H3PO4协同AlCl3改性无序介孔羟基磷灰石催化合成双酚F

用水热法合成无序介孔羟基磷灰石，再通过浸渍法将H₃PO₄、AlCl₃负载到无序介孔羟基磷灰石。采用XRD、FT-IR、N₂吸附 脱附、SEM、Pyridine FT IR和XPS对其进行表征。将H₃PO₄协同AlCl₃改性制备的改性无序介孔羟基磷灰石m-HAP-P/Al作为催化剂，用于催化合成双酚F，考察了不同AlCl3负载量催化剂的催化活性以及反应时间、反应温度、催化剂量、酚/醛摩尔比对双酚F收率及其异构体分布的影响。结果表明，无序介孔羟基磷灰石表面P-OH与H3PO4的P-OH作用形成含有-P-O-P-O-P-的结构，其有利于AlCl₃协同改性形成Cl/Al原子比为2的四元环或六元环结构的改性机理，经H₃PO₄协同AlCl₃改性的无序介孔羟基磷灰石兼具BrØnsted和Lewis酸位，在催化苯酚、甲醛羟烷基化合成双酚F反应中呈现较高活性。当以AlCl₃负载量为15 mmol/g的m HAP P/Al作为催化剂，在反应时间120 min、反应温度90℃、酚/醛摩尔比15、催化剂/甲醛质量比3的反应条件下，双酚F收率达8956%。

Irregular Mesoporous Hydroxyapatite Modified Synergistically With Phosphoric Acid and Aluminium Chloride for Catalytic Synthesis of Bisphenol F

The irregular mesoporous hydroxyapatites(m HAP P/Al) were first synthesized by the hydrothermal method and then were modified synergistically with phosphoric acid and aluminium chloride by the impregnation method. They were characterized by XRD, FT IR, N2 adsorption desorption, SEM, Pyridine FT IR and XPS. m HAP P/Al was then used as catalyst for synthesis of bisphenol F. The effects of aluminium chloride content loaded on m HAP P/Al, and reaction conditions of time, temperature, catalyst content and phenol/formaldehyde molar ratio on bisphenol F yield and its isomers distribution were investigated. The results showed that the P-OH of irregular mesoporous hydroxyapatite reacted with P-OH groups of phosphoric acid to form -P-O-P-O-P- frame structure, which are beneficial for the synergistic modification of AlCl3 to form four membered and/or six membered rings with Cl/Al atom ratio 2. The irregular mesoporous hydroxyapatite modified synergistically with phosphoric acid and aluminium chloride afford both Brnsted acid and Lewis acid sites，and exhibited high catalytic activity in synthesis of bisphenol F. With m HAP P/Al loaded aluminium chloride 15 mmol/g as catalyst, under the optimal reaction conditions of temperature of 90℃, phenol/formaldehyde molar ratio of 15 and catalyst/formaldehyde mass ratio of 3 and time of 120 min, the yield of bisphenol F reached 8956%.