Disproportionation, chain termination

Chain termination can occur by either combination or disproportionation, depending on the conditions of the process (78,79). 

The free-radical polymerization of methacrylic monomers follows a classical chain mechanism in which the chain-propagation step entails the head-to-taH growth of the polymeric free radical by attack on the double bond of the monomer. Chain termination can occur by either combination or disproportionation, depending on the conditions of the process (36). 

Chains terminate by either of two mechanisms combination or disproportionation. Two chain radicals may combine to form a single bond between... 

The mode of chain termination affects the type of block copolymer formed. For example, if a MAI (based essentially on the first monomer A) possessing one central azo bond is decomposed in the presence of monomer B, the growing chain Bn can terminate either by disproportionation or combination, leading to AB and ABA type copolymers, respectively. 

Which mechanism of termination will be preferably applied depends largely on the monomer used. Thus, methyl methacrylate chains terminate to a large extent by disproportionation, whereas styrene chains tend to termination by combination. The ratios of termination rate constants 8 = ktJkic (for disproportionation, td, combination,, c) are 5 == 0 and 5 = 2 for styrene [95] and methyl methacrylate [96], respectively. In the case of styrene, however, the values of 8 reported in the literature are at variance. Berger and Meyerhoff [97] found 8 = 0.2, at 52°C. Therefore, it is possible that a fraction of styrene terminates by disproportionation. 

The most important mechanism for the decay of propagating species in radical polymerization is radical-radical reaction by combination or disproportionation as shown in Scheme 5.1. This process is sometimes simply referred to as bimolecular termination. However, this term is misleading since most chain termination processes are bimolecular reactions. 

Unstable structures are known to arise by chain termination. Mechanisms for radical-radical termination in MMA polymerization have been discussed in Sections 5.2.2.1.2 and 5.2.2.2.2 and these are summarized in Scheme 8.5. It is established that both disproportionation and combination occur to substantial extents. The head-to-head linkages 1 and the unsaturated chain ends 2 both constitute weak links in PMMA.26 2 "33 The presence of these groups account for... 

The chain termination is a result of tertiary alkylperoxyl radical recombination in the solvent cage. The values of the rate constants for chain termination through the disproportionation of tertiary peroxyl radicals are collected in Table 2.15. They vary in the range 103 to 105 L mol 1 s 1 at room temperature. The probability of a pair of alkoxyl radicals to escape cage recombination is sufficiently higher than that of cage recombination. The values of rate constants of the reaction 2 R02 > 2 RO + 02 measured by the EPR technique are presented in Table 2.16. 

The last reaction occurs much rapidly than the disproportionation of two cumylperoxyl radicals and accelerates chain termination in oxidized cumene [15]. The addition of cumene hydroperoxide helps to avoid the influence of the cross termination reaction Me2PhCOO + CH302 on the oxidation of cumene and to measure the pure disproportionation of cumylperoxyl radicals [15]. 

Rate Constants of Chain Termination by the Disproportionation of Tertiary Peroxyl Radicals in Hydrocarbon Solutions (Experimental Data)... 

The mechanisms of chain termination by disproportionation of secondary and tertiary peroxyl radicals are sufficiently different (see Chapter 2). Secondary R02 disproportionate by reaction [4-6]... 

In addition to two peroxyl radicals, H02 and R1R2C(0H)00 , participating in chain propagation in the oxidized alcohols, there are three reactions that are guilty of chain termination in the oxidized alcohols. The most probable reaction between them is disproportionation. 

In addition to disproportionation, another mechanism of the alkylhyroxyperoxyl radical chain termination is recombination [38,39],... 

The rate constants of chain termination by disproportionation of two acylperoxyl radicals are collected in Table 8.4. 

Disproportionation of ester peroxyl radicals occurs very rapidly. Apparently, the ester group influences the rate constant of this reaction by increasing it. The rate constants of chain termination in oxidized esters are collected in Table 9.13. 

Later it was shown [9] that in the case of repeated chain termination with aromatic amines in the oxidation of alcohols the situation is more complicated. In parallel with the reaction of disproportionation with the aminyl radical, the following reactions occur ... 

