Epoxidizable fatty amide-phenol conjugates

Authors: Zerkowski, Jonathan; Haas, Michael

Submitted to: Journal of the American Oil Chemists' Society
Publication Type: Peer Reviewed Journal
Publication Acceptance Date: 2/9/2011
Publication Date: 3/24/2011
Citation: Zerkowski, J.A., Haas, M.J. 2011. Epoxidizable fatty amide-phenol conjugates. Journal of the American Oil Chemists' Society. 88:1229-1237.

Interpretive Summary: There have been many methods developed over the years for converting vegetable oils to useful technological materials. One familiar method is to convert them to epoxy-type resins, which can then be used as conditioning or toughening agents for various kinds of plastics. Unfortunately, the resins thus obtained exhibit only a limited range of properties. The work reported in this paper describes a novel way to increase the chemical diversity of modified vegetable oils. We prepared a new class of compounds where fatty acids, which are obtained from vegetables or oilseeds, are linked to a chemical unit (phenol) that can be obtained by pyrolysis, or burning, of woody biomass. In other words, two streams of bioderived materials have been drawn together so that their chemical features can complement each other. These new molecules are analogous to epoxy vegetable oils, which ARS scientists have previously shown to be useful for preparing cross-linked polymeric materials. The difference, however, is that these new compounds also contain chemical groups that are known to impart toughness and UV-resistance to polymers. Some of the examples can be converted to polystyrenes or polyacrylamides which possess fatty acids extending from the polymer chains. These molecules will be explored as the precursors to a new group of high performance biobased coatings, films, and molded solids, thereby offering new ways of adding value to agricultural byproducts.

Technical Abstract: This paper reports the synthesis of a series of novel compounds where fatty acids have been linked to a phenol through amidomethyl units. One, two, or three fatty acids have been selectively appended to the phenol in yields above 75%. The fatty acid used was oleic acid, which was subsequently epoxidized. Other functional groups, such as amino acids, can be incorporated in these compounds. Examples of monomers that are suitable for polymerization were also prepared: one acrylamide, one styrene, and two types of AB2 diamino acids, all of which contain oleic units that are sites for epoxidation and crosslinking. Fatty acid aryl ethers were prepared using hydroxy fatty acids. These molecules are intended to serve as augmented analogues of epoxidized vegetable oil (EVO). Their amide groups should lead to intermolecular aggregation through hydrogen bonding, and the option to covalently include other functional groups may permit tuning of the macroscopic material properties of films, coatings, or solids constructed from them.