Physical gelation of cellulose acetate propionate solutions mediated by metal carbonyl complexes

The weak physical gelation of cellulose acetate propionate-butyl butyrate solutions as a result of the in-situ decomposition of iron pentacarbonyl complexes was explored. Viscometry and infrared spectroscopy were used to monitor the iron pentacarbonyl decomposition reaction progress and its effect on viscosity. Changes in viscosity in of the cellulosic fluids in general and gelation in particular were found to be dependent upon the environment in which the Fe(CO)₅ decompositions occurred. Systems under inert atmospheres exhibited a marked increase in viscosity, while systems under oxidative atmospheres exhibited a general decrease in viscosity. We propose a hypothesis that explains the dependence of the viscosity of these cellulosic fluids as a function of the environmental conditions during the precursor decomposition. Under nitrogen atmospheres, zero-valent nanoparticles with highly reactive surfaces are synthesized, which form weak, transient bonds with the cellulosic polymer. The iron particles, under these circumstances, serve as weak bridges between adjacent polymer chains. Conversely, the primary particles synthesized under an oxidative atmosphere are metal oxides, which are less attractive to the polymer chain and, therefore, do not yield such bridges. This work demonstrates the capability to apply a simple method to control the viscosity of cellulose ester fluids.