Peroxides radical initiators

With light, peroxides, radical initiators, and in the absence of radical inhibitors a rapid radical-chain addition of hydrogen bromide occurs to yield 80% or more of 1-bromopropane ... 

Phenyl-2-propyl hydroperoxide, 3160 See CYCLIC PEROXIDES, RADICAL INITIATORS... 

Benzoyl peroxide is one of the most widely used peroxide radical initiators in organic synthesis (Scheme 11) [1], It appears as white crystals with melting point 105-106 °C. This compound is decomposed by heat to form phenyl radical and carbon dioxide via benzoyloxy radical (Scheme 12). 

Linford et al. first hypothesized that the spacing species to accommodate alkyl chains on Si(lll) is OH species according to X-ray photoelectron spectroscopy (XPS) observation [6]. The origin of OH might be the peroxide radical initiator or O2 dissolved in the reaction fluid. Most... 

Polymerization reactions. There are two broad types of polymerization reactions, those which involve a termination step and those which do not. An example that involves a termination step is free-radical polymerization of an alkene molecule. The polymerization requires a free radical from an initiator compound such as a peroxide. The initiator breaks down to form a free radical (e.g., CH3 or OH), which attaches to a molecule of alkene and in so doing generates another free radical. Consider the polymerization of vinyl chloride from a free-radical initiator R. An initiation step first occurs ... 

Step 1 Homolytic dissociation of a peroxide produces alkoxy radicals that serve as free radical initiators... 

PEROXIDES AND PEROXIDE COMPOUNDS - ORGANIC PEROXIDES] pol 18) -as initiators [INITIATORS - FREE-RADICAL INITIATORS] pol 14)... 

Usually, free-radical initiators such as azo compounds or peroxides are used to initiate the polymerization of acrylic monomers. Photochemical (72—74) and radiation-initiated (75) polymerizations are also well known. At a constant temperature, the initial rate of the bulk or solution radical polymerization of acrylic monomers is first order with respect to monomer concentration and one-half order with respect to the initiator concentration. Rate data for polymerization of several common acrylic monomers initiated with 2,2 -azobisisobutyronittile (AIBN) [78-67-1] have been determined and are shown in Table 6. The table also includes heats of polymerization and volume percent shrinkage data. 

Oxidation begins with the breakdown of hydroperoxides and the formation of free radicals. These reactive peroxy radicals initiate a chain reaction that propagates the breakdown of hydroperoxides into aldehydes (qv), ketones (qv), alcohols, and hydrocarbons (qv). These breakdown products make an oxidized product organoleptically unacceptable. Antioxidants work by donating a hydrogen atom to the reactive peroxide radical, ending the chain reaction (17). 

LDPE, also known as high pressure polyethylene, is produced at pressures ranging from 82—276 MPa (800—2725 atm). Operating at 132—332°C, it may be produced by either a tubular or a stirred autoclave reactor. Reaction is sustained by continuously injecting free-radical initiators, such as peroxides, oxygen, or a combination of both, to the reactor feed. 

Commercially available MEKP formulations are mixtures of the dihydroperoxide (1), where X = OOH R = H, R = methyl, and R = ethyl (2,2-dihydroperoxybutane [2625-67 ]) and dialkyl peroxide (2), where X = OOH, Y = OOH, R = methyl, and R = ethyl (di(2-hydroperoxy-2-butyl) peroxide [126-76-1J). These formulations are widely used as free-radical initiators in the metal-promoted cure of unsaturated polyester resins at about 20°C. 

Thermal decomposition of hydroxyalkyl hydroperoxyalkyl peroxides produces mixtures of starting carbonyl compounds, mono- and dicarboxyHc acids, cycHc diperoxides, carbon dioxide, and water. One specific hydroxyalkyl hydroperoxyalkyl peroxide from cyclohexanone (2, X = OH, Y = OOH) is a soHd that is produced commercially as a free-radical initiator and bleaching agent (see Table 5). On controlled decomposition, it forms 1,12-dodecanedioic acid (150). 

Organic Peroxides" and "Eree Radical Initiators," Modem PLastics EnjcLopedia, Vol. 62 (13), McGraw-HiU, Book Co., Inc., New York, 1985, p. 166. 

It is virtually impossible to manufacture commercial polymers that do not contain traces of hydroperoxides. The peroxide bond is relatively weak and cleaves homolyticaHy to yield radicals (eqs. 2 and 3). Once oxidation has started, the concentration of hydroperoxides becomes appreciable. The decomposition of hydroperoxides becomes the main source of radical initiators. 

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). 

The chlorination of toluene in the absence of catalysts that promote nuclear substitution occurs preferentially in the side chain. The reaction is promoted by free-radical initiators such as ultraviolet light or peroxides. Chlorination takes place in a stepwise manner and can be controlled to give good yields of the intermediate chlorination products. Small amounts of sequestering agents are sometimes used to remove trace amounts of heavy-metal ions that cause ring chlorination. 

Polyesters. Unsaturated polyester resins based on DCPD, maleic anhydride, and glycols have been manufactured for many years. At least four ways of incorporating DCPD into these resins have been described (45). The resins are mixed with a cross-linking compound, usually styrene, and final polymerization is accompHshed via a free-radical initiator such as methyl ethyl ketone peroxide. 

There has also been a trend in recent years to the use of free-radical initiators that decompose more rapidly than the traditional initiators such as caproyl and lauryl peroxides. Currently used initiators include peroxydicarbonates, t-butylperpiva-late, azobis-(2,4-dimethylvaleronitrile) and acetyl cyclohexylsulphonyl peroxide. 

Work should be on a scale of <0.5 g for novel but potentially explosive material until the hazards have been fully evaluated and <5 g for established, commercially available, substances such as peroxide free-radical initiators. 

Benzoyl peroxide is a commonly used free-radical initiator. It has the formula O O... 

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