高等学校化学学报 ›› 2012, Vol. 33 ›› Issue (07): 1613-1618.doi: 10.3969/j.issn.0251-0790.2012.07.044

• 高分子化学 • 上一篇    下一篇

聚乙烯醇-g-异氰酸酯-脂肪醇梳状接枝共聚物的合成、 结构及热性能

石海峰1,2, 李剑华1, 尹亿平1, 张兴祥1, 王笃金2   

  1. 1. 中空纤维膜材料与膜过程省部共建国家重点实验室培育基地, 天津工业大学功能纤维研究所, 天津 300160;
    2. 中国科学院化学研究所, 工程塑料重点实验室, 北京 100190
  • 收稿日期:2011-08-04 出版日期:2012-07-10 发布日期:2012-07-10
  • 通讯作者: 石海峰, 男, 博士, 副教授, 主要从事高分子材料研究. E-mail: haifeng.shi@gmail.com E-mail:haifeng.shi@gmail.com
  • 基金资助:

    国家自然科学基金(批准号: 20904040, 21174105)和天津市自然科学重点基金(批准号: 12JC2DJC26800)资助.

Synthesis, Structure and Thermal Properties of Poly(vinyl alcohol)-g-isocyanate-fatty Alcohol Comb Copolymers

SHI Hai-Feng1,2, LI Jian-Hua1, YIN Yi-Ping1, ZHANG Xing-Xiang1, WANG Du-Jin2   

  1. 1. State Key Laboratory of Hollow Fiber Membrane Science and Processing, Institute of Functional Fiber, Tianjin Polytechnic University, Tianjin 300160, China;
    2. CAS Key Laboratory of Engineering Plastics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
  • Received:2011-08-04 Online:2012-07-10 Published:2012-07-10

摘要: 通过甲苯-2,4-二异氰酸酯(TDI)的连接作用, 利用接枝共聚法将具有储热功能的长链脂肪醇[如十八醇(C18OH)、 十六醇(C16OH)和十四醇(C14OH)]接枝到聚乙烯醇(PVA)主链上, 制备出储热能力不同的聚乙烯醇-g-TDI-脂肪醇[PVA-g-TDI-C(n)]梳状接枝共聚物. 通过傅里叶变换红外光谱(FTIR)、 差示扫描量热分析(DSC)、 热重分析(TGA)和X射线衍射(XRD)等方法研究了PVA-g-TDI-C(n)共聚物的热行为和结晶结构. 结果表明, PVA-g-TDI-C(n)共聚物具有良好的储热能力, 储热能力随侧链碳原子数目和侧链接枝度的增加而增大, 但明显低于长链脂肪醇的储热能力. PVA-g-TDI-C(n)共聚物具有良好的热稳定性, 失重温度在324~330 ℃之间. 从侧链受限运动角度探讨了影响PVA-g-TDI-C(n)共聚物热性能和有序堆砌结构的原因.

关键词: 聚乙烯醇, 热能储存, 梳状高分子, 相变材料

Abstract: Using the bridging role of tolylene diisocyanate(TDI), poly(vinyl alcohol)-g-tolylene diisocyanate-fatty alcohol copolymers were synthesized with the fatty alcohols as the thermal storage units along the PVA backbone via the "grafting to" method. The thermal storage behavior, thermal stability and crystalline structure of PVA-g-TDI-C(n) copolymers were detailed investigated by Fourier transform infrared spectroscopy(FTIR), differential scanning calorimetry(DSC), thermogravimetric analysis(TGA), X-ray diffraction(XRD). The results show that PVA-g-TDI-C(n) copolymers exhibit the better thermal storage ability, and the value of enthalpy increases with the side-chain length and the grafting ratio. Compared with the pure fatty alcohols, the grafted ones show the decreased thermal storage efficiency due to the confined mobility of longer methylene groups. Besides the confined mobility of methylene groups, the effect of PVA backbones and the bridging units of TDI also contribute to the decrement of thermal storage ability of PVA-g-TDI-C(n) copolymers. Additionally, PVA-g-TDI-C(n) copolymers exhibit the higher thermal stability than that of pure n-fatty alcohol, and the thermal degradation temperature is located at 324-330 ℃, proving that it can be used as the solid-solid phase change materials in the aspects of buildings, fiber and textiles, thermal fluids, etc. So, the packing manner and thermal behavior of PVA-g-TDI-C(n) copolymers were further discussed and analyzed from the viewpoints of microstructural mobility.

Key words: Poly(vinyl alcohol), Thermal energy storage, Comb-like polymer, Phase change material

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