CN105481773B - 一种制备离子液体的新方法 - Google Patents
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- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
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Abstract
本发明公开了一种制备离子液体的新方法，属于化学化工试剂的新技术制备领域。所述方法的特点在于以饱和的阴离子前体无机盐水溶液为反应介质，用盐析的原理实现离子液体产物与饱和水溶液以及副产物分离，反应时间短，成本低。本发明使用的方法以无机盐饱和水溶液为反应介质，饱和溶液可以重复使用，避免了使用污染环境的有机溶剂和价格高昂的银盐，同时可以实现副产物的回收，环境友好。本发明使用的方法不仅适用于疏水性离子液体的制备，而且适用于亲水性离子液体的制备。本发明使用的方法反应时间短，效率高，所需设备简单，操作容易，成本低廉，适合大规模的工业化生产应用。
Description
技术领域
本发明属于化学化工试剂的新技术制备领域，具体的说是一种制备离子液体的新方法。
背景技术
离子液体通常指一类完全由阴、阳离子构成的，熔点低于100 oC的有机熔盐化合物。离子液体同时兼具高温熔盐和有机溶剂的特点：与高温熔盐相比，离子液体是室温液体；与传统有机溶剂相比，离子液体完全是由阴阳离子构成的。强的阴阳离子之间的库仑作用力使得离子液体的蒸汽压极低，几乎可以忽略不计，在使用过程中不会像传统的有机溶剂那样挥发到空气中去污染环境，因此，离子液体被广泛地认为是新一代 “绿色溶剂”。此外，离子液体还具有熔点低、液程宽、电导率高、电化学稳定性高和全离子环境等特点。近30年来，离子液体在学术前沿领域获得了广泛的应用，主要包括合成、催化、电化学、无机材料和生物等方面。
离子液体通常采用两步法制备：首先是烷基季铵化反应，生成由有机阳离子和卤素阴离子组成的前体有机盐；其次是阴离子交换反应，将卤素阴离子置换成“离子液体阴离子”，以降低熔点。其中，第二步是难点和关键步骤，尤其是制备亲水性离子液体时。对于疏水性离子液体，阴离子交换反应通常以水为溶剂，副产物溶于水中，离子液体与水溶液分层，静置分离后真空干燥即可。对于亲水性离子液体，通常有两种方法用于阴离子交换反应。1）以有机溶剂（如丙酮）为溶剂，两个前体化合物和副产物都不溶于有机溶剂，只有离子液体能溶于其中，过滤后真空干燥，得到离子液体产物。这类反应类似固-固反应，需要剧烈搅拌，并且时间长，通常在48小时以上。此外，往往反应不完全，产物中存在大量的前体有机盐。2）以昂贵的银盐作为阴离子交换剂，在水溶液中进行，副产物是卤化银沉淀。该过程简单，反应彻底，产品质量高，但银盐的价格昂贵，不适宜大规模应用。
发明内容
本发明的目的在于针对现有的亲水性离子液体在制备过程中存在的问题，例如使用有机溶剂、反应时间长（通常在48小时以上）、反应不完全、或者大量使用银盐，发明一种不用银盐作为阴离子交换剂、不用有机溶剂、反应时间短、产率高的制备离子液体的新方法。
本发明所使用的一种制备离子液体的新方法既适用于亲水性离子液体的制备，又适用于疏水性离子液体的制备。
本发明所使用的一种制备离子液体的新方法，按下列步骤操作：
（1）将适量的阴离子前体无机盐，如NaBF4，溶于去离子水中，制成阴离子前体无机盐饱和水溶液；
