Polyethylene antioxidants

Keywords Polyethylene, antioxidants, vitamin E, irradiation, kinetic modeling... 

In certain brilliantine compositions, vegetable and animal oils are used as substitutes for mineral oil. In these systems, because of their potential for rancidity, antioxidants must be included. Other alternatives to mineral oils that have found utiHty in brilliantines are the polyethylene glycols which come in a variety of solubiHties and spreading properties. Use of these materials offers the advantage of chemical stabiHty to rancidity. Other additives found in brilliantines to improve their aesthetics include colorants, fragrance, medicated additives, lanolin, and fatty acid esters. 

Increasingly, plastics are being used as parenteral packaging (qv) materials. Plastics such as poly(vinyl chloride), polyethylene, and polypropylene are employed. However, plastics may contain various additives that could leach into the product, such as plasticizers (qv) and antioxidants. PermeabiUty of plastics to oxygen, carbon dioxide, and water vapor must be tested in the selection of plastic containers. Furthermore, the plastic should withstand sterilization. Flaking of plastic particles should not occur and clarity necessary for inspection should be present. 

Single-dose preparations intended for use in eye surgery do not contain excipient ingredients, in order to avoid tissue irritation. However, multiple-dose containers may require antioxidants (qv), antimicrobial preservatives, or buffers to maintain stabiHty and stefiHty. Such solutions are packaged in polyethylene flexible dropper units called droptainers or in glass dropper botdes. 

Antioxidants. The 1,2-dihydroquinolines have been used in a variety of ways as antioxidants (qv). For example, l,2-dihydro-2,2,4-trimethylquinoline along with its 6-decyl [81045-48-9] and 6-ethoxy [91-53-2] derivatives have been used as antio2onants (qv) and stabilizers (68). A polymer [26780-96-1] of l,2-dihydro-2,2,4-trimethylquinoline is used in resins, copolymers, lubricant oils, and synthetic fibers (69). These same compounds react with aldehydes and the products are useful as food antioxidants (70). A cross-linked polyethylene prepared with peroxides and other monomers in the presence of l,2-dihydro-6-ethoxyquinoline produces polymers with a chemically bonded antioxidant (71). 

Nearly all polymeric materials require the addition of antioxidants to retain physical properties and to ensure an adequate service life. The selection of an antioxidant or system of antioxidants is dependent upon the polymer and the anticipated end use. A product that will not be exposed to the elements for a long period of time such as polyethylene grocery bags does not need a long term stabilizer polyethylenes used to iasulate communication cable must be stabilized for many years of service. 

Polyolefins such as polyethylene and polypropylene contain only C—C and C—H bonds and may be considered as high molecular weight paraffins. Like the simpler paraffins they are somewhat inert and their major chemical reaction is substitution, e.g. halogenation. In addition the branched polyethylenes and the higher polyolefins contain tertiary carbon atoms which are reactive sites for oxidation. Because of this it is necessary to add antioxidants to stabilise the polymers against oxidation Some polyolefins may be cross-linked by peroxides. 

Figure 7.7. The synergism of sulphur antioxidants with carbon black as constrasted to the adverse effect shown with conventional antioxidants (in polyethylene)...

Antioxidants may be assessed in a variety of ways. For screening and for fundamental studies the induction period and rate of oxidation of petroleum fractions with and without antioxidants present provide useful model systems. Since the effect of oxidation differs from polymer to polymer it is important to evaluate the efficacy of the antioxidant with respect to some property seriously affected by oxidation. Thus for polyethylene it is common to study changes in flow properties and in power factor in polypropylene, flow properties and tendency to embrittlement in natural rubber vulcanisates, changes in tensile strength and tear strength. 

Oxidation of polyethylene with the formation of carbonyl groups can lead to a serious increase in power factor. Antioxidants are incorporated into compounds for electrical applications in order to reduce the effect. 

