Bio-based poly(ethylene terephthalate) copolyesters made from cyclic monomers derived from tartaric acid

Abstract

Two cyclic acetal compounds, 2,3-O-methylene L-threitol and dimethyl 2,3-O-methylene L-threarate, both coming from naturally-occurring tartaric acid, were used as comonomers to replace ethylene glycol and dimethyl terephthalate respectively, in the preparation of PET-based copolyesters by polycondensation in the melt. Synthesis results, structure and thermal properties of the two afforded copolyester series were evaluated and compared regarding composition and type of comonomer used in each case. All the copolyesters had a random microstructure and molecular weights in the 25,000–35,000 g·mol-1 range. Their thermal properties varied logically with composition along each series but they significantly changed according to which acetal comonomer was used. PET copolyesters made from acetalized L-threitol displayed thermal stability and Tg comparable to PET, whereas these two properties were depressed in the copolyesters containing threarate units. Both types of copolyesters were able to crystallize for contents in tartaric acid derived units up to around 30% by adopting the crystal structure of PET. Crystallization rates and melting temperatures decreased with copolymerization in the two series but this effect was more noticeable in copolyesters made from threitol.