CN112300107B - 一种三蝶烯类功能材料、制备方法及其应用 - Google Patents

一种三蝶烯类功能材料、制备方法及其应用 Download PDF

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CN112300107B
CN112300107B CN202011149426.5A CN202011149426A CN112300107B CN 112300107 B CN112300107 B CN 112300107B CN 202011149426 A CN202011149426 A CN 202011149426A CN 112300107 B CN112300107 B CN 112300107B
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齐美玲
赵慧茹
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Abstract

本发明涉及一种三蝶烯类功能材料、制备方法及其应用，属于气相色谱技术领域。所述功能材料的结构式如下，n≥1：
Figure DDA0002740723290000011
将TPGS与三乙胺溶于有机溶剂，加入对甲苯磺酰氯，制得TPGS对甲苯磺酸酯；将三蝶烯对苯二氢醌、TPGS对甲苯磺酸酯和碳酸钾溶于乙腈中，加热回流反应，分离纯化，得到所述功能材料；所述功能材料可以作为气相色谱固定相，其针对不同性质的分析物及异构体表现出高选择性分离性能；对易发生不可逆吸附或产生变形色谱峰的分析物表现出良好惰性，用于色谱分析测定具有重要应用价值。

Description

一种三蝶烯类功能材料、制备方法及其应用
技术领域
本发明涉及一种三蝶烯类功能材料、制备方法及其应用，属于气相色谱技术领域。
背景技术
气相色谱分析(GC)是各领域广泛应用的一种分析测定方法。在GC分析中，固定相的选择性直接影响样品组分色谱峰的分离程度及其分析测定结果的准确性。目前常用的固定相主要有聚硅氧烷类和聚乙二醇类，这些固定相的选择性多限于某种类型或性质的分析物，而对其他分析物的选择性较低。例如，极性聚乙二醇固定相主要适于极性分析物，而对非极性分析物的保留弱、选择性低。由于实际分析检测的样品中常同时含有多种不同类型或性质的分析物，上述固定相的选择性和分离性能难以满足实际样品分析测定的需求。因此，发展新型高选择性、综合分离性能高的固定相对于色谱分析测定具有重要应用价值。
基于三维富π蝶烯骨架的功能材料具有多孔性、高热稳定性等特性，目前在材料化学领域已得到关注。蝶烯类材料的特异性质使其在色谱分析领域具有很好的应用潜力，但目前除我们前期的研究报道外，尚未见其他研究报道。我们在前期工作中发展了新型蝶烯类离子液体和蝶烯含氧直链二醇类GC固定相。这些蝶烯固定相对弱碱性苯胺类异构体具有高选择性，但对碱性较强的杂环类(如吡啶、甲基吡啶)易发生不可逆吸附或出现变形峰，进而影响其与相邻组分的分离和检测。
发明内容
有鉴于此，本发明的目的在于提供一种三蝶烯类功能材料、制备方法及其应用。所述功能材料为三蝶烯维生素E琥珀酸聚乙二醇酯的功能材料(简称TPT)，所述功能材料可以作为气相色谱固定相，其针对不同性质的分析物及异构体(如二乙苯、二甲苯胺、二氯苯、二甲苯酚等)表现出高选择性分离性能；对易发生不可逆吸附或产生变形色谱峰的分析物(如碱性杂环类、醛类)表现出良好惰性，用于色谱分析测定具有重要应用价值。
本发明的目的是通过以下技术方案实现的。
一种三蝶烯类功能材料，所述功能材料的结构式如下：
Figure BDA0002740723270000021
其中，三蝶烯骨架上有两个相同侧链，侧链结构由维生素E单元、琥珀酰基和聚乙二醇单元构成，三蝶烯骨架两个侧链的聚乙二醇单元的n值相同，n≥1。
