Direct polymer analysis

Infrared spectroscopy is a major tool for polymer and rubber identification [11,12]. Infrared analysis usually suffices for identification of the plastic material provided absence of complications by interferences from heavy loadings of additives, such as pigments or fillers. As additives can impede the unambiguous assignment of a plastic, it is frequently necessary to separate the plastic from the additives. For example, heavily plasticised PVC may contain up to 60% of a plasticiser, which needs to be removed prior to attempted identification of the polymer. Also an ester plasticiser contained in a nitrile rubber may obscure identification of the polymer. Because typical rubber compounds only contain some 50% polymer direct FUR analysis rarely provides a definitive answer. It is usually necessary first... 

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]. 

Even more interest exists in direct in-polymer analysis of intact bulk samples as delivered (powder, granulate, sheet, film, etc.). This is by no means a simple matter. In fact, as plastic materials usually contain several components, analysis of the levels whilst still in the plastic is usually difficult. Some additives can be analysed without extraction... 

The mass spectra of mixtures are often too complex to be interpreted unambiguously, thus favouring the separation of the components of mixtures before examination by mass spectrometry. Nevertheless, direct polymer/additive mixture analysis has been reported [22,23], which is greatly aided by tandem MS. Coupling of mass spectrometry and a flowing liquid stream involves vaporisation and solvent stripping before introduction of the solute into an ion source for gas-phase ionisation (Section 1.33.2). Widespread LC-MS interfaces are thermospray (TSP), continuous-flow fast atom bombardment (CF-FAB), electrospray (ESP), etc. Also, supercritical fluids have been linked to mass spectrometry (SFE-MS, SFC-MS). A mass spectrometer may have more than one inlet (total inlet systems). 

Direct polymer compound analysis by soft ionisation, tandem MS/MS and high-resolution (AC-MS) mass spectrometry, has been reviewed [236]. 

Direct mass analysis of additives in bulk polymers is in principle an attractive methodology, albeit with many restrictions (Table 6.38). Early MS work has focused on direct thermal desorption of additives from the bulk polymer, followed by EI-MS [22,240], CI-MS [22,63] and FI-MS [22]. However, these traditional approaches are limited to polymer additives that are both stable and volatile at the higher temperatures,... 

In direct insertion techniques, reproducibility is the main obstacle in developing a reliable analytical technique. One of the many variables to take into account is sample shape. A compact sample with minimal surface area is ideal [64]. Direct mass-spectrometric characterisation in the direct insertion probe is not very quantitative, and, even under optimised conditions, mass discrimination in the analysis of polydisperse polymers and specific oligomer discrimination may occur. For nonvolatile additives that do not evaporate up to 350 °C, direct quantitative analysis by thermal desorption is not possible (e.g. Hostanox 03, MW 794). Good quantitation is also prevented by contamination of the ion source by pyrolysis products of the polymeric matrix. For polymer-based calibration standards, the homogeneity of the samples is of great importance. Hyphenated techniques such as LC-ESI-ToFMS and LC-MALDI-ToFMS have been developed for polymer analyses in which the reliable quantitative features of LC are combined with the identification power and structure analysis of MS. 

As indicated in Section 6.2.2, DI-CIMS suffers from poor reproducibility. For nonvolatile additives that do not evaporate up to 350 °C, direct quantitative analysis by thermal desorption is not possible. The method depends on polymer formulation standards that are reliably mixed. Wilcken and Geissler [264] described rapid quality control of l- xg paint samples by means of temperature-programmable DI-EIMS with PCA evaluation. 

Applications Quantitative dry ashing (typically at 800 °C to 1200°C for at least 8h), followed by acid dissolution and subsequent measurement of metals in an aqueous solution, is often a difficult task, as such treatment frequently results in loss of analyte (e.g. in the cases of Cd, Zn and P because of their volatility). Nagourney and Madan [20] have compared the ashing/acid dissolution and direct organic solubilisation procedures for stabiliser analysis for the determination of phosphorous in tri-(2,4-di-t-butylphenyl)phosphite. Dry ashing is of limited value for polymer analysis. Crompton [21] has reported the analysis of Li, Na, V and Cu in polyolefins. Similarly, for the determination of A1 and V catalyst residues in polyalkenes and polyalkene copolymers, the sample was ignited and the ash dissolved in acids V5+ was determined photo-absorptiometrically and Al3+ by complexometric titration [22]. 

Table 8.22 shows some rubber analyses by FAAS after dry ashing. The concentration of Rh in polymers was measured by FAAS [128], The accuracy of 10-20% was in agreement with a dissolution procedure the precision obtained for direct solid analysis was between 10 and 20 %. Due to the relatively high analyte content of lead in paint, the determination is mostly performed by FAAS. Typical digestion procedures include dry ashing, wet and microwave digestion. 

