Mechanisms of antioxidant action: The effect of galvinoxyl on the thermal oxidative stability of processed polypropylene

The effectiveness of galvinoxyl (G·(I)) as a thermal antioxidant in polypropylene at 140°C is dependent on the prior processing treatment of the polymer. A characteristic fluctuation of antioxidant activity with time of processing is shown to be associated with the extent of conversion of galvinoxyl to hydrogalvinoxyl (GH) in the polymer. It is concluded that the main stabilisation mechanism involved is deactivation of alkylperoxyl radicals (CB-D) by GH but secondary processes (CB-D and CB-A) involving G· may also make a contribution.     

Mechanisms of antioxidant action: The catalytic rôle of iodine in the stabilisation of polypropylene

It is shown that I₂ is an effective melt stabiliser for polypropylene at 190°C in a closed mixer but that it is much less effective in an open mixer. The formation of HI and unsaturation in the polymer show that a catalytic antioxidant mechanism (CB-A/CB-D) is involved in the antioxidant activity of I₂ in a closed mixer similar to that occurring in the stabilisation of polyolefins with galvinoxyl and nitroxyl radicals.The processed polymer shows slightly greater uv stability than the control with no additive but is essentially similar to the control in thermal oxidative stability. The volatility of HI in an air oven probably accounts for the fact that it has no CB-D activity under these conditions.     

Photostabilization of commercial polypropylene by hindered piperidine compounds: An ESR and luminescence study

The photostabilization of commercial polypropylene by a hindered piperidine stabilizer, bis [2,2,6,6-tetramethyl-4-piperidinyl] sebacate (I) and by a model N-oxy radical compound, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxy (II) is examined using ESR and luminescence spectroscopy. ESR spectroscopy shows that I operates through the formation of a stable nitroxyl radical in the polymer. On the other hand, II disappears rapidly during the early stages of photo-oxidation but continues to act as an effective stabilizer. A low steady-state equilibrium concentration of nitroxyl radicals is believed to be responsible for the high photostabilizing efficiency of I. Both compounds also inhibit the photolysis of the luminescent α,β-unsaturated impurity groups present in the polymer; possible mechanisms are discussed.     

Mechanisms of antioxidant action: Evidence for a regenerative cycle during the melt stabilisation of polypropylene by galvinoxyl

Evidence is presented to show that galvinoxyl (G·), a ‘stable’ aryloxyl radical, is converted to the corresponding phenol(GH) in polypropylene during processing. The redox couple (G·/GH) is a catalytic CB-A/CB-D antioxidant and is capable of deactivating 50 kinetic chains, thus effectively protecting polypropylene against oxidative chain scission for up to 20 min at 200°C in a closed mixer. A reciprocal alternation of the concentration of G· and GH is accounted for by changing conditions in the mixer and G· is slowly and irreversibly destroyed by alkylperoxyl radicals.     

Stabilisation of polymers by catalytic antioxidants

Two types of catalytic antioxidant are now recognised. The first involves the catalytic destruction of hydroperoxides to non-radical products and the second consists of “stable” redox couples with the ability to remove both alkyl (CB-A) and alkylperoxyl (CB-D) radicals in autoxidising systems. The conditions under which both types of antioxidant can operate effectively are reviewed and the limitations to their activity are outlined.     

Mutual Effect of Functional Groups and the Radical Center on the Reactivity of Nitroxyl Radicals

