Functional Thermoplastics from Linear Diols and Diisocyanates Produced Entirely from Renewable Lipid Sources

Abstract

An unsaturated terminal diol, 1,18-octadec-9-endiol (ODEDO), and a saturated terminal diol, 1,9-nonanediol (NDO), were synthesized from oleic acid. The feasibility of utilizing these new diols for the production of thermoplastic polyurethanes (TPUs) was demonstrated by reacting them with a fatty acid-derived diisocyanate, 1,7-heptamethylene diisocyanate (HPMDI), and a commercially available petroleum-derived diisocyanate, 1,6-hexamethylene diisocyanate (HDI). One type of phase structure was obtained for both TPUs in this study, owing to the similarity between the ODEDO and NDO molecular structure. In addition, double yielding behavior (observed for the first time in polyurethanes) was observed in the stress-strain curves for both TPU systems. Compared to the TPUs prepared from HDI, the totally biobased TPUs (ODEDO-NDO-HPDMI) demonstrated comparable properties within acceptable tolerances, considering the impacts on physical properties due to the odd-even effect introduced by the HPDMI. This work is the first that establishes the production of linear thermoplastic polyurethanes entirely from lipid feedstock.

Polymer precursors from catalytic reactions of natural oils

“…52 The diisocyanide can be reacted with 1,9-nonanediol prepared from oleic acid, yielding a polyuethane. 53 Finally, water-borne polyurethanes dispersions (WPUD) have been used from making the modification of starch, yielding to biodegradable materials. 54 Polyesters from natural oils can be obtained in three different ways.…”

Study on the crystallization of poly(alkylene dicarboxylate)s derived from 1,9-nonanediol and mixtures with different ratios of azelaic acid and pimelic acid units

“…Vegetable oils are a promising alternative since coming from abundant and economical biological sources can lead to biodegradable materials. Specifically, potential applications and uses of polyols and polyurethanes derived from plant oils are well known [1][2][3][4].…”

“…oleic acid), which can be used for chemical synthesis of dicarboxylic acid and diol monomers of poly(alkylene dicarboxylate)s. Thus, azelaic acid and 1,9-nonanediol can be obtained by ozonolysis cleavage of the alkene double bond of oleic acid and subsequent oxidation and reduction [3].…”

Preferential Incorporation of Azelaic Acid Units into the Crystalline Phase of the Copoly(Alkylene Dicarboxylate) Derived from 1,9-Nonanediol and an Equimolar Mixture of Pimelic and Azelaic Acids

“…Nevertheless, great efforts are also focused in achieving bio-based diols and dicarboxilic acids with shorter chain lengths as is the case of adipic acid, whose production could be achieved with engineered yeast strains by α-and/or ω-oxidation of long-chain n-alkanes, alcohols, or fatty acid substrates [12]. Other well-known examples correspond to pimelic acid, obtained by oxidation of ricinoleic acid from castor oil, azelaic acid prepared by ozonolysis cleavage of the alkene double bond of oleic acid and subsequent oxidation and 1,9-nonanediol prepared by reduction of azelaic acid [13].…”