Polymer extract analysis

In this context, liquid specimens are polymers dissolved in solvent, in dispersion, or of very low molecular weight. The specimen may contain pigments and additives. If the specimen contains obvious colour and turbidity, then it must be prepared for complete 

For the purpose of IR analysis, in order to establish the nature of the polymer matrix, the sample is pressed 

H3PO4 is being used for transamidation in such a case XRF determines higher phosphorous concentrations than justified on the basis of the phosphite additives. Ion chromatography may then be required. 

To assure consistency and speed in multidisciplinary structure analysis of low-MW compounds involving various techniques (IR, NMR, MS, etc.) most industrial laboratories use a Standard Operating Procedure (SOP). In such schemes IR analysis is frequently used as a cheap filter for a quick starting control and as a means for verification. As IR detects only structural units identification of an unknown compound on the basis of IR is difficult. Mass spectrometry is used as the prime identification tool and is especially important in the determination of the exact mass and gross formulae. While structural prognostication on the basis of MS is difficult for the non-expert, a posteriori interpretation is quite feasible. H NMR is both easy and cheap, however requires greater sample quantities than either 

IR or MS and does not easily distinguish between a monomer and a dimer. NMR is found to be most precious for the identification of P-containing additives. It should be realised that high investments are needed for a universal artificial intelligence structural identification software package based on NMR, MS and IR (Chemical Concepts/Spec Info). 

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Several qualifying features for polymer extract analysis are summarised in Table 2.11. Quantitative separation of polymer and (thermolabile and/or volatile) additives without decomposition of the analyte(s) is difficult for thermoplasts, but even more difficult for... 

Preinjection sample preparation is not a chromatographic issue per se. Nevertheless, it is an important consideration in the successful application of a complete analytical process. Nerin et al. reviewed sample treatment techniques applicable to polymer extract analysis, including headspace methods, supercritical fluid extraction, and solid phase microextraction. 

Table 1.13, which lists the main techniques used for polymer/additive analysis, allows some interesting observations. Classical extraction methods still score very high amongst sample preparation techniques on the other hand, not unexpectedly, inorganic analysis methods are not in frequent use for separation purposes... 

Polymer/additive analysis then usually proceeds by separation of polymer and additives (cf. Scheme 2.12) using one out of many solvent extraction techniques (cf. Chapter 3). After extraction the residue is pressed into a thin film to verify that all extractables have been removed. UV spectroscopy is used for verification of the presence of components with a chromophoric moiety (phenolic antioxidants and/or UV absorbers) and IR spectroscopy to verify the absence of IR bands extraneous to the polymer. The XRF results before and after extraction are compared, especially when the elemental analysis does not comply with the preliminary indications of the nature of the additive package. This may occur for example in PA6/PA6.6 blends where... 

Recent attention has focused on MS for the direct analysis of polymer extracts, using soft ionisation sources to provide enhanced molecular ion signals and less fragment ions, thereby facilitating spectral interpretation. The direct MS analysis of polymer extracts has been accomplished using fast atom bombardment (FAB) [97,98], laser desorption (LD) [97,99], field desorption (FD) [100] and chemical ionisation (Cl) [100]. 

Alternative approaches consist in heat extraction by means of thermal analysis, thermal volatilisation and (laser) desorption techniques, or pyrolysis. In most cases mass spectrometric detection modes are used. Early MS work has focused on thermal desorption of the additives from the bulk polymer, followed by electron impact ionisation (El) [98,100], Cl [100,107] and field ionisation (FI) [100]. These methods are limited in that the polymer additives must be both stable and volatile at the higher temperatures, which is not always the case since many additives are thermally labile. More recently, soft ionisation methods have been applied to the analysis of additives from bulk polymeric material. These ionisation methods include FAB [100] and LD [97,108], which may provide qualitative information with minimal sample pretreatment. A comparison with FAB [97] has shown that LD Fourier transform ion cyclotron resonance (LD-FTTCR) is superior for polymer additive identification by giving less molecular ion fragmentation. While PyGC-MS is a much-used tool for the analysis of rubber compounds (both for the characterisation of the polymer and additives), as shown in Section 2.2, its usefulness for the in situ in-polymer additive analysis is equally acknowledged. 

While most polymer/additive analysis procedures are based on solvent or heat extraction, dissolution/precipita-tion, digestions or nondestructive techniques generally suitable for various additive classes and polymer matrices, a few class-selective procedures have been described which are based on specific chemical reactions. These wet chemical techniques are to be considered as isolated cases with great specificity. 

