Nuclear magnetic resonance polymer analysis

The structure of SPEKs was usually determined by nuclear magnetic resonance (NMR) analysis. For each analysis, 3 wt.% polymer solution was prepared in deuterated dimethyl sulfoxide (DMSO-tfg) for HNMR and 15 wt.% for CNMR. The chemical shift of tetramethylsilane was used as the internal standard reference. The typical HNMR spectrum and its chemical shift assignment for SPEEK obtained by the postsulfonation method are also shown in Figure 5.14. 

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. 

Nuclear magnetic resonance (nmr) requires an atomic nuclei that can absorb a radio-frequency signal impinging it in a strong magnetic field to give a spectmm. The field strength at which the nucleus absorbs is a function of both the nucleus and its immediate electronic environment. The atoms normally used for nmr analysis are as follows (34) H, F, P, Si, and Of these, the most commonly used in polymer analyses are... 

Nuclear Magnetic Resonance (nmr). The nmr analysis has been used in the polymer industry for some time to measure properties such as amount and type of branching, polymerized ethylene oxide content, and hydroxyl content. The same techniques are applicable to waxes, and are used for both characterization and quality control. 

Solid state materials have been studied by nuclear magnetic resonance methods over 30 years. In 1953 Wilson and Pake ) carried out a line shape analysis of a partially crystalline polymer. They noted a spectrum consisting of superimposed broad and narrow lines which they ascribed to rigid crystalline and amorphous material respectively. More recently several books and large articles have reviewed the tremendous developments in this field, particularly including those of McBrierty and Douglas 2) and the Faraday Symposium (1978)3) —on which this introduction is largely based. 

ADMET polymers are easily characterized using common analysis techniques, including nuclear magnetic resonance ( H and 13C NMR), infrared (IR) spectra, elemental analysis, gel permeation chromatography (GPC), vapor pressure osmometry (VPO), membrane osmometry (MO), thermal gravimetric analysis (TGA), and differential scanning calorimetry (DSC). The preparation of poly(l-octenylene) (10) via the metathesis of 1,9-decadiene (9) is an excellent model polymerization to study ADMET, since the monomer is readily available and the polymer is well known.21 The NMR characterization data (Fig. 8.9) for the hydrogenated versions of poly(l-octenylene) illustrate the clean and selective nature of ADMET. 

Perhaps the most revolutionary development has been the application of on-line mass spectroscopic detection for compositional analysis. Polymer composition can be inferred from column retention time or from viscometric and other indirect detection methods, but mass spectroscopy has reduced much of the ambiguity associated with that process. Quantitation of end groups and of co-polymer composition can now be accomplished directly through mass spectroscopy. Mass spectroscopy is particularly well suited as an on-line GPC technique, since common GPC solvents interfere with other on-line detectors, including UV-VIS absorbance, nuclear magnetic resonance and infrared spectroscopic detectors. By contrast, common GPC solvents are readily adaptable to mass spectroscopic interfaces. No detection technique offers a combination of universality of analyte detection, specificity of information, and ease of use comparable to that of mass spectroscopy. 

Crosslinked polymer networks formed from multifunctional acrylates are completely insoluble. Consequently, solid-state nuclear magnetic resonance (NMR) spectroscopy becomes an attractive method to determine the degree of crosslinking of such polymers (1-4). Solid-state NMR spectroscopy has been used to study the homopolymerization kinetics of various diacrylates and to distinguish between constrained and unconstrained, or unreacted double bonds in polymers (5,6). Solid-state NMR techniques can also be used to determine the domain sizes of different polymer phases and to determine the presence of microgels within a poly multiacrylate sample (7). The results of solid-state NMR experiments have also been correlated to dynamic mechanical analysis measurements of the glass transition (1,8,9) of various polydiacrylates. 

Nuclear magnetic resonance (NMR) is a very popular technique in the field of polymer analysis [1-3]. It can be used to measure Mn, but this application relies heavily on the presence of NMR signals due to terminal groups (TEG). As the length of the chains grows, the NMR signal due to TEG becomes weak and the accuracy falls. In practice, above 30 kDa the error level on Mn is so high that the measurement is useless. 

The determination of the various types of geometric isomers associated with unsaturation in Polymer chains is of great importance, for example, in the study of the structure of modern synthetic rubbers. In table below are listed some of the important infrared absorption bands which arise from olefinic groups. In synthetic "natural" rubber, cis-1, 4-polyisoprene, relatively small amounts of 1, 2 and 3, 4-addition can easily be detected, though it is more difficult to distinguish between the cis and trans-configurations. Nuclear magnetic resonance spectroscopy is also useful for this analysis. 

Nuclear magnetic resonance spectroscopy of dilute polymer solutions is utilized routinely for analysis of tacticlty, of copolymer sequence distribution, and of polymerization mechanisms. The dynamics of polymer motion in dilute solution has been investigated also by protoni - and by carbon-13 NMR spectroscopy. To a lesser extent the solvent dynamics in the presence of polymer has been studied.Little systematic work has been carried out on the dynamics of both solvent and polymer in the same systan. 

Infrared spectroscopy has been used for quantitatively measuring the amounts of 1,2-, 3,4-, cis-1,4-, and trans-1,4-polymers in the polymerization of 1,3-dienes its use for analysis of isotactic and syndiotactic polymer structures is very limited [Coleman et al., 1978 Tosi and Ciampelli, 1973]. Nuclear magnetic resonance spectroscopy is the most powerful tool for detecting both types of stereoisomerism in polymers. High-resolution proton NMR and especially 13C NMR allow one to obtain considerable detail about the sequence distribution of stereoisomeric units within the polymer chain [Bovey, 1972, 1982 Bovey and Mirau, 1996 Tonelli, 1989 Zambelli and Gatti, 1978],... 

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. 

It can be concluded that it is very difficult to predict the result from a polymer macrostructure, but it is relatively easy to measure the secondary species generated on irradiation by using known analytical techniques, such as measuring swelling, tensile tests, analysis using nuclear magnetic resonance (NMR), etc. The yield is then expressed by the G value, which represents the number of cross-links, scissions, double bonds, etc., produced for every 100 eV (1.6 X 10 J) dissipated in the material. For example, G (cross-links), abbreviated G(X), = 3.5 means that 3.5 cross-links are formed in the polymer per 100 eV under certain irradiation conditions. Similarly, the number of scissions formed is denoted by G(S). In order to determine the number of crosslinks or G(X), the number of scissions or G(S), etc., it is necessary to know the dose or dose rate and the time of exposure for these irradiation conditions. From the product yields it is possible to estimate what ratio of monomer units in a polymer is affected by irradiation. ... 

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