silyl group at the terminal was 360 Pa · s, and the number average molecular weight was 4800 in GPC measurement (mobile phase chloroform, polystyrene conversion), and the molecular weight distribution was 1.52. Also¹The number of crosslinkable silyl groups per molecule of the polymer determined by 1 H-NMR analysis was 1.66.
[0099]
[Comparative Reference Example 3]
Heat resistance of cured product
1 part by weight of water and 1 part by weight of dibutyltin dimethoxide were mixed with 100 parts by weight of a polymer having a crosslinkable silyl group at the end of Comparative Example 4 and poured into a 2 mm thick formwork. Degassed under reduced pressure and cured by heating at 50 ° C. for 10 days. A part of the obtained cured sheet was put in an oven at 150 ° C., taken out after 24 hours, and the surface state was observed. The surface was dissolved and part of the liquid was flowing out.
[0100]
The results of Reference Example 7 and Comparative Reference Examples 2 and 3 are shown in Table 2.
[0101]
[Table 2]

[0102]
The cured product of the vinyl polymer having a crosslinkable silyl group of the present invention has the same level of heat resistance as that of the silicone polymer, and is superior in heat resistance to the polyisobrylene type, so that heat resistance is required. Can be used for applications.
[0103]
[Reference Example 8]
Accelerated weather resistance
A part of the cured sheet of poly (acrylic acid-n-butyl) having a crosslinkable silyl group obtained in Reference Example 4 was subjected to an accelerated weather resistance test using a sunshine weatherometer, and the surface state was observed. It was. Even after 1000 hours, the surface was not dissolved or discolored.
[0104]
[Comparative Reference Examples 4 and 5]
Instead of the cured product of poly (acrylic acid-n-butyl) having a crosslinkable silyl group obtained in Reference Example 4, in Comparative Reference Example 4, the silicone polymer obtained in Comparative Example 3 was used. Using the polyisobutylene polymer obtained in Comparative Example 4, an accelerated weather resistance test was conducted in the same manner as in Reference Example 8. In Comparative Reference Example 4, the surface did not dissolve or discolor after 1000 hours. On the other hand, in Comparative Reference Example 5, dissolution of the surface started after 500 hours.
[0105]
The composition using the vinyl polymer having a crosslinkable silyl group of the present invention has the same level of weather resistance as that of the silicone polymer composition, and is far superior to the polyisobrylene type. It can be used for applications that require high performance.
[0106]
[Reference Example 9]
One-part deep curing
100 parts by weight of the polymer having a crosslinkable silyl group obtained in Example 5 was azeotropically dehydrated with toluene. Under a nitrogen atmosphere, 1 part by weight of methyltrimethoxysilane and 1 part by weight of dibutyltin diacetylacetonate were sequentially added, and a one-part formulation was prepared by storing in a sealed bottle in a sample bottle. After storing for 1 week in a constant temperature and humidity chamber (23 ° C., 60% RH), the sample was dispensed to the sample tube. As a result of taking out the cured portion after 24 hours from the payout and measuring the thickness in the depth direction, it was 3 mm.
[0107]
[Comparative Reference Examples 6 and 7]
One-part deep curing
Instead of the polymer obtained in Example 5, Comparative Example 6 used the silicone polymer obtained in Comparative Example 3, and Comparative Reference Example 7 used the polyisobutylene polymer obtained in Comparative Example 4 as a reference example. In the same manner as in Example 9, the deep part curability was measured. The deep curability of Comparative Reference Example 6 was 3 mm. In Comparative Reference Example 7, only the thin skin was stretched on the surface, and the inside was not cured.
The vinyl polymer composition having a crosslinkable silyl group of the present invention has the same level of one-component deep-curing property as a silicone composition and is far superior to a polyisobrylene composition. It can be used as a composition such as a liquid sealant.
[0108]
[Reference Example 10]
Adhesiveness
100 parts by weight of poly (acrylic acid-n-butyl) having a crosslinkable silyl group obtained in Example 5, 120 parts by weight of colloidal calcium carbonate, 50 folds of dioctyl phthalate, and a crosslinkable silyl group-containing compound having an amino group 2 parts by weight of A-1120 (manufactured by Nihon Unicar) and 1 part by weight of dibutyltin diacetylacetonate were added and mixed well, and applied on a glass substrate in a bead shape. After standing at room temperature for 7 days, the adhesiveness was evaluated by cutting and peeling off the interface. The destruction situation was cohesive failure of the blended cured product.
The composition of the vinyl polymer having a crosslinkable silyl group of the present invention has sufficient adhesiveness and can be sufficiently used as a curable composition having adhesiveness.
[0109]
[Reference Example 11]
Paintability
To 100 parts by weight of poly (n-butyl acrylate) having a crosslinkable silyl group obtained in Example 5, 10 parts by weight of titanium oxide, 100 parts by weight of colloidal calcium carbonate, 40 parts by weight of heavy calcium carbonate, tin octylate A reaction product of 3 parts by weight and 0.75 part by weight of laurylamine was added and mixed well to prepare a sheet. The day after the sheet was prepared, an acrylic emulsion paint diluted with 10% water (aqueous top, manufactured by Nippon Paint) was applied. We were able to apply without problem.
[0110]
[Comparative Reference Example 8]
Paintability
A similar experiment was conducted using the polydimethylsiloxane having a crosslinkable silicon group obtained in Comparative Example 3 instead of the poly (acrylic acid-n-butyl) having a crosslinkable silyl group obtained in Example 5 in Reference Example 11. I did it. Even if I applied the paint, it repelled immediately.
Unlike the composition using the silicone polymer, the composition using the vinyl polymer having a crosslinkable silyl group of the present invention had sufficient paintability. Therefore, it can be used as a curable composition such as a paintable sealant.
