Thermal decomposition characteristics of BHT and its peroxide (BHTOOH).

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 (Ti) and heat release (QDSC) of DSC were 384.9 K and 865.0 J g-1, respectively. The apparent activation energies (Ea) 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.

Oxidation characteristic and thermal runaway of isoprene.

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 Ton were 371.17 K and 365.84 K, respectively. And the decomposition heat QDSC 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.

Thermal stability of levopimaric acid and its oxidation products.

Biofuels are renewable alternatives to fossil fuels. Levopimaric acid‒base biofuels have attracted increasing attention. However, their stability remains a critical issue in practice. Thus, there is a strong impetus to evaluate the thermal stability of levopimaric acid. Through thermogravimetry (TG) and a custom-designed mini closed pressure vessel test (MCPVT) operating under isothermal and stepped temperature conditions, we investigated thermal oxidation characteristics of levopimaric acid under oxygen atmosphere. Thin-layer chromatography (TLC) and iodimetry were used to measure the hydrogen peroxides generated by levopimaric acid oxidation. A high pressure differential scanning calorimeter (HPDSC) was used to assess hydroperoxide thermal decomposition characteristics. Gas chromatography-mass spectrometry (GC-MS) was used to characterize the oxidation products. The thermal decomposition kinetics of levopimaric acid were thus elucidated, and a high peroxide value was detected in the levopimaric acid. The decomposition heat (QDSC) and exothermic onset temperature (Tonset) of hydroperoxides were 338.75 J g-1 and 375.37 K, respectively. Finally, levopimaric acid underwent a second-stage oxidation process at its melt point (423.15 K), resulting in complex oxidation products. Thermal oxidation of levopimaric acid could yield potential thermal hazards, indicating that antioxidants must be added during levopimaric acid application to protect against such hazardous effects.

Macrolactonization of methyl 15-hydroxypentadecanoate to cyclopentadecanolide using KF-La/γ-Al2O3 catalyst.

It has been a challenge to synthesize macrolide musk in excellent yields with high purity. KF-La/γ-Al2O3 catalyst was prepared from a highly basic mesoporous framework using a mild method. The prepared KF-La/γ-Al2O3 catalyst was employed for the synthesis of cyclopentadecanolide from methyl 15-hydroxypentadecanoate. The morphology and structure of prepared catalysts were characterized using XRD, TG-DTG, SEM, EDX, TEM, BET and CO2-TPD. The results revealed that the K3AlF6 and LaOF are produced on the surface of KF-La/γ-Al2O3, and LaO can promote the dispersion of KF on the surface of Al2O3. Catalysts pore size main distribution ranges between 10 and 30 nm, the maximum CO2 desorption temperature is 715°C when the La loading is 25%. Because F- ion has a higher electronegativity than O2- ion, the KF-promoted metal oxide (Al2O3 or/and La2O3) contained more strong basic sites, compared with that of the corresponding metal oxide. The yield of cyclopentadecanolide obtained at 0.5 g KF-25La/γ-Al2O3 catalyst and a reaction temperature of 190°C for 7 h were 58.50%, and the content after reactive distillation is 98.8%. The KF-La/γ-Al2O3 catalyst has a larger pore size and basic strength, which is more conducive to the macrolactonization of long-chain hydroxy ester.

A novel synthesis method of cyclopentadecanone and cyclopentadecanolide from vegetable oil.

Malania oleifera Chum is a unique renewable plant resource in China, its fruit oil has a high content of 15-tetracosenic acid, and it is a good raw material for the synthesis of cyclopentadecanone and cyclopentadecanolide. A Novel synthesis method of cyclopentadecanone and cyclopentadecanolide from vegetable oil was designed, and the synthesis yields of c cyclopentadecanone and cyclopentadecanolide were 38.5% and 63.0%, respectively. The effect of different ester groups on cyclization of α,ω-difatty acid alkyl ester in cyclopentadecanone synthesis, and effect of catalysts on cyclization ofω-hydroxycarboxylic acid triglyceride in cyclopentadecanolide synthesis were investigated. The designed synthesis strategy has the characteristics of less synthesis steps and high utilization efficiency of 15-tetracosenic acid, which has simple and economic.

