JP4002130B2 - Method for producing polymer, the polymer, and a curable composition using the polymer - Google Patents

Description

アルコキシアミン化合物を開始剤として用いる場合、それが上図で示されているような水酸基等の官能基を有するものを用いると末端に官能基を有する重合体が得られる。これを本発明の方法に利用すると、末端に官能基を有する星型重合体が得られる。
【００２７】
上記のニトロキシド化合物などのラジカル捕捉剤を用いる重合で用いられるモノマー、溶媒、重合温度等の重合条件は、限定されないが、次に説明する原子移動ラジカル重合について用いるものと同様で構わない。
【００２８】
次に、本発明のリビングラジカル重合としてより好ましい原子移動ラジカル重合法について説明する。
【００２９】
この原子移動ラジカル重合では、有機ハロゲン化物、特に、反応性の高い炭素−ハロゲン結合を有する有機ハロゲン化物（例えば、α位にハロゲンを有するエステル化合物や、ベンジル位にハロゲンを有する化合物）、あるいはハロゲン化スルホニル化合物が開始剤として用いられる。触媒としては、周期律表第７族、８族、９族、１０族、または１１族元素を中心金属とする金属錯体が用いられる。金属種としては特に１価の銅、２価のルテニウム、２価の鉄が好適である。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、酢酸第一銅、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、およびその誘導体、１，１０−フェナントロリン、およびその誘導体、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、ヘキサメチルトリエチレンテトラアミン等のポリアミン、等の配位子が添加される。また、二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。この触媒を使用するときは、その活性を高めるためにトリアルコキシアルミニウム等のアルミニウム化合物が添加される。さらに、二価の塩化鉄のトリストリフェニルホスフィン錯体（ＦｅＣｌ₂（ＰＰｈ₃）₃）も触媒として好適である。
【００３０】
この重合法においては有機ハロゲン化物、またはハロゲン化スルホニル化合物が開始剤として用いられる。具体的に例示するならば、
Ｃ₆Ｈ₅−ＣＨ₂Ｘ、
Ｃ₆Ｈ₅−Ｃ（Ｈ）（Ｘ）ＣＨ₃、
Ｃ₆Ｈ₅−Ｃ（Ｘ）（ＣＨ₃）₂、
Ｒ⁷−Ｃ（Ｈ）（Ｘ）−ＣＯ₂Ｒ⁸、
Ｒ⁷−Ｃ（ＣＨ₃）（Ｘ）−ＣＯ₂Ｒ⁸、
Ｒ⁷−Ｃ（Ｈ）（Ｘ）−Ｃ（Ｏ）Ｒ⁸、
Ｒ⁷−Ｃ（ＣＨ₃）（Ｘ）−Ｃ（Ｏ）Ｒ⁸、
Ｒ⁷−Ｃ₆Ｈ₄−ＳＯ₂Ｘ、
（上記の各式において、Ｃ₆Ｈ₅はフェニル基、Ｒ⁷、Ｒ⁸は水素原子または炭素数１〜２０のアルキル基、アリール基、またはアラルキル基であり、同じであっても良いし異なっていても良い。Ｘは塩素、臭素、またはヨウ素）
等が挙げられる。
【００３１】
また、重合を開始するもの以外に官能基を持つ有機ハロゲン化物、またはハロゲン化スルホニル化合物を用いると、容易に末端に官能基が導入された重合体が得られる。このような官能基としては、アルケニル基、ヒドロキシル基、エポキシ基、アミノ基、アミド基、シリル基等が挙げられる。
【００３２】
アルケニル基を有する有機ハロゲン化物としては特に制限はないが、例えば、一般式６に示す構造を有するものが例示される。
Ｒ⁹Ｒ¹⁰Ｃ（Ｘ）−Ｒ¹¹−Ｒ¹²−Ｃ（Ｒ¹³）＝ＣＨ₂ （６）
（式中、Ｒ⁹、Ｒ¹⁰は水素、または炭素数１〜２０の１価のアルキル基、アリール基、またはアラルキル基、または他端において相互に連結したもの、Ｒ¹¹は、−Ｃ（Ｏ）Ｏ−（エステル基）、−Ｃ（Ｏ）−（ケト基）、またはｏ−，ｍ−，ｐ−フェニレン基、Ｒ¹²は直接結合、または炭素数１〜２０の２価の有機基で１個以上のエーテル結合を含んでいても良い、Ｒ¹³は水素、またはメチル基、Ｘは塩素、臭素、またはヨウ素）
これらの化合物は、ハロゲンが結合している炭素がカルボニル基あるいはフェニル基等と結合しており、炭素−ハロゲン結合が活性化されて重合が開始する。
【００３３】
置換基Ｒ⁹、Ｒ¹⁰の具体例としては、水素、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ペンチル基、ヘキシル基等が挙げられる。Ｒ⁹とＲ¹⁰は他端において連結して環状骨格を形成していてもよく、そのような場合、−Ｒ⁹−Ｒ¹⁰−は例えば、−ＣＨ₂ＣＨ₂−、−ＣＨ₂ＣＨ₂ＣＨ₂−、−ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂−、−ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂ＣＨ₂−、等が例示される。
【００３４】
一般式６で示される、アルケニル基を有する有機ハロゲン化物の具体例としては、
ＸＣＨ₂Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＣＨ＝ＣＨ₂、
Ｈ₃ＣＣ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＣＨ＝ＣＨ₂、
（Ｈ₃Ｃ）₂Ｃ（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＣＨ＝ＣＨ₂、
ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＣＨ＝ＣＨ₂、
【００３５】
【化１１】

（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは０〜２０の整数）
ＸＣＨ₂Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_mＣＨ＝ＣＨ₂、
Ｈ₃ＣＣ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_mＣＨ＝ＣＨ₂、
（Ｈ₃Ｃ）₂Ｃ（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_mＣＨ＝ＣＨ₂、
ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_mＣＨ＝ＣＨ₂、
【００３６】
【化１２】

（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは１〜２０の整数、ｍは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ₂−Ｃ₆Ｈ₄−（ＣＨ₂）_n−ＣＨ＝ＣＨ₂、
ｏ，ｍ，ｐ−ＣＨ₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−（ＣＨ₂）_n−ＣＨ＝ＣＨ₂、
ｏ，ｍ，ｐ−ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−（ＣＨ₂）_n−ＣＨ＝ＣＨ₂、（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ₂−Ｃ₆Ｈ₄−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_m−ＣＨ＝ＣＨ₂、
ｏ，ｍ，ｐ−ＣＨ₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_m−ＣＨ＝ＣＨ₂、
ｏ，ｍ，ｐ−ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_mＣＨ＝ＣＨ₂、
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは１〜２０の整数、ｍは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ₂−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）_n−ＣＨ＝ＣＨ₂、
ｏ，ｍ，ｐ−ＣＨ₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）_n−ＣＨ＝ＣＨ₂、
ｏ，ｍ，ｐ−ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）_n−ＣＨ＝ＣＨ₂、
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ₂−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_m−ＣＨ＝ＣＨ₂、
ｏ，ｍ，ｐ−ＣＨ₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_m−ＣＨ＝ＣＨ₂、
ｏ，ｍ，ｐ−ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_m−ＣＨ＝ＣＨ₂、
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは１〜２０の整数、ｍは０〜２０の整数）
アルケニル基を有する有機ハロゲン化物としてはさらに一般式７で示される化合物が挙げられる。
Ｈ₂Ｃ＝Ｃ（Ｒ¹³）−Ｒ¹²−Ｃ（Ｒ⁹）（Ｘ）−Ｒ¹⁴−Ｒ¹⁰ （７）
（式中、Ｒ⁹、Ｒ¹⁰、Ｒ¹²、Ｒ¹³、Ｘは上記に同じ、Ｒ¹⁴は、直接結合、−Ｃ（Ｏ）Ｏ−（エステル基）、−Ｃ（Ｏ）−（ケト基）、または、ｏ−，ｍ−，ｐ−フェニレン基を表す）
Ｒ¹²は直接結合、または炭素数１〜２０の２価の有機基（１個以上のエーテル結合を含んでいても良い）であるが、直接結合である場合は、ハロゲンの結合している炭素にビニル基が結合しており、ハロゲン化アリル化物である。この場合は、隣接ビニル基によって炭素−ハロゲン結合が活性化されているので、Ｒ¹⁴としてＣ（Ｏ）Ｏ基やフェニレン基等を有する必要は必ずしもなく、直接結合であってもよい。Ｒ¹²が直接結合でない場合は、炭素−ハロゲン結合を活性化するために、Ｒ¹⁴としてはＣ（Ｏ）Ｏ基、Ｃ（Ｏ）基、フェニレン基が好ましい。
【００３７】
一般式７の化合物を具体的に例示するならば、
ＣＨ₂＝ＣＨＣＨ₂Ｘ、ＣＨ₂＝Ｃ（ＣＨ₃）ＣＨ₂Ｘ、
ＣＨ₂＝ＣＨＣ（Ｈ）（Ｘ）ＣＨ₃、ＣＨ₂＝Ｃ（ＣＨ₃）Ｃ（Ｈ）（Ｘ）ＣＨ₃、
ＣＨ₂＝ＣＨＣ（Ｘ）（ＣＨ₃）₂、ＣＨ₂＝ＣＨＣ（Ｈ）（Ｘ）Ｃ₂Ｈ₅、
ＣＨ₂＝ＣＨＣ（Ｈ）（Ｘ）ＣＨ（ＣＨ₃）₂、
ＣＨ₂＝ＣＨＣ（Ｈ）（Ｘ）Ｃ₆Ｈ₅、ＣＨ₂＝ＣＨＣ（Ｈ）（Ｘ）ＣＨ₂Ｃ₆Ｈ₅、
ＣＨ₂＝ＣＨＣＨ₂Ｃ（Ｈ）（Ｘ）−ＣＯ₂Ｒ、
ＣＨ₂＝ＣＨ（ＣＨ₂）₂Ｃ（Ｈ）（Ｘ）−ＣＯ₂Ｒ、
ＣＨ₂＝ＣＨ（ＣＨ₂）₃Ｃ（Ｈ）（Ｘ）−ＣＯ₂Ｒ、
ＣＨ₂＝ＣＨ（ＣＨ₂）₈Ｃ（Ｈ）（Ｘ）−ＣＯ₂Ｒ、
ＣＨ₂＝ＣＨＣＨ₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₅、
ＣＨ₂＝ＣＨ（ＣＨ₂）₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₅、
ＣＨ₂＝ＣＨ（ＣＨ₂）₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₅、
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、Ｒは炭素数１〜２０のアルキル基、アリール基、アラルキル基）
等を挙げることができる。
【００３８】
アルケニル基を有するハロゲン化スルホニル化合物の具体例を挙げるならば、
ｏ−，ｍ−，ｐ−ＣＨ₂＝ＣＨ−（ＣＨ₂）_n−Ｃ₆Ｈ₄−ＳＯ₂Ｘ、
ｏ−，ｍ−，ｐ−ＣＨ₂＝ＣＨ−（ＣＨ₂）_n−Ｏ−Ｃ₆Ｈ₄−ＳＯ₂Ｘ、
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは０〜２０の整数）等である。
【００３９】
アルケニル基を持つ開始剤の場合、その開始剤のオレフィンも重合末端と反応する可能性があるため、重合条件および添加するオレフィン化合物との反応条件には注意が必要である。具体的な例としては、重合の早い段階でオレフィン化合物を添加することがあげられる。
【００４０】
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制限はないが、例えば一般式８に示す構造を有するものが例示される。
Ｒ⁹Ｒ¹⁰Ｃ（Ｘ）−Ｒ¹¹−Ｒ¹²−Ｃ（Ｈ）（Ｒ¹³）ＣＨ₂−［Ｓｉ（Ｒ¹⁵）_2-b（Ｙ）_bＯ］_m−Ｓｉ（Ｒ¹⁶）_3-a（Ｙ）_a （８）
（式中、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³、は上記に同じ。Ｒ¹⁵、Ｒ¹⁶は、いずれも炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基、または（Ｒ’）₃ＳｉＯ−（Ｒ’は炭素数１〜２０の１価の炭化水素基であって、３個のＲ’は同一であってもよく、異なっていてもよい）で示されるトリオルガノシロキシ基を示し、Ｒ¹⁵またはＲ¹⁶が２個以上存在するとき、それらは同一であってもよく、異なっていてもよい。Ｙは水酸基または加水分解性基を示し、Ｙが２個以上存在するときそれらは同一であってもよく、異なっていてもよい。ａは０，１，２，または３を、また、ｂは０，１，または２を示す。ｍは０〜１９の整数である。ただし、ａ＋ｍｂ≧１であることを満足するものとする。）
上記Ｙで示される加水分解性基としては、特に限定されず、従来公知のものを用いることができ、具体的には、水素、ハロゲン原子、アルコキシ基、アシルオキシ基、ケトキシメート基、アミノ基、アミド基、酸アミド基、アミノオキシ基、メルカプト基、アルケニルオキシ基等が挙げられ、加水分解性がマイルドで取り扱いやすいという点から、アルコキシ基が特に好ましい。
【００４１】
一般式８の化合物を具体的に例示するならば、
ＸＣＨ₂Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＳｉ（ＯＣＨ₃）₃、
ＣＨ₃Ｃ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＳｉ（ＯＣＨ₃）₃、
（ＣＨ₃）₂Ｃ（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＳｉ（ＯＣＨ₃）₃、
ＸＣＨ₂Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＳｉ（ＣＨ₃）（ＯＣＨ₃）₂、
ＣＨ₃Ｃ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＳｉ（ＣＨ₃）（ＯＣＨ₃）₂、
（ＣＨ₃）₂Ｃ（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＳｉ（ＣＨ₃）（ＯＣＨ₃）₂、
（上記の各式において、Ｘは塩素、臭素、ヨウ素、ｎは０〜２０の整数、）
ＸＣＨ₂Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_mＳｉ（ＯＣＨ₃）₃、
Ｈ₃ＣＣ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_mＳｉ（ＯＣＨ₃）₃、
（Ｈ₃Ｃ）₂Ｃ（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_mＳｉ（ＯＣＨ₃）₃、
ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_mＳｉ（ＯＣＨ₃）₃、
ＸＣＨ₂Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_mＳｉ（ＣＨ₃）（ＯＣＨ₃）₂、
Ｈ₃ＣＣ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_m−Ｓｉ（ＣＨ₃）（ＯＣＨ₃）₂、
（Ｈ₃Ｃ）₂Ｃ（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_m−Ｓｉ（ＣＨ₃）（ＯＣＨ₃）₂、
ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂）_nＯ（ＣＨ₂）_m−Ｓｉ（ＣＨ₃）（ＯＣＨ₃）₂、
（上記の各式において、Ｘは塩素、臭素、ヨウ素、ｎは１〜２０の整数、ｍは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ₂−Ｃ₆Ｈ₄−（ＣＨ₂）₂Ｓｉ（ＯＣＨ₃）₃、
ｏ，ｍ，ｐ−ＣＨ₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−（ＣＨ₂）₂Ｓｉ（ＯＣＨ₃）₃、
ｏ，ｍ，ｐ−ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−（ＣＨ₂）₂Ｓｉ（ＯＣＨ₃）₃、
ｏ，ｍ，ｐ−ＸＣＨ₂−Ｃ₆Ｈ₄−（ＣＨ₂）₃Ｓｉ（ＯＣＨ₃）₃、
ｏ，ｍ，ｐ−ＣＨ₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−（ＣＨ₂）₃Ｓｉ（ＯＣＨ₃）₃、
ｏ，ｍ，ｐ−ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−（ＣＨ₂）₃Ｓｉ（ＯＣＨ₃）₃、
ｏ，ｍ，ｐ−ＸＣＨ₂−Ｃ₆Ｈ₄−（ＣＨ₂）₂−Ｏ−（ＣＨ₂）₃Ｓｉ（ＯＣＨ₃）₃、
ｏ，ｍ，ｐ−ＣＨ₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−（ＣＨ₂）₂−Ｏ−（ＣＨ₂）₃Ｓｉ（ＯＣＨ₃）₃、
ｏ，ｍ，ｐ−ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−（ＣＨ₂）₂−Ｏ−（ＣＨ₂）₃Ｓｉ（ＯＣＨ₃）₃、
ｏ，ｍ，ｐ−ＸＣＨ₂−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）₃Ｓｉ（ＯＣＨ₃）₃、
ｏ，ｍ，ｐ−ＣＨ₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）₃Ｓｉ（ＯＣＨ₃）₃、
ｏ，ｍ，ｐ−ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）₃−Ｓｉ（ＯＣＨ₃）₃、
ｏ，ｍ，ｐ−ＸＣＨ₂−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）₂−Ｏ−（ＣＨ₂）₃−Ｓｉ（ＯＣＨ₃）₃、
ｏ，ｍ，ｐ−ＣＨ₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）₂−Ｏ−（ＣＨ₂）₃Ｓｉ（ＯＣＨ₃）₃、
ｏ，ｍ，ｐ−ＣＨ₃ＣＨ₂Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）₂−Ｏ−（ＣＨ₂）₃Ｓｉ（ＯＣＨ₃）₃、
（上記の各式において、Ｘは塩素、臭素、またはヨウ素）
等が挙げられる。
【００４２】
架橋性シリル基を有する有機ハロゲン化物としてはさらに、一般式９で示される構造を有するものが例示される。
（Ｒ¹⁶）_3-a（Ｙ）_aＳｉ−［ＯＳｉ（Ｒ¹⁵）_2-b（Ｙ）_b］_m−ＣＨ₂−Ｃ（Ｈ）（Ｒ¹³）−Ｒ¹²−Ｃ（Ｒ⁹）（Ｘ）−Ｒ¹⁴−Ｒ¹⁰ （９）
（式中、Ｒ⁹、Ｒ¹⁰、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶、ａ、ｂ、ｍ、Ｘ、Ｙは上記に同じ）
このような化合物を具体的に例示するならば、
（ＣＨ₃Ｏ）₃ＳｉＣＨ₂ＣＨ₂Ｃ（Ｈ）（Ｘ）Ｃ₆Ｈ₅、
（ＣＨ₃Ｏ）₂（ＣＨ₃）ＳｉＣＨ₂ＣＨ₂Ｃ（Ｈ）（Ｘ）Ｃ₆Ｈ₅、
（ＣＨ₃Ｏ）₃Ｓｉ（ＣＨ₂）₂Ｃ（Ｈ）（Ｘ）−ＣＯ₂Ｒ¹⁷、
（ＣＨ₃Ｏ）₂（ＣＨ₃）Ｓｉ（ＣＨ₂）₂Ｃ（Ｈ）（Ｘ）−ＣＯ₂Ｒ¹⁷、
（ＣＨ₃Ｏ）₃Ｓｉ（ＣＨ₂）₃Ｃ（Ｈ）（Ｘ）−ＣＯ₂Ｒ¹⁷、
（ＣＨ₃Ｏ）₂（ＣＨ₃）Ｓｉ（ＣＨ₂）₃Ｃ（Ｈ）（Ｘ）−ＣＯ₂Ｒ¹⁷、
（ＣＨ₃Ｏ）₃Ｓｉ（ＣＨ₂）₄Ｃ（Ｈ）（Ｘ）−ＣＯ₂Ｒ¹⁷、
（ＣＨ₃Ｏ）₂（ＣＨ₃）Ｓｉ（ＣＨ₂）₄Ｃ（Ｈ）（Ｘ）−ＣＯ₂Ｒ¹⁷、
（ＣＨ₃Ｏ）₃Ｓｉ（ＣＨ₂）₉Ｃ（Ｈ）（Ｘ）−ＣＯ₂Ｒ¹⁷、
（ＣＨ₃Ｏ）₂（ＣＨ₃）Ｓｉ（ＣＨ₂）₉Ｃ（Ｈ）（Ｘ）−ＣＯ₂Ｒ¹⁷、
（ＣＨ₃Ｏ）₃Ｓｉ（ＣＨ₂）₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₅、
（ＣＨ₃Ｏ）₂（ＣＨ₃）Ｓｉ（ＣＨ₂）₃Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₅、
（ＣＨ₃Ｏ）₃Ｓｉ（ＣＨ₂）₄Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₅、
（ＣＨ₃Ｏ）₂（ＣＨ₃）Ｓｉ（ＣＨ₂）₄Ｃ（Ｈ）（Ｘ）−Ｃ₆Ｈ₅、
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、Ｒ¹⁷は炭素数１〜２０のアルキル基、アリール基、アラルキル基）
等が挙げられる。
【００４３】
ヒドロキシル基を持つ有機ハロゲン化物、またはハロゲン化スルホニル化合物としては特に制限はないが、下記のようなものが例示される。
ＨＯ−（ＣＨ₂）_n−ＯＣ（Ｏ）Ｃ（Ｈ）（Ｒ¹⁸）（Ｘ）
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、Ｒ¹⁷は水素原子または炭素数１〜２０のアルキル基、アリール基、アラルキル基、ｎは１〜２０の整数）
アミノ基を持つ有機ハロゲン化物、またはハロゲン化スルホニル化合物としては特に制限はないが、下記のようなものが例示される。
Ｈ₂Ｎ−（ＣＨ₂）_n−ＯＣ（Ｏ）Ｃ（Ｈ）（Ｒ¹⁷）（Ｘ）
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、Ｒ¹⁷は水素原子または炭素数１〜２０のアルキル基、アリール基、アラルキル基、ｎは１〜２０の整数）
エポキシ基を持つ有機ハロゲン化物、またはハロゲン化スルホニル化合物としては特に制限はないが、下記のようなものが例示される。
【００４４】
【化１３】

（上記の各式において、Ｘは塩素、臭素、またはヨウ素、Ｒ¹⁷は水素原子または炭素数１〜２０のアルキル基、アリール基、アラルキル基、ｎは１〜２０の整数）
本発明によりオレフィン末端構造を１分子内に２個以上有する重合体を得るためには、２つ以上の開始点を持つ有機ハロゲン化物、またはハロゲン化スルホニル化合物が開始剤として用いられる。具体的に例示するならば、
【００４５】
【化１４】

【００４６】
【化１５】

等があげられる。
《重合条件》
この重合において用いられる重合性オレフィン単量体としては特に制約はなく、既に述べた各種のものを用いることができる。また、ここに示されている重合系はリビング重合であるため、重合性単量体の逐次添加によりブロック共重合体を製造することも可能である。
【００４７】
重合は無溶剤または各種の溶剤中で行うことができる。これらは特に限定されないが、例示するならば、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、単独又は２種以上を混合して用いることができる。また、エマルジョン系もしくは超臨界流体ＣＯ₂を媒体とする系においても重合を行うことができる。これらの中では、触媒安定性向上の効果などから、ニトリル系溶媒が好ましく、アセトニトリルがより好ましい。
【００４８】
また、重合は室温〜２００℃の範囲で行うことができ、好ましくは５０〜１５０℃である。
【００４９】
このような重合の最中または終点（原子移動ラジカル重合によりラジカル重合性単量体の８０重量％が消費された後）において、重合性の低いアルケニル基を有するオレフィン化合物（Ｉ）を添加すると、末端にほぼ１つずつ付加し、その結果として、そのアルケニル化合物の有する官能基が重合体の末端に導入される。末端にアルケニル基を導入するためには重合性の低いアルケニル基を２つ持つ化合物を過剰量添加することが好ましい。
【００５０】
なお、本発明においては、原子移動ラジカル重合によりラジカル重合性単量体の８０重量％が消費された後に、オレフィン化合物（Ｉ）を添加する。ラジカル重合性単量体の８０重量％が消費される前にオレフィン化合物（Ｉ）を添加すると、ビニル系重合体の分子量が設定値よりも小さくなってしまう傾向がある。
オレフィン化合物（Ｉ）は、ラジカル重合性単量体の８０〜９９．９重量％が消費された時点で加えるのが好ましく、８５〜９９重量％が消費された時点で加えるのがより好ましい。なお上記ラジカル重合性単量体の量は、いずれも最終的に重合溶液に仕込んだ量のことである。
《オレフィン化合物（Ｉ）》
重合性の低いアルケニル基を持つオレフィン化合物としては一般式１に示される化合物から選ばれる。
一般式１：
【００５１】
【化１６】

