JP4850988B2 - Polymerization method - Google Patents

Description

【００３０】
（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）ＸＣＨ₂ Ｃ（Ｏ）Ｏ（ＣＨ₂ ）_n Ｏ（ＣＨ₂ ）_m ＣＨ＝ＣＨ₂ 、
Ｈ₃ ＣＣ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂ ）_n Ｏ（ＣＨ₂ ）_m ＣＨ＝ＣＨ₂ 、
（Ｈ₃ Ｃ）₂ Ｃ（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂ ）_n Ｏ（ＣＨ₂ ）_m ＣＨ＝ＣＨ₂ 、
ＣＨ₃ ＣＨ₂ Ｃ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂ ）_n Ｏ（ＣＨ₂ ）_m ＣＨ＝ＣＨ₂ 、
【００３１】
【化２】

【００３２】
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは１〜２０の整数、ｍは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ₂ −Ｃ₆ Ｈ₄ −（ＣＨ₂ ）_n −ＣＨ＝ＣＨ₂ 、
ｏ，ｍ，ｐ−ＣＨ₃ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₄ −（ＣＨ₂ ）_n −ＣＨ＝ＣＨ₂ 、
ｏ，ｍ，ｐ−ＣＨ₃ ＣＨ₂ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₄ −（ＣＨ₂ ）_n −ＣＨ＝ＣＨ₂ 、
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ₂ −Ｃ₆ Ｈ₄ −（ＣＨ₂ ）_n −Ｏ−（ＣＨ₂ ）_m −ＣＨ＝ＣＨ₂ 、
ｏ，ｍ，ｐ−ＣＨ₃ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₄ −（ＣＨ₂ ）_n −Ｏ−（ＣＨ₂ ）_m −ＣＨ＝ＣＨ₂ 、
ｏ，ｍ，ｐ−ＣＨ₃ ＣＨ₂ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₄ −（ＣＨ₂ ）_n −Ｏ−（ＣＨ₂ ）_m ＣＨ＝ＣＨ₂ 、
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは１〜２０の整数、ｍは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ₂ −Ｃ₆ Ｈ₄ −Ｏ−（ＣＨ₂ ）_n −ＣＨ＝ＣＨ₂ 、
ｏ，ｍ，ｐ−ＣＨ₃ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₄ −Ｏ−（ＣＨ₂ ）_n −ＣＨ＝ＣＨ₂ 、
ｏ，ｍ，ｐ−ＣＨ₃ ＣＨ₂ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₄ −Ｏ−（ＣＨ₂ ）_n −ＣＨ＝ＣＨ₂ 、
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ₂ −Ｃ₆ Ｈ₄ −Ｏ−（ＣＨ₂ ）_n −Ｏ−（ＣＨ₂ ）_m −ＣＨ＝ＣＨ₂ 、
ｏ，ｍ，ｐ−ＣＨ₃ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₄ −Ｏ−（ＣＨ₂ ）_n −Ｏ−（ＣＨ₂ ）_m −ＣＨ＝ＣＨ₂ 、
ｏ，ｍ，ｐ−ＣＨ₃ ＣＨ₂ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₄ −Ｏ−（ＣＨ₂ ）_n −Ｏ−（ＣＨ₂ ）_m −ＣＨ＝ＣＨ₂ 、
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは１〜２０の整数、ｍは０〜２０の整数）
【００３３】
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（２）で示される化合物が挙げられる。
Ｈ₂ Ｃ＝Ｃ（Ｒ³ ）−Ｒ⁶ −Ｃ（Ｒ⁴ ）（Ｘ）−Ｒ⁸ −Ｒ⁵ （２）
（式中、Ｒ³ 、Ｒ⁴ 、Ｒ⁵ 、Ｒ⁶ 、Ｘは上記に同じ、Ｒ⁸ 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）
【００３４】
Ｒ⁶ 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、Ｒ⁸ 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。Ｒ⁶ 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、Ｒ⁸ としてはＣ（Ｏ）Ｏ基、Ｃ（Ｏ）基、フェニレン基が好ましい。
【００３５】
式（２）の化合物を具体的に例示するならば、
ＣＨ₂ ＝ＣＨＣＨ₂ Ｘ、ＣＨ₂ ＝Ｃ（ＣＨ₃ ）ＣＨ₂ Ｘ、
ＣＨ₂ ＝ＣＨＣ（Ｈ）（Ｘ）ＣＨ₃ 、ＣＨ₂ ＝Ｃ（ＣＨ₃ ）Ｃ（Ｈ）（Ｘ）ＣＨ₃ 、
ＣＨ₂ ＝ＣＨＣ（Ｘ）（ＣＨ₃ ）₂ 、ＣＨ₂ ＝ＣＨＣ（Ｈ）（Ｘ）Ｃ₂ Ｈ₅ 、
ＣＨ₂ ＝ＣＨＣ（Ｈ）（Ｘ）ＣＨ（ＣＨ₃ ）₂ 、
ＣＨ₂ ＝ＣＨＣ（Ｈ）（Ｘ）Ｃ₆ Ｈ₅ 、ＣＨ₂ ＝ＣＨＣ（Ｈ）（Ｘ）ＣＨ₂ Ｃ₆ Ｈ₅ 、
ＣＨ₂ ＝ＣＨＣＨ₂ Ｃ（Ｈ）（Ｘ）−ＣＯ₂ Ｒ、
ＣＨ₂ ＝ＣＨ（ＣＨ₂ ）₂ Ｃ（Ｈ）（Ｘ）−ＣＯ₂ Ｒ、
ＣＨ₂ ＝ＣＨ（ＣＨ₂ ）₃ Ｃ（Ｈ）（Ｘ）−ＣＯ₂ Ｒ、
ＣＨ₂ ＝ＣＨ（ＣＨ₂ ）₈ Ｃ（Ｈ）（Ｘ）−ＣＯ₂ Ｒ、
ＣＨ₂ ＝ＣＨＣＨ₂ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₅ 、
ＣＨ₂ ＝ＣＨ（ＣＨ₂ ）₂ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₅ 、
ＣＨ₂ ＝ＣＨ（ＣＨ₂ ）₃ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₅ 、
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、Ｒは炭素数１〜２０のアルキル基、アリール基、アラルキル基）
等を挙げることができる。
【００３６】
アルケニル基を有するハロゲン化スルホニル化合物の具体例を挙げるならば、
ｏ−，ｍ−，ｐ−ＣＨ₂ ＝ＣＨ−（ＣＨ₂ ）_n −Ｃ₆ Ｈ₄ −ＳＯ₂ Ｘ、
ｏ−，ｍ−，ｐ−ＣＨ₂ ＝ＣＨ−（ＣＨ₂ ）_n −Ｏ−Ｃ₆ Ｈ₄ −ＳＯ₂ Ｘ、
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、ｎは０〜２０の整数）等である。
【００３７】
上記架橋性シリル基を有する有機ハロゲン化物としては特に限定されず、例えば一般式（３）に示す構造を有するものが例示される。
Ｒ⁴ Ｒ⁵ Ｃ（Ｘ）−Ｒ⁶ −Ｒ⁷ −Ｃ（Ｈ）（Ｒ³ ）ＣＨ₂ −
［Ｓｉ（Ｒ⁹ ）_2-b （Ｙ）_b Ｏ］_m −Ｓｉ（Ｒ¹⁰）_3-a （Ｙ）_a （３）
（式中、Ｒ³ 、Ｒ⁴ 、Ｒ⁵ 、Ｒ⁶ 、Ｒ⁷ 、Ｘは上記に同じ、Ｒ⁹ 、Ｒ¹⁰は、いずれも炭素数１〜２０のアルキル基、アリール基、アラルキル基、または（Ｒ' ）₃ ＳｉＯ−（Ｒ' は炭素数１〜２０の１価の炭化水素基であって、３個のＲ' は同一であってもよく、異なっていてもよい）で示されるトリオルガノシロキシ基を示し、Ｒ⁹ またはＲ¹⁰が２個以上存在するとき、それらは同一であってもよく、異なっていてもよい。Ｙは水酸基または加水分解性基を示し、Ｙが２個以上存在するときそれらは同一であってもよく、異なっていてもよい。ａは０，１，２，または３を、また、ｂは０，１，または２を示す。ｍは０〜１９の整数である。ただし、ａ＋ｍｂ≧１であることを満足するものとする）
【００３８】
一般式（３）の化合物を具体的に例示するならば、
ＸＣＨ₂ Ｃ（Ｏ）Ｏ（ＣＨ₂ ）_n Ｓｉ（ＯＣＨ₃ ）₃ 、
ＣＨ₃ Ｃ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂ ）_n Ｓｉ（ＯＣＨ₃ ）₃ 、
（ＣＨ₃ ）₂ Ｃ（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂ ）_n Ｓｉ（ＯＣＨ₃ ）₃ 、
ＸＣＨ₂ Ｃ（Ｏ）Ｏ（ＣＨ₂ ）_n Ｓｉ（ＣＨ₃ ）（ＯＣＨ₃ ）₂ 、
ＣＨ₃ Ｃ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂ ）_n Ｓｉ（ＣＨ₃ ）（ＯＣＨ₃ ）₂ 、
（ＣＨ₃ ）₂ Ｃ（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂ ）_n Ｓｉ（ＣＨ₃ ）（ＯＣＨ₃ ）₂ 、
（上記の各式において、Ｘは塩素、臭素、ヨウ素、ｎは０〜２０の整数、）
ＸＣＨ₂ Ｃ（Ｏ）Ｏ（ＣＨ₂ ）_n Ｏ（ＣＨ₂ ）_m Ｓｉ（ＯＣＨ₃ ）₃ 、
Ｈ₃ ＣＣ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂ ）_n Ｏ（ＣＨ₂ ）_m Ｓｉ（ＯＣＨ₃ ）₃ 、
（Ｈ₃ Ｃ）₂ Ｃ（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂ ）_n Ｏ（ＣＨ₂ ）_m Ｓｉ（ＯＣＨ₃ ）₃ 、
ＣＨ₃ ＣＨ₂ Ｃ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂ ）_n Ｏ（ＣＨ₂ ）_m Ｓｉ（ＯＣＨ₃ ）₃ 、
ＸＣＨ₂ Ｃ（Ｏ）Ｏ（ＣＨ₂ ）_n Ｏ（ＣＨ₂ ）_m Ｓｉ（ＣＨ₃ ）（ＯＣＨ₃ ）₂ 、
Ｈ₃ ＣＣ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂ ）_n Ｏ（ＣＨ₂ ）_m −Ｓｉ（ＣＨ₃ ）（ＯＣＨ₃ ）₂ 、
（Ｈ₃ Ｃ）₂ Ｃ（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂ ）_n Ｏ（ＣＨ₂ ）_m −Ｓｉ（ＣＨ₃ ）（ＯＣＨ₃ ）₂ 、
ＣＨ₃ ＣＨ₂ Ｃ（Ｈ）（Ｘ）Ｃ（Ｏ）Ｏ（ＣＨ₂ ）_n Ｏ（ＣＨ₂ ）_m −Ｓｉ（ＣＨ₃ ）（ＯＣＨ₃ ）₂ 、
（上記の各式において、Ｘは塩素、臭素、ヨウ素、ｎは１〜２０の整数、ｍは０〜２０の整数）
ｏ，ｍ，ｐ−ＸＣＨ₂ −Ｃ₆ Ｈ₄ −（ＣＨ₂ ）₂ Ｓｉ（ＯＣＨ₃ ）₃ 、
ｏ，ｍ，ｐ−ＣＨ₃ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₄ −（ＣＨ₂ ）₂ Ｓｉ（ＯＣＨ₃ ）₃ 、
ｏ，ｍ，ｐ−ＣＨ₃ ＣＨ₂ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₄ −（ＣＨ₂ ）₂ Ｓｉ（ＯＣＨ₃ ）₃ 、
ｏ，ｍ，ｐ−ＸＣＨ₂ −Ｃ₆ Ｈ₄ −（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃ 、
ｏ，ｍ，ｐ−ＣＨ₃ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₄ −（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃ 、
ｏ，ｍ，ｐ−ＣＨ₃ ＣＨ₂ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₄ −（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃ 、
ｏ，ｍ，ｐ−ＸＣＨ₂ −Ｃ₆ Ｈ₄ −（ＣＨ₂ ）₂ −Ｏ−（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃ 、
ｏ，ｍ，ｐ−ＣＨ₃ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₄ −（ＣＨ₂ ）₂ −Ｏ−（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃ 、
ｏ，ｍ，ｐ−ＣＨ₃ ＣＨ₂ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₄ −（ＣＨ₂ ）₂ −Ｏ−（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃ 、
ｏ，ｍ，ｐ−ＸＣＨ₂ −Ｃ₆ Ｈ₄ −Ｏ−（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃ 、
ｏ，ｍ，ｐ−ＣＨ₃ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₄ −Ｏ−（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃ 、
ｏ，ｍ，ｐ−ＣＨ₃ ＣＨ₂ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₄ −Ｏ−（ＣＨ₂ ）₃ −Ｓｉ（ＯＣＨ₃ ）₃ 、
ｏ，ｍ，ｐ−ＸＣＨ₂ −Ｃ₆ Ｈ₄ −Ｏ−（ＣＨ₂ ）₂ −Ｏ−（ＣＨ₂ ）₃ −Ｓｉ（ＯＣＨ₃ ）₃ 、
ｏ，ｍ，ｐ−ＣＨ₃ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₄ −Ｏ−（ＣＨ₂ ）₂ −Ｏ−（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃ 、
ｏ，ｍ，ｐ−ＣＨ₃ ＣＨ₂ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₄ −Ｏ−（ＣＨ₂ ）₂ −Ｏ−（ＣＨ₂ ）₃ Ｓｉ（ＯＣＨ₃ ）₃ 、
（上記の各式において、Ｘは塩素、臭素、またはヨウ素）
等が挙げられる。
【００３９】
上記架橋性シリル基を有する有機ハロゲン化物としてはさらに、一般式（４）で示される構造を有するものが例示される。
（Ｒ¹⁰）_3-a （Ｙ）_a Ｓｉ−［ＯＳｉ（Ｒ⁹ ）_2-b （Ｙ）_b ］_m −
ＣＨ₂ −Ｃ（Ｈ）（Ｒ³ ）−Ｒ¹¹−Ｃ（Ｒ⁴ ）（Ｘ）−Ｒ⁸ −Ｒ⁵ （４）
（式中、Ｒ³ 、Ｒ⁴ 、Ｒ⁵ 、Ｒ⁷ 、Ｒ⁸ 、Ｒ⁹ 、Ｒ¹⁰、ａ、ｂ、ｍ、Ｘ、Ｙは上記に同じ）
【００４０】
このような化合物を具体的に例示するならば、
（ＣＨ₃ Ｏ）₃ ＳｉＣＨ₂ ＣＨ₂ Ｃ（Ｈ）（Ｘ）Ｃ₆ Ｈ₅ 、
（ＣＨ₃ Ｏ）₂ （ＣＨ₃ ）ＳｉＣＨ₂ ＣＨ₂ Ｃ（Ｈ）（Ｘ）Ｃ₆ Ｈ₅ 、
（ＣＨ₃ Ｏ）₃ Ｓｉ（ＣＨ₂ ）₂ Ｃ（Ｈ）（Ｘ）−ＣＯ₂ Ｒ、
（ＣＨ₃ Ｏ）₂ （ＣＨ₃ ）Ｓｉ（ＣＨ₂ ）₂ Ｃ（Ｈ）（Ｘ）−ＣＯ₂ Ｒ、
（ＣＨ₃ Ｏ）₃ Ｓｉ（ＣＨ₂ ）₃ Ｃ（Ｈ）（Ｘ）−ＣＯ₂ Ｒ、
（ＣＨ₃ Ｏ）₂ （ＣＨ₃ ）Ｓｉ（ＣＨ₂ ）₃ Ｃ（Ｈ）（Ｘ）−ＣＯ₂ Ｒ、
（ＣＨ₃ Ｏ）₃ Ｓｉ（ＣＨ₂ ）₄ Ｃ（Ｈ）（Ｘ）−ＣＯ₂ Ｒ、
（ＣＨ₃ Ｏ）₂ （ＣＨ₃ ）Ｓｉ（ＣＨ₂ ）₄ Ｃ（Ｈ）（Ｘ）−ＣＯ₂ Ｒ、
（ＣＨ₃ Ｏ）₃ Ｓｉ（ＣＨ₂ ）₉ Ｃ（Ｈ）（Ｘ）−ＣＯ₂ Ｒ、
（ＣＨ₃ Ｏ）₂ （ＣＨ₃ ）Ｓｉ（ＣＨ₂ ）₉ Ｃ（Ｈ）（Ｘ）−ＣＯ₂ Ｒ、
（ＣＨ₃ Ｏ）₃ Ｓｉ（ＣＨ₂ ）₃ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₅ 、
（ＣＨ₃ Ｏ）₂ （ＣＨ₃ ）Ｓｉ（ＣＨ₂ ）₃ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₅ 、
（ＣＨ₃ Ｏ）₃ Ｓｉ（ＣＨ₂ ）₄ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₅ 、
（ＣＨ₃ Ｏ）₂ （ＣＨ₃ ）Ｓｉ（ＣＨ₂ ）₄ Ｃ（Ｈ）（Ｘ）−Ｃ₆ Ｈ₅ 、
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、Ｒは炭素数１〜２０のアルキル基、アリール基、アラルキル基）
等が挙げられる。
【００４１】
上記ヒドロキシル基を持つ有機ハロゲン化物、またはハロゲン化スルホニル化合物としては特に限定されず、下記のようなものが例示される。
ＨＯ−（ＣＨ₂ ）_n −ＯＣ（Ｏ）Ｃ（Ｈ）（Ｒ）（Ｘ）
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、Ｒは水素原子または炭素数１〜２０のアルキル基、アリール基、アラルキル基、ｎは１〜２０の整数）
【００４２】
上記アミノ基を持つ有機ハロゲン化物、またはハロゲン化スルホニル化合物としては特に限定されず、下記のようなものが例示される。
Ｈ₂ Ｎ−（ＣＨ₂ ）_n −ＯＣ（Ｏ）Ｃ（Ｈ）（Ｒ）（Ｘ）
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、Ｒは水素原子または炭素数１〜２０のアルキル基、アリール基、アラルキル基、ｎは１〜２０の整数）
【００４３】
上記エポキシ基を持つ有機ハロゲン化物、またはハロゲン化スルホニル化合物としては特に限定されず、下記のようなものが例示される。
【００４４】
【化３】

【００４５】
