Radical trapping, mechanism

Two mechanisms have been suggested to account for the reduction in the heat release rate a barrier mechanism, in which the clay functions as a barrier to mass transfer of the polymer, and a radical trapping mechanism, which occurs due to the presence of iron or other paramagnetic impurities as a structural component in the... 

Phosphoric compounds are frequently used. Their advantage is that they can exert a radical trapping mechanism through reactions with halogen radicals (Mascia, 1974). 

Anti-oxidant free radical trapping mechanism. 

Flame retardancy by intumescence is essentially a special case of a condensed phase activity without apparent involvement of radical trap mechanisms in the gaseous phase. Intumescence involves an increase in the volume of the burning substrate as a result of network or char formation. This char serves as a barrier to the ingress of oxygen to the fuel and also as a medium through which heat can be dissipated (Figure 17.2). 

Figure 4.3 Radical trapping mechanism for BHT, a phenolic antioxidant.

When we incorporate termination reactions into the analysis of monomer sequence formation in copolymerization kinetics, we note that in general the development of the copolymer sequence can be prematurely stopped. If one monomer sequence is being formed during propagation and the chain is terminated by disproportionation, then the result is more of a homopolymer than a copolymer. If the chain is terminated by recombination of a similar molecule, then the same type of homopolymer is formed. In fact, termination reactions usually prevent the formation of block copolymers when both monomers are present in the reactor fluid. With the radical trapping mechanism of the FRRPP process that will be discussed in the next chapter, formation of certain block copolymers becomes feasible in statistical-based radical copolymerizations. This is an apparent contradiction in terms, but the FRRPP process has been shown to break new ground in polymerization systems. 

Prevents ultraviolet degradation in polypropylene, polystyrene, ABS, polyurethanes, polyacetals, and polyamides. It provides outstanding long-term stability by a radical trapping mechanism similar to that of hindered phenols. Very effective for articles with a high surface area such as films and tapes. 

Figure 2 Radical trapping mechanism of phenolic antioxidants.

The large surface area for nanofiller-polymer contact enhances catalytic effects such as the catalysis of charring reactions or radical trapping mechanisms. ... 

Through radical trapping and ESR spectrum the same radical, i.e., A/-methyl-p-toluidine methyl radical, as in the BPO-DMT system was verified but with a weakened signal. Therefore, the above result favored our formerly proposed mechanism as follows ... 

Evaluation of molecular weights after ultrasonic scission of high molecular weight polymers (PMMA and PS) in the presence of a radical trap has been claimed to provide evidence of the termination mechanism.1,1 However, scission gives radicals as shown in Scheme 5.10. 

Many nitrones and nitroso-compounds have been exploited as spin traps in elucidating radical reaction mechanisms by EPR spectroscopy (Section 3.5.2.1). The initial adducts are nitroxides which can trap further radicals (Scheme 5.17). 

An alternative mechanism by which additives may protect polymers from photo-oxidation is radical trapping. Additives which operate by this mechanism are strictly light stabilizers rather than antioxidants. The most common materials in this class are the hindered amines, which are the usual additives for the protection of poly (ethylene) and poly (propylene). The action of these stabilisers is outlined in Reactions 8.3-8.5. 

It is now clearly demonstrated through the use of free radical traps that all organic liquids will undergo cavitation and generate bond homolysis, if the ambient temperature is sufficiently low (i.e., in order to reduce the solvent system s vapor pressure) (89,90,161,162). The sonolysis of alkanes is quite similar to very high temperature pyrolysis, yielding the products expected (H2, CH4, 1-alkenes, and acetylene) from the well-understood Rice radical chain mechanism (89). Other recent reports compare the sonolysis and pyrolysis of biacetyl (which gives primarily acetone) (163) and the sonolysis and radiolysis of menthone (164). Nonaqueous chemistry can be complex, however, as in the tarry polymerization of several substituted benzenes (165). 

