IR laser-induced modification of poly(vinyl acetate): Elimination of monomer and deposition of polar crosslinked films

IR laser-induced modification of poly(vinyl acetate) (PVAC) was examined through ablative and non-ablative thermal processing of bulk PVAC. Both laser-induced processes differ remarkably from conventional heating of PVAC, which yields acetic acid and non-polar carbonaceous residue. The non-ablative treatment at low-fluence irradiations results in the formation of volatile vinyl acetate and acetone and leaves the remaining irradiated polymer having an almost identical structure. The ablative treatment at high-fluence irradiations yields a multitude of volatile compounds (methane, ethane, vinyl acetate, acetone, acetic acid, benzene, H2, CO and CO2) and affords deposition of thin polymeric films that contain reactive conjugated CC bonds and half of the initially present acetate groups. Residual reactivity of the CC bonds leads to polymer crosslinking, substantial decrease in solubility and some increase in thermal stability. The low fluence-induced decomposition stands for the first example of the thermal decomposition of polyvinyls into the monomer and the high-fluence ablative deposition represents a one-step approach to crosslinked (intractable), thermally stable and polar polymeric films from linear-chain polymers with pending functional groups.