CN114011460A - 一种钛系杂多酸离子液体催化剂的制备方法及应用 - Google Patents
一种钛系杂多酸离子液体催化剂的制备方法及应用 Download PDFInfo
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- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 41
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000003608 titanium Chemical class 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
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- 235000015393 sodium molybdate Nutrition 0.000 claims description 7
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 7
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
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- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 3
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- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 2
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-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
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- 229940046892 lead acetate Drugs 0.000 description 1
- XTBFPVLHGVYOQH-UHFFFAOYSA-N methyl phenyl carbonate Chemical compound COC(=O)OC1=CC=CC=C1 XTBFPVLHGVYOQH-UHFFFAOYSA-N 0.000 description 1
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- QIIPQYDSKRYMFG-UHFFFAOYSA-N phenyl hydrogen carbonate Chemical compound OC(=O)OC1=CC=CC=C1 QIIPQYDSKRYMFG-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
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Abstract
本发明涉及一种钛系杂多酸离子液体催化剂的制备方法及应用，一种钛系杂多酸离子液体催化剂，该催化剂的结构包括金属取代钛系缺位Keggin型杂多酸阴离子和咪唑有机阳离子，形成有机‑无机功能杂化材料。制备方法为中间体A‑咪唑离子液体的制备；中间体B‑金属取代钛系缺位Keggin型杂多酸的制备；钛系杂多酸离子液体催化剂的制备。本发明解决现有酯交换法合成碳酸二苯酯的催化剂存在活性较差，反应过程中易生成副产物，稳定性差，易失活等问题。
Description
技术领域
本发明涉及催化剂技术领域，具体涉及一种钛系杂多酸离子液体催化剂的制备方法及应用。
技术背景
