Four maleated soybean oil (SBO) derivatives were synthesized and used as bio‐based reactive diluents (RDs) for alkyd coating systems. The RDs were prepared in a two‐step fashion: (a) Maleation of SBO with maleic anhydride (MA) via an ene reaction followed by (b) a nucleophilic acyl substitution of the grafted succinic anhydride with allyl‐ or methacrylate‐functional molecules. The structures were characterized using 1H NMR, 13C NMR, 13C‐1H heteronuclear single quantum coherence NMR, 13C‐1H heteronuclear multiple bond correlation NMR spectroscopy, FT‐IR (ATR) spectroscopy, and MALDI‐ToF‐MS. The 2D NMR spectroscopy techniques helped confirm that MA was successfully grafted onto SBO. FT‐IR spectroscopy identified new absorption bands at 1780 and 1850 cm−1, following the maleation reaction, corresponding to the anhydride functionality. Alkyd coating formulations were prepared with either 0, 10, 20, or 30 wt% of the different RDs. Brookfield viscosity measurements were conducted on the formulations to measure the efficiency of the SBO‐based RDs. At 20 wt% loading level, the RDs typically reduced the viscosity of the base alkyd resin by 50%–60%. Coatings tests and gel content measurements were also conducted in order to understand the effects that these RDs had on the performance of the alkyd coatings.
Four model alkyds were prepared by the fatty acid process using a single fatty acid (stearic, oleic, linoleic, or linolenic acid) with phthalic anhydride and glycerol. These model alkyds were reacted with methyl methacrylate (MMA) in the presence of benzoyl peroxide or azobis(isobutyronitrile). 1 H NMR, 2D gradient heteronuclear multiple quantum coherence NMR, matrix assisted laser desorption ionization mass spectrometry, solvent extraction, and gas chromatography were used to evaluate each model alkyd system. The conversion of MMA was quantified, and the grafting mechanism of MMA onto each model alkyd was elucidated. In general, both polymerization rates and MMA conversions were inhibited in the presence of alkyd resins. For oleic alkyd model systems, the grafting site was primarily located at the double bond on the fatty acid chain. Both the homopolymerization and copolymerization of the MMA are significantly retarded by chain transfer of the hydrogen from the double allylic site in the linoleic and linolenic model systems. For the linoleic alkyd and linolenic alkyd model systems, the grafting reaction predominately occurred at the activated double allylic methylene group on the fatty acid chain via hydrogen abstraction by the primary radical and MMA radical, followed by grafting in a termination reaction with a propagating MMA radical.
We report on the synthesis and characterization of bent‐core liquid crystal (LC) compounds and the preparation of mixtures that provide an optically isotropic antiferroelectric (OI‐AFLC) liquid crystal display mode over a very wide temperature interval and well below room temperature. From the collection of compounds synthesized during this study, we recognized that several ternary mixtures displayed a modulated SmCaPA phase down to below −40 °C and up to about 100 °C on both heating and cooling, as well as optical tilt angles in the transformed state of approximately 45° (optically isotropic state). The materials were fully characterized and their liquid crystal as well as electro‐optical properties analyzed by polarized optical microscopy, differential scanning calorimetry, synchrotron X‐ray diffraction, dielectric spectroscopy, and electro‐optical tests.
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