Polymers magnetic resonance

Monomer (Section 6 21) The simplest stable molecule from which a particular polymer may be prepared Monosaccharide (Section 25 1) A carbohydrate that cannot be hydrolyzed further to yield a simpler carbohydrate Monosubstituted alkene (Section 5 6) An alkene of the type RCH=CH2 in which there is only one carbon directly bonded to the carbons of the double bond Multiplicity (Section 13 7) The number of peaks into which a signal IS split in nuclear magnetic resonance spectroscopy Signals are described as singlets doublets triplets and so on according to the number of peaks into which they are split... 

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. 

Figure 7.10 Nuclear magnetic resonance spectra of three poly(methyl methacrylate samples. Curves are labeled according to the preominant tacticity of samples. [From D. W. McCall and W. P. Slichter, in Newer Methods of Polymer Characterization, B. Ke (Ed.), Interscience, New York, 1964, used with permission.]...

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. 

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. 

An unusual method for the preparation of syndiotactic polybutadiene was reported by The Goodyear Tire Rubber Co. (43) a preformed cobalt-type catalyst prepared under anhydrous conditions was found to polymerize 1,3-butadiene in an emulsion-type recipe to give syndiotactic polybutadienes of various melting points (120—190°C). These polymers were characterized by infrared spectroscopy and nuclear magnetic resonance (44—46). Both the Ube Industries catalyst mentioned previously and the Goodyear catalyst were further modified to control the molecular weight and melting point of syndio-polybutadiene by the addition of various modifiers such as alcohols, nitriles, aldehydes, ketones, ethers, and cyano compounds. 

The methods used to characterise polymers are partly familiar ones like X-ray diffraction, Raman spectroscopy and electron microscopy, partly less familiar but widespread ones like neutron scattering and nuclear magnetic resonance, and partly... 

Lutnnger, G, Meurer, B, Weill, G Makromol Chem 1989,190, 2815 Majumdar, R N, Harwood, H J Appl Polym Anal Charact 1987,423 A single issue of Magnetic Resonance in Chemistry (1990,28) is devoted exclusively to the NMR of solids, although there are no specific arucles on solid-state fluonne NMR... 

Optically detected magnetic resonance (ODMR) has yielded valuable information about dynamics of long-lived pholoexcitations of conjugated polymers. The technique relies upon the paramagnetic interaction of excitations with an applied magnetic field. For a particle with non-zero spin, placed in a magnetic field, the Hamiltonian is ... 

Muller, K., Kothe, G., and Wassmer, K.-H. Dynamic Magnetic Resonance of Liquid crystal Polymers Molecular Organization and Macroscopic Properties. Vol. 95, pp. 1 — 56. 

Sharkey, W. H. Polymerizations Through the Carbon-Sulphur Double Bond. VoL 17, pp. 73-103. Shimidzu, T. Cooperative Actions in the Nucleophile-Containing Polymers. Vol. 23, pp. 55-102. Slichter, W. P. The Study of High Polymers by Nuclear Magnetic Resonance. VoL 1, pp. 35-74. Small, P. A. Long-Chain Branching in Polymers. VoL 18,pp. 1-64. 

Proton nuclear magnetic resonance spectra of 15-20% solutions of polymers in CC14 were obtained with Varian T-60 or HR-300 spectrometers. Chemical shifts are reported... 

Stickler, IV. P. The Study of High Polymers by Nuclear Magnetic Resonance. Vol. 1, pp. 35-74. 

In the following, some examples of applications of Fourier transform infrared (FTIR) Spectroscopy and of solid-state nuclear magnetic resonance (NMR) to the study of polymorphism in polymers are described. 

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. 

In this review recent theoretical developments which enable quantitative measures of molecular orientation in polymers to be obtained from infra-red and Raman spectroscopy and nuclear magnetic resonance have been discussed in some detail. Although this is clearly a subject of some complexity, it has been possible to show that the systematic application of these techniques to polyethylene terephthalate and polytetramethylene terephthalate can provide unique information of considerable value. This information can be used on the one hand to gain an understanding of the mechanisms of deformation, and on the other to provide a structural understanding of physical properties, especially mechanical properties. 

Another definition, taking into account polymerization conversion, has been more recently proposed.192 Perfect dendrimers present only terminal- and dendritic-type units and therefore have DB = 1, while linear polymers have DB = 0. Linear units do not contribute to branching and can be considered as structural defects present in hyperbranched polymers but not in dendrimers. For most hyperbranched polymers, nuclear magnetic resonance (NMR) spectroscopy determinations lead to DB values close to 0.5, that is, close to the theoretical value for randomly branched polymers. Slow monomer addition193 194 or polycondensations with nonequal reactivity of functional groups195 have been reported to yield polymers with higher DBs (0.6-0.66 range). 

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