CN114835745B - 一种疏水性低共熔溶剂、其制备方法及应用 - Google Patents
一种疏水性低共熔溶剂、其制备方法及应用 Download PDFInfo
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Abstract
本发明属于分析化学的技术领域,具体涉及一种疏水性低共熔溶剂、其制备方法及应用,所述低共熔溶剂由氢键受体和氢键供体组成,所述氢键受体为磷酸三丁酯,所述氢键供体为薄荷醇和/或百里香酚。本发明将由薄荷醇/百里香酚作为氢键供体和磷酸三丁酯作为氢键受体构成的低共熔溶剂用作萃取剂,用于萃取水体中尼泊金酯及其水解产物,具有萃取率高、操作简单、成本低廉、绿色环保等优点,制备方法简单,原子利用率达到100%,一步反应即可制备,无其他后处理步骤。
Description
技术领域
本发明属于分析化学的技术领域,具体涉及一种疏水性低共熔溶剂、其制备方法及应用。
背景技术
低共熔溶剂(DES)是一类新型的环境友好溶剂,由氢键受体和氢键供体按照一定摩尔比通过氢键缔合而成,常温下呈液态。低共熔溶剂具有结构设计性强、制备简单、性质可控、溶解性好、挥发性小等优点。近年来,在有机合成、纳米材料制备、有害气体捕集、金属回收、萃取及分离领域得到广泛应用。
磷酸三丁酯(TBP)是一种典型的中性络合萃取剂,在冶金工业中应用广泛。由于TBP含有较强的极性官能团-P=O,因此具有较高的亲核性,可作为氢键受体;薄荷醇和百里香酚作为天然赋香剂,结构中含有-OH,可作为氢键供体;用TBP和薄荷醇或百里香酚制备DES用作萃取剂,可以克服TBP对弱极性化合物萃取能力不强的缺点,且天然化合物薄荷醇或百里香酚的加入,降低了TBP的毒性。
目前,尼泊金酯及其水解产物的萃取方法主要有超声波辅助萃取、加压溶剂萃取、QuEChERS、固相萃取、磁固相萃取和液液微萃取等。其中,液液微萃取技术作为一种微型化的液液萃取方法,因使用极微量的(μL级)萃取剂,自报道以来受到分离分析领域研究者的广泛青睐。然而,该技术仍然使用传统的有机溶剂为萃取剂,这类传统溶剂具有毒性大、易挥发、成本高等缺点,影响该技术的绿色化程度。因此,制备萃取能力优越且环境友好的DES用于水体中尼泊金酯及其水解产物的萃取和分离具有重要意义。
发明内容
本发明的目的之一在于提供一种疏水性低共熔溶剂,具有萃取率高、操作简单、成本低廉、绿色环保等优点。
本发明的目的之二在于提供一种疏水性低共熔溶剂的制备方法,制备工艺简便,易于调节,适于实验室和产业化应用。
本发明的目的之三在于提供一种疏水性低共熔溶剂的应用。
本发明实现目的之一所采用的方案是:一种疏水性低共熔溶剂,由氢键受体和氢键供体组成,所述氢键受体为磷酸三丁酯,所述氢键供体为薄荷醇和/或百里香酚。
优选地,所述氢键受体与氢键供体的摩尔比为1:3~3:1。
本发明实现目的之二所采用的方案是:一种所述的疏水性低共熔溶剂的制备方法,按一定摩尔比混合氢键受体和氢键供体,并在一定温度下搅拌直至形成均相透明的液体,即得所述疏水性低共熔溶剂。
优选地,所述搅拌温度为70-90℃。
本发明实现目的之三所采用的方案是:一种所述的疏水性低共熔溶剂的应用,将所述疏水性低共熔溶剂作为萃取剂萃取水体中尼泊金酯及其水解产物。
一般来讲,水解产物为尼泊金甲酯、尼泊金乙酯、尼泊金丙酯、尼泊金丁酯、对羟基苯甲酸。萃取方法为:将所述疏水性低共熔溶剂与水样品混合,进行萃取,萃取完成后离心至低共熔溶剂-水体系完全分相。所述萃取的过程为,将疏水性低共熔溶剂与水样品的混合物从容器中多次吸入/排出进行萃取。所述低共熔溶剂与水样品的体积比为1:(16.7~100)。
本发明具有以下优点和有益效果:
(1)将薄荷醇/百里香酚作氢键供体和磷酸三丁酯作氢键受体的低共熔溶剂用于水体中尼泊金酯及其水解产物的萃取,萃取率高、操作简单、成本低廉、绿色环保。
(2)所述低共熔溶剂通过搅拌加热法来制备,原子利用率达到100%,一步反应即可制备,无其他后处理步骤。
(3)本发明研究了低共熔溶剂在水体中尼泊金酯及其水解产物萃取中的应用,对低共熔溶剂的产业化应用具有一定的指导意义。
附图说明
图1为本发明采用磷酸三丁酯(TBP)和薄荷醇制备DES的反应式;
图2磷酸三丁酯、薄荷醇及其DES的红外光谱图;
