CN113769780B - 一种磁性微球负载双酸性离子液体催化剂及其制备和应用 - Google Patents
一种磁性微球负载双酸性离子液体催化剂及其制备和应用 Download PDFInfo
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- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 claims description 2
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
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Abstract
本发明公开了一种磁性微球负载双酸性离子液体催化剂及其制备和应用，属于多相催化技术领域，该磁性微球负载双酸性离子液体催化剂，将双酸性离子液体化学键合在磁性微球上，实现了双酸性离子液体的固载化，变均相催化氧化为多相催化氧化，且通过外加磁场，能很方便地将催化剂从反应体系中分离，使得催化剂可以重复使用。
Description
技术领域
本发明涉及多相催化技术领域，具体涉及一种磁性微球负载双酸性催化剂及其制备和应用方法，该催化剂为非均相催化剂，可应用于催化傅克酰基化反应。
背景技术
傅克酰基化反应是指芳香族化合物和酰基化试剂在芳环上发生的酰基化反应，通过傅克酰基化反应能有效构建芳香酮类化合物结构。而芳香酮类化合物是一种非常重要的精细化工产品，在医药、农药、染料、日用品、石油化工等邻域具有广泛的用途。通过傅克反应制备芳香酮类化合物具有原料易得、反应条件温和、产品收率等优点。传统的傅克酰基化反应是由Lewis酸催化，如氯化铝、氯化锌、氯化铁、四氯化锡等，也可以由强质子酸催化，如氢氟酸和硫酸等。但是，使用这些催化剂往往存在许多缺点，如催化剂用量大、难以回收利用、设备腐蚀严重、产生大量废水严重污染环境等。因此，针对傅克酰基化反应，已经设计了诸如负载型三氯化铝、沸石分子筛、金属氧化物、超强酸、三氟甲酸盐等固体催化剂，以方便催化剂的回收再用。
双酸性离子液体即有Lewis酸性，又有Bronsted酸性，具有许多独特的性能，在一些反应中表现了优异的催化活性。[HPhIm][FeCl4]及其衍生物就是一类双酸性离子液体，能有效催化傅克酰基化反应(Molecules，2020,25:352)，但其回收使用时易流失。Fe3O4磁性粒子具有稳定性好、易于合成与功能化、低毒性以及对外界磁场的快速响应等性能，已引起了人们的广泛关注。通过在Fe3O4磁性粒子表面包覆聚合物可作为进一步修饰和改性的载体，这些载体已经应用在非常多的反应中。这类载体可以在表面固载具有催化活性的有机小分子，待催化反应结束后，固载催化剂可以通过外加磁场非常方便地进行回收。
发明内容
针对现有技术中存在的问题，本发明的目的在于：
(1)提供一种磁性微球固载双酸性离子液体非均相催化剂；
(2)提供一种该非均相催化剂的制备方法；
(3)提供一种将上述方法制备的非均相催化剂用于催化傅克酰基化的方法。
为解决上述问题，本发明采用如下的技术方案。
本发明的第一目的在于提供磁性微球负载双酸性离子液体催化剂，其结构如式(I)所示：
本发明的第二目的在于提供上述的磁性微球负载双酸性离子液体催化剂的制备方法，主要是按照如下方法制备：包括以下步骤：
第一步，以结构如式(II)所示的磁性微球(II)和结构如式(III)所示的4-(1H-咪唑-1-基)苯酚为原料，碱性环境下，例如以氢化钠为碱，在相转移催化剂存在下，氮气保护，在四氢呋喃中回流进行醚化反应，过滤，用四氢呋喃洗涤得到的结构如式(IV)的改性磁性微球(IV)；
第二步，在乙醇溶液中，第一步获得的改性磁性微球(IV)和浓盐酸反应，过滤，用乙醇洗涤得到的结构如式(V)的改性磁性微球(V)；
第三步，在乙醇溶液中，第二步获得的改性磁性微球(V)与六水合三氯化铁室温反应，过滤，用乙醇洗涤，真空干燥至恒重，即得磁性微球负载双酸性离子液体催化剂(I)。
优选的，磁性微球负载双酸性离子液体催化剂的制备方法，包括以下步骤：
第一步，以结构如式(II)所示的磁性微球(II)和结构如式(III)所示的4-(1H-咪唑-1-基)苯酚为原料，以氢化钠为碱，在相转移催化剂存在下，氮气保护，在四氢呋喃中回流进行醚化反应16～32h，过滤，用四氢呋喃洗涤得到的结构如式(IV)的改性磁性微球(IV)；