The question why the aminyl radicals ensure cyclic chain termination in those systems in which the hydroperoxyl and hydroxyalkylperoxyl radicals are formed, but not in the oxidation of hydrocarbons where alkylperoxyl radicals are the chain-propagating species deserves special attention [22 24]. Indeed, the disproportionation of the aminyl and peroxyl radicals... 

The cross-disproportionation of nitroxyl and hydroperoxyl radicals is an exothermic reaction. For example, the enthalpies of disproportionation of TEMPO radical with H02, Me2C(0H)02, and cydo-C(,Y 10(OH)O2 radicals are equal to 109, —92, and 82 kJ mol-1, respectively. The Ee0 value for the abstraction of an H atom from the O—H bond in ROOH by a nitroxyl radical is 45.6 kJ mol 1 and AHe min = —58 kJ mol-1. Since AHe < AHe min, (see Chapter 6), the activation energy of such exothermic reactions for these reactions is low (E 0.5RT), and the rate constant correspondingly is high [31 34]. Therefore, in the systems in which hydroperoxyl, hydroxyperoxyl, and aminoperoxyl radicals participate in chain propagation, the cyclic chain termination mechanism should be realized. 

The reaction of AmO with H02 occurs with AH < A//c min and, subsequently, with a low activation energy (E=0.5RT) and a high rate constant. The latter is higher than 2kt for peroxyl radicals (see Chapter 6), which is important for cyclic chain termination. The inverse situation takes place in reactions of nitroxyl radical disproportionation with alkylperoxyl radicals. For these reactions we observe inequality AH > A//c min and, subsequently, relatively a high activation energy (E> 0.5RT) and a low rate constant. The latter are lower than 2kt for... 

Why are the activation energies of the reactions of nitroxyl radicals with O—H bonds lower than those in their reactions with C—H bonds As in the case of the reaction of R02 with quinones, the difference in E values occurs as a result of the different triplet repulsions in TS [23]. When a TS of the O H O type is formed (the AmO + H02 reaction), the triplet repulsion is close to zero because the O—O bond in the labile compound AmOOH is very weak. Conversely, the triplet repulsion in the reaction of AmO with the C—H bond is fairly great, due to the high dissociation energy of the AmO—R bond. This accounts for the difference between the activation energies and between the rate constants for the reactions considered above. Thus, the possibility of the realization of a cyclic chain termination mechanism in the reactions of nitroxyl radicals with peroxyl radicals, incorporating O—H groups, is caused by the weak triplet repulsion in the TS of such disproportionation reactions... 

The superoxide ion is a very weak hydrogen atom abstractor, which cannot continue the chain, and is destroyed via disproportionation with any peroxyl radical. So, the studies of the mechanisms of cyclic chain termination in oxidation processes demonstrate that they, on the one hand, are extremely diverse and, on the other, that they are highly structurally selective. The 20 currently known mechanisms are presented in Table 16.6. 

This second molecule might be a monomer, polymer, or solvent. Because of chain transfer the end of one polymer chain might be a hydrogen atom, and the beginning of the next the radical formed by removing the hydrogen atom from the solvent molecule. In the same paper, he proposed the two most probable chain termination reactions, mutual combination and disproportionation. 

Although this mechanism is an oversimplification, it does give the basic idea. Chain termination is more complicated than in free radical polymerization. Coupling and disproportionation are not possible since two negative ions cannot easily come together. Termination may result from a proton transfer from a solvent or weak acid, such as water, sometimes present in just trace amounts. 

In certain situations, termination occurs by disproportionation. This termination process involves chain transfer to a hydrogen atom from one chain end to the free radical chain end of another growing chain, resulting in one of the dead polymer chains having an unsaturated chain end (Equations 6.19 and 6.20). 

Chain termination occurs by combination or disproportionation of different polymer radicals. The termination rate, v is proportional to the polymer radical concentration, [ PJ, squared, with kt being the termination rate constant. Other possible chain termination processes are chain transfer and reaction of polymer radicals wifh inhibitors and radical trapping. ... 

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