Phenyl proton spin-lattice relaxation times

Properties.—Carbon-13 and field-dependent proton spin-lattice relaxation times have been measured as a function of temperature and molecular weight for solutions of polycarbonates in CDCI3. The spin-lattice relaxation times were interpreted in terms of segmental motion, characterized by the sharp cut-off model of Jones and Stockmayer, for phenyl group rotation and methyl group rotation. ... 

Fig. 34a-c Proton spin-lattice relaxation time of thermoreversible networks of polybutadiene at different temperatures as a function of the frequency [131], Linear PB (Mm 51,000) was cross-linked by addition of 4-phenyl-l,2,4-triazoUne-3,5-dione (pheny-lurazole, PU). The crossover frequencies between regimes I, 11, and III are shifted depending on the cross-link density. At the lowest temperatures the dispersion slopes tend to be steeper than in ordinary melts (see Eq. 168). a 19 phenylurazole groups per chain, b 28 phenylurazole groups per chain, c 37 phenylurazole groups per chain... 

Another way of using JH NMR to study the dynamics of phenyl protons in BPA-PC consists in selective deuteration of the methyl groups (BPA-d6-PC) [32]. Thus, the temperature dependence of the JH spin-lattice relaxation time, Ti, and spin-lattice relaxation time in the rotating frame, T p, has been determined, and is shown in Fig. 38. 

Levy and coworkers97 have measured 13C spin-lattice relaxation times, 7), for 3- and 4-aminobiphenyls in a number of solvent systems, and of the corresponding ammonium ions in acidic and nonacidic media. The observed 7) values indicated that the molecular tumbling is anisotropic for these species. In addition, the known biphenyl geometry allowed indentification and semiquantitative evaluation of internal rotation-libration motion. The protonated amine function is motionally more restricted by solvent-solute and ion-pair interactions than the corresponding neutral amine. Thus, in the 3-biphenylammonium ion, the principal axis for molecular reorientation is aligned close to the C3—NHj-bond, whereas in the amine the principal axis lies closer to the biphenyl C2-symmetry axis. In both 3- and 4-aminobiphenyls, the unsubstituted phenyl rings are less restricted due to rapid phenyl rotation or libration. Table 14 presents 13C Tj-data for 4-aminobiphenyl 37 (NH2 on C4) and 4-biphenylammonium acetate 38 and trifluoroacetate 39. 

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