第二步，在乙醇溶液中，第一步获得的改性磁性微球(IV)和浓盐酸在0～25℃反应2～5h，过滤，用乙醇洗涤得到的结构如式(V)的改性磁性微球(V)；
第三步，在乙醇溶液中，第二步获得的改性磁性微球(V)与六水合三氯化铁室温反应3～8h，过滤，用乙醇洗涤，真空干燥至恒重，即得磁性微球负载双酸性离子液体催化剂(I)。
本发明中，优选所述磁性微球(II)和4-(1H-咪唑-1-基)苯酚的质量用量比为100：10～30。
本发明中，优选所述相转移催化剂是四丁基溴化铵、四丁基碘化铵、四丁基氯化铵、四甲基氯化铵、四甲基溴化铵、四甲基碘化铵、苄基三乙基氯化铵和十二烷基三甲基氯化铵中的一种或它们的混合物，优选四丁基碘化铵。
优选的，本发明中所述4-(1H-咪唑-1-基)苯酚、氢化钠和相转移催化剂的物质的量比为1：0.8～1.5：0.05～0.2。
优选的，本发明中所述浓盐酸与4-(1H-咪唑-1-基)苯酚的物质的量比为1.5～3.0：1。
优选的，本发明中所述六水合三氯化铁与4-(1H-咪唑-1-基)苯酚的物质的量比为1.0～1.2：1。
优选的，本发明中所述溶剂四氢呋喃质量用量推荐为磁性微球(II)的10～40倍。
优选的，本发明中所述溶剂乙醇质量用量推荐为磁性微球(II)的10～40倍。
进一步的，本发明具体推荐所述的磁性微球负载双酸性离子液体催化剂的制备方法按照以下步骤进行：在四氢呋喃中，加入磁性微球(II)、4-(1H-咪唑-1-基)苯酚、氢化钠和四丁基碘化铵，氮气保护下回流进行醚化反应16～32h，过滤，用四氢呋喃洗涤，得到改性磁性微球(IV)；在乙醇中，加入改性磁性微球(IV)和浓盐酸，0～25℃反应2～5h，过滤，用乙醇洗涤，得到改性磁性微球(V)；在乙醇中，加入改性磁性微球(V)和六水合三氯化铁，室温反应3～8h，过滤，用乙醇洗涤，真空干燥至恒重，得到磁性微球负载双酸性离子液体催化剂(I)；所述磁性微球(II)和4-(1H-咪唑-1-基)苯酚的质量用量比为100：10～30；所述4-(1H-咪唑-1-基)苯酚、氢化钠和相转移催化剂的物质的量比为1：0.8～1.5：0.05～0.2；所述浓盐酸与4-(1H-咪唑-1-基)苯酚的物质的量比为1.5～3.0：1；所述六水合三氯化铁与4-(1H-咪唑-1-基)苯酚的物质的量比为1.0～1.2：1。
本发明的第三目的在于将上述的磁性微球负载双酸性离子液体催化剂用于傅克酰基化反应。具体可用于苯甲醚与苯甲酰氯的傅克酰基化反应中，结果表明，该催化剂催化性能良好，且能回收再用。
本发明所述的合成方法，其有益效果主要在于：
一、将双酸性离子液体化学键合在磁性微球上，实现了双酸性离子液体的固载化，变均相催化氧化为多相催化氧化。
二、通过外加磁场，能很方便地将催化剂从反应体系中分离，催化剂可以重复使用。
附图说明
图1是本发明磁性微球负载双酸性离子液体催化剂的磁滞回归线。
图2是本发明磁性微球负载双酸性离子液体催化剂的TEM电镜图。
具体实施方式
下面通过具体实施例对本发明作进一步说明，但本发明的保护范围并不限于此。
磁性微球(II)的制备：
在5L四口烧瓶中加入111g七水硫酸亚铁(0.4mol)、216g六水氯化铁(0.8mol)和1.4L去离子水，搅拌溶解，通氮气半个小时后，搅拌下滴加1L氨水(由300mL浓氨水稀释得到)、油酸(OA)/10-十一烯酸(UA)(3：1，28mL)，完毕后，溶液升温度到90℃，保温3h。降至室温，磁分离出磁粒子，用去离子水洗至中性，用正辛烷萃取得到磁流体。
将称好的50.0g磁流体、4.5g二乙烯苯、45.5g苯乙烯、22.2g对氯甲基苯乙烯和2.0g正十六烷混合成油相，超声分散20min。在2.5L烧瓶中，加入9.0g十二烷基硫酸钠和1L去离子水，搅拌溶解，然后滴入上述油相，搅拌3h得到黑色悬浮液，将上层悬浮液在细胞粉碎机内细乳化20min，得到均一的细乳液。将得到的细乳液转移至500mL烧瓶中，搅拌，通氮气30min，加入0.38g过硫酸钾，70℃恒温聚合20h。用甲醇破乳，水洗，真空干燥，得到磁性微球(II)。
实施例1：磁性微球负载双酸性离子液体催化剂的制备
向配有磁力搅拌器的500mL的单口瓶中加入10g磁性微球(II)、2.4g的4-(1H-咪唑-1-基)苯酚(15mmol)、氢化钠(15mmol)、四丁基碘化铵(0.15mmol)和300mL四氢呋喃，用氮气置换反应瓶内空气后，加热回流进行醚化反应24h，过滤，用四氢呋喃洗涤，得到改性磁性微球(IV)。