优选聚乙二醇单元相对分子质量为400～2000时，所述三蝶烯类功能材料的相对分子质量2108～5308，适用于作为固定相用于气相色谱分析测定。
一种本发明所述三蝶烯类功能材料的制备方法，所述制备方法步骤如下：
(1)在保护气体的保护下，将维生素E琥珀酸聚乙二醇酯(TPGS)与三乙胺溶于有机溶剂，在20℃～30℃下搅拌，加入对甲苯磺酰氯，反应时间大于等于24h，得到反应产物，分离纯化，得到TPGS对甲苯磺酸酯(简称TPGS-TOS)。
其中，所述保护气体为氮气或惰性气体，优选保护气体为氮气。
优选TPGS与三乙胺的摩尔比为1:26～1:58。
所述有机溶剂为二氯甲烷或三氯甲烷。
优选甲苯磺酰氯与TPGS的摩尔比为1.5:1～2:1。
优选反应温度为25℃。
优选反应时间为24h～28h。
优选采用硅胶柱进行分离纯化。
(2)将三蝶烯对苯二氢醌(TP-2OH)、TPGS-TOS和碳酸钾溶于乙腈中，加热回流，反应时间大于等于24h，冷却，收集产物，分离纯化，得到本发明所述的一种三蝶烯类功能材料。
优选TP-2OH、TPGS-TOS与碳酸钾的摩尔比为1:x:y，其中，x≥2，y≥4。
优选反应时间为24h～28h。
优选冷却时间为0.5h～1h。
优选采用硅胶柱进行分离纯化。
本发明所述三蝶烯对苯二氢醌(TP-2OH)可以采用现有技术制得，优选采用以下方法制得：
将三蝶烯对苯二醌溶解于冰醋酸溶剂中，加热回流大于等于1h，在反应过程中，加入与三蝶烯对苯二醌等摩尔量的氢溴酸，继续反应，反应时间大于等于1h，冷却，收集产物，制得TP-2OH。
优选加热回流1h～2h。
优选继续反应时间为1h～2h。
优选冷却时间为0.5h～1h。
本发明所述三蝶烯对苯二醌可以采用现有技术制得，优选采用以下方法制得：
将蒽与对苯醌溶解于有机溶剂中，加热回流大于等于3h，冷却，收集产物，分离纯化，制得三蝶烯对苯二醌。
优选蒽与对苯醌的摩尔比为1:1～1:2。
优选有机溶剂为沸点为135℃～145℃的有机溶剂，更优选所述有机溶剂为二甲苯。
优选加热回流3h～4h。
优选冷却时间为0.5h～1h。
一种本发明所述三蝶烯类功能材料的应用，所述应用是指将所述功能材料作为气相色谱固定相用于气相色谱分析。
优选将所述功能材料涂渍到毛细管柱内壁上，制成毛细管柱，用于气相色谱分析。
有益效果
1.本发明提供了一种三蝶烯类功能材料，所述功能材料具有热稳定性高的蝶烯骨架，使得所述功能材料作为固定相具有良好的热稳定性，有益于气相色谱分析测定。
2.本发明提供了一种三蝶烯类功能材料，所述功能材料具有三蝶烯骨架、维生素E单元、琥珀酰基和聚乙二醇单元，这些多种不同的结构单元能与不同种类和性质的分析物(如酮、醛、醇、烷烃、脂肪酸酯、杂环类、苯胺类、卤代苯、烷基苯)之间产生不同的选择性分子作用，表现出高选择性和综合分离性能。
3.本发明提供了一种三蝶烯类功能材料，所述功能材料能够高选择性分离那些易发生不可逆吸附或产生变形峰的分析物(如碱性杂环类、醛类、苯胺类、苯酚类)，并且色谱峰对称性良好，表现出良好的色谱惰性，作为GC固定相具有明显的分离优势。
4.本发明提供了一种三蝶烯类功能材料，所述功能材料在有机溶剂中(如二氯甲烷)具有良好的溶解性，易于制备得到高柱效色谱柱，有益于气相色谱分离测定。
5.本发明提供了一种三蝶烯类功能材料的制备方法，所述制备方法简单、原料成本低，有利于推广应用。
6.本发明提供了一种三蝶烯类功能材料的应用，所述功能材料的特异结构单元构成及其与各类分析物之间的特异的分子作用使其作为气相色谱固定表现出高选择性分离性能，并且对碱性杂环类和醛类等易发生不可逆吸附或产生变形峰的分析物表现出良好惰性，解决了其他类似材料在应用中存在的问题，表现出优异的分离性能。
附图说明
图1为实施例1中一种三蝶烯功能材料的1H-NMR图谱。
图2为实施例2中TPT色谱柱气相色谱分析测定含不同种类组分样品的色谱图。
图3为实施例3中TPT色谱柱气相色谱分析测定杂环类组分样品的色谱图。
