The role of solvent polarity and cocatalyst structure in the cationic polymerization of 3,3‐bis(chloromethyl) oxetane

Abstract

SynopsisI n the cationic polymerization of 3,3-bis(chloromethyl)oxetane induced by BTI. 3 the solvent polarity (toluene, methylene chloride, ethylene chloride, nitrobenzene, and nitromethane) does not influence the k,,/k, ratio, where k,, stands for the rate constant of chain transfer to polymer. Increase of the overall polymerization rate is due mainly to the increase of ki. The application of the steady-state conditions in which the slow formation of the active centers is compensated by the unimolecular chain transfer to polymer allowed the determination of k,/k, ratios for several chain-transfer agents of low molecular weight.It was established that the k,,/k, ratio is a linear function of -pK, of the chain-transfer agents.Alcohols and ethers of different basicities were used.

A guide to modern methods for poly(thio)ether synthesis using Earth-abundant metals

“…132 However, a useful draw of this polymerization method is that other cyclic ether species can also be polymerized like THF, trioxane, oxetane, and oxazoline, but these are more reliably produced using BF 3 or other non-Earth-abundant metals. [108][109][110][111]133,134 End group control. As the polymerization proceeds by the ACE mechanism, the polymers are telechelic.…”

“…CROP was originally the main method by which polymers of 4 and higher membered heterocycles were polymerized, such as dioxolane, oxetane, oxathialane, and THF. [108][109][110][111] Traditionally, strong protonic acids are used (e.g., trifluoroacetic acid) to form the tertiary oxonium ion necessary to initiate the ROP. These proceed by the so-callled activated monomer mechanism (AMM).…”