Melt stabilisation of Phillips type polyethylene, Part I: The role of phenolic and phosphorous antioxidants

The role of a phenolic and three phosphorous (phosphite, phosphonite and phosphine) antioxidants in the melt stabilisation of polyethylene was studied in a Phillips type polyethylene by multiple extrusions. The polyethylene was stabilised with a single antioxidant at 700 ppm and with phenolic/phosphorous antioxidant combinations containing 700 ppm of each component. The functional groups (methyl, vinyl, vinylidene, trans-vinylene and carbonyl) of polyethylene and the residual amount of phosphorous antioxidants were analysed quantitatively by FT-IR methods developed in our laboratory. The rheological characteristics, the colour and the residual thermo-oxidative stability of the polymer were determined and compared. Blown films were prepared and their mechanical strength measured by the Elmendorf and Dart-drop tests. The comparison of the different characteristics revealed that the chemical reactions taking place during the first processing of the nascent polymer powder, as well as the chemical composition of the antioxidants determine the reactions taking place in further processing operations. The changes in the characteristics of stabilised polyethylene during processing are controlled by the phosphorous stabiliser. The effect and final result depend on the chemical structure of the given antioxidant. The phenolic antioxidant itself does not hinder the formation of long chain branches. It reduces the rate of oxidation of the various phosphorous stabilisers, but does not modify the mechanism of stabilisation of the phosphonite and the phosphine. The reactions of the phosphite are significantly modified by the presence of a phenolic antioxidant.     

Melt stabilisation of Phillips type polyethylene, Part III: Correlation of film strength with the rheological characteristics of the polymer

Different aspects of the melt stabilising effect of various antioxidant packages were studied in a Phillips type polyethylene in the work described in this series of papers. The polymer was stabilised with various combinations of a phenolic antioxidant with phosphite, phosphonite, and phosphine type secondary antioxidants and processed by multiple extrusions followed by film blowing. After determining the role of the antioxidants in the melt stabilisation process and the effect of antioxidant consumption on polymer properties the correlation of the rheological characteristics of polymer with the tear and impact strengths of films is discussed in this paper. The Elmendorf tear strength of films measured in transverse direction, which is sensitive to long chain branching, correlates closely with viscous compliance determined by creep recovery experiments and the ratio of melt flow indices measured at high and low loads. The relationships are independent of the type and amount of antioxidant added. This makes possible the prediction of the effect of various antioxidant packages on film properties on the basis of rheological measurements. The correlation between the dart drop impact strength of the films and the rheological characteristics of the polymer is less reliable.     

Efficiency and mechanism of phosphorous antioxidants in Phillips type polyethylene

The stabilising efficiency of three phosphorous secondary antioxidants of different chemical structures (phosphonite, phosphite and phosphine) was compared in a Phillips type polyethylene. The polymer was processed by six consecutive extrusions in the presence of 700 ppm primary antioxidant and 700 ppm phosphorous compound. The consumption of the secondary antioxidant was followed quantitatively by Fourier transform infrared (FTIR) spectroscopy. The properties of the polymer were characterised by FTIR spectroscopy, colour and rheological measurements, as well as by the determination of its residual thermo-oxidative stability. The results of the experiments proved that the chemical reactions occurring in the first extrusion of the polymer are different from those taking place in the further processing operations. The rate of antioxidant consumption and the chemical reactions of the polymer are strongly affected by the type of the phosphorous secondary antioxidant. The analysis of the results indicated that the three stabilisers must act according to different mechanisms. The investigated phosphine showed the best melt stabilising efficiency, while phosphonite was found to protect the polymer most effectively from discoloration.     

