有机氟醇改性超支化水性聚氨酯的合成与性能研究

摘要

以三羟甲基丙烷为核,2, 2-二羟甲基丙酸(DMPA)为单体,用"准一步法"合成1、3代超支化聚酯(HBPE-1和HBPE-3).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DMPA为原料,合成-NCO封端的聚氨酯预聚体(PU).再将HBPE与PU反应制得超支化聚氨酯(HBPU);然后利用全氟己基乙醇(S104)改性HBPU,制得两种有机氟醇改性超支化聚氨酯(HBPUF-1和HBPUF-3),最后经中和、加水乳化即制得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)、X-射线光电子能谱仪(XPS)以及接触角测量仪等对其结构和性能进行研究.结果表明:产物具有预期的结构.HBPUF-1和HBPUF-3乳液粒径较PU乳液粒径有所增大,乳胶粒呈较规则球状.HBPUF-1和HBPUF-3膜质量损失为50%所对应的分解温度比 PU 膜分别提高了 17 ℃和29 ℃.XPS测试表明,氟烷基有向表面迁移和定向排列的趋势,这也是HBPUF膜疏水性增强的主要原因.与PU膜相比,HBPUF-1和HBPUF-3膜表面的静态水接触角分别从75.1 °增至95.9 °和107.0 °.%The first and third generations of hyperbranched polyesters (HBPE-1 and HBPE-3) were first fabricated via the pseudo one-pot procedure,using trimethylolpropane as the core and 2,2-bis-methylolpropionic aid (DMPA) as the monomer.A polyurethane prepolymer (PU) containing NCO terminals was then synthesized by the stepwise polymerization of isophorone diisocyanate (IPDI),poly (butylenes adipate) glycol (CMA-1044),DMPA and butanediol.Next,HBPEs were reacted with PU to obtain hyperbranched polyurethanes (HBPU).A couple of organic fluorine alcohol modified hyperbranched polyurethanes (HBPUF-1 and HBPUF-3) were acquired via action between perfluorohexyl ethyl alcohol (S104) and HBPU,finally,HBPUF latexes were obtained by neutralization,adding water,and emulsification operations.Infrared spectrum (IR),proton nuclear magnetic resonance spectrum (1H NMR),transmission electron microscope (TEM),nanoparticle size analyzer,thermogravimetric analyzer (TGA),X-ray photoelectron energy spectrum (XPS) and static contact angle analyzer were utilized to examine its structure and properties.Results showed that the resultant possessed the due structure.The HBPUF latex particles presented a regularly spherical pattern with the increased diameters compared to the PU latex.Furthermore,thermal decomposition temperatures of HBPUF-1 and HBPUF-3 films at half weight loss were increased by 17 ℃ and 29 ℃,respectively,by comparison to PU film.XPS analysis indicated that the fluoroalkyl segments tended to migrate and align directionally to the air-film surface,which is the primary reason for reinforcement of the HBPUF film hydrophobicity.As a result,water static contact angles on HBPUF-1 and HBPUF-3 films were individually increased to 95.9 ° and 107.0 ° in contrast to that on the PU film (75.1 °).