This review considers the correlation between the reactivity of nitroxyl radicals (piperidine, pyrroline, pyrrolidine, imidazoline, dihydroquinoline, tetrahydroquinoline, diphenyl nitroxide, etc.) and their chemical structure in terms of the rate constants of reactions between these radicals and hydrazobenzene. 4,4′-Di(tert-butyl)diphenyl nitroxyl has the highest reactivity, and the nitroxyl radical of benzoindolopyrrolidine is the least reactive (the difference is a factor of ∼10⁴). The effects of the metal atom in stable organometallic nitroxyl radicals and of the halogen atom in halogenated nitroxyl radicals on the reactivity of the nitroxyl center are considered. Data on the effect of the nitroxyl center on the reactivity of functional groups in the piperidine nitroxyl radical are generalized. Nitroxyl radicals with an activated double bond are shown by quantum chemical calculations to form cyclic transition complexes with amines, involving both the paramagnetic center and a double bond. This explains why the activated double bond in nitroxyl radicals is more reactive in nucleophilic additions of amines than the same bond in their diamagnetic analogues. The rate constants of nitroxyl reduction with hydrazobenzene and of nitroxyl oxidation with tetranitromethane are related to the σ_ESR constant derived from isotropic hyperfine coupling constants HFC_(aN), and their correlation with Hammett constants is demonstrated. The role of solvents in the reduction and oxidation of the nitroxyl radicals is considered. The influence of hydroxyl radical-polar solvent complexes and hydroxylamine-polar solvent H complexes on the course of reactions is considered for hydrogen atom transfer in systems of a sterically hindered nitroxyl radical and hydroxylamine.__________Translated from Kinetika i Kataliz, Vol. 46, No. 4, 2005, pp. 506–528.Original Russian Text Copyright © 2005 by Malievskii, Shapiro.     

ESR study of polypropylene photostabilisation by sterically hindered piperidine derivatives

ESR spectra of sterically hindered piperidine derivatives embedded in polypropylene are superpositions of signals arising from radicals of different mobility. Analysis of the spectra at different temperatures gives information on the mobility and distribution of radicals in solution and in polymer media. At the temperature of irradiation, radicals are homogeneously distributed also in a polymer matrix.During irradiation the concentration of radicals first increases then, after reaching a maximum, decreases. This intermediate character is the result of simultaneous formation and reaction of nitroxyl radicals with radicals arising from polypropylene photo-oxidation.Maximum radical concentration is reached at higher dosage, and subsequent decrease in concentration is slower when hydroxy-benzophenone is applied together with the piperidine derivative. In case of joint application of the latter with a nickel complex, on the other hand, no radical formation can be detected in the polymer before, or in the course of irradiation.     

Interaction between antioxidants and hindered piperidine compounds in the photostabilisation of polypropylene: Influence of processing history

The effect of various antioxidants on the photostabilising performance of hindered piperidine compounds in polypropylene has been examined using infra-red, ultra-violet, and ESR spectroscopic techniques. Processing history is shown to play a dominant role in controlling the photostabilising performance of these systems. The destruction of the nitroxyl radical during processing is inhibited by the presence of an antioxidant, and prooxidant activity is assessed by the melt flow index. Antioxidants appear to compete effectively with the nitroxyl radicals for macroradicals. The results are discussed in terms of the importance of antioxidant oxidation versus the formation and destruction of hydroperoxides during processing.     

Thermal and photo-oxidative behaviour of hindered piperidine compounds in polypropylene: Importance of hydroxylamine in stabilisation

The thermal oxidation behaviour of three hindered piperidine compounds has been examined in polypropylene film by oven ageing in air at 140°C together with its subsequent effect on rate of photo-oxidation. The amine, bis[2,2,6,6-tetramethyl-4-piperidinyl] sebacate, shows a rapid growth in nitroxyl radical concentration due to reaction with hydroperoxides whereas the bis-nitroxyl derivative is relatively stable and decreases in concentration very slowly, giving the hydroxylamine. The ageing process results in an improvement in photo-stability and this is associated with the reaction of the nitroxyl radical with a tertiary radical to give the hydroxylamine and ethylenic unsaturation. The mono nitroxyl compound behaves differently during the early stages of ageing in that there is a rapid decrease in concentration and this is followed by a rapid fall in photo-stability. Only during the latter stages of ageing does hydroxylamine production appear to control photo-stability.     

