110-05-4Relevant articles and documents
High-pressure NMR studies of (porphinato)iron-catalyzed isobutane oxidation utilizing dioxygen as the stoichiometric oxidant
Moore,Horvath,Therien
, p. 1791 - 1792 (1997)
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Autoxidation of Biological Molecules. 2. The Autoxidation of a Model Membrane. A Comparison of the Autoxidation of Egg Lecithin Phosphatidylcholine in Water and in Chlorobenzene
Barclay, L.R.C.,Ingold, K.U.
, p. 6478 - 6485 (1981)
The kinetics of autoxidation of egg lecithin phosphatidylcholine in homogeneous solution in chlorobenzene and as a bilayer dispersion in 0.1 M aqueous NaCl has been studied at 30 deg C under 760 torr of O2.The autoxidations were initiated by the thermal decomposition of di-tert-butyl hyponitrile.The efficiency of chain initiation, e, was determined by the induction period method using α-tocopherol as the chain-breaking antioxidant.In chlorobenzene e was ca. 0.66 but in the aqueous dispersion e was only ca. 0.091.The reduced efficiency of initiation in the bilayeris attributed to a reduction in the fraction of tert-butoxyls which escape from the solvent cage, and this in turn is due to the fact that the bilayer has a high microviscosity.The rate of autoxidation of the egg lecithin in chlorobenzene is proportional to the lecithin concentration and to the square root of the rate of chain initiation, and is virtually independent of the oxygen pressure, which means that this autoxidation follows the usual kinetic rate law.In the aqueous dispersion the concentration of egg lecithin in the bilayer cannot be altered, but since the rate of autoxidation is proportional to the square root of the rate of chain initiation and is virtually independent of the oxygen pressure, the usual kinetic rate law would also appear to be followed.The oxidizability of egg lecithin in chlorobenzene is 0.61 M-1/2 s-1/2, and in the aqueous dispension it is 0.0165 M-1/2 s-1/2.The reduction in oxidizability in the bilayer is attributed to the diffusion of the peroxyl radical center, which is a polar moiety, out of the autoxidizable, nonpolar, interior region of the bilayer and into the nonautoxidizable, polar surface region.As a consequence, chain progogation will be retarded and chain termination will be accelerated.
Titanium tetra-tert-butoxide-tert-butyl hydroperoxide oxidizing system: Physicochemical and chemical aspects
Stepovik,Gulenova,Martynova,Mar'Yasin,Cherkasov
, p. 266 - 276 (2008)
The reaction of titanium tetra-tert-butoxide with tert-butyl hydroperoxide (1: 2) (C6H6, 20 C) involves the steps of formation of the titanium-containing peroxide (t-BuO)3TiOOBu-t and peroxytrioxide (t-BuO)3TiOOOBu-t. The latter decomposes with the release of oxygen, often in the singlet form, and also homolytically with cleavage of both peroxy bonds. The corresponding alkoxy and peroxy radicals were identified by ESR using spin traps. The title system oxidizes organic substrates under mild conditions. Depending on the substrate structure, the active oxidant species can be titanium-containing peroxide, peroxytrioxide, and oxygen generated by the system.
Induced decomposition of di(tert-butyl)trioxide
Khursan,Khalizov,Shereshovets
, p. 884 - 887 (1997)
Thermal decomposition of di(tert-butyl)trioxide (ButOOOBut) in a wide range of concentrations was studied by visible and IR chemiluminescence. Induced decomposition of ButOOOBut caused by its reaction with the peroxy radicals formed in the solvent (CH2Cl2) was found and investigated.
Recombination of Tertiary Butyl Peroxy Radicals. Part 1.-Products Yields between 298 and 373 K
Kirsch, Leslie J.,Parkes, David A.
, p. 293 - 308 (1981)
Overall product distributions resulting from the recombination of t-butyl peroxy radicals have been studied over the temperature range 298-373 K.The results indicate that over this range there is a switch from the terminating channels (forming alcohol and aldehyde/ketone) towards non-terminating channels (forming two alkoxy radicals) for the two further recombination processes that follow the initial combination of t-butyl peroxy radicals:.There is also direct evidence for the presence of a terminating channel to form di-t-butyl peroxide.This reaction proceeds at a rate of ca. 0.14 of the non-terminating recombination rate at 298 K, but this fraction falls to 0.025 at 333 K and the reaction is not evident at 373 K.Our results demonstrate the importance of abstraction reactions involving alkoxy radicals (t-butoxy and methoxy) and one of the principal recombination products, t-butyl hydroperoxide.Rate constant ratios involving these processes have been derived from the product distributions and from additional studies in which t-butyl hydroperoxide was added.Rate constants of ca. 10-13 cm3 molecule-1 s-1 for these abstraction processes are consistent with our results.
