Plastics additives, analysis

D.O. Hummel, Atlas of Plastics Additives Analysis by Spectro-metric Methods, Springer-Verlag, Berlin (2002). 

Apart from routine quality control actions, additive analysis is often called upon in relation to testing additive effectiveness as well as in connection with food packaging and medical plastics, where the identities and levels of potentially toxic substances must be accurately known and controlled. Food contact plastics are regulated by maximum concentrations allowable in the plastic, which applies to residual monomers and processing aids as well as additives [64-66]. Analytical measurements provide not only a method of quality control but also a means of establishing the loss of stabilisers as a function of material processing and product ageing. 

J.W. Gooch, Analysis and Deformulation of Polymeric Materials, Paints, Plastics, Additives and Inks, Plenum Press, New York, NY (1997). 

Applications Conventional TLC was the most successful separation technique in the 1960s and early 1970s for identification of components in plastics. Amos [409] has published a comprehensive review on the use of TLC for various additive types (antioxidants, stabilisers, plasticisers, curing agents, antistatic agents, peroxides) in polymers and rubber vulcanisates (1973 status). More recently, Freitag [429] has reviewed TLC applications in additive analysis. TLC has been extensively applied to the determination of additives in polymer extracts [444,445]. 

Howard [772] has been amongst the first to show the usefulness of conventional SEC for polymer/additive systems. Coupek el al. [773] have also reported results with this technique in an early stage their work was limited to synthetic mixtures of additives. The use of open-column SEC in the analysis of plastics additives has been reported [774], Qualitative analysis of additives has been performed by stopped-flow SEC with IR detection [775]. Polypropylene oligomers were isolated from a PP/(Irganox 1010, Irgafos 168, DBS) matrix by dissolution (toluene)/precipitation (methanol) and Soxhlet... 

For more extensive references on the use of IR techniques the reader is referred to previous compilations [41,42,44]. The application of FUR spectroscopy to the analysis of plastic additives has extensively been reviewed [95]. 

NMR spectroscopy is most effective in qualitative analysis when the samples examinated are substantially pure compounds and has been used to confirm the theoretically predicted low-energy conformations of the Af-acylated hindered amine light stabiliser Tinuvin 440 [210]. Trace amounts of PDMS (quantification limit 0.1 ppm) in plastic additives, dyes and pigments were determined by 111 NMR after Soxhlet extraction [211]. ll NMR was also used for the detection of octadecanol, an impurity in Irganox PS 802 (3,3 -dioctadecyl thiodipropionate). NMR has identified the nature of a supposedly UV stabiliser of empirical formula C17H18N3CIO [44] (Scheme 5.2). 

FD-MS is also an effective analytical method for direct analysis of many rubber and plastic additives. Lattimer and Welch [113,114] showed that FD-MS gives excellent molecular ion spectra for a variety of polymer additives, including rubber accelerators (dithiocar-bamates, guanidines, benzothiazyl, and thiuram derivatives), antioxidants (hindered phenols, aromatic amines), p-phcnylenediamine-based antiozonants, processing oils and phthalate plasticisers. Alkylphenol ethoxylate surfactants have been characterised by FD-MS [115]. Jack-son et al. [116] analysed some plastic additives (hindered phenol AOs and benzotriazole UVA) by FD-MS. Reaction products of a p-phenylenediaminc antiozonant and d.v-9-lricoscnc (a model olefin) were assessed by FD-MS [117],... 

The additive analysis reported has been largely confined to conventional polymers (polyolefins, polycondensates, PS, PVC, etc.) Very little work, if any, has been reported on advanced engineering plastics. Similarly, also relatively little research activity has focused on additives in acrylics or blends. 

J.C.J. Bart, Chapter 4 in Plastic Additives, Advanced Industrial Analysis, IOS Press, Amsterdam, 2006. 

In polymer applications derivatives of oils and fats, such as epoxides, polyols and dimerizations products based on unsaturated fatty acids, are used as plastic additives or components for composites or polymers like polyamides and polyurethanes. In the lubricant sector oleochemically-based fatty acid esters have proved to be powerful alternatives to conventional mineral oil products. For home and personal care applications a wide range of products, such as surfactants, emulsifiers, emollients and waxes, based on vegetable oil derivatives has provided extraordinary performance benefits to the end-customer. Selected products, such as the anionic surfactant fatty alcohol sulfate have been investigated thoroughly with regard to their environmental impact compared with petrochemical based products by life-cycle analysis. Other product examples include carbohydrate-based surfactants as well as oleochemical based emulsifiers, waxes and emollients. 

In relation to sample preparation, Raman spectra can be obtained from pure complexes in the bulk state, seeing that for better performance the careful grinding of samples is required. Contrary to FTIR spectroscopy, where samples are mixed with mineral oil (Nujol) or KBr pellets, in Raman spectroscopy a pure substance is used. For this reason, the Raman spectroscopy is called a nondestructive measurement method. Additionally, analysis can be carried out through many containers such as glass, Pyrex reaction vessels, plastic containers, and so on. 

Wang, F.C. Polymer additive analysis by pyrolysis-gas chromatography. I. Plasticizers. J. Chromatogr. A 2000, 883, 199 - 210. 

The emphasis of this work is on the analysis of plastic additives through gas chromatography/mass spectrometry (GC/MS). GC/MS systems are a common analytical tool in quality control and analytical service laboratories and electron impact (El) mass spectra are recognized as reliable data for the identification of organic compounds. Traditional methods have employed a flame ionization detector (FID) with identifications based solely on GC retention time data. These methods lack the specificity necessary to distinguish between components attributable to the sample matrix or the additive(s). 

Freitag, W., Analysis of Additives in Plastics Additives, 4th Edition Edited by R. Gachter and H. Muller, Hanser Publishers, Munich 1993. 

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