Polymer NMR spectra

Several papers compare the properties of sulfobetaine (meth)acrylic polymers. NMR spectra and solution properties of 23a and 23b [59,60] are correlated with data from the corresponding polycarbobetaines [26]. The photophysical and solution properties of pyrene-labeled 23c were studied in terms of fluorescence emission. Addition of surfactants induces the formation of mixed micelles in aqueous solution [61]. Excluded volume effects of the unlabeled polymer were measured by light scattering [62], its adsorption on silica was studied by adsorbance measurement and ellipsometry [62,63], and the electrostimulated shift of the precipitation temperature was followed at various electric held intensities [64]. Polysulfobetaines may accelerate interionic reactions, e.g., oxidation of ferrocyanide by persulfate [65]. The thermal and dielectric properties of polysulfobetaines 23d were investigated. The flexible lateral chain of the polymers decreased Tg, for which a linear relationship with the number of C atoms was shown [66,67]. 

The polymer s microstmcture has an important influence on its properties. Different polymerization processes can lead to differences in a polymer s stmctures, which will introduce additional unique features in the polymer NMR spectra, since the chemical shifts and coupling constants are very sensitive to changes in polymer stmcture and stereochemistry. For example, an introduction of a branch can cause a C chemical shift change of more than 5 ppm. Sometimes, a microstmcture change does not affect chemical shift, but does change coupling constants which can be identified from multidimensional NMR. 

In the earliest studies of the influence of stereochemistry on polymer NMR spectra, spectral assignments were determined by comparing the spectra of model compounds with those from the polymer of interest. For example, in a classic paper, Bovey studied the structure of polystyrene, for which they selected 2,4-diphenylpentane as a model for dyad sequences. Figure 48 shows the ID-NMR spectra of r (62) and m (63) 2,4-diphenylpentane. The original spectrum was displayed with T scale (where TMS was at 10 ppm), which was... 

B. Bom, H. W. Spiess, Ah Initio Calculations of Conformational Effects on NMR Spectra of Amorphous Polymers Springer-Verlag, New York (1997). 

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. 

These protons show a single chemical shift in the NMR spectrum. This is called a racemic (subscript r) structure, since it contains equal amounts of D and L character. In the next section we shall discuss the NMR spectra of stereoregular polymers in more detail. 

It is not the purpose of this book to discuss in detail the contributions of NMR spectroscopy to the determination of molecular structure. This is a specialized field in itself and a great deal has been written on the subject. In this section we shall consider only the application of NMR to the elucidation of stereoregularity in polymers. Numerous other applications of this powerful technique have also been made in polymer chemistry, including the study of positional and geometrical isomerism (Sec. 1.6), copolymers (Sec. 7.7), and helix-coil transitions (Sec. 1.11). We shall also make no attempt to compare the NMR spectra of various different polymers instead, we shall examine only the NMR spectra of different poly (methyl methacrylate) preparations to illustrate the capabilities of the method, using the first system that was investigated by this technique as the example. 

Nuclear Magnetic Resonance Spectroscopy. Bmker s database, designed for use with its spectrophotometers, contains 20,000 C-nmr and H-nmr, as weU as a combined nmr-ms database (66). Sadder Laboratories markets a PC-based system that can search its coUection of 30,000 C-nmr spectra by substmcture as weU as by peak assignments and by fiiU spectmm (64). Other databases include one by Varian and a CD-ROM system containing polymer spectra produced by Tsukuba University, Japan. CSEARCH, a system developed at the University of Vieima by Robien, searches a database of almost 16,000 C-nmr. Molecular Design Limited (MDL) has adapted the Robien database to be searched in the MACCS and ISIS graphical display and search environment (63). Projects are under way to link the MDL system with the Sadder Hbrary and its unique search capabiHties. 

The NMR spectrum of the polymer 14.16 shows two singlets of approximately equal intensities that differ in chemical shift by only 0.17 ppm. This observation is attributed to the formation of equal amounts of isotactic (14.16a, both S=0 groups on the same side of the polymer chain) and syndiotactic (14.16b, S=0 groups on opposite sides of the polymer chain) forms of the polymer. The atacticity is confirmed by the H and NMR spectra. Two resonances are observed for the McaP groups of 14.16a, whereas 14.16b gives rise to only one resonance. 

The structures of these ylide polymers were determined and confirmed by IR and NMR spectra. These were the first stable sulfonium ylide polymers reported in the literature. They are very important for such industrial uses as ion-exchange resins, polymer supports, peptide synthesis, polymeric reagent, and polyelectrolytes. Also in 1977, Hass and Moreau [60] found that when poly(4-vinylpyridine) was quaternized with bromomalonamide, two polymeric quaternary salts resulted. These polyelectrolyte products were subjected to thermal decyana-tion at 7200°C to give isocyanic acid or its isomer, cyanic acid. The addition of base to the solution of polyelectro-lyte in water gave a yellow polymeric ylide. 

Kondo maintained his interest in this area, and with his collaborators [62] he recently made detailed investigations on the polymerization and preparation of methyl-4-vinylphenyl-sulfonium bis-(methoxycarbonyl) meth-ylide (Scheme 27) as a new kind of stable vinyl monomer containing the sulfonium ylide structure. It was prepared by heating a solution of 4-methylthiostyrene, dimethyl-diazomalonate, and /-butyl catechol in chlorobenzene at 90°C for 10 h in the presence of anhydride cupric sulfate, and Scheme 27 was polymerized by using a, a -azobisi-sobutyronitrile (AIBN) as the initiator and dimethylsulf-oxide as the solvent at 60°C. The structure of the polymer was confirmed by IR and NMR spectra and elemental analysis. In addition, this monomeric ylide was copolymerized with vinyl monomers such as methyl methacrylate (MMA) and styrene. 

Rodriguez and Gandini139,14° have recently carried out some work on the structure of the soluble polymers of the two ketones. The purified monomers were polymerized with various acids to give dark soluble products with DP s of 10—20. The ultraviolet, infrared, and NMR spectra and the elemental analysis of these purified substances were compared with those of the starting monomers. It was concluded that, at least for this initial phase, the two systems are characterized by polymerization through the olefinic bond because ... 

Fig. 28. Room temperature 2H NMR spectra of the smectic liquid crystalline polymer (m = 6), oriented in its nematic phase by the magnetic field (8.5 T) of the NMR spectrometer with director ii parallel (left) and perpendicular (right) to the magnetic field...

Fig. 29. Observed and calculated 2H NMR spectra for the mesogenic groups of a) the nematic (m = 2), b) the smectic (m = 6) liquid crystalline polymer in the glassy state, showing the line shape changes due to the freezing of the jump motion of the labelled phenyl ring. The exchange frequency corresponds to the centre of the distribution of correlation times. Note that the order parameters are different, S = 0.65 in the frozen nematic, and S = 0.85 in the frozen smectic system, respectively...

Polyesters are not different from other polymers, and any of the characterization methods commonly used in polymer science can obviously be applied to polyesters and provide information on their structure and properties. In this section, some data specific to polyesters—solubility information, COOH and OH endgroup titration, and infrared (IR) and NMR spectra assignments—are briefly summarized. Most of these data originate from the authors laboratory. References are provided on some particular points only. 

Q.-T. Pham, R. Petiaud, H. Waton, and M.-F. Llauro-Darricades, Proton and Carbon NMR Spectra of Polymers, Penton, London, 1991. 

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