CN104275154B - 一种能分离混二甲苯的复合材料及其制备方法 - Google Patents

一种能分离混二甲苯的复合材料及其制备方法 Download PDF

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CN104275154B
CN104275154B CN201410551134.2A CN201410551134A CN104275154B CN 104275154 B CN104275154 B CN 104275154B CN 201410551134 A CN201410551134 A CN 201410551134A CN 104275154 B CN104275154 B CN 104275154B
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王明亮
陆娇
魏想
吴小娟
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Southeast University
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Abstract

本发明是一种能分离混二甲苯的新型多孔复合材料，该材料由两个单体分子共结晶得到，即由1-乙酰基-3-苯基-5-(9-蒽基)吡唑啉(APPP)和7,7,8,8-四氰基对苯二醌二甲烷(TCNQ)在芳烃溶剂中溶解，经脱除溶剂后烘干得到的共晶。本发明的复合材料在应用于混二甲苯溶剂后，只选择性地吸附混合物中的对二甲苯。

Description

一种能分离混二甲苯的复合材料及其制备方法
技术领域
本发明涉及一种多孔复合材料及其制备方法，该材料能够选择性吸收对二甲苯。
背景技术
二甲苯包括对二甲苯、邻二甲苯、间二甲苯三种异构体，它们都是重要的有机化工原料，在医药、农药、工程塑料、染料、催化剂等方面具有广泛的应用，特别是对二甲苯可用于制备对苯二甲酸,是聚酯(PET)工业的基础。二甲苯异构体的沸点比较接近，传统工业上一般采取精馏等高能耗、高成本的分离方法。近年也报道了多种能吸附二甲苯的吸附材料。一种KY型分子筛，能吸附所有的二甲苯异构体，但没有选择性[IndustrialandEngineeringChemistryProcessDesignandDevelopment,1982,21(3):440]。金属有机MOF-5材料能够吸收邻二甲苯和对二甲苯[MicroporousMesoporousMater.2003,58,105.]，但对邻二甲苯与对二甲苯没有选择性。MOFZn(BDC)-(Dabco)0.5(BDC＝1,4-对苯二甲酸，Dabco＝1,4-二氮杂二环辛烷)能够从混二甲苯中分离邻二甲苯[Chen,B.J.Phys.Chem.C2009,113,13173.]，但是MOF材料制备方法复杂、制备周期冗长且成本较高，难以应用于工业化生产。发明专利CN103977765A公开了一种由芳香稠环的查耳酮分子和7,7,8,8-四氰基对苯二醌二甲烷(TCNQ)共晶复合材料，发明专利CN103949219A公开了一种由1-乙酰基-3-(4-甲氧基苯基)-5-(9-蒽基)吡唑啉(AMPE)和7,7,8,8-四氰基对苯二醌二甲烷(TCNQ)共晶复合材料，这两个专利报道的材料能够吸附大多数芳香烃溶剂，但对二甲苯的异构体的吸附没有选择性。
发明内容
技术问题：本发明提供一种由两种有机分子通过电荷转移作用形成的电荷转移复合材料，。以解决目前报道的材料不能分离混二甲苯的问题。
技术方案：本发明的能分离混二甲苯的复合材料，是由含稠环基团的有机电子供体分子与有机电子受体分子按照1：1的摩尔比在溶剂中溶解，静置24-48小时后，减压脱除溶剂，烘干得到的共晶复合材料。上述含稠环基团的有机电子供体分子是1-乙酰基-3-(4-苯基)-5-(9-蒽基)吡唑啉(即APPP)，分子结构如下：
有机电子受体分子是7,7,8,8-四氰基对苯二醌二甲烷(即TCNQ)，分子结构如下：
本发明上述复合材料的优选方案中，所述的溶剂是甲苯、氯苯或二者的混合物。
本发明的制备上述能分离混二甲苯的复合材料的方法，将含稠环基团的有机电子供体分子与有机电子受体分子按照1：1的摩尔比在溶剂中溶解，静置24-48小时后，减压脱除溶剂，烘干得到所述复合材料，所述含稠环基团的有机电子供体分子是1-乙酰基-3-(4-苯基)-5-(9-蒽基)吡唑啉，分子结构如下：
所述有机电子受体分子是7,7,8,8-四氰基对苯二醌二甲烷，分子结构如下：
本发明上述制备方法的优选方案中，所述的溶剂是甲苯、氯苯或二者的混合物。
本发明复合材料采用芳香烃作溶剂，使有机给体分子和受体分子之间通过芳香环之间的作用形成一种非极性孔道，对二甲苯能进入孔道并与复合物形成氢键，而间二甲苯及邻二甲苯则不能进入，因此该复合材料能够从二甲苯异构体混合物中选择性吸附对二甲苯。
有益效果：与现有技术相比，本发明具有以下优点：相对于专利CN103949219A报道的一种选择吸附芳烃的多孔复合材料，本发明的方法是采用一种新的有机给体分子1-乙酰基-3-(4-苯基)-5-(9-蒽基)吡唑啉，该分子相比于该专利使用的1-乙酰基-3-(4-甲氧基苯基)-5-(9-蒽基)吡唑啉(AMPE)分子，只是苯基对位少了一个甲氧基基团，同时采用芳烃作溶剂的方法，使得给体分子与受体分子之间的芳香环之间的超分子相互作用得到增强，从而使生成的共晶复合材料只能吸附对二甲苯，而不能吸附间二甲苯或邻二甲苯，因此在吸附试验中，能将对二甲苯从对二甲苯和间二甲苯的混合物或对二甲苯和邻二甲苯的混合液中选择性吸附，从而分离出对二甲苯。
附图说明
图1为实施例4中所得产物吸附对二甲苯后的热重分析(上)和差热分析(下)示意图。
图2为实施例4中所得产物吸附对二甲苯后的热重分析(上)和差热分析(下)示意图。
具体实施方式
下面通过实施例对本发明作进一步详细说明，本实施例在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实施例。
本发明是通过以下技术方案实现的，将1-乙酰基-3-苯基-5-(9-蒽基)吡唑啉(APPP)和7,7,8,8-四氰基对苯二醌二甲烷(TCNQ)在溶剂中溶解，静置24小时后，真空减压脱除溶剂，烘干得到多孔复合材料。
所述的溶剂是甲苯、氯苯、乙苯等芳烃溶剂或它们的混合物。
所述的混二甲苯可以是对二甲苯和间二甲苯的混合物，也可以是对二甲苯和邻二甲苯的混合物。
该复合材料加入至对混二甲苯的溶液中，可将混二甲苯中的对二甲苯选择性吸附到复合材料中，而将混二甲苯中的邻二甲苯或间二甲苯保留在溶液中，从而达到分离的效果。
实施例1
72.80gAPPP和40.8gTCNQ在甲苯溶剂中溶解后，静置24小时后，真空减压脱除溶剂，烘干得到多孔复合材料。
实施例2
72.80gAPPP和40.8gTCNQ在氯苯溶剂中溶解后，静置24小时后，真空减压脱除溶剂，烘干得到多孔复合材料。
实施例3
72.80gAPPP和40.8gTCNQ在甲苯与氯苯(体积比1：1)混合溶剂中溶解后，静置24小时后，真空减压脱除溶剂，烘干得到多孔复合材料。
实施例4
将上述实施例中制备得到的多孔复合材料25克加入至对100毫升二甲苯与间二甲苯(1：1)混合物中，搅拌1小时后静置，滤出固体，热重分析(上)和差热分析检测发现吸附了18.52％的对二甲苯(附图1)。
实施例5
将上述实施例中制备得到的多孔复合材料25克加入至对100毫升二甲苯与邻二甲苯(1：1)混合物中，搅拌1小时后静置，滤出固体，热重分析(上)和差热分析检测发现吸附了17.80％(附图2)。
上述实施例仅是本发明的优选实施方式，应当指出：对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和等同替换，这些对本发明权利要求进行改进和等同替换后的技术方案，均落入本发明的保护范围。

