Mechanisms of antioxidant action: Time-controlled stabilisation of polypropylene by transition metal dithiocarbamates

Combinations of iron and nickel dithiocarbamates approach the ‘ideal’ delayed action photo-activators for polypropylene. They give an induction period to photo-oxidation which can be controlled by the amount of the nickel complex and a rapid rate of photo-oxidation at the end of the induction period which is primarily determined by the iron concentration. Combinations of other photo-activators and uv stabilisers show a less ideal behaviour and do not permit such accurate time control.     

Polyolefins with controlled environmental degradability

Antioxidants and stabilisers, developed to increase the durability of polyolefins, in combination with prooxidant transition metal complexes provide industrial products with widely variable but controlled lifetimes. The low molar mass oxidation products formed during photo-oxidation and thermal oxidation are biodegradable and oxo-biodegradable polyolefins are now widely used in agricultural applications and in degradable packaging as examples. The scientific basis for the performance of oxo-biodegradable materials is explained with reference to naturally occurring macromolecules. Comparison with hydro-biodegradable materials is made and the need is demonstrated for performance standards to be developed that mimic nature's resource recovery mechanism, that of oxo-biodegradation.     

Effect of reprocessing on polymers: Part II—Polypropylene

The melt rheology and long-term stability of unstabilised polypropylene are found to be grossly affected during reprocessing. Hydroperoxides are formed which lead to subsequent thermal-oxidative and photo-oxidative instability. Antioxidants and stabilisers show widely different abilities to protect the polymer under all the conditions that may be encountered during polymer recycling and it is concluded that the most cost-effective materials are the light stable transition metal sulphur complexes typified in the present work by the transition metal dithiocarbamates (II).     

Photo-stabilising action of metal chelates in polypropylene—Part I: Excited state quenching versus UV antioxidant action under polychromatic irradiation

The photo-stabilising action of three metal chelates—nickel (II) 2,2′ thiobis (4-tert-octylphenylato) n-butylamine and the nickel and calcium derivatives of bis (ethyl-3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, in polypropylene—is examined using normal and second order derivative ultraviolet, infra-red and phosphorescence spectroscopic techniques and hydroperoxide analysis. Whilst all three stabilisers quenched the phosphorescence emission of a powerful photo-sensitiser, benzophenone, there was no protective action during photo-sensitised oxidation of the polymer. In the case of anthraquinone, there was no quenching and no protection. Processing history plays a dominant rôle in controlling the photo-stabilising performance of the chelates. Each stabiliser operates differently, being dependent on its relative stability during processing and photo-oxidation and on the formation and destruction of polymeric and antioxidant hydroperoxides during processing. Metal chelates operate by inhibiting polymer hydroperoxide formation during processing and acting as ultraviolet stable chain terminators or by giving products during the early stages of photo-oxidation which are themselves effective stabilisers.     

苯乙烯-甲基丙烯酸四甲基哌啶醇酯共聚物光防护行为的研究

本文用力学性能、分子量、ESR、IR等测定方法,研究比较了大分子受阻胺PDS和小分子受阻胺Tinuvin-770对聚丙烯的光防护作用。结果表明,二者的光防护作用都是通过形成>NO·稳定自由基机理;并能有效地接枝在聚丙烯上,而PDS还具有“微交联“作用。光氧化监测表明,PDS较耐光分解,其光氧化防护中所产生的>NO·稳定自由基在整个老化过程中保持一定的浓度,加之大分子化改善了PDS的热稳定性,耐抽提性,相容性,因而使PDS具有较高的光防护效率。     

Quenching of singlet oxygen by hindered amine light stabilisers. A flash photolytic study

Rate constants for the quenching of singlet oxygen (¹O₂, ¹δ_g) for a series of piperidines, piperidine-N-oxyl free radicals and some commercially used hindered amine light stabilisers (HALS) have been measured by a laser flash photolysis method. Quenching rate constants are in the order: piperidine-N-oxyl free radicals ≤ secondary piperidines < tertiary piperidines. For some commercial HALS, ¹O₂ quenching rate constants and the light protective effect towards polypropylene photo-oxidation have been compared. No correlation has been found between the stabilizing action and the quenching efficiency towards ¹O₂. The data obtained point to little contribution of singlet oxygen to the key steps of polyolefin photo-oxidation.     

Stabilising effect of monomers,homopolymers and copolymers of vinyl derivatives of sterically hindered amines on the photo-oxidation of polypropylene

Vinyl derivatives of sterically hindered amines, N-(2,2,6,6-tetramethyl-4-piperidyl)methacrylamide, 2,2,6,6-tetramethyl-4-piperidyl acrylate and methacrylate and 1,2,2,6,6-pentamethyl-4-piperidyl acrylate and methacrylate were prepared. Monomers, homopolymers and copolymers with dodecyl methacrylate (DMA) and octadecyl acrylate (ODA) were tested as stabilisers of the photo-oxidation of polypropylene film. The copolymers exhibited higher efficiency and lower extractability. The photostabilising efficiency increased in the order: homopolymer < monomer < copolymer with DMA < copolymer with ODA.     

