Dimethyl carbonate (DMC) is an environmentally benign chemical currently produced using CO2. Using the conventional Dean–Stark apparatus, a method was developed for the effective and selective removal of the methanol generated in the transesterification of DMC with alcohol. Using this device, various diols (HO-A-OH; A = (CH2)4, (CH2)2O(CH2)2, CH2C6H10CH2, and CH2C6H4CH2) were converted to mixtures of the corresponding MeOC(O)[O-A-OC(O)]OMe and MeOC(O)[O-A-OC(O)]2OMe. Dialkyl carbonates such as dibutyl carbonate, dibenzyl carbonate, and diallyl carbonate were also efficiently prepared from the corresponding alcohols using this device. The compound prepared from 1,4-butanediol, MeOC(O)[O(CH2)4OC(O)]1.5OMe, was subjected to polycondensation with HO(CH2)4[O2CC6H4CO2(CH2)4]1.5OH or HO(CH2)4[O2CC6H4CO2(CH2)4]1.8OH, which directly was prepared from terephthalic acid and 1,4-butanediol. The polycondensation afforded high-molecular-weight poly(1,4-butylene carbonate-co-terephthalate)s (PBCTs) with Mw of 80–270 kDa and 0.40–0.45 terephthalate mole fractions. PBCTs are attractive materials with biodegradability and LDPE-like thermal properties.