[0111]
[Reference Example 12]
Pollution
To 100 parts by weight of poly (n-butyl acrylate) having a crosslinkable silyl group obtained in Example 5, 10 parts by weight of titanium oxide, 100 parts by weight of colloidal calcium carbonate, 40 parts by weight of heavy calcium carbonate, tin octylate The reaction product of 3 parts by weight and 0.75 part by weight of laurylamine was added and mixed well, filled in a granite joint coated with a primer (No. 40, manufactured by Yokohama Rubber), and exposed outdoors. Even after 8 months, the joint area was clean.
[0112]
[Comparative Reference Example 9]
A similar experiment was conducted using the polydimethylsiloxane having a crosslinkable silyl group obtained in Comparative Example 3 in place of the poly (acrylic acid-n-butyl) having a crosslinkable silyl group obtained in Example 5 in Reference Example 12. I did it. After 8 months, the area around the joint was dark and dirty.
Unlike the composition using a silicone polymer, the composition using a vinyl polymer having a crosslinkable silyl group of the present invention was free from granite contamination. Therefore, it can be used as a curable composition such as a sealant without contamination.
[0113]
[Reference Example 13]
Adhesive
40% toluene solution 175 of special rosin ester (Superester A-100, manufactured by Arakawa Chemical Co., Ltd.) was added to 100 parts by weight of poly (acrylic acid-n-butyl) having a crosslinkable silyl group obtained by the same formulation as in Example 4. Part by weight (70 parts by weight as rosin ester) and 2 parts by weight of # 918 (tin catalyst, manufactured by Sansha Co., Ltd.) were mixed and applied onto a PET film using a 100 μm coater. After standing at room temperature for 1 day, it was heated at 50 ° C. for 1 day. According to JIS Z 0237, it was 4.5 N / 25 mm as a result of carrying out 180 degree peeling adhesion.
The vinyl polymer having a crosslinkable silyl group of the present invention can be used as an adhesive.
[0114]
[Example 7]
In a 30 mL pressure-resistant glass reaction vessel, butyl acrylate (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 (217 mg, 1.40 mmol), ethyl acetate (4 mL), and acetonitrile (1 mL) were added and nitrogen bubbling was performed for 10 minutes to remove dissolved oxygen, followed by sealing. The mixture was heated to 130 ° C. and reacted for 2 hours. After the mixture was cooled, methyldimethoxysilylpropyl methacrylate (650 mg, 2.8 mmol) was added and reacted at 100 ° C. for 2 hours. The mixture was cooled, diluted with ethyl acetate (20 mL), the insoluble solid produced was filtered, and the filtrate was washed twice with aqueous ammonium chloride and once with brine. The organic layer is Na₂SO_FourThe volatile matter was distilled off under reduced pressure to obtain 4.78 g of poly (butyl acrylate) having a methyldimethoxysilyl group at the end (90%). The number average molecular weight of the polymer was 7100 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.74. Also,¹According to 1 H NMR analysis, 3.2 silyl groups were introduced per molecule.
[0115]
[Example 8]
In a 1 L pressure-resistant reaction vessel, acrylic acid-n-butyl (112 mL, 100 g, 0.78 mol), the hydroxyl group-containing initiator synthesized in Production Example 1 (3.07 g, 15.6 mmol), cuprous bromide ( 2.24 g, 15.6 mmol), 2,2′-bipyridyl (4.87 g, 31.2 mmol), ethyl acetate (90 mL), acetonitrile (22 mL) were charged, and dissolved oxygen was removed by blowing nitrogen gas for 10 minutes. After that, it was sealed. The mixture was heated to 130 ° C. and allowed to react for 1 hour. The reaction vessel was returned to room temperature, 2-hydroxyethyl methacrylate (3.92 mL, 4.06 g, 31.2 mmol) was added, and the mixture was reacted at 100 ° C. for 1 hour. The mixture was diluted with ethyl acetate, insolubles were filtered off, and the filtrate was 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 82 g of poly (acrylic acid-n-butyl) having a hydroxyl group at the terminal. The number average molecular weight of the polymer was 5900 according to GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.35.
[0116]
Next, undecene was added to a toluene solution (100 mL) of poly (acrylic acid-n-butyl) having a hydroxyl group at the terminal obtained as described above (68 g) and pyridine (14 mL) at 75 ° C. in a nitrogen atmosphere. Acid chloride (7.1 mL, 33.0 mmol) was slowly added dropwise and reacted at 60 ° C. 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) having an alkenyl group at the terminal (64 g). Aluminum silicate (manufactured by Kyowa Chemical: Kyowaard 700PEL) was added to the toluene solution of the polymer and stirred at the reflux temperature to remove trace impurities in the polymer. The alkenyl group introduced per oligomer-1 molecule is¹According to HNMR analysis, the number was 2.8.
[0117]
Next, in a 100 mL pressure-resistant glass reaction vessel, the polymer (25.3 g), dimethoxymethylhydrosilane (4.8 mL, 38.7 mmol), dimethyl orthoformate (1.4 mL, 12.9 mmol), and platinum The catalyst was charged. However, the amount of platinum catalyst used is 10 by molar ratio with respect to the alkenyl group of the polymer.^-FourEquivalent. The reaction mixture was heated at 100 ° C. for 3 hours. The volatile component of the mixture was distilled off under reduced pressure to obtain poly (acrylic acid-n-butyl) having a silyl group at the terminal. The silyl group introduced per oligomer-1 molecule is¹According to 1 H NMR analysis, it was 2.2.
[0118]
[Reference Example 14]
Poly (butyl acrylate) (2.5 g) having a crosslinkable silyl group at the end synthesized in Example 7 and a curing catalyst (manufactured by Nitto Kasei, U-220, 75 mg) were mixed well and poured into a mold. And defoaming 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 54%.
[0119]
[Reference Example 15]
Dibutyltin dimethoxide and water were added to and mixed well with the poly (butyl acrylate) having a silyl group at the end synthesized in Example 8. The amount of tin catalyst and water used was 1 part by weight with respect to the polymer.
