JP3895460B2 - POLYMER, PROCESS FOR PRODUCING THE POLYMER, AND CURABLE COMPOSITION USING THE POLYMER - Google Patents

Description

【００３７】
（上記の各式において、Ｘは、塩素、臭素又はヨウ素を表す。ｎは、０〜２０の整数を表す。）；
ＸＣＨ₂ Ｃ（Ｏ）Ｏ（ＣＨ₂ ）_n Ｏ（ＣＨ₂ ）_m ＣＨ＝ＣＨ₂ 、Ｈ₃ ＣＣ（Ｈ)(Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂ ）_n Ｏ（ＣＨ₂ ）_m ＣＨ＝ＣＨ₂ 、（Ｈ₃ Ｃ）₂ Ｃ（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂ ）_n Ｏ（ＣＨ₂ ）_m ＣＨ＝ＣＨ₂ 、ＣＨ₃ ＣＨ₂ Ｃ（Ｈ)(Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂ ）_n Ｏ（ＣＨ₂ ）_m ＣＨ＝ＣＨ₂ 、
【００３８】
【化２】

【００３９】
（上記の各式において、Ｘは、塩素、臭素又はヨウ素を表す。ｎは、１〜２０の整数を表す。ｍは、０〜２０の整数を表す。）；
ｏ，ｍ，ｐ−ＸＣＨ₂ −Ｃ₆ Ｈ₄ −（ＣＨ₂ ）_n −ＣＨ＝ＣＨ₂ 、ｏ，ｍ，ｐ−ＣＨ₃ Ｃ（Ｈ)(Ｘ）−Ｃ₆ Ｈ₄ −（ＣＨ₂ ）_n −ＣＨ＝ＣＨ₂ 、ｏ，ｍ，ｐ−ＣＨ₃ ＣＨ₂ Ｃ（Ｈ)(Ｘ）−Ｃ₆ Ｈ₄ −（ＣＨ₂ ）_n −ＣＨ＝ＣＨ₂ （上記の各式において、Ｘは、塩素、臭素又はヨウ素を表す。ｎは、０〜２０の整数を表す。）；
ｏ，ｍ，ｐ−ＸＣＨ₂ −Ｃ₆ Ｈ₄ −（ＣＨ₂ ）_n −Ｏ−（ＣＨ₂ ）_m −ＣＨ＝ＣＨ₂ 、ｏ，ｍ，ｐ−ＣＨ₃ Ｃ（Ｈ)(Ｘ）−Ｃ₆ Ｈ₄ −（ＣＨ₂ ）_n −Ｏ−（ＣＨ₂ ）_m −ＣＨ＝ＣＨ₂ 、ｏ，ｍ，ｐ−ＣＨ₃ ＣＨ₂ Ｃ（Ｈ)(Ｘ）−Ｃ₆ Ｈ₄ −（ＣＨ₂ ）_n −Ｏ−（ＣＨ₂ ）_m ＣＨ＝ＣＨ₂ （上記の各式において、Ｘは、塩素、臭素又はヨウ素を表す。ｎは、１〜２０の整数を表す。ｍは、０〜２０の整数を表す。）；
【００４０】
ｏ，ｍ，ｐ−ＸＣＨ₂ −Ｃ₆ Ｈ₄ −Ｏ−（ＣＨ₂ ）_n −ＣＨ＝ＣＨ₂ 、ｏ，ｍ，ｐ−ＣＨ₃ Ｃ（Ｈ)(Ｘ）−Ｃ₆ Ｈ₄ −Ｏ−（ＣＨ₂ ）_n −ＣＨ＝ＣＨ₂ 、ｏ，ｍ，ｐ−ＣＨ₃ ＣＨ₂ Ｃ（Ｈ)(Ｘ）−Ｃ₆ Ｈ₄ −Ｏ−（ＣＨ₂ ）_n −ＣＨ＝ＣＨ₂ （上記の各式において、Ｘは、塩素、臭素又はヨウ素を表す。ｎは、０〜２０の整数を表す。）；
ｏ，ｍ，ｐ−ＸＣＨ₂ −Ｃ₆ Ｈ₄ −Ｏ−（ＣＨ₂ ）_n −Ｏ−（ＣＨ₂ ）_m −ＣＨ＝ＣＨ₂ 、ｏ，ｍ，ｐ−ＣＨ₃ Ｃ（Ｈ)(Ｘ）−Ｃ₆ Ｈ₄ −Ｏ−（ＣＨ₂ ）_n −Ｏ−（ＣＨ₂ ）_m −ＣＨ＝ＣＨ₂ 、ｏ，ｍ，ｐ−ＣＨ₃ ＣＨ₂ Ｃ（Ｈ)(Ｘ）−Ｃ₆ Ｈ₄ −Ｏ−（ＣＨ₂ ）_n −Ｏ−（ＣＨ₂ ）_m −ＣＨ＝ＣＨ₂ （上記の各式において、Ｘは、塩素、臭素又はヨウ素を表す。ｎは、１〜２０の整数を表す。ｍは、０〜２０の整数を表す。）等が挙げられる。
【００４１】
上記アルケニル基を有する有機ハロゲン化物としては、更に、一般式（９）で示される化合物も挙げられる。
Ｈ₂ Ｃ＝Ｃ（Ｒ）−Ｒ¹¹−Ｃ（Ｒ⁸ )(Ｘ）−Ｒ¹²−Ｒ⁹ （９）
（式中、Ｒ、Ｒ⁸ 、Ｒ⁹ 、Ｒ¹¹及びＸは上記に同じ。Ｒ¹²は、直接結合、−Ｃ（Ｏ）Ｏ−（エステル基）、−Ｃ（Ｏ）−（ケト基）、又は、ｏ−，ｍ−，ｐ−フェニレン基を表す。）
【００４２】
上記一般式（９）において、Ｒ¹¹は、直接結合又は炭素数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）を表すが、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いるため、この化合物は、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、Ｒ¹²は、Ｃ（Ｏ）Ｏ基やフェニレン基等である必要は必ずしもなく、直接結合であってもよい。Ｒ¹¹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、Ｒ¹²は、Ｃ（Ｏ）Ｏ基、Ｃ（Ｏ）基又はフェニレン基であることが好ましい。
【００４３】
上記一般式（９）の化合物を具体的に例示するならば、ＣＨ₂ ＝ＣＨＣＨ₂ Ｘ、ＣＨ₂ ＝Ｃ（ＣＨ₃ ）ＣＨ₂ Ｘ、ＣＨ₂ ＝ＣＨＣ（Ｈ）（Ｘ）ＣＨ₃ 、ＣＨ₂ ＝Ｃ（ＣＨ₃ ）Ｃ（Ｈ）（Ｘ）ＣＨ₃ 、ＣＨ₂ ＝ＣＨＣ（Ｘ）（ＣＨ₃ ）₂ 、ＣＨ₂ ＝ＣＨＣ（Ｈ）（Ｘ）Ｃ₂ Ｈ₅ 、ＣＨ₂ ＝ＣＨＣ（Ｈ）（Ｘ）ＣＨ（ＣＨ₃ ）₂ 、ＣＨ₂ ＝ＣＨＣ（Ｈ）（Ｘ）Ｃ₆ Ｈ₅ 、ＣＨ₂ ＝ＣＨＣ（Ｈ）（Ｘ）ＣＨ₂ Ｃ₆ Ｈ₅ 、ＣＨ₂ ＝ＣＨＣＨ₂ Ｃ（Ｈ）（Ｘ）−ＣＯ₂ Ｒ、ＣＨ₂ ＝ＣＨ（ＣＨ₂ ）₂ Ｃ（Ｈ）（Ｘ）−ＣＯ₂ Ｒ、ＣＨ₂ ＝ＣＨ（ＣＨ₂ ）₃ Ｃ（Ｈ）（Ｘ）−ＣＯ₂ Ｒ、ＣＨ₂ ＝ＣＨ（ＣＨ₂ ）₈ Ｃ（Ｈ）（Ｘ）−ＣＯ₂ Ｒ、ＣＨ₂ ＝ＣＨＣＨ₂ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₅ 、ＣＨ₂ ＝ＣＨ（ＣＨ₂ ）₂ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₅ 、ＣＨ₂ ＝ＣＨ（ＣＨ₂ ）₃ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₅ （上記の各式において、Ｘは、塩素、臭素又はヨウ素を表す。Ｒは、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基又は炭素数７〜２０のアラルキル基を表す。）等を挙げることができる。
【００４４】
上記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 −Ｃ₆ Ｈ₄ −ＳＯ₂ Ｘ、ｏ−，ｍ−，ｐ−ＣＨ₂ ＝ＣＨ−（ＣＨ₂ ）_n −Ｏ−Ｃ₆ Ｈ₄ −ＳＯ₂ Ｘ、（上記の各式において、Ｘは、塩素、臭素又はヨウ素を表す。ｎは、０〜２０の整数を表す。）等である。
【００４５】
上記アルケニル基を有する開始剤を用いて重合を行った場合、重合反応中に、開始剤のアルケニル基が重合成長末端と反応する可能性があるため、反応温度、反応時間等の重合条件には注意が必要である。
【００４６】
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特に限定されず、例えば、一般式（１２）に示す構造を有するものが例示される。
Ｒ⁸ Ｒ⁹ Ｃ（Ｘ）−Ｒ¹⁰−Ｒ¹¹−Ｃ（Ｈ)(Ｒ）ＣＨ₂ −［Ｓｉ（Ｒ¹³）_2-b （Ｙ）_b Ｏ］_m −Ｓｉ（Ｒ¹⁴）_3-a （Ｙ）_a （１２）
（式中、Ｒ、Ｒ⁸ 、Ｒ⁹ 、Ｒ¹⁰、Ｒ¹¹、Ｒ¹³、Ｒ¹⁴、Ｘ、ａ、ｂ及びｍは、上記と同じ。）
【００４７】
上記一般式（１２）の化合物を具体的に例示するならば、ＸＣＨ₂ Ｃ（Ｏ）Ｏ（ＣＨ₂ ）_n Ｓｉ（ＯＣＨ₃ ）₃ 、ＣＨ₃ Ｃ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂ ）_n Ｓｉ（ＯＣＨ₃ ）₃ 、（ＣＨ₃ ）₂ Ｃ（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂ ）_n Ｓｉ（ＯＣＨ₃ ）₃ 、ＸＣＨ₂ Ｃ（Ｏ）Ｏ（ＣＨ₂ ）_n Ｓｉ（ＣＨ₃ ）（ＯＣＨ₃ ）₂ 、ＣＨ₃ Ｃ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂ ）_n Ｓｉ（ＣＨ₃ ）（ＯＣＨ₃ ）₂ 、（ＣＨ₃ ）₂ Ｃ（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂ ）_n Ｓｉ（ＣＨ₃ ）（ＯＣＨ₃ ）₂ （上記の各式において、Ｘは塩素、臭素又はヨウ素を表す。ｎは、０〜２０の整数を表す。）；
【００４８】
ＸＣＨ₂ Ｃ（Ｏ）Ｏ（ＣＨ₂ ）_n Ｏ（ＣＨ₂ ）_m Ｓｉ（ＯＣＨ₃ ）₃ 、Ｈ₃ ＣＣ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂ ）_n Ｏ（ＣＨ₂ ）_m Ｓｉ（ＯＣＨ₃ ）₃ 、（Ｈ₃ Ｃ）₂ Ｃ（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂ ）_n Ｏ（ＣＨ₂ ）_m Ｓｉ（ＯＣＨ₃ ）₃ 、ＣＨ₃ ＣＨ₂ Ｃ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂ ）_n Ｏ（ＣＨ₂ ）_m Ｓｉ（ＯＣＨ₃ ）₃ 、ＸＣＨ₂ Ｃ（Ｏ）Ｏ（ＣＨ₂ ）_n Ｏ（ＣＨ₂ ）_m Ｓｉ（ＣＨ₃ ）（ＯＣＨ₃ ）₂ 、Ｈ₃ ＣＣ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂ ）_n Ｏ（ＣＨ₂ ）_m −Ｓｉ（ＣＨ₃ ）（ＯＣＨ₃ ）₂ 、（Ｈ₃ Ｃ）₂ Ｃ（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂ ）_n Ｏ（ＣＨ₂ ）_m −Ｓｉ（ＣＨ₃ ）（ＯＣＨ₃ ）₂ 、ＣＨ₃ ＣＨ₂ Ｃ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂ ）_n Ｏ（ＣＨ₂ ）_m −Ｓｉ（ＣＨ₃ ）（ＯＣＨ₃ ）₂ （上記の各式において、Ｘは塩素、臭素又はヨウ素を表す。ｎは、１〜２０の整数を表す。ｍは、０〜２０の整数を表す。）；
【００４９】
ｏ，ｍ，ｐ−ＸＣＨ₂ −Ｃ₆ Ｈ₄ −（ＣＨ₂ ）₂ Ｓｉ（ＯＣＨ₃ ）₃ 、ｏ，ｍ，ｐ−ＣＨ₃ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₄ −（ＣＨ₂ ）₂ Ｓｉ（ＯＣＨ₃ ）₃ 、ｏ，ｍ，ｐ−ＣＨ₃ ＣＨ₂ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₄ −（ＣＨ₂ ）₂ Ｓｉ（ＯＣＨ₃ ）₃ 、ｏ，ｍ，ｐ−ＸＣＨ₂ −Ｃ₆ Ｈ₄ −（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃ 、ｏ，ｍ，ｐ−ＣＨ₃ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₄ −（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃ 、ｏ，ｍ，ｐ−ＣＨ₃ ＣＨ₂ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₄ −（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃ 、ｏ，ｍ，ｐ−ＸＣＨ₂ −Ｃ₆ Ｈ₄ −（ＣＨ₂ ）₂ −Ｏ−（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃ 、ｏ，ｍ，ｐ−ＣＨ₃ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₄ −（ＣＨ₂ ）₂ −Ｏ−（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃ 、ｏ，ｍ，ｐ−ＣＨ₃ ＣＨ₂ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₄ −（ＣＨ₂ ）₂ −Ｏ−（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃ 、ｏ，ｍ，ｐ−ＸＣＨ₂ −Ｃ₆ Ｈ₄ −Ｏ−（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃ 、ｏ，ｍ，ｐ−ＣＨ₃ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₄ −Ｏ−（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃ 、ｏ，ｍ，ｐ−ＣＨ₃ ＣＨ₂ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₄ −Ｏ−（ＣＨ₂ ）₃ −Ｓｉ（ＯＣＨ₃ ）₃ 、ｏ，ｍ，ｐ−ＸＣＨ₂ −Ｃ₆ Ｈ₄ −Ｏ−（ＣＨ₂ ）₂ −Ｏ−（ＣＨ₂ ）₃ −Ｓｉ（ＯＣＨ₃ ）₃ 、ｏ，ｍ，ｐ−ＣＨ₃ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₄ −Ｏ−（ＣＨ₂ ）₂ −Ｏ−（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃ 、ｏ，ｍ，ｐ−ＣＨ₃ ＣＨ₂ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₄ −Ｏ−（ＣＨ₂ ）₂ −Ｏ−（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃ （上記の各式において、Ｘは、塩素、臭素又はヨウ素を表す。）等が挙げられる。
【００５０】
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、更に、一般式（１３）で表される化合物も例示される。
（Ｒ¹⁴）_3-a （Ｙ）_a Ｓｉ−［ＯＳｉ（Ｒ¹³）_2-b （Ｙ）_b ］_m −ＣＨ₂ −Ｃ（Ｈ)(Ｒ）−Ｒ¹¹−Ｃ（Ｒ⁸ )(Ｘ）−Ｒ¹²−Ｒ⁹ （１３）
（式中、Ｒ、Ｒ⁸ 、Ｒ⁹ 、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、ａ、ｂ、ｍ、Ｘ及びＹは上記に同じ。）
【００５１】
このような化合物を具体的に例示するならば、（ＣＨ₃ Ｏ）₃ ＳｉＣＨ₂ ＣＨ₂ Ｃ（Ｈ）（Ｘ）Ｃ₆ Ｈ₅ 、（ＣＨ₃ Ｏ）₂ （ＣＨ₃ ）ＳｉＣＨ₂ ＣＨ₂ Ｃ（Ｈ）（Ｘ）Ｃ₆ Ｈ₅ 、（ＣＨ₃ Ｏ）₃ Ｓｉ（ＣＨ₂ ）₂ Ｃ（Ｈ）（Ｘ）−ＣＯ₂ Ｒ、（ＣＨ₃ Ｏ）₂ （ＣＨ₃ ）Ｓｉ（ＣＨ₂ ）₂ Ｃ（Ｈ）（Ｘ）−ＣＯ₂ Ｒ、（ＣＨ₃ Ｏ）₃ Ｓｉ（ＣＨ₂ ）₃ Ｃ（Ｈ）（Ｘ）−ＣＯ₂ Ｒ、（ＣＨ₃ Ｏ）₂ （ＣＨ₃ ）Ｓｉ（ＣＨ₂ ）₃ Ｃ（Ｈ）（Ｘ）−ＣＯ₂ Ｒ、（ＣＨ₃ Ｏ）₃ Ｓｉ（ＣＨ₂ ）₄ Ｃ（Ｈ）（Ｘ）−ＣＯ₂ Ｒ、（ＣＨ₃ Ｏ）₂ （ＣＨ₃ ）Ｓｉ（ＣＨ₂ ）₄ Ｃ（Ｈ）（Ｘ）−ＣＯ₂ Ｒ、（ＣＨ₃ Ｏ）₃ Ｓｉ（ＣＨ₂ ）₉ Ｃ（Ｈ）（Ｘ）−ＣＯ₂ Ｒ、（ＣＨ₃ Ｏ）₂ （ＣＨ₃ ）Ｓｉ（ＣＨ₂ ）₉ Ｃ（Ｈ）（Ｘ）−ＣＯ₂ Ｒ、（ＣＨ₃ Ｏ）₃ Ｓｉ（ＣＨ₂ ）₃ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₅ 、（ＣＨ₃ Ｏ）₂ （ＣＨ₃ ）Ｓｉ（ＣＨ₂ ）₃ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₅ 、（ＣＨ₃ Ｏ）₃ Ｓｉ（ＣＨ₂ ）₄ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₅ 、（ＣＨ₃ Ｏ）₂ （ＣＨ₃ ）Ｓｉ（ＣＨ₂ ）₄ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₅ （上記の各式において、Ｘは、塩素、臭素又はヨウ素を表す。Ｒは、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基又は炭素数７〜２０のアラルキル基を表す。）等が挙げられる。
【００５２】
上記ヒドロキシル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としては特に限定されず、下記のような化合物が例示される。
ＨＯ−（ＣＨ₂ ）_n −ＯＣ（Ｏ）Ｃ（Ｈ)(Ｒ)(Ｘ）
（式中、Ｘは、塩素、臭素又はヨウ素を表す。Ｒは、水素、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、又は、炭素数７〜２０のアラルキル基を表す。ｎは、１〜２０の整数を表す。）
【００５３】
上記アミノ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としては特に限定されず、下記のような化合物が例示される。
Ｈ₂ Ｎ−（ＣＨ₂ ）_n −ＯＣ（Ｏ）Ｃ（Ｈ)(Ｒ)(Ｘ）
（式中、Ｘは、塩素、臭素又はヨウ素を表す。Ｒは、水素、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、又は、炭素数７〜２０のアラルキル基を表す。ｎは、１〜２０の整数を表す。）
【００５４】
上記エポキシ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としては特に限定されず、下記のような化合物が例示される。
【００５５】
【化３】

