de
Espinosa, L. M., Kempe, K., Schubert, U. S., Hoogenboom, R. and Meier,
M. A. R. (2012), Side-Chain Modification and Grafting Onto via Olefin
Cross-Metathesis. Macromol. Rapid Commun.. doi: 10.1002/marc.201200487
In this paper, Grubbs second generation catalyst is used to
"efficiently" functionalize polymer ends. By adding a large excess of
acrylate and tuning terminal alkene with acrylate steric bulk, they are
able to discourage self-metathesis that leads to cyclic structures in
order to gain the desired product with reasonable PDIs. A combination of
SEC, FTIR-ATR, and NMR are used to differentiate cross-metathesis and
self-metathesis products though with difficulty. SEC shows, in general
higher MW shoulders in their traces suggesting that self-metathesis is
still occurring, while high conversions of terminal alkenes are seen via
NMR. According to the authors, the main advantages of this method are
the introduction of various functional groups and the maintenance of
double bond functionality (as opposed to thiol-ene chemistry).
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