Random and block copolymers of 1.3‐dioxolane, styrene and 3.3‐bis (chloromethyl) oxacyclobutane

Abstract Copolymerizations of combinations of 1.3‐dioxolane (DOL), styrene (St) and 3.3‐bis(chloromethyl) oxacyclobutane (BCMO), and terpolymerization of these monomers were investigated with the use of Et3OBF4 as an initiator. A random copolymer of DOL and St with molecular weight as high as 3 × 105 was prepared. By utilizing a “living” nature of the polymerization of DOL by this initiator, a block copolymer (I) consisting of a DOL homopolymer block and a DOL‐St copolymer block was synthesized by two step copolymerization in which St monomer was added to a solution of “living” DOL polymer In a similar way, a block copolymer (II) was also prepared from DOL and BCMO: Terpolymerization of DOL, St and BCMO gave a resinous material, partly insoluble in hot benzene. At least the insoluble part was confirmed to be a terpolymer by elemental analysis and solubility tests. Two step terpolymerization by adding BCMO monomer into a solution of “living” DOL‐St copolymer yielded a benzene soluble product which was supposed to be a block copolymer (III) composed of a DOL‐St copolymer block and a DOL‐St‐BCMO terpolymer block: It is concluded by the successful preparation of terpolymers of DOL, St and BCMO that the latter two monomers which do not copolymerize with each other can be incorporated into a copolymer chain through the intermediary of DOL monomer.