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

为了开发具有热塑性和物理性能几乎与目前常见的合成聚合物相当的塑料材料，最实用的纤维素衍生物，二乙酸纤维素（ds2.1 -2.2）（CDA）通过环酯的开环接枝聚合以及马来酸酐与单环氧化合物或多羟基醇的混炼反应进行了塑化。与脂肪族聚酯共混也能达到相同的增塑效果。另一方面，关于包括木质纤维素在内的生物质液化，已知在苯酚、水和催化量硫酸的存在下，即使在120℃下，也可以很容易地进行液化。在这种情况下，还发现解聚木质素的再缩合反应得到了良好的抑制，液化机制为异解机制。同时，虽然在苯酚或多羟基乙醇存在下玉米皮的液化是困难的，但首先发现了使其更容易液化的条件，并对液化产物的性质、液化产物与适量甲醛共缩合的树脂化反应以及多羟基乙醇液化产物的聚氨酯成型进行了研究。另一方面，研究了这些塑件和泡沫的使用毒性。将样品粉碎，用沸水或乙醇/水溶液在80℃下提取72小时，浓缩提取物。对这些浓缩提取物进行了umu试验，检测了其致突变性和致癌性。并检测了浓缩提取物是否显示内分泌干扰物的作用。结果表明，目前的成型样品和液化生物质泡沫在日常使用中是相当安全的。考察了生物质和纤维素制备的高分子材料的生物降解性和一般毒性，得到了有意义的结果。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