Mechanism of interaction of diallylmethylamine and its protonated and quaternary forms with their own radicals in solvent

Timofeeva, L. M.; Vasilieva, Yu. A.; Kleshcheva, N. A.; Topchiev, D. A.

doi:10.1007/bf02494626

Cited by 14 publications

(20 citation statements)

References 19 publications

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“…The carbonyl carbon of 6 and 7 appeared at 167.68 and 169.58, respectively [not shown in Figure 2(c,d)]. The absence of any residual alkene proton or carbon signal in the spectra of 5–7 indicated the chain transfer process for the termination reaction involving the macroradical abstracting the labile allylic hydrogen of the monomer 45–47. The absence of the signals for the methyl protons and carbon of OCH 2 CH 3 at ∼δ1.4 [Figure 1(c)] and δ14.5 [Figure 2(c)], respectively, ascertained the complete hydrolysis of the ester functionality in 5 giving 6 .…”

Section: Resultsmentioning

confidence: 99%

Cyclopolymerization protocol for the synthesis of a poly(zwitterion‐alt‐sulfur dioxide) to investigate the polyzwitterion‐to‐poly(anion‐zwitterion) transition

Ali

Haladu

2012

J of Applied Polymer Sci

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The zwitterionic monomer, 3‐(N,N‐diallyl,N‐carboethoxymethylammonio)propanesulfonate, on cocyclopolymerization with sulfur dioxide in DMSO using azoisobutyronitrile as the initiator afforded the polyzwitterion (PZ) copolymer in excellent yields. The PZ on acidic hydrolysis of the ester groups led to the corresponding polyzwitterionic acid (PZA). The pH‐responsive PZA on treatment with sodium hydroxide gave the new poly(eletrolyte‐zwitterion) (PEZ). The solubility, viscosity behaviors, and solution properties of the salt‐tolerant PZ, PZA, and PEZ were studied in detail. Like common PZs, PZ was found to be insoluble in salt‐free but soluble in salt‐added water. The apparent basicity constants of the carboxyl group in PEZ have been determined. As the name implies, the PEZ possesses dual type of structural feature common to both conventional anionic polyelectrolytes and PZs, and its aqueous solution behavior is found to be similar to that observed for a typical alternating anionic‐zwitterionic copolymer. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

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Section: Resultsmentioning

confidence: 99%

Cyclopolymerization protocol for the synthesis of a poly(zwitterion‐alt‐sulfur dioxide) to investigate the polyzwitterion‐to‐poly(anion‐zwitterion) transition

Ali

Haladu

2012

J of Applied Polymer Sci

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“…and , respectively. The absence of any residual alkene proton or carbon signal in the spectra indicated the chain transfer process for the termination reaction involving the macroradical abstracting the labile allylic hydrogen of monomer 7 . Note that the NMR signals of PSB 16 are shifted downfield than that of APE 17 as a result of the former having the presence of electron‐withdrawing positive nitrogens (Fig.…”

Section: Resultsmentioning

confidence: 93%

Synthesis and cyclopolymerization of diallylammoniomethanesulfonate

Ali

Hamouz

2013

Polymer Engineering & Sci

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N,N‐Diallylammoniomethanesulfonate, a new zwitterionic monomer having a sulfobetaine (SB) motif, has been synthesized by reacting diallylamine with formaldehyde and sodium bisulfite. While the monomer underwent cyclopolymerization to give the unstable polysulfobetaine (PSB) in low yields, copolymerization with sulfur dioxide gave the stable PSB/SO2 copolymer in excellent yields. The polymers, as a consequence of having unquenched nitrogen valency in the repeating units, are pH‐responsive. The PSB/SO2 copolymer, upon treatment with sodium hydroxide, was converted into a water‐soluble anionic polyelectrolyte (APE). The strong zwitterionic interactions inherent in the PSB/SO2 made it insoluble in salt‐free water; the presence of large concentration (>3M) of low molecular weight salts (e.g., NaCl, KI etc,) was required to neutralize the intragroup zwitterionic interactions and promote dissolution. The PSB/SO2 represents the first example of a sulfobetaine polymer having a single methylene spacer separating the charge centers. The stability of the copolymer is explained in terms of electron density on the nitrogens. POLYM. ENG. SCI., 53:2378–2388, 2013. © 2013 Society of Plastics Engineers

