Abstract: | Oligo(spiroorthocarbonate)s 1 , which were synthesized by the polycondensation of pentaerythritol derivatives with tetraethylorthocarbonate, were employed as comonomers in the cationic polymerization of epoxide initiated by sulfonium salt. In the copolymerization, the spiroorthocarbonate moiety of 1 underwent double ring‐opening reaction, leading to the efficient diminution of the volume shrinkage upon the copolymerization. Thermal properties of the resulting networked polymers were evaluated by TGA. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1564–1568 |