【００５６】
（式中、Ｘは、塩素、臭素又はヨウ素を表す。Ｒは、水素、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、又は、炭素数７〜２０のアラルキル基を表す。ｎは、１〜２０の整数を表す。）
【００５７】
上記リビングラジカル重合において、開始剤として、２つ以上の開始点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て重合を行うと、上記一般式（１）で表されるアルケニル基を１分子内に２つ以上有するビニル系重合体を製造することができる。すなわち、２つの開始点を持つ開始剤を用いて重合を行った場合、上記一般式（５）で表される構造を両末端に有するビニル系重合体が得られる。この末端ハロゲンを、アルケニル基含有オキシアニオンで置換することによって、アルケニル基を両末端に有するビニル系重合体が得られる。この開始剤を具体的に例示すれば、
【００５８】
【化４】

【００５９】
（式中、Ｃ₆ Ｈ₄ は、フェニレン基を表す。Ｘは、塩素、臭素又はヨウ素を表す。Ｒは、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基又は炭素数７〜２０のアラルキル基を表す。ｎは、０〜２０の整数を表す。）；
【００６０】
【化５】

【００６１】
（式中、Ｘは、塩素、臭素又はヨウ素を表す。ｎは、０〜２０の整数を表す。Ｃ₆ Ｈ₄ は、フェニレン基を表す。）等が挙げられる。
【００６２】
上記リビングラジカル重合は、無溶剤又は各種の溶剤中で行うことができる。上記溶剤としては、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等のエーテル系溶媒；塩化メチレン、クロロホルム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、上記重合は、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。
【００６３】
上記リビングラジカル重合の触媒として用いられる遷移金属錯体としては特に限定されず、好ましいものとして、１価の銅、２価のルテニウム、２価の鉄又は２価のニッケルの錯体が挙げられる。なかでも、銅の錯体が好ましい。１価の銅化合物を具体的に例示するならば、塩化第一銅、臭化第一銅、ヨウ化第一銅、シアン化第一銅、酸化第一銅、過塩素酸第一銅等である。銅化合物を用いる場合、触媒活性を高めるために２，２′−ビピリジル及びその誘導体、１，１０−フェナントロリン及びその誘導体、ペンタメチルジエチレントリアミン等のポリアミン等の配位子が添加される。また、２価の塩化ルテニウムのトリストリフェニルホスフィン錯体（ＲｕＣｌ₂ （ＰＰｈ₃ ）₃ ）も触媒として好適である。ルテニウム化合物を触媒として用いる場合は、活性化剤としてアルミニウムアルコキシド類が添加される。更に、２価の鉄のビストリフェニルホスフィン錯体（ＦｅＣｌ₂ （ＰＰｈ₃ ）₂ ）、２価のニッケルのビストリフェニルホスフィン錯体（ＮｉＣｌ₂ （ＰＰｈ₃ ）₂ ）、及び、２価のニッケルのビストリブチルホスフィン錯体（ＮｉＢｒ₂ （ＰＢｕ₃ ）₂ ）も、触媒として好適である。
【００６４】
本発明の製造方法における重合は、上記リビングラジカル重合以外に、ハロゲン化物を連鎖移動剤（テローゲン）として用いる重合であってもよい。上記ハロゲン化物としては、四塩化炭素、四臭化炭素、塩化メチレン、臭化メチレン等が用いられる。
【００６５】
上記製造方法により製造された、上記一般式（５）で表される基を少なくとも１つの主鎖末端に有するビニル系重合体の末端ハロゲンを、上記一般式（６）で表されるアルケニル基含有オキシアニオンで置換することにより、本発明のアルケニル基を主鎖末端に有するビニル系重合体が得られる。以下に、アルケニル基含有オキシアニオンによる置換法について詳述する。
【００６６】
上記アルケニル基含有オキシアニオンを表す一般式（６）において、Ｒ³ 及びＲ⁴ は、上記のものと同じ置換基であり、これらの具体例としては、上で例示したものが全て使用できる。特に、Ｒ³ が、−Ｃ（Ｏ）−Ｒ⁵ −で表される場合には、上記一般式（６）は、上記一般式（６′）で表される。
【００６７】
上記一般式（６）において、Ｍ⁺ は、オキシアニオンの対カチオンであり、アルカリ金属イオン又は４級アンモニウムイオンを表す。上記アルカリ金属イオンとしては、リチウムイオン、ナトリウムイオン、カリウムイオン等が挙げられ、好ましくは、ナトリウムイオン又はカリウムイオンである。上記４級アンモニウムイオンとしては、テトラメチルアンモニウムイオン、テトラエチルアンモニウムイオン、トリメチルベンジルアンモニウムイオン、トリメチルドデシルアンモニウムイオン、テトラブチルアンモニウムイオン、ジメチルピペリジニウムイオン等が挙げられる。
【００６８】
上記一般式（６）で表されるアルケニル基含有オキシアニオンの前駆体としては、Ｈ₂ Ｃ＝ＣＨ−ＣＨ₂ −ＯＨ、Ｈ₂ Ｃ＝ＣＨ−ＣＨ（ＣＨ₃ ）−ＯＨ、Ｈ₂ Ｃ＝Ｃ（ＣＨ₃ ）−ＣＨ₂ −ＯＨ、Ｈ₂ Ｃ＝ＣＨ−（ＣＨ₂ ）_n −ＯＨ（ｎは、２〜２０の整数を表す。）、Ｈ₂ Ｃ＝ＣＨ−ＣＨ₂ −Ｏ−（ＣＨ₂ ）₂ −ＯＨ、Ｈ₂ Ｃ＝ＣＨ−Ｃ（Ｏ）Ｏ−（ＣＨ₂ ）₂ −ＯＨ、Ｈ₂ Ｃ＝Ｃ（ＣＨ₃ ）−Ｃ（Ｏ）Ｏ−（ＣＨ₂ ）₂ −ＯＨ、ｏ−，ｍ−，ｐ−Ｈ₂ Ｃ＝ＣＨ−Ｃ₆ Ｈ₄ −ＯＨ、ｏ−，ｍ−，ｐ−Ｈ₂ Ｃ＝ＣＨ−ＣＨ₂ −Ｃ₆ Ｈ₄ −ＯＨ、ｏ−，ｍ−，ｐ−Ｈ₂ Ｃ＝ＣＨ−ＣＨ₂ −Ｏ−Ｃ₆ Ｈ₄ −ＯＨ、ｏ−，ｍ−，ｐ−Ｈ₂ Ｃ＝ＣＨ−Ｃ₆ Ｈ₄ −ＣＨ₂ −ＯＨ、ｏ−，ｍ−，ｐ−Ｈ₂ Ｃ＝ＣＨ−ＣＨ₂ −Ｃ₆ Ｈ₄ −ＣＨ₂ −ＯＨ、ｏ−，ｍ−，ｐ−Ｈ₂ Ｃ＝ＣＨ−ＣＨ₂ −Ｏ−Ｃ₆ Ｈ₄ −ＣＨ₂ −ＯＨ等が挙げられる。
【００６９】
更に、上記一般式（６）で表されるアルケニル基含有オキシアニオンの前駆体として、Ｈ₂ Ｃ＝ＣＨ−Ｃ（Ｏ）−ＯＨ、Ｈ₂ Ｃ＝Ｃ（ＣＨ₃ ）−Ｃ（Ｏ）−ＯＨ、Ｈ₂ Ｃ＝ＣＨ−ＣＨ₂ −Ｃ（Ｏ）−ＯＨ、Ｈ₂ Ｃ＝ＣＨ−（ＣＨ₂ ）_n −Ｃ（Ｏ）−ＯＨ（ｎは、２〜２０の整数を表す。）、Ｈ₂ Ｃ＝ＣＨ−（ＣＨ₂ ）_n −ＯＣ（Ｏ）−（ＣＨ₂ ）_m −Ｃ（Ｏ）−ＯＨ（ｍ及びｎは、同一又は異なって、０〜１９の整数を表す。）、ｏ−，ｍ−，ｐ−Ｈ₂ Ｃ＝ＣＨ−Ｃ₆ Ｈ₄ −Ｃ（Ｏ）−ＯＨ、ｏ−，ｍ−，ｐ−Ｈ₂ Ｃ＝ＣＨ−ＣＨ₂ −Ｃ₆ Ｈ₄ −Ｃ（Ｏ）−ＯＨ、ｏ−，ｍ−，ｐ−Ｈ₂ Ｃ＝ＣＨ−ＣＨ₂ −Ｏ−Ｃ₆ Ｈ₄ −Ｃ（Ｏ）−ＯＨ、ｏ−，ｍ−，ｐ−Ｈ₂ Ｃ＝ＣＨ−（ＣＨ₂ ）_n −ＯＣ（Ｏ）−Ｃ₆ Ｈ₄ −Ｃ（Ｏ）−ＯＨ（ｎは、０〜１３の整数を表す。）等も挙げられる。これらは、上記一般式（６′）で表すことができる化合物でもある。
【００７０】
上記前駆体を塩基と作用させることによって、上記一般式（６）で表されるアルケニル基含有オキシアニオンを調製することができる。上記塩基としては各種のものを使用できる。例示すると、ナトリウムメトキシド、カリウムメトキシド、リチウムメトキシド、ナトリウムエトキシド、カリウムエトキシド、リチウムエトキシド、ナトリウム−ｔｅｒｔ−ブトキシド、カリウム−ｔｅｒｔ−ブトキシド、炭酸ナトリウム、炭酸カリウム、炭酸リチウム、炭酸水素ナトリウム、水酸化ナトリウム、水酸化カリウム、水素化ナトリウム、水素化カリウム、メチルリチウム、エチルリチウム、ｎ−ブチルリチウム、ｔｅｒｔ−ブチルリチウム、リチウムジイソプロピルアミド、リチウムヘキサメチルジシラジド；トリメチルアミン、トリエチルアミン、トリブチルアミン等のアルキルアミン；テトラメチルエチレンジアミン、ペンタメチルジエチレントリアミン等のポリアミン；ピリジン、ピコリン等のピリジン系化合物等が挙げられる。上記塩基の使用量は、上記前駆体に対して、０．５〜５当量、好ましくは０．８〜１．２当量である。
【００７１】
上記前駆体と上記塩基を反応させる際に用いられる溶媒としては、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等のエーテル系溶媒；塩化メチレン、クロロホルム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；ジメチルホルムアミド、ジメチルアセトアミド等のアミド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。
【００７２】
上記一般式（６）で表されるアルケニル基含有オキシアニオンの具体的な製法について、更に説明する。例えば、前駆体として、ｏ−，ｍ−，ｐ−Ｈ₂ Ｃ＝ＣＨ−ＣＨ₂ −Ｃ₆ Ｈ₄ −ＯＨを使用する場合であれば、不活性ガス雰囲気下の反応容器に、塩基、例えば、カリウム−ｔｅｒｔ−ブトキシドを仕込み、ジメチルアセトアミド等の溶媒中で懸濁分散させる。この分散液中に上記アリルフェノールを等モル加え、室温〜７０℃で３０分〜１時間反応させることにより、酸性プロトンがカリウムに置換されたアルケニル基含有オキシアニオンが得られる。
【００７３】
Ｍ⁺ が４級アンモニウムイオンであるアルケニル基含有オキシアニオンは、上記前駆体にアルキルアミン又はピリジン系化合物を直接作用させることにより得られるが、上記のような方法でＭ⁺ がアルカリ金属イオンであるものを調製し、これに４級アンモニウムハライドを作用させることによっても得られる。上記４級アンモニウムハライドとしては、テトラメチルアンモニウムハライド、テトラエチルアンモニウムハライド、トリメチルベンジルアンモニウムハライド、トリメチルドデシルアンモニウムハライド、テトラブチルアンモニウムハライド等が例示される。
【００７４】
上記のような方法で調整される一般式（６）のアルケニル基含有オキシアニオンを、既に述べた重合法により得られた一般式（５）の末端構造を有するビニル系重合体と反応させることにより、一般式（１）で表されるアルケニル基を主鎖末端に有するビニル系重合体を得ることができる。この反応は、既に述べた溶媒中、０〜１５０℃で行うことができる。一般式（６）のアルケニル基含有オキシアニオンの使用量は、一般式（５）の末端構造に対して、１〜５当量であり、好ましくは１〜１．２当量である。
【００７５】
上述した架橋性シリル基を主鎖末端に有するビニル系重合体は、上記アルケニル基を主鎖末端に有するビニル系重合体を上述の方法により製造し、次いで、この重合体のアルケニル基に、上述した架橋性シリル基を有するヒドロシラン化合物を付加させることにより得られる。
【００７６】
上記架橋性シリル基を有するヒドロシラン化合物を、主鎖末端にアルケニル基を有するビニル系重合体に付加させる際には、ヒドロシリル化触媒が使用される。このヒドロシリル化触媒としては特に限定されず、有機過酸化物やアゾ化合物等のラジカル開始剤、及び、遷移金属触媒等が挙げられる。
【００７７】
上記ラジカル開始剤としては特に限定されず、各種のものを用いることができる。例示するならば、ジ−ｔ−ブチルペルオキシド、２，５−ジメチル−２，５−ジ（ｔ−ブチルペルオキシ）ヘキサン、２，５−ジメチル−２，５−ジ（ｔ−ブチルペルオキシ）−３−ヘキシン、ジクミルペルオキシド、ｔ−ブチルクミルペルオキシド、α，α' −ビス（ｔ−ブチルペルオキシ）イソプロピルベンゼンのようなジアルキルペルオキシド、ベンゾイルペルオキシド、ｐ−クロロベンゾイルペルオキシド、ｍ−クロロベンゾイルペルオキシド、２，４−ジクロロベンゾイルペルオキシド、ラウロイルペルオキシド等のジアシルペルオキシド；過安息香酸−ｔ−ブチル等の過酸エステル；過ジ炭酸ジイソプロピル、過ジ炭酸ジ−２−エチルヘキシル等のペルオキシジカーボネート；１，１−ジ（ｔ−ブチルペルオキシ）シクロヘキサン、１，１−ジ（ｔ−ブチルペルオキシ）−３，３，５−トリメチルシクロヘキサン等のペルオキシケタール等が挙げられる。
【００７８】
また、上記遷移金属触媒としては特に限定されず、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等が挙げられる。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 ・ Ｈ₂ Ｏ、ＮｉＣｌ₂ 、ＴｉＣｌ₄ 等が挙げられる。これらの触媒は単独で用いてもよく、２種類以上を併用してもかまわない。
【００７９】
本発明のアルケニル基を主鎖末端に有するビニル系重合体より、これを主剤とする硬化性組成物を得ることができる。すなわち、本発明の硬化性組成物は、（Ａ）本発明のアルケニル基を主鎖末端に有するビニル系重合体、及び、（Ｂ）ヒドロシリル基含有化合物を含有するものである。
【００８０】
（Ａ）成分のビニル系重合体は、単独で用いてもよく、また、２種類以上を混合して用いてもよい。（Ａ）成分の分子量としては特に限定されず、５００〜１０００００の範囲にあるのが好ましく、３０００〜５００００の範囲にあるのがより好ましい。５００以下であると、ビニル系重合体の本来の特性が発現されにくく、１０００００以上であると、非常に高粘度又は溶解性が低くなり、取り扱いが困難になる。
【００８１】
（Ｂ）成分のヒドロシリル基含有化合物としては特に限定されず、各種のものを用いることができる。すなわち、下記一般式（１４）又は（１５）で表される鎖状ポリシロキサン；
Ｒ¹⁵ ₃ ＳｉＯ−［Ｓｉ（Ｒ¹⁵）₂ Ｏ］_a −［Ｓｉ（Ｈ）（Ｒ¹⁶）Ｏ］_b −［Ｓｉ（Ｒ¹⁶）（Ｒ¹⁷）Ｏ］_C −ＳｉＲ¹⁵ ₃ （１４）
ＨＲ¹⁵ ₂ ＳｉＯ−［Ｓｉ（Ｒ¹⁵）₂ Ｏ］_a −［Ｓｉ（Ｈ）（Ｒ¹⁶）Ｏ］_b −［Ｓｉ（Ｒ¹⁶）（Ｒ¹⁷）Ｏ］_C −ＳｉＲ¹⁵ ₂ Ｈ （１５）
（式中、Ｒ¹⁵及びＲ¹⁶は、同一若しくは異なって、炭素数１〜６のアルキル基、又は、フェニル基を表す。Ｒ¹⁷は、炭素数１〜１０のアルキル基又は炭素数７〜１０のアラルキル基を表す。ａは、０〜１００の整数を表す。ｂは、２〜１００の整数を表す。ｃは、０〜１００の整数を表す。）、及び、
下記一般式（１６）で表される環状ポリシロキサン；
【００８２】
【化６】