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“…[24], the free electrostatic solvation energies of cationogenic monomers and radicals are well reproduced by the computational method used.…”

Section: Reagentsmentioning

confidence: 92%

“…Obviously, this introduces no considerable error when comparing the energetics of the chain propagation and chain trans-fer reactions for the same reaction system because the initial reagents remain the same, the structures of the TS are almost identical, and the volumes of the cavities for the transition states of chain propagation and chain transfer, according to our calculations, are equal for each of the systems I-III. It was shown [24] that elimination of the ⌬G V terms introduces the maximum error no more than 0.2 kcal/ mol when comparing the E 0,S values for the reactions occurring in different systems (relative energetics): systems I and III or systems II and III (the volumes of the cavities occupied by the reagents and the TS in systems I and II are virtually equal). It was shown also [24] that the error of the determination of the E 0,S absolute value (which is expressed by the ⌬G V Ϫ ¥ ⌬G V r term, where ⌬G V is the free nonelectrostatic solvation energy of the TS and ¥ ⌬G V r is the sum of the contributions of the free nonelectrostatic solvation energies of the reagents) will be no more than 1 kcal/mol.…”

Section: Appendix Amentioning

confidence: 99%

“…It was shown [24] that elimination of the ⌬G V terms introduces the maximum error no more than 0.2 kcal/ mol when comparing the E 0,S values for the reactions occurring in different systems (relative energetics): systems I and III or systems II and III (the volumes of the cavities occupied by the reagents and the TS in systems I and II are virtually equal). It was shown also [24] that the error of the determination of the E 0,S absolute value (which is expressed by the ⌬G V Ϫ ¥ ⌬G V r term, where ⌬G V is the free nonelectrostatic solvation energy of the TS and ¥ ⌬G V r is the sum of the contributions of the free nonelectrostatic solvation energies of the reagents) will be no more than 1 kcal/mol. Thus, the E 0,S values were calculated using the equation.…”

Section: Appendix Amentioning

confidence: 99%

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Radical polymerization of diallylamine compounds: From quantum chemical modeling to controllable synthesis of high‐molecular‐weight polymers

Timofeeva

Vasilieva

Kleshcheva

et al. 2002

Int J of Quantum Chemistry

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ABSTRACT:We investigated the possibility to obtain high-molecular-weight (HMW) polymers from the monomers of the diallylamine (DAA) series using quantum chemical and experimental methods. Such monomers are known to polymerize into oligomeric products due to the reaction of the degradative chain transfer to the monomer. We studied potential energy profiles of the chain propagation and competing chain transfer reactions, viz., the free radical double bond addition and ␣-hydrogen radical abstraction, respectively, for a number of polymerization processes. Calculations were carried in the framework of the polarized continuum solvent model utilizing the procedure based on the semiempirical MNDO-PM3 background. It was found that the necessary condition for decreasing competitiveness of the chain transfer to the monomer is the availability of monomer molecules in only protonated form in the polymerizing system. Using these results, we developed the strategy for obtaining HMW polymers based on said monomers. We synthesized a monomer system (the equimolar salt of N,N-diallyl-N-methylamine and trifluoroacetic acid) that fully corresponds to such requirements. Novel HMW polymers were then synthesized by radical polymerization of this salt at soft conditions. We established that chain termination is controlled by the bimolecular mechanism. We showed that the degradative chain transfer transforms into the effective chain transfer. The mechanisms of the observed phenomena are discussed.

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Mechanism of interaction of diallylmethylamine and its protonated and quaternary forms with their own radicals in solvent

Cited by 14 publications

References 19 publications

Cyclopolymerization protocol for the synthesis of a poly(zwitterion‐alt‐sulfur dioxide) to investigate the polyzwitterion‐to‐poly(anion‐zwitterion) transition

Cyclopolymerization protocol for the synthesis of a poly(zwitterion‐alt‐sulfur dioxide) to investigate the polyzwitterion‐to‐poly(anion‐zwitterion) transition

Synthesis and cyclopolymerization of diallylammoniomethanesulfonate

Radical polymerization of diallylamine compounds: From quantum chemical modeling to controllable synthesis of high‐molecular‐weight polymers

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