Kinetics and Mechanism of Copolymerization of Linalool with Acrylonitrile

Linalool (LIN) and acrylonitrile (AN) were copolymerized by benzoyl peroxide (BPO) in xylene at 75°C for 60 min. The system follows ideal kinetics with bimolecular termination and results in the formation of an alternating copolymer as evidenced from the values of reactivity ratios as r1(AN)=0.011 and r2(LIN)=0.017. The overall activation energy is 35.2 kJ/mol. The FTIR spectrum of the copolymer shows the presence of the band at 3467 cm−1 due to hydroxy group of LIN and at 2240 cm−1 due to a cyanide group of AN. The 1H-NMR spectrum shows peaks at 7.0–7.7 δ due to alcoholic group of LIN. 13C-NMR spectrum of copolymer has peaks at δ ppm=116–120 of –CN, and δ ppm=75–77 of –C–OH. The TGA and DSC studies show that the copolymer is highly stable thermally and has glass transition temperature (Tg)=50°C. The mechanism of copolymerization has been elucidated. This paper also reports the measurement of Mark Houwink constants in THF at 25°C by means of GPC as α=0.50 and K=2.24×10−3 dl/g.