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1、硕 士 学 位 论 文苄基疏水化改性淀粉及其衍生物的合成和性能研究Studies on preparation and properties of benzyl-modified starch and starch derivatives作 者 姓 名： 夏婷婷 学科、专业 ： 应用化学 学 号 ： 20307240 指 导 教 师： 具本植 完 成 日 期： 2006年6月9日 大连理工大学Dalian University of Technology独创性说明作者郑重声明：本硕士学位论文是我个人在导师指导下进行的研究工作及取得研究成果。尽我所知，除了文中特别加以标注和致谢的地方外，论文中不
2、包含其他人已经发表或撰写的研究成果，也不包含为获得大连理工大学或者其他单位的学位或证书所使用过的材料。与我一同工作的同志对本研究所做的贡献均已在论文中做了明确的说明并表示了谢意。作者签名： 日期： 大连理工大学硕士学位论文摘 要淀粉及其衍生物疏水化改性后具有更优良的物理和化学特性，具有广阔的应用前景，本文以苄基作疏水基团，对苄基淀粉和苄基淀粉衍生物的制备及性能进行了研究。以异丙醇和水混合溶液作溶剂，苄基氯为疏水化试剂，合成了高取代度的苄基淀粉。研究了溶剂中异丙醇含量、碱用量、反应温度和时间，以及催化剂的种类和用量对取代度和反应效率的影响，并对催化剂催化的可能历程进行了探讨。建立了紫外分光光度法
3、测定苄基淀粉苄基取代度的新方法，该法简单、快速，准确度高，结果满意。在羟乙基淀粉和苄基淀粉的合成研究基础上，制备了一系列不同取代度的苄基羟乙基淀粉，并考察了合成方法、催化剂，以及苄基氯和氯乙醇用量对苄基和羟乙基取代度的影响。在催化剂存在下，采用一步法制备的苄基羟乙基淀粉中苄基取代度达0.09以上，羟乙基取代度为0.801.01。用自制的苄基取代度不同的苄基淀粉为原料，制备了苄基取代度为0.0100.158，羧甲基取代度为0.200.84的苄基羧甲基淀粉，考察了苄基淀粉中苄基取代度、氯乙酸用量、溶剂中含水量、反应温度和时间，以及碱用量对羧甲基取代度和反应效率的影响。研究结果表明制备苄基羧甲基最佳
4、工艺条件为：溶剂中含水量为3.8，n(NaOH):n(氯乙酸)2.0:1反应温度为60，反应时间6 h。对制备的苄基淀粉进行了水溶性和表面活性考察，取代度为0.0250.105的苄基淀粉在80水中溶解度95，其溶液表面张力可下降到53.0 mNm-1。同时考察了苄基羟乙基淀粉和苄基羧甲基淀粉的表面活性，主要受苄基引入量的影响，溶液表面张力分别降低到48.7 mNm-1和42.0 mNm-1。对苄基羧甲基淀粉进行了详细的粘度性能研究，结果显示苄基的引入对羧甲基取代度较低的苄基羧甲基淀粉具有增粘作用。与羧甲基淀粉相比，苄基羧甲基淀粉具有一定的抗盐性能。关键词：苄基淀粉；苄基羟乙基淀粉；苄基羧甲基淀
5、粉；表面活性；粘度Studies on preparation and properties of benzyl-modified starch and starch derivativesAbstractHydrophobic modified products of starch and its derivatives have good physical and chemical properties. They show wide application prospects in various areas. In this thesis, benzyl group was selec
6、ted as the hydrophobic group. And preparation and properties of benzyl starch and its derivatives were studied.Benzyl starch with high degree of substitution(DS) was prepared by reaction of starch with benzyl chloride which was used as hydrophobic reagent in the mixed solvent containing isopropanol
7、and water. The effects of some reaction factors on DS, such as amount of isopropanol in the solvent, dosage of alkali, reaction time, reaction temperature, and type and dosage of catalyst were investigated. Besides, the possible catalyzing process was discussed. A new UV-spectrometric method for det
8、ermination of DS of benzyl in benzyl starch was developed. This new method is rapid, simple, and accurate, with more operational possibilities and satisfactory results.On the basis of syntheses of benzyl starch and hydroxyethyl starch, benzyl hydroxyethyl starch with different DS of benzyl and hydro
9、xyethyl parts was prepared by reaction of starch with both benzylchloride and chlorohydrin. The effects of reaction method, catalyst, dosage of benzyl chlorid and chlorohydrin on DS of benzyl and hydroxyethyl groups were studied. With the help of catalyst, DS of benzyl groups of the derivative is ab
10、ove 0.09, and molar degree of substitution of hydroxyethyl groups is 0.801.01 using one-step method.Benzyl carboxymethyl starch was prepared in isopropanol with some water, using self-made benzyl starch with different DS of benzyl group as raw material. DS of carboxymethyl part was affected by DS of
11、 benzyl group in benzyl starch, dosage of chloroactic acid, content of water in solvent, reaction time and temperature, as well as dosage of alkali. The optimal reaction conditions are obtained and they are 60, 6 hours in isopropanol with 3% water, and the ratio of NaOH to benzyl chloride of 2.0. Su
12、rface tensions of the solutions of benzyl starch, benzyl hydroxyethyl starch and benzyl carboxymethyl starch were examined, and they were 53.0 mNm-1, 48.7 mNm-1 and 42.0 mNm-1 respectively. These results are mainly affected by DS of benzyl group. Benzyl starch with DS of benzyl part of 0.0250.105 ha
13、s good water-solubility at 80. And it is also concluded by study on viscosity of benzyl carboxymethylstarch that benzyl group increases the viscosity of the starch derivative with low DS of carboxymethyl and makes it less affected by salt.Key Words：benzyl starch；benzyl hydroxyethyl starch；benzyl car
14、boxymethyl starch； surface reactivity；viscosity目 录 前 言11 文献综述21.1 淀粉的基本知识21.1.1 淀粉的来源与生产21.1.2 淀粉的结构21.1.3 淀粉的基本性质31.1.4 变性淀粉41.2 疏水化改性淀粉51.2.1 疏水基团的疏水效应51.2.2 淀粉的疏水化改性方法61.2.2.1 按溶剂分类61.2.2.2 按照疏水化试剂和反应类型分类61.2.3 原淀粉的疏水化改性研究进展71.2.3.1苄基淀粉醚71.2.3.2 烷基淀粉醚81.2.3.3 疏水性淀粉酯81.2.3.4 疏水接枝淀粉91.2.4 水溶性淀粉的疏水化
15、改性研究进展91.2.4.1 羧甲基淀粉及疏水化改性羧甲基淀粉101.2.4.2 羟乙基淀粉及疏水化改性羟乙基淀粉111.2.4.3 疏水化阳离子淀粉131.2.5 疏水化改性淀粉的应用151.2.5.1 高分子表面活性剂151.2.5.2 造纸工业151.2.5.3 污水处理161.2.5.4 土壤改良161.2.5.5 涂料塑料添加剂161.3 本论文的设计思想172 总 论182.1 苄基淀粉的制备182.1.1 反应原理182.1.2 正交实验综合考察影响因素182.1.2.1 溶剂中异丙醇浓度对苄基淀粉取代度和反应效率的影响202.1.2.2 反应对苄基取代度的影响212.1.2.3 反应时间对苄基取代度的影响232.1.2.4 碱用量对取代度的影响242.1.3 催化剂对苄基淀粉取代度的影响252.1.3.1 催化剂的选择252.1.3.2 催化剂用量对苄基淀粉取代度及反应效率影响262.1.3.3 催化机理分析272.1.4