Photo-stabilising action of metal chelates in polypropylene—Part II: Photolysis versus photo-sensitised oxidation under monochromatic irradiation

The photo-stabilising action of three metal chelates in unprocessed and processed polypropylene is examined using normal and second order derivative ultraviolet and infra-red spectroscopic techniques and hydroperoxide analysis. The effects of photolysis with 254 nm light versus photo-sensitised oxidation with 365 nm light are compared. For each exposure condition the rate of carbonyl formation in the polymer is compared with the rate of decomposition of the metal complex. On photolysis, carbonyl growth commences well before the complete destruction of the complexes and none offers protection to the polymer. In fact, all three chelates behave as photo-sensitisers, indicating that stabiliser photolysis products are photo-active. On photo-sensitised oxidation, while the initial hydroperoxide concentration appears to control the onset of carbonyl growth in the polymer, the rate of decomposition of the complexes shows no dependence on hydroperoxide concentration. Solution experiments indicate that there are no dark reactions with hydroperoxides apart from one of the nickel chelates (Cyasorb UV 1084) at high concentrations (～ 10^?2m) only. Essentially, the metal chelates operate by scavenging macroalkyl radical species (P·) and not alkoxy (PO·) and hydroxy radicals (·OH) during photo-oxidation. They also inhibit hydroperoxide formation during processing and one of the nickel chelates (UV 1084) gives products during the early stages of photo-oxidation which appear to operate as effective stabilisers.     

Mechanisms of antioxidant action: Behaviour of a hindered piperidine and related oxidation products during processing and photo-oxidation of polypropylene

Evidence is presented to show that a commercial hindered piperidine (I(A)) is not an effective melt stabiliser for polypropylene whereas related nitroxyl radicals (II(A)) and (II(B)) and hydroxylamine (III(B)) are highly effective. These results are explained on the basis of an oxidative transformation of the piperidine to the nitroxyl during processing and the involvement of the latter in a cyclical regenerative process in which the nitroxyl acts as a chain-breaking acceptor (CB-A) antioxidant and the derived hydroxylamine as a chain-breaking donor (CB-D) antioxidant.The same CB-A/CB-D cycle operates during photo-oxidation of polymer films containing each of the additives. The nitroxyl radical concentration reaches a stationary concentration in the polymer, irrespective of whether it is added as nitroxyl or as parent amine. The derived hydroxylamines are substantially more effective than the nitroxyl radicals as ultraviolet stabilisers.     

Destruction of carbonyl and hydroperoxide groups in oxidised polypropylene: Effect on photo-oxidation

The effect of destroying carbonyl and hydroperoxide groups in oxidised polypropylene on the subsequent rate of photo-oxidation has been examined using infra-red spectroscopy. The results show that carbonyl groups dominate the rate of photo-oxidation in severely oxidised polymer. In mildly oxidised polymer hydroperoxide groups control the rate, but to a much smaller extent. Destruction of the photo-active carbonyl and hydroperoxide groups in the unoxidised and oxidised polymers by prior photolysis in an inert atmosphere gave rise to some interesting and complex effects on subsequent photo-oxidation. The results indicate that although carbonyl and hydroperoxide groups may control the rates of photo-oxidation of thermally oxidised/processed polymer, their importance as primary photo-initiators is highly questionable. Oxygen-polymer charge transfer complexes appear to be the more likely photo-initiators.     

Effects of melt processing conditions on photo-oxidation of PP/PPgMA/OMMT composites

This article reports the studies of photo-oxidative behaviour of polypropylene/maleic anhydride-grafted polypropylene/organic modified montmorillonite (PP/PPgMA/OMMT) composites prepared by two different melt processing methods. Samples of pristine polypropylene (PP) and PP/PPgMA/OMMT composites were prepared in an internal mixer and in a twin screw extruder. The samples were exposed to long wavelength radiations (λ > 300 nm) for the photo-oxidation. The samples were examined by FTIR, X-ray diffraction and microscopy. Similar to the pristine (PP), it is found that the photo-oxidation process in the composites depends on the melt processing conditions, which could cause the deterioration of organic modifier of the clay and the polymer matrix. The new radicals formed in addition to the iron impurities in the montmorillonite accelerate the photo-oxidation.     

Ageing,weathering and stabilisation of polymers

The common chemical basis of thermal ageing and weathering are outlined, and the mechanisms of antioxidant action which follow from thermal and photo-oxidation are discussed. The physical behaviour of antioxidants and stabilisers in polymers is assuming increasing importance as the polymer environment becomes more aggressive, and the rationale for the development of polymer-bound antioxidants is discussed.     

