Poly‐C‐vinyltetrazoles: A new type of polyacid

Annenkov, Vadim V.; Kruglova, V. A.

doi:10.1002/pola.1993.080310729

Cited by 4 publications

(8 citation statements)

References 5 publications

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“…Neither a glass transition nor a melting temperature could be observed. A high degree of hydrogen bonding between the amide and tetrazole groups was thought to be responsible for the low solubility of the material, which has also been an issue for literature‐known poly(vinyltetrazole)s 3. A reduced solubility in water conforms, furthermore, with the well‐established higher lipophilicity of tetrazoles in comparison with their corresponding carboxylic acid analogues.…”

Section: Resultsmentioning

confidence: 99%

“…Although vinyl monomers with carboxylic acid groups are well known in polymer synthesis (e.g., acrylic acid, methacrylic acid, and 4‐vinylbenzoic acid), few reports have dealt with polymerizable tetrazoles. To the best of our knowledge, the only known examples consist of 5‐vinyltetrazole ( 1 ) and 5‐isopropenyltetrazole ( 2 ) 1–3. However, their preparation from acrylonitrile (or 3‐hydroxypropionitrile) or methacrylonitrile requires the use of azides, which not only are highly toxic but also risk the formation of potentially explosive byproducts.…”

Section: Introductionmentioning

confidence: 99%

“…To the best of our knowledge, the only known examples consist of 5-vinyltetrazole (1) and 5-isopropenyltetrazole (2). [1][2][3] However, their preparation from acrylonitrile (or 3-hydroxypropionitrile) or methacrylonitrile requires the use of azides, which not only are highly toxic but also risk the formation of potentially explosive byproducts. Polytetrazoles have similarly been derived from poly(acrylonitrile) by a polymer-analogous reaction involving the cycloaddition of NaN 3 to the polymer's nitrile groups: 4,5 In this article, we report a short and facile synthetic route toward the polymerizable (meth)acrylamides 5-(acrylamido)tetrazole (3) and 5-(methacrylamido)tetrazole (4), which both contain a tetrazole substituent.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis and polymerization of 5‐(methacrylamido)tetrazole, a water‐soluble acidic monomer

Taden

Tait

Kraft

2002

J. Polym. Sci. A Polym. Chem.

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The reaction of methacryloyl chloride with 5‐aminotetrazole gave the polymerizable methacrylamide derivative 5‐(methacrylamido)tetrazole (4) in one step. The monomer had an acidic tetrazole group with a pKa value of 4.50 ± 0.01 in water methanol (2:1). Radical polymerization proceeded smoothly in dimethyl formamide or, after the conversion of monomer 4 into sodium salt 4‐Na, even in water. A superabsorbent polymer gel was obtained by the copolymerization of 4‐Na and 0.08 mol % N,N′‐methylenebisacrylamide. Its water absorbency was about 200 g of water/g of polymer, although the extractable sol content of the gel turned out to be high. The consumption of 4‐Na and acrylamide (as a model compound for the crosslinker) during a radical polymerization at 57 °C in D2O was followed by 1H NMR spectroscopy. Fitting the changes in the monomer concentration to the integrated form of the copolymerization equation gave the reactivity ratios r4‐Na = 1.10 ± 0.05 and racrylamide = 0.45 ± 0.02, which did not differ much from those of an ideal copolymerization. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4333–4343, 2002

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Synthesis and polymerization of 5‐(methacrylamido)tetrazole, a water‐soluble acidic monomer

Taden

Tait

Kraft

2002

J. Polym. Sci. A Polym. Chem.

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“…For the purposes of proton conduction, it is the least studied azole to date due to the arduous synthesis typically involved. However, 1 H -tetrazoles are particularly attractive for proton conducting applications due to their high potential degree of coordination and acidity. , A variety of synthetic strategies have been developed to access functionalized azoles with intact N–H protons, which enable structural proton transport. − In the absence of a free proton, these materials require additional proton sources (e.g., −SO 3 H, H 3 PO 4 ) to generate mobile protons.…”

