Hydrogen peroxide as initiator

In chemically-cured materials, one example of an initiator/activator system is hydrogen peroxide as initiator, ascorbic acid as activator and cupric sulphate as co-activator. In light-cured materials, camphorquinone is used as a visible-light photochemical initiator, sodium p-toluene-sulphinate as activator and ethyl 4-dimethylaminobenzoate as photoaccelerator. 

The first polymerization product of N-vinylpyrrolidone was soluble polyvinylpyrrolidone, which was patented in 1939. Fig. 2 and 3 show mechanisms of polymerization free-radical polymerization in water using hydrogen peroxide as initiator or in 2-propanol using an organic peroxide as initiator [1,141]. 

Gore-Tex nonabsorbable monofilament suture is made from a highly crystalhne hnear PIPE. This fully fluorinated thermoplastic is an addition polymer and is formed by the free radical polymerization route in aqueous dispersion under pressure with persulfates and hydrogen peroxide as initiators. The monomer (tetrafluoroethylene) is made from a two-step process the fluorination of chloroform by HF to produce CHClFj which is subsequently dimerized by pyrolysis to form tetrafluoroethylene. FI FE has the highest enthalpy and entropy of polymerization (-156 kJ/mol and -112 J/ mol-deg, respectively) among the vinyls (Joshi and Zwolinski, 1967). Its molecular weight can be as high as 5 x l(p. 

There is a discussion of some of the sources of radicals for mechanistic studies in Section 11.1.4 of Part A. Some of the reactions discussed there, particularly the use of azo compounds and peroxides as initiators, are also important in synthetic chemistry. One of the most useful sources of free radicals in preparative chemistry is the reaction of halides with stannyl radicals. Stannanes undergo hydrogen abstraction reactions and the stannyl radical can then abstract halogen from the alkyl group. For example, net addition of an alkyl group to a reactive double bond can follow halogen abstraction by a stannyl radical. 

In the early studies on luminol and related hydrazides the systems used were composed of either sodium or potassium hydroxide, as base, hydrogen peroxide as the oxidizing agent (more recently molecular oxygen, hypochlorite, iodide, and permanganate have also been used), and some type of initiator or activator. This initiator was frequently hypochlorite, persulfate, a transition metal... 

The oxidation of primary and secondary alcohols in the presence of 1-naphthylamine, 2-naphthylamine, or phenyl-1-naphthylamine is characterized by the high values of the inhibition coefficient / > 10 [1-7], Alkylperoxyl, a-ketoperoxyl radicals, and (3-hydroxyperoxyl radicals, like the peroxyl radicals derived from tertiary alcohols, appeared to be incapable of reducing the aminyl radicals formed from aromatic amines. For example, when the oxidation of tert-butanol is inhibited by 1-naphthylamine, the coefficient /is equal to 2, which coincides with the value found in the inhibited oxidation of alkanes [3], However, the addition of hydrogen peroxide to the tert-butanol getting oxidized helps to perform the cyclic chain termination mechanism (1-naphthylamine as the inhibitor, T = 393 K, cumyl peroxide as initiator, p02 = 98 kPa [8]). This is due to the participation of the formed hydroperoxyl radical in the chain termination ... 

Commercially viable systems for the decolorisation of spent dyebaths can be based on hydrogen peroxide treatment initiated by UV radiation. A representative selection of six disulphonated monoazo acid dyes and two disazo disulphonated types was exposed for various times in a pilot-scale photochemical reactor of this kind. The controlling parameters were dye structure, pH, peroxide dosage and UV light intensity [39]. In a wider survey of the response of various classes of dyes to the combination of UV radiation and hydrogen peroxide, viable candidates for further in-plant treatment trials were the water-soluble reactive, direct, acid and basic classes. On the other hand, water-insoluble colorants such as disperse and vat dyes did not appear to be viable [40]. 

Figure 3.29.A shows a flow-cell of 20 iL inner volume used to hold immobilized anti-mouse IgG bound to a rigid beaded support (activated Pierce trisacryl GF-2000). The cell was used to develop a two-site immunoassay for mouse IgG by consecutive injection of the sample, acridinium ester-labelled antibody and alkaline hydrogen peroxide to initiate the chemiluminescence, which started the reaction sequence shown in Fig. 3.29.B. Regenerating the sensor entailed subsequent injection of an acid solution, which resulted in a determination time of ca. 12 min (this varied as a fimction of the flow-rate used, which also determined the detection limit achieved, viz. 50 amol for an overall analysis time of 18 min) [218]. The sensor was used for at least one week with an inter-assay RSD of 5.9%. Attempts at automating the hydrodynamic system for use in routine analyses are currently under way.

Apart from this mathematical aspect I think that the useful concept of critical antioxidant concentration is valid for degenerate chain branching where the effect of the presence of antioxidant on hydroperoxide decomposition is relatively minor but not when it is the predominant initiation reaction. For metals reacting with hydroperoxides the number of radicals formed may even exceed unity. Kolthoff and Medalia [/. Am. Chem. Soc. 71,3777 (1949) ] demonstrated that for the reaction of ferrous ion with hydrogen peroxide as many as six ferrous atoms can be oxidized by one molecule of hydrogen peroxide as a result of this effect. I do not think, therefore, that the critical antioxidant concentration should be applied to those cases in which the so-called antioxidant is the catalyst. 

Several oxidizing reagents react with alkenes under mild conditions to give, as the overall result, addition of hydrogen peroxide as HO—OH. Of particular importance are alkaline permanganate (MnO40) and osmium tetroxide (0s04), both of which react in an initial step by a suprafacial cycloaddition mechanism like that postulated for ozone. 

In the absence of a catalyst, the disproportionation is too slow to be observed at room temperature. Rapid, exothermic, and potentially explosive decomposition of hydrogen peroxide is initiated, however, by heat and by a broad range of catalysts, including transition metal ions, certain anions (such as I-), metal surfaces, blood (Figure 14.9), and even tiny particles of dust. Because decomposition is accelerated by light, hydrogen peroxide is stored in dark bottles. It is best handled in dilute aqueous solutions concentrated solutions and the pure liquid are extremely hazardous materials. 

Thermoplasticization of Wood by Heterogeneous Graft Copolymerization (Redox Initiation). A redox grafting method using ferrous sulfate-hydrogene peroxide as the initiator was conducted to copolymerize MMA to wood meal. The results of grafting are shown in Table III. 

Table III. Redox Graft Copolymerization of MMA onto Wood Using Ferrous Sulfate - Hydrogen Peroxide as an Initiator...

Hydroxytelechelic polymer synthesis with redox systems requires hydrogen peroxide as an oxidizing agent and, generally, takes place in aqueous media (to solubilize the salts). This kind of polymerization is possible at lower temperatures compared to polymerizations initiated by thermal decomposition of H202. Therefore, the less frequent transfer reactions improve the polymer functionality and its polydispersity. 

Oxidation sometimes gives the carboxylic acid, but the use of hydrogen peroxide (as with other free radical initiators) causes polymerization. Under the influence of radical initiators it is possible to induce thiols to add in an anti-Markownikov manner across an -vinyl group (Scheme 139), while ionic catalysts promote normal electrophilic addition <75CHE1416). 

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