【作者】 洪伟；

【导师】 邢广忠； 李青山；

【作者基本信息】 燕山大学 ， 高分子材料， 2013， 博士

【摘要】 随着越来越多的消费者倾向于购买功能性纺织品，开发功能/智能面料、增加纺织品的技术含量、提高服饰的功能性，已成为纺织行业的一大趋势，同时也成为纺织品企业在国内外市场占据优势地位的条件之一。本文首先设计并制备了一系列水性聚氨酯相变储能材料（WPUPCM），然后采用纺前共混的方法，通过湿法纺丝工艺，使用WPUPCM和粘胶制备了水性聚氨酯智能调温粘胶纤维（WTRVF）。本研究采用溶胶-凝胶法制备了PEG/SiO2PCM，然后使用后整理方法，制备了PEG/SiO2智能调温粘胶纤维（PEG/SiO2TRVF），并对通过直接成纤和后整理制备的两类智能调温纤维（WTRVF和PEG/SiO2TRVF）进行了比较。首先，本文以MDI、HDI、PEG、扩链剂（DMPA、BDO、EDA）、催化剂（DBTDL）、中和剂（TEA）等为主要原料，制备了一系列M-WPUPCM和H-WPUPCM的乳液、膜和块。应用正交试验法，以乳液粒度为评价指标，确定了制备乳液的最佳方案。FTIR测试结果表明，实验合成了M-WPUPCM和H-WPUPCM。热性能测试表明，WPUPCM是相变过程可逆、热循环稳定性很好的调温材料。对微观形貌的分析显示，WPUPCM膜的表面粗糙度随乳液粒径的增大而提高。POM测试表明：室温下PUPCM仍以结晶态存在，但比PEG的晶体尺寸小；WPUPCM的相转变过程实质上是样品中PEG的无定形态和结晶态的交替过程。TG-FTIR测试表明：PUPCM热分解过程的主要产物是CO2。以M-WPUPCM乳液、H-WPUPCM乳液和粘胶纤维原液为原料，应用工厂小试设备，采用湿法纺丝制备了M-WTRVF和H-WTRVF。微观形貌分析表明，WPUPCM与VF结合良好，H-WTRVF的截面比M-WTRVF的更规整。FTIR测试表明，WPUPCM与VF没有发生化学反应。热性能测试表明，WTRVF的相变焓随WPUPCM含量的增加而增大，M-WTRVF的熔融焓比H-WTRVF低；WTRVF的相变过程可逆、热循环稳定性很好。WTRVF可实现工业化生产，且其热性能明显优于现有市售产品，具有很高的市场应用价值。耐水洗性能测试显示，WTRVF的耐水洗性能良好。极限氧指数（LOI）测试表明，WPUPCM的加入未增加VF产品的火灾隐患。TG-FTIR测试显示，WTRVF的高温燃烧产物主要为H2O和CO2，无有毒有害气体产生。WTRVF的干态强度、断裂伸长率较VF都稍有下降，与微胶囊TRVF的降幅相当，但WTRVF的相变焓明显高于后者；添加WPUPCM后，纤维的摩擦阻力变小，回潮率提高，手感稍有改善，柔软、平滑度有一定提高。WPUPCM的加入使VF的蓬松度稍有改善。随着WPUPCM含量的增加，WTRVF的升温（降温）速率减小，而且保持缓慢升温（降温）的时间也延长，即调温效果提高；升、降温达到600s时，WTRVF与普通VF的最大温差分别7℃和6.5℃。采用溶胶-凝胶法制备了PEG/SiO2PCM。PEG/SiO2PCM中二氧化硅的网络结构对PEG进行了有效包裹，解决了固-液相变过程中漏液的问题。在此基础上制备的PEG/SiO2TRVF具有良好的调温效果。织物的手感比处理前稍差，这是由于纤维表面存在许多细小颗粒。随着PEG/SiO2PCM含量的增加，纤维织物的调温能力提高；升、降温达到600s时，PEG/SiO2TRVF与普通VF的最大温差分别为8.2℃和6.2℃。水洗对调温织物热性能影响较大，但仍然保持较大的相变焓。与PEG/SiO2TRVF相比较，WTRVF的服用性能和耐水洗性能优势明显。更多还原