Stabilisation of metallocene ethylene-1-octene copolymers during multiple extrusions

The melt stabilising efficiency of antioxidants with different structures based on hindered phenols, phosphite esters, phosphonite and a lactone was examined during multi-pass extrusions at 265 °C in three metallocene ethylene-1-octene copolymers (m-LLDPE) having different extent of short chain branching (SCB) and one Zeigler copolymer (z-LLDPE) containing the same level of SCB corresponding to one of the m-LLDPE polymers. The effect of the different antioxidants, when used separately and in combination, was investigated by characterising the changes in the polymer's rheological behaviour, colour formation and structural changes based on unsaturated groups and carbonyl content during five multi-pass extrusions. The results showed that all stabilisation systems examined offered higher efficiency in the metallocene polymers compared to the Zeigler. The effect of the extent of SCB in the metallocene polymers on the stabilising efficacy of the antioxidant systems was also examined, and it was shown that it had a significant effect, with both single and combinations of antioxidants giving higher efficiency in the m-LLDPE polymer containing higher extent of SCB. The presence of the lactone HP136 in mixtures containing hindered phenol-phosphite antioxidant systems gave a higher melt stabilisation efficiency than in its absence and this has been attributed to a co-operative antioxidant reaction steps that take place between the antioxidants resulting in the possible regeneration of the lactone antioxidant through a redox reaction. In all the metallocene PE polymers examined, the biologically hindered phenol, Irganox E, was shown to be more effective than the conventionally hindered phenol Irganox 1076, when examined alone or in combination with phosphite esters.     

BREAKTHROUGH CHEMISTRY FOR PROCESSING STABILIZATION OF POLYPROPYLENE

Traditional stabilization systems for polypropylene are typically based on a binary combination of a phenolic antioxidant and a phosphorus based melt processing stabilizer. The phenolic antioxidant provides melt processing stability as a hydrogen atom donor and free radical scavenger; it also provides the polymer with some desired level of short-term or long-term thermal stability, simply for storage or throughout the lifetime of the final article. The phosphorus based melt processing stabilizer, usually a phosphite or phosphonite, functions as a hydroperoxide decomposer above the melting point of the polymer, during melt compounding and processing. Both chemistries work together synergistically to help maintain the original molecular architecture of the polymer.

Recently, a new class of additives, 3-aryl-benzofuranones (lactones) has been introduced and adopted commercially. Lactones are highly efficient at scavenging both carbon and oxygen centered radicals during melt processing of polyolefins. Investigations have been underway to examine the impact of low concentrations of lactone in regard to enhancing the performance of traditional stabilization systems. The presumed stabilization mechanism of a lactone and the optimum composition of ternary stabilizer blends for polypropylene are discussed.     

High temperature reactions of an aryl-alkyl phosphine, an exceptionally efficient melt stabiliser for polyethylene

Bis(diphenylphosphino)-2,2-dimethylpropane (PMP) is a highly efficient melt stabiliser of polyethylene. This aryl-alkyl phosphine hinders the degradation of the polymer during processing even in small concentrations and in combination with a phenolic antioxidant its consumption rate is considerably slower than that of phosphites and phosphonites. In this study the reactions of PMP were studied at temperatures corresponding to those used for the processing of polyethylene in order to explore the processing stabilisation mechanism of this additive. Thermal and thermo-oxidative stability were determined by DSC and TGA, respectively by heating PMP in argon and oxygen at 200 and 240 °C. Reactions with peroxy, carbon-centred and oxy radicals, as well as with hydroperoxide were investigated at 200 °C. Reaction products were identified by FT-IR and solution-state NMR spectroscopy. The results revealed that the phosphine studied has sufficient thermal- and thermo-oxidative stability under the processing conditions of polyethylene. It oxidises easily with any oxidising agent including molecular oxygen of air. Consequently, PMP does not only decompose hydroperoxide groups and react with oxy macroradicals during the processing of polyethylene, as claimed by most references on phosphorous antioxidants, but it can also hinder the formation of peroxy macroradicals, i.e., the initiation reaction of thermo-oxidative degradation.     

Extraction and quantification of antioxidants from low-density polyethylene by microwave energy and liquid chromatography

In this paper a experimental design is applied to optimize the quantification of hindered phenol Irganox 1076, phosphite antioxidant Irgafos 168 and their oxidized product tri[2,4-di-tert-butylphenyl]phosphate from low-density polyethylene (LDPE). The developed analytical method consists of two steps: microwave-assisted extraction and reversed-phase liquid chromatography (LC) coupled with ultraviolet diode-array detector. A Plackett-Burman design was carried out in order to find the significant experimental parameters affecting the antioxidants extraction by microwave energy. These parameters were subsequently optimized by a central composite design. The performed method allows extracting the studied antioxidants at low temperature in a short time without degradation of phosphite antioxidant Irgafos 168.     