｛上の式中、Ｒ³は、水酸基、アミノ基、エポキシ基、カルボン酸基、エステル基、エーテル基、アミド基、シリル基、あるいは一般式２：
【００５２】
【化１７】

（Ｒ⁴は水素原子あるいはメチル基を表す）で表される基、あるいは重合性のオレフィンを含まない炭素数１〜２０の有機基であり、Ｒ¹は炭素数１〜２０のアルキル基あるいは一般式３：
【００５３】
【化１８】

（上の式中、Ｒ⁵は酸素原子、窒素原子を有してもよい炭素数１〜２０の有機基、Ｒ⁶は水素原子あるいはメチル基であり同じでも異なっていてもよい）の構造を持つ基であり、且つ、Ｒ²は水素原子あるいはメチル基である｝
その内、アルケニル基を導入するために用いられる重合性の低いアルケニル基を２つ持つ化合物としては一般式４に示される化合物から選ばれる。
【００５４】
【化１９】

｛上の式中、Ｒ¹は炭素数１〜２０のアルキル基あるいは一般式３：
【００５５】
【化２０】

（上の式中、Ｒ⁵は酸素原子、窒素原子を有してもよい炭素数１〜２０の有機基、Ｒ⁶は水素原子あるいはメチル基であり同じでも異なっていてもよい）
の構造を持つ基であり、且つ、Ｒ²、Ｒ⁴は、水素原子あるいはメチル基である｝
Ｒ²、Ｒ³については水素原子あるいはメチル基であるが、水素原子が好ましい。Ｒ¹が炭素数１〜２０のアルキル基である場合、その構造に制約はないが、一般式５に示す化合物が例示される。
【００５６】
【化２１】

原料入手の容易さから、ｎは２、４、６のものが好ましい。
【００５７】
一般式１において、Ｒ¹の具体例としては、
−（ＣＨ₂）_n− （ｎは１〜２０の整数）、
−ＣＨ（ＣＨ₃）−、 −ＣＨ（ＣＨ₂ＣＨ₃）−、−Ｃ（ＣＨ₃）₂−、 −Ｃ（ＣＨ₃）（ＣＨ₂ＣＨ₃）−、−Ｃ（ＣＨ₂ＣＨ₃）₂−、 −ＣＨ₂ＣＨ（ＣＨ₃）−、
−（ＣＨ₂）_n−Ｏ−ＣＨ₂− （ｎは１〜１９の整数）、
−ＣＨ（ＣＨ₃）−Ｏ−ＣＨ₂−、−ＣＨ（ＣＨ₂ＣＨ₃）−Ｏ−ＣＨ₂−、 −Ｃ（ＣＨ₃）₂−Ｏ−ＣＨ₂−、−Ｃ（ＣＨ₃）（ＣＨ₂ＣＨ₃）−Ｏ−ＣＨ₂−、−Ｃ（ＣＨ₂ＣＨ₃）₂−Ｏ−ＣＨ₂−、
−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_m−
（ｍ、ｎは１〜１９の整数、ただし２≦ｍ＋ｎ≦２０）、
−（ＣＨ₂）_n−Ｃ（Ｏ）Ｏ−（ＣＨ₂）_m−
（ｍ、ｎは１〜１９の整数、ただし２≦ｍ＋ｎ≦２０）、
−（ＣＨ₂）_n−ＯＣ（Ｏ）−（ＣＨ₂）_m−Ｃ（Ｏ）Ｏ−（ＣＨ₂）_l−、
（ｌは０〜１８の整数、ｍ，ｎは１〜１７の整数、ただし２≦ｌ＋ｍ＋ｎ≦１８）、
−（ＣＨ₂）_n−ｏ−，ｍ−，ｐ−Ｃ₆Ｈ₄−、
−（ＣＨ₂）_n−ｏ−，ｍ−，ｐ−Ｃ₆Ｈ₄−（ＣＨ₂）_m−、
（ｍは０〜１３の整数、ｎは１〜１４の整数、ただし１≦ｍ＋ｎ≦１４）、
−（ＣＨ₂）_n−ｏ−，ｍ−，ｐ−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）_m−、
（ｍは０〜１３の整数、ｎは１〜１４の整数、ただし１≦ｍ＋ｎ≦１４）、
−（ＣＨ₂）_n−ｏ−，ｍ−，ｐ−Ｃ₆Ｈ₄−Ｏ−ＣＨ（ＣＨ₃）−、
（ｎは１〜１２の整数）、
−（ＣＨ₂）_n−ｏ−，ｍ−，ｐ−Ｃ₆Ｈ₄−Ｏ−ＣＨ（ＣＨ₃）₂−、
（ｎは１〜１１の整数）、
−（ＣＨ₂）_n−ｏ−，ｍ−，ｐ−Ｃ₆Ｈ₄−Ｃ（Ｏ）Ｏ−（ＣＨ₂）_m−、
（ｍ，ｎは１〜１２の整数、ただし２≦ｍ＋ｎ≦１３）、
−（ＣＨ₂）_n−ＯＣ（Ｏ）−ｏ−，ｍ−，ｐ−Ｃ₆Ｈ₄−Ｃ（Ｏ）Ｏ−（ＣＨ₂）_m−、
（ｍ，ｎは１〜１１の整数、ただし２≦ｍ＋ｎ≦１２）、
−（ＣＨ₂）_n−ｏ−，ｍ−，ｐ−Ｃ₆Ｈ₄−ＯＣ（Ｏ）−（ＣＨ₂）_m−、
（ｍ，ｎは１〜１２の整数、ただし２≦ｍ＋ｎ≦１３）、
−（ＣＨ₂）_n−Ｃ（Ｏ）Ｏ−ｏ−，ｍ−，ｐ−Ｃ₆Ｈ₄−（ＣＨ₂）_m−、
（ｍ，ｎは１〜１１の整数、ただし２≦ｍ＋ｎ≦１２）、
等が挙げられる。
Ｒ³としては、以下のような基が例示される。
【００５８】
【化２２】

（式中、Ｒ¹⁸、Ｒ¹⁹は、いずれも炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基、または（Ｒ’）₃ＳｉＯ−（Ｒ’は炭素数１〜２０の１価の炭化水素基であって、３個のＲ’は同一であってもよく、異なっていてもよい）で示されるトリオルガノシロキシ基を示し、Ｒ¹⁸またはＲ¹⁹が２個以上存在するとき、それらは同一であってもよく、異なっていてもよい。Ｙは水酸基または加水分解性基を示し、Ｙが２個以上存在するときそれらは同一であってもよく、異なっていてもよい。ａは０，１，２，または３を、また、ｂは０，１，または２を示す。ｍは０〜１９の整数である。ただし、ａ＋ｍｂ≧１であることを満足するものとする。Ｒ²⁰は炭素数１〜２０の炭化水素基である。）
Ｒ²⁰としては、具体的には以下のような基が例示される。
−（ＣＨ₂）_n−ＣＨ₃、
−ＣＨ（ＣＨ₃）−（ＣＨ₂）_n−ＣＨ₃、
−ＣＨ（ＣＨ₂ＣＨ₃）−（ＣＨ₂）_n−ＣＨ₃、
−ＣＨ（ＣＨ₂ＣＨ₃）₂、
−Ｃ（ＣＨ₃）₂−（ＣＨ₂）_n−ＣＨ₃、
−Ｃ（ＣＨ₃）（ＣＨ₂ＣＨ₃）−（ＣＨ₂）_n−ＣＨ₃、
−Ｃ₆Ｈ₅
−Ｃ₆Ｈ₅（ＣＨ₃）、
−Ｃ₆Ｈ₄（ＣＨ₃）₂、
−（ＣＨ₂）_n−Ｃ₆Ｈ₅、
−（ＣＨ₂）_n−Ｃ₆Ｈ₄（ＣＨ₃）、
−（ＣＨ₂）_n−Ｃ₆Ｈ₃（ＣＨ₃）₂、
（ｎは０以上の整数で、各基の合計炭素数は２０以下）
シリル基としては、限定はされないが、上記式においてｍ＝０のものが好ましい。
【００５９】
アミノ基、水酸基あるいはカルボン酸基を持つ化合物を重合末端に反応させる場合には、そのまま反応させても構わないが、それらの基が、重合末端あるいは触媒に影響を与える場合があるので、その場合には保護基をつけた化合物を用いても構わない。保護基としては、アセチル基、シリル基、アルコキシ基などが挙げられる。
【００６０】
これらの官能基を導入するために用いられる化合物を添加する量は、特に限定されない。これらの化合物のアルケニル基の反応性はあまり高くないため、反応速度を高めるためには添加量を増やすことが好ましく、一方、コストを低減するためには添加量は成長末端に対して等量に近い方が好ましく、状況により適正化する必要がある。
【００６１】
また、末端にアルケニル基を導入するために重合性の低いアルケニル基を２つ以上持つ化合物を添加する量は、重合成長末端に対して過剰量であることが好ましい。等量あるいは末端より少量の場合、２つのオレフィンの両方ともが反応し、重合末端をカップリングしてしまう可能性がある。２つのオレフィンの反応性が等しい化合物の場合、カップリングの起こる確率は、過剰に添加する量に応じて統計的に決まってくる。よって、好ましくは１．５倍以上、さらに好ましくは３倍以上、特に好ましくは５倍以上である。
《化合物（ＩＩ）》
重合性の低いアルケニル基を有するオレフィン化合物（Ｉ）を添加するとき、オレフィン化合物（Ｉ）の種類によっては、反応系の極性が低下して、触媒活性が不十分になる場合がある。この場合、オレフィン化合物（Ｉ）より誘電率の高い化合物（ＩＩ）を添加することで反応系の極性を上げることができる。化合物（ＩＩ）としては特に限定されないが、例示するならば、ベンゼン、トルエン等の炭化水素系化合物；ジエチルエーテル、テトラヒドロフラン等のエーテル系化合物；塩化メチレン、クロロホルム等のハロゲン化炭化水素系化合物；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化合物；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化合物；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化合物；酢酸エチル、酢酸ブチル等のエステル系化合物、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化合物等が挙げられる。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、また重合に使用した溶媒と同じであっても良いし、異なっていても良いが、反応後の回収の容易さを考慮すると、同じであるほうが好ましい。化合物（ＩＩ）の誘電率は、オレフィン化合物（Ｉ）より３以上高いことが好ましく、５以上高いことがより好ましく、１０以上高いことがさらに好ましい。化合物（ＩＩ）の誘電率は高いほうが、より極性改善の効果が見込める。なおここで誘電率は２０℃での値である。またこれらの内では、触媒安定性向上の効果等から、ニトリル系化合物が好ましく、アセトニトリルがより好ましい。化合物（ＩＩ）の使用量は、ラジカル重合性単量体１００重量部に対して１〜１０００重量部であるが、３〜１０００重量部であることが好ましく、５〜５００重量部であることがより好ましく、１０〜１００重量部であることがさらに好ましい。あるいは、化合物（ＩＩ）の使用量は、オレフィン化合物（Ｉ）１００重量部に対して１〜１００００重量部であることが好ましく、１０〜１０００重量部であることがより好ましい。化合物（ＩＩ）の使用量が少ないと極性向上の効果が発揮されないことがあり、また多いと、重合後、重合体からの回収が困難になる恐れがある。
【００６２】
なお、本発明においては、原子移動ラジカル重合によりラジカル重合性単量体の８０重量％が消費された後に、化合物（ＩＩ）を添加する。ラジカル重合性単量体の８０重量％が消費される前に化合物（ＩＩ）を添加すると、ビニル系重合体の分子量が設定値よりも小さくなってしまう傾向がある。
化合物（ＩＩ）は、ラジカル重合性単量体の８０〜９９．９重量％が消費された時点で加えるのが好ましく、８５〜９９重量％が消費された時点で加えるのがより好ましい。なお上記ラジカル重合性単量体の量は、いずれも最終的に重合溶液に仕込んだ量のことである。
《末端構造》
重合の最中または終点（すなわち原子移動ラジカル重合によりラジカル重合性単量体の８０％が消費された後）において、重合性の低いアルケニル基を有するオレフィン化合物（Ｉ）を添加すると、末端にほぼ１つずつ付加し、その結果として、そのアルケニル化合物の有する官能基が重合体の末端に導入される。このときの末端構造は一般式１０で示される。この末端構造を有するラジカル重合性単量体の重合体は、ヘテロ原子を介することなく、直接、炭素−炭素結合のみにより、また、末端基が重合体の末端一つにつきほぼ一つ結合していることが特徴である。
【００６３】
【化２３】

｛上の式中、Ｒ³は、水酸基、アミノ基、エポキシ基、カルボン酸基、エステル基、エーテル基、アミド基、シリル基、あるいは一般式２：
【００６４】
【化２４】

（Ｒ⁴は水素原子あるいはメチル基を表す）で表される基、あるいは重合性のオレフィンを含まない炭素数１〜２０の有機基であり、Ｒ¹は炭素数１〜２０のアルキル基、あるいは一般式３：
【００６５】
【化２５】

（上の式中、Ｒ⁵は酸素原子、窒素原子あるいは炭素数１〜２０の有機基、Ｒ⁶は水素原子あるいはメチル基であり同じでも異なっていてもよい）
の構造を持つ基であり、且つ、Ｒ²は水素原子あるいはメチル基であり、Ｘはハロゲン基、ニトロキシド基、スルフィド基あるいはコバルトポルフィリン錯体である｝一般式１０において、Ｒ¹の具体例としては、
−（ＣＨ₂）_n−（ｎは１〜２０の整数）、
−ＣＨ（ＣＨ₃）−、−ＣＨ（ＣＨ₂ＣＨ₃）−、−Ｃ（ＣＨ₃）₂−、−Ｃ（ＣＨ₃）（ＣＨ₂ＣＨ₃）−、−Ｃ（ＣＨ₂ＣＨ₃）₂−、−ＣＨ₂ＣＨ（ＣＨ₃）−、−（ＣＨ₂）_n−Ｏ−ＣＨ₂−（ｎは１〜１９の整数）、
−ＣＨ（ＣＨ₃）−Ｏ−ＣＨ₂−、−ＣＨ（ＣＨ₂ＣＨ₃）−Ｏ−ＣＨ₂−、−Ｃ（ＣＨ₃）₂−Ｏ−ＣＨ₂−、−Ｃ（ＣＨ₃）（ＣＨ₂ＣＨ₃）−Ｏ−ＣＨ₂−、−Ｃ（ＣＨ₂ＣＨ₃）₂−Ｏ−ＣＨ₂−、
−（ＣＨ₂）_n−Ｏ−（ＣＨ₂）_m−
（ｍ、ｎは１〜１９の整数、ただし２≦ｍ＋ｎ≦２０）、
−（ＣＨ₂）_n−Ｃ（Ｏ）Ｏ−（ＣＨ₂）_m−
（ｍ、ｎは１〜１９の整数、ただし２≦ｍ＋ｎ≦２０）、
−（ＣＨ₂）_n−ＯＣ（Ｏ）−（ＣＨ₂）_m−Ｃ（Ｏ）Ｏ−（ＣＨ₂）_l−、
（ｌは０〜１８の整数、ｍ，ｎは１〜１７の整数、ただし２≦ｌ＋ｍ＋ｎ≦１８）、
−（ＣＨ₂）_n−ｏ−，ｍ−，ｐ−Ｃ₆Ｈ₄−、
−（ＣＨ₂）_n−ｏ−，ｍ−，ｐ−Ｃ₆Ｈ₄−（ＣＨ₂）_m−、
（ｍは０〜１３の整数、ｎは１〜１４の整数、ただし１≦ｍ＋ｎ≦１４）、
−（ＣＨ₂）_n−ｏ−，ｍ−，ｐ−Ｃ₆Ｈ₄−Ｏ−（ＣＨ₂）_m−、
（ｍは０〜１３の整数、ｎは１〜１４の整数、ただし１≦ｍ＋ｎ≦１４）、
−（ＣＨ₂）_n−ｏ−，ｍ−，ｐ−Ｃ₆Ｈ₄−Ｏ−ＣＨ（ＣＨ₃）−、
（ｎは１〜１２の整数）、
−（ＣＨ₂）_n−ｏ−，ｍ−，ｐ−Ｃ₆Ｈ₄−Ｏ−ＣＨ（ＣＨ₃）₂−、
（ｎは１〜１１の整数）、
−（ＣＨ₂）_n−ｏ−，ｍ−，ｐ−Ｃ₆Ｈ₄−Ｃ（Ｏ）Ｏ−（ＣＨ₂）_m−、
（ｍ，ｎは１〜１２の整数、ただし２≦ｍ＋ｎ≦１３）、
−（ＣＨ₂）_n−ＯＣ（Ｏ）−ｏ−，ｍ−，ｐ−Ｃ₆Ｈ₄−Ｃ（Ｏ）Ｏ−（ＣＨ₂）_m−、
（ｍ，ｎは１〜１１の整数、ただし２≦ｍ＋ｎ≦１２）、
−（ＣＨ₂）_n−ｏ−，ｍ−，ｐ−Ｃ₆Ｈ₄−ＯＣ（Ｏ）−（ＣＨ₂）_m−、
（ｍ，ｎは１〜１２の整数、ただし２≦ｍ＋ｎ≦１３）、
−（ＣＨ₂）_n−Ｃ（Ｏ）Ｏ−ｏ−，ｍ−，ｐ−Ｃ₆Ｈ₄−（ＣＨ₂）_m−、
（ｍ，ｎは１〜１１の整数、ただし２≦ｍ＋ｎ≦１２）、
等が挙げられる。Ｒ³としては、以下のような基が例示される。
【００６６】
【化２６】

式中、Ｒ¹⁸、Ｒ¹⁹は、いずれも炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基、または（Ｒ’）₃ＳｉＯ−（Ｒ’は炭素数１〜２０の１価の炭化水素基であって、３個のＲ’は同一であってもよく、異なっていてもよい）で示されるトリオルガノシロキシ基を示し、Ｒ¹⁸またはＲ¹⁹が２個以上存在するとき、それらは同一であってもよく、異なっていてもよい。Ｙは水酸基または加水分解性基を示し、Ｙが２個以上存在するときそれらは同一であってもよく、異なっていてもよい。ａは０，１，２，または３を、また、ｂは０，１，または２を示す。ｍは０〜１９の整数である。ただし、ａ＋ｍｂ≧１であることを満足するものとする。
【００６７】
Ｒ²⁰は炭素数１〜２０の炭化水素基であり、具体的には以下のような基が例示される。
−（ＣＨ₂）_n−ＣＨ₃、
−ＣＨ（ＣＨ₃）−（ＣＨ₂）_n−ＣＨ₃、
−ＣＨ（ＣＨ₂ＣＨ₃）−（ＣＨ₂）_n−ＣＨ₃、
−ＣＨ（ＣＨ₂ＣＨ₃）₂、
−Ｃ（ＣＨ₃）₂−（ＣＨ₂）_n−ＣＨ₃、
−Ｃ（ＣＨ₃）（ＣＨ₂ＣＨ₃）−（ＣＨ₂）_n−ＣＨ₃、
−Ｃ₆Ｈ₅、
−Ｃ₆Ｈ₅（ＣＨ₃）、
−Ｃ₆Ｈ₄（ＣＨ₃）₂、
−（ＣＨ₂）_n−Ｃ₆Ｈ₅、
−（ＣＨ₂）_n−Ｃ₆Ｈ₄（ＣＨ₃）、
−（ＣＨ₂）_n−Ｃ₆Ｈ₃（ＣＨ₃）₂、
（ｎは０以上の整数で、各基の合計炭素数は２０以下）
一般式１０において、Ｒ²は水素原子あるいはメチル基であるが、水素原子が好ましい。Ｘについては、ハロゲン基、ニトロキシド基、スルフィド基あるいはコバルトポルフィリン錯体であるが、製造の容易さからハロゲン基が、そして特にブロモ基が好ましい。
【００６８】
アルケニル基が末端に導入されている場合において、Ｒ¹が炭素数１〜２０のアルキル基である場合、その構造に制約はないが、以下のものが例示される。
【００６９】
【化２７】

