Cationic polymerization of selected α- and β-substituted vinyl ethers

Summary The cationic polymerization of various α- and β-substituted vinyl ethers, initiated by 1-iodo-1-(2-methylpropyloxy)ethane 1 and tetrabuty lammonium perchlorate (TBAP) was investigated. The polymerization of 2,3-dihydrofuran (DHF, 3a) in CH₂Cl₂ at -40°C proceeds via opening of the ethylenic double bond and yields polymers with narrow molar mass distributions and high glass transitions. The number average of molar mass increased linearly with conversion. Under these conditions, a controlled polymerization of two propenyl ethers (1-ethoxypropene 2a and 2-methoxypropene 2b) and two other cyclic unsaturated ethers (3,4-dihydro-2H-pyran 3b and 5-methyl-2,3-dihydrofuran 3c) could not be achieved. Either transfer reactions or the decomposition of 1 prevented the formation of high molar mass polymers of these vinyl ethers.