Living cationic polymerization of vinyl monomers: New initiators and functional polymer synthesis

Abstract This paper focuses on two recent topics in living cationic polymerization of vinyl monomers, i.e., (a) Development of new initiating systems: RCOOH/Lewis acid for vinyl ethers; CH3CH(C6H5)Cl/SnCl4/nBu4NCl for styrene. (b) Synthesis of shape‐controlled poly(vinyl ethers): Tri‐armed star polymers; Multi‐armed spherical polymers. For the RCOOH‐based systems, a generalized concept of living cationic polymerization was discussed on the basis of the effects of the counteranions (or R) and Lewis acids (ZnCl2 and EtAlCl2). The CH3CH(C6H5)Cl‐based system permitted a truly living cationic polymerization of styrene. The tri‐ and multi‐armed poly(vinyl ethers) included new amphiphilic polymers of unique topology, solubility, etc., all of which were prepared by living cationic polymerization.