Section: Introductionmentioning

confidence: 99%

“…1 H -Tetrazole-bearing polymers are known. ,,,,, However, few have been studied in their capacity as materials capable of anhydrous proton transport. − The majority of these materials are derived from poly(acrylonitrile), where the tetrazole is directly bound to the backbone and is highly dependent on backbone flexibility for increased conductivity or where the reaction of 5-amino-1 H -tetrazole, having modified acid–base properties, is reacted with suitable electrophilic precursor polymers. The nature and length of the side chain connecting 1 H -tetrazole to the polymer backbone (e.g., shortest in PAN-derived materials) are likely to have a great impact on material properties through both its electronic effects and effects on the local environment of the tethered tetrazole.…”

Section: Introductionmentioning

confidence: 99%

Tetrazolation of Side Chains and Anhydrous Conductivity in a Hydrophobic Polymer

et al. 2014

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1H-Tetrazoles possess the lowest pK a within the azole family of nitrogen-containing heterocycles, making them attractive amphoteric moieties for anhydrous proton conduction. The synthesis of a styrenic, random coil polymer with pendent C-substituted 1H-tetrazoles is described in detail. This facile route results in a polymer containing free proton-bearing tetrazoles, limits side reactions, and proceeds using low polarity, halogenated solvents (e.g., 1,2dichlorobenzene or chlorobenzene), which improve solubility during tetrazole cyclization. The resulting polymer, when probed by NMR spectroscopy and elemental analysis, had no measurable salt content, ensuring accurate proton conductivity measurements. Utilizing interdigitated electrodes (IDEs) in conjunction with electrochemical impedance spectroscopy (EIS), undoped anhydrous proton conductivities were measured to be as high as 10 −5 S cm −1 at 120 °C. This weakly acidic, 1H-tetrazole-bearing polymer is thermally stable to 210 °C, possesses two distinct glass transitions (T g ) at 49 and 74 °C, and exhibits surprisingly low water uptake, despite its acidic and amphoteric nature. Reduction of T g s, achieved by synthesis of low molecular weight poly(4-vinylphenol) via acid polymerization, shows a minimal dependence of anhydrous proton conductivity on backbone motion.

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Well-Defined (Co)polymers with 5-Vinyltetrazole Units via Combination of Atom Transfer Radical (Co)polymerization of Acrylonitrile and “Click Chemistry”-Type Postpolymerization Modification

et al. 2004

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Well-defined homo- and copolymers of acrylonitrile were prepared by atom transfer radical polymerization, which were further modified using a “click chemistry” reaction with sodium azide and zinc chloride to yield polymeric materials with 5-vinyltetrazole units. Using optimized reaction conditions ([NaN3]:[ZnCl2]:[RCN] = 4:1:1 in DMF at 120 °C for 48−50 h), essentially complete transformation of the nitrile groups was achieved, as judged from IR and 13C NMR spectra. The produced tetrazole-containing polymers had markedly better solubility or swellability in protic solvents (methanol or aqueous base solutions) compared to the precursors. Random copolymers of acrylonitrile and styrene were also grown from polystyrene and silica particles with immobilized initiator groups and were similarly modified to the corresponding tetrazole-containing polymers. All materials were characterized by means of thermogravimetry, which showed that the polymeric tetrazoles started to decompose with evolution of significant amounts of gas at 120−190 °C, i.e., at lower (by 60−130 °C) temperature than the starting nitrile-based materials.

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Poly‐C‐vinyltetrazoles: A new type of polyacid

Cited by 4 publications

References 5 publications

Synthesis and polymerization of 5‐(methacrylamido)tetrazole, a water‐soluble acidic monomer

Synthesis and polymerization of 5‐(methacrylamido)tetrazole, a water‐soluble acidic monomer

Tetrazolation of Side Chains and Anhydrous Conductivity in a Hydrophobic Polymer

Well-Defined (Co)polymers with 5-Vinyltetrazole Units via Combination of Atom Transfer Radical (Co)polymerization of Acrylonitrile and “Click Chemistry”-Type Postpolymerization Modification

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