【作者】 李强；

【导师】 吴明华；

【作者基本信息】 浙江理工大学 ， 纺织化学与染整工程， 2012， 硕士

【摘要】 涂料印花因其具有工艺简单、色谱齐全、印花后无需水洗、节能、减排等优点，而被纺织行业列为推行清洁生产的工艺之一。但当前，在我国广泛应用的聚丙烯酸酯类涂料印花粘合剂普遍存在胶膜耐水性差、“热黏冷脆”、不耐沾污以及涂料印花色牢度与手感矛盾等缺陷，限制了涂料印花的普及和发展。为此，课题拟通过制备一种双端丙烯酰氧基聚醚硅油，对聚丙烯酸酯改性，合成一种有机硅改性聚丙烯酸酯涂料印花粘合剂，在提高印花织物耐摩擦色牢度的同时，改善印花织物的手感，以实现二者的统一。论文主要分为三部分：第一部分为双端丙烯酰氧基聚醚硅油（DTAPS）的制备及表征。本部分以丙烯酸和双端羟基封端聚醚硅油为原料，通过酯化反应制备双端丙烯酰氧基聚醚硅油（DTAPS）,实验研究了催化剂用量、反应温度和时间、甲苯溶剂用量、阻聚剂用量等因素对酯化率的影响，并用红外光谱仪和核磁共振波谱仪对产物的结构进行了表征。结果表明：酯化反应的最佳条件为催化剂和甲苯溶剂用量分别为反应物总质量的5%、70%，阻聚剂用量为丙烯酸质量的0.75%，反应温度为110℃，反应时间为4h；红外光谱和核磁谱图显示产物结构为丙烯酰氧基聚醚硅油。第二部分为有机硅改性聚丙烯酸酯涂料印花粘合剂的制备及性能。本部分在前人实验的基础上，固定软硬单体比为2.5:1，交联单体N-羟甲基丙烯酰胺用量为2%，丙烯酸用量为3%，研究了双端丙烯酰氧基聚醚硅油（DTAPS）加入方式、阴/非乳化体系、双端丙烯酰氧基聚醚硅油（DTAPS）分子中聚硅氧烷链段分子量、双端丙烯酰氧基聚醚硅油（DTAPS）用量等因素对乳液性能、乳胶膜性能及涂料印花性能的影响，并用扫描电镜(SEM)、水接触角分析仪、红外光谱仪、透射电镜（TEM）、粒径分析仪、热重分析仪（TG）等仪器对胶乳及胶膜的结构和性能进行了分析。结果表明：双端丙烯酰氧基聚醚硅油（DTAPS）与丙烯酸酯类单体混合乳化聚合，可以有效提高乳液的聚合稳定性；当阴/非乳化剂配比为2:1，用量为5%时，乳液聚合具有较高的单体转化率和较低的凝聚率，胶乳各项稳定性良好；双端丙烯酰氧基聚醚硅油（DTAPS）分子中聚硅氧烷链段分子量越大，通过共聚接枝到聚丙烯酸酯分子链上的量越少，胶膜焙烘过程中相分离现象和未聚合双端丙烯酰氧基聚醚硅油（DTAPS）富集团聚形成的大颗粒越多，涂料印花性能越差；聚硅氧烷链段分子量约为1600的有机硅单体用量为6%-8%时，乳液聚合稳定性较好，改性胶膜耐水性能及力学性能较高，印花织物干、湿摩可达4级，手感柔软；红外谱图显示聚丙烯酸酯大分子中含有聚硅氧烷链段成分；透射电镜（TEM）和粒径分析仪显示乳胶粒呈规则的圆球状，粒径大小为85nm,粒径分布较窄；胶膜表面水接触角和热重分析显示，经有机硅改性后，胶膜表面疏水性变大，耐热稳定性变好。第三部分为有机硅改性聚丙烯酸酯涂料印花粘合剂的应用研究。本部分主要探讨了自制硅丙共聚涂料印花粘合剂用量、焙烘温度、焙烘时间等因素对棉织物涂料印花性能的影响，并与市场上使用的商品粘合剂的性能进行了比较。结果表明：自制硅丙共聚涂料印花粘合剂用量为16%，焙烘温度为160℃，焙烘时间4min时,印花织物干、湿摩均可达4级，手感柔软，均好于市场上目前所用的涂料印花粘合剂。论文研究表明采用无APEO阴/非乳化剂、自制双端丙烯酰氧基聚醚硅油（DTAPS）、丙烯酸酯类单体，通过混合乳化滴加法制备的硅丙共聚涂料印花粘合剂应用于涂料印花后，印花织物具有较好的手感，耐干、湿摩擦色牢度可达4级，基本实现了涂料印花色牢度和织物手感二者的统一，即具有良好的色牢度和柔软顺滑的手感。更多还原

