Synthesis Of Poly (2,3-Dibromopropionyloxy Acrylate)-G-Poly (Styrene-Block-t-Butyl Acrylate) By The Combination Of Reversible Addition-Fragment Chain Transfer Polymerizaion And Atom Transfer Radical Polymerization

In the present dissertation, Novel comb-like copolymers poly((2,3-dibromopropionyloxy)propyl acrylate)-graft-ploy(styrene-block-t-butyl acrylate) (pDBPPA-graft-(pSt-block-ptBuA)) have been synthesized by the "grafting from" approach using the combination of reversible addition-fragment chain transfer polymerization (RAFT) and atom transfer radical polymerization (ATRP).In the first part of this dissertation, (2,3-dibromopropionyloxy)propyl acrylate(DBPPA) (d) was synthesized by reacting 2,3-dihydroxypropyl acrylate(c) with 2-bromopropionyl bromide and purified by column chromatogram; (c) was synthesized by hydrolysis of the (2,2-dimethyl-1,3-dioxolan-4-yl)methyl acrylate(b); (b) was synthesized by acryloyl chloride and isopropylidene glycerol(a); (a) was synthesized by the reaction glycerol with acetone. Their structures were characterized by 1H NMR. In the second part of this dissertation, three macroinitiators with different molecular weight, poly((2,3-dibromopropionyloxy) propyl acrylate), containing two initiating site at each repeating unit of backbone, were prepared by reversible addition-fragmentation polymerization(RAFT) of (2,3-dibromopropionyloxy) propyl acrylate(DBPPA) using AIBN as initiator and 2-(ethoxycarbonyl)prop-2-yl dithiobenzoate as chain transfer agent. Their molecular weights and structures were characterized by GPC, 1H NMR.In the third part of this dissertation, comb-like polystyrenes were prepared through ATRP of styrene initiated with poly((2,3-dibromopropionyloxy) propyl acrylate), and polymerization kinetic was studied. Another comb-like copolymers, poly((2,3-dibromopropionyloxy)propyl acrylate)-graft-ploy(styrene-block-tert-butyl acrylate), were synthesized by ATRP of t-butyl acrylate using comb-like polystyrenes as macroinitiators, and polymerization kinetic was studied. The hydrolysis of the PtBuA block of the side chains resulted amphiphilic comb-like copolymers, poly((2,3-dibromopropionyloxy)propyl acrylate)-graft-ploy(styrene-block-AA). The formation of well-defined comb-like copolymers was confirmed by GPC and 1H NMR. In addition, the cleavage was carried out on comb-like polystyrenes, poly((2,3-dibromopropionyloxy) propyl acrylate)-graft- ploystyrene. Conversion dependence of molecular weights and molecular weight distribution of cleaved ploystyrene was investigated.