Development of Novel Biodegradable Polymer from Lignocellulose and confirmation of its innoxiousness on the biodegradation process

为了开发具有与目前常见合成聚合物几乎相同的热成型性和物理性能的塑料材料，通过环酯的开环接枝聚合以及马来酸酐与一元环氧化物或多元醇的捏合反应，对最实用的纤维素衍生物二乙酸酯(DS 2.1-2.2)(CDA)进行了增塑。通过与脂肪族聚酯共混，CDA也能达到同样的增塑效果。另一方面，关于生物质包括木质纤维素的液化，人们知道，即使在120℃的条件下，在苯酚、水和催化量的硫酸存在下也很容易进行液化。在这种情况下，还发现解聚木质素的再缩合反应受到了有利的抑制，液化机理为异解机理。同时，尽管玉米皮在苯酚或多羟基a-…存在下液化首次发现较多的醇类较难合成，找出了较易合成醇类的条件，并对液化产物的表征、与适量甲醛共缩合的树脂化反应以及多元醇类液化产物的聚亚安酯成型进行了研究。另一方面，对所制得的模塑料和泡沫塑料的无害性进行了研究。这些样品被粉碎，用开水或乙醇/水溶液在80℃下提取72h，提取液浓缩。用UMU试验检测了这些浓缩提取物的致突变性和致癌性。还对浓缩提取物是否揭示内分泌干扰物的作用进行了检查。结果表明，目前的液化生物质模塑样品和泡沫在日常使用中是相当安全的。对由生物质和纤维素制备的聚合物材料的生物降解性和一般毒性进行了测试，得到了有意义的结果。较少

In order to develop plastic materials having thermo-moldability and physical properties almost equal to those for the currently common synthetic polymers, the most practical cellulose derivative, cellulose diacetates (DS 2.1-2.2)(CDA) have been plasticized by the ring-opening graft-polymerization of cyclic esters as well as by kneading reactions of maleic acid anhydride and monoepoxides or polyhydric alcohols. The same plasticization of CDA has been also found to be achieved by blending with aliphatic polyesters. On the other hand, concerning liquefaction of biomass including lignocellulosics, it was known that it could be easily proceeded in the presences of phenol, water and a catalytic amounts of sulfuric acid, even at 120℃. In this case, it was also found that recondensation reactions of depolymerized lignin were favorably depressed, and that the liquefaction mechanism is heterolytic one. At the same time, although liquefaction of corn bran in the presence of phenol or polyhydric a … More lcohols was first found to be difficult, the conditions which made them easier were found, the characterization of the liquefied products, resinification of the liquefied products by co-condensation with formaldehyde in suitable small amounts, as well as polyurethane forming of polyhydric alcohol liquefied products were studied. On the other hand, innoxiousness for using these moldings and foams thus obtained was studied. These samples were pulverized, extracted with boiled water or ethanol/water solution at 80℃ for 72 hrs and the extracts were concentrated. For these concentrated extracts, mutagenicity and carcinogenicity were checked by umu-test. The concentrated extracts were also examined whether they reveal endocrine disruptor's effect or not. The results revealed that the present molded samples and foams from liquefied biomass are quite safety for daily use. The biodegradability and the general toxicity of the polymeric materials prepared from biomass and cellulose were examined and meaningful results could be obtained. Less