Studies on Polysiloxane-based Alicyclic Episulfide Resin

The polysiloxane-based alicyclic episulfide resin (PSCER) was synthesized through substitution of oxygen atoms in 1,3-bis2-(3{7-oxabicyclo4,1,0]hepyl})ethyl]-tetramethyldisiloxane with sulfur atoms using potassium thiocyanate (KSCN) as the reagent. The product was purified by column chromatography, and the by-products were isolated. It was found by ¹H-NMR and ¹³C-NMR that the by-products were cycloolefins formed by desulfurization of the episulfide groups. PSCER was unstable; desulfurization took place easily, especially at high temperatures. The PSCER resin could not be cured with methylhexahydrophthalic anhydride (MeHPPA). When m-phenylenediamine or isophorondiamine was used as curing agent, PSCER showed a higher reactivity compared with the parent epoxide. However, the reactivity of the alicyclic episulfide was much lower than the polysiloxane based aliphatic episulfide for the steric hindrance of the six member ring. Desulfurization took place upon curing of the alicyclic episulfide resin, therefore the cured resin showed poor mechanical properties. Thermal stability of cured PSCER resin was also poor on account of low bonding energy of C-S and crosslinking density.