Synthesis and Characterization of Poly(N‐vinylimidazole‐co‐acrylonitrile) and Determination of Monomer Reactivity Ratios

Abstract

Summary: Radical‐initiated solution copolymerization of N‐vinylimidazole (VIM) and acrylonitrile (AN) was carried out with 2,2′‐azobisisobutyronitrile (AIBN) as an initiator in benzene at 70 °C in nitrogen atmosphere. The structure and composition of synthesized copolymers for a wide range of monomer feeds were determined by FTIR, 1H and 13C NMR spectroscopy with the aid of recorded analytical absorption bands for VIM (667 cm−1, CN of imidazole ring) and AN (2 242 cm−1, CN group), as well as by using the areas of proton and carbon atom signals from corresponding functional groups of monomer units. Monomer reactivity ratios for VIM (M1)‐AN (M2) pair were determined by nonlinear regression (NLR), Kelen–Tüdös (KT) and Fineman–Ross (FR) methods. They were found to be r1 = 0.24 and r2 = 0.15 for the NLR method, r1 = 0.22 and r2 = 0.094 for the KT method, and r1 = 0.24 and r2 = 0.12 for the FR method, respectively. The relatively high activity observed of VIM growing macroradical and the results of FTIR and 1H NMR structural analysis of copolymers suggest the formation of complexed linkages between monomers and growing radicals in chain propagation reactions. Similar complexation between monomer–comonomer units in the structure of formed macromolecules showed an increase in isotactic triad fractions in the copolymer.Complex formation between the imidazole ring and nitrile group in both the monomer mixture and chain growing reactions.imageComplex formation between the imidazole ring and nitrile group in both the monomer mixture and chain growing reactions.

Measurement of ionic conductivity of poly (N-vinylimidazole) and its fluoroborate salt in solid state

“…1. In PVIM, the peak at 3,109.25 cm −1 is due to C-H (ring)stretching, 2,958.80 cm −1 is due to C-H and CH 2 (main chain) stretching, 1,658.78 cm −1 is due to C=C (ring) stretching, 1,504.48 cm −1 is due to C-C and C=N (ring) stretching; the peaks at 1,284.59, 1,228.66, 1,083.99 cm −1 are due to C-H (ring) in plane bending, C-N (ring) stretching; the peak at 914.26 cm −1 is due to ring stretching and in plane bending and at 663.51 cm −1 is due to C-N (ring) stretching [22]. In PVIM-HBF 4 , the peak at 3,153.61 cm −1 is due to C-H (ring) stretching, 2,875.86 cm −1 is due to C-H and CH 2 (main chain) stretching, 1,633.71 cm −1 is due to C=C (ring) stretching, 1,452.40 cm −1 is due to C-C and C=N (ring) stretching; the peaks at 1,294.24, 1,259.52, and 1,089.78 cm −1 are due to C-H (ring) in plane bending, C-N (ring) stretching; the peak at 653.87 cm −1 is due to C-N (ring) stretching [23].…”

“…2. The spectrum of PVIM contains the characteristic proton signals from imidazole ring (multiplet with 6.6-7.2 ppm), backbone CH 2 (1.8-2.2 ppm) group, and splitting chain CH group (2.6-2.8 ppm) [22]. The spectrum of PVIM-HBF 4 contain the characteristic proton signals from imidazole ring (7-7.5 ppm), backbone CH 2 (2.2-2.9 ppm) group, and splitting chain CH group (3.9-4.1 ppm).…”

Quaternized poly(1-vinylimidazole) hydrogel for anion adsorption

“…These are used as a carrier agent for protein separations [12,13] and for the preparation of strong anion exchange membranes [14] and new steric stabilizers for polyaniline colloids [15,16]. Particular attention has been focused on copolymers of quaternized VIm derivatives because of a promising set of valuable properties being exhibited by these substances.…”

Removal of As(V), Cr(III) and Cr(VI) from aqueous environments by poly(acrylonitril-co-acrylamidopropyl-trimethyl ammonium chloride)-based hydrogels

“…Herein, acrylonitrile (AN) and 3-acrylamidopropyl-trimethyl ammonium chloride (APTMACl) monomers were used for co-polymeric hydrogel preparation as p(APTMACl-co-AN) and then amidoximated for use in the removal of ions such as As(V) and Cr(III) and Cr(VI) from aqueous solutions. The cyano groups in the acrylonitrile structure can be chemically changed by chemical modification to induce new chemical and physical properties on the polymer substrate (Pekel et al, 2004;Mostafa, 2009;Sahiner et al, 2011b). P(APTMACl) is an attractive cationic smart material possessing quaternary ammonium salt which renders a natural positive charge on the polymer chains (Sahiner and Ilgın, 2010).…”