RAFT mediated copolymerizations the challenge of random copolymer blocks.

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Investigation into the initialization behaviour of RAFT-mediated styrene-maleic anhydride copolymerizations

The living radical alternating copolymerization of styrene and maleic anhydride mediated by the reversible addition–fragmentation chain transfer (RAFT) polymerization process has been studied at short chain lengths using two different dithiobenzoate RAFT agents. The results indicate specificity of addition of the RAFT-agent leaving groups for either styrene or maleic anhydride. The addition rate of the monomers and the fact that monomers are added individually favour the penultimate unit model of polymer propagatio

Investigation into the initialization behaviour of RAFT-mediated styrene-maleic anhydride copolymerizations

The living radical alternating copolymerization of styrene and maleic anhydride mediated by the reversible addition–fragmentation chain transfer (RAFT) polymerization process has been studied at short chain lengths using two different dithiobenzoate RAFT agents. The results indicate specificity of addition of the RAFT-agent leaving groups for either styrene or maleic anhydride. The addition rate of the monomers and the fact that monomers are added individually favour the penultimate unit model of polymer propagatio

Investigation into the initialization behaviour of RAFT-mediated styrene-maleic anhydride copolymerizations

The living radical alternating copolymerization of styrene and maleic anhydride mediated by the reversible addition–fragmentation chain transfer (RAFT) polymerization process has been studied at short chain lengths using two different dithiobenzoate RAFT agents. The results indicate specificity of addition of the RAFT-agent leaving groups for either styrene or maleic anhydride. The addition rate of the monomers and the fact that monomers are added individually favour the penultimate unit model of polymer propagatio

RAFT for the Control of Monomer Sequence Distribution – Single Unit Monomer Insertion (SUMI) into Dithiobenzoate RAFT Agents

In this paper we explore RAFT (reversible addition-fragmentation chain transfer) single unit monomer insertion (SUMI) into dithiobenzoates. Styrene and N-isopropylacrylamide (NIPAm) were successfully inserted into 2-cyanopropan-2-yl dithiobenzoate. Attempted SUMI of methyl methacylate (MMA) provided an oligomeric insertion product due to the low transfer constant of the dithiobenzoate in MMA polymerization. A very low yield with maleic anhydride (MAH) reflects the low reactivity of MAH towards 2-cyanopropan-2-yl radicals. We also examined insertion of MAH, styrene and NIPAm into the styrene SUMI product. Insertion of MAH was rapid and efficient. SUMI with styrene and NIPAm was slower, which is attributed both to the low monomer concentrations used and the poor leaving group ability of the propagating species. The reaction with NIPAm is additionally complicated by initiator-derived by-products