【作者】 张兵；

【导师】 柳明珠；

【作者基本信息】 兰州大学 ， 化学·高分子化学与物理， 2012， 博士

【摘要】 据有关资料报道,2012年甘肃省马铃薯种植面积达到70万公顷,是我国马铃薯种植第二大省份。如何突破马铃薯淀粉深加工过程中存在的科学和技术瓶颈,并为产品找到出路,对经济欠发达的甘肃无疑具有重要的现实意义。羧甲基淀粉(CMS)是一种重要的变性淀粉,具有亲水性强、易糊化、透明度高、粘度高等优点。CMS被誉为“工业味精”,已被广泛地应用于食品、医药、石油、纺织、造纸等行业。目前纺织品印花工艺中一般以海藻酸钠(SA)作糊料,但由于其资源有限,而且成本昂贵,因此,寻找可替代海藻酸钠的印花糊料是国内外学者共同感兴趣的研究课题,也是纺织品印染行业亟待解决的技术难题。本学位论文以甘肃马铃薯淀粉(St)为原料,氢氧化钠(SH)为催化剂,氯乙酸(CA)为醚化剂,环氧氯丙烷(Ep)为交联剂,聚氧乙烯醚(JFC)为渗透剂,乙醇(Alc)为溶剂,分别在小反应釜(2 L)、中釜(36 L)和大釜(3 nm3)中通过半干法制备了兼具高取代度(DS)和高粘度(η)的CMS;首次采用遗传算法(GA)和神经元算法(BP)对中釜和大釜通过半干法制备CMS的工艺条件进行了模拟、优化;用傅里叶变换红外分光光度计(FTIR)、X-射线衍射分析仪(XRD)、示差扫描量热仪(DSC)以及扫描电子显微镜(SEM)等手段对CMS的微观结构进行了表征;以大釜生产的CMS为基料,将其与氧化瓜尔胶(OGG)、羧甲基纤维素(CMC)和聚乙烯吡咯烷酮(PVP)进行多元复配,制备了复合印花糊料(CMS/OGG/CMC/PVP);首次将模糊数学理论用于印花织物手感的定量分析,并将所得结果与产品实际性能进行了比较。本学位论文取得的主要结果有:1.小釜中获得制备CMS的最佳工艺条件为:mst=100g;nSH/nCA=2.2;VEp=6 d;VAlc= 100 mL;VJFC= 1.9 mL;一次反应时间(t1)= 1 h;一次反应温度(T1)= 350℃;二次反应时间(t2)= 4h;二次反应温度(T2)= 520℃;搅拌速率(R)= 1000 rpm。2.大釜中在最佳条件下制备的CMS的取代度为0.98,浓度为4%(w/w)的CMS的水溶液的粘度为22000 mPa·s,含水率为9.34%,盐含量为19.02%,水不溶物含量为0.23%。3.实验结果表明:羧甲基化反应之后,淀粉的结晶结构由多晶颗粒转变为无定型结构;羧甲基化反应不仅发生在淀粉颗粒表面,还发生在淀粉颗粒内部。4.复合印花糊料(CMS/OGG/CMC/PVP)原糊的流体性质属假塑性流体;浓度为8%(w/w)的该糊料的水溶液粘度>150000mPa·s;糊料的稳定性、抗盐性、抗稀释性以及抱水性均较好;将此复合糊料用于活性染料印花,印花织物得色量高,得色均匀,色牢度优于纯海藻酸钠,花纹轮廓清晰,色泽鲜艳。研究结果表明,本学位论文研究开发的CMS/OGG/CMC/PVP复合印花糊料不仅在使用效果上可替代海藻酸钠,而且具有显著的价格优势。该研究结果对由马铃薯淀粉生产羧甲基淀粉,并将其用于纺织品印花糊料,不仅具有参考和借鉴意义,而且具有重要的应用价值和潜在的经济效益。更多还原

