A Facile Approach to Produce Star Polymers Based on Coordination Polymerization.

Many efforts have been devoted to preparing star polymers. Research into coordination polymerization, the most powerful stereoselective process to endow polymers with superb properties, lags far behind those achieved by radical polymerization and ionic polymerization. Herein, we propose a facile strategy to prepare star polymers with regular arms based on coordination polymerization via an insertion reaction between the carbon-heteroatom unsaturated bond and the metal-alkyl species. Terminating a living cis-1,4-selective isoprene polymerization by using isocyanate as cross-linker (CL), a star polyisoprene with low polydispersity was obtained in high yield (91.8 %). A kinetic study showed the star polymer was formed via a step-growth procedure. The types of CL and the ratio of [CL] 0  : [Cat.] 0 are key factors to determine the arm number and the yield of star polymer. Finally, synthetic IR rubber with a green strength up to 1.99 MPa superior to natural rubber (1.43 MPa) was prepared for the first time.