Living Radical Polymerization using Organic Selenium Compounds

使用有机硒化合物的活性自由基聚合

基本信息

批准号：
10650865
负责人：
YUKI Yasuo
金额：
$ 2.3万
依托单位：
Nagoya Institute of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1998
资助国家：
日本
起止时间：
1998 至 2000
项目状态：
已结题

项目摘要

Organic selenium compounds are very useful in organic chemistry. We found that the organic selenium compounds (benzyl phenyl senide or diphenyl diselenide) works as a photoiniferter in radical polymerization of styrene and methyl methacrylate.The carbon-selenium bond of benzyl phenyl selenide undergoes homolytic cleavage on photoirradiation to afford phenylseleno and benzyl radicals, and styrene monomer insert to these radicals to afford polymer with higher molecular weight. The resulting polystyrene having phenylseleno group at theω-end works also as a polymeric photoiniferter, and can apply to the synthesis of block copolymer. Further, the phenylseleno group at theω-end is eliminated by hydrogen peroxide to give carbon-carbon double bond and, followed the resulting polystyrene is converted to epoxy terminated polystyrene, and then macromonomer.1, 4-Bis (p-tert-butylphenylselenomethyl) benzene was used as a bifunctional photoiniferter for the polymerization of styrene and methyl methacrylate. Photoirradiation of telechelic polystyrene having phenylseleno groups at both ends as polymeric photoiniferter in the presence of methyl methacrylarte afforded effectively corresponding to the ABA type triblock copolymers.p-Phenylselenomethylstyrene was synthesized as a novel-selenium-containing vinyl monomer and polymerized with azobisisobutyronitrile to afford corresponding homopolymer. Photoirradiation of the copolymer of this monomer and styrene as a polymeric photoiniferter in the presence of methyl methacrylarte effectively afforded a graft copolymer. On the other hand, the homopolymerization of this monomer under UV irradiation gave a hyperbranched polystyrene.

有机硒化合物在有机化学中非常有用。我们发现有机硒化合物（苄基苯基硒化物或二苯基二硒化物）在苯乙烯和甲基丙烯酸甲酯的自由基聚合中充当光引发剂。苄基苯基硒化物的碳-硒键发生均裂。光照射产生苯基硒基和苄基自由基以及苯乙烯所得的在ω-末端具有苯基硒基的聚苯乙烯也可作为聚合光引发剂，并且可以应用于嵌段共聚物的合成。用过氧化氢消除，得到碳-碳双键，然后将所得聚苯乙烯转化为环氧封端的聚苯乙烯，然后形成大分子单体。 1、 4-双（对叔丁基苯基硒甲基）苯用作苯乙烯和甲基丙烯酸甲酯的聚合的双功能光引发剂，在甲基丙烯酸甲酯存在下，对两端具有苯基硒基的遥爪聚苯乙烯作为聚合光引发剂进行光照射，得到有效的对应产物。 ABA型三嵌段合成对苯基硒甲基苯乙烯作为一种新型含硒乙烯基单体，并与偶氮二异丁腈聚合得到相应的均聚物。在甲基丙烯酸甲酯存在下，对该单体和苯乙烯的共聚物作为聚合光引发剂进行光照射，有效地得到接枝共聚物。另一方面，该物质的均聚单体在紫外线照射下产生超支化聚苯乙烯。