（上記の各式において、Ｘは塩素、臭素、またはヨウ素、Ｒは水素原子または炭素数１〜２０のアルキル基、アリール基、アラルキル基、ｎは１〜２０の整数）
【００４６】
上記リビングラジカル重合において、開始剤として、２つ以上の開始点を有する有機ハロゲン化物又はハロゲン化スルホニル化合物を用いて重合を行うと、ハロゲン基を両末端に有するビニル系重合体が得られる。この開始剤を具体的に例示すれば、
【００４７】
【化４】

【００４８】
（式中、Ｒは炭素数１〜２０のアルキル基、炭素数６〜２０アリール基、または炭素数７〜２０アラルキル基を表す。Ｃ₆ Ｈ₄ は、フェニレン基を表す。ｎは０〜２０の整数を表す。Ｘは塩素、臭素、またはヨウ素を表す。）
【００４９】
【化５】

【００５０】
（式中、Ｒは炭素数１〜２０のアルキル基、炭素数６〜２０アリール基、または炭素数７〜２０アラルキル基を表す。Ｃ₆ Ｈ₄ は、フェニレン基を表す。ｎは０〜２０の整数を表す。Ｘは塩素、臭素、またはヨウ素を表す。）
等が挙げられる。
【００５１】
＜触媒＞
原子移動ラジカル重合の触媒として用いられる遷移金属錯体としては特に限定されず、ＰＣＴ／ＵＳ９６／１７７８０に記載されているものが利用可能である。中でも好ましいものとして、０価の銅、１価の銅、２価のルテニウム、２価の鉄又は２価のニッケルの錯体が挙げられる。なかでも、銅の錯体が好ましい。１価の銅化合物を具体的に例示するならば、塩化第一銅、臭化第一銅、ヨウ化第一銅、シアン化第一銅、酸化第一銅、過塩素酸第一銅等である。また、２価の塩化ルテニウムのトリストリフェニルホスフィン錯体（ＲｕＣｌ₂ （ＰＰｈ₃ ）₃ ）も触媒として好適である。ルテニウム化合物を触媒として用いる場合は、活性化剤としてアルミニウムアルコキシド類が添加される。更に、２価の鉄のビストリフェニルホスフィン錯体（ＦｅＣｌ₂ （ＰＰｈ₃ ）₂ ）、２価のニッケルのビストリフェニルホスフィン錯体（ＮｉＣｌ₂ （ＰＰｈ₃ ）₂ ）、及び、２価のニッケルのビストリブチルホスフィン錯体（ＮｉＢｒ₂ （ＰＢｕ₃ ）₂ ）も、触媒として好適である。
【００５２】
触媒として銅化合物を用いる場合、その配位子として、ＰＣＴ／ＵＳ９６／１７７８０に記載されている配位子の利用が可能である。特に限定はされないが、アミン系配位子が良く、好ましくは、２，２′−ビピリジル及びその誘導体等のビピリジル化合物、１，１０−フェナントロリン及びその誘導体、ヘキサメチルトリエチレンテトラアミン、ビスピコリルアミン、トリアルキルアミン、テトラメチルエチレンジアミン、ペンタメチルジエチレントリアミン、ヘキサメチル（２−アミノエチル）アミン等の脂肪族アミン等の配位子である。本発明においては、これらの内では、ポリアミン化合物、特にペンタメチルジエチレントリアミン、ヘキサメチル（２−アミノエチル）アミン等の脂肪族ポリアミンが好ましい。また、触媒として銅化合物を用いる場合の配位子として、ポリアミン化合物、ピリジン系化合物、又は脂肪族アミン化合物を用いる場合には、これらの配位子がアミノ基を３つ以上持つものであることが好ましい。なお、本発明におけるアミノ基とは、窒素原子−炭素原子結合を有する基を表すが、この中でも、窒素原子が炭素原子及び／又は水素原子とのみ結合する基であることが好ましい。
【００５３】
本発明の脱水条件での重合という点において、末端ハロゲン基の消失は重合系中の塩基性にも影響を受けるので、アミン類、特に脂肪族アミン類を配位子として用いる場合において、本発明の効果は大きい。
【００５４】
触媒は、触媒活性を持つ錯体の状態で、重合装置に加えてもよいし、触媒の前駆体である遷移金属化合物と配位子を重合装置中で混合して錯体化しても構わない。公知の原子移動ラジカル重合においては、一般にこの錯体化の操作は、開始剤を添加する前に行われる。それに対し、本発明では、配位子を、開始剤を添加した後に重合系中に添加し、触媒の前駆体である遷移金属化合物と錯体化させ、触媒活性を発現し、重合を開始する、及び／または、触媒活性を制御することが開示される。
【００５５】
また、本発明のニトリル系化合物存在下で重合を行う場合、開始剤を錯体形成後に添加する通常の原子移動ラジカル重合の開始方法においても、錯体前駆体遷移金属化合物とニトリル系化合物を配位子よりも先に混合しておくことが、錯体の分散性が高まるので好ましい。
【００５６】
上記のような配位子を用いる量は、通常の原子移動ラジカル重合の条件では、遷移金属の配位座の数と、配位子の配位する基の数から決定され、ほぼ等しくなるように設定されている。例えば、通常、２，２′−ビピリジル及びその誘導体をＣｕＢｒに対して加える量はモル比で２倍であり、ペンタメチルジエチレントリアミンの場合はモル比で１倍である。本発明において配位子を添加して重合を開始する、及び／または、配位子を添加して触媒活性を制御する場合は、特に限定はされないが、金属原子が配位子に対して過剰になる方が好ましい。配位座と配位する基の比は好ましくは１．２倍以上であり、更に好ましくは１．４倍以上であり、特に好ましくは１．６倍以上であり、特別に好ましくは２倍以上である。
【００５７】
本発明においては、ニトリル系化合物を添加する代わりに、最初からニトリル系化合物が配位した遷移金属錯体を触媒前駆体の遷移金属化合物として用いても同様の効果が得られる。このような錯体としては、特に限定はされないが、ニトリル系化合物が過剰に存在する状態に、遷移金属化合物を添加しニトリル系化合物を配位させ、過剰のニトリル系化合物を除くことにより得られる錯体が例示される。また、ＣｕＢｒ（ＮＣ−Ｒ）_n 、ＣｕＣｌ（ＮＣ−Ｒ）_n （式中、Ｒはメチルなどの一価の有機基、ｎは１以上の整数）等も例示される。
【００５８】
＜溶媒、添加剤＞
本発明の重合は無溶媒又は各種の溶媒中で行うことができる。上記溶媒としては、例えば、ベンゼン、トルエン等の炭化水素系溶媒；ジエチルエーテル、テトラヒドロフラン、ジフェニルエーテル、アニソール、ジメトキシベンゼン等のエーテル系溶媒；塩化メチレン、クロロホルム、クロロベンゼン等のハロゲン化炭化水素系溶媒；アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン系溶媒；メタノール、エタノール、プロパノール、イソプロパノール、ｎ−ブチルアルコール、ｔｅｒｔ−ブチルアルコール等のアルコール系溶媒；アセトニトリル、プロピオニトリル、ベンゾニトリル等のニトリル系溶媒；酢酸エチル、酢酸ブチル等のエステル系溶媒；エチレンカーボネート、プロピレンカーボネート等のカーボネート系溶媒等が挙げられる。これらは、単独又は２種以上を混合して用いることができる。
【００５９】
これらの溶媒の中ではアプロティックな溶媒が好ましい。また、極性の高い溶媒は一般的に吸水性が高く、また、末端消失反応も速い傾向があるので、本発明の脱水条件での重合はより有効である。基準としては、２５℃における比誘電率が１０以上の溶媒を用いた場合が挙げられる。本発明において添加剤として用いることが提示されているニトリル系化合物は、溶媒として用いても構わない。
【００６０】
これらの溶媒、あるいは他に重合系に添加される添加剤としては、触媒として用いられる金属化合物に対して配位し、触媒活性を持たない錯体を形成するが、配位子が添加されると活性な触媒となるものが好ましい。溶媒が配位性を持たない場合でも、配位子の追加による触媒活性の制御は可能であるが、配位子のない状態のＣｕＢｒ等の金属化合物の分散性が不十分で、器壁に付着したりなどして、安定した活性制御が容易ではない場合がある。このような要件を満たす例として、ＣｕＢｒを金属化合物として用い、溶媒としてニトリル系溶媒を用いる組み合わせが挙げられる。ＰＣＴ／ＵＳ９６／１７７８０においては、アセトニトリルは重合触媒の好ましい配位子として記述されているが、実際には、ＣｕＢｒのアセトニトリル錯体は重合活性を持たないことが確認された。しかし、この錯体は、結晶性が高く、不均一でも適切な攪拌により、重合系中に良好に分散することが我々の研究で明らかになった。そして、ペンタメチルジエチレントリアミンなどの配位子の添加により、速やかに活性な錯体を形成し、重合を触媒する。
【００６１】
＜水分量＞
本発明の実質上の脱水条件とは、好ましくは、水分量が重合系全体で１０００ｐｐｍ以下であることであり、更に好ましくは３００ｐｐｍ以下であり、特に好ましくは５０ｐｐｍ以下であることである。
【００６２】
また、重合系中の水分は末端ハロゲン基を等量反応的に攻撃するので、この末端ハロゲン基と水分量の比という視点も重要であり、水分量は末端ハロゲン基に対して等量以下が好ましく、更に好ましくは５０％以下であり、特に好ましくは１０％以下である。
【００６３】
＜ニトリル系化合物＞
本発明において用いられるニトリル系化合物は、特に限定されないが、以下の化合物が例示される。アセトニトリル、プロピオニトリル、ブチロニトリル、イソブチロニトリル、バレロニトリル、イソバレロニトリル、２−メチルバレロニトリル、トリメチルアセトニトリル、ヘキサンニトリル、４−メチルバレロニトリル、ヘプチルシアニド、オクチルシアニド、ウンデカンニトリル、ウンデシルシアニド、ペンタデカンニトリル、ステアロニトリル、マロノニトリル、スクシノニトリル、グルタロニトリル、２−メチルグルタロニトリル、１，４−ジシアノブタン、１，５−ジシアノペンタン、１，６−ジシアノヘキサン、アゼラニトリル、セバコニトリル、１，１，３，３−プロパンテトラカルボニトリル等の飽和脂肪族系ニトリル類、シクロプロピルシアニド、シクロペンタンカルボニトリル、シクロヘプチルシアニド、２−ノルボルナンカルボニトリル、１−アダマンタンカルボニトリル等の脂肪族環状系ニトリル類、グリコロニトリル、ラクトニトリル、３−ヒドロキシプロピオニトリル、アセトンシアノヒドリン、シクロヘキサノンシアノヒドリン等のヒドロキシル基含有ニトリル類、メトキシアセトニトリル、メチルチオアセトニトリル、３−メトキシプロピオニトリル、３−エトキシプロピオニトリル、３，３−ジエトキシプロピオニトリル、２−シアノエチルエーテル、ジエトキシアセトニトリル、３，３−ジメトキシプロピオニトリル、３−シアノプロピオンアルデヒドジメチルアセタール、３−シアノプロピオンアルデヒドジエチルアセタール等のエーテル基含有ニトリル類、シアンアミド、ジメチルシアンアミド、ジエチルシアンアミド、ジイソプロピルシアンアミド、１−ピロリジンカルボニトリル、１−ピペリジンカルボニトリル、４−モルフォリンカルボニトリル、１，４−ピペラジンジカルボニトリル等のシアンアミド類、ジメチルアミノアセトニトリル、２−（ジエチルアミノ）アセトニトリル、イミノジアセトニトリル、Ｎ−メチル−β−アラニンニトリル、３，３−イミノジプロピオンニトリル、３−（ジメチルアミノ）プロピオニトリル、１−ピペリジンプロピオニトリル、４，４′−トリメチレンビス（１−ピペリジンプロピオニトリル）、４−モルフォリンプロピオニトリル、１−ピロリジンブチロニトリル等のアミノ基含有ニトリル類、トリス（２−シアノエチル）ニトロメタン等のニトロ基含有ニトリル類、ピルボニトリル、４−メチル−２−オキソペンタンニトリル、５−オキソヘキサンニトリル、２−オキソオクタンニトリル、アセチルマロノニトリル、２−オキソ−１−シクロヘキサンプロピオニトリル等のシアノケトン類、メチルシアノフォルメート、エチルシアノフォルメート、１，１−ジシアノエチルアセテート、メチルシアノアセテート、メチルイソシアノアセテート、エチルシアノアセテート、エチルイソシアノアセテート、ブチルシアノアセテート、オクチルシアノアセテート等のシアノカルボネート類、ベンジルシアニド、αメチルベンジルシアニド、ベンゾニトリル、置換基を持つベンゾニトリル等の芳香族ニトリル類が挙げられる。
【００６４】
本発明においてニトリル系化合物を重合系に添加する量は特に制限はないが、重合系全体の体積比で５０％以下が好ましく、通常は３０％以下が好ましく、更に１０％以下が好ましく、特に５％以下が好ましい。
【００６５】
また、ニトリル系化合物は遷移金属原子に対し、配位するので、その添加量は、遷移金属原子とのモル比で規定しても構わない。特に限定はされないが、遷移金属原子に対して、好ましくは、４倍以上で、１００倍以下、更に好ましくは３０倍以下、特に好ましくは１０倍以下である。４倍より少なすぎると、十分な効果を発揮しないことがある。
【００６６】
＜触媒活性を制御する方法＞
本発明の触媒活性を制御する方法としては特に限定されないが、触媒である錯体自体を重合開始後に追加添加する方法、及び、配位子と錯体を形成して触媒となりうるが配位子がない状態では触媒活性がないあるいは低い金属化合物を、初期には配位子に対し過剰に系中に添加しておき、後に配位子を追加する方法、すなわち、重合触媒の金属錯体の配位子を重合開始後に追加添加することにより、重合中に触媒の活性を変化させて重合速度を制御する方法が挙げれる。これらの中では、限定はされないが後者が好ましい。
【００６７】
触媒となる錯体は多くの場合、不均一であり、これを制御して追加することは困難である場合があるので、後者の方が好ましい。触媒錯体及び配位子は、単独で添加しても、適当な溶媒の溶液あるいは分散液にして添加しても構わない。
【００６８】
これらの化合物を追加する時期は、特に限定されない。連続的に添加しても構わないし、逐次に分割して添加しても構わない。
【００６９】
追加する量は特に限定されないが、配位子を追加する場合、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。
【００７０】
理想的な条件であれば、原子移動ラジカル重合においては、重合速度は一般に、触媒量に対して一次の関係、成長末端の量に対して一次の関係、モノマーの量に対して一次の関係であると考えられている。よって、特に限定はされないが例示すると、バッチ重合で、単位時間当たりのモノマーの重合量を一定にしようとする場合、モノマーの残存量と活性な触媒量の積が一定になるように触媒量を調整していけば良いことになる。また、モノマーを追加していくセミバッチ重合では、モノマーの追加に伴い全体積が増加し、触媒及び成長末端の濃度が低下するので、例えば、最終的な重合速度が好ましくなるように最終的な触媒濃度を決定し、この時の触媒濃度と成長末端濃度の積と、モノマー追加中の各時点での触媒濃度と成長末端濃度の積が等しくなるように触媒の必要量を計算することが考えられる。
【００７１】
＜重合条件＞
重合は、特に限定されないが、０〜２００℃の範囲で行うことができ、好ましくは、室温〜１５０℃の範囲である。
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。
【００７２】
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。
【００７３】
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。
【００７４】
＜末端ハロゲン残存率＞
本発明の方法は、末端のハロゲン基が高率で残存する重合体を与える効果を有する。末端のハロゲン基が高率で残存するとは、通常、ハロゲン基の残存率が２０％以上のものを示すが、好ましくは５０％以上、更に好ましくは８０％以上である。
【００７５】
一般に、末端ハロゲン基の残存率は、モノマーの重合率が高い場合に問題になる場合が多い。重合率が低い場合には、重合速度（単位時間当たりのモノマーの重合する量）が充分に速く、競争反応である末端基消失があまり目立たないが、重合率が高くなってくると、重合速度が落ちるため、末端基消失が目立ってくる。また、重合率が高まってから末端基が消失しても、数平均分子量、分子量分布等にはあまり大きな影響を与えないので、見過ごされる場合が多い。本発明の方法は、高重合率でより効果を発揮し、好ましくはモノマーの重合率がモル数で５０％以上、更に好ましくは８０％以上、特に好ましくは９０％以上である。
【００７６】
＜分子量分布＞
本発明の方法によれば、限定はされないが、一般に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で表される分子量分布の狭い重合体が得られる。分子量分布は、一般に１．８未満であり、好ましくは１．５以下、更に好ましくは１．２以下、特に好ましくは１．１５以下である。
【００７７】
＜スケール＞
本発明の方法は、実験室レベルの重合だけでなく、更に大きなスケールへの利用が可能であり、スケールが大きくなればなるほど発熱量や重合時間を制御する必要が高まるので、効果が大きい。好ましくは重合系全体の体積が１Ｌ以上、更に好ましくは１０Ｌ以上、特に好ましくは１０００Ｌ以上である。
【００７８】
本発明によって見出されたこれら４つの条件；（１）実質上脱水条件、及び／または、（２）ニトリル化合物存在下、及び／または、（３）重合触媒の配位子を系中に添加して重合を開始する、及び／または、（４）重合中に触媒の活性を変化させて重合速度を制御する、は、それぞれ単独でも原子移動ラジカル重合を制御する方法として有効であるが、それぞれは密接な関与を持っており、それぞれを組み合わせることにより、より大きな効果を発揮することができる。
【００７９】
例えば、次のような一連の操作が挙げられる。ＣｕＢｒを乾燥したアセトニトリルと混合して錯体化させておき、乾燥したモノマー及び開始剤を加えて加熱する。ここに、乾燥したペンタメチルジエチレントリアミンを添加して重合を開始する。その後、重合の進行に伴い、乾燥したペンタメチルジエチレントリアミンを追加していき、触媒活性を向上させる。
