JP2004210858A - Method for producing vinylic polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a vinylic polymer, by which the atom transfer radical polymerization of a vinylic monomer is advanced, while the living property of the polymer is stably maintained from the initial time of the polymerization to the final time. <P>SOLUTION: This method for producing the vinylic polymer, comprising polymerizing the vinylic monomer by an atom transfer radical polymerization using an organic halide compound or a sulfonyl halide compound as a polymerization initiator and a transition metal complex as a polymerization catalyst, is characterized by starting the polymerization when the early charging monomer and the polymerization initiator are charged into a reactor, and then starting the addition of the additionally charging monomer when the conversion of the polymerization in the system becomes 10 to 60%. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【００２４】
（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）
ＸＣＨ_２Ｃ（Ｏ）Ｏ（ＣＨ_２）_ｎＯ（ＣＨ_２）_ｍＣＨ＝ＣＨ_２、
Ｈ_３ＣＣ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ_２）_ｎＯ（ＣＨ_２）_ｍＣＨ＝ＣＨ_２、
（Ｈ_３Ｃ）_２Ｃ（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ_２）_ｎＯ（ＣＨ_２）_ｍＣＨ＝ＣＨ_２、
ＣＨ_３ＣＨ_２Ｃ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ_２）_ｎＯ（ＣＨ_２）_ｍＣＨ＝ＣＨ_２、
【００２５】
【化２】

【００２６】
（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−ＸＣＨ_２−Ｃ_６Ｈ_４−（ＣＨ_２）_ｎ−ＣＨ＝ＣＨ_２、
ｏ，ｍ，ｐ−ＣＨ_３Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−（ＣＨ_２）_ｎ−ＣＨ＝ＣＨ_２、
ｏ，ｍ，ｐ−ＣＨ_３ＣＨ_２Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−（ＣＨ_２）_ｎ−ＣＨ＝ＣＨ_２、
（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−ＸＣＨ_２−Ｃ_６Ｈ_４−（ＣＨ_２）_ｎ−Ｏ−（ＣＨ_２）_ｍ−ＣＨ＝ＣＨ_２、
ｏ，ｍ，ｐ−ＣＨ_３Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−（ＣＨ_２）_ｎ−Ｏ−（ＣＨ_２）_ｍ−ＣＨ＝ＣＨ_２、
ｏ，ｍ，ｐ−ＣＨ_３ＣＨ_２Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−（ＣＨ_２）_ｎ−Ｏ−（ＣＨ_２）_ｍＣＨ＝ＣＨ_２、
（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−ＸＣＨ_２−Ｃ_６Ｈ_４−Ｏ−（ＣＨ_２）_ｎ−ＣＨ＝ＣＨ_２、
ｏ，ｍ，ｐ−ＣＨ_３Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−Ｏ−（ＣＨ_２）_ｎ−ＣＨ＝ＣＨ_２、
ｏ，ｍ，ｐ−ＣＨ_３ＣＨ_２Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−Ｏ−（ＣＨ_２）_ｎ−ＣＨ＝ＣＨ_２、
（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−ＸＣＨ_２−Ｃ_６Ｈ_４−Ｏ−（ＣＨ_２）_ｎ−Ｏ−（ＣＨ_２）_ｍ−ＣＨ＝ＣＨ_２、
ｏ，ｍ，ｐ−ＣＨ_３Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−Ｏ−（ＣＨ_２）_ｎ−Ｏ−（ＣＨ_２）_ｍ−ＣＨ＝ＣＨ_２、
ｏ，ｍ，ｐ−ＣＨ_３ＣＨ_２Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−Ｏ−（ＣＨ_２）_ｎ−Ｏ−（ＣＨ_２）_ｍ−ＣＨ＝ＣＨ_２、
（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）
等が挙げられる。
【００２７】
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。
Ｈ_２Ｃ＝Ｃ（Ｒ^１３）−Ｒ^１２−Ｃ（Ｒ^９）（Ｘ）−Ｒ^１４−Ｒ^１０ （７）
（式中、Ｒ^９、Ｒ^１０、Ｒ^１２、Ｒ^１３、Ｘは上記に同じ、Ｒ^１４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）
【００２８】
Ｒ^１２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、Ｒ^１４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。Ｒ^１２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、Ｒ^１４としてはＣ（Ｏ）Ｏ基、Ｃ（Ｏ）基、フェニレン基が好ましい。
【００２９】
一般式７の化合物を具体的に例示するならば、
ＣＨ_２＝ＣＨＣＨ_２Ｘ、ＣＨ_２＝Ｃ（ＣＨ_３）ＣＨ_２Ｘ、
ＣＨ_２＝ＣＨＣ（Ｈ）（Ｘ）ＣＨ_３、ＣＨ_２＝Ｃ（ＣＨ_３）Ｃ（Ｈ）（Ｘ）ＣＨ_３、
ＣＨ_２＝ＣＨＣ（Ｘ）（ＣＨ_３）_２、ＣＨ_２＝ＣＨＣ（Ｈ）（Ｘ）Ｃ_２Ｈ_５、
ＣＨ_２＝ＣＨＣ（Ｈ）（Ｘ）ＣＨ（ＣＨ_３）_２、
ＣＨ_２＝ＣＨＣ（Ｈ）（Ｘ）Ｃ_６Ｈ_５、ＣＨ_２＝ＣＨＣ（Ｈ）（Ｘ）ＣＨ_２Ｃ_６Ｈ_５、
ＣＨ_２＝ＣＨＣＨ_２Ｃ（Ｈ）（Ｘ）−ＣＯ_２Ｒ、
ＣＨ_２＝ＣＨ（ＣＨ_２）_２Ｃ（Ｈ）（Ｘ）−ＣＯ_２Ｒ、
ＣＨ_２＝ＣＨ（ＣＨ_２）_３Ｃ（Ｈ）（Ｘ）−ＣＯ_２Ｒ、
ＣＨ_２＝ＣＨ（ＣＨ_２）_８Ｃ（Ｈ）（Ｘ）−ＣＯ_２Ｒ、
ＣＨ_２＝ＣＨＣＨ_２Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_５、
ＣＨ_２＝ＣＨ（ＣＨ_２）_２Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_５、
ＣＨ_２＝ＣＨ（ＣＨ_２）_３Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_５、
（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、またはアラルキル基）
等を挙げることができる。
【００３０】
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−ＣＨ_２＝ＣＨ−（ＣＨ_２）_ｎ−Ｃ_６Ｈ_４−ＳＯ_２Ｘ、
ｏ−，ｍ−，ｐ−ＣＨ_２＝ＣＨ−（ＣＨ_２）_ｎ−Ｏ−Ｃ_６Ｈ_４−ＳＯ_２Ｘ、
（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。
【００３１】
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。
【００３２】
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。
Ｒ^９Ｒ^１０Ｃ（Ｘ）−Ｒ^１１−Ｒ^１２−Ｃ（Ｈ）（Ｒ^１３）ＣＨ_２−［Ｓｉ（Ｒ^１５）_２−ｂ（Ｙ）_ｂＯ］_ｍ−Ｓｉ（Ｒ^１６）_３−ａ（Ｙ）_ａ （８）
（式中、Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３は上記に同じ。Ｒ^１５、Ｒ^１６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、Ｒ^１５またはＲ^１６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。）
【００３３】
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。
【００３４】
一般式８の化合物を具体的に例示するならば、
ＸＣＨ_２Ｃ（Ｏ）Ｏ（ＣＨ_２）_ｎＳｉ（ＯＣＨ_３）_３、
ＣＨ_３Ｃ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ_２）_ｎＳｉ（ＯＣＨ_３）_３、
（ＣＨ_３）_２Ｃ（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ_２）_ｎＳｉ（ＯＣＨ_３）_３、
ＸＣＨ_２Ｃ（Ｏ）Ｏ（ＣＨ_２）_ｎＳｉ（ＣＨ_３）（ＯＣＨ_３）_２、
ＣＨ_３Ｃ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ_２）_ｎＳｉ（ＣＨ_３）（ＯＣＨ_３）_２、
（ＣＨ_３）_２Ｃ（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ_２）_ｎＳｉ（ＣＨ_３）（ＯＣＨ_３）_２、
（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）
ＸＣＨ_２Ｃ（Ｏ）Ｏ（ＣＨ_２）_ｎＯ（ＣＨ_２）_ｍＳｉ（ＯＣＨ_３）_３、
Ｈ_３ＣＣ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ_２）_ｎＯ（ＣＨ_２）_ｍＳｉ（ＯＣＨ_３）_３、
（Ｈ_３Ｃ）_２Ｃ（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ_２）_ｎＯ（ＣＨ_２）_ｍＳｉ（ＯＣＨ_３）_３、
ＣＨ_３ＣＨ_２Ｃ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ_２）_ｎＯ（ＣＨ_２）_ｍＳｉ（ＯＣＨ_３）_３、
ＸＣＨ_２Ｃ（Ｏ）Ｏ（ＣＨ_２）_ｎＯ（ＣＨ_２）_ｍＳｉ（ＣＨ_３）（ＯＣＨ_３）_２、
Ｈ_３ＣＣ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ_２）_ｎＯ（ＣＨ_２）_ｍ−Ｓｉ（ＣＨ_３）（ＯＣＨ_３）_２、
（Ｈ_３Ｃ）_２Ｃ（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ_２）_ｎＯ（ＣＨ_２）_ｍ−Ｓｉ（ＣＨ_３）（ＯＣＨ_３）_２、
ＣＨ_３ＣＨ_２Ｃ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ_２）_ｎＯ（ＣＨ_２）_ｍ−Ｓｉ（ＣＨ_３）（ＯＣＨ_３）_２、
（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−ＸＣＨ_２−Ｃ_６Ｈ_４−（ＣＨ_２）_２Ｓｉ（ＯＣＨ_３）_３、
ｏ，ｍ，ｐ−ＣＨ_３Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−（ＣＨ_２）_２Ｓｉ（ＯＣＨ_３）_３、
ｏ，ｍ，ｐ−ＣＨ_３ＣＨ_２Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−（ＣＨ_２）_２Ｓｉ（ＯＣＨ_３）_３、
ｏ，ｍ，ｐ−ＸＣＨ_２−Ｃ_６Ｈ_４−（ＣＨ_２）_３Ｓｉ（ＯＣＨ_３）_３、
ｏ，ｍ，ｐ−ＣＨ_３Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−（ＣＨ_２）_３Ｓｉ（ＯＣＨ_３）_３、
ｏ，ｍ，ｐ−ＣＨ_３ＣＨ_２Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−（ＣＨ_２）_３Ｓｉ（ＯＣＨ_３）_３、
ｏ，ｍ，ｐ−ＸＣＨ_２−Ｃ_６Ｈ_４−（ＣＨ_２）_２−Ｏ−（ＣＨ_２）_３Ｓｉ（ＯＣＨ_３）_３、
ｏ，ｍ，ｐ−ＣＨ_３Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−（ＣＨ_２）_２−Ｏ−（ＣＨ_２）_３Ｓｉ（ＯＣＨ_３）_３、
ｏ，ｍ，ｐ−ＣＨ_３ＣＨ_２Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−（ＣＨ_２）_２−Ｏ−（ＣＨ_２）_３Ｓｉ（ＯＣＨ_３）_３、
ｏ，ｍ，ｐ−ＸＣＨ_２−Ｃ_６Ｈ_４−Ｏ−（ＣＨ_２）_３Ｓｉ（ＯＣＨ_３）_３、
ｏ，ｍ，ｐ−ＣＨ_３Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−Ｏ−（ＣＨ_２）_３Ｓｉ（ＯＣＨ_３）_３、
ｏ，ｍ，ｐ−ＣＨ_３ＣＨ_２Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−Ｏ−（ＣＨ_２）_３−Ｓｉ（ＯＣＨ_３）_３、
ｏ，ｍ，ｐ−ＸＣＨ_２−Ｃ_６Ｈ_４−Ｏ−（ＣＨ_２）_２−Ｏ−（ＣＨ_２）_３−Ｓｉ（ＯＣＨ_３）_３、
ｏ，ｍ，ｐ−ＣＨ_３Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−Ｏ−（ＣＨ_２）_２−Ｏ−（ＣＨ_２）_３Ｓｉ（ＯＣＨ_３）_３、
ｏ，ｍ，ｐ−ＣＨ_３ＣＨ_２Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_４−Ｏ−（ＣＨ_２）_２−Ｏ−（ＣＨ_２）_３Ｓｉ（ＯＣＨ_３）_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。
【００３５】
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。
（Ｒ^１６）_３−ａ（Ｙ）_ａＳｉ−［ＯＳｉ（Ｒ^１５）_２−ｂ（Ｙ）_ｂ］_ｍ−ＣＨ_２−Ｃ（Ｈ）（Ｒ^１３）−Ｒ^１２−Ｃ（Ｒ^９）（Ｘ）−Ｒ^１４−Ｒ^１０ （９）
（式中、Ｒ^９、Ｒ^１０、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６、ａ、ｂ、ｍ、Ｘ、Ｙは上記に同じ）
【００３６】
このような化合物を具体的に例示するならば、
（ＣＨ_３Ｏ）_３ＳｉＣＨ_２ＣＨ_２Ｃ（Ｈ）（Ｘ）Ｃ_６Ｈ_５、
（ＣＨ_３Ｏ）_２（ＣＨ_３）ＳｉＣＨ_２ＣＨ_２Ｃ（Ｈ）（Ｘ）Ｃ_６Ｈ_５、
（ＣＨ_３Ｏ）_３Ｓｉ（ＣＨ_２）_２Ｃ（Ｈ）（Ｘ）−ＣＯ_２Ｒ^１７、
（ＣＨ_３Ｏ）_２（ＣＨ_３）Ｓｉ（ＣＨ_２）_２Ｃ（Ｈ）（Ｘ）−ＣＯ_２Ｒ^１７、
（ＣＨ_３Ｏ）_３Ｓｉ（ＣＨ_２）_３Ｃ（Ｈ）（Ｘ）−ＣＯ_２Ｒ^１７、
（ＣＨ_３Ｏ）_２（ＣＨ_３）Ｓｉ（ＣＨ_２）_３Ｃ（Ｈ）（Ｘ）−ＣＯ_２Ｒ^１７、
（ＣＨ_３Ｏ）_３Ｓｉ（ＣＨ_２）_４Ｃ（Ｈ）（Ｘ）−ＣＯ_２Ｒ^１７、
（ＣＨ_３Ｏ）_２（ＣＨ_３）Ｓｉ（ＣＨ_２）_４Ｃ（Ｈ）（Ｘ）−ＣＯ_２Ｒ^１７、
（ＣＨ_３Ｏ）_３Ｓｉ（ＣＨ_２）_９Ｃ（Ｈ）（Ｘ）−ＣＯ_２Ｒ^１７、
（ＣＨ_３Ｏ）_２（ＣＨ_３）Ｓｉ（ＣＨ_２）_９Ｃ（Ｈ）（Ｘ）−ＣＯ_２Ｒ^１７、
（ＣＨ_３Ｏ）_３Ｓｉ（ＣＨ_２）_３Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_５、
（ＣＨ_３Ｏ）_２（ＣＨ_３）Ｓｉ（ＣＨ_２）_３Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_５、
（ＣＨ_３Ｏ）_３Ｓｉ（ＣＨ_２）_４Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_５、
（ＣＨ_３Ｏ）_２（ＣＨ_３）Ｓｉ（ＣＨ_２）_４Ｃ（Ｈ）（Ｘ）−Ｃ_６Ｈ_５、
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、Ｒ^１７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）
等が挙げられる。
【００３７】
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−（ＣＨ_２）_ｎ−ＯＣ（Ｏ）Ｃ（Ｈ）（Ｒ^１７）（Ｘ）
（上記の式において、Ｘは塩素、臭素、またはヨウ素、Ｒ^１７は水素原子、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、ｎは１〜２０の整数）
【００３８】
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。
Ｈ_２Ｎ−（ＣＨ_２）_ｎ−ＯＣ（Ｏ）Ｃ（Ｈ）（Ｒ^１７）（Ｘ）
（上記の式において、Ｘは塩素、臭素、またはヨウ素、Ｒ^１７は水素原子、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、ｎは１〜２０の整数）
【００３９】
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。
【００４０】
【化３】