Effect of hindered piperidine compounds on the thermal reduction of p-benzoquinone in polypropylene and its effect on photo-oxidation

The effect of a hindered piperidine compound and stable nitroxyl radical on the thermal reduction of p-benzoquinone in polypropylene has been examined using ESR, uv-visible and fluorescence spectroscopy. Thermal reduction to hydroquinone was inhibited by both compounds. With the hindered amine the nitroxyl radical was regenerated through the formation of the hydroxylamine whereas, with the nitroxyl radical, there was quantitative conversion to the hydroxylamine and no nitroxyl radical regeneration. Both inhibition processes were found to antagonise the photo-stabilising action of the hindered piperidine compounds due to the regeneration of the quinone.     

Formation of polymer-bonded nitroxyl radicals in the UV stabilization of polypropylene by a bifunctional hindered amine light stabilizer

The formation of polymer-bonded stabilizer derivatives during photooxidation of isotactic polypropylene, which contains the hindered amine light stabilizer bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate and the corresponding bisnitroxyl radical, was investigated. The photooxidized polypropylene films that contain these additives were studied by ESR, IR, and nitrogen analysis before and after exhaustive solvent extraction of the photooxidized films. ESR showed that under the conditions in use a maximum of 20% of the nitroxyl radicals formed from the hindered amine was bonded to the polymer chain. Regeneration of nitroxyl radicals from the polymer-bonded stabilizer derivatives under photooxidative conditions indicated that the stabilizer was bonded to the polymer chain by O-alkyl-substituted hydroxylamine linkages >N? O? PP.     

Photo-stabilising action of a polymeric hindered piperidine compound in polypropylene film: Influence of processing

The effect of a phenolic antioxidant on the photo-stabilising performance of a polymeric hindered piperidine compound in polypropylene has been examined using infra-red and ESR spectroscopic techniques. Processing history is shown to play a dominant rôle in controlling the photo-stabilising performance of these systems. Whilst the antioxidant gave enhanced performance, in most cases its effect is antagonistic. The ESR results suggest that maximum stabilisation is associated with the conversion of the amine to the substituted hydroxylamine and not the nitroxyl radical.     

Reactions of stabilizer compounds. IV. ESR studies of the formation of stable nitroxyl radicals in the photooxidation of polypropylene containing hindered amine light stabilizers

ESR studies of the formation of stable nitroxyl radicals in the photooxidation of polypropylene containing 2,2,6,6-tetramethyl-4-hydroxypiperidine (II) and the commercial light stabilizer bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate (III) are described. Spectra of the stable nitroxyl radicals in solid polymer and in solution after extraction from the polymer were obtained. The extract from photooxidized polypropylene containing the bifunctional stabilizer (III) showed only the mononitroxyl radical. The possible formation of polymer-bonded nitroxyl radicals from (III) is discussed.     

Photostabilising action of a p-hydroxybenzoate light stabiliser in polyolefins: Part IV—Catalyst effects and additive interactions in linear low density polyethylene

The photostabilising action of a p-hydroxybenzoate light stabiliser (Cyasorb® UV2908) is examined in linear low density polyethylene (LLDPE). The efficiency of this light stabiliser is shown to be significantly influenced by levels of residual catalyst such as Ti and Al. Deactivation of the catalysts with phosphoric acid in 2-propanol markedly improves both the performance and light stability of the stabiliser. Processing history reduces the efficiency of the stabiliser whereas its light stability increases linearly with processing time and is associated with the ability of the residual catalyst to destroy hydroperoxides during processing. Stabilising efficiency, however, is reduced by a corresponding reduction in stabiliser concentration during processing. The stabiliser synergises effectively during both oven ageing and photo-oxidation with a hindered piperidine light stabiliser due to the complementary function of each additive. Thus, whilst the former terminates primarily alkoxy/hydroxy radicals produced from the decomposition of hydroperoxides, the latter destroys hydroperoxides in a stoichiometric reaction and through the nitroxyl radical intermediate which selectively reacts with macroalkyl (P^?) radicals and through the hydroxylamine which reacts with peroxy radicals (PO₂^?). Strong synergism is also observed with TiO₂ (rutile).     

