权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

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（苯并苯基苯乙烯或二苯二硒）在苯乙烯和甲基丙烯酸甲酯自由基聚合中起光干扰剂的作用。苯基苯基硒化物的碳-硒键在光照射下发生均解裂解，生成苯基硒基和苯基自由基，苯乙烯单体插入到这些自由基上，生成更高分子量的聚合物。所得的聚苯乙烯ω端有苯基硒基，也可作为聚合光干扰剂，可用于嵌段共聚物的合成。此外，ω端苯基硒基被过氧化氢消除，形成碳碳双键，随后得到的聚苯乙烯转化为环氧端聚苯乙烯，然后是大单体。以1,4 -二（对叔丁基苯基硒甲基）苯为双官能团光干扰剂，用于苯乙烯和甲基丙烯酸甲酯的聚合。在甲基丙烯酸甲酯存在下，将两端有苯基硒基的远旋聚苯乙烯作为聚合光干扰剂进行光照射，可有效地与ABA型三嵌段共聚物相对应。合成了一种新型含硒乙烯基单体对苯基硒甲基苯乙烯，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，将该单体的共聚物与苯乙烯作为聚合物光干扰物进行光照射，有效地得到接枝共聚物。另一方面，该单体在紫外线照射下均聚得到超支化聚苯乙烯。