When polyethylene is to be used in long-term applications where a low power factor is to be maintained and/or where it is desired to provide thermal protection during processing, antioxidants are incorporated into the polymers. These were discussed extensively in Chapter 7 but a few particular points with regard to their use in polyethylene should be made. Although amines have been used widely in the past phenols are now used almost exclusively. 

Table 10.8 Comparison oE antioxidants in polyethylene in both the absence and presence of copper powder and carbon black (data based on ICI literature). Induction time assessed from oxygen uptake measurements using a Barcroft manometer...

Figure lO.U. Oxidation of polyethylene in air at 105°C, Effect of adding 0.1% antioxidant on power factor. A, blank. B, /V,/V -diphenyl-p-phenylenediamine. C, 4,4 -thiobis-(6-butyl-m-cresol). D, Nonox WSP. E, N./V -di-pl-naphthyl-p-phenylenediamine... 

Further variations in the properties of polyethylenes may be achieved by incorporating additives. These include rubber, antioxidants and glass fibres and their effects will be discussed further in Section 11.1.4. 

The electrical properties of polypropylene are very similar to those of high-density polyethylenes. In particular the power factor is critically dependent on the amount of catalyst residues in the polymer. Some typical properties are given in Table 11.3 but it should be noted that these properties are dependent on the antioxidant system employed as well as on the catalyst residues. 

Polypropylene differs from polyethylene in its chemical reactivity because of the presence of tertiary carbon atoms occurring alternately on the chain backbone. Of particular significance is the susceptibility of the polymer to oxidation at elevated temperatures. Some estimate of the difference between the two polymers can be obtained from Figure 1J.7, which compares- the rates of oxygen uptake of eaeh polymer at 93°C. Substantial improvements can be made by the inclusion of antioxidants and such additives are used in all commercial compounds. Whereas polyethylene cross-links on oxidation, polypropylene degrades to form lower molecular weight products. Similar effects are noted... 

Stabilisers. Stabilisers prevent deterioration of the polymer due to environmental factors. Antioxidants are added to ABS, polyethylene and polystyrene. Heat stabilisers are required in processing polyvinyl chloride. Stabilisers also prevent deterioration due to ultra-violet radiation. 

R. G. Lichtenthaler and F. Ranfelt, Determination of antioxidants and their transformation products in polyethylene by high-performance liquid chromatography , J. Chromatogr. 149 553-560 (1978). 

Antioxidant additive in the polyethylene resin. While such an additive can prevent oxidation, and thus odor, it also can contribute directly to the odor. If an antioxidant is needed, it must be FRA approved, should have a high melting point, and should be used at a minimum level consistent with the extrusion process. Catalyst residues and antioxidants present in polyethylene sometimes interact to form odorous products. 

In order to support and meet this demand, an all-around development has taken place on the material front too, be it an elastomer new-generation nanofiller, surface-modified or plasma-treated filler reinforcing materials like aramid, polyethylene naphthenate (PEN), and carbonfiber nitrosoamine-free vulcanization and vulcanizing agents antioxidants and antiozonents series of post-vulcanization stabUizers environment-friendly process oil, etc. 

Acid-treated clay catalyst Engelhard F-24 was found to be very effective for the alkylation of diphenylamine (DPA) with an olefin such as a-methyl styrene (AMS) to obtain a mixture of mono and dialkylated diphenylamines (Chitnis and Sharma, 1995). For example, alkylation of DPA with AMS produced a mixture of 4-(a,a-dimethyl benzyl) diphenylamine, i.e. monocumyl-diphenylamine (MCDPA) and 4,4 -bis(a,a-dimethylbenzyl) diphenylamine, i.e. dicumyldiphenylamine (DCDPA) (Eqn.(l 1)). The dialkylated diphenylamine, i.e. DCDPA, is indu.strially important as an antioxidant and heat stabilizer. DCDPA is reported to be an ideal antioxidant for many materials like polyethylene, polypropylene, polyether polyol, polyacetals, nylon 6, synthetic lubricants, hot melt adhesives, etc. 

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