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林产化学与工业 ›› 2024, Vol. 44 ›› Issue (1): 1-8.doi: 10.3969/j.issn.0253-2417.2024.01.001

• 研究报告 • 上一篇    下一篇

松香基非异氰酸酯聚氨酯的制备及其性能研究

张博文1,2(), 周月敏2, 刘鹤2,*(), 刘仕伟1, 商士斌2, 宋湛谦2   

  1. 1. 青岛科技大学 化工学院, 山东 青岛 266042
    2. 中国林业科学研究院 林产化学工业研究所, 江苏 南京 210042
  • 收稿日期:2022-09-19 出版日期:2024-02-28 发布日期:2024-02-23
  • 通讯作者: 刘鹤 E-mail:zhangbw1510@163.com;liuhe_caf@163.com
  • 作者简介:刘鹤, 研究员, 博士生导师, 研究领域为松脂资源深加工利用; E-mail: liuhe_caf@163.com
    张博文(1996—), 男, 山东枣庄人, 博士生, 从事生物基功能高分子材料的研究;E-mail:zhangbw1510@163.com
  • 基金资助:
    国家自然科学基金资助项目(32071708)

Preparation and Properties of Rosin-based Non-isocyanate Polyurethane

Bowen ZHANG1,2(), Yuemin ZHOU2, He LIU2,*(), Shiwei LIU1, Shibin SHANG2, Zhanqian SONG2   

  1. 1. College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
    2. Institute of Chemical Industry of Forest Products, CAF, Nanjing 210042, China
  • Received:2022-09-19 Online:2024-02-28 Published:2024-02-23
  • Contact: He LIU E-mail:zhangbw1510@163.com;liuhe_caf@163.com

摘要:

以松香衍生物丙烯海松酸(APA)为原料合成了丙烯海松酸二缩水甘油醚(AE),并进一步制得丙烯海松酸环碳酸酯(AC), 利用AC中环碳酸酯基团与聚乙烯亚胺(PEI)、聚酯多元胺(Priamine 1074)中的氨基反应制备得到了松香基非异氰酸酯聚氨酯(ACPP)薄膜材料。采用红外光谱(FT-IR)、热重(TG)、动态热机械法(DMA)等技术对ACPP材料的结构和性能进行了表征。研究结果表明:随着AC含量的增加, 松香结构中氢化菲环刚性结构的引入量增加, 从而使ACPP的力学性能增强, 当氨基/环碳酸酯基物质的量比值为1时材料(ACPP1)的拉伸强度可达到15 MPa;同时ACPP材料的玻璃化转变温度(Tg)显著增大, 均大于40 ℃,当氨基/环碳酸酯基物质的量比值为0.8时, 制备得到的材料(ACPP0.8)的Tg达到最大值, 为49.4 ℃。自愈合性能测试结果显示:当带有划痕的ACPP1在160 ℃、5 MPa条件下, 加热1 h后可以实现划痕的完全愈合, 愈合率高达100%;另外, ACPP1分别经过物理再加工和化学回收再加工后, 力学性能仍可以恢复到原始强度的85%, 展现出了优异的回收再加工性能。

关键词: 丙烯海松酸, 非异氰酸酯聚氨酯, 自愈合, 再加工

Abstract:

Acrylpimaric acid diglycidyl ether(AE) was synthesized from acrylpimaric acid(APA), a rosin derivative, and acrylpimaric acid cyclocarbonate(AC) was further prepared. Then the rosin-based non-isocyanate polyurethane(ACPP) film materials was prepared by the reaction of the cyclic carbonate groups of AC with the amino group in polyethylenimine(PEI) and the polyester polyamine(Priamine 1074). The structure and properties of ACPP materials were characterized by Fourier transform infrared spectroscopy(FT-IR), thermogravimetric(TG), dynamic thermomechanical analysis(DMA) and other techniques. The results showed that with the increase of AC content, the introduction of rigid structure of hydrogenated phenanthrene ring in the rosin structure increased, resulting in the enhancement of the mechanical properties of ACPP. The tensile strength of the material (ACPP1) could reach 15 MPa when the amino/cyclocarbonate group molar ratio value was 1. At the same time, the glass transition temperature(Tg) of ACPP material increased significantly, which were greater than 40 ℃. When the molar ratio of amino group to cyclocarbonate group was 0.8, the Tg of ACPP0.8 reached the maximum value of 49.4 ℃. The results of self-healing performance test showed that the scratch healing of ACPP1 material with scratch could be achieved after 1 h heating at the condition of 160 ℃ and 5 MPa, and the healing rate was up to 100%. In addition, after physical reprocessing and chemical recovery and reprocessing, the mechanical properties of ACPP1 materials could still be restored to 85% of the original strength, showing excellent recovery and reprocessing performance.

Key words: acrylimaric acid, non-isocyanate polyurethane(NIPU), self-healing, reprocessing

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