Long-Chain Linear C-19 and C-23 Monomers and Polycondensates from Unsaturated Fatty Acid Esters

作者：Stempfle Florian; Quinzler Dorothee; Heckler Ilona; Mecking Stefan^*

来源：Macromolecules, 2011, 44(11): 4159-4166.

DOI：10.1021/ma200627e

Isomerizing alkoxycarbonylation of methyl oleate and ethyl erucate, respectively, yielded dimethyl 1,19-nonadecanedioate and diethyl 1,23-tricosanedioate in >99% purity. With [kappa(2)-((P) over cap P)Pd(OTf)][OTf] as a defined catalyst precursor ((P) over capP = 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 H-2, 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] T-m 92, T-c 75 degrees C. Thermal properties of novel long-chain polyamides are reported.

• 出版日期2011-6-14