On the edge between organic solvent nanofiltration and ultrafiltration: Characterization of regenerated cellulose membrane with aspect on dendrimer purification and recycling

The performance of commercial cellulose membranes with pore size on the border between ultra-and nano-filtration in selected organic solvents was studied focusing on rejection of small solutes and applicability for dendrimer purification. Organic markers in the MW range 100 - 700 Da and polarity range from nonpolar to polar protic compounds (aliphatics, aromatics, ethers, esters and alcohols) were used for membrane character-ization. Transmission experiments in mixtures of methanol and dichloromethane of variable ratio showed the suitability of tested membranes for intended purpose, bringing information on structural factors affecting the rejection. Besides solute molar volume, its polarity type, or affinity, most conveniently expressed by Hansen solubility parameters, was found to be a crucial factor; with increasing size of solute molecule the spatial arrangement becomes also important. Solvent composition influences not only the behavior of solutes, but it also affects the membrane structure: poor solvation of cellulose by less polar solvents causes partial pore collapse, resulting in a decrease of membrane molecular weight cutoff. This effect can be used to improve the retention of a target product, as was shown for the first generation amphiphilic dendron. In addition, a simple mathematical model, allowing to estimate the course of nanofiltration and to optimize its conditions in a semicontinuous dead-end setup, is presented.