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

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

doi:10.1002/qua.10205

Cited by 18 publications

(11 citation statements)

References 27 publications

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“…In relation with this, of special interest is the high biocidal efficiency of novel water-soluble nonquaternary polymers of poly(diallylammonium) salts series (PDAAs) discovered by the authors, namely, the secondary poly(diallylammonium trifluoroacetate) (PDAATFA) and tertiary poly(diallylmethylammonium trifluoroacetate) (PDAMATFA), which have been synthesized recently. , The antimicrobial activity of secondary and tertiary PDAAs had not been reported before. Due to difficulties in preparation of polymers from monomers of the diallylamine (DAA) series in nonquaternary form, which are related to degradative chain transfer to monomer and kinetic chain termination, up to recently it was not possible to obtain secondary and tertiary PDAAs with a sufficiently high molecular mass. − We have proposed an approach that is essentially based on the creation in the polymerizing medium of a dominant amount of monomers of the DAA series in protonated form, owing to which the competitive ability of the chain transfer to monomer reaction diminishes and the degradative chain transfer transforms into the effective one . In accordance with this approach, the methods has been employed for the synthesis of novel monomer systems, namely trifluoroacetic salts of the monomers of DAA series, and the cationic polyelectrolytes on their bases.…”

Section: Introductionmentioning

confidence: 99%

Secondary and Tertiary Polydiallylammonium Salts: Novel Polymers with High Antimicrobial Activity

et al. 2009

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Antimicrobial activity of secondary and tertiary poly(diallylammonium) salts (PDAAs) had not been reported before. Due to difficulties with preparation of polymers from the monomers of the diallylamine (DAA) series in the nonquaternary form, up to recently it was not possible to obtain PDAAs with a sufficiently high molecular mass. Here, we describe the investigations of antimicrobial activity of novel water-soluble cationic polyelectrolytes of the PDAA series, namely secondary poly(diallylammonium trifluoroacetate) (PDAATFA) and tertiary poly(diallylmethylammonium trifluoroacetate) (PDAMATFA), in synthesis of which we have recently succeeded, against gram-positive and gram-negative bacteria, and fungi. We have studied the effect of molecular weight (polymeric chain length) and ionic strength of solution on the biocidal efficiency of those polymers; in addition, the concentration dependences of PDAATFA reduced viscosity in salt-free and KCl aqueous solutions have been investigated. The antimicrobial properties of polybase polydiallylamine (BPDAA), which was obtained in an aqueous solution of PDAATFA in presence of alkali, have been also studied as well as biocidal activity of commercial open-chain polybase branched PEI. Those PDAATFA, BPDAA and PEI polymers served as the systems to study the structure-activity relationships. Transmission electronic microscopy study was carried out to characterize the mode of antimicrobial action of PDAATFA using E. coli . It was shown that the synthesized PDAATFA and PDAMATFA exhibit, unlike the quaternary polymers of this series, a rather high biocidal efficiency that is comparable with the activity of known effective cationic polymer biocides or exceeds it. Novel polyelectrolytes exhibit quite strong biocidal properties at different conditions including aqueous solutions of moderate ionic strength (serum, 0.01 M/0.1 M) and aqueous-alkaline solutions (pH 10.5) until the macrochain retains some positive charge, but complete neutralization of the polyelectrolyte in a 1 M salt solution results in the loss of its biocidal activity. The obtained results evidence that the structure of links, which combine the hydrophobic pyrrolidinium rings with the hydrophilic secondary/tertiary ammonium groups, is responsible for the high biocidal activity of the PDAAs. Polymeric nature of the synthesized compounds is one of the most significant factors of their bactericidal efficiency, unlike their high fungicidal activity, which is evidently related to the secondary/tertiary pyrrolidinium cycle.