【００８０】
本発明の方法により製造された高率で末端にハロゲン基を持つ重合体は、そのままで、あるいは様々な変換反応により水酸基、アルケニル基やシリル基等の様々な官能基を導入し、硬化性組成物等に利用できる。
【００８１】
【実施例】
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例にのみ限定されるものではない。
下記実施例中、「数平均分子量」および「分子量分布（重量平均分子量と数平均分子量の比）」は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いた標準ポリスチレン換算法により算出した。ただし、ＧＰＣカラムとしてポリスチレン架橋ゲルを充填したもの、ＧＰＣ溶媒としてクロロホルムを用いた。
また、系中の水分はカールフィッシャー滴定法により測定した。末端官能基量は、¹ Ｈ−ＮＭＲを利用して定量した。
【００８２】
実施例１
１００ｍＬのガラス反応容器に、脱水した試薬；アクリル酸ブチル（５０．０ｍＬ、４４．７ｇ、３４９ｍｍｏｌ）、臭化第一銅（６２５ｍｇ、４．３６ｍｍｏｌ）、ペンタメチルジエチレントリアミン（０．９１０ｍＬ、７５６ｍｇ、４．３６ｍｍｏｌ）、およびアセトニトリル（５ｍＬ）を仕込み、冷却後減圧脱気したのち窒素ガスで置換した。よく撹拌した後、２ーブロモプロピオン酸メチル（０．２４３ｍＬ、３６４ｍｇ、２．１８ｍｍｏｌ）を添加し、７０℃で加熱撹拌した。７０℃で加熱撹拌を７時間継続し、時々、サンプリングを実施した。反応混合物は活性アルミナで処理して触媒を除去した後、溶媒及び残存モノマーを減圧下加熱して留去した。３００分でのサンプリング物は、重合率が６７％、生成した重合体の数平均分子量はＧＰＣ測定（ポリスチレン換算）により１６６００、分子量分布は１．１０であった。開始剤基準の官能基残存率は０．８であった。最終生成物は、重合率が８４％、数平均分子量は２１５００、分子量分布は１．１２で、官能基残存率は０．７であった。
この重合系に含まれている水分量は、末端に対し１４％（１２０ｐｐｍ）であった。
【００８３】
実施例２
実施例１と同様に脱水した試薬；アクリル酸ブチル（５０．０ｍＬ、４４．７ｇ、３４９ｍｍｏｌ）、臭化第一銅（６２５ｍｇ、４．３６ｍｍｏｌ）、ペンタメチルジエチレントリアミン（０．９１０ｍＬ、７５６ｍｇ、４．３６ｍｍｏｌ）、アセトニトリル（５ｍＬ）、２，５−ジブロモアジピン酸ジエチル（７８５ｍｇ、２．１８ｍｍｏｌ）を７０℃で重合を８時間実施し、両末端にブロモ基を持つ重合体を製造した。最終生成物は、重合率が９０％、数平均分子量は２３６００、分子量分布は１．１４で、官能基残存率は１．４６であった。
【００８４】
実施例３
実施例１と同様にして、脱水した試薬；アクリル酸ブチル（３００．０ｍＬ、２６８ｇ、２０９０ｍｍｏｌ）、臭化第一銅（３．００ｇ、２０．９ｍｍｏｌ）、ペンタメチルジエチレントリアミン（４．３７ｍＬ、３．６３ｇ、２０．９ｍｍｏｌ）、アセトニトリル（３０ｍＬ）、２，５−ジブロモアジピン酸ジエチル（１８．８ｇ、５２．３ｍｍｏｌ）を７０℃で重合を４５０分間実施し、両末端にブロモ基を持つ重合体を製造した。３４０分で重合率が８４％、数平均分子量は４７００、分子量分布は１．４０で、官能基残存率は１．９０であった。最終生成物は、重合率が９９％、数平均分子量は５４００、分子量分布は１．３７で、官能基残存率は１．７３であった。
【００８５】
比較例１
実施例１と同様にして、脱水していない試薬；アクリル酸ブチル（１０．０ｍＬ、８．９４ｇ、６９．８ｍｍｏｌ）、臭化第一銅（２５０ｍｇ、１．７４ｍｍｏｌ）、ペンタメチルジエチレントリアミン（０．３６４ｍＬ、３０２ｍｇ、１．７４ｍｍｏｌ）、トルエン（１ｍＬ）、２ーブロモプロピオン酸メチル（０．０４９ｍＬ、７２．８ｍｇ、０．４４ｍｍｏｌ）を７０℃で重合を８時間実施した。１２０分で重合率が９３％、数平均分子量は２２５００、分子量分布は１．２６で、官能基残存率は０．１４であった。最終生成物は、重合率が９６％、数平均分子量は２４２００、分子量分布は１．２８で、官能基残存率は０であった。
【００８６】
参考例１ 末端基消失のモデル実験
２−ブロモブチル酸エチル（１．２９ｍｌ、１．７０ｇ、８．７２ｍｍｏｌ）、臭化第一銅（１．２５ｇ、８．７２ｍｍｏｌ）、ペンタメチルジエチレントリアミン（１．８２ｍＬ、１．５１ｇ、８．７２ｍｍｏｌ）、アセトニトリル（５ｍＬ）を７０℃で加熱攪拌し、ガスクロマトグラフィーで２−ブロモブチル酸エチルの残存量を定量した。結果は参考例２と共に記す。
【００８７】
参考例２
参考例１の条件に蒸留水（０．１５７ｍｌ、０．１５７ｇ、８．７２ｍｍｏｌ）添加し、同条件で反応させた。約１０時間後に、水を添加していない参考例１では２−ブロモブチル酸エチルの残存率が５６％、水を添加した参考例２では３８％であった。
【００８８】
実施例４
ＣｕＢｒ（６２５ｍｇ、４．３６ｍｍｏｌ）、アセトニトリル（５ｍｌ）、アクリル酸ブチル（５０ｍｌ、４４．７０ｇ、３４８．８ｍｍｏｌ）、ペンタメチルジエチレントリアミン（０．９１０ｍｌ、７５６ｍｇ、４．３６ｍｍｏｌ）を攪拌機のついたフラスコ中に加え、冷却減圧脱気し、窒素置換した。この混合物を７０℃の油浴中で加熱攪拌した。器壁に付着した触媒は全くなく、攪拌により、触媒は反応系全体に均一に拡散していた。この混合物に重合開始剤である２−ブロモプロピオン酸メチル（０．９７３ｍｌ、１．４５６ｇ、８．７２ｍｍｏｌ）を添加した。すぐに重合が開始したことが、重合系の昇温により確認された。４０分後に８６℃まで昇温し、その後、徐々に低下し浴温と一致した。重合率は３０分後に３８％、６０分後に８４％であった。３０分後のゲルパーミエーションクロマトグラフィーによるポリスチレン基準の数平均分子量Ｍｎ＝２４００、重量平均分子量と数平均分子量の比Ｍｗ／Ｍｎ＝１．１８、６０分後のＭｎ＝５１００、比Ｍｗ／Ｍｎ＝１．１１であった。この反応混合物は、２４０分後に重合率が９９％に達した時点まで、器壁への触媒の付着は見られず、攪拌による均一な拡散が保たれていた。
【００８９】
実施例５
ＣｕＢｒ（２５０ｍｇ、１．７４ｍｍｏｌ）、アセトニトリル（５ｍｌ）、アクリル酸ブチル（５０ｍｌ、４４．７０ｇ、３４８．８ｍｍｏｌ）、ペンタメチルジエチレントリアミン（０．３６４ｍｌ、３０２ｍｇ、１．７４ｍｍｏｌ）を攪拌機のついたフラスコ中に加え、冷却減圧脱気し、窒素置換した。この混合物を７０℃の油浴中で加熱攪拌した。器壁に付着した触媒は全くなく、攪拌により、触媒は反応系全体に均一に拡散していた。この混合物に重合開始剤である２−ブロモプロピオン酸メチル（０．９７３ｍｌ、１．４５６ｇ、８．７２ｍｍｏｌ）を添加した。すぐに重合が開始したことが、重合系の昇温により確認された。５０分後に７７℃まで昇温し、その後、徐々に低下し浴温と一致した。重合率は３０分後に２３％、６０分後に４６％、１２０分後に８４％であった。６０分後のゲルパーミエーションクロマトグラフィーによるポリスチレン基準の数平均分子量Ｍｎ＝２７００、重量平均分子量と数平均分子量の比Ｍｗ／Ｍｎ＝１．１５、１２０分後のＭｎ＝４６００、比Ｍｗ／Ｍｎ＝１．１１であった。この反応混合物は、２４０分後に重合率が９５％に達した時点まで、器壁への触媒の付着は見られず、攪拌による均一な拡散が保たれていた。
実施例４と５の結果を総合して、ニトリル系化合物（本実施例ではアセトニトリル）の添加により、重合中終始、重合触媒が系中で均一に拡散し、また、この効果として、触媒量により重合速度が制御できていることが明らかである。
【００９０】
比較例２
ＣｕＢｒ（６２５ｍｇ、４．３６ｍｍｏｌ）、トルエン（５ｍｌ）、アクリル酸ブチル（５０ｍｌ、４４．７０ｇ、３４８．８ｍｍｏｌ）、ペンタメチルジエチレントリアミン（０．９１０ｍｌ、７５６ｍｇ、４．３６ｍｍｏｌ）を攪拌機のついたフラスコ中に加え、冷却減圧脱気し、窒素置換した。この混合物を７０℃の油浴中で加熱攪拌した。この時点ですでに一部の触媒が器壁に付着していた。この混合物に重合開始剤である２−ブロモプロピオン酸メチル（０．９７３ｍｌ、１．４５６ｇ、８．７２ｍｍｏｌ）を添加した。すぐに重合が開始したことが、重合系の昇温により確認された。２５分後に１０４℃まで昇温し、その後、徐々に低下し浴温と一致した。重合率は１５分後に４３％、３０分後に９０％であった。１５分後のゲルパーミエーションクロマトグラフィーによるポリスチレン基準の数平均分子量Ｍｎ＝１７００、重量平均分子量と数平均分子量の比Ｍｗ／Ｍｎ＝１．３４、３０分後のＭｎ＝５１００、比Ｍｗ／Ｍｎ＝１．１６であった。この反応混合物は、６０分後に重合率が９６％に達した時点で加熱を止めたが、重合の進行に伴い、触媒の器壁への付着が増加した。
【００９１】
比較例３
ＣｕＢｒ（２５０ｍｇ、１．７４ｍｍｏｌ）、トルエン（５ｍｌ）、アクリル酸ブチル（５０ｍｌ、４４．７０ｇ、３４８．８ｍｍｏｌ）、ペンタメチルジエチレントリアミン（０．３６４ｍｌ、３０２ｍｇ、１．７４ｍｍｏｌ）を攪拌機のついたフラスコ中に加え、冷却減圧脱気し、窒素置換した。この混合物を７０℃の油浴中で加熱攪拌した。器壁に付着した触媒は全くなく、攪拌により、触媒は反応系全体に均一に拡散していた。この混合物に重合開始剤である２−ブロモプロピオン酸メチル（０．９７３ｍｌ、１．４５６ｇ、８．７２ｍｍｏｌ）を添加した。発熱は観察されず、重合は２４０分後でもほとんど進行しなかった。
比較例２、３の結果を総合し、実施例４、５の結果と比較すると、ニトリル系化合物を添加していない条件では、触媒の拡散が不十分で、器壁への触媒の付着が観察され、また、触媒量を変化させた場合の反応速度の制御が困難であることが明らかである。
【００９２】
実施例６
ＣｕＢｒ（１．２５１ｇ、８．７２ｍｍｏｌ）、アセトニトリル（５ｍｌ）、アクリル酸ブチル（５０ｍｌ、４４．７０ｇ、３４８．８ｍｍｏｌ）を攪拌機のついたフラスコ中に加え、冷却減圧脱気し、窒素置換した。この混合物を７０℃の油浴中で加熱攪拌した。ＣｕＢｒは白色の結晶になり、器壁に付着した触媒は全くなく、攪拌により反応系全体に均一に拡散していた。この混合物に重合開始剤である２−ブロモプロピオン酸メチル（０．９７３ｍｌ、１．４５６ｇ、８．７２ｍｍｏｌ）を添加した。３６０分間加熱攪拌したが、重合は全く進行しなかった。
【００９３】
これに、ペンタメチルジエチレントリアミン（１．８２１ｍｌ、１．５１１ｇ、８．７２ｍｍｏｌ）を添加すると、すぐに反応系全体に緑色の錯体が現れ、これは攪拌により均一に拡散した。添加と同時に発熱し重合が開始したことが確認された。重合率は１５分後に８５％、３０分後に９６％であった。この反応混合物は、最後まで、器壁への触媒の付着は見られず、攪拌による均一な拡散が保たれていた。
この結果より、アミン配位子がない状態では、ニトリル系化合物が配位した錯体は触媒活性をほとんど持たないことが確認された。よって、遷移金属原子がアミン配位子等の触媒配位子に対して過剰な場合、触媒配位子が配位していないと考えられる遷移金属原子は、触媒活性を持たないことが確認された。
【００９４】
実施例７
攪拌機付きの１００ｍｌの丸底フラスコに、ＣｕＢｒ（２５０ｍｇ、１．７４ｍｍｏｌ）、アセトニトリル（５ｍｌ）を入れ、よく攪拌した。これにアクリル酸ブチル（１５．０ｍｌ、１３．４ｇ、０．１０５ｍｏｌ）を添加し、冷凍減圧脱気し、窒素置換した。オイルバス中７０℃で３０分間攪拌した。ＣｕＢｒの淡緑色の沈殿はなくなり、白色結晶が均一に分散した状態になった。これによく攪拌しながら、ペンタメチルジエチレントリアミン（０．０５８３ｍｌ、４８．４ｍｇ、０．２８ｍｍｏｌ）（これ以降トリアミンと表す）を加えた。混合物の色が、薄い緑色になった。ここに７０℃で、２官能開始剤である２、５−ジブロモアジピン酸ジエチル（１．５７０ｇ、４．３６ｍｍｏｌ）をアクリル酸ブチル（５．０ｍｌ、４．４７ｇ、３４．９ｍｍｏｌ）に溶解させたものを添加した。わずかに発熱しながら、重合が開始した。３０分後から、アクリル酸ブチル（３０．０ｍｌ、２６．８ｇ、０．２０９ｍｏｌ）を約６．３ｍｌ／時間の速度で連続的に滴下した。時々、サンプリングし、モノマーの残存量をガスクロマトグラフィーで確認しながら、２時間後にトリアミン（０．１０ｍｌ、８３ｍｇ、０．４８ｍｍｏｌ）を添加した。トリアミンを添加するとすぐにわずかな発熱が観察され、重合速度が回復したことが確認された。この後も４時間３０分後にトリアミン（０．０６ｍｌ、５０ｍｇ、０．２９ｍｍｏｌ）、５時間１０分後にトリアミン（０．１０ｍｌ、８３ｍｇ、０．４８ｍｍｏｌ）添加した。７時間後に重合を終了した。モノマーの添加量、残存量、消費量の時間に対するグラフを図１に示す。アクリル酸ブチルは添加に合わせて消費され、残存量がよく制御されていることが明らかである。生成物のゲルパーミエーションクロマトグラフィーによるポリスチレン基準の数平均分子量は、モノマーの消費量に比例して設定通り上昇した。重合終了時点での重合率は９３％で、生成物の数平均分子量Ｍｎ＝１１７００、重量平均分子量と数平均分子量の比で表される分子量分布Ｍｗ／Ｍｎ＝１．１８で、両末端の臭素基の残存量は、１分子当たり１．８個であった。重合全体を通じて内温の最高は、浴温＋４℃であり、上記の結果とも併せ、重合速度は非常によく制御されたことが明らかである。
【００９５】
実施例８
攪拌機付きの５００ｍｌの丸底フラスコに、ＣｕＢｒ（３．００ｇ、２０．９ｍｏｌ）、アセトニトリル（３０ｍｌ）を入れ、よく攪拌した。これにアクリル酸ブチル（１００．０ｍｌ、８９．４ｇ、０．６８０ｍｏｌ）を添加し、冷凍減圧脱気し、窒素置換した。オイルバス中７０℃で３０分間攪拌した。ＣｕＢｒの淡緑色の沈殿はなくなり、白色結晶が均一に分散した状態になった。これに２官能開始剤である２、５−ジブロモアジピン酸ジエチル（１８．８３ｇ、５２．３ｍｍｏｌ）をアクリル酸ブチル（２０．０ｍｌ、１７．９ｇ、１４０ｍｍｏｌ）に溶解させたものを添加した。この時点では、開始剤存在下でも重合は全く進行していなかった。ここに７０℃で、よく攪拌しながらペンタメチルジエチレントリアミン（０．１７５ｍｌ、１４５ｍｇ、０．８４ｍｍｏｌ）（これ以降トリアミンと表す）を加えた。混合物の色が、薄い緑色になり、すぐにわずかな発熱を伴いながら、重合が開始した。３０分後から、アクリル酸ブチル（１８０．０ｍｌ、１６１ｇ、１．２６ｍｏｌ）を約３８ｍｌ／時間の速度で連続的に滴下した。時々、サンプリングし、モノマーの残存量をガスクロマトグラフィーで確認しながら、３０分から１時間置きにトリアミンを０．０２ｍｌ（１７ｍｇ、０．１０ｍｍｏｌ）から０．０４ｍｌ（３３ｍｇ、０．１９ｍｍｏｌ）を添加した。トリアミンを添加するとすぐにわずかな発熱が観察され、重合速度が回復したことが確認された。７時間３０分後に重合を終了した。モノマーの添加量、残存量、消費量の時間に対するグラフを図２に示す。アクリル酸ブチルは添加に合わせて消費され、残存量がよく制御されていることが明らかである。生成物のゲルパーミエーションクロマトグラフィーによるポリスチレン基準の数平均分子量は、モノマーの消費量に比例して設定通り上昇した。重合終了時点での重合率は９９％で、生成物の数平均分子量Ｍｎ＝５４００、重量平均分子量と数平均分子量の比で表される分子量分布Ｍｗ／Ｍｎ＝１．３７で、両末端の臭素基の残存量は、１分子当たり１．７個であった。重合スケールが実施例７に比較して大きくなったが、重合全体を通じて内温は浴温＋８℃以下に保たれ、上記の結果とも併せ、重合速度は非常によく制御されたことが明らかである。
【００９６】
実施例９
ＣｕＢｒ（１．２５１ｇ、８．７２ｍｍｏｌ）、アセトニトリル（５ｍｌ）、アクリル酸ブチル（５０ｍｌ、４４．７０ｇ、３４８．８ｍｍｏｌ）を攪拌機のついたフラスコ中に加え、冷却減圧脱気し、窒素置換した。この混合物を７０℃の油浴中で加熱攪拌した。ＣｕＢｒは白色の結晶になり、器壁に付着した触媒は全くなく、攪拌により反応系全体に均一に拡散していた。この混合物に重合開始剤である２−ブロモプロピオン酸メチル（０．９７３ｍｌ、１．４５６ｇ、８．７２ｍｍｏｌ）を添加した。３６０分間加熱攪拌したが、重合は全く進行しなかった。
【００９７】
これに、ペンタメチルジエチレントリアミン（１．８２１ｍｌ、１．５１１ｇ、８．７２ｍｍｏｌ）を添加すると、すぐに反応系全体に緑色の錯体が現れ、これは攪拌により均一に拡散した。添加と同時に発熱し重合が開始したことが確認された。重合率は１５分後に８５％、３０分後に９６％であった。
この反応混合物は、最後まで、器壁への触媒の付着は見られず、攪拌による均一な拡散が保たれていた。
この結果より、アミン配位子がない状態では、ニトリル系化合物が配位した錯体は触媒活性をほとんど持たないことが確認された。よって、遷移金属原子がアミン配位子等の触媒配位子に対して過剰な場合、触媒配位子が配位していないと考えられる遷移金属原子は、触媒活性を持たないことが確認された。
【００９８】
比較例４