碳酸二苯酯(DPC)是一种重要的有机反应中间体，作为取代剧毒的光气与双酚A合成聚碳酸酯的关键原料。酯交换法合成碳酸二苯酯因其不产生三废，原子利用率高达100％，其产业链之源头为石油化工产业生成丙烯的衍生物环氧丙烷和温室气体CO2，其最终产物聚碳酸酯和H2O，完全不产生三废，其前景之广可想而知，完全符合国家倡导的绿色经济发展的要求。
迄今为止，酯交换法合成碳酸二苯酯的催化剂可分为大体分为三代，第一代主要是以路易斯金属盐为主，比如氯化铝、氯化铁、氯化钛等，主要筛选出了Ti、SnII、Pb、V四种金属活性位点，但其活性较差，反应过程中易生成副产物，稳定性差，易失活，其后第二代催化剂主要以有机锡钛为主，比如钛酸四丁酯、二丁基氧化锡。虽然活性和选择性有所提高，但稳定性较差，易失活，且具有毒性，第三代催化剂是目前主要研究的催化剂，有分子筛类、水滑石类、二氧化钛负载型类、杂多化合物类。
发明内容
发明目的：本发明提出一种钛系杂多酸离子液体催化剂的制备方法及应用，其目的在于解决现有酯交换法合成碳酸二苯酯的催化剂存在活性较差，反应过程中易生成副产物，稳定性差，易失活等问题。
技术方案：
一种钛系杂多酸离子液体催化剂，该催化剂的结构包括金属取代钛系缺位Keggin型杂多酸阴离子和咪唑有机阳离子，形成有机-无机功能杂化材料。
进一步的，该催化剂为Bmim5[SnII(H2O)TiMo11O39]、Bmim5[Zn(H2O)TiMo11O39]、Bmim5[FeII(H2O)TiMo11O39]、Bmim5[Cu(H2O)TiMo11O39]、Bmim5[Ti(H2O)TiMo11O39]、Bmim5[Pb(H2O)TiMo11O39]。
优选的，该催化剂为Bmim5[Ti(H2O)TiMo11O39]。
一种钛系杂多酸离子液体的制备方法，
(1)中间体A-咪唑离子液体的制备
称取一定量的N-甲基咪唑于反应器中，冷凝回流条件下以10-100mL/s速率缓慢滴加一定量的氯代正丁烷，反应温度控制在70-90℃，反应22-26h后，将反应液用乙腈洗涤滤3-5次，经旋蒸，70-90℃干燥5-8h，得到浅黄色中间体A；
(2)中间体B-金属取代钛系缺位Keggin型杂多酸的制备
称取一定量的钼酸钠溶解于适量蒸馏水中，并加热至微沸，调节pH为4-5，冷凝回流并以10-100ml/s速率缓慢滴加一定量的TiCl4，滴加完毕反应2h后，同样以10-100mL/s速率缓慢滴一定量的配位金属盐，滴加完毕继续反应2h后，加入一定量氯化钾，有白色沉淀析出，过滤除去不溶物，低温下再加入无水乙醇反复提纯3-5次，析出产物中间体B，80℃干燥5-8h，得不同配位金属的钛系缺位Keggin型杂多酸中间体B；
(3)钛系杂多酸离子液体催化剂的制备
将一定量中间体B加入到装有蒸馏水的三口烧瓶中，搅拌溶解后，再将一定量中间体A以10-100ml/s速率缓慢滴入三口烧瓶中，立即有沉淀析出，过滤出沉淀物，用蒸馏水反复洗涤3-5次，70-90℃干燥5-8h，得到终产物钛系杂多酸离子液体催化剂。
进一步的，步骤(1)中N-甲基咪唑与氯代正丁烷的摩尔比为1:1.2；
步骤(2)中钼酸钠与TiCl4和配位金属盐的摩尔比为11：1:1；
步骤(2)中配位金属盐为金属锡、锌、铁、铜、钛或铅中的一种；
步骤(3)中中间体A与中间体B的摩尔比例5:1。
一种钛系杂多酸离子液体催化剂的应用，其特征在于：该催化剂用于催化苯酚与碳酸二甲酯酯交换法合成碳酸二苯酯。
有益效果：
1.发明制备的6种钛系杂多酸离子液体催化剂活对碳酸二甲酯与苯酚的酯交换反应具有很好的活性，其碳酸二苯酯和甲基苯基碳酸酯的总收率在21％-45％之间，酯交换选择性在93.85％-98.89％之间。
2.杂多酸离子液体相对于一般离子液体，其具备了不同于常规离子液体所不具备的高熔点的特性，该性能使其具备了“高温熔化反应-低温凝固分离”的温控型反应自分离的优良特性。
3.杂多酸离子液体催化剂基于离子液体，其蒸气压为零，可用于真空及高压条件下的反应。不易燃烧、不爆炸、不氧化，具有较好的热稳定性和化学稳定性。
附图说明
图1为产物杂多酸离子液体催化剂红外谱图；
图2为催化剂Bmim5[Ti(H2O)TiMo11O39的]XRD谱图；
图3为催化剂Bmim5[Ti(H2O)TiMo11O39的热失重图谱。
具体实施方式
以下结合说明书附图更详细的说明本发明。