Reactivity and kinetics of 1,3-butadiene under ultraviolet irradiation at 254 nm.

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.

Calcium Glycerolate Catalyst Derived from Eggshell Waste for Cyclopentadecanolide Synthesis.

The synthesis costs of macrolide musks are higher than those of other commercial musks. To make this process less expensive, eggshell waste was calcined at a low temperature to obtain a catalyst for the cyclopentadecanolide production via reactive distillation using a glycerol entrainer. X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy analyses of the original and recovered catalysts revealed that the main catalytic ingredient was calcium glycerolate (CaG) and not calcium diglyceroxide (CaDG). The basic strengths of CaG and CaDG obtained by Hammett indicators were 7.2 < H_≤ 15.0 and 9.8 < H_≤15.0, while the corresponding base amounts were 1.9 and 7.3 mmol/ g, respectively. Because CaG was soluble in glycerine, the catalyst was efficiently reused. The reaction product containing over 95.0% cyclopentadecanolide with a yield of 49.8% was obtained at a temperature of 190°C and catalyst amount of 12 wt% after 7 h of reaction. Thus, eggshell waste may be directly placed into the reaction mixture after calcination at 600°C to synthesise a large amount of cyclopentadecanolide within a relatively short time. The results of this work indicate that eggshell waste can serve as a potential eco-friendly and affordable catalyst source for the production of macrolide musks.

Thermal stability and oxidation characteristics of α-pinene, ß-pinene and α-pinene/ß-pinene mixture.

Turpentine is a renewable resource, has good combustion performance, and is considered to be a fuel or promising additive to diesel fuel. This is very important for the investigation of thermal stability and energy oxidation characteristics, because evaluation of energy or fuel quality assurance and use safety are necessary. The main components of turpentine are α-pinene and ß-pinene, which have unsaturated double bonds and high chemical activity. By investigating their thermal stability and oxidation reaction characteristics, we know the chemical thermal properties and thermal explosion hazard of turpentine. In this present study, the thermal stability and oxidation characteristics of α-pinene, ß-pinene and α-pinene/ß-pinene mixture were investigated using a high sensitivity accelerating rate calorimeter (ARC) and C80 calorimeter. The important parameters of oxidation reaction and thermal stability were obtained from the temperature, pressure and exothermic behavior in chemical reaction. The results show that α-pinene and ß-pinene are thermally stable without chemical reaction under a nitrogen atmosphere even when the temperature reaches 473 K. The initial exothermic temperature of the two pinenes and their mixture is 333-338 K, and the heat release (-ΔH) of their oxidation is 2745-2973 J g-1. The oxidation activation energy (E a) of α-pinene, ß-pinene and α-pinene/ß-pinene mixture is 116.25 kJ mol-1, 121.85 kJ mol-1, and 115.95 kJ mol-1, respectively. There are three steps in the oxidation of pinenes: the first is the induction period of the oxidation reaction; the second is the main oxidation stage, and the pressure is reduced; the third is thermal decomposition to produce gas.

Thermal stability and pathways for the oxidation of four 3-phenyl-2-propene compounds.

