CN109400923B - 一种超交联多孔聚离子液体材料的制备方法及应用 - Google Patents
一种超交联多孔聚离子液体材料的制备方法及应用 Download PDFInfo
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Abstract
本发明提供一种离子热聚合制备超交联多孔聚离子液体材料的方法及其应用，该方法首先将烯基叔胺与二氯亚砜进行季铵化，形成刚性双烯离子液体单体，并通过离子交换引入合适配阴离子，接着，在氯化锌/氯化钾复合熔盐体系中进行离子热聚合，得超交联多孔聚离子液体材料，所得材料有广泛的应用前景。本发明的优点：(1)产率高，为92～97％；(2)制备材料比表面积大，在200m2/g以上；(3)材料具有全离子液体骨架，活性组分含量高；(4)制备过程简便，原料易得；(5)材料应用广泛，通过调整原料、配阴离子及聚合条件，可有效调节材料结构，可用于催化、气体吸附、废水处理、分离等领域；(6)材料回收重用简便，可通过过滤回收。
Description
技术领域
本发明涉及一种超交联多孔聚离子液体材料的制备方法及应用，属于高分子化学合成技术领域。
背景技术
离子液体性能优异，应用广泛，但存在回收难、价格贵、粘度高、降解差、无法成型等缺点。固载化可较好解决以上问题，但传统负载法将大体积离子液体接枝在载体上，易造成孔道堵塞，负载量低。多孔聚离子液体结合离子液体特定性能和高分子可加工成型、稳定持久、结构可调等优点，在催化、吸附分离、电化学等领域有广泛应用。
多孔聚离子液体，特别是纯聚离子液体骨架多孔材料研究较少，最常用合成方法是复合共聚。韩布兴课题组[Y.Xie,Angew.Chem.Int.Ed.2007,46:7255]将乙烯咪唑离子液体与二乙烯苯共聚，制备了催化性能优于离子液体及其自聚物的交联聚合材料。肖丰收课题组[F.Liu,J.Am.Chem.Soc.2012,134:16948]采用乙烯咪唑与二乙烯苯共聚、季铵化及离子交换，合成材料对生物柴油制备表现了优于硫酸活性。但共聚材料孔道源于聚二乙烯苯，离子液体接枝在聚合链上，非离子液体骨架，仍属负载型。Yuan等[Q.Zhao,Adv.Mater.2015,27:2913]将聚离子液体与有机多酸进行离子交联，形成多孔聚离子液体复合材料，通过调节羧酸结构和合成过程，可调控材料孔结构和形貌，成功用于CO2吸附、催化、高敏传感器等。但这类材料是聚离子液体复合物，离子交联稳定性未知，且无离子交换能力。单体直接聚合是最简便合成多孔聚离子液体材料的方法，但由于离子液体单体的极性较大，在聚合过程中随着聚合链的增长，链间极性增强，极易沉淀析出，因此，超交联聚离子液体制备的关键是形成高溶胀刚性超交联聚合网络。超交联聚合网络需在强溶剂化作用下形成，保证聚合链充分溶胀，溶剂挥发后，聚合链倾向收缩紧密堆积，降低表面能，但刚性超交联结构限制构象转换，阻止收缩，原溶剂占据空间成为孔结构]。与中性聚合物不同，聚离子链极性大，随反应进行，极性持续增加，易过早从溶剂沉淀析出，形成紧密堆积的无孔结构。为解决以上问题，本发明将烯丙基卤代物或者苯乙烯苄基卤代物进行聚合，形成高分子量的线性聚卤代物，将联吡啶与盐酸进行1:2酸化后，与聚卤代烃进行混合，在亚硝酸钠/硝酸锂复合熔盐体系中进行离子热季铵化交联，利用季铵化形成离子中心与熔盐间强静电库仑作用，离子热强化条件，促进季铵化交联高效完成，保证形成高溶胀刚性超交联聚离子液体网络，并通过配阴离子调节材料结构性能，制备超交联多孔聚离子液体。
发明内容
本发明的目的是为了解决上述现有技术的不足而提供一种超交联多孔聚离子液体材料的制备方法。
为了实现上述目的，本发明所设计的一种超交联多孔聚离子液体材料的制备方法，其将烯丙基溴、烯丙基氯、2-乙烯基苄氯、4-乙烯基苄氯、4-乙烯基苄溴中的一种进行聚合，形成高分子量的线性聚卤代物，将联吡啶与盐酸进行1∶2酸化后，与聚卤代烃进行混合，在亚硝酸钠/硝酸锂复合熔盐体系中进行离子热季铵化交联，得到超交联多孔聚离子液体材料。
所用熔盐为亚硝酸钠/硝酸锂复合熔盐，可与聚离子网络形成强静电库仑作用，很好溶胀交联聚离子液体网络，形成交联聚离子液体凝胶，熔盐中亚硝酸钠/硝酸锂的质量比为100∶45～100。
优选的，所述联吡啶为4，4′-联吡啶、2，2′-联吡啶中的一种。
优选的，通过离子交换将卤素离子交换成四氟硼酸根、六氟磷酸根、二氰胺根、三氟甲磺酸根、双三氟甲磺酰亚胺根离子中的一种，调整相应配阴离子，调节超交联聚离子液体材料的比表面和亲疏水性。
一种超交联多孔聚离子液体材料的应用，根据实际应用的要求，引入相应配阴离子，进行催化、气体吸附、废水处理方面的应用，材料经过滤回收后可进行重复使用。
