Living cationic polymerization of vinyl monomers: Mechanism and synthesis of new polymers

Abstract This paper reviews the recent progress in our research on the living cationic polymerization of vinyl compounds by the hydrogen iodide/iodine (HI/I2) initiating system, with emphasis on its scope, mechanism, and applications to new polymer synthesis. The scope of the living cationic polymerization has been expanded to include vinyl ethers, propenyl ethers, unsaturated cyclic ethers, and styrene derivatives as monomers. The initiation/propagation mechanism was discussed on the basis of recent direct analysis on the living system by NMR and UV/visible spectroscopy. The proposed mechanism involves a quantitative formation of Hl‐vinyl ether adduct [CH3‐CH(OR)‐I; l] that is by itself incapable of initiating polymerization. In the presence of iodine, however, the CH‐I bond of l is electrophilically activated by iodine and living propagation occurs via the insertion of vinyl ether to the activated CH‐I bond. Such living polymerizations were found to proceed in not only nonpolar but polar solvents (CH2Cl2) as well. Quenching the living end with amines gave polymers capped with an amino group that in turn enabled us to determine the living end concentration. Applications of the HI/I2‐initiated living process to the synthesis of new bifunctional and block polymers were also described.