The influence of iron(III) chloride, FeCl3, on the degradation of polyisopr
ene and polybutadiene was investigated. From a 2(3) factorial design the ef
fects of polymer concentration, FeCl3 concentration and temperature on the
polymer degradation were evaluated. In solution, efflux time measurements,
unsaturation degree and viscometric molar mass determinations were combined
with H-1 NMR and infra-red spectroscopies. In the solid state, films of po
lymers doped with FeCl3 were exposed for several temperatures for different
periods in air. It was verified that in solution the FeCl3 induces more de
gradation of polyisoprene than of poly butadiene. In the solid state, where
the mobility of polymer chains is lowered, the FeCl3 induces more cross-li
nking of polybutadiene than of polyisoprene, if the polymers are exposed, f
or the same period, at temperatures equal or superior to 80 degrees C. The
results lead us to conclude that the degradation occurs by scission of the
double beads of the polymers, which is judged to be initiated by cationic s
pecies. It is suggested that the intermediate species formed in the polybut
adiene chains are less stable than in the polyisoprene ones. The difference
in stability would be due to the methyl group on the polyisoprene chains.
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