【００４１】
（上記の式において、Ｘは塩素、臭素、またはヨウ素、Ｒ^１７は水素原子、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、ｎは１〜２０の整数）
【００４２】
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、
【００４３】
【化４】

【００４４】
【化５】

【００４５】
等があげられる。
【００４６】
《重合条件》
この重合において用いられるビニル系モノマーとしては特に制約はなく、既に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、異なる種類のビニル系モノマー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、エマルション系もしくは超臨界流体ＣＯ_２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、さらに好ましくは６０〜１００℃である。
【００４９】
重合の雰囲気は、特に限定されないが、酸素不存在雰囲気が好ましい。ラジカルは酸素による影響を受けるし、また、酸素存在下では、触媒が酸化され活性を失う可能性がある。
【００５０】
重合混合物はよく攪拌されることが好ましい。特に、触媒金属錯体あるいは配位子を添加する際には、速やかに均一に拡散させるためにも、十分な攪拌が好ましい。
【００５１】
重合の方法としては、バッチ重合、モノマーを追加していくセミバッチ重合、連続重合等に適用できる。セミバッチ重合の追加方式は、連続方式、分割方式、連続方式と分割方式の組み合わせのいずれかを適用できる。
【００５２】
セミバッチ重合の場合、初期仕込みモノマーの量はモノマー全量に対して５０重量％以下であることが好ましく、３０重量％以下であることがより好ましい。また下限は１０重量％以上が好ましい。
【００５３】
セミバッチ方式におけるモノマー追加時間は、全ビニル系モノマー（初期仕込みモノマーと追加仕込みモノマーの合計）のうち９０重量％以上を添加するのに要する時間が０．５時間以上２．５時間以下の範囲内であることが好ましく、全ビニル系モノマー（初期仕込みモノマーと追加仕込みモノマーの合計）の添加を０．５時間以上２．５時間以下の範囲内で完了させることが特に好ましい。添加時間が長くなった場合は、反応速度が低下し、生産性が低下するとともに、触媒活性を向上させる操作が必要となる場合が多い。
【００５４】
重合触媒の金属錯体の配位子は、触媒金属原子に対し配位飽和する以上に添加しても、それ以上の活性の向上は期待できないので、そうならないように、金属化合物は最終的な配位子の添加量に対して過剰であることが好ましい。また、金属化合物をも後から追加しても構わないが、最初から必要な全量を添加しておく方が工程上好ましい。
【００５５】
重合触媒の金属錯体の配位子は２回以上に分割して添加することが好ましく、３回以上に分割して添加することがより好ましい。上限は１０回以下が好ましく、６回以下がより好ましい。少量づつ添加すると総添加量が同じであっても触媒活性が低い場合が多く見られる。
【００５６】
重合中の転化率は、モノマー追加開始時で系中の転化率を１０％以上になるまで重合を進行させておくことが好ましい。より好ましくは２０％以上である。また上限としては６０％以下が好ましく、５０％以下がより好ましい。１０％を下回る様な転化率が低い場合にモノマー追加を開始した場合、急な発熱によって除熱不能となり暴走する場合が多くみられる。一方、転化率が高い場合、モノマー減少によって副反応が生じ易く、特に７０％を越えると触媒活性が低下する場合が多く見られる。
【００５７】
また、モノマー追加終了時の系中の転化率を４０％以上になるまで重合を進行させておくことが好ましい。より好ましくは５０％以上である。また上限としては９５％以下が好ましく、９０％以下がより好ましい。未反応モノマーが多い状態で追加が終了した場合、モノマー添加による顕熱による除熱効果が期待できないために、除熱能力不足となる傾向がある。転化率が９５％を超えると、副反応が生じ易くなり重合体の分子量分布が著しく増大する傾向がある。
【００５８】
重合の最中または終点において、重合性の低いアルケニル基を有する化合物（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。重合の終点とは、モノマーの好ましくは８０％以上が反応した時点、さらに好ましくは９０％以上、特に好ましくは９５％以上、特別に好ましくは９９％以上が反応した時点である。
【００５９】
重合の終点においては、引き続いて化合物（Ｉ）を添加することができ、一旦未反応モノマーや重合溶媒を蒸発留去してから化合物（Ｉ）を添加することもできる。
【００６０】
また、化合物（Ｉ）を添加するときに、誘電率が化合物（Ｉ）よりも高い化合物（ＩＩ）を併用添加することにより、末端に確実に官能基を導入することができる。
【００６１】
《化合物（Ｉ）》
重合性の低いアルケニル基を持つ化合物としては一般式１に示される化合物が挙げられる。
一般式１：
【００６２】
【化６】

【００６３】
｛上の式中、Ｒ^３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７】

【００６５】
（Ｒ^４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、Ｒ^１は炭素数１〜２０のアルキル基あるいは一般式３：
【００６６】
【化８】

【００６７】
（上の式中、Ｒ^５は酸素原子、窒素原子あるいは炭素数１〜２０の有機基、Ｒ^６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、Ｒ^２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に示される化合物が挙げられる。
【００６８】
【化９】

【００６９】
｛上の式中、Ｒ^１は炭素数１〜２０のアルキル基あるいは一般式３：
【００７０】
【化１０】

【００７１】
（上の式中、Ｒ^５は酸素原子、窒素原子あるいは炭素数１〜２０の有機基、Ｒ^６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、Ｒ^２、Ｒ^４は水素原子あるいはメチル基である｝
【００７２】
一般式４で表される化合物のＲ^２、Ｒ^４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。Ｒ^１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。
【００７３】
【化１１】

【００７４】
式５中、ｎは１〜２０の整数であるが、原料入手の容易さから、ｎは２、４または６であることが好ましい。
一般式１において、Ｒ^１の具体例としては、
−（ＣＨ_２）_ｎ− （ｎは１〜２０の整数）、
−ＣＨ（ＣＨ_３）−、−ＣＨ（ＣＨ_２ＣＨ_３）−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＨ_３）（ＣＨ_２ＣＨ_３）−、−Ｃ（ＣＨ_２ＣＨ_３）_２−、−ＣＨ_２ＣＨ（ＣＨ_３）−、
−（ＣＨ_２）_ｎ−Ｏ−ＣＨ_２− （ｎは１〜１９の整数）、
−ＣＨ（ＣＨ_３）−Ｏ−ＣＨ_２−、−ＣＨ（ＣＨ_２ＣＨ_３）−Ｏ−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−Ｏ−ＣＨ_２−、−Ｃ（ＣＨ_３）（ＣＨ_２ＣＨ_３）−Ｏ−ＣＨ_２−、−Ｃ（ＣＨ_２ＣＨ_３）_２−Ｏ−ＣＨ_２−、
−（ＣＨ_２）_ｎ−Ｏ−（ＣＨ_２）_ｍ−
（ｍ、ｎは１〜１９の整数、ただし２≦ｍ＋ｎ≦２０）、
−（ＣＨ_２）_ｎ−Ｃ（Ｏ）Ｏ−（ＣＨ_２）_ｍ−
（ｍ、ｎは１〜１９の整数、ただし２≦ｍ＋ｎ≦２０）、
−（ＣＨ_２）_ｎ−ＯＣ（Ｏ）−（ＣＨ_２）_ｍ−Ｃ（Ｏ）Ｏ−（ＣＨ_２）_ｌ−、
（ｌは０〜１８の整数、ｍ，ｎは１〜１７の整数、ただし２≦ｌ＋ｍ＋ｎ≦１８）、
−（ＣＨ_２）_ｎ−ｏ−，ｍ−，ｐ−Ｃ_６Ｈ_４−、
−（ＣＨ_２）_ｎ−ｏ−，ｍ−，ｐ−Ｃ_６Ｈ_４−（ＣＨ_２）_ｍ−、
（ｍは０〜１３の整数、ｎは１〜１４の整数、ただし１≦ｍ＋ｎ≦１４）、
−（ＣＨ_２）_ｎ−ｏ−，ｍ−，ｐ−Ｃ_６Ｈ_４−Ｏ−（ＣＨ_２）_ｍ−、
（ｍは０〜１３の整数、ｎは１〜１４の整数、ただし１≦ｍ＋ｎ≦１４）、
−（ＣＨ_２）_ｎ−ｏ−，ｍ−，ｐ−Ｃ_６Ｈ_４−Ｏ−ＣＨ（ＣＨ_３）−、
（ｎは１〜１２の整数）、
−（ＣＨ_２）_ｎ−ｏ−，ｍ−，ｐ−Ｃ_６Ｈ_４−Ｏ−ＣＨ（ＣＨ_３）_２−、
（ｎは１〜１１の整数）、
−（ＣＨ_２）_ｎ−ｏ−，ｍ−，ｐ−Ｃ_６Ｈ_４−Ｃ（Ｏ）Ｏ−（ＣＨ_２）_ｍ−、
（ｍ，ｎは１〜１２の整数、ただし２≦ｍ＋ｎ≦１３）、
−（ＣＨ_２）_ｎ−ＯＣ（Ｏ）−ｏ−，ｍ−，ｐ−Ｃ_６Ｈ_４−Ｃ（Ｏ）Ｏ−（ＣＨ_２）_ｍ−、
（ｍ，ｎは１〜１１の整数、ただし２≦ｍ＋ｎ≦１２）、
−（ＣＨ_２）_ｎ−ｏ−，ｍ−，ｐ−Ｃ_６Ｈ_４−ＯＣ（Ｏ）−（ＣＨ_２）_ｍ−、
（ｍ，ｎは１〜１２の整数、ただし２≦ｍ＋ｎ≦１３）、
−（ＣＨ_２）_ｎ−Ｃ（Ｏ）Ｏ−ｏ−，ｍ−，ｐ−Ｃ_６Ｈ_４−（ＣＨ_２）_ｍ−、
（ｍ，ｎは１〜１１の整数、ただし２≦ｍ＋ｎ≦１２）、
等が挙げられる。
一般式１において、Ｒ^３としては、以下のような基が例示される。
【００７５】
【化１２】

【００７６】
（式中、Ｒ^１８、Ｒ^１９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、Ｒ^１８またはＲ^１９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。Ｒ^２０は炭素数１〜２０の炭化水素基である。）
【００７７】
Ｒ^２０としては、具体的には以下のような基が例示される。
−（ＣＨ_２）_ｎ−ＣＨ_３、
−ＣＨ（ＣＨ_３）−（ＣＨ_２）_ｎ−ＣＨ_３、
−ＣＨ（ＣＨ_２ＣＨ_３）−（ＣＨ_２）_ｎ−ＣＨ_３、
−ＣＨ（ＣＨ_２ＣＨ_３）_２、
−Ｃ（ＣＨ_３）_２−（ＣＨ_２）_ｎ−ＣＨ_３、
−Ｃ（ＣＨ_３）（ＣＨ_２ＣＨ_３）−（ＣＨ_２）_ｎ−ＣＨ_３、
−Ｃ_６Ｈ_５、
−Ｃ_６Ｈ_４（ＣＨ_３）、
−Ｃ_６Ｈ_３（ＣＨ_３）_２、
−（ＣＨ_２）_ｎ−Ｃ_６Ｈ_５、
−（ＣＨ_２）_ｎ−Ｃ_６Ｈ_４（ＣＨ_３）、
−（ＣＨ_２）_ｎ−Ｃ_６Ｈ_３（ＣＨ_３）_２、
（ｎは０以上の整数で、各基の合計炭素数は２０以下）
【００７８】
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。
【００７９】
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。
【００８０】
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。
【００８１】
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場合の、その添加量は、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、重合末端どうし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、添加量に応じて統計的に決まってくる。よって、重合性の低いアルケニル基を２つ以上持つ化合物の添加量は、好ましくは重合成長末端の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。
【００８２】
《化合物（ＩＩ）》
重合性の低いアルケニル基を有する化合物（Ｉ）を添加するとき、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、化合物（Ｉ）より極性の高い化合物（ＩＩ）を添加することで極性を向上させることができる。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、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、全ビニル系モノマー（初期仕込みモノマーと追加仕込みモノマーの合計）１００重量部に対して１〜１０００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、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。
【００８３】
《末端構造》
重合の最中または終点において、重合性の低いアルケニル基を有する化合物（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ビニル系重合体は、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、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。
【００８４】
【化１３】

【００８５】
｛上の式中、Ｒ^３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：
【００８６】
【化１４】

【００８７】
（Ｒ^４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、Ｒ^１は炭素数１〜２０のアルキル基、あるいは一般式３：
【００８８】
【化１５】

