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对清洁合成己二酸反应中的钨酸盐催化剂进行了改性,制备了一种含长碳链的亲油性钨过氧酸盐双功能催化剂[C7H7C12H25(CH3)2N]2W2O3(O2)4,通过元素分析、重量法、化学滴定、TG-DSC和IR光谱对催化剂的组成和结构进行了表征。与已报道的钨酸盐类催化体系相比,该配合物在温和的、不需助催化剂的条件下,能有效地催化w(H2O2)=30%双氧水氧化环己烯、环己醇、环己酮和1,2-环己二醇生成己二酸。以环己烯作底物,讨论了催化剂用量、反应温度、时间、H2O2用量4个因素对反应的影响,得到的较佳合成条件(以100 mmol环己烯计)为:反应温度90℃,反应时间12 h,n(环己烯)∶n(催化剂)∶n(H2O2)=100∶1.2∶538,己二酸收率可达85.8%。同样条件下,催化剂对1,2-环己二醇、环己醇和环己酮的活性分别为88.5%、58.3%和52.0%。
The tungstate catalyst used in the clean synthesis of adipic acid was modified to prepare a lipophilic tungstophosphate bifunctional catalyst [C7H7C12H25 (CH3) 2N] 2W2O3 (O2) 4 with a long carbon chain. The composition and structure of the catalyst were characterized by elemental analysis, gravimetric method, chemical titration, TG-DSC and IR spectra. Compared with the reported tungstate-type catalytic system, the complex can catalyze the oxidation of cyclohexene oxide, cyclohexanol, cyclohexanol, Hexanone and 1,2-cyclohexanediol generate adipic acid. Using cyclohexene as a substrate, the influences of the amount of catalyst, reaction temperature, time and the dosage of H2O2 on the reaction were discussed. The optimum synthesis conditions (based on 100 mmol cyclohexene) were as follows: reaction temperature 90 ℃, The reaction time was 12 h, n (cyclohexene): n (catalyst): n (H2O2) = 100: 1.2: 538, the yield of adipic acid was up to 85.8%. Under the same conditions, the catalytic activities of 1,2-cyclohexanediol, cyclohexanol and cyclohexanone were 88.5%, 58.3% and 52.0%, respectively.