图4为实施例4中TPT色谱柱气相色谱分析测定二乙苯异构体的色谱图。
图5为实施例5中TPT色谱柱气相色谱分析测定二甲苯胺异构体的色谱图。
图6为实施例6中TPT色谱柱气相色谱分析测定二氯苯异构体的色谱图。
图7为实施例7中TPT色谱柱气相色谱分析测定二甲苯酚异构体的色谱图。
具体实施方式
下面结合附图和具体实施方式对本发明作进一步阐述，其中，所述方法如无特别说明均为常规方法，所述原材料如无特别说明均能从公开商业途径而得。
实施例1
一种三蝶烯类功能材料的制备方法，所述制备方法具体步骤如下：
(1)蒽与对苯醌按摩尔比1:1溶解于二甲苯中，加热回流4h，冷却1h，过滤收集固体产物，在二甲苯中重结晶，得到三蝶烯对苯二醌。
(2)将三蝶烯对苯二醌溶解于冰醋酸溶剂中，加热回流1h，在反应过程中，滴加与三蝶烯对苯二醌等摩尔量的氢溴酸，继续反应1h，冷却1h，过滤收集固体产物，得到三蝶烯对苯二氢醌(TP-2OH)。
(3)在氮气保护下，将TPGS-1000与三乙胺按摩尔比1:35溶于二氯甲烷中，在25℃下搅拌，加入对甲苯磺酰氯，TPGS-1000与对甲苯磺酰氯的摩尔比为1:2，反应24h，采用硅胶柱分离纯化(V二氯甲烷:V甲醇＝20:1)，得到TPGS-1000对甲苯磺酸酯(TPGS-TOS)。
(4)将步骤(2)制备的TP-2OH与步骤(3)制得的TPGS-TOS和碳酸钾溶于乙腈中，TP-2OH、TPGS-TOS与碳酸钾的摩尔比为1:2.2:4，加热回流24h，冷却1h，收集产物，将产物依次用蒸馏水、饱和食盐水洗涤，硫酸钠干燥，采用硅胶柱分离纯化(V二氯甲烷:V甲醇:V石油醚＝10:3:3)，得到终产物。
针对本实施例制备的终产物进行结构测试，采用核磁共振氢谱进行表征，可知所述终产物为本发明所述的一种三蝶烯类功能材料，其相对分子质量为3308，结果如下：1HNMR(400MHz，CHCl3)δ：7.36-7.38(s,4H)，6.94-6.96(s,4H)，6.45-6.50(d,2H)，5.83-5.88(d,2H)，4.28-4.26(m,4H)，3.71-3.54(m,PEG)，3.38(s,6H)，2.93(t,J＝7.2Hz,4H)，2.79(t,J＝7.2Hz,4H)，2.58(t,J＝6.8Hz,4H)，2.43(s,6H)，2.08(s,6H)，2.01(s,6H)，1.97(s,6H)，1.70-1.84(m,4H)，1.04-1.55(m,32H)，0.83-0.87(m,24H)。
将本实施例制备得到的三蝶烯类功能材料作为气相色谱固定相，采用静态法制备毛细管色谱柱，步骤如下：
将本实施例制备的三蝶烯类材料溶于二氯甲烷中，配成固定相溶液(0.25％，w/v)，将固定相溶液通入10m的熔融石英毛细管柱内，将所述毛细管柱一端密封并将另一端连接真空系统，溶剂挥散完全后取下所述毛细管柱，置于柱箱内在氮气保护下采用程序升温的方式进行老化，程序升温具体为：初始温度40℃，以1℃/min的速率升到180℃，保持7h，即制备得到采用本实施例制得的所述功能材料的毛细管色谱柱(简称为TPT色谱柱)。
实施例2
将实施例1制得的TPT色谱柱应用于气相色谱分析中，对含有庚酮、庚醛、辛酮、辛醛、壬酮、壬醛、辛醇、十三烷、壬酸甲酯、壬醇、十四烷、癸酸甲酯、癸醇、十五烷和十一酸甲酯的样品进行分离。色谱条件如下：纯度为99.99％的氮气为载气，流速0.6mL/min，程序升温40℃～160℃(升温速度10℃/min)，进样口温度250℃，检测器温度300℃。
分离结果如图2所示，图中色谱峰1～15依次为：庚酮、庚醛、辛酮、辛醛、壬酮、壬醛、辛醇、十三烷、壬酸甲酯、壬醇、十四烷、癸酸甲酯、癸醇、十五烷和十一酸甲酯。由图2可见，所述TPT色谱柱能够分离各类组分，其中易吸附或拖尾组分(醛、醇)的色谱峰对称性良好，表明了所述TPT色谱柱的高选择性分离性能和良好惰性。
实施例3
