Abstract
The quaternization of some of the side-chain tertiary amine groups of poly[thio-1-(N,N-diethyl aminomethyl)ethylene] (P TDAE) was attempted in order to water-solubilize the weak polybases regardless of the pH. CH3I readily quaternized amino groups but a simultaneous degradation of the polythioether backbone occurred. Methylating conditions were adjusted to limit the decrease in molecular weight. Copolymers having 17,22, 35, and 48% (Q-P TDAE 17, 22, 35, and 48) of quaternized repeat units were prepared. The addition of HCl to solutions of these compounds (dibasic form) gives rise to: first, an ion-exchange reaction on quaternary ammonium groups: NR4+OH− ⇌s NR4+ Cl−, and second, a protonation reaction of tertiary amine groups. Only the latter increases the charge density of the polymer chains. The resulting changes in pH and viscosity are discussed. Surprisingly, for Q-P TDAE 17 and 22, a high buffering region similar to that found for precipitating P TDAE, was observed on potentiometric titration curves in the zone corresponding to the protonation of tertiary amine groups. Further, viscometric titration curves exhibited a linear variation of the reduced viscosity in the same zone. Neither of these features appeared for Q-P TDAE 35 and 48, or in 80:20 (v/v) methanol–water mixture, whatever the degree of quaternization. A polysoap-like to extended coil conformational transition with an all-or-nothing cooperative mechanism is proposed to account of particularities in the physicochemical behavior of Q-P TDAE 17 and 22.
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Vallin, D., Huguet, J. & Vert, M. Partial Methylation of Poly[thio-1-(N,N-dimethylaminomethyl)ethylene] and Conformational Behavior of Resulting Dibasic Polyelectrolytes. Polym J 12, 113–124 (1980). https://doi.org/10.1295/polymj.12.113
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DOI: https://doi.org/10.1295/polymj.12.113
