Depletion mechanism of antioxidants in MDPE-clay nanocomposites under thermal aging

The depletion behavior of two types of hindered phenolic antioxidants (AO), Irganox^® 1010 (I-1010) and Irganox^®1076 (I-1076), in medium density polyethylene (MDPE)/nanoclay composite was evaluated by incubating samples in a forced air oven at 85 °C. The presence of 4 wt% nanoclay accelerated the depletion of both types of AO, particularly at the surface region of the sample. However, the depletion mechanism in the interior of sample was governed by the AO molecular structure. For samples containing the bulky Irganox®1010, OIT decreased exponentially with aging time consistent with a first order reaction. In contrast, an increase of OIT was detected in first 60 days of heat aging for sample containing I-1076 and afterward the OIT decreased slowly with aging time. The hypothesis for the initial increase of OIT is that the relatively small and linear structure of I-1076 may enable it to be trapped inside the nanoclay galleries and then subsequently released into the polymer matrix during heat aging.     

Quantification of hindered phenols in polyamide 11 during thermal aging

Polyamide 11 films stabilized by Irganox^® 1098, Irganox^® 1010 or Irganox^® 245 were subjected to thermal oxidation at 110 °C. The residual phenol content was assessed by comparing three analytical methods: high performance liquid chromatography (HPLC), determination of the Oxidation Induction Time (OIT) and Onset Oxidation Temperature (OOT) by thermal analyses. Both OIT and OOT are reliable for virgin PA11 after a relevant calibration by HPLC measurement. In the case of oxidized samples, OOT measurements have the benefits of being more easily interpretable than OIT and less time-consuming than HPLC measurements.     

NOR and nitroxide-based HAS in accelerated photooxidation of carbon-chain polymers; Comparison with secondary HAS: An ESRI and ATR FTIR study

Understanding processes resulting in heterogeneous degradation in polymers is of extreme importance for improving their stabilization and minimizing negative impact of photooxidation on the material properties. We adopted modern physical techniques for studies of spatial distribution of intermediates and products of photodegradation during accelerated ageing of four commodity polymers, polypropylene (PP), polyethylene (PE), polystyrene (PS) and poly(ethylene-co-norbornene) (Topas^®, TP) stabilized with hindered amine stabilizer (HAS). Concentration profiles of nitroxides inside polymer plaques along the direction perpendicular to their surface were determined by electron spin resonance imaging (ESRI) as a function of the duration of the accelerated photooxidation. We present data characterizing stabilization activity of three alkoxyamine derivatives of HAS (Tinuvin^® NOR 123, Tinuvin^® NOR 371, Flamestab^® NOR 116), Chimasorb^® 119 structurally similar to Flamestab^® NOR 116, and nitroxide-based HAS Dastib^® 1045 and compare them with the data characterizing stabilization activity of the secondary HAS (>NH) Tinuvin^® 770. ESRI data are complemented by ATR FTIR spectroscopic detection of oxidation products on the surface and inside the plaques and by data characterizing diffusive optical transmittance of the polymer plaques in the spectral region 280-400 nm (terrestrial range of the solar UV radiation).     

HALS和抗氧剂对PE辐射致色的影响

聚乙烯;稳定剂;HALS和抗氧剂对PE辐射致色的影响     

The diffusion and solubility of Irganox 1098 in polyamide 6

Diffusion coefficients (D) and solubilities (S) of a phenolic antioxidant (Irganox^® 1098) in polyamide 6 were determined in the temperature range of 139-180 °C. D and S show Arrhenius and van’t Hoff dependences on temperature respectively, with discontinuities at the melting temperature of the antioxidant. The activation energies for diffusion and enthalpies of solution are lower above than below the melting temperature. Based on the determined parameters for diffusion and solubility, the blooming of Irganox^® 1098 as a function of temperature and time was calculated.     

TMP与受阻酚Irganox 1010在异辛烷溶液中并用时光稳定作用的研究

本文研究了2,2,6,6-四甲基哌啶醇(简称TMP)和2,2,6,6-四甲基哌啶醇氮氧自由基(简称TMPO·)分别与四[3-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯(简称Irganox 1010)在异辛烷溶液中并用时的光稳定作用。结果表明:TMP与Irganox 1010的并用体系有反协同作用:Irganox 1010对异辛烷溶液的光氧化有敏化作用;TMP与Irganox 1010并用时,TMPO·的累积速率变慢,浓度极大值比只含TMP的样品低;TMPO·与Irganox 1010并用时,TMPO·的衰减比只含TMPO·的样品快得多。根据实验事实提出:TMPO·与Irganox 1010之间起了某种反应,该反应引起的氮氧自由基浓度的降低可能是受阻胺与受阻酚并用时产生反协同效应的主要原因。     

