以可溶性聚锍阳离子为前驱体合成高分子量线型聚苯硫醚的研究

Study on Synthesis of High Molecular Weight Linear Polyphenylene Sulfide with Soluble Polyfluorene Cation as Precursor

以苯甲硫醚为起始原料,在常温下经亲电取代合成中间体4-(硫苯基)苯甲硫醚(MPS),再经氧化反应合成聚合物单体4-(硫苯基)苯甲亚砜(PSO),单体通过阳离子聚合生成可溶性聚锍阳离子前驱体聚[甲基[4-(苯硫基)-苯基]锍三氟甲磺酸盐](PPST),最后经去甲基合成聚苯硫醚(PPS)。此路线绿色高效,且产品总收率高达72%。采用红外光谱(FTIR)、拉曼光谱(Raman)、X射线衍射(XRD)、示差扫描量热(DSC)、热失重(TG)、热失重速率(DTG)、黏度法分子量测定、灰分测定等多种表征手段对产品进行定性定量分析。所得PPS产品的重均分子量Mw可达1. 98×10^5,灰分含量为0. 06%,与传统工艺相比,产品在纯度、分子量、热力学性能等方面有着显著的提升。

Phenyl sulfide was used as the raw material, the intermediate 4-( thiophenyl) phenyl sulfide( MPS) was electrophilically substituted at room temperature, and then the polymer monomer 4-( thiophenyl) benzene sulfoxide( PSO) was synthesized by oxidation reaction. The monomer was cationically polymerized to form a soluble polyfluorene cation precursor poly [methyl [4-( phenylthio)-phenyl] indole trifluoro methane sulfonate]( PPST),and finally demethylated to synthesize polyphenylene sulfide( PPS).The total recovery of the product could achieve 72%and the route was green and efficient. The structure and qualitative and quantitative analysis of the product could be characterized by fourier transform infrared( FTIR), Raman spectra, X-ray diffraction( XRD), differential scanning calorimetry( DSC),thermogravimetry( TG),derivative thermogravimetry( DTG),viscosity molecular weight determination and ash determination. The weight average molecular weight of the obtained PP product could achieve 1. 98×10^5 and the ash content was 0. 06%. Comparing with the traditional method, the obtained product had a significant improvement in purity,molecular weight and thermodynamic properties.