Souvagya Biswas, Jason S. Fisk, Michael Telgenhoff, Karin Spiers, Muhunthan Sathiosatham, Thu Vi, Matthew S. Jeletic, Jessica E. Nichols, Travis W. Scholtz
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引用次数: 0
Abstract
This study details the route selection, process development, and scale-up of a reactive silicone acrylate monomer, 3-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)propyl methacrylate. A direct hydrosilylation reaction between allyl (meth)acrylate and 1,1,1,3,5,5,5-heptamethyltrisiloxane in the presence of Karstedt’s catalyst yielded the desired monomer in 46% yield. Two other byproducts were identified: an oxy-silyl ester and a propene hydrosilylated product. Prior to scale-up, the heat release associated with the hydrosilylation reaction was measured using a combination of isothermal reaction microcalorimetry and postreaction differential scanning calorimetry (DSC). The total heat release of hydrosilylation in the observed microcalorimetry experiment was −415 J/g. DSC studies detected the decomposition of the monomer at 280 °C, thereby revealing the risk of decomposition at elevated temperatures. Finding an inhibitor to prevent unwanted free radical polymerization of the monomer during scale-up and product isolation was crucial. 4-Hydroxy TEMPO was identified as the inhibitor of choice during the scale-up and distillation steps to isolate the monomer. Overall, the process optimization described here enabled a reliable, robust, and scalable method to produce multikilogram quantities of the 3-(1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)propyl methacrylate monomer. This approach is also expected to be suitable for other reactive silicone-acrylate-based monomers.
期刊介绍：
The journal Organic Process Research & Development serves as a communication tool between industrial chemists and chemists working in universities and research institutes. As such, it reports original work from the broad field of industrial process chemistry but also presents academic results that are relevant, or potentially relevant, to industrial applications. Process chemistry is the science that enables the safe, environmentally benign and ultimately economical manufacturing of organic compounds that are required in larger amounts to help address the needs of society. Consequently, the Journal encompasses every aspect of organic chemistry, including all aspects of catalysis, synthetic methodology development and synthetic strategy exploration, but also includes aspects from analytical and solid-state chemistry and chemical engineering, such as work-up tools，process safety, or flow-chemistry. The goal of development and optimization of chemical reactions and processes is their transfer to a larger scale; original work describing such studies and the actual implementation on scale is highly relevant to the journal. However, studies on new developments from either industry, research institutes or academia that have not yet been demonstrated on scale, but where an industrial utility can be expected and where the study has addressed important prerequisites for a scale-up and has given confidence into the reliability and practicality of the chemistry, also serve the mission of OPR&D as a communication tool between the different contributors to the field.
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