Aliphatic polyesters hold promise as biodegradable plastics. However, aliphatic polyesters with number average molecular weight (
Mn) exceeding 10000 still cannot be obtained in all cases by the polycondensation of dicarboxylic acids (or diesters) with diols. To achieve this purpose, chain extension (bridging) reactions of lower molecular weight polyesters synthesized from various diesters and diols were carried out in the present study.
The diesters used were dimethyl succinate (DMS), dimethyl adipate (DMA), and dimethyl suberate (DMSb) and the diols were ethylene glycol (EG), 1, 4-butanediol (BD), and 1, 6-hexanediol (HD). The polyesters prepared from EG with diesters were not used in the present chain extension reactions becaus of their low yield and molecular weight. When chain extension of all polyesters was carried out under the optimum conditions determined preliminarily using hexamethylene diisocyanate (HMD) as the chain extender,
Mn of the polyesters exceeded that prior to chain extension by a factor of 2, and all chain extended polyesters except DMA/BD polyester were film-formable. At least one of two end-groups of the original polyesters would thus appear to be a hydroxy group (-OH), and reaction between this end-group and isocyanate group of HMD may produce urethane bonds, indicating efficient chain extension.
Changes in thermal properties and enzymatic degradation by cholesterol esterase of the polyesters were also studied before and after chain extension. These parameters, however, generally remained essentially the same as those of the original polyesters. The enzymatic degradation of DMS/BD polyester was considerably less than that of other polyesters, its melting point (
ca. 116°C) being much higher than those (5060°C) of the others.
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