Chemical industry peroxide involvement

There is a strong incentive to oxyfunctionalise hydrocarbons because it opens the way to important chemical intermediates such as alcohols, ketones and carboxylic acids. Selective oxidations can be achieved using sacrificial oxidants such as hydrogen peroxide, but O2 in air is the oxidant of choice for reasons of economy. Many current oxidations are operated industrially that involve complex multistep reactions, solvents and give unwanted by-products, so there is a clear need for clean and efficient catalytic alternatives. 

Many of these processes find practical use. For example, some processes that appear to Involve MAH reactions are used In chemical Industry the commercial polymerization of styrene often Is self-Initiated (7) the autoxldatlon of acetaldehyde Is Initiated by ppm levels of ozone ( ) and some halogenatlons are clearly MAH processes (1,9). Electron-transfer reactions find practical use as low-temperature Initiation systems for example, benzoyl peroxide and dlmethylanlllne produce radicals at temperatures as low as 10°, perhaps by an electron transfer process (3,... 

The CL monomer is obtained by the traditional Baeyer-Villiger reaction, starting from cyclohexanone as substrate. However, this synthetic route is not environmentally friendly, which has involved the development of two greener routes (1) use of a peroxycarboxylic acid (such as 3-chloroperbenzoic acid or peracetic acid) in dichloromethane at 40 ° C, and (2) use of hydrogen peroxide as oxidizer and zeolite/tin catalysis.The second process is considered the greenest because the main by-product is exclusively water and the tin-impregnated zeolite is an environmentally friendly catalyst. Nowadays, CL is produced by several manufacturers like BASF (USA), Perstorp (UK), and Daicel Chemical Industries Ltd. (Japan). 

The xanthate method [62] is considered as one of the most promising methods for industrial chemical modification. The principal involved in the xanthate method of grafting is that cellulosic xanthate either ferrated or in acidic conditions reacts with hydrogen peroxide to produce macroradicals. The following reaction mechanism has been proposed ... 

The second option involves the use of a CIO2 scrubber. This is a technique presently used in the paper and pulp industry. In the scrubber, the chlorine dioxide reacts with another chemical, such as a sulphite, DMSO, white spirit or an alkaline hydrogen peroxide solution. The hydrogen peroxide solution is most suited to the process described in this chapter as there are no waste streams. The reaction of chlorine dioxide with the alkaline hydrogen peroxide solution is rapid [10]. The reaction equation is as follows ... 

The production of industrially important perfluoroalkane sulfonic acids is generally accomplished by electrochemical fluorination. This method of preparation remains expensive and proceeds in good yields only for short hydrocarbon chains.30 Recently however, Wakselman and Tordeux have described a chemical method for the preparation of trifluoromethane sulfonic acid.31 The procedure involves reaction of a metal selected from zinc, cadmium, manganese, and aluminum with sulfur dioxide in DMF, followed by the introduction of trifluoromethyl bromide under slight pressure. The intermediate sulfinate is subsequently oxidized by hydrogen peroxide, and then hydrolyzed which leads to formation of the trifluoromethane sulfonic acid. Successful extension of the sulfination process to the modification of PCTFE should result in the formation of a sulfinated polymer which can ultimately be oxidized to give a sulfonic-acid modified polymer. 

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