TY - JOUR
T1 - Initiation of RAFT Polymerization
T2 - Electrochemically Initiated RAFT Polymerization in Emulsion (Emulsion eRAFT), and Direct PhotoRAFT Polymerization of Liquid Crystalline Monomers
AU - Bray, Caroline
AU - Li, Guoxin
AU - Postma, Almar
AU - Strover, Lisa T.
AU - Wang, Jade
AU - Moad, Graeme
N1 - Funding Information:
JW thanks CSIRO Manufacturing for an Industrial Traineeship and her supervisor from Ecole Nationale Supérieure de Chimie de Rennes, Eric Le Fur. AP thanks CSIRO for a Julius Career Award. CB and LTS thank CSIRO for Research+ Postdoctoral Fellowships. CB thanks her supervisory team Richard Evans, Nino Malic, and George Simon for helpful discussion. We are grateful to Mike Horne and Bita Bayatsarmadi (CSIRO Minerals) for advice on electrochemistry, to Ben Muir, Shaun Howard, and Weidong Yang for assistance with high-throughput experimentation, to George Maurdev (CSIRO Manufacturing) for assistance with dynamic light scattering and Oliver Hutt and Simon Saubern (CSIRO Manufacturing) for helpful discussion.
Publisher Copyright:
© 2021 Journal Compilation
PY - 2021/1/1
Y1 - 2021/1/1
N2 - We report on two important advances in radical polymerization with reversible addition-fragmentation chain transfer (RAFT polymerization). (1) Electrochemically initiated emulsion RAFT (eRAFT) polymerization provides rapid polymerization of styrene at ambient temperature. The electrolytes and mediators required for eRAFT are located in the aqueous continuous phase separate from the low-molar-mass-dispersity macroRAFT agent mediator and product in the dispersed phase. Use of a poly(N,N-dimethylacrylamide)-block-poly(butyl acrylate) amphiphilic macroRAFT agent composition means that no added surfactant is required for colloidal stability. (2) Direct photoinitiated (visible light) RAFT polymerization provides an effective route to high-purity, low-molar-mass-dispersity, side chain liquid-crystalline polymers (specifically, poly(4-biphenyl acrylate)) at high monomer conversion. Photoinitiation gives a product free from low-molar-mass initiator-derived by-products and with minimal termination. The process is compared with thermal dialkyldiazene initiation in various solvents. Numerical simulation was found to be an important tool in discriminating between the processes and in selecting optimal polymerization conditions.
AB - We report on two important advances in radical polymerization with reversible addition-fragmentation chain transfer (RAFT polymerization). (1) Electrochemically initiated emulsion RAFT (eRAFT) polymerization provides rapid polymerization of styrene at ambient temperature. The electrolytes and mediators required for eRAFT are located in the aqueous continuous phase separate from the low-molar-mass-dispersity macroRAFT agent mediator and product in the dispersed phase. Use of a poly(N,N-dimethylacrylamide)-block-poly(butyl acrylate) amphiphilic macroRAFT agent composition means that no added surfactant is required for colloidal stability. (2) Direct photoinitiated (visible light) RAFT polymerization provides an effective route to high-purity, low-molar-mass-dispersity, side chain liquid-crystalline polymers (specifically, poly(4-biphenyl acrylate)) at high monomer conversion. Photoinitiation gives a product free from low-molar-mass initiator-derived by-products and with minimal termination. The process is compared with thermal dialkyldiazene initiation in various solvents. Numerical simulation was found to be an important tool in discriminating between the processes and in selecting optimal polymerization conditions.
UR - http://www.scopus.com/inward/record.url?scp=85093533508&partnerID=8YFLogxK
U2 - 10.1071/CH20260
DO - 10.1071/CH20260
M3 - Article
AN - SCOPUS:85093533508
VL - 74
SP - 56
EP - 64
JO - Australian Journal of Chemistry
JF - Australian Journal of Chemistry
SN - 0004-9425
IS - 1
ER -