Preparation Of Vinyl Monomers And Cyclic Ester Monomer Block Polymers In Series With ATRP And ROP

Reverse atom transfer radical polymerization (R-ATRP) and ring opening polymerization (ROP) are two representatives of active polymerization techniques of the most promising introductive, and they have very wide range of potential applications in the field of polymer research. At present, many controlled block copolymers were synthesized by combining theses two technologies. We utilized a facile, efficient, and stable reagent, cooper ammonium (2-hydroxyethyl) dithiocarbamate (Cu(S(S=C)(N-CH3)CH2CH2OH)2), which hiding the hydroxyl into the pseudohalogen.The vinyl polymer chain end was attached with the hydroxyl through R-ATRP, and directly used to prepare the block copolymers by initiating ROP of cyclic ester monomer.The radical polymerizations of vinyl monomers such as methyl methacrylate (MMA), styrene (St) and diethylaminoethyl mathacrylate) (DEAEMA), were firstly carried out with AIBN/Cu(S(S=C)(N-CH3)CH2CH2OH)2/PMDETA catalytic system The polymers were with controlled molecular weight and narrow molecular weight distribution, were as polymer initiators to initiate ROP of ε-caprolactone. The results of GPC and!H NMR showed that the block copolymer were successfully synthesized, and confirmed the processes of R-ATRP of vinyl monomers as well as ROP of ε-caprolactone were accord with the living polymerization characteristics.Furthermore, along with the development of the combination technology of ATRP and ROP, Y-type block copolymers were successfully synthesized by tandem ATRP and ROP. Therefore, based on the study of other researchers and our laboratory, We utilized a facile, and efficient reagent, cooper ammonium bis(2-hydroxyethyl) dithiocarbamate (Cu(S(S=C)N(CH2CH2OH)2)2), which hiding the hydroxyl into the pseudohalogen.The vinyl polymer chain end was attached with the hydroxyl through R-ATRP, and directly used to prepare the Y-type block copolymers by initiating ROP of cyclic ester monomer.The radical polymerizations of methyl methacrylate (MMA) were firstly carried out with AIBN/Cu(S(S=C)N(CH2CH2OH)2)2/TPP catalytic system The polymers with controlled molecular weight and narrow molecular weight distribution, were as polymer initiators to initiate ROP of ε-caprolactone. The results of GPC and 1H NMR showed that the Y-type block copolymer were successfully synthesized, and confirmed the processes of R-ATRP of vinyl monomers as well as ROP of ε-caprolactone were accord with the living polymerization characteristics.