Fractionation of unsubstituted cellulose from solutions in either Ni-tren or (N,N-dimethylacetamide + LiCl)

Starting from solutions of unsubstituted cellulose (Avicel PH101, M w = 30.1 kg/mol and M w /M n = 3 or Solucell 500, M w = 230 kg/mol, M w /M n = 2.8) in either Nitren (0.8 M aqueous solution of the dihydroxotris(2-aminoethly)amine nickel(II) complex) or in a mixed solvent DMAc+LiCl (consisting of N,N-dimethylacetamide plus lithium chloride) it was investigated whether the segregation of a second phase caused by the addition of suitable precipitants leads to polymer fractionation. With Ni-tren the long chains accumulate in the precipitate formed upon the addition of sulfuric acid; as the pH falls below 9, the solution is free of cellulose. Nevertheless this route option for fractionation m…

Cover Picture: Macromol. Mater. Eng. 5/2004

Formation of micro- and nano-spheric particles (filter dust) during the preparation of cellulose acetate membranes

Abstract Membranes were prepared from six samples of cellulose acetate (CA) differing in their average molecular weight (75–260 kg/mole) and molecular weight distribution using methyl acetate as solvent and 2-propanole as precipitant. The routes through the phase diagram and the evaporation times were varied in these experiments. Electron microscopy demonstrates that the amount of filter dust (CA particles deposited on the membrane surface) decreases as the fraction of low molecular weight material in the starting polymer becomes less. For low average molar mass of CA and moderate polymer concentrations in the casting solution the dust consists of individual spheres of relatively uniform si…

Fractionation of cellulose acetate for the investigation of molecular weight influences on the morphology of membranes

Abstract Cellulose acetate (CA) with an apparent weight average molar mass, M w ∗ , of 150 kg/mol was fractionated with respect to M by means of the mixed solvent methyl acetate (MeAc)/2-propanol (2-POH) applying a new method that uses spinning nozzles to promote the rapid attainment of phase equilibria. Two of the fractions obtained in this manner were employed to prepare membranes from solutions in methyl acetate with 2-propanol as coagulating agent. Electron micrographs demonstrate that the molar mass of CA influences the morphology of the membranes markedly under otherwise identical conditions. For M w ∗ =128  kg/mol, one obtains considerably denser structures than for M w ∗ =263  kg/mo…

Large Scale Fractionation of Macromolecules

Access to sufficiently large amounts of material with adequate molecular and chemical uniformity from polydisperse natural products or synthetic materials has been a long-standing challenge to polymer scientists. We have developed a broadly applicable preparative fractionation method consisting of a special kind of continuous extraction removing the easier soluble components from the initial product. It is rendered possible by the use of spinning nozzles throught which a concentrated polymer solution is pressed into a liquid of tailored thermodynamic quality. The initially produced jets of the source phase disintegrate rapidly into minute droplets of typically 50 μm diameter. This efficient…

Basis for the Preparative Fractionation of a Statistical Copolymer (SAN) with Respect to Either Chain Length or Chemical Composition

The possibilities to fractionate copolymers with respect to their chemical composition on a preparative scale by means of the establishment of liquid/liquid phase equilibria were studied for random copolymers of styrene and acrylonitrile (SAN). Experiments with solutions of SAN in toluene have shown that fractionation does in this quasi-binary system, where demixing results from marginal solvent quality, take place with respect to the chain length of the polymer only. On the other hand, if phase separation is induced by a second, chemically different polymer, one can find conditions under which fractionation with respect to composition becomes dominant. This opportunity is documented for th…