Cationic polymerizations of two series of divinyl ethers were carried out to clarify the effects of their central spacer chain structure on their crosslinking polymerization behavior. One series of the monomers involves divinyl ethers with an oligooxyethylene central spacer chain: diethylene glycol divinyl ether (O-3), triethylene glycol divinyl ether (O-4), tetraethylene glycol divinyl ether (O-5), pentaethylene glycol divinyl ether (O-6), and heptaethylene glycol divinyl ether (O-8) (see Scheme 1). The other series includes divinyl ethers with an oligomethylene central spacer chain: 1,4-butanediol divinyl ether (C-4), 1,6-hexanediol divinyl ether (C-6), and 1,8-octanediol divinyl ether (C-8). Cationic polymerizations of these monomers were carried out with the hydrogen chloride/zinc chloride (HCl/ZnCl2) initiating system in methylene chloride (CH2Cl2) at -30 degreesC ([Monomer](0) = 0.15 M; [HCl](0) = 5.0 mM; [ZnCl2](0) = 0.5 mM). The polymerizations of the oligomethylene-based divinyl ethers C-6 and C-8 caused gel formation at high monomer conversions (similar to90%), whereas C-4 formed soluble polymers even at almost 100% monomer conversion. The oligooxyethylene-based divinyl ethers O-3, O-4, O-5, and O-6 underwent gel-free polymerizations up to 100% monomer conversion and O-8 did so at least up to similar to80% conversion. The content of unreacted pendant vinyl groups of the obtained soluble polymers was measured by H-1 NMR spectroscopy. In the polymerizations of the oligomethylene-based divinyl ethers (C-4, C-6, and C-8), the vinyl contents of the polymers decreased monotonously with increasing monomer conversion, and their number-average molecular weights (M-n's) and polydispersity ratios (M-w/M-n's) increased considerably just before the gelation occurred. On the contrary, the vinyl contents of the polymers obtained from the oligooxyethylene-based divinyl ethers (O-3, O-4, O-5, O-6, and O-8) decreased steeply even in the early stage of the polymerizations and almost all the pendant vinyl ether groups were consumed in the soluble polymers at the final stage of the polymerizations. The oligooxyethylene spacer units adjacent to the pendant unreacted vinyl ether groups may solvate intramolecularly with the carbocationic active center to accelerate frequent occurrence of intramolecular crosslinking reactions. (C) 2004 Wiley Periodicals, Inc.