ABSTRACT:Measurements of 13 C spin-lattice relaxation times, T1, and nuclear Overhauser effects, NOE, were carried out as a function of temperature at two magnetic fields for iso-poly(2-vinylpyridine) (iso-P2VP) in 1,4-dioxane-d8 and iso-poly(2-vinylpyridinium chloride) (iso-P2VPC1), in D 2 0 to investigate the effects of electrostatic interactions on local chain dynamics. For main chain carbons of both polymers, the experimental T 1 and NOE data are in good agreement with the Dejean-Laupretre-Monnerie (DLM) model in the entire temperature range. It was found that the local conformational transitions of main chain and the libration are more restricted for iso-P2VPC1 than iso-P2VP. For pyridyl ring carbons, the experimental data were reproduced by the models combining the DLM model and restricted ring rotations. The angular amplitude rx of ring rotation of iso-P2VPC1 is smaller than that of iso-P2VP. These results imply that both local motions of main chain and side chain are affected by the electrostatic interactions.KEY WORDS ' 3 C Nuclear Magnetic Resonance Relaxation I Poly(2-vinylpyridine) I Poly(2-vinylpyridinium chloride) 1 Electrostatic Interactions I Local Chain Dynamics I Spin-Lattice Relaxation Time I Nuclear Overhauser Effect I Effects of electrostatic interactions on local chain conformation or chain stiffness have been extensively studied theoretically and experimentally. 1 -4 However, few studies have been reported on their effects on local chain dynamics.Among various dynamic methods such as NMR relaxation, 5 dielectric relaxation, 6 · 7 and time-resolved fluorescence methods, 8 the NMR relaxation method is a very powerful technique because it provides detailed information about molecular motions of different parts of chain through the spectral density function, which is the Fourier transformation of correlation function of the relaxing dipoles in different environments of chain.Poly(2-vinylpyridine) (P2VP) and poly( 4-vinylpyridine) (P4VP) are suitable model polyelectrolytes because they can be converted to ionized polymer from nonionic one by neutralizing pyridyl ring by relevant acid without the significant change of chemical structure. Chachaty et al. studied the local chain dynamics of P2VP and P4VP, and their ionized polymers, poly(2-vinylpyridinium chloride) (P2VPC1) and poly(4-vinylpyridinium bromide) (P4VPBr) in solutions and reported that electrostatic interactions affect local chain dynamics. 9 -11 However, the effects of electrostatic interactions remain unclear yet, since the chain motions were not analyzed by reliable motional models such as conformational jump models in their papers.Recently, Ravindranathan eta/. studied the local chain dynamics of ata-P2VP in chloroform, 12 and reported that all the experimental data of main chain carbons are in good agreement with the Dejean-Laupretre-Monnerie (DLM) model, 13 which was modified from the Hall-To whom correspondence should be addressed. 614Weber-Helfand (HWH) model describing the main chain motions in terms of the conformational tra...
Measurement of 13 C spin-lattice relaxation times, T1, and nuclear Overhauser effects, NOE, was made as a function of temperature at two magnetic fields for poly(t-butyl crotonate), PTBC, and poly(t-butyl methacrylate), PTBM, in toluene-d 8 to study the effects of #-substitution on local chain motions. For main chain carbons of PTBC and PTBM, experimental T 1 and NOE data were well reproduced by the Dejean-Laupretre-Monnerie (DLM) model in the entire temperature range. The model parameters thus obtained differed between PTBC and PTBM. For methyl carbons in the /-butyl ester group, the experimental data were analyzed by the models combining the DLM model and multiple internal rotations. The model parameters were almost the same for the two polymers. These results indicate that #-substitution affects the local motion of main chains as well as chain stiffness, but does not significantly affect the local motion of methyl carbons at the ends of side-chains. The correlation between the local dynamics of various polymer chains and chain stiffness is discussed. KEY WORDS 13 C NMR Relaxation I Poly(t-butyl crotonate) I Spin-Lattice Relaxation Time I Nuclear Overhauser Effect j #-Substitution I Local Chain Motions I Chain Stiffness I
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