《《羧甲基淀粉及其酰胺衍生物的制备与性能研究》-公开DOC·毕业论文》由会员分享，可在线阅读，更多相关《《羧甲基淀粉及其酰胺衍生物的制备与性能研究》-公开DOC·毕业论文（100页珍藏版）》请在金锄头文库上搜索。
1、硕 士 学 位 论 文羧甲基淀粉及其酰胺衍生物的制备与性能研究Studies on the Preparation and Properties of Carboxymethyl Starch and its Amide Derivatives 作 者 姓 名： 学科、 专业： 应用化学 学 号： 指 导 教 师： 完 成 日 期： 大连理工大学Dalian University of Technology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，在石油开采、造纸工业、土壤改良、污水处理等方面都有了广泛的应用，具有广阔的应用前景。本文以一系列碳链长度不同的脂肪胺作疏水基团，对
2、羧甲基淀粉进行了疏水化改性，合成了羧甲基淀粉脂肪酰胺，并详细研究了其合成工艺和性能。首先通过一次羧甲基化制备了DScm=2.2的高取代度羧甲基玉米淀粉(CMCS)。研究了氢氧化钠用量、反应介质、反应时间和反应温度对反应效率(REcm)和取代度(DScm)的影响。当氯乙酸和淀粉AGU摩尔比为4时，最佳反应条件为氢氧化钠和氯乙酸摩尔比为2.5、异丙醇中水的用量为2mL、反应温度50、反应时间为2h，最佳反应条件下制得CMCS的DScm和REcm分别达到2.2和55%。另外，发现在此反应体系下，通过改变氯乙酸和氢氧化钠的用量可以制备取代度从1.69到2.55的CMCS，REcm依然可以达到55%，最
3、后用红外光谱表征了CMCS的结构。然后，研究了以高取代度的CMCS为原料制备羧甲基淀粉酰胺衍生物的方法，研究表明：采用铵盐在高温下脱水的方法，虽然可以得到相应的产品，但由于反应过程中存在着复杂的氧化降解和交联问题，不利于讨论亲水基和疏水基对产品粘度性质的影响。改用以DCC为脱水剂，DMAP为催化剂，异丙胺为例的方法在温和条件下制备羧甲基淀粉酰胺衍生物。分别考察了DCC用量，异丙胺用量，DMAP用量，不同溶剂，反应温度，反应时间对羧甲基淀粉酰胺衍生物的DSa取代度的影响，当n(H2SO4): n(DCC)=1.5，反应温度为30，反应时间为24小时，n(DMAP):n(DCC)= 0.05，DC
4、C与异丙胺的摩尔比为1:1，DMSO的用量为15mL/g，为反应的较佳反应条件，反应效率可以达到40%以上，并用红外光谱对产品结构进行了表征。在上述反应条件下制备了一系列取代度和不同疏水链长的羧甲基淀粉酰胺衍生物。最后，研究了高取代度羧甲基淀粉对金属的螯合性质，并与取代度为1 的产品进行了比较；研究了高取代度羧甲基淀粉酰胺衍生物的粘度性质和表面活性性质。关键字：羧甲基淀粉；羧甲基淀粉酰胺；表面活性；粘度；螯合Studies on the Preparation and Properties of CarboxymethylStarch and its Amide DerivativesAbst
5、ractHydrophobic modified products of starch and their derivatives have good physical and chemical properties. They are widely used in petroleum exploiting, paper making, soil improvement, wastewater treatment, etc. And they show promising prospects in various areas. In this thesis, a series of amide
6、 derivatives of carboxymethyl corn starch (CMCSa) were synthesized through the reaction of carboxymethyl corn starch (CMCS) with different amines which were selected as the hydrophobic reagent. Synthesis and properties of CMCS and CMCSa were studied.A high degree of substitution (DS=2.2) carboxymeth
7、yl corn starch (CMCS) was prepared by one-step carboxymethylation. The effects of the amounts of sodium hydroxide, reaction medium, reaction temperature, reaction time on the degree of substitution (DScm) and reaction efficiency (REcm) were studied. When the molar ratio of starch to chloroacetic aci
8、d was 4, the optimum reaction conditions were that the molar ratio of sodium hydroxide to chloroacetic acid was 2.5, reaction temperature was 50, reaction time was 2h and the amount of water in isopropyl alcohol was 2ml, CMCS prepared under optimal conditions showed the highest DScm and REcm, which
