【作者】 孙建平；

【导师】 范宏；

【作者基本信息】 浙江大学 ， 化学工艺， 2013， 硕士

【摘要】 氨基改性硅油使用范围广泛,应用于各种织物的后整理,能赋予织物柔软、滑糯和舒适的优良手感。但是经其整理的织物存在易黄变,亲水性差,防静电能力降低,染色织物难以回修和复染等缺点。将聚醚链段引入氨基硅油分子,能有效的增强织物的亲水性和抗黄变能力。同时,随着人们对织物功能性要求的增多,开发具有复合性整理功能的硅油产品成为纺织助剂领域的研究热点。长链烷基与氨基共改性硅油不仅能赋予织物柔软、滑爽等手感,还能增加织物的亲水性、蓬松感和丰满程度等。本文第一部分研究了[AB]nA型聚醚嵌段氨基硅油的合成与表征。首先以八甲基环四硅氧烷(D4)、四甲基二氢二硅氧烷(TMDS)为原料,酸性白土为催化剂,反应温度为60℃,反应时间为24h,氮气氛围保护的条件下平衡聚合制备了α,ω-二氢聚二甲基硅氧烷(PHMS)o通过调节D4与TMDS的摩尔比例,合成了四种具有不同分子量的PHMS。经过FTIR和1HNMR分析表明,Si-H键成功引入二甲基硅氧烷两端。对比含氢量滴定、核磁氢谱和凝胶渗透色谱(GPC)计算的PHMS分子量,发现由前两种方法计算的分子量与理论设计的分子量较为接近,且由GPC分析的PHMS分子量分布为1.4-1.7。然后以PHMS和烯丙基缩水甘油醚为原料,氯铂酸／异丙醇为催化剂,在甲苯体系进行硅氢加成制备双环氧封端聚二甲基硅氧烷(PEMS). FTIR和1H NMR图谱中Si-H键对应的红外吸收峰和核磁共振峰完全消失,并通过氢谱和碳谱确定了产物结构,表明合成了既定结构的PEMS。通过环氧值滴定、核磁氢谱和碳谱计算PEMS的分子量,结果表明分子量较原料PHMS与小幅增加。最后利用不同分子量的PEMS和氨基聚醚进行开环反应,制备了十二种[AB]nA型聚醚嵌段氨基硅油。利用FTIR和’HNMR分析了产物结构,结果表明产物分子中含有聚硅氧烷链段和聚醚链段。第二部分研究了自制[AB]nA型聚醚嵌段氨基硅油的乳化工艺及其应用性能。筛选了六种市售的非离子表面活性剂,并且复配了两种HLB≈10.5的乳化剂对AB-67-13嵌段硅油进行乳化,发现经XL-449复配乳化剂乳化的硅油乳液均一透明,蓝光充足,且稳定性良好。同时探讨了乳化方法、乳化剂用量、乳液pH值和乳化时间等工艺条件对乳液外观、稳定性和应用性能的影响。结果表明,不同的工艺参数对其外观和稳定性有较大的影响。经过方法一(乳化剂与硅油充分混合,根据体系粘度外观调节加入HAc水溶液和水的速率)、乳化剂用量为体系的4%、乳液pH=6、乳化转相时间为5min时,得到的乳液均一细腻,且稳定性良好。以筛选的最佳条件制备嵌段硅油乳液,并将其应用于纯棉和纯涤纶两种织物的后整理。通过整理织物的弯曲刚度、折皱回复角、白度和亲水性的比较,选择最适合纯棉和纯涤纶织物的嵌段硅油为AB-69-9和AB-137-13,且其最佳浓度为10%和15%。整理的织物手感柔软、滑糯和舒适,白度无明显变化,亲水性得到极大的提高。最后,研究了聚醚嵌段氨基硅油对染色织物色牢度和色度的影响。结果表明,经嵌段整理的纯棉织物(黑色)色牢度较空白样变化不大,但是色力度下降,颜色变浅、偏绿、偏蓝、色泽偏亮,总色差介于0.53-1.12之间。第三部分研究了长链烷基和氨基共改性硅油的合成和应用性能。首先以D4、高含氢硅油和六甲基二硅氧烷(MM)为原料,酸性白土为催化剂,制备具有一定含氢量的低含氢硅油。然后与烯丙基缩水甘油醚和α-烯烃进行硅氢加成反应,合成了环氧基和长链烷基共改性硅油中间体,利用核磁氢谱和碳谱对产物结构进行了分析和确认。最后与N,N-二甲基丙二胺开环制备了长链烷基与氨基共改性硅油。用FTIR、核磁氢谱和碳谱对每一步反应的结构进行了确认,表明合成了既定结构的产物。将辛基、癸基或十二烷基和氨基共改性硅油乳化,应用于纯棉织物的后整理。通过场发射扫描电镜(FESEM)发现,经过十二烷基与氨基共改性硅油整理的棉织物表面变的平滑,凹槽和沟壑消失或者变浅。随着长链烷基碳链增长,织物柔软性稍有降低。最后研究了不同氨值和不同烷基值的十二烷基与氨基共改性硅油对织物整理性能的影响,结果表明氨值越高,织物的柔软性越好；烷基值增加,织物的柔软性有所降低,蓬松感和丰满程度越好。更多还原

