【作者】 郭云飞；

【导师】 刘振东；

【作者基本信息】 北京服装学院 ， 纺织化学与染整工程， 2008， 硕士

【摘要】 有机硅由于其独特的结构而具有表面张力低、耐氧化、热稳定和生物相容等一系列优异性能,但存在力学强度低、附着力差等缺点。聚氨酯具有良好的物理和机械性能,但热稳定性较差。通过改性手段将有机硅与聚氨酯两者的优异性能结合起来,既可以克服有机硅机械性能差的缺点,又可以弥补聚氨酯耐候性差的不足,具有很好的发展前景。合成革是模仿天然皮革的物理结构和实用性能,并做为其部分代用材料的塑料制品。随着环境保护的发展,目前已替代天然皮革应用于服装、皮包、沙发等方面。涂饰可有效提高合成革的物理-机械性能、增加合成革的花样、色泽,改善合成革的表面性能。本论文以异佛尔酮二异氰酸酯(IPDI)、聚氧化丙烯二醇(PPG)、端羟基聚二甲基硅氧烷(DHPDMS、1,4-丁二醇(BDO)以及三羟甲基丙烷(TMP)为主要原料,合成了一系列溶剂型有机硅改性聚氨酯(Si-PU)嵌段聚合物。红外表征表明有机硅链段已经嵌入到聚氨酯大分子链段中。考察了反应条件对反应以及Si-PU溶液性能的影响,结果表明,反应的最佳温度为65℃,以乙酸丁酯和丁酮做混合溶剂,催化剂用量为反应物总质量的0.54%。研究了物料配比对Si-PU溶液以及Si-PU膜的性能的影响。结果表明,有机硅的引入(在Si-PU中的质量百分比小于16%时)没有明显降低膜的机械性能;交联剂含量达到7%时Si-PU膜的耐溶剂性大为提高,机械性能变化不大;当总n(OH)/n(NCO)比值为1.05,预聚n(OH)/n(NCO)比值为0.25时,Si-PU溶液能够保持较小的粘度和和较佳的储存稳定性;有机硅的引入使得Si-PU的热稳定性得到提高。将Si-PU溶液应用到合成革上,探讨了有机硅的质量分数对涂层的三防性能和与革面附着力的影响。结果表明,有机硅的含量由0%上升到10%时,涂层表面的水接触角由76.8°升到102.5°,耐油级别由2级升到5级(参照AATCC118-2002),有机硅含量超过10%时接触角和耐油级别均稳定不变,说明有机硅的引入使涂层获得了拒水拒油的表面效果;当DHPDMS的含量在10%-16%时,涂层与革面的附着力可以达到2级。考察了整理工艺对涂层性能的影响,结论是较佳的整理工艺为:稀释剂为乙酸丁酯,稀释倍数为2.0-2.5,整理剂用量为7 g/m2左右,固化温度为150℃,固化时间为2.5h,固化方式为热风烘燥。更多还原

【Abstract】 Silicone possesses excellent properties such as low surface energy, thermal stability, oxidation resistance and biocompatibility. But the mechanical and adhesive performance is poor. However, polyurethane has superior mechanical properties but not-so-good thermal stability. Silicone modified polyurethane(Si-PU)combines the advantages of both, overcome the disadvantage. It’s a promising polymeric material.Synthetic leather is a kind of plastic product, which imitates the physical structure and applied properties of leather and has partially taken place of the leather materials. As the development of environmental protecting, now synthetic leather has been widely used for clothing, portfolio, sofa etc. Coating can effectively improve synthetic leather’s physical and mechanical performances, color and luster of the surface properties.Solvent type Silicone Modified Polyurethane (Si-PU) block polymers were synthesized with isophorone diisocyanate (IPDI), Polyoxypropyleneglycol (PPG), hydroxy-terminated poly-dimethylsiloxane(DHPDMS), 14-Butanediol(BDO), trimethylolpropane(TMP). The FT-IR spectroscopy showed that the silicone chain segment was incorporated into PU macromolecule. The influence of reaction conditions on reaction and Si-PU solvent was studied. Results showed that the optimal temperature is 65℃, the solvent is mixed MEK and BA, the quantity of catalyst is about 0.54wt% of all reactants. The influence of the ratio of the materials on the properties of Si-PU solution and film was explored.The results showed that Si-PU film possess similar mechanical properties with PU film when the content of poly-dimethylsiloxane (PDMS) segment is below 16wt%. It had good solvent resistance without obvious loss of mechanical property when the content of TMP is 7wt%. It had relatively small viscosity and better storage stability and similar mechanical property with PU film when the ratio of n(OH)/n(NCO) in all is about 1.05 and the ratio of n(OH)/n(NCO) is about 0.25 in the prepolymerization stage. The thermal stability is improved. Si-PU solution was applied on synthetic leather as coating agnet. The influence of the mass fraction of PDMS on the property and adhesion of Si-PU coating was explored. The results showed that the water contact angle of the coating surface was increased from 66o to 102o when the mass fraction of PDMS was increased from 0 to 10wt% without obvious loss of mechanical property. Meanwhile, the oil resistance level is increased from grade 2 to grade 5 (AATCC118-2002). The water and oil resistance of coating can be kept when the content of PDMS is over 10wt%. Adhesion level can be kept on grade 2 when the content of PDMS is 10-16wt%. The study on the influence of finishing process showed that the optimum diluent is BA, dilution ratio is 2.0-2.5, the usage of finishing agent is 7g/m2, cure temperature is 150℃, cure time is 2.5 hours, cure method is hot blast.更多还原