The composition thus obtained was poured into a mold, degassed under reduced pressure, and heated and cured at 50 ° C. for 20 hours to obtain a sheet-like cured product having rubber elasticity. The cured product was immersed in toluene for 24 hours, and the gel fraction was measured from the weight change before and after and was 88%.
[0120]
A 2 (1/3) type dumbbell specimen was punched from the sheet-like cured product, and a tensile test was performed using an autograph manufactured by Shimadzu (measurement conditions: 23 ° C., 200 mm / min). The breaking strength was 0.32 MPa and the breaking elongation was 34%.
[0121]
[Example 9]
Next, in a 30 mL pressure-resistant glass reaction vessel, butyl acrylate (2.5 mL, 2.24 g, 17.45 mmol), α, α′-dibromo-p-xylene (92.5 mg, 0.35 mmol), bromide Cuprous (50 mg, 0.35 mmol), 2,2′-bipyridyl (163 mg, 1.05 mmol), ethyl acetate (2 mL), acetonitrile (0.5 mL) were charged, and nitrogen gas was blown for 10 minutes to dissolve oxygen. Was removed and sealed. The mixture was heated to 130 ° C. and allowed to react for 1 hour. After cooling to room temperature, allyloxyethyl methacrylate (600 mg, 3.5 mmol) obtained in Production Example 1 was added under a nitrogen gas atmosphere and sealed. The mixture was heated to 80 ° C. and reacted for 1 hour. The mixture was diluted with ethyl acetate (20 mL) and the insoluble solid produced was filtered, and then the filtrate was washed twice with dilute hydrochloric acid and once with brine. The organic layer is Na₂SO_FourThe volatile matter was distilled off under reduced pressure to obtain 1.97 g of polybutyl acrylate having an alkenyl group at both ends represented by the following formula (polymerization yield: 88%). The number average molecular weight of the polymer was 6700 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.60. The alkenyl group introduced per oligomer molecule is¹From HNMR analysis, it was 5.4.
[0122]
[Chemical 6]

[0123]
[Example 10]
In a 30 mL pressure-resistant glass reaction vessel, butyl acrylate (5 mL, 4.47 g, 34.9 mmol), α, α′-dibromo-p-xylene (180 mg, 0.69 mmol), cuprous bromide (98 mg, 0 .69 mmol), 2,2′-bipyridyl (319 g, 2.06 mmol), ethyl acetate (4 mL), and acetonitrile (1 ml) were charged, nitrogen gas was blown for 10 minutes to remove dissolved oxygen, and the tube was sealed. The mixture was heated to 130 ° C. and allowed to react for 1 hour. After cooling the mixture, allyltributyltin (0.51 mL, 1.64 mmol) was added under a nitrogen atmosphere and reacted at 100 ° C. for 1 hour. The mixture was diluted with ethyl acetate (20 mL) and the insoluble solid produced was filtered, and then the filtrate was washed twice with dilute hydrochloric acid and once with brine. The organic layer is Na₂SO_FourThen, the volatile matter was distilled off under reduced pressure to obtain a mixture of butyl acrylate and bromotributyltin having alkenyl groups at both ends as shown in the following formula (yield 4.48 g). The number average molecular weight of the polymer was 6300 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.57. The alkenyl group introduced per oligomer molecule is¹According to 1 H NMR analysis, it was 2.2.
[0124]
[Chemical 7]

[0125]
Example 11
The 50 mL 2-necked flask was purged with nitrogen, and 2-allyloxyethanol (2.5 mL, 23.4 mmol), pyridine (3 mL), and THF (10 mL) were charged. The solution was cooled to 0 ° C. and 2-bromopropionic acid chloride (2 mL, 19.52 mmol) was slowly added dropwise. After stirring at the same temperature for 1 hour, ethyl acetate (10 mL) was added, and the resulting hydrochloride of pyridine was removed by filtration. The filtrate was diluted with dilute hydrochloric acid (10 mL), NaHCO 3_ThreeWashed with aqueous solution (10 mL) and then brine (10 mL). The organic layer is Na₂SO_FourThe volatile matter was distilled off under reduced pressure. The resulting crude product was distilled under reduced pressure to obtain allyloxyethyl-2-bromopropionate represented by the following formula. (78.5-81 degreeC (1.3mmHg), 2.986g).
[0126]
CH_ThreeC (H) (Br) C (O) O-CH₂CH₂-O-CH₂CH = CH₂
Next, in a 30 mL pressure-resistant glass reaction vessel, butyl acrylate (2.5 mL, 2.24 g, 17.45 mmol), an initiator having the alkenyl group obtained above (165 mg, 0.698 mmol), A cuprous (100 mg, 0.698 mmol), 2,2′-bipyridyl (218 mg, 1.40 mmol), acetonitrile (0.5 mL), and ethyl acetate (2 mL) were charged, and dissolved oxygen was removed by blowing nitrogen gas for 10 minutes. And then sealed. The mixture was heated to 130 ° C. and reacted for 50 minutes. After cooling to room temperature, the mixture was diluted with ethyl acetate (20 mL), the insoluble solid produced was filtered, and the filtrate was washed twice with dilute hydrochloric acid and once with brine. The organic layer is Na₂SO_FourThe volatile matter was distilled off under reduced pressure to obtain 1.90 g of poly (butyl acrylate) having an alkenyl group at one end and bromine at the other end (79%). The number average molecular weight of the polymer was 3600 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.51. The alkenyl group introduced per oligomer molecule is¹According to 1 H NMR analysis, it was 0.75.
[0127]
Next, a polymer (1.90 g) obtained as described above, Na, and a 50 mL three-necked flask equipped with a stirrer and a reflux condenser were added.₂S ・ 9H₂O (70.2 mg, 0.293 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 (10 mL) and dilute hydrochloric acid (10 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 1.69 g of poly (acrylic acid) butyl having alkenyl groups at both ends as shown in the following formula. The number average molecular weight of the polymer was 5100 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.73.