（2）在步骤（1）的基础上，继续加入相同的阴离子前体无机盐，制成过饱和水溶液，加入的量是去离子水的质量的0.1-1.5倍；
（3）将阳离子前体有机盐，如1-丁基-3-甲基咪唑氯盐BMImCl，加入至步骤（2）中的过饱和溶液之中，加入的量与步骤（2）中所加入的阴离子前体无机盐的摩尔量相当，充分搅拌，使之充分反应；
（4）反应结束后静置，溶液分为三层：上层为离子液体溶液，中层为饱和水溶液，底层为固体无机盐副产物，将溶液转移至分液漏斗中，剩下的底层固体无机盐副产物待用；
（5）溶液在分液漏斗中静置分层后分液处理，上层离子液体溶液留在分液漏斗中，收集下层饱和水溶液待用；
（6）在分液漏斗中，用新制备的阴离子前体无机盐饱和水溶液洗涤离子液体溶液2-3次，每次的使用量为离子液体溶液体积的0.1-0.5倍，以除去离子液体溶液中残余的前体化合物，收集洗液待用；
（7）将步骤（6）洗涤后的离子液体溶液真空干燥，静置后过滤，得到纯度大于98%的离子液体产物；
（8）将步骤（4）中的固体无机盐副产物过滤，用新制备的纯的固体无机盐副产物的饱和水溶液冲洗2-3次，每次的使用量为步骤（1）中饱和水溶液体积的0.2-0.8倍；
（9）将步骤（8）中的固体无机盐副产物真空干燥处理，得到纯度大于98%的无机盐副产物；
（10）将步骤（5）收集的下层饱和水溶液和步骤（6）收集的洗液混合得混合液，混合液是主要含阴离子前体无机盐的饱和水溶液，可以重复使用，即重复上述的步骤（2）、（3）、（4）、（5）、（6）、（7）、（8）、（9）。
步骤（3）中的搅拌反应时间短，≤0.5小时。
步骤（7）和步骤（9）所述的真空干燥条件随产物不同而不同：温度为室温～150℃、真空度为10-2-10Pa，时间为5-20小时。
本发明所使用的阴离子前体无机盐是NaBF4、KPF6、NaNO3、Ba(ClO4)2、KSCN、KHCO2、KCH3CO2、NaCF3CO2、NaN(CN)2或Li(CF3SO2)2N中的一种。
本发明所使用的阳离子前体有机盐是咪唑类、吡啶类、吡咯类、哌啶类、吗啉类、叔硫类、季铵类或季磷类之一的氯盐或溴盐或碘盐。
本发明所生产的离子液体产物包括以[BF4]-，[PF6]-，[NO3]-，[ClO4]-，[SCN]-，[HCO2]-，[CH3CO2]-，[CF3CO2]-，[N(CN)2]-或[(CF3SO2)2N]-其中之一为阴离子的咪唑类离子液体、吡啶类离子液体、吡咯类离子液体、哌啶类离子液体、吗啉类离子液体、叔硫类离子液体、季铵类离子液体和季磷类离子液体，相关产物的结构式如下：
式（Ⅰ）中的R1为CH3，CH2CH3，CH2CH2CH3或者CH2CH2CH2CH3中的一种。
式（Ⅰ）中的R2为-CH3，-CH2CH3，-CH2CH2CH3，-CH2CH2CH2CH3，-CH2CH2CH2CH2CH3，-CH2OCH3，-CH2OCH2CH3，-CH2CH2OCH3，-CH2CH2OCH2CH3，-CN，-CH2CH2CH2CN，-CH2CO2CH3，-CH2CO2CH2CH3，中的一种。
式（Ⅰ）的中X-为阴离子，是[BF4]-，[PF6]-，[NO3]-，[ClO4]-，[SCN]-，[HCO2]-，[CH3CO2]-，[CF3CO2]-，[N(CN)2]-，[(CF3SO2)2N]-中的一种。
本发明以无机盐饱和水溶液为溶剂，将阴离子交换反应置于其中进行，用盐析的原理将离子液体产物与饱和水溶液以及副产物分离，反应结束后，静置分层，分液即可获得上层离子液体溶液，其基本原理及反应过程如图Ⅰ所示。