Cinnamaldehyde, cinnamyl alcohol, ß-methylstyrene and cinnamic acid are four important biomass 3-phenyl-2-propene compounds. In the field of perfume and organic synthesis, their thermal stability and oxidation pathways deserve attention. This paper reports a new attempt to investigate the thermal stability and reactivity by a custom-designed mini closed pressure vessel test (MCPVT). The pressure and temperature behaviors were measured by MCPVT under nitrogen and oxygen atmosphere. The temperature of initial oxygen absorption (T a) and rapid oxidation (T R) were calculated. The results showed that four 3-phenyl-2-propene compounds were stable under nitrogen atmosphere. The T a of cinnamaldehyde, cinnamyl alcohol, ß-methylstyrene, and cinnamic acid was 271.25 K, 292.375 K, 323.125 K, and 363.875 K, and their T R was 301.125 K, 332.75 K, 357.91 K, and 385.375 K, respectively. The oxidation reactivity order was derived to be cinnamaldehyde > cinnamyl alcohol > ß-methylstyrene > cinnamic acid. The oxidation kinetics were determined using n versus time (n-t) plots, which showed a second-order reaction. Peroxide was determined by iodimetry, and the oxidation products were analyzed by gas chromatography-mass spectrometry (GC-MS). The results showed that the peroxide value of cinnamaldehyde, cinnamyl alcohol, ß-methylstyrene, and cinnamic acid reached 18.88, 15.07, 9.62, and 4.24 mmol kg-1 at 373 K for 6 h, respectively. The common oxidation products of four 3-phenyl-2-propene compounds were benzaldehyde, benzoic acid, and epoxide, which resulted from the carbon-carbon double bond oxidation. The substituents' oxidation products were obtained from the oxidation of cinnamaldehyde, cinnamyl alcohol, and ß-methylstyrene. In particular, the difference is that no oxidation products of the carboxyl group of cinnamic acid were detected. The common oxidation products of the four 3-phenyl-2-propene compounds were benzaldehyde, benzoic acid, and epoxide, which resulted from the carbon-carbon double bond oxidation. The substituents' oxidation products were caught in the oxidation of cinnamaldehyde, cinnamyl alcohol, and ß-methylstyrene. In particular, the difference is that no oxidation products of the carboxyl group of cinnamic acid were detected. According to the complex oxidation products, important insights into the oxidation pathways were provided.

Thermal Stability Evaluation of Resin Acids and Rosin Modified Resins.

Rosin is a sustainable resource, which is mainly composed of resin acid. Rosin-modified resin is widely used in adhesives, inks, coatings, and other fields, and its stability is very important for the production, storage, and use of products. Thermal stability and reactivity of three resin acids (levopimaric acid, neoabietic acid, and dehydroabietic acid) and four rosin-modified resins were studied using an accelerating rate calorimeter (ARC). They are stable, and exothermic reactions do not occur even when they were heated to 200 °C under a nitrogen atmosphere, but they are unstable under an oxygen atmosphere. The mechanism of the oxidation reaction process was found: first, resin acids absorb oxygen, and then an exothermic oxidation occurs. The initial exothermic temperature (T 0) of levopimaric acid, neoabietic acid, and dehydroabietic acid are 354.01, 353.83, and 398.20 K, the initial oxidation kinetics shows a second-order reaction, and the activation energies (E a) are 42.90, 58.05, and 46.60 kJ/mol, respectively. Peroxide concentration of three resin acids were determined by iodometry. The T 0 values of hydrogenated rosin, disproportionated rosin, hydrogenated rosin glyceride, and hydrogenated rosin pentaerythritol ester, the four rosin-modified resin, are 353.71, 348.32, 412.85, and 412.44 K. Levopimaric acid and neoabietic acid have higher oxidative reactivity and easily undergoes an oxidation reaction at lower temperature. Rosin-modified resins are stable and find it difficult to undergo oxidation reactions.

Characteristics and hazards of the cinnamaldehyde oxidation process.

Pressure and temperature behavior of the cinnamaldehyde oxidation process was determined using a custom-designed mini closed pressure vessel test (MCPVT), which is a new method to investigate the stability and hazard assesment of the cinnamaldehyde oxidation reaction. The oxidation products were analyzed by gas chromatography-mass spectrometry (GC-MS). The results showed that cinnamaldehyde was stable under nitrogen atmosphere but very unstable under oxygen atmosphere. The initial oxidation products were analyzed by iodimetry and the cinnamaldehyde peroxide value could reach 139.44 mmol kg-1 when the oxidation temperature was 308 K. The oxidation kinetics of cinnamaldehyde were studied by using the pressure versus time (P-t) curves obtained from the MCPVT process. The reaction is a second-order reaction, the kinetic equation is ln k = -2233.66 × (1/T) + 11.19, and the activation energy E a is 18.57 kJ mol-1 at 308-338 K. The explosion of the cinnamaldehyde oxidation reaction was observed by MCPVT, in which the onset temperature was 373 K. The main products of cinnamaldehyde oxidation are acetaldehyde, benzaldehyde, phenylacetaldehyde, acetophenone, 2-hydroxyphenyl acetone, cinnamaldehyde epoxide, benzoic acid, and cinnamic acid. Oxidation is a three-step process: (1) cinnamaldehyde reacts with oxygen to form peroxides; (2) complex oxidation reactions are caused by the thermal decomposition of peroxides; (3) rapid oxidation and thermal decomposition lead to explosion hazard.