[0128]
[Chemical 8]

[0129]
Example 12
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
In a 1 L pressure-resistant reaction vessel, acrylic acid-n-butyl (112 mL, 100 g, 0.78 mol), the hydroxyl group-containing initiator obtained above (3.07 g, 15.6 mmol), cuprous bromide (2. 24 g, 15.6 mmol), 2,2′-bipyridyl (4.87 g, 31.2 mmol), ethyl acetate (90 mL), acetonitrile (22 mL) were added, nitrogen bubbling was performed to remove dissolved oxygen, and the sealed tube did. The mixture was heated to 130 ° C. and reacted for 2 hours. The reaction vessel was returned to room temperature, 2-hydroxyethyl methacrylate (3.92 mL, 4.06 g, 31.2 mmol) was added, and the mixture was reacted at 110 ° C. for 2 hours. The mixture was diluted with ethyl acetate (200 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 82 g of poly (acrylic acid-n-butyl) having a hydroxyl group at the terminal. The number average molecular weight of the polymer was 5100 according to GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.29.
[0130]
Next, poly (acrylic acid-n-butyl) having a hydroxyl group at the terminal obtained as described above (50 g) and a toluene solution (100 mL) of pyridine (10 mL) were added to undecene at 75 ° C. in a nitrogen atmosphere. Acid chloride (7.22 mL, 6.81 g, 33.6 mmol) was slowly added dropwise and stirred at 75 ° 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 polymer was 5400 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.30. The alkenyl group introduced per oligomer molecule is¹According to HNMR analysis, the number was 2.28.
[0131]
[Chemical 9]

[0132]
[Comparative Example 5]
Poly (n-butyl acrylate) having hydroxyl groups at both ends was synthesized according to Production Example 3 of JP-A-6-219922. That is, 2-hydroxyethyl disulfide (30.8 g, 24.4 mL, 0.2 mol) was added to a 100 mL three-necked flask equipped with a stirring bar and a dropping funnel. The flask was heated to 100 ° C., and a mixture of n-butyl acrylate (12.8 g, 14.32 mL, 0.1 mol) and AIBN (0.328 g, 0.002 mol) was added dropwise over 30 minutes. The mixture was stirred for an additional hour at 100 ° C. Toluene (20 mL) was added, the mixture was placed in a separatory funnel, and the lower layer was separated. The top layer is washed 3 times with water and Na₂SO_FourAfter drying, the volatile matter was distilled off under reduced pressure to obtain poly (acrylic acid-n-butyl) having hydroxyl groups at both ends (12.18 g, 95%). The number average molecular weight of the polymer was 4300 according to GPC measurement (polystyrene conversion), and the molecular weight distribution was 4.22.
[0133]
Next, poly (acrylic acid-n-butyl) having a terminal hydroxyl group (10.51 g) and a pyridine (2 mL) solution in toluene (15 mL) obtained as described above were added at 60 ° C. in a nitrogen atmosphere. Undecenoic acid chloride (0.898 mL, 848 mg, 4.18 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) (7.45 g) having an alkenyl group at the end represented by the following formula. The number average molecular weight of the polymer was 4400, and the molecular weight distribution was 4.31, as measured by GPC (polystyrene conversion).
[0134]
[Reference Examples 16 to 19 and Comparative Reference Example 10]
Making a cured product
Poly (butyl acrylate) having alkenyl groups at both ends obtained in Examples 9 to 12 and Comparative Example 5 was dissolved in toluene, and the same amount of aluminum silicate as the polymer (Kyowa Chemical Co., Ltd .: Kyoward 700PEL) Was added and stirred for 1 hour to remove trace impurities in the polymer.
[0135]
Next, each of the purified poly (butyl acrylate), a polyvalent hydrogen silicon compound represented by the following formula, and 1,1,3,3-tetramethyl-1,3-divinyldioxide of zero-valent platinum Siloxane complex (8.3 × 10^-8mol / L xylene solution) was mixed well. The amount of polyvalent hydrogen silicon compound used is such that the alkenyl group of the polymer and the hydrosilyl group of the hydrogen silicon compound are 1 / 1.2 in molar ratio, and the amount of platinum catalyst used is the alkenyl group of the polymer. 10 molar ratio to the group^-Four-10^-3Equivalent.
[0136]
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 3.
[0137]
Embedded image

[0138]
[Table 3]

[0139]
Example 13
In Example 9, poly (methyl acrylate) having an alkenyl group at the terminal was obtained in the same manner except that methyl acrylate was used instead of n-butyl acrylate (yield 93%). The number average molecular weight of the polymer was 7900 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 2.0. Moreover, the average number of alkenyl groups introduced per molecule of the oligomer was 3.3 based on 1H NMR analysis.
[0140]
Example 14
In a 500 mL three-necked flask with a reflux tube, cuprous bromide (1.50 g, 10.5 mmol) as a catalyst, pentamethyldiethylenetriamine (1.65 mL) as a ligand, and diethyl-2,5-dibromo as an initiator Using adipate (9.42 g, 26.2 mol) and acetonitrile (30 mL) as a solvent, acrylic acid-n-butyl (300 mL) was polymerized at 70 ° C. in a nitrogen atmosphere, and the polymerization rate of acrylic acid-n-butyl was At 93%, 1,7-octadiene (38.6 mL, 0.261 mol) was added and heated at the same temperature. The reaction mixture was diluted with ethyl acetate, the catalyst was removed through an activated alumina column, and the volatile component was distilled off under reduced pressure to obtain a polymer having an alkenyl group at the terminal. The number average molecular weight of the polymer was 13800 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.28. The alkenyl group introduced per oligomer-1 molecule is¹From 1 H NMR analysis, it was 1.84.