与背景技术相比，本发明的优点是：(1)产率高，为90～94％；(2)制备材料比表面积大，在100m2/g以上；(3)材料具有全离子液体骨架，活性组分含量高；(4)材料应用广泛，通过调整原料、配阴离子及聚合条件，可有效调节材料结构，可用于催化、气体吸附、废水处理、分离等领域；(5)材料回收重用简便，可通过过滤回收。
具体实施方式
下面结合实施例对本发明进一步说明。
实施例1
本实施例提供的一种超交联多孔聚离子液体材料的制备方法，其具体的操作步骤如下：
称4-乙烯苄基氯，加入乙酸乙酯，配成40％的溶液后，加入引发剂，引发剂用量为总质量的1％，在70℃下搅拌48h后，进行过滤，依次用乙酸乙酯、乙醚进行洗涤3次后，在60℃进行真空干燥，得聚4-乙烯苄基氯，将4，4′-联吡啶溶于一定甲醇后，加入盐酸，盐的摩尔用量为联吡啶物质的量的2倍，保证酸化完成，减压蒸馏去除溶剂后，在70℃进行真空干燥，得4，4′-联吡啶盐酸盐，聚卤代烃和联吡啶盐按照摩尔比2:1进行研磨混合均匀后，加入亚硝酸钠/硝酸锂复合熔盐，亚硝酸钠和硝酸锂质量比为100：50，复合盐用量为上述混合物质量的20倍，均匀混合后，转入管式马弗炉，在氮气保护下，置于130℃下加热季铵化交联反应24h，冷却至室温，将凝胶产物加入10％的稀盐酸中，进行加热回流，去除熔盐，所得聚离子液体依次用乙酸乙酯、乙醚洗涤3次，进行80℃烘箱中干燥12h，即得多孔聚离子液体材料，比表面积为226m2/g。
实施例2-4
除以下不同外，其余与实施例1相同,分别采用表1所示的卤代烃和联吡啶。
表1
实施例5-9
除以下不同外，其余与实施例1,分别采用表3所示的配阴离子。
表2
实施例10-12
除以下不同外，其余与实施例1相同,分别采用表3所示的混合固体与熔盐的质量比。
表3
实施例13
以实施例10的超交联聚离子液体材料催化苯甲醛与氰乙酸乙酯的脑文格反应。将苯甲醛与氰乙酸乙酯按摩尔比1：1.5进行混合，加入质量比1％的催化剂进行70℃加热搅拌4小时，GC测定收率达99％。催化剂经过滤回收，洗涤烘干后，重用8次，催化活性不变。
实施例14
以实施例4的超交联聚离子液体材料用于二氧化碳的吸附。取一定量的超交联聚离子液体材料，抽真空后，通入二氧化碳气体至大气压，然后，氮气吹扫后，GC在线测量二氧化碳的吸附量。结果表明材料对二氧化碳吸附具有很好的性能，吸附量高达38mg/g。
实施例15
以实施例4的超交联聚离子液体材料用于甲基橙染料废水处理。取甲基橙含量为40mg/L的废水中加入3％的超交联聚离子液体吸附剂，在室温搅拌30min后，采用紫外分光光度计测试，甲基橙的脱除率在99％，得无色透明水溶液。通过乙醇洗涤多次后，吸附剂可以重复循环使用。
以上仅为本发明的优选实施方式，应当指出，对于高分子化学合成技术领域的普通技术人员来说，在不脱离本发明技术原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (4)
1.一种超交联多孔聚离子液体材料的制备方法，其特征在于：将烯丙基溴、烯丙基氯、2-乙烯基苄氯、4-乙烯基苄氯、4-乙烯基苄溴中的一种进行聚合，形成高分子量的线性聚卤代物，将联吡啶与盐酸进行1∶2酸化后，与聚卤代烃进行混合，在亚硝酸钠/硝酸锂复合熔盐体系中进行离子热季铵化交联，所述熔盐中亚硝酸钠/硝酸锂的质量比为100∶45～100，得到超交联多孔聚离子液体材料。
2.根据权利要求1所述的一种超交联多孔聚离子液体材料的制备方法，其特征在于：所述联吡啶为4，4′-联吡啶、2，2′-联吡啶中的一种。
3.根据权利要求1所述的一种超交联多孔聚离子液体材料的制备方法，其特征在于：通过离子交换将卤素离子交换成四氟硼酸根、六氟磷酸根、二氰胺根、三氟甲磺酸根、双三氟甲磺酰亚胺根离子中的一种。
4.根据权利要求1～3中任一项所述的一种超交联多孔聚离子液体材料的制备方法，其特征是包含以下的具体步骤：
将烯丙基溴、烯丙基氯、2-乙烯基苄氯、4-乙烯基苄氯、4-乙烯基苄溴中的一种，加入乙酸乙酯或四氢呋喃，配成40％的溶液后，加入引发剂，引发剂用量为总质量的1％，在65～80℃下搅拌12～72h后，进行过滤，依次用乙酸乙酯、乙醚进行洗涤3次后，在60℃进行真空干燥，得聚卤代烃，将联吡啶溶于有机溶剂后，加入盐酸，盐的摩尔用量为联吡啶的2倍，保证酸化完成，减压蒸馏去除溶剂后，在70℃进行真空干燥，得联吡啶盐，聚卤代烃和联吡啶盐按照摩尔比2:1进行研磨混合均匀后，加入亚硝酸钠/硝酸锂复合熔盐，亚硝酸钠和硝酸锂质量比为100∶45～100，复合盐用量为上述混合物质量的10～30倍，均匀混合后，转入管式马弗炉，在氮气保护下，置于85～150℃下加热季铵化交联反应12～72h，冷却至室温，将凝胶产物加入10％的稀盐酸中，进行加热回流，去除熔盐，所得聚离子液体依次用乙酸乙酯、乙醚洗涤3次，进行80℃烘箱中干燥12h，即得多孔聚离子液体材料。
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