The determination of small amounts of organic hydroperoxides in the presence of hindered amine light stabilizers and their nitroxyls

A method for the quantitative determination of hydroperoxide (ROOH) in the presence of hindered amine light stabilizers (HALS) and/or their nitroxyl free radical derivatives has been elaborated. The method is based on the quantitative reduction of hydroperoxides by triphenyl phosphine. The resulting compounds (alcohols) are then determined by GLC using the internal standard technique. The method has been tested on the hydroperoxides derived from 2,4-dimethylpentane. Its sensitivity and reproducibility appear to be comparable with other methods for ROOH determination but, unlike the latter, it has the advantage that its results are not influenced by the presence of HALS and/or their nitroxyl radical derivatives in the analyzed medium.     

Antagonism between hindered amine light stabilizers and sulfur-containing compounds

Antagonism between hindered amine light stabilizers (HALS) and sulfur-containing compounds has been examined using esr and uv spectroscopic techniques. Evidence is presented to show that formation of nitroxyl from HALS and/or its disappearance is not affected by a sulfur-containing compound itself, but considerably by its acidic transformation product. From the results obtained in this study, a new mechanism of antagonism is proposed.     

Organic Phosphites as Polymer Stabilizers

The antioxidative action of phosphonites and phosphites depends on their structure, the nature of the polymer to be stabilized and the aging conditions. Phosphorus compounds can act in different ways: as hydroperoxide decomposers (secondary antioxidants), as free-radical scavengers (primary antioxidants), as well as metal-complex forming agents. The stabilizing action of phosphites and phosphonites is due to three basic mechanisms: oxidation by hydroperoxides, substitution by alkoxyl radicals and hydrolysis to acidic phosphorus compounds and phenols. Modification of phosphites with additional functional groups such as hindered amine moieties leads to new stabilizing properties. An intramolecular synergistic effect is observed.     

Effect of thermooxidation on tinuvin 783 in LDPE films: Characterization by UV and ftir spectroscopy

The effect of thermooxidation on Tinuvin 783 which is a hindered amine light stabilizer in LDPE films has been investigated by UV and FTIR spectroscopy. Initially, a standard curve describing the variation of the concentration of Tinuvin 783 in LDPE films was plotted using the method of integration of the band area. The relation obtained was: band area = 19.6249 × [Tinuvin 783]. This equation was then applied to measure the variation of the concentration of Tinuvin 783 in the 0.2%_wt stabilized samples which have undergone thermooxidation at 90°C for 98 days. The results showed a considerable decrease in the concentration of Tinuvin 783 by 35% during the first 30 days due to probably the formation of nitroxyl radicals. After this, the concentration was observed to be unchanged and may correspond to the phase of nitroxyl radical regeneration. On the other hand, no chemical change in the stabilized LDPE films was observed by FTIR spectroscopy at 90°C during 98 days while the band characteristic of ketone groups (1720 cm⁻¹) was detected for the unstabilized samples after only 11 days. (LDPE: low density polyethylene; HALS: hindered amine light stabilizer)     

ESR molecular dynamics study at the oxidation sites of polypropylene with nitroxyl spin labels and spin probes

Novel methods suitable for the selective insertion of nitroxyl spin labels and spin probes at the oxidation sites of isotactic polypropylene have been developed based on reactions with the oxidation products, on spin trapping with nitroso and nitrone compounds and taking advantage of the spontaneous generation of nitroxyl radicals as intermediates in the stabilization mechanism by the HALS. The analysis of the esr spectra of the doxyl spin label and of the spin probes from the HALS, performed according to the stochastic Liouville theory, has allowed information to be obtained on the molecular mobility at the oxidation sites as a function of the temperature.     

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.     

