The effects of thermal processing on PVC—X. The interaction between bound antioxidants and tin stabilizers

It is shown that a thiol u.v. stabilizer and a thiol heat stabilizer can be effectively bound to PVC during processing in the presence of an alkyltin stabilizer. Thiol u.v. stabilizer interferes with the processing stability of PVC to a lesser extent than does a conventional u.v. stabilizer (2-hydroxy-4-octoxybenzophenone).     

The effect of processing on the light stability of stabilized and unstabilized polyethylene

It is shown that antioxidants previously reported to be u.v. stabilizers can be distinguished by their mode of action into two categories. These are melt stabilizers, which destroy hydroperoxides during the processing operation, and u.v. stabilizers, which have the additional ability to destroy hydroperoxides during u.v. exposure. The interdependence of the chemical changes occurring during processing and on u.v. exposure are demonstrated.     

The effects of thermal processing on PVC—IX. A polymer reactive u.v. stabilizer as a thermal stabilizer for PVC

It is shown that a thiol u.v. stabilizer (4-ethoxymercaptoaceto-2-hydroxybenzophenone, EBHPT) becomes efficiently bound to PVC during normal processing at 170° in the presence of dibutyltin maleate (DBTM). This combination is an effective melt stabilizer and shows synergism as a heat stabilizer at 140°. This is shown to be due to the protection of DBTM by the PD antioxidant function in EBHPT and a synergistic optimum is observed. In the absence of DBTM or in the presence of a thiotin stabilizer binding of the u.v. stabilizer is incomplete.     

Mechanisms of antioxidant action: Synergism between tin stabilizers and polymer-bound antioxidants in the u.v. stabilization of PVC

It is shown that a conventional tin stabilizer (dibutyltin maleate) (DBTM) forms an effective synergistic u.v. stabilizing combination when used in conjunction with a bound phenolic antioxidant (BHBM) and a bound u.v. stabilizer (EBHPT). These additives become bound to the polymer through sulphur during processing in the presence of DBTM and it is suggested that the sulphide of the adduct makes its own contribution to u.v. stabilization by acting as a peroxide decomposing (PD-C) antioxidant during photo-oxidation. However, the 2-hydroxybenzophenone function appears to be an essential part of the system and is probably involved in quenching of excited states of the intermediate sulphoxides which precede the formation of the PD-C antioxidant.     

Mechanisms of antioxidant action. Effect of the polymer medium on the antioxidant efficiency of the dithiolates

Peroxide decomposing antioxidants (e.g. nickel dithiophosphates and thiophosphoryl disulphides) control hydroperoxide formation during processing and on exposure to light. However, these additives are more efficient u.v. stabilizers in polypropylene (PP) than in low density polyethylene (LDPE). It is suggested that this difference results from the more rapid formation of hydroperoxides in the more oxidisable substrate under normal processing conditions. In contrast, nickel xanthates are completely destroyed in PP under the same processing conditions and the transformation products obtained in this case are less effective u.v. stabilizers than the original xanthates. Nickel dialkyl dithiophosphates stabilise both LDPE and PP very effectively, while nickel alkyl xanthates are much less effective u.v. stabilisers in both matrices. However, the difference between the efficiencies of the two dithiolates is much less in the case of LDPE. The nickel dithiophosphates and xanthates effectively synergise with the commercial u.v. absorber Cyasorb u.v. 531 (HOBP) but they show antagonism towards a typical chain breaking antioxidant, Irganox 1076, during u.v. exposure. They are however synergists under thermal oxidative conditions.     

Mechanisms of antioxidant action: Antioxidant behaviour of nickel complex u.v. stabilisers

The antioxidant mechanisms involved in the u.v. stabilising activity of two nickel complexes, nickel dibutyl dithiocarbamate (NiDBC) and nickel acetophenone oxime (NiOx), have been investigated both by oxygen absorption measurements and in peroxide decomposition studies. NiDBC gives rise to a powerful catalyst for non-radical hydroperoxide decomposition; the rate of the reaction is faster in the presence than in the absence of light although the overall mechanisms appear to be very similar. NiOx is decomposed by hydroperoxides in a series of stoichiometric reactions which involve the consumption of at least six molecules of hydroperoxide per molecule of NiOx. Again the reaction is catalysed by light but the mechanism, which does not involve free-radical formation, is the same in the presence and absence of light. NiOx also appears to have weak radical trapping properties. Attempts to show that NiDBC and NiOx might interact sacrificially with photo-excited states of molecules (triplet carbonyl and singlet oxygen) were unsuccessful; the rates of photo-destruction of both complexes were unaffected by the presence of ketones both in the presence and absence of oxygen. This work confirms earlier conclusions that the nickel complex u.v. stabilisers function by auto-synergistic mechanisms involving u.v. screening and conventional chain-breaking and preventive antioxidant processes which operate during thermal processing operations as well as during environmental exposure. Although excited state quenching processes may occur, they appear to be less important in the overall scheme than the well established antioxidant mechanism.     