杂多酸离子液体一般是通过离子液体的阳离子取代杂多酸上的质子形成的，本质上属于离子交换。一般情况下，离子液体的稳定性主要是通过调节阳离子进行控制，而其化学功能性是通过阴离子控制的，杂多酸离子液体本质上与双酸型离子液体一样，同属于功能型离子液体，是根据化学反应活性的实际需求，将结构易于调节、可功能化设计的有机材料—离子液体和具有高活化性，易设计性的无机材料—杂多酸进行组装结合，形成有机-无机杂化材料，不仅能保持阴阳离子在结构上不发生改变，也使其化学特性不发生改变，使其具备二者共同的特性。此外，杂多酸离子液体不同于大多数离子液体，因杂多酸直径较大，电荷含量高，与阳离子合成离子液体后对称性强，导致其阴阳离子间库仑力远大于其他离子液体，使其具备了不同于常规离子液体所不具备的高熔点的特性，该性能使其具备了“高温熔化反应-低温凝固分离”的温控型反应自分离的优良特性，杂多酸本身所具备的高于一般催化剂的酸性和氧化性的特点，以及在与有机阳离子的作用下所具备的反应自分离易回收的特点，使其不仅具备了一般催化剂所不具备的高催化反应活性，也使其具备了离子液体所具备的高稳定性和易回收的双重优点。
本发明提出六种金属取代钛系缺位Keggin型杂多酸离子液体催化剂及其制备方法与应用，其目的在于通过离子交换将离子液体的阳离子取代杂多酸的质子形成有机-无机杂化材料-钛系杂多酸离子液体，将结构易于调节、可功能化设计的有机材料离子液体和具有高活化性，易设计性的无机材料杂多酸进行组装，不仅能保持阴阳离子在结构上的完整性和化学特性，而且金属与金属、金属与咪唑阳离子之间均存在着协同催化作用。与传统的钛锡类和离子液体催化剂相比，该催化剂由于有机阳离子的存在，在反应过程中使得碳酸二甲酯羰基碳的亲电性更强，从而更有利于酚氧负离子的进攻，使得酯交换反应速率显著加快，不仅提高催化效率，而且还可以循环使用，节能省耗，经济环保。
本文主要共设计并制备了六种金属取代钛系缺位Keggin型杂多酸离子液体催化剂，用于催化碳酸二甲酯与苯酚的酯交换法合成碳酸二苯酯。
实施例1
(1)中间体A-咪唑离子液体的制备
称取一定量的N-甲基咪唑于反应器中，冷凝回流条件下以10-100mL/s速率缓慢滴加一定量的氯代正丁烷，反应温度控制在70℃，反应26h后，将反应液用乙腈洗涤滤4次，经旋蒸，70℃干燥8h，得到浅黄色中间体A。
(2)中间体B-金属取代钛系缺位Keggin型杂多酸的制备
称取一定量的钼酸钠溶解于适量蒸馏水中，并加热至微沸，调节pH为4，冷凝回流并以10-100ml/s速率缓慢滴加一定量的TiCl4盐酸水溶液，滴加完毕反应2h后，同样以10-100mL/s速率缓慢滴一定量的SnCl2盐酸水溶液，滴加完毕继续反应2h后，加入一定量氯化钾，有白色沉淀析出，过滤除去不溶物，低温下再加入无水乙醇反复提纯3次，析出产物中间体B，70℃干燥8h，得不同配位金属的钛系缺位Keggin型杂多酸中间体B。
(3)钛系杂多酸-Sn-离子液体催化剂的制备
将一定量中间体B加入到装有蒸馏水的三口烧瓶中，搅拌溶解后，再将一定量中间体A以10-100ml/s速率缓慢滴入三口烧瓶中，立即有沉淀析出，过滤出沉淀物，用蒸馏水反复洗涤3次，70℃干燥8h，得到终产物钛系杂多酸离子液体催化剂，记为Bmim5[SnII(H2O)TiMo11O39]。红外谱图如图1所示。
实施例2
(1)中间体A-咪唑离子液体的制备
称取一定量的N-甲基咪唑于反应器中，冷凝回流条件下以10-100mL/s速率缓慢滴加一定量的氯代正丁烷，反应温度控制在90℃，反应22h后，将反应液用乙腈洗涤滤5次，经旋蒸，90℃干燥5h，得到浅黄色中间体A。
(2)中间体B-金属取代钛系缺位Keggin型杂多酸的制备
称取一定量的钼酸钠溶解于适量蒸馏水中，并加热至微沸，调节pH为5，冷凝回流并以10-100ml/s速率缓慢滴加一定量的TiCl4盐酸水溶液，滴加完毕反应2h后，同样以10-100mL/s速率缓慢滴一定量的乙酸锌水溶液，滴加完毕继续反应2h后，加入一定量氯化钾，有白色沉淀析出，过滤除去不溶物，低温下再加入无水乙醇反复提纯3次，析出产物中间体B，90℃干燥5h，得不同配位金属的钛系缺位Keggin型杂多酸中间体B。
