Petroleum resin was nitrated, reduced, and diazotized. Decomposition of the resultant diazonium chloride in aqueous methanol was found to follow the firstoorder kinetics and showed rate constants of 3.43, 5.84, and 45.40 x 10-5 sec-1 at 11°C, 20°C, and °C, respectively, the apparent activation energy being 9030 cal/mol. Upon decomposition, the petroleum resin molecule formed radicals, which served as sites for grafting with acrylamide. Thegraft reactions were carried out in acidic and alkaline media at 90°C and 95°C. The products were fractionated and examined by means of infrared spectrophotometry. The effects of ferric chloride catalyst and the amount of the monomer were investigated. It was suggested that only a part of the macroradicals so formed were able to initiate the graft reactions.
Direct syntheses of alkyl acrylates from acrylic acid and olefins have been studied. Thus, tert-butyl acrylate was obtained in 73% yield upon treatment of 1 mol acrylic acid with 1.1 mol isobutylene in ethylene dichloride in the presence of 0.05 mol sulfuric acid at 20°C., for 4 hrs under 2 atm pressure. Similarly, cyclohexyl acrylate was obtained in 80% yield upon treatment of 1 mol acrylic acid with 1.2 mol cyclohexene in ethylene dichloride in the presence of 0.05 mol sulfuric acid at 140°C., for 5 hrs under 40 atm pressure. The apparent activation energy was 18.4 kcal/mol and the reaction was first order in cyclohexene concentration.