Radical chain polymerization inhibition

Five different types of rate constants are of concern in radical chain polymerization—those for initiation, propagation, termination, chain transfer, and inhibition. The use of polymerization data under steady-state conditions allows the evaluation of only the initiation rate constant kd (or kt for thermal initiation). The ratio kp/k J2 or kp/kl can be obtained from Eq. 3-25, since Rp, Rj, and [M] are measurable. Similarly, the chain-transfer constant k /kp and the inhibition constant kz/kp can be obtained by any one of several methods discussed. However, the evaluation of the individual kp, k ktr, and kz values under steady-state conditions requires the accurate determination of the propagating radical concentration. This would allow the determination of kp from Eq. 3-22 followed by the calculation of kt, kIr, and kz from the ratios kp/ltj2, ktr/kp, and kz/kp. 

Although the presence of water is generally not an issue in free-radical chain polymerization (indeed water may be a suitable medium for polymerization as in Protocols 5-7) unlike, for example, chain-growth polymerization initiated by anionic species, it is always advisable to use solvents of the highest purity and this will generally include some element of predrying. In general, solvents should be distilled, particularly as a number of suitable solvents for polymerization reactions contain stabilizers which usually serve to mop up free radicals and therefore inhibit the polymerization... 

The basic chemistry upon curing is the homopolymerization of a (meth)acrylate functionality as is depicted in Scheme 16.26. This polymerization is a radical chain polymerization. The propagating radical is carbon-centered, and therefore this polymerization is sensitive to oxygen inhibition as oxygen can quench carbon-centered radicals very effectively. As a result of this oxygen inhibition the top layer is generally not as thoroughly cured as the bulk of the material. 

Anything that breaks the chain by converting the active chain-carrying species into an ordinary uncreactive molecule inhibits the reaction, and since the chains are often long an inhibitor may be effective in very small traces. The chain-starting catalysts may also be effective in very small amounts provided that no inhibitor is also present. The fact that a reaction is a chain reaction sensitive to small amounts of catalysts and inhibitors does not necesssarily mean that it is a radical chain, but the nature of the substances effective as catalysts or inhibitors will usually differentiate a radical chain from an ionic one. An example of an ionic chain reaction is the polymerization of an olefin-Lewis acid system when water is added as a co-catalyst. Water is so very effective that it is suspected that the polymerization observed in some cases with the driest obtainable reaction mixtures is due to the presence of minute and unavoidable amounts of water. 

To be effective as autoxidation inhibitors radical scavengers must react quickly with peroxyl or alkyl radicals and lead thereby to the formation of unreactive products. Phenols substituted with electron-donating substituents have relatively low O-H bond dissociation enthalpies (Table 3.1 even lower than arene-bound isopropyl groups [68]), and yield, on hydrogen abstraction, stable phenoxyl radicals which no longer sustain the radical chain reaction. The phenols should not be too electron-rich, however, because this could lead to excessive air-sensitivity of the phenol, i.e. to rapid oxidation of the phenol via SET to oxygen (see next section). Scheme 3.17 shows a selection of radical scavengers which have proved suitable for inhibition of autoxidation processes (and radical-mediated polymerization). 

The cw-isomers were formed in excess. Styrene inhibited the formation of the carbenoid and polymerized under the reaction conditions. This indicates that a free radical chain mechanism is involved in the formation of the carbenoid reagent. ... 

At this same time there are data that arylsulfanamides may inhibit radical-chain process of destruction. Kinetics of inhibited radical polymerization of methyl methacrylate, initiated by dinitrile of azo - bis - isobutyric acid, was studied to evaluate inhibiting activity of carbazolsulphonamides. 

---