(3)钛系杂多酸-Zn-离子液体催化剂的制备
将一定量中间体B加入到装有蒸馏水的三口烧瓶中，搅拌溶解后，再将一定量中间体A以10-100ml/s速率缓慢滴入三口烧瓶中，立即有沉淀析出，过滤出沉淀物，用蒸馏水反复洗涤3次，90℃干燥5h，得到终产物钛系杂多酸离子液体催化剂，记为Bmim5[Zn(H2O)TiMo11O39]。红外谱图如图1所示。
实施例3
(1)中间体A-咪唑离子液体的制备
称取一定量的N-甲基咪唑于反应器中，冷凝回流条件下以10-100mL/s速率缓慢滴加一定量的氯代正丁烷，反应温度控制在80℃，反应24h后，将反应液用乙腈洗涤滤3次，经旋蒸，80℃干燥6h，得到浅黄色中间体A。
(2)中间体B-金属取代钛系缺位Keggin型杂多酸的制备
称取一定量的钼酸钠溶解于适量蒸馏水中，并加热至微沸，调节pH为5，冷凝回流并以10-100ml/s速率缓慢滴加一定量的TiCl4盐酸水溶液，滴加完毕反应2h后，同样以10-100mL/s速率缓慢滴一定量的FeSO4水溶液，滴加完毕继续反应2h后，加入一定量氯化钾，有白色沉淀析出，过滤除去不溶物，低温下再加入无水乙醇反复提纯3次，析出产物中间体B，80℃干燥8h，得不同配位金属的钛系缺位Keggin型杂多酸中间体B。
(3)钛系杂多酸-Fe-离子液体催化剂的制备
将一定量中间体B加入到装有蒸馏水的三口烧瓶中，搅拌溶解后，再将一定量中间体A以10-100ml/s速率缓慢滴入三口烧瓶中，立即有沉淀析出，过滤出沉淀物，用蒸馏水反复洗涤3次，80℃干燥6h，得到终产物钛系杂多酸离子液体催化剂，记为Bmim5[FeII(H2O)TiMo11O39]。红外谱图如图1所示。
实施例4
实施例4与实施例3步骤基本相同，将实施例3中(2)中的配位金属原子盐由SnCl2盐酸水溶液换为CuSO4水溶液，得钛系杂多酸离子液体催化剂，记为Bmim5[Cu(H2O)TiMo11O39]。红外谱图如图1所示。
实施例5
实施例5与实施例3步骤基本相同，将实施例3中(2)中的配位金属原子盐由SnCl2盐酸水溶液换为TiCl4盐酸水溶液，得钛系杂多酸离子液体催化剂，记为Bmim5[Ti(H2O)TiMo11O39]。红外谱图如图1所示，XRD谱图如图2所示，热失重图谱如图3所示。
图2是Bmim5[Ti(H2O)TiMo11O39]的XRD谱图。由图可知，咪唑的衍射特征峰出现在14.42°、16.75°、23.14°、26.05°处，杂多酸的衍射特征峰出现在23.14°、26.05°、25.18与31.15处，这说明了Keggin结构没有被破坏。此外，MoO6的特征峰出现在23.14°与26.05°处，TiO4特征衍射峰出现在25.18°、31.15°处，这说明了催化剂Bmim5[Ti(H2O)TiMo11O39]是目标产物。
图3是Bmim5[Ti(H2O)TiMo11O39]的TG曲线图。由图可知，催化剂开始热分解温度在310℃左右，而催化反应的温度为160-180℃。这说明该催化剂的热稳定性很好，满足催化反应的温度要求。
实施例6
实施例6与实施例3步骤基本相同，将实施例3中(2)中的配位金属原子盐由SnCl2盐酸水溶液换为乙酸铅水溶液，得钛系杂多酸离子液体催化剂，记为Bmim5[Pb(H2O)TiMo11O39]。红外谱图如图1所示。
一种杂多酸离子液体催化剂的应用，该催化剂应用于碳酸二苯酯合成反应应用的方法如下：
称取苯酚18.84g(0.2mol)，量取碳酸二甲酯36.03g(0.4mol)，混合加入到带有回流冷凝装置的三口烧瓶中，N2保护下加入钛系双酸性离子液体催化剂0.5g，其质量为反应物总质量的1％；将反应体系搅拌并加热到160-180℃，调节回流比为3:1，反应7-9h后，将反应体系冷却至室温(25℃)，然后将反应液进行减压蒸馏，用气相色谱仪检测产物纯度，并计算转化率、选择性和收率。
将实施例1-6制备的六种钛系杂多酸离子液体催化剂分别催化苯酚和碳酸二甲酯合成碳酸二苯酯，同样条件下将对比的传统催化剂钛酸四丁酯和二丁基氧化锡与离子液体催化剂进行催化苯酚与碳酸二甲酯酯交换反应生成碳酸二苯酯，以转化率、选择性和产率为考察指标，对比研究其催化性能，其中MPC是碳酸单苯酯，DPC为碳酸二苯酯，结果见表1。