聚乙烯光引发交联过程中的表面光氧化和光稳定

通过测定凝胶含量并利用红外-光声光谱和光电子能谱对光交联聚乙烯表面氧化程度和氧化产物进行了研究.结果表明,聚乙烯光交联过程中随着光照时间的增加,表面光氧化加剧,氧化产物主要是氢过氧化物和含羰基的化合物.考察了预辐照和添加受阻胺型光稳定剂对聚乙烯光交联过程的影响,发现这两种方法都能有效地降低光交联聚乙烯(XLPE)的表面氧化,但有些光稳定剂会降低XLPE的交联度.     

Synergism of hindered amine light stabilizers and UV-absorbers

The synergism of hindered amine light stabilizers (HALS) and UV-absorbers is very important in the practical photo-stabilization of polymers. As very little is known, however, the relationship between the composition of the mixture of the two kinds of light stabilizer and its photo-stabilizing efficiency was investigated in four common polymers. A high level of synergism was observed in polypropylene, high density polyethylene and ABS resin. A moderate synergistic effect was obtained in polystyrene. The maximum efficiency was observed at mixing ratios of hindered amine light stabilizer to UV-absorber of about 75:25 in polypropylene and high density polyethylene, 90:10 in ABS resin and 80:20 in crystal polystyrene.The synergism is due to different stabilizing mechanisms of hindered amine light stabilizer and UV-absorber, and is explained by the diffusion of very effective hindered amine light stabilizer from the polymer bulk, which is protected by the UV-absorber, towards the surface layer where photo-oxidation proceeds.     

耐辐射致色聚烯烃的研究

研究了在γ射线辐照条件下受阻胺光稳定剂 (简称HALS)、各种抗氧剂对聚丙烯 (PP)和聚乙烯 (PE)的黄度 (YI)的影响。结果表明五甲基HALS比相应的四甲基HALS更能有效地阻止聚烯烃的辐射致色。抗氧剂Irganox 10 76比Irgafos16 8或IrganoxPS 80 2更有效。当抗氧剂和HALS并用时显示出协同效应 ,10 76和PDS并用时聚丙烯的黄度比单独添加 10 76或PDS的聚丙烯的黄度都低。     

Photogeneration of carbon dioxide from polypropylene film stabilized by hindered amines

Infrared spectrometric measurements have been used to measure the amount of carbon dioxide generated by UVA irradiation of polypropylene film stabilized with 0.5% of three different hindered amine light stabilizers (HALS). The measurements were made in situ, using a specially constructed glass cell fitted with CaF₂ windows. In each case the amount of photogenerated carbon dioxide was less than that from a HALS-free polypropylene film of similar thickness. The amount of photogenerated CO₂ was greatest in oxygen that had been pre-saturated with water and the amount of CO₂ evolved depended on the grade of HALS. In dry oxygen, although the differences between the films containing different HALS were much reduced the amount of CO₂ continued to be smaller than that from the HALS-free polymer. The sensitivity of CO₂ photogeneration to the presence of HALS provides new evidence of the relevance of the CO₂ photogeneration method to the diagnosis of photosensitivity of polymers and the influence of stabilizing additives.     

Influerce of chemical structure of nitroxyl spin labels on their reduction by ascorbic acid

The Influence of structure on the reduction of nitroxyl spin labels by ascorbic acid was examined using both piperidine and pyrrolidine nitroxyls. A five-fold molar excess of ascorbic acid and pH of 7.4 were used. The nitroxyl concentration was measured by electron spin resonance spectrometry. The five-membered (pyrrolidine) nitroxyls were more stable than the six-meabered derivatives. Ring substituents also influenced the reaction. The anionic derivatives were more stable than the unionized compounds which, in turn, were more stable than the amines (cations at pH 7.4).     

Oxidation of organic amide ions by dioxygen

The products of base-catalyzed oxidation of secondary aromatic amines were identified by the GC-MS and EPR techniques as nitroxyls, quinone nitrones, quinone imines, and for diarylamines also as the products of C-N bond cleavage-substituted nitrobenzenes, anilines and phenols. It was shown that nitroxyl radicals are the primary paramagnetic products of the reaction and do not form by the interaction of aminyl radicals with dioxygen. A mechanism of the amide ion oxidation through the nonradical addition of dioxygen to the amide ion at the rate-limiting stage is suggested and discussed.The previous report see Ref. 1.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1746–1751, October, 1994.     

