Fundamental studies that gain understanding of the tunability of the physical properties of natural product-based polymers is vital for optimizing their performance in extensive applications. Variation of glass transition temperature (Tg) was studied as a function of the side chain structure and molar mass for linear poly(glucose carbonate)s. A wide Tg range from 38 to 125 °C was achieved by varying the alkyloxycarbonyl protecting groups, of which the trend was rationalized by free volume evolution with comprehensive effects derived from side-chain steric hindrance and flexibility. The impact of molar mass on Tg was investigated for two series of polymers and discrete oligomers synthesized and fractionated with precise control over the degrees of polymerization. Tg variations with molar mass, among wide ranges of 13–125 °C and -25–38 °C for neopentyloxycarbonyl-protected poly(gulcose carbonate)s and 2-ethylhexyloxycarbonyl-protected poly(glucose carbonate)s, respectively, are both well fitted to the Flory-Fox theory. It is especially interesting to note the enormous decrease of Tg from bicyclic monomers to monocyclic ring-opened unimers in both situations, which provided strong demonstration of the rigidity loss with ring opening of the six-membered glucose carbonate ring. This work represents an important advance in the development of glucose-based polycarbonates, as materials that possess high degrees of functionalizability to be capable of exhibiting diversified physicochemical and thermal properties by simple side chain modification.

Advancing the development of highly-functionalizable glucose-based polycarbonates by tuning of the glass transition temperature

2019 Fall National Meeting

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