【００８９】
（上の式中、Ｒ^５は酸素原子、窒素原子あるいは炭素数１〜２０の有機基、Ｒ^６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、Ｒ^２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｝
【００９０】
一般式１０において、Ｒ^１の具体例としては、
−（ＣＨ_２）_ｎ− （ｎは１〜２０の整数）、
−ＣＨ（ＣＨ_３）−、−ＣＨ（ＣＨ_２ＣＨ_３）−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＨ_３）（ＣＨ_２ＣＨ_３）−、−Ｃ（ＣＨ_２ＣＨ_３）_２−、−ＣＨ_２ＣＨ（ＣＨ_３）−、
−（ＣＨ_２）_ｎ−Ｏ−ＣＨ_２− （ｎは１〜１９の整数）、
−ＣＨ（ＣＨ_３）−Ｏ−ＣＨ_２−、−ＣＨ（ＣＨ_２ＣＨ_３）−Ｏ−ＣＨ_２−、−Ｃ（ＣＨ_３）_２−Ｏ−ＣＨ_２−、−Ｃ（ＣＨ_３）（ＣＨ_２ＣＨ_３）−Ｏ−ＣＨ_２−、−Ｃ（ＣＨ_２ＣＨ_３）_２−Ｏ−ＣＨ_２−、
−（ＣＨ_２）_ｎ−Ｏ−（ＣＨ_２）_ｍ−
（ｍ、ｎは１〜１９の整数、ただし２≦ｍ＋ｎ≦２０）、
−（ＣＨ_２）_ｎ−Ｃ（Ｏ）Ｏ−（ＣＨ_２）_ｍ−
（ｍ、ｎは１〜１９の整数、ただし２≦ｍ＋ｎ≦２０）、
−（ＣＨ_２）_ｎ−ＯＣ（Ｏ）−（ＣＨ_２）_ｍ−Ｃ（Ｏ）Ｏ−（ＣＨ_２）_ｌ−、
（ｌは０〜１８の整数、ｍ，ｎは１〜１７の整数、ただし２≦ｌ＋ｍ＋ｎ≦１８）、
−（ＣＨ_２）_ｎ−ｏ−，ｍ−，ｐ−Ｃ_６Ｈ_４−、
−（ＣＨ_２）_ｎ−ｏ−，ｍ−，ｐ−Ｃ_６Ｈ_４−（ＣＨ_２）_ｍ−、
（ｍは０〜１３の整数、ｎは１〜１４の整数、ただし１≦ｍ＋ｎ≦１４）、
−（ＣＨ_２）_ｎ−ｏ−，ｍ−，ｐ−Ｃ_６Ｈ_４−Ｏ−（ＣＨ_２）_ｍ−、
（ｍは０〜１３の整数、ｎは１〜１４の整数、ただし１≦ｍ＋ｎ≦１４）、
−（ＣＨ_２）_ｎ−ｏ−，ｍ−，ｐ−Ｃ_６Ｈ_４−Ｏ−ＣＨ（ＣＨ_３）−、
（ｎは１〜１２の整数）、
−（ＣＨ_２）_ｎ−ｏ−，ｍ−，ｐ−Ｃ_６Ｈ_４−Ｏ−ＣＨ（ＣＨ_３）_２−、
（ｎは１〜１１の整数）、
−（ＣＨ_２）_ｎ−ｏ−，ｍ−，ｐ−Ｃ_６Ｈ_４−Ｃ（Ｏ）Ｏ−（ＣＨ_２）_ｍ−、
（ｍ，ｎは１〜１２の整数、ただし２≦ｍ＋ｎ≦１３）、
−（ＣＨ_２）_ｎ−ＯＣ（Ｏ）−ｏ−，ｍ−，ｐ−Ｃ_６Ｈ_４−Ｃ（Ｏ）Ｏ−（ＣＨ_２）_ｍ−、
（ｍ，ｎは１〜１１の整数、ただし２≦ｍ＋ｎ≦１２）、
−（ＣＨ_２）_ｎ−ｏ−，ｍ−，ｐ−Ｃ_６Ｈ_４−ＯＣ（Ｏ）−（ＣＨ_２）_ｍ−、
（ｍ，ｎは１〜１２の整数、ただし２≦ｍ＋ｎ≦１３）、
−（ＣＨ_２）_ｎ−Ｃ（Ｏ）Ｏ−ｏ−，ｍ−，ｐ−Ｃ_６Ｈ_４−（ＣＨ_２）_ｍ−、
（ｍ，ｎは１〜１１の整数、ただし２≦ｍ＋ｎ≦１２）、
等が挙げられる。
Ｒ^３としては、以下のような基が例示される。
【００９１】
【化１６】

【００９２】
式中、Ｒ^１８、Ｒ^１９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、Ｒ^１８またはＲ^１９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。
【００９３】
Ｒ^２０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。
−（ＣＨ_２）_ｎ−ＣＨ_３、
−ＣＨ（ＣＨ_３）−（ＣＨ_２）_ｎ−ＣＨ_３、
−ＣＨ（ＣＨ_２ＣＨ_３）−（ＣＨ_２）_ｎ−ＣＨ_３、
−ＣＨ（ＣＨ_２ＣＨ_３）_２、
−Ｃ（ＣＨ_３）_２−（ＣＨ_２）_ｎ−ＣＨ_３、
−Ｃ（ＣＨ_３）（ＣＨ_２ＣＨ_３）−（ＣＨ_２）_ｎ−ＣＨ_３、
−Ｃ_６Ｈ_５、
−Ｃ_６Ｈ_４（ＣＨ_３）、
−Ｃ_６Ｈ_３（ＣＨ_３）_２、
−（ＣＨ_２）_ｎ−Ｃ_６Ｈ_５、
−（ＣＨ_２）_ｎ−Ｃ_６Ｈ_４（ＣＨ_３）、
−（ＣＨ_２）_ｎ−Ｃ_６Ｈ_３（ＣＨ_３）_２、
（ｎは０以上の整数で、各基の合計炭素数は２０以下）
【００９４】
一般式１０において、Ｒ^２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。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。
【００９５】
アルケニル基が末端に導入されている場合において、Ｒ^１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。
【００９６】
【化１７】