Deterioration of polyethylene pipes exposed to water containing chlorine dioxide

Chlorine species used as disinfectants in tap water have a deteriorating effect on many materials including polyethylene. There are only very few scientific reports on the effect on polyethylene pipes of water containing chlorine dioxide. Medium-density polyethylene pipes stabilized with hindered phenol and phosphite antioxidants were pressure tested with water containing 4 ppm chlorine dioxide at 90 °C and pH = 6.8 as internal medium. The stabilizers were rapidly consumed towards the inner pipe wall; the rate of consumption was four times greater than in chlorinated water (4 ppm, pH = 6.8) at the same temperature. The depletion of stabilizer occurred far into the pipe wall. A supplementary study on a polymer analogue (squalane) containing the same stabilizer package showed that the consumption of the phenolic antioxidant was 2.5 times faster when exposed water containing chlorine dioxide than on exposure to chlorinated water. The subsequent polymer degradation was an immediate surface reaction. It was confirmed by differential scanning calorimetry, infrared spectroscopy and size exclusion chromatography that in the surface layer which came into contact with the oxidising medium, the amorphous component of the polymer was heavily oxidized leaving a highly crystalline powder with many carboxylic acid chain ends in extended and once-folded chains. Scanning electron microscopy showed that propagation of cracks through the pipe wall was assisted by polymer degradation.     

Reaction mechanism and rheological properties of polypropylene irradiated under various atmospheres

It is well-known that the melt-strength properties of a polymer increases with molecular weight and with long chain branching due to the increase in the entanglement level. This study is a contribution for the understanding of the following points: — the role of branching, crosslinking and degradation on melt strength properties; — the mechanism and the kinetics of PP irradiation with time of irradiation and the importance of double bond formation.

The results showed that degradation was the major reaction in the initial step of irradiation no matter the atmosphere and or antioxidant. However, double bond formation increased the production of branching and crosslinking reactions. Double bond formation had no effect on the crystallization kinetics, on the other hand, long chain branching had a marked effect on the crystallization temperature.     

Hydrolytic stability and hydrolysis reaction mechanism of bis(2,4-di-tert-butyl)pentaerythritol diphosphite (Alkanox P-24)

The excellent processing stability afforded by the commercial phosphate antioxidant, Alkanox P-24 is well known in the literature. However, it is known that Alkanox P-24 is hydrolytically unstable. Enhancement of its hydrolytic stability is therefore a key objective in this work and some binary and ternary blends were developed using other additives that are often used for polymer stabilisation, including the primary antioxidant tetrakis[methylene-3-(3′,5′-di-tert-butyl-4-hydroxyhyphenyl)propionate]methane (Anox 20), acid scavengers calcium stearate (DW) and the hydrotalcite like compound (DHT-4A). An improvement in the hydrolytic stability of Alkanox P-24 was found when it was blended with these additives. A comparison with different physical forms of blends (traditional powders versus recently introduced Non-Dust Blends) was undertaken. Better performance was observed with NDB relative to the free flowing mixed powders. Spectroscopic studies (FTIR, and mass spectrometry) were also undertaken to elucidate the hydrolysis mechanism of the phosphite antioxidant Alkanox P-24. Mechanistic schemes were devised and interpreted. Hydrolysis products of Alkanox P-24 are believed to be involved in the mechanism of stabilisation. In this programme of work, the role of the hydrolysis products was investigated by controlled thermomechanical degradation in an extruder and stabilisation activity evaluated by following the yellowness index and the melt flow rate. The influence of partially hydrolysed Alkanox P-24 on polymer processing was studied. It was found that some active hydrolysis products showed significant antioxidant activity and retarded polymer degradation during processing. Mechanisms for their formation and identity are elucidated.     

