亲水扩链剂对超支化水性聚氨酯皮革涂饰剂成膜性能的影响∗

摘要

超支化聚氨酯具有粘度低、溶解能力增强、成膜性能好、良好的耐水性、热稳定性、物理机械性能等优点,所以在理论和应用上超支化聚氨酯逐渐成为皮革涂饰领域研究的热点。首先,以二乙醇胺(DEA)和丁二酸酐为原料,甲醇为溶剂,合成一种新型羧酸型亲水单体(DMCA),优化得到DMCA的最佳条件为温度0℃,n(DEA)∶n(丁二酸酐)＝1∶1．2,时间为80 min,甲醇用量为300 mL/mol (DEA),在最佳条件下DMCA的转化率为86．18％。采用红外(FT-IR)、核磁(1 H NMR)、X射线衍射(XRD)、热重(TG)、元素分析等手段对DMCA进行结构和性能的表征。其次,以DEA、丙烯酸甲酯(MA)、三羟甲基丙烷(TMP)为主要原料,甲醇为溶剂,采用有核“一步法”制备端羟基超支化聚合物(HPAE)。最后,以一代端羟基超支化聚合物为代表,将其与聚四氢呋喃(PTMG, Mn＝1000)、异佛尔酮二异氰酸酯(IPDI)、1,4-丁二醇为主要原料,使用羧酸型单体二羟甲基丙酸(DMPA)、二羟甲基丁酸(DMBA)、自制羧酸型单体(DMCA)为亲水扩链剂分别合成3种超支化水性聚氨酯皮革涂饰剂。通过红外光谱(FT-IR)、扫描电镜(SEM)、原子力显微镜(AFM)、乳液粒径、热重(TG )、示差热分析(DSC)等现代仪器对3种涂饰剂结构和性质进行表征,并对3种薄膜的物理机械性能、薄膜接触角、耐热耐水耐溶剂性能进行对比研究。%Hyperbranched polyurethane has low viscosity,solubility enhancement,film-forming performance was good,good water resistance,thermal stability and physical and mechanical properties,so hyperbranched polyurethane gradually becomes a hotspot in research of leather finishing field in theory and applications. Firstly,with diethanolamine (DEA)and succinic anhydride as raw materials and methanol alcohol as sol-vent,synthesized a new carboxylic acid type of hydrophilic monomer DMCA,the best conditions for synthetic hydrophilic monomer were:the temperature was 0 ℃,the mole ratio was 1∶1.2,the time was 80 min,solvent dosage was 300 mL/mol (DEA),under the best conditions the conversion rate reached 86.18%.Charaterized the structure and performance adopting infrared (FT-IR),nuclear magnetic (1 H NMR),X-ray diffraction (XRD),thermogravimetric (TG),element analysis and so on. Then,using diethanolamine (DEA),methyl acrylate (MA),trimethylolpropane (TMP)as the main raw materials,methanol alcohol as solvent,hydroxyl-terminated hyperbranched polymer (HPAE)was prepared using nuclear “one-step”. Lastly,represented by a generation of hydroxyl-terminated hyperbranched polymer,with the polyethylene tetrahydrofuran (PTMG,Mn=1 000),wasophorone diisocyanate (IPDI),1,4-butanediol (BDO)as the main raw materials,the use of carboxylic acid type monomers of dihydroxy methyl propionic acid (DMPA),di-hydroxy methyl butyric acid (DMBA)and homemade carboxylic acid monomer DMCA as hydrophilic chain ex-tender to synthesize three kinds of carboxylic acid hyperbranched waterborne polyurethane leather finishing agents respectively.Charaterized the structures and properties of three kinds of leather finishing agents by infra-red spectroscopy (FT-IR),scanning electron microscope (SEM),atomic force microscope (AFM),the emul-sion particle size,thermogravimetric (TG),DSC and other modern instruments,and physical and mechanical properties of thin films,film contact angles,heat resistance,water resistance and solvent resistance were stud-ied for comparison.