Extraction and Antioxidant Activities of Magnolia kwangsiensis Figlar & Noot. Leaf Polyphenols.

Microwave-assisted extraction was employed to extract polyphenols from the leaf of Magnolia kwangsiensis Figlar & Noot. The yield of polyphenols was 2.44±0.02 % under the optimal conditions of RSM: acetone concentration of 70 %, ratio of solvent to material of 21 mL⋅g-1 and extraction time of 16 min. The antioxidant activities were evaluated in terms of total antioxidant ability, reducing power, DPPH⋅ and ⋅ OH scavenging activity. Results showed the polyphenols presented potential antioxidant activities, especially the stronger scavenging activity on ⋅ OH. In term of ⋅ OH scavenging activity, the IC50 value of NKA-9 purification was 0.335 mg mL-1 , equivalent to 35.23 % of VC . The IC50 values of crude extract and ethyl acetate extract were 0.580 and 0.828 mg mL-1 , equivalent to 60.99 % and 87.07 % of VC . Results indicated that M. kwangsiensis leaf polyphenols present potential antioxidant activities that make it beneficial for human health by preventing or reducing oxidative damage.

Characteristics and Kinetics of Rosin Pentaerythritol Ester via Oxidation Process under Ultraviolet Irradiation.

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.

Asymmetric reduction of acetophenone into R-(+)-1-phenylethanol by endophytic fungus Neofusicoccum parvum BYEF07 isolated from Illicium verum.

Seventy-nine strains of endophytic fungi isolated from the healthy leaves, twigs and fruits of Illicium verum were screened for the asymmetric reduction activities to acetophenone. Strain BYEF07, which showed relatively high reduction activities, has been classified as Neofusicoccum parvum, and the main product was confirmed to be (R)-(+)-1-phenylethanol by GC-MS and chiral HPLC methods. The bio-reduction conditions of acetophenone by cells of N. parvum BYEF07 were investigated in detail. Under the conditions of 1.8 g/L of acetophenone, 100 g/L of microorganism cells and 10 g/L of glucose in 40 mL Na2HPO4 KH2PO4 buffer solution at pH7.5, 30 °C and 150 rpm, after 48 h reaction, the production yield of 1-phenylethanol and enantiomeric excess value of (R)-(+)-1-phenylethanol were 78% and 96%, respectively.

Extraction of polysaccharides and its antitumor activity on Magnolia kwangsiensis Figlar & Noot.

The crude polysaccharides from the leaves of Magnolia kwangsiensis Figlar & Noot. were extracted by hot water extraction, the yield was 5.09%. Two polysaccharide fractions (P-2 and P-3) were isolated by DEAE-52 cellulose chromatography and Sephadex G-100 column chromatography in order, respectively. P-2 and P-3 were characterized by IR, HPGPC and GC-MS. P-2 was comprised of only glucose. Its molecular weight was 11.2×10(3) Da and the formula was C414H690O345. P-3 was comprised of xylose and rhamnose in the ratio of 1:4. Its molecular weight was 7.8×10(3)Da, and the formula was C319H528O220. The antitumor activities of P-2 and P-3 on the growth of human lung cancer (A549) cells and human gastric carcinoma (SGC7901) cells in vitro were evaluated. The results indicated that P-3 exhibited marked antitumor activities with IC50 value of 8.48 and 5.66 µg/mL.

