Rapid, regioselective living ring-opening metathesis polymerization of bio-derivable asymmetric tricyclic oxanorbornenes

Abstract

The synthesis of a range of alkyl esters (methyl, n-butyl, and n-decyl) prepared via Steglich esterification of the thermodynamically controlled exo, exo Diels–Alder adduct of furfuryl alcohol and maleic anhydride is reported. Subsequent ring-opening metathesis polymerization of these bio-derivable tricyclic oxanorbornene analogs delivers polymers with targeted molar mass and low molar mass dispersity. The polymerizations are rapid with complete monomer conversion achieved within 15 min. Significantly, the presence of the cyclic lactone at the bridgehead of these monomers leads to polymers with high regioregularity (>85% head-to-tail) and high stereoregularity (>75% trans). The resultant polymers display both high thermal stability and high glass transition temperatures. This new class of oxanorbornene monomer, accessed from bio-derivable furfuryl alcohol and maleic anhydride, may be further tailored to incorporate a range of functional moieties. Furthermore, the exceptional properties of the derived polymers indicate potential in a range of applications.