原料入手の容易さから、ｎは２、４、６のものが好ましい。
【００７０】
重合体１分子中に含まれる末端基の数には特に制約はないが、硬化性組成物などに用いられる場合には、０．５〜５個含まれることが好ましく、１〜３個含まれることがより好ましく、１．５〜２．５個含まれることがさらに好ましい。
【００７１】
本発明で得られる重合体は、分子量分布、すなわち、ゲルパーミエーションクロマトグラフィーで測定した重量平均分子量と数平均分子量の比が好ましくは１．８以下であり、さらに好ましくは１．６以下であり、最も好ましくは１．３以下である。
【００７２】
本発明で得られる重合体の数平均分子量は５００〜１０００００の範囲が好ましく、３０００〜５００００がさらに好ましい。分子量が５００以下であると、（メタ）アクリル系重合体の本来の特性が発現されにくく、また、１０００００以上であると、ハンドリングが困難になる。
【００７３】
本発明において製造された重合体は、その導入された官能基をそのまま利用する、あるいは更なる変換反応を行って別の官能基にして利用される。具体的には、アルケニル基は、架橋性シリル基を持つヒドロシリル化合物によるヒドロシリル化反応により、架橋性シリル基に変換される。末端にアルケニル基を有するビニル系重合体としては、既に説明した方法により得られるものをすべて好適に用いることができる。
【００７４】
ヒドロシラン化合物としては特に制限はないが、代表的なものを示すと、一般式１２
Ｈ−［Ｓｉ（Ｒ²¹）_2-b（Ｙ）_bＯ］_m・Ｓｉ（Ｒ²²）_3-a（Ｙ）_a （１２）
（式中、Ｒ²¹、Ｒ²²は、いずれも炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基、または（Ｒ’）₃ＳｉＯ−（Ｒ’は炭素数１〜２０の１価の炭化水素基であって、３個のＲ’は同一であってもよく、異なっていてもよい）で示されるトリオルガノシロキシ基を示し、Ｒ²⁰またはＲ²²が２個以上存在するとき、それらは同一であってもよく、異なっていてもよい。Ｙは水酸基または加水分解性基を示し、Ｙが２個以上存在するときそれらは同一であってもよく、異なっていてもよい。ａは０，１，２，または３を、また、ｂは０，１，または２を示す。ｍは０〜１９の整数である。ただし、ａ＋ｍｂ≧１であることを満足するものとする）
で表される化合物が例示される。
【００７５】
上記Ｙで示される加水分解性基としては、特に限定されず、従来公知のものを用いることができ、具体的には、水素、ハロゲン原子、アルコキシ基、アシルオキシ基、ケトキシメート基、アミノ基、アミド基、酸アミド基、アミノオキシ基、メルカプト基、アルケニルオキシ基等が挙げられ、加水分解性がマイルドで取り扱いやすいという点から、アルコキシ基が特に好ましい。該加水分解性基や水酸基は１個のケイ素原子に１〜３個の範囲で結合することができ、ａ＋ｍｂ、すなわち、加水分解性基の総和は、１〜５の範囲が好ましい。加水分解性基や水酸基が反応性ケイ素基中に２個以上結合するときは、それらは同一であっても、異なっていてもよい。架橋性ケイ素化合物を構成するケイ素原子は、１個でもよく、２個以上であってもよいが、シロキサン結合により連結されたケイ素原子の場合には２０個程度まであってもよい。
【００７６】
一般式１２におけるＲ²¹、Ｒ²²の具体例としては、例えば、メチル基やエチル基などのアルキル基、シクロヘキシル基等のシクロアルキル基、フェニル基などのアリール基、ベンジル基などのアラルキル基、Ｒ’がメチル基やフェニル基等である（Ｒ’）₃ＳｉＯ−で示されるトリオルガノシリル基等が挙げられる。
【００７７】
これらヒドロシラン化合物の中でも、特に一般式１３
Ｈ−Ｓｉ（Ｒ²²）_3-a（Ｙ）_a （１３）
（式中、Ｒ²⁰、Ｙ、ａは前記と同じ。）で表される架橋性基を有するヒドロシラン化合物が、入手容易な点から好ましい。一般式１２または１３で示される架橋性基を有するヒドロシラン化合物の具体例としては、
ＨＳｉＣｌ₃、 ＨＳｉ（ＣＨ₃）Ｃｌ₂、 ＨＳｉ（ＣＨ₃）₂Ｃｌ、ＨＳｉ（ＯＣＨ₃）₃、 ＨＳｉ（ＣＨ₃）（ＯＣＨ₃）₂、 ＨＳｉ（ＣＨ₃）₂ＯＣＨ₃、ＨＳｉ（ＯＣ₂Ｈ₅）₃、 ＨＳｉ（ＣＨ₃）（ＯＣ₂Ｈ₅）₂、
ＨＳｉ（ＣＨ₃）₂ＯＣ₂Ｈ₅、 ＨＳｉ（ＯＣ₃Ｈ₇）₃、
ＨＳｉ（Ｃ₂Ｈ₅）（ＯＣＨ₃）₂、 ＨＳｉ（Ｃ₂Ｈ₅）₂ＯＣＨ₃、
ＨＳｉ（Ｃ₆Ｈ₅）（ＯＣＨ₃）₂、 ＨＳｉ（Ｃ₆Ｈ₅）₂（ＯＣＨ₃）、
ＨＳｉ（ＣＨ₃）（ＯＣ（Ｏ）ＣＨ₃）₂、
ＨＳｉ（ＣＨ₃）₂Ｏ−［Ｓｉ（ＣＨ₃）₂Ｏ］₂・Ｓｉ（ＣＨ₃）（ＯＣＨ₃）₂、
ＨＳｉ（ＣＨ₃）［Ｏ−Ｎ＝Ｃ（ＣＨ₃）₂］₂
（ただし、上記化学式中、Ｃ₆Ｈ₅はフェニル基を示す）
等が挙げられる。
【００７８】
このような架橋性シリル基を有するヒドロシラン化合物を、末端にアルケニル基を有する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。このようなヒドロシリル化触媒としては、有機過酸化物やアゾ化合物等のラジカル開始剤、および遷移金属触媒が挙げられる。
【００７９】
ラジカル開始剤としては特に制限はなく各種のものを用いることができる。例示するならば、ジ−ｔ−ブチルペルオキシド、２，５−ジメチル−２，５−ジ（ｔ−ブチルペルオキシ）ヘキサン、２，５−ジメチル−２，５−ジ（ｔ−ブチルペルオキシ）−３−ヘキシン、ジクミルペルオキシド、ｔ−ブチルクミルペルオキシド、α，α’−ビス（ｔ−ブチルペルオキシ）イソプロピルベンゼンのようなジアルキルペルオキシド、ベンゾイルペルオキシド、ｐ−クロロベンゾイルペルオキシド、ｍ−クロロベンゾイルペルオキシド、２，４−ジクロロベンゾイルペルオキシド、ラウロイルペルオキシドのようなジアシルペルオキシド、過安息香酸−ｔ−ブチルのような過酸エステル、過ジ炭酸ジイソプロピル、過ジ炭酸ジ−２−エチルヘキシルのようなペルオキシジカ−ボネ−ト、１，１−ジ（ｔ−ブチルペルオキシ）シクロヘキサン、１，１−ジ（ｔ−ブチルペルオキシ）−３，３，５−トリメチルシクロヘキサンのようなペルオキシケタ−ル等が挙げられる。
【００８０】
また、遷移金属触媒としては、例えば、白金単体、アルミナ、シリカ、カ−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−ル、アルデヒド、ケトン等との錯体、白金−オレフィン錯体、白金（０）−ジビニルテトラメチルジシロキサン錯体が挙げられる。白金化合物以外の触媒の例としては、ＲｈＣｌ（ＰＰｈ₃）₃，ＲｈＣｌ₃，ＲｕＣｌ₃，ＩｒＣｌ₃，ＦｅＣｌ₃，ＡｌＣｌ₃，ＰｄＣｌ₂・Ｈ₂Ｏ，ＮｉＣｌ₂，ＴｉＣｌ₄等が挙げられる。これらの触媒は単独で用いてもよく、２種類以上を併用してもかまわない。触媒量としては特に制限はないが、（Ａ）成分のアルケニル基１ｍｏｌに対し、１０^-1〜１０^-8ｍｏｌの範囲で用いるのが良く、好ましくは１０^-3〜１０^-6ｍｏｌの範囲で用いるのがよい。１０^-8ｍｏｌより少ないと硬化が十分に進行しない場合があり、またヒドロシリル化触媒は高価であるので１０^-1ｍｏｌ以上用いないのが好ましい。
【００８１】
アリルアルコールあるいはメタリルアルコールを重合末端に反応させた場合には、ハロゲン基などの活性基とヒドロキシル基が隣り合わせた炭素原子上にある末端が生成する。この末端は、環化させてエポキシ基に変換することができる。この環化反応を行う方法は特に限定されないが、アルカリ性化合物を反応させるのが好ましい。アルカリ性化合物としては、特に限定されないが、ＫＯＨ、ＮａＯＨ、Ｃａ（ＯＨ）₂や、アンモニア、各種アミン類などが挙げられる。
【００８２】
末端の水酸基は、アリルクロライドやアリルブロマイドとのアルカリ性化合物を用いた縮合反応によりアルケニル基に変換される。また、エピクロロヒドリンを用いた同様の反応によりエポキシ基に変換される。
【００８３】
また、末端の水酸基あるいはアミノ基は、水酸基あるいはアミノ基と反応する官能基と架橋性シリル基を併せ持つ化合物との反応により、架橋性シリル基にも変換できる。水酸基あるいはアミノ基と反応する官能基としては、例えばハロゲン、カルボン酸ハライド、カルボン酸、イソシアネート基等が挙げられるが、化合物の入手容易性や、水酸基と反応させる際の反応条件がマイルドで、架橋性シリル基の分解が起こりにくい点で、イソシアネート基が好ましい。
【００８４】
このような、架橋性シリル基を有するイソシアネート系化合物としては特に制限はなく、公知のものを使用することができる。具体例を示すならば、
（ＣＨ₃Ｏ）₃Ｓｉ−（ＣＨ₂）_n−ＮＣＯ、
（ＣＨ₃Ｏ）₂（ＣＨ₃）Ｓｉ−（ＣＨ₂）_n−ＮＣＯ、
（Ｃ₂Ｈ₅Ｏ）₃Ｓｉ−（ＣＨ₂）_n−ＮＣＯ、
（Ｃ₂Ｈ₅Ｏ）₂（ＣＨ₃）Ｓｉ−（ＣＨ₂）_n−ＮＣＯ、
（ｉ−Ｃ₃Ｈ₇Ｏ）₃Ｓｉ−（ＣＨ₂）_n−ＮＣＯ、
（ｉ−Ｃ₃Ｈ₇Ｏ）₂（ＣＨ₃）Ｓｉ−（ＣＨ₂）_n−ＮＣＯ、
（ＣＨ₃Ｏ）₃Ｓｉ−（ＣＨ₂）_n−ＮＨ−（ＣＨ₂）_m−ＮＣＯ、
（ＣＨ₃Ｏ）₂（ＣＨ₃）Ｓｉ−（ＣＨ₂）_n−ＮＨ−（ＣＨ₂）_m−ＮＣＯ、
（Ｃ₂Ｈ₅Ｏ）₃Ｓｉ−（ＣＨ₂）_n−ＮＨ−（ＣＨ₂）_m−ＮＣＯ、
（Ｃ₂Ｈ₅Ｏ）₂（ＣＨ₃）Ｓｉ−（ＣＨ₂）_n−ＮＨ−（ＣＨ₂）_m−ＮＣＯ、
（ｉ−Ｃ₃Ｈ₇Ｏ）₃Ｓｉ−（ＣＨ₂）_n−ＮＨ−（ＣＨ₂）_m−ＮＣＯ、
（ｉ−Ｃ₃Ｈ₇Ｏ）₂（ＣＨ₃）Ｓｉ−（ＣＨ₂）_n−ＮＨ−（ＣＨ₂）_m−ＮＣＯ、
（上記式中、ｎ、ｍは１〜２０の整数）
等が挙げられる。
【００８５】
末端に水酸基を有する（メタ）アクリル系重合体と、架橋性シリル基を有するイソシアネート化合物の反応は、無溶媒、または各種の溶媒中で行うことができ、反応温度は、０℃〜１００℃、好ましくは、２０℃〜５０℃である。この際、水酸基とイソシアネート基の反応を促進するために既に例示したスズ系触媒、３級アミン系触媒を使用することができる。
《組成物》
これらの末端に官能基を持つ重合体は、様々な架橋反応を利用した硬化性組成物にすることができる。末端にアルケニル基を有する重合体から、（Ａ）アルケニル基を有する重合体、（Ｂ）ヒドロシリル基含有化合物、を含有する硬化性組成物を得ることができる。
【００８６】
（Ａ）成分の末端にアルケニル基を有するビニル系重合体は、単独で用いても、また、２種類以上を混合して用いても良い。（Ａ）成分の分子量としては特に制限はないが、５００〜１０００００の範囲にあるのが好ましく、３０００〜４００００がさらに好ましい。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、非常に高粘度あるいは溶解性が低くなり、取り扱いが困難になる。
【００８７】
（Ｂ）成分のヒドロシリル基含有化合物としては特に制限はなく、各種のものを用いることができる。すなわち、一般式１４または１５で表される鎖状ポリシロキサン
Ｒ²³ ₃ＳｉＯ−［Ｓｉ（Ｒ²³）₂Ｏ］_a−［Ｓｉ（Ｈ）（Ｒ²⁴）Ｏ］_b−［Ｓｉ（Ｒ²⁴）（Ｒ²⁵）Ｏ］_c−ＳｉＲ²³ ₃ （１４）
ＨＲ²³ ₂ＳｉＯ−［Ｓｉ（Ｒ²³）₂Ｏ］_a−［Ｓｉ（Ｈ）（Ｒ²⁴）Ｏ］_b−［Ｓｉ（Ｒ²⁴）（Ｒ²⁵）Ｏ］_c−ＳｉＲ²³ ₂Ｈ （１５）
（式中Ｒ²³およびＲ²⁴は炭素数１〜６のアルキル基、または、フェニル基、Ｒ²⁵は炭素数１〜１０のアルキル基または炭素数７〜１０のアラルキル基、ａは０≦ａ≦１００、ｂは２≦ｂ≦１００、ｃは０≦Ｃ≦１００の整数を示す）、
一般式１６で表される環状シロキサン
【００８８】
【化２８】

（式中Ｒ²³およびＲ²⁴は炭素数１〜６のアルキル基、または、フェニル基、Ｒ²⁵は炭素数１〜１０のアルキル基または炭素数７〜１０のアラルキル基、ｄは０≦ｄ≦８、ｅは２≦ｅ≦１０、ｆは０≦ｆ≦８の整数を示し、かつ３≦ｄ＋ｅ＋ｆ≦１０である）を用いることができる。
【００８９】
これらは単独で用いても２種以上を混合して用いてもかまわない。これらのシロキサンの中でも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、一般式１７、１８で示される鎖状シロキサンや、一般式１９、２０で示される環状シロキサンが好ましい。
（ＣＨ₃）₃ＳｉＯ−［Ｓｉ（Ｈ）（ＣＨ₃）Ｏ］_g−［Ｓｉ（Ｃ₆Ｈ₅）₂Ｏ］_h−Ｓｉ（ＣＨ₃）₃ （１７）
（ＣＨ₃）₃ＳｉＯ−［Ｓｉ（Ｈ）（ＣＨ₃）Ｏ］_g−［Ｓｉ（ＣＨ₃）｛ＣＨ₂Ｃ（Ｈ）（Ｒ²⁶）Ｃ₆Ｈ₅｝Ｏ］_h−
Ｓｉ（ＣＨ₃）₃ （１８）
（式中、Ｒ²⁶は水素またはメチル基、ｇは２≦ｇ≦１００、ｈは０≦ｈ≦１００の整数、Ｃ₆Ｈ₅はフェニル基を示す）
【００９０】
【化２９】

（式中、Ｒ²⁶は水素、またはメチル基、ｉは２≦ｉ≦１０、ｊは０≦ｊ≦８、かつ３≦ｉ＋ｊ≦１０である整数、Ｃ₆Ｈ₅はフェニル基）
（Ｂ）成分の少なくとも２個以上のヒドロシリル基を有する硬化剤としてはさらに、分子中に２個以上のアルケニル基を有する低分子化合物に対し、一般式１４〜２０に示したヒドロシリル基含有化合物を、反応後にも一部のヒドロシリル基が残るようにして付加反応させて得られる化合物を用いることもできる。分子中に２個以上のアルケニル基を有する化合物としては、各種のものを用いることができる。例示するならば、１，４−ペンタジエン、１，５−ヘキサジエン、１，６−ヘプタジエン、１，７−オクタジエン、１，８−ノナジエン、１，９−デカジエン等の炭化水素系化合物、Ｏ，Ｏ’−ジアリルビスフェノ−ルＡ、３，３’−ジアリルビスフェノ−ルＡ等のエ−テル系化合物、ジアリルフタレ−ト、ジアリルイソフタレ−ト、トリアリルトリメリテ−ト、テトラアリルピロメリテ−ト等のエステル系化合物、ジエチレングリコ−ルジアリルカ−ボネ−ト等のカ−ボネ−ト系化合物が挙げられる。この場合、一般式１４〜２０に示した過剰量のヒドロシリル基含有化合物に対し、ヒドロシリル化触媒の存在下、上に挙げたアルケニル基含有化合物をゆっくり滴下することにより該化合物を得ることができる。このような化合物のうち、原料の入手容易性、過剰に用いたシロキサンの除去のしやすさ、さらには（Ａ）成分の重合体への相溶性を考慮して、下記のものが好ましい。
【００９１】
【化３０】