【００８３】
（式中、Ｒ¹⁵及びＲ¹⁶は、炭素数１〜６のアルキル基、又は、フェニル基を表す。Ｒ¹⁷は、炭素数１〜１０のアルキル基又は炭素数７〜１０のアラルキル基を表す。ｄは、０〜８の整数を表す。ｅは、２〜１０の整数を表す。ｆは、０〜８の整数を表す。なお、ｄ、ｅ及びｆは、３≦ｄ＋ｅ＋ｆ≦１０を満たす。）を用いることができる。
【００８４】
これらは単独で用いても２種以上を混合して用いてもかまわない。これらのポリシロキサンの中でも、ビニル系重合体との相溶性の観点から、フェニル基を有するポリシロキサンが好ましい。このような化合物の例として、下記一般式（１７）又は（１８）で表される鎖状ポリシロキサン、及び、下記一般式（１９）又は（２０）で表される環状ポリシロキサンが挙げられる。
（ＣＨ₃ ）₃ ＳｉＯ−［Ｓｉ（Ｈ）（ＣＨ₃ ）Ｏ］_g −［Ｓｉ（Ｃ₆ Ｈ₅ ）₂ Ｏ］_h −Ｓｉ（ＣＨ₃ ）₃ （１７）
（ＣＨ₃ ）₃ ＳｉＯ−［Ｓｉ（Ｈ）（ＣＨ₃ ）Ｏ］_g −［Ｓｉ（ＣＨ₃ ）｛ＣＨ₂ Ｃ（Ｈ）（Ｒ¹⁸）Ｃ₆ Ｈ₅ ｝Ｏ］_h −Ｓｉ（ＣＨ₃ ）₃ （１８）
（式中、Ｒ¹⁸は、水素又はメチル基を表す。ｇは、２〜１００の整数を表す。ｈは、０〜１００の整数を表す。Ｃ₆ Ｈ₅ は、フェニル基である。）
【００８５】
【化７】

【００８６】
（式中、Ｒ¹⁸は、水素又はメチル基を表す。ｉは、２〜１０の整数を表す。ｊは、０〜８の整数を表す。なお、ｉ及びｊは、３≦ｉ＋ｊ≦１０の関係を満たす。Ｃ₆ Ｈ₅ は、フェニル基である。）
【００８７】
更に、（Ｂ）成分のヒドロシリル基含有化合物として、上記一般式（１４）〜（２０）で表されるポリシロキサンに対して、分子中に２個以上のアルケニル基を有する低分子化合物を、反応後にも一部のヒドロシリル基が残るようにして付加反応させて得られる化合物を用いることもできる。上記の２個以上のアルケニル基を有する低分子化合物としては、各種のものを用いることができる。例示するならば、１，４−ペンタジエン、１，５−ヘキサジエン、１，６−ヘプタジエン、１，７−オクタジエン、１，８−ノナジエン、１，９−デカジエン等の炭化水素系化合物；Ｏ，Ｏ' −ジアリルビスフェノールＡ、３，３' −ジアリルビスフェノールＡ等のエーテル系化合物；ジアリルフタレート、ジアリルイソフタレート、トリアリルトリメリテート、テトラアリルピロメリテート等のエステル系化合物；ジエチレングリコールジアリルカーボネート等のカーボネート系化合物等が挙げられる。
【００８８】
このような化合物は、ヒドロシリル化触媒の存在下、上記一般式（１４）〜（２０）のポリシロキサンに対して、少量の上記アルケニル基含有低分子化合物をゆっくり滴下することにより得られる。このような化合物のうち、原料の入手容易性、過剰に用いたヒドロシリル基含有化合物の除去のしやすさ、及び、（Ａ）成分であるビニル系重合体への相溶性を考慮して、下記のものが好ましい。
【００８９】
【化８】

【００９０】
（ｎは、２、３又は４である。ｍは、５〜１０の整数である。）
【００９１】
本発明の硬化性組成物において、ビニル系重合体（Ａ）とヒドロシリル基含有化合物（Ｂ）は、任意の割合で混合することができるが、硬化性の面から、アルケニル基とヒドロシリル基のモル比が、０．２〜５の範囲にあることが好ましく、０．４〜２．５であることがより好ましい。モル比が５以上になると、硬化が不十分でべとつきのある強度の小さい硬化物しか得られず、また、０．２より小さいと、硬化後も硬化物中に活性なヒドロシリル基が大量に残るので、クラックやボイドが発生し、均一で強度のある硬化物が得られない。
【００９２】
成分（Ａ）と成分（Ｂ）との硬化反応は、２成分を混合して加熱することにより進行するが、反応をより迅速に進めるために、ヒドロシリル化触媒を更に添加してもよい。このようなヒドロシリル化触媒としては特に限定されず、既に述べたものを全て用いることができる。触媒量としては特に制限はないが、（Ａ）成分のアルケニル基１ｍｏｌに対し、１０^-1〜１０^-8ｍｏｌの範囲で用いるのが好ましく、より好ましくは１０^-3〜１０^-6 ｍｏｌの範囲である。１０^-8ｍｏｌより少ないと硬化が十分に進行しない。また、ヒドロシリル化触媒は高価であるので、１０^-1ｍｏｌ以上は用いないのが好ましい。
【００９３】
上記硬化性組成物において、２成分（Ａ）及び（Ｂ）と、必要に応じて上記ヒドロシリル化触媒とを混合し硬化させれば、発泡等の現象を伴わずに、深部硬化性の優れた均一な硬化物を得ることができる。硬化条件については特に限定されず、一般に０℃〜２００℃、好ましくは３０℃〜１５０℃で、１０秒〜２４時間硬化するのがよい。特に、８０℃〜１５０℃の高温では１０秒〜１時間程度の短時間で硬化するものも得られる。硬化物の性状は、用いる（Ａ）ビニル系重合体及び（Ｂ）ヒドロシリル基含有化合物の主鎖骨格や分子量に依存するが、ゴム状のものから樹脂状のものまで幅広く作成することができる。上記硬化性組成物から得られる硬化物の具体的な用途を挙げるならば、シーリング材、接着剤、粘着材、弾性接着剤、塗料、粉体塗料、発泡体、電気電子用ポッティング材、フィルム、ガスケット、各種成形材料、人工大理石等である。
【００９４】
本発明においては、上記の架橋性シリル基を主鎖末端に有するビニル系重合体を主成分とする硬化性組成物を調製することもできる。
この硬化性組成物においては、主成分である架橋性シリル基を主鎖末端に有するビニル系重合体を、単独で用いても、また、２種類以上を混合して用いてもよい。その分子量については特に制限はないが、５００〜１０００００の範囲にあるのが好ましく、３０００〜５００００の範囲がより好ましい。分子量が５００以下であると、架橋性シリル基を主鎖末端に有するビニル系重合体の本来の特性が発現されにくく、また、１０００００以上であると、ハンドリングが困難になる。
【００９５】
架橋性シリル基を主鎖末端に有するビニル系重合体は、水分と接触すると、架橋反応により３次元化して硬化する。加水分解速度は、温度、湿度、及び、架橋性シリル基の種類により変化するので、使用条件に応じて適切な架橋性シリル基を選択しなければならない。また、架橋性シリル基を主鎖末端に有するビニル系重合体の保存の際には、水分との接触を可能な限り断つ必要がある。
【００９６】
上記硬化性組成物の硬化反応を促進するために、硬化触媒を添加してもよい。触媒としては、アルキルチタン酸塩、有機ケイ素チタン酸塩；オクチル酸錫、ジブチル錫ジラウレート等のカルボン酸の金属塩；ジブチルアミン−２−エチルヘキソエート等のアミン塩等が挙げられ、また、他の酸性触媒及び塩基性触媒も使用しうる。その使用量としては特に制限はないが、架橋性シリル基を主鎖末端に有するビニル系重合体に対し、０．０１〜５重量％用いるのが好ましい。
【００９７】
主成分である架橋性シリル基を主鎖末端に有するビニル系重合体に、必要に応じて上記硬化触媒を混合し硬化させれば、均一な硬化物を得ることができる。硬化条件としては特に限定されず、一般に０〜１００℃、好ましくは１０〜５０℃で１時間〜１週間程度である。硬化物の性状は、用いる重合体の主鎖骨格や分子量に依存するが、ゴム状のものから樹脂状のものまで幅広く作成することができる。
【００９８】
上記硬化物の具体的な用途を挙げるならば、シーリング材、接着剤、粘着材、弾性接着剤、塗料、粉体塗料、発泡体、電気電子用ポッティング材、フィルム、ガスケット、各種成形材料、人工大理石等である。
【００９９】
【実施例】
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例にのみ限定されるものではない。
【０１００】
実施例１
３０ｍＬの耐圧反応器に、アクリル酸メチル（７．５ｍＬ、７．１７ｇ、８３．４ｍｍｏｌ）、α，α' −ジブロモ−ｐ−キシレン（４３８ｍｇ、１．６７ｍｍｏｌ）、臭化第一銅（２３９ｍｇ、１．６７ｍｍｏｌ）、２，２' −ビピリジル（５１８ｍｇ、３．３４ｍｍｏｌ）、酢酸エチル（６．０ｍＬ）、及び、アセトニトリル（１．５ｍＬ）を仕込み、１０分以上、窒素を吹き込んで、溶存酸素を除去した後、封管した。この混合物を１３０℃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、希塩酸で３回、ブラインで１回洗浄した。有機層をＮａ₂ ＳＯ₄ で乾燥し、揮発分を減圧下留去し、下式に示すポリ（アクリル酸メチル）を得た（収量６．０１ｇ）。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１．２６であった。
【０１０１】
【化９】

【０１０２】
５０ｍＬの三口丸底フラスコに、還流管をつけ、窒素雰囲気下で反応容器にカリウム−ｔｅｒｔ−ブトキシド（１６０ｍｇ、１．４３ｍｍｏｌ）、ジメチルアセトアミド（３ｍＬ）を仕込み、Ｏ−アリルフェノ−ル（１９２ｍｇ、１．４３ｍｍｏｌ）を等モル加え、室温で３０分間反応させたのち、上記で得られたポリ（アクリル酸メチル）（２．０ｇ）のジメチルアセトアミド（２ｍＬ）溶液を滴下し、室温で２時間反応させた。反応溶液を氷水−塩酸で中和し、酢酸エチル（３０ｍＬ）で抽出した。有機層を希塩酸で２回、ブラインで１回洗浄した。有機層をＮａ₂ ＳＯ₄ で乾燥し、揮発分を減圧下留去し、少量の酢酸エチルに溶解し、ヘキサンから再沈することにより、下式に示す両末端にアルケニル基を有するポリ（アクリル酸メチル）を得た（収量１．７０ｇ）。生成物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−ワ−ド７００ＰＥＬ）を添加して還流温度で１時間撹拌し、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、 ¹Ｈ ＮＭＲ分析より、１．２４個であった。
【０１０３】
【化１０】

【０１０４】
次に、精製されたポリ（アクリル酸メチル）を酢酸エチル（２ｍＬ）に溶解し、下式に示す多価ハイドロジェンシリコン化合物、及び、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^-9ｍｏｌ／Ｌキシレン溶液）を、上記のポリ（アクリル酸メチル）溶液に加えて、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^-3当量とした。
【０１０５】
【化１１】

【０１０６】
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−ト上にて硬化試験を行い、ゲル化時間を測定すると、４分であった。また、残りの組成物を型枠に流し込んで、揮発分を減圧留去し、１００℃で１４時間加熱硬化させ、ゴム状の硬化物を得た。硬化物をアセトンに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、４５％であった。
【０１０７】
製造例１
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⁺
【０１０８】
実施例２
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Ｎａ₂ ＳＯ₄ で乾燥し、揮発分を減圧下留去し、下式に示す両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。
【０１０９】
【化１２】

【０１１０】
次に、上記のようにして得られた末端にハロゲンを有するポリ（アクリル酸−ｎ−ブチル）（５．００ｇ）、製造例１で合成されたウンデシレン酸のカリウム塩（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、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）４．７７ｇを得た。生成物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−ワ−ド７００ＰＥＬ）を添加して２時間撹拌し、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、 ¹Ｈ ＮＭＲ分析より、１．７０個であった。
【０１１１】
【化１３】

