Protection and polymerization of functional monomers, 14. Anionic living polymerization of 4‐[N,N‐bis(trimethylsilyl)‐aminomethyl]styrene and 4‐{2‐[N,N‐bis(trimethylsilyl)amino]ethyl}styrene
Protection and polymerization of functional monomers, 14. Anionic living polymerization of 4‐[N,N‐bis(trimethylsilyl)‐aminomethyl]styrene and 4‐{2‐[N,N‐bis(trimethylsilyl)amino]ethyl}styrene
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功能单体的保护和聚合，14. 4-[N,N-双(三甲基硅基)氨基甲基]苯乙烯和4-{2-[N,N-双(三甲基硅基)氨基]乙基}苯乙烯的阴离子活性聚合
DOI：
10.1002/macp.1989.021901120
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发表时间：
1989
期刊：
影响因子：
--
通讯作者：
S. Nakahama
中科院分区：
文献类型：
--
作者：
Ken Suzuki;A. Hirao;S. Nakahama
4-[N，N-双（三甲基甲硅烷基）氨基甲基]苯乙烯（1）和4-{2-[N，N-双（三甲基甲硅烷基）氨基]乙基}苯乙烯（2）的阴离子聚合在−78°C下在四氢呋喃（THF）/戊烷混合物中与丁基锂、低聚（α-甲基苯乙烯基）锂、低聚（α-甲基苯乙烯基）钾和枯基钾进行。当丁基锂或低聚（α-甲基苯乙烯基）锂作为引发剂时，1和2的聚合不发生链转移和终止反应，得到稳定的“活性聚合物”。所得聚合物具有可预测的分子量和窄的分子量分布（重均分子量与数均分子量之比，Mw/Mn = 1.04 - 1.14）。在温和的酸性条件下（pH 3-5的THF/水溶液），聚合物中的NSi键完全断裂，得到结构明确的聚（4-氨甲基）苯乙烯和聚[4-（2-氨乙基）苯乙烯]。苯乙烯-嵌段-聚（1）-嵌段-聚苯乙烯和苯乙烯-嵌段-聚（2）-嵌段-聚苯乙烯的三嵌段共聚物通过苯乙烯与活性聚（1）或活性聚（2）的顺序聚合容易地以定量产率制备。
Anionic polymerization of 4-[N,N-bis(trimethylsilyl)aminomethyl]styrene (1) and 4-{2-[N,N-bis(trimethylsilyl)amino]ethyl}styrene (2) were carried out at −78°C in tetrahydrofuran (THF)/pentane mixtures with butyllithium, oligo(α-methylstyryl)lithium, oligo(α-methylstyryl)potassium, and cumylpotassium. Polymerizations of 1 and 2 proceed without chain transfer and termination reactions to give stable “living polymers” when butyllithium or oligo(α-methylstyryl)lithium are used as initiator. The resulting polymers have predictable molecular weights and narrow molecular weight distributions (ratio of weight- to number-average molecular weights, Mw/Mn = 1,04–1,14). Under mild acidic conditions (pH 3–5 in THF/water), cleavage of the NSi bonds in the polymers is completely achieved to give well-defined poly(4-aminomethyl)styrene and poly[4-(2-aminoethyl)styrene]. The triblock copolymers of polystyrene-block-poly(1)-block-polystyrene and polystyrene-block-poly(2)-block-polystyrene are readily prepared in quantitative yields by sequential polymerization of styrene with living poly(1) or living poly(2).