Additives in polymers

Table 7.1 summarises the blooming expectancies of additives in polymer compounds but it should be stressed that there may be exceptions to these very general rules. 

The usual means of identifying and quantifying the level of these additives in polymer samples is performed by dissolution of the polymer in a solvent, followed by precipitation of the material. The additives in turn remain in the Supernatant liquid. The different solubilites of the additives, high reactivity, low stability, low concentrations and possible co-precipitation with the polymer may pose problems and lead to inconclusive results. Another sample pretreatment method is the use of Soxhlet extraction and reconcentration before analysis, although this method is very time consuming, and is still limited by solubility dependence. Other approaches include the use of supercritical fluids to extract the additives from the polymer and Subsequent analysis of the extracts by microcolumn LC (2). 

A multidimensional system using capillary SEC-GC-MS was used for the rapid identification of various polymer additives, including antioxidants, plasticizers, lubricants, flame retardants, waxes and UV stabilizers (12). This technique could be used for additives having broad functionalities and wide volatility ranges. The determination of the additives in polymers was carried out without performing any extensive manual sample pretreatment. In the first step, microcolumn SEC excludes the polymer matrix from the smaller-molecular-size additives. There is a minimal introduction of the polymer into the capillary GC column. Optimization of the pore sizes of the SEC packings was used to enhance the resolution between the polymer and its additives, and smaller pore sizes could be used to exclude more of the polymer... 

Additives In Polymers Industrial Analysis And Applications J. C. J. Bart 2005 John Wiley Sons, Ltd ISBN 0-470-85062-0... 

Critical expert forums for all aspects related to the analytics of additives in polymers are the ACS Analytical Division, SPE Polymer Analysis and Polymer Modifiers Additives Analysis Divisions or the German Arbeitskreis Polymeranalytik (cf. homepage DKI). 

As shown in Appendix II there is a multitude of books concerning various aspects of additives in polymers (either commercial information or technical/scientific principles). However, in the past, only a fairly restricted... 

Figure 1.4 Level of abstraction of analytical tools on additives in polymers with delimitations adopted in the text (shaded)...

Many polymer companies have not maintained a cadre of experts on the analysis of additives in polymers. Consequently, there is a need to train a new generation of people about additives and methods of deformulating them. Outsourcing of polymer/additive... 

Analytical techniques for the quantitative determination of additives in polymers generally fall into two classes indirect (or destructive) and direct (or nondestructive). Destructive methods require an irreversible alteration to the sample so that the additive can be removed from the plastic material for subsequent detention. This chapter separates the additive wheat from the polymer chaff , and deals with sample preparation techniques for indirect analysis. 

Various models of SFE have been published, which aim at understanding the kinetics of the processes. For many dynamic extractions of compounds from solid matrices, e.g. for additives in polymers, the analytes are present in small amounts in the matrix and during extraction their concentration in the SCF is well below the solubility limit. The rate of extraction is then not determined principally by solubility, but by the rate of mass transfer out of the matrix. Supercritical gas extraction usually falls very clearly into the class of purely diffusional operations. Gere et al. [285] have reported the physico-chemical principles that are the foundation of theory and practice of SCF analytical techniques. The authors stress in particular the use of intrinsic solubility parameters (such as the Hildebrand solubility parameter 5), in relation to the solubility of analytes in SCFs and optimisation of SFE conditions. 

As diffusion to the surface of a polymer is one of the limiting steps in extraction, the particle size or film thickness of a sample is also important [278,333,337-340]. With the typical diffusion coefficients of additives in polymers a particle diameter of about 0.3 mm is required for an extraction time of about 1000 s at 40 °C. An exception to this is the extraction of thin films and foams, for which the shortest dimension is small. It is not surprising that no more than 50 % of antioxidants could be extracted from PP pellets as opposed to 90 % recoveries from the same polymer extruded into film [341]. Grinding of the polymer is usually an essential step before extraction. Care should be taken to avoid loss of volatile additives owing to the heat generated in such processes. Therefore, cryogrind-ing is preferred. 

Applications The majority of SFE applications involves the extraction of dry solid matrices. Supercritical fluid extraction has demonstrated great utility for the extraction of organic analytes from a wide variety of solid matrices. The combination of fast extractions and easy solvent evaporation has resulted in numerous applications for SFE. Important areas of analytical SFE are environmental analysis (41 %), food analysis (38 %) and polymer characterisation (11%) [292], Determination of additives in polymers is considered attractive by SFE because (i) the SCF can more quickly permeate throughout the polymer matrix compared to conventional solvents, resulting in a rapid extraction (ii) the polymer matrix is (generally) not soluble in SCFs, so that polymer dissolution and subsequent precipitation are not necessary and (iii) organic solvents are not required, or are used only in very small quantities, reducing preparation time and disposal costs [359]. 