【００９７】
式中、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。ｎは１〜２０の整数であるが、原料入手の容易さから、ｎは２、４、または６であることが好ましい。
【００９８】
重合体１分子中に含まれる、一般式１０で表さ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。
【００９９】
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。
【０１００】
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、ビニル系重合体の本来の特性が発現されにくく、また、１０００００以上であると、ハンドリングが困難になる。
【０１０１】
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か、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、架橋性シリル基を持つヒドロシラン化合物によるヒドロシリル化反応により、アルケニル基を架橋性シリル基に変換することができる。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。
【０１０２】
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（Ｒ^２１）_２−ｂ（Ｙ）_ｂＯ］_ｍ−Ｓｉ（Ｒ^２２）_３−ａ（Ｙ）_ａ （１２）
（式中、Ｒ^２１、Ｒ^２２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、Ｒ^２１またはＲ^２２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。
【０１０３】
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。
【０１０４】
一般式１２におけるＲ^２１、Ｒ^２２の具体例としては、例えば、メチル基やエチル基などのアルキル基、シクロヘキシル基等のシクロアルキル基、フェニル基などのアリール基、ベンジル基などのアラルキル基、Ｒ’がメチル基やフェニル基等であるＲ’_３ＳｉＯ−で示されるトリオルガノシリル基等が挙げられる。
これらヒドロシラン化合物の中でも、特に一般式１３
Ｈ−Ｓｉ（Ｒ^２２）_３−ａ（Ｙ）_ａ （１３）
（式中、Ｒ^２２、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、
ＨＳｉＣｌ_３、ＨＳｉ（ＣＨ_３）Ｃｌ_２、ＨＳｉ（ＣＨ_３）_２Ｃｌ、ＨＳｉ（ＯＣＨ_３）_３、ＨＳｉ（ＣＨ_３）（ＯＣＨ_３）_２、ＨＳｉ（ＣＨ_３）_２ＯＣＨ_３、
ＨＳｉ（ＯＣ_２Ｈ_５）_３、ＨＳｉ（ＣＨ_３）（ＯＣ_２Ｈ_５）_２、
ＨＳｉ（ＣＨ_３）_２ＯＣ_２Ｈ_５、ＨＳｉ（ＯＣ_３Ｈ_７）_３、
ＨＳｉ（Ｃ_２Ｈ_５）（ＯＣＨ_３）_２、ＨＳｉ（Ｃ_２Ｈ_５）_２ＯＣＨ_３、
ＨＳｉ（Ｃ_６Ｈ_５）（ＯＣＨ_３）_２、ＨＳｉ（Ｃ_６Ｈ_５）_２（ＯＣＨ_３）、
ＨＳｉ（ＣＨ_３）（ＯＣ（Ｏ）ＣＨ_３）_２、
ＨＳｉ（ＣＨ_３）_２Ｏ−［Ｓｉ（ＣＨ_３）_２Ｏ］_２−Ｓｉ（ＣＨ_３）（ＯＣＨ_３）_２、
ＨＳｉ（ＣＨ_３）［Ｏ−Ｎ＝Ｃ（ＣＨ_３）_２］_２
（ただし、上記化学式中、Ｃ_６Ｈ_５はフェニル基を示す）
等が挙げられる。
【０１０５】
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。
【０１０６】
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。
【０１０７】
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ール、アルデヒド、ケトン等との錯体、白金−オレフィン錯体、白金（０）−ジビニルテトラメチルジシロキサン錯体が挙げられる。白金化合物以外の触媒の例としては、ＲｈＣｌ（ＰＰｈ_３）_３，ＲｈＣｌ_３，ＲｕＣｌ_３，ＩｒＣｌ_３，ＦｅＣｌ_３，ＡｌＣｌ_３，ＰｄＣｌ_２・Ｈ_２Ｏ，ＮｉＣｌ_２，ＴｉＣｌ_４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、ビニル系重合体のアルケニル基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。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。
【０１０８】
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。
【０１０９】
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。
【０１１０】
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。
【０１１１】
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、
（ＣＨ_３Ｏ）_３Ｓｉ−（ＣＨ_２）_ｎ−ＮＣＯ、
（ＣＨ_３Ｏ）_２（ＣＨ_３）Ｓｉ−（ＣＨ_２）_ｎ−ＮＣＯ、
（Ｃ_２Ｈ_５Ｏ）_３Ｓｉ−（ＣＨ_２）_ｎ−ＮＣＯ、
（Ｃ_２Ｈ_５Ｏ）_２（ＣＨ_３）Ｓｉ−（ＣＨ_２）_ｎ−ＮＣＯ、
（ｉ−Ｃ_３Ｈ_７Ｏ）_３Ｓｉ−（ＣＨ_２）_ｎ−ＮＣＯ、
（ｉ−Ｃ_３Ｈ_７Ｏ）_２（ＣＨ_３）Ｓｉ−（ＣＨ_２）_ｎ−ＮＣＯ、
（ＣＨ_３Ｏ）_３Ｓｉ−（ＣＨ_２）_ｎ−ＮＨ−（ＣＨ_２）_ｍ−ＮＣＯ、
（ＣＨ_３Ｏ）_２（ＣＨ_３）Ｓｉ−（ＣＨ_２）_ｎ−ＮＨ−（ＣＨ_２）_ｍ−ＮＣＯ、
（Ｃ_２Ｈ_５Ｏ）_３Ｓｉ−（ＣＨ_２）_ｎ−ＮＨ−（ＣＨ_２）_ｍ−ＮＣＯ、
（Ｃ_２Ｈ_５Ｏ）_２（ＣＨ_３）Ｓｉ−（ＣＨ_２）_ｎ−ＮＨ−（ＣＨ_２）_ｍ−ＮＣＯ、
（ｉ−Ｃ_３Ｈ_７Ｏ）_３Ｓｉ−（ＣＨ_２）_ｎ−ＮＨ−（ＣＨ_２）_ｍ−ＮＣＯ、
（ｉ−Ｃ_３Ｈ_７Ｏ）_２（ＣＨ_３）Ｓｉ−（ＣＨ_２）_ｎ−ＮＨ−（ＣＨ_２）_ｍ−ＮＣＯ、
（上記式中、ｎ、ｍは１〜２０の整数）
等が挙げられる。
【０１１２】
末端に水酸基を有するビニル系重合体と、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。
【０１１３】
【実施例】
以下実施例により本発明を更に詳しく説明するが、本発明は以下の実施例にのみ限定されるものではない。なお、本実施例中の系中の転化率の測定にはガスクロマトグラフィーを用い、重合溶媒を内部標準物質として、重合開始前のモノマーと溶媒の面積比の数値と、任意の時間でサンプリングされたモノマーと溶媒の面積比の数値を比較し、その数値の減少の割合より転化率を算出した。
（実施例１）
２Ｌの重合槽に臭化第一銅（１０．０７ｇ）を投入し、真空脱揮と窒素で圧戻しを３回繰り返した。３００ｒｐｍで撹拌を開始して、アセトニトリル（６５．５ｇ）を投入した。２Ｌ重合槽のジャケットを加熱昇温し、内温が７０℃に到達して１５分後、初期モノマー（ブチルアクリレート ２４０．００ｇ）を仕込み、更に、ジエチル２，５−ジブロモアジペート２１．０７ｇを予め溶解させておいたアセトニトリル４０．００ｇを仕込んだ。その後、内温を７５℃に回復した後、０．２０ｇのペンタメチルジエチレントリアミンを追加して重合を開始した。図１に内温、総モノマー量に対するモノマー仕込み率および系中の転化率の経時変化の結果を示す。内温は上昇を示し７８℃を示した。その５分後、更に０．２０ｇのペンタメチルジエチレントリアミンを追加した。その１０分後、０．４１ｇのペンタメチルジエチレントリアミンを追加し１０分間攪拌混合した。内温は上昇を示し８０℃を示した。この直後サンプリングを行ない、ガスクロマトクラフィーにて未反応モノマーの残存量を測定した処、転化率は３０％であった。その後、２時間かけて追加モノマー（ブチルアクリレート ９６０．００ｇ）を、内温を８５℃〜９０℃に保ちながら連続添加した。モノマー追加開始時、モノマー追加開始３０分後、および６０分後に０．４１ｇのペンタメチルジエチレントリアミンを追加し、転化率カーブをコントロールした。モノマー追加終了後、サンプリングを行ない、ガスクロマトクラフィーにて未反応モノマーの残存量を測定した処、転化率は６９％であった。モノマー追加終了後７８分で、ガスクロマトグラフィーにより重合度が９５％以上になったことを確認した後、反応系を１０Ｔｏｒｒで６０分以上脱揮して、溶剤回収を行った後に、１，７−オクタジエンを１２８．９７ｇ追加した。アセトニトリルを３１６．５０ｇ追加した後に、ペンタメチルジエチレントリアミンを４．０６ｇ追加し、６時間加熱攪拌混合した後、１０Ｔｏｒｒで６０分以上脱揮し、未反応オクタジエン及びアセトニトリルを脱揮した。混合物を活性アルミナで処理した生成した重合体のＧＰＣ測定（ポリスチレン換算）結果は、１，７−オクタジエンの添加直前で、数平均分子量２４８０１、分子量分布Ｍｗ／Ｍｎ＝１．１６で、最終生成物は、数平均分子量２５６５４、分子量分布Ｍｗ／Ｍｎ＝１．２６であった。
【０１１４】
（実施例２）
２Ｌの重合槽に臭化第一銅（１０．０７ｇ）を投入し、真空脱揮と窒素で圧戻しを３回繰り返した。３００ｒｐｍで攪拌を開始して、アセトニトリル（６５．５ｇ）を投入した。２Ｌ重合槽のジャケットを加熱昇温し、内温が７０℃に到達して１５分後、初期モノマー（ブチルアクリレート ２４０．００ｇ）を仕込み、更に、ジエチル２，５−ジブロモアジペート２１．０７ｇを予め溶解させておいたアセトニトリル４０．００ｇを仕込んだ。その後、内温を７５℃に回復した後、０．２０ｇのペンタメチルジエチレントリアミンを追加して重合を開始した。図２に内温、総モノマー量に対するモノマー仕込み率および系中の転化率の経時変化の結果を示す。内温は上昇を示し８０℃を示した。その１０分後、更に０．２０ｇのペンタメチルジエチレントリアミンを追加した。その１０分後、０．４１ｇのペンタメチルジエチレントリアミンを追加し１０分間攪拌混合した。内温は上昇を示し８７℃を示した。この直後サンプリングを行ない、ガスクロマトクラフィーにて未反応モノマーの残存量を測定した処、転化率は４５％であった。その後、２時間かけて追加モノマー（ブチルアクリレート ９６０．００ｇ）を、内温を８５℃〜９０℃に保ちながら連続添加した。モノマー追加開始時、モノマー追加開始３０分後、および６０分後に０．２０ｇのペンタメチルジエチレントリアミンを追加し、転化率カーブをコントロールした。モノマー追加終了後、サンプリングを行ない、ガスクロマトクラフィーにて未反応モノマーの残存量を測定した処、転化率は７８％であった。モノマー追加終了後１０５分で、ガスクロマトグラフィーにより重合度が９５％以上になったことを確認した。混合物を活性アルミナで処理した。生成した重合体のＧＰＣ測定（ポリスチレン換算）結果は、数平均分子量２５２５２、分子量分布Ｍｗ／Ｍｎ＝１．１７であった。
【０１１５】
（実施例３）
２Ｌの重合槽に臭化第一銅（１１．１５ｇ）を投入し、真空脱揮と窒素で圧戻しを３回繰り返した。３００ｒｐｍで撹拌を開始して、アセトニトリル（５０．０７ｇ）を投入した。２Ｌ重合槽のジャケットを加熱昇温し、内温が７０℃に到達して１５分後、初期モノマー（ブチルアクリレート ６６．３９ｇ、エチルアクリレート ９５．４２ｇ、２−メトキシエチルアクリレート ７８．２０ｇ）を仕込み、更に、ジエチル２，５−ジブロモアジペート ３１．０８ｇを予め溶解させておいたアセトニトリル ５０．０７ｇを仕込んだ。その後、内温を７５℃に回復した後、０．２２ｇのペンタメチルジエチレントリアミンを追加して重合を開始した。図３に内温、総モノマー量に対するモノマー仕込み率および系中の転化率の経時変化の結果を示す。内温は上昇を示し７８℃を示した。その１０分後、更に０．２２ｇのペンタメチルジエチレントリアミンを追加した。その１０分後、０．４５ｇのペンタメチルジエチレントリアミンを追加し１０分間攪拌混合した。内温は上昇を示し８０℃を示した。この直後サンプリングを行ない、ガスクロマトクラフィーにて未反応モノマーの残存量を測定した処、転化率は３０％であった。その後、２時間かけて追加モノマー（ブチルアクリレート ２６５．５５ｇ、エチルアクリレート ３８１．６７ｇ、２−メトキシエチルアクリレート ３１２．７８ｇ）を、内温を８５℃〜９０℃に保ちながら連続添加した。モノマー追加開始時、モノマー追加開始３０分後、および６０分後に０．４５ｇのペンタメチルジエチレントリアミンを追加し、転化率カーブをコントロールした。モノマー追加終了後、サンプリングを行ない、ガスクロマトクラフィーにて未反応モノマーの残存量を測定した処、転化率は６９％であった。モノマー追加終了後６０分で、ガスクロマトグラフィーにより重合度が９５％以上になったことを確認した後、反応系を１０Ｔｏｒｒで６０分以上脱揮して、溶剤回収を行った後に、１，７−オクタジエンを２８５．４０ｇ追加した。アセトニトリルを３００．３９ｇ追加した後に、ペンタメチルジエチレントリアミンを４．４９ｇ追加し、６時間加熱攪拌混合した後、１０Ｔｏｒｒで６０分以上脱揮し、未反応オクタジエン及びアセトニトリルを脱揮した。混合物を活性アルミナで処理した。生成した重合体のＧＰＣ測定（ポリスチレン換算）結果は、１，７−オクタジエンの添加直前で、数平均分子量１７２０１、分子量分布Ｍｗ／Ｍｎ＝１．１１で、最終生成物は、数平均分子量１７５００、分子量分布Ｍｗ／Ｍｎ＝１．１４、^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１．７７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。
【０１１６】
（実施例４）
２５０Ｌの重合槽を真空脱揮した後、窒素で圧戻しを行い、アセトニトリル（３９５５ｇ）、臭化第一銅（１００７．３ｇ）を投入し、窒素圧戻しを行い、窒素加圧と圧抜きを３回繰り返した。その後、２５０Ｌ重合槽のジャケットを加熱昇温し、１６０ｒｐｍで攪拌を開始した。内温が７０℃に到達して１５分後、初期モノマー（ブチルアクリレート ２４０００ｇ）を仕込み、更に、ジエチル２，５−ジブロモアジペート２１０６．８ｇを予め溶解させておいたアセトニトリル５０００ｇを仕込んだ。その後、内温を７０℃に回復した後、２０．３ｇのペンタメチルジエチレントリアミンを追加した。図４に内温、総モノマー量に対するモノマー仕込み率および系中の転化率の経時変化の結果を示す。内温は上昇を示し７５℃を示した。その１０分後、更に２０．３ｇのペンタメチルジエチレントリアミンを追加した。その１０分後、４０．６ｇのペンタメチルジエチレントリアミンを追加し１０分間攪拌混合した。内温は上昇を示し７６℃を示した。この直後サンプリングを行ない、ガスクロマトクラフィーにて未反応モノマーの残存量を測定した処、転化率は５１％であった。その後、２時間かけて追加モノマー（ブチルアクリレート ９６０００ｇ）を、内温を８５℃〜９０℃に保ちながら連続添加した。モノマー追加開始時、モノマー追加開始３０分後、および６０分後に４０．６ｇのペンタメチルジエチレントリアミンを追加し、転化率カーブをコントロールした。モノマー追加終了後、サンプリングを行ない、ガスクロマトクラフィーにて未反応モノマーの残存量を測定した処、転化率は８３％であった。モノマー追加終了後６７分で、ガスクロマトグラフィーにより重合度が９５％以上になったことを確認した後、反応系を０．６７ＫＰａで６０分以上脱揮して、溶剤回収を行った後に、１，７−オクタジエンを２８３７３ｇ追加した。アセトニトリルを１０５５０ｇ追加した後に、ペンタメチルジエチレントリアミンを４０６ｇを追加し、６時間加熱攪拌混合した後、０．６７ＫＰａで６０分以上脱揮し、未反応オクタジエン及びアセトニトリルを脱揮した。混合物を活性アルミナで処理した。生成した重合体のＧＰＣ測定（ポリスチレン換算）結果は、１，７−オクタジエンの添加直前で、数平均分子量２４８０１、分子量分布Ｍｗ／Ｍｎ＝１．１６で、最終生成物は、数平均分子量２６３５３、分子量分布Ｍｗ／Ｍｎ＝１．２５、^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１．９８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。
【０１１７】
（実施例５）
２５０Ｌの重合槽を真空脱揮した後、窒素で圧戻しを行い、アセトニトリル（３９５５ｇ）、臭化第一銅（１１０８ｇ）を投入し、窒素圧戻しを行い、窒素加圧と圧抜きを３回繰り返した。その後、２５０Ｌ重合槽のジャケットを加熱昇温し、１６０ｒｐｍで攪拌を開始した。内温が７０℃に到達して１５分後、初期モノマー（ブチルアクリレート ６６００ｇ、エチルアクリレート ９４８６ｇ、２−メトキシエチルアクリレート ７７７４ｇ）を仕込み、更に、ジエチル２，５−ジブロモアジペート ３０９０ｇを予め溶解させておいたアセトニトリル ５０００ｇを仕込んだ。その後、内温を７０℃に回復した後、２２．３ｇのペンタメチルジエチレントリアミンを追加して重合を開始した。図５に内温、総モノマー量に対するモノマー仕込み率および系中の転化率の経時変化の結果を示す。内温は上昇を示し７２℃を示した。その１０分後、更に２２．３ｇのペンタメチルジエチレントリアミンを追加した。その１０分後、４４．６ｇのペンタメチルジエチレントリアミンを追加し１０分間攪拌混合した。内温は上昇を示し７３℃を示した。この直後サンプリングを行ない、ガスクロマトクラフィーにて未反応モノマーの残存量を測定した処、転化率は２５％であった。その後、２時間かけて追加モノマー（ブチルアクリレート ２６４００ｇ、エチルアクリレート ３７９４４ｇ、２−メトキシエチルアクリレート ３１０９５ｇ）を、内温を８５℃〜９０℃に保ちながら連続添加した。モノマー追加開始時、モノマー追加開始３０分後、および６０分後に４４．６ｇのペンタメチルジエチレントリアミンを追加し、転化率カーブをコントロールした。モノマー追加終了後、サンプリングを行ない、ガスクロマトクラフィーにて未反応モノマーの残存量を測定した処、転化率は８０％であった。モノマー追加終了後７５分で、ガスクロマトグラフィーにより重合度が９５％以上になったことを確認した後、反応系を０．６７ＫＰａで６０分以上脱揮して、溶剤回収を行った後に、１，７−オクタジエンを２８３７３ｇ追加した。アセトニトリルを９９５５ｇ追加した後に、ペンタメチルジエチレントリアミンを４４６ｇ追加し、６時間加熱攪拌混合した後、０．６７ＫＰａで６０分以上脱揮し、未反応オクタジエン及びアセトニトリルを脱揮した。混合物を活性アルミナで処理した。生成した重合体のＧＰＣ測定（ポリスチレン換算）結果は、１，７−オクタジエンの添加直前で、数平均分子量１７１７８、分子量分布Ｍｗ／Ｍｎ＝１．１１で、最終生成物は、数平均分子量１７７９８、分子量分布Ｍｗ／Ｍｎ＝１．１４、^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１．９４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。
【０１１８】
（比較例１）
２００ｍｌ丸底フラスコに臭化第一銅（３．７５ｇ）を投入し、真空脱揮と窒素で圧戻しを３回繰り返した。マグネットスターラーにて撹拌を開始して、アセトニトリル（２４．５ｇ）を投入した。オイルバスを加熱昇温し、内温が７０℃に到達して１５分後、初期モノマー（ブチルアクリレート ８９．４ｇ）を仕込み、更に、ジエチル２，５−ジブロモアジペート７．８５ｇを予め溶解させておいたアセトニトリル１４．８ｇを仕込んだ。その後、内温を８３℃に回復した後、０．１５ｇのペンタメチルジエチレントリアミンを追加して重合を開始した。図６に内温、系中の転化率およびモノマー量の一次反応プロットの経時変化の結果を示す。さらに１０分後、２０分後に０．１５ｇのペンタメチルジエチレントリアミンを追加して重合を開始した。重合開始から４０分後に転化率は７０％となったが、その後重合反応速度は失速しリビング性は著しく失われたため実験を終了した。
【０１１９】
（比較例２）
２００ｍｌ丸底フラスコに臭化第一銅（３．７５ｇ）を投入し、真空脱揮と窒素で圧戻しを３回繰り返した。マグネットスターラーにて撹拌を開始して、アセトニトリル（２４．５ｇ）を投入した。オイルバスを加熱昇温し、内温が７０℃に到達して１５分後、初期モノマー（ブチルアクリレート ８９．４ｇ）を仕込み、更に、ジエチル２，５−ジブロモアジペート７．８５ｇを予め溶解させておいたアセトニトリル１４．８ｇを仕込んだ。その後、内温を８３℃に回復した後、０．４５ｇのペンタメチルジエチレントリアミンを追加して重合を開始した。図７に内温、系中の転化率およびモノマー量の一次反応プロットの経時変化の結果を示す。内温は最大９５℃まで上昇したが、１０分後から温度は下がり始め、転化率７０％くらいから反応がほとんど進行しなくなった。重合全体を通してリビング性が著しく悪い反応となったため実験を終了した。
【０１２０】
【発明の効果】
モノマーや重合触媒を一括添加した場合、重合初期の除熱が困難となり、高温のためにラジカルリビング性が低下あるいはストップする場合が頻繁に生じ、安定した重合を実現することが困難となる。本発明の方法によれば、初期仕込みモノマーと重合開始剤を重合反応器に仕込んでから重合を開始した後、モノマー追加開始時の系中の転化率を１０〜６０％とすることにより、重合初期の副反応や重合後半におけるラジカルリビング性の低下を押さえ、ラジカルリビング重合における重合発熱を容易にコントロールする事ができる。
この効果は、スケールが大きくなるほど大きくなり、原子移動ラジカル重合の工業化において極めて重要である。
【図面の簡単な説明】
【図１】実施例１の製造方法における内温、系中の転化率、総モノマー量に対するモノマー仕込み率の経時変化を示したグラフ
【図２】実施例２の製造方法における内温、系中の転化率、総モノマー量に対するモノマー仕込み率の経時変化を示したグラフ
【図３】実施例３の製造方法における内温、系中の転化率、総モノマー量に対するモノマー仕込み率の経時変化を示したグラフ
【図４】実施例４の製造方法における内温、系中の転化率、総モノマー量に対するモノマー仕込み率の経時変化を示したグラフ
【図５】実施例５の製造方法における内温、系中の転化率、総モノマー量に対するモノマー仕込み率の経時変化を示したグラフ
【図６】比較例１の製造方法における内温、系中の転化率、モノマー量の一次反応プロットの経時変化を示したグラフ
【図７】比較例２の製造方法における内温、系中の転化率、モノマー量の一次反応プロットの経時変化を示したグラフ[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing a vinyl polymer and a vinyl polymer obtained thereby.
[0002]
[Prior art]
In recent years, the living radical polymerization method has been developed, and various groups have been actively researching it. Examples thereof include those using a cobalt porphyrin complex (Non-Patent Document 1), those using a radical scavenger such as a nitroxide compound (Non-Patent Document 2), and those using an organic halide or the like as an initiator and a transition metal complex as a catalyst. "Atom Transfer Radical Polymerization (ATRP)" and the like.
[0003]
Among the "living radical polymerization methods", the "atom transfer radical polymerization method" in which a vinyl monomer is polymerized using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is the above-mentioned "living radical polymerization method". In addition to the features described above, the production of vinyl polymers having specific functional groups is possible because of having a halogen or the like at the terminal that is relatively advantageous for the functional group conversion reaction and having a high degree of freedom in designing initiators and catalysts. The method is more preferable. As this atom transfer radical polymerization method, for example, Patent Documents 1 and 2, Non-Patent Documents 3 to 6, and the like can be mentioned.
[0004]
When a polymer is produced industrially using living radical polymerization, if the concentration of the growth terminal of the polymer, the concentration of the polymerization catalyst, or the concentration of the monomer is set to a high state, the polymerization temperature cannot be controlled due to strong heat generation, and the control of the structure of the product is difficult. Since this is an obstacle, it is necessary to appropriately control the polymerization rate. A polymerization method of controlling polymerization activity by adding a ligand of a metal complex serving as a polymerization catalyst after addition of a polymerization initiator is exemplified in Patent Literature 3, but the conversion rate curve is optimal for polymerization. For the addition of the polymerization catalyst and the optimum conditions for the dividing method are not described.
[Patent Document 1]
WO96 / 30421
[Patent Document 2]
WO97 / 18247
[Patent Document 3]
JP 2000-72809 A
[Non-patent document 1]
J. Am. Chem. Soc. 1994, 116, 7943.
[Non-patent document 2]
Macromolecules, 1994, 27, 7228.
[Non-Patent Document 3]
J. Am. Chem. Soc. 1995, 117, 5614
[Non-patent document 4]
Macromolecules, 1995, 28, 7901
[Non-Patent Document 5]
Science, 1996, 272, 866.
[Non-Patent Document 6]
Macromolecules, 1995, 28, 1721
[0005]
[Problems to be solved by the invention]
In the case of living polymerization, the polymer has a feature that a polymer chain grows by addition of a monomer and a polymer having a high molecular weight and a uniform composition can be obtained as long as deactivation of a polymerization active point does not occur. The deactivation of the active sites causes a part of the polymer to stop growing, and a side reaction such as chain transfer occurs to deteriorate the uniformity of the polymer composition.
[0006]
As a method of living polymerization, there are a conventional batch method in which monomers are charged all at once into a stirred tank, and a semi-batch method in which monomers are sequentially added.However, it stabilizes heat removal industrially to create a polymer safely. In order to do so, a semi-batch type polymerization method by sequentially adding a polymerization catalyst and a monomer is preferable. Usually, in the semi-batch polymerization by successive addition of a polymerization catalyst and a monomer, the amount of the initially charged monomer is divided into 0 to 50% by weight, the amount of the additional monomer is divided into about 100 to 50% by weight, and the polymerization catalyst is used in an amount of 2 to 50%. Control is performed so that the amount of heat generated by polymerization per unit time is approximately constant by dividing and using about three times. However, in the case of living radical polymerization, since a large amount of heat is involved, even a small polymerization reactor of about 1 L is used. At the time of addition of a polymerization catalyst or at the start of addition of a monomer, heat cannot be removed, the polymerization temperature greatly exceeds 100 ° C., and the progress of polymerization becomes unstable. . It is possible to realize a heat-removable polymerization reaction by sequentially adding a polymerization catalyst and an additional monomer at an extremely slow rate, but in this case, too, the progress of polymerization becomes unstable, and a polymerization catalyst exceeding the usual amount is required. And Increasing the amount of the polymerization catalyst not only broadens the molecular weight distribution of the polymer, but also eventually causes the polymerization catalyst to become an impurity in the polymer and need to remove it. There is a problem that the removal process becomes complicated and the operation time is lengthened. Therefore, in order to stably produce a polymer on an industrial scale where the scale is greatly increased, it is necessary to sequentially add a polymerization catalyst and a monomer so as to obtain a conversion curve that can remove heat and maintain a living property. Need to be implemented.
[0007]
[Means for Solving the Problems]
In view of the above situation, the present invention provides a method for promoting the polymerization of a vinyl monomer while maintaining a living property stably from the initial stage to the final stage of polymerization. It is an object of the present invention to provide a polymerization method in which a ligand and a monomer of a complex are sequentially added.
[0008]
That is, the present invention is a method for producing a vinyl polymer by polymerizing a vinyl monomer by atom transfer radical polymerization using an organic halide or a sulfonyl halide compound as a polymerization initiator and a transition metal complex as a polymerization catalyst,
The present invention relates to a production method in which after the polymerization is started after charging the initially charged monomer and the polymerization initiator into the polymerization reactor, the addition of the additional charged monomer is started when the conversion in the system is 10 to 60%.
[0009]
Further, the present invention is a method for producing a vinyl polymer by polymerizing a vinyl monomer by atom transfer radical polymerization using an organic halide or a sulfonyl halide compound as a polymerization initiator and a transition metal complex as a polymerization catalyst,
After the polymerization is started after charging the initially charged monomer and the polymerization initiator into the polymerization reactor, the addition of the additional charged monomer is started when the conversion rate in the system is 10 to 60%, and the conversion rate in the system is reduced. The present invention also relates to a production method of sequentially adding a ligand of a transition metal complex of the polymerization catalyst and the additional charged monomer to a system so that the addition of the additional charged monomer is completed at a time of 40 to 95%.
[0010]
In the present invention, the addition method of the ligand of the transition metal complex of the polymerization catalyst and the additional monomer may be a continuous method, a divided method, or a method combining the divided method and the continuous method. However, regarding the ligand of the transition metal complex of the polymerization catalyst, a division method is preferable, a division range of 2 to 10 times is more preferable, and a division of 3 to 6 times is more preferable.
[0011]
In the present invention, polymerization is usually started by adding an amine compound. In the present invention, the amount of the initially charged monomer is usually 50% by weight or less based on the total amount of vinyl monomers, but is preferably 10% by weight or more and 30% by weight or less. The amount of the ligand of the metal complex of the polymerization catalyst to be added in the initial stage of the polymerization is usually 以下 or less of the total amount added, preferably １ ／ or less, and more preferably 1/10 or less. More preferred.
[0012]
In the present invention, the transition metal complex is usually a metal complex having an element selected from the group consisting of elements of Groups 7, 8, 9, 10, and 11 of the periodic table as a central metal. , Copper, nickel, ruthenium, and iron, preferably a metal complex, and more preferably a copper complex. The ligand which forms the transition metal complex of the present invention is usually an amine compound, but is preferably a polyamine compound, and is preferably a group consisting of tetramethylethylenediamine, pentamethyldiethylenetriamine and hexamethyltriethylenetetraamine. More preferably, it is a selected compound. The amount of the ligand used is determined from the number of coordination sites of the transition metal and the number of coordinating groups of the ligand under ordinary conditions of atom transfer radical polymerization, and is set to be substantially equal. I have. For example, usually, the amount of 2,2'-bipyridyl and its derivative added to CuBr is twice the molar ratio, and in the case of pentamethyldiethylenetriamine, the molar ratio is one time. In the present invention, when the polymerization is initiated by adding a ligand and / or when the catalyst activity is controlled by adding a ligand, there is no particular limitation. Is more preferable. The ratio between the coordination site and the coordinating group is preferably at least 1.2 times, more preferably at least 1.4 times, particularly preferably at least 1.6 times, particularly preferably at least 2 times. It is.
[0013]
In the present invention, the vinyl monomer is generally a (meth) acrylic acid monomer, but is preferably an acrylic acid monomer, and more preferably an acrylate ester.
[0014]
The “initial charge monomer” in the present invention refers to a vinyl monomer initially charged in a polymerization reactor. In the present invention, atom transfer radical polymerization is started after the “initial charge monomer” is charged. The “additional charged monomer” in the present invention refers to a vinyl monomer newly charged into the polymerization reactor after the polymerization of the “initial charged monomer” is started. In the present invention, the polymerization of the “additional charged monomer” is performed after the polymerization of the “initial charged monomer”. The “initial charged monomer” and the “additional charged monomer” may be the same or different. In the present invention, the “conversion rate in the system” refers to a value obtained by converting the ratio of the weight of the polymer in the polymerization reactor to the sum of the weight of the polymer in the polymerization reactor and the weight of the unreacted monomer into percent.
[0015]
BEST MODE FOR CARRYING OUT THE INVENTION
《Vinyl monomer》
The vinyl monomer used in the production method of the present invention is not particularly limited, and various types can be used. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n- (meth) acrylate Butyl, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acryl Acid n-heptyl, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, (meth) Stearyl acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, ) Benzyl acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, an ethylene oxide adduct of (meth) acrylic acid, Trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate , 2-perfluoroethyl (meth) acrylate, (meth) acrylic Perfluoromethyl acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl (meth) acrylate, 2-perfluorohexylethyl (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 thereof Styrene-based 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. Monoalkyl Teru and dialkyl esters; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide, etc. Maleimide monomers of the following; vinyl monomers containing nitrile groups such as acrylonitrile and methacrylonitrile; vinyl monomers containing amide groups such as acrylamide and methacrylamide; vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate Vinyl esters such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride and chloride Examples thereof include vinylidene, allyl chloride, and allyl alcohol. These may be used alone or a plurality of them may be copolymerized. Of these, styrene-based monomers and (meth) acrylic-acid-based monomers are preferred in view of the physical properties of the product, and acryl-based monomers are preferred because of the high reactivity of the functional group introduction reaction and the low glass transition point of the present invention. Acid ester monomers are more preferred.
[0016]
《Atom transfer radical polymerization》
The atom transfer radical polymerization method used in the present invention will be described.
In this atom transfer radical polymerization, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, an ester compound having a halogen at the α-position or a compound having a halogen at the benzyl position) or a halogen A sulfonyl halide compound is used as a polymerization initiator.
[0017]
As the polymerization catalyst, a metal complex having an element of Group 7, 8, 9, 10 or 11 of the periodic table as a central metal is used. As the metal species, monovalent copper, divalent ruthenium, and divalent iron are particularly preferable. Specific examples include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous acetate, cuprous perchlorate, and the like. . When a copper compound is used, 2,2′-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, alkylamines such as tributylamine, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyl A ligand such as a polyamine such as triethylenetetraamine is added. Also, a tristriphenylphosphine complex of divalent ruthenium chloride (RuCl₂(PPh₃)₃) Are also suitable as catalysts. When this catalyst is used, an aluminum compound such as trialkoxyaluminum is added to enhance the activity. Further, a tristriphenylphosphine complex of divalent iron chloride (FeCl₂(PPh₃)₃) Are also suitable as catalysts.
[0018]
In this polymerization method, an organic halide or a sulfonyl halide compound is used as an initiator. To give a concrete example,
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,
(In each of the above equations, C₆H₅Is a phenyl group, R⁷, R⁸Is a hydrogen atom or an alkyl group, an aryl group, or an aralkyl group having 1 to 20 carbon atoms, which may be the same or different. X is chlorine, bromine, or iodine)
And the like.
[0019]
When an organic halide or a sulfonyl halide compound having a functional group other than the one that initiates the polymerization is used, a polymer having a functional group easily introduced into a terminal can be obtained. Examples of such a functional group include an alkenyl group, a hydroxyl group, an epoxy group, an amino group, an amide group, and a crosslinkable silyl group.
[0020]
The organic halide having an alkenyl group is not particularly limited, and examples thereof include those having a structure represented by the general formula 6.
R⁹R¹⁰C (X) -R¹¹-R¹²-C (R^Thirteen) = CH₂    (6)
(Where R⁹, R¹⁰Is hydrogen, a monovalent alkyl group, aryl group, or aralkyl group having 1 to 20 carbon atoms, or those mutually linked at the other end;¹¹Is -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.^ThirteenIs hydrogen or methyl, X is chlorine, bromine or iodine)
[0021]
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.
Substituent R⁹, R¹⁰Specific examples include hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, pentyl group, hexyl group and the like. R⁹And R¹⁰May be linked at the other end to form a cyclic skeleton, in which case -R⁹-R¹⁰-Is, for example, -CH₂CH₂-, -CH₂CH₂CH₂-, -CH₂CH₂CH₂CH₂-, -CH₂CH₂CH₂CH₂CH₂-, Etc. are exemplified.
[0022]
Specific examples of the organic halide having an alkenyl group represented by the general formula 6 include:
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,
[0023]
Embedded image