Stabilization of γ-sterilized biomedical polyolefins by synergistic mixtures of oligomeric stabilizers. Part II. Polypropylene matrix

In our previous study we have found the synergistic combinations of stabilizers which follow different mechanisms of stabilization and are approved for food contact and biomedical applications. The present attempt is to test the potentials of those systems in stabilizing γ-sterilized isotactic polypropylene (i-PP). Isotactic polypropylene was melt-mixed with hindered amine stabilizers (HAS), phenolic antioxidants and organo-phosphites (hydroperoxide decomposer) and sterilized with different doses of γ-radiation. Stabilization was monitored in terms of changes in the functional groups (oxidation products), tensile properties, yellowing and surface morphology by FTIR spectroscopy, Instron, colorimetry (reflectance) and scanning electron microscopy (SEM), respectively. The trend in stabilizing the efficiency of binary (1:1), ternary (1:1:1) and quaternary (1:1:1:1) additive systems was confirmed by comparing the stabilizing efficiency of mixtures with and without phenol system as well as with their counter parts of EP copolymer matrix. The binary system of secondary HAS and tertiary HAS, has shown antagonistic effect of stabilization whereas their combination with organo-phosphite has exhibited synergistic effect even at higher doses of γ-sterilization. Due to the oxidation of hindered phenol, phenol systems have shown discoloration and it was reduced by mixing with secondary HAS, tertiary HAS and organo-phosphite. The response of the stabilizer systems is better to ethylene-propylene (EP) copolymer than to i-PP in terms of stabilization.     

Photo-stabilisation of polypropylene by a hindered piperidine compound: Influence of hydroperoxide and carbonyl groups

The influence of prior thermally generated hydroperoxides and added benzophenone on the photo-stabilising action of a hindered piperidine compound, bis[2,2,6,6-tetramethyl-4-piperidinyl]-sebacate, in polypropylene film has been examined. The hindered piperidine compound was found to effectively inhibit both the hydroperoxide and carbonyl group sensitised photo-oxidation of the polymer. Using ESR spectroscopy, evidence is presented to show that the hindered piperidine compound reacts stoichiometrically with the hydroperoxide groups generated by thermal oxidation to give a stable nitroxyl radical. The photo-stabilising effects observed are discussed in relation to our understanding of the ultraviolet anti-oxidant action of the hindered piperidine systems.     

A Kinetic Evidence for the Nitroxyl Radicals Recycling Mechanism in the Photostabilizing Process of HALS

The photoinduced bulk polymerization of a reactive-hindered amine fight stabilizers(r-HALS), 4-acryloyl-2, 2, 6, 6-tetramethylpiperidinyl (ATMP), was performed at 80℃ by using a DPC technique. An unique periodic exponential attenuation-type oscillating curve was found when the polymerization was carried out in air, but this phenomenon was not found in nitrogen.It is supposed that this unique kinetic performance may be attributed to nitroxyl radicals that are produced in situ from the oxidation of ATMP. ATMP polymer with narrow polydispersity (d =1.03) can be obtained by photoinduced solution polymerization of ATMP. The signal detected in ESR may be assigned to the nitroxyl radicals in the matrix of ATMP polymer. Since this kind of recycling of nitroxyl radicals is well documented for the photostabilizing mechanism of HALS, the present results may serve as a kinetic evidence for this mechanism.     