攪拌機付きの１００ｍｌの丸底フラスコに、ＣｕＢｒ（６２５ｍｇ、４．３６ｍｍｏｌ）、アセトニトリル（５ｍｌ）、ペンタメチルジエチレントリアミン（０．９１０ｍｌ、７５６ｍｇ、４．３６ｍｍｏｌ）を入れ、アクリル酸ブチル（２０．０ｍｌ、１７．９ｇ、１４０ｍｍｏｌ）を添加し、冷凍減圧脱気し、窒素置換した。オイルバス中７０℃で３０分間攪拌した。少し冷却した後、１官能開始剤である２−ブロモプロピオン酸メチル（０．９７３ｍｌ、１．４６ｇ、８．７２ｍｍｏｌ）を添加し、７０℃のオイルバス中で加熱すると共に、アクリル酸ブチル（３０．０ｍｌ、２６．８ｇ、２０９ｍｍｏｌ）を６．３ｍｌ／分の速度で連続的な滴下を開始した。すぐに発熱が起こり、８７℃まで内温が上がった。わずかに発熱しながら、重合が開始した。３０分後から、アクリル酸ブチル（３０．０ｍｌ、２６．８ｇ、０．２０９ｍｏｌ）を約６．３ｍｌ／時間の速度で連続的に滴下した。時々、サンプリングし、モノマーの残存量をガスクロマトグラフィーで確認した。モノマーの添加量、残存量、消費量の時間に対するグラフを図３に示す。アクリル酸ブチルの消費が昇温のためもあり、初期に非常に大きく、その後は、残存量が増加する傾向にあることが確認できる。８時間後に重合を終了した時点でも、アクリル酸ブチルの重合率は７６％であった。この結果から、通常の方法では、重合速度の制御に問題があることが確認できる。
【００９９】
実施例１０ ＴＲＥＮ配位子を用いた重合
３０ｍＬのガラス反応容器に窒素雰囲気下、臭化第一銅（１２．５ｍｇ、０．０８７１ｍｍｏｌ）、アセトニトリル（１．０ｍＬ）を加え、７０℃で加熱攪拌し、錯体化した。これに２，５−ジブロモアジピン酸ジエチル（０．３１４ｇ、０．８７２ｍｍｏｌ）をアクリル酸ブチル（１０．０ｍＬ、６９．８ｍｍｏｌ）に溶解させたものを添加した。７０℃で攪拌しながら、トリス（ジエチルアミノエチル）アミン（１６μＬ、０．０６９９ｍｍｏｌ）を少量ずつ添加した。３１０分後、加熱を停止し、この時ＧＣ測定よりアクリル酸ブチルの消費率は９３．６％であった。混合物をトルエンで希釈して活性アルミナで処理した後、揮発分を減圧下加熱して留去することで無色透明重合体を得た。得られた重合体のＧＰＣ測定（ポリスチレン換算）により、数平均分子量は１２１００、重量平均分子量１３４００、分子量分布は１．１０、数平均分子量基準の臭素基導入率は１．９９であった。
【０１００】
実施例１１ ４ｋｇＢＡセミバッチ重合
１０Ｌのガラス反応容器に窒素雰囲気下、臭化第一銅（３５．３ｇ、０．２４６ｍｏｌ）、アセトニトリル（４７０ｍＬ）を投入し、７０℃で６０分間加熱した。これにアクリル酸ブチル（９４０ｍＬ、６．５６ｍｏｌ）を加えてさらに６０分攪拌した。これにペンタメチルジエチレントリアミン（２．００ｍＬ、９．５８ｍｍｏｌ）を加えると反応溶液の穏やかな発熱が観測され、重合が開始した。５５分後からアクリル酸ブチル（３．７６Ｌ、２６．２ｍｏｌ）を２６０分かけて加えた。この最中、反応溶液のサンプリングを行って反応を追跡しながら、ペンタメチルジエチレントリアミン（５．００ｍＬ、２４．０ｍｍｏｌ）を少量ずつ加えた。ペンタメチルジエチレントリアミンの投入時には速やかに穏やかな発熱が見られ、触媒活性が向上したことが確認された。アクリル酸ブチルの添加後さらに９０分加熱を続けた。この時ＧＣ測定よりアクリル酸ブチルの消費率は９７．１％であった。混合物をトルエンで希釈して活性アルミナで処理した後、揮発分を減圧下加熱して留去することで無色透明重合体を得た。得られた重合体のＧＰＣ測定（ポリスチレン換算）により、数平均分子量は１０８００、重量平均分子量１２４００、分子量分布は１．１５、数平均分子量基準の臭素基導入率は１．８であった。
【０１０１】
実施例１２ ５ｋｇアルケニル末端ＢＡセミバッチ重合
１０Ｌのガラス反応容器に窒素雰囲気下、臭化第一銅（４１．９ｇ、０．２９３ｍｏｌ）、アセトニトリル（５５９ｍＬ）投入し、７０℃で４５分間加熱した。これにアクリル酸ブチル（１．１２Ｌ、７．８０ｍｏｌ）を加えてさらに４０分間加熱した。これにペンタメチルジエチレントリアミン（４．００ｍＬ、１９．２ｍｍｏｌ）を加えると反応溶液の発熱が観測された。７０℃で加熱攪拌を続け、６０分後からアクリル酸ブチル（４．４７Ｌ、３１．２ｍｏｌ）を１９０分かけて加えた。この最中、反応溶液のサンプリングを行って反応を追跡しながら、ペンタメチルジエチレントリアミン（４．００ｍＬ、１９．２ｍｍｏｌ）を少量ずつ加えた。ペンタメチルジエチレントリアミンの投入時速やかに穏やかな発熱が見られ、触媒活性が向上したことが確認された。アクリル酸ブチルの添加終了後さらに６０分加熱を続けた。この時ＧＣ測定よりアクリル酸ブチルの消費率は９３．２％であった。１，７−オクタジエン（１．４４Ｌ、９．７５ｍｏｌ）およびペンタメチルジエチレントリアミン（２０．５ｍＬ、９８．２ｍｍｏｌ）を加えて２１０分加熱を続けた。混合物をトルエンで希釈して活性アルミナで処理した後、揮発分を減圧下加熱して留去することで淡黄色重合体を得た。得られた重合体のＧＰＣ測定（ポリスチレン換算）により、数平均分子量は１４０００、重量平均分子量１８８００、分子量分布は１．３４、数平均分子量基準のアルケニル基導入率は２．４９であった。
【０１０２】
実施例１３
１００ｍＬのガラス反応容器に窒素雰囲気下、臭化第一銅（０．３７５ｇ、２．６２ｍｍｏｌ）、アセトニトリル（１．６７ｍＬ）を加え、７０℃で２５分間加熱攪拌した。これに２，５−ジブロモアジピン酸ジエチル（１．５７ｇ、４．３６ｍｍｏｌ）をアクリル酸ブチル（５０．０ｍＬ、０．３４９ｍｏｌ）に溶解させたものを添加した。７０℃で６０分攪拌した。これにペンタメチルジエチレントリアミン（９０．０μＬ、０．４３７ｍｍｏｌ）を添加すると速やかに重合が開始した。最終的なアクリル酸ブチルの重合率は９８％であった。
【０１０３】
【発明の効果】
本発明によれば、原子移動ラジカル重合により末端のハロゲン基が高率で残存したビニル系重合体が得られる。また、不均一な重合触媒を用いた場合でも、触媒が器壁に付着したりなどせず、攪拌によって均一に拡散させることができ、重合のスケールアップ時等には、反応制御を容易にする。更に、この効果から、添加した触媒量により、重合速度を調整することが容易になる。そして、原子移動ラジカル重合において、重合速度を重合反応中に任意に調整することができ、発熱量なども制御することができる。これにより、一般に、初期の大きな発熱と重合時間のバランスが問題になるリビング重合において、初期の発熱を抑制し、且つ、重合時間の短縮も可能にする方法を与える。この効果は、スケールが大きくなるほど大きくなり、本発明は、原子移動ラジカル重合の工業化において非常に重要である。
【図面の簡単な説明】
【図１】実施例７におけるモノマーの添加量、残存量、消費量の時間に対するグラフ
【図２】実施例８におけるモノマーの添加量、残存量、消費量の時間に対するグラフ
【図３】比較例４におけるモノマーの添加量、残存量、消費量の時間に対するグラフ[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for controlling atom transfer radical polymerization.
[0002]
[Prior art]
Various living polymerizations have been developed so far, and polymers having controlled molecular weight, molecular weight distribution, terminal structure and the like have been produced. Examples include coordinated anionic polymerization of polypropylene glycol, living cationic polymerization using an iniferter and a Lewis acid catalyst. In addition to these, in recent years, living radical polymerization has been developed that makes it possible to control radical polymerization which has been considered to be very difficult to control.
[0003]
Living radical polymerization is radical polymerization in which the activity at the polymerization terminal is maintained without loss. In the narrow sense, living polymerization refers to polymerization in which the terminal always has activity, but generally includes pseudo-living polymerization in which the terminal is inactivated and the terminal is in equilibrium. . The definition in the present invention is also the latter. In recent years, living radical polymerization has been actively researched by various groups. Examples include cobalt porphyrin complexes (J. Am. Chem. Soc. 1994, 116, 7943), those using radical scavengers such as nitroxide compounds (Macromolecules, 1994, 27, 7228), organic halides, etc. Examples thereof include atom transfer radical polymerization (ATRP) using a transition metal complex as a catalyst. Atom transfer radical polymerization is generally a metal complex having an organic halide, a sulfonyl halide compound or the like as an initiator, and a group 7, 7, 9, 10, or 11 element of the periodic table as a central metal. Is polymerized using the catalyst. (See, for example, Matyjaszewski et al., J. Am. Chem. Soc. 1995, 117, 5614, Macromolecules 1995, 28, 7901, Science 1996, 272, 866, or Sawamoto et al., Macromolecules 1995, 28, 1721). According to these methods, in general, the polymerization rate is very high, and the radical polymerization is likely to cause a termination reaction such as coupling between radicals, but the polymerization proceeds like a living and the molecular weight distribution is narrow (Mw / Mn = 1.1-1.5) A polymer is obtained, and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator. In the present specification, the term “molecular weight distribution” refers to the value of the ratio of weight average molecular weight / number average molecular weight measured by gel permeation chromatography.
[0004]
And as the name of atom transfer radical polymerization indicates, a halogen group derived from an initiator is usually present at the growth terminal of the polymer. However, in reality, it becomes a problem to disappear due to various side reactions.
[0005]
Some catalysts used for atom transfer radical polymerization are completely dissolved in the polymerization system to become a homogeneous system, but many are not completely dissolved but are used in a heterogeneous system. For example, in the polymerization using CuCl or CuBr, when 2,2'-bipyridyl, which is one of the most frequently used as a ligand, is used, the polymerization system is usually heterogeneous. As a device for making this uniform, there is a method of substituting an alkyl group on the pyridine ring of bipyridyl, and it has been reported that when a 1-butylpentyl group or the like is substituted, a uniform system is obtained. It has also been reported that when a highly polar solvent such as ethylene carbonate is used, the solubility of the complex increases and it approaches a homogeneous system (Macromolecules, 1998, 31, 1535). However, this also describes that when the amount of the solvent is decreased, the solubility is decreased and the speed is decreased.
[0006]
Recently, it has been reported that an aliphatic polyamine such as pentamethyldiethylenetriamine which is inexpensive and industrially available is an effective ligand instead of a bipyridyl-based ligand. However, even when this ligand is used, the polymerization system is not completely homogeneous. When the polymerization system is non-uniform, the catalyst settles or adheres to the vessel wall, so that the polymerization rate is not easily stabilized, and it is difficult to control the polymerization rate by changing the catalyst amount.
[0007]
On the other hand, the use of acetonitrile as a solvent is exemplified in the patent (WO97 / 18247), but the special effect is not described at all, and this is not the case with aliphatic polyamine ligands. Nor is it written that something is suitable. Furthermore, these descriptions are all descriptions as solvents, and there is no description of adding a small amount of acetonitrile or a nitrile compound as an additive.
