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A Further Study on Solvation in Cellulose Triacetate Solutions by Pulse-Fourier 1H and 13C NMR Method

An attempt was made by pulse-Fourier 1H and 13C NMR to measure the chemical shift δ of the O-acetyl-methyl (AMH) and -carbonyl carbon (ACC) of cellulose triacetate (CTA, the total degree of substitution « F » =2.92) in various deuterated solvents and to determine whether the possibility of the solvation depends on the position (C2, C3, or C6) of the O-acetyl group or not and if so, to evaluate the positions of the O-acetyl group, to which the solvent molecules are preferentially solvated. Among N,N-dimethylsulfoxide (DMSO), pyridine (Py), trichloromethane (TCM) and acetone, the spin-lattice relaxation time of AMH at C2 carbon and that of ACC at C2, C3, and C6 carbons were maximum in acetone, indicating that acetone molecules interact the most weakly with O-acetyl group. The difference of δ of AMH at each carbon position (C2, C3, and C6) between DMSO or Py or TCM and acetone was positive in DMSO and negative in Py, TCM. The similar difference of δ of ACC was always positive, except the case of ACC at C2 and C3 positions in Py, where the difference was zero. Assuming no specific interaction between acetone and CTA we can conclude that DMSO and TCM molecules solvate equally with O-acetyl group at C2, C3, and C6 positions, but the pyridine molecule solvates only with O-acetyl group at C6 positions.