高等学校化学学报 ›› 2011, Vol. 32 ›› Issue (2): 379.

• 研究论文 • 上一篇    下一篇

两种聚磷腈的合成及溶液性质

陈轩,刘桂华,姬相玲,薄淑琴   

  1. 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
  • 收稿日期:2010-04-27 修回日期:2010-06-08 出版日期:2010-02-10 发布日期:2011-02-23
  • 通讯作者: 姬相玲 E-mail:xlji@ciac.jl.cn
  • 基金资助:

    国家自然科学基金(批准号: 50921062, 50633030)和长春市科技局项目(批准号: 2008228)资助.

Synthesis and Solution Property of Two Polyphosphazenes

CHEN Xuan, LIU Gui-Hua, JI Xiang-Ling*, BO Shu-Qin   

  1. State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
  • Received:2010-04-27 Revised:2010-06-08 Online:2010-02-10 Published:2011-02-23
  • Contact: JI Xiang-Ling E-mail:xlji@ciac.jl.cn
  • Supported by:

    国家自然科学基金(批准号: 50921062, 50633030)和长春市科技局项目(批准号: 2008228)资助.

摘要: 六氯环三磷腈高温开环聚合得到聚二氯磷腈,再与不同种类的醇钠和酚钠取代反应合成了两种分子量高于3×106g/mol的聚双苯氧基磷腈(PDPP)与聚双乙氧基磷腈(PDEP). 利用GPC与三检测器(包括示差、粘度、多角度静态激光光散射MALLS)联用的方法研究了其在THF(含有0.1%的四正丁基溴化铵)中分子链的构象和形态,得到这些样品的重均分子量Mw,特性粘数[η],Z均回转半径(简写为Rg,Z),以及[η]与重均分子量Mw、 Rg,Z与Mw之间的单分散标度关系. PDPP与PDEP的标度关系分别为 [η]=1.71×10-2Mw0.64,Rg,Z=0.80×10-2Mw0.60; [η]=9.10×10-2Mw0.58,Rg,Z=1.62×10-2Mw0.58. 这些结果表明这两种聚磷腈在THF中都具有线性柔性链无规线团的构象.  

关键词: 聚磷腈, 合成, 溶液性质, 分子链构象

Abstract: Firstly, polydichlorophosphazene was synthesized through ring-opening polymerization of phosphonitrilic chloride trimer at high temperature. Then the two polyphosphazene samples with different side groups were synthesized through reaction of polydichlorophosphazene with different sodium alkoxides or sodium phenolates. These polymers have high Mw up to 3×106 and are studied with gel permeation chromatography (GPC) coupled with multidetectors including refractive index detector, viscometer, multi-angle laser light scattering (MALLS) in THF with 0.1% tetra-n-butylammonium bromide at 35 oC. Rg/Rh of polydiphenoxyphosphazene (PDPP) and polydiethoxyphosphazene (PDEP) is 2.17 and 2.23. Their scaling relations are [η]=9.10×10-2Mw0.58 and <Rg>Z=1.62×10-2Mw0.58 for PDEP while [η]=1.71×10-2Mw0.64 and <Rg>Z=0.80×10-2Mw0.60 for PDPP. It indicates that both polyphosphazenes exhibit a random coil conformation in THF.

Key words: polyphosphazene, synthesis, solution property, chain conformation

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