Facile Synthesis of Functional Polyperoxides by Radical Alternating Copolymerization of 1,3-Dienes with Oxygen

We have developed a facile synthesis of degradable polyperoxides by the radical alternating copolymerization of 1,3-diene monomers with molecular oxygen at an atmospheric pressure. In this review, the synthesis, the degradation behavior, and the applications of functional polyperoxides are Summarized. The alkyl sorbates as the conjugated 13-dienes gave a regiospecific alternating copolymer by exclusive 5,4-addition during polymerization and the resulting polyperoxides decomposed by the homolysis of a peroxy linkage followed by successive P-scissions. The preference of 5,4-addition was well rationalized by theoretical calculations. The degradation of the polyperoxides occurred with various stimuli, Such as heating, UV irradiation, a redox reaction with amines, and an enzyme reaction. The various functional polyperoxides were synthesized by following two methods, one is the direct copolymerization of functional 1,3-dienes, and the other is the functionalization of the precursor polyperoxides. Water soluble polyperoxides were also prepared, and the LCST behavior and the application to a drug carrier in the drug delivery system were investigated. In order to design various types of degradable polymers and gels we developed a method for the introduction of dienyl groups into the precursor polymers. The resulting dienyl-functionalized polymers were used for the degradable gels. The degradable branched copolymers showed a microphase-separated structure, which changed owing to the degradation of the polyperoxide segments. (C) 2009 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 9: 247-257; 2009: Published online in Wiley InterScience (www.interscience.wiley.com) DOI 10.1002/tcr.200900009