【０１１２】
次に、精製されたポリ（アクリル酸ブチル）に、実施例１で用いた多価ハイドロジェンシリコン化合物、及び、白金触媒を加えて、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当量とした。
【０１１３】
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−ト上にて硬化試験を行い、ゲル化時間を測定すると、６０秒であった。また、残りの組成物を型枠に流し込んで、減圧脱気し、１００℃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、８５％であった。
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０．２３ＭＰａ、破断伸びは１２８％であった。
【０１１４】
製造例２
アルケニル基を有するカルボン酸塩の製造２
カリウムメトキシド（１６．８３ｇ、０．２４０ｍｏｌ）をメタノール（２００ｍＬ）に溶解し、４−ペンテン酸（２４．５６ｇ、０．２４５ｍｏｌ）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。粗生成物を酢酸エチルで洗浄後、減圧下加熱することにより下式に示す４−ペンテン酸のカリウム塩の白色固体を得た（２９．２ｇ、収率８８％）。
ＣＨ₂ ＝ＣＨ−（ＣＨ₂ ）₂ −ＣＯ₂ ^- Ｋ⁺
【０１１５】
実施例３
５００ｍＬの耐圧ガラス反応容器に、アクリル酸−ｎ−ブチル（１１２ｍＬ、１００ｇ、０．７８ｍｏｌ）、α，α' −ジブロモ−ｐ−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）、及び、アセトニトリル（２２．４ｍＬ）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、２．０時間反応させた。混合物を酢酸エチル（３００ｍＬ）で希釈し、生成した不溶固体をろ過した後、濾液をさらに酢酸エチル（２００ｍＬ）で希釈した。濾液を希塩酸で２回、ブラインで１回洗浄した。有機層をＮａ₂ ＳＯ₄ で乾燥し、揮発分を減圧下留去し、両末端にハロゲンを有するポリ（アクリル酸−ｎ−ブチル）を８５．９ｇ得た（重合収率８６％）。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１．３７であった。
【０１１６】
次に、還流管をつけた５０ｍＬの三口丸底フラスコに、上記のようにして得られた末端にハロゲンを有するポリ（アクリル酸−ｎ−ブチル）（８３．９ｇ）、製造例２で合成された４−ペンテン酸のカリウム塩（７．７４ｇ、５６．０ｍｍｏｌ）、及びジメチルアセトアミド（８０ｍＬ）を仕込み、窒素雰囲気下、７０℃で６時間反応させた。混合物を酢酸エチル（２００ｍＬ）で希釈し、水で３回、ブラインで１回洗浄した。有機層をＮａ₂ ＳＯ₄ で乾燥し、揮発分を減圧下留去することにより重合体を単離した。重合体と等量の珪酸アルミ（協和化学製：キョ−ワ−ド７００ＰＥＬ）を添加して１００℃で２時間撹拌し、重合体中の微量不純物を除去することにより、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、１．７３個であった。
【０１１７】
【化１４】

【０１１８】
実施例４
２００ｍＬの耐圧ガラス反応容器に、実施例３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）（６０．０ｇ）、ジメトキシメチルヒドロシラン（８．４ｍＬ、６８．１ｍｍｏｌ）、オルトぎ酸ジメチル（２．５ｍＬ、２２．９ｍｍｏｌ）、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、下式に示す、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、１．５９個であった。
【０１１９】
【化１５】

【０１２０】
次に、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、９３％であった。
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０．２６ＭＰａ、破断伸びは７５％であった。
【０１２１】
実施例５
還流管をつけた１００ｍＬの三口丸底フラスコに臭化第一銅（０．６２５ｇ、１５．６ｍｍｏｌ）、アセトニトリル（５．０ｍＬ）、及び、ペンタメチルジエチレントリアミン（０．９１ｍＬ）を仕込み、窒素ガスで置換した。アクリル酸−ｎ−ブチル（５０ｍＬ、４４．７ｇ、０．３９ｍｏｌ）、及び、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７時間加熱撹拌した。混合物を酢酸エチルで希釈し、活性アルミナで処理した。揮発分を減圧下留去し、下式に示す両末端にハロゲンを有するポリ（アクリル酸−ｎ−ブチル）を３５．０ｇ得た（重合収率８７％）。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１０７００、分子量分布は１．１５であった。
【０１２２】
【化１６】

【０１２３】
次に、還流管をつけた２００ｍＬの三口丸底フラスコに、上記のようにして得られた末端にハロゲンを有するポリ（アクリル酸−ｎ−ブチル）（３５．０ｇ）、製造例２で合成された４−ペンテン酸のカリウム塩（２．２３ｇ、１６．１ｍｍｏｌ）、及び、ジメチルアセトアミド（３５ｍＬ）を仕込み、窒素雰囲気下、７０℃で４時間反応させた。混合物を酢酸エチルで希釈し、２％塩酸、ブラインで洗浄した。有機層をＮａ₂ ＳＯ₄ で乾燥し、揮発分を減圧下留去することにより重合体を単離した。重合体と等量の珪酸アルミ（協和化学製：キョ−ワ−ド７００ＰＥＬ）を添加して１００℃で４時間撹拌し、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、１．８２個であった。
【０１２４】
【化１７】

【０１２５】
実施例６
２００ｍＬの耐圧ガラス反応容器に、実施例５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）（１５．０ｇ）、ジメトキシメチルヒドロシラン（１．８ｍＬ、１４．５ｍｍｏｌ）、オルトぎ酸ジメチル（０．２６ｍＬ、２．４２ｍｍｏｌ）、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２×１０^-4当量とした。反応混合物を１００℃で４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、下式に示す、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、１．４６個であった。
【０１２６】
【化１８】

【０１２７】
次に、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、９８％であった。
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０．３５ＭＰａ、破断伸びは７７％であった。
【０１２８】
製造例３
アルケニル基を有するカルボン酸塩の製造３
２００ｍＬ丸底フラスコにカリウム−ｔｅｒｔ−ブトキシド（５．６１ｇ、５０ｍｍｏｌ）を仕込み、０℃でメタノール（５０ｍＬ）をゆっくり滴下した。撹拌しながら０℃でこの溶液にメタクリル酸（４．４ｍＬ、５２．０ｍｍｏｌ）をゆっくり滴下することにより白色結晶が析出した。室温まで反応溶液を昇温し、析出した白色結晶を濾別し、室温で減圧乾燥することにより下式に示すメタクリル酸のカリウム塩を得た（３．３１ｇ、収率５３％）。
ＣＨ₂ ＝Ｃ（ＣＨ₃ ）−ＣＯ₂ ^- Ｋ⁺
【０１２９】
実施例７
実施例３で得られた末端にハロゲンを有するポリ（アクリル酸−ｎ−ブチル）（２５９ｍｇ）、製造例３で合成されたメタクリル酸のカリウム塩（１４．９ｍｇ、０．１２ｍｍｏｌ）、及び、ジメチルアセトアミド（２．５ｍＬ）を仕込み、室温で６１時間反応させた。メタクリル酸のカリウム塩を１７．３ｍｇ追加し、同温でさらに２２時間反応させた。混合物を酢酸エチルで希釈し、水で洗浄した。有機層の揮発分を減圧留去することにより、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）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、１．６６個であった。
【０１３０】
【化１９】

