王玉龙,李雅琼,林泽,刘云正,李振中

• 1:太原工业学院 材料工程系，山西 太原 030008

摘要(Abstract)：

为解决自修复聚氨酯脲(PUU)弹性体兼具高修复效率和优异力学性能的问题，提出在PUU弹性体主链引入动态双硫键或双硒键。以聚碳酸酯二醇(PCDL)为软段，异佛尔酮二异氰酸酯(IPDI)为硬段，分别以胱胺(CY)、硒代胱胺(SeCY)和1,6-己二胺(HDA)为扩链剂，通过溶液法制备3种PUU弹性体，即含动态双硫键的PUU试样(SPU)、含动态双硒键的PUU试样(SePU)和对照组PUU试样(CPU)。通过红外、X射线衍射、拉伸测试、光学显微、热分析等对3种试样的结构和性能进行表征。结果表明，SPU的力学性能和自修复性能达到较好的平衡，拉伸强度和断裂伸长率分别达到53.1 MPa和400.5%，80 ℃修复12 h后的自修复效率分别为87.2% 和75.7%；SePU具有最优的自修复性能，80 ℃修复12 h后的自修复效率达到98.9%和95.3%。

关键词(KeyWords)： 双硫键;双硒键;自修复;聚氨酯脲;机械性能

Abstract:

Keywords:

基金项目(Foundation): 山西省高校科技创新基金(2021L551)；太原工业学院引进人才科研资助项目(2022TG0706)

作者(Author): 王玉龙,李雅琼,林泽,刘云正,李振中

DOI: 10.3969/j.issn.1003-9015.2023.03.009

参考文献(References)：

• [1] 刘厚钧. 聚氨酯弹性体手册 [M]. 北京: 化学工业出版社, 2012. LIU H J. Polyurethane elastomer manual [M]. Beijing: Chemical Industry Press, 2012.
  [2] NEVEJANS S, BALLARD N, RIVILLA I, et al. Synthesis of mechanically strong waterborne poly(urethane-urea)s capable of self-healing at elevated temperatures [J]. European Polymer Journal, 2019, 112: 411-422.
  [3] 黄辉, 李娟华, 吴广东, 等. 硬段类型和含量对嵌段聚氨酯脲性能的影响 [J]. 高分子材料科学与工程, 2020, 36(1): 63-69. HUANG H, LI J H, WU G D, et al. Effect of hard segment structure and content on properties of block polyurethane ureas [J]. Polymer Materials Science and Engineering, 2020, 36(1): 63-69.
  [4] WU H H, LIU X D, SHENG D K, et al. High performance and near body temperature induced self-healing thermoplastic polyurethane based on dynamic disulfide and hydrogen bonds [J]. Polymer, 2020, 124: 123261.
  [5] GUO H S, HAN Y, ZHAO W Q, et al. Universally autonomous self-healing elastomer with high stretchability [J]. Nature Communications, 2020, 11: 1-10.
  [6] LI C H, WANG C, KEPLINGER C, et al. A highly stretchable autonomous self-healing elastomer [J]. Nature Chemistry, 2016, 8: 618-624.
  [7] REKONDO A, MARTIN R, LUZURIAGE A R, et al. Catalyst-free room-temperature self-healing elastomers based on aromatic disulfide metathesis [J]. Materials Horizons, 2014, 1(2): 237-240.
  [8] JI S B, CAO W, YU Y, et al. Dynamic diselenide bonds: Exchange reaction induced by visible light without catalysis [J]. Angewandte Chemie International Edition, 2014, 126(26): 6899-6903.
  [9] QIAN Y Q, AN X W, HUANG X F, et al. Recyclable self-healing polyurethane cross-linked by alkyl diselenide with enhanced mechanical properties [J]. Polymers, 2019, 11(5): 773-784.
  [10] LIU M C, ZHONG J, LI Z J, et al. A high stiffness and self-healable polyurethane based on disulfide bonds and hydrogen bonding [J]. European Polymer Journal, 2020, 124: 109475-109499.
  [11] FAN W H, JIN Y, HUANG Y H, et al. Room-temperature self-healing and reprocessing of diselenide-containing waterborne polyurethanes under visible light [J]. Journal of Applied Polymer Science, 2018, 136(7): 47071-47082.
  [12] LIU J, MA X N, TONG Y P, et al. Syntheses of diselenide-containing dynamic polymers and their application in polymer alloys [J]. Applied Surface Science, 2018, 467: 477-485.
  [13] DU W N, JIN Y, PAN J Z, et al. Thermal induced shape-memory and self-healing of segmented polyurethane containing diselenide bonds [J]. Journal of Applied Polymer Science, 2018, 135(22): 46326-46335.
  [14] AN X W, AGUIRRESAROBE R H, IRUSTA L, et al. Aromatic diselenide crosslinkers to enhance the reprocessability and self-healing of polyurethane thermosets [J]. Polymer Chemistry, 2017, 8(23): 3641-3646.
  [15] JO Y H, LI S Q, ZUO C, et al. Self-healing solid polymer electrolyte facilitated by a dynamic cross-linked polymer matrix for lithium-ion batteries [J]. Macromolecules, 2020, 53(3): 1024-1032.
  [16] 王玉龙, 胡国胜, 张静婷, 等. 基于双硫键和氢键协效的高性能自修复聚氨酯脲的研制 [J]. 化工进展, 2021, 40(1): 324-331. WANG Y L, HU G S, ZHANG J T, et al. Development of self-healing poly(urethane urea) with high performances based on the synergistic effect of disulfide bonds and hydrogen bonds [J]. Chemical Industry and Engineering Progress, 2021, 40(1): 324-331.
  [17] FAN W H, JIN Y, SHI L J, et al. Transparent, eco-friendly, super-tough “living” supramolecular polymers with fast room-temperature self-healability and reprocessability under visible light [J]. Polymer, 2020, 190: 122199-122210.
  [18] WANG Y L, YI J M, PENG X H, et al. Structure-property relationships of novel fluorinated polycarbonate polyurethane films with high transparency and thermal stability [J]. Polymer, 2019, 45: 845-862.
  [19] SHI Z, KANG J, ZHANG L. Water-enabled room-temperature self-healing and recyclable polyurea materials with super-strong strength, toughness, and large stretchability [J]. ACS Applied Materials & Interfaces, 2020, 12(20), 23484-23493.
  [20] WANG Y L, LI Y Q, HE M Y, et al. Effect of chain extender on microphase structure and performance of self-healing polyurethane and poly(urethane-urea) [J]. Journal of Applied Polymer Science, 2021, 138(46): 51371-51382.