Synthesis, characterization of triphenyltin grafted on SBA-15 mesoporous silica and its catalytic performance for the synthesis of 4-methylacetophenone

doi:10.1016/j.cjche.2013.12.001

Abstract

Abstract: The production of Ph₃Sn-O-SBA-15 (Ph₃SnSBA) was achieved by heating triphenyltin chloride and SBA-15 in N-methylpyrrolidone at 190℃ for 5 h using triethylamine as a catalyst. The composition, structure, and surface physical and chemical properties of Ph₃SnSBA were characterized using inductively coupled plasma-atomic emission spectroscopy (ICP-AES), ¹³C, ¹¹⁹Sn and ²⁹Si solid-state nuclear magnetic resonance (NMR) spectroscopy in situ pyridine infrared spectroscopy (Py-IR), N₂ adsorption-desorption isotherms, X-ray diffraction (XRD) and transmission electron microscopy (TEM). The results of ICP-AES and organic elemental analysis showed that the grafting yield of Sn was 17% (by mass) for Ph₃SnSBA. The elemental analysis and solid-state NMR results for Ph₃SnSBA were consistent with grafting of triphenyltin on SBA-15. The N₂ adsorption-desorption, XRD and TEM analyses showed that Ph₃SnSBA retained an ordered hexagonal mesoporous structure, resulting in decreases in the surface area, pore size and mesopore volume, and an increase in acidity as compared with SBA-15. The Hammett acidity function (H₀) value and the number of acid sites for Ph₃SnSBA, obtained by the Hammett methods, were 2.77-3.30 and 2.07 mmol·g^-1, respectively. The Friedel-Crafts acylation of toluene and acetic anhydride over Ph₃SnSBA was investigated. The yield of methylacetophenone (MAP) and the selectivity for 4-methylacetophenone (PMAP) were 79.56% and 97.12%, respectively, when the conditions were n(toluene):n(anhydride)=2.0:1.0 with 6% (by mass) catalyst, and heating under reflux for 5 h. The PMAP selectivity still reached 93.11% when Ph₃SnSBA was used for the fifth time under the same reaction conditions.

Key words: SBA-15, Triphenyltin chloride, Grafting reaction, Catalysis, Friedel-Crafts

摘要： The production of Ph₃Sn-O-SBA-15 (Ph₃SnSBA) was achieved by heating triphenyltin chloride and SBA-15 in N-methylpyrrolidone at 190℃ for 5 h using triethylamine as a catalyst. The composition, structure, and surface physical and chemical properties of Ph₃SnSBA were characterized using inductively coupled plasma-atomic emission spectroscopy (ICP-AES), ¹³C, ¹¹⁹Sn and ²⁹Si solid-state nuclear magnetic resonance (NMR) spectroscopy in situ pyridine infrared spectroscopy (Py-IR), N₂ adsorption-desorption isotherms, X-ray diffraction (XRD) and transmission electron microscopy (TEM). The results of ICP-AES and organic elemental analysis showed that the grafting yield of Sn was 17% (by mass) for Ph₃SnSBA. The elemental analysis and solid-state NMR results for Ph₃SnSBA were consistent with grafting of triphenyltin on SBA-15. The N₂ adsorption-desorption, XRD and TEM analyses showed that Ph₃SnSBA retained an ordered hexagonal mesoporous structure, resulting in decreases in the surface area, pore size and mesopore volume, and an increase in acidity as compared with SBA-15. The Hammett acidity function (H₀) value and the number of acid sites for Ph₃SnSBA, obtained by the Hammett methods, were 2.77-3.30 and 2.07 mmol·g^-1, respectively. The Friedel-Crafts acylation of toluene and acetic anhydride over Ph₃SnSBA was investigated. The yield of methylacetophenone (MAP) and the selectivity for 4-methylacetophenone (PMAP) were 79.56% and 97.12%, respectively, when the conditions were n(toluene):n(anhydride)=2.0:1.0 with 6% (by mass) catalyst, and heating under reflux for 5 h. The PMAP selectivity still reached 93.11% when Ph₃SnSBA was used for the fifth time under the same reaction conditions.

关键词: SBA-15, Triphenyltin chloride, Grafting reaction, Catalysis, Friedel-Crafts

Qigang Deng, Zhile Qin, Ying Yang, Weiming Song. Synthesis, characterization of triphenyltin grafted on SBA-15 mesoporous silica and its catalytic performance for the synthesis of 4-methylacetophenone[J]. , 2015, 23(2): 384-388.

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