Postpolymerization Functionalization of Copolymers
Produced from Carbon Dioxide and 2‑Vinyloxirane: Amphiphilic/Water-Soluble
CO<sub>2</sub>‑Based Polycarbonates
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Abstract
Common CO<sub>2</sub>-based polycarbonates
are known to be highly
hydrophobic, and this “inert” property makes them difficult
for the covalent immobilization of bioactive molecules. A practical
method for modifying polymers is to introduce various functional groups
that permit decoration of polymer chains with bioactive substances.
In this report, CO<sub>2</sub>-based poly(2-vinyloxirane carbonate)
(PVIC) with more than 99% carbonate linkages is isolated from the
CO<sub>2</sub>/2-vinyloxirane alternating copolymerization catalyzed
by the bifunctional catalyst [(1<i>R</i>,2<i>R</i>)-SalenCo(III)(DNP)<sub>2</sub>] (<b>1</b>) (DNP = 2,4-dinitrophenolate)
bearing a quaternary ammonium salt on the ligand framework. It was
also observed that the presence of propylene oxide significantly activates
2-vinyloxirane for incorporation into the polymer chain as well as
inhibits the formation of cyclic carbonate in the terpolymerization
process. DSC studies demonstrate that the glass transition temperature
(<i>T</i><sub>g</sub>) decreases with the increase in the
content of vinyl groups in the polycarbonate. By way of thiol–ene
coupling, showing mainly “click” characteristics and
nearly quantitative yields, amphiphilic polycarbonates (PVIC-OH and
PVIC-COOH) with multiple hydroxy or carboxy functionalities have been
prepared, providing suitable reactivities for further modifications
(ring-opening of l-aspartic acid anhydride hydrochloride
salt and deprotonation by aqueous ammonium hydroxide (NH<sub>4</sub>OH<sub>(aq)</sub>)) to successfully isolate the water-soluble CO<sub>2</sub>-based polycarbonate PVIC-COONH<sub>4</sub>, and the PVIC-OH-Asp
polymer which shows particles dispersed in water with an average hydrodynamic
diameter <i>D</i><sub>n</sub> = 32.2 ± 8.8 nm. It is
presumed that this emerging class of amphiphilic/water-soluble polycarbonates
could embody a powerful platform for bioconjugation and drug conjugation.
In contrast to lower <i>T</i><sub>g</sub>s of PVIC, (PVIC-<i>co</i>-PC), PVIC-OH, and PVIC-COOH, the polycarbonates PVIC-OH-Asp
and PVIC-COONH<sub>4</sub> show higher <i>T</i><sub>g</sub>s as a consequence of their intrinsic ionic property (ammonium salts)