Recent Advances in Rochow‐Müller Process Research: Driving to Molecular Catalysis and to A More Sustainable Silicone Industry

Abstract The Rochow‐Müller process, an old process that has been known for more than seventy years, is for the direct synthesis of methylchlorosilane. However, due to its unique economic efficiency, it is still extremely important in silicone industry, e. g., about 90 % of starting materials for producing silicones are obtained by this route. Although significant progress has been made in exploring high‐efficient catalysts and understanding its mechanism, a quantitative description of this reaction is still far‐fetched due to its high complexity. In addition, sustainable use and recycling of by‐products and waste solid have become imperative nowadays due to the increasing demands for atom economy and environmental protection. This paper provides a comprehensive overview and insights into Rochow‐Müller process from its catalysis to sustainable issues, including the catalyst development and reaction mechanism investigation, waste reutilization and their derived products. In addition, several emerging novel processes originated from Rochow‐Müller process are summarized. Lastly, challenges and perspectives with respect to this reaction are discussed. We hope this work has accurately reflected and recorded the transition of Rochow‐Müller process to modern molecular catalysis, and can promote a much more sustainable silicone industry.