端氟烷基超支化聚氨酯乳液的合成及性能

Synthesis and Properties of Fluoroalkyl-terminated Hyperbranched Polyurethane Latex

摘要:

摘要：以异氟尔酮二异氰酸酯（IPDI）、聚己二酸丁二醇酯（CMA-1044）、1,4-丁二醇（BDO）和二羟甲基丙酸（DMPA）为原料采用丙酮法合成了-NCO封端的聚氨酯预聚体（PU）；然后加入端羟基超支化聚合物进行改性，合成了超支化聚氨酯（HBPU）；再通过接枝反应使全氟己基乙醇（S104）与HBPU反应制得一种新型端氟烷基超支化聚氨酯（HBPUF），最后经中和、加水分散即制得HBPUF乳液。用红外光谱（IR）、核磁共振氢谱（1H NMR）、透射电镜（TEM）、纳米粒度仪、热重分析仪（TGA）、光电子能谱仪（XPS）以及静态接触角测量仪分别对产物结构、乳胶粒形貌、粒径大小及分布、胶膜热性能、膜表面化学组成以及膜疏水性进行研究。结果表明，氟醇成功地接入HBPU的末端形成了端氟烷基超支化聚氨酯。HBPUF乳胶粒具有明显的核壳结构，乳液稳定性良好。与PU、HBPU膜相比，HBPUF膜的热稳定性有所提高。XPS分析表明HBPUF膜中氟链段有向表面迁移并富集的趋势，造成HBPUF胶膜表面的水接触角从PU胶膜的77.8?增至113.9?，吸水率从PU胶膜的136.2%降到11.1%，膜疏水性增加。

Abstract:

Abstract：Polyurethane prepolymer (PU) was prepared via the acetone process using isophorone diisocyanate (IPDI), polybutylene adipate (CMA-1044), 1,4-butanediol (BDO) and dimethylolpropionic acid (DMPA) as raw materials. Hyperbranched polyurethane (HBPU) was synthesized through modification of PU by hydroxyl-terminated hyperbranched polymer. Then, novel fluoroalkyl-terminated hyperbranched polyurethane (HBPUF) was prepared by the grafting reaction of perfluorohexyl ethyl alcohol and HBPU. Finally, HBPUF emulsion was obtained by neutralization, adding water, and high-speed stirring operations. Infrared spectrum (IR), proton nuclear magnetic resonance (1H NMR), Transmission electron microscope (TEM), nano particle size, thermogravimetry analyzer (TGA), X-ray photoelectron spectroscopy (XPS) and static contact angle analyzer were utilized to characterize structure of the resultants, particle morphology and average size, thermal stability, chemical compositions as well as hydrophobicity of the latex film. Results showed that fluorinated monoalcohol was successfully linked to the HBPU end to form HBPUF. HBPUF latex possessed the core-shell particle structure and the favorable stability. Thermal stability of HBPUF film was enhanced by comparison with PU and HBPU films. The fluoroalkyl groups had the tendency to enrich at the film-air interface by XPS, which engendered water contact angle on HBPUF film increase from 77.8?on PU film to 113.9?and water absorption of HBPUF film reduce from 136.2% of PU film to 11.1%. Hydrophobicity of the HBPUF film was accordingly improved.