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Section: Introductionmentioning

confidence: 99%

Secondary and Tertiary Polydiallylammonium Salts: Novel Polymers with High Antimicrobial Activity

et al. 2009

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“…Davis and coworkers26, 27 used methyl radical addition to model the propagation reaction to probe the Q–e (activity charge) scheme. The methyl radical was chosen as a model for the propagating radical by Timofeeva et al,28 who carried out quantum chemical modeling of the radical polymerization of diallylamine compounds and achieved controllable syntheses of high‐molecular‐weight polymers.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and modeling of new phosphorus‐containing acrylates

Salman

Albayrak

Avcı

et al. 2005

J. Polym. Sci. A Polym. Chem.

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New methacrylate monomers containing phosphonic acid or both phosphonic and carboxylic acids were synthesized through the reaction of t-butyl a-bromomethyl acrylate with triethyl phosphite followed by the selective hydrolysis of the phosphonate or t-butyl ester groups with trimethylsilyl bromide and trifluoroacetic acid. The copolymerization of these monomers with 2-hydroxyethylmethacrylate was investigated with photodifferential scanning calorimetry at 40 8C with 2,2 0 -dimethoxy-2-phenyl acetophenone as a photoinitiator. Quantum mechanical tools were also used to understand the mechanistic behavior of the polymerization reactions of these synthesized monomers. The propagation and chain-transfer reactions were considered and rationalized. A strong effect of the monomer structure on the rate of polymerization was observed. The polymerization reactivities of the monomers increased with decreasing steric hindrance and/or increasing hydrogen-bonding capacity because of the hydrolysis of the phosphonate and the t-butyl ester groups.

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“…We studied the potential energy profiles and the kinetics of chain propagation and the competing chain transfer reactions by considering the addition of the free radical to the double bond and the α‐hydrogen abstraction as shown in Figure 4. This strategy has already been used by Timofeeva et al 30, who carried out quantum chemical modeling of the radical polymerization of diallylamine compounds and had achieved controllable synthesis of high molecular weight polymers.…”

Section: Computational Methodologymentioning

confidence: 99%

Modeling the free radical polymerization of acrylates

Günaydın

Salman

Tüzün

et al. 2005

Int J of Quantum Chemistry

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ABSTRACT:Acrylates have gained importance because of their ease of conversion to high-molecular-weight polymers and their broad industrial use. Methyl methacrylate (MMA) is a well-known monomer for free radical polymerization, but its ␣-methyl substituent restricts the chemical modification of the monomer and therefore the properties of the resulting polymer. The presence of a heteroatom in the methyl group is known to increase the polymerizability of MMA. Methyl ␣-hydroxymethylacrylate (MHMA), methyl ␣-methoxymethylacrylate (MC 1 MA), methyl ␣-acetoxymethylacrylate (MAcMA) show even better conversions to high-molecular-weight polymers than MMA. In contrast, the polymerization rate is known to decrease as the methyl group is replaced by ethyl in ethyl ␣-hydroxymethylacrylate (EHMA) and t-butyl in t-butyl ␣-hydroxymethylacrylate (TBHMA). In this study, quantum mechanical tools (B3LYP/6-31G*) have been used in order to understand the mechanistic behavior of the free radical polymerization reactions of acrylates. The polymerization rates of MMA, MHMA, MC 1 MA, MAcMA, EHMA, TBHMA, MC 1 AN (␣-methoxymethyl acrylonitrile), and MC 1 AA (␣-methoxymethyl acrylic acid) have been evaluated and rationalized. Simple monomers such as allyl alcohol (AA) and allyl chloride (AC) have also been modeled for comparative purposes.

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

Cited by 18 publications

References 27 publications

Secondary and Tertiary Polydiallylammonium Salts: Novel Polymers with High Antimicrobial Activity

Secondary and Tertiary Polydiallylammonium Salts: Novel Polymers with High Antimicrobial Activity

Synthesis and modeling of new phosphorus‐containing acrylates

Modeling the free radical polymerization of acrylates

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