A novel plasticizer derived from cardanol, and epoxied cardanol glycidyl ether (ECGE), was synthesized and characterized by 1 H-NMR and 13 C-NMR. The effects of ECGE combined with the commercial plasticizer dioctyl phthalate (DOP), in soft poly(vinyl chloride) (PVC) films, were studied. The mechanical properties of PVC films showed both tensile strength and percent elongation increases with increasing ECGE content. Thermogravimetric analysis (TGA) was performed to characterize the thermal stabilities of the plasticized samples and showed the stability of films increased on increasing the content of ECGE. The properties of volatility, extraction, and exudation resistance of plasticizers were tested and analysis by means of solubility parameters as reported in the literature suggests the ECGE has similar or higher stability for these properties than DOP. FTIR analysis of the films also revealed that ECGE interacted with PVC. Due to its inherent chemical backbone and the modified epoxy groups, ECGE properly balanced the properties and improved the performance of PVC films compared with the neat DOP plasticizer.

The reaction of 2,6-diisopropylaniline-based bis-imine ligands (4, 9) with M(CH2Ph)4 (M = Hf, Zr) led to formation of novel imino−amido tribenzyl complexes via migratory insertion of a benzyl group into a CN bond. Imino−amido complexes were found to undergo unprecedented dibenzyl elimination to form ene−diamido complexes. Imino−amido complexes were found to be active ethylene polymerization catalysts.

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We report a facile Ru-catalyzed route to alkenes from unsaturated fatty acids (alkenoic fatty acids) via readily accessible catalyst precursors, [Ru­(CO)­2RCO2] n and Ru3(CO)12. The catalyst apparently functions in a tandem mode by dynamically isomerizing the positions of double bonds in an aliphatic chain and, subsequently, decarboxylating specific isomers with lower activation barriers. Substrates capable of tandem isomerization-decarboxylation processes (oleic acid, undecylenic acid) are readily converted to mixtures of alkenes. A catalytic cycle is proposed that relies on isomerization positioning double bonds proximate to the acid function to enable facile decarboxylation. To elucidate the proposed mechanistic pathway, substrates that do not undergo decarboxylation under these catalytic conditions (methyl oleate) are compared with those that cannot isomerize the position of unsaturation (cinnamic acid). Both were shown to be operational under these catalytic reaction conditions. Another illustrative comparison shows that the saturated octadecanoic acid is 28 times less reactive than the unsaturated counterpart when reacted using this precatalyst.

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We report a biobased route to methacrylic acid via selective decarboxylation of itaconic acid utilizing catalytic ruthenium carbonyl propionate in an aqueous solvent system. High selectivity (>90%) was achieved at low catalyst loading (0.1 mol %) with high substrate concentration (5.5 M) at low temperature (200−225 °C) and pressure (≤425 psig) relative to previous contributions in this area. Direct decarboxylation of itaconic acid was achieved as opposed to the conjugate base reported previously, thereby avoiding basification and acidification steps. Also investigated was catalytic manganese(II) oxalate (5 mol %), but low yield (4.8%) and evolution of carbon monoxide via oxalate decomposition was problematic. Attempts at stabilization of the catalyst with triphenylphosphine were unsuccessful, but it exhibited greater catalytic efficacy (14.0% yield) than the manganese catalyst (4.8% yield) at 5 mol %. Neither carbon monoxide nor propylene (excessive decarboxylation) were detected during ruthenium-catalyzed decarboxylation. In addition, cosolvents such as tetraglyme lowered vapor pressures within the reaction vessel by >100 psig while minimizing decomposition of starting acids. In combination, these findings represent improvements over existing methodologies that may facilitate sustainable production of methacrylic acid, an important petrochemically based monomer for the plastics industry.

Vegetable oils containing thioether groups have been synthesized and used to effectively remove heavy metal ions from aqueous solution. The use of thioether-functionalized corn oil (TF-corn oil) and thioether-functionalized canola oil (TF-canola oil) were both effective in the extraction of Ag+ from a 600 ppm aqueous silver nitrate solution. The TF-corn oil reduced the observed silver in solution to a level below the detection limit, whereas the TF-canola oil was only able to remove slightly over 50% of the concentration. A study of the absorption rate is also reported, where both the TF-corn oil and the TF-canola oil removed the Ag+ rapidly, at nearly the same rate. Preliminary results suggest that the efficacy and capacity of silver removal relates directly to the fatty acid composition of the oil precursor.

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