重合体（Ａ）と硬化剤（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５〜０．２の範囲にあることが好ましく、さらに、２．５〜０．４であることが特に好ましい。モル比が５以上になると硬化が不十分でべとつきのある強度の小さい硬化物しか得られず、また、０．２より小さいと、硬化後も硬化物中に活性なヒドロシリル基が大量に残るので、クラック、ボイドが発生し、均一で強度のある硬化物が得られない。
【００９２】
重合体（Ａ）と硬化剤（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が添加される。このようなヒドロシリル化触媒としては、すでに述べた各種のものが用いられる。
【００９３】
末端に架橋性シリル基を持つ重合体は、これを主成分とする硬化性組成物にすることができる。
【００９４】
末端に架橋性シリル基を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、加水分解性基の種類により変化するので、使用条件に応じて適切な加水分解性基を選択しなければならない。
【００９５】
硬化反応を促進するために硬化触媒を添加してもよい。縮合触媒としてはテトラブチルチタネート、テトラプロピルチタネート等のチタン酸エステル；ジブチル錫ジラウレート、ジブチル錫マレエート、ジブチル錫ジアセテート、オクチル酸錫、ナフテン酸錫等の有機錫化合物；オクチル酸鉛、ブチルアミン、オクチルアミン、ジブチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、ジエチレントリアミン、トリエチレンテトラミン、オレイルアミン、オクチルアミン、シクロヘキシルアミン、ベンジルアミン、ジエチルアミノプロピルアミン、キシリレンジアミン、トリエチレンジアミン、グアニジン、ジフェニルグアニジン、２，４，６−トリス（ジメチルアミノメチル）フェノール、モルホリン、Ｎ−メチルモルホリン、１，３−ジアザビシクロ（５，４，６）ウンデセン−７等のアミン系化合物あるいはそれらのカルボン酸塩；過剰のポリアミンと多塩基酸から得られる低分子量ポリアミド樹脂；過剰のポリアミンとエポキシ化合物の反応生成物；アミノ基を有するシランカップリング剤、例えば、γ−アミノプロピルトリメトキシシラン、Ｎ−（β−アミノエチル）アミノプロピルメチルジメトキシシラン等の公知のシラノール触媒１種または２種以上を必要に応じて用いればよい。使用量は末端に架橋性シリル基を有するビニル系重合体に対し、０〜１０重量％で使用するのが好ましい。加水分解性基Ｙとしてアルコキシ基が使用される場合は、この重合体のみでは硬化速度が遅いので、硬化触媒を使用することが好ましい。
【００９６】
主成分である末端に架橋性シリル基を有するビニル系重合体に、必要に応じて縮合触媒を混合し硬化させれば、均一な硬化物を得ることができる。硬化条件としては特に制限はないが、一般に０〜１００℃、好ましくは１０〜５０℃で１時間〜１週間程度である。硬化物の性状は用いる重合体の主鎖骨格や分子量に依存するが、ゴム状のものから樹脂状のものまで幅広く作成することができる。
【００９７】
主成分である末端に架橋性シリル基を有するビニル系重合体に、必要に応じて縮合触媒を混合し硬化させれば、均一な硬化物を得ることができる。硬化条件としては特に制限はないが、一般に０〜１００℃、好ましくは１０〜５０℃で１時間〜１週間程度である。硬化物の性状は用いる重合体の主鎖骨格や分子量に依存するが、ゴム状のものから樹脂状のものまで幅広く作成することができる。
【００９８】
上記の各種の方法で得られる、末端に水酸基を有するビニル系重合体は、これを主成分とする硬化性組成物にすることができる。
【００９９】
この硬化性組成物は以下の２成分：（Ａ）末端に水酸基を有するビニル系重合体、（Ｂ）水酸基と反応しうる官能基を２個以上有する化合物、を必須成分とするものである。
【０１００】
（Ａ）成分の末端に水酸基を有するビニル系重合体は単独で用いても２種類以上を混合して用いてもよい。分子量としては特に制限はないが、５００〜１０００００の範囲にあるのが好ましい。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以上になると、非常に高粘度あるいは溶解性が低くなり、取り扱いが困難になる場合がある。
【０１０１】
（Ｂ）成分の水酸基と反応しうる官能基を２個以上有する化合物としては、特に限定はないが、例えば、１分子中に２個以上のイソシアネート基を有する多価イソシアネート化合物、メチロール化メラミンおよびそのアルキルエーテル化物または低縮合化物等のアミノプラスト樹脂、多官能カルボン酸およびそのハロゲン化物等が挙げられる。
【０１０２】
１分子中に２個以上のイソシアネート基を有する多価イソシアネート化合物としては従来公知のものを使用することができ、例えば、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、４，４’−ジフェニルメタンジイソシアネート、ヘキサメチレンジイソシアネート、キシリレンジイソシアネート、メタキシリレンジイソシアネート、１，５−ナフタレンジイソシアネート、水素化ジフェニルメタンジイソシアネート、水素化トリレンジイソシアネート、水素化キシリレンジイソシアネート、イソホロンジイソシアネート、一方社油脂製Ｂ−４５のごときトリイソシアネート、等のイソシアネート化合物、スミジュールＮ（住友バイエルウレタン社製）のごときビュレットポリイソシアネート化合物、デスモジュールＩＬ、ＨＬ（バイエルＡ．Ｇ．社製）、コロネートＥＨ（日本ポリウレタン工業社製）のごときイソシアヌレート環を有するポリイソシアネート化合物、スミジュールＬ（住友バイエルウレタン社製）のごときアダクトポリイソシアネート化合物、コロネートＨＬ（日本ポリウレタン社製）のごときアダクトポリイソシアネート化合物等を挙げることができる。また、ブロックイソシアネートを使用しても構わない。これらは単独で使用しても、２種類以上を併用してもよい。
【０１０３】
末端に水酸基を有する重合体と２個以上のイソシアネート基を有する化合物との配合比については特に限定されないが、例えば、イソシアネート基と末端に水酸基を有するビニル系重合体の水酸基の比率（ＮＣＯ／ＯＨ（モル比））が０．５〜３．０であることが好ましく、０．８〜２．０であることがより好ましい。
【０１０４】
本発明の組成物である末端に水酸基を有するビニル系重合体と２個以上のイソシアネート基を有する化合物の硬化反応を促進させるために、必要に応じて、有機スズ化合物や３級アミン等の公知の触媒を添加してもよい。
【０１０５】
有機スズ化合物の具体例としては、オクチル酸スズ、ジブチルスズジアセテート、ジブチルスズジラウレート、ジブチルスズメルカプチド、ジブチルスズチオカルボキシレート、ジブチルスズジマレエート、ジオクチルスズチオカルボキシレート等が挙げられる。また、３級アミン系触媒としては、トリエチルアミン、Ｎ，Ｎ−ジメチルシクロヘキシルアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルプロパン１，３−ジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルヘキサン１，６−ジアミン、Ｎ，Ｎ，Ｎ’，Ｎ”，Ｎ”−ペンタメチルジエチレントリアミン、Ｎ，Ｎ，Ｎ’，Ｎ”，Ｎ”−ペンタメチルジプロピレントリアミン、テトラメチルグアニジン、トリエチレンジアミン、Ｎ，Ｎ’−ジメチルピペラジン、Ｎ−メチルモルホリン、１，２−ジメチルイミダゾール、ジメチルアミノエタノール、ジメチルアミノエトキシエタノール、Ｎ，Ｎ，Ｎ’−トリメチルアミノエチルエタノールアミン、Ｎ−メチル−Ｎ’−（２−ヒドロキシエチル）ピペラジン、Ｎ−（２−ヒドロキシエチル）モルホリン、ビス（２−ジメチルアミノエチル）エーテル、エチレングリコールビス（３−ジメチル）アミノプロピルエーテル等が例示される。
【０１０６】
本発明における硬化性組成物に使用されるアミノプラスト樹脂としては特に限定はなく、メラミンとホルムアルデヒドとの付加反応物（メチロール化合物）、メラミンとホルムアルデヒドの低縮合物、それらのアルキルエーテル化物、ならびに尿素樹脂等が挙げられる。これらは単独で用いても２種以上を併用しても構わない。末端に水酸基を有する（メタ）アクリル系重合体と、アミノプラスト樹脂の硬化反応を促進する目的で、パラトルエンスルホン酸、ベンゼンスルホン酸等の公知の触媒を添加してもよい。
【０１０７】
本発明の硬化性組成物に用いられる、１分子中に２個以上のカルボキシル基を有する化合物としては、特に限定されず、例えば、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、フタル酸、無水フタル酸、テレフタル酸、トリメリット酸、ピロメリット酸、マレイン酸、無水マレイン酸、フマル酸、イタコン酸などの多官能カルボン酸またはその無水物、および、これらのハロゲン化物等が挙げられ、これらは単独で用いても２種類以上を併用してもよい。
【０１０８】
本発明の２成分（Ａ）、（Ｂ）、および必要に応じて硬化触媒を混合し硬化させれば、深部硬化性に優れた均一な硬化物が得られる。硬化条件については特に制限はないが、一般に０℃〜１００℃、好ましくは２０℃〜８０℃である。
【０１０９】
硬化物の性状は用いる（Ａ）成分の重合体および（Ｂ）成分の硬化剤の主鎖骨格や分子量に依存するが、ゴム状のものから樹脂状のものまで幅広く作成することができる。
【０１１０】
末端にエポキシ基を持つ重合体からは、（Ａ）末端にエポキシ基を持つ重合体、（Ｂ）硬化剤、を含有する硬化性組成物を得ることができる。（Ｂ）硬化剤としては、各種のものが使用できる。例示するならば、脂肪族アミン類、芳香族アミン類、酸無水物、ユリア、メラミン、フェノール樹脂である。
【０１１１】
以上のような本発明の組成物の具体的な用途として、シーリング材、接着剤、粘着材、弾性接着剤、塗料、粉体塗料、発泡体、電気電子用ポッティング材、フィルム、成形材料、人工大理石等を挙げることができる。
【０１１２】
【実施例】
以下に、本発明の具体的な実施例を示すが、本発明は、下記実施例に限定されるものではない。下記実施例および比較例中、「部」および「％」は、それぞれ「重量部」および「重量％」を表す。「数平均分子量」および「分子量分布（重量平均分子量と数平均分子量の比）」は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いた標準ポリスチレン換算法により算出した。ただし、ＧＰＣカラムとしてポリスチレン架橋ゲルを充填したもの（ｓｈｏｄｅｘ ＧＰＣ Ｋ−８０４；昭和電工（株）製）を、ＧＰＣ溶媒としてクロロホルムを用いた。重合体１分子当たりに導入された官能基数は、¹Ｈ−ＮＭＲによる濃度分析、及びＧＰＣにより求まる数平均分子量を基に算出した。
（実施例１）
２５０Ｌ耐圧反応器に臭化銅（Ｉ）１．０１ｋｇ（７．０２ｍｏｌ）、アセトニトリル１０．６ｋｇを仕込み、窒素気流下６５℃で１６分間加熱攪拌した。これに２，５−ジブロモアジピン酸ジエチル２．１１ｋｇ（５．８５ｍｏｌ）、アクリル酸ブチル２４．０ｋｇ（１８７ｍｏｌ）を加え、さらに６５℃で４０分間加熱攪拌した。これにペンタメチルジエチレントリアミン（以後トリアミンと称す）２０．３ｇ（０．１１７ｍｏｌ）を加えて反応を開始し、８０℃で加熱攪拌を続けた。さらにトリアミンを１０１．５ｇ（０．５８５ｍｏｌ）追加した。反応開始４６分後から断続的にアクリル酸ブチル９６．０ｋｇ（７４９ｍｏｌ）を１８０分かけて滴下した。またこの間にトリアミン８１．２ｇ（０．４６８ｍｏｌ）を追加した。反応開始から３４６分後、アクリル酸ブチルの反応率は９５．９％に達した。反応容器内を減圧にし、揮発分を除去した。反応開始から４３４分後、アセトニトリル３１．７ｋｇ、１，７−オクタジエン１２．９ｋｇ（１１７ｍｏｌ）、トリアミン４０６ｇ（２．３４ｍｏｌ）を添加し、引き続き８０℃で加熱攪拌を続け、反応開始から８０９分後加熱を停止し、重合体［１］を含む溶液を得た。得られた重合体［１］の数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）で２６４００、分子量分布は１．２３であり、また¹Ｈ−ＮＭＲ分析より求めた重合体１分子あたりのアルケニル基の個数は１．９個、アルケニル基の導入されていない末端の個数は０個であった。
（実施例２）
上記の重合体［１］を含む混合物を濃縮した後、メチルシクロヘキサンで希釈し、固形分を除去した。重合体１００部に対して吸着剤４部（キョーワード５００ＳＨ ２部／キョーワード７００ＳＬ ２部：共に協和化学（株）製）を重合体のメチルシクロヘキサン溶液に加え、酸素・窒素混合ガス雰囲気下で加熱攪拌した。固形分を除去した後、重合体溶液を濃縮して重合体［１’］を得た。重合体［１’］の分子量分布は１．３０であった。
（実施例３）
２Ｌフラスコに臭化銅（Ｉ）８．３９ｇ（５８．５ｍｍｏｌ）、アセトニトリル１１２ｍＬ（８７．９ｇ）を仕込み、窒素気流下７０℃で２０分間加熱攪拌した。これに２，５−ジブロモアジピン酸ジエチル１７．６ｇ（４８．８ｍｍｏｌ）、アクリル酸ブチル２２４ｍＬ（２００ｇ、１．５６ｍｏｌ）を加え、さらに８０℃で４０分間加熱攪拌した。これにペンタメチルジエチレントリアミン（以後トリアミンと称す）０．４１ｍＬ（０．３３８ｇ、１．９５ｍｍｏｌ）を加えて反応を開始した。さらにトリアミンを１．２３ｍＬ（１．０１ｇ、５．８５ｍｍｏｌ）追加した。８０℃で加熱攪拌を続け、反応開始３５分後から断続的にアクリル酸ブチル８９５ｍＬ（８００ｇ、６．２４ｍｏｌ）を１４５分かけて滴下した。またこの間にトリアミン０．４１ｍＬ（０．３３８ｇ、１．９５ｍｍｏｌ）を追加した。反応開始から２４０分後、アクリル酸ブチルの反応率は９５．９％に達した。反応容器内を減圧にし、揮発分を除去した。反応開始から３６０分後、アセトニトリル３３６ｍＬ（２６４ｇ）、１，７−オクタジエン１４４ｍＬ（１０７ｇ、０．９７５ｍｏｌ）、トリアミン４．１ｍＬ（３．３８ｇ、１９．５ｍｍｏｌ）添加し、引き続き８０℃で加熱攪拌を続け、反応開始から７４０分後加熱を停止し、重合体［２］を含む溶液を得た。得られた重合体［２］の数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）で２４０００、分子量分布は１．１７であり、また¹Ｈ−ＮＭＲ分析より求めた重合体１分子あたりのアルケニル基の個数は１．７個、アルケニル基の導入されていない末端の個数は０個であった。
（実施例４）
上記の重合体［２］を含む混合物を濃縮した後、トルエンで希釈し、固形分を除去した。重合体１００部に対して吸着剤４部（キョーワード５００ＳＨ ２部／キョーワード７００ＳＬ ２部：共に協和化学（株）製）を重合体のトルエン溶液に加え、酸素・窒素混合ガス雰囲気下で加熱攪拌した。固形分を除去した後、重合体溶液を濃縮した。これをＮ，Ｎ−ジメチルアセトアミドに希釈し、酢酸カリウム共存下１００℃で８時間加熱撹拌した。重合体溶液を濃縮後、トルエンで希釈して固形分を除去した。重合体１００部に対して吸着剤５０部（キョーワード７００ＰＥＬ ５０部：協和化学（株）製）を重合体のキシレン溶液に加え、酸素・窒素混合ガス雰囲気下で加熱攪拌した。固形分を除去した後、溶液を濃縮して重合体を得た。この重合体に、ジメトキシメチルシラン（アルケニル基に対して３モル当量）、オルトギ酸メチル（アルケニル基に対して１モル当量）、白金触媒（ビス（１，３−ジビニル−１，１，３，３−テトラメチルジシロキサン）白金錯体のキシレン溶液：以下白金触媒という）（白金として重合体１ｋｇに対して３０ｍｇ）を混合し、窒素雰囲気下、８０℃で１時間加熱攪拌した。アルケニル基が反応により消失したことを¹Ｈ−ＮＭＲで確認し、反応混合物を濃縮して目的とするメトキシシリル基含有重合体［２’］を得た。重合体［２’］の数平均分子量は２５６００、分子量分布は１．２６であった。重合体１分子当たりに導入されたシリル基の数は１．８個であった。
（実施例５）
実施例４で得られたメトキシシリル基含有重合体［２’］１００部、炭酸カルシウム（白艶華ＣＣＲ：白石工業製）１５０部とＤＯＰ（ジオクチルフタレート：協和醗酵製）５０部を混合し、更に３本ペイントロールを用いて充分混合した後、４価Ｓｎ触媒（ジブチル錫ジアセチルアセトナート）を用いて、室内で２日、その後５０℃で３日硬化養生させ、シート状の硬化物を得た。硬化物の引張物性（島津製オートグラフ使用、測定温度：２３℃、引張速度：２００ｍｍ／ｓｅｃ、２（１／３）号形ダンベル試験片）を評価した。破断強度は０．７７ＭＰａ、破断伸びは４３０％であった。
（実施例６）
２５０Ｌ耐圧反応器に臭化銅（Ｉ）１．１１ｋｇ（７．７２ｍｏｌ）、アセトニトリル９．９５ｋｇを仕込み、窒素気流下６５℃で１５分間加熱攪拌した。これに２，５−ジブロモアジピン酸ジエチル３．０９ｋｇ（８．５８ｍｏｌ）、アクリル酸ブチル６．６０ｋｇ（５１．５ｍｏｌ）、アクリル酸エチル９．４９ｋｇ（９４．７ｍｏｌ）、アクリル酸２−メトキシエチル７．７７ｋｇ（５９．７ｍｏｌ）、さらに６５℃で４３分間加熱攪拌した。これにペンタメチルジエチレントリアミン（以後トリアミンと称す）２２．３ｇ（０．１２９ｍｏｌ）を加えて反応を開始し、８０℃で加熱攪拌を続けた。さらにトリアミンを１１２ｇ（０．６４４ｍｏｌ）追加した。反応開始５７分後から断続的にアクリル酸ブチル２６．４ｋｇ（２０６ｍｏｌ）、アクリル酸エチル３７．９ｋｇ（３７９ｍｏｌ）、アクリル酸２−メトキシエチル３１．３ｋｇ（２３９ｍｏｌ）を１８０分かけて滴下した。またこの間にトリアミン８９．２ｇ（０．５１５ｍｏｌ）を追加した。反応開始から６０２分後、反応容器内を減圧にし、揮発分を除去した。反応開始から７２０分後、アクリル酸エチル・アクリル酸ブチル・アクリル酸２−メトキシエチルの反応率は平均９５．３％に達した。アセトニトリル９．９５ｋｇ、１，７−オクタジエン２８．４ｋｇ（２５７ｍｏｌ）、トリアミン４４６ｇ（２．５７ｍｏｌ）添加し、引き続き８０℃で加熱攪拌を続け、反応開始から１３４０分後加熱を停止し、重合体［３］を含む溶液を得た。得られた重合体［３］の数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）で１７１００、分子量分布１．１６であり、また¹Ｈ−ＮＭＲ分析より求めた重合体１分子あたりのアルケニル基の個数は１．６個、アルケニル基の導入されていない末端の個数は０個であった。
（実施例７）
重合体［３］を含む混合物を重合体溶液を濃縮した後、トルエンで希釈し、固形分を除去した。重合体１００部に対して吸着剤４部（キョーワード５００ＳＨ２部／キョーワード７００ＳＬ ２部：共に協和化学（株）製）を重合体のトルエン溶液に加え、酸素・窒素混合ガス雰囲気下で加熱攪拌した。固形分を除去した後、重合体溶液を濃縮した。これをＮ，Ｎ−ジメチルアセトアミドに希釈し、酢酸カリウム共存下１００℃で８時間加熱撹拌した。重合体溶液を濃縮した後、重合体１００部に対して吸着剤１０部（キョーワード５００ＳＨ ５部／キョーワード７００ＳＬ ５部：共に協和化学（株）製）を重合体のトルエン溶液に加え、酸素・窒素混合ガス雰囲気下で加熱攪拌した。固形分を除去した後、重合体溶液を濃縮して重合体［３’］を得た。
（実施例８）
重合体［３’］１００部、鎖状シロキサン（分子中に平均５個のヒドロシリル基と平均５個の置換基［−ＣＨ₂−ＣＨ（ＣＨ₃）−Ｃ₆Ｈ₅］を含有し、Ｓｉ−Ｈ基量は３．７０ｍｍｏｌ／ｇである）をアルケニル基に対して１．８モル当量混合した。この混合物に対し、白金触媒（白金として重合体１ｋｇに対して１０〜１００ｍｇ）を加え、均一混合し、１３０℃に加熱すると、速やかに硬化して、ゴム状の硬化物が得られた。硬化物の引張物性（島津製オートグラフ使用、測定温度：２３℃、引張速度：２００ｍｍ／ｓｅｃ、２（１／３）号形ダンベル試験片）を評価した。破断強度は０．５５ＭＰａ、破断伸びは２３０％であった。
（比較例１）
５００ｍＬフラスコに臭化銅（Ｉ）２．５２ｇ（１７．６ｍｍｏｌ）、アセトニトリル３３．６ｍＬ（２６．４ｇ）を仕込み、窒素気流下７０℃で３０分間加熱攪拌した。これに２，５−ジブロモアジピン酸ジエチル５．２７ｇ（１４．６ｍｍｏｌ）、アクリル酸ブチル３３６ｍＬ（３００ｇ、２．３４ｍｏｌ）を加え、さらに７０℃で２０分間加熱攪拌した。これにペンタメチルジエチレントリアミン（以後トリアミンと称す）０．１２２ｍＬ（０．１０１ｇ、０．５８５ｍｍｏｌ）を加えて反応を開始し、８０℃で加熱攪拌を続けた。さらにトリアミンを０．３６６ｍＬ（０．３０３ｇ、１．７６ｍｍｏｌ）追加した。反応開始から２００分後、アクリル酸ブチルの反応率は９８．６％に達した。１，７−オクタジエン４３．２ｍＬ（３２．２ｇ、０．２９３ｍｏｌ）、トリアミン１．２２ｍＬ（１．０１ｇ、５．８５ｍｍｏｌ）を添加し、引き続き８０℃で加熱攪拌を続け、反応開始から４４０分後加熱を停止し、重合体［４］を含む溶液を得た。得られた重合体［４］の数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）で２６８００、分子量分布１．３２であり、また¹Ｈ−ＮＭＲ分析より求めた重合体１分子あたりのアルケニル基の個数は２．９個、アルケニル基の導入されていない末端の個数は０．３個であった。
（比較例２）
上記の重合体［４］を含む混合物を、実施例２と同様にして処理して重合体［４’］を得た。重合体［４’］の分子量分布は１．５１であった。
（比較例３）
還流管および攪拌機付きの２０Ｌの反応器に、ＣｕＢｒ８３．９ｇ（０．５８５ｍｏｌ）を仕込み、反応容器内を窒素置換した。アセトニトリル８７９ｇを加え、オイルバス中７０℃で４５分間攪拌した。これにアクリル酸ブチル２．００ｋｇ（２５．６ｍｏｌ）、２，５−ジブロモアジピン酸ジエチル（１７６ｇ、０．４８８ｍｏｌ）、ペンタメチルジエチレントリアミン４．０７ｍＬ（３．３８ｇ、１９．５ｍｍｏｌ）（これ以降トリアミンと表す）を加え、反応を開始した。さらにトリアミン８．１４ｍＬ（６．７６ｇ、３９．０ｍｍｏｌ）を追加し、７０℃で加熱攪拌を続けた。反応開始後６０分後からアクリル酸ブチル８．００ｋｇ（１０２ｍｏｌ）を１７０分かけて連続的に滴下した。アクリル酸ブチルの滴下途中にトリアミン８．１４ｍＬ（６．７６ｇ、３９．０ｍｍｏｌ）を追加した。反応開始から４５０分後、アクリル酸ブチルの反応率は９６．７％に達した。１，７−オクタジエン２．８８Ｌ（２．１５ｋｇ、１９．５ｍｏｌ）、トリアミン３０．５ｍＬ（２５．４ｇ、１４６ｍｍｏｌ）を添加し、さらに７０℃で２４０分加熱攪拌を続けた。
【０１１３】
反応混合物をトルエンで希釈して固形分を除去した後、活性アルミナカラムを通し、揮発分を減圧留去することにより末端にアルケニル基を有する重合体［５］を得た。重合体［５］はＧＰＣ測定（ポリスチレン換算）により数平均分子量は２５１００、分子量分布は１．３４であり、重合体１分子当たりに導入された平均のアルケニル基の数を¹Ｈ−ＮＭＲ分析により求めたところ、３．１個であった。
（比較例４）
重合体［５］をＮ，Ｎ−ジメチルアセトアミドに希釈し、酢酸カリウム共存下１００℃で８時間加熱撹拌した。減圧加熱処理後、トルエンで希釈して固形分を除去した。重合体１００部に対して吸着剤１５部（キョーワード５００ＳＨ １０部／キョーワード７００ＳＬ ５部：共に協和化学（株）製）を重合体のトルエン溶液に加えて１３０℃で加熱攪拌した。固形分を除去した後、重合体溶液を濃縮して重合体を得た。この重合体に、ジメトキシメチルシラン（アルケニル基に対して３モル当量）、オルトギ酸メチル（アルケニル基に対して１モル当量）、白金触媒（白金として重合体１ｋｇに対して６０ｍｇ）を混合し、１００℃で５時間加熱攪拌した。アルケニル基が反応により消失したことを¹Ｈ−ＮＭＲで確認し、反応混合物を濃縮して目的とするメトキシシリル基含有重合体［５’］を得た。数平均分子量は２８９００、分子量分布は１．９０であった。重合体１分子当たりに導入されたシリル基の数は１．９個であった。
（比較例５）
比較例４で得られたメトキシシリル基含有重合体［５’］１００部、炭酸カルシウム（白艶華ＣＣＲ：白石工業製）１５０部とＤＯＰ（ジオクチルフタレート：協和醗酵製）５０部を混合し、更に３本ペイントロールを用いて充分混合した後、４価Ｓｎ触媒（ジブチル錫ジアセチルアセトナート）を用いて、室内で２日、その後５０℃で３日硬化養生させ、シート状の硬化物を得た。硬化物の引張物性（島津製オートグラフ使用、測定温度：２３℃、引張速度：２００ｍｍ／ｓｅｃ、２（１／３）号形ダンベル試験片）を評価した。破断強度は０．９５ＭＰａ、破断伸びは３２０％であった。
（比較例６）
５０Ｌ反応器に臭化銅（Ｉ）２７０ｇ（１．８８ｍｏｌ）、アセトニトリル２．４３ｋｇを仕込み、窒素気流下６５℃で１９分間加熱攪拌した。これに２，５−ジブロモアジピン酸ジエチル７５３ｇ（２．０９ｍｏｌ）、アクリル酸ブチル１．６１ｋｇ（１２．６ｍｏｌ）、アクリル酸エチル２．３１ｋｇ（２３．１ｍｏｌ）、アクリル酸２−メトキシエチル１．９０ｋｇ（１４．６ｍｏｌ）を加え、さらに８０℃で３０分間加熱攪拌した。これにペンタメチルジエチレントリアミン（以後トリアミンと称す）１３．１ｍＬ（１０．８ｇ、６２．８ｍｍｏｌ）を加えて反応を開始した。さらにトリアミンを２６．２ｍＬ（２１．６ｇ、１２６ｍｍｏｌ）追加した。８０℃で加熱攪拌を続け、反応開始６５分後から断続的にアクリル酸ブチル６．４４ｋｇ（５０．４ｍｏｌ）、アクリル酸エチル９．２４ｋｇ（９２．４ｍｏｌ）、アクリル酸２−メトキシエチル７．６０ｋｇ（５８．４ｍｏｌ）を１０３分かけて滴下した。またこの間にトリアミン２６．２ｍＬ（２１．６ｇ、１２６ｍｍｏｌ）を追加した。反応開始から３０５分後、アクリル酸エチル・アクリル酸ブチル・アクリル酸２−メトキシエチルの反応率は平均９６．８％に達した。１，７−オクタジエン６．９２ｋｇ（６２．８ｍｏｌ）、トリアミン１３１ｍＬ（１０９ｇ、０．６２８ｍｏｌ）添加し、引き続き８０℃で加熱攪拌を続け、反応開始から６０５分後加熱を停止し、重合体［６］を含む溶液を得た。得られた重合体［６］の数平均分子量はＧＰＣ測定（移動相クロロホルム、ポリスチレン換算）で１７０００、分子量分布１．１３であり、また¹Ｈ−ＮＭＲ分析より求めた重合体１分子あたりのアルケニル基の個数は２．５個であった。
（比較例７）
重合体［６］を含む混合物を減圧加熱処理した後、トルエンで希釈し、固形分を除去した。これをＮ，Ｎ−ジメチルアセトアミドに希釈し、酢酸カリウム共存下１００℃で８時間加熱撹拌した。減圧加熱処理後、トルエンで希釈して固形分を除去した。重合体１００部に対して吸着剤１５部（キョーワード５００ＳＨ １０部／キョーワード７００ＳＬ ５部：共に協和化学（株）製）を重合体のトルエン溶液に加えて１３０℃で加熱攪拌した。固形分を除去した後、重合体溶液を濃縮して重合体［６’］を得た。
（比較例８）
重合体［６’］１００部、鎖状シロキサン（分子中に平均５個のヒドロシリル基と平均５個の置換基［−ＣＨ₂−ＣＨ（ＣＨ₃）−Ｃ₆Ｈ₅］を含有し、Ｓｉ−Ｈ基量は３．７０ｍｍｏｌ／ｇである）をアルケニル基に対して１．８モル当量混合した。この混合物に対し、白金触媒（白金として重合体１ｋｇに対して１０〜１００ｍｇ）を加え、均一混合し、１３０℃に加熱すると、速やかに硬化して、ゴム状の硬化物が得られた。硬化物の引張物性（島津製オートグラフ使用、測定温度：２３℃、引張速度：２００ｍｍ／ｓｅｃ、２（１／３）号形ダンベル試験片）を評価した。破断強度は０．６１ＭＰａ、破断伸びは１６０％であった。
以上の結果を下表に示す。
【０１１４】
【表１】

