Applications of supercritical fluids to the extraction and analysis of oligomers and polymer additives
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Abstract
Supercritical fluids (SF)s have several physicochemical properties that can often make them superior to conventional liquid solvents. These characteristics include relatively high densities, low viscosities, zero surface tension and high diffusivities. This unique combination of properties allows them to have solvating strengths that can approach those of pure liquids while maintaining many of the advantageous transport qualities of gases. In the past decade SFs have seen increased use as solvents for both extraction (SFE) and chromatography (SFC). A particularly exciting area of applications has been in the field of polymeric materials. Since polymers are not discrete molecules, but, rather broad distributions of very similar compounds (oligomers), they can pose interesting challenges for the separation chemist. SFs are uniquely suited to meet these challenges. The goal of the work done in this laboratory over the past few years has been to use SFs to extract and characterize both oligomers and additives from polymeric materials.
A method for the post-polymerization fractionation of a low molecular weight, high density polyethylene wax using analytical scale SFE equipment was developed. Supercritical CO₂ was used to separate very narrow molecular weight distributions (MWD)s from the polyethylene feedstock. The resulting MWDs were characterized by SFC and high temperature gel permeation chromatography (GPC) and found to have polydispersities and molecular weights much lower than the parent wax. Supercritical propane was used to fractionate higher MWDs from the feedstock, however its greater solvating strength for the polyethylene oligomers resulted in larger polydispersities. A dual pump SFE system was used to deliver a dynamic mixture of propane in CO₂. The resulting fractions were very similar to those achieved by pure CO₂, but the recoveries were much higher. Increasing the temperature appeared to have both a kinetic and thermodynamic contribution to oligomer extraction.
Supercritical CO₂ was also used to extract additives from an insoluble polymeric nitrocellulose (NC). The primary stabilizer additive (diphenylamine) and its nitrated derivatives were extracted from the propellant. The SF extracted stabilizer profile was characterized using liquid chromatography (LC), gas chromatography (GC) and SFC. SFC was shown to provide separations of propellant additives that were superior to the existing LC method while maintaining lower temperatures than GC. Extracts from propellants stored at elevated surveillance temperatures contained more highly nitrated stabilizer derivatives. However, some question was raised as to the actual validity of elevated temperature programs for propellant screening due to potential differences in reaction mechanisms.
A LC-thermospray mass spectrometry (MS) interface was modified for use wtih packed column SFC. The system was used as a chemical ionization (CI) source for the high CO₂ flow rates emanating from packed columns. Methane was used as a reagent gas (RG) for positive chemical ionization (PCI). The resulting CO₂ + CH₄ mixed RG was studied at CO₂ pump pressures typical of SFC pressure programming. The background ions varied widely with CO₂ partial pressure and source temperature, however, spectra of a propellant test mixture were relatively unaffected by changing RG. The system was also used to perform negative CI (NCI) using the mobile phase CO₂ as a RG. This method was found to be very useful for nitrated derivatives of diphenylamine. SFC-CH₄-PCI-MS confirmed the intact elution of thermally labile N-nitroso compounds thought to exist in propellants. SFC-CI-MS, both NCI and PCI, was used to characterize the SF extracts of polymeric nitrocellulose and was demonstrated to have potential for the analysis of a wide range of compounds found in the propellant industry. SFC-CH₄-PCI was also determined to be compatible with methanol modified mobile phases. The mobile phases in this case were delivered from premixed cylinders. However, severe limitations regarding the reliability of premixed mobile phases in SFC were shown to exist.