The Sythsis Of The Chrial RAFT Reagent--Dithioesters Substituted By Menthyl And The Research Of Polymerazation

There has been rapid progress in living free radical polymerization in the past decade.Reversible Addition Fragmentation chain Transfer（RAFT） radical polymerization has got much attention since its discovery.It can be carried out in bulk, solution,suspensionand also emulsion.The polymers with targeted structures can be synthesized through this method.In addition,its polymerization conditiona are similar to those of traditional free radical polymerization and a wide range of monomers can be used in RAFT polymerization.Therefore,RAFT has bright future for application and attracts the attention of many polymer researchers.As we know,RAFT polymerization technology has improved a lot since it was invented several years ago. However,asymmetric reversible addition fragmentation chain transfer（RAFT） polymerization has not been report so far.Preparation of chiral RAFT reagents and applied to asymmetric RAFT polymerization had great future.Three kinds of chiral dithioesters had been prepared and had been tried to apply in polymerization of TrMA and PDBSMA in this research.In this article,two series of chrial dithioesters had been synthsised in two different methods.（1R,2R,5S）-S-(（1S,2S,5R）-2-isopropyl-5-（methyl-cyclohexyl）-2-isopropyl-5-Methylcyclohexane carbothioate,S-（1S,2S,5R）-2-isopropyl-5-methyl cyclohexyl benzothioate and S-（1S,2S,5R）-2-isopropyl-5-methylcyclohexyl-2-phenylethanethioate was synthsised with mercaptan,acid and P₄S₁₀.And （1R,2S,5R）-2-isopropyl-5-methylcyclohexyl-2-（phenylcarbonothioylthio）propanoate and（3S）-ethyl-3-methyl-2-（phenylcarbonothioylthio）pentanoate had been synthisised with benzenyl magnesium bromide,CS₂,（1R,2S,5R）-2-isopropyl-5-methyl-cyclohexyl -2-bromopropanoate and（2S,3S）-ethyl-2-bromo-3-methylpentanoate.Furthermore,the two kinds of the chrial dithioesters——（1R,2R,5S）-（（1S,2S, 5R）-2-isopropyl-5-methylcyclohexyl）-2-isopropyl-5-methylcyclohexanecarbodithioate and（1S,2S,5R）-2-isopropyl-5-methylcyclohexyl benzodithioate had been applied in polymerrization of TrMA and PDBSMA.