侧链型水性含氟聚氨酯的制备及性能研究
Synthesis and Properties of Side Chained Waterborne Fluorinated Polyurethanes
作者：杨维(四川大学 纺织研究所, 四川 成都 610065)；王海波(四川大学 纺织研究所, 四川 成都 610065)；成煦(四川大学 纺织研究所, 四川 成都 610065)；杜宗良(四川大学 纺织研究所, 四川 成都 610065)
Author：YANG Wei(Textile Inst., Sichuan Univ., Chengdu 610065, China)；WANG Haibo(Textile Inst., Sichuan Univ., Chengdu 610065, China)；CHENG Xu(Textile Inst., Sichuan Univ., Chengdu 610065, China)；DU Zongliang(Textile Inst., Sichuan Univ., Chengdu 610065, China)
收稿日期：2018-04-06 年卷（期）页码：2019,51(3):212-220
期刊名称：工程科学与技术
Journal Name：Advanced Engineering Sciences
关键字：水性含氟聚氨酯;含氟侧链长度;表面自由能;氢键
Key words：waterborne fluorinated polyurethane;the length of fluorinated side chains;surface free energy;hydrogen bonding
基金项目：国家自然科学基金项目（51503130）；厦门南方海洋研究中心项目（14GZP004NF04；14GQT61HJ31）
中文摘要
为了制备兼具优异疏水性能和力学性能的水性含氟聚氨酯（WFPUs），合成了3种含氟侧链长度不同的端羟基含氟聚丙烯酸酯（P3FMA、P6FMA和P12FMA），将其引入水性聚氨酯（WPUs）分子链中，分别制备了3种WFPUs：WFPUs-P3FMA、WFPUs-P6FMA和WFPUs-P12FMA。傅里叶红外光谱（FTIR）分析表明成功将以上3种端羟基含氟聚丙烯酸酯引入了WPUs的分子链中，FTIR分峰结果显示，随着含氟侧链长度增加，硬段氢键化羰基含量增加，这表明较长的含氟侧链能促使WFPUs硬段氢键作用增加，从而使硬段间的相互作用增加。静态接触角测试和表面自由计算表明：3种WFPUs乳胶膜的静态接触角均随着氟含量增加先增加，随后再继续增加氟含量，静态接触角不变。此时，3种WFPUs乳胶膜的表面自由能分别为34.78、32.41和15.94 mN/m，由此可知，含氟侧链最长的WFPUs乳胶膜的表面自由能最低，疏水性能最好。X光电子能谱分析（XPS）显示，氟表面含量随氟本体含量增加而增加，含氟侧链最长的P12FMA在WFPUs乳胶膜表面的富集性能最好。X射线衍射（XRD）分析表明，氟含量相同时，WFPUs乳胶膜硬段的结晶度随含氟侧链长度增加而增加。力学性能测试结果表明，在氟含量相同的条件下，含氟侧链长度最长的乳胶膜WFPU2-P12FMA的断裂强度和断裂伸长率最大，并且高于WPUs乳胶膜。因此，采用P12FMA改性WPUs，可制备具有较好疏水性能和力学性能的WFPUs乳胶膜。
英文摘要
In order to prepare waterborne fluorinated polyurethanes (WFPUs) with excellent hydrophobic and mechanical properties, three kinds of hydroxyl-terminated poly(fluoroalkyl methacrylates) (P3FMA, P6FMA and P12FMA) with different length of fluorinated side chains were introduced into waterborne polyurethanes (WPUs) and three series of side chained waterborne fluorinated polyurethane (WFPUs) (WFPUs-P3FMA, WFPUs-P6FMA and WFPUs-P12FMA) were synthesized. The analysis of infrared spectroscopy FTIR confirmed the successful introduction of hydroxyl-terminated poly(fluoroalkyl methacrylates) into WPUs molecular. The deconvolution results of FTIR showed that the content of hydrogen bonded carbonyl increased with the increase of fluorinated side chains and the longer fluorinated side chains could strengthen the hydrogen bonding interaction and the interaction of hard segments. The measurements of static contact angle and surface free energy indicated that the static contact angle of the three kinds of WFPUs films firstly increased with the increase of fluorine content, and then kept a constant value, at the moment, the surface free energy of the three kinds of WFPUs films was 34.78, 32.41 and 15.94 mN/m respectively. Thus, the WFPUs films with the longest fluorinated side chains had the lowest surface free energy and the excellent hydrophobic properties. The studies of X-ray photoelectron spectroscopy (XPS) revealed that the surface fluorine content increased with the increase of the bulk fluorine content and confirmed that P12FMA with the longest fluorinated side chains had the best fluorine surface enrichment properties. The results of X-ray diffraction (XRD) revealed that the crystallinity of the hard segment of WFPUs was enhanced with the increase of fluorinated side chains length. The results of mechanical properties showed that the films of WFPU2-P12FMA with the highest strength and elongation at break when the bulk fluorine content of the three kinds of WFPUs films was the same. Therefore, WFPUs films with outstanding hydrophobic and mechanical properties could be obtained through P12FMA modifying WPUs.
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