Determination of reactivity ratios and kinetics of free radical copolymerization of linalool with styrene

Copolymerization of acyclic monoterpenoid, namely linalool (LIN), with styrene (STY) initiated by benzoyl peroxide (BPO) p ‐acetyl benzylidene triphenyl arsonium ylide ( p ‐ABTAY) in xylene separately at 80°C for 180 min under inert atmosphere of nitrogen was performed. The results give a nearly alternating copolymer as evidenced from reactivity ratios ( r 1  = 0.016, r 2  = 0.057) w.r.t. BPO; ( r 1  = 0.017, r 2  = 0.052) w.r.t. p‐ABTAY (i.e. r 1  = 0.0165 ± 0.0005 and r 2  = 0.0545 ± 0.0025 per initiator set) using Kelen–Tudos method. The FT‐IR spectrum shows a band at 3026 cm −1 due to the aromatic ring of polystyrene and an alcoholic band of linalool at 3408 cm −1 . 1 H‐NMR spectrum shows peaks at δ 7.0–7.7 ppm of OH protons and peaks at δ 7.5–8.0 ppm due to phenyl protons of styrene. The system follows ideal kinetics i.e. Rp ∝ [LIN] 1.0 [STY] 1.0 [BPO] 0.5 /[p‐ABTAY] 0.5 . The overall energy of activation in the temperature range 75–85°C is 77.0 kJ mol −1 and 90.0 kJ mol −1 , respectively. The values for Mark–Houwink constants for the functional copolymer has been evaluated as a  = 0.40 and K = 1.60 × 10 −4 with the help of gel permeation chromatography (GPC). Alfrey–Price, Q and e parameters for linalool have been evaluated as Q 2  = 0.80; e 2  = 1.25 w.r.t. BPO and Q 2  = 0.90; e 2  = 1.54 w.r.t. p‐ABTAY. Thermal properties of copolymers were investigated by thermogravimetric analysis (TGA) techniques. Copyright © 2004 John Wiley & Sons, Ltd.