图3实施例2制备的DES的稳定性验证图。
具体实施方式
为更好地理解本发明,下面的实施例是对本发明的进一步说明,但本发明的内容不仅仅局限于下面的实施例。
I、术语
本发明中所述“水样品”一词,在没有特别说明或限定的情况下是指湖水、河水或水库水等环境水体样品。
本发明采用液相色谱分析仪对本发明所提供的低共熔溶剂作为萃取剂萃取水体中尼泊金酯及其水解产物的萃取效率(EE)进行评价,具体方法如下:
待低共熔溶剂和水样品完全分相后,取出上层低共熔溶剂相,使用液相色谱分析仪(LC-20AT HPLC Shimadzu)进行分析检测。
所述萃取效率的计算公式如式(I)所示:
式(I)中:
EE表示萃取效率;
CD表示萃取后DES相中尼泊金酯及其水解产物的浓度,μg mL-1;
VD表示萃取后DES相的体积,mL;
CW表示水样品中尼泊金酯及其水解产物的浓度,μg mL-1;
VW表示水样品的体积,mL。
对于液液微萃取水体中尼泊金酯及其水解产物而言,萃取剂的选择至关重要。萃取剂萃取能力取决于其极性、粘度、溶解能力等物理性质。良好的萃取剂的特征是:极性接近于尼泊金酯及其水解产物;粘度较低便于萃取传质;对尼泊金酯及其水解产物具有高溶解度和对水具有低溶解度;与水相存在较大的密度差,便于相分离。
如图1所示,为本发明采用磷酸三丁酯(TBP)和薄荷醇制备DES的反应式。
实施例1:
磷酸三丁酯-薄荷醇DES的制备步骤:称取适量的薄荷醇于100mL的圆底烧瓶中,然后缓慢滴加磷酸三丁酯,(磷酸三丁酯/薄荷醇摩尔比为1:3),滴加完毕后,将上述混合物置于70℃的油浴中,连续搅拌加热直至形成均匀透明的液体。即得到磷酸三丁酯-薄荷醇DES(DES-1)。
实施例2:
磷酸三丁酯-薄荷醇DES的制备步骤:称取适量的薄荷醇于100mL的圆底烧瓶中,然后缓慢滴加磷酸三丁酯,(磷酸三丁酯/薄荷醇摩尔比为1:2),滴加完毕后,将上述混合物置于70℃的油浴中,连续搅拌加热直至形成均匀透明的液体。即得到磷酸三丁酯-薄荷醇DES(DES-2)。
实施例3:
磷酸三丁酯-薄荷醇DES的制备步骤:称取适量的薄荷醇于100mL的圆底烧瓶中,然后缓慢滴加磷酸三丁酯,(磷酸三丁酯/薄荷醇摩尔比为1:1),滴加完毕后,将上述混合物置于70℃的油浴中,连续搅拌加热直至形成均匀透明的液体。即得到磷酸三丁酯-薄荷醇DES(DES-3)。
实施例4:
磷酸三丁酯-薄荷醇DES的制备步骤:称取适量的薄荷醇于100mL的圆底烧瓶中,然后缓慢滴加磷酸三丁酯,(磷酸三丁酯/薄荷醇摩尔比为2:1),滴加完毕后,将上述混合物置于70℃的油浴中,连续搅拌加热直至形成均匀透明的液体。即得到磷酸三丁酯-薄荷醇DES(DES-4)。
实施例5:
磷酸三丁酯-薄荷醇DES的制备步骤:称取适量的薄荷醇于100mL的圆底烧瓶中,然后缓慢滴加磷酸三丁酯,(磷酸三丁酯/薄荷醇摩尔比为3:1),滴加完毕后,将上述混合物置于70℃的油浴中,连续搅拌加热直至形成均匀透明的液体。即得到磷酸三丁酯-薄荷醇DES(DES-5)。
实施例6:
磷酸三丁酯-百里香酚DES的制备步骤:称取适量的百里香酚于100mL的圆底烧瓶中,然后缓慢滴加磷酸三丁酯,(磷酸三丁酯/百里香酚摩尔比为1:2),滴加完毕后,将上述混合物置于70℃的油浴中,连续搅拌加热直至形成均匀透明的液体。即得到磷酸三丁酯-百里香酚DES(DES-6)。
实施例7:
取一定量水样品于10mL离心管中,加入水样品量4%(v:v)的低共熔溶剂(DES-1)与之混合,用注射器从离心管中吸入/排出循环萃取5次,5000rpm离心1min至低共熔溶剂-水体系完全分相。取上层清液进入液相色谱仪进行分析检测,对尼泊金甲酯、尼泊金乙酯、尼泊金丙酯、尼泊金丁酯、对羟基苯甲酸的萃取率分别为91.1%、94.3%、93.7%、96.2%和56.1%。
实施例8:
取一定量水样品于10mL离心管中,加入水样品量4%(v:v)的低共熔溶剂(DES-2)与之混合,用注射器从离心管中吸入/排出循环萃取5次,5000rpm离心1min至低共熔溶剂-水体系完全分相。取上层清液进入液相色谱仪进行分析检测,对尼泊金甲酯、尼泊金乙酯、尼泊金丙酯、尼泊金丁酯、对羟基苯甲酸的萃取率分别为90.4%、92.8%、91.5%、94.7%和72.9%。
实施例9:
