Synthesis of Multifunctional Oligomethylsilsesquioxanes by Catalyst-Free Hydrolytic Polycondensation of Methyltrimethoxysilane under Microwave Radiation.

The catalyst-free hydrolytic polycondensation of methyltrimethoxysilane under microwave radiation has been studied. The effect of molar ratios of the reagents (MTMS/HO = 1/0.5-1/9), radiation power (20-300 W), temperature (30-50 °C) and duration of exposure (2.5-90 min) on the course of the process is considered. It has been shown that the use of microwave radiation promotes the activation of the process, and almost complete conversion of the monomer can be achieved in 5 min at 30 °C, 20 W and an MTMS/HO ratio of 1/3. The optimal radiation power for the maximum conversion of the monomer and MeO-groups is in the range from 20 to 100 W. An increase in the water amount, the duration and temperature of the process contribute to an increase in the monomer conversion, a decrease in the content of residual MeO-groups and the yield of non-volatile oligomethylsilsesquioxanes. The limits of this approach using to the synthesis of multifunctional branched polyorganosilsesquioxanes are determined. Depending on the process conditions, homogeneous water-alcohol solutions of oligomethylsilsesquioxane with a concentration of 20 to 50 wt.% can be obtained. The OH-group content and the molecular weight of the obtained oligomers vary from 10 to 30 wt.% and from 1000 to 600 Da, respectively.