Long-chain linear C19 and C23 monomers and polycondensates from unsaturated fatty acid esters

Abstract

Isomerizing alkoxycarbonylation of methyl oleate and ethyl erucate, respectively, yielded dimethyl 1,19-nonadecanedioate and diethyl 1,23-tricosanedioate in >99% purity. With [κ2-(P̂ P)Pd(OTf)][OTf] as a defined catalyst precursor (P̂P = 1,2-bis[(di-tert- butylphosphino)methyl]benzene) the reaction can be carried out without the need for additional added diphosphine. Saponification of the diesters yielded 1,19-nonadecanedicarboxylic acid and 1,23-tricosanedicarboxylic acid in >99% purity. By ruthenium-catalyzed reduction of the diesters with H2, 1,19-nonadecanediole and 1,23-tricosanediole were formed in high yield and purity (>99%). From the latter, 1,19-nonadecanediamine and 1,23-tricosanediamine were generated. Polyesters with commercially available shorter-chain petrochemical or renewable diols exhibit high melting points due to the crystallizable long-chain methylene segments from the dicarboxylic acid component, e.g., poly[1,6-hexadiyl-1,23-tricosanedioate] Tm 92, Tc 75 °C. Thermal properties of novel long-chain polyamides are reported. © 2011 American Chemical Society.