Comparative analysis of essential oil composition from flower and leaf of Magnolia kwangsiensis Figlar & Noot.

The essential oils from Magnolia kwangsiensis Figlar & Noot. were obtained using hydrodistillation, and analysed by GC and GC-MS. A total of 31, 27 and 26 constituents were identified in the oils from male flower, female flower and leaf of M. kwangsiensis, and they comprised 99.2, 98.5 and 96.2% of the oils, respectively. Monoterpene hydrocarbons predominated in the oils and accounted for 48.3% of male flower oil, 54.0% of female flower oil and 44.6% of leaf oil. The compositions of flower oils were quite similar but with different content, and were different from those of leaf oil.

Kinetics and Thermodynamics of Reserpine Adsorption onto Strong Acidic Cationic Exchange Fiber.

The kinetics and thermodynamics of the adsorption process of reserpine adsorbed onto the strong acidic cationic exchange fiber (SACEF) were studied by batch adsorption experiments. The adsorption capacity strongly depended on pH values, and the optimum reserpine adsorption onto the SACEF occurred at pH = 5 of reserpine solution. With the increase of temperature and initial concentration, the adsorption capacity increased. The equilibrium was attained within 20 mins. The adsorption process could be better described by the pseudo-second-order model and the Freundlich isotherm model. The calculated activation energy Ea was 4.35 kJ/mol. And the thermodynamic parameters were: 4.97<ΔH<7.44 kJ/mol, -15.29<ΔG<-11.87 kJ/mol and 41.97<ΔS<47.35 J/mol·K. The thermodynamic parameters demonstrated that the adsorption was an endothermic, spontaneous and feasible process of physisorption within the temperature range between 283 K and 323 K and the initial concentration range between 100 mg/L and 300 mg/L. All the results showed that the SACEF had a good adsorption performance for the adsorption of reserpine from alcoholic solution.

An innovative method for preparation of acid-free-water-soluble low-molecular-weight chitosan (AFWSLMWC).

The ozone generated from compressed oxygen by a laboratory-scale corona discharge generator was used for the preparation of acid-free-water-soluble low-molecular-weight chitosan (AFWSLMWC). Factors affecting the percent yield of AFWSLMWC were studied in batch experiments. AFWSLMWC with a molecular weight of 4.3-13.1kDa was obtained. IR spectra demonstrated that the chemical structures of AFWSLMWC were not modified during the depolymerisation process. There was no significant change of the total degree of deacetylation (DD) of AFWSLMWC, compared with the initial chitosan. The method is promisingly suitable for scale-up manufacture of acid-free-water-soluble low-molecular-weight chitosan.

[Extraction and determination of volatile constituents in leaves of Eucalyptus citriodora].

The volatile constituents in leaves of Eucalyptus citriodora, including oil fraction and water-soluble fraction, were extracted and determined. Oil fraction of volatile components was obtained through steam distillation. Ether was used as the solvent to extract the water-soluble fraction of volatile compounds from the liquid left after steam distillation in order to know the quantity and constituents of volatile compounds dissolved in the water phase. The oil yield in the oil fraction was 1.36%, and the oil yield in the water-soluble fraction was 0.48% (both on fresh weight basis). Both oil fraction and water-soluble fraction were analyzed by gas chromatography-mass spectrometry (GC-MS) method. The results showed that 37 compounds (97.36%) in the oil fraction and 10 compounds (82.05%) in the water-soluble fraction were identified. There were 12 hydrocarbon compounds and 25 oxygenated compounds identified in oil fraction. The major constituents in oil fraction were citronellal (57.00%), followed by citronellol (15.89%) and citronellyl acetate (15.33%). Alcohols dominated the compounds in water-soluble fraction. cis-p-Menthane-3, 8-diol (53.43%) and trans-p-menthane-3, 8-diol (16. 48%) were found to be the major compounds, which have the activity to repel insects. It is concluded that the comprehensive utilization value of leaves of Eucalyptus citriodora was enhanced owing to the extraction of water-soluble volatile components.