【Abstract】 Pigment printing was regarded as one of clean production process by textile industrybecause of its many advantages, such as simple process, complete color chromatography,needless washing after fixation, energy saving, emission reduction. However, the polyacrylatelatex as binder for pigment printing which was used widely in our country generally existedmany defects, such as poor property of waterproof and stain resistance of latex film and hotsticky-cool brittle performance of the film, and there are contradiction between handle and colorfastness of printed fabric, which limited the popularity and development of pigment printing. Inview of the above, a double terminated acryloyl-polyether silicon oil was synthesized andapplied in the preparation of silicon-modified polyacrylate latex for pigment printing, in order toimprove the color fastness and the handle of printed fabric. There are3parts in this research.Part1: Synthesis and characterization of double terminated acryloyl-polyether silicon oilIn this part, a double terminated acryloyl-polyether silicon oil (DTAPS) was prepared byesterification reaction with acrylic acid and polyether silicon oil terminated by double hydroxylas raw materials. The influences of reaction factors such as amount of catalyst, reactiontemperature and time, dosage of solvent and inhibitor on the esterification rate were investigated,and the structure of product was characterized by FTIR and1H-NMR. The results showed thatthe optimal esterification condition was that the amounts of catalyst and solvent were5%and70%of total reactant mass respectively, the dosage of inhibitor were0.75%of the amounts ofacrylic acid, reaction temperature was110℃and reaction time was4h. FTIR and1H-NMRanalysis indicated that the structure of product was acryloyl-polyether silicon oil.Part2: Preparation and properties of silicon-modified polyacrylate latex for pigmentprintingOn the basis of previous experiments, fixed the mole ratio soft monomer and hardmonomer is2.5:1, the amounts of cross-linking monomers(NMA) is2%, the dosage of acrylic is3%, the effects of addition methods of DTAPS, emulsification system, molecular weight ofpolysiloxane in the DTAPS, the amounts of DTAPS on the properties of organic silicon modified polyacrylate latex, latex film and pigment printing were studied, the structure and propertieswere analyzed by SEM, FTIR, TEM, particle size analyzer, water contact angle analyzer, and thethermo-gravimetric analyzer. The results showed that the method of which DTAPS and acrylicmonomers polymerized after blinding, could effectively increase the stability of the emulsionpolymerization. When the mass ratio of anionic emulsifier to nonionic emulsifier was2:1and theamount of compound emulsifier was5%, the emulsion polymerization exhibited highermonomer conversion and lower polymerization coagulation rate, the latex had good stability. Thehigher molecular weight of polysiloxane was, the less content of organic silicon monomer whichgrafted to the polyacrylate molecular chain by copolymerization was, the larger particle whichwas formed by enrichment and agglomeration of the organic silicon was, the poorer properties ofpigment printing was. The amount of organic silicon monomer with1600molecular weight was6%-8%, the stability of emulsion polymerization was good, water resistance and mechanicalproperties were good, the dry and wet rubbing fastness of pigment printing fabric reached4grades, and the printed fabric’s handle became softer. FTIR analysis indicated that organicsilicon monomer had grafted to polyacrylate molecular chain, TEM and particle size analysisdisplayed latex particle showed a regular ball shape, the average diameter was85nm anddistribution was narrow, water contact angle analysis and TG analysis indicated thathydrophobicity and heat-resistant stability of the modified film improved obviously.Part3: Research on the application of organic silicone modified polyacrylate binder in thepigment printingIn this part, the influences of the amounts of organic silicone modified polyacrylate latexbinder, curing temperature and curing time on properties of pigment printing for cotton fabricwere studied, and the organic silicone modified polyacrylate binder was compared with otherpigment printing binder. It was found that when the binder was16%, curing temperature was160℃, curing time was4min, the printed fabric had good handle, and dry rubbing fastness and wetrubbing fastness can reach grade4. Compared with other pigment printing binder, the fabricprinted with silicone modified polyacrylate binder had better handle and color fastness.The research showed that after the silicone modified polyacrylate latex as binder forpigment printing which being synthesized with non-APEO emulsifier, double terminatedacryloyl-polyether silicon oil and acrylate monomers was applied in pigment printing, the printed fabric had better handle, and the dry and wet rubbing fastness of the printed fabric reached4grades, basically achieved the unification of handle and colorfastness.更多还原