[0141]
Example 15
In a 30 mL pressure-resistant glass reaction vessel, acrylic acid-n-butyl (7.5 mL, 6.72 g, 51.3 mmol), α, α′-dibromo-p-xylene (270 mg, 1.03 mmol), first bromide Copper (150 mg, 1.03 mmol), 2,2′-bipyridyl (322 mg, 2.06 mmol), ethyl acetate (6 mL), and acetonitrile (1.5 mL) were charged, and nitrogen gas was blown for 10 minutes to dissolve dissolved oxygen. After removal, the tube was sealed. The mixture was heated to 130 ° C. and reacted for 1.5 hours. The mixture was diluted with ethyl acetate (20 mL) and the insoluble solid produced was filtered, and then the filtrate was washed twice with dilute hydrochloric acid and once with brine. The organic layer is Na₂SO_FourThe volatile matter was distilled off under reduced pressure to obtain 5.0 g of poly (acrylic acid-n-butyl) having a halogen at the terminal (polymerization yield: 75%). The number average molecular weight of the polymer was 5600 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.32.
[0142]
The above polymer (5.00 g), undecylenic acid potassium salt synthesized in Production Example 2 (476 mg, 2.14 mmol), and dimethylacetamide (10 mL) were charged and reacted at 70 ° C. for 6 hours in a nitrogen atmosphere. . Volatiles of the mixture were removed under reduced pressure, ethyl acetate was added, and insolubles were filtered off. The filtrate was evaporated under reduced pressure to obtain 4.77 g of poly (n-butyl acrylate) having an alkenyl group at the terminal. The alkenyl group introduced per oligomer-1 molecule is¹From 1 H NMR analysis, it was 1.70.
[0143]
Example 16
In the same manner as in Example 15, cuprous bromide (1.50 g, 10.5 mmol) as a catalyst, pentamethyldiethylenetriamine (0.69 mL) as a ligand, and diethyl-2,5-dibromoadipate (initiator) 9.42 g, 26.2 mol), and acetonitrile (30 mL) as a solvent, acrylate-n-butyl (300 mL) was polymerized at 70 ° C. in a nitrogen atmosphere, and poly (acrylic acid-n-) having a halogen at the terminal was polymerized. Butyl) was obtained. The number average molecular weight of the polymer was 11300 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.16.
[0144]
Next, poly (acrylic acid-n-butyl) having an alkenyl group at the terminal was obtained by the same operation as in Example 15 using the pentenoic acid potassium salt produced in Production Example 3 as the carboxylate. The alkenyl group introduced per oligomer-1 molecule is¹From 1 H NMR analysis, it was 1.84.
[0145]
[Example 17]
In a 30 mL pressure-resistant glass reaction vessel, acrylic acid-n-butyl (5 mL, 4.47 g, 34.9 mmol), α, α′-dibromo-p-xylene (180 mg, 0.69 mmol), cuprous bromide ( 98 mg, 0.69 mmol), 2,2′-bipyridyl (319 g, 2.06 mmol), ethyl acetate (4 mL), and acetonitrile (1 ml) were charged, and nitrogen gas was blown for 10 minutes to remove dissolved oxygen. Tubed. The mixture was heated to 130 ° C. and allowed to react for 1 hour. After cooling the mixture, allyltributyltin (0.51 mL, 1.64 mmol) was added under a nitrogen atmosphere and reacted at 100 ° C. for 1 hour. The mixture was diluted with ethyl acetate (20 mL) and the insoluble solid produced was filtered, and then the filtrate was washed twice with dilute hydrochloric acid and once with brine. The organic layer is Na₂SO_FourThe volatile matter was distilled off under reduced pressure to obtain a mixture of poly-n-butyl acrylate having an alkenyl group at the end and bromotributyltin (yield 4.48 g). The number average molecular weight of the polymer was 6300 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.57. The alkenyl group introduced per oligomer molecule is¹According to 1 H NMR analysis, it was 2.2.
[0146]
Example 18
In a 30 mL pressure-resistant glass reaction vessel, methyl acrylate (5 mL, 4.78 g, 55.5 mmol), allyl 2-methyl-2-bromopropionate (0.354 mL, 460 mg, 2.22 mmol), cuprous bromide (318 mg, 2.22 mmol), 2,2′-bipyridyl (1.04 g, 6.66 mmol), acetonitrile (1 mL), and ethyl acetate (4 mL) were charged, and the vacuum was degassed three times to remove dissolved oxygen. After that, it was sealed. The mixture was heated to 80 ° C. and reacted for 3 hours. After cooling to room temperature, the mixture was diluted with ethyl acetate (20 mL), the insoluble solid produced was filtered, and the filtrate was washed twice with dilute hydrochloric acid and once with brine. The organic layer is Na₂SO_FourThe volatile matter was distilled off under reduced pressure to obtain 3.93 g of poly (methyl acrylate) having an alkenyl group at one end and bromine at the other end (75%). The number average molecular weight of the polymer was 2700 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.48. The alkenyl group introduced per oligomer molecule is¹According to 1 H NMR analysis, it was 0.81.
[0147]
Next, a 50 mL three-necked flask equipped with a stirrer and a reflux condenser was added to the polymer (1.17 g) obtained as described above, Na₂S ・ 9H₂O (57.6 mg, 0.240 mmol) and ethanol (2 mL) were charged, and the mixture was stirred at reflux temperature for 3 hours. After cooling to room temperature, ethyl acetate (10 mL) and dilute hydrochloric acid (10 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 1.11 g of poly (methyl acrylate) having an alkenyl group at the terminal. The number average molecular weight of the polymer was 4200 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.71.
