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

Abstract

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

Proton Conducting Copolymer Electrolytes Based on Vinyl Phosphonic Acid and 5‐(Methacrylamido)tetrazole

“…The peak located at around 167 ppm belongs to carbon of the carbonyl group. Additionally, the tetrazole ring carbon gave a peak around 150 ppm in the aminotetrazole ring …”

“…Additionally, the tetrazole ring carbon gave a peak around 150 ppm in the aminotetrazole ring. [ 1,39 ] All copolymers contain several types of hydrogen that have three different functional groups such as amide, tetrazole ring (-NH), and phosphonic acid groups. These -NH and -OH hydrogens are mobile due to the formation of hydrogen-bonding network between MTet groups and phosphonic acid units of VPA, so we cannot only determine the structure with 1 H NMR spectra.…”

Metal derivatives of tetrazoles

“…Copolymerisation of this salt with 0.08 mol.% of N,N H -methylenebis(acrylamide) affords a polymeric gel absorbing up to 200 g of water per gram. 18 …”

Novel composite polymer electrolyte membranes based on poly(vinyl phosphonic acid) and poly (5-(methacrylamido)tetrazole)

“…Tetrazole functional methacrylamide based monomer (MTet) was synthesized according to literature as depicted in Fig. . Methacryloyl chloride (10.7 g, 10.0 mL, 102 mmol) was added dropwise to a suspension of 5‐aminotetrazole monohydrate (10.0 g, 97.0 mmol) in tetrahydrofuran (THF) (250 mL) and distilled water (H 2 O) (12 mL) at room temperature.…”

“…The reaction mixture was then added dropwise to methanol (250 mL)/concentrated HCl (5 mL) solution. The colorless solid was collected by filtration, washed with methanol (4 × 20 mL), and dried in vacuo at 80°C . 1 H‐NMR (400MHz, DMSO‐d 6 , δ): 0.85 (br m, 3H, CH 3 ), 2.09, 2.34 (br s, 2H, CH 2 ), 11.65 (br s, 1H, CONH), 15.90 (br s, 1H, tetrazole‐NH).…”