Partial methylation of poly[thio-1-(n,n-dimethylaminomethyl)ethylene] and conformational behavior of resulting dibasic polyelectrolytes

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. SIMILAR CONTENT BEING VIEWED BY OTHERS POLYMERIZATION OF EXPANDED L-AMINO ACIDS CONTAINING TERMINAL PYRIDYL GROUPS BY SILVER(I) IONS IN

NONPOLAR SOLVENT Article 20 April 2022 SYNTHESIS AND CHARACTERIZATION OF ESTER-FREE POLY(TRIMETHYLENE CARBONATE) BEARING LONG-ALKYL MOIETIES AND ITS DEGRADATION Article 15 November 2024

DEGRADATION OF POLY(CONJUGATED ESTER)S USING A CONJUGATE SUBSTITUTION REACTION WITH VARIOUS AMINES AND AMINO ACIDS IN AQUEOUS MEDIA Article 15 December 2023 ARTICLE PDF REFERENCES * M. Vert,

in “_Polyelectrolytes_,” E. Selegny, Ed., Reidel Publishing Co., Dordrecht, 1974, p 347. Google Scholar  * M. Vert, in “_Optically Active Polymers_,” E. Selegny, Ed., Reidel Publishing Co.,

Dordrecht, 1979, p 291. Google Scholar  * J. Huguet, M. Vert, N. Spassky, and E. Selegny, _Makromol. Chem._, 170, 23 (1973). * J. Huguet, M. Vert, and E. Selegny, _Eur. Polym. J._, 10, 261

(1974). * J. Huguet, _Nouv. J. Chim._, 3, 293 (1979). * A. Shatkay and I. Michaeli, _J. Phys. Chem._, 70, 3777 (1966). * A. L. Barney, _U.S. Patent 2 677 679_ (march 4, 1954) to Du Pont. *

Yu. E. Kirsh, N. R. Pavlova, and V. A. Kabanov, _Eur. Polym. J._, 11, 47 (1975). * M. Fred Hoover, _J. Macromol. Sci., Chem._, A4, 1327 (1970). * N. Spassky, P. Dumas, M. Sepulchre, and P.

Sigwalt, _J. Polym. Sci., Polym. Symp._, No. 52, 237 (1975). * L. F. Fieser and M. Fieser, in “_Reagent for Organic Synthesis_,” John Wiley and Sons, Inc., New-York, N.Y., 1967, p 682.

Google Scholar  * L. F. Fieser and M. Fieser, in “_Reagent for Organic Synthesis_,” John Wiley and Sons, Inc., New York, N.Y., 1967, p 1210. Google Scholar  * D. Van Ooteghem, W. Van

Craenest, and E. J. Goethals, _Makromol. Chem._, 175, 1309 (1974). * R. P. Simonds, E. J. Goethals, and N. Spassky, _Makromol. Chem._, 179, 1851 (1978). * A. Katchalsky, N. Shavit, and H.

Eisenberg, _J. Polym. Sci._, 13, 69 (1954). * H. Morawetz, in “_Macromolecules in Solution_,” John Wiley and Sons, Inc., New York, N.Y., 1975, p 380. Google Scholar  * J. C. Fenyo, J.

Beaumais, and E. Selegny, _J. Polym. Sci., Polym. Chem. Ed._, 12, 2659 (1974). * M. Mandel and J. C. Leyte, _J. Polym. Sci., A_, 2, 3771 (1964). * K. Linderstrom-Lang, _Arch. Biochem._, 11,

191 (1946). * I. Michaeli, _J. Phys. Chem._, 71, 3384 (1967). * J. Engel and G. Schwarz, _Angew. Chem., Intern. Edit._, 9, 389 (1970). * M. Sepulchre, N. Spassky, J. Huguet, M. Vert, and P.

Granger, _Polymer_, 20, 833 (1979). * G. Muller, J. C. Fenyo, C. Braud, and E. Selegny, in “_Polyelectrolytes and their Applications_,” A. Rembaum and E. Selegny, Ed., Reidel Publishing Co.,

Dordrecht, 1975, p 15. Google Scholar  * M. Nagasawa and A. Holtzer, _J. Am. Chem. Soc._, 86, 536 (1964). Download references AUTHOR INFORMATION AUTHORS AND AFFILIATIONS * Laboratoire de

Chimie Macromoléculaire, ERA CNRS n° 471, Université de Haute-Normandie, Didier Vallin, Jovanka Huguet & Michel Vert Authors * Didier Vallin View author publications You can also search

for this author inPubMed Google Scholar * Jovanka Huguet View author publications You can also search for this author inPubMed Google Scholar * Michel Vert View author publications You can

also search for this author inPubMed Google Scholar RIGHTS AND PERMISSIONS Reprints and permissions ABOUT THIS ARTICLE CITE THIS ARTICLE 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 Download citation * Issue Date: 01 February 1980 * DOI: https://doi.org/10.1295/polymj.12.113 SHARE THIS ARTICLE Anyone you share the following link

with will be able to read this content: Get shareable link Sorry, a shareable link is not currently available for this article. Copy to clipboard Provided by the Springer Nature SharedIt

content-sharing initiative KEYWORDS * Polyamines * Quaternization * Partially Quaternized * Poly(tertiary amine)s * Dibasic Polyelectrolytes * Conformational Transition * Cooperativity *

Buffering Effect