取一定量水样品于10mL离心管中,加入水样品量4%(v:v)的低共熔溶剂(DES-3)与之混合,用注射器从离心管中吸入/排出循环萃取5次,5000rpm离心1min至低共熔溶剂-水体系完全分相。取上层清液进入液相色谱仪进行分析检测,对尼泊金甲酯、尼泊金乙酯、尼泊金丙酯、尼泊金丁酯、对羟基苯甲酸的萃取率分别为87.8%、89.7%、87.5%、90.7%和73.9%。
实施例10:
取一定量水样品于10mL离心管中,加入水样品量4%(v:v)的低共熔溶剂(DES-4)与之混合,用注射器从离心管中吸入/排出循环萃取5次,5000rpm离心1min至低共熔溶剂-水体系完全分相。取上层清液进入液相色谱仪进行分析检测,对尼泊金甲酯、尼泊金乙酯、尼泊金丙酯、尼泊金丁酯、对羟基苯甲酸的萃取率分别为81.0%、86.4%、85.3%、86.0%和75.7%。
实施例11:
取一定量水样品于10mL离心管中,加入水样品量4%(v:v)的低共熔溶剂(DES-5)与之混合,用注射器从离心管中吸入/排出循环萃取5次,5000rpm离心1min至低共熔溶剂-水体系完全分相。取上层清液进入液相色谱仪进行分析检测,对尼泊金甲酯、尼泊金乙酯、尼泊金丙酯、尼泊金丁酯、对羟基苯甲酸的萃取率分别为79.5%、82.5%、81.5%、84.5%和77.7%。
实施例12:
取一定量水样品于10mL离心管中,加入水样品量4%(v:v)的低共熔溶剂(DES-6)与之混合,用注射器从离心管中吸入/排出循环萃取5次,5000rpm离心1min至低共熔溶剂-水体系完全分相。取上层清液进入液相色谱仪进行分析检测,对尼泊金甲酯、尼泊金乙酯、尼泊金丙酯、尼泊金丁酯、对羟基苯甲酸的萃取率分别为77.4%、88.0%、89.7%、97.4%和11.1%。
低共熔溶剂的组分间存在的氢键相互作用可用红外光谱验证,其结果如图2所示(1281cm-1波数为TBP的P=O的吸收峰,按摩尔比(TBP:M)3:1、2:1、1:1、1:2和1:3混合后分别红移至1268cm-1、1266cm-1、1263cm-1、1262cm-1和1260cm-1;3252cm-1波数为薄荷醇的O-H吸收峰,按摩尔比(TBP:M)3:1、2:1、1:1、1:2和1:3混合后分别蓝移至3440cm-1,3438cm-1,3432cm-1,3431cm-1and 3390cm-1,这些结果证实了TBP与薄荷醇分子之间氢键相互作用,即DES生成。
采用实施例2制备的DES进行稳定性验证,通过比较干燥DES、水饱和DES、保存2周DES、饱和DES的水相的1H NMR图谱,其结果如图3所示(水饱和DES与干燥DES1HNMR图谱一致,说明制得的DES在与水接触时良好的稳定性和疏水性;与DES充分接触的水相1H NMR图谱未出现DES氢谱,也说明DES良好的疏水性;保存2周DES与干燥DES1H NMR图谱一致,也说明DES的稳定性)。
应当注意的是,以上所述的实施例仅用于解释本发明,并不构成对本发明的任何限制。通过参照典型实施例对本发明进行了描述,但应当理解为其中所用的词语为描述性和解释性词汇,而不是限定性词汇。可以按规定在本发明权利要求的范围内对本发明做出修改,以及在不背离本发明的范围和精神内对本发明进行修订。尽管其中描述的本发明涉及特定的方法、材料和实施例,但是并不意味着本发明限于其中公开的特定例,相反,本发明可扩展至其他所有具有相同功能的方法和应用。
Claims (4)
1.一种疏水性低共熔溶剂,其特征在于:由氢键受体和氢键供体组成,所述氢键受体为磷酸三丁酯,所述氢键供体为薄荷醇和/或百里香酚;
所述氢键受体与氢键供体的摩尔比为1:3~3:1。
2.一种如权利要求1所述的疏水性低共熔溶剂的制备方法,其特征在于:按一定摩尔比混合氢键受体和氢键供体,并在一定温度下搅拌直至形成均相透明的液体,即得所述疏水性低共熔溶剂。
3.根据权利要求2所述的疏水性低共熔溶剂的制备方法,其特征在于:所述搅拌温度为70-90℃。
4.一种如权利要求1所述的疏水性低共熔溶剂或权利要求2或3所述的制备方法制备的疏水性低共熔溶剂的应用,其特征在于:将所述疏水性低共熔溶剂作为萃取剂萃取水体中的尼泊金甲酯、尼泊金乙酯、尼泊金丙酯、尼泊金丁酯、对羟基苯甲酸。
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