本发明所需的设备简单，操作容易，成本低，反应时间短（约30分钟），适合大规模生产的应用。
本发明绿色环保，以无机盐前体化合物的饱和水溶液为反应介质，反应结束后，剩余的中层饱和水溶液可以连续使用，不使用污染环境的有机溶剂，且副产物无机盐沉于底部易于回收，不产生三废。
本发明普适性高，不仅可用于亲水性离子液体的制备，避免了有机溶剂或者昂贵的Ag+试剂的使用，还可用于疏水性离子液体的制备，回收无机盐副产物。
本发明所制备的离子液体都经分析纯度均在98%以上。
附图说明
图1：本发明基本原理及反应过程示意图。
具体实施步骤
除非特别说明，本发明中所用的技术手段均为本领域技术人员所公知的方法。另外，实施方案应理解为说明性的，而非限制本发明的范围，本发明的实质和范围仅由权利要求书所限定。对于本领域技术人员而言，在不背离发明实质和范围的前提下，对这些实施方案中的反应条件，分离纯化条件的各种改变或变动也属于本发明的保护范围。
以下的实施例可以使本专业技术人员更全面地理解本发明，但不以任何方式限制本发明。
实施例：以制备离子液体1-丁基-3-甲基咪唑四氟硼酸盐（BMImBF4）为例具体说明本发明方法；
（1）在室温约25 oC下，将103 g四氟硼酸钠（NaBF4）加入装有100 mL去离子水的500mL烧瓶中，机械搅拌30分钟，使之形成饱和NaBF4水溶液，底部有少量固体残存；
（2）在上述饱和溶液中继续加入0.5 mol/55 g NaBF4与0.5 mol/87 g 1-丁基-3-甲基咪唑氯盐BMImCl；
（3）机械搅拌30分钟，使之充分反应；
（4）反应结束后静置，溶液分为三层：上层主要为离子液体BMImBF4，中层为饱和水溶液，底层主要为固体无机盐副产物NaCl，将溶液转移至分液漏斗中，剩下的底层固体无极副产物NaCl待用。
（5）溶液在分液漏斗中静置分层，上层为离子液体溶液，下层为饱和水溶液，分液处理，离子液体留在分液漏斗中，收集下层饱和水溶液待用。
（6）往上述装有离子液体溶液的分液漏斗中加入新配置的NaBF4饱和水溶液20mL，充分摇匀后，静置分层。分液处理，离子液体溶液留在分液漏斗中，收集洗液待用，如此再重复两次；
（7）将上述洗涤后的离子液体溶液转移至250 mL磨口圆底烧瓶中，在磁力搅拌、80oC和0.1 Pa条件下真空干燥10小时，静置后过滤，得90 g无色离子液体BMImBF4，产率为80%。
（8）将上述步骤（4）所得固体无机盐副产物NaCl过滤，用新配置的NaCl饱和水溶液冲洗3次，每次的用量为50 mL；
（9）将上述无机盐NaCl转移至50 mL烧杯中，在80 oC和0.1 Pa真空烘箱中干燥10小时，得到20 g白色固体NaCl，副产物回收率为70%；
（10）将步骤（5）收集的下层饱和水溶液和步骤（6）收集的洗液混合得混合液，混合液是主要含阴离子前体无机盐的饱和水溶液，可以重复使用，即重复上述的步骤（2）、（3）、（4）、（5）、（6）、（7）、（8）、（9）。
对上述所获的无色液体进行FT-IR、1H-NMR、13C-NMR、MS、EA以及ISE分析，结构为BMImBF4离子液体，综合纯度为99.1%。
对上述所获的白色固体进行元素分析与ISE分析，表组成为NaCl，纯度为98.5%。
说明副产物无机盐可以通过该方法得到很好的回收。
Claims (3)
1.一种制备离子液体的新方法，其特征在于按下列步骤操作：
