Hydrocarbons oxidative polymerization

It occurs during the chain cracking and radiolysis of hydrocarbons [38], radical polymerization and oligomerization of monomers [39], thermal and thermooxidative destruction of polymers (see Chapter 19) and hydrocarbon oxidation at low dioxygen pressure. 

The mechanism of antioxidant action on the oxidation of carbon-chain polymers is practically the same as that of hydrocarbon oxidation (see Chapters 14 and 15 and monographs [29 10]). The peculiarities lie in the specificity of diffusion and the cage effect in polymers. As described earlier, the reaction of peroxyl radicals with phenol occurs more slowly in the polymer matrix than in the liquid phase. This is due to the influence of the polymeric rigid cage on a bimolecular reaction (see earlier). The values of rate constants of macromolecular peroxyl radicals with phenols are collected in Table 19.7. 

Polymeric materials used as fuel components of pyrolants are classified into two types active polymers and inert polymers. Typical active polymers are nitropoly-mers, composed of nitrate esters containing hydrocarbon and oxidizer structures, and azide polymers, containing azide chemical bonds. Hydrocarbon polymers such as polybutadiene and polyurethane are inert polymers. When both active and inert polymers are mixed with crystalline oxidizers, polymeric pyrolants are formed. 

Many of the significant reactions of unsaturated hydrocarbons (hydrogenation, isomerization, carbonylation, oxidation, polymerization) are catalyzed heterogeneously by metals in or near Group VIII or homogeneously by salts and complexes of these elements. Those reactions effected in both systems are discussed in terms of probable common intermediates anomalies, where they occur, are ascribed either to the ability of surfaces to form intermediate species which cannot be stabilized by single metal atoms or to the ability of the latter to coordinate simultaneously more than one hydrocarbon molecule. 

Good reviews on hydrocarbon oxidation acetylene polymerization, etc. 

Gesammelte Abhandlungen zur Kenntnis der Kohle (1915-30). This series contains good reviews on hydrocarbon oxidation, acetylene polymerization, etc. 

Phenols are oxidized by NaBiO3 to polyphenylene oxides, quinones, or cyclohexa-2,4-dienone derivatives, depending on the substituents and the reaction conditions [263]. For example, 2,6-xylenol is oxidized in AcOH to afford a mixture of cyclohexa-dienone and diphenoquinone derivatives (Scheme 14.123) [264] and is oxidatively polymerized in benzene under reflux to give poly(2,6-dimethyl-l,4-phenylene) ether (Scheme 14.124) [265]. Substituted anilines and a poly(phenylene oxide) are oxidatively depolymerized by NaBiO, to afford the corresponding anils [266]. Nal iO, oxidizes olefins to vicinal hydroxy acetates or diacetates in low to moderate yield [267]. Polycyclic aromatic hydrocarbons bearing a benzylic methylene group are converted to aromatic ketones in AcOH under reflux (Scheme 14.125) [268]. 

Examples of indirect initiation will be encountered later in this chapter in the Rice-Herzfeld mechanisms and hydrocarbon oxidation (see next section). Also, initiation of radical polymerization usually is a two-step process (see Section 11.3). 

Oxidation, which can occur by autoxidation or photo-oxidation (initiation by light), is a complex chain reaction. The initial step of oxidation is the formation of hydroperoxides. This initial step is followed by secondary reactions in which species, such as aldehydes, acids, alcohols and hydrocarbons, are formed. Since it is a mechanism based on the formation of radicals, dimerization of some intermediates can occur, leading to formation of higher molecular weight products. Oxidative polymerization can also occur. In addition to these mechanisms, fuel deterioration can also occur hydrolytically through the presence of water. A detailed book on oxidation has been published by Frankel (2005). 

Special consideration is required for exterior columns and auxiliaries that may contain unstable compounds (e.g., peroxides, nitro compounds, hydrocarbon oxides, acetylenic compounds, etc.). Here an external fire may cause overheating and polymerization, which in turn can lead to a runaway reaction and a decomposition explosion. These reactions will be related to the fire. Five major ethylene oxide column explosions caused by this sequence of events are cited in Ref. 209a. At least one involved a fatality, and in several the column was destroyed with column fragments travelling a long distance. 

Butadiene polymerization hydrocarbon oxidation olefin hydrofor-itylation... 

Oxides of Cr, Mo, and W are usually used for catalysts as mixed oxides with other oxides such as alumina and silica which are prepared by coprecipitation, impregnation, etc. They are seldom put to practical use as simple oxides. Principal reactions catalyzed by these oxides, unlike those observed for silica-alumina or zeolites, often involve redox-type reaction steps, and during these steps reaction intermediates having covalent carbon-metal bonds are formed. Examples of those reactions are dehydrogeneration, hydrogenation and skeletal isomerization of hydrocarbons, and polymerization of olefms, as well as metathesis of olefins and hydrodesulfurization. Therefore, acid-base properties of catalysts usually play secondary roles in catalysts. 

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