Vinylsulfide-containing polyesters and copolyesters from fatty acids: Thiol-yne monomer synthesis and thiol-ene functionalization

10.1002/macp.201400191The synthesis of a vinylsulfide-containing hydroxy acid (VSHA) from undecylenic fatty acid via thiol-yne monoaddition is described. Metal- and enzymatic-catalyzed polycondensation of VSHA is investigated to obtain functional polyesters with a view to further modification. Higher molecular weights are obtained when using enzymatic polymerization. Random copolymers are prepared by direct enzymatic copolymerization of VSHA and e-caprolactone (CL) and triblock CL-VSHA-CL copolymers are obtained by consecutive VSHA self-condensation and ring-opening polymerization. The copolymers display semicrystalline behavior and a good thermal stability with no significant weight loss below 300 °C. Thiol-ene chemistry-type crosslinking and surface functionalization are employed to open new application fields. Evidence of the successful reactions is obtained by NMR, IR, and fluorescence measurements