Applications Pressurised fluid extraction (ASE , ESE ) is still in its early stage of development, both for polymeric and other samples. At present, most applications are found in the environmental, food, pharmaceutical and nutraceutical areas. Few reports describe the application of PEE to the extraction of monomers, oligomers and additives from polymers and most work is very recent. An application note [488] has provided some guiding principles for ASE applied to additives in polymers, namely as follows ... 

Many SFC applications in the literature concern the analysis of UV-active additives in polymers and coatings after extraction [319-335], On-line SFE-SFC has also been used [319,321-325,333-335] (cf. Section 7.1.1.4). cSFC is often a matter of choice because every kind of polymer additive can be detected with FID [326,328,330,331,335-337], Some publications show interesting examples of pSFC with UV detection [329,332,337-339]. Figure 4.5 shows the pSFC separation developed for routine formulation control of... 

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]. 

Applications Applications of IC extend beyond the measurement of anions and cations that initially contributed to the success of the technique. Polar organic and inorganic species can also be measured. Ion chromatography can profitably be used for the analysis of ionic degradation products. For example, IC permits determination of the elemental composition of additives in polymers from the products of pyrolysis or oxidative thermal degradation. The lower detection limit for additives in polymers are 0.1% by PyGC... 

LDPE or HDPE extracts has been determined colorimet-rically at 430 nm by oxidation with H202 in the presence of H2S04 [66]. p-Phenylenediamine derivatives such as Flexzone 3C, used as antiozonants in rubber products, have been determined colorimetrically after oxidation to the corresponding Wurster salts [67]. A wide range of amine AOs in polyolefins has been determined by the p-nitroaniline spectrophotometric procedure [68]. Monoethanolamine (MEA) in a slip agent in PE film has been determined as a salicylaldehyde derivative by spectrophotometric quantification at 385 nm [69]. Table 5.6 contains additional examples of the use of 1JV/VIS spectrophotometry for the determination of additives in polymers. 

Composition and structure of newly developed additives are commonly examined by IR, NMR, MS and elemental analysis, e.g. recently developed higher MW antioxidants [115]. Infrared spectroscopy is also well suited to the direct verification of compound composition and quantitative determination of additives in polymers. Gray and Neri [116] have used Soxhlet... 

In principle, measurement of the phosphorescence characteristics of samples obtained after extraction of polymers with organic solvents may also yield useful information regarding the nature and concentration of the additives present. Parker and Hatchard [157] have examined the possibilities of phosphorescence measurements for V-phenyl-2-naphthylamine. Although it should be possible to determine various analytes simultaneously by correct choice of ex and em wavelengths and phosphorescence decay, no pertinent reports are available. Phosphorescence finds limited application for the direct determination of additives in polymers (without prior extraction). 

The application of partial relaxation FTNMR in the determination of unreacted monomers, solvent, water, and additives in polymers, polymer degradation, and functional group and chain structure characterisation has been reviewed [255]. Hummel [95] underestimates the contribution of NMR to polymer/additive analysis. 

Mass spectrometry has a number of features and advantages that can make it a very valuable tool for the identification of organic additives in polymers (Table 6.2). The range of products that can be studied is limited by the ionisation method used and the performance of the mass spectrometer. Mass spectrometry... 

Despite these numerous advantages, mass spectrometry has often been used more as an auxiliary, rather than a primary, identification method for additives in polymers, paints, coatings, etc. Nevertheless, mass spectrometry can be used for direct determination of the composition of unknown admixtures. More difficult is the MS examination of substances of low volatility, as the sample has to be introduced in the gas phase. This requires volatilisation, which often leads to fragmentation. 

Application of mass spectrometry to analysis of additives in polymers is mainly used as a qualitative tool and relates to three main areas ... 

Applications Mass spectrometry has often been used more as an auxiliary, rather than a primary, identification method for additives in polymers. Table 6.5 shows the suitability of various ionisation modes for oligomer (and polymer) analysis. 

Many additives fragment quite extensively with FAB. The observation of molecular ion and many fragment ions for each additive makes the determination of the number of additives in the extract difficult if not impossible. Moreover, due to the matrix effect , not all the additives in polymer extracts are detected under FAB. 

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