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第 7 期 闫 磊，等: Brønsted 酸性离子液体催化双酚芴的合成 ·1363·

3 结论 diamine benzoxazine[J]. Chemical Jouranl of Chinese Universities
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以 1-甲基咪唑、1,3-丙磺酸内酯和质子酸为原 [6] Bal’tser A E, Zaitsev D A, Zubritskaya N G, et al. Effect of
料，合成了 4 种 Brønsted 酸性离子液体，通过 FTIR、 processing parameters on the synthesis of bisphenols, monomers for
producing polyester polymers and fibres[J]. Fibre Chemistry, 2015,
NMR 及 TG 对其结构进行了表征；利用 257 nm 和
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275 nm 两种检测波长的液相色谱对双酚芴合成中 9-
[7] Jason P H, Welton T. Room-temperature ionic liquids: solvents for
芴酮的转化率和双酚芴的选择性进行准确定量；探 synthesis and catalysis. 2[J]. Chemical Reviews, 2011, 111:
索了酸性离子液体的 H 0 与 9-芴酮的转化率和双酚 3508-3576.
芴选择性的关系。得出结论如下： [8] Sun W Z, Zheng W Z, Xie W X, et al. Understanding structure−
（1）以 4-硝基苯胺为指示剂，通过紫外-可见光 property relationship of SO 3H-functionalized ionic liquids together
with sulfuric acid in catalyzing isobutane alkylation with C4
谱测定合成离子液体的酸度 H 0 ，实验结果表明阴离
olefin[J]. Industrial & Engineering Chemistry Research, 2018, 57:
子结构对离子液体酸度 H 0 有重要影响。
15310-15318.
（2）单变量法优化了离子液体 IL1 和巯基乙酸 [9] Liu X, Ma H, Wu Y, et al. Esterification of glycerol with acetic acid
组合催化双酚芴合成的反应条件。得到较优的反应 using double SO 3H-functionalized ionic liquids as recoverable
条件为：苯酚与 9-芴酮及 IL1 的物质的量比为 6∶ catalysts[J]. Green Chemistry, 2011, 13(3): 697-701.
[10] Liu X, Chen C, Xiu Y, et al. Asymmetric transfer hydrogenation of
1∶0.125，离子液体与巯基乙酸的物质的量比为 5∶
ketones catalyzed by thermoregulated ionic liquid-regulating
2，反应温度 110 ℃，反应时间 6 h。在较优反应条
ruthenium complexes[J]. Catalysis Communications, 2015, 67: 90-
件下，除阴离子为 H 2 PO 4 ˉ的离子液体 IL3 外，离子 94.
液体 IL1、IL2、IL4 催化的双酚芴合成反应，9-芴 [11] Baj S, Chrobok A, Slupska R. The Baeyer-Villiger oxidation of
酮转化率均为 100%，双酚芴的选择性约为 87%；硫 ketones with bis (trimethylsilyl) peroxide in the presence of ionic
liquids as the solvent and catalyst[J]. Green Chemistry, 2009, 11(2):
酸对该反应的催化效果与离子液体基本相当。
279-282.
（3）Brønsted 酸性催化剂在双酚芴合成反应中
[12] Abbott A P, Capper G, Davies D L, et al. Quaternary ammonium
的催化效果与其 H 0 有关。当酸性催化剂的 H 0 ≤ zinc- or tin-containing ionic liquids: water insensitive, recyclable
1.94 时，催化剂对 9-芴酮缩合反应有催化作用；当 catalysts for Diels–Alder reactions[J]. Green Chemistry, 2002, 4(1):
酸性催化剂的 H 0 ≤1.69 时，均能使 9-芴酮完全转 24-26.
化，催化剂有应用价值。 [13] Liu X, Zhou J, Guo X, et al. SO 3H-functionalized ionic liquids for
selective alkylation of m-cresol with tert-butanol[J]. Acta Petrolei
（4）酸性离子液体 IL1 在双酚芴合成反应中连
Sinica, 2011, 9(1): 1-7.
续使用 5 次后催化活性无明显变化。说明离子液体 [14] Thomazeau C, Olivier B H, Magna L, et al. Determination of an
催化剂可以回收、循环使用，具有一定的应用前景。 acidic scale in room temperature ionic liquids[J]. Journal of the
American Chemical Society, 2003, 125(18): 5264-5265.
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benzoxazine resins using a new hyperbranched polyether epoxy as a Pigment & Resin Technology, 2008, 37: 9-15.
non-phase-separation modifier[J]. Polymer, 2017, 121: 217-227. [17] Peng Xiaoping (彭小平)，Huang Bailing (黄柏玲)，Xiong Boyuan
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