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以钨酸-有机酸性添加剂为催化体系,在无有机溶剂和相转移剂的情况下,催化30%过氧化氢氧化环己酮合成己二酸。当钨酸∶有机酸性添加剂∶环己酮∶过氧化氢=11∶4∶01∶76(摩尔比,钨酸用量为2.5mmol)时,使用有机酸性添加剂来调节钨酸催化活性,结果表明以钨酸-磺酸水杨酸氧化环己酮效果最优,反应8h时己二酸分离产率达86.8%、纯度为99.9%;以间苯二酚或邻苯二酚为添加剂时,己二酸分离产率分别达到85.9%和84.5%,纯度约为100%;而不使用任何添加剂时,己二酸分离产率只有68.1%、纯度为95.2%。当使用磺酸水杨酸、草酸等为有机酸性添加剂时,随反应时间的延长,己二酸分离产率均升高。当磺酸水杨酸用量为2.5mmol时,己二酸分离产率和纯度均较高。钨酸-磺酸水杨酸和钨酸-草酸催化体系重复使用5次后,己二酸分离产率仍分别可达80.2%和80.9%。
Using tungstic acid - organic acid additive as catalyst system, cyclohexanone was catalyzed by 30% hydrogen peroxide to synthesize adipic acid in the absence of organic solvent and phase transfer agent. When tungstic acid: organic acid additive: cyclohexanone: hydrogen peroxide = 11:4:01:76 (molar ratio, the amount of tungstic acid is 2.5mmol), the organic acid additive was used to adjust the catalytic activity of tungstic acid. Tungstic acid - sulfonic acid salicylic acid oxidation of cyclohexanone optimum, 8h reaction adipic acid isolated yield of 86.8%, a purity of 99.9%; with resorcinol or catechol as additives, hexylene two The yield of acid separation reached 85.9% and 84.5%, respectively, with a purity of about 100%. Without any additives, the yield of adipic acid was only 68.1% and the purity was 95.2%. When using sulfosalicylic acid and oxalic acid as organic acid additives, the yield of adipic acid increased with the increase of reaction time. When the dosage of sulfosalicylic acid is 2.5mmol, the yield and purity of adipic acid are higher. Tungstic acid - sulfonic acid salicylic acid and tungstic acid - oxalic acid catalytic system repeated 5 times, adipic acid isolated yield was still up to 80.2% and 80.9%.