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The Kinetics of Surface‐Initiated RAFT Polymerization of Butyl acrylate Mediated by Trithiocarbonates
Author(s) -
Moehrke Julia,
Vana Philipp
Publication year - 2017
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.201600506
Subject(s) - raft , chain transfer , polymerization , chemistry , reversible addition−fragmentation chain transfer polymerization , polymer chemistry , acrylate , kinetics , butyl acrylate , radical polymerization , polymer , copolymer , organic chemistry , physics , quantum mechanics
Stationary and time‐resolved electron spin resonance spectroscopy measurements are employed to investigate the kinetics of the surface‐initiated reversible addition fragmentation chain transfer (RAFT) polymerization of n ‐butyl acrylate from silica nanoparticles using both R‐ and Z‐group‐attached trithiocarbonates as RAFT agents. The obtained kinetic parameters reveal that the addition rate coefficient in the main equilibrium of RAFT graft polymerizations is significantly smaller than the one for comparable RAFT polymerizations in solution phase, as translational diffusion of surface‐attached molecules is limited. In comparison to the R‐group approach, the equilibrium constants of the Z‐group approach are about one to two orders of magnitude smaller due to a stronger shielding of the RAFT moieties.