表1实施例1-6催化性能评价结果
从表中数据可看出，在相同反应条件下，传统催化剂钛酸四丁酯与二氯二茂钛具有一定的催化活性，但其反应速率慢，反应周期长，与杂多酸离子液体存在较大差距；通过实验发现，传统ILs中缺少将DMC羰基碳活化的活性位点，使其在催化酯交换反应过程中的催化活性并不理想，存在转化率低、产率低、和选择性差等问题。为了进一步解决传统ILs中缺少活性位点的问题，提高酯交换反应的产率，我们基于离子液体与杂多酸可设计性强的优点，重点研究了杂多酸离子液体催化该酯交换反应，根据上表可知Bmim5[Ti(H2O)TiMo11O39]催化性能最好，苯酚的转化率为45.16％，MPC与DPC的选择性为98.89％，其余杂多酸离子液体不同配位金属的催化活性依次为：Ti>Sn>Fe>Pb>Zn>Cu。
Claims (6)
1.一种钛系杂多酸离子液体催化剂，其特征在于：该催化剂的结构包括金属取代钛系缺位Keggin型杂多酸阴离子和咪唑有机阳离子，形成有机-无机功能杂化材料。
2.根据权利要求1所述的钛系杂多酸离子液体催化剂，其特征在于：该催化剂为Bmim5[SnII(H2O)TiMo11O39]、Bmim5[Zn(H2O)TiMo11O39]、Bmim5[FeII(H2O)TiMo11O39]、Bmim5[Cu(H2O)TiMo11O39]、Bmim5[Ti(H2O)TiMo11O39]、Bmim5[Pb(H2O)TiMo11O39]。
3.根据权利要求1所述的钛系杂多酸离子液体催化剂，其特征在于：该催化剂为Bmim5[Ti(H2O)TiMo11O39]。
4.一种如权利要求1所述钛系杂多酸离子液体的制备方法，其特征在于：
(1)中间体A-咪唑离子液体的制备
称取一定量的N-甲基咪唑于反应器中，冷凝回流条件下以10-100mL/s速率缓慢滴加一定量的氯代正丁烷，反应温度控制在70-90℃，反应22-26h后，将反应液用乙腈洗涤滤3-5次，经旋蒸，70-90℃干燥5-8h，得到浅黄色中间体A；
(2)中间体B-金属取代钛系缺位Keggin型杂多酸的制备
称取一定量的钼酸钠溶解于适量蒸馏水中，并加热至微沸，调节pH为4-5，冷凝回流并以10-100ml/s速率缓慢滴加一定量的TiCl4，滴加完毕反应2h后，同样以10-100mL/s速率缓慢滴一定量的配位金属盐，滴加完毕继续反应2h后，加入一定量氯化钾，有白色沉淀析出，过滤除去不溶物，低温下再加入无水乙醇反复提纯3-5次，析出产物中间体B，80℃干燥5-8h，得不同配位金属的钛系缺位Keggin型杂多酸中间体B；
(3)钛系杂多酸离子液体催化剂的制备
将一定量中间体B加入到装有蒸馏水的三口烧瓶中，搅拌溶解后，再将一定量中间体A以10-100ml/s速率缓慢滴入三口烧瓶中，立即有沉淀析出，过滤出沉淀物，用蒸馏水反复洗涤3-5次，70-90℃干燥5-8h，得到终产物钛系杂多酸离子液体催化剂。
5.根据权利要求4所述钛系杂多酸离子液体的制备方法，其特征在于：
步骤(1)中N-甲基咪唑与氯代正丁烷的摩尔比为1:1.2；
步骤(2)中钼酸钠与TiCl4和配位金属盐的摩尔比为11：1:1；
步骤(2)中配位金属盐为金属锡、锌、铁、铜、钛或铅中的一种；
步骤(3)中中间体A与中间体B的摩尔比例5:1。
6.一种如权利要求1所述钛系杂多酸离子液体催化剂的应用，其特征在于：该催化剂用于催化苯酚与碳酸二甲酯酯交换法合成碳酸二苯酯。
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| CN115160144A (zh) * | 2022-06-14 | 2022-10-11 | 北京理工大学 | 一种过渡金属取代型杂多酸基离子液体阻燃剂、制备方法及其应用 |
| CN115160144B (zh) * | 2022-06-14 | 2024-02-27 | 北京理工大学 | 一种过渡金属取代型杂多酸基离子液体阻燃剂、制备方法及其应用 |
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