基于CuAAC反应链间自交联有机-无机杂化水性聚氨酯的合成及性能

Synthesis and Properties of Intermolecular Self-crosslinking Organic-inorganic Hybrid Waterborne Polyurethane Based on CuAAC Reaction

利用4,4'-二羟甲基-1,4-庚二炔功能单体作为扩链剂合成了一系列炔基接枝量不同的水性聚氨酯(WPU),然后基于铜催化的叠氮-炔基环加成(CuAAC)反应,采用3-叠氮基丙基三乙氧基硅烷(APTES-N3)改性炔基功能化WPU,制备了室温链间自交联有机-无机杂化WPU.采用红外光谱(FTIR)和核磁氢谱(1H NMR)表征了自交联有机-无机杂化WPU.探讨了APTES-N3接枝量对WPU膜性能和WPU乳液形态的影响.结果表明,随着APTES-N3含量增加,WPU膜的结晶性逐渐下降;耐水性、耐溶剂性和热稳定性逐渐增强;WPU乳液粒子黏连程度增加.当APTES-N3质量分数从0增大到12%时,WPU膜的拉伸强度从14.3MPa增加到28.6 MPa.

A series of waterborne polyurethane （WPU） bearing the varying quantities of alkyne functions as pendant groups located along the backbone was synthesized via the 4,4＇-bis （hydroxymethyl） -1,4-heptadiyne functional monomer as a chain extender. The room temperature intermolecular self-crosslinking organic-inor- ganic hybrid WPU was prepared based on the Cu（ I ）-catalyzed azide-alkyne cycloaddition（CuAAC） reaction between alkyne-functionalized WPU and azide propyltriethoxysilane （APTES-N3 ）. The self-crosslinking organic-inorganic hybrid WPU was prepared, which was confirmed by FTIR and 1H NMR. The influences of the grafting amount of APTES-N3 on properties of the WPU films and the emulsion particle morphology of WPU were studied. The results indicate that with the increase of APTES-N3, crystallinity of the WPU films decreasedand resistance to water, solvent resistance and thermal stability of the WPU films increased, and the degree of mutual adhesion of emulsion particles enhanced. As the mass fraction of APTES-N3 increases from 0 to 12%, the tensile strength of the WPU film increases from 14.3 MPa to 28.6 MPa. Synthetically taking into account the emulsion stability, water resistance and mechanical properties of WPU, when the mass fraction of APTES-N3 is 12%, the integrative performances of WPU is the best.