The Kinetics of Surface‐Initiated RAFT Polymerization of Butyl acrylate Mediated by Trithiocarbonates

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 tri...

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Bibliographic Details
Published in:Macromolecular chemistry and physics 2017-03, Vol.218 (6), p.np-n/a
Main Authors: Moehrke, Julia, Vana, Philipp
Format: Article
Language:English
Subjects:
Acrylics
Addition polymerization
Chain transfer
Chemical equilibrium
Chemical industry
Coefficients
Diffusion
Diffusion rate
Electron paramagnetic resonance
Electron spin
Electrons
ESR/EPR
kinetics (polymerization)
nanoparticles
Polymerization
Rafts
Reagents
reversible addition fragmentation chain transfer (RAFT)
Shielding
Silicon dioxide
Spectroscopic analysis
Spin resonance
surface
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Summary: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. Electron spin resonance spectroscopy is employed to investigate the kinetics of the reversible addition fragmentation chain transfer (RAFT) polymerization from silica nanoparticles. The obtained kinetic parameters reveal that the addition rate coefficient in the main equilibrium of RAFT graft polymerizations is smaller than the one for comparable RAFT polymerizations in solution phase, as translational diffusion of surface‐attached molecules is limited.
ISSN:1022-1352
1521-3935
DOI:10.1002/macp.201600506