[0148]
Example 19
In a 1 L pressure-resistant reaction vessel, acrylic acid-n-butyl (112 mL, 100 g, 0.78 mol), the hydroxyl group-containing initiator obtained in Production Example 3 (3.07 g, 15.6 mmol), cuprous bromide ( 2.24 g, 15.6 mmol), 2,2′-bipyridyl (4.87 g, 31.2 mmol), ethyl acetate (90 mL), acetonitrile (22 mL) were charged, and nitrogen bubbling was performed to remove dissolved oxygen. Sealed. The mixture was heated to 130 ° C. and reacted for 2 hours. The reaction vessel was returned to room temperature, 2-hydroxyethyl methacrylate (3.92 mL, 4.06 g, 31.2 mmol) was added, and the mixture was reacted at 110 ° C. for 2 hours. The mixture was diluted with ethyl acetate (200 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 82 g of poly (acrylic acid-n-butyl) having a hydroxyl group at the terminal. The number average molecular weight of the polymer was 5100 according to GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.29.
[0149]
Next, poly (acrylic acid-n-butyl) having a hydroxyl group at the terminal obtained as described above (50 g) and a toluene solution (100 mL) of pyridine (10 mL) were added to undecene at 75 ° C. in a nitrogen atmosphere. Acid chloride (7.22 mL, 6.81 g, 33.6 mmol) was slowly added dropwise and stirred at 75 ° 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) having an alkenyl group at the terminal (43 g).
[0150]
[Reference Examples 20-29]
Making a cured product
The polymer having an alkenyl group at the terminal obtained in Production Examples 13 to 19 was treated with aluminum silicate (manufactured by Kyowa Chemical Co., Ltd., Kyoward 700PEL) to remove trace impurities in the polymer.
[0151]
Next, the purified poly (acrylic acid ester), the polyvalent hydrogen silicon compound, and the 1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex of zero-valent platinum (8.3) × 10^-8mol / L xylene solution) was mixed well. As the polyvalent hydrogen silicon compound, the following compounds (S-1, S-2) or methyl hydrogen siloxane partially modified with α-methylstyrene (S-3: SiH value 7.69 mmol / g) Using. The amount of the polyvalent hydrogen silicon compound used was such that the molar ratio of the alkenyl group of the polymer to the SiH group of the hydrogen silicon compound was 1 / 1.2-1 / 1.5. Moreover, the usage-amount of the platinum catalyst added predetermined amount with respect to the alkenyl group of a polymer.
[0152]
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, and heated to 100 ° C. 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 4.
[0153]
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[0154]
[Table 4]

[0155]
Example 20
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 4 (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. Moreover, the average number of hydroxyl groups per polymer molecule was 3.3 by NMR measurement. When the viscosity of this polymer was measured with an E-type viscosity system (shear rate: 10 sec.^-123 ° C.) and 388 poise.
[0156]
Embedded image

[0157]
[Comparative Example 6]
According to Example 1 of JP-A-5-262808, poly (acrylic acid-n-butyl) having hydroxyl groups at both ends was synthesized. That is, 2-hydroxyethyl disulfide (30.8 g, 24.4 mL, 0.2 mol) was added to a 100 mL three-necked flask equipped with a stirring bar and a dropping funnel. The flask was heated to 100 ° C., and a mixture of n-butyl acrylate (12.8 g, 14.32 mL, 0.1 mol) and AIBN (0.328 g, 0.002 mol) was added dropwise over 30 minutes. The mixture was stirred for an additional hour at 100 ° C. Toluene (20 mL) was added, the mixture was placed in a separatory funnel, and the lower layer was separated. The top layer is washed 3 times with water and Na₂SO_FourAfter drying, the volatile matter was distilled off under reduced pressure to obtain poly (acrylic acid-n-butyl) having hydroxyl groups at both ends (12.18 g, 95%). The number average molecular weight of the polymer was 4300 according to GPC measurement (polystyrene conversion), and the molecular weight distribution was 4.22. When the viscosity of this polymer was measured with an E-type viscosity system (shear rate: 10 sec.^-123 ° C.) and 490 poise. Also,¹The average number of hydroxyl groups per polymer molecule determined by 1 H-NMR analysis was 1.42.
[0158]
Table 5 summarizes the properties of the polymers obtained in Example 20 and Comparative Example 6.
[0159]
[Table 5]

[0160]
The polymer of Example 20 has a lower viscosity than the polymer of Comparative Example 6, although the number average molecular weight is considerably higher. Here, the advantage of the narrow molecular weight distribution of the polymer of the present invention is clear.
[0161]
[Reference Example 30 and Comparative Reference Example 11]
Making urethane cured product
Poly (n-butyl acrylate) having hydroxyl groups at both ends obtained in Example 20 and Comparative Example 6, respectively, are trifunctional isocyanate compounds represented by the following formula (B-45, manufactured by Yushi Co., Ltd.), and It was mixed well with a tin-based catalyst (Nitto Kasei, U-220, dibutyltin diacetylacetonate). 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.
[0162]
Each of the above mixtures was degassed under reduced pressure, poured into a mold and cured by heating at 80 ° C. for 15 hours. A part of the obtained sheet-like cured product was immersed in toluene for 24 hours, and the gel fraction was calculated from the weight change before and after. Moreover, the No. 3 dumbbell based on JISK6301 was punched out from the sheet-like cured product, and a tensile test was performed at a tensile speed of 200 mm / min. The results are shown in Table 6.
[0163]
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[0164]
[Table 6]

[0165]
Reference Example 30 is higher than Comparative Reference Example 11 in all of break strength, elongation, and gel fraction. The inventive step of the polymer of the present invention is clear.
