Synthesis of Block Copolymers Utilizing Alkoxycarbonylation or Aminocarbonylation of Growing Chain End in Pd-Catalyzed Living Polymerization of Olefins

Diimine Pd catalysts have been known to promote the living polymerization of olefins. Treatment of the living polyolefin with carbon monoxide followed by the addition of alcohols or amines results in alkoxycarbonylation or aminocarbonylation of the living chain end. The alkoxycarbonylation or aminocarbonylation using polymers having hydroxy or amino terminal group leads to direct linking of the end-functionalized polymer with the living polyolefins. The introduction of hydroxy, amino, and 2-bromoisobutyrate functional groups on the terminal of the polyolefin is also possible by the alkoxycarbonylation or aminocarbonylation. The end-functionalized polyolefin having 2-bromoisobutyryl terminal group acts as a macroinitiator for living radical polymerization of styrene to give poly(olefin-block-styrene).