Benzoyl peroxide-p-acetylbenzylidenetriphenyl arsoniumylide initiated copolymerization of citronellol and styrene

Alternating copolymers, containing styrene and citronellol sequences, have been synthesized by radical polymerization using benzoylperoxide (BPO)-p-ac etylbenzylidenetriphenyl arsoniumylide (pABTAY) as initiator, in xylene at 80 +/- 1 degreesC for 3 h under inert atmosphere. The kinetic expression is R-p proportional to [BPO](0.88) [citronellol](0.68) [styrene](0.56) with B PO and R-p proportional to [pABTAY](0.27) [citronellol](0.76) [styrene](0.6 3) with pABTAY, ie the system follows non-ideal kinetics in both cases, bec ause of primary radical termination and degradative chain transfer reaction s. The activation energy with BPO and pABTAY is 94kJ mol(-1) and 134 kj mol (-1), respectively. Different spectral techniques, such as IR, FTIR, H-1 NM R and C-13 NMR, have been used to characterize the copolymer, demonstrating the presence of alcoholic and phenyl groups of citronellol and styrene. Th e 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 (pABTAY), which are calculated by the Finemann-Ross method. A mechanism of copolymerization is proposed. Copyrigh t (C) 2001 Society of Chemical Industry.