Nitroxyl radical polymers

M. Kamachi, M. Tamaki, Y. Morishima, S. Nozakura, W. Mori, and M. Kishita, Electron exchange phenomena of polymers containing nitroxyl radicals, Polym. J-, 14, 363 (1982). 

Irg 1076, AO-3 (CB), are used in combination with metal dithiolates, e.g., NiDEC, AO-30 (PD), due to the sensitized photoxidation of dithiolates by the oxidation products of phenols, particularly stilbenequinones (SQ, see reaction 9C) (Table 3). Hindered piperidines exhibit a complex behavior when present in combination with other antioxidants and stabilizers they have to be oxidized initially to the corresponding nitroxyl radical before becoming effective. Consequently, both CB-D and PD antioxidants, which remove alkyl peroxyl radicals and hydroperoxides, respectively, antagonise the UV stabilizing action of this class of compounds (e.g.. Table 3, NiDEC 4- Tin 770). However, since the hindered piperidines themselves are neither melt- nor heat-stabilizers for polymers, they have to be used with conventional antioxidants and stabilizers. 

These additives are thus able to trap both alkyl and peroxy radicals. In this way they interfere with the propagating steps of the degradation process. Since overall the nitroxyl radicals are not consumed in this mechanism these additives are effective at low concentrations in the polymer. 

The oriented elongation of the polymer increases the packing of macromolecules and decreases the molecular mobility in the polymer. This was observed by the EPR spectra of the nitroxyl radical in these films. Therefore, one can expect an increase in radical pair recombination in the cage with an increase in y. However, experiment showed an opposite pattern the more the y, the higher the e value. These results found explanation within the scope of the... 

The theory of diffusion in polymers as heterogeneous media was discussed in Refs. [68,74,81-85], The correlation between the frequency of rotation vT of the nitroxyl radical (TEMPO) and diffusion coefficient of oxygen D (298 K) was found [86]. 

Antioxidants that break chains by reactions with alkyl radicals. These are compounds, such as quinones, nitrones, iminoquinones, methylenequinones, stable nitroxyl radicals, and nitrocompounds that readily accept alkyl radicals. Such antioxidants are efficient at very low concentrations of dioxygen and in solid polymers. 

Cyclic chain termination by antioxidants. Oxidation of some substances, such as alcohols or aliphatic amines, gives rise to peroxyl radicals of multiple (oxidative and reductive) activity (see Chapters 7 and 9). In the systems containing such substances, antioxidants are regenerated in the reactions of chain termination. In other words, chain termination occurs as a catalytic cyclic process. The number of chain termination events depends on the proportion between the rates of inhibitor consumption and regeneration reactions. Multiple chain termination may take place, for instance, in polymers. Inhibitors of multiple chain termination are aromatic amines, nitroxyl radicals, and variable-valence metal compounds. 

Nitroxyl radicals as alkyl radical acceptors are known to be very weak antioxidants due to the extremely fast addition of dioxygen to alkyl radicals (see Chapter 2). They retard the oxidation of solid polymers due to specific features of free radical reactions in the solid polymer matrix (see Chapter 19). However, the combination of two inhibitors, one is the peroxyl radical acceptor (phenol, aromatic amine) and another is the alkyl radical acceptor (nitroxyl radical) showed the synergistic action [44-46]. The results of testing the combination of nitroxyl radical (>NO ) (2,2,6,6-tetramethyl-4-benzoylpiperidine-l-oxyl) + amine (phenol) in the autoxidation of nonene-1 at 393 K are given here ([>NO ]o + [InH]o = 1.5 x 10 4mol L 1 p02 98 kPa) [44]. 

Rotational diffusion of particles occurs in polymer much slowly than in liquids. Therefore, the observed difference in liquid (k ) and solid polymer (ks) rate constants can be explained by the different rates of reactant orientation in the liquid and polymer. The EPR spectra were obtained for the stable nitroxyl radical (2,2,6,6-tetramethyl-4-benzoyloxypiperidine-l-oxyl). The molecular mobility was calculated from the shape of the EPR spectrum of this radical [14,15], These values were used for the estimation of the orientation rate of reactants in the liquid and polymer cage. The frequency of orientation of the reactant pairs was calculated as vor = Pvrot> where P is the steric factor of the reaction, and vIol is the frequency of particle rotation to the angle equal to 4tt. The results of this comparison are given in Table 19.2. 

