Original diols from sunflower and ricin oils: Synthesis, characterization, and use as polyurethane building blocks

Abstract

International audienceA series of novel fatty acid-based diols were designed and synthesized from sunflower and ricin oils using optimized chemical reactions and purifications. These diols were categorized in two different types: (i) fatty acid-based monoester containing diols (FAmE-1 to FAmE-6) and (ii) fatty acid-based diester containing diols (FAdE-1 to FAdE-8). Their synthesis involved a series of reactions such as transesterification, epoxidation, ring opening of epoxide, and thiol-ene additions. Analyses of these new fatty acid-based diols were performed by HPLC/GC and NMR spectroscopy. The latter were then demonstrated as polyurethane (PU) precursors in the bulk polymerization with isophorone diisocyanate in the presence of dibutyl tin dilaurate as a catalyst. The effects of the diol nature and purity on the PU synthesis and properties were investigated. The structural characterization of the different PUs was carried out by means of FTIR, 1H NMR, and 1H DOSY NMR spectroscopy. The thermomechanical and rheological properties of these new PUs were found dependent on the chemical structure and purity of the diol building block. (C) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 201

Preparation and Spectroscopic Characterization of Si‐Coated Vegetable Oils and their Application in In Situ Curing of Hybrid Coatings

“…[4] Their chemical structures allow chemical modifications leading to various compounds. [4,[6][7][8] All these oxidized triglycerides have been employed in composite materials or in further modifications such as acrylation for photopolymerizable coatings or acetylation for a range of biosourced plasticizers. [4,[6][7][8] All these oxidized triglycerides have been employed in composite materials or in further modifications such as acrylation for photopolymerizable coatings or acetylation for a range of biosourced plasticizers.…”

“…[12][13][14] The insertion of nitrogen elements has also been investigated. [4,17,[19][20][21] The insertion of elements such as silicon and titanium is a very interesting way to modify vegetable oils, since it opens the way to cross-link oils through the sol-gel process. [7,17,18] In addition, sulfur elements through thiol-ene coupling (TEC) remain a versatile tool to modify vegetable oils into polyesters and polyurethanes.…”

Monomers and polymers from plant oils via click chemistry reactions

“…41 A dramatic reduction of the thiol-ene addition reaction time was reported by Cramail and coworkers when carried out the functionalization of similar oleic acid-based structures with 1,5-pentanediol (M27) and polyethyleneglycols of different length (13 and 45 repeating units, M29 and M30) spacers. 39 Using photochemical initiation (225 nm) and a thiol to C@C molar ratio of 6:1, 90% conversion determined by 1 H NMR spectroscopy was achieved at 0 C after 2 h demonstrating a temperature effect in the dissociation rate of the radical generated from addition of thiyl radicals to C@C bonds. 42 Finally, esterification of oleic or 10-undecenoic acids with allyl alcohol followed by the double hydrothiolation with T1 was proved as an alternative way to transform both fatty acids into diols (M32 and M33).…”

Preparation of bio-polymeric materials, their microstructures and physical functionalities

“…A strong stretching band located at around 3317 cm -1 characteristic of the N-H group and a stretching vibration band centered around 1708 cm -1 characteristic of the C=O group are present in the FTIR spectra. 7,8,15 There are also two stretching regions attributed to the C=O group. The band centered at around 1768cm -1 corresponds to the free carbonyl group.…”

“…[1][2][3][4][5][6][7] Vegetable oils are abundant and cheap renewable resources that represent a major potential alternative source of chemicals suitable for developing safe, environmentally products. [8][9][10] The use of vegetable oils and natural fatty acids as starting raw materials offers numerous advantages: for example, inexpensive, abundant, low toxicity, and inherent biodegradability, thus they are considered to be one of the most important classes of renewable resources for the production of bio-based polymeric materials. [11][12][13][14][15][16][17] Polyurethanes (PUs) form a versatile class of polymers, which are used in a broad range of applications, for example, as elastomers, sealants, fibers, foams, coatings, adhesives, and biomedical materials.…”