[0024]
(In each of 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,
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,
[0025]
Embedded image

[0026]
(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-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,
(In each of the above formulas, X is chlorine, bromine, or iodine, and n is an integer of 0 to 20.)
o, m, p-XCH₂-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,
(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-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,
(In each of the above formulas, X is chlorine, bromine, or iodine, and n is an integer of 0 to 20.)
o, m, p-XCH₂-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,
(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.)
And the like.
[0027]
Examples of the organic halide having an alkenyl group further include a compound represented by the general formula 7.
H₂C = C (R^Thirteen) -R¹²-C (R⁹) (X) -R¹⁴-R¹⁰  (7)
(Where R⁹, R¹⁰, R¹², R^Thirteen, 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)
[0028]
R¹²Is a direct bond, or a divalent organic group having 1 to 20 carbon atoms (which may contain one or more ether bonds). The group is attached and is a halogenated allylic compound. In this case, since the carbon-halogen bond is activated by the adjacent vinyl group, R¹⁴Need not necessarily have a C (O) O group, a phenylene group, etc., and may be a direct bond. R¹²Is not a direct bond, to activate the carbon-halogen bond, R¹⁴Are preferably a C (O) O group, a C (O) group and a phenylene group.
[0029]
If the compound of the general formula 7 is specifically exemplified,
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,
(In each of the above formulas, X is chlorine, bromine, or iodine, and R is an alkyl group, an aryl group, or an aralkyl group having 1 to 20 carbon atoms.)
And the like.
[0030]
If specific examples of the sulfonyl halide compound having an alkenyl group are given,
o-, m-, p-CH₂= CH- (CH₂)_n-C₆H₄-SO₂X,
o-, m-, p-CH₂= CH- (CH₂)_n-OC₆H₄-SO₂X,
(In each of the above formulas, X is chlorine, bromine, or iodine, and n is an integer of 0 to 20).
[0031]
In the case of an initiator having an alkenyl group, the olefin of the initiator may also react with the polymerization terminal, so care must be taken in the polymerization conditions and the reaction conditions with the olefin compound to be added. A specific example is adding an olefin compound at an early stage of polymerization.
[0032]
The organic halide having a crosslinkable silyl group is not particularly limited. For example, an organic halide having a structure represented by the general formula 8 is exemplified.
R⁹R¹⁰C (X) -R¹¹-R¹²-C (H) (R^Thirteen) CH₂− [Si (R^Fifteen)_2-b(Y)_bO]_m-Si (R¹⁶)_3-a(Y)_a  (8)
(Where R⁹, R¹⁰, R¹¹, R¹², R^ThirteenIs the same as above. R^Fifteen, R¹⁶Is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′)₃A triorganosiloxy group represented by SiO- (R 'is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different); , R^FifteenOr 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 Ys 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 is assumed that a + mb ≧ 1 is satisfied. )
[0033]
The hydrolyzable group represented by Y is not particularly limited, and conventionally known groups can be used. Specifically, hydrogen, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide Examples thereof include a group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. An alkoxy group is particularly preferable because the hydrolyzability is mild and easy to handle.
[0034]
If the compound of the general formula 8 is specifically exemplified,
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,
(In each of the above formulas, X is chlorine, bromine, or iodine, and n is an integer of 0 to 20.)
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,
(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-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,
(In each of the above formulas, X is chlorine, bromine, or iodine.)
And the like.
[0035]
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 (R^Fifteen)_2-b(Y)_b]_m-CH₂-C (H) (R^Thirteen) -R¹²-C (R⁹) (X) -R¹⁴-R¹⁰  (9)
(Where R⁹, R¹⁰, R¹², R^Thirteen, R¹⁴, R^Fifteen, R¹⁶, A, b, m, X and Y are the same as above)
[0036]
If these compounds are specifically exemplified,
(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,
(In each of the above formulas, X is chlorine, bromine, or iodine;¹⁷Is an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group)
And the like.
[0037]
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) (R¹⁷) (X)
(In the above formula, X is chlorine, bromine or iodine, R¹⁷Is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, and n is an integer of 1 to 20)
[0038]
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 the above formula, X is chlorine, bromine or iodine, R¹⁷Is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, and n is an integer of 1 to 20)
[0039]
The organic halide having an epoxy group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.
[0040]
Embedded image