【Abstract】 With more and more people preferring to buy functional textiles, developingfunctional/intelligent fabrics, increasing technological content of textiles or improving thefunctionality of clothing has become a major trend in textile industry as well as animportant condition for textile companies to occupy dominant position in domestic andforeign markets. In this dissertation, the author first designed and prepared waterbornepolyurethane phase change material (WPUPCM); moreover, utilizing spinning blendingmethod and wet spinning process, waterborne polyurethane thermo-regulated viscose fiber(WTRVF) was prepared by adding WPUPCM to viscose. Meanwhile, PEG/SiO2PCMwas prepared by adopting sol-gel technique, then PEG/SiO2thermo-regulated viscosefiber (PEG/SiO2TRVF) was prepared by employing after-treating method. Finally,WTRVF and PEG/SiO2TRVF, prepared respectively by directly fiber forming methodand after-treating method, were compared.In the first place, taking MDI, HDI, PEG, chain extenders (DMPA、BDO、EDA),catalyst (DBTDL) and neutralizer (TEA) as the raw materials, a series of emulsions, filmsand blocks about M-WPUPCM and H-WPUPCM were prepared. Moreover, the bestsolution to preparing emulsions has been determined by utilizing orthogonal experimentalmethod and taking emulsion particle size as evaluation index. FTIR result indicated thatthe experiment has successfully synthesized M-WPUPCM and H-WPUPCM. Thermalperformance test showed that WPUPCM, the phase transition of which is reversible, is athermo-regulated material with excellent thermal cycling stability. Microstructure analysisrevealed that the surface roughness of WPUPCM film improved with the increase ofemulsion particle size. POM test indicated that PUPCM still exists in crystalline state atroom temperature, but the crystal size is smaller than that of PEG; essentially, the phasetransition process of WPUPCM is the alternating process between amorphous state andcrystalline state. According to TG-FTIR test, the main product of PUPCM thermaldecomposition was CO2. By applying wet spinning method to small production line in industry and usingM-WPUPCM emulsion, H-WPUPCM emulsion and viscose fiber dope as raw materials,the author prepared M-WTRVF and H-WTRVF. Microstructure analysis revealed thatWPUPCM could well combine with VF and no obvious interface appeared, andH-WTRVF displayed more regular section than M-WTRVF. FTIR test indicated that nochemical reaction occurred between WPUPCM and VF. And thermal performance testdemonstrated that the phase transition enthalpy of WTRVF increased with the raise ofWPUPCM content, and the melting enthalpy of M-WTRVF was lower than that ofH-WTRVF; in addition, WTRVF, with reversible phase transition, possesses great thermalcycling stability. Therefore, WTRVF can be industrialized, and its’ thermal performance isapparently superior to existing commercial products, thus possessing high applicationvalue. Washing performance test showed that WTRVF displays excellent washingperformance. And according to Limiting Oxygen Index (LOI) test, the addition ofWPUPCM did not increase fire hazard of VF products. TG-FTIR test indicated that, afterhigh temperature combustion, WTRVF products were mainly H2O and CO2and no toxicor harmful gases appeared. Meanwhile, WTRVF mechanical property declined slightlythan that of VF, being similar to microcapsule RVF in the aspect of reducing magnitude,whereas, the phase transition enthalpy of WTRVF was visibly higher than that ofmicrocapsule RVF; the addition of WPUPCM decreased the frictional resistance,improved the moisture regain and the handle as well as softness and smoothness of fiber;moreover, VF bulkiness was also slightly improved due to the addition of WPUPCM.With the increase of WPUPCM content, the heating (cooling) rate of WTRVF reduced,and time for maintaining a slow heating (cooling) extended, namely,temperature-adjustable effect improved; the maximum temperature difference betweenWTRVF and ordinary VF was7℃as heating reached600s, and it was6.5℃as coolingreached600s.Furthermore, PEG/SiO2PCM was prepared by employing sol-gel technique. And thenetwork structure of SiO2has effectively wrapped PCM, thereby solving the liquid leakageproblem in the process of solid-liquid phase change. PEG/SiO2TRVF, which was further prepared, has excellent temperature-adjustable effect. The fabric handle is slightly worsethan after-treating for many tiny particles appeared on fiber surface. Thetemperature-adjustable ability improves with the increase of PEG/SiO2PCM content; themaximum temperature difference between PEG/SiO2TRVF and ordinary VF was8.2℃as the heating reached600s, while it was6.2℃as the cooling was600s. Thetemperature-adjustable fabric had a large phase change enthalpy despite the great effect ofwashing on the thermal performance of it. In summary, compared with PEG/SiO2TRVF,WTRVF has obvious advantages in the aspect of wearing property and washingperformance.更多还原