Complex polymer systems

FT rheometry is a powerful technique to document the nonlinear viscoelastic behavior of pure polymers as observed when performing large amplitude oscillatory strain (LAOS) experiments. When implemented on appropriate instmments, this test technique can readUy be applied on complex polymer systems, for instance, filled mbber compounds, in order to yield significant and reliable information. Any simple polymer can exhibit nonlinear viscoelastic properties when submitted to sufficiently large strain in such a case the observed behavior is so-called extrinsic... 

Whereas SEC is the dominant technique for the characterisation of polymers, various nonexclusion liquid chromatographic (NELC) methods, such as GPEC and LACCC offer equally valid possibilities for deformulation of complex polymer systems. In fact, molecular characterisation of polymers in the precip-itation/adsorption mode (gradient HPLC) enables differences in chemical structure and composition to be... 

Our results demonstrated clearly that the lifetime data are more sensitive to subtleties of the micromechanistic photophysics. In this case we were able to establish inadequacies of the two-component model that were not detected by intensity quenching measurements alone. It is also clear that resolution of the detailed mechanism in these complex polymer systems will require even better lifetime data than we are able to obtain with a conventional flash lamp-based time-correlated photon counting system. 

While the use of these methods can be shown to be of benefit to a large number of polymer research programs, the widespread implementation of these concepts has not been realized. Thus, we would encourage those working in complex polymer systems to carefully consider the examples provided in this volume and identify how these could be implemented in their research work. 

SEC became the most widely used method for molar mass and molar mass distribution determination due to its broad applicability, easy sample preparation, and the large amount of information resulting from the full distribution curve. The commercially available SEC systems work automatically with small sample amounts and even at elevated temperatures. In addition, chromatographic systems coupled with spectroscopic methods giving chemical information on the separated fractions gain more and more importance for analysis of complex polymer systems and mixtures. 

The important feature of many polymers is simultaneous presence of distributions in two and several molecular characteristics. Polymers exhibiting multiple distributions are called the complex polymers or complex polymer systems. A detailed discussion of molecular characteristics of polymers and their average values and distributions can be found in numerous monographs and reviews, for example [34,35]. For the present purpose, it is important to repeat that all synthetic polymers and also polysaccharides are polydisperse in their nature. Only mother nature is able to produce macromolecules, for example many proteins, with uniform molar mass. The latter are often improperly called monodisperse(d) polymers. 

The significant intrinsic limitation of SEC is the dependence of retention volumes of polymer species on their molecular sizes in solution and thus only indirectly on their molar masses. As known (Sections 16.2.2 and 16.3.2), the size of macromolecnles dissolved in certain solvent depends not only on their molar masses but also on their chemical structure and physical architecture. Consequently, the Vr values of polymer species directly reflect their molar masses only for linear homopolymers and this holds only in absence of side effects within SEC column (Sections 16.4.1 and 16.4.2). In other words, macromolecnles of different molar masses, compositions and architectures may co-elute and in that case the molar mass values directly calculated from the SEC chromatograms would be wrong. This is schematically depicted in Figure 16.10. The problem of simultaneous effects of two or more molecular characteristics on the retention volumes of complex polymer systems is further amplifled by the detection problems (Section 16.9.1) the detector response may not reflect the actual sample concentration. This is the reason why the molar masses of complex polymers directly determined by SEC are only semi-quantitative, reflecting the tendencies rather than the absolute values. To obtain the quantitative molar mass data of complex polymer systems, the coupled (Section 16.5) and two (or multi-) dimensional (Section 16.7) polymer HPLC techniques must be engaged. 

Numerous LC CC applications were performed by Pasch, Schulz, and Falkenhagen in Germany on (high)polymers and by Trathnigg in Austria on oligomers (for review see Ref [23]). Presently, the LC CC method is rather widely used in the separation of complex polymer systems [26-28,31-33,173-194]. 

In conclusion, eluent gradient polymer HPLC represents a useful tool for separation of complex polymer system. It belongs to the important constituents of several two-dimensional polymer HPLC procedures. 

As explained in Sections 16.4 and 16.5, the comprehensive characterization of complex polymer systems is hardly possible by the SEC alone. SEC employs only one retention mechanism which simnltaneonsly responds to all molecular characteristics of sample. Similarly, also the coupling of the different retention mechanisms within one single column only exceptionally allows fulfilling this task. Evidently several retention mechanisms should be applied in a tandem approach that is within at least two different on-line chromatographic systems. This is the basic idea of the two- and multidimensional polymer HPLC. In the present section, the principles of two-dimensional polymer HPLC, 2D polymer HPLC or (2D-LC) will be briefly elucidated. There are several reviews available [23-31,249,250] dealing with the 2D polymers. It is anticipated that also the three- and multidimensional polymer HPLC will be developed in future. 

In any 2D HPLC, it is important to attain certain degree of both the complementarity and the orthogonality between the two separation dimensions [255-257]. The so far most universal approach to 2D polymer HPLC assumes the partial or possibly full suppression of the molar mass effect in the first dimension of the separation so that the complex polymer is separated mainly or even exclusively according to its chemical structure. Selected coupled methods of polymer HPLC are to be applied to this purpose. In the second dimension of separation—it is usually SEC—the fractions from the first dimension are further discriminated according to their molecular size. Exceptionally, SEC can be used as the first dimension to separate complex polymer system according to the molecular size. This approach is applicable when the size of polymer species does not depend or only little depends on their second molecular characteristic, as it is the case of the stereoregular polymers... 

A useful approach to detection in polymer HPLC presents the on-line hyphenation of different measurement principles. For example, an RI detector combined with a UV photometer produces valuable additional information on the composition of some copolymers. Further progress was brought with the triple detection RI plus LALS plus VISCO [313], which is especially suitable for branched macromolecules and the tetra detection UV plus RI plus LALS plus VISCO, which enables characterization of some complex polymer systems, exhibiting a distribution not only in their molar mass and architecture, but also in their chemical composition such as long chain branched copolymers. 

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