[0041]
(In the above formula, X is chlorine, bromine or iodine, R¹⁷Is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, and n is an integer of 1 to 20)
[0042]
In order to obtain a polymer having two or more olefinic 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. To give a concrete example,
[0043]
Embedded image

[0044]
Embedded image

[0045]
And the like.
[0046]
<< Polymerization conditions >>
There are no particular restrictions on the vinyl monomer used in this polymerization, and the various monomers described above can be used. Further, since the polymerization system shown here is living polymerization, it is also possible to produce a block copolymer by successive addition of different types of vinyl monomers.
[0047]
The polymerization can be carried out without solvent or in various solvents. These are not particularly limited, but examples thereof include hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether and tetrahydrofuran; halogenated hydrocarbon solvents such as methylene chloride and chloroform; acetone, methyl ethyl ketone, and methyl. Ketone solvents such as isobutyl ketone; alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol and tert-butyl alcohol; nitrile solvents such as acetonitrile, propionitrile and benzonitrile; ethyl acetate and butyl acetate Ester solvents such as ethylene carbonate, propylene carbonate and the like; and carbonate solvents such as ethylene carbonate and propylene carbonate can be used alone or in combination of two or more. In addition, emulsion-based or supercritical fluid CO₂Polymerization can also be carried out in a system using as a medium. Among these, a nitrile-based solvent is preferable, and acetonitrile is more preferable, from the viewpoint of improving the catalyst stability.
[0048]
The polymerization can be carried out at room temperature to 200 ° C., preferably at 50 to 150 ° C., and more preferably at 60 to 100 ° C.
[0049]
The polymerization atmosphere is not particularly limited, but is preferably an oxygen-free atmosphere. Radicals are affected by oxygen, and in the presence of oxygen, the catalyst may be oxidized and lose activity.
[0050]
Preferably, the polymerization mixture is well stirred. In particular, when the catalytic metal complex or ligand is added, sufficient stirring is preferable in order to promptly and uniformly diffuse.
[0051]
The method of polymerization can be applied to batch polymerization, semi-batch polymerization in which a monomer is added, continuous polymerization, and the like. As the additional system of the semi-batch polymerization, any one of a continuous system, a divided system, and a combination of the continuous system and the divided system can be applied.
[0052]
In the case of semi-batch polymerization, the amount of initially charged monomers is preferably 50% by weight or less, more preferably 30% by weight or less based on the total amount of monomers. The lower limit is preferably 10% by weight or more.
[0053]
The monomer addition time in the semi-batch method is within a range of 0.5 hours to 2.5 hours required to add 90% by weight or more of all vinyl monomers (total of initially charged monomers and additionally charged monomers). It is particularly preferable that the addition of all the vinyl monomers (the sum of the initially charged monomers and the additionally charged monomers) be completed within a range of 0.5 to 2.5 hours. When the addition time is long, the reaction rate is reduced, the productivity is reduced, and an operation for improving the catalyst activity is often required.
[0054]
Even if the ligand of the metal complex of the polymerization catalyst is added beyond the coordination saturation with respect to the catalyst metal atom, no further improvement in the activity can be expected. It is preferable that the amount is excessive relative to the addition amount of the ligand. In addition, the metal compound may be added later, but it is preferable in the process to add a necessary whole amount from the beginning.
[0055]
The ligand of the metal complex of the polymerization catalyst is preferably added in two or more portions, more preferably three or more portions. The upper limit is preferably 10 times or less, more preferably 6 times or less. When added little by little, the catalyst activity is often low even when the total amount is the same.
[0056]
As for the conversion during the polymerization, it is preferable to advance the polymerization until the conversion in the system becomes 10% or more at the start of the monomer addition. It is more preferably at least 20%. The upper limit is preferably 60% or less, more preferably 50% or less. When the monomer addition is started when the conversion rate is lower than 10%, the heat cannot be removed due to sudden heat generation, and runaway often occurs. On the other hand, when the conversion is high, a side reaction is likely to occur due to a decrease in the monomer. Particularly, when the conversion exceeds 70%, the catalytic activity often decreases.
[0057]
Further, it is preferable that the polymerization is allowed to proceed until the conversion in the system at the end of the monomer addition becomes 40% or more. It is more preferably at least 50%. The upper limit is preferably 95% or less, more preferably 90% or less. When the addition is completed in a state where the amount of unreacted monomer is large, the heat removal effect by sensible heat due to the addition of the monomer cannot be expected, and thus the heat removal ability tends to be insufficient. If the conversion exceeds 95%, side reactions tend to occur and the molecular weight distribution of the polymer tends to increase significantly.
[0058]
During or at the end of the polymerization, when the compound (I) having an alkenyl group having low polymerizability is added, the compound is added almost one by one to the terminal. be introduced. In order to introduce an alkenyl group at the terminal, it is preferable to add an excessive amount of a compound having two alkenyl groups having low polymerizability. The end point of the polymerization is the time when preferably 80% or more of the monomer has reacted, more preferably 90% or more, particularly preferably 95% or more, and particularly preferably 99% or more.
[0059]
At the end point of the polymerization, the compound (I) can be added subsequently, and the compound (I) can be added after the unreacted monomer and the polymerization solvent are once distilled off.
[0060]
In addition, when compound (I) is added, by adding together compound (II) having a higher dielectric constant than compound (I), a functional group can be surely introduced into the terminal.
[0061]
<< Compound (I) >>
Examples of the compound having an alkenyl group having low polymerizability include a compound represented by the following general formula 1.
General formula 1:
[0062]
Embedded image

[0063]
Ｒ In the above formula, R³Is 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 compound of the general formula 2:
[0064]
Embedded image

[0065]
(R⁴Represents a hydrogen atom or a methyl group)
Or an organic group having 1 to 20 carbon atoms not containing a polymerizable olefin,¹Is an alkyl group having 1 to 20 carbon atoms or a general formula 3:
[0066]
Embedded image

[0067]
(Where R is⁵Is an oxygen atom, a nitrogen atom or an organic group having 1 to 20 carbon atoms, R⁶Is a hydrogen atom or a methyl group and may be the same or different.)
And a group having the structure of²Is a hydrogen atom or a methyl group.
Among them, a compound having two low alkenyl groups having low polymerizability used for introducing an alkenyl group includes a compound represented by the general formula 4.
[0068]
Embedded image

[0069]
Ｒ In the above formula, R¹Is an alkyl group having 1 to 20 carbon atoms or a general formula 3:
[0070]
Embedded image

[0071]
(Where R is⁵Is an oxygen atom, a nitrogen atom or an organic group having 1 to 20 carbon atoms, R⁶Is a hydrogen atom or a methyl group and may be the same or different.)
And a group having the structure of², R⁴Is a hydrogen atom or a methyl group.
[0072]
R of the compound represented by the general formula 4², R⁴Is a hydrogen atom or a methyl group, but a hydrogen atom is preferred. R¹Is a C1-C20 alkyl group, the structure is not limited, but a compound represented by the general formula 5 is exemplified.
[0073]
Embedded image

[0074]
In Formula 5, n is an integer of 1 to 20, but n is preferably 2, 4 or 6 from the viewpoint of easy availability of raw materials.
In the general formula 1, R¹As a specific example,
− (CH₂)_n-(N is an integer of 1 to 20),
-CH (CH₃)-, -CH (CH₂CH₃)-, -C (CH₃)₂-, -C (CH₃) (CH₂CH₃)-, -C (CH₂CH₃)₂-, -CH₂CH (CH₃)-,
− (CH₂)_n-O-CH₂-(N is an integer of 1 to 19),
-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 and n are integers of 1 to 19, provided that 2 ≦ m + n ≦ 20),
− (CH₂)_n-C (O) O- (CH₂)_m−
(M and n are integers of 1 to 19, provided that 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, provided that 2 ≦ l + m + n ≦ 18),
− (CH₂)_n-O-, m-, pC₆H₄−,
− (CH₂)_n-O-, m-, pC₆H₄− (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-, pC₆H₄-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-, pC₆H₄-O-CH (CH₃)-,
(N is an integer of 1 to 12),
− (CH₂)_n-O-, m-, pC₆H₄-O-CH (CH₃)₂−,
(N is an integer of 1 to 11),
− (CH₂)_n-O-, m-, pC₆H₄-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-, pC₆H₄-C (O) O- (CH₂)_m−,
(M and n are integers of 1 to 11, where 2 ≦ m + n ≦ 12),
− (CH₂)_n-O-, m-, pC₆H₄-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-, pC₆H₄− (CH₂)_m−,
(M and n are integers of 1 to 11, where 2 ≦ m + n ≦ 12),
And the like.
In the general formula 1, R³Examples thereof include the following groups.
[0075]
Embedded image

[0076]
(Where R¹⁸, R¹⁹Is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′)₃A triorganosiloxy group represented by SiO- (R 'is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's 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 Ys 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 is assumed that a + mb ≧ 1 is satisfied. R²⁰Is a hydrocarbon group having 1 to 20 carbon atoms. )
[0077]
R²⁰Specific examples thereof include the following groups.
− (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,
-C₆H₄(CH₃),
-C₆H₃(CH₃)₂,
− (CH₂)_n-C₆H₅,
− (CH₂)_n-C₆H₄(CH₃),
− (CH₂)_n-C₆H₃(CH₃)₂,
(N is an integer of 0 or more, and the total carbon number of each group is 20 or less)
[0078]
Although the silyl group is not limited, those having m = 0 in the above formula are preferable.
[0079]
When a compound having an amino group, a hydroxyl group or a carboxylic acid group is reacted with the polymerization terminal, the reaction may be carried out as it is.However, since those groups may affect the polymerization terminal or the catalyst, the May be a compound having a protecting group. Examples of the protecting group include an acetyl group, a silyl group, and an alkoxy group.
[0080]
The amount of the compound used to introduce these functional groups is not particularly limited. Since the reactivity of the alkenyl group of these compounds is not very high, it is preferable to increase the amount added in order to increase the reaction rate. On the other hand, in order to reduce the cost, the amount added is equal to the growth terminal. Closer is preferable, and it is necessary to optimize according to the situation.
[0081]
In addition, when a compound having two or more alkenyl groups having low polymerizability is added to introduce an alkenyl group at a terminal, the amount of the compound added is preferably an excessive amount with respect to the polymerization growth terminal. In the case of an equal amount or a smaller amount than the terminal, both of the two olefins may react and couple the polymerization terminals. In the case of a compound in which two olefins have the same reactivity, the probability of occurrence of coupling is statistically determined according to the added amount. Therefore, the addition amount of the compound having two or more alkenyl groups having low polymerizability is preferably 1.5 times or more, more preferably 3 times or more, and particularly preferably 5 times or more of the polymerization growth terminal.
[0082]
<< Compound (II) >>
When the compound (I) having an alkenyl group having low polymerizability is added, depending on the type of the compound (I), the polarity of the reaction system may be reduced and the catalytic activity may be insufficient. In this case, the polarity can be improved by adding a compound (II) having a higher polarity than the compound (I). The compound (II) is not particularly restricted but includes, for example, hydrocarbon compounds such as benzene and toluene; ether compounds such as diethyl ether and tetrahydrofuran; halogenated hydrocarbon compounds such as methylene chloride and chloroform; , Methyl ethyl ketone, methyl isobutyl ketone and the like; ketone compounds such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol and tert-butyl alcohol; nitrile compounds such as acetonitrile, propionitrile and benzonitrile; acetic acid Ester compounds such as ethyl and butyl acetate; and carbonate compounds such as ethylene carbonate and propylene carbonate. These can be used alone or as a mixture of two or more kinds, and may be the same as or different from the solvent used for the polymerization, but in consideration of the recovery after the reaction, the same is preferable. preferable. The dielectric constant of compound (II) is preferably higher than compound (I) by 3 or more, more preferably higher by 5 or more, further preferably higher by 10 or more. 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 preferred, and acetonitrile is more preferred, from the viewpoint of improving the catalyst stability. The amount of the compound (II) to be used is preferably 1 to 1000 parts by weight, more preferably 5 to 500 parts by weight, per 100 parts by weight of all vinyl monomers (total of initially charged monomers and additional charged monomers). More preferably, it is still more preferably 10 to 100 parts by weight. Alternatively, the amount of compound (II) to be used is preferably from 1 to 10,000 parts by weight, more preferably from 10 to 1,000 parts by weight, based on 100 parts by weight of compound (I). If the amount of the compound (II) is small, the effect of improving the polarity may not be exhibited, and if it is too large, it may be difficult to recover the compound from the polymer after polymerization.
[0083]
《Terminal structure》
During or at the end of the polymerization, when the compound (I) having an alkenyl group having low polymerizability is added, the compound is added almost one by one to the terminal. be introduced. The terminal structure at this time is represented by general formula 10. The vinyl polymer having this terminal structure is characterized in that almost one terminal group is bonded to each terminal of the polymer by only a carbon-carbon bond directly without through a hetero atom.
[0084]
Embedded image

