Identity of Low-Molecular-Weight Species Formed in End-To-End Cyclization Reactions Performed in THF

Abstract

Cyclic polymers were produced by end-to-end coupling of telechelic linear polymers under dilute conditions in THF, using intramolecular atom transfer radical coupling or click chemistry. In addition to the expected shift to longer elution times on gel permeation chromatography (GPC) indicative of the formation of cyclic product, lower molecular weight species were consistently observed upon analysis of the unpurified cyclization reaction mixture. By systematically removing or altering single reaction components in the highly dilute cyclization reaction, it was found that THF itself was responsible for the low-molecular-weight material, forming oligomeric chains of poly(THF) regardless of the other reaction components. When the reactions were performed at higher concentrations and for shorter time intervals, conducive to intermolecular chain-end-joining reactions, the low-molecular-weight peaks were absent. Isolation of the material and analysis by 1H NMR confirmed that poly(THF) was being formed in the highly dilute conditions required for cyclization by end-to-end coupling. When a series of mock cyclization reactions were performed with molar ratios of the reactants held constant, but concentrations changed, it was found that lower concentrations of reactants led to higher amounts of poly(THF) side product.