【０１３１】
【発明の効果】
本発明によれば、これまで製造するのが困難であった、主鎖末端にアルケニル基を高い比率で有するビニル系重合体を簡便に得ることができる。また、このビニル系重合体から、主鎖末端に架橋性シリル基を有するビニル系重合体を容易に得ることができる。本発明のビニル系重合体は、これらの架橋性官能基が確実に主鎖末端に導入されているので、硬化特性の優れた硬化物を得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a vinyl polymer having an alkenyl group or a crosslinkable silyl group at at least one main chain terminal, a method for producing the polymer, and a curable composition using the polymer.
[0002]
[Prior art]
A polymer having an alkenyl group as a crosslinkable functional group at the end of the main chain is cross-linked by using a hydrosilyl group-containing compound or the like as a curing agent, or by using a photoreaction, and has excellent heat resistance, durability, etc. It is known to give a cured product. Such a main chain skeleton of a polymer having an alkenyl group at the end of the main chain includes polyether polymers such as polyethylene oxide; carbonization such as polyisobutylene, polybutadiene, polyisoprene, polychloroprene, or hydrogenated products thereof. Examples of hydrogen polymers include polyester polymers such as polyethylene terephthalate, polybutylene terephthalate, and polycaprolactone. These are used for various applications based on the main chain skeleton and the crosslinking type.
[0003]
These polymers can be obtained by ionic polymerization or condensation polymerization, but vinyl polymers obtained by radical polymerization and having a crosslinkable functional group at the end of the main chain have hardly been put to practical use. Among vinyl polymers, (meth) acrylic polymers have characteristics that cannot be obtained with the above-mentioned polyether polymers and polyester polymers, such as high weather resistance and transparency. A (meth) acrylic polymer having a group in a side chain instead of a main chain end is used for a highly weather-resistant paint or the like.
[0004]
With respect to such a vinyl polymer having an alkenyl group in the side chain, a cured product having excellent cured properties can be obtained with a vinyl polymer having an alkenyl group at the end of the main chain. Therefore, many researchers have studied simple manufacturing methods so far, but it is not easy to industrially manufacture them. Japanese Patent Application Laid-Open No. 4-132706 discloses a method of introducing a hydroxyl group by converting a halogen group at the end of the polymer. However, when a polymer having a hydroxyl group at the end of the main chain is crosslinked, there is a problem in toxicity and stability. Since it is often necessary to use a certain isocyanate compound, an alkenyl group or a crosslinkable silyl group is preferred as the crosslinkable end group.
[0005]
JP-A-1-247403 discloses a method of synthesizing a vinyl polymer having alkenyl groups at both ends by using an alkenyl group-containing disulfide as a chain transfer agent. JP-A-6-221922 also synthesizes a vinyl polymer having hydroxyl groups at both ends using a disulfide having hydroxyl groups as a chain transfer agent, and further utilizes the reactivity of hydroxyl groups at both ends. Discloses a method for synthesizing a vinyl polymer having an alkenyl group. However, in these methods, in order to introduce alkenyl groups reliably at both ends, a large amount of chain transfer agent must be used, and there is a problem in the production process. In these methods, since normal radical polymerization is used, it is difficult to control the molecular weight and molecular weight distribution (ratio of weight average molecular weight to number average molecular weight) of the obtained polymer.
[0006]
[Problems to be solved by the invention]
In view of the above situation, the present invention is produced by adding a vinyl-based polymer having an alkenyl group introduced at a high ratio to at least one main chain end and a hydrosilane compound having a crosslinkable silyl group to the polymer. An object of the present invention is to provide a vinyl polymer having a crosslinkable silyl group at at least one main chain terminal, a method for producing these polymers, and a curable composition using these polymers. It is.
[0007]
[Means for Solving the Problems]
That is, the present invention is a vinyl polymer having an alkenyl group represented by the following general formula (1) at at least one main chain terminal. In particular, R^Three Is -C (O) -R^Five -Is a vinyl polymer having an alkenyl group represented by the following general formula (1 ') at at least one main chain terminal.
-CH₂ -C (R¹ ) (R² ) -O-R^Three -C (R^Four ) = CH₂ (1)
-CH₂ -C (R¹ ) (R² ) -OC (O) -R^Five -C (R^Four ) = CH₂ (1 ')
Where R¹ And R² Are the same or different and each represents a monovalent organic group. R^Three Represents a C1-C20 divalent organic group which may contain one or more ether bonds or ester bonds. R^Four Represents 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. R^Five Represents a direct bond or a divalent organic group having 1 to 19 carbon atoms which may contain one or more ether bonds or ester bonds.
[0008]
The present invention is also a vinyl polymer having a crosslinkable silyl group at the end of at least one main chain formed by adding a hydrosilane compound having a crosslinkable silyl group to the above polymer.
[0009]
In the present invention, a vinyl monomer is further polymerized to produce a vinyl polymer having at least one main chain terminal having a group represented by the following general formula (5). Is represented by the following general formula (6), or R^Three Is -C (O) -R^Five In the method for producing a polymer having the alkenyl group substituted with an alkenyl group-containing oxyanion represented by the following general formula (6 ′) at the terminal of the main chain, is there.
-CH₂ -C (R¹ ) (R² ) (X) (5)
Where R¹ And R² Is the same as above. X represents chlorine, bromine or iodine.
M⁺ O^- -R^Three -C (R^Four ) = CH₂   (6)
M⁺ O^- -C (O) -R^Five -C (R^Four ) = CH₂ (6 ')
Where R^Three , R^Four And R^Five Is the same as above. M⁺ Represents an alkali metal ion or a quaternary ammonium ion.
[0010]
The present invention further provides the above crosslinkable silyl, wherein a vinyl polymer having an alkenyl group at the main chain end is produced by the above production method, and then a hydrosilane compound having a crosslinkable silyl group is added to the alkenyl group. It is also a method for producing a vinyl polymer having a group at the main chain terminal.
[0011]
The present invention is also a curable composition containing (A) a vinyl polymer having the alkenyl group at the main chain terminal and (B) a hydrosilyl group-containing compound. The present invention is also a curable composition mainly comprising a vinyl polymer having the crosslinkable silyl group at the end of the main chain.
The present invention is described in detail below.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
The vinyl polymer having an alkenyl group at the main chain terminal of the present invention is a vinyl polymer having an alkenyl group represented by the general formula (1) at at least one main chain terminal. In particular, in the general formula (1), R^Three Is -C (O) -R^Five -Is a vinyl polymer having an alkenyl group represented by the above general formula (1 ') at at least one main chain terminal.
In the general formula (1) or (1 ′), R¹ And R² Are the same or different and each represents a monovalent organic group. The monovalent organic group is not particularly limited as long as it is a monovalent organic group derived from a group bonded to a vinyl group of a vinyl monomer used for production of a polymer main chain.
[0013]
In the general formula (1), R^Three Represents a C1-C20 divalent organic group which may contain one or more ether bonds or ester bonds. As a specific example,-(CH₂ )_n -(N represents an integer of 1 to 20); -CH (CH_Three )-, -CH (CH₂ CH_Three )-, -C (CH_Three )₂ -, -C (CH_Three ) (CH₂ CH_Three )-, -C (CH₂ CH_Three )₂ -, -CH₂ CH (CH_Three )-;-( CH₂ )_n -O- (n represents an integer of 1 to 20); -CH (CH_Three ) -O-, -CH (CH₂ CH_Three ) -O-, -C (CH_Three )₂ -O-, -C (CH_Three ) (CH₂ CH_Three ) -O-, -C (CH₂ CH_Three )₂ -O-;-(CH₂ )_n -O-CH₂ -(N represents an integer of 1 to 19); -CH (CH_Three ) -O-CH₂ -, -CH (CH₂ CH_Three ) -O-CH₂ -, -C (CH_Three )₂ -O-CH₂ -, -C (CH_Three ) (CH₂ CH_Three ) -O-CH₂ -, -C (CH₂ CH_Three )₂ -O-CH₂ -,-(CH₂ )₂ -OC (O)-;-(CH₂ )_n -OC (O)-(CH₂ )_m -(M and n are the same or different and represent an integer of 0 to 19. However, 0 ≦ m + n ≦ 19 is satisfied);₂ )_n -C (O) O- (CH₂ )_m -(M and n are the same or different and each represents an integer of 0 to 19, provided that 0≤m + n≤19 is satisfied); -CH₂ -C (O) O- (CH₂ )₂ -O-CH₂ -, -CH (CH_Three ) -C (O) O- (CH₂ )₂ -O-CH₂ -, -CH (CH₂ CH_Three ) -C (O) O- (CH₂ )₂ -O-, -C (CH_Three )₂ -C (O) O-, -C (CH_Three ) (CH₂ CH_Three ) -C (O) O-, -C (CH₂ CH_Three )₂ -C (O) O- etc. are mentioned.
[0014]
R^Three May contain a benzene ring. Specific examples in this case are o-, m-, p-C.₆ H_Four -, O-, m-, p-C₆ H_Four -CH₂ -, O-, m-, p-C₆ H_Four -O-, o-, m-, p-C₆ H_Four -O-CH₂ -, O-, m-, p-C₆ H_Four -O-CH (CH_Three )-, O-, m-, p-C₆ H_Four -O-C (CH_Three )₂ -; O-, m-, p-C₆ H_Four -(CH₂ )_n -(N represents an integer of 0 to 14); o-, m-, p-C₆ H_Four -O- (CH₂ )_n -(N represents an integer of 0 to 14); o-, m-, p-CH₂ -C₆ H_Four -, O-, m-, p-CH₂ -C₆ H_Four -CH₂ -, O-, m-, p-CH₂ -C₆ H_Four -O-, o-, m-, p-CH₂ -C₆ H_Four -O-CH₂ -, O-, m-, p-CH₂ -C₆ H_Four -O-CH (CH_Three )-; O-, m-, p-CH₂ -C₆ H_Four -O-C (CH_Three )₂ -; O-, m-, p-CH₂ -C₆ H_Four -(CH₂ )_n -(N represents an integer of 0 to 13); o-, m-, p-CH₂ -C₆ H_Four -O- (CH₂ )_n -(N represents an integer of 0 to 13); o-, m-, p-C₆ H_Four -C (O) O-, o-, m-, p-CH₂ -C₆ H_Four -C (O) O-; o-, m-, p-C (O) -C₆ H_Four -C (O) O- (CH₂ )_n -(N represents an integer of 0 to 12).
[0015]
Of these, preferred are those represented by the general formula (2);
-C₆ H_Four -(CH₂ )_n -(2)
The divalent organic group represented by these is mentioned. Where C₆ H_Four Represents a phenylene group. n represents an integer of 0 to 14.
[0016]
In addition, the above R^Three Is a general formula (3);
-C (O) -R^Five -(3)
The bivalent organic group represented by these may be sufficient. At this time, the general formula (1) can be expressed by the general formula (1 ′). Where R^Five Represents a direct bond or a divalent organic group having 1 to 19 carbon atoms which may contain one or more ether bonds or ester bonds. Specific examples of the divalent organic group include R^Three And those already exemplified above. R above^Five Is preferably a direct bond or a general formula (4);
-(CH₂ )_n -(4)
It is a bivalent organic group represented by these. In the formula, n represents an integer of 1 to 19.
[0017]
In the general formula (1) or (1 ′), R^Four Represents 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. As a preferable thing, hydrogen or a methyl group is mentioned from a reactive viewpoint at the time of using the polymer of this invention as curable resin.
[0018]
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, Various things 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, stearyl (meth) acrylate, glycidyl (meth) acrylate, (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.
[0019]
The vinyl polymer having an alkenyl group at the end of the main chain of the present invention has a molecular weight distribution, that is, a ratio (Mw) of weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography (GPC). / Mn) is preferably 1.8 or less. More preferably, it is 1.6 or less, More preferably, it is 1.3 or less. In the GPC measurement in the present invention, chloroform is usually used as a 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.
[0020]
The number average molecular weight of the vinyl polymer having an alkenyl group at the end of the main chain of the present invention is not particularly limited, but is preferably in the range of 500 to 100,000, more preferably in the range of 3000 to 50,000. 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.
[0021]
The present invention also provides a vinyl polymer having a crosslinkable silyl group at the end of at least one main chain formed by adding a hydrosilane compound having a crosslinkable silyl group to the vinyl polymer having the alkenyl group at the main chain end. It is a polymer.
[0022]
It does not specifically limit as a hydrosilane compound which has the said crosslinkable silyl group, When a typical thing is shown, the compound represented by General formula (10) will be illustrated.
H- [Si (R¹³)_2-b (Y)_b O]_m -Si (R¹⁴)_3-a (Y)_a (10)
[In the formula, R¹³And R¹⁴Are the same or different and are an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′)._Three Triorganosiloxy represented by SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different). Represents a group. R¹³Or R¹⁴When 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 are present, they may be the same or different. a represents 0, 1, 2 or 3. b represents 0, 1 or 2. m represents an integer of 0 to 19. However, it shall be satisfied that a + mb ≧ 1. ]
[0023]
The hydrolyzable group represented by Y is not particularly limited, and conventionally known ones can be used. Specifically, hydrogen, halogen, alkoxy group, acyloxy group, ketoximate group, amino group, amide group, Examples thereof include an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Of these, an alkoxy group is preferred because it is mildly hydrolyzable and easy to handle. The hydrolyzable group and / or hydroxyl group as Y can be bonded to one silicon atom in the range of 1 to 3. Moreover, the range of 1-5 is preferable for the sum total of a + mb, ie, a hydrolysable group and / or a hydroxyl group. When two or more hydrolyzable groups are bonded to one silicon atom, they may be the same or different. The number of silicon atoms constituting the hydrosilane compound may be one or two or more, but in the case of silicon atoms linked by a siloxane bond, it may be up to about 20.
In the present specification, the crosslinkable silyl group refers to a silyl group to which the above-mentioned group Y is bonded, and a hydroxyl group or a hydroxyl group generated by hydrolysis of a hydrolyzable group causes -Si-O-Si-bridged. Can be formed.
[0024]
R in the general formula (10)¹³And R¹⁴Specific examples of these include, for example, an alkyl group such as a methyl group or an ethyl group; a cycloalkyl group such as a cyclohexyl group; an aryl group such as a phenyl group; an aralkyl group such as a benzyl group; and R ′ is a methyl group or a phenyl group. Yes (R ')_Three Examples include triorganosilyl groups represented by SiO-.
[0025]
Specific examples of the hydrosilane compound represented by the general formula (10) include HSiCl._Three , HSi (CH_Three ) Cl₂ , HSi (CH_Three )₂ Cl, HSi (OCH_Three )_Three , HSi (CH_Three ) (OCH_Three )₂ , HSi (CH_Three )₂ OCH_Three , HSi (OC₂ H_Five )_Three , HSi (CH_Three ) (OC₂ H_Five )₂ , HSi (CH_Three )₂ OC₂ H_Five , HSi (OC_Three H₇ )_Three , HSi (C₂ H_Five ) (OCH_Three )₂ , HSi (C₂ H_Five )₂ OCH_Three , HSi (C₆ H_Five ) (OCH_Three )₂ , HSi (C₆ H_Five )₂ (OCH_Three ), HSi (CH_Three ) (OC (O) CH_Three )₂ , HSi (CH_Three )₂ O- [Si (CH_Three )₂ O]₂-Si (CH_Three ) (OCH_Three )₂ , HSi (CH_Three ) [O-N = C (CH_Three )₂]₂ (In each formula, C₆ H_Five Is a phenyl group. ) And the like.
[0026]
Among the hydrosilane compounds of the general formula (10), in particular, the general formula:
H-Si (R¹⁴)_3-a (Y)_a
(Wherein R¹⁴, Y and a are the same as above. ) Is preferred from the viewpoint of easy availability.
The vinyl polymer having the hydrolyzable silyl group at the end of the main chain can be produced by a method described in detail later.
[0027]
The polymer having an alkenyl group at the main chain end of the present invention can be obtained, for example, by the following production method. That is, a vinyl monomer is polymerized to produce a vinyl polymer having at least one main chain terminal having a group represented by the general formula (5). The polymer of the present invention can be obtained by substitution with an alkenyl group-containing oxyanion represented by the formula (6).
[0028]
It does not specifically limit as a vinyl-type monomer used in the said manufacturing method, What was already illustrated etc. are used.
[0029]
The vinyl polymer having a group represented by the general formula (5) at the end of the main chain may be polymerized using a halogen chain transfer agent or living radical polymerization (for example, Matyjazewski et al. , Journal of Chemical Society (J. Am. Chem. Soc.), 1995, 117, 5614; Macromolecules, 1995, 28, 7901; Science, 1996, 272, 866, or Sawamoto et al., Macromolecules, 1995, 28, 1721). Among these, the latter living radical polymerization is preferable because the reaction and the structure of the product are easily controlled.
Below, the manufacturing method of the vinyl polymer which has the terminal structure represented by the said General formula (5) using the living radical polymerization method is explained in full detail.
[0030]
The living radical polymerization uses an organic halide (for example, an ester compound having a halogen at the α-position or a compound having a halogen at the benzyl position) or a sulfonyl halide as an initiator, and a transition metal complex as a catalyst. And vinyl monomers are polymerized. When this polymerization method is used, it is possible to control the molecular weight and molecular weight distribution of the vinyl polymer, which has been difficult with conventional radical polymerization (molecular weight distribution: 1.1 to 1.8).
[0031]
In the above organic halide or sulfonyl halide compound, the carbon to which the halogen is bonded is bonded to the carbonyl group, phenyl group or sulfonyl group, so that the carbon-halogen bond is easily activated and functions as an initiator. obtain. Specific examples of these compounds include C₆ H_Five -CH₂ X, C₆ H_Five -C (H) (X) CH_Three , C₆ H_Five -C (X) (CH_Three )₂ (Where C₆ H_Five Represents a phenyl group. X represents chlorine, bromine or iodine. ; R⁶ -C (H) (X) -CO₂ R⁷ , R⁶ -C (CH_Three ) (X) -CO₂ R⁷ , R⁶ -C (H) (X) -C (O) R⁷ , R⁶ -C (CH_Three ) (X) -C (O) R⁷ (Wherein R⁶ And R⁷ Are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. X represents chlorine, bromine or iodine. ; R⁶ -C₆ H_Four -SO₂ X (wherein R⁶ Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. X represents chlorine, bromine or iodine. ) And the like.
[0032]
As the living radical polymerization initiator, an organic halide or sulfonyl halide compound having a functional group other than the functional group for initiating polymerization can be used. In such a case, a vinyl polymer having a structure represented by the general formula (5) at the end of one main chain and a functional group at the other main chain end is produced. Examples of such functional groups include alkenyl groups, crosslinkable silyl groups, hydroxyl groups, epoxy groups, amino groups, amide groups, and the like.
[0033]
It does not specifically limit as an organic halide which has the said alkenyl group, For example, what has a structure shown to General formula (8) is illustrated.
R⁸ R⁹ C (X) -R^Ten-R¹¹-C (R) = CH₂ (8)
(In the formula, R represents hydrogen or a methyl group. R⁸ And R⁹ Are the same or different and each represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms;⁸ And R⁹ May be connected to each other at the other end. R^TenRepresents -C (O) O- (ester group), -C (O)-(keto group), or o-, m-, p-phenylene group. R¹¹Represents a direct bond or a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds. X represents chlorine, bromine or iodine. )
[0034]
The above substituent R⁸ And R⁹ Specific examples thereof include hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, pentyl group, hexyl group and the like. R⁸ And R⁹ May be connected at the other end to form a cyclic skeleton.
[0035]
Specific examples of the organic halide having an alkenyl group represented by the general formula (8) include XCH₂ C (O) O (CH₂ )_n CH = CH₂ , H_Three CC (H) (X) C (O) O (CH₂ )_n CH = CH₂ , (H_Three C)₂ C (X) C (O) O (CH₂ )_n CH = CH₂ , CH_Three CH₂ C (H) (X) C (O) O (CH₂ )_n CH = CH₂ ,
[0036]
[Chemical 1]

[0037]
(In each of the above formulas, X represents chlorine, bromine or iodine. N represents an integer of 0 to 20);
XCH₂ C (O) O (CH₂ )_n O (CH₂ )_m CH = CH₂ , H_Three CC (H) (X) C (O) O (CH₂ )_n O (CH₂ )_m CH = CH₂ , (H_Three C)₂ C (X) C (O) O (CH₂ )_n O (CH₂ )_m CH = CH₂ , CH_Three CH₂ C (H) (X) C (O) O (CH₂ )_n O (CH₂ )_m CH = CH₂ ,
[0038]
[Chemical formula 2]

