Thermal degradation of polystyrene has been investigated in the presence of
water under subcritical conditions (hydrous pyrolysis). The experiments we
re carried out in closed systems under inert atmosphere, in the temperature
range 300-350 degrees C, at pressures up to 180 atm, for 1-120 h. The resu
lts showed that the presence of water increases the yields of volatile prod
ucts, mainly in the first steps of the pyrolytic process, with a high selec
tivity in the monomer. In order to improve the phase contact between water
and polymer during the pyrolysis, some runs have been carried out on silica
-supported polystyrene and using a stirred reactor. Under these conditions,
the above effects appeared to be greatly enhanced. The best recovery of st
yrene, close to 71 %, has been achieved at 320 degrees C and 8 h.