Spinning of hydroalcoholic chitosan solutions

•We reported the spinning of hydroalcoholic chitosan solutions.•The resulting chitosan fibers only contain chitosan and residual physisorbated water.•The crystalline morphology was controlled by the hydration degree of chitosan chains.•Anhydrous crystals formed without significant degradation of the polymer.•Different post-extrusion thermal treatments were studied. We investigated the spinning of hydroalcoholic chitosan solutions. The dope composition was optimized in order to obtain a continuous alcogel fiber by water evaporation on heating the extruded hydroalcoholic solution. This alcogel fiber was then neutralized in aqueous alkali baths and washed in water to eliminate the residual alcohol and salts before final drying. Depending on the alcohol content in the filament at the neutralization step, on specific alcohol–chitosan interactions and on the nature and concentration of the coagulation base, the process yielded semicrystalline chitosan fibers with different proportions of anhydrous and hydrated allomorphs. Contrarily to the classical annealing method, the formation of mainly anhydrous crystals was obtained without significant molecular weight decrease by neutralizing the polymer in hydrophobic conditions. The control of allomorph content was shown to be related to the hydrophobicity of the solvent (alcohol fraction) at the neutralization step.