Determination of the concentration profile and homogeneity of antioxidants and degradation products in a cross-linked polyethylene type A (PEXa) pipe

A solvent extraction technique has been developed to determine the concentration profile of two antioxidants and five degradation products of antioxidants in cross-linked polyethylene (PEX) materials. Irganox^® 1076 and two degradation products in a PEX pipe type A (PEXa) were detected after extraction in chloroform. Fick's second law of diffusion was used to verify that 24 h of extraction at room temperature was sufficient to extract Irganox^® 1076 and the degradation products from PEX materials with a thickness of 5 μm. With the use of gas chromatography and mass spectrometry, the concentration profile was measured at four different places on a 100 m PEXa pipe. A two-way ANOVA analysis showed that the composition of Irganox^® 1076 was homogenous in the radial direction and heterogeneous in the longitudinal direction. Two degradation products of antioxidants were detected, 2,6-di-tert-butyl-p-benzoquinone and 2,4-di-tert-butyl phenol. The composition of 2,6-di-tert-butyl-p-benzoquinone was found to be homogeneous in the radial and longitudinal direction. 2,4-Di-tert-butyl phenol was homogeneous in the radial direction but heterogeneous in the longitudinal direction.     

Structural identification of hindered amine light stabilisers in coil coatings using electrospray ionisation tandem mass spectrometry

Hindered amine light stabilisers (HALS) are the most effective antioxidants currently available for polymer systems in post‐production, in‐service applications, yet the mechanism of their action is still not fully understood. Structural characterisation of HALS in polymer matrices, particularly the identification of structural modifications brought about by oxidative conditions, is critical to aid mechanistic understanding of the prophylactic effects of these molecules. In this work, electrospray ionisation tandem mass spectrometry (ESI‐MS/MS) was applied to the analysis of a suite of commercially available 2,2,6,6‐tetramethylpiperidine‐based HALS. Fragmentation mechanisms for the [M + H]⁺ ions are proposed, which provide a rationale for the product ions observed in the MS/MS and MS³ mass spectra of N‐H, N‐CH₃, N‐C(O)CH₃ and N‐OR containing HALS (where R is an alkyl substituent). A common product ion at m/z 123 was identified for the group of antioxidants containing N‐H, N‐CH₃ or N‐C(O)CH₃ functionality, and this product ion was employed in precursor ion scans on a triple quadrupole mass spectrometer to identify the HALS species present in a crude extract from of a polyester‐based coil coating. Using MS/MS, two degradation products were unambiguously identified. This technique provides a simple and selective approach to monitoring HALS structures within complex matrices. Copyright © 2010 John Wiley & Sons, Ltd.     

Natural weathering test for films of various formulations of low density polyethylene (LDPE) and linear low density polyethylene (LLDPE)

Natural (outdoor) weathering test was performed to investigate the UV stability of thin films (0.06 mm) of linear low density polyethylene (LLDPE) and low density polyethylene (LDPE). The PE films were prepared from various formulations of LLDPE and LDPE resins. Some of these films contained a single high molecular mass HALS only, along with a primary antioxidant (i.e. Irganox 1010) and a secondary antioxidant (i.e. Irgafos 168 or Alkanox TNPP), while others contained HALS and UVA (i.e. Chimassorb 81 or Tinuvin P or Tinuvin 326) along with these antioxidants. The HALS used was either an oligomeric or a synergistic mixture of a high molecular mass (HMM) hindered amine stabilizer and co-additives. The UV stability was investigated by exposing the prepared films at 45° towards south in the direct sunshine up to 365 days. Fifty percent of tensile strength retention was determined for all these exposed films and it was found that the films containing a single HALS gained improved UV stability by about two to 12 fold over the pure films. On the other hand, films that contained a combination of HALS and UVA obtained further improved UV stability over the films containing a single HALS (both have antioxidants). Films containing a single HALS reached 50% TS retention within 205 days, whereas, films containing a combination of HALS and UVA reached 50% TS retention within 590 days, which is about three times further improvement in UV stability.     