Nitroxyl radicals and nitroxylethers beyond stabilization: radical generators for efficient polymer modification

Beyond traditional polymer stabilization, sterically hindered piperidine derivatives move into new application areas where radical functions are key elements. Recent achievements in using nitroxyl derivatives in degradation, polymerization and grafting processes are discussed together with the involved chemical reactions and the resulting material properties. The examples shown cover selected nitroxylethers (NORs) performing as flame retardants and flame retardant synergists or replacing peroxides in manufacturing controlled rheology polypropylene (PP). Furthermore, NORs and nitroxyl radicals mediate radical polymerization processes resulting in tailor-made intermediates for polymer modification via radical and condensation steps and offer access to complex polymer architecture. To cite this article: R. Pfaendner, C.R. Chimie 9 (2006).     

Effective 2,6-substitution of piperidine nitroxyl radical by carbonyl compound

Nitroxyl radicals (nitroxides) with unpaired electron are widely used as antioxidants, contrast agents, and spin probes. Although piperidine nitroxyl radicals have many applications, these are mainly tetramethylpiperidine compounds, and only a few reports consider the substitution of N-O surround as a reaction site, such as 2,2,6,6-tetrasubstituted piperidine nitroxyl radicals. Our results revealed that the 2,6-position of the 2,2,6,6-tetramethylpiperidin-4-one compound was substituted by cyclohexyl groups to produce 2,2,6,6-tetrasubstituted piperidin-4-one derivatives under mild reaction conditions. An interesting result was obtained by using ¹⁵N-labeled NH₄Cl instead of ¹⁴NH₄Cl: it gave ¹⁵N-labeled 2,2,6,6-tetrasubstituted piperidin-4-one-1-oxyls with a high ¹⁵N content. In conclusion, the new method for the synthesis of nitroxyl radicals readily yields 2,2,6,6-tetrasubstituted piperidin-4-one under mild conditions.     

Inhibition of the anthraquinone photosensitised oxidation of polypropylene by a hindered piperidine stabiliser: A spectroscopic study

A hindered piperidine stabiliser, bis{2,2,6,6-tetramethyl-4-piperidinyl}-sebacate, has been found to inhibit the photo-sensitising effect of anthraquinone in polypropylene. On flash photolysis in n-hexane solution transient formation due to the semi-quinone radical (AH·) at 370 nm and subsequent formation of the hydroquinone (9,10-dihydroxyanthracene (AH₂) were found to be effectively inhibited by the corresponding nitroxyl radical but not by the amine. The absence of the hydroquinone photoproduct was confirmed using fluorescence spectroscopy. With the aid of phosphorescence spectroscopy it is concluded that the nitroxyl radical is the effective stabilising species and operates by a radical scavenging mechanism to form the hydroxylamine, and not by excited state quenching.     

Mechanisms of antioxidant action: Transformations of 4-hydroxy-2,2,6,6-tetramethylpiperidinoxyl (HTMPO) in polypropylene during processing

When 4-hydroxy-2,2,6,6-tetramethyl piperidinoxyl (HTMPO) is processed in polypropylene in a closed mixer, almost 50% is converted to other products during the first few minutes whilst the applied torque in the mixer is high. There is associated formation of unsaturation and this fact, in conjunction with the almost complete regeneration of nitroxyl within five minutes, suggests that the corresponding hydroxylamine (HTMPOH), which can be qualitatively identified, is the major transformation product. A study of the UV stability of PP films fabricated from polymer processed for varying times shows that UV stability is related to the quantity of the redox couple (HTMPO + HTMPOH) remaining in the polymer. This is considerably reduced by severe processing. The redox capable has almost no thermal antioxidant (oven aging) activity.     

Radically different antioxidants: thermally generated carbon-centered radicals as chain-breaking antioxidants

A new class of thermally activated chain-breaking antioxidants is presented. Dimers of persistent carbon-centered radicals are able to inhibit the autoxidation of cumene and styrene with better rate constants than the commercial antioxidant Irganox HP-136 and 3,5-di-tert-butyl-4-hydroxyanisole. A dramatic increase in antioxidant activity is observed with increasing temperature as more dimers dissociate to their corresponding persistent radicals.