Long-Chain Linear C'9 and C23 Monomers and Polycondensates from Unsaturated Fatty Acid Esters

ABSTRACT: Isomerizing alkoxycarbonylation of methyl ole- unsaturated fatty acids ~ ~ ate and ethyl erucate, respectively, yielded dimethyl 1,19- ~gH R /1 ""-. R nonadecanedioate and diethyl 1,23-tricosanedioate in>99 %./ ' ""'-purity. With [K2-(PP)Pd(OTf)][OTf] as a defined catalyst 0 0 A HO~OH H~H precursor (pp = 1,2-bis[(di-tert-butylphosphino)methyl]ben- t= ~ II zene) the reaction can be carried out without the need for • + additional added diphosphine. Saponification of the diesters H2N~NH2 yielded 1,19-nonadecanedicarboxylic acid and 1,23-tricosane- E3. I dicarboxylic 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 7S 0c, Thermal properties of novel long-chain polyamides are reported