两种聚磷腈的合成及溶液性质  

Synthesis and Solution Properties of Two Polyphosphazenes

作　　者：陈轩[1] 刘桂华[1] 姬相玲[1] 薄淑琴[1] 

机构地区：[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

出　　处：《高等学校化学学报》2011年第2期379-382,共4页Chemical Journal of Chinese Universities

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

摘　　要：由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2种分子量高于3×106的聚双苯氧基磷腈(PDPP)和聚双乙氧基磷腈(PDEP).利用GPC与三检测器[包括示差、黏度、多角度静态激光光散射(MALLS)]联用的方法研究了PDPP和PDEP在THF(含有质量分数0.1%的四正丁基溴化铵)中分子链的构象和形态,得到其重均分子量(Mw)、特性黏数[η]与Z均回转半径(Rg,z)的单分散标度关系分别为[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.研究结果表明,2种聚磷腈在THF中都具有线性柔性链无规线团的构象.Polydichlorophosphazene was synthesized through ring-opening polymerization of phosphonitrilic chloride trimer at high temperature.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 ℃.R-g/R-h of polydiphenoxyphosphazene（PDPP） and polydiethoxyphosphazene（PDEP） are 2.17 and 2.23.Their scaling relations are [η]=9.10×10-2 M0.58-w and R-{g,z}=1.62×10-2 M-w0.58 for PDEP while [η]=1.71×10-2 M-w0.64 and R-{g,z=0.80×10-2 M-w0.60 for {PDPP.} It indicates that both polyphosphazenes exhibit a random coil conformation in THF.

关 键 词：聚磷腈 溶液性质 分子链构象 

分 类 号：O631[理学—高分子化学] O635[理学—化学]