A general and
efficient method for the preparation of bottle-brush brushes is presented via
the combination of self-initiated photografting and photopolymerization (SIPGP)
and rare earth metal-mediated group transfer polymerization (REM-GTP). This strategy
involves the creation of poly(3-((2,6-dimethylpyridin-4-yl)oxy)propyl
methacrylate) (PDMPPMA) brush and the successive conversion to a surface-grafted
macroinitiator through the C–H bond activation by Cp2YCH2TMS(THF)
complex. The surface-bound macroinitiator
exhibits high activity and no initiation period in the polymerization of
monomers following a group-transfer polymerization mechanism, resulting in the
formation of side chains along the PDMPPMA backbone. The versatile approach is not only applicable
to the polymerization of conventional MMA, but also active for the
polymerization of hetero-atom containing monomers, e.g. vinylphosphonate,
2-vinylpyridine and 2-vinyl-oxazoline, thus affording bottle-brush brushes
which cannot be efficiently realized by conventional polymerization technique.
http://pubs.acs.org/doi/10.1021/acs.macromol.7b01966