Applications Specific applications of the direct spectrometric analysis methods of solid samples of Table 8.36 are given under the specific headings. One investigation that is practically only possible by direct solids analysis is checking the homogeneity of polymers [136,137] this is of significance for reference materials and for quality control. A method for the assessment of microhomogeneity should meet various requirements [223] ... 

For samples that meet the solubility requirements of the SEC approach, analyses were also reported for additives in polymers such as PVC and PS [28,29]. Direct SEC analysis of PVC additives such as plasticisers and thermal stabilisers in dissolution mode has been described [28,30,31 ]. In the analysis of a dissolved PS sample using a SEC column of narrow pore size, the group of additives was separated on a normal-phase column after elution of the polymer peak [21]. Column-loading capacity of HPSEC for the analysis of additives, their degradation products and any other low-MW compounds present in plastics has been evaluated for PS/HMBT, PVC/TNPP and PVC/TETO (glyceryl tri[l-14C] epoxyoleate) [31]. It was shown that HPSEC can be used to separate low-MW compounds from relatively large amounts of polymers without serious loss of resolution of the additives the technique has also been used for the group analysis of chlorohydrin transformation products of the TETO model compound [32]. 

Principles and Characteristics The qualifying features for the application of solution NMR to extracts of polymeric materials have already been outlined in Section 5.4. For NMR spectroscopy, which is a powerful analytical tool for identification and quantification, extraction of additives from the polymer is not required. Recent NMR developments suggest various possibilities for direct additive analysis ... 

Despite well-deserved attention and considerable efforts, direct polymer/additive analysis (without separation) has not been turned into routinely workable concepts. Table 10.27 shows the main approaches. 

The purpose of this monograph, the first to be dedicated exclusively to the analytics of additives in polymers, is to evaluate critically the extensive problemsolving experience in the polymer industry. Although this book is not intended to be a treatise on modem analytical tools in general or on polymer analysis en large, an outline of the principles and characteristics of relevant instrumental techniques (without hands-on details) was deemed necessary to clarify the current state-of-the-art of the analysis of additives in polymers and to accustom the reader to the unavoidable professional nomenclature. The book, which provides an in-depth overview of additive analysis by focusing on a wide array of applications in R D, production, quality control and technical service, reflects the recent explosive development of the field. Rather than being a compendium, cookery book or laboratory manual for qualitative and/or quantitative analysis of specific additives in a variety of commercial polymers, with no limits to impractical academic exoticism (analysis for its own sake), the book focuses on the fundamental characteristics of the arsenal of techniques utilised industrially in direct relation... 

The numerical coefficients in these equations as well as the numerical constants Av>i in Eq. (32) are given in Table 5. In fact, Eq. (32) approximates the results of direct numerical analysis to within 3% for 0.0015< d< 0.15, N> 0.05, and L/d > 5, the conditions which are fulfilled by most stiff-chain polymer solution systems studied so far. Equation (32) is more accurate at small N than our previous theory [18], in which slightly different empirical equations for c, and cA were proposed. 

Sanbe H, Haginaka J (2003) Restricted access media-molecularly imprinted polymer for propranolol and its application to direct injection analysis of beta-blockers in biological fluids. Analyst 128(6) 593-597... 

In this contribution, the experimental concept and a phenomenological description of signal generation in TDFRS will first be developed. Then, some experiments on simple liquids will be discussed. After the extension of the model to polydisperse solutes, TDFRS will be applied to polymer analysis, where the quantities of interest are diffusion coefficients, molar mass distributions and molar mass averages. In the last chapter of this article, it will be shown how pseudostochastic noise-like excitation patterns can be employed in TDFRS for the direct measurement of the linear response function and for the selective excitation of certain frequency ranges of interest by means of tailored pseudostochastic binary sequences. 

The application of modern surface analysis techniques, such as XPS, to the analysis of modified polymer surfaces, has demonstrated that in most of the above processes the polymer is oxidized. Many functional groups such as hydroxyl, carbonyl, ether, carboxyl, ester, peroxide, epoxide, etc., have been detected by direct XPS analysis or after derivatization of functional groups. The interaction between evaporated metal films and several of such functional groups has been clearly demonstrated (3). 

It was possible to estimate the relative contribution of site C by direct chemical analysis of the supernatant fluid, and such measurements are described in Chapter 12. We found that the concentration of the PEO inside the gel (sites A, B and D combined) was about one-half the concentration outside the gel [12], The partial exclusion of polymer molecules from the gel phase must lead to some osmotic pressure due to the excess molecules in the supernatant fluid. 

---