Alisa Zlatanić

Epoxidation of soybean oil in toluene with peroxoacetic and peroxoformic acids - kinetics and side reactions

The kinetics of the epoxidation of soybean oil and the extent of side reactions were studied at 40, 60, and 80 °C. Epoxidation was carried out in toluene with “in situ” formed peroxoacetic and peroxoformic acid and in the presence of an ion exchange resin as the catalyst. The reaction was found to be first-order with respect to the double bond concentration. At higher temperatures and at higher conversions a deviation from the first-order kinetics was observed. The rate constants for the epoxidation with peroxoacetic acid were 0.118 (h−1) at 40 °C, 0.451 (h−1) at 60 °C and 1.278 (h−1) at 80 °C, while those for peroxoformic acid were 0.264, 0.734, and 1.250 (h−1). The activation energy was found to be 54.7 kJ/mol for the epoxidation with peroxoacetic acid and 35.9 kJ/mol for that with peroxoformic acid. Three factors indicated that side reactions did not occur on a large scale: The absence of an OH band in the IR spectra, the formation of less than 2% of higher molecular weight products from gel permeation chromatography and the selectivity values between 0.9 and 1.

Effect of OH/NCO Molar Ratio on Properties of Soy-Based Polyurethane Networks

Polyurethane networks from soybean oil have a number of valuable properties, which are determined by their chemical composition and cross-linking density. Changing the molar ratio of reacting groups can vary the latter. In this work we have varied the NCO/OH molar ratio (isocyanate index) from 1.05 to 0.40 in a soy polyol/MDI system, and tested physical and mechanical properties. The degree of swelling in toluene increased from 52–206% by decreasing isocyanate index from 1.05–0.4. The sol fractions and network densities determined from swelling in toluene were compared with ones obtained using the network formation theory based on branching processes. The comparison of experimental sol fractions and network densities with those predicted by theory of network formation suggest that ∼5–10% of bonds are lost in cycles and that high entanglement contributions increase the network densities. Polymers prepared with NCO/OH ratios from 1.05–0.8 were glassy while the others were rubbery, and that was reflected in their properties. Glass transition temperature (DSC) of the networks decreased from 64–7°C, tensile strength from 47–0.3 MPa, and elongation at break increased from 7–232%. The activation energy of the glass transition, determined from dielectric spectra, varied from 222–156 kJ/mol as the molar ratio of NCO to OH groups decreased from 1.05–0.4.

Polyurethane molded foams with high content of hyperbranched polyols from soybean oil

This paper examines the feasibility of using polyols from vegetable oils as base polyols (i.e. with 50% or more in a blend with petrochemical polyols) for flexible molded polyurethane foams. A series of hyperbranched (HB) polyols were synthesized by transesterification of hydroxy fatty acid methyl esters and different modifiers to control viscosity, hydrophilicity, molecular weight, and functionality. All HB polyols had hydroxyl numbers around 85 mg KOH/g, with the exception of one which was 105 mg KOH/g. When mixed with petrochemical polyols with OH numbers 35 and 28 mg KOH/g, the HB polyols acted primarily as high molecular weight crosslinkers that increased the stiffness of the polymeric network and the load-bearing properties but decreased the tensile strength, elongation, and tear strength. However, most of the foams met the targeted tensile and tear strength values while some of the foam formulations provided satisfactory elongation. The best mechanical properties were obtained from foams with phthalic anhydride-modified HB polyols. It was demonstrated that flexible molded foams with satisfactory properties can be obtained with 50% and 65% of HB soy polyols in a blend with PPO polyols.