[0008]
Initiation of atom transfer radical polymerization is generally performed by mixing the monomer / catalyst / solvent and finally adding an initiator. When a liquid initiator is used, it can be easily added by a syringe or the like, and even in the case of a solid, it can be added in the same manner after being dissolved in a solvent. Since the polymerization is started immediately from the time when the initiator is added, in order to obtain a polymer having a narrow molecular weight distribution, it is necessary to add the initiator all at once. However, if an initiator is added at once and polymerization starts immediately, it tends to be accompanied by a large exotherm. This heat generation is very dangerous when scaling up. In order to avoid this problem, it is conceivable to add the catalyst last after mixing the monomer / initiator / solvent. In this case, it can be added while observing the start of polymerization, and danger can be avoided. In the case of a catalyst, as compared with the case of the above-described initiator, even if it is added over time, in principle, the molecular weight distribution of the product is not greatly affected. However, the catalyst for atom transfer radical polymerization is often a metal complex and a solid. In addition, as described above, there are many catalysts in which the polymerization system becomes heterogeneous, and it is not easy to dissolve in a solvent. Therefore, it is not easy to start polymerization by adding a catalyst, and it has never been reported so far. .
[0009]
In general, in the living polymerization, the polymerization activity at the growth end is maintained from the initial stage to the final stage of the polymerization, and as a result, the polymerization rate has a substantially linear relationship with the monomer concentration. When living polymerization is performed by batch polymerization, in which the total amount of monomers used for polymerization is initially added to the reactor, the amount of monomer polymerized per unit time is the largest at the initial stage and gradually decreases as the monomer is consumed. I will do it. In order to avoid dangers such as runaway polymerization that are of particular concern in the case of radical polymerization, there is a similar problem in the semi-batch polymerization method in which monomers are added successively or continuously thereafter. In this case, even if the amount of monomer remaining in the polymerization system is kept constant, the initial concentration of the growth end and the catalyst is highest at the initial stage, and dilution is caused by accumulation of the produced polymer. As a result, as in the batch polymerization method, the amount of monomer polymerized per unit time is the largest at the initial stage and gradually decreases. Since the amount of monomer polymerized per unit time determines the heat generation amount, in industrial polymerization, how to control and stabilize the heat generation is very important. However, in the living polymerization as described above, a large amount of heat is usually generated in the initial stage for the reasons described above, which is an obstacle to scale-up and product structure control. If the catalyst activity is lowered to suppress this heat generation, the total polymerization time may become too long as a result. In industrial production, productivity is a very important factor, but if the catalytic activity is increased in order to shorten the total polymerization time, this causes a dilemma that the initial heat generation becomes too large.
[0010]
[Problems to be solved by the invention]
The present invention solves problems such as difficulty in adjusting the polymerization rate due to the precipitation of the catalyst and changes in the amount of the catalyst by leaving the terminal halogen group at a high rate in the atom transfer radical polymerization. It is an object of the present invention to provide an initiation method, to provide a method for controlling the polymerization rate, and to show an improvement method for the polymerization method.
[0011]
[Means for Solving the Problems]
The present invention is characterized in that atom transfer radical polymerization of a vinyl monomer is performed under at least one condition selected from the group consisting of the following (1), (2), (3) and (4). It is a polymerization method.
(1) Substantially dehydrated conditions
(2) In the presence of a nitrile compound
(3) Polymerization is started by adding a polymerization catalyst ligand to the system.
(4) The polymerization rate is controlled by changing the activity of the polymerization catalyst during the polymerization.
[0012]
In atom transfer radical polymerization, an equilibrium reaction consisting of an initiator and a growth end and a transition metal complex catalyst is mediated, but basically, a radical is generated at the growth end, and this radical polymerizes the monomer. Polymerization. Generally, industrially, radical polymerization is not affected by water, as shown by being carried out in water, such as emulsion polymerization or dispersion polymerization. In atom transfer radical polymerization, it is shown in literatures and patents that emulsion polymerization and dispersion polymerization are possible. Furthermore, there is no report that water should not be added even though there is a description that there is no problem even if water is added to the polymerization system. The success or failure of the polymerization control is usually determined based on the number average molecular weight and molecular weight distribution, and the terminal group residual ratio is difficult to quantify and is hardly discussed. Atom transfer radical polymerization can also be carried out in bulk, and in literatures, etc., examples of using distilled monomers are disclosed, but the total water content including the catalyst and initiator and the terminal group residual ratio are also disclosed. Is not mentioned, especially when solvents are used.
[0013]
As a result of diligent research, we found that water in the polymerization system is deeply related to the disappearance of terminal halogen groups, and by removing this, a polymer with terminal halogen groups remaining at a high rate can be obtained. I found. Furthermore, this technique is effective when using a polar compound having relatively high hydrophilicity, such as the nitrile compound or catalyst ligand of the present invention.
[0014]
As a result of intensive studies, we have found that the addition of a nitrile compound has the effect of improving the diffusibility of the catalyst due to its coordination power to the transition metal compound. In order to enhance this effect, it is preferable to mix a precursor transition metal compound of a catalyst such as CuBr with a nitrile compound before adding a ligand such as amine.
[0015]
The above-mentioned effect obtained by the present invention is different from the effect using a simple polar solvent. When using a catalyst in which the polymerization system is a heterogeneous system, the solubility of the catalyst is generally improved when a polar solvent is used. This results in a decrease (Macromolecules, 1998, 31, 1535). On the other hand, the addition of the nitrile compound of the present invention is effective even when added in a small amount, and does not simply improve the solubility of the catalyst. It prevents adhesion and sedimentation, and as a result, achieves uniform diffusion in stirring. And this technique is effective also in order to raise the diffusibility of the metal complex or salt before ligand addition in the polymerization start by the catalyst ligand addition described below.
[0016]
Furthermore, as a result of intensive studies, we have found a method for initiating polymerization by adding an atom transfer radical polymerization ligand. That is, only a metal salt such as CuBr having no ligand is added to the polymerization system, and when a catalyst ligand is added, a complex is formed in the system, exhibiting catalytic activity, and polymerization is started. The As described above, many catalysts for atom transfer radical polymerization have a non-uniform polymerization system, and it is not easy to add them as they are or after dissolving them in a solvent. On the other hand, many ligands themselves are liquid or can be easily dissolved in a solvent, and it is easy to add them. The metal complex (salt) before the addition of the ligand is often poorer in solubility and diffusibility than the metal complex serving as the catalyst, and the metal complex (salt) before the addition of the ligand is the wall of the vessel. If it adheres, complex formation may not be immediately possible even when a ligand is added. In order to prevent this, the addition of the above-mentioned nitrile compound is effective.
[0017]
We have also found, as a result of research, that the polymerization is controlled by changing the activity of the catalyst during the polymerization to control the polymerization rate. As a method of changing the catalyst activity, a method of adding a catalyst and a method of adding a ligand of a transition metal complex that becomes a catalyst in the same manner as the above-described initiation reaction are presented. The transition metal complex serving as the catalyst of the present invention is preferably a copper complex, and it is preferable to add a solvent or additive that forms a complex with the transition metal but does not have catalytic activity.
[0018]
These four conditions (1) to (4) having the above-mentioned values found by the present invention are effective as a method for controlling atom transfer radical polymerization alone, but a greater effect can be obtained by combining them. It can be demonstrated.
[0019]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
<Outline of atom transfer radical polymerization>
The “living radical polymerization method” is a radical polymerization that is difficult to control because it has a high polymerization rate and is likely to cause a termination reaction due to coupling between radicals. However, the termination reaction is difficult to occur and the molecular weight distribution is narrow (Mw / Mn is about 1.1 to 1.5), a polymer is obtained, and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator.
[0020]
Accordingly, the “living radical polymerization method” can obtain a polymer having a narrow molecular weight distribution and a low viscosity, and a monomer having a specific functional group can be introduced at almost any position of the polymer. The method for producing the vinyl polymer having the specific functional group is more preferable.
[0021]
Among the “living radical polymerization methods”, the “atom transfer radical polymerization method” for polymerizing vinyl monomers using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is the above “living radical polymerization method”. In addition to the features of ”, it has a halogen, which is relatively advantageous for functional group conversion reaction, at the end, and has a high degree of freedom in designing initiators and catalysts, so the production of vinyl polymers having specific functional groups The method is more preferable. As this atom transfer radical polymerization method, in addition to the above-mentioned documents, for example, WO96 / 30421, WO97 / 18247, WO98 / 01480, WO98 / 40415, JP-A-9-208616, Kaihei 8-41117 gazette etc. are mentioned.
[0022]
In addition to the usual atom transfer radical polymerization using an organic halide or sulfonyl halide compound as an initiator as described above, a general free radical polymerization initiator such as peroxide and copper (II) “Reverse atom transfer radical polymerization”, which is a combination of such high oxidation state complexes of the usual atom transfer radical polymerization catalyst, is also included in the atom transfer radical polymerization.
[0023]
<Monomer>
It does not specifically limit as a vinyl-type monomer used for this invention, Various things can be used. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n- Butyl, isobutyl (meth) acrylate, (tert-butyl) (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acryl Acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl, (meth) Phenyl acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate (Meth) acrylic acid-3-methoxybutyl, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid stearyl, (meth) acrylic acid glycidyl, (meth) 2-aminoethyl acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate , 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate , (Perfluoromethylmethyl) (meth) acrylate, (me T) 2-perfluoromethyl-2-perfluoroethylmethyl acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluoro (meth) acrylate (Meth) acrylic acid monomers such as hexadecylethyl; styrene monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and their salts; perfluoroethylene, perfluoropropylene, vinylidene fluoride, etc. Fluorine-containing vinyl monomers; silicon-containing vinyl monomers such as vinyltrimethoxysilane and vinyltriethoxysilane; maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid; fumaric acid, monoalkyl esters of fumaric acid and Dialkyl esters; maleimide monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; nitrile groups such as acrylonitrile and methacrylonitrile Vinyl monomers; amide group-containing vinyl monomers such as acrylamide and methacrylamide; vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; alkenes such as ethylene and propylene; butadiene And conjugated dienes such as isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like. These may be used alone or a plurality of these may be copolymerized. Although not limited, among them, styrenic monomers and (meth) acrylic acid monomers are preferable in view of physical properties of the product. More preferred are acrylic ester monomers and methacrylic ester monomers, and even more preferred is butyl acrylate. In the present invention, these preferable monomers may be copolymerized with other monomers, and in this case, it is preferable that these preferable monomers are contained in an amount of 40% or more by weight.
[0024]
<Initiator>
In the atom transfer radical polymerization, an organic halide (for example, an ester compound having a halogen at the α-position or a compound having a halogen at the benzyl position) or a sulfonyl halide is generally used as an initiator. In addition, a group in place of halogen may be used. For example,
C₆ H_Five -CH₂ X,
C₆ H_Five -C (H) (X) CH_Three ,
C₆ H_Five -C (X) (CH_Three )₂ ,
(However, in the above chemical formula,₆ H_Five Is a phenyl group, X is chlorine, bromine, or iodine)
R¹ -C (H) (X) -CO₂ R² ,
R¹ -C (CH_Three ) (X) -CO₂ R² ,
R¹ -C (H) (X) -C (O) R² ,
R¹ -C (CH_Three ) (X) -C (O) R² ,
(Wherein R¹ And R² Are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, X is chlorine, bromine, or iodine)
R¹ -C₆ H_Four -SO₂ X,
(In each of the above formulas, R¹ And R² Are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, X is chlorine, bromine, or iodine)
Etc.
[0025]
As an initiator for living radical polymerization, an organic halide or a sulfonyl halide compound having a functional group other than the functional group for initiating polymerization can also be used. In such a case, a vinyl polymer having a functional group at one main chain terminal and a halogen group at the other main chain terminal is produced. Examples of such functional groups include alkenyl groups, crosslinkable silyl groups, hydroxyl groups, epoxy groups, amino groups, amide groups, and the like.
[0026]
It does not limit as an organic halide which has an alkenyl group, For example, what has a structure shown in General formula (1) is illustrated.
R^Four R^Five C (X) -R⁶ -R⁷ -C (R^Three ) = CH₂ (1)
(Wherein R^Three Is hydrogen or a methyl group, R^Four , R^Five Is hydrogen, or a monovalent alkyl group having 1 to 20 carbon atoms, an aryl group, or aralkyl, or those interconnected at the other end, R⁶ -C (O) O- (ester group), -C (O)-(keto group), or o-, m-, p-phenylene group, R⁷ Is a direct bond, or a divalent organic group having 1 to 20 carbon atoms and may contain one or more ether bonds, X is chlorine, bromine, or iodine)
[0027]
Substituent R^Four , R^Five Specific examples thereof include hydrogen, methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, pentyl group, hexyl group and the like. R^Four And R^Five May be linked at the other end to form a cyclic skeleton.
[0028]
Specific examples of the organic halide having an alkenyl group represented by the general formula (1) include
XCH₂ C (O) O (CH₂ )_n CH = CH₂ ,
H_Three CC (H) (X) C (O) O (CH₂ )_n CH = CH₂ ,
(H_Three C)₂ C (X) C (O) O (CH₂ )_n CH = CH₂ ,
CH_Three CH₂ C (H) (X) C (O) O (CH₂ )_n CH = CH₂ ,
[0029]
[Chemical 1]

[0030]
(In each of the above formulas, X is chlorine, bromine, or iodine, n is an integer of 0 to 20) XCH₂ C (O) O (CH₂ )_n O (CH₂ )_m CH = CH₂ ,
H_Three CC (H) (X) C (O) O (CH₂ )_n O (CH₂ )_m CH = CH₂ ,
(H_Three C)₂ C (X) C (O) O (CH₂ )_n O (CH₂ )_m CH = CH₂ ,
CH_Three CH₂ C (H) (X) C (O) O (CH₂ )_n O (CH₂ )_m CH = CH₂ ,
[0031]
[Chemical 2]

[0032]
(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 -C₆ H_Four -(CH₂ )_n -CH = CH₂ ,
o, m, p-CH_Three C (H) (X) -C₆ H_Four -(CH₂ )_n -CH = CH₂ ,
o, m, p-CH_Three CH₂ C (H) (X) -C₆ H_Four -(CH₂ )_n -CH = CH₂ ,
(In the above formulas, X is chlorine, bromine or iodine, and n is an integer of 0 to 20)
o, m, p-XCH₂ -C₆ H_Four -(CH₂ )_n -O- (CH₂ )_m -CH = CH₂ ,
o, m, p-CH_Three C (H) (X) -C₆ H_Four -(CH₂ )_n -O- (CH₂ )_m -CH = CH₂ ,
o, m, p-CH_Three CH₂ C (H) (X) -C₆ H_Four -(CH₂ )_n -O- (CH₂ )_m CH = CH₂ ,
(In each of the above formulas, X 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 -C₆ H_Four -O- (CH₂ )_n -CH = CH₂ ,
o, m, p-CH_Three C (H) (X) -C₆ H_Four -O- (CH₂ )_n -CH = CH₂ ,
o, m, p-CH_Three CH₂ C (H) (X) -C₆ H_Four -O- (CH₂ )_n -CH = CH₂ ,
(In the above formulas, X is chlorine, bromine or iodine, and n is an integer of 0 to 20)
o, m, p-XCH₂ -C₆ H_Four -O- (CH₂ )_n -O- (CH₂ )_m -CH = CH₂ ,
o, m, p-CH_Three C (H) (X) -C₆ H_Four -O- (CH₂ )_n -O- (CH₂ )_m -CH = CH₂ ,
o, m, p-CH_Three CH₂ C (H) (X) -C₆ H_Four -O- (CH₂ )_n -O- (CH₂ )_m -CH = CH₂ ,
(In each of the above formulas, X is chlorine, bromine, or iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20)
[0033]
Examples of the organic halide having an alkenyl group further include a compound represented by the general formula (2).
H₂ C = C (R^Three -R⁶ -C (R^Four ) (X) -R⁸ -R^Five (2)
(Wherein R^Three , R^Four , R^Five , R⁶ , X is the same as above, R⁸ Represents a direct bond, —C (O) O— (ester group), —C (O) — (keto group), or o-, m-, p-phenylene group)
[0034]
R⁶ Is a direct bond or a divalent organic group having 1 to 20 carbon atoms (which may contain one or more ether bonds). The groups are bonded and are allylic halides. In this case, since the carbon-halogen bond is activated by the adjacent vinyl group, R⁸ It is not always necessary to have a C (O) O group or a phenylene group, and a direct bond may be used. R⁶ In order to activate the carbon-halogen bond,⁸ Is preferably a C (O) O group, a C (O) group, or a phenylene group.
[0035]
If the compound of Formula (2) is specifically illustrated,
CH₂ = CHCH₂ X, CH₂ = C (CH_Three ) CH₂ X,
CH₂ = CHC (H) (X) CH_Three , CH₂ = C (CH_Three ) C (H) (X) CH_Three ,
CH₂ = CHC (X) (CH_Three )₂ , CH₂ = CHC (H) (X) C₂ H_Five ,
CH₂ = CHC (H) (X) CH (CH_Three )₂ ,
CH₂ = CHC (H) (X) C₆ H_Five , CH₂ = CHC (H) (X) CH₂ C₆ H_Five ,
CH₂ = CHCH₂ C (H) (X) -CO₂ R,
CH₂ = CH (CH₂ )₂ C (H) (X) -CO₂ R,
CH₂ = CH (CH₂ )_Three C (H) (X) -CO₂ R,
CH₂ = CH (CH₂ )₈ C (H) (X) -CO₂ R,
CH₂ = CHCH₂ C (H) (X) -C₆ H_Five ,
CH₂ = CH (CH₂ )₂ C (H) (X) -C₆ H_Five ,
CH₂ = CH (CH₂ )_Three C (H) (X) -C₆ H_Five ,
(In the above formulas, X is chlorine, bromine, or iodine, R is an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group)
Etc.
