Organic peroxides, decomposition products

Decomposition Hazards. The main causes of unintended decompositions of organic peroxides are heat energy from heating sources and mechanical shock, eg, impact or friction. In addition, certain contaminants, ie, metal salts, amines, acids, and bases, initiate or accelerate organic peroxide decompositions at temperatures at which the peroxide is normally stable. These reactions also Hberate heat, thus further accelerating the decomposition. Commercial products often contain diluents that desensitize neat peroxides to these hazards. Commercial organic peroxide decompositions are low order deflagrations rather than detonations (279). 

On the basis of mechanistic studies, mainly on these isolable cychc four-membered peroxides (1 and 2), two main efficient chemiexcitation mechanisms can be defined in organic peroxide decomposition (i) the unimolecular decomposition or rearrangement of high-energy compounds leading to the formation of excited-state products, exemplified here in the case of the thermal decomposition of 1,2-dioxetane (equation i)". 5,i9. 

The type of initiator utilized for a solution polymerization depends on several factors, including the solubiUty of the initiator, the rate of decomposition of the initiator, and the intended use of the polymeric product. The amount of initiator used may vary from a few hundredths to several percent of the monomer weight. As the amount of initiator is decreased, the molecular weight of the polymer is increased as a result of initiating fewer polymer chains per unit weight of monomer, and thus the initiator concentration is often used to control molecular weight. Organic peroxides, hydroperoxides, and azo compounds are the initiators of choice for the preparations of most acryUc solution polymers and copolymers. 

The decomposition kinetics of an organic peroxide, as judged by 10-h HLT, largely determines the suitabiUty of a particular peroxide initiator in an end use appHcation (22). Other important factors ate melting point, solubiUty, cost, safety, efficiency, necessity for refrigerated storage and shipment, compatibihty with production systems, effects on the finished product, and potential for activation. 

The effect of the decomposition products of the polymerization initiator incorporated at the beginning of the chain is a controversial one. If the polymerization of vinyl chloride is initiated with organic peroxides, which decompose according to Eqs. (13) and (14) ... 

The dry material is readily ignited, bums very rapidly and is moderately sensitive to heat, shock, friction or contact with combustible materials. When heated above its m.p. (103-105°C), instantaneous and explosive decomposition occurs without flame, but the decomposition products are flammable. If under confinement (or in large bulk), decomposition may be violently explosive [1], An explosion which occurred when a screw-capped bottle of the peroxide was opened was attributed to friction initiating a mixture of peroxide and organic dust in the cap threads [2], Waxed paper tubs are recommended to store this and other sensitive solids [3], Crystallisation of the peroxide from hot chloroform solution involves a high risk of explosion. Precipitation from cold chloroform solution by methanol is safer [4], Water- or plasticiser-containing pastes of dibenzoyl peroxide are much safer for industrial use. 

Although zinc dialkyl dithiophosphates, [(RO)2PS2]2Zn, have been used as antioxidants for many years, the detailed mechanism of their action is still not known. However, it is certain that they are efficient peroxide decomposers. The effect of a number of organic sulfur compounds, including a zinc dithiophosphate, on the rate of decomposition of cumene hydroperoxide in white mineral oil at 150°C. was investigated by Kennerly and Patterson (13). Each compound accelerated the hydroperoxide decomposition, the zinc salt being far superior in its activity to the others. Further, in each case the principal decomposition product... 

The entire complex situation is untypical of hydrogen peroxide. Decomposition of H202 starts from dissociation by O—O-bond to hydroxyl radicals, which then in gas-phase (refer to Chapter 4) and liquid-phase (refer to Chapter 6) decomposition lead to final products H20 and 02. Here one deals with a single complex reaction with a definite set of subsequently proceeding elementary reactions, but not with several sets as for decomposition of organic peroxides. 

Thus the induced H202 dissociation and auto-induced decomposition of organic peroxides (initiators) are accompanied by a change of, at least, one of three reaction parameters (a) stoichiometric equation of the reaction (decomposition products remain typical of the current substance) (b) reaction type and (c) reaction pathway (mechanism) with decomposition overall stoichiometric equation preserved. 

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