[0085]
Ｒ In the above formula, R³Is 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 compound of the general formula 2:
[0086]
Embedded image

[0087]
(R⁴Represents a hydrogen atom or a methyl group)
Or an organic group having 1 to 20 carbon atoms not containing a polymerizable olefin,¹Is an alkyl group having 1 to 20 carbon atoms, or general formula 3:
[0088]
Embedded image

[0089]
(Where R is⁵Is an oxygen atom, a nitrogen atom or an organic group having 1 to 20 carbon atoms, R⁶Is a hydrogen atom or a methyl group and may be the same or different.)
And a group having the structure of²Is a hydrogen atom or a methyl group, and X is a halogen group, a nitroxide group, a sulfide group, or a cobalt porphyrin complex.
[0090]
In the general formula 10, R¹As a specific example,
− (CH₂)_n-(N is an integer of 1 to 20),
-CH (CH₃)-, -CH (CH₂CH₃)-, -C (CH₃)₂-, -C (CH₃) (CH₂CH₃)-, -C (CH₂CH₃)₂-, -CH₂CH (CH₃)-,
− (CH₂)_n-O-CH₂-(N is an integer of 1 to 19),
-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 and n are integers of 1 to 19, provided that 2 ≦ m + n ≦ 20),
− (CH₂)_n-C (O) O- (CH₂)_m−
(M and n are integers of 1 to 19, provided that 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, provided that 2 ≦ l + m + n ≦ 18),
− (CH₂)_n-O-, m-, pC₆H₄−,
− (CH₂)_n-O-, m-, pC₆H₄− (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-, pC₆H₄-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-, pC₆H₄-O-CH (CH₃)-,
(N is an integer of 1 to 12),
− (CH₂)_n-O-, m-, pC₆H₄-O-CH (CH₃)₂−,
(N is an integer of 1 to 11),
− (CH₂)_n-O-, m-, pC₆H₄-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-, pC₆H₄-C (O) O- (CH₂)_m−,
(M and n are integers of 1 to 11, where 2 ≦ m + n ≦ 12),
− (CH₂)_n-O-, m-, pC₆H₄-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-, pC₆H₄− (CH₂)_m−,
(M and n are integers of 1 to 11, where 2 ≦ m + n ≦ 12),
And the like.
R³Examples thereof include the following groups.
[0091]
Embedded image

[0092]
Where R¹⁸, R¹⁹Is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′)₃A triorganosiloxy group represented by SiO- (R 'is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's 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 Ys 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 is assumed that a + mb ≧ 1 is satisfied.
[0093]
R²⁰Is a hydrocarbon group having 1 to 20 carbon atoms, and specific examples include the following groups.
− (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,
-C₆H₄(CH₃),
-C₆H₃(CH₃)₂,
− (CH₂)_n-C₆H₅,
− (CH₂)_n-C₆H₄(CH₃),
− (CH₂)_n-C₆H₃(CH₃)₂,
(N is an integer of 0 or more, and the total carbon number of each group is 20 or less)
[0094]
In the general formula 10, R²Is a hydrogen atom or a methyl group, but a hydrogen atom is preferred. X is a halogen group, a nitroxide group, a sulfide group or a cobalt porphyrin complex, but a halogen group, and particularly a bromo group, is preferable from the viewpoint of ease of production.
[0095]
When an alkenyl group is introduced at the terminal, R¹Is a C1 to C20 alkyl group, the structure is not limited, and the following are exemplified.
[0096]
Embedded image