For polymer/additive analysis complete dissolution is not a prerequisite. Rather, the solvent should at least swell the polymer by diffusion, which allows the physically blended additives to dissolve. True dissolution occurs predominantly when polymer chain lengths are small, on the order of 5000-10 000 Da. Solvent choice for dissolution or extraction should take into account restrictions imposed by further analysis steps (compatibility with chromatographic and/or spectroscopic requirements). When microwave extraction of additives from a polymer is followed by HPLC analysis, the solvent must be compatible with the HPLC mobile phase so that solvent exchange is not required before analysis. 

It can be shown that multistep extraction is advisable, i.e. it is always better to use several small portions of solvent (e.g. 5 x 20 cm3) to extract a sample than to extract with one large portion (e.g. 1 x 100 cm3) [77]. As mentioned already, for general purposes a recovery of greater than 90% is usually considered acceptable in polymer/additive analysis no analytical recovery is required. A flow-chart for LSE is available [3]. 

Table 3.4 summarises the main characteristics of a variety of sample preparation modes for in-polymer additive analysis. Table 3.5 is a short literature evaluation of various extraction techniques. Majors [91] has recently reviewed the changing role of extraction in preparation of solid samples. Vandenburg and Clifford [4] and others [6,91-95] have reviewed several sample preparation techniques, including polymer dissolution, LSE and SEE, microwave dissolution, ultra-sonication and accelerated solvent extraction. 

Applications Shake-flask extraction nowadays finds only limited application in polymer/additive analysis. Carlson et al. [108] used this technique to extract antioxidants from rubber vulcanisates for identification purposes (NMR, IR, MS). Wrist-action shaking at room temperature was also used as the sample preparation step for the UV and IR determination of Ionol CP, Santonox R and oleamide extracted from pelletised polyethylene using different solvents [78]. BHT could be extracted in 98 % yield from powdered PP by shaking at room temperature for 30 min with carbon disulfide. 

Some typical applications in SFE of polymer/additive analysis are illustrated below. Hunt et al. [333] found that supercritical extraction of DIOP and Topanol CA from ground PVC increased with temperature up to 90 °C at 45 MPa, then levelled off, presumably as solubility became the limiting factor. The extraction of DOP and DBP plasticisers from PVC by scC02 at 52 MPa increased from 50 to 80 °C, when extraction was almost complete in 25 min [336]. At 70 °C the amount extracted increased from 79 to 95 % for pressures from 22 to 60 MPa. SFE has the potential to shorten extraction times for traces (<20ppm) of additives (DBP and DOP) in flexible PVC formulations with similar or even better extraction efficiencies compared with traditional LSE techniques [384]. Marin et al. [336] have used off-line SFE-GC to determine the detection limits for DBP and DOP in flexible PVC. The method developed was compared with Soxhlet liquid extraction. At such low additive concentrations a maximum efficiency in the extractive process and an adequate separative system are needed to avoid interferences with other components that are present at high concentrations in the PVC formulations, such as DINP. Results obtained... 

The popularity of MAE methods for in-polymer additive analysis is reflected in a limited list of reported applications. This is both on account of the former lack of dedicated microwave equipment designed specially for small analytical samples and the relatively recent commercial introduction of the technique. Microwave extraction for analytical purposes is a relatively new growth area [441]. 

Applications Dissolution/reprecipitation is claimed to be the most widespread approach to polymer/additive analysis [603], but recent round-robins cast some doubt on this statement. Dissolution appears to be practised much less than LSEs. However, in cases where exhaustive extraction is difficult, e.g. for polyolefins containing high-MW (polymeric) additives, a dissolution/precipitation method is preferred. 

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]. 

Major applications of modern TLC comprise various sample types biomedical, pharmaceutical, forensic, clinical, biological, environmental and industrial (product uniformity, impurity determination, surfactants, synthetic dyes) the technique is also frequently used in food science (some 10% of published papers) [446], Although polymer/additive analysis takes up a small share, it is apparent from deformulation schemes presented in Chapter 2 that (HP)TLC plays an appreciable role in industrial problem solving even though this is not reflected in a flood of scientific papers. TLC is not only useful for polymer additive extracts but in particular for direct separations based on dissolutions. 

Applications Open-column chromatography was used for polymer/additive analysis mainly in the 1950-1970 period (cf. Vimalasiri et al. [160]). Examples are the application of CC to styrene-butadiene copoly-mer/(additives, low-MW compounds) [530] and rubbers accelerators, antioxidants) [531]. Column chromatography of nine plasticisers in PVC with various elution solvents has been reported [44], as well as the separation of CHCI3 solvent extracts of PE/(BHT, Santonox R) on an alumina column [532]. Similarly, Santonox R and Ionol CP were easily separated using benzene and Topanol CA and dilaurylthiodipropionate using cyclohexane ethyl acetate (9 1 v/v) [533]. CC on neutral alumina has been used for the separation of antioxidants, accelerators and plasticisers in rubber extracts [534]. Column chromatography of polymer additives has been reviewed [160,375,376]. 

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