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壳聚糖的改性及其在制革工业中的应用
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摘要
这篇论文探索了壳聚糖通过降解、改性制备具有水溶性低分子羧甲基壳聚糖的工艺及羧甲基壳聚糖在制革染色的应用,得出在一定条件下降解改性的羧甲基化壳聚糖在制革染色中的优化工艺,促进制革清洁化技术的实行。
     ①壳聚糖的降解:为了改善壳聚糖的水溶性,用过氧化氢/醋酸体系,在60℃下降解高脱乙酰度壳聚糖,通过碘量法动态监测降解过程H202浓度的变化,用黏度法测定壳聚糖降解产物的黏均分子量,用电位滴定法测其脱乙酰度等。结果表明:其体系H202浓度随降解时间的延长而基本呈线性降低;相对分子量和脱乙酰度随降解时间的延长而递减;水溶性逐渐增加。壳聚糖降解的较佳方案是:H202与壳聚糖p-1,4糖苷键物质的量比值为1,mc(体系壳聚糖质量):mw(体系水的质量)=1:20,醋酸质量分数为1%,T(反应温度)=60℃,t(反应时间)=6h。
     ②壳聚糖羧甲基化改性:为了增加壳聚糖的水溶性,用氯乙酸/乙醇体系对降解壳聚糖羧甲基化改性,用红外等手段进行结构表征,设计六因素五水平L25(5-6)正交实验以及单因素实验,通过测其O-羧甲基取代度、N-羧甲基取代度确定较佳的羧甲基化方案:NaOH溶液质量分数为40%,其体积与原料质量比为6,氯乙酸与原料质量比为4(即mc:mNaOH:mClCH2COOH=1:2.4:4),碱化时间2h,反应温度为60℃,反应时间为3h。
     ③羧甲基壳聚糖的制革染色应用实验:通过羧甲基壳聚糖在染色工艺中的配比单因素水平实验分析以及不同加入顺序对染色结果的影响。结果表明:羧甲基化壳聚糖作为制革工业中的染色助剂,起到增深增艳的效果,其染色上染率、匀染性以及干湿擦等性能也得到提高。得出优化的染色工艺为:在常规工艺条件加酸固色前20min加入0.2%-0.3%羧甲基化壳聚糖
The degradation and modification chitosan were explored in this paper. Some water-soluble carboxymethyl chitosan was applied to dyeing process of leather making. The optimized process of dyeing with carboxymethyl chitosan in leather process is provided in this study,which will promote clean-production of leather industry.
     ①Degradation of Chitosan:
     Chitosan was degrading at 60℃in H2O2/HAc reaction system.The H2O2 concentration variation was monitoring during whole degrading process by iodimetry, the viscosity-average molecular weight was measured by colloidal titration and the degree of deacetylation was determined by potentiometric titration with different degradation time. Those results show that H2O2 concentration has been linear reducing and both viscosity-average molecular weight and degree of deacetylation are decreasing with the prolonging of degradation reaction time.The better process technology is as follows: m(the quality of chitosan):m(the quality of water)=1:20 n(the mole ratio of chitosan):n(the mole ratio of H2O2)=1:1 c(the mass fraction of HAc)=1% T(reaction temperature)=60℃t(reaction time)=6h
     ②arboxymethylation of Chitosan Reaction:
     Carboxymethylation chitosan was prepared with low-molecular weight chitosan in ClCH2COOH/CH3CH2OH reaction system. Its structure was characterized by fourier transform infrared spectroscopy (FTIR). Schemes of single factor experiment about reaction time and reaction temperature and a scheme of orthogonal experiment, which includes 6 factors and 5 levels, were designed. The range analysis was done to the result of the experiments, the better structure and component had been decided according to the analysis result, then the optimal condition for carboxymethylation chitosan is as follows: c(the mass fraction of NaOH solution)=40% m(chitosan):m(NaOH):m(ClCH2COOH)=1:2.4:4 t(alkalinization time)=2h T(reaction temperature)=60℃t(carboxymethylation reaction time)=3h
     ③Application of Carboxymethylation Chitosan in Dyeing of Leather Manufacture:
     The single factor experiment for ratio of chitosan was carried out, the order of the addition of carboxymethylation chitosan had great influence on dyeing effect. Carboxy methylation chitosan is used to be dyeing additive in leather making, the results show that, it has darkening and brightening effect and can increase dye update, also can improve wet and dry rubbing fastness and level dyeing property of finish leather. The optimizing process of dyeing with carboxymethylation chitosan is obtained, that is:0.2%-0.3% carboxy methylation chitosan is added to the system 20 minutes before dye fixation process in conbentional leather-making process.
引文
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