Chemical Synthesis of Biodegradable Polyesters Utilizing Sugar Biomasses.

1.含糖二醇聚酯及相关聚合物的合成：以糖基原料为原料，合成了系列聚酯、聚酯酰胺S、聚碳酸酯S和聚碳酸酯。在缩聚反应中，1，4：3，6-二脱水-D-葡萄糖醇(DAG)、1，4：3，6-二脱水-D-甘露醇(DAM)、1，4：3，6-二脱水-L二醇(DAL)等糖二醇是主要的二醇组分。在某些情况下，含有呋喃基团的二元酸衍生物被用作二元酸成分。糖基聚酯及其相关聚合物的生物降解性：通过土壤埋藏降解、活性污泥处理和酶降解试验三种不同的方法研究了糖基聚酯及其相关聚合物的生物降解性。生物降解性变化很大，取决于聚合物的分子结构。总的来说，含有非对称DAG单元的聚合物表现出比含有对称DAM和DAI单元的相应聚合物更高的生物降解性。甲壳素接枝低聚物及相关聚合物的合成：以水为介质，在部分脱乙酰甲壳素存在下，通过ε-己内酯开环聚合制备了甲壳素接枝低聚物。在磷酸盐缓冲液/甲醇中，PDC的氨基与丙烯酸乙酯发生迈克尔式亲核加成反应，合成了一种新型N-选择性酯功能化甲壳素衍生物。以聚乙烯醇和ε-己内酯为原料，在二甲基亚砜中反应，合成了聚乙烯醇接枝低聚酯。对这些聚合物膜的生物降解性以及热性能和表面性能进行了详细的测试。在本研究的基础上，已经建立了有用和重要的指导方针，用于从可再生的糖基原料中设计具有受控生物降解性的聚酯和相关聚合物。

1. Synthesis of Polyesters and Related Polymers Containing Sugar Diols : Series of polyesters, poly (ester amide) s, poly (ester carbonate) s, and polycarbontes were synthesized from sugar-based raw materials. Sugar diols such as 1, 4:3, 6-dianhydro-D-glucitol (DAG), 1, 4:3, 6-dianhydro-D-mannitol (DAM), 1, 4:3, 6-dianhydro-L-iditol (DAl) were chiefly employed as diol components in polycondensations. Dicarboxylic acid derivatives containing furan moieties were used as dicarboxylic acid components in some cases.2. Biodegradability of Sugar-Based Polyesters and Related Polymers : The biodegradability of the sugar-based polyesters and the related polymers were examined by three different methods, i. e., soil burial degradation, activated sludge treatment, and enzymatic degradation tests. The biodegradability varied widely, depending on the molecular structure of the polymers. In general, polymers containing unsymmetrical DAG units showed higher biodegradability than the corresponding polymers containing symmetrical DAM and DAI units.3. Synthesis of Chitin-graft-oligoesters and Related Polymer : Chitin-graft-oligoesters were prepared by the ring-opening polymerization of ε-caprolactone in the presence of partially deacetylated chitin (PDC) using water as a medium. A novel N-selective ester functionalized chitin derivative was prepared by a Michael-type nucleophilic addition of an amino group of PDC to ethyl acrylate in phosphate buffer/methanol. Poly (vinyl alcohol)-graft-oligoester was synthesized by the reaction of PVA and ε-caprolactone in DMSO. The biodegradability as well as the thermal and surface properties of these polymer films were examined in detail. On the basis of the present research, useful and important guidelines have been established for designing polyesters and related polymers having a controlled biodegradability from renewable sugar-based raw materials.