Polymeric Products Derived from Industrial Oilseed for Paints, Coatings, and Other Applications
Hayes, D. G., and M. J. Dumont.  2016.  Industrial Oilseed Crops, T. A. McKeon, D.G. Hayes, D. F. Hildebrand, R. J. Weselake, eds., Amsterdam, Elsevier, pp. 43-73 (Ch. 3).

Industrial oilseeds are viable feedstocks for the preparation of polymeric materials, particularly thermosetting polymers: liquid-phase polymers that are cured irreversibly via heat, irradiation, or chemical reactions, to form an insoluble polymeric network. Paints, coatings, adhesives, foams, and gels are commonly thermosets. Biobased feedstocks are receiving increasing attentions as replacements for petroleum in the preparation of thermosets and other polymers due to the reduced environmental impact associated with their derivation (no mining involved, approximately neutral in the net production of the greenhouse gas, CO2) and increased cost competitiveness. This chapter focuses upon the preparation of thermosets, polyesters, and other polymers from industrial oilseeds. Nature has provided a few examples of plant oils that possess multiple functional groups needed for polymer synthesis, such as castor (Ricinus communis), lesquerella (L. fendleri), and vernonia (V. galamensis) oils, enriched in VOH and epoxide-functionalized fatty acids: ricinoleic, lesquerolic, and vernolic acid, respectively (Table 1). Many common plant seed oils (e.g., soybean, cottonseed, corn, soybean, safflower, sunflower, canola, jatropha, and olive oils) are enriched inC16 V C18 saturated and mono- and di-unsaturated fatty acids, such as palmitic (16:0), oleic (18:1-9c), and linoleic (18:2-9c,12c) acids, and lesser amounts of [alpha] -linolenic acid (18:3-9c,12c,15c); however, linseed (flax seed), carmelina (C. sativa), perilla (P. frutescens), and conophor (Tetracarpidium conophorum), oils possesses a relatively large amount of the latter compared to other common seed oils (5-10%). To make use of free fatty acids (FFA), fatty acid methyl esters (FAME), and triacylglycerols (TAG) from the above-mentioned common oils as monomers, additional functional groups must be incorporated, such as hydroxy, epoxy, or maleinate groups (Figure 1). The hydroxy and epoxy groups can in turn serve as sites to add other functional groups (Figure 1). Oils enriched in polyunsaturated fatty acids, such as [alpha] - or [gamma] -linolenic acid or elostearic acid, possess additional utility; for instance, they have been employed as wood varnishes and in flooring for centuries. Particularly attractive are those oils enriched in conjugated double bonds, as contained in elostearic and licanic acyl groups, such as tung oil (Table 1), which can undergo additional reactions such as Diels-Alder.