高固含量无机锆盐/复合酸型聚氨酯乳液的制备与性能

Synthesis and Properties of InorganicZirconium Salts/ Mixed Acid-based Polyurethane Emulsion of High Solid Content

摘要:

采用丙酮法，以聚己内酯二元醇（PCL-1000）和异佛尔酮二异氰酸酯（IPDI）为原料，以羧酸盐型二羟甲基丁酸（DMBA），磺酸盐型乙二胺基乙磺酸钠（AAS）、二胺磺酸钠（PPS）为亲水性扩链剂，碳酸锆铵（AZC）为交联剂，分别制备了纯DMBA型聚氨酯、DMBA/PPS型、DMBA/AAS型高固含量无机锆盐/复合酸型聚氨酯（WPU）乳液。利用FT-IR、TEM、TGA对乳液及其乳胶膜进行了结构表征，对乳液的固含量、粒径、黏度，乳胶膜的吸水率、拉伸强度、断裂伸长率及胶粘剂的剥离强度进行了测定。红外光谱分析证实了分子中磺酸基团和Zr的存在。研究了不同羧酸/磺酸的质量比及碳酸锆铵盐对胶膜性能的影响。结果表明，相对于纯DMBA型WPU乳液，DMBA型含锆盐WPU乳液的粒径由81.8nm增至114.8nm，其胶膜对应的T10%(℃)及T50%(℃)分别从207.25℃、338.8℃，提高至303.41℃、363.17℃，说明碳酸锆铵的引入提高了胶膜的热稳定性；在最佳原料配比〔m(DMBA):m(AAS)=7∶3〕下，制备的含锆盐DMBA/AAS 型WPU乳液固含量从50.8%提高至51.2%，胶膜吸水率从25.00%降至12.97%，拉伸强度从18.88MPa提高至49.9MPa，断裂伸长率从337.28%提高至411.12%，橡胶-皮革试样剥离强度从9.24N/cm提高至15.21N/cm。与DMBA/PPS型WPU相比，DMBA/AAS型WPU具有更优异的性能。

Abstract:

Inorganic zirconium salt/mixed acid-based polyurethane (WPU) emulsion of high solid content was synthesized via acetone method，using polycaprolactone diol (PCL-1000) as soft chain segment, isophorone diisocyanate (IPDI) as hard chain segment, dimethylmethyl butyric acid (DMBA), 2-[(2-aminoethyl)amino]-ethanesulfonicacidmonosodiumsalt (AAS), and sodium diamine sulfonate (PPS) as hydrophilic chain extender, ammonium zirconium carbonate (AZC) as crosslinking agent. The resultant emulsions were designated as DMBA based WPU, DMBA/AAS based WPU, DMBA/PPS based WPU, respectively. The structure of WPU containing sulfonic acid groups and Zr was confirmed by infrared spectroscopic analysis. Effects of the ratio of carboxyl acid to sulfonic acid and zirconium carbonate were systematically investigated. Compared with pure DMBA based WPU emulsion, the particle size of the WPU emulsion prepared with ammonium zirconium carbonate increased from 81.8nm to 114.8nm, and the T10%(℃) and T50%(℃) of the film increased from 207.25℃to 303.41℃, 338.8℃ to 363.17℃, respectively. It demonstrated the introduction of ammonium zirconium carbonate improved the thermal stability of the film.The WPU emulsion prepared with 7:3 DMBA/AAS displayed the optimum properties, the solid content increased from 50.8% to 51.2%, the water absorption increased from 25% to 12.97%, tensile strength increased from 18.88MPa to 49.9MPa, elongation at break increased from 337.28% to 411.12%, and the peel strength increased from 9.24N/cm to 15.21N/cm, respectively. In comparison with DMBA/PPS based WPU, DMBA/AAS based WPU was endowed with better performance.