Hydrosilylation is one of the most ubiquitous reactions in silicone chem., used to make and cure a variety of products that consumers interact with on a daily basis.A longstanding complication with this reaction is the propensity of platinum catalysts to isomerize terminal alkenes to internal alkenes that are far less reactive toward hydrosilylation.Here, we demonstrate that with the appropriate choice of Si-H substrate and control over the reaction conditions, these internal isomers can be reisomerized to the terminal alkene to then undergo hydrosilylation with Karstedt′s catalyst, an industry standard platinum catalyst.This ultimately leads to hydrosilylation products with no residual isomer content, on time scales relevant for industrial productionOnly -SiMe₂H (M′) substrates were capable of producing isomer free products, with -SiMeH- (D′) units as substrates resulting in high (>13 mol %) residual isomerized alkenes.Using this technol., low-isomer silicone polyether materials were synthesized with a final isomer content <1 mol %.Due to the propensity of residual isomerized species to undergo hydrolysis to propionaldehyde and other malodorous acetals, this technol. is expected to reduce the odor of residual alkenyl species in silicone polyether materials in a cost-effective manner for industrial production

09 Jun 2024·2024 IEEE 52nd Photovoltaic Specialist Conference (PVSC)

Accelerated Aging Study of Backsheet Repair with Flowable Silicone Sealant

Author: Kenney, Kayla ; Jadot, Emmanuel ; Beaucarne, Guy ; Eder, Gabriele ; Gassner, Anika ; Garcia, Jorge Lima

26 Jan 2024·ScienceQ1 · CROSS-FIELD

Directed evolution of enzymatic silicon-carbon bond cleavage in siloxanes

Q1 · CROSS-FIELD

Article

Author: Reddel, Jordan C T ; Roberts, John M ; Sarai, Nicholas S ; Johnston, Kadina E ; Brinkmann-Chen, Sabine ; Katsoulis, Dimitris E ; O'Meara, Ryen L ; Fulton, Tyler J ; Arnold, Frances H ; Maar, Ryan R ; Tecklenburg, Ron E

Volatile methylsiloxanes (VMS) are man-made, nonbiodegradable chemicals produced at a megaton-per-year scale, which leads to concern over their potential for environmental persistence, long-range transport, and bioaccumulation. We used directed evolution to engineer a variant of bacterial cytochrome P450 BM3 to break silicon-carbon bonds in linear and cyclic VMS. To accomplish silicon-carbon bond cleavage, the enzyme catalyzes two tandem oxidations of a siloxane methyl group, which is followed by putative [1,2]-Brook rearrangement and hydrolysis. Discovery of this so-called siloxane oxidase opens possibilities for the eventual biodegradation of VMS.

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