THE EFFECTS OF HOST-CELL REACTIVATION ON ASSAY OF U.V.-IRRADIATED HAEMOPHILUS INFLUENZAE TRANSFORMING DNA

Abstract— The host cell reactivation (HCR) mechanism in Haemophilus influenzae cells is inhibited by sub-microgram concentrations of acriflavine (as is already known to be true for Escherichia coli ). Exposure of these cells to similar concentrations of the drug during bacterial transformation increases the apparent ultraviolet light (u.v.) sensitivity of previously irradiated transforming DNA, indicating a repair of this DNA after uptake by the cells under normal conditions. Repair is inhibited by applying acriflavine at any time up to one hour after competent cells contact the irradiated transforming DNA. The fraction of the u.v. damage repaired by HCR is very different for different genetic markers. Those markers which are most u.v. sensitive when assayed in the absence of acriflavine are most poorly repaired, suggesting that this is the reason for their higher sensitivity. For all markers the fraction of the damage repairable by in vitro photoreactivation is approximately constant, and strongly overlaps the damage repairable by HCR. The degree of HCR achieved can be altered by experimental treatment of the H. influenzae DNA prior to transformation. Thus treatment of irradiated DNA with an enzyme from Micrococcus lysodeikticus –known to attack u.v. damaged, but not undamaged DNA–prevents subsequent intracellular repair of the same u.v. lesions whose repair is inhibited by acriflavine. Similarly, partial replacement of the thymine in transforming DNA by 5-bromouracil (BU) strongly inhibits repair of subsequent u.v. damage. As in bacteriophage, the BU effect is relieved if the u.v. exposure occurs in the presence of cysteamine. It is clear that intracellular repair must be considered in interpreting experiments with u.v.-irradiated transforming DNA.     

Mechanism of antioxidant action. Transformation involved in the antioxidant function of nickel dithiolates—2

The initial transformation products from nickel dialkyl dithiophosphates and nickel alkyl xanthates have been identified by spectrophotometric and kinetic methods. A common mechanism of action is involved for both nickel complexes and the distribution of products from complexes during their reaction with hydroperoxides suggests a greater contribution from an ionic mechanism in the case of dithiophosphate. Nickel dialkyl dithiophosphate is more stable to u.v. light than nickel alkyl xanthate and its reaction with tert. butyl hydroperoxide in the presence and absence of light is 7–8 times faster than that of the xanthate.     

Photo-initiated oxidation of polyethylene effect of photo-sensitizers

Several important classes of u.v. activator for polymers have been studied in polyethylene. The progress of the oxidation was followed by measuring carbonyl formation in polyethylene films (carbonyl index) and by following the change in dynamic modulus of the polymer with time. The two procedures gave good agreement on the rates and extents of the two degradative reactions occurring.Three different kinds of u.v. oxidative behaviour were observed. The first, typical of the efficient triplet activators such as benzophenone and its derivatives, caused an initial rapid oxidation, increasing with ketone concentration, followed by auto-retardation. The second, typical of transition metal ions, caused an auto-accelerating rate of oxidation increasing with concentration, the third, characteristic of sulphur-containing metal complexes, showed an initial induction period which increased with increasing concentration, followed by rapid autoacceleration to physical disintegration. It is shown that, in each class, the u.v. behaviour is an extension of the function of the additive in the polymer melt during processing.     

Heteroadamantanes and their derivatives. 6. Synthesis and mass-spectrometric investigation of 5-mono- and 5,6-disubtituted 6-oxo-1,3-diazaadamantanes

The corresponding 5-mono- and 5,7-disubstituted 6-oxo-1,3-diazaadamantanes were obtained with high yields by the condensation of mono- and ,'-disubstituted acetones with hexamethylenetetramine in the presence of glacial acetic acid, and their structures were confirmed by IR and PMR spectra. The behavior of the compounds under electron impact was studied, and the main fragmentation paths of their molecules were determined.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1679–1685, December, 1985.     

Influence of additives on some physical properties of high density polyethylene-II. commercial u.v. stabilizers

The changes in mechanical properties of processed high density polyethylene, when “u.v. stabilizers” are added, are examined using tensile and melt flow measurements. The results show that, at low additive concentrations, antioxidant effects predominate; at high concentrations, a reinforcement effect is observed. Degradation measurements show that the u.v. stabilizers behave as excellent oxidation inhibitors in the dark; this finding has implications regarding their mechanistic action.     

