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Termination of Surface Radicals and Kinetic Analysis of Surface‐Initiated RAFT Polymerization on Flat Surfaces
Author(s) -
Zhou Dapeng,
Mastan Erlita,
Zhu Shiping
Publication year - 2012
Publication title -
macromolecular theory and simulations
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.37
H-Index - 56
eISSN - 1521-3919
pISSN - 1022-1344
DOI - 10.1002/mats.201200043
Subject(s) - raft , radical , reversible addition−fragmentation chain transfer polymerization , chain transfer , surface (topology) , polymer , polymerization , radical polymerization , chemistry , polymer chemistry , surface modification , chemical physics , photochemistry , materials science , organic chemistry , geometry , mathematics
si‐RAFT polymerization is widely used for surface modification. However, how the surface radicals terminate requires further elucidation. A kinetic model is developed for si‐RAFT via the R group approach. The model describes the molecular weight of grafted polymers as well as polymer layer thickness and various chain concentrations. It is shown that surface/surface radical termination plays an important role. The termination is facilitated by the migration of surface radicals through “hopping” and “rolling” mechanisms. “Hopping” occurs through activation/deactivation cycles between surface and solution chains, dependent on the RAFT concentration in solution. “Rolling” occurs through transfers between surface/surface chains, dependent on the grafting density at surface.