【Abstract】 Amino-modified silicone oil (ASO) has been widely used. Applied in the field of textile finishing, it can impart a unique soft, smooth and comfortable sensation for various kinds of fabrics. However, the fabric treated by ASO is hydrophobic, easy to turn yellow, poor in anti-electrostatic property, and the dyed fabric is difficult to re-work and redye. Introducing the polyether segment into ASO molecules, the hydrophilicity and anti-yellowing capability of treated fabric can be effectively improved.Nowadays, as demands for multifunctional fabric increases, the research has focused on the development of silicone oil with complex function in the field of textile auxiliary. The long chain alkyl and amino co-modified silicone oil can not only render fabrics soft and smooth handle, but also improve the hydrophilic property and increase the fluffy and full sence for treated fabrics.The synthesis and characterization of [AB]nA-type polyether block amino silicone oil were studied in the first part of this thesis. With octamethylcyclo-tetrasiloxane (D4) and tetramethyldisiloxane (TMDS) as raw materials, emathlite as catalyst, hydrogen-terminated polydimethylsiloxane (PHMS) was prepared via equilibrium polymerization in nitrogen atmosphere, and the reaction temperature was60℃, the reaction time was24hrs. The PHMS with four different molecular weight were prepared by adjusting the molar ratio of D4and TMDS. It was found that Si-H had been introduced into two terminals of polydimethysiloxane skeleton by FTIR and.’H NMR analysis. The molecular weight of PHMS was investigated by the ways of hydrogen content tritration,1H NMR and gel permeation chromatography (GPC). The results showed that the molecular weight calculated by tritration and1H NMR was closer to the design of molecular weight, and molecular weight distribution was1.4-1.7by GPC analysis. Then with the chloroplatinic acid/isopropyl alchohol as catalyst, toluene as solvent, epoxy-terminated polydimethylsiloxane was prepared via hydrosilylation reaction of PHMS with allyl glycidyl ether (AGE). The IR absorption peak and’H NMR peak of Si-H in the corresponding spectrums were absolutely disappeared. The product structure was identified by1H NMR and13C NMR, which showed that the PEMS with established structure was synthesized. The molecular weight of PEMS was investigated by the ways of expoxy content tritration,:H NMR and13C NMR. It was showed that Mw of PEMS was slightly higher than PHMS. Finally, twelve [AB]nA-type polyether block amino silicone oil were prepared via ring-opening reaction of PEMS and amino-terminated polyether with different molecular weight.The emulsification process and application performance of homemade polyether block amino silicone oil (PEBASO) were investigated in the second part of this thesis. AB-67-13was emulsified using six kinds of commercially available nonionic surfactants and two self-made emulsifier with HLB≈10.5, respectively. It was found that the emulsion was uniform transparent, and had adequate blue light and good stability using XL-449as emulsifier. Meanwhile, the effect of process conditions including the emulsion method, the emulsifier dosage, pH value of emulsion and emulsification time on the emulsion appearance, stability and appilication performance were also discussed. The results showed that the different process parameters had great impact on the emulsion appearance and stability. The emulsion with uniform transparent appearance and good stability was obtained with the first method,4wt%emulsifier dosage, pH=6and5min in phase inversion emulsification.100%cotton fabric and100%polyether fabric were treated by above-mentioned PEBASO emulsion using optimum emulsifying conditions. The most suitable PEBASO and emulsion concentration were screened by comparing the bending rigidity, crease revovery angle, whiteness and hydrophilic properties treated by different block silicone oil and emulsion concentration, the best choices were AB-69-9(10%) for cotton fabric and AB-137-13(15%) for polyether fabric. The treated fabric feels soft, smooth and comfortabele, the whiteness had little change and the hydrophilic property of fabrics was greatly improved. Finally, the effect of different PEBASO on the color fastness and color shading of dyed cotton fabric was studied. The results indicated that the color fastness had little change, the color strength decreased. The treated fabric was lighter, more green and blue in color, the total aberration was between0.53and1.12.The preparation and application performance of long chain alkyl and amino co-modified silicone oil were researched. With D4, concentrate hydrosilicone oil and hexamethyldisiloxane (MM) as raw metarials, emathlite as the catalyst, the low-hydro silicone oil was prepared via telomerization. Then the epoxy group and long chain alkyl co-modified silicone oil intermediate was synthesized by hydroslylation of low-hydro silicone oil with allyl glycidyl ether and α-olefins (1-octene,1-decene and1-dodecene). At last, the long chain alkyl and amino co-midified silicone oil was synthesized by ring-opening reaction of above-me ntioned intermediate and N,N-dimethyl-1,3-propanediamine. The product structure of each step were identified by FTIR,1H NMR and13C NMR analysis, which indicated that the products with established structure were synthesized.. Then the octyl, decyl or dodecyl and amino co-modified silicone oil (LASO-8, LASO-10and LASO-12) were emulsified, and the emulsion were applied in the finishing process of100%cotton fabric. The observation of field emission scanning electron microscopy (FESEM) showed that the surface of cotton fabric treated by dodecyl and amino co-modified silicone oil changed smooth, and the groove and gap in the surface disappeared or shallowed. It was indicated that the fabric softness slightly decreased. The properties of fabric treated by LASO-12with different amino value and different alkyl value were also discussed. It turned out that the fabric became more soft as the amino value increased, less soft and more fluffy with the alkyl value increased.更多还原