Some important factors which influence the photo-oxidation of polypropylene

The influence of bromination, treatment with sulphur dioxide and light filtration on the rate of photo-oxidation of unstabilised polypropylene film has been examined using infra-red and derivative ultraviolet-visible absorption spectroscopic techniques. Whilst bromination removes unsaturation and sensitises polymer photo-oxidation, sulphur dioxide treatment stabilises the polymer, probably by destroying hydroperoxides. Removal of infra-red radiation extends the induction period prior to carbonyl formation while removal of light wavelengths <370nm extends the induction period by a factor of at least 10. These results lead to some important conclusions about the mechanisms of polypropylene photo-oxidation.     

Mechanisms of antioxidant action: Nitrosamines as heat and light stabilisers for polypropylene

N-Nitrosamines are shown to be very effective melt stabilisers for polypropylene and one of these, derived from the hindered amine light stabiliser, Tinuvin 770, is almost twice as effective as the latter. The mechanism is believed to involve the formation of two kinds of nitroxyl radical, the first derived from the amine and the second formed by the reaction of nitric oxide with alkyl, and possibly alkoxyl, radicals. Nitrosamines which do not dissociate to NO are neither melt stabilisers nor uv stabilisers.     

Photodegradation of bisphenol A polycarbonate

When bisphenol A polycarbonate is subjected to weathering conditions this polymer shows two different degradation mechanisms depending on the used irradiation wavelengths, i.e. photo-oxidation and photo-Fries rearrangement. The relative importance of these mechanisms in outdoor exposure conditions is still unknown. In this study bisphenol A polycarbonate is exposed to simulated weathering conditions. Different analysing techniques show that photo-oxidation is the most dominant degradation reaction. However, fluorescence spectroscopy shows that small amounts of photo-Fries rearrangement products are formed. With model compounds blended in polypropylene it is shown that the photo-Fries reaction increases the photo-oxidation rate, thus in PP the photo-Fries reaction can proceed through radical intermediates. However, this is not the case in PC, ageing at condition causing an increased photo-Fries reaction rate did not result in a higher oxidation rate. This implies that in PC the photo-Fries reaction does not initiate its oxidation and thus does not proceed through radicals.     

The inhibited photo-oxidation of polystyrene and styrene/HALS copolymers

The influence of molecular weight and the mode of binding of HALS stabilisers on their efficiency in the inhibited photo-oxidation of polystyrene and styrene/HALS copolymers was investigated. Photo-oxidation was performed with radiation of λ > 310 nm and 366 nm. The following functionalised HALS stabilisers were prepared: 4-methacryloylamino-2,2,6,6-tetramethylpiperidine, 4-methacryloyloxy-2,2,6,6-tetramethylpiperidine, 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine and 15-methacryloyl-7,15-diazadispiro [5.1,5.3] hexadecane-14,16-dione. Binding by copolymerisation is substantially less efficient than addition of low molecular weight stabiliser.     

聚丙烯膜光氧化过程中表层光氧化产物的X-射线光电子能谱(XPS)的研究

本文用X-射线光电子能谱(XPS)研究了聚丙烯膜表层的光氧化产物,得出几种主要氧化产物的相对含量随氧化时间变化的规律并将其与缸外光谱所测结果及文献报道的相比较,证明膜表层光氧化和膜整体光氧化规律有所不同。根据实验结果提出了反应机理。     

Mechanisms of antioxidant action: Mechanochemical addition of thiol antioxidants to ABS

It is shown that thiol-containing antioxidants and stabilisers can be chemically reacted with ABS in high yields and in substantial concentrations under conditions of high temperature and high shear during processing. The resulting antioxidant concentrates are shown to be very effective thermal and photo-oxidative stabilisers for ABS when used as masterbatch additives for unstabilised ABS. Synergistic combinations of a bound antioxidant (BHBM (I(a))) and a bound uv stabiliser (EBHPT (II)) confer a high level of uv stability on ABS when incorporated into ABS. All the antioxidants show a high resistance to removal from the polymer by solvent extraction. The effect of the mechano-chemical process on the efficiency of adduct formation and on the effectiveness of the stabilisers so formed is discussed.     

Photo-oxidation of polypropylene: Relationship between unsaturation and induction period

Evidence is presented to show that there is a correlation between the amount of unsaturation in polypropylene and its induction period during photo-oxidation. Hexane extraction, which removes unsaturation, has a destabilising effect, while doping the polymer with hexane extracts causes an increase in stability. Destruction of the unsaturation with light of wavelengths <300 nm in an inert atmosphere also destabilises the polymer.