【０１１５】
【表２】

【０１１６】
【表３】

本発明の方法により、末端に確実に官能基が導入された重合体が得られる。また官能基が導入されていない末端は重合体の熱安定性に悪影響を及ぼすが、表１に示すように、本発明の方法により熱安定性の向上した重合体が得られる。さらに、表２および表３に示すように、本発明の方法で得られた重合体は、末端に確実に官能基が導入されているので、伸びに優れた硬化物を与える。
【０１１７】
【発明の効果】
本発明によりビニル系重合体の末端に確実に官能基を導入することができる。末端に官能基を持つビニル系重合体は、末端基が主鎖に炭素炭素結合で繋がっているため安定であり、末端の構造はオレフィンが一つだけとよく制御されているため、硬化性組成物などへの利用に有用である。また、本発明の製造方法によれば、様々なビニル系単量体から、重合系に本発明で示された重合性の低いオレフィンと様々な官能基を併せ持つ化合物を添加することにより容易に上述した末端に様々な官能基を持つ重合体を製造することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a polymer, a vinyl polymer having a functional group at the terminal produced thereby, and a curable composition comprising the polymer.
[0002]
[Prior art]
It is known that a polymer having a functional group at a polyfunctional end is crosslinked by itself or in combination with an appropriate curing agent to give a cured product having excellent heat resistance and durability. Among them, polymers having an alkenyl group, a hydroxyl group or a crosslinkable silyl group at the terminal are representative examples thereof. A polymer having an alkenyl group at the terminal is crosslinked and cured by using a hydrosilyl group-containing compound as a curing agent or by utilizing a photoreaction. A polymer having a hydroxyl group at the end forms a urethane crosslink by reacting with a polyisocyanate and cures. Moreover, the polymer which has a crosslinkable silyl group at the terminal gives a hardened | cured material by absorbing moisture in presence of a suitable condensation catalyst.
[0003]
Examples of the main chain skeleton of a polymer having an alkenyl group, a hydroxyl group or a crosslinkable silyl group at the end include polyether polymers such as polyethylene oxide, polypropylene oxide, and polytetramethylene oxide, polybutadiene, polyisoprene, poly Examples include hydrocarbon polymers such as chloroprene, polyisobutylene, or hydrogenated products thereof, and polyester polymers such as polyethylene terephthalate, polybutylene terephthalate, and polycaprolactone. It is used for.
[0004]
Among the polymers obtained by ionic polymerization or condensation polymerization exemplified above, vinyl polymers obtained by radical polymerization and having a functional group at the terminal have not been practically used yet. Among vinyl polymers, (meth) acrylic polymers have characteristics that cannot be obtained with the above polyether polymers, hydrocarbon polymers, or polyester polymers, such as high weather resistance and transparency. Those having an alkenyl group or a crosslinkable silyl group in the side chain are used for highly weather-resistant paints. On the other hand, the polymerization control of the acrylic polymer is not easy because of the side reaction, and it is very difficult to introduce a functional group at the terminal.
[0005]
If a vinyl polymer having an alkenyl group at the molecular chain terminal can be obtained by a simple method, a cured product having excellent cured product properties can be obtained as compared with those having a crosslinkable group in the side chain. Therefore, many researchers have studied the production method so far, but it is not easy to produce them industrially.
[0006]
JP-A-5-255415 discloses a method for synthesizing a (meth) acrylic polymer having alkenyl groups at both ends using an alkenyl group-containing disulfide as a chain transfer agent, and JP-A-5-262808 discloses a hydroxyl group. A (meth) acrylic polymer having hydroxyl groups at both ends is synthesized using a disulfide having a hydroxyl group, and further, a (meth) acrylic polymer having alkenyl groups at both ends is utilized by utilizing the reactivity of hydroxyl groups. Although synthetic methods are disclosed, it is not easy to reliably introduce alkenyl groups at both ends by these methods. Also, in order to reliably introduce a functional group at the terminal, a large amount of chain transfer agent must be used, which is a problem in the production process.
[0007]
[Problems to be solved by the invention]
We separately add a compound having both a polymerizable alkenyl group and a low polymerizable alkenyl group after polymerization of the vinyl polymer, and react the polymerizable alkenyl group with the polymer terminal, thereby polymer terminal. Has invented a method of introducing olefins. However, in this method, even if the polymerization is living, it is not easy to reliably introduce only one olefin at the end. The structure will be polymerized and the structure is more difficult to control.
[0008]
On the other hand, in radical polymerization, it is generally known that an unactivated olefin such as an α-olefin does not polymerize. The same applies to living radical polymerization, which has been actively studied recently.
[0009]
In addition, we found that adding an unactivated (low-polymerization) olefin to the living radical polymerization system adds almost one to the growth terminal, and by using this, it was found that We have invented a method for producing polymers having various functional groups. However, in this conventional method, the functional group may not be reliably introduced.
[0010]
Therefore, in the present invention, a method for producing a polymer of a radically polymerizable vinyl monomer in which a functional group is reliably introduced at the terminal, and the polymer, and a curable composition comprising the produced polymer It is an issue to provide.
[0011]
[Means for Solving the Problems]
The present invention provides an olefin compound (I) having a low polymerization property and a compound (II) having a higher dielectric constant than that of the olefin compound (I) after 80% by weight of the radical polymerizable monomer is consumed by atom transfer radical polymerization. A method for producing a vinyl polymer in which an olefin compound (I) is added to a terminal, wherein 1 to 1000 parts by weight of compound (II) is added to 100 parts by weight of the radical polymerizable monomer. The present invention relates to a method for producing a vinyl polymer, characterized by being added. The olefin compound (I) preferably has a functional group. Here, the amount of the radical polymerizable monomer is the amount finally charged in the polymerization solution. The dielectric constant of the present invention is generally also referred to as a relative dielectric constant.
[0012]
The olefin compound (I) of the present invention is preferably a compound represented by the above general formula 1, general formula 4, or general formula 5. The olefin compound (I) is more preferably 1,5-hexadiene, 1,7-octadiene or 1,9-decadiene. In the present invention, it is preferable to add an excessive amount of the olefin compound (I) with respect to the growth terminal of the polymer.
In the present invention, the olefin compound (I) is represented by the formula R^ThreeIs preferably a group selected from a hydroxyl group, an amino group, an epoxy group, a carboxylic acid group, an ester group, an ether group, an amide group, and a silyl group.
In the present invention, the olefin compound (I) is represented by the formula R²Is preferably a hydrogen atom.
In the present invention, the olefin compound (I) is preferably alkenyl alcohol or alkenylamine.
[0013]
In the present invention, the dielectric constant of the compound (II) is preferably 3 or more, more preferably 5 or more, and even more preferably 10 or more than the olefin compound (I).
In the present invention, the compound (II) is preferably a nitrile compound, and more preferably acetonitrile.
In the present invention, 1 to 1000 parts by weight of the compound (II) is added to 100 parts by weight of the radical polymerizable monomer, but it is preferable to add 3 to 1000 parts by weight of the compound (II). It is more preferable to add 5-500 parts by weight of compound (II), and it is more preferable to add 10-100 parts by weight of compound (II). Here, the amount of the radical polymerizable monomer is the amount finally charged in the polymerization solution.
In the present invention, it is preferable to add 1 to 10000 parts by weight of compound (II), more preferably 10 to 1000 parts by weight of compound (II), relative to 100 parts by weight of olefin compound (I). preferable.
[0014]
In the present invention, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn) measured by gel permeation chromatography of the vinyl polymer is preferably less than 1.8. .
The present invention relates to a polymer produced by the above method and a curable composition containing the polymer produced by the above method.
[0015]
The polymer having a functional group at the terminal obtained in the present invention can be made into a curable composition by appropriate functional group conversion such as hydrosilylation or epoxidation or addition of a crosslinking agent.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
《Monomer》
There is no restriction | limiting in particular as a radically polymerizable monomer used for the polymerization method of this invention, A various thing can be used. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n- Butyl, isobutyl (meth) acrylate, (tert-butyl) (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acryl Acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl, (meth) Stearyl acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, (meth ) Benzyl acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, ( (Meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid glycidyl, (meth) acrylic acid 2-aminoethyl, γ- (methacryloyloxypropyl) trimethoxysilane, (meth) acrylic acid ethylene oxide adduct, ( Trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate , 2-Perfluoroethyl (meth) acrylate, (meth) acrylic Perfluoromethyl acid, diperfluoromethyl methyl (meth) acrylate, 2-perfluoromethyl-2-perfluoroethyl methyl (meth) acrylate, 2-perfluorohexyl ethyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid monomers such as 2-perfluorodecylethyl acid and 2-perfluorohexadecylethyl (meth) acrylate; styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts, etc. Styrene monomers; fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene fluoride; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, and maleic acid mono Alkyl beauty treatment salon Fumaric acid, monoalkyl esters and dialkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide, etc. Maleimide monomers; nitrile group-containing vinyl monomers such as acrylonitrile and methacrylonitrile; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate, etc. Vinyl esters; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride and vinyl chloride Examples thereof include redene, allyl chloride, and allyl alcohol, and these may be used alone or a plurality thereof may be copolymerized. Among these, styrenic monomers and (meth) acrylic acid monomers are preferred from the viewpoint of physical properties of the product, and acrylic monomers are preferred due to the high reactivity of the functional group introduction reaction of the present invention and the low glass transition point. Acid ester monomers are more preferred.
《Living polymerization》
The “living radical polymerization method” is a radical polymerization that is difficult to control because it has a high polymerization rate and is likely to cause a termination reaction due to coupling between radicals. However, the termination reaction is difficult to occur and the molecular weight distribution is narrow (Mw / Mn is about 1.1 to 1.5), a polymer is obtained, and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.
[0017]
Accordingly, the “living radical polymerization method” can obtain a polymer having a narrow molecular weight distribution and a low viscosity, and a monomer having a specific functional group can be introduced at almost any position of the polymer. The method for producing the vinyl polymer having the specific functional group is more preferable.
[0018]
In the narrow sense, living polymerization refers to polymerization in which the terminal always has activity and the molecular chain grows, but in general, the terminal is inactivated and the terminal is activated. Pseudo-living polymerization that grows in an equilibrium state is also included. The definition in the present invention is also the latter.
[0019]
The “living radical polymerization method” has been actively researched by various groups in recent years. Examples thereof include those using a cobalt porphyrin complex as shown in, for example, Journal of American Chemical Society (J. Am. Chem. Soc.), 1994, 116, 7943, Macromolecules. (Macromolecules), 1994, Vol. 27, p. 7228, using a radical scavenger such as a nitroxide compound, and “atom transfer radical polymerization” using an organic halide as an initiator and a transition metal complex as a catalyst ( Atom Transfer Radical Polymerization (ATRP).
[0020]
Among the “living radical polymerization methods”, the “atom transfer radical polymerization method” for polymerizing vinyl monomers using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is the above “living radical polymerization method”. In addition to the features of ”, it has a halogen, which is relatively advantageous for functional group conversion reaction, at the end, and has a high degree of freedom in designing initiators and catalysts, so the production of vinyl polymers having specific functional groups More preferable as a method. As this atom transfer radical polymerization method, for example, Matyjazewski et al., Journal of American Chemical Society (J. Am. Chem. Soc.) 1995, 117, 5614, Macromolecules (1995), 28, 7901, Science 1996, 272, 866, WO 96/30421, WO 97/18247 or Sawamoto et al., Macromolecules, 1995, 28, 1721, etc. Is mentioned.
[0021]
In the present invention, any of these methods is not particularly limited, but the atom transfer radical polymerization method is preferable because of easy control.
[0022]
Among these living radical polymerizations, first, a method using a radical scavenger such as a nitroxide compound will be described. In this polymerization, a stable nitroxy free radical (= N—O.) Is generally used as a radical capping agent. Examples of such compounds include, but are not limited to, 2,2,6,6-substituted-1-piperidinyloxy radical, 2,2,5,5-substituted-1-pyrrolidinyloxy radical, and the like. Nitroxy free radicals from cyclic hydroxyamines are preferred. As the substituent, an alkyl group having 4 or less carbon atoms such as a methyl group or an ethyl group is suitable. Specific nitroxy free radical compounds include, but are not limited to, 2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO), 2,2,6,6-tetraethyl-1- Piperidinyloxy radical, 2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy radical, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy radical, 1, Examples include 1,3,3-tetramethyl-2-isoindolinyloxy radical, N, N-di-t-butylamineoxy radical, and the like. Instead of the nitroxy free radical, a stable free radical such as a galvinoxyl free radical may be used.
[0023]
The radical capping agent is used in combination with a radical generator. It is considered that the reaction product of the radical capping agent and the radical generator serves as a polymerization initiator and the polymerization of the addition polymerizable monomer proceeds. The combination ratio of both is not particularly limited, but 0.1 to 10 mol of radical initiator is appropriate for 1 mol of radical capping agent.
[0024]
Although various compounds can be used as the radical generator, a peroxide capable of generating a radical under polymerization temperature conditions is preferred. Examples of the peroxide include, but are not limited to, diacyl peroxides such as benzoyl peroxide and lauroyl peroxide, dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide, diisopropyl peroxydicarbonate, bis There are peroxycarbonates such as (4-t-butylcyclohexyl) peroxydicarbonate, alkyl peresters such as t-butylperoxyoctate and t-butylperoxybenzoate. Benzoyl peroxide is particularly preferable. Furthermore, radical generators such as radical-generating azo compounds such as azobisisobutyronitrile may be used instead of peroxide.
[0025]
As reported in Macromolecules 1995, 28, 2993, instead of using a radical capping agent and a radical generator together, an alkoxyamine compound as shown below may be used as an initiator.
[0026]
[Chemical Formula 10]

  When an alkoxyamine compound is used as an initiator, if it has a functional group such as a hydroxyl group as shown in the above figure, a polymer having a functional group at the terminal can be obtained. When this is utilized in the method of the present invention, a star polymer having a functional group at the terminal can be obtained.
[0027]
Polymerization conditions such as a monomer, a solvent, and a polymerization temperature used in polymerization using a radical scavenger such as the above nitroxide compound are not limited, but may be the same as those used for atom transfer radical polymerization described below.
[0028]
Next, a more preferred atom transfer radical polymerization method as the living radical polymerization of the present invention will be described.
[0029]
In this atom transfer radical polymerization, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, an ester compound having a halogen at the α-position or a compound having a halogen at the benzyl-position), or halogen Sulfonyl compounds are used as initiators. As the catalyst, a metal complex having an element as a central metal of Group 7, Group 8, Group 9, Group 10, or Group 11 of the periodic table is used. As the metal species, monovalent copper, divalent ruthenium, and divalent iron are particularly preferable. Specifically, cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous acetate, cuprous perchlorate, etc. . In the case of using a copper compound, 2,2′-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, alkylamines such as tributylamine, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyl and the like to increase the catalytic activity A ligand such as a polyamine such as triethylenetetraamine is added. In addition, tristriphenylphosphine complex of divalent ruthenium chloride (RuCl₂(PPh_Three)_Three) Is also suitable as a catalyst. When this catalyst is used, an aluminum compound such as trialkoxyaluminum is added to increase its activity. Furthermore, tristriphenylphosphine complex of divalent iron chloride (FeCl₂(PPh_Three)_Three) Is also suitable as a catalyst.
[0030]
In this polymerization method, an organic halide or a sulfonyl halide compound is used as an initiator. For example,
C₆H_Five-CH₂X,
C₆H_Five-C (H) (X) CH_Three,
C₆H_Five-C (X) (CH_Three)₂,
R⁷-C (H) (X) -CO₂R⁸,
R⁷-C (CH_Three) (X) -CO₂R⁸,
R⁷-C (H) (X) -C (O) R⁸,
R⁷-C (CH_Three) (X) -C (O) R⁸,
R⁷-C₆H_Four-SO₂X,
(In the above equations, C₆H_FiveIs a phenyl group, R⁷, R⁸Are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, which may be the same or different. X is chlorine, bromine or iodine)
Etc.
[0031]
In addition, when an organic halide having a functional group or a halogenated sulfonyl compound is used in addition to the one that initiates polymerization, a polymer having a functional group introduced at the end can be easily obtained. Examples of such functional groups include alkenyl groups, hydroxyl groups, epoxy groups, amino groups, amide groups, silyl groups, and the like.
[0032]
Although there is no restriction | limiting in particular as an organic halide which has an alkenyl group, For example, what has a structure shown in General formula 6 is illustrated.
R⁹R^TenC (X) -R¹¹-R¹²-C (R¹³) = CH₂    (6)
(Wherein R⁹, R^TenIs hydrogen, or a monovalent alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, or those connected to each other at the other end, R¹¹-C (O) O- (ester group), -C (O)-(keto group), or o-, m-, p-phenylene group, R¹²Is a direct bond or a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds, R¹³Is hydrogen or a methyl group, X is chlorine, bromine, or iodine)
In these compounds, the carbon to which the halogen is bonded is bonded to a carbonyl group or a phenyl group, and the carbon-halogen bond is activated to initiate polymerization.
[0033]
Substituent R⁹, R^TenSpecific examples thereof include hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, pentyl group, hexyl group and the like. R⁹And R^TenMay be linked at the other end to form a cyclic skeleton.⁹-R^Ten-Is, for example, -CH₂CH₂-, -CH₂CH₂CH₂-, -CH₂CH₂CH₂CH₂-, -CH₂CH₂CH₂CH₂CH₂-, Etc. are exemplified.
[0034]
Specific examples of the organic halide having an alkenyl group represented by the general formula 6 include
XCH₂C (O) O (CH₂)_nCH = CH₂,
H_ThreeCC (H) (X) C (O) O (CH₂)_nCH = CH₂,
(H_ThreeC)₂C (X) C (O) O (CH₂)_nCH = CH₂,
CH_ThreeCH₂C (H) (X) C (O) O (CH₂)_nCH = CH₂,
[0035]
Embedded image

(In the above formulas, X is chlorine, bromine or iodine, and n is an integer of 0 to 20)
XCH₂C (O) O (CH₂)_nO (CH₂)_mCH = CH₂,
H_ThreeCC (H) (X) C (O) O (CH₂)_nO (CH₂)_mCH = CH₂,
(H_ThreeC)₂C (X) C (O) O (CH₂)_nO (CH₂)_mCH = CH₂,
CH_ThreeCH₂C (H) (X) C (O) O (CH₂)_nO (CH₂)_mCH = CH₂,
[0036]
Embedded image

(In each of the above formulas, X is chlorine, bromine, or iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20)
o, m, p-XCH₂-C₆H_Four-(CH₂)_n-CH = CH₂,
o, m, p-CH_ThreeC (H) (X) -C₆H_Four-(CH₂)_n-CH = CH₂,
o, m, p-CH_ThreeCH₂C (H) (X) -C₆H_Four-(CH₂)_n-CH = CH₂(In the above formulas, X is chlorine, bromine, or iodine, and n is an integer of 0 to 20)
o, m, p-XCH₂-C₆H_Four-(CH₂)_n-O- (CH₂)_m-CH = CH₂,
o, m, p-CH_ThreeC (H) (X) -C₆H_Four-(CH₂)_n-O- (CH₂)_m-CH = CH₂,
o, m, p-CH_ThreeCH₂C (H) (X) -C₆H_Four-(CH₂)_n-O- (CH₂)_mCH = CH₂,
(In each of the above formulas, X is chlorine, bromine, or iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20)
o, m, p-XCH₂-C₆H_Four-O- (CH₂)_n-CH = CH₂,
o, m, p-CH_ThreeC (H) (X) -C₆H_Four-O- (CH₂)_n-CH = CH₂,
o, m, p-CH_ThreeCH₂C (H) (X) -C₆H_Four-O- (CH₂)_n-CH = CH₂,
(In the above formulas, X is chlorine, bromine or iodine, and n is an integer of 0 to 20)
o, m, p-XCH₂-C₆H_Four-O- (CH₂)_n-O- (CH₂)_m-CH = CH₂,
o, m, p-CH_ThreeC (H) (X) -C₆H_Four-O- (CH₂)_n-O- (CH₂)_m-CH = CH₂,
o, m, p-CH_ThreeCH₂C (H) (X) -C₆H_Four-O- (CH₂)_n-O- (CH₂)_m-CH = CH₂,
(In each of the above formulas, X is chlorine, bromine, or iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20)
  The organic halide having an alkenyl group further includes a compound represented by the general formula 7.
H₂C = C (R¹³-R¹²-C (R⁹) (X) -R¹⁴-R^Ten    (7)
(Wherein R⁹, R^Ten, R¹², R¹³, X is the same as above, R¹⁴Represents a direct bond, —C (O) O— (ester group), —C (O) — (keto group), or o-, m-, p-phenylene group)
  R¹²Is a direct bond or a divalent organic group having 1 to 20 carbon atoms (which may contain one or more ether bonds). In the case of a direct bond, vinyl is bonded to the carbon to which the halogen is bonded. The groups are bonded and are allylic halides. In this case, since the carbon-halogen bond is activated by the adjacent vinyl group, R¹⁴It is not always necessary to have a C (O) O group or a phenylene group, and a direct bond may be used. R¹²In order to activate the carbon-halogen bond,¹⁴Is preferably a C (O) O group, a C (O) group, or a phenylene group.
[0037]
To specifically illustrate the compound of general formula 7,
CH₂= CHCH₂X, CH₂= C (CH_Three) CH₂X,
CH₂= CHC (H) (X) CH_Three, CH₂= C (CH_Three) C (H) (X) CH_Three,
CH₂= CHC (X) (CH_Three)₂, CH₂= CHC (H) (X) C₂H_Five,
CH₂= CHC (H) (X) CH (CH_Three)₂,
CH₂= CHC (H) (X) C₆H_Five, CH₂= CHC (H) (X) CH₂C₆H_Five,
CH₂= CHCH₂C (H) (X) -CO₂R,
CH₂= CH (CH₂)₂C (H) (X) -CO₂R,
CH₂= CH (CH₂)_ThreeC (H) (X) -CO₂R,
CH₂= CH (CH₂)₈C (H) (X) -CO₂R,
CH₂= CHCH₂C (H) (X) -C₆H_Five,
CH₂= CH (CH₂)₂C (H) (X) -C₆H_Five,
CH₂= CH (CH₂)_ThreeC (H) (X) -C₆H_Five,
(In the above formulas, X is chlorine, bromine, or iodine, R is an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group)
Etc.
[0038]
If the specific example of the sulfonyl halide compound which has an alkenyl group is given,
o-, m-, p-CH₂= CH- (CH₂)_n-C₆H_Four-SO₂X,
o-, m-, p-CH₂= CH- (CH₂)_n-OC₆H_Four-SO₂X,
(In the above formulas, X is chlorine, bromine, or iodine, and n is an integer of 0 to 20).
[0039]
In the case of an initiator having an alkenyl group, since the olefin of the initiator may also react with the polymerization terminal, it is necessary to pay attention to the polymerization conditions and the reaction conditions with the olefin compound to be added. As a specific example, an olefin compound is added at an early stage of polymerization.
[0040]
Although there is no restriction | limiting in particular as an organic halide which has a crosslinkable silyl group, For example, what has a structure shown in General formula 8 is illustrated.
R⁹R^TenC (X) -R¹¹-R¹²-C (H) (R¹³) CH₂-[Si (R¹⁵)_2-b(Y)_bO]_m-Si (R¹⁶)_3-a(Y)_a  (8)
(Wherein R⁹, R^Ten, R¹¹, R¹², R¹³Is the same as above. R¹⁵, R¹⁶Are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ')_ThreeA triorganosiloxy group represented by SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different). , R¹⁵Or R¹⁶When two or more are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y are present, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer of 0-19. However, it shall be satisfied that a + mb ≧ 1. )
The hydrolyzable group represented by Y is not particularly limited, and conventionally known hydrolyzable groups can be used. Specifically, hydrogen, halogen atom, alkoxy group, acyloxy group, ketoximate group, amino group, amide can be used. Groups, acid amide groups, aminooxy groups, mercapto groups, alkenyloxy groups and the like, and alkoxy groups are particularly preferred from the viewpoint that they are mild and easy to handle.
[0041]
If the compound of the general formula 8 is specifically exemplified,
XCH₂C (O) O (CH₂)_nSi (OCH_Three)_Three,
CH_ThreeC (H) (X) C (O) O (CH₂)_nSi (OCH_Three)_Three,
(CH_Three)₂C (X) C (O) O (CH₂)_nSi (OCH_Three)_Three,
XCH₂C (O) O (CH₂)_nSi (CH_Three) (OCH_Three)₂,
CH_ThreeC (H) (X) C (O) O (CH₂)_nSi (CH_Three) (OCH_Three)₂,
(CH_Three)₂C (X) C (O) O (CH₂)_nSi (CH_Three) (OCH_Three)₂,
(In the above formulas, X is chlorine, bromine, iodine, n is an integer of 0-20)
XCH₂C (O) O (CH₂)_nO (CH₂)_mSi (OCH_Three)_Three,
H_ThreeCC (H) (X) C (O) O (CH₂)_nO (CH₂)_mSi (OCH_Three)_Three,
(H_ThreeC)₂C (X) C (O) O (CH₂)_nO (CH₂)_mSi (OCH_Three)_Three,
CH_ThreeCH₂C (H) (X) C (O) O (CH₂)_nO (CH₂)_mSi (OCH_Three)_Three,
XCH₂C (O) O (CH₂)_nO (CH₂)_mSi (CH_Three) (OCH_Three)₂,
H_ThreeCC (H) (X) C (O) O (CH₂)_nO (CH₂)_m-Si (CH_Three) (OCH_Three)₂,
(H_ThreeC)₂C (X) C (O) O (CH₂)_nO (CH₂)_m-Si (CH_Three) (OCH_Three)₂,
CH_ThreeCH₂C (H) (X) C (O) O (CH₂)_nO (CH₂)_m-Si (CH_Three) (OCH_Three)₂,
(In the above formulas, X is chlorine, bromine, iodine, n is an integer of 1-20, m is an integer of 0-20)
o, m, p-XCH₂-C₆H_Four-(CH₂)₂Si (OCH_Three)_Three,
o, m, p-CH_ThreeC (H) (X) -C₆H_Four-(CH₂)₂Si (OCH_Three)_Three,
o, m, p-CH_ThreeCH₂C (H) (X) -C₆H_Four-(CH₂)₂Si (OCH_Three)_Three,
o, m, p-XCH₂-C₆H_Four-(CH₂)_ThreeSi (OCH_Three)_Three,
o, m, p-CH_ThreeC (H) (X) -C₆H_Four-(CH₂)_ThreeSi (OCH_Three)_Three,
o, m, p-CH_ThreeCH₂C (H) (X) -C₆H_Four-(CH₂)_ThreeSi (OCH_Three)_Three,
o, m, p-XCH₂-C₆H_Four-(CH₂)₂-O- (CH₂)_ThreeSi (OCH_Three)_Three,
o, m, p-CH_ThreeC (H) (X) -C₆H_Four-(CH₂)₂-O- (CH₂)_ThreeSi (OCH_Three)_Three,
o, m, p-CH_ThreeCH₂C (H) (X) -C₆H_Four-(CH₂)₂-O- (CH₂)_ThreeSi (OCH_Three)_Three,
o, m, p-XCH₂-C₆H_Four-O- (CH₂)_ThreeSi (OCH_Three)_Three,
o, m, p-CH_ThreeC (H) (X) -C₆H_Four-O- (CH₂)_ThreeSi (OCH_Three)_Three,
o, m, p-CH_ThreeCH₂C (H) (X) -C₆H_Four-O- (CH₂)_Three-Si (OCH_Three)_Three,
o, m, p-XCH₂-C₆H_Four-O- (CH₂)₂-O- (CH₂)_Three-Si (OCH_Three)_Three,
o, m, p-CH_ThreeC (H) (X) -C₆H_Four-O- (CH₂)₂-O- (CH₂)_ThreeSi (OCH_Three)_Three,
o, m, p-CH_ThreeCH₂C (H) (X) -C₆H_Four-O- (CH₂)₂-O- (CH₂)_ThreeSi (OCH_Three)_Three,
(In the above formulas, X is chlorine, bromine, or iodine)
Etc.
[0042]
Examples of the organic halide having a crosslinkable silyl group further include those having a structure represented by the general formula 9.
(R¹⁶)_3-a(Y)_aSi- [OSi (R¹⁵)_2-b(Y)_b]_m-CH₂-C (H) (R¹³-R¹²-C (R⁹) (X) -R¹⁴-R^Ten  (9)
(Wherein R⁹, R^Ten, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, A, b, m, X, Y are the same as above)
If such a compound is specifically illustrated,
(CH_ThreeO)_ThreeSiCH₂CH₂C (H) (X) C₆H_Five,
(CH_ThreeO)₂(CH_Three) SiCH₂CH₂C (H) (X) C₆H_Five,
(CH_ThreeO)_ThreeSi (CH₂)₂C (H) (X) -CO₂R¹⁷,
(CH_ThreeO)₂(CH_Three) Si (CH₂)₂C (H) (X) -CO₂R¹⁷,
(CH_ThreeO)_ThreeSi (CH₂)_ThreeC (H) (X) -CO₂R¹⁷,
(CH_ThreeO)₂(CH_Three) Si (CH₂)_ThreeC (H) (X) -CO₂R¹⁷,
(CH_ThreeO)_ThreeSi (CH₂)_FourC (H) (X) -CO₂R¹⁷,
(CH_ThreeO)₂(CH_Three) Si (CH₂)_FourC (H) (X) -CO₂R¹⁷,
(CH_ThreeO)_ThreeSi (CH₂)₉C (H) (X) -CO₂R¹⁷,
(CH_ThreeO)₂(CH_Three) Si (CH₂)₉C (H) (X) -CO₂R¹⁷,
(CH_ThreeO)_ThreeSi (CH₂)_ThreeC (H) (X) -C₆H_Five,
(CH_ThreeO)₂(CH_Three) Si (CH₂)_ThreeC (H) (X) -C₆H_Five,
(CH_ThreeO)_ThreeSi (CH₂)_FourC (H) (X) -C₆H_Five,
(CH_ThreeO)₂(CH_Three) Si (CH₂)_FourC (H) (X) -C₆H_Five,
(In each of the above formulas, X is chlorine, bromine, or iodine, R¹⁷Is a C1-C20 alkyl group, aryl group, aralkyl group)
Etc.
[0043]
The organic halide having a hydroxyl group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.
HO- (CH₂)_n-OC (O) C (H) (R¹⁸) (X)
(In each of the above formulas, X is chlorine, bromine, or iodine, R¹⁷Is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)
The organic halide having an amino group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.
H₂N- (CH₂)_n-OC (O) C (H) (R¹⁷) (X)
(In each of the above formulas, X is chlorine, bromine, or iodine, R¹⁷Is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)
Although there is no restriction | limiting in particular as an organic halide with an epoxy group, or a halogenated sulfonyl compound, The following are illustrated.
[0044]
Embedded image

