Abstract
Alternating copolymers, containing styrene and citronellol sequences, have been synthesized by radical polymerization using benzoylperoxide (BPO)–p‐acetylbenzylidenetriphenyl arsoniumylide (__p__ABTAY) as initiator, in xylene at 80 ± 1 °C for 3 h under inert atmosphere. The kinetic expression is R~p~ ∝ [BPO]^0.88^ [citronellol]^0.68^ [styrene]^0.56^ with BPO and R~p~ ∝ [__p__ABTAY]^0.27^ [citronellol]^0.76^ [styrene]^0.63^ with __p__ABTAY, ie the system follows non‐ideal kinetics in both cases, because of primary radical termination and degradative chain transfer reactions. The activation energy with BPO and __p__ABTAY is 94 kJ mol^−1^ and 134 kJ mol^−1^, respectively. Different spectral techniques, such as IR, FTIR, ^1^H NMR and ^13^C NMR, have been used to characterize the copolymer, demonstrating the presence of alcoholic and phenyl groups of citronellol and styrene. The alternating nature of the copolymer is shown by the product of reactivity ratios r~1~ (Sty) = 0.81 and r~2~ (Citro) = 0.015 using BPO and r~1~ (Sty) = 0.37 and r~2~ (Citro) = 0.01 using (__p__ABTAY), which are calculated by the Finemann–Ross method. A mechanism of copolymerization is proposed.
© 2001 Society of Chemical Industry