Hydrogen peroxide polymerization

Acrylonitrile is a colourless liquid with a boiling point of 77-3 C and is sparingly soluble in water. It polymerizes readily in aqueous solution in the presence of a suitable catalyst such as benzoyl peroxide, azo-2-2 -di-iso-butyronitrile, or ferrous sulphate and hydrogen peroxide. Polymerization... 

Initiators. Initiators are typically water-soluble peroxo compounds such as alkali persulfates, ammonium persulfate, or hydrogen peroxide. Polymerization temperatures for these initiators is usually between 50 and 85°C. Amounts of initiator used are in the range 0.2-0.5 wt% based on the monomer. The initiator concentration can improve the stability of the dispersion by providing additional stabilization, or it can adversely affect the dispersion stability due to the electrolyte content. These can also lower the molecular mass of the product. 

Derivative Formation. Hydrogen peroxide is an important reagent in the manufacture of organic peroxides, including tert-huty hydroperoxide, benzoyl peroxide, peroxyacetic acid, esters such as tert-huty peroxyacetate, and ketone derivatives such as methyl ethyl ketone peroxide. These are used as polymerization catalysts, cross-linking agents, and oxidants (see Peroxides and peroxide compounds). 

The most common water-soluble initiators are ammonium persulfate, potassium persulfate, and hydrogen peroxide. These can be made to decompose by high temperature or through redox reactions. The latter method offers versatility in choosing the temperature of polymerization with —50 to 70°C possible. A typical redox system combines a persulfate with ferrous ion ... 

In aqueous solution, all the sodium peroxoborates dissociate for the most part into boric acid, or its anion, and hydrogen peroxide. Peroxoborate species are also present in these solutions, depending on the pH and the concentration for the species type. The nature of these species has been extensively examined by classical physicochemical methods (13), by nmr, and by Raman spectroscopy (14—17). Both monomeric and polymeric species are usually present. There is some evidence (18) suggesting that these peroxoborates are more reactive than hydrogen peroxide alone under similar conditions. 

Because the peroxodisulfate salts are all made electrochemicaHy, the electrical energy cost is a significant part of thek manufacturing cost. The 1994 world capacity for peroxodisulfate salts was about 75,000 metric tons, valued at about 30 x 10 . The principal appHcations are in polymerization catalysis and the market broadly tracks the plastics business. The Caro s acid business is difficult to quantify because the product itself is not commercial but made on-site from purchased hydrogen peroxide. 

Polymeric OC-Oxygen-Substituted Peroxides. Polymeric peroxides (3) are formed from the following reactions ketone and aldehydes with hydrogen peroxide, ozonization of unsaturated compounds, and dehydration of a-hydroxyalkyl hydroperoxides consequendy, a variety of polymeric peroxides of this type exist. Polymeric peroxides are generally viscous Hquids or amorphous soHds, are difficult to characterize, and are prone to explosive decomp o sition. 

Polymeric -peroxides (3) from hydrogen peroxide and lower carbon ketones have been separated by paper or column chromatography and have been characterized by conversion to the bis(p-(nitro)peroxybenzoates). Oligomeric peroxides (3, R = methyl, R = ethyl, n = 1-4) from methyl ethyl ketone have been separated and interconverted by suitable treatment with ketone and hydrogen peroxide (44). 

Polymeric diacyl peroxides (26) can be prepared from the reaction of dibasic acid chlorides, eg, succinoyl, fumaryl, sebacoyl, and terephthaloyl chlorides, with sodium or hydrogen peroxide (187). 

After apphcation to the fabric, the compounds are polymerized by reaction with gaseous ammonia (11,12), then oxidized to phosphine oxides by reaction with hydrogen peroxide. The stmcture of the polymer is shown (13). 

Miscellaneous Reactions. Epoxy compounds yield chlorosubstituted carbonates (45). The reaction of chloroformates with hydrogen peroxide or metal peroxides results in the formation of peroxydicarbonates that are used as free-radical initiators of polymerization of vinyl chloride, ethylene, and other unsaturated monomers (46,47). 

Chemical Reactivity - Reactivity with Water. Forms solution of hydrogen peroxide. The reaction is nonhazardous Reactivity with Common Materials There are no significant reactions under ordinary conditions and temperatures. At 50 °C (122 of) the chemical reacts with dust and rubbish Stability During Transport Stable below 60 °C (140 of) Neutralizing Agents for Acids and Caustics Not pertinent Polymerization Not pertinent Inhibitor of Polymerization Not pertinent. 

Inorganic peroxides [hydrogen peroxide (63), persulfate (41), peroxymonosulfate and peroxydiphosphate (64)] generally have limited usefulness as initiators in bulk or solution polymerization due to their poor solubility in... 

One of the most used systems involves use of horseradish peroxidase, a 3-diketone (mosl commonly 2,4-pentandione), and hydrogen peroxide." " " Since these enzymes contain iron(II), initiation may involve decomposition of hydrogen peroxide by a redox reaction with formation of hydroxy radicals. However, the proposed initiation mechanism- involves a catalytic cycle with enzyme activation by hydrogen peroxide and oxidation of the [3-diketone to give a species which initiates polymerization. Some influence of the enzyme on tacticity and molecular... 

Hydrogen peroxide (H2O2) has shown to be an excellent source of oxygen in a plasma. The reaction has several steps beginning by the formation of a gaseous monosilicic acid, followed by polymerization and the removal of H2O, as follows 0 1... 

Trialkyltin methoxides react with anhydrous hydrogen peroxide in ether to give the rather unstable bis(trialkyltin) peroxides, RsSnOOSnRs (214). Under the same conditions, dialkyltin dimethox-ides give polymeric peroxides, (RzSnOO), but, if an aldehyde is present, monomeric peroxides of the following structure are obtained (215). 

A bi-enzymatic system (glucose oxidase -I- HRP) was also used to catalyze the synthesis of phenolic polymers. The polymerization of phenol, albeit in moderate yield, was accomplished in the presence of glucose avoiding the addition of hydrogen peroxide (Scheme 2 ), which was formed in situ by the oxidation of glucose catalyzed by glucose oxidase. 

The degree of dissociation is very small but the diphenylcyanomethyl radical is sufficiently reactive to induce polymerization in styrene. Methyl radicals or hydrogen atoms bring about polymerization of vinyl monomers in the gas phase.Hydrogen peroxide in the presence of ferrous ions initiates polymerization in the aqueous phase or in aqueous emulsions through generation of hydroxyl radicals according to the Haber-Weiss mechanism... 

The presence of two hydroxyl groups per molecule in poly-(methyl methacrylate) and in polystyrene, each polymerized in aqueous media using the hydrogen peroxide-ferrous ion initiation system, has been established " by chemical analysis and determination of the average molecular weight. Poly-(methyl methacrylate) polymerized by azo-bis-isobutyronitrile labeled with radioactive has been shown to... 

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