亚砜还原法合成聚苯醚硫醚的结构与性能研究

以氟苯和氯化亚砜反应合成了4,4’-二氟二苯亚砜,并将其与4,4’二羟基二苯硫醚在N-甲基吡咯烷酮溶剂中进行亲核取代反应合成了聚苯醚硫醚醚亚砜,用乙二酰氯/四丁基碘化铵还原该亚砜聚合物制备了聚苯醚硫醚。用红外光谱和核磁共振谱对合成单体的结构进行了确认,同时对聚合物进行了红外光谱、核磁共振、元素分析、X射线光电子能谱、X射线衍射、DSC分析、TG/DTG以及溶解性测试。结果表明聚苯醚硫醚样品具有氧醚和硫醚交替的线性结构,特性粘度为0.55 dL/g的PPSE熔点达236℃,在氮气条件下,样品起始分解温度和最大分解速率处温度分别为359℃和514℃,在700℃时的重量保留率为43.3%,且在加热条件下能溶解于N-甲基吡咯烷酮(NMP)、二甲基乙酰胺(DMAc)、二甲基甲酰胺(DMF)等极性有机溶剂中。

The structure and property characterization of poly(phenylene sulfide/ether)synthesized by reduction of sulfoxide polymer

4,4′-difluorodiphenyl sulfoxide was prepared from fluorobenzene and thionyl chloride,and used as a raw material to react with 4,4′-dihydroxy diphenyl sulfide for the preparation of poly(phenylene ether sulfide ether sulfoxide).From the sulfoxide containing polymer,poly(phenylene sulfide/ether)(PPSE)was obtained by reduction reaction in solvents.The structure and property of sulfoxide containing polymer and PPSE were characterized by FT-IR,NMR,elemental analysis,XPS,XRD,DSC,TG/DTG and solubility test.The results showed that the synthesized poly(phenylene sulfide/ether)samples have a linear structure composed of alternative phenylene ether and phenylene sulfide.The melting temperature of sample with intrinsic viscosity of 0.55dL/g was found to be 236℃;and the initial and maximum degradation of PPSE occured at 359℃ and 514℃ in nitrogen and the weight residue at 700℃ was about 43.3%.Solubility measurement indicates that PPSE could dissolve in some polar solvents,such as 1-methyl-2-pyrrolidone(NMP),dimethylacetamide(DMAC)and N,N-dimethylformamide(DMF)at elevated temperatures.