高等学校化学学报 ›› 2013, Vol. 34 ›› Issue (12): 2871.doi: 10.7503/cjcu20130789

• 高分子化学 • 上一篇    下一篇

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

李兴建, 胡静, 孙道兴, 张宜恒   

  1. 青岛科技大学环境与安全工程学院, 青岛 266042
  • 收稿日期:2013-08-15 出版日期:2013-12-10 发布日期:2013-10-23
  • 作者简介:张宜恒,男,博士,特聘教授,主要从事表面物理化学研究. E-mail:yhzhangqust@163.com
  • 基金资助:

    国家自然科学基金(批准号:21176128,51172116)和山东省自然科学基金(批准号:ZR2010BL022)资助.

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

LI Xing-Jian, HU Jing, SUN Dao-Xing, ZHANG Yi-Heng   

  1. Department of Environment and Safety Engineering, Qingdao University of Science & Technology, Qingdao 266042, China
  • Received:2013-08-15 Online:2013-12-10 Published:2013-10-23

摘要:

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14.3 MPa增加到28.6 MPa.

关键词: 铜催化的1,3-偶极环加成反应, 有机-无机杂化水性聚氨酯, 室温链间自交联

Abstract:

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-inorganic 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 decreased and 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.

Key words: Copper catalyzed 1,3-dipolar cycloaddition reaction, Organic-inorganic hybrid waterborne polyurethane, Room temperature intermolecular self-crosslinking

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