Photostabilising action of Zn and Ni salts of 3,5-DI-t.-butyl-4-hydroxybenzoic acid in polypropylene

The photostabilising action of two metal chelates of the commercial antioxidant Shell acid (3,5-di-t.-butyl-4-hydroxybenzoic acid) viz. its zinc and nickel salts, is examined, using i.r. and derivative u.v.-visible spectroscopy and hydroperoxide analysis. The polymeric matrix was commercial polypropylene. The results show that both salts operate by inhibiting hydroperoxide formation during melt processing and thermo-oxidative conditions. The latter effect is attributed to a chain breaking donor mechanism which terminates, not alkylperoxyl, but macroalkyl radicals. Both salts are relatively efficient photostabilisers when compared with the parent antioxidant, probably because of their good photostability to both polychromatic and monochromatic radiation. The latter also shows that the nickel salt may also operate by scavenging alkoxyl and hydroxyl radicals during photo-oxidation. The addition of calcium stearate in conjunction with the salts produces some interesting effects which are explained in terms of metal exchange.     

Photooxidative stability of electron-beam and U.V. cured di- and triacrylate resins: Role of hydroperoxides

The post-cured photooxidative stabilities of electron-beam and u.v. cured resin films derived from triacrylate and amine diacrylate oligomers have been examined using i.r. and second-order derivative u.v. spectroscopic techniques and iodimetric analysis for hydroperoxides. Hydroperoxides are shown to be key intermediates in the photooxidative process, their behaviour being dependent on the curing process, activity of the initiator and structure of the resin. During the early stages of irradiation, the production of hydroperoxides in the triacrylate resin is rapid in the presence of benzophenone; thereafter the rate decreases to a photostationary equilibrium. This behaviour is consistent with the depletion of benzophenone. Addition of a tertiary amine reduces the initial rapid growth of hydroperoxides to a steady photostationary equilibrium, the effect being dependent on the amine concentration. In the amine terminated resin, there is an initial consumption of hydroperoxides followed by a very low photostationary equilibrium. The results clearly show that the presence of the amine is competing effectively with the resin structure for oxygen, thus inhibiting photooxidation. Sulphur dioxide treatment of cured resin films to destroy the initial hydroperoxides demonstrates that, while these chromophores may not be important in initiating photooxidation of the resins as measured by hydroxyl index at 3450 cm⁻¹, they are key initiators in the formation of χ,β-unsaturated carbonyl groups resulting in yellowing of the amine terminated resin. Possible mechanisms are proposed to account for these observations.     

Photochemistry of tobacco mosaic virus RNA. Effect of HCN

Abstract— In attempting to sort out possible mechanisms of photoreactivation of tobacco mosaic virus RNA (TMV-RNA) inactivated by ultraviolet radiation (u.v.) in buffer of ionic strength 0.25, we have investigated the effect of HCN on the quantum yield for u.v. inactivation of TMV-RNA and on the percent photoreactivation of inactivated TMV-RNA. Some photo-products produced by irradiation of model substances, polyuridylic acid (poly U) and polycytidylic acid (poly C), in the presence of HCN have also been studied. The ratio of the quantum yield for inactivation of TMV-RNA in the presence of HCN to that in the absence of HCN is 1.5, under non-photoreactivating conditions. By comparison, the ratio of the initial rates of loss of uracil residues in poly U under comparable conditions is 1.6; by contrast, the rate of loss of cytosine residues in poly C is unaffected by HCN. This similarity of ratios between poly U and TMV-RNA suggests that two of the mechanisms of u.v. inactivation of TMV-RNA at high ionic strength are akin to known reactions of uracil residues in poly U, i.e. hydrate and dimer formation. The photohydration reaction in poly U, as measured by the heat reversal of hydrated residues to uracil residues, is almost abolished by HCN, and the rate of dimerization, as measured by the appearance of dimer containing oligonucleotides following enzymatic hydrolysis of irradiated poly U, is reduced to half by HCN. HCN does not affect the rate of hydration of cytosine residues in poly C. Since photoreactivation of RNA inactivated in presence of HCN is only 60 per cent of that in absence of HCN it is suggested that uracil dimers are somehow involved in photoreactivation of TMV-RNA inactivated at high ionic strength.     

Triterpene Glycosides of Astragalus and Their Genins. LXI. Occurrence of Cycloartane 6-O-Monodesmosides

Cyclosiversigenin 6-O--L-rhamnopyranoside and 6-O--D-glucopyranoside were isolated fromAstragalus coluteocarpusBoiss. (Leguminosae) andAstragalus dissectusB. Fedtsch. et N. Ivanova, respectively. Cyclosiversigenin 5-O--L-rhamnopyranoside was shown to be an artifact forAstragalus coluteocarpus.Thus, the cyclosiversigenin 6-O--D-glucopyranoside that was isolated from certainAstragalusspecies is hypothesized also to be an artifact. Glycosylation of the 6 -hydroxyl group of cycloartanes by D-glucose and D-xylose, in contrast with other substituents, does not change the low-field position of the PMR signal of the 4-CH ₃ group (1.65 2.01 ppm) that is caused by the influence of deuteropyridine directly on the 6 -hydroxyl. Obviously one of the hydroxyls of the -D-glucopyranoside or -D-xylopyranoside residues has the same effect in this instance.     

