Star‐shaped cyclopolymers: A new category of star polymer with rigid cyclized arms prepared by controlled cationic cyclopolymerization and subsequent microgel formation of divinyl ethers

The combination of living/controlled cationic cyclopolymerization and crosslinking polymerization of bifunctional vinyl ethers (divinyl ethers) was applied to the synthesis of core‐crosslinked star‐shaped polymers with rigid cyclized arms. Cyclopolymerization of 4,4‐bis(vinyloxymethyl)cyclohexene (1), a divinyl ether with a cyclohexene group, was investigated with the hydrogen chloride/zinc chloride (HCl/ZnCl₂) initiating system in toluene at 0 °C. The reaction proceeded quantitatively to give soluble poly(1)s in organic solvents. The content of the unreacted vinyl groups in the produced polymers was less than ∼3 mol%, and therefore, the degree of cyclization of the polymers was determined to be ∼97%. The number‐average molecular weight (Mₙ) of the polymers increased in direct proportion to monomer conversion and further increased on addition of a fresh monomer feed to the almost completely polymerized reaction mixture, indicating that living cyclopolymerization of 1 occurred. The chain linking reactions among the formed living cyclopolymers with 1,4‐bis(vinyloxy)cyclohexane (3) as a crosslinker in toluene at 0 °C produced core‐crosslinked star‐shaped cyclopoly(1)s [star‐poly(1)s] in high yield (100%). Dihydroxylation of the cyclohexene double bonds of star‐poly(1) gave hydrophilic water‐soluble star‐shaped polymers with rigid arm structure [star‐poly(1)‐OH] with thermo‐responsive function in water. Tgs of star‐poly(1) and star‐poly(1)‐OH were 135 °C and 216 °C, respectively; these values are very high as vinyl ether‐based star‐shaped polymers. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 1094–1102