[0097]
In the formula, X is a halogen group, a nitroxide group, a sulfide group, or a cobalt porphyrin complex. n is an integer of 1 to 20, but n is preferably 2, 4, or 6, from the viewpoint of easy availability of raw materials.
[0098]
The number of terminal groups represented by the general formula 10 contained in one molecule of the polymer is not particularly limited, but when used in a curable composition or the like, it may be contained in 0.5 to 5 pieces. Preferably, it contains 1 to 3 pieces, more preferably 1.5 to 2.5 pieces.
[0099]
The polymer obtained in the present invention has a molecular weight distribution, that is, a 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 1.3 or less.
[0100]
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 intrinsic properties of the vinyl polymer are hardly exhibited, and when it is 100,000 or more, handling becomes difficult.
[0101]
The polymer produced in the present invention may be used as it is, or may be subjected to a further conversion reaction to obtain another functional group. Specifically, an alkenyl group can be converted to a crosslinkable silyl group by a hydrosilylation reaction using a hydrosilane compound having a crosslinkable silyl group. As the vinyl polymer having an alkenyl group at the terminal, any of those obtained by the methods described above can be suitably used.
[0102]
The hydrosilane compound is not particularly limited, but a typical one is represented by the general formula 12
H- [Si (R²¹)_2-b(Y)_bO]_m-Si (R²²)_3-a(Y)_a  (12)
(Where R²¹, R²²Is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′)₃A triorganosiloxy group represented by SiO- (R 'is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and three R's may be the same or different); , R²¹Or R²²When 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 Ys 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 is assumed that a + mb ≧ 1 is satisfied.)
Are exemplified.
[0103]
The hydrolyzable group represented by Y is not particularly limited, and conventionally known groups can be used. Specifically, hydrogen, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide Examples thereof include a group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. An alkoxy group is particularly preferable because the hydrolyzability is mild and easy to handle. The hydrolyzable group or hydroxyl group can be bonded to one silicon atom in a range of 1 to 3 and a + mb, that is, the sum of the hydrolyzable groups 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. In the case of silicon atoms connected by a siloxane bond, the number may be up to about 20.
[0104]
R in general formula 12²¹, R²²Specific examples 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. Some R '₃And a triorganosilyl group represented by SiO—.
Among these hydrosilane compounds, in particular, general formula 13
H-Si (R²²)_3-a(Y)_a  (13)
(Where R²², Y and a are the same as above. The hydrosilane compound having a crosslinkable group represented by ()) is preferable 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:
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) [ON = C (CH₃)₂]₂
(However, in the above chemical formula, C₆H₅Represents a phenyl group)
And the like.
[0105]
When such a hydrosilane compound having a crosslinkable silyl group is added to a vinyl polymer having an alkenyl group at a terminal, a hydrosilylation catalyst is used. Examples of such a hydrosilylation catalyst include a radical initiator such as an organic peroxide and an azo compound, and a transition metal catalyst.
[0106]
The radical initiator is not particularly limited, and various types 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, peroxyesters such as t-butyl perbenzoate, peroxydicabonones such as diisopropyl percarbonate and di-2-ethylhexyl percarbonate. G, 1,1-di (t-butylperoxy) Peroxyketals such as chlorohexane and 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane.
[0107]
As the transition metal catalyst, for example, platinum solid, alumina, silica, a dispersion of platinum solids on a carrier such as carbon black, chloroplatinic acid, a complex of chloroplatinic acid with alcohol, aldehyde, ketone, etc. , A platinum-olefin complex, and a platinum (0) -divinyltetramethyldisiloxane complex. Examples of catalysts other than platinum compounds include RhCl (PPh₃)₃, RhCl₃, RuCl₃, IrCl₃, FeCl₃, AlCl₃, PdCl₂・ H₂O, NiCl₂, TiCl₄And the like. These catalysts may be used alone or in combination of two or more. The amount of the catalyst is not particularly limited, but may be 10 to 1 mol of the alkenyl group of the vinyl polymer.^-1-10^-8mol in the range of 10 mol, preferably 10 mol.^-3-10^-6It is good to use in the range of mol. 10^-8If it is less than 10 mol, curing will not proceed sufficiently. Also, since hydrosilylation catalysts are expensive,^-1It is preferable not to use more than mol.
[0108]
When allyl alcohol or methallyl alcohol is reacted with the polymerization terminal, a terminal is formed in which an active group such as a halogen group and a hydroxyl group are located on adjacent carbon atoms. This end can be cyclized and converted to an epoxy group. The method for performing this cyclization reaction is not particularly limited, but it is preferable to react with an alkaline compound. Although it does not specifically limit as an alkaline compound, KOH, NaOH, Ca (OH)₂And ammonia and various amines.
[0109]
The terminal hydroxyl group is converted to an alkenyl group by a condensation reaction with an allyl chloride or allyl bromide using an alkaline compound. Further, it is converted into an epoxy group by a similar reaction using epichlorohydrin.
[0110]
The terminal hydroxyl group or amino group can also be converted into 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 a halogen, a carboxylic acid halide, a carboxylic acid, and an isocyanate group.The availability of the compound and the reaction conditions when reacting with the hydroxyl group are mild, Isocyanate groups are preferred in that the decomposition of the reactive silyl group hardly occurs.
[0111]
Such an isocyanate-based compound having a crosslinkable silyl group is not particularly limited, and a known one can be used. To show a specific example,
(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,
(Where n and m are integers of 1 to 20)
And the like.
[0112]
The reaction between the vinyl polymer having a hydroxyl group at the terminal and the isocyanate compound having a crosslinkable silyl group can be performed without a solvent or in various solvents, and the reaction temperature is 0 ° C to 100 ° C, preferably, 20 ° C to 50 ° C. In this case, the tin-based catalyst and the tertiary amine-based catalyst described above for promoting the reaction between the hydroxyl group and the isocyanate group can be used.
[0113]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples. The conversion rate in the system in this example was measured by gas chromatography, using the polymerization solvent as an internal standard substance, sampling the value of the area ratio between the monomer and the solvent before the start of polymerization, and sampling at an arbitrary time. The numerical value of the area ratio between the monomer and the solvent was compared, and the conversion was calculated from the rate of decrease in the numerical value.
(Example 1)
Cuprous bromide (10.07 g) was charged into a 2 L polymerization tank, and vacuum devolatilization and depressurization with nitrogen were repeated three times. Stirring was started at 300 rpm, and acetonitrile (65.5 g) was charged. The jacket of the 2L polymerization tank was heated and heated, and 15 minutes after the internal temperature reached 70 ° C, the initial monomer (240.00 g of butyl acrylate) was charged, and 21.07 g of diethyl 2,5-dibromoadipate was added in advance. 40.00 g of dissolved acetonitrile was charged. Then, after the internal temperature was restored to 75 ° C., 0.20 g of pentamethyldiethylenetriamine was added to initiate polymerization. FIG. 1 shows the results of changes over time in the internal temperature, the monomer charge ratio with respect to the total monomer amount, and the conversion ratio in the system. The internal temperature showed an increase and was 78 ° C. Five minutes later, another 0.20 g of pentamethyldiethylenetriamine was added. Ten minutes later, 0.41 g of pentamethyldiethylenetriamine was added and mixed with stirring for 10 minutes. The internal temperature showed an increase and was 80 ° C. Immediately after this, sampling was performed, and the residual amount of the unreacted monomer was measured by gas chromatography to find that the conversion was 30%. Thereafter, an additional monomer (960.00 g of butyl acrylate) was continuously added over 2 hours while maintaining the internal temperature at 85 ° C to 90 ° C. 0.41 g of pentamethyldiethylenetriamine was added at the start of monomer addition, 30 minutes after monomer addition, and 60 minutes after monomer addition, to control the conversion curve. After the addition of the monomer was completed, sampling was carried out, and the residual amount of the unreacted monomer was measured by gas chromatography to find that the conversion was 69%. 78 minutes after the addition of the monomer was completed, after confirming that the degree of polymerization was 95% or more by gas chromatography, the reaction system was devolatilized at 10 Torr for 60 minutes or more, and the solvent was recovered. 128.97 g of octadiene were added. After 316.50 g of acetonitrile was added, 4.06 g of pentamethyldiethylenetriamine was added, and the mixture was heated and mixed for 6 hours, and then devolatilized at 10 Torr for 60 minutes or more to devolatilize unreacted octadiene and acetonitrile. GPC measurement (in terms of polystyrene) of the resulting polymer obtained by treating the mixture with activated alumina showed that immediately before addition of 1,7-octadiene, the number average molecular weight was 24801 and the molecular weight distribution was Mw / Mn = 1.16. Was a number average molecular weight 25654 and a molecular weight distribution Mw / Mn = 1.26.
[0114]
(Example 2)
Cuprous bromide (10.07 g) was charged into a 2 L polymerization tank, and vacuum devolatilization and depressurization with nitrogen were repeated three times. Stirring was started at 300 rpm, and acetonitrile (65.5 g) was charged. The jacket of the 2L polymerization tank was heated and heated, and 15 minutes after the internal temperature reached 70 ° C, the initial monomer (240.00 g of butyl acrylate) was charged, and 21.07 g of diethyl 2,5-dibromoadipate was added in advance. 40.00 g of dissolved acetonitrile was charged. Then, after the internal temperature was restored to 75 ° C., 0.20 g of pentamethyldiethylenetriamine was added to initiate polymerization. FIG. 2 shows the results over time of the internal temperature, the monomer charge ratio with respect to the total monomer amount, and the conversion ratio in the system. The internal temperature showed an increase and was 80 ° C. Ten minutes later, another 0.20 g of pentamethyldiethylenetriamine was added. Ten minutes later, 0.41 g of pentamethyldiethylenetriamine was added and mixed with stirring for 10 minutes. The internal temperature showed an increase and was 87 ° C. Immediately after this, sampling was performed, and the residual amount of the unreacted monomer was measured by gas chromatography to find that the conversion was 45%. Thereafter, an additional monomer (960.00 g of butyl acrylate) was continuously added over 2 hours while maintaining the internal temperature at 85 ° C to 90 ° C. 0.20 g of pentamethyldiethylenetriamine was added at the start of monomer addition, 30 minutes after monomer addition, and 60 minutes after monomer addition started to control the conversion curve. After the addition of the monomer was completed, sampling was performed, and the residual amount of the unreacted monomer was measured by gas chromatography, whereby the conversion was 78%. 105 minutes after the addition of the monomer was completed, the degree of polymerization was confirmed to be 95% or more by gas chromatography. The mixture was treated with activated alumina. As a result of GPC measurement (in terms of polystyrene) of the produced polymer, the number average molecular weight was 25252 and the molecular weight distribution Mw / Mn was 1.17.
[0115]
(Example 3)
Cuprous bromide (11.15 g) was charged into a 2 L polymerization tank, and vacuum devolatilization and depressurization with nitrogen were repeated three times. Stirring was started at 300 rpm, and acetonitrile (50.07 g) was charged. The jacket of the 2L polymerization tank was heated and heated, and 15 minutes after the internal temperature reached 70 ° C., the initial monomers (66.39 g of butyl acrylate, 95.42 g of ethyl acrylate, 78.20 g of 2-methoxyethyl acrylate) were charged. Further, 50.07 g of acetonitrile in which 31.08 g of diethyl 2,5-dibromoadipate was previously dissolved was charged. Then, after the internal temperature was restored to 75 ° C., 0.22 g of pentamethyldiethylenetriamine was added to initiate polymerization. FIG. 3 shows the results over time of the internal temperature, the monomer charge ratio with respect to the total monomer amount, and the conversion ratio in the system. The internal temperature showed an increase and was 78 ° C. Ten minutes later, another 0.22 g of pentamethyldiethylenetriamine was added. Ten minutes later, 0.45 g of pentamethyldiethylenetriamine was added and mixed with stirring for 10 minutes. The internal temperature showed an increase and was 80 ° C. Immediately after this, sampling was performed, and the residual amount of the unreacted monomer was measured by gas chromatography to find that the conversion was 30%. Thereafter, additional monomers (265.55 g of butyl acrylate, 381.67 g of ethyl acrylate, 312.78 g of 2-methoxyethyl acrylate) were continuously added over 2 hours while maintaining the internal temperature at 85 ° C to 90 ° C. 0.45 g of pentamethyldiethylenetriamine was added at the start of monomer addition, 30 minutes after monomer addition, and 60 minutes after monomer addition to control the conversion curve. After the addition of the monomer was completed, sampling was carried out, and the residual amount of the unreacted monomer was measured by gas chromatography to find that the conversion was 69%. After confirming that the degree of polymerization reached 95% or more by gas chromatography 60 minutes after the addition of the monomer was completed, the reaction system was devolatilized at 10 Torr for 60 minutes or more, and the solvent was recovered. 285.40 g of octadiene were added. After adding 300.39 g of acetonitrile, 4.49 g of pentamethyldiethylenetriamine was added and mixed while heating and stirring for 6 hours, and then devolatilized at 10 Torr for 60 minutes or more to devolatilize unreacted octadiene and acetonitrile. The mixture was treated with activated alumina. As a result of GPC measurement (in terms of polystyrene) of the produced polymer, immediately before addition of 1,7-octadiene, the number average molecular weight was 17,201, the molecular weight distribution Mw / Mn = 1.11, and the final product was number average molecular weight 17,500. Molecular weight distribution Mw / Mn = 1.14,¹The number of alkenyl groups per polymer molecule determined by H-NMR analysis was 1.77, and the number of terminals to which no alkenyl group was introduced was 0.
[0116]
(Example 4)
After devolatilizing the 250 L polymerization tank in vacuum, the pressure was reduced with nitrogen, acetonitrile (3955 g) and cuprous bromide (1007.3 g) were charged, the nitrogen pressure was reduced, and the nitrogen pressure and pressure were released. Repeated three times. Thereafter, the jacket of the 250 L polymerization tank was heated and heated, and stirring was started at 160 rpm. 15 minutes after the internal temperature reached 70 ° C., an initial monomer (24000 g of butyl acrylate) was charged, and further, 5000 g of acetonitrile in which 2106.8 g of diethyl 2,5-dibromoadipate had been previously dissolved was charged. Then, after the internal temperature was restored to 70 ° C., 20.3 g of pentamethyldiethylenetriamine was added. FIG. 4 shows the results over time of the internal temperature, the monomer charge ratio with respect to the total monomer amount, and the conversion ratio in the system. The internal temperature showed a rise and was 75 ° C. Ten minutes later, another 20.3 g of pentamethyldiethylenetriamine was added. Ten minutes later, 40.6 g of pentamethyldiethylenetriamine was added and mixed with stirring for 10 minutes. The internal temperature showed a rise and was 76 ° C. Immediately after this, sampling was performed, and the residual amount of the unreacted monomer was measured by gas chromatography to find that the conversion was 51%. Thereafter, an additional monomer (96,000 g of butyl acrylate) was continuously added over 2 hours while maintaining the internal temperature at 85 ° C to 90 ° C. 40.6 g of pentamethyldiethylenetriamine was added at the start of monomer addition, 30 minutes after monomer addition, and 60 minutes after monomer addition started to control the conversion curve. After the addition of the monomer was completed, sampling was carried out, and the residual amount of the unreacted monomer was measured by gas chromatography to find that the conversion was 83%. 67 minutes after the completion of the monomer addition, after confirming that the degree of polymerization was 95% or more by gas chromatography, the reaction system was devolatilized at 0.67 KPa for 60 minutes or more, and the solvent was recovered. , 7-octadiene was added by 28373 g. After 10550 g of acetonitrile was added, 406 g of pentamethyldiethylenetriamine was added, and the mixture was heated and stirred for 6 hours, and then devolatilized at 0.67 KPa for 60 minutes or more to devolatilize unreacted octadiene and acetonitrile. The mixture was treated with activated alumina. As a result of GPC measurement (in terms of polystyrene) of the produced polymer, immediately before addition of 1,7-octadiene, the number average molecular weight was 24801, the molecular weight distribution was Mw / Mn = 1.16, and the final product was a number average molecular weight of 26353. Molecular weight distribution Mw / Mn = 1.25,¹The number of alkenyl groups per polymer molecule determined by H-NMR analysis was 1.98, and the number of terminals to which no alkenyl group was introduced was 0.
[0117]
(Example 5)
After devolatilizing the 250 L polymerization tank in vacuum, the pressure was reduced with nitrogen, acetonitrile (3955 g) and cuprous bromide (1108 g) were charged, the nitrogen pressure was reduced, and nitrogen pressurization and depressurization were performed three times. Repeated. Thereafter, the jacket of the 250 L polymerization tank was heated and heated, and stirring was started at 160 rpm. 15 minutes after the internal temperature reached 70 ° C., the initial monomers (6600 g of butyl acrylate, 9486 g of ethyl acrylate, and 7774 g of 2-methoxyethyl acrylate) were charged, and 3090 g of diethyl 2,5-dibromoadipate was previously dissolved. 5000 g of acetonitrile was charged. Then, after the internal temperature was recovered to 70 ° C., 22.3 g of pentamethyldiethylenetriamine was added to initiate polymerization. FIG. 5 shows the results of changes over time in the internal temperature, the monomer charge ratio with respect to the total monomer amount, and the conversion ratio in the system. The internal temperature rose and showed 72 ° C. Ten minutes later, another 22.3 g of pentamethyldiethylenetriamine was added. Ten minutes later, 44.6 g of pentamethyldiethylenetriamine was added and mixed with stirring for 10 minutes. The internal temperature showed an increase and was 73 ° C. Immediately after this, sampling was performed, and the residual amount of the unreacted monomer was measured by gas chromatography to find that the conversion was 25%. Thereafter, additional monomers (26400 g of butyl acrylate, 37944 g of ethyl acrylate, 31095 g of 2-methoxyethyl acrylate) were continuously added over 2 hours while maintaining the internal temperature at 85 ° C to 90 ° C. 44.6 g of pentamethyldiethylenetriamine was added at the start of monomer addition, 30 minutes after monomer addition, and 60 minutes after monomer addition, to control the conversion curve. After the addition of the monomer, sampling was performed, and the residual amount of the unreacted monomer was measured by gas chromatography, whereby the conversion was 80%. 75 minutes after the addition of the monomer was completed, after confirming that the degree of polymerization was 95% or more by gas chromatography, the reaction system was devolatilized at 0.67 KPa for 60 minutes or more, and the solvent was recovered. , 7-octadiene was added by 28373 g. After 9955 g of acetonitrile was added, 446 g of pentamethyldiethylenetriamine was added, and the mixture was heated with stirring and mixed for 6 hours, and then devolatilized at 0.67 KPa for 60 minutes or more to devolatilize unreacted octadiene and acetonitrile. The mixture was treated with activated alumina. As a result of GPC measurement (in terms of polystyrene) of the produced polymer, immediately before addition of 1,7-octadiene, the number average molecular weight was 17178, the molecular weight distribution was Mw / Mn = 1.11, and the final product was a number average molecular weight of 17798. Molecular weight distribution Mw / Mn = 1.14,¹The number of alkenyl groups per polymer molecule determined by H-NMR analysis was 1.94, and the number of terminals to which no alkenyl group was introduced was 0.
[0118]
(Comparative Example 1)
Cuprous bromide (3.75 g) was charged into a 200 ml round bottom flask, and vacuum devolatilization and depressurization with nitrogen were repeated three times. Stirring was started with a magnetic stirrer, and acetonitrile (24.5 g) was charged. The oil bath was heated and heated, and 15 minutes after the internal temperature reached 70 ° C., the initial monomer (89.4 g of butyl acrylate) was charged, and 7.85 g of diethyl 2,5-dibromoadipate was further dissolved in advance. 14.8 g of acetonitrile was charged. Thereafter, after the internal temperature was restored to 83 ° C., 0.15 g of pentamethyldiethylenetriamine was added to initiate polymerization. FIG. 6 shows the results of the change over time in the primary reaction plot of the internal temperature, the conversion in the system, and the amount of the monomer. Further, after 10 minutes and 20 minutes, 0.15 g of pentamethyldiethylenetriamine was added to initiate polymerization. After 40 minutes from the start of the polymerization, the conversion became 70%, but thereafter the polymerization reaction rate was stalled and the living property was significantly lost, so the experiment was terminated.
[0119]
(Comparative Example 2)
Cuprous bromide (3.75 g) was charged into a 200 ml round bottom flask, and vacuum devolatilization and depressurization with nitrogen were repeated three times. Stirring was started with a magnetic stirrer, and acetonitrile (24.5 g) was charged. The oil bath was heated and heated, and 15 minutes after the internal temperature reached 70 ° C., the initial monomer (89.4 g of butyl acrylate) was charged, and 7.85 g of diethyl 2,5-dibromoadipate was further dissolved in advance. 14.8 g of acetonitrile was charged. Then, after the internal temperature was restored to 83 ° C., 0.45 g of pentamethyldiethylenetriamine was added to initiate polymerization. FIG. 7 shows the results of the change over time in the primary reaction plot of the internal temperature, the conversion rate in the system, and the amount of the monomer. The internal temperature rose to a maximum of 95 ° C., but after 10 minutes, the temperature began to drop, and the reaction hardly proceeded from a conversion of about 70%. The experiment was terminated because the living property was extremely poor throughout the polymerization.
[0120]
【The invention's effect】
When a monomer or a polymerization catalyst is added all at once, it becomes difficult to remove heat in the initial stage of polymerization, and the radical living property often decreases or stops due to high temperature, making it difficult to realize stable polymerization. According to the method of the present invention, after starting the polymerization after charging the initially charged monomer and the polymerization initiator into the polymerization reactor, the conversion in the system at the time of starting the monomer addition is set to 10 to 60%. It is possible to suppress the decrease in radical living property in the initial side reaction and the latter half of the polymerization, and easily control the heat generated by the polymerization in the radical living polymerization.
This effect increases as the scale increases, and is extremely important in the industrialization of atom transfer radical polymerization.
[Brief description of the drawings]
FIG. 1 is a graph showing the change over time of the monomer charging rate with respect to the internal temperature, the conversion rate in the system, and the total monomer amount in the production method of Example 1.
FIG. 2 is a graph showing the change over time of the monomer charge rate with respect to the internal temperature, the conversion rate in the system, and the total monomer amount in the production method of Example 2.
FIG. 3 is a graph showing the change over time of the monomer charging rate with respect to the internal temperature, the conversion rate in the system, and the total monomer amount in the production method of Example 3.
FIG. 4 is a graph showing the change over time of the monomer charging rate with respect to the internal temperature, the conversion rate in the system, and the total monomer amount in the production method of Example 4.
FIG. 5 is a graph showing the change over time of the monomer charging rate with respect to the internal temperature, the conversion rate in the system, and the total monomer amount in the production method of Example 5.
FIG. 6 is a graph showing a temporal change in a primary reaction plot of an internal temperature, a conversion rate in a system, and a monomer amount in the production method of Comparative Example 1.
FIG. 7 is a graph showing a temporal change in a primary reaction plot of an internal temperature, a conversion rate in a system, and a monomer amount in the production method of Comparative Example 2.

Claims (16)

A method for producing a vinyl polymer by polymerizing a vinyl monomer by atom transfer radical polymerization using an organic halide or a sulfonyl halide compound as a polymerization initiator and a transition metal complex as a polymerization catalyst,
After the polymerization is started after charging the initially charged monomer and the polymerization initiator into the polymerization reactor, the addition of the additional charged monomer is started when the conversion in the system is 10 to 60%. . A method for producing a vinyl polymer by polymerizing a vinyl monomer by atom transfer radical polymerization using an organic halide or a sulfonyl halide compound as a polymerization initiator and a transition metal complex as a polymerization catalyst,
After the polymerization was started after charging the initially charged monomer and the polymerization initiator into the polymerization reactor, the addition of the additional charged monomer was started when the conversion rate in the system was 10 to 60%, and the conversion rate in the system was lowered. A production method characterized by sequentially adding a ligand of a transition metal complex of the polymerization catalyst and the additional charged monomer to the system so that the addition of the additional charged monomer is completed at a time of 40 to 95%. 3. The polymerization method according to claim 1, wherein the additional monomer is added in a divided manner. The polymerization method according to claim 1 or 2, wherein the additional charged monomer is added in a continuous manner. 3. The polymerization method according to claim 1, wherein the additional monomer is added in a combination of a split system and a continuous system. The polymerization method according to any one of claims 1 to 5, wherein the ligand of the metal complex of the polymerization catalyst is divided and sequentially added. The production method according to claim 6, wherein the ligand of the transition metal complex of the polymerization catalyst is divided and added sequentially in the range of 2 to 10 times. The transition metal complex is a metal complex having an element selected from the group consisting of elements of Groups 7, 8, 9, 10 and 11 of the periodic table as a central metal. The method according to any one of claims 1 to 7. The method according to claim 8, wherein the transition metal complex is a complex of a metal selected from the group consisting of copper, nickel, ruthenium, and iron. The method according to claim 9, wherein the transition metal complex is a copper complex. The method according to claim 1, wherein the ligand forming the transition metal complex is an amine compound. The method according to any one of claims 1 to 10, wherein the ligand forming the transition metal complex is a polyamine-based compound. The ligand forming a transition metal complex is a compound selected from the group consisting of tetramethylethylenediamine, pentamethyldiethylenetriamine, and hexamethyltriethylenetetraamine. The method according to 1. The method according to any one of claims 1 to 13, wherein the vinyl monomer is a (meth) acrylic acid monomer. The method according to any one of claims 1 to 13, wherein the vinyl monomer is an acrylate ester. A vinyl polymer obtained by the production method according to claim 1.

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