The present invention discloses a class of highly stable zirconium-based chiral catalysts and their preparation methods and applications. The catalytic material has the following chemical formulas: Zr6O4 (OH) 4 (salen_M) 6, in which salen_M is a chiral bissalicylaldehyde ethylenediamine-based metal complex and M is a metal ion Zn2+, Cu2+, Ni2+, Co2+, Fe2+, Mn3+, Cr3+, V4+ or Ti4+ with catalytic activity. . The zirconium-based chiral catalyst of the present invention adopts solvothermal synthesis method, takes ZrCl4 (or ZrOCl2) and salen_M as raw materials, organic acids as regulators, organic solvents as solvents, and heats up to 80-120 C for 72_96 hours. After the reaction, the crude product is obtained by cooling to room temperature, and then the series of zirconium-based products are obtained by washing with organic solvents. Chiral catalysts. The method adopted is environment-friendly, simple and easy to operate, low in cost and high in yield, and is conducive to industrial production. The prepared zirconium-based chiral catalysts have potential applications in asymmetric catalysis, chiral separation, drug synthesis and CO2 fixation.
【技术实现步骤摘要】
一类高稳定锆基手性催化剂及制备方法与其应用
本专利技术涉及功能配合物、多孔材料、有机催化领域,具体涉及到一类高稳定锆基手性催化剂及制备方法与其在催化领域的应用。
技术介绍
金属salen(N,N'-bis-(saliylaldehyde)ethylendiamine)配合物由于合成方便、高效、低毒等优点,近年来广泛地应用于多种有机合成反应中,如烯烃氧化、环丙烷化、仲醇氧化、氰硅化、CO2转化、环氧化物水解动力学拆分等(C.andH.Garcia,Chem.Rev.,2006,106,3987;A.Decortes,A.M.CastillaandA.W.Kleij,Angew.Chem.Int.Ed.,2010,49,9822;M.North,S.C.Z.Quek,N.E.Pridmore,A.C.WhitwoodandX.Wu,ACSCatal.,2015,5,3398;Y.W.Ren,J.Chen,C.R.QiandH.F.Jiang,ChemCatChem,2015,7,1535;X.Y.Huang,T.Zhuang,P.A.Kates,H.X.Gao,X.Y.ChenandJ.T.Groves,J.Am.Chem.Soc.,2017,139,15407)。然而,金属salen均相催化剂在溶液中不稳定,易发生不可逆的二聚使催化活性降低,而且在反应后难于从体系中分离出来,不易重复使用,限制了其实际应用。目前,解决上述问题的重要途径之一是采用均相催化剂的多相化,如传统的无机材料分子筛、活性炭以及硅材料等都已经成功地实现金属salen的固载。金属有机框架(m ...
【技术保护点】
1.一类高稳定锆基手性催化剂,其特征在于其化学式为Zr6O4(OH)4(salen‑M)6,其中salen‑M是手性双水杨醛缩乙二胺基金属配合物,M为具有催化活性的金属离子Zn2+, Cu2+, Ni2+, Co2+, Fe2+, Mn3+, Cr3+, V4+或Ti4+,手性诱导基团为环己二胺,二苯基二胺或2‑甲基‑乙二胺。
【技术特征摘要】
1.一类高稳定锆基手性催化剂,其特征在于其化学式为Zr6O4(OH)4(salen-M)6,其中salen-M是手性双水杨醛缩乙二胺基金属配合物,M为具有催化活性的金属离子Zn2+,Cu2+,Ni2+,Co2+,Fe2+,Mn3+,Cr3+,V4+或Ti4+,手性诱导基团为环己二胺,二苯基二胺或2-甲基-乙二胺。2.根据权利要求1所述的一类高稳定锆基手性催化剂,其特征在于:所述一类高稳定锆基手性催化剂为晶态材料,空间群为F432;热稳定性为300~450℃;具有空腔,空腔为四面体和八面体两种,窗口尺寸为边长1.7~2.0纳米的等边三角形;比表面积为998~1226m2/g。3.根据权利要求1所述的一类高稳定锆基手性催化剂,其特征在于:在水、酸性溶液、碱性溶液中保持框架结构稳定性;所述酸性溶液为pH=0-7,所述碱性溶液为pH=7-11。4.制备权利要求1~3任一项所述一类高稳定锆基手性催化剂的方法,其特征在于,包括以下步骤:将锆盐、salen-M、调节剂溶于溶剂中,搅拌均匀后,加热升温至80...
【专利技术属性】
技术研发人员:任颜卫,李嘉伟,江焕峰,
申请(专利权)人:华南理工大学,
类型:发明
国别省市:广东,44
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