Termination reactions disproportionation

Both of the major termination reactions, disproportionation and recombination, involve two radicals. The termination rate, r can thus be written as in Eq. 13.16, where both the exponent and the factor of two reflect this feature of termination. 

The monomer continues to react with the end of the growing polymer chain throughout an addition polymerization reaction until the reactive intermediate is destroyed in a termination reaction. Disproportionation and dimerization are two possible termination reactions. In disproportionation, a hydrogen atom at a carbon atom a to the radical center is abstracted by a radical in another chain. This produces a double bond in one polymer molecule, and the other polymer molecule becomes saturated. Because no new radical intermediates are formed, the propagation steps are terminated. 

The assumption that k values are constant over the entire duration of the reaction breaks down for termination reactions in bulk polymerizations. Here, as in Sec. 5.2, we can consider the termination process—whether by combination or disproportionation to depend on the rates at which polymer molecules can diffuse into (characterized by kj) or out of (characterized by k ) the same solvent cage and the rate at which chemical reaction between them (characterized by kj.) occurs in that cage. In Chap. 5 we saw that two limiting cases of Eq. (5.8) could be readily identified ... 

Although primary and secondary alkyl hydroperoxides are attacked by free radicals, as in equations 8 and 9, such reactions are not chain scission reactions since the alkylperoxy radicals terminate by disproportionation without forming the new radicals needed to continue the chain (53). Overall decomposition rates are faster than the tme first-order rates if radical-induced decompositions are not suppressed. 

The minimum polydispersity index from a free-radical polymerization is 1.5 if termination is by combination, or 2.0 if chains ate terminated by disproportionation and/or transfer. Changes in concentrations and temperature during the reaction can lead to much greater polydispersities, however. These concepts of polymerization reaction engineering have been introduced in more detail elsewhere (6). 

The main reason that the decreases as the polymerization temperature increases is the increase in the initiation and termination reactions, which leads to a decrease in the kinetic chain length (Fig. 17). At low temperature, the main termination mechanism is polystyryl radical coupling, but as the temperature increases, radical disproportionation becomes increasingly important. Termination by coupling results in higher PS than any of the other termination modes. 

Termination reaction with vinyl acetate is nearly exclusively by disproportionation (216), although there are reports that recombination increases in... 

Depending on the termination reaction of the vinyl monomer, termination by disproportionation or termination by combination occurs. As a result, AB or ABA block copolymers might be obtained. 

The nature of the termination reaction in MMA polymerization has been investigated by a number of groups using a wide range of techniques (Tabic 5.5), There is general agreement that there is substantial disproportionation. However, there is considerable discrepancy in the precise values of k tk. In some cases the difference has been attributed to variations in the way molecular weight data are interpreted or to the failure to allow for other modes of termination under the polymerization conditions (chain transfer, primary radical termination).154 In other eases the reasons for the discrepancies are less clear. MALDI-TOF mass... 

Chains with uttdesired functionality from termination by combination or disproportionation cannot be totally avoided. Tn attempts to prepare a monofunctional polymer, any termination by combination will give rise to a difunctional impurity. Similarly, when a difunctional polymer is required, termination by disproportionation will yield a monofunctional impurity. The amount of termination by radical-radical reactions can be minimized by using the lowest practical rate of initiation (and of polymerization). Computer modeling has been used as a means of predicting the sources of chain ends during polymerization and examining their dependence on reaction conditions (Section 7.5.612 0 J The main limitations on accuracy are the precision of rate constants which characterize the polymerization. 

Based on the literature data available for styrene polymerized with benzoyl peroxide, (10,12,14) transfer to monomer and termination by disproportionation will be neglected. For the Initiation step, only primary and Induced decomposition reactions will be considered. 

The three possible termination reactions have been written as combination reactions when, in fact, disproportionation reactions may also occur. Under a given set of experimental conditions, only one of the three chain breaking steps (4a), (4b), or (4c) can be expected to be important. 

In the absence of any transfer, only the type of termination reaction has to be taken into account to obtain the number average degree of polymerisation (or chain length) Xn. Indeed, if the reaction terminates by addition, two radicals give one chain, while if the reaction terminates by disproportionation, one radical generates one chain. Using 0.5 < x < 1, one obtains... 

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]. 

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]... 

When the termination involves only combination, the polymerization gives a polymer with two initiator fragments at its chain ends. Because termination in the bulk polymerization of St with AIBN at a moderate temperature occurs by combination, the polymer obtained has two initiator fragments at both chain ends. In the radical polymerization of most monomers, however, termination by disproportionation and chain transfer reactions occur it is therefore impossible to control these termination reactions, i.e., the chain-end structure. Therefore, the number of initiator fragments per one molecule is always less than two. 

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. 

The step or steps in a chain reaction in which reactive intermediates are stabilized and rendered inactive, thus ending the chain reaction. For example, a common termination reaction is the combination of two radicals Le., R- + R - R—R. Another type of termination reaction is disproportionation e.g., 2CH3—CH2- ethane + ethene. 2. The quenching of a reaction. 3. The halting of any process. 

For a radical polymerization with bimolecular termination, the polymer produced contains 1.30 initiator fragments per polymer molecule. Calculate the relative extents of termination by disproportionation and coupling, assuming that no chain-transfer reactions occur. 

The kinetic chain length is given by the number of monomer molecules consumed per initiation step. Since the efficiency of most initiators is not known quantitatively it is necessary to compare the rate of the propagation reaction with either the rate of initiation or the rate of termination. If there is no chain transfer, the kinetic chain length v for termination by disproportionation is equal to the number-average degree of polymerization ... 

Termination reactions convert radicals to closed-shell compounds. Radical-radical coupling reactions are the reverse of homolytic cleavage reactions and are common, but radicals with (3-hydrogen atoms also react in disproportionation reactions as shown for 13. The selectivity of radical-radical terminations is low because the... 

The propagation reactions proceed at multiple radical sites until the monomer is exhausted, or until one of two common types of termination reactions occur either combination or disproportionation. 

Bamford and Tompa (93) considered the effects of branching on MWD in batch polymerizations, using Laplace Transforms to obtain analytical solutions in terms of modified Bessel functions of the first kind for a reaction scheme restricted to termination by disproportionation and mono-radicals. They also used another procedure which was to set up equations for the moments of the distribution that could be solved numerically the MWD was approximated as a sum of a number of Laguerre functions, the coefficients of which could be obtained from the moments. In some cases as many as 10 moments had to be computed in order to obtain a satisfactory representation of the MWD. The assumption that the distribution function decreases exponentially for large DP is built into this method this would not be true of the Beasley distribution (7.3), for instance. 

In consideration of the kinetic law obtained, Rp i0 of magnitude range, one can conclude that the common polymerization mechanism, based on bimolecular termination reactions, is no longer valid for these multifunctional systems when irradiated in condensed phase. Indeed, for conventional radical-induced polymerizations, the termination step consists of the interaction of a growing polymer radical with another radical from the initiator (R), monomer (M) or polymer (P) through recombination or disproportionation reactions ... 

---