[0039]
(In each of the above formulas, X represents chlorine, bromine or iodine. N represents an integer of 1 to 20. m represents an integer of 0 to 20);
o, m, p-XCH₂ -C₆ H_Four -(CH₂ )_n -CH = CH₂ , O, m, p-CH_Three C (H) (X) -C₆ H_Four -(CH₂ )_n -CH = CH₂ , O, m, p-CH_Three CH₂ C (H) (X) -C₆ H_Four -(CH₂ )_n -CH = CH₂ (In each of the above formulas, X represents chlorine, bromine or iodine. N represents an integer of 0 to 20);
o, m, p-XCH₂ -C₆ H_Four -(CH₂ )_n -O- (CH₂ )_m -CH = CH₂ , O, m, p-CH_Three C (H) (X) -C₆ H_Four -(CH₂ )_n -O- (CH₂ )_m -CH = CH₂ , O, m, p-CH_Three CH₂ C (H) (X) -C₆ H_Four -(CH₂ )_n -O- (CH₂ )_m CH = CH₂ (In each of the above formulas, X represents chlorine, bromine or iodine. N represents an integer of 1 to 20. m represents an integer of 0 to 20);
[0040]
o, m, p-XCH₂ -C₆ H_Four -O- (CH₂ )_n -CH = CH₂ , O, m, p-CH_Three C (H) (X) -C₆ H_Four -O- (CH₂ )_n -CH = CH₂ , O, m, p-CH_Three CH₂ C (H) (X) -C₆ H_Four -O- (CH₂ )_n -CH = CH₂ (In each of the above formulas, X represents chlorine, bromine or iodine. N represents an integer of 0 to 20);
o, m, p-XCH₂ -C₆ H_Four -O- (CH₂ )_n -O- (CH₂ )_m -CH = CH₂ , O, m, p-CH_Three C (H) (X) -C₆ H_Four -O- (CH₂ )_n -O- (CH₂ )_m -CH = CH₂ , O, m, p-CH_Three CH₂ C (H) (X) -C₆ H_Four -O- (CH₂ )_n -O- (CH₂ )_m -CH = CH₂ (In each of the above formulas, X represents chlorine, bromine or iodine. N represents an integer of 1 to 20. m represents an integer of 0 to 20.).
[0041]
Examples of the organic halide having an alkenyl group further include a compound represented by the general formula (9).
H₂ C = C (R) -R¹¹-C (R⁸ ) (X) -R¹²-R⁹ (9)
(Where R, R⁸ , R⁹ , R¹¹And X are the same as above. R¹²Represents a direct bond, —C (O) O— (ester group), —C (O) — (keto group), or o-, m-, p-phenylene group. )
[0042]
In the general formula (9), R¹¹Represents a direct bond or a divalent organic group having 1 to 20 carbon atoms (which may contain one or more ether bonds), and in the case of a direct bond, The compound is a halogenated allylic compound because the groups are attached. In this case, since the carbon-halogen bond is activated by the adjacent vinyl group, R¹²Is not necessarily a C (O) O group or a phenylene group, and may be a direct bond. R¹¹In order to activate the carbon-halogen bond,¹²Is preferably a C (O) O group, a C (O) group or a phenylene group.
[0043]
When the compound of the general formula (9) is specifically exemplified, CH₂ = CHCH₂ X, CH₂ = C (CH_Three ) CH₂ X, 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) C₂ H_Five , CH₂ = CHC (H) (X) CH (CH_Three )₂ , CH₂ = CHC (H) (X) C₆ H_Five , CH₂ = CHC (H) (X) CH₂ C₆ H_Five , CH₂ = CHCH₂ C (H) (X) -CO₂ R, CH₂ = CH (CH₂ )₂ C (H) (X) -CO₂ R, CH₂ = CH (CH₂ )_Three C (H) (X) -CO₂ R, CH₂ = CH (CH₂ )₈ C (H) (X) -CO₂ R, CH₂ = CHCH₂ C (H) (X) -C₆ H_Five , CH₂ = CH (CH₂ )₂ C (H) (X) -C₆ H_Five , CH₂ = CH (CH₂ )_Three C (H) (X) -C₆ H_Five (In each of the above formulas, X represents chlorine, bromine or iodine. R represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms. And the like.
[0044]
Specific examples of the sulfonyl halide compound having the alkenyl group include o-, m-, p-CH.₂ = CH- (CH₂ )_n -C₆ H_Four -SO₂ X, o-, m-, p-CH₂ = CH- (CH₂ )_n -OC₆ H_Four -SO₂ X, (in each of the above formulas, X represents chlorine, bromine, or iodine. N represents an integer of 0 to 20).
[0045]
When polymerization is carried out using an initiator having the above alkenyl group, the polymerization conditions such as reaction temperature and reaction time may be used because the alkenyl group of the initiator may react with the polymerization growth terminal during the polymerization reaction. Caution must be taken.
[0046]
It does not specifically limit as said organic halide which has a crosslinkable silyl group, For example, what has a structure shown to General formula (12) is illustrated.
R⁸ R⁹ C (X) -R^Ten-R¹¹-C (H) (R) CH₂ -[Si (R¹³)_2-b (Y)_b O]_m -Si (R¹⁴)_3-a (Y)_a   (12)
(Where R, R⁸ , R⁹ , R^Ten, R¹¹, R¹³, R¹⁴, X, a, b and m are the same as above. )
[0047]
If the compound of the general formula (12) is specifically exemplified, XCH₂ C (O) O (CH₂ )_n Si (OCH_Three )_Three , CH_Three C (H) (X) C (O) O (CH₂ )_n Si (OCH_Three )_Three , (CH_Three )₂ C (X) C (O) O (CH₂ )_n Si (OCH_Three )_Three , XCH₂ C (O) O (CH₂ )_n Si (CH_Three ) (OCH_Three )₂ , CH_Three C (H) (X) C (O) O (CH₂ )_n Si (CH_Three ) (OCH_Three )₂ , (CH_Three )₂ C (X) C (O) O (CH₂ )_n Si (CH_Three ) (OCH_Three )₂ (In the above formulas, X represents chlorine, bromine or iodine. N represents an integer of 0 to 20);
[0048]
XCH₂ C (O) O (CH₂ )_n O (CH₂ )_m Si (OCH_Three )_Three , H_Three CC (H) (X) C (O) O (CH₂ )_n O (CH₂ )_m Si (OCH_Three )_Three , (H_Three C)₂ C (X) C (O) O (CH₂ )_n O (CH₂ )_m Si (OCH_Three )_Three , CH_Three CH₂ C (H) (X) C (O) O (CH₂ )_n O (CH₂ )_m Si (OCH_Three )_Three , XCH₂ C (O) O (CH₂ )_n O (CH₂ )_m Si (CH_Three ) (OCH_Three )₂ , H_Three CC (H) (X) C (O) O (CH₂ )_n O (CH₂ )_m -Si (CH_Three ) (OCH_Three )₂ , (H_Three C)₂ C (X) C (O) O (CH₂ )_n O (CH₂ )_m -Si (CH_Three ) (OCH_Three )₂ , CH_Three CH₂ C (H) (X) C (O) O (CH₂ )_n O (CH₂ )_m -Si (CH_Three ) (OCH_Three )₂ (In each of the above formulas, X represents chlorine, bromine or iodine. N represents an integer of 1 to 20. m represents an integer of 0 to 20);
[0049]
o, m, p-XCH₂ -C₆ H_Four -(CH₂ )₂ Si (OCH_Three )_Three , O, m, p-CH_Three C (H) (X) -C₆ H_Four -(CH₂ )₂ Si (OCH_Three )_Three , O, m, p-CH_Three CH₂ C (H) (X) -C₆ H_Four -(CH₂ )₂ Si (OCH_Three )_Three , O, m, p-XCH₂ -C₆ H_Four -(CH₂ )_Three Si (OCH_Three )_Three , O, m, p-CH_Three C (H) (X) -C₆ H_Four -(CH₂ )_Three Si (OCH_Three )_Three , O, m, p-CH_Three CH₂ C (H) (X) -C₆ H_Four -(CH₂ )_Three Si (OCH_Three )_Three , O, m, p-XCH₂ -C₆ H_Four -(CH₂ )₂ -O- (CH₂ )_Three Si (OCH_Three )_Three , O, m, p-CH_Three C (H) (X) -C₆ H_Four -(CH₂ )₂ -O- (CH₂ )_Three Si (OCH_Three )_Three , O, m, p-CH_Three CH₂ C (H) (X) -C₆ H_Four -(CH₂ )₂ -O- (CH₂ )_Three Si (OCH_Three )_Three , O, m, p-XCH₂ -C₆ H_Four -O- (CH₂ )_Three Si (OCH_Three )_Three , O, m, p-CH_Three C (H) (X) -C₆ H_Four -O- (CH₂ )_Three Si (OCH_Three )_Three , O, m, p-CH_Three CH₂ C (H) (X) -C₆ H_Four -O- (CH₂ )_Three -Si (OCH_Three )_Three , O, m, p-XCH₂ -C₆ H_Four -O- (CH₂ )₂ -O- (CH₂ )_Three -Si (OCH_Three )_Three , O, m, p-CH_Three C (H) (X) -C₆ H_Four -O- (CH₂ )₂ -O- (CH₂ )_Three Si (OCH_Three )_Three , O, m, p-CH_Three CH₂ C (H) (X) -C₆ H_Four -O- (CH₂ )₂ -O- (CH₂ )_Three Si (OCH_Three )_Three (In the above formulas, X represents chlorine, bromine or iodine).
[0050]
Examples of the organic halide having a crosslinkable silyl group further include a compound represented by the general formula (13).
(R¹⁴)_3-a (Y)_a Si- [OSi (R¹³)_2-b (Y)_b ]_m -CH₂ -C (H) (R) -R¹¹-C (R⁸ ) (X) -R¹²-R⁹ (13)
(Where R, R⁸ , R⁹ , R¹¹, R¹², R¹³, R¹⁴, A, b, m, X and Y are the same as above. )
[0051]
To specifically illustrate such a compound, (CH_Three O)_Three SiCH₂ CH₂ C (H) (X) C₆ H_Five , (CH_Three O)₂ (CH_Three ) SiCH₂ CH₂ C (H) (X) C₆ H_Five , (CH_Three O)_Three Si (CH₂ )₂ C (H) (X) -CO₂ R, (CH_Three O)₂ (CH_Three ) Si (CH₂ )₂ C (H) (X) -CO₂ R, (CH_Three O)_Three Si (CH₂ )_Three C (H) (X) -CO₂ R, (CH_Three O)₂ (CH_Three ) Si (CH₂ )_Three C (H) (X) -CO₂ R, (CH_Three O)_Three Si (CH₂ )_Four C (H) (X) -CO₂ R, (CH_Three O)₂ (CH_Three ) Si (CH₂ )_Four C (H) (X) -CO₂ R, (CH_Three O)_Three Si (CH₂ )₉ C (H) (X) -CO₂ R, (CH_Three O)₂ (CH_Three ) Si (CH₂ )₉ C (H) (X) -CO₂ R, (CH_Three O)_Three Si (CH₂ )_Three C (H) (X) -C₆ H_Five , (CH_Three O)₂ (CH_Three ) Si (CH₂ )_Three C (H) (X) -C₆ H_Five , (CH_Three O)_Three Si (CH₂ )_Four C (H) (X) -C₆ H_Five , (CH_Three O)₂ (CH_Three ) Si (CH₂ )_Four C (H) (X) -C₆ H_Five (In each of the above formulas, X represents chlorine, bromine or iodine. R represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. ) And the like.
[0052]
It does not specifically limit as said organic halide or halogenated sulfonyl compound which has a hydroxyl group, The following compounds are illustrated.
HO- (CH₂ )_n -OC (O) C (H) (R) (X)
(In the formula, X represents chlorine, bromine or iodine. R represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. N represents an integer of 1 to 20.)
[0053]
It does not specifically limit as said organic halide or halogenated sulfonyl compound which has an amino group, The following compounds are illustrated.
H₂ N- (CH₂ )_n -OC (O) C (H) (R) (X)
(In the formula, X represents chlorine, bromine or iodine. R represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. N represents an integer of 1 to 20.)
[0054]
It does not specifically limit as an organic halide or halogenated sulfonyl compound which has the said epoxy group, The following compounds are illustrated.
[0055]
[Chemical Formula 3]

[0056]
(In the formula, X represents chlorine, bromine or iodine. R represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. N represents an integer of 1 to 20.)
[0057]
In the living radical polymerization, when polymerization is performed using an organic halide or a sulfonyl halide compound having two or more starting points as an initiator, an alkenyl group represented by the general formula (1) is formed in one molecule. A vinyl polymer having two or more can be produced. That is, when polymerization is performed using an initiator having two initiation points, a vinyl polymer having the structure represented by the general formula (5) at both ends is obtained. By replacing this terminal halogen with an alkenyl group-containing oxyanion, a vinyl polymer having an alkenyl group at both ends can be obtained. To illustrate this initiator specifically,
[0058]
[Formula 4]

[0059]
(Where C₆ H_Four Represents a phenylene group. X represents chlorine, bromine or iodine. R represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. n represents an integer of 0 to 20. );
[0060]
[Chemical formula 5]

[0061]
(In the formula, X represents chlorine, bromine or iodine. N represents an integer of 0 to 20. C.₆ H_Four Represents a phenylene group. ) And the like.
[0062]
The living radical 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 and tetrahydrofuran; halogenated hydrocarbon solvents such as methylene chloride and chloroform; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Solvents: Alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol and tert-butyl alcohol; Nitrile solvents such as acetonitrile, propionitrile and benzonitrile; Ester solvents such as ethyl acetate and butyl acetate And carbonate solvents such as ethylene carbonate and propylene carbonate. These can be used individually or in mixture of 2 or more types. Moreover, the said superposition | polymerization can be performed in the range of room temperature-200 degreeC, Preferably, it is the range of 50-150 degreeC.
[0063]
The transition metal complex used as the catalyst for the living radical polymerization is not particularly limited, and preferred examples include a complex of monovalent 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, a ligand such as 2,2′-bipyridyl and its derivative, 1,10-phenanthroline and its derivative, and a polyamine such as pentamethyldiethylenetriamine is added to increase the catalytic activity. In addition, tristriphenylphosphine complex of divalent ruthenium chloride (RuCl₂ (PPh_Three )_Three ) Is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, 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.
[0064]
The polymerization in the production method of the present invention may be polymerization using a halide as a chain transfer agent (telogen) in addition to the living radical polymerization. As the halide, carbon tetrachloride, carbon tetrabromide, methylene chloride, methylene bromide and the like are used.
[0065]
The terminal halogen of the vinyl polymer having the group represented by the general formula (5) produced at the end of at least one main chain, produced by the production method, contains an alkenyl group represented by the general formula (6). By replacing with an oxyanion, a vinyl polymer having an alkenyl group of the present invention at the end of the main chain is obtained. Below, the substitution method by an alkenyl group containing oxyanion is explained in full detail.
[0066]
In the general formula (6) representing the alkenyl group-containing oxyanion, R^Three And R^Four Are the same substituents as described above, and as specific examples thereof, all of those exemplified above can be used. In particular, R^Three Is -C (O) -R^Five When represented by-, the general formula (6) is represented by the general formula (6 ').
[0067]
In the general formula (6), M⁺ Is a counter cation of an oxyanion and represents an alkali metal ion or a quaternary ammonium ion. Examples of the alkali metal ions include lithium ions, sodium ions, potassium ions, and the like, preferably sodium ions or potassium ions. Examples of the quaternary ammonium ion include tetramethylammonium ion, tetraethylammonium ion, trimethylbenzylammonium ion, trimethyldodecylammonium ion, tetrabutylammonium ion, dimethylpiperidinium ion, and the like.
[0068]
Examples of the precursor of the alkenyl group-containing oxyanion represented by the general formula (6) include H₂ C = CH-CH₂ -OH, H₂ C = CH-CH (CH_Three ) -OH, H₂ C = C (CH_Three ) -CH₂ -OH, H₂ C = CH- (CH₂ )_n -OH (n represents an integer of 2 to 20), H₂ C = CH-CH₂ -O- (CH₂ )₂ -OH, H₂ C = CH—C (O) O— (CH₂ )₂ -OH, H₂ C = C (CH_Three ) -C (O) O- (CH₂ )₂ -OH, o-, m-, pH₂ C = CH-C₆ H_Four -OH, o-, m-, pH₂ C = CH-CH₂ -C₆ H_Four -OH, o-, m-, pH₂ C = CH-CH₂ -OC₆ H_Four -OH, o-, m-, pH₂ C = CH-C₆ H_Four -CH₂ -OH, o-, m-, pH₂ C = CH-CH₂ -C₆ H_Four -CH₂ -OH, o-, m-, pH₂ C = CH-CH₂ -OC₆ H_Four -CH₂ -OH etc. are mentioned.
[0069]
Furthermore, as a precursor of the alkenyl group-containing oxyanion represented by the general formula (6), H₂ C = CH—C (O) —OH, H₂ C = C (CH_Three ) -C (O) -OH, H₂ C = CH-CH₂ -C (O) -OH, H₂ C = CH- (CH₂ )_n -C (O) -OH (n represents an integer of 2 to 20), H₂ C = CH- (CH₂ )_n -OC (O)-(CH₂ )_m -C (O) -OH (m and n are the same or different and represent an integer of 0 to 19), o-, m-, p-H.₂ C = CH-C₆ H_Four -C (O) -OH, o-, m-, pH₂ C = CH-CH₂ -C₆ H_Four -C (O) -OH, o-, m-, pH₂ C = CH-CH₂ -OC₆ H_Four -C (O) -OH, o-, m-, pH₂ C = CH- (CH₂ )_n -OC (O) -C₆ H_Four -C (O) -OH (n represents an integer of 0 to 13) and the like are also included. These are also compounds that can be represented by the general formula (6 ′).
[0070]
The alkenyl group-containing oxyanion represented by the general formula (6) can be prepared by reacting the precursor with a base. Various types of bases can be used. For example, sodium methoxide, potassium methoxide, lithium methoxide, sodium ethoxide, potassium ethoxide, lithium ethoxide, sodium tert-butoxide, potassium tert-butoxide, sodium carbonate, potassium carbonate, lithium carbonate, hydrogen carbonate Sodium, sodium hydroxide, potassium hydroxide, sodium hydride, potassium hydride, methyl lithium, ethyl lithium, n-butyl lithium, tert-butyl lithium, lithium diisopropylamide, lithium hexamethyldisilazide; trimethylamine, triethylamine, tri Alkylamines such as butylamine; polyamines such as tetramethylethylenediamine and pentamethyldiethylenetriamine; pyridine compounds such as pyridine and picoline It is below. The usage-amount of the said base is 0.5-5 equivalent with respect to the said precursor, Preferably it is 0.8-1.2 equivalent.
[0071]
Examples of the solvent used in the reaction of the precursor with the base include hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether and tetrahydrofuran; halogenated hydrocarbons such as methylene chloride and chloroform. Solvents; Ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; Alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, and tert-butyl alcohol; Nitriles such as acetonitrile, propionitrile, and benzonitrile Solvents; ester solvents such as ethyl acetate and butyl acetate; carbonate solvents such as ethylene carbonate and propylene carbonate; amide solvents such as dimethylformamide and dimethylacetamide. These can be used individually or in mixture of 2 or more types.
[0072]
A specific method for producing the alkenyl group-containing oxyanion represented by the general formula (6) will be further described. For example, as a precursor, o-, m-, pH₂ C = CH-CH₂ -C₆ H_Four When -OH is used, a base, for example, potassium tert-butoxide, is charged into a reaction vessel under an inert gas atmosphere, and suspended and dispersed in a solvent such as dimethylacetamide. An alkenyl group-containing oxyanion in which acidic protons are substituted with potassium is obtained by adding equimolar amounts of allylphenol to the dispersion and reacting at room temperature to 70 ° C. for 30 minutes to 1 hour.
[0073]
M⁺ An alkenyl group-containing oxyanion in which is a quaternary ammonium ion can be obtained by directly acting an alkylamine or a pyridine compound on the precursor.⁺ Can be obtained by preparing an alkali metal ion and allowing a quaternary ammonium halide to act on it. Examples of the quaternary ammonium halide include tetramethylammonium halide, tetraethylammonium halide, trimethylbenzylammonium halide, trimethyldodecylammonium halide, and tetrabutylammonium halide.
[0074]
By reacting the alkenyl group-containing oxyanion of the general formula (6) prepared by the method as described above with a vinyl polymer having a terminal structure of the general formula (5) obtained by the polymerization method described above. A vinyl polymer having an alkenyl group represented by the general formula (1) at the end of the main chain can be obtained. This reaction can be performed at 0 to 150 ° C. in the solvent already described. The usage-amount of the alkenyl group containing oxyanion of General formula (6) is 1-5 equivalent with respect to the terminal structure of General formula (5), Preferably it is 1-1.2 equivalent.
[0075]
The above-mentioned vinyl polymer having a crosslinkable silyl group at the main chain end is produced by the above-mentioned method by producing the vinyl polymer having the above alkenyl group at the main chain end. It is obtained by adding a hydrosilane compound having a crosslinkable silyl group.
[0076]
When the hydrosilane compound having a crosslinkable silyl group is added to a vinyl polymer having an alkenyl group at the end of the main chain, a hydrosilylation catalyst is used. The hydrosilylation catalyst is not particularly limited, and examples thereof include radical initiators such as organic peroxides and azo compounds, transition metal catalysts, and the like.
[0077]
The radical initiator is not particularly limited, and various types can be used. Illustratively, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) -3 Hexyne, dicumyl peroxide, t-butylcumyl peroxide, dialkyl peroxides such as α, α′-bis (t-butylperoxy) isopropylbenzene, benzoyl peroxide, p-chlorobenzoyl peroxide, m-chlorobenzoyl peroxide, 2 1,2-dichlorobenzoyl peroxide, diacyl peroxide such as lauroyl peroxide; peroxyesters such as perbenzoic acid-t-butyl; peroxydicarbonates such as diisopropyl percarbonate and di-2-ethylhexyl percarbonate; Di (t-butylperoxy) cyclohexane 1,1-di (t-butylperoxy) -3,3,5-peroxy ketals, such as trimethyl cyclohexane.
[0078]
Further, the transition metal catalyst is not particularly limited, and examples thereof include a platinum solid dispersed in a carrier such as platinum alone, alumina, silica, carbon black, chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, ketone, etc. And a platinum-olefin complex, a platinum (0) -divinyltetramethyldisiloxane complex, and the like. Examples of catalysts other than platinum compounds include RhCl (PPh_Three )_Three , RhCl_Three , RuCl_Three , IrCl_Three , FeCl_Three AlCl_Three , PdCl₂ ・ H₂ O, NiCl₂ TiCl_Four Etc. These catalysts may be used alone or in combination of two or more.
[0079]
From the vinyl polymer having an alkenyl group at the end of the main chain of the present invention, a curable composition comprising this as a main component can be obtained. That is, the curable composition of the present invention comprises (A) a vinyl polymer having the alkenyl group of the present invention at the main chain terminal, and (B) a hydrosilyl group-containing compound.
[0080]
The vinyl polymer of the component (A) may be used alone or in combination of two or more. (A) It does not specifically limit as molecular weight of a component, It is preferable to exist in the range of 500-100000, and it is more preferable to exist in the range of 3000-50000. When it is 500 or less, the original characteristics of the vinyl polymer are hardly exhibited, and when it is 100,000 or more, the viscosity or solubility is very low, and handling becomes difficult.
[0081]
The hydrosilyl group-containing compound (B) is not particularly limited, and various compounds can be used. That is, a linear polysiloxane represented by the following general formula (14) or (15);
R¹⁵ _Three SiO- [Si (R¹⁵)₂ O]_a -[Si (H) (R¹⁶) O]_b -[Si (R¹⁶) (R¹⁷) O]_C -SiR¹⁵ _Three   (14)
HR¹⁵ ₂ SiO- [Si (R¹⁵)₂ O]_a -[Si (H) (R¹⁶) O]_b -[Si (R¹⁶) (R¹⁷) O]_C -SiR¹⁵ ₂ H (15)
(Wherein R¹⁵And R¹⁶Are the same or different and each represents an alkyl group having 1 to 6 carbon atoms or a phenyl group. R¹⁷Represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. a represents an integer of 0 to 100. b represents an integer of 2 to 100. c represents an integer of 0 to 100. ),as well as,
Cyclic polysiloxane represented by the following general formula (16);
[0082]
[Chemical 6]

