Calcium and zinc salts of epoxidized linolenic acid were synthesized and used as multifunctional additives, to minimize or prevent the reaction of epoxidized soybean oil (ESO) with liberated hydrochloric acid (HCl) during the thermal degradation of poly(vinyl chloride) (PVC) in particular. These metal epoxy salts were incorporated as thermal stabilizers for both diisodecyl phthalate and ESO–plasticized PVC blends that underwent thermal degradation studies at 170°C. The overall performance of these metal epoxy salts was examined by thermal gravimetric analysis and visual color retention of the PVC blends. The weight loss profiles of the metal salt stabilized PVC were comparable to those of blends containing metal stearates. There were, however, vast improvements in color retention of the plasticized PVC using these novel additives. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41736.

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Acid-catalyzed decomposition of dicumyl peroxide in dodecane from 60 to 130 °C produces α-methylstyrene and phenol as the major products. Pseudo-first-order rate constants were determined as a function of the temperature for the reaction of DCP with dodecylbenzenesulfonic acid in dodecane and resulted in an Arrhenius plot exhibiting two distinct kinetic regimes with differing activation energies: 76.9 kJ/mol at low temperatures (measured from 60 to 90 °C) and 8.50 kJ/mol at higher temperatures (measured from 90 to 130 °C). With employment of a combination of kinetics, product analysis, and trapping experiments, evidence is presented to show the intermediacy of cumene hydroperoxidea reactive intermediate absent from previous mechanistic descriptions of this process. The yield of cumene hydroperoxide production is discussed, and the mechanistic pathways for formation of the observed products are presented.

Supplemental Information S1. Materials Glycine (≥98.5%), 13 C 2-Glycine (99 atom % 13 C), paraformaldehyde (powder, 95%), 13 C-formaldehyde (20 wt. % in H2O, 99 atom % 13 C), L-serine, sarcosine, sodium hydroxide (NaOH), and LC-MS grade water were all purchased from Sigma-Aldrich and used as is. Reactions of Glycine and Formaldehyde Glycine (unlabeled and 13 C 2-labeled) was dissolved in pH 6, 8 or 10 aqueous sodium phosphate buffered solution. Varying molar equivalents of formaldehyde (unlabeled and 13 C-labeled) were then added to the glycine solution. The resulting mixtures was allowed to react at RT, 50°C and 70°C for periods up to two weeks. By varying the stoichiometry, temperature and pH, the optimal reaction conditions for glyoxylate yield could be determined. 13 C NMR Analysis 13 C NMR data were obtained using a Bruker Avance II-500 spectrometer and a Bruker Avance III-400

The reactions of glycine, a simple amino acid, with glyoxylate, a simple α-oxocarboxylate, were investigated in water as a function of time, pH, and temperature and followed using a combination of quantitative 13 C nuclear magnetic resonance and high-resolution mass spectrometry. Three sets of experiments are reported: (1) reaction of 13 C-labeled glycine with unlabeled glyoxylate, (2) reaction of unlabeled glycine with 13 C-labeled glyoxylate, and (3) the reaction of 13 C-labeled glycine with 13 C-labeled glyoxylate. Competing transaminations, aldol reactions, and decarboxylations were observed; the mechanistic description for each of these processes is presented. 3-Hydroxy-2-aminosuccinate, a product of reaction between glycine and glyoxylate, was shown to promote both the decarboxylation of glyoxylate and transamination of glyoxylate to glycine. These observations may have implications for the mechanism of attenuation of ethylene glycol toxicity.

Cross-linked polyethylene (XLPE) is an important class of materials with critical applications  including pipes and high voltage electric cables. An organic peroxide such as bis­(1-methyl-1-phenylethyl) peroxide (BMPEP) is a commonly used radical initiator in the cross-linking process along with a secondary antioxidant such as bis­(octadecyloxycarbonylethyl) sulfide (BOCES). Herein is described a detailed investigation into the complex interactions of the radical initiator BMPEP and the secondary antioxidant BOCES in dodecane solvent–a model for the polyethylene polymer. Kinetic and spectroscopic experiments along with DFT calculations provide the foundation for a detailed mechanistic description for the roles of BMPEP, BOCES, atmospheric oxygen, and trace amounts of water in the overall process.