Hydrolysis of polydimethylsiloxane fluids in controlled aqueous solutions.

Accelerated degradation tests were performed on polydimethylsiloxane (PDMS) fluids in aqueous solutions and in extreme chemical conditions (pH 2-4 and 9-12). Results confirmed that silicones can be degraded by hydrolysis. Higher degradation levels were achieved in very acidic and alkaline conditions. Degradation products are probably polar siloxanols. In alkaline conditions, the counter-ion was found to have a strong influence on degradation level. Degradation kinetic studies (46 days) were also performed at different pH values. Supposing zeroth-order kinetics, degradation rate constants at 24 °C were estimated to 0.28 mgSi L(-1) day(-1) in NaOH solution (pH 12), 0.07 mgSi L(-1) day(-1) in HCl solution (pH 2) and 0.002 mgSi L(-1) day(-1) in demineralised water (pH 6). From these results, the following hypothesis was drawn: PDMS hydrolysis could occur in wastewater treatment plants and in landfill cells. It may be a first step in the formation of volatile organic silicon compounds (VOSiCs, including siloxanes) in biogas: coupled to biodegradation and (self-) condensation of degradation products, it could finally lead to VOSiCs.

Silicone-based surfactant degradation in aqueous media.

The increasing use of surfactants, such as modified polydimethylsiloxane-graft-polyethylene oxide (PDMS-g-PEO), requires studies on the fate of these compounds in the environment, and in particular in wastewater systems. A kinetic study, performed under three different pH conditions (pH2, 5.3 and 11) and using (1)H NMR (Nuclear Magnetic Resonance), proves that hydrolysis of the siloxane chain takes place in all cases, with higher rates for the two extreme conditions. Steric exclusion chromatography (SEC) clearly showed a decrease in the average molecular weight of the copolymer leading to a new molecular weight distribution, especially in acidic conditions. Degradation products, analyzed by (29)Si NMR, were found to be similar whatever the degradation pathway, namely silanediols and cyclic volatile compounds (degradation products of PDMS) and also PEO-modified silanediols and cyclic compounds. After one year, the siloxane chain completely disappeared under acidic conditions. Real wastewater medium has a strong effect on polymer stability, indicating that pH is not the only parameter which influences degradation rate.