【作者】 张敏；

【导师】 张淑芬； 杨锦宗；

【作者基本信息】 大连理工大学 ， 应用化学， 2009， 博士

【摘要】 阳离子淀粉是通过醚化、酯化或接枝共聚等反应向淀粉中引入阳离子基团而得到的一类应用广泛的淀粉衍生物。目前开发新型阳离子化试剂、改进合成工艺、提高性能、扩大应用领域等是阳离子淀粉方面的研究热点,由于季铵型阳离子淀粉无论在酸性、碱性还是中性条件下都呈阳离子状态,性能优越,因此目前主要集中于季铵型阳离子淀粉的研发上。本文研究了酯化和醚化型两种季铵阳离子淀粉的制备与应用。论文首先研究有机溶剂法制备酯化型阳离子淀粉—甜菜碱淀粉酯的适宜条件,发现该制备工艺存在操作复杂、污染环境、腐蚀设备等问题,因此,建立了以双氰胺为脱水剂的环境友好干法工艺。采用干法工艺制备了两种醚化型阳离子淀粉（淀粉-2-羟丙基三甲基氯化铵）—低粘度阳离子淀粉及非水溶阳离子淀粉。通过红外光谱、核磁共振、X-光衍射和扫描电镜等对甜菜碱淀粉酯和低粘度阳离子淀粉进行了表征。设计电导滴定法测定低粘度的甜菜碱淀粉酯的取代度是可行的,操作简单、快速、用量少。甜菜碱淀粉酯对高岭土的絮凝效果随着取代度的增大而提高,随着分子量的增大而提高,表明絮凝作用主要是通过电荷中和与架桥作用来实现的。取代度为0.330的交联甜菜碱淀粉酯浓度为3ppm时,浊度去除率可达90.5%,近于传统醚化型阳离子淀粉的去除率。甜菜碱淀粉酯的絮凝效果随着悬浊液盐含量的增大而变差,pH值在5-7时絮凝效果较好。低粘度阳离子淀粉通过酸解淀粉阳离子化而制得,其适于无盐染色。染料固色率随着低粘度醚化型阳离子淀粉取代度的提高而增大,匀染性随着醚化型阳离子淀粉粘度的降低而提高。当低粘度醚化型阳离子淀粉CHS₆（DS=0.70）的浓度分别为30、22.5和17.5g/L时,活性染料C.I.活性红2、C.I.活性蓝19和C.I.活性黄145的固色率分别可达69.4%、73.8%和75.3%,比传统有盐竭染的固色率分别提高20.3%、0.9%和18.4%,而且匀染性良好,染料耐洗牢度优异。非水溶阳离子淀粉ICS通过交联淀粉阳离子化而得到,其适合作为染料废液的吸附剂,对C.I.酸性红1、C.I.酸性黄4、C.I.酸性黄17和C.I.酸性橙7四支染料的吸附速度快,15min都可达到平衡,吸附符合假-二级动力学模型。吉布斯函数变为负值证明了吸附行为是自发的。吸附平衡遵循Langmuir等温吸附模型,吸附量随着ICS取代度的提高而增大,证明吸附是单分子层吸附,而且吸附主要是通过ICS表面阳离子活性质点与染料阴离子的静电引力作用实现的离子交换吸附。由Langmuir等温吸附模型得出非水溶阳离子淀粉（DS=0.65）对C.I.酸性红1、C.I.酸性黄17、C.I.酸性黄4和C.I.酸性橙7四支染料的最大吸附量分别为1.27、1.16、2.44、2.92mmol/g。对于有羟基的酸性染料适用pH范围更宽些。更多还原

【Abstract】 Cationic starches are a kind of starch derivatives obtained by introduction of cationic groups through etherifying,esterifying or grafting reaction of starch.They are widely used in many fields.The researches on developing new cationizing reagents,innovating synthesis process,improving application properties and enlarging application area,becomes intensive topics and focus is mainly made on quaternary ammonium cationic starch because they are stable both in acidic,neutral and basic conditions.In this thesis,synthesis and application of esterified/etherified quaternary ammonium cationic starch were studied.The optimum synthesis conditions of esterified cationic starch—starch betainate by organic solvent method were firstly studied in detail.In view of complicated process, environmental pollution and corrosion of equipment resulted from organic solvent method, eco-friendly dry method was established to prepare starch betainate with dicyandiamide as a dehydrating reagent.Two etherified cationic starches—starch-2-hydroxypropyltrimethylammonium chloride derivative with low viscosity and water-insoluble cationic starch were prepared by dry method.The etherified cationic starch with low viscosity and starch betainate were characterized by FTIR spectroscopy,NMR spectroscopy,X-ray diffraction,scanning electronic microscopy,etc.Conductometric titration was designed to determine the DS of starch betainate with low viscosity,and the results showed that the method was feasible,which was simply,quick and the amount of starch betainate used in titration was small.Starch betainate was applied in flocculation of kaolin suspension.The flocculation efficiency of starch betainate increased with the increase of both DS and molecular weight of starch betainate,which demonstrated that the flocculation was realized mainly by charge neutralization and bridging of the particles.When the dose of crosslinked starch betainate with DS of 0.330 was 3ppm,the removal ratio of turbidity could reach 90.5%,which was similar to the effect of traditional etherified cationic starch.The flocculation efficiency of starch betainate decreased with the increasing amount of salt in the kaolin suspension.Besides. pH of 5-7 was shown reasonable in application.Etherified cationic starch with low viscosity was prepared by cationization of hydrolyzed starch,which was suitable for application in salt-free dyeing.Dye fixation increased along with the increase of DS of etherified cationic starch,and the property of level dyeing was good when decreasing the viscosity of etherified cationic starch.The highest dye fixation for C.I.Reactive Red 2,C.I.Reactive Blue 19 and C.I.Reactive Yellow 145 was 69.4%,73.8% and 75.3%,respectively,and the corresponding concentrations of CHS6 were 30 g/L,22.5 g/L and 17.5 g/L,respectively,which was higher than that of conventional exhaust dyeing by 20.3%,0.9%and 18.4%,respectively.Besides,level dyeing and good wash fastness were achieved by pretreating cotton with cationic starch with low viscosity.Water-insoluble etherified cationic starch was obtained by cationizing crosslinked starch. The adsorption behaviors of water-insoluble etherified cationic starch for C.I.Acid Red 1,C.I. Acid Yellow 4,C.I.Acid Yellow 17 and C.I.Acid Orange 7 were investigated,and this starch derivative was proved to be good adsorbent for acid dyes.The adsorption process was so quick and adsorption reached equilibrium nearly in 15min.The adsorption fit the pseudo-second-order model.The negative△G~θfor the adsorption showed the spontaneous nature of the process.The adsorption equilibrium data correlated well with the Langmuir isotherm model,and the adsorption capacity increased with the increasing DS of water-insoluble cationic starch,which demonstrated that the adsorption mechanism was adsorption of unimoleeular layer and the adsorption was mainly ion exchange adsorption realized by the electrostatic attraction between the anions of the dyes and the cations of the water-insoluble cationic starch.The corresponding maximam of adsorption capacity from the Langmuir isotherm model for C.I.Acid Red 1,C.I.Acid Yellow 4,C.I.Acid Yellow 17 and C.I.Acid Orange 7 were 1.27、1.16、2.44、2.92mmol/g,respectively.The optimum pH rang for the adsorption of the acid dyes with hydroxyl group was wider than that of the dyes without hydroxyl group.更多还原