Hydroxymethylation and polymerization of plant oil triglycerides

The ene reaction between plant oil triglycerides (such as soybean and sunflower oils) and paraformaldehyde was used to introduce a homoallylic hydroxyl functionality on the triglyceride. Paraformaldehyde and triglyceride were reacted in the presence of a Lewis acid catalyst, ethylaluminum dichloride, and hydroxymethyl derivatives were obtained at yields of 42 and 55% for sunflower oil and soybean oil, respectively. In the next step, hydroxymethyl products were reacted with maleic anhydride at 100degreesC to produce the maleate half esters. The average number of maleate groups per triglycerides was found to be 1.7 for soybean oil and 1.3 for sunflower oil. In the final step, the free-radical-initiated copolymerization of the maleinized triglycerides with styrene produced rigid polymers. Characterization of new monomers and polymers was done by H-1-NMR, C-13-NMR, and infrared and mass spectrometries. The swelling behavior of the crosslinked network polymers was determined in different solvents. The glass-transition temperature of the cured resin was also determined by differential scanning calorimetry to be 40degreesC for soybean-based polymer and 30degreesC for sunflower-based polymer. (C) 2004 Wiley Periodicals, Inc.