Stabilization of γ-sterilized biomedical polyolefins by synergistic mixtures of oligomeric stabilizers

The stabilization of polyolefins against γ-sterilization has been studied with single or binary additive system. The present attempt is to utilize synergistic mixtures of stabilizers which are approved for food contact applications. Ethylene-propylene (EP) copolymer has been melt-mixed with hindered amine stabilizers (HAS), phenolic antioxidants and organo-phosphites (hydroperoxide decomposer). Samples were sterilized with different doses of γ-radiation. Stabilization was characterized in terms of changes in the functional groups (oxidation products), tensile properties, yellowing and surface morphology by FTIR spectroscopy, Instron, colorimetry (reflectance) and scanning electron microscopy (SEM), respectively. Results were discussed by comparing the stabilizing efficiency of mixtures with and without phenol system. Among phenol containing systems, where we mostly observe discoloration due to the oxidation of hindered phenol and the combination of secondary HAS, tertiary HAS, organo-phosphite and hindered phenol exhibited improved stabilization efficiency than single or binary additive systems. The mixture of secondary HAS and tertiary HAS, has shown antagonistic effect of stabilization whereas their combination with organo-phosphite has exhibited synergistic effect of stabilization even at higher doses of γ-sterilization. The effects have been explained through the interaction between the stabilizers.     

Tailoring the desired optical and mechanical performance of polyester‐plasticized PVC films: the role of different light stabilizers on the photo‐degradation

Effect of hindered amine light stabilizer (HALS: C944) and ultraviolet absorbers (UVAs: UV326, UV531) on the photo‐stabilities of polyester‐plasticized poly(vinyl chloride) (PVC) and polyester‐plasticized PVC/pigment yellow (PY) films were studied systematically. Both ultraviolet absorbers (UVAs) and hindered amine light stabilizer (HALS) could slow down the discoloration of polyester‐plasticized PVC and polyester‐plasticized PVC/PY films. However, the addition of UVAs protected polyester‐plasticized PVC films from being discolored and its efficiency is higher than HALS. The specific order of stabilizing effect on the photo‐oxidation is UV326 > UV531 > C944. For the optical performance, both UVAs and HALS could help to maintain the transmittance of visible light after photo‐degradation. The former could effectively adsorb ultraviolet (UV) light and resulted in lower transmittance of UV light. For the polyester‐plasticized PVC/PY systems, even though HALS and UVAs cannot help to maintain the shielding ability in high‐energy visible region after UV irradiation, they can help prevent the loss in transmittance of visible light. The surface morphology exhibited small holes on the surface of the films that contain UV531 or UV326; while large and deep holes were observed on the surface of PVC films without additives, C944‐doped and C944/PY‐doped films, indicating the higher UV‐stabilizing effect of UVAs. With regard to mechanical properties, UVAs and HALS can help to prevent the loss. Our present study systematically revealed the role of different stabilizers on the polyester‐plasticized PVC and polyester‐plasticized PVC/PY systems and paved the way to offer PVC materials with functional optical performance and desired long‐term performance using different light stabilizers. Copyright © 2017 John Wiley & Sons, Ltd.     

Organophosphorus antioxidants—VIII. Kinetics and mechanism of the reaction of organic phosphites with peroxyl radicals

Trialkyl phosphites react with cyanoisopropylperoxyl radicals, generated by thermolysis of azobis(isobutyronitrile) in the presence of oxygen, to give the corresponding phosphates with rate constants of the order of 10³ M⁻¹ sec⁻¹ at 65°C. Phenyl phosphites are oxidized also. A small amount of cyanoisopropyl phosphite is formed by substitution of the phosphite by alkyloxyl radicals leading to phenoxyl radicals. Sterically hindered aryl phosphites react with cyanoisopropylperoxyl radicals to yield the corresponding phosphates and alkoxyl radicals which in a second step react with phosphite by substitution releasing a sterically hindered phenoxyl radical. Therefore, sterically hindered phosphites are capable of acting as chain-terminating primary antioxidants. Because the rate constants of reaction of these phosphites with peroxyl radicals are only in the range of 10² M⁻¹ sec⁻¹ and 100 times smaller than those of phenols, phosphites should be less active as primary antioxidants than phenols.     

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.     

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.