Radical catalyst

The reaction rate of fumarate polyester polymers with styrene is 20 times that of similar maleate polymers. Commercial phthaHc and isophthaHc resins usually have fumarate levels in excess of 95% and demonstrate full hardness and property development when catalyzed and cured. The addition polymerization reaction between the fumarate polyester polymer and styrene monomer is initiated by free-radical catalysts, commercially usually benzoyl peroxide (BPO) and methyl ethyl ketone peroxide (MEKP), which can be dissociated by heat or redox metal activators into peroxy and hydroperoxy free radicals. 

A considerable amount of hydrobromic acid is consumed in the manufacture of inorganic bromides, as well as in the synthesis of alkyl bromides from alcohols. The acid can also be used to hydrobrominate olefins (qv). The addition can take place by an ionic mechanism, usually in a polar solvent, according to Markownikoff s rule to yield a secondary alkyl bromide. Under the influence of a free-radical catalyst, in aprotic, nonpolar solvents, dry hydrogen bromide reacts with an a-olefin to produce a primary alkyl bromide as the predominant product. Primary alkyl bromides are useful in synthesizing other compounds and are 40—60 times as reactive as the corresponding chlorides (6). 

Polymerization. Chloroprene is normally polymerized with free-radical catalysts in aqueous emulsion, limiting the conversion of monomer to avoid formation of cross-linked insoluble polymer. At a typical temperature of 40°C, the polymer is largely head-to-taH in orientation and trans in configuration, but modest amounts of head-to-head, cis, 1,2, and 3,4 addition units can also be detected. A much more regular and highly crystalline polymer can be made at low temperature (11). Chloroprene can also be polymerized with cationic polymerization catalysts, giving a polymer with... 

Type AD-G is used in an entirely different sort of formulation. The polymer is designed for graft polymerisation with methyl methacrylate. Typically, equal amounts of AD-G and methyl methacrylate are dissolved together in toluene, and the reaction driven to completion with a free-radical catalyst, such as bensoyl peroxide. The graft polymer is usually mixed with an isocyanate just prior to use. It is not normally compounded with resin. The resulting adhesive has very good adhesion to plasticised vinyl, EVA sponge, thermoplastic mbber, and other difficult to bond substrates, and is of particular importance to the shoe industry (42,43). 

Chemical Reactivity - Reactivity with Water No reaction Reactivity with Common Materials No reactions Stability During Transport Stable Neutralizing Agemsfor Acids and Caustics Not pertinent Polymerization Polymerizes when exposed to heat, ultraviolet light, or free-radical catalysts Inhibitor of Polymerization 200 ppm Hydroquinone. 

The reaction given here has been described before as a general reaction,2 and there can be a wide variety of alkyl, aryl, and halo substituents on the diene and phosphorus. Dibromophosphines are appreciably more reactive than dichlorophosphincs. If a free-radical catalyst is used instead of an inhibitor, the copolymers can be made in good yield.3 The 1,4-addition of dichloro-phosphines to 1,3-dienes is of theoretical interest because of its analogy to the well-known 1,4-addition of sulfur dioxide to 1,3-dienes. 

Rather low yields were obtained by reaction of olefins with phosphorous acid in the presence of free radical catalysts. The reactants were dissolved in 50% aqueous dioxane, dibenzoyl peroxide was added, and the solution was heated for 6 h at 90°C [93,94] see Eq. (66) ... 

Radiative cooling, 23 13-14 Radiative heating/cooling, 23 25-26 Radical catalysts, 14 274 Radical cations, 12 249 Radical chain reactions, 14 274 Radical cyclization approach, 21 147 Radical decomposition reaction, 10 600 Radical generating systems, alternative, 14 299... 

R. V. Williams, K. Chanau, /. Chem. Soc., Chem. Commun. 1991,1672—1673 adducts of type 279 are also obtained in very good yield when arylallenes are added in the presence of a cation radical catalyst to permethyl-cydopentadiene, i.e. the allene functions as the dienophile here, see M. Schmittel,... 

The "ene reaction of MAH with a polymer containing unsaturation occurs at elevated temperatures in the absence of a catalyst. The presence of a radical catalyst is necessary to promote the reaction between MAH and a saturated polymer. However, the mere generation of radical sites on the polymer, e.g. by shear or attack by catalyst radicals, is insufficient to promote reaction to a significant extent. Thus, the appendage of MAH onto PE requires the use of either high concentrations of catalyst or the use of a catalyst which has a short half-life at the reaction temperature. 

The reaction between MAH, PE, clay and the catalyst must take place essentially simultaneously. If the clay is first reacted with MAH at elevated temperatures, analogous to the treatment of clay with silane coupling agents, a clay maleate half ester or diester is probably formed. The latter does not readily react with PE even in the presence of a free radical catalyst. 

