TY - JOUR
T1 - Anthraquinone-Mediated Reduction of a Trithiocarbonate Chain-Transfer Agent to Initiate Electrochemical Reversible Addition-Fragmentation Chain Transfer Polymerization
AU - Strover, Lisa T.
AU - Postma, Almar
AU - Horne, Michael D.
AU - Moad, Graeme
N1 - Funding Information:
L.T.S. acknowledges the CSIRO Research Office for funding in the form of a ResearchPlus postdoctoral fellowship. a
Publisher Copyright:
©
PY - 2020/12/8
Y1 - 2020/12/8
N2 - A goal in applying electrochemical methods to reversible addition-fragmentation chain transfer (RAFT) polymerization is to use electrochemical reduction to activate RAFT agents (SC(Z)S-R) to also act as initiators. The use of a mediator can limit side reactions that would otherwise inhibit polymerization. In this work, we present the use of anthraquinone (AQ) to mediate the electrochemical reduction of a trithiocarbonate RAFT agent, 4-cyano-4-(((dodecylthio)carbonothioyl)thio)pentanoic acid, and thereby initiate RAFT polymerization of methyl methacrylate (MMA). In a representative eRAFT reaction conducted in DMSO with a target degree of polymerization (DP) of 100, conversion reached 67% in 24 h at ambient temperature, with C = 1.19. The effect of reaction conditions on polymerization was studied - in general, the conversion rate was found to decrease as target DP increases. Dispersity increases as (i) target DP increases and (ii) mediator concentration increases. The livingness of AQ-mediated eRAFT polymerization was confirmed by eRAFT chain extension with MMA and by thermally initiated RAFT with styrene to form a block copolymer. AQ-mediated eRAFT was found to be unsuitable for polymerization of monosubstituted monomers (styrene, butyl acrylate, N,N-dimethylacrylamide, and N-vinylpyrrolidone). These results support the hypothesis that mediated electrochemical reduction of RAFT agents can yield an initiating species (R•), although polymerization is strongly dependent on diffusion and fragmentation kinetics.
AB - A goal in applying electrochemical methods to reversible addition-fragmentation chain transfer (RAFT) polymerization is to use electrochemical reduction to activate RAFT agents (SC(Z)S-R) to also act as initiators. The use of a mediator can limit side reactions that would otherwise inhibit polymerization. In this work, we present the use of anthraquinone (AQ) to mediate the electrochemical reduction of a trithiocarbonate RAFT agent, 4-cyano-4-(((dodecylthio)carbonothioyl)thio)pentanoic acid, and thereby initiate RAFT polymerization of methyl methacrylate (MMA). In a representative eRAFT reaction conducted in DMSO with a target degree of polymerization (DP) of 100, conversion reached 67% in 24 h at ambient temperature, with C = 1.19. The effect of reaction conditions on polymerization was studied - in general, the conversion rate was found to decrease as target DP increases. Dispersity increases as (i) target DP increases and (ii) mediator concentration increases. The livingness of AQ-mediated eRAFT polymerization was confirmed by eRAFT chain extension with MMA and by thermally initiated RAFT with styrene to form a block copolymer. AQ-mediated eRAFT was found to be unsuitable for polymerization of monosubstituted monomers (styrene, butyl acrylate, N,N-dimethylacrylamide, and N-vinylpyrrolidone). These results support the hypothesis that mediated electrochemical reduction of RAFT agents can yield an initiating species (R•), although polymerization is strongly dependent on diffusion and fragmentation kinetics.
UR - http://www.scopus.com/inward/record.url?scp=85097893223&partnerID=8YFLogxK
U2 - 10.1021/acs.macromol.0c02392
DO - 10.1021/acs.macromol.0c02392
M3 - Article
AN - SCOPUS:85097893223
VL - 53
SP - 10315
EP - 10322
JO - Macromolecules
JF - Macromolecules
SN - 0024-9297
IS - 23
ER -