Claims (4)

1.一种能分离混二甲苯的复合材料，其特征在于，该复合材料是由含稠环基团的有机电子供体分子与有机电子受体分子按照1：1的摩尔比在溶剂中溶解，静置24-48小时后，减压脱除溶剂，烘干得到的共晶，所述含稠环基团的有机电子供体分子是1-乙酰基-3-(4-苯基)-5-(9-蒽基)吡唑啉，分子结构如下：
所述有机电子受体分子是7,7,8,8-四氰基对苯二醌二甲烷，分子结构如下：
2.根据权利要求1所述的能分离混二甲苯的复合材料，其特征在于，所述的溶剂为甲苯、氯苯或二者的混合物。
3.一种制备权利要求1或2所述能分离混二甲苯的复合材料的方法，其特征在于，该方法将含稠环基团的有机电子供体分子与有机电子受体分子按照1：1的摩尔比在溶剂中溶解，静置24-48小时后，减压脱除溶剂，烘干得到所述复合材料，所述含稠环基团的有机电子供体分子是1-乙酰基-3-(4-苯基)-5-(9-蒽基)吡唑啉，分子结构如下：
所述有机电子受体分子是7,7,8,8-四氰基对苯二醌二甲烷，分子结构如下：
4.根据权利要求3所述的制备能分离混二甲苯的复合材料的方法，其特征在于，所述的溶剂是甲苯、氯苯或二者的混合物。
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CN1749226A (zh) * 2005-08-18 2006-03-22 复旦大学 苯二取代物异构体在疏水硅沸石上复相吸附分离方法
CN103949219A (zh) * 2014-05-13 2014-07-30 东南大学 一种选择吸附芳烃的多孔复合材料的制备方法
CN103977765A (zh) * 2014-05-27 2014-08-13 东南大学 一种多孔复合材料的制备方法

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CN1749226A (zh) * 2005-08-18 2006-03-22 复旦大学 苯二取代物异构体在疏水硅沸石上复相吸附分离方法
CN103949219A (zh) * 2014-05-13 2014-07-30 东南大学 一种选择吸附芳烃的多孔复合材料的制备方法
CN103977765A (zh) * 2014-05-27 2014-08-13 东南大学 一种多孔复合材料的制备方法

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