(In each of the above formulas, X is chlorine, bromine, or iodine, R¹⁷Is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)
  In order to obtain a polymer having two or more olefin terminal structures in one molecule according to the present invention, an organic halide having two or more starting points or a sulfonyl halide compound is used as an initiator. For example,
[0045]
Embedded image

[0046]
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Etc.
<Polymerization conditions>
  There is no restriction | limiting in particular as a polymerizable olefin monomer used in this superposition | polymerization, The various things already stated can be used. Further, since the polymerization system shown here is living polymerization, it is also possible to produce a block copolymer by sequential addition of polymerizable monomers.
[0047]
The polymerization can be carried out without solvent or in various solvents. Although these are not particularly limited, for example, hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether and tetrahydrofuran; halogenated hydrocarbon solvents such as methylene chloride and chloroform; acetone, methyl ethyl ketone, methyl Ketone solvents such as isobutyl ketone; alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol; nitrile solvents such as acetonitrile, propionitrile, benzonitrile; ethyl acetate, butyl acetate And ester solvents such as ethylene carbonate and propylene carbonate, and the like, and may be used alone or in admixture of two or more. Also, emulsion system or supercritical fluid CO₂Polymerization can also be carried out in a system in which is used as a medium. Among these, nitrile solvents are preferable and acetonitrile is more preferable from the viewpoint of improving the catalyst stability.
[0048]
Moreover, superposition | polymerization can be performed in the range of room temperature-200 degreeC, Preferably it is 50-150 degreeC.
[0049]
During the polymerization or at the end point (after 80% by weight of the radical polymerizable monomer is consumed by atom transfer radical polymerization), when the olefin compound (I) having a low polymerizable alkenyl group is added, Almost one is added to the terminal, and as a result, the functional group of the alkenyl compound is introduced to the terminal of the polymer. In order to introduce an alkenyl group at the terminal, it is preferable to add an excessive amount of a compound having two low-polymerizability alkenyl groups.
[0050]
In the present invention, the olefin compound (I) is added after 80% by weight of the radical polymerizable monomer is consumed by atom transfer radical polymerization. If the olefin compound (I) is added before 80% by weight of the radical polymerizable monomer is consumed, the molecular weight of the vinyl polymer tends to be smaller than the set value.
The olefin compound (I) is preferably added when 80 to 99.9% by weight of the radical polymerizable monomer is consumed, and more preferably added when 85 to 99% by weight is consumed. The amount of the radical polymerizable monomer is the amount finally charged in the polymerization solution.
<< Olefin compound (I) >>
The olefin compound having a low polymerizable alkenyl group is selected from compounds represented by the general formula 1.
General formula 1:
[0051]
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{In the above formula, R^ThreeIs a hydroxyl group, an amino group, an epoxy group, a carboxylic acid group, an ester group, an ether group, an amide group, a silyl group, or a general formula 2:
[0052]
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(R^FourIs a hydrogen atom or a methyl group), or an organic group having 1 to 20 carbon atoms that does not contain a polymerizable olefin, and R¹Is an alkyl group having 1 to 20 carbon atoms or a general formula 3:
[0053]
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(In the above formula, R^FiveIs an organic group having 1 to 20 carbon atoms which may have an oxygen atom or a nitrogen atom, R⁶Are hydrogen atoms or methyl groups, which may be the same or different), and R²Is a hydrogen atom or a methyl group}
  Among them, the compound having two low-polymerizability alkenyl groups used for introducing the alkenyl group is selected from compounds represented by the general formula 4.
[0054]
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{In the above formula, R¹Is an alkyl group having 1 to 20 carbon atoms or a general formula 3:
[0055]
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(In the above formula, R^FiveIs an organic group having 1 to 20 carbon atoms which may have an oxygen atom or a nitrogen atom, R⁶Are hydrogen atoms or methyl groups, which may be the same or different)
And a group having the structure of R², R^FourIs a hydrogen atom or a methyl group}
  R², R^ThreeIs a hydrogen atom or a methyl group, preferably a hydrogen atom. R¹When is an alkyl group having 1 to 20 carbon atoms, the structure is not limited, but the compound represented by Formula 5 is exemplified.
[0056]
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From the viewpoint of easy availability of raw materials, n is preferably 2, 4, or 6.
[0057]
In general formula 1, R¹As a specific example of
-(CH₂)_n-(N is an integer from 1 to 20),
-CH (CH_Three)-, -CH (CH₂CH_Three)-, -C (CH_Three)₂-, -C (CH_Three) (CH₂CH_Three)-, -C (CH₂CH_Three)₂-, -CH₂CH (CH_Three-,
-(CH₂)_n-O-CH₂-(N is an integer from 1 to 19),
-CH (CH_Three) -O-CH₂-, -CH (CH₂CH_Three) -O-CH₂-, -C (CH_Three)₂-O-CH₂-, -C (CH_Three) (CH₂CH_Three) -O-CH₂-, -C (CH₂CH_Three)₂-O-CH₂−,
-(CH₂)_n-O- (CH₂)_m−
(M and n are integers of 1 to 19, where 2 ≦ m + n ≦ 20),
-(CH₂)_n-C (O) O- (CH₂)_m−
(M and n are integers of 1 to 19, where 2 ≦ m + n ≦ 20),
-(CH₂)_n-OC (O)-(CH₂)_m-C (O) O- (CH₂)_l−,
(L is an integer from 0 to 18, m and n are integers from 1 to 17, where 2 ≦ l + m + n ≦ 18),
-(CH₂)_n-O-, m-, p-C₆H_Four−,
-(CH₂)_n-O-, m-, p-C₆H_Four-(CH₂)_m−,
(M is an integer of 0 to 13, n is an integer of 1 to 14, where 1 ≦ m + n ≦ 14),
-(CH₂)_n-O-, m-, p-C₆H_Four-O- (CH₂)_m−,
(M is an integer of 0 to 13, n is an integer of 1 to 14, where 1 ≦ m + n ≦ 14),
-(CH₂)_n-O-, m-, p-C₆H_Four-O-CH (CH_Three-,
(N is an integer from 1 to 12),
-(CH₂)_n-O-, m-, p-C₆H_Four-O-CH (CH_Three)₂−,
(N is an integer from 1 to 11),
-(CH₂)_n-O-, m-, p-C₆H_Four-C (O) O- (CH₂)_m−,
(M and n are integers of 1 to 12, where 2 ≦ m + n ≦ 13),
-(CH₂)_n-OC (O) -o-, m-, p-C₆H_Four-C (O) O- (CH₂)_m−,
(M and n are integers of 1 to 11, where 2 ≦ m + n ≦ 12),
-(CH₂)_n-O-, m-, p-C₆H_Four-OC (O)-(CH₂)_m−,
(M and n are integers of 1 to 12, where 2 ≦ m + n ≦ 13),
-(CH₂)_n-C (O) O-o-, m-, p-C₆H_Four-(CH₂)_m−,
(M and n are integers of 1 to 11, where 2 ≦ m + n ≦ 12),
Etc.
R^ThreeAs such, the following groups are exemplified.
[0058]
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(Wherein R¹⁸, R¹⁹Are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ')_ThreeA triorganosiloxy group represented by SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different). , R¹⁸Or R¹⁹When two or more are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y are present, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer of 0-19. However, it shall be satisfied that a + mb ≧ 1. R²⁰Is a hydrocarbon group having 1 to 20 carbon atoms. )
  R²⁰Specifically, the following groups are exemplified.
-(CH₂)_n-CH_Three,
-CH (CH_Three)-(CH₂)_n-CH_Three,
-CH (CH₂CH_Three)-(CH₂)_n-CH_Three,
-CH (CH₂CH_Three)₂,
-C (CH_Three)₂-(CH₂)_n-CH_Three,
-C (CH_Three) (CH₂CH_Three)-(CH₂)_n-CH_Three,
-C₆H_Five
-C₆H_Five(CH_Three),
-C₆H_Four(CH_Three)₂,
-(CH₂)_n-C₆H_Five,
-(CH₂)_n-C₆H_Four(CH_Three),
-(CH₂)_n-C₆H_Three(CH_Three)₂,
(N is an integer of 0 or more, and the total carbon number of each group is 20 or less)
  The silyl group is not limited, but preferably m = 0 in the above formula.
[0059]
When a compound having an amino group, a hydroxyl group or a carboxylic acid group is reacted at the polymerization terminal, it may be reacted as it is, but those groups may affect the polymerization terminal or the catalyst. A compound having a protecting group may be used. Examples of the protecting group include an acetyl group, a silyl group, and an alkoxy group.
[0060]
The amount of the compound used for introducing these functional groups is not particularly limited. Since the reactivity of the alkenyl group of these compounds is not so high, it is preferable to increase the addition amount in order to increase the reaction rate. On the other hand, to reduce the cost, the addition amount is equal to the growth terminal. The closer one is preferable, and it is necessary to optimize it according to the situation.
[0061]
Moreover, it is preferable that the amount of the compound having two or more low-polymerizable alkenyl groups to introduce an alkenyl group at the terminal is an excessive amount with respect to the polymerization growth terminal. If the amount is equal or less than the end, both of the two olefins may react and couple the polymerization end. In the case of compounds having the same reactivity of two olefins, the probability of coupling will be statistically determined according to the amount added in excess. Therefore, it is preferably 1.5 times or more, more preferably 3 times or more, and particularly preferably 5 times or more.
<< Compound (II) >>
When the olefin compound (I) having an alkenyl group having low polymerization property is added, depending on the type of the olefin compound (I), the polarity of the reaction system may be lowered, and the catalyst activity may be insufficient. In this case, the polarity of the reaction system can be increased by adding the compound (II) having a dielectric constant higher than that of the olefin compound (I). Although it does not specifically limit as compound (II), For example, Hydrocarbon compounds, such as benzene and toluene; Ether compounds, such as diethyl ether and tetrahydrofuran; Halogenated hydrocarbon compounds, such as a methylene chloride and chloroform; Acetone Ketone compounds such as methyl ethyl ketone and methyl isobutyl ketone; alcohol compounds such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol and tert-butyl alcohol; nitrile compounds such as acetonitrile, propionitrile and benzonitrile; acetic acid Examples thereof include ester compounds such as ethyl and butyl acetate, and carbonate compounds such as ethylene carbonate and propylene carbonate. These may be used alone or in combination of two or more, and may be the same as or different from the solvent used in the polymerization, but the same in consideration of the ease of recovery after the reaction Is preferable. The dielectric constant of the compound (II) is preferably 3 or more, more preferably 5 or more, still more preferably 10 or more than the olefin compound (I). The higher the dielectric constant of compound (II), the more the effect of improving the polarity can be expected. Here, the dielectric constant is a value at 20 ° C. Of these, nitrile compounds are preferable and acetonitrile is more preferable from the viewpoint of improving the catalyst stability. The amount of compound (II) used is 1-1000 parts by weight with respect to 100 parts by weight of the radically polymerizable monomer, preferably 3-1000 parts by weight, and preferably 5-500 parts by weight. More preferred is 10 to 100 parts by weight. Or it is preferable that it is 1-10000 weight part with respect to 100 weight part of olefin compound (I), and, as for the usage-amount of compound (II), it is more preferable that it is 10-1000 weight part. If the amount of compound (II) used is small, the effect of improving the polarity may not be exhibited. If it is large, recovery from the polymer may be difficult after polymerization.
[0062]
In the present invention, compound (II) is added after 80% by weight of the radical polymerizable monomer is consumed by atom transfer radical polymerization. If compound (II) is added before 80% by weight of the radical polymerizable monomer is consumed, the molecular weight of the vinyl polymer tends to be smaller than the set value.
Compound (II) is preferably added when 80 to 99.9% by weight of the radical polymerizable monomer is consumed, and more preferably added when 85 to 99% by weight is consumed. The amount of the radical polymerizable monomer is the amount finally charged in the polymerization solution.
《Terminal structure》
During the polymerization or at the end point (that is, after 80% of the radical polymerizable monomer is consumed by the atom transfer radical polymerization), when the olefin compound (I) having a low polymerizable alkenyl group is added, the terminal is almost One by one is added, and as a result, the functional group of the alkenyl compound is introduced into the end of the polymer. The terminal structure at this time is represented by the general formula 10. The polymer of the radically polymerizable monomer having this terminal structure is directly bonded only by a carbon-carbon bond without interposing a heteroatom, and the terminal group is bonded approximately one per terminal of the polymer. It is a feature.
[0063]
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{In the above formula, R^ThreeIs a hydroxyl group, an amino group, an epoxy group, a carboxylic acid group, an ester group, an ether group, an amide group, a silyl group, or a general formula 2:
[0064]
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(R^FourIs a hydrogen atom or a methyl group), or an organic group having 1 to 20 carbon atoms that does not contain a polymerizable olefin, and R¹Is an alkyl group having 1 to 20 carbon atoms, or a general formula 3:
[0065]
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(In the above formula, R^FiveIs an oxygen atom, a nitrogen atom or an organic group having 1 to 20 carbon atoms, R⁶Are hydrogen atoms or methyl groups, which may be the same or different)
And a group having the structure of R²Is a hydrogen atom or a methyl group, and X is a halogen group, a nitroxide group, a sulfide group or a cobalt porphyrin complex}¹As a specific example of
-(CH₂)_n-(N is an integer from 1 to 20),
-CH (CH_Three)-, -CH (CH₂CH_Three)-, -C (CH_Three)₂-, -C (CH_Three) (CH₂CH_Three)-, -C (CH₂CH_Three)₂-, -CH₂CH (CH_Three)-,-(CH₂)_n-O-CH₂-(N is an integer from 1 to 19),
-CH (CH_Three) -O-CH₂-, -CH (CH₂CH_Three) -O-CH₂-, -C (CH_Three)₂-O-CH₂-, -C (CH_Three) (CH₂CH_Three) -O-CH₂-, -C (CH₂CH_Three)₂-O-CH₂−,
-(CH₂)_n-O- (CH₂)_m−
(M and n are integers of 1 to 19, where 2 ≦ m + n ≦ 20),
-(CH₂)_n-C (O) O- (CH₂)_m−
(M and n are integers of 1 to 19, where 2 ≦ m + n ≦ 20),
-(CH₂)_n-OC (O)-(CH₂)_m-C (O) O- (CH₂)_l−,
(L is an integer from 0 to 18, m and n are integers from 1 to 17, where 2 ≦ l + m + n ≦ 18),
-(CH₂)_n-O-, m-, p-C₆H_Four−,
-(CH₂)_n-O-, m-, p-C₆H_Four-(CH₂)_m−,
(M is an integer of 0 to 13, n is an integer of 1 to 14, where 1 ≦ m + n ≦ 14),
-(CH₂)_n-O-, m-, p-C₆H_Four-O- (CH₂)_m−,
(M is an integer of 0 to 13, n is an integer of 1 to 14, where 1 ≦ m + n ≦ 14),
-(CH₂)_n-O-, m-, p-C₆H_Four-O-CH (CH_Three-,
(N is an integer from 1 to 12),
-(CH₂)_n-O-, m-, p-C₆H_Four-O-CH (CH_Three)₂−,
(N is an integer from 1 to 11),
-(CH₂)_n-O-, m-, p-C₆H_Four-C (O) O- (CH₂)_m−,
(M and n are integers of 1 to 12, where 2 ≦ m + n ≦ 13),
-(CH₂)_n-OC (O) -o-, m-, p-C₆H_Four-C (O) O- (CH₂)_m−,
(M and n are integers of 1 to 11, where 2 ≦ m + n ≦ 12),
-(CH₂)_n-O-, m-, p-C₆H_Four-OC (O)-(CH₂)_m−,
(M and n are integers of 1 to 12, where 2 ≦ m + n ≦ 13),
-(CH₂)_n-C (O) O-o-, m-, p-C₆H_Four-(CH₂)_m−,
(M and n are integers of 1 to 11, where 2 ≦ m + n ≦ 12),
Etc. R^ThreeAs such, the following groups are exemplified.
[0066]
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Where R¹⁸, R¹⁹Are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ')_ThreeA triorganosiloxy group represented by SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different). , R¹⁸Or R¹⁹When two or more are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y are present, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer of 0-19. However, it shall be satisfied that a + mb ≧ 1.
[0067]
R²⁰Is a hydrocarbon group having 1 to 20 carbon atoms, and specific examples thereof include the following groups.
-(CH₂)_n-CH_Three,
-CH (CH_Three)-(CH₂)_n-CH_Three,
-CH (CH₂CH_Three)-(CH₂)_n-CH_Three,
-CH (CH₂CH_Three)₂,
-C (CH_Three)₂-(CH₂)_n-CH_Three,
-C (CH_Three) (CH₂CH_Three)-(CH₂)_n-CH_Three,
-C₆H_Five,
-C₆H_Five(CH_Three),
-C₆H_Four(CH_Three)₂,
-(CH₂)_n-C₆H_Five,
-(CH₂)_n-C₆H_Four(CH_Three),
-(CH₂)_n-C₆H_Three(CH_Three)₂,
(N is an integer of 0 or more, and the total carbon number of each group is 20 or less)
In general formula 10, R²Is a hydrogen atom or a methyl group, preferably a hydrogen atom. X is a halogen group, a nitroxide group, a sulfide group, or a cobalt porphyrin complex, and a halogen group is preferable, and a bromo group is particularly preferable because of ease of production.
[0068]
In the case where an alkenyl group is introduced at the terminal, R¹When is an alkyl group having 1 to 20 carbon atoms, the structure is not limited, but the following are exemplified.
[0069]
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From the viewpoint of easy availability of raw materials, n is preferably 2, 4, or 6.
[0070]
Although there is no restriction | limiting in particular in the number of the terminal groups contained in 1 molecule of polymers, When using for a curable composition etc., it is preferable that 0.5-5 pieces are contained, and 1-3 pieces are contained. It is more preferable that 1.5 to 2.5 is more preferable.
[0071]
The polymer obtained in the present invention has a molecular weight distribution, that is, the ratio of the weight average molecular weight to the number average molecular weight measured by gel permeation chromatography is preferably 1.8 or less, more preferably 1.6 or less. Most preferably, it is 1.3 or less.
[0072]
The number average molecular weight of the polymer obtained in the present invention is preferably in the range of 500 to 100,000, more preferably 3000 to 50,000. When the molecular weight is 500 or less, the original characteristics of the (meth) acrylic polymer are hardly expressed, and when it is 100,000 or more, handling becomes difficult.
[0073]
The polymer produced in the present invention is used as it is by using the introduced functional group as it is or by carrying out a further conversion reaction. Specifically, the alkenyl group is converted to a crosslinkable silyl group by a hydrosilylation reaction with a hydrosilyl compound having a crosslinkable silyl group. As the vinyl polymer having an alkenyl group at the terminal, any polymer obtained by the method described above can be preferably used.
[0074]
Although there is no restriction | limiting in particular as a hydrosilane compound, When a typical thing is shown, it is General formula 12
H- [Si (R^{twenty one})_2-b(Y)_bO]_m・ Si (R^{twenty two})_3-a(Y)_a  (12)
(Wherein R^{twenty one}, R^{twenty two}Are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ')_ThreeA triorganosiloxy group represented by SiO— (R ′ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R ′ may be the same or different). , R²⁰Or R^{twenty two}When two or more are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y are present, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer of 0-19. However, it shall be satisfied that a + mb ≧ 1)
The compound represented by these is illustrated.
[0075]
The hydrolyzable group represented by Y is not particularly limited, and conventionally known hydrolyzable groups can be used. Specifically, hydrogen, halogen atom, alkoxy group, acyloxy group, ketoximate group, amino group, amide can be used. Groups, acid amide groups, aminooxy groups, mercapto groups, alkenyloxy groups and the like, and alkoxy groups are particularly preferred from the viewpoint that they are mild and easy to handle. The hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3, and the sum of a + mb, that is, the hydrolyzable group is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the reactive silicon group, they may be the same or different. The number of silicon atoms constituting the crosslinkable silicon compound may be one or two or more, but in the case of silicon atoms linked by a siloxane bond, it may be up to about 20.
[0076]
R in general formula 12^{twenty one}, R^{twenty two}Specific examples of these include, for example, an alkyl group such as a methyl group or an ethyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, an aralkyl group such as a benzyl group, and R ′ is a methyl group or a phenyl group. Yes (R ')_ThreeExamples include triorganosilyl groups represented by SiO-.
[0077]
Among these hydrosilane compounds, in particular, the general formula 13
H-Si (R^{twenty two})_3-a(Y)_a  (13)
(Wherein R²⁰, Y and a are the same as described above. The hydrosilane compound having a crosslinkable group represented by (2) is preferred from the viewpoint of easy availability. Specific examples of the hydrosilane compound having a crosslinkable group represented by the general formula 12 or 13 include
HSiCl_Three, HSi (CH_Three) Cl₂, HSi (CH_Three)₂Cl, HSi (OCH_Three)_Three, HSi (CH_Three) (OCH_Three)₂, HSi (CH_Three)₂OCH_Three, HSi (OC₂H_Five)_Three, HSi (CH_Three) (OC₂H_Five)₂,
HSi (CH_Three)₂OC₂H_Five, HSi (OC_ThreeH₇)_Three,
HSi (C₂H_Five) (OCH_Three)₂, HSi (C₂H_Five)₂OCH_Three,
HSi (C₆H_Five) (OCH_Three)₂, HSi (C₆H_Five)₂(OCH_Three),
HSi (CH_Three) (OC (O) CH_Three)₂,
HSi (CH_Three)₂O- [Si (CH_Three)₂O]₂・ Si (CH_Three) (OCH_Three)₂,
HSi (CH_Three) [O-N = C (CH_Three)₂]₂
(However, in the above chemical formula, C₆H_FiveRepresents a phenyl group)
Etc.
[0078]
When such a hydrosilane compound having a crosslinkable silyl group is added to a vinyl polymer having an alkenyl group at the terminal, a hydrosilylation catalyst is used. Such hydrosilylation catalysts include radical initiators such as organic peroxides and azo compounds, and transition metal catalysts.
[0079]
There is no restriction | limiting in particular as a radical initiator, Various things can be used. For example, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) -3 Hexyne, dicumyl peroxide, t-butylcumyl peroxide, dialkyl peroxides such as α, α′-bis (t-butylperoxy) isopropylbenzene, benzoyl peroxide, p-chlorobenzoyl peroxide, m-chlorobenzoyl peroxide, 2 , 4-dichlorobenzoyl peroxide, diacyl peroxides such as lauroyl peroxide, peracid esters such as perbenzoic acid-tert-butyl, peroxydicarbonates such as diisopropyl percarbonate, di-2-ethylhexyl percarbonate 1,1-di (t-butylperoxy) si Examples thereof include peroxyketals such as chlorohexane and 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane.
[0080]
The transition metal catalyst includes, for example, platinum simple substance, alumina, silica, carbon black and the like dispersed in a platinum solid, chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, ketone, etc. And a platinum-olefin complex and a platinum (0) -divinyltetramethyldisiloxane complex. Examples of catalysts other than platinum compounds include RhCl (PPh_Three)_Three, RhCl_Three, RuCl_Three, IrCl_Three, FeCl_Three, AlCl_Three, PdCl₂・ H₂O, NiCl₂, TiCl_FourEtc. These catalysts may be used alone or in combination of two or more. Although there is no restriction | limiting in particular as a catalyst amount, It is 10 with respect to 1 mol of alkenyl groups of (A) component.^-1-10^-8It should be used in the range of mol, preferably 10^-3-10^-6It is good to use in the range of mol. 10^-8If the amount is less than mol, curing may not proceed sufficiently, and the hydrosilylation catalyst is expensive.^-1It is preferable not to use more than mol.
[0081]
When allyl alcohol or methallyl alcohol is reacted at the polymerization terminal, a terminal having an active group such as a halogen group and a hydroxyl group on the adjacent carbon atom is formed. This end can be cyclized and converted to an epoxy group. The method for carrying out this cyclization reaction is not particularly limited, but it is preferable to react an alkaline compound. Although it does not specifically limit as an alkaline compound, KOH, NaOH, Ca (OH)₂And ammonia and various amines.
[0082]
The terminal hydroxyl group is converted to an alkenyl group by a condensation reaction using an alkaline compound with allyl chloride or allyl bromide. Moreover, it converts into an epoxy group by the same reaction using epichlorohydrin.
[0083]
The terminal hydroxyl group or amino group can be converted to a crosslinkable silyl group by reaction with a compound having both a functional group that reacts with the hydroxyl group or amino group and a crosslinkable silyl group. Examples of the functional group that reacts with a hydroxyl group or an amino group include halogen, carboxylic acid halide, carboxylic acid, and isocyanate group. An isocyanate group is preferable in that the decomposition of the functional silyl group hardly occurs.
[0084]
There is no restriction | limiting in particular as such an isocyanate type compound which has a crosslinkable silyl group, A well-known thing can be used. For example,
(CH_ThreeO)_ThreeSi- (CH₂)_n-NCO,
(CH_ThreeO)₂(CH_Three) Si- (CH₂)_n-NCO,
(C₂H_FiveO)_ThreeSi- (CH₂)_n-NCO,
(C₂H_FiveO)₂(CH_Three) Si- (CH₂)_n-NCO,
(I-C_ThreeH₇O)_ThreeSi- (CH₂)_n-NCO,
(I-C_ThreeH₇O)₂(CH_Three) Si- (CH₂)_n-NCO,
(CH_ThreeO)_ThreeSi- (CH₂)_n-NH- (CH₂)_m-NCO,
(CH_ThreeO)₂(CH_Three) Si- (CH₂)_n-NH- (CH₂)_m-NCO,
(C₂H_FiveO)_ThreeSi- (CH₂)_n-NH- (CH₂)_m-NCO,
(C₂H_FiveO)₂(CH_Three) Si- (CH₂)_n-NH- (CH₂)_m-NCO,
(I-C_ThreeH₇O)_ThreeSi- (CH₂)_n-NH- (CH₂)_m-NCO,
(I-C_ThreeH₇O)₂(CH_Three) Si- (CH₂)_n-NH- (CH₂)_m-NCO,
(In the above formula, n and m are integers of 1 to 20)
Etc.
[0085]
The reaction of the (meth) acrylic polymer having a hydroxyl group at the terminal and the isocyanate compound having a crosslinkable silyl group can be carried out in the absence of a solvent or in various solvents, and the reaction temperature is 0 ° C. to 100 ° C., Preferably, it is 20 to 50 ° C. At this time, the tin-based catalyst and the tertiary amine-based catalyst already exemplified for promoting the reaction between the hydroxyl group and the isocyanate group can be used.
"Composition"
These polymers having functional groups at the terminals can be made into curable compositions utilizing various crosslinking reactions. From the polymer having an alkenyl group at the terminal, a curable composition containing (A) a polymer having an alkenyl group and (B) a hydrosilyl group-containing compound can be obtained.
[0086]
(A) The vinyl polymer which has an alkenyl group at the terminal of a component may be used independently, or 2 or more types may be mixed and used for it. Although there is no restriction | limiting in particular as molecular weight of (A) component, it exists in the range of 500-100000, and 3000-40000 is further more preferable. 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 becomes very low, and handling becomes difficult.
[0087]
There is no restriction | limiting in particular as a hydrosilyl group containing compound of (B) component, Various things can be used. That is, a linear polysiloxane represented by the general formula 14 or 15
R^{twenty three} _ThreeSiO- [Si (R^{twenty three})₂O]_a-[Si (H) (R^{twenty four}) O]_b-[Si (R^{twenty four}) (R^{twenty five}) O]_c-SiR^{twenty three} _Three  (14)
HR^{twenty three} ₂SiO- [Si (R^{twenty three})₂O]_a-[Si (H) (R^{twenty four}) O]_b-[Si (R^{twenty four}) (R^{twenty five}) O]_c-SiR^{twenty three} ₂H (15)
(Where R^{twenty three}And R^{twenty four}Is an alkyl group having 1 to 6 carbon atoms, or a phenyl group, R^{twenty five}Is an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, a is 0 ≦ a ≦ 100, b is 2 ≦ b ≦ 100, and c is an integer of 0 ≦ C ≦ 100),
Cyclic siloxane represented by general formula 16
[0088]
Embedded image

