The preparation of three new benzhydryl 2-propanoyl-functionalized trithiocarbonate RAFT agents, benzhydryl 2-(ethylsulfanylthiocarbonylsulfanyl)propanoate, benzhydryl 2-(butylsulfanylthiocarbonylsulfanyl)propanoate, benzhydryl 2-(dodecylsulfanylthiocarbonylsulfanyl)propanoate is described. The RAFT polymerization of styrene, mediated by the appropriate benzhydryl 2-(alkylsulfanylthiocarbonylsulfanyl)propanoate as the chain transfer agent, with AIBN as initiator at 70 ⁰C, proceeds via reversible-deactivation radical polymerization processes to produce the corresponding α-benzhydryl 2-propanoyl polystyrene derivative, with the benzhydryl ester group introduced at the α-terminus of the polymer chain. Polymerization kinetics measurements show that each RAFT polymerization reaction follows first order rate kinetics with respect to percentage monomer consumption and the number average molecular weights of the functionalized polymers increase linearly with the percentage monomer conversion to produce functionalized polymers with narrow molecular weight distributions. The percentage monomer conversion with time for each polymerization reaction was monitored by ¹H NMR spectroscopy by evaluating the consumption of styrene with respect to polymerization time. Post-RAFT polymerization chain end modification of α-benzhydryl 2-propanoyl-functionalized polystyrene by the acid catalyzed ester hydrolysis reactions with concentrated sulfuric acid afforded the corresponding α-carboxyl functionalized polystyrene derivative, with the retention of the thiocarbonylthio moiety at the ω-terminus of the polymer chain. The benzhydryl 2-propanoyl-functionalized trithiocarbonate chain transfer agents and the different functionalized polystyrene derivatives were characterized by ¹H NMR, ¹³C NMR and FTIR spectroscopy, size exclusion chromatography, thin layer chromatography and mass spectrometry measurements.

制备三种新型2-丙酰基官能化三硫代碳酸酯RAFT剂，2-(乙基硫代羰基硫烷基)丙酸二苯甲酯、2-(丁基硫磺基硫羰基硫烷基)丙酸二苯甲酯、2-(十二烷基硫代羰基硫羰基硫烷基)丙酸二苯甲酯。苯乙烯的 RAFT 聚合，以合适的 2-(烷基硫代羰基硫烷基)丙酸二苯甲酯为链转移剂，以 AIBN 为引发剂，在 70 ⁰C，通过可逆-失活自由基聚合过程进行以产生相应的 α-二苯甲基 2-丙酰基聚苯乙烯衍生物，在聚合物链的 α-末端引入二苯甲基酯基团。聚合动力学测量表明，每个 RAFT 聚合反应都遵循关于单体消耗百分比的一级速率动力学，并且官能化聚合物的数均分子量随单体转化百分比线性增加，以产生具有窄分子量分布的官能化聚合物。每个聚合反应随时间的单体转化百分比通过¹通过评估苯乙烯消耗与聚合时间相关的 H NMR 光谱。通过与浓硫酸的酸催化酯水​​解反应对 α-二苯甲基 2-丙酰基官能化聚苯乙烯进行 RAFT 后聚合链端改性，得到相应的 α-羧基官能化聚苯乙烯衍生物，而硫代羰基硫基部分保留在 ω-末端聚合物链。通过¹ H NMR、¹³ C NMR 和 FTIR 光谱、尺寸排阻色谱、薄层色谱和质谱测量对二苯甲基 2-丙酰基官能化三硫代碳酸酯链转移剂和不同官能化聚苯乙烯衍生物进行表征。