9、were 2.2 and 55%, respectively. CMCS with different DScm from 1.69 to 2.55 was also prepared under the same reaction conditions and the REcm obtained was also above 55%. In addition, CMCS was characterized by IR spectra. CMCSa with different degree of substitution (DSa) of hydrophobic groups can be
10、prepared from ammonium salt but the complicated oxidative degradation and crosslinking restrict the discussion of the results. So CMSa was prepared by reaction of CMCS with DCC DMAP and amines under mild reaction conditions. The effects of the amounts of DCC, DMAP amines, reaction medium, reaction t
11、emperature and reaction time on degree of substitution（DSa） and reaction efficiency（REa） were studied. n(H2SO4):n(DCC)=1.5, n(DMAP):n(DCC)=0.05, reaction temperature 30, reaction time 24h, the molar ratio of DCC to amine was 1, the amount of DMSO 15mL/g were the optimal reaction conditions. REa of t
12、he CMCSa prepared under the optimal conditions got to 40%. In addition, CMCSa was characterized by IR spectra. The chelation of heavy metal of CMCS was investigated, the behaviors were also compared with that of CMCS (DScm=1). And viscosity behaviors and surface properties of the CMSa were also stud
13、ied.Key Words: CMCS; CMCSa; surface activity; viscosity; chelantlw目 录摘 要IAbstractII引 言11 文献综述21.1 羧甲基淀粉21.1.1 羧甲基淀粉的合成21.1.2 羧甲基淀粉应用性能的研究31.1.3 羧甲基淀粉精细结构的表征31.1.4 超高取代度羧甲基淀粉的合成31.2 水溶性疏水化改性淀粉41.2.1 水溶性疏水缔合聚合物41.2.2 羧甲基淀粉及其衍生物的疏水化改性51.2.3 阳离子淀粉的疏水化改性71.2.4 其他水溶性淀粉的疏水化改性81.3 水溶性疏水化淀粉衍生物的应用81.3.1 高分子表面
14、活性剂81.3.2 造纸工业91.3.3 污水处理91.3.4 土壤改良91.3.5 涂料塑料添加剂101.4 本论文设计思想102 实验部分122.1 实验药品122.2 实验仪器132.3 实验部分132.3.1 高取代度(DS=2.2)羧甲基玉米淀粉的制备132.3.2 羧甲基淀粉的钠盐的酸化132.3.3 羧甲基淀粉铵盐的合成142.3.4 羧甲基淀粉铵盐脱水酰胺化142.3.5 一步法制备羧甲基淀粉酰胺142.4 取代度测定152.4.1 羧甲基取代度测定硫酸铜络合滴定法152.4.2 羧甲基淀粉铵盐、羧甲基淀粉酰胺衍生物取代度的测定152.5 性能测定162.5.1 红外光谱测定1
15、62.5.2 表面张力性能测定162.5.3 粘度的测定162.5.4 金属螯合性质的测定173 结果与讨论183.1 高取代度羧甲基淀粉的制备与结构解析183.1.1 高取代度羧甲基淀粉的合成及条件考察183.1.2 反应时间对羧甲基取代度和反应效率的影响203.1.3 溶剂组成对羧甲基取代度和反应效率的影响213.1.4 水用量对羧甲基取代度和反应效率的影响223.1.5 氢氧化钠对羧甲基取代度和反应效率的影响233.1.6 氯乙酸对羧甲基取代度和反应效率的影响243.1.7 反应温度对羧甲基取代度和反应效率的影响253.1.8 CMCS的红外谱图263.2 羧甲基淀粉酰胺衍生物的合成与结构解析263.2.1 高取代度羧甲基淀粉铵盐的合成263.2.2 羧甲基淀粉酰胺衍生物的制备313.3 一步法制备羧甲基淀粉酰胺363.3.1 DCC用量对酰胺取代度的影响373.3.2 异丙胺用量对酰胺取代度的影响383.3.3 DMAP用量对酰胺取代度的影响383.3.4 反应温度对酰胺