[0036]
If the specific example of the sulfonyl halide compound which has an alkenyl group is given,
o-, m-, p-CH₂ = CH- (CH₂ )_n -C₆ H_Four -SO₂ X,
o-, m-, p-CH₂ = CH- (CH₂ )_n -OC₆ H_Four -SO₂ X,
(In the above formulas, X is chlorine, bromine, or iodine, and n is an integer of 0 to 20).
[0037]
It does not specifically limit as said organic halide which has a crosslinkable silyl group, For example, what has a structure shown in General formula (3) is illustrated.
R^Four R^Five C (X) -R⁶ -R⁷ -C (H) (R^Three ) CH₂ −
[Si (R⁹ )_2-b (Y)_b O]_m -Si (R^Ten)_3-a (Y)_a (3)
(Wherein R^Three , R^Four , R^Five , R⁶ , R⁷ , X is the same as above, R⁹ , R^TenAre all alkyl groups having 1 to 20 carbon atoms, aryl groups, aralkyl groups, or (R ′)._Three A 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). , R⁹ Or R^TenWhen two or more are present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y exist, they may be the same or different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer of 0-19. However, it shall be satisfied that a + mb ≧ 1)
[0038]
If the compound of general formula (3) is specifically illustrated,
XCH₂ C (O) O (CH₂ )_n Si (OCH_Three )_Three ,
CH_Three C (H) (X) C (O) O (CH₂ )_n Si (OCH_Three )_Three ,
(CH_Three )₂ C (X) C (O) O (CH₂ )_n Si (OCH_Three )_Three ,
XCH₂ C (O) O (CH₂ )_n Si (CH_Three ) (OCH_Three )₂ ,
CH_Three C (H) (X) C (O) O (CH₂ )_n Si (CH_Three ) (OCH_Three )₂ ,
(CH_Three )₂ C (X) C (O) O (CH₂ )_n Si (CH_Three ) (OCH_Three )₂ ,
(In the above formulas, X is chlorine, bromine, iodine, n is an integer of 0-20)
XCH₂ C (O) O (CH₂ )_n O (CH₂ )_m Si (OCH_Three )_Three ,
H_Three CC (H) (X) C (O) O (CH₂ )_n O (CH₂ )_m Si (OCH_Three )_Three ,
(H_Three C)₂ C (X) C (O) O (CH₂ )_n O (CH₂ )_m Si (OCH_Three )_Three ,
CH_Three CH₂ C (H) (X) C (O) O (CH₂ )_n O (CH₂ )_m Si (OCH_Three )_Three ,
XCH₂ C (O) O (CH₂ )_n O (CH₂ )_m Si (CH_Three ) (OCH_Three )₂ ,
H_Three CC (H) (X) C (O) O (CH₂ )_n O (CH₂ )_m -Si (CH_Three ) (OCH_Three )₂ ,
(H_Three C)₂ C (X) C (O) O (CH₂ )_n O (CH₂ )_m -Si (CH_Three ) (OCH_Three )₂ ,
CH_Three CH₂ C (H) (X) C (O) O (CH₂ )_n O (CH₂ )_m -Si (CH_Three ) (OCH_Three )₂ ,
(In the above formulas, X is chlorine, bromine, iodine, n is an integer of 1 to 20, and m is an integer of 0 to 20)
o, m, p-XCH₂ -C₆ H_Four -(CH₂ )₂ Si (OCH_Three )_Three ,
o, m, p-CH_Three C (H) (X) -C₆ H_Four -(CH₂ )₂ Si (OCH_Three )_Three ,
o, m, p-CH_Three CH₂ C (H) (X) -C₆ H_Four -(CH₂ )₂ Si (OCH_Three )_Three ,
o, m, p-XCH₂ -C₆ H_Four -(CH₂ )_Three Si (OCH_Three )_Three ,
o, m, p-CH_Three C (H) (X) -C₆ H_Four -(CH₂ )_Three Si (OCH_Three )_Three ,
o, m, p-CH_Three CH₂ C (H) (X) -C₆ H_Four -(CH₂ )_Three Si (OCH_Three )_Three ,
o, m, p-XCH₂ -C₆ H_Four -(CH₂ )₂ -O- (CH₂ )_Three Si (OCH_Three )_Three ,
o, m, p-CH_Three C (H) (X) -C₆ H_Four -(CH₂ )₂ -O- (CH₂ )_Three Si (OCH_Three )_Three ,
o, m, p-CH_Three CH₂ C (H) (X) -C₆ H_Four -(CH₂ )₂ -O- (CH₂ )_Three Si (OCH_Three )_Three ,
o, m, p-XCH₂ -C₆ H_Four -O- (CH₂ )_Three Si (OCH_Three )_Three ,
o, m, p-CH_Three C (H) (X) -C₆ H_Four -O- (CH₂ )_Three Si (OCH_Three )_Three ,
o, m, p-CH_Three CH₂ C (H) (X) -C₆ H_Four -O- (CH₂ )_Three -Si (OCH_Three )_Three ,
o, m, p-XCH₂ -C₆ H_Four -O- (CH₂ )₂ -O- (CH₂ )_Three -Si (OCH_Three )_Three ,
o, m, p-CH_Three C (H) (X) -C₆ H_Four -O- (CH₂ )₂ -O- (CH₂ )_Three Si (OCH_Three )_Three ,
o, m, p-CH_Three CH₂ C (H) (X) -C₆ H_Four -O- (CH₂ )₂ -O- (CH₂ )_Three Si (OCH_Three )_Three ,
(In the above formulas, X is chlorine, bromine, or iodine)
Etc.
[0039]
Examples of the organic halide having a crosslinkable silyl group further include those having a structure represented by the general formula (4).
(R^Ten)_3-a (Y)_a Si- [OSi (R⁹ )_2-b (Y)_b ]_m −
CH₂ -C (H) (R^Three -R¹¹-C (R^Four ) (X) -R⁸ -R^Five (4)
(Wherein R^Three , R^Four , R^Five , R⁷ , R⁸ , R⁹ , R^Ten, A, b, m, X, Y are the same as above)
[0040]
If such a compound is specifically illustrated,
(CH_Three O)_Three SiCH₂ CH₂ C (H) (X) C₆ H_Five ,
(CH_Three O)₂ (CH_Three ) SiCH₂ CH₂ C (H) (X) C₆ H_Five ,
(CH_Three O)_Three Si (CH₂ )₂ C (H) (X) -CO₂ R,
(CH_Three O)₂ (CH_Three ) Si (CH₂ )₂ C (H) (X) -CO₂ R,
(CH_Three O)_Three Si (CH₂ )_Three C (H) (X) -CO₂ R,
(CH_Three O)₂ (CH_Three ) Si (CH₂ )_Three C (H) (X) -CO₂ R,
(CH_Three O)_Three Si (CH₂ )_Four C (H) (X) -CO₂ R,
(CH_Three O)₂ (CH_Three ) Si (CH₂ )_Four C (H) (X) -CO₂ R,
(CH_Three O)_Three Si (CH₂ )₉ C (H) (X) -CO₂ R,
(CH_Three O)₂ (CH_Three ) Si (CH₂ )₉ C (H) (X) -CO₂ R,
(CH_Three O)_Three Si (CH₂ )_Three C (H) (X) -C₆ H_Five ,
(CH_Three O)₂ (CH_Three ) Si (CH₂ )_Three C (H) (X) -C₆ H_Five ,
(CH_Three O)_Three Si (CH₂ )_Four C (H) (X) -C₆ H_Five ,
(CH_Three O)₂ (CH_Three ) Si (CH₂ )_Four C (H) (X) -C₆ H_Five ,
(In the above formulas, X is chlorine, bromine, or iodine, R is an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group)
Etc.
[0041]
The organic halide having a hydroxyl group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.
HO- (CH₂ )_n -OC (O) C (H) (R) (X)
(In the above formulas, X is chlorine, bromine, or iodine, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)
[0042]
The organic halide having an amino group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.
H₂ N- (CH₂ )_n -OC (O) C (H) (R) (X)
(In the above formulas, X is chlorine, bromine, or iodine, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)
[0043]
The organic halide having the epoxy group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.
[0044]
[Chemical Formula 3]

[0045]
(In the above formulas, X is chlorine, bromine, or iodine, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 20)
[0046]
In the living radical polymerization, when polymerization is performed using an organic halide or sulfonyl halide compound having two or more starting points as an initiator, a vinyl polymer having halogen groups at both ends is obtained. To illustrate this initiator specifically,
[0047]
[Formula 4]

[0048]
(In the formula, R represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. C₆ H_Four Represents a phenylene group. n represents an integer of 0 to 20. X represents chlorine, bromine, or iodine. )
[0049]
[Chemical formula 5]

[0050]
(In the formula, R represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. C₆ H_Four Represents a phenylene group. n represents an integer of 0 to 20. X represents chlorine, bromine, or iodine. )
Etc.
[0051]
<Catalyst>
The transition metal complex used as a catalyst for atom transfer radical polymerization is not particularly limited, and those described in PCT / US96 / 17780 can be used. Among these, a complex of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron, or divalent nickel is preferable. Of these, a copper complex is preferable. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, etc. is there. In addition, tristriphenylphosphine complex of divalent ruthenium chloride (RuCl₂ (PPh_Three )_Three ) Is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, an aluminum alkoxide is added as an activator. Furthermore, a divalent iron bistriphenylphosphine complex (FeCl₂ (PPh_Three )₂ ) Bivalent nickel bistriphenylphosphine complex (NiCl)₂ (PPh_Three )₂ ), And a bivalent nickel bistributylphosphine complex (NiBr)₂ (PBu_Three )₂ ) Is also suitable as a catalyst.
[0052]
When a copper compound is used as the catalyst, the ligand described in PCT / US96 / 17780 can be used as the ligand. Although not particularly limited, amine-based ligands are preferable, and bipyridyl compounds such as 2,2'-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, hexamethyltriethylenetetraamine, bispicolylamine , Ligands such as aliphatic amines such as trialkylamine, tetramethylethylenediamine, pentamethyldiethylenetriamine, and hexamethyl (2-aminoethyl) amine. In the present invention, among these, polyamine compounds, particularly aliphatic polyamines such as pentamethyldiethylenetriamine and hexamethyl (2-aminoethyl) amine are preferred. Moreover, when using a polyamine compound, a pyridine-type compound, or an aliphatic amine compound as a ligand in the case of using a copper compound as a catalyst, these ligands must have three or more amino groups. Is preferred. The amino group in the present invention represents a group having a nitrogen atom-carbon atom bond, and among these, a group in which a nitrogen atom is bonded only to a carbon atom and / or a hydrogen atom is preferable.
[0053]
In the point of polymerization under the dehydration conditions of the present invention, the disappearance of the terminal halogen group is also affected by the basicity in the polymerization system. Therefore, when amines, particularly aliphatic amines are used as ligands, The effect of is great.
[0054]
The catalyst may be added to the polymerization apparatus in the form of a complex having catalytic activity, or a transition metal compound that is a catalyst precursor and a ligand may be mixed in the polymerization apparatus to form a complex. In known atom transfer radical polymerizations, this complexing operation is generally performed before the initiator is added. On the other hand, in the present invention, the ligand is added to the polymerization system after adding the initiator, is complexed with a transition metal compound that is a catalyst precursor, exhibits catalytic activity, and starts polymerization. And / or controlling catalyst activity is disclosed.
[0055]
In addition, when the polymerization is carried out in the presence of the nitrile compound of the present invention, the complex precursor transition metal compound and the nitrile compound are combined with the ligand in the usual atom transfer radical polymerization initiation method in which the initiator is added after the complex formation. It is preferable to mix them earlier than this because the dispersibility of the complex is enhanced.
[0056]
The amount of the ligand as described above is determined from the number of coordination sites of the transition metal and the number of groups coordinated by the ligand under the conditions of normal atom transfer radical polymerization, so that they are almost equal. Is set to For example, the amount of 2,2'-bipyridyl and its derivatives added to CuBr is usually twice as much as the molar ratio, and in the case of pentamethyldiethylenetriamine, it is once as high as the molar ratio. In the present invention, when a ligand is added to initiate polymerization, and / or when a catalyst activity is controlled by adding a ligand, there is no particular limitation, but the metal atom is excessive relative to the ligand. Is preferred. The ratio between the coordination position and the coordinating group is preferably 1.2 times or more, more preferably 1.4 times or more, particularly preferably 1.6 times or more, and particularly preferably 2 times or more. It is.
[0057]
In the present invention, the same effect can be obtained by using a transition metal complex coordinated with a nitrile compound from the beginning as the transition metal compound of the catalyst precursor instead of adding the nitrile compound. Such a complex is not particularly limited, but is a complex obtained by adding a transition metal compound and coordinating the nitrile compound in a state where the nitrile compound is excessively present, and removing the excess nitrile compound. Is exemplified. CuBr (NC-R)_n , CuCl (NC-R)_n (Wherein, R is a monovalent organic group such as methyl, and n is an integer of 1 or more).
[0058]
<Solvent, additive>
The polymerization of the present invention can be carried out without solvent or in various solvents. Examples of the solvent include hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether, tetrahydrofuran, diphenyl ether, anisole and dimethoxybenzene; halogenated hydrocarbon solvents such as methylene chloride, chloroform and chlorobenzene; acetone Ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol and tert-butyl alcohol; nitrile solvents such as acetonitrile, propionitrile and benzonitrile; acetic acid Examples thereof include ester solvents such as ethyl and butyl acetate; carbonate solvents such as ethylene carbonate and propylene carbonate. These can be used individually or in mixture of 2 or more types.
[0059]
Among these solvents, aprotic solvents are preferable. In addition, a highly polar solvent generally has high water absorption and tends to have a fast terminal elimination reaction, so that the polymerization under the dehydration conditions of the present invention is more effective. As a reference, a case where a solvent having a relative dielectric constant of 10 or more at 25 ° C. is used. The nitrile compound proposed to be used as an additive in the present invention may be used as a solvent.
[0060]
These solvents, or other additives added to the polymerization system, coordinate with the metal compound used as a catalyst to form a complex having no catalytic activity, but when a ligand is added What becomes an active catalyst is preferable. Even if the solvent does not have coordinating properties, it is possible to control the catalytic activity by adding a ligand, but the dispersibility of a metal compound such as CuBr in the absence of the ligand is insufficient, so Stable activity control may not be easy due to adhesion or the like. As an example satisfying such requirements, there is a combination using CuBr as a metal compound and a nitrile solvent as a solvent. In PCT / US96 / 17780, acetonitrile is described as a preferred ligand for the polymerization catalyst, but it was actually confirmed that the CuBr acetonitrile complex has no polymerization activity. However, our studies have shown that this complex is highly crystalline and well dispersed in the polymerization system with proper stirring, even when it is non-uniform. Then, by adding a ligand such as pentamethyldiethylenetriamine, an active complex is rapidly formed to catalyze the polymerization.
[0061]
<Moisture content>
The substantial dehydration condition of the present invention is preferably that the water content is 1000 ppm or less in the entire polymerization system, more preferably 300 ppm or less, and particularly preferably 50 ppm or less.
[0062]
In addition, since moisture in the polymerization system attacks the terminal halogen group in an equivalent amount, the viewpoint of the ratio of the terminal halogen group to the amount of water is also important. Preferably, it is 50% or less, more preferably 10% or less.
