A new linear saturated terminal diisocyanate was synthesized from oleic acid via Curtius rearrangement, and its chemical structure was identified by FTIR, (1)H and (13)C NMR, and MS. The feasibility of utilizing this new diisocyanate for the production of polyurethanes (PUs) was demonstrated by reacting it with commercial petroleum-derived polyols and canola oil-derived polyols, respectively. The physical properties of the PUs prepared from fatty acid-derived diisocyanate were compared to those prepared from the same polyols with a similar but petroleum-derived commercially available diisocyanate: 1,6-hexamethylene diisocyanate. It was found that the fatty acid-derived diisocyanate was capable of producing PUs with comparable properties within acceptable tolerances. This work is the first that establishes the production of linear saturated terminal diisocyanate derived from fatty acids and corresponding PUs mostly from lipid feedstock.

Rigid polyurethane (PU) foams were prepared using three North American seed oil starting materials. Polyol with terminal primary hydroxyl groups synthesized from canola oil by ozonolysis and hydrogenation based technology, commercially available soybean based polyol and crude castor oil were reacted with aromatic diphenylmethane diisocyanate to prepare the foams. Their physical and thermal properties were studied and compared using dynamic mechanical analysis and thermogravimetric analysis techniques, and their cellular structures were investigated by scanning electron microscope. The chemical diversity of the starting materials allowed the evaluation of the effect of dangling chain on the properties of the foams. The reactivity of soybean oil-derived polyols and of unrefined crude castor oil were found to be lower than that of the canola based polyol as shown by their processing parameters (cream, rising and gel times) and FTIR. Canola-PU foam demonstrated better compressive properties than Soybean-PU foam but less than Castor-PU foam. The differences in performance were found to be related to the differences in the number and position of OH-groups and dangling chains in the starting materials, and to the differences in cellular structure.

Polyols synthesized by ozonolysis and hydrogenation from canola oil were reacted with aliphatic 1,6-hexamethylene diisocyanates (HDI) to produce polyurethane (PU) elastomers. The properties of the materials were examined by dynamic mechanical analysis (DMA), thermomechanical analysis (TMA), modulated differential scanning calorimetry (MDSC), and thermogravimetric analysis (TGA), and measurements were taken of tensile properties. The effect of dangling chains on network properties was assessed. The formation of hydrogen bonds was observed by FTIR. The measured properties were found to be strongly dependent on processing-dependent factors such as the crosslinking density and the molar ratio of polyols to HDI component. The glass transition temperatures (T g ) of the elastomers were found to increase as the OH/NCO molar ratio decreased. With the same OH/NCO molar ratio, T g of canola-oil-based PU was higher than that of soybean-oil-based PU. The TGA thermographs showed two well-defined steps of degradation for all the elastomers. In the first step, up to 30% weight loss, the fastest rate of loss was found at 345°C for canola-oil-based PU while soybean-oilbased PU lost most of the weight in the second step. With the same OH/NCO molar ratio, the elastomers made from canola-oil-based polyol showed slightly higher Young's modulus and tensile strength.

Polyurethane (PUR) plastic sheets were prepared by reacting polyols synthesized from canola oil with aromatic diphenylmethane diisocyanate. The properties of the material were measured by dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA) as well as tensile properties measurements. The effect of stoichiometric balance (i.e., OH/NCO molar ratio) on the final properties was evaluated. The concentration of elastically active network chains (EANCs), ν e , of the polymer networks was calculated using rubber elasticity theory. The glass transition temperatures (T g ) for the plastic sheets with OH/NCO molar ratios of 1.0/1.0, 1.0/1.1, and 1.0/1.2 were found to be 23, 41, and 43°C, respectively. The kinetic studies of the degradation process of the PUR plastics showed three well-defined steps of degradation. The PUR plastic sheets with OH/NCO molar ratio 1.0/1.1 had the highest ν e , lowest number-average molecule weight between crosslinks, M C , and excellent mechanical properties, indicating that this is the optimum ratio in the PUR formulations.

The feasibility of a method based on ozonolysis and hydrogenation reactions for the production of polyols from unsaturated canola oil has been demonstrated. Polyol products with primary alcohol functional groups at position nine of each fatty acid ester in the original triacylglycerol have been produced from canola oil. Short straight-chain alcohols were also produced and were removed by wiped-blade molecular distillation. The pure components of the polyol, i.e. mono-ol, diol and triol were separated by flash chromatography, and identified by Fourier-transform infrared (FTIR), 1 H-nuclear magnetic resonance (NMR), 13 C-NMR as well as mass spectrometry. Polyol identification was facilitated by the use of a simple high-performance liquid chromatography (HPLC) method to determine the composition of the polyol mixture, which can be exploited as a qualitycontrol mechanism in designing novel polyol feedstocks. Basic correlations were established between the molecular diversity of the polyols and their physicochemical properties, such as hydroxyl number, acidity number, and viscosity. It has been found that the produced polyols are suitable for processing methods employing polyols for the production of polyurethanes and can be manipulated to create polyurethanes with desirable properties.

A novel long chain linear unsaturated terminal diisocyanate, 1,16‐diisocyanatohexadec‐8‐ene (HDEDI) was synthesized from oleic acid via Curtius rearrangement. Its chemical structure was identified by FTIR, 1H NMR, 13C NMR, and HRMS. This diisocyanate was used as a starting material for the preparation of entirely bio‐based polyurethanes (PUs) by reacting it with canola diol and canola polyol, respectively. The physical properties and crystalline structure of the PUs prepared from this diisocyanate were compared to their counterparts prepared from similar fatty acid‐derived diisocyanate, 1,7‐heptamethylene diisocyanate (HPMDI). The HDEDI based PUs demonstrated various different properties compared to those of HPMDI based PUs. For example, HDEDI based PUs exhibited a triclinic crystal form; whereas HPMDI based PUs exhibited a hexagonal crystal lattice. In addition, canola polyol‐HDEDI PU demonstrated a higher tensile strength at break than that of canola polyol‐HPMDI, attributed to the higher degree of hydrogen bonding associated with the former sample. Nevertheless, lower Young's modulus and higher elongation in canola polyol‐HDEDI PU were obtained because of the flexibility of the long chain introduced by the HDEDI diisocyanate. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3302–3310, 2010

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.

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