(Where R^{twenty three}And R^{twenty four}Is an alkyl group having 1 to 6 carbon atoms, or a phenyl group, R^{twenty five}Is an alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, d is 0 ≦ d ≦ 8, e is 2 ≦ e ≦ 10, f is an integer of 0 ≦ f ≦ 8, and 3 ≦ d + e + f ≦ 10).
[0089]
These may be used alone or in combination of two or more. Among these siloxanes, chain siloxanes represented by general formulas 17 and 18 and cyclic siloxanes represented by general formulas 19 and 20 having a phenyl group are preferable from the viewpoint of compatibility with a vinyl polymer.
(CH_Three)_ThreeSiO- [Si (H) (CH_Three) O]_g-[Si (C₆H_Five)₂O]_h-Si (CH_Three)_Three  (17)
(CH_Three)_ThreeSiO- [Si (H) (CH_Three) O]_g-[Si (CH_Three) {CH₂C (H) (R²⁶) C₆H_Five} O]_h−
Si (CH_Three)_Three  (18)
(Wherein R²⁶Is hydrogen or a methyl group, g is 2 ≦ g ≦ 100, h is an integer of 0 ≦ h ≦ 100, C₆H_FiveRepresents a phenyl group)
[0090]
Embedded image

(Wherein R²⁶Is hydrogen or a methyl group, i is 2 ≦ i ≦ 10, j is an integer satisfying 0 ≦ j ≦ 8 and 3 ≦ i + j ≦ 10, C₆H_FiveIs a phenyl group)
As the curing agent having at least two or more hydrosilyl groups as the component (B), the hydrosilyl group-containing compound represented by the general formulas 14 to 20 is used for a low molecular compound having two or more alkenyl groups in the molecule. A compound obtained by addition reaction such that a part of the hydrosilyl group remains after the reaction can also be used. Various compounds can be used as the compound having two or more alkenyl groups in the molecule. For example, hydrocarbon compounds such as 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, O, O Ether compounds such as' -diallyl bisphenol A, 3,3'-diallyl bisphenol A, diallyl phthalate, diallyl isophthalate, triallyl trimellitate, tetraallyl pyromellite -Ester-based compounds such as diethylene glycol, and carbonate-based compounds such as diethylene glycol diallyl carbonate. In this case, the compound can be obtained by slowly dropping the above-mentioned alkenyl group-containing compound in the presence of a hydrosilylation catalyst with respect to the excessive amount of the hydrosilyl group-containing compound represented by the general formulas 14 to 20. Of these compounds, the following are preferred in view of the availability of raw materials, the ease of removal of the excessively used siloxane, and the compatibility of the component (A) with the polymer.
[0091]
Embedded image