[0063]
<Nitrile compound>
Although the nitrile compound used in the present invention is not particularly limited, the following compounds are exemplified. Acetonitrile, propionitrile, butyronitrile, isobutyronitrile, valeronitrile, isovaleronitrile, 2-methylvaleronitrile, trimethylacetonitrile, hexanenitrile, 4-methylvaleronitrile, heptyl cyanide, octyl cyanide, undecane nitrile, undecyl cyani , Pentadecanenitrile, stearonitrile, malononitrile, succinonitrile, glutaronitrile, 2-methylglutaronitrile, 1,4-dicyanobutane, 1,5-dicyanopentane, 1,6-dicyanohexane, azeronitrile, sebacononitrile Saturated aliphatic nitriles such as 1,1,3,3-propanetetracarbonitrile, cyclopropyl cyanide, cyclopentanecarbonitrile, cycloheptyl cyanide, 2-norbo Aliphatic cyclic nitriles such as nancarbonitrile and 1-adamantancarbonitrile, hydroxyl group-containing nitriles such as glycolonitrile, lactonitrile, 3-hydroxypropionitrile, acetone cyanohydrin, cyclohexanone cyanohydrin, methoxyacetonitrile, methylthioacetonitrile , 3-methoxypropionitrile, 3-ethoxypropionitrile, 3,3-diethoxypropionitrile, 2-cyanoethyl ether, diethoxyacetonitrile, 3,3-dimethoxypropionitrile, 3-cyanopropionaldehyde dimethyl acetal , Ether group-containing nitriles such as 3-cyanopropionaldehyde diethyl acetal, cyanamide, dimethyl cyanamide, diethyl cyanamide, diisopropyl Cyanamides such as cyanamide, 1-pyrrolidinecarbonitrile, 1-piperidinecarbonitrile, 4-morpholinecarbonitrile, 1,4-piperazinedicarbonitrile, dimethylaminoacetonitrile, 2- (diethylamino) acetonitrile, iminodiacetonitrile, N -Methyl-β-alanine nitrile, 3,3-iminodipropiononitrile, 3- (dimethylamino) propionitrile, 1-piperidinepropionitrile, 4,4'-trimethylenebis (1-piperidinepropionitrile) Amino group-containing nitriles such as 4-morpholine propionitrile and 1-pyrrolidinebutyronitrile, nitro group-containing nitriles such as tris (2-cyanoethyl) nitromethane, pyronitrile, 4-methyl-2-oxopentanenitrile Cyanoketones such as 5-oxohexanenitrile, 2-oxooctanenitrile, acetylmalononitrile, 2-oxo-1-cyclohexanepropionitrile, methyl cyanoformate, ethyl cyanoformate, 1,1-dicyanoethyl acetate, methyl Cyanoacetates such as cyanoacetate, methylisocyanoacetate, ethylcyanoacetate, ethylisocyanoacetate, butylcyanoacetate, octylcyanoacetate, benzylcyanide, α-methylbenzylcyanide, benzonitrile, substituted benzonitriles Aromatic nitriles such as
[0064]
In the present invention, the amount of the nitrile compound added to the polymerization system is not particularly limited, but it is preferably 50% or less, usually 30% or less, more preferably 10% or less, particularly 5% in terms of the volume ratio of the entire polymerization system. % Or less is preferable.
[0065]
Further, since the nitrile compound is coordinated to the transition metal atom, the addition amount may be defined by the molar ratio with the transition metal atom. Although not particularly limited, the transition metal atom is preferably 4 times or more, 100 times or less, more preferably 30 times or less, and particularly preferably 10 times or less. If it is less than 4 times, sufficient effects may not be exhibited.
[0066]
<Method for controlling catalyst activity>
The method for controlling the catalytic activity of the present invention is not particularly limited, but a method in which a catalyst complex itself is additionally added after the start of polymerization, and a ligand can be formed as a catalyst to form a catalyst, but there is no ligand. In this state, a metal compound having no or low catalytic activity is initially added to the system in excess of the ligand, and the ligand is added later, that is, the ligand of the metal complex of the polymerization catalyst. A method of controlling the polymerization rate by changing the activity of the catalyst during the polymerization by additionally adding is added after the polymerization is started. Of these, the latter is preferred although not limited.
[0067]
The latter is preferred because the catalyst complex is often heterogeneous and may be difficult to control and add. The catalyst complex and the ligand may be added alone or in the form of a solution or dispersion in a suitable solvent.
[0068]
The time when these compounds are added is not particularly limited. It may be added continuously, or may be added in divided portions.
[0069]
The amount to be added is not particularly limited. However, when a ligand is added, the activity cannot be further improved even if it is added beyond the coordination saturation with respect to the catalytic metal atom. The compound is preferably in excess with respect to the final ligand loading. Moreover, although a metal compound may be added later, it is preferable in terms of the process to add all necessary amounts from the beginning.
[0070]
Under ideal conditions, in atom transfer radical polymerization, the polymerization rate generally has a linear relationship with the amount of catalyst, a linear relationship with the amount of growth ends, and a linear relationship with the amount of monomer. It is thought that there is. Thus, although not particularly limited, for example, in batch polymerization, when attempting to make the polymerization amount of the monomer per unit time constant, the catalyst amount is set so that the product of the residual monomer amount and the active catalyst amount becomes constant. It will be good if you adjust. In addition, in the semi-batch polymerization in which the monomer is added, the total volume increases with the addition of the monomer, and the concentration of the catalyst and the growth terminal decreases. For example, the final catalyst can be improved so that the final polymerization rate is preferable. It is conceivable to determine the concentration and calculate the required amount of catalyst so that the product of the catalyst concentration and the growth end concentration at this time is equal to the product of the catalyst concentration and the growth end concentration at each time point during the monomer addition. .
[0071]
<Polymerization conditions>
Although superposition | polymerization is not specifically limited, It can carry out in the range of 0-200 degreeC, Preferably, it is the range of room temperature-150 degreeC.
The polymerization atmosphere is not particularly limited, but an oxygen-free atmosphere is preferable. Radicals are affected by oxygen, and in the presence of oxygen, the catalyst may be oxidized and lose activity.
[0072]
The polymerization mixture is preferably stirred well. In particular, when a catalytic metal complex or a ligand is added, sufficient stirring is preferable in order to diffuse quickly and uniformly.
[0073]
The polymerization method can be applied to batch polymerization, semi-batch polymerization in which monomers are added, continuous polymerization, and the like.
[0074]
<Terminal halogen residual ratio>
The method of the present invention has the effect of giving a polymer in which the terminal halogen groups remain at a high rate. The fact that the terminal halogen group remains at a high rate usually indicates that the residual rate of the halogen group is 20% or more, preferably 50% or more, more preferably 80% or more.
[0075]
In general, the residual rate of terminal halogen groups often becomes a problem when the polymerization rate of the monomer is high. When the polymerization rate is low, the polymerization rate (the amount of monomer polymerization per unit time) is sufficiently fast, and the end group disappearance, which is a competitive reaction, is not very noticeable, but when the polymerization rate increases, the polymerization rate As a result, the end group disappears. Further, even if the terminal group disappears after the polymerization rate is increased, the number average molecular weight, the molecular weight distribution, etc. are not so much affected, and are often overlooked. The method of the present invention is more effective at a high polymerization rate, and the polymerization rate of the monomer is preferably 50% or more, more preferably 80% or more, and particularly preferably 90% or more in terms of moles.
[0076]
<Molecular weight distribution>
According to the method of the present invention, a polymer having a narrow molecular weight distribution represented by the ratio of the weight average molecular weight and the number average molecular weight, which is generally measured by gel permeation chromatography, is obtained, although not limited. The molecular weight distribution is generally less than 1.8, preferably 1.5 or less, more preferably 1.2 or less, and particularly preferably 1.15 or less.
[0077]
<Scale>
The method of the present invention can be used not only for laboratory-level polymerization but also for larger scales, and the larger the scale, the greater the need to control the calorific value and the polymerization time, so the effect is great. The volume of the entire polymerization system is preferably 1 L or more, more preferably 10 L or more, and particularly preferably 1000 L or more.
[0078]
These four conditions found by the present invention; (1) substantially dehydrating conditions and / or (2) in the presence of a nitrile compound and / or (3) a ligand of a polymerization catalyst is added to the system Initiating the polymerization and / or (4) controlling the polymerization rate by changing the activity of the catalyst during the polymerization is effective as a method for controlling the atom transfer radical polymerization, respectively, Are closely related, and by combining them, a greater effect can be achieved.
[0079]
For example, the following series of operations can be mentioned. CuBr is mixed with dried acetonitrile to be complexed, and the dried monomer and initiator are added and heated. Here, dried pentamethyldiethylenetriamine is added to initiate polymerization. Thereafter, as the polymerization proceeds, dried pentamethyldiethylenetriamine is added to improve the catalytic activity.
[0080]
The polymer having a halogen group at the terminal with a high rate produced by the method of the present invention can be used as it is or by introducing various functional groups such as a hydroxyl group, an alkenyl group, and a silyl group by various conversion reactions, and a curable composition. It can be used for things.
[0081]
【Example】
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
In the following Examples, “number average molecular weight” and “molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)” were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, a GPC column packed with polystyrene cross-linked gel and chloroform as a GPC solvent were used.
The water content in the system was measured by the Karl Fischer titration method. The amount of terminal functional group is¹ Quantification was performed using 1 H-NMR.
[0082]
Example 1
In a 100 mL glass reaction vessel, dehydrated reagents; butyl acrylate (50.0 mL, 44.7 g, 349 mmol), cuprous bromide (625 mg, 4.36 mmol), pentamethyldiethylenetriamine (0.910 mL, 756 mg, 4 .36 mmol) and acetonitrile (5 mL) were charged, degassed under reduced pressure after cooling, and then replaced with nitrogen gas. After stirring well, methyl 2-bromopropionate (0.243 mL, 364 mg, 2.18 mmol) was added and stirred with heating at 70 ° C. Heating and stirring were continued at 70 ° C. for 7 hours, and sampling was performed from time to time. The reaction mixture was treated with activated alumina to remove the catalyst, and then the solvent and residual monomer were distilled off by heating under reduced pressure. The sampled product at 300 minutes had a polymerization rate of 67%, the number average molecular weight of the produced polymer was 16600 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.10. The functional group residual ratio based on the initiator was 0.8. The final product had a polymerization rate of 84%, a number average molecular weight of 21,500, a molecular weight distribution of 1.12, and a functional group residual rate of 0.7.
The amount of water contained in this polymerization system was 14% (120 ppm) with respect to the terminal.
[0083]
Example 2
Reagents dehydrated as in Example 1; butyl acrylate (50.0 mL, 44.7 g, 349 mmol), cuprous bromide (625 mg, 4.36 mmol), pentamethyldiethylenetriamine (0.910 mL, 756 mg, 4. 36 mmol), acetonitrile (5 mL) and diethyl 2,5-dibromoadipate (785 mg, 2.18 mmol) were polymerized at 70 ° C. for 8 hours to produce a polymer having bromo groups at both ends. The final product had a polymerization rate of 90%, a number average molecular weight of 23600, a molecular weight distribution of 1.14, and a functional group residual ratio of 1.46.
[0084]
Example 3
Dehydrated reagents as in Example 1; butyl acrylate (300.0 mL, 268 g, 2090 mmol), cuprous bromide (3.00 g, 20.9 mmol), pentamethyldiethylenetriamine (4.37 mL, 3. 63 g, 20.9 mmol), acetonitrile (30 mL), diethyl 2,5-dibromoadipate (18.8 g, 52.3 mmol) were polymerized at 70 ° C. for 450 minutes, and a polymer having bromo groups at both ends was obtained. Manufactured. In 340 minutes, the polymerization rate was 84%, the number average molecular weight was 4,700, the molecular weight distribution was 1.40, and the functional group residual rate was 1.90. The final product had a polymerization rate of 99%, a number average molecular weight of 5400, a molecular weight distribution of 1.37, and a functional group residual ratio of 1.73.
[0085]
Comparative Example 1
Reagent not dehydrated as in Example 1; butyl acrylate (10.0 mL, 8.94 g, 69.8 mmol), cuprous bromide (250 mg, 1.74 mmol), pentamethyldiethylenetriamine (0. Polymerization of 364 mL, 302 mg, 1.74 mmol), toluene (1 mL), methyl 2-bromopropionate (0.049 mL, 72.8 mg, 0.44 mmol) was carried out at 70 ° C. for 8 hours. In 120 minutes, the polymerization rate was 93%, the number average molecular weight was 22500, the molecular weight distribution was 1.26, and the functional group residual ratio was 0.14. The final product had a polymerization rate of 96%, a number average molecular weight of 24200, a molecular weight distribution of 1.28, and a functional group residual rate of 0.
[0086]
Reference example 1Model experiment of terminal group disappearance
Ethyl 2-bromobutyrate (1.29 ml, 1.70 g, 8.72 mmol), cuprous bromide (1.25 g, 8.72 mmol), pentamethyldiethylenetriamine (1.82 mL, 1.51 g, 8.72 mmol) Acetonitrile (5 mL) was heated and stirred at 70 ° C., and the residual amount of ethyl 2-bromobutyrate was quantified by gas chromatography. The results are shown together with Reference Example 2.
[0087]
Reference example 2
Distilled water (0.157 ml, 0.157 g, 8.72 mmol) was added to the conditions of Reference Example 1 and reacted under the same conditions. After about 10 hours, in Reference Example 1 in which water was not added, the residual ratio of ethyl 2-bromobutyrate was 56%, and in Reference Example 2 to which water was added, it was 38%.
[0088]
Example 4
CuBr (625 mg, 4.36 mmol), acetonitrile (5 ml), butyl acrylate (50 ml, 44.70 g, 348.8 mmol), pentamethyldiethylenetriamine (0.910 ml, 756 mg, 4.36 mmol) in a flask equipped with a stirrer. In addition, the mixture was degassed by cooling under reduced pressure and purged with nitrogen. This mixture was heated and stirred in an oil bath at 70 ° C. There was no catalyst adhering to the vessel wall, and the catalyst was uniformly diffused throughout the reaction system by stirring. To this mixture, methyl 2-bromopropionate (0.973 ml, 1.456 g, 8.72 mmol) as a polymerization initiator was added. It was confirmed by the temperature rise of the polymerization system that the polymerization started immediately. After 40 minutes, the temperature was raised to 86 ° C., and then gradually decreased to coincide with the bath temperature. The polymerization rate was 38% after 30 minutes and 84% after 60 minutes. Number average molecular weight Mn based on polystyrene by gel permeation chromatography after 30 minutes = 2400, ratio Mw / Mn = 1.18 of weight average molecular weight and number average molecular weight, Mn = 5100 after 60 minutes, ratio Mw / Mn = 1.11. In this reaction mixture, no catalyst was adhered to the vessel wall until the polymerization rate reached 99% after 240 minutes, and uniform diffusion by stirring was maintained.
[0089]
Example 5
CuBr (250 mg, 1.74 mmol), acetonitrile (5 ml), butyl acrylate (50 ml, 44.70 g, 348.8 mmol), pentamethyldiethylenetriamine (0.364 ml, 302 mg, 1.74 mmol) in a flask equipped with a stirrer. In addition, the mixture was degassed by cooling under reduced pressure and purged with nitrogen. This mixture was heated and stirred in an oil bath at 70 ° C. There was no catalyst adhering to the vessel wall, and the catalyst was uniformly diffused throughout the reaction system by stirring. To this mixture, methyl 2-bromopropionate (0.973 ml, 1.456 g, 8.72 mmol) as a polymerization initiator was added. It was confirmed by the temperature rise of the polymerization system that the polymerization started immediately. After 50 minutes, the temperature was raised to 77 ° C., and then gradually decreased to coincide with the bath temperature. The polymerization rate was 23% after 30 minutes, 46% after 60 minutes, and 84% after 120 minutes. Number average molecular weight Mn based on polystyrene by gel permeation chromatography after 60 minutes = 2700, ratio Mw / Mn = 1.15 of weight average molecular weight and number average molecular weight, Mn = 4600 after 120 minutes, ratio Mw / Mn = 1.11. In this reaction mixture, no catalyst was adhered to the vessel wall until the polymerization rate reached 95% after 240 minutes, and uniform diffusion by stirring was maintained.
By combining the results of Examples 4 and 5, the addition of a nitrile compound (acetonitrile in this example) allowed the polymerization catalyst to diffuse uniformly throughout the system throughout the polymerization. It is clear that the polymerization rate can be controlled.
[0090]
Comparative Example 2
CuBr (625 mg, 4.36 mmol), toluene (5 ml), butyl acrylate (50 ml, 44.70 g, 348.8 mmol), pentamethyldiethylenetriamine (0.910 ml, 756 mg, 4.36 mmol) in a flask equipped with a stirrer. In addition, the mixture was degassed by cooling under reduced pressure and purged with nitrogen. This mixture was heated and stirred in an oil bath at 70 ° C. At this point, some catalyst had already adhered to the vessel wall. To this mixture, methyl 2-bromopropionate (0.973 ml, 1.456 g, 8.72 mmol) as a polymerization initiator was added. It was confirmed by the temperature rise of the polymerization system that the polymerization started immediately. After 25 minutes, the temperature was raised to 104 ° C., and then gradually decreased to coincide with the bath temperature. The polymerization rate was 43% after 15 minutes and 90% after 30 minutes. Number average molecular weight Mn based on polystyrene by gel permeation chromatography after 15 minutes = 1700, ratio Mw / Mn = 1.34 of weight average molecular weight to number average molecular weight, Mn = 5100 after 30 minutes, ratio Mw / Mn = 1.16. The reaction mixture was stopped when the polymerization rate reached 96% after 60 minutes, but as the polymerization proceeded, the adhesion of the catalyst to the vessel wall increased.
[0091]
Comparative Example 3
CuBr (250 mg, 1.74 mmol), toluene (5 ml), butyl acrylate (50 ml, 44.70 g, 348.8 mmol), pentamethyldiethylenetriamine (0.364 ml, 302 mg, 1.74 mmol) in a flask equipped with a stirrer In addition, the mixture was degassed by cooling under reduced pressure and purged with nitrogen. This mixture was heated and stirred in an oil bath at 70 ° C. There was no catalyst adhering to the vessel wall, and the catalyst was uniformly diffused throughout the reaction system by stirring. To this mixture, methyl 2-bromopropionate (0.973 ml, 1.456 g, 8.72 mmol) as a polymerization initiator was added. No exotherm was observed and the polymerization hardly proceeded even after 240 minutes.
Comparing the results of Comparative Examples 2 and 3 and comparing with the results of Examples 4 and 5, under conditions where no nitrile compound was added, the catalyst was not sufficiently diffused and the catalyst was observed to adhere to the vessel wall. In addition, it is apparent that it is difficult to control the reaction rate when the amount of the catalyst is changed.