[0166]
Example 21
Synthesis of poly (acrylic acid-n-butyl) having a hydroxyl group at the terminal
In a 1 L pressure-resistant reaction vessel, acrylic acid-n-butyl (112 mL, 100 g, 0.78 mol), the hydroxyl group-containing initiator obtained in Production Example 4 (3.07 g, 15.6 mmol), cuprous bromide ( 2.24 g, 15.6 mmol), 2,2′-bipyridyl (4.87 g, 31.2 mmol), ethyl acetate (90 mL), acetonitrile (20 mL) were charged, and nitrogen bubbling was performed to remove dissolved oxygen. Sealed. The mixture was heated to 130 ° C. and reacted for 2 hours. The reaction vessel was returned to room temperature, 2-hydroxyethyl methacrylate (3.92 mL, 4.06 g, 31.2 mmol) was added, and the mixture was reacted at 110 ° C. for 2 hours. The mixture was diluted with ethyl acetate (200 mL), insolubles were filtered off, the filtrate was washed with 10% hydrochloric acid and brine, and the organic layer was washed with Na.₂SO_FourAnd dried. The solvent was distilled off under reduced pressure to obtain 82 g of poly (acrylic acid-n-butyl) having a hydroxyl group at the terminal. This polymer had a viscosity of 25 Pa · s, a number average molecular weight of 5100 as measured by GPC (mobile phase chloroform, polystyrene conversion), and a molecular weight distribution of 1.29. Also,¹The average number of hydroxyl groups per polymer molecule determined by 1 H-NMR analysis was 2.39.
Synthesis of poly (acrylic acid-n-butyl) having a crosslinkable silyl group at the terminal
The poly (n-butyl acrylate) having a hydroxyl group at the terminal synthesized above (4.94 g, OH = 2.30 mmol) was subjected to azeotropic dehydration at 50 ° C. in the presence of toluene. To this, tin octylate (4.9 mg) and toluene (6 mL) were added, and methyldimethoxysilylpropyl isocyanate (0.524 g, 2.77 mmol) was added dropwise at 50 ° C. After completion of the dropping, the reaction temperature was raised to 70 ° C. and the reaction was continued for 4 hours. It was judged that there was no unreacted hydroxyl group due to disappearance of the signal (3.8 ppm) of the methylene group to which the hydroxyl group was bonded in 1H-NMR. Volatile components were distilled off under reduced pressure to obtain poly (acrylic acid-n-butyl) having a crosslinkable silyl group at the terminal. The polymer had a viscosity of 22 Pa · s, a number average molecular weight of 4900, as measured by GPC (mobile phase chloroform, converted to polystyrene), and a molecular weight distribution of 1.60.
[0167]
[Reference Example 31]
To 100 parts by weight of the polymer having a crosslinkable silyl group at the terminal obtained in Example 21, 1 part by weight of dibutyltin diacetylacetonate was mixed, poured into a mold, and defoamed at room temperature using a vacuum dryer. . A uniform rubber-like cured product sheet was obtained by heating and curing at 50 ° C. for 20 hours. The gel fraction determined by toluene extraction was 93%.
A 2 (1/3) type dumbbell test piece was punched from the rubber-like cured sheet, and a tensile test was performed using an autograph (200 mm / min). The breaking strength was 0.31 MPa and the breaking elongation was 35%. It was.
[0168]
[Comparative Example 7]
Synthesis of poly (acrylic acid-n-butyl) having a crosslinkable silyl group at the end using a hydroxyl group-containing disulfide
A poly (acrylic acid-n-butyl) having a hydroxyl group at the terminal synthesized in Comparative Example 6 (4.52 g, OH = 1.85 mmol) was subjected to azeotropic dehydration at 50 ° C. in the presence of toluene. To this, tin octylate (4.52 mg) and toluene (6 mL) were added, and methyldimethoxysilylpropyl isocyanate (0.421 g, 2.22 mmol) was added dropwise at 50 ° C. After completion of the dropping, the reaction temperature was raised to 70 ° C. and the reaction was continued for 4 hours. It was judged that there was no unreacted hydroxyl group due to disappearance of the signal (3.8 ppm) of the methylene group to which the hydroxyl group was bonded in 1H-NMR. Volatile components were distilled off under reduced pressure to obtain poly (acrylic acid-n-butyl) having a crosslinkable silyl group at the terminal. This polymer had a viscosity of 53 Pa · s, a number average molecular weight of 4700, as determined by GPC measurement (mobile phase chloroform, polystyrene conversion), and a molecular weight distribution of 3.71.
[0169]
[Comparative Reference Example 12]
1 part by weight of dibutyltin diacetylacetonate was mixed with 100 parts by weight of the polymer having a crosslinkable silyl group at the end of Comparative Example 7, poured into a mold, and defoamed at room temperature using a vacuum dryer. A uniform rubber-like cured product sheet was obtained by heating and curing at 50 ° C. for 20 hours. The gel fraction determined by toluene extraction was 82%. Concentrate the extract¹H-NMR was measured, but no crosslinkable silyl group was present therein.
[0170]
A 2 (1/3) type dumbbell test piece was punched from the rubber-like cured sheet, and a tensile test was performed using an autograph (200 mm / min). The breaking strength was 0.21 MPa and the breaking elongation was 93%. It was.
[0171]
[Example 22]
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), acetonitrile (1 mL), nitrogen bubbling was performed for 10 minutes to remove dissolved oxygen, and then 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.
[0172]
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[0173]
Example 23
In Example 20, 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 polymer molecule was 2.2.
[0174]
Example 24
In Example 20, 5.75 g of poly (acrylic acid-n-butyl) shown in Chemical formula 7 was obtained in the same manner except that 7.5 mL of acrylic acid-n-butyl was used (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,¹By 1 H NMR measurement, the average number of hydroxyl groups per molecule of the polymer was 2.1.
[0175]
Example 25
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 4 (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.
[0176]
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.
[0177]
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[0178]
[Reference Examples 32-35]
Making a cured product
Poly (acrylic acid-n-butyl) having hydroxyl groups at both ends obtained in Examples 22 to 25, a trifunctional isocyanate compound represented by the following formula (B-45 manufactured by Yushi Co., Ltd.), and a tin-based catalyst (Nitto) Kasei, U-220, dibutyltin diacetylacetonate) were 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.
[0179]
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 7.