The polymer (A) and the curing agent (B) can be mixed at an arbitrary ratio, but from the viewpoint of curability, the molar ratio of the alkenyl group to the hydrosilyl group is preferably in the range of 5 to 0.2. Furthermore, it is particularly preferably 2.5 to 0.4. When the molar ratio is 5 or more, curing is insufficient and only a cured product having low tackiness and a low strength can be obtained. When the molar ratio is less than 0.2, a large amount of active hydrosilyl groups remain in the cured product even after curing. Cracks and voids are generated, and a uniform and strong cured product cannot be obtained.
[0092]
The curing reaction between the polymer (A) and the curing agent (B) proceeds by mixing and heating the two components, but a hydrosilylation catalyst is added to advance the reaction more rapidly. As such a hydrosilylation catalyst, the various catalysts already described are used.
[0093]
The polymer having a crosslinkable silyl group at the terminal can be made into a curable composition containing this as a main component.
[0094]
When a vinyl polymer having a crosslinkable silyl group at the 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 hydrolyzable group, an appropriate hydrolyzable group must be selected according to the use conditions.
[0095]
A curing catalyst may be added to accelerate the curing reaction. Condensation catalysts include titanic acid esters such as tetrabutyl titanate and tetrapropyl titanate; organotin compounds such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate and tin naphthenate; lead octylate, butylamine and octyl Amine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, octylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2, 4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 1,3-diazabicyclo (5,4, ) Amine compounds such as undecene-7 or their carboxylates; low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; reaction products of excess polyamines and epoxy compounds; silane coupling agents having amino groups For example, one or more known silanol catalysts such as γ-aminopropyltrimethoxysilane and N- (β-aminoethyl) aminopropylmethyldimethoxysilane may be used as necessary. The amount used is preferably 0 to 10% by weight based on the vinyl polymer having a crosslinkable silyl group at the terminal. When an alkoxy group is used as the hydrolyzable group Y, it is preferable to use a curing catalyst because the curing rate is slow only with this polymer.
[0096]
A uniform cured product can be obtained by mixing a vinyl catalyst having a crosslinkable silyl group at the terminal, which is the main component, with a condensation catalyst, if necessary, and curing. Although there is no restriction | limiting in particular as hardening conditions, Generally 0-100 degreeC, Preferably it is about 10-50 degreeC for about 1 hour-1 week. The properties of the cured product depend on the main chain skeleton and molecular weight of the polymer to be used, but can be widely prepared from rubbery to resinous.
[0097]
A uniform cured product can be obtained by mixing a vinyl catalyst having a crosslinkable silyl group at the terminal, which is the main component, with a condensation catalyst, if necessary, and curing. Although there is no restriction | limiting in particular as hardening conditions, Generally 0-100 degreeC, Preferably it is about 10-50 degreeC for about 1 hour-1 week. The properties of the cured product depend on the main chain skeleton and molecular weight of the polymer to be used, but can be widely prepared from rubbery to resinous.
[0098]
The vinyl polymer having a hydroxyl group at the terminal obtained by the various methods described above can be made into a curable composition containing this as a main component.
[0099]
This curable composition has the following two components as essential components: (A) a vinyl polymer having a hydroxyl group at the terminal, and (B) a compound having two or more functional groups capable of reacting with a hydroxyl group.
[0100]
The vinyl polymer having a hydroxyl group at the end of the component (A) may be used alone or in combination of two or more. Although there is no restriction | limiting in particular as molecular weight, It is preferable to exist in the range of 500-100000. If it is 500 or less, the original characteristics of the vinyl polymer are hardly expressed, and if it is 100,000 or more, the viscosity or solubility may be very low and handling may be difficult.
[0101]
(B) Although it does not specifically limit as a compound which has 2 or more of functional groups which can react with the hydroxyl group of a component, For example, the polyvalent isocyanate compound which has 2 or more isocyanate groups in 1 molecule, methylolated melamine, and Examples thereof include aminoplast resins such as alkyl etherified products or low-condensed products, polyfunctional carboxylic acids, and halides thereof.
[0102]
As the polyvalent isocyanate compound having two or more isocyanate groups in one molecule, conventionally known ones can be used. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4 '-Diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, metaxylylene diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate -Isocyanate compound such as triisocyanate such as -45, Buret polyisocyanate compound such as Sumidur N (manufactured by Sumitomo Bayer Urethane Co., Ltd.), Desmodur A polyisocyanate compound having an isocyanurate ring such as IL, HL (manufactured by Bayer AG), coronate EH (manufactured by Nippon Polyurethane Industry Co., Ltd.), an adduct polyisocyanate compound such as Sumidur L (manufactured by Sumitomo Bayer Urethane Co., Ltd.), Examples thereof include adduct polyisocyanate compounds such as Coronate HL (manufactured by Nippon Polyurethane Co., Ltd.). Moreover, you may use block isocyanate. These may be used alone or in combination of two or more.
[0103]
The compounding ratio of the polymer having a hydroxyl group at the terminal and the compound having two or more isocyanate groups is not particularly limited. For example, the ratio of the hydroxyl group of the vinyl polymer having a hydroxyl group at the isocyanate group and the terminal (NCO / OH (Molar ratio)) is preferably 0.5 to 3.0, more preferably 0.8 to 2.0.
[0104]
In order to accelerate the curing reaction of the vinyl-based polymer having a hydroxyl group at the terminal and the compound having two or more isocyanate groups, which is a composition of the present invention, an organic tin compound, a tertiary amine or the like is publicly known. The catalyst may be added.
[0105]
Specific examples of the organic tin compound include tin octylate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, dibutyltin dimaleate, and dioctyltin thiocarboxylate. Further, as the tertiary amine catalyst, triethylamine, N, N-dimethylcyclohexylamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropane 1,3 -Diamine, N, N, N ', N'-tetramethylhexane 1,6-diamine, N, N, N', N ", N" -pentamethyldiethylenetriamine, N, N, N ', N ", N "-Pentamethyldipropylenetriamine, tetramethylguanidine, triethylenediamine, N, N'-dimethylpiperazine, N-methylmorpholine, 1,2-dimethylimidazole, dimethylaminoethanol, dimethylaminoethoxyethanol, N, N, N ' -Trimethylaminoethylethanolamine, N-methyl-N '-(2-hydroxyethyl) pipera Emissions, N- (2- hydroxyethyl) morpholine, bis (2-dimethylaminoethyl) ether, ethylene glycol bis (3-dimethylaminopropyl) aminopropyl ether and the like.
[0106]
The aminoplast resin used in the curable composition in the present invention is not particularly limited, and is an addition reaction product (methylol compound) of melamine and formaldehyde, a low condensate of melamine and formaldehyde, an alkyl etherified product thereof, and urea. Examples thereof include resins. These may be used alone or in combination of two or more. For the purpose of promoting the curing reaction between the (meth) acrylic polymer having a hydroxyl group at the terminal and the aminoplast resin, a known catalyst such as paratoluenesulfonic acid or benzenesulfonic acid may be added.
[0107]
The compound having two or more carboxyl groups in one molecule used in the curable composition of the present invention is not particularly limited. For example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, phthalate Examples thereof include polyfunctional carboxylic acids such as acid, phthalic anhydride, terephthalic acid, trimellitic acid, pyromellitic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid or their anhydrides, and halides thereof. These may be used alone or in combination of two or more.
[0108]
If the two components (A) and (B) of the present invention and, if necessary, a curing catalyst are mixed and cured, a uniform cured product excellent in deep part curability can be obtained. Although there is no restriction | limiting in particular about hardening conditions, Generally 0 to 100 degreeC, Preferably it is 20 to 80 degreeC.
[0109]
The properties of the cured product depend on the main chain skeleton and molecular weight of the polymer of component (A) and the curing agent of component (B) to be used, but can be widely prepared from rubbery to resinous.
[0110]
From the polymer having an epoxy group at the terminal, a curable composition containing (A) a polymer having an epoxy group at the terminal and (B) a curing agent can be obtained. (B) Various kinds of curing agents can be used. Illustrative examples include aliphatic amines, aromatic amines, acid anhydrides, urea, melamine, and phenol resins.
[0111]
Specific applications of the composition of the present invention as described above include sealing materials, adhesives, pressure-sensitive adhesives, elastic adhesives, paints, powder paints, foams, potting materials for electric and electronic materials, films, molding materials, artificial materials A marble etc. can be mentioned.
[0112]
【Example】
Specific examples of the present invention are shown below, but the present invention is not limited to the following examples. In the following Examples and Comparative Examples, “part” and “%” represent “part by weight” and “% by weight”, respectively. “Number average molecular weight” and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)” were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, a GPC column filled with polystyrene cross-linked gel (shodex GPC K-804; manufactured by Showa Denko KK) was used as the GPC solvent with chloroform. The number of functional groups introduced per molecule of polymer is¹Calculation was based on concentration analysis by H-NMR and number average molecular weight determined by GPC.
Example 1
A 250 L pressure-resistant reactor was charged with 1.01 kg (7.02 mol) of copper (I) bromide and 10.6 kg of acetonitrile, and heated and stirred at 65 ° C. for 16 minutes in a nitrogen stream. To this were added 2.11 kg (5.85 mol) of diethyl 2,5-dibromoadipate and 24.0 kg (187 mol) of butyl acrylate, and the mixture was further heated and stirred at 65 ° C. for 40 minutes. To this, 20.3 g (0.117 mol) of pentamethyldiethylenetriamine (hereinafter referred to as triamine) was added to start the reaction, and heating and stirring were continued at 80 ° C. Further, 101.5 g (0.585 mol) of triamine was added. From 46 minutes after the start of the reaction, 96.0 kg (749 mol) of butyl acrylate was intermittently added dropwise over 180 minutes. During this period, 81.2 g (0.468 mol) of triamine was added. After 346 minutes from the start of the reaction, the reaction rate of butyl acrylate reached 95.9%. The reaction vessel was evacuated to remove volatiles. 434 minutes after the start of the reaction, 31.7 kg of acetonitrile, 12.9 kg (117 mol) of 1,7-octadiene and 406 g (2.34 mol) of triamine were added, and the mixture was continuously heated and stirred at 80 ° C., and 809 minutes after the start of the reaction. Heating was stopped to obtain a solution containing the polymer [1]. The number average molecular weight of the obtained polymer [1] is 26400 by GPC measurement (mobile phase chloroform, polystyrene conversion), and the molecular weight distribution is 1.23.¹The number of alkenyl groups per polymer molecule determined by 1 H-NMR analysis was 1.9, and the number of terminals having no alkenyl group introduced was 0.
(Example 2)
After concentrating the mixture containing said polymer [1], it diluted with methylcyclohexane and the solid content was removed. To 100 parts of polymer, 4 parts of adsorbent (2 parts of KYOWARD 500SH / 2 parts of KYOWARD 700SL: both manufactured by Kyowa Chemical Co., Ltd.) are added to the methylcyclohexane solution of the polymer, and in an oxygen / nitrogen mixed gas atmosphere. Stir with heating. After removing the solid content, the polymer solution was concentrated to obtain a polymer [1 ']. The molecular weight distribution of the polymer [1 ′] was 1.30.
(Example 3)
A 2 L flask was charged with 8.39 g (58.5 mmol) of copper (I) bromide and 112 mL (87.9 g) of acetonitrile, and the mixture was heated and stirred at 70 ° C. for 20 minutes under a nitrogen stream. To this was added 17.6 g (48.8 mmol) of diethyl 2,5-dibromoadipate and 224 mL (200 g, 1.56 mol) of butyl acrylate, and the mixture was further heated and stirred at 80 ° C. for 40 minutes. To this was added 0.41 mL (0.338 g, 1.95 mmol) of pentamethyldiethylenetriamine (hereinafter referred to as triamine) to initiate the reaction. Further, 1.23 mL (1.01 g, 5.85 mmol) of triamine was added. Stirring at 80 ° C. was continued, and 895 mL of butyl acrylate (800 g, 6.24 mol) was intermittently added dropwise over 145 minutes 35 minutes after the start of the reaction. During this time, 0.41 mL (0.338 g, 1.95 mmol) of triamine was added. 240 minutes after the start of the reaction, the reaction rate of butyl acrylate reached 95.9%. The reaction vessel was evacuated to remove volatiles. 360 minutes after the start of the reaction, 336 mL of acetonitrile (264 g), 144 mL of 1,7-octadiene (107 g, 0.975 mol), and 4.1 mL of triamine (3.38 g, 19.5 mmol) were added, followed by heating and stirring at 80 ° C. Subsequently, heating was stopped after 740 minutes from the start of the reaction to obtain a solution containing the polymer [2]. The number average molecular weight of the obtained polymer [2] is 24000 as measured by GPC (mobile phase chloroform, polystyrene conversion), and the molecular weight distribution is 1.17.¹The number of alkenyl groups per polymer molecule determined by 1 H-NMR analysis was 1.7, and the number of terminals having no alkenyl group introduced was 0.
Example 4
After concentrating the mixture containing said polymer [2], it diluted with toluene and removed solid content. Add 100 parts of polymer to 4 parts of adsorbent (2 parts of KYOWARD 500SH / 2 parts of KYOWARD 700SL: both manufactured by Kyowa Chemical Co., Ltd.) to the toluene solution of the polymer and heat in an oxygen / nitrogen mixed gas atmosphere. Stir. After removing the solid content, the polymer solution was concentrated. This was diluted with N, N-dimethylacetamide and stirred with heating at 100 ° C. for 8 hours in the presence of potassium acetate. The polymer solution was concentrated and then diluted with toluene to remove solids. To 100 parts of the polymer, 50 parts of an adsorbent (Kyoward 700PEL 50 parts: manufactured by Kyowa Chemical Co., Ltd.) was added to the xylene solution of the polymer, and the mixture was heated and stirred in an oxygen / nitrogen mixed gas atmosphere. After removing the solid content, the solution was concentrated to obtain a polymer. To this polymer, dimethoxymethylsilane (3 molar equivalents relative to alkenyl groups), methyl orthoformate (1 molar equivalent relative to alkenyl groups), platinum catalyst (bis (1,3-divinyl-1,1,3, (3-tetramethyldisiloxane) platinum complex xylene solution: hereinafter referred to as platinum catalyst) (30 mg as platinum relative to 1 kg of polymer) was mixed and heated and stirred at 80 ° C. for 1 hour in a nitrogen atmosphere. That the alkenyl group disappeared due to the reaction.¹As confirmed by 1 H-NMR, the reaction mixture was concentrated to obtain the desired methoxysilyl group-containing polymer [2 ']. The number average molecular weight of the polymer [2 ′] was 25600, and the molecular weight distribution was 1.26. The number of silyl groups introduced per polymer molecule was 1.8.
(Example 5)
100 parts of the methoxysilyl group-containing polymer [2 ′] obtained in Example 4, 150 parts of calcium carbonate (Shiraka Hana CCR: manufactured by Shiroishi Kogyo) and 50 parts of DOP (dioctyl phthalate: manufactured by Kyowa Hakko) are mixed, and further 3 After sufficiently mixing using this paint roll, a cured product in sheet form was obtained by using a tetravalent Sn catalyst (dibutyltin diacetylacetonate) for curing for 2 days indoors and then at 50 ° C. for 3 days. Tensile properties (use of Shimadzu Autograph, measurement temperature: 23 ° C., tensile speed: 200 mm / sec, 2 (1/3) type dumbbell test piece) of the cured product were evaluated. The breaking strength was 0.77 MPa and the breaking elongation was 430%.
(Example 6)
Into a 250 L pressure-resistant reactor, 1.11 kg (7.72 mol) of copper (I) bromide and 9.95 kg of acetonitrile were charged, and the mixture was heated and stirred at 65 ° C. for 15 minutes in a nitrogen stream. To this, 3.09 kg (8.58 mol) of diethyl 2,5-dibromoadipate, 6.60 kg (51.5 mol) of butyl acrylate, 9.49 kg (94.7 mol) of ethyl acrylate, 7-methoxyethyl acrylate 7 .77 kg (59.7 mol) and further heated and stirred at 65 ° C. for 43 minutes. To this, 22.3 g (0.129 mol) of pentamethyldiethylenetriamine (hereinafter referred to as “triamine”) was added to start the reaction, and heating and stirring were continued at 80 ° C. Further, 112 g (0.644 mol) of triamine was added. From 57 minutes after the start of the reaction, 26.4 kg (206 mol) of butyl acrylate, 37.9 kg (379 mol) of ethyl acrylate, and 31.3 kg (239 mol) of 2-methoxyethyl acrylate were added dropwise over 180 minutes. During this period, 89.2 g (0.515 mol) of triamine was added. After 602 minutes from the start of the reaction, the pressure in the reaction vessel was reduced to remove volatile components. After 720 minutes from the start of the reaction, the average reaction rate of ethyl acrylate / butyl acrylate / 2-methoxyethyl acrylate reached 95.3%. 9.95 kg of acetonitrile, 28.4 kg (257 mol) of 1,7-octadiene and 446 g (2.57 mol) of triamine were added, and the mixture was continuously heated and stirred at 80 ° C. After 1340 minutes from the start of the reaction, the heating was stopped and the polymer [ 3] was obtained. The number average molecular weight of the obtained polymer [3] is 17100 as measured by GPC (mobile phase chloroform, polystyrene conversion), and the molecular weight distribution is 1.16.¹The number of alkenyl groups per molecule of polymer determined by 1 H-NMR analysis was 1.6, and the number of terminals to which no alkenyl group was introduced was 0.
(Example 7)
The mixture containing the polymer [3] was concentrated with the polymer solution and then diluted with toluene to remove the solid content. Add 100 parts of polymer with 4 parts of adsorbent (2 parts Kyoward 500SH / 2 parts Kyoward 700SL: both manufactured by Kyowa Chemical Co., Ltd.) to the toluene solution of the polymer, and heat and stir in an oxygen / nitrogen mixed gas atmosphere. did. After removing the solid content, the polymer solution was concentrated. This was diluted with N, N-dimethylacetamide and stirred with heating at 100 ° C. for 8 hours in the presence of potassium acetate. After concentrating the polymer solution, 10 parts of adsorbent (5 parts of Kyoward 500SH / 5 parts of Kyoward 700SL: both manufactured by Kyowa Chemical Co., Ltd.) are added to the toluene solution of the polymer with respect to 100 parts of the polymer. -The mixture was heated and stirred under a nitrogen mixed gas atmosphere. After removing the solid content, the polymer solution was concentrated to obtain a polymer [3 '].
(Example 8)
100 parts of polymer [3 '], chain siloxane (average 5 hydrosilyl groups and average 5 substituents [-CH₂-CH (CH_Three-C₆H_FiveAnd the amount of Si—H group is 3.70 mmol / g) was mixed with 1.8 molar equivalents with respect to the alkenyl group. A platinum catalyst (10 to 100 mg as platinum relative to 1 kg of the polymer) was added to the mixture, and the mixture was uniformly mixed. When heated to 130 ° C., the mixture rapidly cured and a rubber-like cured product was obtained. Tensile properties (use of Shimadzu Autograph, measurement temperature: 23 ° C., tensile speed: 200 mm / sec, 2 (1/3) type dumbbell test piece) of the cured product were evaluated. The breaking strength was 0.55 MPa, and the breaking elongation was 230%.
(Comparative Example 1)
A 500 mL flask was charged with 2.52 g (17.6 mmol) of copper (I) bromide and 33.6 mL (26.4 g) of acetonitrile, and heated and stirred at 70 ° C. for 30 minutes in a nitrogen stream. To this were added 5.27 g (14.6 mmol) of diethyl 2,5-dibromoadipate and 336 mL (300 g, 2.34 mol) of butyl acrylate, and the mixture was further heated and stirred at 70 ° C. for 20 minutes. To this, 0.122 mL (0.101 g, 0.585 mmol) of pentamethyldiethylenetriamine (hereinafter referred to as “triamine”) was added to start the reaction, and the heating and stirring were continued at 80 ° C. Further, 0.366 mL (0.303 g, 1.76 mmol) of triamine was added. 200 minutes after the start of the reaction, the reaction rate of butyl acrylate reached 98.6%. After adding 43.2 mL (32.2 g, 0.293 mol) of 1,7-octadiene and 1.22 mL (1.01 g, 5.85 mmol) of triamine, the mixture was continuously heated and stirred at 80 ° C., and 440 minutes after the start of the reaction. Heating was stopped to obtain a solution containing the polymer [4]. The number average molecular weight of the obtained polymer [4] is 26800 by GPC measurement (mobile phase chloroform, polystyrene conversion), and the molecular weight distribution is 1.32.¹The number of alkenyl groups per molecule of the polymer determined by 1 H-NMR analysis was 2.9, and the number of terminals having no alkenyl group introduced was 0.3.
(Comparative Example 2)
The mixture containing the above polymer [4] was treated in the same manner as in Example 2 to obtain a polymer [4 ']. The molecular weight distribution of the polymer [4 '] was 1.51.
(Comparative Example 3)
CuBr (83.9 g, 0.585 mol) was charged into a 20 L reactor equipped with a reflux tube and a stirrer, and the inside of the reaction vessel was purged with nitrogen. Acetonitrile 879g was added and it stirred at 70 degreeC for 45 minutes in the oil bath. To this, 2.00 kg (25.6 mol) of butyl acrylate, diethyl 2,5-dibromoadipate (176 g, 0.488 mol), 4.07 mL (3.38 g, 19.5 mmol) of pentamethyldiethylenetriamine (hereinafter referred to as triamine) The reaction was started. Furthermore, 8.14 mL (6.76 g, 39.0 mmol) of triamine was added, and the heating and stirring were continued at 70 ° C. From 60 minutes after the start of the reaction, 8.00 kg (102 mol) of butyl acrylate was continuously added dropwise over 170 minutes. During the dropwise addition of butyl acrylate, 8.14 mL (6.76 g, 39.0 mmol) of triamine was added. 450 minutes after the start of the reaction, the reaction rate of butyl acrylate reached 96.7%. 1,7-octadiene 2.88 L (2.15 kg, 19.5 mol) and triamine 30.5 mL (25.4 g, 146 mmol) were added, and the mixture was further heated and stirred at 70 ° C. for 240 minutes.
[0113]
The reaction mixture was diluted with toluene to remove the solid content, and then passed through an activated alumina column, and the volatile content was distilled off under reduced pressure to obtain a polymer [5] having an alkenyl group at the terminal. The polymer [5] has a number average molecular weight of 25,100 and a molecular weight distribution of 1.34 according to GPC measurement (polystyrene conversion). The average number of alkenyl groups introduced per molecule of the polymer is¹It was 3.1 when it calculated | required by the H-NMR analysis.
(Comparative Example 4)
The polymer [5] was diluted with N, N-dimethylacetamide and heated and stirred at 100 ° C. for 8 hours in the presence of potassium acetate. After the heat treatment under reduced pressure, the solid content was removed by dilution with toluene. To 100 parts of the polymer, 15 parts of an adsorbent (10 parts of KYOWARD 500SH / 5 parts of KYOWARD 700SL: both manufactured by Kyowa Chemical Co., Ltd.) was added to the toluene solution of the polymer, and the mixture was heated and stirred at 130 ° C. After removing the solid content, the polymer solution was concentrated to obtain a polymer. This polymer was mixed with dimethoxymethylsilane (3 molar equivalents relative to the alkenyl group), methyl orthoformate (1 molar equivalent relative to the alkenyl group), platinum catalyst (60 mg as platinum relative to 1 kg of the polymer), The mixture was heated and stirred at 100 ° C. for 5 hours. That the alkenyl group disappeared due to the reaction.¹As confirmed by 1 H-NMR, the reaction mixture was concentrated to obtain the desired methoxysilyl group-containing polymer [5 ']. The number average molecular weight was 28900, and the molecular weight distribution was 1.90. The number of silyl groups introduced per molecule of polymer was 1.9.
(Comparative Example 5)
100 parts of the methoxysilyl group-containing polymer [5 ′] obtained in Comparative Example 4 is mixed with 150 parts of calcium carbonate (Shiraka Hana CCR: manufactured by Shiroishi Kogyo) and 50 parts of DOP (dioctyl phthalate: manufactured by Kyowa Hakko), and further 3 After sufficiently mixing using this paint roll, a cured product in sheet form was obtained by using a tetravalent Sn catalyst (dibutyltin diacetylacetonate) for curing for 2 days indoors and then at 50 ° C. for 3 days. Tensile properties (use of Shimadzu Autograph, measurement temperature: 23 ° C., tensile speed: 200 mm / sec, 2 (1/3) type dumbbell test piece) of the cured product were evaluated. The breaking strength was 0.95 MPa, and the breaking elongation was 320%.
(Comparative Example 6)
Into a 50 L reactor, 270 g (1.88 mol) of copper (I) bromide and 2.43 kg of acetonitrile were charged, and the mixture was heated and stirred at 65 ° C. for 19 minutes in a nitrogen stream. To this, 753 g (2.09 mol) of diethyl 2,5-dibromoadipate, 1.61 kg (12.6 mol) of butyl acrylate, 2.31 kg (23.1 mol) of ethyl acrylate, 1.90 kg of 2-methoxyethyl acrylate (14.6 mol) was added, and the mixture was further heated and stirred at 80 ° C. for 30 minutes. To this, 13.1 mL (10.8 g, 62.8 mmol) of pentamethyldiethylenetriamine (hereinafter referred to as triamine) was added to initiate the reaction. Further, 26.2 mL (21.6 g, 126 mmol) of triamine was added. Stirring was continued at 80 ° C., and 65 minutes after the start of the reaction, intermittently 6.44 kg (50.4 mol) of butyl acrylate, 9.24 kg (92.4 mol) of ethyl acrylate, 7.60 kg of 2-methoxyethyl acrylate (58.4 mol) was added dropwise over 103 minutes. During this time, 26.2 mL (21.6 g, 126 mmol) of triamine was added. 305 minutes after the start of the reaction, the average reaction rate of ethyl acrylate / butyl acrylate / 2-methoxyethyl acrylate reached 96.8%. 6.92 kg (62.8 mol) of 1,7-octadiene and 131 mL of triamine (109 g, 0.628 mol) were added, and the mixture was continuously heated and stirred at 80 ° C. After 605 minutes from the start of the reaction, the heating was stopped and the polymer [6 ] Was obtained. The number average molecular weight of the obtained polymer [6] is 17000 in GPC measurement (mobile phase chloroform, polystyrene conversion), molecular weight distribution 1.13,¹The number of alkenyl groups per polymer molecule determined by 1 H-NMR analysis was 2.5.
(Comparative Example 7)
The mixture containing the polymer [6] was heat-treated under reduced pressure and then diluted with toluene to remove the solid content. This was diluted with N, N-dimethylacetamide and stirred with heating at 100 ° C. for 8 hours in the presence of potassium acetate. After the heat treatment under reduced pressure, the solid content was removed by dilution with toluene. To 100 parts of the polymer, 15 parts of an adsorbent (10 parts of KYOWARD 500SH / 5 parts of KYOWARD 700SL: both manufactured by Kyowa Chemical Co., Ltd.) was added to the toluene solution of the polymer, and the mixture was heated and stirred at 130 ° C. After removing the solid content, the polymer solution was concentrated to obtain a polymer [6 '].
(Comparative Example 8)
100 parts of polymer [6 '], chain siloxane (average 5 hydrosilyl groups and average 5 substituents [-CH₂-CH (CH_Three-C₆H_FiveAnd the amount of Si—H group is 3.70 mmol / g) was mixed with 1.8 molar equivalents with respect to the alkenyl group. A platinum catalyst (10 to 100 mg as platinum relative to 1 kg of the polymer) was added to the mixture, and the mixture was uniformly mixed. When heated to 130 ° C., the mixture rapidly cured and a rubber-like cured product was obtained. Tensile properties (use of Shimadzu Autograph, measurement temperature: 23 ° C., tensile speed: 200 mm / sec, 2 (1/3) type dumbbell test piece) of the cured product were evaluated. The breaking strength was 0.61 MPa and the breaking elongation was 160%.
The above results are shown in the table below.
[0114]
[Table 1]

[0115]
[Table 2]

[0116]
[Table 3]

By the method of the present invention, a polymer in which a functional group is reliably introduced into the terminal can be obtained. Moreover, although the terminal in which the functional group is not introduced has a bad influence on the thermal stability of the polymer, as shown in Table 1, a polymer having improved thermal stability can be obtained by the method of the present invention. Furthermore, as shown in Tables 2 and 3, the polymer obtained by the method of the present invention has a functional group reliably introduced into the terminal, and therefore gives a cured product excellent in elongation.
[0117]
【The invention's effect】
According to the present invention, a functional group can be reliably introduced into the terminal of the vinyl polymer. A vinyl polymer with a functional group at the end is stable because the end group is connected to the main chain by a carbon-carbon bond, and the terminal structure is well controlled with only one olefin, so a curable composition Useful for things. Further, according to the production method of the present invention, from the various vinyl monomers, the above-described process can be easily performed by adding a compound having both a low-polymerizable olefin and various functional groups shown in the present invention to the polymerization system. Polymers having various functional groups at the terminal ends can be produced.

Claims (28)

After 80% by weight of the radical polymerizable monomer is consumed by the atom transfer radical polymerization, the olefin compound (I) having a low polymerization property and the compound (II) having a dielectric constant higher than that of the olefin compound (I) are added, A method for producing a vinyl polymer having an olefin compound (I) added to a terminal,
The compound (II) having a higher dielectric constant than that of the olefin compound (I) is added, and the olefin compound (I) having a low polymerization property is reacted with the end of the vinyl polymer.
A method for producing a vinyl polymer, characterized in that:
However, the low polymerizable olefin compound (I) is represented by the general formula 1:

{In the above formula, R ³ represents a hydroxyl group, amino group, epoxy group, carboxylic acid group, ester group, ether group, amide group, silyl group, or general formula 2:

(R ⁴ represents a hydrogen atom or a methyl group)
Or an organic group having 1 to 20 carbon atoms, and R ¹ is an alkyl group having 1 to 20 carbon atoms or a general formula 3:

(In the above formula, R ⁵ is an oxygen atom, a nitrogen atom or an organic group having 1 to 20 carbon atoms, and R ⁶ is a hydrogen atom or a methyl group, which may be the same or different), R ² is a hydrogen atom or a methyl group}
It is a compound shown by these.
The compound (II) having a dielectric constant higher than that of the olefin compound (I) includes hydrocarbon compounds, ether compounds, halogenated hydrocarbon compounds, ketone compounds, alcohol compounds, nitrile compounds, ester compounds and carbonates. At least one selected from the group consisting of a series compound,
The addition amount is 1-1000 parts by weight with respect to 100 parts by weight of the radical polymerizable monomer.
The radical polymerizable monomer includes (meth) acrylic acid monomer, styrene monomer, fluorine-containing vinyl monomer, silicon-containing vinyl monomer, maleic anhydride, maleic acid, monoalkyl ester and dialkyl ester of maleic acid, fumarate acid, monoalkyl esters and dialkyl esters of fumaric acid, maleimide monomers, nitrile group-containing vinyl monomers, amide group-containing vinyl monomers, vinyl esters, alkenes, conjugated di-enes, vinyl chloride, vinylidene chloride, allyl chloride And at least one selected from the group consisting of allyl alcohol.   The vinyl polymer according to claim 1, wherein the olefin compound (I) has a functional group, and the vinyl polymer to which the olefin compound (I) is added at the terminal has the functional group at the terminal. Manufacturing method. The olefin compound (I) is represented by the general formula 4:

{In the above formula, R ¹ is an alkyl group having 1 to 20 carbon atoms or a general formula 3:

(In the above formula, R ⁵ is an oxygen atom, a nitrogen atom or an organic group having 1 to 20 carbon atoms, and R ⁶ is a hydrogen atom or a methyl group, which may be the same or different), R ² and R ⁴ are a hydrogen atom or a methyl group}
The method for producing a vinyl polymer according to claim 1, further comprising adding an excess amount of the olefin compound (I) to the growth terminal of the polymer. The olefin compound (I) is represented by the general formula 5:

(N is an integer from 1 to 20)
The method for producing a vinyl polymer according to any one of claims 1 to 3, wherein the compound is represented by the formula:   The method for producing a vinyl polymer according to claim 4, wherein the olefin compound (I) is 1,5-hexadiene, 1,7-octadiene or 1,9-decadiene.   2. The vinyl type compound according to claim 1, wherein the olefin compound (I) is a group selected from the group consisting of hydroxyl group, amino group, epoxy group, carboxylic acid group, ester group, ether group, amide group and silyl group in the general formula 1. A method for producing a polymer.   The method for producing a vinyl polymer according to any one of claims 1 to 6, wherein the olefin compound (I) is represented by the general formula 1, wherein R2 is a hydrogen atom.   The method for producing a vinyl polymer according to any one of claims 1, 2, 6, and 7, wherein the olefin compound (I) is alkenyl alcohol or alkenylamine.   The method for producing a vinyl polymer according to any one of claims 1 to 8, wherein the dielectric constant of the compound (II) is 3 or more higher than that of the olefin compound (I).   The method for producing a vinyl polymer according to any one of claims 1 to 8, wherein the dielectric constant of the compound (II) is 5 or more higher than that of the olefin compound (I).   9. The method for producing a vinyl polymer according to claim 1, wherein the dielectric constant of the compound (II) is 10 or more higher than that of the olefin compound (I).   The method for producing a vinyl polymer according to any one of claims 1 to 11, wherein the compound (II) is a nitrile compound.   The method for producing a vinyl polymer according to claim 12, wherein the nitrile compound is acetonitrile.   The method for producing a vinyl polymer according to any one of claims 1 to 13, wherein 3 to 1000 parts by weight of the compound (II) is added to 100 parts by weight of the radical polymerizable monomer.   The method for producing a vinyl polymer according to any one of claims 1 to 13, wherein 5 to 500 parts by weight of the compound (II) is added to 100 parts by weight of the radical polymerizable monomer.   The method for producing a vinyl polymer according to any one of claims 1 to 13, wherein 10 to 100 parts by weight of the compound (II) is added to 100 parts by weight of the radical polymerizable monomer.   The method for producing a vinyl polymer according to any one of claims 1 to 13, wherein 1 to 10,000 parts by weight of the compound (II) is added to 100 parts by weight of the olefin compound (I).   The method for producing a vinyl polymer according to any one of claims 1 to 13, wherein 10 to 1000 parts by weight of the compound (II) is added to 100 parts by weight of the olefin compound (I).   The method for producing a vinyl polymer according to any one of claims 1 to 18, wherein the vinyl polymer is a (meth) acrylic acid ester polymer.   The method for producing a vinyl polymer according to any one of claims 1 to 19, wherein the vinyl polymer is an acrylate polymer.   The method for producing a vinyl polymer according to any one of claims 1 to 20, wherein the metal complex used as a catalyst for atom transfer radical polymerization is a complex of copper, nickel, ruthenium, and iron.   The method for producing a vinyl polymer according to claim 21, wherein the metal complex used as a catalyst is a copper complex.   The method for producing a vinyl polymer according to any one of claims 1 to 22, wherein the initiator is an organic halide having a functional group or a halogenated sulfonyl compound having a functional group.   The method for producing a vinyl polymer according to any one of claims 1 to 23, wherein the initiator is an organic halide or a sulfonyl halide compound having two or more initiation points.   The number average molecular weight of a polymer is 500-100000, The manufacturing method of the vinyl polymer as described in any one of Claims 1-24.   The value of the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography of the polymer is less than 1.8. A method for producing a vinyl polymer as described in 1. above. A general formula (10) produced by the method according to any one of claims 1 to 26:

{In the above formula, R ³ represents a hydroxyl group, amino group, epoxy group, carboxylic acid group, ester group, ether group, amide group, silyl group, or general formula 2:

(R ⁴ represents a hydrogen atom or a methyl group), or an organic group having 1 to 20 carbon atoms that does not contain a polymerizable olefin, and R ¹ is an alkyl group having 1 to 20 carbon atoms, or General formula 3:

(Wherein R ⁵ is an oxygen atom, a nitrogen atom or an organic group having 1 to 20 carbon atoms, and R ⁶ is a hydrogen atom or a methyl group, which may be the same or different), R ² is a hydrogen atom or a methyl group, and X is a halogen group }
A vinyl polymer having a terminal structure represented by
Before Symbol vinyl polymer, (meth) acrylic monomer, styrene monomer, fluorine-containing vinyl monomers, silicon-containing vinyl monomers, maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid, fumaric acid , monoalkyl esters and dialkyl esters of fumaric acid, maleimide monomers, nitrile group-containing Yubi alkenyl monomers, amide group-containing vinyl monomers, vinyl esters, alkenes, conjugated dienes, vinyl chloride, vinylidene chloride, allyl chloride And a vinyl polymer which is a polymer of at least one radical polymerizable monomer selected from the group consisting of allyl alcohol.   A curable composition containing the vinyl polymer according to claim 27.