Reactions of antioxidants with molecular oxygen. Part III: Influence of phenolic stabiliser structures on their oxidation in an inert matrix

The oxidation of five different phenolic antioxidants in inert substrates has been investigated varying the temperature and oxygen pressure conditions. The stabiliser consumption in this reaction has been quantified by steric exclusion chromatography. The tendency of the variation of the residual antioxidant concentration with exposure time in the presence of oxygen shows a simple apparent first order process in all cases. The kinetic parameters were determined applying this simple kinetic model. The influence of structural characteristics of stabilisers under study on kinetic parameters of the direct reaction with the oxygen has been analysed. On the other hand, the information obtained about reaction products generated for each antioxidant helped us to explain the results obtained.     

聚合物长支链的流变学表征方法

在聚合物中引入长支链能够显著地提高熔体强度,改善聚合物在拉伸流场中的加工性能,因此对长支链的表征显得十分重要。流变学被证实是一种非常有效且敏感的表征手段,近来受到普遍关注。本文总结了近年来国内外关于长支链聚合物流变学表征研究的最新进展,比较了不同类型流场下对长支链的流变学判断方法,尽量结合高分子链段分子结构解释了各种表征现象的含义,阐述了借助流变学对大分子拓扑结构的定性表征以及对长支链含量的定量表征方面的应用。     

Determination of antioxidants by solid-phase extraction method in aqueous food simulants

An analytical method for the determination of specific migration levels of phenolic antioxidants and one phosphite antioxidant in the aqueous food simulants established by European legislation has been developed. This method involves solid-phase extraction (SPE) of the antioxidants with silica C₁₈ cartridge and their determination by liquid chromatography (LC) with diode-array detection. The achieved results in the studies of elution volume determination, breakthrough volume and accuracy are showed. Recoveries in the range of 78–104% and a relative standard deviation between 2.0 and 7.7% have been achieved.     

Effect of Antioxidants on the Stability of Poly(ether ether ketone) and the Investigation on the Effect Mechanism of the Antioxidants to Poly(ether ether ketone)

Two types of antioxidants (a phenolic antioxidant and a phosphorous antioxidant) were used to improve the stability of poly (ether ether ketone) (PEEK). To evaluate the effect of the antioxidants on the properties of PEEK and the stabilization mechanism, some characterization methods were carried out, such as rheometer, TGA, and electron spin resonance (ESR). The results indicated that the efficiency of the phosphorous antioxidant (DS) in improving the stability of PEEK was better than that of the phenolic antioxidant (DN) and the thermal stability of PEEK sample containing 0.07 wt% DS was the best among all samples due to the decrease of the free radicals density, as proven by ESR measurement. The possible stabilization mechanism of the antioxidants to PEEK was proposed to reveal the reason that caused the different performances of the two types of antioxidants to PEEK.     

Assessing the long-term performance of polyethylene stabilised with phenolic antioxidants exposed to water containing chlorine dioxide

The addition of chlorine dioxide disinfectant to tap water prevents the spread of infection but has a serious drawback in that it degrades materials used in piping, including pipes made of polyethylene. Efficient methods are required to assess the long-term performance of different combinations of antioxidants and polyethylene grades. We have previously presented a screening method which exposes solutions of phenolic antioxidants in squalane (a liquid, low molar mass analogue of polyethylene) to 70 °C water containing either chlorine dioxide or chlorine. This method assesses the stability of the antioxidants towards these aqueous chlorinated media by determining the oxidation induction time through differential scanning calorimetry. The same experimental set-up with two modifications was used in developing a new method. A 0.3 mm thick polyethylene tape replaced the squalane phase and the supply of fresh water containing chlorine dioxide (10 ppm at pH = 6.8) was continuous; this required minimum attention from the operator over the longer exposure time periods used. Tapes of medium-density polyethylene containing 0.1 wt.% of six different phenolic antioxidants were studied. A linear relationship was established between the times to reach antioxidant depletion in the polyethylene tape samples and the times in the squalane samples (with the same antioxidants at the same concentration). A linear relationship was also found between the initial antioxidant consumption rates in polyethylene and squalane. Infrared spectroscopy and scanning electron microscopy of drawn samples revealed the onset of surface oxidation and surface embrittlement in tape samples exposed beyond the time for antioxidant depletion.     

