Mechanisms of antioxidant action: The behaviour of a bound antioxidant as an antiozonant

A rubber reactive antioxidant, 4-(mercapto acetamido)diphenylamine (I, MADA) was found to be more effective as an antiozonant when prereacted with the rubber chain (MADA-B) than when present as a conventional compounding ingredient (MADA-A) at the same molar concentration. In bound form after extraction MADA-B is as effective as an unextracted commercial antiozonant, iso-propylaminodiphenylamine (IPPD), at the same molar concentration. This result casts some doubt on the currently accepted view that antiozonants must migrate to the surface of the rubber in order to exert their protective effect.     

Stabilisation of EPDM at high temperatures by polymer-bound antioxidants: Part 1—Air oven ageing: Stress relaxation and mechanical property change

EPDM modified by adduct formation using mercaptoacetamido diphenylamine (MADA) and mercaptopropionamido diphenylamine (MPDA) has been evaluated in a heat ageing (air oven) test at 150°C and 180°C by stress relaxation and physical property change. Both antioxidants were found to be more effective than conventional heat ageing antioxidants under these conditions and MADA-B is more effective at 1% than a commercial oligomeric arylamine (Flectol H) at 2%. Vulcanisation characteristics are also reported and it is concluded that by-products formed from MADA during binding interfere to some extent with the curing process and with antioxidant performance.     

多官能团单体对马来酸酐接枝聚丙烯流变行为的影响

研究了多官能团辅助单体偏苯三酸三丙烯酯(TATM)对马来酸酐接枝聚丙烯的熔体流动速率(MFR)和流变行为的影响.当以不含抗氧剂的聚丙烯粉料为原料时,TATM的加入对稳定接枝产物MFR的效果并不理想.但将聚丙烯粉料添加抗氧剂并造粒后,TATM的加入则可有效稳定体系的MFR,各种流变曲线显示出接枝产物的熔体弹性明显提高,说明有枝化或交联结构出现.针对PP粉料和粒料间接枝产物流变行为存在的重大差异,结合熔体自由基接枝反应的机理进行了解释.TATM能够起到稳定MFR的效果是由于其提高了接枝物的熔体弹性,从而抵消了聚丙烯熔体接枝反应中所不可避免的β断链所造成的剪切黏度下降.聚丙烯粉料和粒料中抗氧剂的差异对聚丙烯的加工降解有严重影响,造成了TATM在不同聚丙烯体系中效果的差异.     

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.     

Relevance of High Temperature Oxidative Stability Testing to Long Term Polymer Durability

In polymer degradation and durability studies, as well as predicting shelf-life for medical devices, one is confronted with the need for accurate prediction and difficulties of long term real-time evaluation. Various ways to accelerate the degradation process have met with mixed success. However, recently, in our own studies, a ‘master curve’ like behavior was found to be valid for polypropylene samples studied. Evidently, for samples obeying the master curve, very few data points at high temperatures can be scaled to obtain reasonably accurate estimates on long term durability. Nevertheless, in a reference medium density polyethylene (MDPE) film material, the high temperature oxidative induction time data appear to diverge when run under air atmosphere compared with oxygen environments. In this article, we will present data on many of the polymer systems studied with an emphasis on extrapolation schemes for high temperature accelerated data to lower temperature very long-term durability. In this context, polymer and antioxidant reactivity toward oxygen, morphology, and mechanical property dependence on extent of degradation all need to be considered. And the potential and limitations of this approach will be discussed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Mechanisms of antioxidant action: polymer grafted antioxidants

It is shown that the antioxidant 3,5-di-tert-butyl-4-hydroxybenzyl acrylate, may be grafted to the surface of polymer artefacts. The antioxidant activity of the resulting “efficiently dispersed” antioxidant is very much higher than that of low molecular weight antioxidants containing the same functional group. Even after extraction with an effective solvent for the antioxidant-monomer and derived polymer, the oxidative stability of the polymer films is very much greater than that of polymer containing the antioxidant-monomer or antioxidant-polymer incorporated by a conventional melt technique without extraction. Optimum activity is believed to be associated with the formation of frequent short chain grafts in the surface of the polymer and is achieved by the use of a polymerization photo-activator such as benzophenone which also terminates kinetic chains.Surface grafted antioxidants are also found to be effective u.v. stabilizers for polypropylene in contrast to the normal ineffectiveness of chain terminating antioxidants incorporated into the polymer by conventional techniques.     

