过氧类自引发单体的合成及其用于制备支化聚苯乙烯

Synthesis of peroxide self-initiating monomer and polymerization of branched polystyrene

以叔丁基过氧化氢为过氧化物母体,在氢氧化钠存在下与甲基丙烯酰氯反应合成自引发单体甲基丙烯酸过氧叔丁酯,并尝试与苯乙烯组成自引发共聚合反应体系简易制备支化聚苯乙烯。采用高效液相色谱、拉曼光谱、核磁共振波谱和差示扫描量热法等对引发单体结构和物性进行表征,并利用三检测体积排除色谱表征了支化聚苯乙烯的相对分子质量及其分布、特性黏度及支化结构。结果表明:制备了高纯度的目标引发单体,纯度大于98%;其过氧键分解行为与过氧化苯甲酰相近;与苯乙烯组成的自引发共聚合反应体系得到的聚苯乙烯具有较高的相对分子质量和支化程度。

Methacryloyl chloride was used to react with tert-butyl hydroperoxide in the presence of sodium hydroxide to synthesize the self-initiating monomer,tert-butyl peroxymethacrylate(BPM),which was used as initiator and branching agent to prepare branched polystyrene through co-polymerization with styrene(St).The structure and physical properties of the initiating monomers were characterized by highperformance liquid chromatography(HPLC),Raman spectra(RS),proton nuclear magnetic resonance (1H-NMR),and differential scanning calorimeter(DSC).The molecular weight and its distribution,intrinsic viscosity and branching structure of the obtained polymers were characterized by triple-detection size exclusion chromatography.The results show that the self-initiating monomers have high purity of larger than 98%.The decomposition behaviors of the peroxide bond in the monomers are similar to that of benzoyl peroxide.The polystyrene prepared in the self-initiating system of St and BPM has relatively high molecular weight and high degree of branching.