Interactions of stabilizers during oxidation processes

The antioxidative action of mixtures of phenols, phosphites, HALS, ^a) and some of their transformation products in various compositions has been studied in the thermo- and photo-oxidation of hydrocarbons and polypropylene under different conditions. In the AIBN-initiated oxidation of hydrocarbons at low temperatures (< 80°C), hindered phenols, hindered aryl phosphites and the nitroxyl derivatives of HALS act antioxidatively when used individually in appropriate concentrations. Secondary HALS do not show any induction period, but a certain retardation of the oxidation process after some reaction time. The inhibiting efficiency of nitroxyls observed cannot be explained completely by the currently accepted action mechanisms of HALS, but is also related to the reaction of the nitroxyls with alkylperoxyl radicals. In mixtures with hindered phenols, HALS have almost no influence on the rate of thermooxidation at low temperatures. Their nitroxyl derivatives, however, always exhibit synergism, most pronounced when both stabilizers are used in equimolar ratios. During the photooxidation phenols lower the efficiency of HALS. The influence of mixtures of stabilizers on the oxidative stability of polypropylene is rather different and depends on the oxidation conditions, the structure, the concentration and the ratio of the stabilizers. Synergistic as well as antagonistic effects are observed. Both aliphatic and aromatic phosphites studied act synergistically when used together and with phenols. This demonstrates that for acting as synergist for phenols, the hydrogen peroxide decomposing capability of the phosphites, but not their chain breaking activity is important. HALS-phosphites and phosphonites, containing amine and phosphorus units in one molecule, are highly effective inhibitors of photo- and thermooxidation and exhibit lower critical antioxidant concentrations and longer induction periods than phosphites alone. They even exceed the efficiency of phenols in many cases. Transformation products of phenolic antioxidants investigated act differently and in many cases contrarily under photo- and thermooxidative conditions. Therefore, they influence the efficiency of stabilizer mixtures also in a different way.     

Synergistic Effect of Phosphite with FuUerene C60 and Fullerenol C60（OH）24 as Antioxidants in Polypropylene

Polypropylene samples with fullerene C60, fullerenol C60（OH）24, 1010, C60/168, C60-OH/168 and 1010/168 as antioxidants were prepared by extrusions. MFR, YI, TGA and OIT of all the samples were tested. According to the results of MFR, during the melt extrusion, fullerene showed excellent stability effect on PP. The antioxidative ability of fullerene was comparable to the traditional antioxidant 1010. The antioxidative ability of fullerenol was not significant in the first extrusion and it accelerated the degradation of PP in the second and the third extrusions. TGA and OIT tests showed that the stability effects of fullerene and fullerenol were slightly lower than antioxidant 1010. In the first time, antioxidant 168 was reported to show great synergistic effects with fullerene and fullerenol as antioxidants, which sussested a simple way to enhance the antioxidative abilities of fullerene and fullerenol.     

Dihydromyricetin

A study on the efficiency of bio-based compound as stabilizer for linear low density polyethylene (LLDPE) is reported. A water extract from Ampelopsis grossedentata (Dihydromyricetin) is used. Its stabilizing activity is compared with two commercial phenolic antioxidants: methyl gallate (MG) and Irganox 1010. Based on the measurement of the oxidation onset temperature (OOT) of LLDPE/antioxidant samples, it is found that the antioxidant ability of the three kinds of antioxidants is in the following order: DMY > 1010 > MG. The antioxidant ability and thermal decomposition activation energy (E _a) of antioxidants are further examined by thermal gravimetric analysis. The effects of water extraction on the migration resistance of LLDPE/antioxidants are also evaluated by monitoring the OOT change, demonstrating that DMY retained high stability against migration.     

Thermal oxidation and molding feasibility of cycloolefin copolymers (COCs) with high glass transition temperature

Cycloolefin copolymers (COCs) with high glass transition temperature (T_g = 203 °C) have been synthesized and pelletized by extrusion molding. However, their colors change from transparent to yellow during extrusion molding because of thermal oxidation and generation of alkene groups. We have successfully blended several antioxidants (Irganox 1010, Irgafos 168, Irganox HP2225 and Irganox HP2921) into lab-made COCs to avoid the discoloration. The experimental results show that Irganox HP2921 is the best antioxidant among the antioxidants used and can effectively not only suppress thermal oxidation but also eliminate the color stain.     

Photochemical behaviour of fire-retarded polymers

The influence of a non-halogenated intumescent fire retardant on the photooxidation of polypropylene is reported. The photooxidation of polypropylene stabilised with a phenolic antioxidant and two redox antioxidants (HALS), without and with the flame retardant has been studied. The chemical modifications resulting from UV-light exposure with wavelengths above 300 nm in the presence of oxygen were followed by IR and UV-visible spectroscopies. Special attention was given to the influence of each component on the rate of oxidation of the polymeric matrix. The photooxidation of the fire-retarded polymer can be described by two independent phenomena: the photooxidation of the intumescent agent and the photooxidation of the polymer. The results obtained offer new insight in the formulation of stabilised fire-retarded PP for outdoors applications.     