STUDIES ON THE PORE FORMATION MECHANISM OF β-CRYSTALLINE POLYPROPYLENE UNDER STRETCHING*

The pore formation mechanism of,β-crystalline polypropylene under stretching was investigated. The porosity of the samples increases rapidly with stretching, having a maximum at draw ratios around 2 and then decreases monotonically. An abrupt formation process of initial micropores at very low draw ratios was evidenced by in situ SAXS measurements. At the same time the phase transition from ,β-crystal to α-crystal proceeds slowly in the whole deformation process up to large draw ratios around 5. Comparative studies of α- and ,β-crystalline polypropylene samples before stretching indicate that in addition to difference in crystal forms the α- and β-crystalline polypropylene samples exhibit quite different morphological features. There are a lot of interfaces in ,β-crystalline polypropylene samples, which may have a lower density value and can be easily etched by argon ions and penetrated by small molecules. It was concluded from these experimental facts that the pore formation and crystal transition are two independent phenomena during the deformation of β-crystalline polypropylene samples, and phase transition from ,β-crystal to α-crystal could hardly be the origin of pore formation. A defect initiation mechanism was proposed to understand the pore formation behavior of β-crystalline polypropylenes.     

Study the effect of antioxidants on biological activity and on homopolypropylene; mechanical and physical properties

Exposure of polymers to temperature, atmospheric oxygen, or even light could result in some degradation of the polymer properties and features during processing (application), storage and end use. In hydrocarbon polymers, the polymer tend to free radical formation, eventually resulting in chain damage or crosslinking that leads to degradation. Antioxidants are used to terminate these chain reactions by removing radicals. Antioxidants are used in most hydrocarbon polymers including, polypropylene. a good addiction package must be existed to overcome the effect of degradation and save the polymer shape and characteristics. The practical experiment was carried out on a pure polypropylene (intermediate polypropylene resin without additives) and another practical experiment but with adding several types of additives with a certain concentration and study the behavior of polypropylene in all cases with successive extrusions. On other hand Flexible molecular docking on heme oxygenase, an important stress protein that is involved in cellular protection, antioxidant and anti-inflammatory activities, justified the antioxidant activity of the isolated compounds. From the binding energy 3114 and 1680 they could consider to be powerful and available antioxidant.     

Determination of antioxidants in polyolefins by pressurized liquid extraction prior to high performance liquid chromatography

The effect that a high amount of mineral filler might have on the extraction process of antioxidants from polyethylene and polypropylene was investigated. Extraction of Irganox 1010, Irganox 1076 and Irgafos 168, along with its oxidation product 2,4-di-tert-butylphenol, from freeze ground polyethylene–based (PE–based) and polypropylene–based (PP–based) mineral concentrates of 85 w/w calcium carbonate (CaCO₃) and 75 w/w talc was carried out by pressurized fluid extraction (PLE) prior to high performance liquid chromatography (HPLC). Results indicate that 85 w/w CaCO₃ did not affect the extraction process from PE or PP. For talc concentrates, additive recovery from PE and PP was considerably lower. The relation of recovery yield and mixing time was investigated for the talc concentrates and it was concluded that the presence of talc seemed to accelerate the rate of antioxidant consumption during sample processing, thus, less antioxidant was left to be extracted from the polyolefin; rather than talc has limited the extraction process. The method developed in this work has been applied to determine these compounds in several commercial samples.     

Evaluation of the melt stabilization performance of hydroxytyrosol (3,4-dihydroxy-phenylethanol) in polypropylene

The use of hydroxytyrosol (3,4-dihydroxy-phenylethanol) as a potential alternative to synthetic compounds in the melt stabilization of polyolefins is considered. Hydroxytyrosol was found to play a role in enhancing the oxidative stability of olive oil, and a similar reduction in polyolefins’ thermo-oxidative degradation during processing is expectable. Rheological tests (melt flow index and viscosity vs. shear rate) showed the good antioxidant performance of hydroxytyrosol during polypropylene processing as was also demonstrated by the increase in apparent activation energies and oxidation induction parameters after addition to polypropylene (0.1 wt%). Results were compared to those obtained for a commercial synthetic phenolic antioxidant and for a natural compound widely used in polymer stabilization (α-tocopherol). The main conclusion of this work is the good performance of hydroxytyrosol in polypropylene stabilization during processing and consequently the possibility of its use in formulations with improved resistance to oxidative degradation.     

Stabiliser partitioning and oxidative degradation in rubber-toughened polypropylene

Solubility measurements on an antioxidant and a UV stabiliser in polypropylene and an ethylene/propylene rubber are correlated with partitioning between the two bulk polymers and between the phases of a blend. At low concentrations, partitioning concentrates the additive in the rubber; the effect increases with temperature, so that most of the additive will be in this phase at processing temperatures. Calculations suggest that the additives can diffuse between phases fast enough to compensate for consumption in either at service temperatures. At processing temperatures, diffusion of antioxidant from the more stable rubber phase to the polypropylene phase may be slow enough to limit protection from oxidation.     

