Synthesis of Deuterated Poly(4-acetoxystyrene) by a Polymer-analogous Reaction Sequence

This study describes a new simple method for preparing deuterated poly(4-acetoxystyrene). The new
method offers cost-effective and alternative route to preparing deuterated polymers that otherwise have to
be prepared from the deuterated monomers. Deuterated poly(4-acetylstyrene) (ACPS-d4) and poly(4-
acetoxystyrene) (APS-d4) were synthesised from deuterated polystyrene under thermal reactions. The
polystyrene-d5 (PS-d5) was acetylated using cyclohexane as solvent instead of carbon disulfide (a highly
toxic and flammable solvent) and acetyl chloride as the acetylating agent. Using commercially available
reagents, the acetyl group was converted to an acetoxy group by Baeyer-Villiger oxidation. The oxidation
of ACPS was carried out with various agents and reaction conditions. The oxidation kinetics with
peracetic acid was followed by FT-IR spectroscopy. The duterated polymers were characterised by
nuclear magnetic resonance (NMR) and fourier transform infrared spectroscopy (FTIR). The optimised
procedure will make future work using neutron scattering possible.
Keywords: polystyrene-d5, thermal reactions, Baeyer-Villiger oxidation