Benzoyl peroxide-initiated copolymerization of citronellol and vinyl acetate

The radical copolymerization of citronellol with vinyl acetate (VA) in xylene at 60 +/- 0.1 degreesC for 90 min in the presence of benzoyl peroxide follows ideal kinetics and results in the formation of an alternating copolymer as demonstrated by the values of the reactivity ratios [r(1) (VA) = 0.02 and r(2) (citronellol) = 0.0002], which have been calculated with the Kelen-Tudos method. The overall activation energy is computed to be 75 kJ/mol. The IR spectrum of the copolymer shows the presence of bands at 3400 cm(-1) due to an alcoholic group and 1750 cm(-1) due to a >C=O group. The values of the Mark-Houwink constants for this copolymer system have been determined with gel permeation chromatography to be alpha = 0.375 and K = 2.4 X 10(-4). The glass-transition temperature, determined with differential scanning calorimetry, is 68.32 degreesC. The mechanism has been elucidated. (C) 2002 Wiley Periodicals, Inc.