Vegetable oil‐based triols from hydroformylated fatty acids and polyurethane elastomers

Abstract

Novel bio-based polyols were prepared from hydroformylated oleic acid (9/10-hydroxymethyl-octadecanoic acid) methyl esters (HFME) and trimethylolpropane by transesterification. Hydroformylation produces primary hydroxyls, which allow relatively lower transesterification temperatures and better yields than hydroxy fatty acids with secondary hydroxyl groups. These non-crystallizing polyols have no double bonds and their viscosities are acceptable. Polyurethane (PU) elastomers prepared by reaction of these polyols with diphenylmethane diisocyanate had glass transition temperatures from -33 to -56 7C, depending on the molecular weight of the triols. Tensile strength and Shore A hardness were higher, and elongation, swelling and sol fraction lower than those of corresponding networks from polyricinoleic acid polyols. The plasticizing effect of longer dangling chains in HFME-based PU compensated, to a degree, the presence of double bonds in ricinoleic acid, effectively resulting in similar glass transitions between the two families of polyols. Lipid Sci. Technol. 2010, 112, 97-102 97 Practical applicationsNovel triols of high molecular weight, suitable as base polyols for flexible foams, were prepared and tested in cast polyurethane elastomers. The polyols exhibit excellent reactivity, high enough molecular weight and high regularity as well as low glass transitions. The polyurethane networks displayed good elastomeric properties.

Fats and oils as renewable feedstock for chemistry

“…Branched o-hydroxy fatty esters having a primary hydroxyl group are advantageous and were obtained, e.g., by hydroformylation of the methyl ester of high oleic sunflower oil and hydrogenation of the formyl ester. Distillation gave methyl 9/10-hydroxymethyl-octadecanoate of high purity, suitable for self-polymerization and cocondensation with trimethylolpropane to give polyestertriols with M n 1000-6000, suited for flexible polyurethane foams [56]. These polyols are being commercialized by Cargill as BiOH ™ polyols.…”

Polymers From Biological Oils

“…Polymers obtained by reacting these Polyols with diphenylmethane diisocyanate (MDI) were crosslinked elastomers with glass transitions from -33 to -58 o C, tensile strengths from 7 to 0.7 MPa, elongations from 47-110% and Shore A hardness from 85 to 33. Analogous polyurethanes from ricinoleic acid triol and MDI had lower glass transitions, lower hardness and higher elongations [21].…”

Fette und Öle als nachwachsende Rohstoffe in der Chemie

“…[91] Neue biobasierte Polyole wurden durch Hydroformylierung von 1 b und einigen nativen Ölen in Gegenwart homogener Rhodiumkatalyatoren erhalten. [92][93][94][95] Homogene Rhodiumkomplexe wurden des Weiteren für die Hydroaminomethylierung von Alkenen eingesetzt. [96] [83] Schema 10.…”