在乙醇中，加入改性磁性微球(IV)和浓盐酸(30mmol)，5℃下反应3h，过滤，用乙醇洗涤，得到改性磁性微球(V)；在乙醇中，加入改性磁性微球(V)和六水合三氯化铁(15mmol)，室温反应6h，过滤，用乙醇洗涤，真空干燥至恒重，得到磁性微球负载双酸性离子液体催化剂。
实施例2：磁性微球负载双酸性离子液体催化剂的制备制备过程同实施例1，加入4-(1H-咪唑-1-基)苯酚用量改为1.6g(10mmol)，氢化钠用量改为12mmol，四丁基碘化铵用量改为
0.12mmol，浓盐酸用量改为24mmol，六水合三氯化铁用量改为12mmol，最后制得磁性微球负载双酸性离子液体催化剂。
实施例3：磁性微球负载双酸性离子液体催化剂在傅克酰基化反应中的应用
在50mL烧瓶中加入苯甲醚(20mmol)，苯甲酰氯(50mmol)，磁性微球负载双酸性离子液体催化剂2g(实施例1制得)，无水二氯乙烷20mL，氮气保护，100℃下搅拌反应2h，取样，用GC监测，苯甲醚的转化率为95.5％，产物(4-甲氧基苯基)(苯基)甲酮的选择性为97.2％。过柱分离，得产物分离收率为88％，核磁表征数据为1H NMR(500MHz,CDCl3)δ7.82-7.83(m,2H),7.74-7.76(m,2H),7.54-7.57(m,1H),7.45-7.48(m,2H),6.95-6.96(m,2H),3.88(s,3H)。
实施例4：磁性微球负载双酸性离子液体催化剂在傅克酰基化反应中的应用
用外加磁场吸附实施例3中的磁性催化剂，倾倒出反应液，用二氯甲烷洗涤催化剂，将回收得到的磁性微球负载双酸性离子液体催化剂重复用于苯甲醚与苯甲酰氯的傅克反应中，使用方法同实施例3。
回收五次，得到的反应结果如表1所示：
表1回收磁性微球负载双酸性离子液体催化剂用于苯甲醚与苯甲酰氯的傅克反应
Claims (10)
1.一种磁性微球负载双酸性离子液体催化剂，其特征在于：所述液体催化剂的结构如式(I)所示：
2.根据权利要求1所述的一种磁性微球负载双酸性离子液体催化剂的制备方法，其特征在于：包括以下步骤：
第一步，以结构如式(II)所示的磁性微球(II)和结构如式(III)所示的4-(1H-咪唑-1-基)苯酚为原料，碱性环境下，在相转移催化剂存在下，氮气保护，在四氢呋喃中回流进行醚化反应，过滤，用四氢呋喃洗涤得到的结构如式(IV)的改性磁性微球(IV)；
第二步，在乙醇溶液中，第一步获得的改性磁性微球(IV)和浓盐酸反应，过滤，用乙醇洗涤得到的结构如式(V)的改性磁性微球(V)；
第三步，在乙醇溶液中，第二步获得的改性磁性微球(V)与六水合三氯化铁室温反应，过滤，用乙醇洗涤，真空干燥至恒重，即得磁性微球负载双酸性离子液体催化剂(I)；
3.根据权利要求2所述的一种磁性微球负载双酸性离子液体催化剂的制备方法，其特征在于：第一步的磁性微球(II)和4-(1H-咪唑-1-基)苯酚的质量用量比为100：10～30。
4.根据权利要求2所述的一种磁性微球负载双酸性离子液体催化剂的制备方法，其特征在于：第一步所述相转移催化剂是四丁基溴化铵、四丁基碘化铵、四丁基氯化铵、四甲基氯化铵、四甲基溴化铵、四甲基碘化铵、苄基三乙基氯化铵和十二烷基三甲基氯化铵中的一种或它们的混合物。
5.根据权利要求2所述的一种磁性微球负载双酸性离子液体催化剂的制备方法，其特征在于：第一步所述4-(1H-咪唑-1-基)苯酚、氢化钠和相转移催化剂的物质的量比为1：0.8～1.5：0.05～0.2。
6.根据权利要求2所述的一种磁性微球负载双酸性离子液体催化剂的制备方法，其特征在于：第一步所述四氢呋喃质量用量为磁性微球(II)的10～40倍。
7.根据权利要求2所述的一种磁性微球负载双酸性离子液体催化剂的制备方法，其特征在于：第二步所述浓盐酸与4-(1H-咪唑-1-基)苯酚的物质的量比为1.5～3.0：1。
8.根据权利要求2所述的一种磁性微球负载双酸性离子液体催化剂的制备方法，其特征在于：第三步所述六水合三氯化铁与4-(1H-咪唑-1-基)苯酚的物质的量比为1.0～1.2：1。
9.根据权利要求2所述的一种磁性微球负载双酸性离子液体催化剂的制备方法，其特征在于：第二步和第三步中所述乙醇质量用量均为磁性微球(II)的10～40倍。
10.根据权利要求1所述的一种磁性微球负载双酸性离子液体催化剂在傅克酰基化反应中的应用。
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