Thermal decomposition studies of the polyhedral oligomeric silsesquioxane, POSSh, and when it is impregnated with the metallocene bis(eta5-cyclopentadienyl)zirconium (IV) dichloride or immobilized on silica.

Thermal decomposition studies of the free polyhedral oligomeric silsesquioxane, POSSh, and when this compound has been impregnated with Cp2ZrCl2 (Cp = eta5-C5H5) or immobilized on SiO2 were conducted using infrared emission spectroscopy (IES) over a 100-1000 degrees C temperature range and by thermogravimetric analysis (TGA). The organic groups in POSS(h) apparently decompose thermally into Si-CH3, Si-H and other fragments. Upon impregnation with Cp2ZrCl2, however, a different thermal decomposition pathway was followed and new infrared emission bands appeared in the 1000-900 cm(-1) region suggesting the formation of Si-O-Zr moieties. When immobilized on SiO2 and subjected to thermal decomposition, the POSSh compound lost its organic groups and the inorganic structure remaining was incorporated into the SiO2 framework.

Vibrational spectra of silsesquioxanes impregnated with the metallocene catalyst bis(eta(5)-cyclopentadienyl)zirconium(IV) dichloride.

FT-IR photoacoustic and Raman spectroscopy have been used to study the interactions between the metallocene catalyst, Cp(2)ZrCl(2) (Cp=eta(5)-C(5)H(5)), and two polyhedral oligomeric silsesquioxanes (POSS) supports. The first silsesquioxane support, POSS(h), contains (beta-hydroxyl)-tertiary amine groups, while in the second one, POSS(u), these -OH groups have been converted into N-(p-toluyl) urethane groups. The vibrational spectra of the Cp(2)ZrCl(2):POSS(h) and Cp(2)ZrCl(2):POSS(u) samples show that the Cp(2)ZrCl(2) catalyst reacts with the C-OH groups of POSS(h) and also interacts with N-H and >CO groups of POSS(u). Furthermore, Cp(2)ZrCl(2) can react with the Si-OH groups of the POSS supports and also interact with the O atoms that are bonded to the benzene rings and the N atoms of the tertiary amines in both silsesquioxanes. As a result of the interactions between Cp(2)ZrCl(2) and the POSS supports, acidic species are generated. The Cp(2)ZrCl(2):POSS(h) mass ratio seems to be an important parameter in the formation of Zr-O bonds and the acidic species.