Characterization and Some Insights into the Reaction Chemistry of Polymethylsilsesquioxane or Methyl Silicone Resins

Structural characterization of a polymethylsilsesquioxane (PMSQ) and a DT-type methyl silicone resin (MeDT) has been carried out by various instrumental analyses including GPC, NMR, gas chromatography, and gas chromatography-mass spectrometry. Although the PMSQ had aMwaround 5000, the resin contained a significant amount of low molecular weight species consisting of T2[MeSi(OH)O2/2] and T3[MeSiO3/2] units, ranging from to including many isomers. One isomer of was isolated of which structure was determined as a cage structure. The species are supposed to consist mainly of cyclotetra- and cyclopentasiloxanes, but presence of strained rings such as cyclotrisiloxane rings also was suggested. In MeDT, species in which the T2units in the molecules from PMSQ is replaced with D2[Me2SiO2/2] were found, for example, , suggesting that general silicone resins consist of similar structures as silsesquioxanes. The Mark-Houwink exponent for these methyl resins was~0.3, indicating the molecular shape to be compact. Investigation on the formation chemistry of the cubic octamers indicates that siloxane bond rearrangement is an important mechanism in the molecule build-up process.