Recently, we have demonstrated another sort of homogeneous sonocatalysis in the sonochemical oxidation of alkenes by O2. Upon sonication of alkenes under O2 in the presence of Mo(C0) , 1-enols and epoxides are formed in one to one ratios. Radical trapping and kinetic studies suggest a mechanism involving initial allylic C-H bond cleavage (caused by the cavitational collapse), and subsequent well-known autoxidation and epoxidation steps. The following scheme is consistent with our observations. In the case of alkene isomerization, it is the catalyst which is being sonochemical activated. In the case of alkene oxidation, however, it is the substrate which is activated. 

Organometallic radicals are important intermediates in biological and catalytic reactions. The structure and formation mechanism of radicals trapped in y-irradiated molecular sieves exposed to methanol and ethylene have been studied by EPR spectroscopy. It was found that Ag CH2OH+ radical with one-electron bond between Ag and C is formed by the attack of -CH2OH hydroxymethyl radical on Ag+ cation. 

There have also been several papers [61-63] on the importance of carefully establishing the reaction mechanism when attempting the copolymerization of olefins with polar monomers since many transition metal complexes can spawn active free radical species, especially in the presence of traces of moisture. The minimum controls that need to be carried out are to run the copolymerization in the presence of various radical traps (but this is not always sufficient) to attempt to exclude free radical pathways, and secondly to apply solvent extraction techniques to the polymer formed to determine if it is truly a copolymer or a blend of different polymers and copolymers. Indeed, even in the Drent paper [48], buried in the supplementary material, is described how the true transition metal-catalyzed random copolymer had to be freed of acrylate homopolymer (free radical-derived) by solvent extraction prior to analysis. 

Oxidative Alkoxylation of Nitrones to a-Alkoxy Nitrones and a-Alkoxy Substituted Nitroxyl Radicals The first direct experimental evidence of the possibility to carry out radical cation nucleophilic addition to nitrones with the formation of nitroxyl radicals has been cited in Section 2.4. Further, such a reaction route was referred to as inverted spin trapping this route is an alternative to a conventional spin trapping (508-512). Realization of either mechanism depends on the reaction conditions namely, on the strength of both nucleophile and oxidant. The use of strong oxidants in weak nucleophilic media tends to favour the radical cation mechanism... 

In the absence of radical traps, the radical R is converted immediately into the carbanion R by an ECE or a DISP mechanism, according to the distance from the electrode where it has been formed. B is a strong base (or nucleophile) that will react with any acid (or electrophile) present. Scheme 2.21 illustrates the case where a proton donor, BH, is present. The overall reduction process then amounts to a hydrogenolysis reaction with concomitant formation of a base. This is a typical example of how singleelectron-transfer electrochemistry may trigger an ionic chemistry rather than a radical chemistry. This is not always the case, and the conditions that drive the reaction in one direction or the other will be the object of a summarizing discussion at the end of this chapter (Section 2.7). 

Brown proposed a mechanism where the enolate radical resulting from the radical addition reacts with the trialkylborane to give a boron enolate and a new alkyl radical that can propagate the chain (Scheme 24) [61]. The formation of the intermediate boron enolate was confirmed by H NMR spectroscopy [66,67]. The role of water present in the system is to hydrolyze the boron enolate and to prevent its degradation by undesired free-radical processes. This hydrolysis step is essential when alkynones [68] and acrylonitrile [58] are used as radical traps since the resulting allenes or keteneimines respectively, react readily with radical species. Maillard and Walton have shown by nB NMR, ll NMR und IR spectroscopy, that tri-ethylborane does complex methyl vinyl ketone, acrolein and 3-methylbut-3-en-2-one. They proposed that the reaction of triethylborane with these traps involves complexation of the trap by the Lewis acidic borane prior to conjugate addition [69]. 

Extended studies later showed that the radical cation mechanism of equations (6) and (7) is prevalent in strongly oxidizing systems (Eberson, 1992 Eberson and Nilsson, 1993), especially under photolytic conditions where excited states are formed (Eberson, 1994). The latter normally can act as strong oxidants or reductants, as in equation (11), and thus can create radical ions under seemingly mild conditions. Since this type of mechanism was judged to be much more common than thought, the name inverted spin trapping was coined for it in view of the inverted situation of electron demand which appears when an electron is formally transferred between the spin trap and the nucleophile or electrophile see equations (13)-(16). 

---