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.     

Use of two-dimensional liquid chromatography in the analysis of additives in cellulose acetate polymer

Summary The capability of elution-elution multi-dimensional liquid chromatography was investigated. A column scaling approach was evaluated for the quantification of low-molecular-weight additives in cellulose acetate. A small-bore (1-mm i.d.) gel-permeation column was used to separate the higher-molecular-weight polymer from the lower-molecular-weight components. Once separated these additives were transferred to a C₁₈ reversed-phase column via a switching valve. The reversed-phase system successfully separated and quantified individual additives.Analysis time for an ultraviolet inhibitor, Tinuvin^®P, in cellulose acetate, including re-equilibration, was approximately 30 minutes. Both accuracy and precision were good. Precision over a three day period was about 1.5%.     

Prevention of degradation of γ-irradiated EPDM using phenolic antioxidants

The mitigation of oxidative degradation under γ-irradiation promoted by eight commercial antioxidants: Ethanox 330, Hostanox O3, Irganox 1010, Topanol OC, Ionox 220, Santonox R, Santowhite, Cyanox 2246 loaded onto ethylene-propylene terpolymer at the concentration of 0.5 phr in respect of a pristine polymer was studied. The polymer samples were exposed to various doses up to 500 kGy. The kinetic parameters of oxidations: oxidation induction times, onset oxidation temperature, oxidation rates were evaluated by CL measurements. They validated the differences in the stabilisa-tion activities by limitation of the oxidation gradient. The high efficiency of some of the antioxidants studied, such as Ionox 220 and Santowhite, ensured the delay in degradation even at a high irradiation dose (500 kGy). For the environments with γ-radiation exposure, a relevant sequence in the increasing protection efficiency could be established: Topanol OC; Hostanox O3; Irganox 1010; Cyanox 2246; Santonox R; Ionox 220; Santowhite. The FT-IR spectra were recorded for the calculation of the radiochemical yields resulting from the modifications occuring in the concentrations of oxygenated structures. The accumulations of hydroxyl- and carbonyl-containing products were calculated to evaluate the irradiation effects in EPDM-based products during a severe accident. The options for EPDM stabilisation are discussed based on chemiluminescence and FTIR analyses.     

The effects of gamma irradiation on the fate of hindered phenol antioxidants in food contact polymers. Analytical and 14C-labelling studies

The extractable levels of two hindered phenol antioxidants (Irganox 1076 and Irganox 1010) present in PVC, polyethylene and polypropylene, have been monitored by HPLC techniques following progressive exposure of the polymers to ⁶⁰Co γ radiation. There is a gradual diminution in the extractable levels of each antioxidant as irradiation progresses as a result of transformation of the antioxidants in the oxidation reactions ensuing during irradiation. Experiments involving the use of a ¹⁴C-labelled sample of Irganox 1076 in polyolefins have provided evidence of covalent binding of antioxidant degradation products to the polymer following gamma irradiation. However, there is also evidence of the formation of extractable degradation products, the identity of which is as yet unknown.     

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.     

Polyethylene stabilization against thermal oxidation by a trimethylquinoleine oligomer

The thermal oxidation at 110 and 120 °C of polyethylene (PE) films stabilized by 0.1, 0.2 and 0.5% of a trimethylquinoleine (TMQ) oligomer has been studied by IR spectroscopy (carbonyl build-up) and by DSC (measurement of the oxidation induction time at 200 °C). The induction period increases almost proportionally to the TMQ concentration and the TMQ efficiency (as estimated by the ratio t_ind/[TMQ]₀) increases when lowering the temperature. Some features of stabilizer consumption kinetics and the dependence of maximum oxidation rate with initial stabilizer concentration were compared to experimental results obtained for stabilization by hindered phenols (Irganox 1010) and to literature data for sacrificial (e.g. hindered phenols) and regenerative (Hindered Amine Stabilizers) antioxidants. These comparisons led to classify TMQ in the category of Hindered Amine Stabilizers (HAS), which was confirmed by a kinetic analysis. Only the scheme taking into account the specific features of HAS (role of NO radicals, regeneration from alkoxyamines) was able to correctly simulate the oxidation behaviour of TMQ stabilized PE.