Degradation of Monophenylheptamethylcyclotetrasiloxane and 2,6-cis-Diphenylhexamethylcycloterasiloxane in Londo Soil

The natural degradation of monophenylheptamethylcyclotetrasiloxane and 2,6-cis-diphenylhexamethylcyclotetrasiloxane in soil was evaluated under laboratory conditions. Both monophenyl and 2,6-cis underwent rapid degradation in dry soil generating the same products in varying proportions. During the first 24 hr, approximately 99% of the two materials underwent significant chemical transformations forming silanols of various structures, dimethyl cyclic siloxanes of the structure (Me₂SiO)x, and rearrangement products (geometrical isomers) of diphenylhexamethylcyclotetrasiloxane. Among the silanols, the following were identified as trimethylsilyl derivatives: HOSiMe₂OH, HOSiMePhOH, HOSiMe₂OSiMe₂OH, HOSiMePhOSiMe₂OH, HOSiMePhOSiMePhOH, HOSiMe₂OSiMe₂OSiMe₂OH, HOSiMePhOSiMe₂OSiMe₂OH, HOSiMe₂OSiMePhOSiMe₂OH, HOSiMePhSiMe₂OSiMePhOH, HOSiMePhOSiMePhOSiMe₂OH, HOSiMePhOSiMe₂OSiMe₂OSiMe₂OH, HOSiMe₂OSiMePhOSiMe₂OSiMe₂OH, HOSiMePhOSiMe₂OSiMePhOSiMe₂OH, HOSiMePhOSiMePhOSiMe₂OSiMe₂OH, HOSiMePhOSiMe₂OSiMe₂OSiMePhOH, HOSiMe₂OSiMePh-OSiMePhOSiMe₂OH. Derivatization was carried out using bis(trimethylsilyl)trifluoroacetamide. Gas chromatography-mass spectrometry and liquid chromatography-mass spectrometry (atmospheric pressure chemical ionization) analyses were used to derive structures. Structures were confirmed by gas chromatography-mass spectrometry comparisons of synthetic standards. Degradation was slower in wet soil. Nevertheless, in 14 days, the chemical transformation was essentially found to be complete as soil was allowed to dry. Detection of phenol as one of the degradation products revealed the occurrence of carbon–silicon bond cleavage promoted by soil.     

Speciation and quantitation of degradation products of silicones (Silane/Siloxane Diols) by gas chromatography—mass spectrometry and stability of dimethylsilanediol

Gas chromatography-mass spectrometry (GC-MS) methodology was developed to speciate and quantitate several degradation products of polydimethylsiloxane (PDMS) in soil. We have demonstrated that the major degradation product,viz., dimethylsilanediol, can be readily analyzed by GC-MS without derivatization as commonly practiced in analyzing such materials. A mixture of linear siloxane diols (n = 1–5, wheren is the number of Me₂SiO units), and cyclic dimethylsiloxanes (n = 4–6) was resolved by GC-MS. We also found that peak identity of various diols required that GC-MS is done in the chemical ionization (CI) mode, since the electron impact (EI) ionization mode produced similar mass fragmentation patterns for diols and cyclics containing the same number of silicon atoms. For siloxane diols, detection limits ranged from 100 pg (forn = 1) to 1 ng (for n = 5). For cyclics, the detection limit was about 1 pg. Dimethylsilanediol, known to be unstable even in the solid state, was shown by NMR techniques to be stable in aqueous solution at <0.1% concentration. A 100-ppm solution was stable for over a year. Purity check for dimethylsilanediol is best carried out by Si-29 solid-state NMR technique.