Polymer Design by Iniferter Technique

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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.