Hence, the phenomena of the low reaction rate in the polymer matrix cannot be explained by the limiting rate of reactant orientation (rotational diffusion) in the cage. This result becomes the impetus to formulate the conception of the rigid cage of polymer matrix [16-20]. In addition to the experiments with comparison of the rate constants in the liquid phase and polymer matrix, experiments on the kinetic study of radical reactions in polymers with different amounts of introduced plasticizer were carried out [7,9,15,21], A correlation between the rate constant of the reaction k and the frequency of rotation vOT of the nitroxyl radical (2,2,6,6-tetramethyl-4-benzoyloxypiperidine-/Y-oxyI) was found. The values of the rate constants for the reaction... 

The Values of Er and Eor for Bimolecular Reactions of Nitroxyl Radicals with Phenols Calculated According to the Rigid Cage Model for Reaction in a Polymer Matrix (Equation (19.7)) [7,9,14,15,21]... 

FIGURE 19.2 The correlation of rate constants of various free radical reactions with molecular mobility of nitroxyl radical in the polymer matrix of different polymers with addition of plastificator I in IPP, II in preliminary oxidized IPP, III in PE, and IV in PS. Line 1 for the reaction of 2,6-bis(l,l-dimethy-lethyl)phenoxyl radical with hydroperoxide groups at T — 295 K line 2 for the reaction of 2,2,6, 6-tetramethyl-4-bcnzoyloxypiperidinc-/V-oxyl with 1-naphthol at T = 333 K line 3 for the reaction of 2,2,6,6-tetramethyl-4-benzoyloxypiperidine-iV-oxyl with 2,6-bis(l,l-dimethylethyl)phenol at T = 333 K line 4 for the same reaction at 7 — 303 K line 5 for the same reaction at T = 313 K and line 6 for the same reaction at T — 323 K [18]. 

Dependence of Rate Constant on the Volume of Reactants for Bimolecular Reactions of Nitroxyl Radicals with Phenols in Polymer Matrix [8,10,11]—continued... 

Reactions described earlier were not limited by rotational diffusion of reactants. It is evident that such bimolecular reactions can occur that are limited not by translational diffusion but by the rate of reactant orientation before forming the TS. We discussed the reactions of sterically hindered phenoxyl recombination in viscous liquids (see Chapter 15). We studied the reaction of the type radical + molecule, which are not limited by translational diffusion in a solution but are limited by the rate of reactant orientation in the polymer matrix [28]. This is the reaction of stable nitroxyl radical addition to the double bond of methylenequinone. 

Acceptors of alkyl radicals are known to be very weak inhibitors of liquid-phase hydrocarbon oxidation because they compete with dioxygen, which reacts very rapidly with alkyl radicals. The situation dramatically changes in polymers where an alkyl radical acceptor effectively terminates the chains [3,49], The study of the inhibiting action of p-benzoquinone [50], nitroxyl radicals [51-53], and nitro compounds [54] in oxidizing PP showed that these alkyl radical acceptors effectively retard the oxidation of the solid polymer at concentrations ( 10-3 mol L 1) at which they have no retarding effect on liquid hydrocarbon oxidation. It was proved from experiments on initiated PP oxidation at different p02 that these inhibitors terminate chains by the reaction with alkyl macroradicals. The general scheme of such inhibitors action on chain oxidation includes the following steps ... 

Nitroxyl radicals are formed as intermediates in reactions of polymer stabilization by steri-cally hindered amines as light stabilizers (HALS) [30,34,39,59]. The very important peculiarity of nitroxyl radicals as antioxidants of polymer degradation is their ability to participate in cyclic mechanisms of chain termination. This mechanism involves alternation of reactions involving alkyl and peroxyl radicals with regeneration of nitroxyl radical [60 64],... 

This calculation shows that the discussed reaction is very exothermic. The activation energy of this reaction calculated by the IPM method (see Chapter 6) is equal to 8.7 kJ mol 1 and rate constant is k = 7.3 x 106 L mol-1 s-1 at T= 400 K. This rate constant is close to that of the acceptance of the alkyl macroradical by the nitroxyl radical. Hence, this reaction is rapid enough to be the efficient step in cyclic chain termination in polymer. 

Another mechanism of nitroxyl radical regeneration was proposed and discussed in the literature [67-71]. The alkoxyamine AmOR is thermally unstable. At elevated temperatures it dissociates with cleavage of the R—O bond, which leads to the appearance of an [AmO + R ] radical pair in the cage of polymer. The disproportionation of this radical pair gives hydroxylamine and alkene. The peroxyl radical reacts rapidly with hydroxylamine thus... 

A study of the polymerization kinetics of methyl methacrylate, in the presence of PBN, and of molecular-mass properties of the obtained polymers shows that the systems react by the pseudoliving mechanism (699). In the first stages of the polymerization process, PBN reacts with oligomeric radicals, forming stable nitroxyl radical-spin adducts A-, see Scheme 2.207. 

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