[0180]
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[0181]
[Table 7]

[0182]
Example 26
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 represented by the following formula was obtained. The number average molecular weight of the produced polymer was 10200, and the molecular weight distribution was 1.14.
[0183]
The obtained poly (acrylic acid-n-butyl) (5.00 g), 4-hydroxybutyric acid sodium salt (0.248 g, 1.967 mmol) were mixed in N, N-dimethylacetamide (10 mL), and 70 Stir for 3 hours at ° C. 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.
[0184]
[Reference Example 36]
Poly (acrylic acid-n-butyl) having a hydroxyl group at both ends obtained in Example 26 and a trifunctional isocyanate compound (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. The 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 from the change in weight before and after and was 97%.
[0185]
【The invention's effect】
Since the vinyl polymer having a crosslinkable silyl group, alkenyl group, or hydroxyl group at the end of the present invention is produced by utilizing living radical polymerization, the molecular weight distribution is narrow. Therefore, it is expected to be easy to handle when used as a curable composition because it has a lower viscosity than a polymer having an equivalent molecular weight produced by ordinary radical polymerization.

Claims (12)

At least one hydroxyl group per molecule at the molecular end, the ratio of the weight average molecular weight to the number average molecular weight measured by gel permeation chromatography is less than 1.8, and the main chain is a (meth) acrylic polymer A vinyl polymer,
A vinyl polymer in which a hydroxyl group is bonded to a main chain in a form represented by any one of formulas 8 to 12.
HO-R ^6- (8)
HO-R ⁷ -O- (9)
HO—R ⁷ —OC (O) — (10)
HO—R ⁷ —C (O) O— (11)
HO—R ⁷ —OC (O) O— (12)
(Wherein R ⁶ represents — (CH ₂ ) _n — (n is an integer of 2 to 20), —CH (CH ₃ ) CH ₂ —, —CH (CH ₃ ) (CH ₂ ) ₂ —, —CH ₂ CH (CH ₃ ) —, — (CH ₂ ) _n —O— (CH ₂ ) _m — (n, m is an integer of 1 to 19 , where n + m ≦ 20), o−, m−, pC ₆ H ₄ -, _{or, o-, m-, p- (CH} 2) n -C 6 H 4 - represents a (n, m is an integer of 0 to 14, provided that _{n + m ≦ 14) - (} CH 2) m.
R ⁷ represents an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an aralkylene group having 7 to 20 carbon atoms, and may contain one or more ether bonds. ) The crosslinkability represented by the general formula 1 is obtained by reacting the vinyl polymer having a hydroxyl group according to claim 1 with a compound having a crosslinkable silyl group and an isocyanate group, at least one molecule per molecule. Vinyl polymer having a silyl group.
_{^{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (1)
(In Formula (1), R ¹ and R ² are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or aralkyl groups having 7 to 20 carbon atoms, or (R ′) _3. A triorganosiloxy group represented by Si 2 O 3-(R 'is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different). When two or more R ¹ or R ² 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 is 0, 1, 2, or 3, and b is 0, 1, or 2. m is an integer of 0-19. However, it shall be satisfied that a + mb ≧ 1.) The vinyl polymer according to claim 1 or 2, wherein the ratio of the weight average molecular weight to the number average molecular weight measured by gel permeation chromatography is 1.7 or less. The vinyl polymer according to any one of claims 1 to 3, wherein the ratio of the weight average molecular weight to the number average molecular weight measured by gel permeation chromatography is 1.6 or less. The vinyl polymer according to any one of claims 1 to 4, wherein the ratio of the weight average molecular weight to the number average molecular weight measured by gel permeation chromatography is 1.5 or less. The vinyl polymer according to any one of claims 1 to 5, wherein the main chain is an acrylic ester polymer. The vinyl polymer according to any one of claims 1 to 6, wherein the main chain is produced by atom transfer radical polymerization. The vinyl polymer having a hydroxyl group is produced by converting a halogen group at the terminal of the vinyl polymer into a hydroxyl group represented by any one of the general formulas 8 to 12. Vinyl polymer. Y in general formula 1 is a hydrogen atom, halogen, hydroxyl group, alkoxy group, acyloxy group, ketoximate group, amino group, amide group, aminooxy group, mercapto group or alkenyloxy group, and when Y is 2 or more The vinyl polymer having a crosslinkable silyl group at the end according to any one of claims 2 to 8, which may be the same or different. The vinyl polymer according to claim 9, wherein Y in the general formula 1 is an alkoxy group. The molecular terminal which makes the vinyl polymer which has a hydroxyl group in any one of Claims 1-8 react with an alkenyl group containing halide, an alkenyl group containing isocyanate compound, an alkenyl group containing acid halide, or an alkenyl group containing carboxylic acid. And a method for producing a vinyl polymer having at least one alkenyl group per molecule. The vinyl polymer having a hydroxyl group according to any one of claims 1 to 8 is reacted with an alkenyl group-containing halide, an alkenyl group-containing isocyanate compound, an alkenyl group-containing acid halide, or an alkenyl group-containing carboxylic acid to form a molecule. A vinyl polymer having at least one alkenyl group per molecule at the end is prepared, and a hydrosilane compound having a crosslinkable silyl group is added to the vinyl polymer having the alkenyl group. A method for producing a vinyl polymer having at least one crosslinkable silyl group represented by the general formula 1.
_{^{- [Si (R 1) 2}} -b (Y) b O] m -Si (R 2) 3-a (Y) a (1)
(In Formula (1), R ¹ and R ² are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or aralkyl groups having 7 to 20 carbon atoms, or (R ′) _3. A triorganosiloxy group represented by Si 2 O 3-(R 'is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different). When two or more R ¹ or R ² 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 is 0, 1, 2, or 3, and b is 0, 1, or 2. m is an integer of 0-19. However, it shall be satisfied that a + mb ≧ 1.)