Disproportionation of free radicals

Chain termination can occur by any reaction resulting in combination or disproportionation of free radicals. 

The first reported controlled polymerization based on the OMRP-RT principle appears to have been presented by Minoura in a series of articles starting in 1978, where the redox initiating system BPO/Cr was used for the polymerization of vinyl monomers.Not only were the kinetics different than in free-radical polymerization (very low reaction orders in Cif and BPO), but also the polymerization was observed to continue after all Cr had been converted by the peroxide to Cr and the degree of polymerization was found to increase with monomer conversion at low temperatures (<30 0). These studies included the report of a block copolymer (PMMA-b-PAN). Polydispersity indexes were not reported for these studies. Minoura formulated the mechanistic hypothesis of the formation of a metal complex with the free radical and stated that "the recombination of free radicals formed by the dissociation of the complexed radicals competes with a disproportionation of free radicals". However, these studies did not have a great impact in the polymer community, being cited only a handful of times before 1994. A few subsequent contributions reported the application of similar conditions to other metals but well-controlled polymerizations were not found."- " ... 

Tlie formation of initiator radicals is not the only process that determines the concentration of free radicals in a polymerization system. Polymer propagation itself does not change the radical concentration it merely changes one radical to another. Termination steps also occur, however, and these remove radicals from the system. We shall discuss combination and disproportionation reactions as modes of termination. 

In the period 1910-1950 many contributed to the development of free-radical polymerization.1 The basic mechanism as we know it today (Scheme 1.1), was laid out in the 1940s and 50s.7 9 The essential features of this mechanism are initiation and propagation steps, which involve radicals adding to the less substituted end of the double bond ("tail addition"), and a termination step, which involves disproportionation or combination between two growing chains. 

Catalase is a heme protein belonging to the class of oxidoreductases with ferripro-toporphyrin-IX at the redox center, and it catalyzes the disproportionation of hydrogen peroxide into oxygen and water without the formation of free radicals. 

Diffusion of particles in the polymer matrix occurs much more slowly than in liquids. Since the rate constant of a diffusionally controlled bimolecular reaction depends on the viscosity, the rate constants of such reactions depend on the molecular mobility of a polymer matrix (see monographs [1-4]). These rapid reactions occur in the polymer matrix much more slowly than in the liquid. For example, recombination and disproportionation reactions of free radicals occur rapidly, and their rate is limited by the rate of the reactant encounter. The reaction with sufficient activation energy is not limited by diffusion. Hence, one can expect that the rate constant of such a reaction will be the same in the liquid and solid polymer matrix. Indeed, the process of a bimolecular reaction in the liquid or solid phase occurs in accordance with the following general scheme [4,5] ... 

Besides the mirror and addition reactions already discussed, gas phase radicals dimerize, disproportionate, transfer hydrogen, and polymerize olefins. Similar reactions in the liquid phase are an indication (but not proof) of free radical intermediates. 

As for any chain reaction, radical-addition polymerization consists of three main types of steps initiation, propagation, and termination. Initiation may be achieved by various methods from the monomer thermally or photochemically, or by use of a free-radical initiator, a relatively unstable compound, such as a peroxide, that decomposes thermally to give free radicals (Example 7-4 below). The rate of initiation (rinit) can be determined experimentally by labeling the initiator radioactively or by use of a scavenger to react with the radicals produced by the initiator the rate is then the rate of consumption of the initiator. Propagation differs from previous consideration of linear chains in that there is no recycling of a chain carrier polymers may grow by addition of monomer units in successive steps. Like initiation, termination may occur in various ways combination of polymer radicals, disproportionation of polymer radicals, or radical transfer from polymer to monomer. 

The reverse of disproportionation is referred to as com-proportionation. A special case of disproportionation (or dismutation) is radical disproportionation which serves as a termination process in the fate of free radicals. For example, 2 CH3CH2- CH3CH3 + CH2=CH2. 

Many reactive intermediates can decay via self-reactions, giving dimers or disproportionation products, as is the case of free radicals and carbenes. When these self-reactions are not the ones under study, it is desirable to keep the transient concentration low enough to minimize this type of interference. For example, for a radical that dimerizes with fet = 3 x 10 M s and a concentration c of lO M, its first half-life (ti/2 = 1/kc) would be 33 ps. Note that excited triplet states also undergo bimolecular decay by triplet-triplet... 

Free radicals and radical ions are some of the most important primary photochemical products. These are open-shell species, since they have one unpaired electron so that their total spin quantum number is ( ). They can disappear finally only through reactions with other open-shell molecules such reactions involve in many cases the addition or the disproportionation of two radicals (e.g. Figure 4.84). 

A summary of the major chemical reactions of free radicals is given in Table 4.3. Broadly speaking these can be classified as unimolecular reactions of dissociations and isomerizations, and bimolecular reactions of additions, disproportionations, substitutions, etc. The complexity of many photochemical reactions stems in fact from these free radical reactions, for a single species formed in a simple primary process can lead to a variety of final products. 

Biaglow JE, Kachur AV (1997) The generation of hydroxyl radicals in the reaction of molecular oxygen with polyphosphate complexes of ferrous ion. Radiat Res 148 181-187 Biaglow JE, Field KD, Manevich Y, Tuttle S, Kachur A, Uckun F (1996) Role of guanosine triphosphate in ferric ion-linked Fenton chemistry. Radiat Res 145 554-562 Bielski BHJ (1991) Studies of hypervalent iron. Free Radical Res Commun 12/13 469-477 Bielski BHJ, Allen AO, Schwarz HA (1981) Mechanism of disproportionation of ascorbate radicals. J Am Chem Soc 103 3516-3518... 

Figure 2. Polydispersity index of the polymer produced in Interval II of an emulsion polymerization terminated solely by disproportionation as a function of the average number of free radicals per particle.

The formation of paramagnetic sites in the reactions of DOSGs with saturated hydrocarbon molecules indicate that, in one of the steps, the system is transformed into the biradical state. The 0-0 bond of the cycle is the most probable precursor for formation reactive in such processes. It can be assumed that, in both cases, the process occurs through the biradical state. However, in the first case, the low-molecular radical escapes from the reaction zone through the gas phase, and paramagnetic sites are formed. In the second case, the spatial separation of free radical sites is impossible, and they combine or disproportionate to form non-paramagnetic reaction products. 

The decay of free radicals taking part in oxidation of a polymer may occur as a recombination or disproportionation of alkyl radicals, alkyl and peroxyl radicals, or peroxyl radicals ... 

Thus it can be concluded that traces of chloroform in the reaction mixture and traces of silicic acid from TLC plates catalyze the formation of free radicals and lead to the disproportionation of to and 12 (Scheme II). The radical 3 is stabilized by the benzene ring and the allylic activation of the C-10 ben-zlic hydrogen. 

Formation of Free Radicals by Molecular Disproportionation. A significant conclusion that may be drawn from considerations of rate and equilibrium constants for molecular disproportionation is that this path can provide appreciable concentrations of free radicals in many systems long after most weak chemical bonds have ruptured and bond homolysis has ceased to be a major source of free radicals. In "pure tetralin, for instance, trace concentrations of 1,2-dihydronaphthalene are expected to equilibrate with tetralin and tetralyl radicals,... 

The cyclohexylethyl radical appears to abstract hydrogen more rapidly from hydrogen chloride than from cyclohexane and more rapidly than it adds to ethylene to yield cyclohexylbutyl or higher molecular weight radicals. Chain termination presumably occurs by condensation or disproportionation of a pair of free radicals, or by any other of the chain-terminating reactions which normally occur. No attempt was made to isolate or identify the so-formed byproducts. 

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