Synthesis and properties of tetrazole-containing polyelectrolytes based on chitosan, starch, and arabinogalactan

Abstract

The synthesis of tetrazole-containing derivatives of chitosan, starch, and arabinogalactan was carried out by a sequence of reactions including cyanoethylation of polysaccharides and subsequent azidation of cyanoethyl derivatives. The reaction of cyanoethylation of polysaccharides with acrylonitrile proceeds in the temperature range 40–60°C in the presence of NaOH. The transformation of nitrile groups into tetrazole rings (azidation) of cyanoethylated polysaccharide derivatives was carried out with a mixture of sodium azide with ammonium chloride in DMF at 105°C. The reaction with the participation of derivatives of starch and arabinogalactan is characterized by the degree of conversion of nitrile groups into tetrazole rings, which is close to the maximum. The introduction of unsubstituted tetrazole rings into the structure of polysaccharides of acidic N–H substantially changes some of their properties. Like other carbo- and hetero-chain polymers containing N–H unsubstituted tetrazole rings in the structure, tetrazolated polysaccharides exhibit the properties of acidic polyelectrolytes. Tetrazole-containing derivatives of chitosan exhibit the properties of polyampholytes. The presence of tetrazole rings in the structure of modified polysaccharides allows the reaction with epoxy compounds to yield network polymers capable of limited swelling in aqueous media with the formation of polyelectrolyte hydrogels.

Keywords

• macromolecular reactions
• polysaccharides
• tetrazole cycle
• polyelectrolytes
• hydrogels