Thermal decomposition, peroxide

Crosslinking time is directly dependent on the rate of decomposition of the peroxide. The effectiveness of the overall crosslinking reaction is thus dependent on the type of peroxide and polymer radicals produced during the process. Cure time and temperature can, in a peroxide cure system, be determined solely from knowledge of the rate of peroxide thermal decomposition. 

Hydroxyalkyl Hydroperoxyalkyl Peroxides. There is evidence that hydroxyalkyl hydroperoxyalkyl peroxides (2, X = OH, Y = OOH) exist in equilibrium with their corresponding carbonyl compounds and other o -oxygen-substituted peroxides. Thermal decomposition of hydroxyalkyl hydroperoxyalkyl peroxides produces mixtures of starting carbonyl compounds, mono and dicarboxylic acids, cyclic diperoxides, catbon dioxide, and water. 

Step I The addition of heat causes peroxide thermal decomposition (i.e., the oxygen bonds break via homolysis). One unpaired electron remains in each oxygen atom and promotes the formation of peroxide radicals. 

Decomposition of peroxides thermal decomposition to generate additional free radicals,... 

Three-dimensional networks of polyethylene are manufactured through peroxide-initiated covalent bonding between preformed linear molecules. These peroxide-thermal-decomposition reactions lead to free radical Intermediates which abstract hydrogen atoms from the polyethylene backbone to produce long chain polymer radicals. Combinations of these chain polymer radicals lead to a crossllnked network. ( ) (Figure 1)... 

Time/Temperature as a Function of the Half-Life The peroxide thermal decomposition reaction is the first one in the curing or cross-linking sequence, and determines the rate. This reaction follows first-order kinetics. The kinetic order was determined by partially curing compounds for varying cure times and... 

The Et4>rBr addition into the reaction medium in concentration which is one order less (6.00 10 M) than peroxides concentration ([ROOH]o=5.0010- M, [ROOR]o = 5.2410 M) leads to significant increasing of reaction rate as compared with peroxides thermal decomposition (343 K). The salt concentration during the reaetion proceeding and in the end of reaction remains constant. This fact shows the catalytic character of tetraethylammonium bromide aetion upon a-oxycyelohexylperoxides decomposition. 

The thermal decomposition of thia2ol-2-yl-carbonyl peroxide in benzene, bromobenzene, or cumene affords thiazole together with good yields of 2-arylthiazoles but negligible amounts of esters. Thiazol-4-ylcarbonyl peroxide gives fair yields of 4-arylthiazoles, but the phenyl ester is also a major product in benzene, indicating reactions of both thiazol-4-yl radicals and thiazol-4-carbonyloxy radicals. Thiazole-5-carbonyl peroxide gives... 

Lithium Oxide. Lithium oxide [12057-24-8], Li20, can be prepared by heating very pure lithium hydroxide to about 800°C under vacuum or by thermal decomposition of the peroxide (67). Lithium oxide is very reactive with carbon dioxide or water. It has been considered as a potential high temperature neutron target for tritium production (68). 

Classical chemiluminescence from lucigenin (20) is obtained from its reaction with hydrogen peroxide in water at a pH of about 10 Qc is reported to be about 0.5% based on lucigenin, but 1.6% based on the product A/-methylacridone which is formed in low yield (46). Lucigenin dioxetane (17) has been prepared by singlet oxygen addition to an electron-rich olefin (16) at low temperature (47). Thermal decomposition of (17) gives of 1.6% (47). 

Decomposition of diphenoylperoxide [6109-04-2] (40) in the presence of a fluorescer such as perylene in methylene chloride at 24°C produces chemiluminescence matching the fluorescence spectmm of the fluorescer with perylene was reported to be 10 5% (135). The reaction follows pseudo-first-order kinetics with the observed rate constant increasing with fluorescer concentration according to = k [flr]. Thus the fluorescer acts as a catalyst for peroxide decomposition, with catalytic decomposition competing with spontaneous thermal decomposition. An electron-transfer mechanism has been proposed (135). 

