Polymer analysis methods

Near-IR light-fibre spectroscopy is particularly well suited for assessing product quality of polymeric materials, with minimal or no sample preparation. This is actually one of the most active fields in the application of NIRS to polymers. However, it is necessary to have reasonably accurate training sets of the types of polymer to be analysed. NIRS has replaced many conventional methods in polymer analysis. Methods exist for the determination of OH number, acid value, chain length and cross-linking, methyl and methylene end-groups, primary... 

For both copolymers and stereoregular polymers, experimental methods for characterizing the products often involve spectroscopy. We shall see that nuclear magnetic resonance (NMR) spectra are particularly well suited for the study of tacticity. This method is also used for the analysis of copolymers. 

Most polymer processing methods involve heating and cooling of the polymer melt. So far the effect of the surroundings on the melt has been assumed to be small and experience in the situations analysed has proved this to be a reasonable assumption. However, in most polymer flow studies it is preferable to consider the effect of heat transfer between the melt and its surroundings. It is not proposed to do a detailed analysis of heat transfer techniques here, since these are dealt with in many standard texts on this subject. Instead some simple methods which may be used for heat flow calculations involving plastics are demonstrated. 

TSK-GEL PW and TSK-GEL PWxl columns are shown in Pig. 4.11. Although many methods for polymer analysis have been developed satisfactorily on TSK-GEL PW columns, higher resolution can often be achieved with a TSK-GEL PWxL column. The smaller particle sizes of the resins packed in TSK-GEL PWxL columns provide almost 2.5 times the resolution of their TSK-GEL PW counterparts. In addition, with shorter TSK-GEL PWxl columns, higher resolution separations are possible in less than half the time, as shown in Pig. 4.12. 

In particular, for copolymers this required an orthogonal coupling of one GPC to another to achieve the desired cro fractionation before application of dual detectors. This method is really a new polymer analysis member of a family of approaches developed in the literature which we are now terming "Orthogonal Chromatogr hy . It not only provides both a cro fractionation approach for copolymers and a new way of determining the GPC s "imperfect resolution" it also enables separation mechanisms previously reserved for the liquid chromatography of small molecules to be used for polymer analysis. 

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... 

More recently, the same author [41] has described polymer analysis (polymer microstructure, copolymer composition, molecular weight distribution, functional groups, fractionation) together with polymer/additive analysis (separation of polymer and additives, identification of additives, volatiles and catalyst residues) the monograph provides a single source of information on polymer/additive analysis techniques up to 1980. Crompton described practical analytical methods for the determination of classes of additives (by functionality antioxidants, stabilisers, antiozonants, plasticisers, pigments, flame retardants, accelerators, etc.). Mitchell... 

Although PFE lacks a proven total concept for in-polymer analysis, as in the case of closed-vessel MAE (though limited to polyolefins), a framework for method development and optimisation is now available which is expected to be an excellent guide for a wide variety of applications, including non-polyolefinic matrices. Already, reported results refer to HDPE, LDPE, LLDPE, PP, PA6, PA6.6, PET, PBT, PMMA, PS, PVC, ABS, styrene-butadiene rubbers, while others may be added, such as the determination of oil in EPDM, the quantification of the water-insoluble fraction in nylon, as well as the determination of the isotacticity of polypropylene and of heptane insolubles. Thus PFE seems to cover a much broader polymer matrix range than MAE and appears to be quite suitable for R D samples. 

David et al. [184] have shown that cool on-column injection and the use of deactivated thermally stable columns in CGC-FID and CGC-F1D-MS for quantitative determination of additives (antistatics, antifogging agents, UV and light stabilisers, antioxidants, etc.) in mixtures prevents thermal degradation of high-MW compounds. Perkins et al. [101] have reported development of an analysis method for 100 ppm polymer additives in a 500 p,L SEC fraction in DCM by means of at-column GC (total elution time 27 min repeatability 3-7 %). Requirements for the method were (i) on-line (ii) use of whole fraction (LVI) and (iii) determination of high-MW compounds (1200 Da) at low concentrations. Difficult matrix introduction (DMI) and selective extraction can be used for GC analysis of silicone oil contamination in paints and other complex analytical problems. 

