Research Article Vegetable-based building-blocks for the synthesis of thermoplastic renewable polyurethanes and polyesters Arvind S. More 1,2 , Lise Maisonneuve 1,2 , Thomas Lebarbe ´ 1,2 , Benoit Gadenne 3 , Carine Alfos 3 and Henri Cramail 1,2 1 University Bordeaux, LCPO, UMR 5629, Pessac, France 2 CNRS, LCPO, UMR 5629, Pessac, France 3 ITERG, Pessac, France Fatty acid derivatives, viz, methyl oleate and methyl 10-undecenoate were systematically explored to obtain a set of monomers with defined functionality. More specifically, AB-type self-condensable monomers containing hydroxyl-acyl azide functionality and diols with pre-formed ester linkage were synthesized. A series of polyurethanes was prepared using two methods: (i) AB-type self-polycondensation reaction of hydroxyl-acyl azide moiety, and (ii) polymerization of diols with isophorone diisocyanate and methylene diphenyl diisocyanate. The diols were also reacted with a bio-sourced diester using organocatalyst to obtain a set of polyesters. The obtained polyurethanes and polyesters were thoroughly analyzed with fourier- transformed infrared, nuclear magnetic resonance, size exclusion chromatography, differential scanning calorimetry and thermogravimetric analysis experiments. The polymers displayed amorphous to semi- crystalline behaviors with regard to the structure of the monomers. Both, polyurethanes and polyesters displayed a good thermal stability with no significant weight loss below 2008C. Keywords: Methyl undecenoate / Methyl oleate / Vegetable oils / Thermoplastic polyesters / Thermoplastic polyurethanes Received: May 2, 2012 / Revised: June 21, 2012 / Accepted: July 9, 2012 DOI: 10.1002/ejlt.201200172 : Supporting information available online. 1 Introduction Most of the monomers available today to prepare polymers are necessarily derived from the petroleum sources and it accounts for about 7% of worldwide oil [1]. As the fossil resources are finite, numerous initiatives intended at replacing these petroleum sources with renewable counterparts have generated [1–9]. Vegetable oils (triglycerides) or fatty acid derivatives are raw materials of great promise and offer new tailor-made structures with variable functionalities [2, 5, 8–23]. Triglycerides, in general, can be derivatized through double bonds and ester functions by means of transesterification [14, 15], amidation [16, 17], epoxidation [18, 19] followed by ring-opening of the epoxide [20], ozonolysis [21], and more recently using, carbo- nation [22], metathesis [23, 24], and thiol-ene coupling reac- tions [25]. Being easy to obtain and having ability to mimic petroleum-based products, most of the vegetable oil based chemistry has been centered on the synthesis of polyols. A broad range of polyols [11–30] with pure hydrocarbon units, or preformed ester, amide, ether, carbonate linkages have been prepared particularly for the production of polyurethanes and polyesters. There has been a plethora of examples in the synthesis of polyols and their utilization in the chemistry of polyurethanes [11–30] and polyesters [31–34]. For instance, recently Narine et al. reported the synthesis of fatty acid- based polyols for the synthesis of polyurethanes [26, 27]. Meier et al. have extensively employed fatty acids as starting materials to synthesize well-defined polyols using metathesis Correspondence: Prof. Henri Cramail, University Bordeaux, LCPO, UMR 5629, F-33600 Pessac, France E-mail: cramail@enscbp.fr Fax: þ33 05 40 00 84 87 Abbreviations: C20dE, dimethyl 1,20-eicos-10-enedioate; DBTDL, Grubbs 2nd generation catalyst and dibutyltin dilaurate; DCM, dichloromethane; DMA, dynamical mechanical analysis; DMF, dimethylformamide; FTIR, fourier-transformed infrared; HETOAz, 10-[(2-hydroxyethyl)thio]octa- decanoyl azide; HETUAz, 11-[(2-hydroxyethyl)thio]undecanoyl azide; IPDI, isophorone diisocyanate; MCET, 2-mercaptoethanol; MDI, 4,40-methylene- diphenyl-diisocyanate; NMR, nuclear magnetic resonance; OlME, methyl oleate; PS, polystyrene; SEC, size exclusion chromatography; TBD, 1,5,7- triazabicyclo[4.4.0]dec-5-ene; TEA, triethyl amine; TGA, thermogravimetric analysis; THF, tetrahydrofuran; UndME, Methyl 10-undecenoate Eur. J. Lipid Sci. Technol. 2012, 000, 0000–0000 1 ß 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.ejlst.com