Mechanisms of antioxidant action: autosynergistic antioxidants containing chain-breaking and peroxidolytic functions

Antioxidant activities, both in model substrate oxidation and in polypropylene under technological conditions, have been examined for a series of alkyl (3,5-di-tert-butyl-4-hydroxybenzyl) sulphides (I). They were found to be intrinsically much more active than typical commercial chain-breaking antioxidants in a closed system. This higher activity is attributed to an additional antioxidant function resulting from the presence of the sulphur atom. The latter is the precursor for a highly active peroxidolytic species which leads to autosynergism. In a thermal-oxidative (air-oven) test I (R, C₂—C₁₈) increases in activity with decreasing volatility but effectiveness as melt stabilizer during the processing of polypropylene and as u.v. stabilizer appears to depend more on the physical state of the additive in the polymer than on its volatility.     

Mechanisms of antioxidant action: Metal complexes as u.v. stabilisers in polyethylene

In order to evaluate the importance of u.v. screening, peroxide decomposition and excited state quenching in the mechanism of action of a variety of metal complex stabilisers, screening and additive studies were carried out in high density polyethylene and in model hydrocarbons. All the metal complexes studied were found to be u.v. screening agents when contained in a separate phase between the u.v. source and the polymer and all were rather more effective than a typical commercial u.v. absorber (2-hydroxy-4-octyl-oxybenzophenone, HOBP). However, when used as additives, all the stabilisers had an additional function. In the case of the transition metal dibutyl dithiocarbamates (NiDBC and FeDBC), the additional stabilisation mechanism is consistent with their known peroxide decomposing behaviour. In the case of the 2-hydroxy-acetophenone oxime complexes (NiOx and CuOx), the initial function is a stoichiometric reaction with hydroperoxides to give non-radical products. An amine complex of nickel bis-octylphenol sulphide (NiBOPS) appeared to behave primarily as a screen. Only one of the metal complexes (FeOx) appeared to be capable of functioning as an excited state quencher and this complex is effectively sensitised by triplet carbonyl to give a photo-pro-oxidant effect in cumene. It is concluded that the concept of excited state quenching, although it may occur with some metal complexes, is not a sufficient criterion of u.v. stabilising activity.     

Kinetic analysis of thermogravimetric data. XXVI

Ten metal and ammonium salts of the acid H₂[ReCl₆] were obtained by double decomposition reactions, and their pyrolyses in air atmosphere were studied by means of DSC measurements. The kinetic parameters of these reactions were derived and are discussed.

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Zusammenfassung 10 Metall- und Ammoniumsalze der Säure H₂[ReCl₆] wurden durch Doppelzersetzungsreaktionen erhalten. Die Pyrolyse dieser Salze in Luft wurde mittels DSC untersucht. Die kinetischen Parameter dieser Reaktionen wurden ermittelt und diskutiert.

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H₂[ReCl₆]. . .

     

Mechanisms of antioxidant action: the role of 2-hydroxybenzophenones in photo-oxidizing media

A study of the photo-stability of 2-hydroxy-4-octyloxybenzophenone (HOBP) in the presence of possible photo-sensitizers present in polymers shows that this u.v. stabilizer is readily destroyed by them in the presence of light. HOBP is destroyed by carbonyl compounds and therefore appears to interfere with their photolysis at least partly by a sacrificial quenching process.     

Photooxidative stability of electron-beam and u.v.-cured di- and triacrylate resins. Influence of resin/initiator structure

The post-cured photooxidative stabilities of electron-beam and u.v.-cured di- and triacrylate based resins have been examined using i.r. and second order derivative u.v. spectroscopic techniques. Using hydroxyl index at 3450 cm¹ as a measure of the rate of photooxidation of the resin films, their stabilities were found to be strongly dependent on the curing process and structure of the residual photoinitiator. The structure of the resin also played a major role in influencing the development of potentially active intermediate chromophores. Resins containing a terminal secondary amine group developed a strong absorption band at 250–300 nm during photooxidation, which paralleled the production of i.r. bands at 1680 and 1605 cm¹. The development of this chromophore is strongly influenced by the nature of the curing process and residual photoinitiator and is shown to be produced through an oxidative mechanism. The chromophore is associated with an α,β-unsaturated carbonyl species and is considered to be a key intermediate in the process of photoyellowing. Resins with no terminal secondary amine groups exhibited no such characteristic spectral changes. Possible mechanistic schemes are proposed to account for the observations.