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

Abstract EN

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 a Mw around 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 T3 4T2 3 to T3 8T2 2 including many isomers.

One isomer of T3 6T2 2 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 T2 units in the molecules from PMSQ is replaced with D2 [Me2SiO2/2] were found, for example, T3 6D2 2, 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.