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Polymer Design by Iniferter Technique

采用 Iniferter 技术进行聚合物设计

基本信息

批准号：
60850163
负责人：
OTSU Takayuki
金额：
$ 2.56万
依托单位：
Osaka City University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Developmental Scientific Research
财政年份：
1985
资助国家：
日本
起止时间：
1985 至 1986
项目状态：
已结题

项目摘要

Studies on novel polymer synthesis and design were investigated by using various thermal and photo-iniferters. The results obtained are summerized as follows.1. Phenylazotriphenylmethane and tetraphenylsuccinodinitrile were found to serve as thermal iniferters and to induce living radical polymerization of methyl methacrylate (MMA). The oligomer and polymer obtained could further act as iniferters of the polymerization of styrene(St), and the AB block copolymer was obtained efficiently.2. Benzyl diethyldithiocarbamate and p-xylylene bis(diethyldithiocarbamate) were observed to serve as excellent photo-iniferters of St and MMA leading to AB and ABA block copolymers consisting of homopolymer and random or alternating copolymer sequence, respectively. When tetrakis(diethyldithiocarbamyl)benzene was used as a tetrafunctional photoiniferter, the star or cross-linked polymer was produced. Moreover, the tailor-made synthesis of graft copolymer was possible by using vinylbenzyl diethyldithiocarbamate as a monomer-iniferter.3. Since it was difficult to synthesize block copolymers free from homopolymers by iniferter technique, the preparation of pure multiblock copolymers was impossible. So, the dithiocarbamate iniferter attached to a polystyrene gel through a hydrolyzable ester spacer was used. After repeated polymerizations and extractions, pure tri- and tetrablock copolymers were isolated by alkaline hydrolysis.

利用不同的热和光干涉仪对新型聚合物的合成和设计进行了研究。所获得的结果总结如下：1.苯基偶氮三苯基甲烷和四苯基丁二腈被发现作为热诱导剂，并诱导甲基丙烯酸甲酯(MMA)的活性自由基聚合。所得齐聚物和聚合物可进一步作为苯乙烯(St)聚合的引发剂，有效地得到了AB嵌段共聚物。二乙基二硫代氨基甲酸苄酯和对二甲苯二(二乙基二硫代氨基甲酸酯)是St和MMA的优良光传导剂，它们分别由均聚物和无规或交替的共聚序列组成AB和ABA嵌段共聚物。当四(二乙基二硫代氨基甲酰基)苯被用作四官能团的光诱导剂时，生成星形或交联型聚合物。此外，以乙烯基苄基二乙基二硫代氨基甲酸酯为单体合成接枝共聚物是有可能的。由于不含均聚物的嵌段共聚物的合成难度较大，因此制备纯多嵌段共聚物是不可能的。因此，二硫代氨基甲酸二硫代氨基甲酸酯通过可水解酯间隔连接到聚苯乙烯凝胶上。经过多次聚合和提取，碱水解法分离得到纯的三嵌段和四嵌段共聚物。