[0083]
(Wherein R¹⁵And R¹⁶Represents an alkyl group having 1 to 6 carbon atoms or a phenyl group. R¹⁷Represents an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. d represents an integer of 0 to 8. e represents an integer of 2 to 10. f represents an integer of 0 to 8. Note that d, e, and f satisfy 3 ≦ d + e + f ≦ 10. ) Can be used.
[0084]
These may be used alone or in combination of two or more. Among these polysiloxanes, a polysiloxane having a phenyl group is preferable from the viewpoint of compatibility with a vinyl polymer. Examples of such compounds include linear polysiloxanes represented by the following general formula (17) or (18) and cyclic polysiloxanes represented by the following general formula (19) or (20).
(CH_Three )_Three SiO- [Si (H) (CH_Three ) O]_g -[Si (C₆ H_Five )₂ O]_h -Si (CH_Three )_Three   (17)
(CH_Three )_Three SiO- [Si (H) (CH_Three ) O]_g -[Si (CH_Three ) {CH₂ C (H) (R¹⁸) C₆ H_Five } O]_h -Si (CH_Three )_Three   (18)
(Wherein R¹⁸Represents hydrogen or a methyl group. g represents an integer of 2 to 100. h represents an integer of 0 to 100. C₆ H_Five Is a phenyl group. )
[0085]
[Chemical 7]

[0086]
(Wherein R¹⁸Represents hydrogen or a methyl group. i represents an integer of 2 to 10. j represents an integer of 0 to 8. Note that i and j satisfy the relationship of 3 ≦ i + j ≦ 10. C₆ H_Five Is a phenyl group. )
[0087]
Further, as the hydrosilyl group-containing compound of component (B), a low molecular compound having two or more alkenyl groups in the molecule is reacted with the polysiloxane represented by the general formulas (14) to (20). A compound obtained by an addition reaction so that a part of the hydrosilyl group remains may be used later. Various compounds can be used as the low molecular compound having two or more alkenyl groups. For example, hydrocarbon compounds such as 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene; Ether compounds such as' -diallyl bisphenol A, 3,3'-diallyl bisphenol A; ester compounds such as diallyl phthalate, diallyl isophthalate, triallyl trimellitate, tetraallyl pyromellitate; carbonates such as diethylene glycol diallyl carbonate System compounds and the like.
[0088]
Such a compound can be obtained by slowly dropping a small amount of the alkenyl group-containing low molecular weight compound into the polysiloxanes of the general formulas (14) to (20) in the presence of a hydrosilylation catalyst. Among such compounds, considering the availability of raw materials, the ease of removal of excessively used hydrosilyl group-containing compounds, and the compatibility with the vinyl polymer as component (A), the following Are preferred.
[0089]
[Chemical 8]

[0090]
(N is 2, 3 or 4. m is an integer of 5 to 10.)
[0091]
In the curable composition of the present invention, the vinyl polymer (A) and the hydrosilyl group-containing compound (B) can be mixed at an arbitrary ratio, but from the viewpoint of curability, the moles of the alkenyl group and the hydrosilyl group. The ratio is preferably in the range of 0.2 to 5, more preferably 0.4 to 2.5. When the molar ratio is 5 or more, curing is insufficient and only a cured product having low tackiness and a low strength can be obtained. When the molar ratio is less than 0.2, a large amount of active hydrosilyl groups remain in the cured product even after curing. Therefore, cracks and voids are generated, and a uniform and strong cured product cannot be obtained.
[0092]
The curing reaction between the component (A) and the component (B) proceeds by mixing and heating the two components, but a hydrosilylation catalyst may be further added to advance the reaction more rapidly. Such a hydrosilylation catalyst is not particularly limited, and any of those already described can be used. Although there is no restriction | limiting in particular as a catalyst amount, It is 10 with respect to 1 mol of alkenyl groups of (A) component.^-1-10^-8It is preferably used in the range of mol, more preferably 10^-3-10^-6  The range is mol. 10^-8If it is less than mol, curing does not proceed sufficiently. Also, since hydrosilylation catalysts are expensive, 10^-1It is preferable not to use more than mol.
[0093]
In the curable composition, if the two components (A) and (B) and the hydrosilylation catalyst are mixed and cured as necessary, the deep curability is excellent without causing a phenomenon such as foaming. A uniform cured product can be obtained. It does not specifically limit about hardening conditions, Generally it is 0 to 200 degreeC, Preferably it is good to harden | cure at 30 to 150 degreeC for 10 second-24 hours. In particular, a material that cures in a short time of about 10 seconds to 1 hour at a high temperature of 80 ° C. to 150 ° C. can be obtained. The properties of the cured product depend on the main chain skeleton and molecular weight of the (A) vinyl polymer and (B) hydrosilyl group-containing compound to be used, but can be widely prepared from rubbery to resinous. If the specific use of the hardened | cured material obtained from the said curable composition is given, a sealing material, an adhesive agent, an adhesive material, an elastic adhesive agent, a coating material, a powder coating material, a foam, the potting material for electrical and electronic devices, a film, Gaskets, various molding materials, artificial marble, etc.
[0094]
In the present invention, it is also possible to prepare a curable composition containing as a main component a vinyl polymer having the crosslinkable silyl group at the main chain terminal.
In this curable composition, a vinyl polymer having a crosslinkable silyl group as a main component at the end of the main chain may be used alone or in combination of two or more. Although there is no restriction | limiting in particular about the molecular weight, It is preferable to exist in the range of 500-100000, and the range of 3000-50000 is more preferable. When the molecular weight is 500 or less, the original characteristics of the vinyl polymer having a crosslinkable silyl group at the end of the main chain are hardly expressed, and when it is 100,000 or more, handling becomes difficult.
[0095]
When a vinyl polymer having a crosslinkable silyl group at the main chain terminal is brought into contact with moisture, it is three-dimensionalized and cured by a crosslinking reaction. Since the hydrolysis rate varies depending on the temperature, humidity, and type of the crosslinkable silyl group, an appropriate crosslinkable silyl group must be selected depending on the use conditions. Further, when storing a vinyl polymer having a crosslinkable silyl group at the end of the main chain, it is necessary to cut off contact with moisture as much as possible.
[0096]
In order to accelerate the curing reaction of the curable composition, a curing catalyst may be added. Examples of the catalyst include alkyl titanates, organosilicon titanates; metal salts of carboxylic acids such as tin octylate and dibutyltin dilaurate; amine salts such as dibutylamine-2-ethylhexoate, etc. Other acidic and basic catalysts can also be used. Although there is no restriction | limiting in particular as the usage-amount, It is preferable to use 0.01 to 5weight% with respect to the vinyl polymer which has a crosslinkable silyl group in the principal chain terminal.
[0097]
A uniform cured product can be obtained by mixing the above-mentioned curing catalyst with a vinyl polymer having a crosslinkable silyl group as the main component at the end of the main chain as required. It does not specifically limit as hardening conditions, Generally 0-100 degreeC, Preferably it is about 10-50 degreeC for about 1 hour-1 week. The properties of the cured product depend on the main chain skeleton and molecular weight of the polymer used, but can be widely prepared from rubbery to resinous.
[0098]
Specific applications of the cured products include sealing materials, adhesives, adhesives, elastic adhesives, paints, powder paints, foams, electrical and electronic potting materials, films, gaskets, various molding materials, and artificial materials. Such as marble.
[0099]
【Example】
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
[0100]
Example 1
To a 30 mL pressure-resistant reactor, methyl acrylate (7.5 mL, 7.17 g, 83.4 mmol), α, α′-dibromo-p-xylene (438 mg, 1.67 mmol), cuprous bromide (239 mg, 1.67 mmol), 2,2′-bipyridyl (518 mg, 3.34 mmol), ethyl acetate (6.0 mL), and acetonitrile (1.5 mL) are charged, and nitrogen is blown in for 10 minutes or more to dissolve dissolved oxygen. After removal, the tube was sealed. The mixture was heated to 130 ° C. and reacted for 1 hour. The mixture was diluted with ethyl acetate (20 mL) and washed 3 times with dilute hydrochloric acid and once with brine. The organic layer is Na₂ SO_Four The volatile matter was distilled off under reduced pressure to obtain poly (methyl acrylate) represented by the following formula (yield 6.01 g). The number average molecular weight of the polymer was 5600 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.26.
[0101]
[Chemical 9]

[0102]
A 50 mL three-necked round bottom flask was equipped with a reflux tube, and potassium-tert-butoxide (160 mg, 1.43 mmol) and dimethylacetamide (3 mL) were charged into a reaction vessel under a nitrogen atmosphere, and O-allylphenol (192 mg, 1 .43 mmol) was added in an equimolar amount and allowed to react at room temperature for 30 minutes, and then a solution of poly (methyl acrylate) (2.0 g) obtained above in dimethylacetamide (2 mL) was added dropwise and reacted at room temperature for 2 hours. It was. The reaction solution was neutralized with ice water-hydrochloric acid and extracted with ethyl acetate (30 mL). The organic layer was washed twice with dilute hydrochloric acid and once with brine. The organic layer is Na₂ SO_Four The volatile matter was distilled off under reduced pressure, dissolved in a small amount of ethyl acetate, and reprecipitated from hexane to obtain poly (methyl acrylate) having alkenyl groups at both ends as shown in the following formula ( Yield 1.70 g). The product was dissolved in toluene, and an equivalent amount of aluminum silicate (manufactured by Kyowa Chemical Co., Ltd .: Kyowaard 700PEL) was added to the polymer, followed by stirring at reflux temperature for 1 hour to remove trace impurities in the polymer. The alkenyl group introduced per oligomer-1 molecule is¹From 1 H NMR analysis, it was 1.24.
[0103]
Embedded image

[0104]
Next, the purified poly (methyl acrylate) was dissolved in ethyl acetate (2 mL), and a polyvalent hydrogen silicon compound represented by the following formula and 1,1,3,3-tetramethyl- 1,3-divinyldisiloxane complex (8.3 × 10^-9mol / L xylene solution) was added to the poly (methyl acrylate) solution and 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^-3Equivalent.
[0105]
Embedded image

[0106]
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 to be 4 minutes. Further, the remaining composition was poured into a mold, volatile components were distilled off under reduced pressure, and heat-cured at 100 ° C. for 14 hours to obtain a rubber-like cured product. The cured product was immersed in acetone for 24 hours, and the gel fraction was measured from the weight change before and after, and it was 45%.
[0107]
Production Example 1
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⁺
[0108]
Example 2
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 Na₂ SO_Four The volatile matter was distilled off under reduced pressure to obtain 5.0 g of poly (acrylic acid-n-butyl) having halogens at both ends represented by the following formula (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.
[0109]
Embedded image

[0110]
Next, poly (acrylic acid-n-butyl) having halogen at the terminal obtained as described above (5.00 g), potassium salt of undecylenic acid synthesized in Production Example 1 (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 (acrylic acid-n-butyl) having an alkenyl group at the terminal, as shown in the following formula. The product was dissolved in toluene, and an equivalent amount of aluminum silicate (manufactured by Kyowa Chemical: Kyowaard 700PEL) was added to the polymer and stirred for 2 hours to remove trace impurities in the polymer. The alkenyl group introduced per oligomer-1 molecule is¹From 1 H NMR analysis, it was 1.70.
[0111]
Embedded image

