Zwitterionic ring expansion polymerization of tert-butyl glycidyl ether with B(C₆F₅)₃ towards the generation of cyclic chains

The synthesis of cyclic polymers via zwitterionic ring expansion polymerization is limited to a few number of monomer and catalyst pairs. Herein we report the synthesis of cyclic poly(tert-butyl glycidyl ether) through the polymerization of tert-butyl glycidyl ether (tBGE) with B(C6F5)(3) in different reaction conditions that include different solvents, monomer to initiator ratio, monomer concentration and temperature. We found that bimodal molecular weight distribution is formed in almost all reaction conditions caused by cyclization of short chains. Subsequent chain elongation leads to the formation of cycles of higher molecular weight, particularly in cyclohexane and under bulk conditions. The formation of non-cyclic byproducts is common in all the systems investigated. Low molecular weight cyclic chains (M-n = 0.7 kDa, & ETH; = 1.1) of high topological purity were successfully isolated by preparative gel permeation chromatography. By using a click scavenging protocol, the non-cyclic byproducts were eliminated from the high molecular weight fraction (M-n = 3 kDa, & ETH; = 1.3) generating pure cyclic chains. Mechanistic investigation using density functional theory calculations was performed on the formation of zwitterionic intermediates and the transfer reaction to the monomer, which notably affects chain growth by the attack of the glycidyl oxygen of the monomer on the growing chain.