Precision polymers: a kinetic approach for functional poly(norbornenes)

Abstract

Control over monomer sequence in the ring-opening metathesis polymerization of functional norbornenes is explored based on the difference in reactivity of endo and exo isomers.

Degradable precision polynorbornenes via ring‐opening metathesis polymerization

“…A few examples in the literature involve the synthesis of alternating copolymers using ROMP, as a result of the catalyst‐monomers pairing, such as in the case of dienes and diacrylates . We previously studied the use of exo norbornenes as functional monomers that when added to the ROMP of the slower endo norbornenes, were rapidly incorporated in the growing polymer chain, thus resulting in copolymers with some control over the monomer sequence . Nevertheless, when attempting the introduction of a single exo norbornene moiety, the precision was limited.…”

The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2014

“…Control of the functional moieties in a ROMP-derived chain was accomplished through addition of exo norbornene monomers (kinetically faster in ROMP compared to endo) in small batches to growing chains of endo-derived polymers [405]. Some titanium and zirconium olefin addition polymerization catalysts that contain a 6-(2-(diethylboryl)phenyl)pyridyl-2-yl ligand were observed to undergo ROMP reactions as an unwanted side reaction [406].…”

Recent developments in the synthesis of sequence controlled polymers

“…O'Reilly and coworkers [62] reported kinetic control approach in ring-opening metathesis polymerization (ROMP) of norbornenes. This approach based on the fact that the reactivity of exo norbornene was higher than endo isomers.…”