[0112]
Next, the polyvalent hydrogen silicon compound used in Example 1 and the platinum catalyst were added to the purified poly (butyl acrylate) and 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^-FourEquivalent.
[0113]
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 to be 60 seconds. The remaining composition was poured into a mold, degassed under reduced pressure, and heated and cured at 100 ° 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 it was 85%.
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 0.23 MPa and the breaking elongation was 128%.
[0114]
Production Example 2
Production of carboxylate having alkenyl group 2
Potassium methoxide (16.83 g, 0.240 mol) was dissolved in methanol (200 mL), and 4-pentenoic acid (24.56 g, 0.245 mol) was slowly added dropwise at 0 ° C. with stirring. Volatile components were distilled off under reduced pressure to obtain a crude product. The crude product was washed with ethyl acetate and then heated under reduced pressure to obtain a white solid of potassium salt of 4-pentenoic acid represented by the following formula (29.2 g, yield 88%).
CH₂ = CH- (CH₂ )₂ -CO₂ ^- K⁺
[0115]
Example 3
In a 500 mL pressure-resistant glass reaction vessel, acrylic acid-n-butyl (112 mL, 100 g, 0.78 mol), α, α′-dibromo-p-xylene (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 (22.4 mL) were charged and dissolved by blowing nitrogen gas for 10 minutes. After removing oxygen, the tube was sealed. The mixture was heated to 130 ° C. and reacted for 2.0 hours. The mixture was diluted with ethyl acetate (300 mL), the insoluble solid produced was filtered, and the filtrate was further diluted with ethyl acetate (200 mL). The filtrate was washed twice with dilute hydrochloric acid and once with brine. The organic layer is Na₂ SO_Four The volatile matter was distilled off under reduced pressure to obtain 85.9 g of poly (acrylic acid-n-butyl) having halogen at both ends (polymerization yield 86%). The number average molecular weight of the polymer was 5700 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.37.
[0116]
Next, poly (acrylic acid-n-butyl) having halogen at the terminal obtained as described above (83.9 g) was synthesized in Production Example 2 in a 50 mL three-necked round bottom flask equipped with a reflux tube. 4-Pentenoic acid potassium salt (7.74 g, 56.0 mmol) and dimethylacetamide (80 mL) were charged, and the mixture was reacted at 70 ° C. for 6 hours in a nitrogen atmosphere. The mixture was diluted with ethyl acetate (200 mL) and washed 3 times with water and once with brine. The organic layer is Na₂ SO_Four And the polymer was isolated by removing the volatiles under reduced pressure. By adding an equivalent amount of aluminum silicate (produced by Kyowa Chemical Co., Ltd .: Kyowaard 700PEL) to the polymer and stirring at 100 ° C. for 2 hours to remove trace impurities in the polymer, the terminal shown in the following formula is obtained. Poly (butyl acrylate) having an alkenyl group was obtained. The alkenyl group introduced per oligomer-1 molecule is¹From 1 H NMR analysis, it was 1.73.
[0117]
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[0118]
Example 4
In a 200 mL pressure-resistant glass reaction vessel, poly (n-butyl acrylate) having an alkenyl group at the end obtained in Example 3 (60.0 g), dimethoxymethylhydrosilane (8.4 mL, 68.1 mmol), ortho Dimethyl formate (2.5 mL, 22.9 mmol) and a platinum catalyst were charged. However, the amount of platinum catalyst used is 10 by molar ratio to the alkenyl group of the polymer.^-FourEquivalent. The reaction mixture was heated at 100 ° C. for 3 hours. By distilling off the volatile components of the mixture under reduced pressure, poly (acrylic acid-n-butyl) having a silyl group at the terminal, represented by the following formula, was obtained. The silyl group introduced per oligomer-1 molecule is¹According to 1 H NMR analysis, it was 1.59.
[0119]
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[0120]
Next, dibutyltin dimethoxide and water were added to poly (butyl acrylate) having a silyl group at the terminal and mixed well. 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 it was 93%.
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 0.26 MPa and the breaking elongation was 75%.
[0121]
Example 5
A 100 mL three-necked round bottom flask equipped with a reflux tube was charged with cuprous bromide (0.625 g, 15.6 mmol), acetonitrile (5.0 mL), and pentamethyldiethylenetriamine (0.91 mL). Replaced. Acrylic acid-n-butyl (50 mL, 44.7 g, 0.39 mol) and diethyl-2,5-dibromoadipate (1.57 g, 4.36 mmol) were added, and the mixture was heated and stirred at 70 ° C. for 7 hours. The mixture was diluted with ethyl acetate and treated with activated alumina. Volatile components were distilled off under reduced pressure to obtain 35.0 g of poly (acrylic acid-n-butyl) having halogen at both ends represented by the following formula (polymerization yield: 87%). The number average molecular weight of the polymer was 10700 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.15.
[0122]
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[0123]
Next, in a 200 mL three-necked round bottom flask equipped with a reflux tube, poly (acrylic acid-n-butyl) (35.0 g) having halogen at the terminal obtained as described above was synthesized in Production Example 2. 4-Pentenoic acid potassium salt (2.23 g, 16.1 mmol) and dimethylacetamide (35 mL) were charged, and the mixture was reacted at 70 ° C. for 4 hours in a nitrogen atmosphere. The mixture was diluted with ethyl acetate and washed with 2% hydrochloric acid, brine. The organic layer is Na₂ SO_Four And the polymer was isolated by removing the volatiles under reduced pressure. An equivalent amount of aluminum silicate (manufactured by Kyowa Chemical Co., Ltd .: Kyowaard 700PEL) was added to the polymer and stirred for 4 hours at 100 ° C. to obtain poly (butyl acrylate) having an alkenyl group at the terminal end shown in the following formula It was. The alkenyl group introduced per oligomer-1 molecule is¹According to 1 H NMR analysis, it was 1.82.
[0124]
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[0125]
Example 6
In a 200 mL pressure-resistant glass reaction vessel, poly (n-butyl acrylate) having an alkenyl group at the end obtained in Example 5 (15.0 g), dimethoxymethylhydrosilane (1.8 mL, 14.5 mmol), ortho Dimethyl formate (0.26 mL, 2.42 mmol) and a platinum catalyst were charged. 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 4 hours. By distilling off the volatile components of the mixture under reduced pressure, poly (acrylic acid-n-butyl) having a silyl group at the terminal, represented by the following formula, was obtained. The silyl group introduced per oligomer-1 molecule is¹From 1 H NMR analysis, it was 1.46.
[0126]
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[0127]
Next, dibutyltin dimethoxide and water were added to poly (butyl acrylate) having a silyl group at the terminal and mixed well. 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 it was 98%.
A 2 (1/3) type dumbbell test piece 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 0.35 MPa and the breaking elongation was 77%.
[0128]
Production Example 3
Production of carboxylate having alkenyl group 3
To a 200 mL round bottom flask was charged potassium-tert-butoxide (5.61 g, 50 mmol), and methanol (50 mL) was slowly added dropwise at 0 ° C. Methacrylic acid (4.4 mL, 52.0 mmol) was slowly added dropwise to this solution at 0 ° C. with stirring to precipitate white crystals. The temperature of the reaction solution was raised to room temperature, and the precipitated white crystals were separated by filtration and dried under reduced pressure at room temperature to obtain a potassium salt of methacrylic acid represented by the following formula (3.31 g, yield 53%).
CH₂ = C (CH_Three -CO₂ ^- K⁺
[0129]
Example 7
Poly (acrylic acid-n-butyl) having halogen at the terminal obtained in Example 3 (259 mg), potassium salt of methacrylic acid synthesized in Production Example 3 (14.9 mg, 0.12 mmol), and dimethyl Acetamide (2.5 mL) was charged and reacted at room temperature for 61 hours. 17.3 mg of methacrylic acid potassium salt was added, and the mixture was further reacted at the same temperature for 22 hours. The mixture was diluted with ethyl acetate and washed with water. By distilling off the volatile components of the organic layer under reduced pressure, poly (acrylic acid-n-butyl) having an alkenyl group at the terminal represented by the following formula was obtained. The alkenyl group introduced per oligomer-1 molecule is¹According to 1 H NMR analysis, it was 1.66.
[0130]
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[0131]
【The invention's effect】
According to the present invention, a vinyl polymer having a high ratio of alkenyl groups at the ends of the main chain, which has been difficult to produce, can be easily obtained. In addition, a vinyl polymer having a crosslinkable silyl group at the end of the main chain can be easily obtained from this vinyl polymer. In the vinyl polymer of the present invention, since these crosslinkable functional groups are surely introduced into the ends of the main chain, a cured product having excellent curing characteristics can be obtained.

Claims (25)

A vinyl polymer having an alkenyl group represented by the following general formula (1) at the end of at least one main chain, wherein the main chain is obtained by polymerization of a (meth) acrylic acid monomer. A vinyl polymer.
—CH ₂ —C (R ¹ ) (R ² ) —O—R ³ —C (R ⁴ ) ═CH ₂ (1)
(Wherein R ¹ and R ² are the same or different and each represents a hydrogen atom or a monovalent organic group derived from a group bonded to the vinyl group of the (meth) acrylic acid monomer. R ³ represents one the .R ⁴ where represents a divalent organic group having or more ether bonds or ester bonds carbon atoms which may contain 1 to 20, hydrogen, alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms Or, it represents an aralkyl group having 7 to 10 carbon atoms.) The polymer according to claim 1, wherein, in the general formula (1), R ³ is a divalent organic group represented by the following general formula (2).
_{-C 6 H 4 - (CH 2} ) n - (2)
_(Wherein, C 6 _{H 4} is .n representing the phenylene group represents an integer of 0 to 14.) The polymer according to claim 1, wherein, in the general formula (1), R ³ is a divalent organic group represented by the following general formula (3).
—C (O) —R ⁵ — (3)
(In the formula, R ⁵ represents a direct bond or a divalent organic group having 1 to 19 carbon atoms which may contain one or more ether bonds or ester bonds.) The polymer according to claim 3, wherein R ⁵ in the general formula (3) is a direct bond or a divalent organic group represented by the following general formula (4).
_{- (CH 2) n - (} 4)
(In the formula, n represents an integer of 1 to 19.)   The polymer according to any one of claims 1 to 4, wherein the (meth) acrylic acid monomer is an acrylate monomer.   The polymer according to any one of claims 1 to 4, wherein the (meth) acrylic acid monomer is a methacrylic acid ester monomer.   The polymer according to claim 5, wherein the acrylate monomer is butyl acrylate. A vinyl polymer having an alkenyl group represented by the following general formula (1) at at least one main chain terminal, wherein the main chain is obtained by polymerizing a styrene monomer. Vinyl polymer.
—CH ₂ —C (R ¹ ) (R ² ) —O—R ³ —C (R ⁴ ) ═CH ₂ (1)
(In the formula, R ¹ and R ² are the same or different and each represents a hydrogen atom or a monovalent organic group. R ³ represents a divalent organic group represented by the following general formula (2). R ⁴ represents 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.)
_{-C 6 H 4 - (CH 2} ) n - (2)
_(Wherein, C 6 _{H 4} is .n representing the phenylene group represents an integer of 0 to 14.)   The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography is a value of 1.8 or less. Polymer.   The polymer according to any one of claims 1 to 9, wherein the number average molecular weight is in the range of 500 to 100,000. At least one hydrosilane compound having a crosslinkable silyl group is added to a vinyl polymer having an alkenyl group represented by the following general formula (1) at at least one main chain terminal. A vinyl polymer having a crosslinkable silyl group at the end of the main chain.
—CH ₂ —C (R ¹ ) (R ² ) —O—R ³ —C (R ⁴ ) ═CH ₂ (1)
(In the formula, R ¹ and R ² are the same or different and each represents a hydrogen atom or a monovalent organic group. R ³ has 1 to 1 carbon atoms which may contain one or more ether bonds or ester bonds. Represents a divalent organic group of 20. R ⁴ represents 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.)   Vinyl monomers used for the production of the main chain are (meth) acrylic acid monomers, styrene monomers, fluorine-containing vinyl monomers, silicon-containing vinyl monomers, maleic anhydride, maleic acid, monoalkyl esters of maleic acid and dialkyl Esters, fumaric acid, monoalkyl and dialkyl esters of fumaric acid, maleimide monomers, nitrile group-containing vinyl monomers, amide group-containing vinyl monomers, vinyl esters, alkenes, conjugated dienes, vinyl chloride, vinylidene chloride, The vinyl polymer according to claim 11, which is one selected from the group consisting of allyl chloride and allyl alcohol. A vinyl monomer is polymerized to produce a vinyl polymer having at least one main chain terminal having a group represented by the following general formula (5). 6) A method for producing a vinyl polymer having an alkenyl group represented by the following general formula (1) at at least one main chain terminal, which is substituted with an alkenyl group-containing oxyanion represented by 6).
—CH ₂ —C (R ¹ ) (R ² ) (X) (5)
(In the formula, R ¹ and R ² are the same or different and each represents a hydrogen atom or a monovalent organic group derived from a group bonded to a vinyl group of a vinyl-based monomer. X represents chlorine, bromine or iodine. .)
M ⁺ O ⁻ —R ³ —C (R ⁴ ) ═CH ₂ (6)
(In the formula, R ³ represents a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds or ester bonds. R ⁴ represents hydrogen or an alkyl having 1 to 10 carbon atoms. A group, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, and M ⁺ represents an alkali metal ion or a quaternary ammonium ion.)
—CH ₂ —C (R ¹ ) (R ² ) —O—R ³ —C (R ⁴ ) ═CH ₂ (1)
(In the formula, R ¹ and R ² are the same or different and each represents a hydrogen atom or a monovalent organic group. R ³ has 1 to 1 carbon atoms which may contain one or more ether bonds or ester bonds. Represents a divalent organic group of 20. R ⁴ represents 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.) Alkenyl-containing oxyanion, in general formula (6), R ³ is The process of claim 13, wherein those which are divalent organic group represented by the following general formula (3).
—C (O) —R ⁵ — (3)
(In the formula, R ⁵ represents a direct bond or a divalent organic group having 1 to 19 carbon atoms which may contain one or more ether bonds or ester bonds.) The production method according to claim 13 or 14, wherein M ⁺ is a sodium ion or a potassium ion.   The production method according to claim 13, 14 or 15, wherein an organic halide or a sulfonyl halide compound is used as an initiator, and a vinyl monomer is polymerized using a transition metal complex as a catalyst.   The method according to claim 16, wherein the transition metal complex is a metal complex selected from the group consisting of copper, nickel, ruthenium and iron.   The production method according to claim 17, wherein the transition metal complex is a copper complex.   The production method according to claim 13, 14 or 15, wherein a vinyl monomer is polymerized using a chain transfer agent. By polymerizing a vinyl monomer, a vinyl polymer having at least one main chain terminal having a group represented by the following general formula (5) is produced. To obtain a vinyl polymer having an alkenyl group at at least one main chain end, and then adding a hydrosilane compound having a crosslinkable silyl group to the alkenyl group. The method for producing a vinyl polymer having a crosslinkable silyl group at the end of the main chain according to claim 11 or 12.
—CH ₂ —C (R ¹ ) (R ² ) (X) (5)
(In the formula, R ¹ and R ² are the same or different and each represents a hydrogen atom or a monovalent organic group derived from a group bonded to a vinyl group of a vinyl-based monomer. X represents chlorine, bromine or iodine. .)
M ⁺ O ⁻ —R ³ —C (R ⁴ ) ═CH ₂ (6)
(In the formula, R ³ represents a divalent organic group having 1 to 20 carbon atoms which may contain one or more ether bonds or ester bonds. R ⁴ represents hydrogen or an alkyl having 1 to 10 carbon atoms. A group, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, and M ⁺ represents an alkali metal ion or a quaternary ammonium ion.) (A) A curable composition comprising a vinyl polymer having an alkenyl group represented by the following general formula (1) at at least one main chain terminal, and (B) a hydrosilyl group-containing compound. object.
—CH ₂ —C (R ¹ ) (R ² ) —O—R ³ —C (R ⁴ ) ═CH ₂ (1)
(In the formula, R ¹ and R ² are the same or different and each represents a hydrogen atom or a monovalent organic group. R ³ has 1 to 1 carbon atoms which may contain one or more ether bonds or ester bonds. Represents a divalent organic group of 20. R ⁴ represents 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.)   The curable composition according to claim 21, wherein the molar ratio of the alkenyl group contained in component (A) to the hydrosilyl group contained in component (B) is in the range of 0.2-5.   The curable composition according to claim 21 or 22, further comprising a hydrosilylation catalyst.   A curable composition comprising, as a main component, a vinyl polymer having a crosslinkable silyl group at the end of the main chain according to claim 11.   25. The curable composition according to claim 24, which contains a curing catalyst in an amount of 0.01 to 5% by weight based on the polymer according to claim 11 or 12.