Benzoyl peroxide–p‐acetylbenzylidenetriphenyl arsoniumylide initiated copolymerization of citronellol and styrene

Abstract

AbstractAlternating copolymers, containing styrene and citronellol sequences, have been synthesized by radical polymerization using benzoylperoxide (BPO)–p‐acetylbenzylidenetriphenyl arsoniumylide (pABTAY) as initiator, in xylene at 80 ± 1 °C for 3 h under inert atmosphere. The kinetic expression is Rp ∝ [BPO]0.88 [citronellol]0.68 [styrene]0.56 with BPO and Rp ∝ [pABTAY]0.27 [citronellol]0.76 [styrene]0.63 with pABTAY, 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 pABTAY is 94 kJ mol−1 and 134 kJ mol−1, respectively. Different spectral techniques, such as IR, FTIR, 1H NMR and 13C 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 r1 (Sty) = 0.81 and r2 (Citro) = 0.015 using BPO and r1 (Sty) = 0.37 and r2 (Citro) = 0.01 using (pABTAY), which are calculated by the Finemann–Ross method. A mechanism of copolymerization is proposed.© 2001 Society of Chemical Industry