Analysis and Identification of Polymers

The analysis and identification of polymers with chromophores absorbing UV/Vis photons (e.g., carbonyl and aromatic groups). 

Applications Rather intractable samples, such as organic polymers, are well suited to FD, which avoids the need for volatilisation of the sample. Since molecular ions are normally the only prominent ions formed in the FD mode of analysis, FD-MS can be a very powerful tool for the characterisation of polymer chemical mixtures. Application areas in which FD-MS has played a role in the characterisation of polymer chemicals in industry include chemical identification (molecular weight and structure determination) direct detection of components in mixtures off-line identification of LC effluents characterisation of polymer blooms and extracts and identification of polymer chemical degradation products. For many of these applications, the samples to be analysed are very complex... 

NMR analysis and identification of hydrolysis products, have shown that the polymerization of 1,2-anhydro sugars proceeds exclusively by opening of the oxirane ring and that the polymer contains exclusively pyranose rings 6). 

Honda T, Lu R, Kitano N, Kamiya Y, Miyakoshi T. Applied analysis and identification of ancient lacquer based on pyrolysis-gas chromatoraphy/mass spectrometry. J. Appl. Polym. Sci. 2010 118 897-901. 

This technique is extremely powerful for the analysis and characterisation of polymers and is ofter based on the use of controlled chromatography - mass spectroscopy to measure a polymer s decomposition with techniques such as pyrolysis, followed by chromatography to separate any breakdown product, and, finally, mass spectroscopy, to achieve an unequivocal identification of the pyrolysis products obtained. The detail that can be obtained by such methods includes structure of the polymer backbone, branching, end groups, isomeric detail and fine detail in the struaure of copolymers,... 

Bark, L. S. and N. S. Ailed (eds.), Analysis of Polymer Systems , Applied Science, London, 1982. Each chapter deals with a particular technique for the analysis, characterization of additives, molecular weight and structure, and identification of polymer systems. 

Applications Identification of polymer additives by TLC-IR is labour intensive and comprises extraction, concentration of extracts, component separation by TLC on silica, drying, removal of spots, preparation of KBr pellets and IR analysis. The method was illustrated with natural rubber formulations, where N-cyclohexyl-2-benzothiazyl sulfenamide, IPPD and 6PPD antioxidants, and a naphthenic plasticiser were readily quantified [765]. An overview of polymer/additive type compounds analysed by transfer TLC-FTIR is given in Table 7.80. 

MALDI-MS was developed for the analysis of nonvolatile samples and was heralded as an exciting new MS technique for the identification of materials with special use in the identification of polymers. It has fulfilled this promise to only a limited extent. While it has become a well-used and essential tool for biochemists in exploring mainly nucleic acids and proteins, it has been only sparsely employed by synthetic polymer chemists. This is because of lack of congruency between the requirements of MALDI-MS and most synthetic polymers. 

Nuclear magnetic resonance (NMR) spectroscopy is a most effective and significant method for observing the structure and dynamics of polymer chains both in solution and in the solid state [1]. Undoubtedly the widest application of NMR spectroscopy is in the field of structure determination. The identification of certain atoms or groups in a molecule as well as their position relative to each other can be obtained by one-, two-, and three-dimensional NMR. Of importance to polymerization of vinyl monomers is the orientation of each vinyl monomer unit to the growing chain tacticity. The time scale involved in NMR measurements makes it possible to study certain rate processes, including chemical reaction rates. Other applications are isomerism, internal relaxation, conformational analysis, and tautomerism. 

Fig. 10.19 The analysis domain and identification of the cross sections used in the discussion on boundary conditions below. [Reprinted by permission from T. Katziguara, Y. Nagashima, Y. Nakano, and K. Funatsu, Numerical Study of Twin Screw Extruders by 3-D Flow Analysis -Development of Analysis Technique and Evaluation of Mixing Performance for Full Flight Screws, Polym. Eng. Sci., 36, 2142 (1996).]...

The isolation and concentration of petroleum products can be performed in several ways. The most efficient method is passive adsorption. In this method, the sample along with a tube filled with Tenax TA adsorbent is placed in a thermostated (60-70 °C) tightly closed container, such as a glass jar, for over 10 h. Under these conditions, a balance between compounds present in the headspace of the sample and the sample adsorbed on the polymer adsorbent is established. Adsorbed compounds are subjected to thermodesorbtion then, the desorbed compounds together with the carrier gas are injected onto a GC column, where they are separated and then identified. This approach has enabled easy detection and identification of trace amounts of petroleum products. Headspace analysis with passive adsorption on Tenax TA is normally used for separation and concentration of analytes. Gas chromatography coupled with an autothermal desorber and a mass spectrometer (ATD-GC-MS) is the best technique for separation of multicomponent mixtures... 

An important aspect of the use of analytical pyrolysis is its capability to provide complementary information to other analytical techniques used for polymer characterization. One such technique is IR analysis of polymers. Although IR spectra can be used as fingerprints for polymer identification, the success of this technique can be questionable when the polymer is not pure or is in a mixture with other compounds. The IR spectra are particularly difficult to use when a polymer is present only at a low level in a particular material and cannot be easily separated. The use of Py-GC/MS allows identification of polymers even in low concentration in specific mixtures because it couples pyrolysis with a chromatographic technique. On the other hand, some polymers generate by pyrolysis a low proportion of easily identifiable molecules, producing mainly char and small uncharacteristic molecules such as HF, H2O, CO2, etc. In these cases, IR is the technique of choice. Since for an unknown sample each technique can be misleading, the use of both types of information is always beneficial. 

Analytical pyrolysis has a number of characteristics that can make it a very powerful tool in the study of polymers and composite materials. The technique usually requires little sample and can be set with very low limits of detection for a number of analytes. For Py-GC/MS the identification capability of volatile pyrolysate components is exceptionally good. A range of information can be obtained using this technique, including results for polymer identification, polymer structure, thermal properties of polymers, identification of polymer additives, and for the generation of potentially harmful small molecules from polymer decomposition. In most cases of analysis of a polymer or composite material, the technique does not require any sample preparation, not even solubilization of the sample, which may be a difficult task for the type of materials analyzed. The analysis can be easily automated and does not require expensive instrumentation (beyond the cost of the instrument used for pyrolysate analysis). 

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