Synthesis, properties and mechanism of the ion exchange resins based on 2-methyl-5-vinylpyridine and divinylbenzene in the catalytic disproportionation of trichlorosilane

• Published in: Applied catalysis. B, Environmental Environmental, 2018-05, Vol.224, p.621-633
• Main Authors: Vorotyntsev, Andrey V., Petukhov, Anton N., Makarov, Dmitriy A., Razov, Evgeny N., Vorotyntsev, Ilya V., Nyuchev, Alexander V., Kirillova, Natalia I., Vorotyntsev, Vladimir M.
• Format: Article
• Language: English
• Subjects: Catalysis; Catalysts; Catalytic activity; Catalytic disproportionation; Chemical synthesis; Chlorides; Crosslinking; Desorption; Disproportionation; Divinylbenzene; Heptanes; Heterogeneous catalysis; Ion exchange; Ion exchange resins; Kinetics; Nitrogen; Polymers; Protonation; Pyridines; Reaction kinetics; Resins; Silane; Silicon; Stationary processes; Surface area; Suspension polymerization; Temperature effects; The ion exchange resin; Toluene; Trichlorosilane
• ISSN: 0926-3373; 1873-3883
• DOI: 10.1016/j.apcatb.2017.10.062

[Display omitted] •The 2M5VP/DVB resins were synthesized for disproportionation of TCS.•The 2M5VP/DVB resin works for temperature range 333.2 K to 453.2K.•The 2M5VP resins were subjected to deactivation by thermodegradation with CHCl3 formation.•The limiting stage for disproportionation of TCS is the desorption of STC from active sites. The variety of catalysts based on macroporous ion exchange resins using 2-methyl-5-vinylpyridine cross-linked with divinylbenzene (2M5VP/DVB) was investigated in the disproportionation of trichlorosilane (TCS) in a continuous-flow reactor. The effects of the reaction temperature and surface area on TCS disproportionation kinetics was invesitigated using three types of catalysts based on 2M5VP/DVB with a different pore ratios (toluene(tol)/heptane(hep)) and in the temperature range of 333.2K and 453.2K. The results indicate that within this range, the higher reaction temperatures result in an increase in the conversion rate to TCS at equilibrium. The effects on the specific catalyst surfaces were determined and the catalyst (2M5VP/DVB-hep/tol) with the highest specific surface area exhibited better catalytic activity. Variable temperature studies on the catalytic activity of 2M5VP/DVB-hep/tol revealed an activation energy of 24,06±0.72kJmol−1 for 2M5VP-hep/tol and 34.30±1.03kJmol−1 for Amberlyst A-21 resins. TCS disproportionation was investigated using a non-stationary process and showed the desorption of STC from the active sites of the catalyst to be the rate determining step. Using FTIR analysis, we have already established that the resin after exposure to HCl or TCS undergoes protonation of the nitrogen atom in the pyridine ring with intermediate formation of N+H⋯Cl−/N+H⋯SiCl3−. Based on the reaction data obtained in this study, a probable mechanism of the reaction has been proposed.