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含大位阻脲键的功能化聚氨酯丙烯酸酯的制备与性能

李英昊 王新灵

李英昊, 王新灵. 含大位阻脲键的功能化聚氨酯丙烯酸酯的制备与性能[J]. 功能高分子学报,2022,35(5):1-8 doi: 10.14133/j.cnki.1008-9357.20211228001
引用本文: 李英昊, 王新灵. 含大位阻脲键的功能化聚氨酯丙烯酸酯的制备与性能[J]. 功能高分子学报,2022,35(5):1-8 doi: 10.14133/j.cnki.1008-9357.20211228001
LI Yinghao, WANG Xinling. Synthesis and Properties of Functional Polyurethane-Acrylates Bearing Hindered Urea Bonds[J]. Journal of Functional Polymers. doi: 10.14133/j.cnki.1008-9357.20211228001
Citation: LI Yinghao, WANG Xinling. Synthesis and Properties of Functional Polyurethane-Acrylates Bearing Hindered Urea Bonds[J]. Journal of Functional Polymers. doi: 10.14133/j.cnki.1008-9357.20211228001

含大位阻脲键的功能化聚氨酯丙烯酸酯的制备与性能

doi: 10.14133/j.cnki.1008-9357.20211228001
详细信息
    作者简介:

    李英昊(1997—),女,上海人,硕士生,主要研究方向为3D打印聚氨酯。E-mail:lyh_sjtu@sina.com

    通讯作者:

    王新灵, E-mail:xlwang@sjtu.edu.cn

  • 中图分类号: TQ322.4

Synthesis and Properties of Functional Polyurethane-Acrylates Bearing Hindered Urea Bonds

  • 摘要: 以双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯(TMPCA)为软段、1,3-双(1-异氰酸酯-1-甲基乙基)苯(TMXDI)为硬段、甲基丙烯酸异冰片酯(IBOMA)为反应性稀释单体,经甲基丙烯酸羟乙酯(HEMA)封端后得到含有大位阻脲键的聚氨酯丙烯酸酯预聚体;预聚体经紫外光固化,制备得到光敏树脂材料。随后,通过微量热和变温红外对体系中大位阻脲键的热解离机理进行探索,并对光敏树脂的修复性、形状记忆性和二次塑形能力进行了研究。结果表明:大位阻脲键在46~56 °C范围内存在吸热效应,预聚体和固化后树脂中均可以观察到异氰酸酯含量随温度改变发生动态变化;即体系具有动态共价高分子的特点。固化后的光敏树脂修复性能良好,修复后试样的拉伸强度由13.8 MPa恢复至18.4 MPa,且修复界面宽度小于50 μm。此外,含有大位阻脲键的光敏树脂展现出良好的形状记忆和二次塑形能力,并且二次塑形后材料仍能保持80%的弯曲强度。

     

  • 图  1  以TMPCA为软段、TMXDI为硬段的异氰酸酯齐聚物的合成路线示意图

    Figure  1.  Synthetic route of PU oligomer with TMPCA as soft segment and TMXDI as hard segment

    图  2  含大位阻脲键的的光敏树脂的DMA分析

    Figure  2.  DMA analysis of photopolymers with hindered urea bonds

    图  3  含大位阻脲键的预聚体的微量热表征

    Figure  3.  MicroDSC analysis of prepolymer with hindered urea bonds

    图  4  含大位阻脲键的预聚体的变温红外表征

    Figure  4.  Temperature-dependent FT-IR spectra of prepolymer with hindered urea bonds

    图  5  不同温度下光敏树脂的NCO特征峰峰面积

    Figure  5.  Effect of temperature on NCO peak area

    图  6  修复试样的制备

    Figure  6.  Preparation for repairability sample

    图  7  修复前后含大位阻脲键的光敏树脂的应力-应变曲线

    Figure  7.  Stress-stain curves of photopolymers with hindered urea bonds before and after the repair

    图  8  修复试样拉伸断面的 (a) 形貌示意图与 (b) SEM照片

    Figure  8.  (a) Diagrammatic cross-section and (b) SEM image of cross-section of a repaired sample

    图  9  含大位阻脲键的光敏树脂的形状记忆过程

    Figure  9.  Shape memory process of photopolymers with hindered urea bonds

    图  10  含大位阻脲键的光敏树脂的二次塑形过程

    Figure  10.  Reshaping process of photopolymers with hindered urea bonds

    图  11  二次塑形前后含大位阻脲键的光敏树脂的弯曲强度

    Figure  11.  Flexural strength of photopolymers with hindered urea bonds before and after being reshaped

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出版历程
  • 收稿日期:  2021-12-28
  • 录用日期:  2022-03-16
  • 网络出版日期:  2022-03-25

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