[0092]
Example 6
CuBr (1.251 g, 8.72 mmol), acetonitrile (5 ml) and butyl acrylate (50 ml, 44.70 g, 348.8 mmol) were added to a flask equipped with a stirrer, and the mixture was degassed by cooling and purged with nitrogen. This mixture was heated and stirred in an oil bath at 70 ° C. CuBr became white crystals, no catalyst adhered to the vessel wall, and evenly diffused throughout the reaction system by stirring. To this mixture, methyl 2-bromopropionate (0.973 ml, 1.456 g, 8.72 mmol) as a polymerization initiator was added. The mixture was heated and stirred for 360 minutes, but polymerization did not proceed at all.
[0093]
As soon as pentamethyldiethylenetriamine (1.821 ml, 1.511 g, 8.72 mmol) was added thereto, a green complex appeared in the entire reaction system, which was uniformly diffused by stirring. It was confirmed that the polymerization was initiated by exotherm at the same time as the addition. The polymerization rate was 85% after 15 minutes and 96% after 30 minutes. In the reaction mixture, no catalyst was adhered to the vessel wall until the end, and uniform diffusion by stirring was maintained.
From this result, it was confirmed that the complex coordinated with the nitrile compound has almost no catalytic activity in the absence of the amine ligand. Therefore, when the transition metal atom is excessive with respect to the catalyst ligand such as an amine ligand, it is confirmed that the transition metal atom considered not to coordinate with the catalyst ligand has no catalytic activity. It was.
[0094]
Example 7
CuBr (250 mg, 1.74 mmol) and acetonitrile (5 ml) were placed in a 100 ml round bottom flask equipped with a stirrer and stirred well. To this was added butyl acrylate (15.0 ml, 13.4 g, 0.105 mol), degassed by freezing under reduced pressure, and purged with nitrogen. The mixture was stirred for 30 minutes at 70 ° C. in an oil bath. The light green precipitate of CuBr disappeared and the white crystals were uniformly dispersed. While stirring well, pentamethyldiethylenetriamine (0.0583 ml, 48.4 mg, 0.28 mmol) (hereinafter referred to as triamine) was added. The color of the mixture became light green. The difunctional initiator 2,5-dibromoadipate diethyl (1.570 g, 4.36 mmol) was dissolved in butyl acrylate (5.0 ml, 4.47 g, 34.9 mmol) at 70 ° C. Things were added. The polymerization started with a slight exotherm. After 30 minutes, butyl acrylate (30.0 ml, 26.8 g, 0.209 mol) was continuously added dropwise at a rate of about 6.3 ml / hour. From time to time, triamine (0.10 ml, 83 mg, 0.48 mmol) was added after 2 hours while sampling and checking the residual amount of monomer by gas chromatography. A slight exotherm was observed as soon as the triamine was added, confirming that the polymerization rate was restored. After this, triamine (0.06 ml, 50 mg, 0.29 mmol) was added after 4 hours and 30 minutes, and triamine (0.10 ml, 83 mg, 0.48 mmol) was added after 5 hours and 10 minutes. The polymerization was completed after 7 hours. A graph of the added amount of monomer, the remaining amount, and the consumption amount with respect to time is shown in FIG. It is clear that butyl acrylate is consumed as it is added and the remaining amount is well controlled. The polystyrene-based number average molecular weight of the product by gel permeation chromatography increased as set in proportion to the monomer consumption. The polymerization rate at the end of the polymerization was 93%, the number average molecular weight Mn of the product was 11700, the molecular weight distribution Mw / Mn = 1.18 represented by the ratio of the weight average molecular weight to the number average molecular weight, The remaining amount was 1.8 per molecule. The highest internal temperature throughout the polymerization is bath temperature + 4 ° C., and together with the above results, it is clear that the polymerization rate was very well controlled.
[0095]
Example 8
CuBr (3.00 g, 20.9 mol) and acetonitrile (30 ml) were placed in a 500 ml round bottom flask equipped with a stirrer and stirred well. To this was added butyl acrylate (100.0 ml, 89.4 g, 0.680 mol), and the mixture was degassed by freezing under reduced pressure and replaced with nitrogen. The mixture was stirred for 30 minutes at 70 ° C. in an oil bath. The light green precipitate of CuBr disappeared and the white crystals were uniformly dispersed. To this was added bifunctional initiator diethyl 2,5-dibromoadipate (18.83 g, 52.3 mmol) dissolved in butyl acrylate (20.0 ml, 17.9 g, 140 mmol). At this point, polymerization did not proceed at all even in the presence of the initiator. At 70 ° C., pentamethyldiethylenetriamine (0.175 ml, 145 mg, 0.84 mmol) (hereinafter referred to as triamine) was added thereto with good stirring. The color of the mixture became light green and polymerization started immediately with a slight exotherm. After 30 minutes, butyl acrylate (180.0 ml, 161 g, 1.26 mol) was continuously added dropwise at a rate of about 38 ml / hour. Occasionally sampling and adding 0.02 ml (17 mg, 0.10 mmol) to 0.04 ml (33 mg, 0.19 mmol) of triamine every 30 minutes to 1 hour while checking the residual amount of monomer by gas chromatography. . A slight exotherm was observed as soon as the triamine was added, confirming that the polymerization rate was restored. The polymerization was completed after 7 hours and 30 minutes. A graph of the added amount of monomer, the remaining amount, and the consumption amount versus time is shown in FIG. It is clear that butyl acrylate is consumed as it is added and the remaining amount is well controlled. The polystyrene-based number average molecular weight of the product by gel permeation chromatography increased as set in proportion to the monomer consumption. The polymerization rate at the end of the polymerization was 99%, the number average molecular weight Mn of the product was 5400, the molecular weight distribution Mw / Mn = 1.37 expressed by the ratio of the weight average molecular weight to the number average molecular weight, The remaining amount was 1.7 per molecule. Although the polymerization scale was larger than that of Example 7, it was clear that the internal temperature was kept at a bath temperature of + 8 ° C. or lower throughout the polymerization, and the polymerization rate was controlled very well together with the above results. .
[0096]
Example 9
CuBr (1.251 g, 8.72 mmol), acetonitrile (5 ml) and butyl acrylate (50 ml, 44.70 g, 348.8 mmol) were added to a flask equipped with a stirrer, and the mixture was degassed by cooling and purged with nitrogen. This mixture was heated and stirred in an oil bath at 70 ° C. CuBr became white crystals, no catalyst adhered to the vessel wall, and evenly diffused throughout the reaction system by stirring. To this mixture, methyl 2-bromopropionate (0.973 ml, 1.456 g, 8.72 mmol) as a polymerization initiator was added. The mixture was heated and stirred for 360 minutes, but polymerization did not proceed at all.
[0097]
As soon as pentamethyldiethylenetriamine (1.821 ml, 1.511 g, 8.72 mmol) was added thereto, a green complex appeared in the entire reaction system, which was uniformly diffused by stirring. It was confirmed that the polymerization was initiated by exotherm at the same time as the addition. The polymerization rate was 85% after 15 minutes and 96% after 30 minutes.
In the reaction mixture, no catalyst was adhered to the vessel wall until the end, and uniform diffusion by stirring was maintained.
From this result, it was confirmed that the complex coordinated with the nitrile compound has almost no catalytic activity in the absence of the amine ligand. Therefore, when the transition metal atom is excessive with respect to the catalyst ligand such as an amine ligand, it is confirmed that the transition metal atom considered not to coordinate with the catalyst ligand has no catalytic activity. It was.
[0098]
Comparative Example 4
CuBr (625 mg, 4.36 mmol), acetonitrile (5 ml), pentamethyldiethylenetriamine (0.910 ml, 756 mg, 4.36 mmol) were placed in a 100 ml round bottom flask equipped with a stirrer, and butyl acrylate (20.0 ml, 17 ml) was added. 0.9 g, 140 mmol) was added, and the mixture was degassed by freezing under reduced pressure and purged with nitrogen. The mixture was stirred for 30 minutes at 70 ° C. in an oil bath. After cooling a little, a monofunctional initiator, methyl 2-bromopropionate (0.973 ml, 1.46 g, 8.72 mmol) was added, heated in an oil bath at 70 ° C., and butyl acrylate (30 (0.0 ml, 26.8 g, 209 mmol) was continuously added dropwise at a rate of 6.3 ml / min. An exotherm occurred immediately, and the internal temperature rose to 87 ° C. The polymerization started with a slight exotherm. After 30 minutes, butyl acrylate (30.0 ml, 26.8 g, 0.209 mol) was continuously added dropwise at a rate of about 6.3 ml / hour. Sampling was performed occasionally, and the residual amount of monomer was confirmed by gas chromatography. A graph of the added amount of monomer, the remaining amount, and the consumption amount versus time is shown in FIG. It can be confirmed that the consumption of butyl acrylate is very large in the initial stage due to the temperature rise, and thereafter the residual amount tends to increase. Even when the polymerization was terminated after 8 hours, the polymerization rate of butyl acrylate was 76%. From this result, it can be confirmed that there is a problem in controlling the polymerization rate in the ordinary method.
[0099]
Example 10Polymerization using TREN ligand
In a 30 mL glass reaction vessel, cuprous bromide (12.5 mg, 0.0871 mmol) and acetonitrile (1.0 mL) were added under a nitrogen atmosphere, and the mixture was heated and stirred at 70 ° C. to form a complex. To this was added a solution of diethyl 2,5-dibromoadipate (0.314 g, 0.872 mmol) in butyl acrylate (10.0 mL, 69.8 mmol). While stirring at 70 ° C., tris (diethylaminoethyl) amine (16 μL, 0.0699 mmol) was added in small portions. After 310 minutes, the heating was stopped, and at this time, the consumption rate of butyl acrylate was 93.6% from the GC measurement. The mixture was diluted with toluene and treated with activated alumina, and then the volatile components were distilled off by heating under reduced pressure to obtain a colorless transparent polymer. According to GPC measurement (polystyrene conversion) of the obtained polymer, the number average molecular weight was 12,100, the weight average molecular weight was 13400, the molecular weight distribution was 1.10, and the bromine group introduction rate based on the number average molecular weight was 1.99.
[0100]
Example 114kgBA semi-batch polymerization
A 10 L glass reaction vessel was charged with cuprous bromide (35.3 g, 0.246 mol) and acetonitrile (470 mL) under a nitrogen atmosphere and heated at 70 ° C. for 60 minutes. To this was added butyl acrylate (940 mL, 6.56 mol) and the mixture was further stirred for 60 minutes. When pentamethyldiethylenetriamine (2.00 mL, 9.58 mmol) was added thereto, a mild exotherm of the reaction solution was observed, and polymerization started. After 55 minutes, butyl acrylate (3.76 L, 26.2 mol) was added over 260 minutes. During this time, pentamethyldiethylenetriamine (5.00 mL, 24.0 mmol) was added in small portions while sampling the reaction solution and monitoring the reaction. When pentamethyldiethylenetriamine was added, a mild exotherm was quickly observed, confirming that the catalytic activity was improved. Heating was continued for another 90 minutes after the addition of butyl acrylate. At this time, the consumption rate of butyl acrylate was 97.1% from GC measurement. The mixture was diluted with toluene and treated with activated alumina, and then the volatile components were distilled off by heating under reduced pressure to obtain a colorless transparent polymer. According to GPC measurement (polystyrene conversion) of the obtained polymer, the number average molecular weight was 10,800, the weight average molecular weight was 12400, the molecular weight distribution was 1.15, and the bromine group introduction rate based on the number average molecular weight was 1.8.
[0101]
Example 125kg alkenyl-terminated BA semi-batch polymerization
In a 10 L glass reaction vessel, cuprous bromide (41.9 g, 0.293 mol) and acetonitrile (559 mL) were charged under a nitrogen atmosphere and heated at 70 ° C. for 45 minutes. To this was added butyl acrylate (1.12 L, 7.80 mol) and heated for an additional 40 minutes. When pentamethyldiethylenetriamine (4.00 mL, 19.2 mmol) was added thereto, an exotherm of the reaction solution was observed. Stirring was continued at 70 ° C., and 60 minutes later, butyl acrylate (4.47 L, 31.2 mol) was added over 190 minutes. During this time, pentamethyldiethylenetriamine (4.00 mL, 19.2 mmol) was added in small portions while sampling the reaction solution and monitoring the reaction. When pentamethyldiethylenetriamine was added, a mild exotherm was quickly observed, confirming that the catalytic activity was improved. Heating was continued for another 60 minutes after the addition of butyl acrylate. At this time, the consumption rate of butyl acrylate was 93.2% from GC measurement. 1,7-octadiene (1.44 L, 9.75 mol) and pentamethyldiethylenetriamine (20.5 mL, 98.2 mmol) were added and heating was continued for 210 minutes. After diluting the mixture with toluene and treating with activated alumina, the volatile component was heated and evaporated under reduced pressure to obtain a pale yellow polymer. According to GPC measurement (polystyrene conversion) of the obtained polymer, the number average molecular weight was 14,000, the weight average molecular weight was 18800, the molecular weight distribution was 1.34, and the alkenyl group introduction rate based on the number average molecular weight was 2.49.
[0102]
Example 13
Under a nitrogen atmosphere, cuprous bromide (0.375 g, 2.62 mmol) and acetonitrile (1.67 mL) were added to a 100 mL glass reaction vessel, and the mixture was heated and stirred at 70 ° C. for 25 minutes. A solution prepared by dissolving diethyl 2,5-dibromoadipate (1.57 g, 4.36 mmol) in butyl acrylate (50.0 mL, 0.349 mol) was added thereto. The mixture was stirred at 70 ° C. for 60 minutes. When pentamethyldiethylenetriamine (90.0 μL, 0.437 mmol) was added thereto, polymerization started immediately. The final polymerization rate of butyl acrylate was 98%.
[0103]
【The invention's effect】
According to the present invention, a vinyl polymer in which a terminal halogen group remains at a high rate by atom transfer radical polymerization can be obtained. In addition, even when a heterogeneous polymerization catalyst is used, the catalyst does not adhere to the vessel wall and can be uniformly diffused by stirring, facilitating reaction control when the polymerization is scaled up. . Furthermore, this effect makes it easy to adjust the polymerization rate depending on the amount of catalyst added. In atom transfer radical polymerization, the polymerization rate can be arbitrarily adjusted during the polymerization reaction, and the amount of heat generated can also be controlled. This generally provides a method for suppressing initial heat generation and shortening the polymerization time in living polymerization in which the balance between large initial heat generation and polymerization time is a problem. This effect increases as the scale increases, and the present invention is very important in the industrialization of atom transfer radical polymerization.
[Brief description of the drawings]
FIG. 1 is a graph of monomer addition amount, residual amount, and consumption amount over time in Example 7.
FIG. 2 is a graph with respect to time of addition amount, residual amount, and consumption amount of monomer in Example 8.
FIG. 3 is a graph of monomer addition amount, remaining amount, and consumption amount with respect to time in Comparative Example 4;

Claims (16)

Atom transfer radical polymerization of vinyl monomers catalyzed by transition metal complexes of copper, nickel, ruthenium or iron is added to the catalyst during the polymerization by adding the ligand of the metal complex of the polymerization catalyst after the addition of the initiator. A polymerization method characterized by controlling the polymerization rate by changing the activity of
A polymerization method wherein the ligand of the metal complex is a polyamine compound, a bipyridyl compound or an aliphatic amine compound. The polymerization method according to claim 1, which is carried out in the presence of a nitrile compound. Polymerization catalyst, polymerization method according to any one of claim 1 to 2 which is a copper complex. The polymerization method according to claim 3 , wherein the copper complex is prepared from CuCl or CuBr. The polymerization method according to any one of claims 1 to 4 , wherein the vinyl monomer is a (meth) acrylic monomer. The polymerization method according to claim 5 , wherein the (meth) acrylic monomer is an acrylate ester monomer. The polymerization method according to any one of claims 1 to 4 , wherein the vinyl monomer is a styrene monomer. The polymerization method according to any one of claims 1 to 7 , wherein the water content is 300 ppm or less in the entire polymerization system. The polymerization method according to claim 8 , wherein the water content is 50 ppm or less in the entire polymerization system. The polymerization method according to any one of claims 1 to 7 , wherein the amount of water is equal to or less than the molar amount relative to the amount of halogen groups at the growth end of the polymerization in the entire polymerization system. The polymerization method according to any one of claims 2 to 10 , wherein the nitrile compound is acetonitrile. The polymerization method according to any one of claims 2 to 11 , wherein the addition amount of the nitrile compound is 4 to 100 times in molar ratio with respect to the amount of the transition metal atom. Polyamine compounds, polymerization process of claim 1, wherein those having an amino group three or more. Polyamine compound having an amino group three or more, pentamethyldiethylenetriamine, hexamethyl (2-aminoethyl) amine, hexamethyltriethylenetetramine, and claim 13, wherein at least one selected from the group consisting of bis-picolylamine amine Polymerization method. Polymerization, the polymerization method according to any one of claims 1 to 14 as a batch polymerization. The polymerization method according to any one of claims 1 to 14 , wherein the polymerization is semi-batch polymerization.

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