Primary and secondary dialkyl peroxides undergo thermal decompositions more rapidly than expected owing to radical-induced decompositions (73). Such radical-induced peroxide decompositions result in inefficient generation of free radicals. 

Thermal decompositions of di-Z fZ-cycloalkyl peroxides produce Z fZ-cycloalkoxy radicals which undergo ring -scission to give acycHc ketones,diketones, and other products (44) ... 

Thermal decomposition of dihydroperoxides results in initial homolysis of an oxygen—oxygen bond foUowed by carbon—oxygen and carbon—carbon bond cleavages to yield mixtures of carbonyl compounds (ketones, aldehydes), esters, carboxyHc acids, hydrocarbons, and hydrogen peroxide. 

Chemical Properties. Diacyl peroxides (20) decompose when heated or photoly2ed (<300 mm). Although photolytic decompositions generally produce free radicals (198), thermal decompositions can produce nonradical and radical iatermediates, depending on diacyl peroxide stmcture. Symmetrical aUphatic diacyl peroxides of certain stmctures, ie, diacyl peroxides (20, = alkyl) without a-branches or with a mono-cx-methyl... 

Free-Radical Addition. In free-radical addition polymerisation, the propagating species is a free radical. The free radicals, R-, ate most commonly generated by the thermal decomposition of a peroxide or aso initiator, 1 (see Initiators, free-RADICAl) ... 

Cobalt salts are used as activators for catalysts, fuel cells (qv), and batteries. Thermal decomposition of cobalt oxalate is used in the production of cobalt powder. Cobalt compounds have been used as selective absorbers for oxygen, in electrostatographic toners, as fluoridating agents, and in molecular sieves. Cobalt ethyUiexanoate and cobalt naphthenate are used as accelerators with methyl ethyl ketone peroxide for the room temperature cure of polyester resins. 

Fig. 12.3. NMR spectra recorded during thermal decomposition of dibenzoyl peroxide. Singlet at high field is due to benzene other signals are due to dibenzoyl peroxide. [From H. Fischer and J. Bargon, Acc. Chem. Res. 2 110 (1969). Reproduced by permission of the American Chemical Society.]...

The thermal decompositions described above are unimolecular reactions that should exhibit first-order kinetics. Under many conditions, peroxides decompose at rates faster than expected for unimolecular thermal decomposition and with more complicated kinetics. This behavior is known as induced decomposition and occurs when part of the peroxide decomposition is the result of bimolecular reactions with radicals present in solution, as illustrated below specifically for diethyl peroxide. 

Aryl migrations are promoted by steric crowding in the initial radical site. This trend is illustrated by data from the thermal decomposition of a series of diacyl peroxides. The amount of product derived from rearrangement increases with the size and number of substituents ... 

In the absence of oxygen or oxidizable material, the peroxides (except Li202) are stable towards thermal decomposition up to quite high temperatures, e.g. Na202 675°C, CS2O2 590°C. 

The thermal decomposition of diacyl peroxides has been the most frequently employed process for the generation of alkyl radicals. The rate and products of the unimolecular decomposition of acetyl peroxide have been the subject of many studies. Acetyl peroxide decomposes at a convenient rate at 70-80°C both in the solution and in the gas... 

Goldschmidt and Beer have examined the products formed during the thermal decomposition of diacyl peroxides of the type [COgMe —(CHziw—CHz—COO] 2, where n = 1 and 3, in the presence of a series of organic compounds including pyridine and acridine. The products and yields of the reaction with some aromatic and heterocyclic compounds are shown in Table VI. As expected, acridine and... 

Free-radical carboxymethylation of several aromatic compounds has been reported, " the -CHaCOOH radical being produced by the thermal decomposition of benzoyl peroxide in acetic acid. More recently the carboxymethylation of dibenzofuran brought about by the thermal decomposition of chloroacetylpolyglycolic acid (41) has... 

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