Unsaturated polyester was prepared with adipic acid (AA), fumaric acid (FA), itaconic acid (IA) and 1, 6-hexanediol (HD) by enzyme-catalyzed polmerization. The insoluble gel fraction (Qs), as the cross-linking degree of cured unsaturated polyesters which could be self-cross-linked at high temperature through C=C in it, was got by Soxhlet Extraction. The properties were investigated by FT-IR, 1H NMR, DSC, XRD and so on. The results indicated that the C=C in unsaturated diacids reduced the acitvity of N435, which affected the polmerization. With the introduction of C=C of IA or FA, the Mn of polyester reduced. The C=C could self-cross-link under high temperature for lengthy time. The higher the temperature and the longer the time, the Qs increased. As the C=C of IA was in the side chain, it could move easily. Then Qs of poly (AA-co-IA-co-HD) was higher than ploy (AA-co-FA-co-HD). With the increased content of unsaturated diacid, Qs increased. And the biodegradation of cross-linked polyesters became worse.

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