(1)将适量的阴离子前体无机盐溶于去离子水中，制成阴离子前体无机盐饱和水溶液；
(2)在步骤(1)的基础上，继续加入相同的阴离子前体无机盐，制成过饱和水溶液，加入的量是去离子水的质量的0.1-1.5倍；
(3)将阳离子前体有机盐加入至步骤(2)中的过饱和溶液之中，加入的量与步骤(2)中所加入的阴离子前体无机盐的摩尔量相当，充分搅拌，使之充分反应；
(4)反应结束后静置，溶液分为三层：上层为离子液体溶液，中层为饱和水溶液，底层为固体无机盐副产物，将溶液转移至分液漏斗中，剩下的底层固体无机盐副产物待用；
(5)溶液在分液漏斗中静置分层后分液处理，上层离子液体溶液留在分液漏斗中，收集下层饱和水溶液待用；
(6)在分液漏斗中，用新制备的阴离子前体无机盐饱和水溶液洗涤离子液体溶液2-3次，每次的使用量为离子液体溶液体积的0.1-0.5倍，以除去离子液体溶液中残余的前体化合物，收集洗液待用；
(7)将步骤(6)洗涤后的离子液体溶液真空干燥，静置后过滤，得到纯度大于98％的离子液体产物；
(8)将步骤(4)中的固体无机盐副产物过滤，用新制备的纯的固体无机盐副产物的饱和水溶液冲洗2-3次，每次的使用量为步骤(1)中饱和水溶液体积的0.2-0.8倍；
(9)将步骤(8)中的固体无机盐副产物真空干燥处理，得到纯度大于98％的无机盐副产物；
(10)将步骤(5)收集的下层饱和水溶液和步骤(6)收集的洗液混合得混合液，混合液是主要含阴离子前体无机盐的饱和水溶液，可以重复使用，即重复上述的步骤(2)-(9)；
所述阴离子前体无机盐是NaBF4、KPF6、NaNO3、Ba(ClO4)2、KSCN、KHCO2、KCH3CO2、NaCF3CO2、NaN(CN)2或Li(CF3SO2)2N中的一种；
所述阳离子前体有机盐是咪唑类、吡啶类、吡咯类、哌啶类、吗啉类、叔硫类、季铵类或季磷类之一的氯盐或溴盐或碘盐；
所述离子液体产物包括以[BF4]-，[PF6]-，[NO3]-，[ClO4]-，[SCN]-，[HCO2]-，[CH3CO2]-，[CF3CO2]-，[N(CN)2]-或[(CF3SO2)2N]-其中之一为阴离子的咪唑类离子液体、吡啶类离子液体、吡咯类离子液体、哌啶类离子液体、吗啉类离子液体、叔硫类离子液体、季铵类离子液体和季磷类离子液体，相关产物的结构式如下：
式(Ⅰ)中的R1为CH3，CH2CH3，CH2CH2CH3或者CH2CH2CH2CH3中的一种；
式(Ⅰ)中的R2为-CH3，-CH2CH3，-CH2CH2CH3，-CH2CH2CH2CH3，-CH2CH2CH2CH2CH3，-CH2OCH3，-CH2OCH2CH3，-CH2CH2OCH3，-CH2CH2OCH2CH3，-CN，-CH2CH2CH2CN，-CH2CO2CH3，-CH2CO2CH2CH3，中的一种；
式(Ⅰ)的中X-为阴离子，是[BF4]-，[PF6]-，[NO3]-，[ClO4]-，[SCN]-，[HCO2]-，[CH3CO2]-，[CF3CO2]-，[N(CN)2]-，[(CF3SO2)2N]-中的一种。
2.根据权利要求1所述的一种制备离子液体的新方法，其特征在于步骤(3)中的搅拌反应时间≤0.5小时。
3.根据权利要求1所述的一种制备离子液体的新方法，其特征在于步骤(7)和步骤(9)所述的真空干燥条件随产物不同而不同：温度为室温～150℃、真空度为10-2-10Pa，时间为5-20小时。
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