Apart from paints, electrokinetic separations find limited application for synthetic polymers [905], mainly because of solvent compatibility (CE is mostly an aqueous technique) and competition of SEC (reproducibility). Reasons in favour of the use of CE-like methods for polymer analysis are speed, sample throughput and low solvent consumption. Nevertheless, CE provides some interesting possibilities for polymer separation. Electrokinetic methods have been developed based on differences in ionisation, degree of interaction with solvent constituents, and molecular size and conformation. 

Recently a decreased level of CE activity has been noticed with a shift of attention towards other separation techniques such as electrochromatography. CE is apparently not more frequently used partly because of early instrumental problems associated with lower sensitivity, sample injection, and lack of precision and reliability compared with HPLC. CE has slumped in many application areas with relatively few accepted routine methods and few manufacturers in the market place. While the slow acceptance of electrokinetic separations in polymer analysis has been attributed to conservatism [905], it is more likely that as yet no unique information has been generated in this area or eventually only the same information has been gathered in a more efficient manner than by conventional means. The applications of CE have recently been reviewed [949,950] metal ion determination by CE was specifically addressed by Pacakova et al. [951]. 

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. 

Principles and Characteristics Mass-spectral analysis methods may be either indirect or direct. Indirect mass-spectral analysis usually requires some pretreatment (normally extraction and separation) of the material, to separate the organic additives from the polymers and inorganic fillers. The mass spectrometer is then used as a detector. Direct mass-spectrometric methods have to compete with separation techniques such as GC, LC and SFC that are more commonly used for quantitative analysis of polymer additives. The principal advantage of direct mass-spectrometric examination of compounded polymers (or their extracts) is speed of analysis. However, quite often more information can be... 

LC-IR using surface-enhanced IR absorption spectroscopy (SEIRAS) was recently designed in order to develop a highly sensitive and rapid analysis method for polymer additives [506]. The method, which consists of spraying the LC eluents on to a metal film of Ag on a BaF2 substrate, allows an enhancement factor of about 90. 

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] ... 

Isolation may occur by liquid-solid interaction (extraction, dissolution) or heat (thermal, pyrolytic, laser). Extraction methods easily handle qualitative screening for low- to medium-MW compounds fail for high-MW components or polymer-bound functionalities and are less reliable quantitatively (analyte dependent). When applicable, dissolution methods suffer from sensitivity, because of the dilution effect on account of the polymer. In-polymer analysis performs well for qualitative screening, but is as yet not strongly performing for quantitative analysis, except for some specific questions. 

In polymer/additive deformulation (of extracts, solutions and in-polymer), spectroscopic methods (nowadays mainly UV, IR and to a lesser extent NMR followed at a large distance by Raman) play an important role, and even more so in process analysis, where the time-consuming chromatographic techniques are less favoured. Some methods, as NMR and Raman spectrometry, were once relatively insensitive, but seem poised to become better performing. Quantitative polymer/additive analysis may benefit from more extensive use of 600-800 MHz 1-NMR equipped with a high-temperature accessory (soluble additives only). 

Some general characteristics of direct solid-state polymer/additive analysis methods have already been... 

The best method or the most suitable combination of methods can be discussed only in regard to the actual analytical problem. The ideal method for polymer analysis in an industrial environment is often essentially that practical one which identifies and quantitates the desired components at the lowest acceptable total cost for the customer, compatible with the desired accuracy and time constraints. Three examples may illustrate the necessary pragmatic trade-off. Despite being old methods, classical polymer/additive analysis techniques, based on initial additive separation from the polymer matrix through solvent extraction methods followed by preconcentration, still enjoy great popularity. This... 

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