2,6-Di-tert-butyl-4-methylphenol (BHT) is an excellent antioxidant that is easily oxidized to 2,6-di-tert-butyl-4-hydroperoxyl-4-methyl-2,5-cyclohexadienone (BHTOOH). For the safety of BHT production and usage, it is meaningful to study the thermal stability and decomposition properties of BHT and BHTOOH. In this paper, the thermal decomposition properties of BHT and BHTOOH were compared by the mini closed pressure vessel test (MCPVT) and differential scanning calorimetry (DSC). Their kinetics of thermal decomposition were studied using thermogravimetric analysis (TGA). The thermal decomposition products of BHT and BHTOOH were analyzed by gas chromatography-mass spectrometry (GC–MS). The results show that there was no significant change in temperature pressure when BHT was warmed up under a nitrogen atmosphere, indicating that BHT was stable within 400 K. The thermal decomposition reaction of BHTOOH was rapid with an initial reaction temperature of 375.2 K. The initial exothermic temperature (T_i) and heat release (Q_DSC) of DSC were 384.9 K and 865.0 J g⁻¹, respectively. The apparent activation energies (E_a) for the thermal decomposition reactions of BHT and BHTOOH calculated by the Kissinger method were 151.8 kJ mol⁻¹ and 66.07 kJ mol⁻¹, respectively. The main decomposition products of BHT were isobutene and 2-tert-butyl-4-methylphenol. The thermal decomposition products of BHTOOH included BHT, 2,6-di-tert-butyl-4-ethylphenol, 3,5-di-tert-butyl-4-hydroxybenzaldehyde, 4,4′-(1,2-ethanediyl) bis [2,6-bis (1,1-dimethylethyl) phenol, etc. Based on the thermal decomposition behavior and products, the reaction pathway has been described. These results indicate that BHT is a potential thermal hazard during production, storage and application. For the safety of the chemical industry, the oxidation of BHT should be avoided.

A self-designed reaction device was used as a promising equipment to investigate the oxidation characteristics and kinetics of rosin pentaerythritol ester (RPE) under UV irradiation. Photo-oxidation kinetics and the initial quantum yield (Φ) of RPE were calculated. The initial oxidation product of the photo-oxidation reaction—peroxide was analyzed by iodimetry. The peroxide concentration is related to the light intensity (I) and the temperature (T), and the increasing T and I would destabilize the RPE by accelerating peroxide forming. Photo-oxidation of RPE follows the pseudo first-order reaction kinetics. The relationship between activation energy and logarithm of light intensity (ln I) is linear, and it is expressed as Ea = −4.937ln I + 45.565. Φ was calculated by the photo-oxidation kinetics, and the average value of Φ was 7.19% in the light intensity range of 200–800 μW cm⁻². This research can provide fundamental information for application of RPE, and help obtain a better understanding of the stability of rosin esters.

In this study, the oxidation characteristics of isoprene were investigated using a custom-designed mini closed pressure vessel test (MCPVT). The results show that isoprene is unstable and polymerization occurs under a nitrogen atmosphere. Under an oxygen atmosphere, the oxidation process of isoprene was divided into three stages: (1) isoprene reacts with oxygen to produce peroxide; (2) Peroxides produce free radicals through thermal decomposition; (3) Free radicals cause complex oxidation and thermal runaway reactions. The oxidation of isoprene conforms to the second-order reaction kinetics, and the activation energy was 86.88 kJ·mol⁻¹. The thermal decomposition characteristics of the total oxidation product and purified peroxide mixture were determined by differential scanning calorimetry (DSC). The initial exothermic temperatures T_on were 371.17 K and 365.84 K, respectively. And the decomposition heat Q_DSC were 816.66 J·g⁻¹ and 991.08 J·g⁻¹, respectively. It indicates that high concentration of isoprene peroxide has a high risk of thermal runaway. The results of thermal runaway experiment showed that the temperature and pressure of isoprene oxidation were prone to rise rapidly, which indicates that the oxidation reaction was dangerous. The reaction products of isoprene were analyzed by gas chromatography-mass spectrometry (GC–MS). The main oxidation products were methyl vinyl ketone, methacrolein, 3-methylfuran, etc. The main thermal runaway products were dimethoxymethane, 2,3-pentanedione, naphthalene, etc. Based on the reaction products, the possible reaction pathway of isoprene was proposed.

The reaction process of gaseous 1,3-butadiene following ultraviolet irradiation at the temperature range from 298 to 323 K under nitrogen atmosphere was monitored by UV–vis spectrophotometry. A gaseous mini-reactor was used as a reaction vessel and could be directly monitored in a UV–vis spectrophotometer. We investigated the reactivity and kinetics of 1,3-butadiene under non-UV and UV irradiation to evaluate its photochemical stability. A second-order kinetic model with 50.48 kJ·mol^–1 activation energy fitted the reaction data for non-UV irradiation, whereas a first-order kinetic model was appropriate in the case of UV irradiation with activation energies of 19.92–43.65 kJ mol^–1. This indicates that ultraviolet light could accelerate the photolysis reaction rate of 1,3-butadiene. In addition, the reaction products were determined using gas chromatography-mass spectrometry (GC–MS), and the reaction pathways were identified. The photolysis of 1,3-butadiene gave rise to various volatile products by cleavage and rearrangement of single C–C bonds. The differences between dimerization and dissociation of 1,3-butadiene under ultraviolet irradiation were elucidated by combining experimental and theoretical methods. The present findings provide fundamental insight into the photochemistry of 1,3-butadiene compounds.