HETEROGENEOUS CATALYSIS IN THE LIQUID-PHASE OXIDATION OF OLEFINS. - 4. THE ACTIVITY OF A SUPPORTED VANADIUM OR CHROMIUM OXIDE CATALYST IN THE DECOMPOSITION OF t-BUTYL HYDROPEROXIDE.
Takehira,Hayakawa,Ishikawa
, p. 2103 - 2110 (1980)
The liquid-phase decomposition of t-butyl hydroperoxide (t-BuOOH) has been carried out in benzene under an N//2 atmosphere using a vanadium or chromium oxide, supported on gamma -Al//2O//3 or SiO//2 as the catalyst, for the purpose of clarifying the reaction mechanism of the cyclohexane oxidation. The decomposition of t-BuOOH on the supported oxide catalyst was a first-order reaction; the main products were t-butyl alcohol, di-ti-butyl peroxide, and acetone, suggesting that t-BuOOH is decomposed homolytically on the catalyst by the Haber-Weiss mechanism. The effect of the vanadium-chromium binary system formation was small, but the interaction between metal oxides and the supports appeared to be important in the t-BuOOH decomposition.
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Milas,Plesnicar
, p. 4450 (1968)
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Process for producing organic peroxides
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Paragraph 0097-0099, (2021/09/29)
The present invention relates to a method for producing organic peroxides and separating, purifying and concentrating sulfuric acid from aqueous effluents of said organic peroxide production process.
Method for continuously producing tert-butyl hydroperoxide
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Paragraph 0024-0028, (2020/12/15)
The invention relates to a method for continuously producing tert-butyl hydroperoxide, wherein the method comprises the following steps: adding tert-butyl alcohol and hydrogen peroxide into a reactiondevice, and carrying out catalytic heating to obtain a mixture of tert-butyl alcohol, water, tert-butyl hydroperoxide and di-tert-butyl peroxide; a water phase and an oil phase are separated, the oilphase is rectified, a tert-butyl hydroperoxide product is produced at a tower kettle of a rectifying tower, a mixture of water, tert-butyl alcohol and di-tert-butyl peroxide is produced at the towertop of the rectifying tower, part of a water layer flows back after the mixture is layered through a reflux tank, a mixture of tert-butyl alcohol and di-tert-butyl peroxide is produced at an oil layer, and the oil layer is washed with water and then layered; the separated oil layer is di-tert-butyl peroxide, the water layer is stripped by a stripping tower, the tower top of the stripping tower isa tert-butyl alcohol aqueous solution, the tert-butyl alcohol aqueous solution returns to the reaction device for reaction, and water at the tower kettle of the stripping tower is recycled. The process is continuous in production, convenient for automatic control, high in recovery rate and high in separation rate. The reaction, separation and purification processes are optimized, the wastewater amount is reduced, the product purity is high, and the quality is stable.
Di-tert-butyl peroxide production process
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Paragraph 0008-0009, (2019/07/10)
The invention relates to the field of processing and production of oxides, particularly to a di-tert-butyl peroxide production process, which comprises: (1) selecting raw materials; and (2) adding hydrogen peroxide into a reaction kettle, starting stirring, opening a coolant valve, slowly adding sulfuric acid to the reaction kettle, slowly adding t-butanol into the reaction kettle, closing the coolant valve after completing the adding, heating with hot water, carrying out a reaction for 1-3 h, closing the stirring, standing, separating the waste acid to enter a waste acid storage tank, placingthe upper layer organic phase (crude product) in a washing kettle, washing for 8-12 min with a sodium hydroxide solution, standing, separating the waste liquid, washing twice with a large amount of water, standing, separating the waste liquid, adding dry magnesium sulfate, stirring, opening a kettle bottom valve, placing a standing device spread with a filtering cloth, standing, carrying out filtering and packaging, and analyzing the content. According to the present invention, the production process has beneficial effects of process simplifying, production cycle shortening, energy consumption reducing and pollution reducing.