【Abstract】 It is well reported that Gansu province is the second biggest province in the potato planting area in China.In 2012,the planting area has been reached to 0.7 million hectares.Therefore,there is no doubt that resolving the scientific and technological critical problems in the further processing procedure of potato starch and finding a way out for the products play a important role to the undeveloped Gansu province.Carboxymethyl starch(CMS)is a very important kind of modified starch which has a lot of advantages such as strong hydrophilicity,easy gelatinization,high clarity and viscosity and so on.CMS,honored as "industrial monosodium glutamate",has been widely used in food,drug,petroleum,textile and paper industries.Currently,sodium alginate(SA)could always be used as the paste in the textile printing.However,the natural resources of SA are limited and the cost of SA is expensive.Consequently,searching for the printing paste which can be used as a replacement for the SA is the common research interest among the scholars at home and abroad and also is the technological problem needed to be solved immediately in the textile printing industry.This dissertation uses potato starch(St)as raw material,sodium hydroxide(SH)as catalyst,chloroacetic acid(CA)as etherifying agent,epichlorohydrin(Ep)as cross-linking agent,polyoxyethlene ether(JFC)as penetrating agent,alcohol(Ale)as solvent to synthesize the CMS of high degree of substitution(DS)and viscosity(η)with a semi-dry process in the small(2 L),middle(36 L)and large kettle(3 m3).This is the first time to adopt the genetic algorithm(GA)and the back propagation(BP)to simulate and optimize the reaction conditions of synthesizing the CMS with a semi-dry process in the middle and large kettle.The microstructure of CMS is characterized by fourier transform infrared(FTIR)spectroscope,X-ray diffractometer(XRD),differential scanning calorimeter(DSC)and scanning electron microscope(SEM).We use the CMS synthesized in the large kettle as basic material,compound multiply it with the oxidized guar gum(OGG),carboxymethyl cellulose(CMC)and polyvinylpyrrolidone(PVP)and prepare the compound printing paste(CMS/OGG/CMC/PVP).This is the first time to use the fuzzy mathematics for the quantitative analysis of the handle of the printing fabric and compare the results with the practical properties of product.The primary consequences were summarized as follows:1.The optimum reaction conditions of synthesizing the CMS in the small kettle:mSt= 100 g,nSH/nCA = 2.2,VEp＝6 d,VAlc=100 mL,VJFC = 1.9 mL,the each time interval between adding base and acid(τ1)= 6 min,the primary total reaction time(t1)= 1 h,the primary reaction temperature(T1)= 35℃,the secondary total reaction time(t2)= 4 h;the secondary reaction temperature(T2)= 52℃,the rate of agitation(R)= 1000 rpm.2.The DS of CMS synthesized under the optimum reaction conditions in the large kettle is 0.98,the viscosity of 4%(w/w)aqueous solution of CMS is 22000 mPa·s,water content is 9.34%,salt content is 19.02%and the undissolved substance content is 0.23%.3.The experimental results show that the crystalline structures of starch have already been altered from the crystalline region to the amorphous region after carboxymethylation.Carboxymethylation occurs not only on the surface of granule of starch,but also internal part of it.4.The fluid properties of compound printing paste(CMS/OGG/CMC/PVP)belong to the pseudoplastic fluid,the viscosity of 8%(w/w)aqueous solution of this paste is greater than 150000 mPa·s,and it also has the desirable stability,salt resistance,dilutability resistance and holding water capacity.We use compound paste for the reactive dye printing,and the color yield,evenness and fastness of printing fabric are much better than that of fabric using SA solely.Meanwhile,the fabric has the distinct outline of figure and the bright color.The research results indicate that this thesis study and develop this compound printing paste(CMS/OGG/CMC/PVP)which not only can replace the SA in the applying effect,but also has the notable advantage in the price.For the CMS produced by the potato starch and the application on the textile printing paste,these results have not only meaningful reference but also the significant application and potential economic benefit.更多还原