Versatile Cascade Esterification Route to MQ Resins.

We describe a versatile cascade route for manufacturing MQ resins using alkoxysilanes (e.g., tetraethoxysilane (TEOS)) or equivalent oligomers (e.g., ethyl polysilicate (polyTEOS)), a carboxylic acid (typically acetic acid), and hexamethyldisiloxane (MM) as starting materials; a strong acid catalyst is also employed in the one-pot reaction. The siloxane resin synthesis is accompanied by esterification of the carboxylic acid to give ethyl acetate, which acts as an important solvent, making the process more controllable. Contrary to traditional sol-gel methods, no water is introduced in the experiments, but is generated in situ. The strategy offers several advantages, including reproducibility, high yields of siloxane resins with excellent batch-to-batch consistency and without gel formation, narrow dispersity, low Si-hydroxyl residues in the final products, and the ability of increasing the molecular weight by thermal treatment. The process utilizes the green chemistry concepts of lower pollutant formation and higher atom efficiency.