高等学校化学学报 ›› 2021, Vol. 42 ›› Issue (8): 2651.doi: 10.7503/cjcu20200824

• 高分子化学 • 上一篇    下一篇

基于肟-氨基甲酸酯的超强自修复水性聚氨酯胶粘剂的制备及性能分析

李聪, 刘欢欢, 杨桂花(), 田中建, 颜家强, 吉兴香, 韩文佳, 陈嘉川()   

  1. 齐鲁工业大学(山东省科学院)生物基材料与绿色造纸国家重点实验室/ 制浆造纸科学与技术教育部重点实验室, 济南 250353
  • 收稿日期:2020-11-20 出版日期:2021-08-10 发布日期:2021-08-05
  • 通讯作者: 杨桂花 E-mail:ygh@qlu.edu.cn;chenjc@qlu.edu.cn
  • 作者简介:陈嘉川, 男, 博士, 教授, 主要从事制浆造纸方面的研究. E-mail:chenjc@qlu.edu.cn
  • 基金资助:
    国家重点研发计划项目(2019YFC1905904);山东省自然科学基金(ZR2019MEM002);山东省科教产融合创新试点工程(2020KJC-ZD14);齐鲁工业大学(山东省科学院)生物基材料与绿色造纸国家重点实验室自主课题项目(ZR20190205)

Preparation and Performance Analysis of Extremely High Strength Self-repairing Waterborne Polyurethane Adhesive Based on Oxime-carbamate

LI Cong, LIU Huanhuan, YANG Guihua(), TIAN Zhongjian, YAN Jiaqiang, JI Xingxiang, HAN Wenjia, CHEN Jiachuan()   

  1. State Key Laboratory of Biobased Materials and Green Papermaking Co?founded by Shandong and the Ministry of Science and Technology/Key Laboratory of Pulp & Paper Science and Technology of Education Ministry,Qilu University of Technology (Shandong Academy of Sciences),Jinan 250353,China
  • Received:2020-11-20 Online:2021-08-10 Published:2021-08-05
  • Contact: YANG Guihua E-mail:ygh@qlu.edu.cn;chenjc@qlu.edu.cn

摘要:

基于肟-氨基甲酸酯热可逆成键原理, 利用可工业批量获得的二甲基乙二肟为构建单元, 设计合成了一类具有高强动态网络结构的水性乳液, 制备出综合性能与重复利用兼顾的聚氨酯胶粘剂; 通过变温红外光谱结合差式扫描量热仪分析了肟-氨基甲酸酯升温过程的可逆成键特性, 并利用动态力学谱仪对变温过程的网络松弛行为进行了研究. 结果表明, 合理的硬段含量与结构设计赋予了胶粘剂极高的粘结强度(25 MPa, 一般商业通用热熔胶的粘结强度< 6 MPa)、 优异的乳液稳定性(粒径<100 nm)以及接近97%的修复效率(160 ℃, 10 min下的剪切搭接实验). 该类乳液具有超强、 稳定及工艺可放大等特性, 为水性自修复胶粘剂的商业化开发提供了新途径和新思路.

关键词: 水性聚氨酯, 粘结强度, 二甲基乙二肟, 自修复

Abstract:

From the perspective of recycling, commercial polyurethane hot-melt adhesives (HMA) could be reused many times via hot melting. However, the performance degradation after recylcing seriously impaired the reuse value. Although thermosetting structures could improve the performance, the material would not be reused once it was cured in view of the above challenges. A new water-based emulsion with high strength and dynamic network structure was synthesized from dimethylglyoxime, which was based on the thermal reversible bonding of carbamate ester, a commercially available chemical as the building block. In this paper, the rever-sible bonding characteristics of oxime-carbamate were analyzed by variable temperature infrared spectroscopy and differential scanning calorimetry. The dynamic dissociation phenomenon of the network at high temperature was strongly verified. The corresponding network relaxation behavior was quantitatively studied by dynamic mechanical spectrometer. The results showed that the proper hard segment content and structural design would give the adhesive the extremely high bonding strength (25 MPa, the commercially available hot-melt adhesive <6 MPa), excellent emulsion stability (particle size <100 nm), and the repair efficiency closed to 97% (lap shear test at 160 ℃ for 10 min). These waterborne emulsions had the characteristics of high strength, self repair and expandability, which opened up a feasible way for commercial application of this functional material in the field of adhesives.

Key words: Waterborne polyurethane, Adhesive strength, Dimethylglyoxime, Self-repairing

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