【作者】 王炜；

【导师】 陈水林；

【作者基本信息】 东华大学 ， 纺织化学与染整工程， 2005， 博士

【摘要】 本论文以不同分子量聚醚多元醇、端羟基聚硅氧烷、异佛尔酮二异氰酸酯、六亚甲基二异氰酸酯等为原料，合成了多种水性聚氨酯，对各自合成条件、水分散稳定性及生成物性能进行研究。并以端羟基聚硅氧烷、异佛尔酮二异氰酸酯（IPDI）和聚醚二元醇、三元醇为原料，设计合成了一种新型羊毛防毡缩整理剂。整个硅改性聚氨酯羊毛防毡缩整理剂合成与研究工作可以分为3个主要部分：（1）水性聚氨酯整理剂的合成与其分散体系的分散稳定性研究；（2）水性聚氨酯整理剂对织物物理机械性能以及染色性能影响；（3）羊毛防毡缩整理工艺优化与整理效果评价。成功将聚硅氧烷链段引入聚氨酯防毡缩整理剂中，合成一只有机硅嵌段水性聚氨酯羊毛防毡缩整理剂Simorene Pro（自己命名，取意Silicone Modified），系统地研究了IPDI、HDI、MDI、TDI等合成水性聚氨酯预聚反应的各影响因素。解释了硅氧烷参与预聚进行的机理，通过考察预聚体加水分散过程中粘度及电导率的变化，研究了预聚体在乳化过程中相转变行为，并推测了的预聚体聚集态状态变化的过程。考察了不同溶剂条件下的封端反应，研究结果表明：分散过程包括链段微离子聚集体的解聚集和疏水链段的聚集过程。依据分散体系粘度和电导率的变化，随着软段分子量的升高，分散体系的相转变点后延；亚硫酸氢钠封端剂与水用量也对分散体系的相转变产生影响。研究得出的规律为水性聚氨酯合成条件的优化提供了理论依据。研究了整理剂对毛织物的染色性能与颜色的影响，发现：合成的有机硅改性整理剂对本白呢坯均造成一定色变，选用IPDI或HDI作为整理剂的异氰酸酯组分显示出较小的色变；而MDI与TDI因为分子中存在较大苯环等双键共轭体系，色变较大。在未进行染色的呢坯上经整理剂处理后染色的初染力降低，但随着时间的延长上色率会达到未处理的织物水平；对于染色后毛织物整理剂对毛织物颜色会造成一定颜色差异，对常用的毛用染料均有影响，但颜色的变化很小，可以控制在4—5级左右。总体看来，新整理剂没有对染色性能造成显著影响，对染色呢坯色变也不大，可以在工厂推广使用。通过考察整理浴pH值、整理剂浓度、整理浴温度、带液率以及不同碱剂对面积毡缩率影响，系统研究了硅改性聚氨酯羊毛防毡缩整理剂对毛织物整理工艺条件。研究结果表明：在使用NaHCO₃为碱剂、pH10.5、整理浴温度为室温、带液率为65％，160℃焙烘5min，可获得优异的防毡缩效果。通过考察端羟基聚硅氧烷所占比例与整理织物的物理机械性能如手感、垂悬度、平滑度的影响，研究了聚硅氧烷含量与手感悬垂度的相关性。与现整理剂对比试验结果显示：Simorene Pro整理防毡缩性达到国际羊毛局TM-31机可洗标准，整理织物在手感、垂悬度等方面优于现有整理剂，强力测试与扫描电镜显示整理后羊毛纤维无损伤。更多还原

【Abstract】 In this thesis, a series of water-borne polyurethanes was successfullyprepared with isophorone diisocyanate（IPDI）, 2,4-toluene diisocyanate（TDI）and poly （propylene oxide triols and diols ） with different molecular weights,and the modified with polysiloxanes. A novel bisulfite adduct of siloxanemodified polyurethane aqueous system was designed and synthesized withhydroxyl end-grouped polysiloxane and IPDI for shrink-resist treatment ofwool. The study consisted of three main parts:ⅰ) the synthesis of thepolyurethane aqueous system and discussion of their phase inversion andstability,ⅱ) the preparation of siloxane modified water-born polyurethane andtheir blockingreaction,ⅲ)The effects of the treatment on the dyeing prepertyof wool fabric and on the color of dyed wool.The introduction of polysiloxane segment into IPDI-based polyurethaneled to a new product with satisfactory shrink resistance and good handle,named Simorene Pro. Every factor of the prepolymerization of IPDI, TDI withpolyols was examined. The mechanism of reaction between the IPDI andhydroxyl group ended polysiloxane was proposed and the dispersion behaver ofthe prepolymer in the system was discussed. The sodium bisulfite blockingreaction of the prepolymer was investigated. the behaver of the phaseinversion of bisulfite adduct of siloxane modified polyurethane was alsostudied. The results showed that the dispersion included the phase dismissingof aggregate of hydrophilic segments and aggregation of hydrophobic segments.According to the change of viscosity and conductivity, the point of phaseinversion increased with increase of molecular weight of polyols. The ratio ofsolvent to water and amounts of sodium bisulfite and water also affected thebehaver of phase inversion. The results of study provided the theories basis ofsynthesis of water born polyurethane. The appearance, the dispersion character, the viscosity, the stability at highand low temperature, the stability to pH, the tability to electrolyte of SimorenePro prepared were investigated. The results showed that the Simorene Proexhibited good stabilities in all conditions, it could be stored at 50℃for aperiod as long as 12 months, it could be used as a mixture with 10% NaClsolution at any concentration, it could also be used when the pH was lower than9.By means of investigation of effects of the pH value, the temperature, thekind and amount of alkali in the finishing bath on area shrinkage of the treatedfabric, the process of finishing were discussed systematically. It was applied forwool fabrics with NaHCO₃ as alkali; pH 10.5, at the room temperature, the pickup was 65%, for shrink-resist treatment by traditional pad-dry-cure process.The treated fabric possessed good shrinking-resistance and handle withpermanent effect.The measurement and subjective evaluation showed that theintroduction of polysiloxanes into PU resin can also give good anti-feltingeffect. While the ultra-thin fih-n over the surface of wool fiber was fort-ned tominimize the Different Frictional Effect of the wool fiber. The introduction ofpolysilicone segments into polyurethane aqueous system could significantlyimprove the handle of treated fabric.A comparison of Simorene Pro with the other treatment agents availablefrom the market was arranged, the results also indicated that the polysiloxanemodified water-born polyurethane could endow the wool fabric with shrinkresistant property that meet the standard of IWS TM-31 and better handle anddrape-ability than the others, the results also showed that the strength and othermechanical properties of fabric were almost unchanged by treatment withSimorene Pro.更多还原