Some new developments in vinyl ether polymerization

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Abstract
Different combinations of acetals with trimethylsilyl iodide have been explored as new initiating systems for the vinyl ether polymerization. The resulting polymers are characterized by controlled molecular weights and narrow molecular weight distributions, confirming the living polymerization mechanism.Acetals can also be used as transfer agents in the polymerization of vinyl ethers. When using 1,1‐diethoxyethane (DEE) as transfer agent and isobutyl vinyl ether (IBVE) as monomer, a transfer constant of 0.2 was obtained (at −40°C in toluene). This method, transposed to functional acetals, provides a new way to prepare polyvinyl ethers with one or two functional end groups.The cationic polymerization of isobutyl vinyl ether initiated with the combination triflic acid/thietane, where thietane acts as electron donating moderator, leads to star‐shaped polyvinylether‐polythietane block‐copolymers (at −40°C in dichloromethane). The block‐copolymer structure is obtained because the vinyl ether polymerization is stopped when the α‐alkoxy thietanium ion (active species) is attacked by a thietane molecule, which is at the same time an initiation reaction for the thietane polymerization. The star‐shaped structure of the block‐polymer is the result of the intermolecular termination in the cationic polymerization of thietane. When using a bifunctional initiator system, a polymer network is obtained consisting of linear polyIBVE‐segments interconnected by branched polythietane segments. These findings support the sulfonium ion structure of the active species in the cationic polymerization of vinyl ethers initiated by the acid‐sulfide system.