应用化学 ›› 2017, Vol. 34 ›› Issue (10): 1110-1116.DOI: 10.11944/j.issn.1000-0518.2017.10.170231

• 研究论文 • 上一篇    下一篇

多元醇对对苯二异氰酸酯基聚氨酯微孔弹性体的形态与性能影响

郇彦ab,李肖肖ab,田雨濛ad,王杰c*(),杨小牛ac*()   

  1. a中国科学院长春应用化学研究所,高分子复合材料工程实验室 长春 130022
    b中国科学院大学 北京 100049
    c中国科学院长春应用化学研究所,高分子物理与化学国家重点实验室 长春 130022
    d中国科学技术大学 合肥 230026
  • 收稿日期:2017-06-27 接受日期:2017-07-20 出版日期:2017-09-29 发布日期:2017-09-29
  • 通讯作者: 王杰,杨小牛
  • 基金资助:
    吉林省重点科技攻关项目资助(20160204031GX)

Effect of Polyols on the Morphology and Properties of 1,4-Phenylene Diisocyanate-Based Microcellular Polyurethane Elastomers

HUAN Yanab,LI Xiaoxiaoab,TIAN Yumengad,WANG Jiec*(),YANG Xiaoniuac*()   

  1. aPolymer Composites Engineering Laboratory,Changchun Institute of Applied Chemistry Chinese Academy of Sciences,Changchun 130022,China
    bUniversity of Chinese Academy of Sciences,Beijing 100049,China
    cState Key Laboratory of Polymer Physics and Chemistry,Changchun Institute of Applied Chemistry Chinese Academy of Sciences,Changchun 130022,China
    dUniversity of Science and Technology of China,Hefei 230026,China
  • Received:2017-06-27 Accepted:2017-07-20 Published:2017-09-29 Online:2017-09-29
  • Contact: WANG Jie,YANG Xiaoniu
  • Supported by:
    Supported by the Jilin Province Key Scientific and Technological Projects(No.20160204031GX)

摘要:

以对苯二异氰酸酯(PPDI)、1,4-丁二醇、水、聚四氢呋喃醚多元醇(PTMEG)和氢化端羟基丁二烯多元醇(HLBH)为原料,采用两步法制备出聚氨酯微孔弹性体样品。 通过傅里叶变换衰减全反射红外光谱(FTIR-ATR)、动态机械分析(DMA)、差示扫描量热仪(DSC)、万能材料试验机等技术手段对样品的微相分离、耐低温性能、动态生热进行了系统表征。 结果表明,两种多元醇结构对泡孔尺寸影响不大,微孔尺寸在100~300 μm之间,其中以150 μm尺寸左右的泡孔居多;HLBH制备的聚氨酯微孔弹性体硬段形成的氢键数量多于PTMEG制备的微孔弹性体,具有更好的微相分离;由于较好的微相分离结构,HLBH样品在-30~150 ℃具有很宽的模量平台区,而PTMEG样品受软段的低温结晶影响,在0 ℃以下模量急剧上升,HLBH样品低温下的刚度变化优于PTMEG样品;同时HLBH样品的滞后生热亦小于PTMEG样品,具有更好的动态疲劳性能。

关键词: 聚氨酯材料, 聚氨酯微孔弹性体, 微相分离, 低温, 对苯二异氰酸酯

Abstract:

Microcellular polyurethane elastomers were obtained by a two-step polymerization using 1,4-phenylene diisocyanate(PPDI), 1,4-butanediol(BDO), water, polyethylene tetrahydrofuran ether polyol(PTMEG) and hydrogenated hydroxyl-terminated butadiene polyols(HLBH) as raw materials. Fourier reflection infrared(FTIR-ATR), dynamic mechanical analysis(DMA), differential scanning calorimetry(DSC), universal material testing machine, dynamic fatigue testing machine were used to systematically characterize the microphase separation, low temperature resistance, dynamic heat build-up of the samples. The results show that the microcellular size of the specimens based on two polyols is 100~300 μm wherein the 150 μm is the majority, indicating that the structure of polyols has little influence on the microcellular size. Due to more H-bonds between hard segments, HLBH-based microcellular polyurethane elastomers show better microphase separation than that of PTMEG. There is a wide modulus platform region at -30~150 ℃ in the modulus-temperature curve for HLBH-based specimens due to its proper microphase separation structure. However, due to the crystallization of the soft segments at low temperature, the modulus of PTMEG-based specimens increases dramatically under 0 ℃. The stiffness of HLBH-based specimens surpasses that of PTMEG-based specimens at low temperature, and the hysteresis heat production of HLBH-based specimens is less than that of PTMEG-based specimens. Therefore, the former shows better dynamic fatigue performance.

Key words: polyurethane material, microcellular polyurethane elastomer, microphase separation, low temperature, phenylene diisocyanate