Polymerization of Hydroxy-Containing Diazoacetates: Synthesis of Hydroxy-Containing 鈥淧oly(substituted methylene)s鈥?by Palladium-Mediated Polymerization and Poly(ester鈥揺ther)s by Polycondensation throu

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• 作者：Hiroaki Shimomoto ; Erika Itoh ; Tomomichi Itoh ; Eiji Ihara ; Naohiro Hoshikawa ; Naoki Hasegawa
• 刊名：Macromolecules
• 出版年：2014
• 出版时间：July 8, 2014
• 年：2014
• 卷：47
• 期：13
• 页码：4169-4177
• 全文大小：381K
• ISSN：1520-5835

文摘

Two types of polymerization of hydroxy-containing diazoacetates are described. The polymerization of hydroxy-containing diazoacetates using palladium complexes proceeded successfully under chain-growth mechanism even without a protecting group to give C鈥揅 main chain polymers bearing a hydroxy-containing ester substituent on each carbon of the backbone. The resulting polymers had a slightly branched structure due to chain transfer reaction with the hydroxy groups, while the polymers obtained by polymerization of silyl-protected diazoacetates and subsequent deprotection had a completely linear structure. The hydroxy-containing polymers with an appropriate hydrophilic/hydrophobic balance showed a lower critical solution temperature-type phase separation in an aqueous medium. On the other hand, the polymerization of hydroxy-containing diazoacetates using InCl₃ as a catalyst proceeded under step-growth mechanism to give oligomers having a distinct repeating unit (ester鈥揺ther), where a new ether bond was generated through O鈥揌 insertion reaction of diazocarbonyl groups into hydroxy groups.