The compatibilization of clay with LDPE and HDFE is accomplished by the in situ polymerization of MAH or its precursor maleic acid, in the presence of a radical catalyst. The latter must be capable of initiating the homopolymerization of MAH, i.e. it must be present in high concentration and/or have a half-life of less than 30 min at the reaction temperature, e.g. t-butyl per-benzoate (tBFB) at 150°C. In a one-step process, the clay and PE are mixed with MAH-tBPB in the desired PE/clay ratio. In the preferred two-step process, a 70/30-90/10 clay/PE concentrate is prepared initially in the presence of MAH-tBPB and then blended with additional PE to the desired clay loading. The compatibil-ized or coupled PE-MAH-clay composites have better physical properties, including higher impact strengths, than unfilled PE or PE-clay mixtures prepared in the absence of MAH-tBPB. 

Synthesis of aldehydes from alcohols is an important transformation in several applications. In small scale oxidations still chromic acid is being used as a stoichiometric oxidant of alcohols, which leads to a large amount of toxic waste and it is also expensive. Catalytic routes have been reported using palladium catalyst [18], or TEMPO (see also Figure 15.13) as a radical catalyst for the oxidation of alcohols [19], or combinations of TEMPO and copper [20] related work is mentioned in the references of these articles. The mechanism of... 

In the suspension polymerization process, the autoclave reactor is filled with water. PVA, polyvinyl alcohol is the dispersing agent that helps stabilize the suspension. Lauroyl peroxide is the free radical catalyst that starts it all off. The reaction temperature is around 130°F, and the process takes 10—12 hours per batch, with 95% conversion. 

Manufacture Introduced in 1937 Emulsion polymerization Free radical catalyst 10-40% Acrylonitrile... 

Ethylene is conveniently polymerized in the laboratory at atmospheric pressure using a titanium-based coordination catalyst [34]. It may also be polymerized less conveniently in the laboratory under high pressures using free radical catalysts at high and low temperatures [35-37]. Other olefins such as propylene, 1-butene, or 1-pentene homopolymerize free radically only to low molecular weight polymers and require ionic or coordination catalysts to afford high molecu-... 

They can be handled analogous to thermosetting resins, and thus the use of highly volatile comonomers, such as ethene or prop-ene is prohibitive. Instead, other vinyl monomers are used. A heat curable formulation uses a mixture of tetracyclododecene, 2-norbomene, 5-vinyl-2-norbomene, and divinylbenzene as reactive components (41). The mixture further contains 3,5-di-ferf-butylhy-droxyanisole as antioxidant and a hybrid catalyst system containing a zirconium based metathesis catalyst and a radical catalyst. The metathesis catalyst is benzylidene (l,3-dimesitylimidazolidin-2-yl-idene)(tricyclohexylphosphine)ruthenium dichloride and the radical catalyst is di-ferf-butyl peroxide. 

The most important feature of ionizing radiations is, as the term implies, ionization to give ionic intermediates in irradiated systems. Though radiation-induced radical polymerization had long been studied, it is only a decade since radiation-induced ionic polymerization was first found. In 1957, Davison et al. obtained polymer from isobutene, which is known not to be polymerized by radical catalysts, by irradiating at low temperature with y-rays (7). Before long, the radiation-induced polymerization of styrene was proved to proceed as an ionic mechanism in suitable solvents (2,3,4). Since these pioneering researches, the study of the chemical kinetics of radiation-induced ionic polymerization has been extended to several vinyl, diene and cyclic monomers. 

Side-chain bromination of methylthiophenes with NBS is a facile reaction (63AHC(l)l). The results are better if the reactive ring positions are blocked or deactivated by suitable -I, -M substituents. Both mono- and di-bromination are possible (Scheme 98). It has been shown that molecular bromine can also be used for side-chain bromination the reaction is carried out in the presence of a radical catalyst (azobisisobutyronitrile) by the action of light. Depending on the substrate, one, two or three bromine atoms may be... 

Consideration of reasonable mechanisms for producing formic acid from an aldose led to the hypothesis that the sugar forms an addition product with the hydroperoxide anion, comparable with an aldehyde sulfite or the addition product of aldoses with chlorous acid (52). The intermediate product (12) could decompose by a free-radical or an ionic mechanism. In the absence of a free-radical catalyst, the ionic mechanism of Scheme VIII seems probable. By either mechanism the products are formic acid and the next lower sugar. The lower sugar then repeats the process, with the result that the aldose is degraded stepwise to formic acid. Addition of the hydroperoxide anion to the carbonyl carbon is in accord with its strong nucleophilic character (53) and with certain reaction mechanisms suggested in the literature (54) for related substances. 

The Anelli oxidation of alcohols to aldehydes and ketones has been accomplished using polymer-supported nitroxyl radical catalysts. The practicality of removing polymer-supported reagents by filtration to simplify product purification is highlighted by these examples. Bolm and coworkers11 demonstrated that a silica-supported nitroxyl catalyst is easily filtrated after use from the reaction solution, recovered and recycled, and the residual inorganic salts present in the reaction mixture are separated from the organic product by aqueous extraction (Table II, entry 7). 

Bromination in the absence of free radical catalysts, for example, gives high yields of 1-bromoadamantane (Eq. (53)) 18s The Koch 189> and Ritter 188> 19°) reactions, which involve the initial generation of the 1-ada.-mantyl cation either by means of hydride transfer to the t-butyl cation or... 

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