Establishing Relationship between Vitamins,Total Phenolic and Total Flavonoid Content and Antioxidant Activities in Various Honey Types

Honey is a well-known natural sweetener and is rich in natural antioxidants that prevent the occurrence of oxidative stress, which is responsible for many human diseases. Some of the biochemical compounds in honey that contribute to this property are vitamins and phenolic compounds such as phenolic acids and flavonoids. However, the extent to which these molecules contribute towards the antioxidant capacity in vitro is inconsistently reported, especially with the different analytical methods used, as well as other extrinsic factors that influence these molecules’ availability. Therefore, by reviewing recently published works correlating the vitamin, total phenolic, and flavonoid content in honey with its antioxidant activities in vitro, this paper will establish a relationship between these parameters. Based on the literature, vitamins do not contribute to honey’s antioxidant capacity; however, the content of phenolic acids and flavonoids has an impact on honey’s antioxidant activity.     

P-C Bond formation via direct and three-component conjugate addition catalyzed by 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD)

The direct addition of P(O)-H bonds (dialkyl phosphites and diphenyl phosphonite) across various activated alkenes was catalyzed effectively by 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD). This is a mild, rapid and efficient protocol to generate P-C bonds. This simple procedure allows a series of dialkyl alkylphosphonates and trisubstituted phosphine oxides to be prepared in high yields. Further investigation resulted in a convenient one-pot, three-component reaction containing diphenyl phosphonite, malononitrile and an aldehyde.     

Review on the production process and uses of controlled rheology polypropylene—Gamma radiation versus electron beam processing

Controlled rheology polypropylene grades are established commodities in the polymer processing market. However, new types, mainly the so-called high melt strength polypropylene (HMSPP) grades, are being introduced in the last two decades and radiation processing has played an important role. The melt strength properties of a polymer increases with molecular weight and with long-chain branching due to the increase in the entanglement level. As polypropylene (PP) is a linear polymer, the way to improve its elongational viscosity is by the production of a bi-modal polymer. Basell's patents claim the production of long-chain branching on PP by irradiating with electrons under oxygen free atmosphere, followed by two heating steps to allow radical recombination and annihilation reaction. Some other companies have issued patents using electron beam processing, but so far there is no actual production other than the Basell one. As a result of a research joint effort, IPEN, BRASKEM (the biggest Brazilian polymer producer) and EMBRARAD (the major Brazilian radiation processing center) developed a new process to produce HMSPP based on gamma processing. This paper will address some characteristics of each technology and the main industrial opportunities.     

Organic-Inorganic Hybrid Fillers for The Controlled Release of Antioxidants

the barrier provided by the inorganic domains of organic-inorganic hybrids towards the absorption of low molecular weight penetrants was used in this study as a basis for the development of systems capable of desorbing antioxidants at a slow rate. Polyethyleneoxide-silica hybrids, compatibilized with glycidoxylpropyltrimethoxysilane, were used as carriers of conventional stabilizers for polymers, respectively two phenolic antioxidants and one hindered aromatic diamine system. Ternary phase diagrams were produced in order to determine the “compatibile compositions” using DSC to measure changes in melting point and enthalpy of the antioxidant and polyethylene oxide (PEO). A compatible composition of PEO-silica-BHT (tert. butyl hydroxyl toluene) was used to produce a filler, which was pressed on the form of a fine powder between two polyamide-6 films and subsequently sandwiched with further seven layers of fresh films. The multiple-film stack was aged first in an air circulated oven at 60 °C for 360 days and then for further 475 days at ambient atmospheric conditions. The concentration of carbonyl groups in the aged films was monitored by ATR-IR spectroscopy. A sigmoidal increase was found for the amount of new carbonyl groups formed, starting from the inside layer nearest to the source of antioxidant. This confirms that the antioxidant has diffused from the filler into the surrounding polymer matrix and has reduced the rate of evolution of carbonyl groups resulting from oxidative degradation reactions.     

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.