Fire retardant systems based on melamine hydrobromide: Part I—Fire retardant behaviour

The fire retardant characteristics of additives based on mixtures of melamine hydrobromide-free radical initiator-basic bismuth carbonate (or antimony trioxide) are discussed on the basis of the dependence of oxygen index on composition in the case of polypropylene.It is shown that the free radical initiator enhances the effectiveness of the fire retardant action of melamine hydrobromide. A further significant decrease of flammability, as measured by oxygen index, is induced by addition of the metal compound. Thus, polypropylene can be fire retarded with very small amounts of additive (<2%) without excessive formation of smoke which is typical of the most common halogenated additives. This seems to be due to a smoke suppressant activity of the melamine structure.These additives act by a condensed phase mechanism which seems not to be limited to induction of extensive dripping of the polymer on burning.     

Study on the antioxidant activities of benzofuranones in melt processing of polypropylene

The antioxidant activities of four benzofuranones in melt processing of polypropylene (PP) have been investigated using multiple extrusions. The antioxidant activities of those four benzofuranones with different substituent groups have been evaluated using melt flow index (MFI) and yellowness index (Y.I.) of multiple-extruded PP stabilized with those antioxidants. The change of MFI values indicates as follows: firstly, the position of substituent group has a very important effect on the antioxidant activity of benzofuranone in the melt processing of PP i.e. methyl group of 2′-position may prevent the hydrogen donation of benzofuranone toward PP radicals and make the antioxidant activity of benzofuranone in PP decrease; secondly, electronic property of substituent group of para position to 3-reactive hydrogen has little influence on the antioxidant activity. Furthermore, the theory that the formation of antioxidative products due to the dimerization and disproportionation of benzofuranyl radicals is the main reason that induces the discoloration of stabilized PP has been predicted for the first time.     

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。     

Determination of oxidation parameters by DSC for polypropylene stabilized with hydroxytyrosol (3,4-dihydroxy-phenylethanol)

Oxidation thermal parameters on samples of polypropylene (PP) stabilized with hydroxytyrosol were determined. For comparison purposes, α-tocopherol and a synthetic phenolic commercial antioxidant (Irganox 1076), were also analyzed. Oxidation induction time (OIt) and oxidation induction temperature (OIT) were determined by differential scanning calorimetry (DSC). The addition of hydroxytyrosol 0.1 mass% to PP was enough to obtain efficient stabilization during processing. Certain decrease in stabilizing properties of natural antioxidants was observed for compression moulded materials at high temperatures. However, these samples were still efficiently stabilized in comparison to the pure material. Hydroxytyrosol showed good performance as polypropylene antioxidant and it might be considered as promising alternative to the use of phenolic synthetic compounds.     

Antioxidants and stabilizers: Part CVI—Mechanism of antioxidant action of dithiobisphenols

A disulfidic bridge connecting two alkylated phenolic moieties is considered to be a decisive structural factor in the high antioxidant efficiency of dithiobisphenols in polypropylene (PP) autoxidation and tert-butylhydro-peroxide (TBH) decomposition. Strong retardation of the later phases of the autoxidation of PP doped with two dithiobisphenols (I(d), II(d)) is a consequence of the stepwise accumulation of antioxidant-active S-oxidation products. Thermolabile thiosulfonate and sulfoxide are formed (among other transformation products) and are considered to be sources of peroxidolytic species. The latter are involved, as very efficient agents after depletion of the originally present dithiobisphenols, in the overstoichiometric phase of hydroperoxide decomposition. Calcium (II) salts may partially reduce the overall hydroperoxide decomposition efficiency of dithiobisphenols.     

高熔体强度聚丙烯及发泡珠粒的制备与研究

使用直接聚合法制备了具有宽分子量分布的高熔体强度聚丙烯。利用反应釜浸渍法,以上述高熔体强度聚丙烯为基础树脂可以制备聚丙烯发泡珠粒。利用扫描电子显微镜和熔体强度测试仪考察了聚丙烯发泡珠粒的制备工艺及基础树脂的熔体强度对泡孔结构的影响。结果表明,与普通商业化聚丙烯如T30S相比,较高的熔体强度有利于泡孔结构的控制。     

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.     

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.     

Mechanisms of antioxidant action: Chemical binding of a thiol antioxidant into polypropylene by means of uv irradiation

3,5-Di-t-butyl-4-hydroxybenzyl mercaptan (BHBM) became chemically combined to polypropylene to the extent of 68% of the antioxidant present when films containing BHBM were exposed to uv irradiation. In addition to the radical coupling reaction of the thiyl radical derived from BHBM with the polymer, a second technologically less useful process also occurs, leading to the formation of a derived stilbenequinone. The latter absorbs strongly both in the visible and in the near uv and consequently slows down the subsequent loss of the bound antioxidant from the polymer.