将实施例1制得的TPT色谱柱应用于气相色谱分析中，对含有噻吩、吡啶、3-甲基吡啶、吡咯和吡唑的样品进行分离。色谱条件如下：纯度为99.99％的氮气为载气，流速1mL/min，程序升温40℃～160℃(升温速度10℃/min)，进样口温度250℃，检测器温度300℃。
分离结果如图3所示，图中色谱峰1～5依次为:噻吩、吡啶、3-甲基吡啶、吡咯和吡唑。由图3可见，所述TPT色谱柱能基线分离5种杂环类组分，其中易吸附或拖尾的碱性组分(吡啶、3-甲基吡啶、吡唑)均得到对称的色谱峰，表明了所述TPT色谱柱对碱性杂环类组分的具有高选择性分离性能和良好惰性。
实施例4
将实施例1制得的TPT色谱柱应用于气相色谱分析中，对二乙苯异构体进行分离。色谱条件如下：纯度为99.99％的氮气为载气，流速0.4mL/min，柱温80℃，进样口温度250℃，检测器温度300℃。
分离结果如图4所示，图中色谱峰1～3依次为间二乙苯、对二乙苯以及邻二乙苯。由图4可见，采用所述TPT色谱柱能够基线分离二乙苯异构体并且峰形对称性良好，证明了所述TPT色谱柱对弱极性二乙苯异构体的高选择性分离性能和良好惰性。
实施例5
将实施例1制得的TPT色谱柱应用于气相色谱分析中，对二甲苯胺异构体进行分离。色谱条件如下：纯度为99.99％的氮气为载气，流1mL/min，柱温95℃，进样口温度250℃，检测器温度300℃。
分离结果如图5所示，图中色谱峰1～6依次为2,6-二甲苯胺、2,4-二甲苯胺、2,5-二甲苯胺、3,5-二甲苯胺、2,3-二甲苯胺和3,4-二甲苯胺。由图5可见，采用所述TPT色谱柱能够基线分离6种二甲苯胺异构体并且这些碱性组分色谱峰的对称性良好，表明所述TPT色谱柱对极性二甲苯胺异构体的高选择性分离性能和良好惰性。
实施例6
将实施例1制得的TPT色谱柱应用于气相色谱分析中，对二氯苯异构体进行分离。色谱条件如下：纯度为99.99％的氮气为载气，流速1mL/min，柱温80℃，进样口温度250℃，检测器温度300℃。
分离结果如图6所示，图中色谱峰1～3依次为邻二氯苯、间二氯苯、对二氯苯。由图6可见，采用所述TPT色谱柱能够基线分离二氯苯异构体并且色谱峰的对称性良好，表明所述TPT色谱柱对极性二氯苯异构体的高选择性分离性能和良好惰性。
实施例7
将实施例1制得的TPT色谱柱应用于气相色谱分析中，对二甲苯酚异构体进行分离。色谱条件如下：纯度为99.99％的氮气为载气，流速1mL/min，柱温120℃，进样口温度250℃，检测器温度300℃。
分离结果如图7所示，图中色谱峰1～5依次为2,6-二甲苯酚、2,5-二甲苯酚、2,3-二甲苯酚、3,5-二甲苯酚和3,4-二甲苯酚。由图7可见，采用所述TPT色谱柱能够基线分离二甲苯酚异构体并且色谱峰的对称性良好，表明所述TPT色谱柱对弱酸性二甲苯酚异构体的高选择性分离性能和良好惰性。
以上实施例表明，本发明实施例1中的三蝶烯类功能材料(TPT)作为色谱固定相能够高选择性分离不同极性或酸碱性的各类分析物，表现出高选择性分离性能和良好惰性。
虽然本发明仅提供例如实施例1制备得到一种三蝶烯类功能材料(相对分子质量为3308)，并且对其应用进行了验证，但是所述三蝶烯类功能材料的制备和应用同样适应于其他相对分子质量的三蝶烯类功能材料。本发明所述三蝶烯类功能材料的相对分子质量取决于结构中聚乙二醇单元数(聚乙二醇单元的相对分子质量的范围为400～2000)。实施例1中聚乙二醇单元的相对分子质量为1000，由本领域的公知常识可知，聚乙二醇在所述相对分子质量范围内的色谱选择性没有明显差异。因此，本发明中其他相对分子质量(2108～5308)的三蝶烯类功能材料的色谱选择性与所述实例1的选择性没有明显差异。
综上所述，发明包括但不限于以上实施例，凡是在本发明的精神和原则之下进行的任何等同替换或局部改进，都将视为在本发明的保护范围之内。

Claims (9)

1.一种三蝶烯类功能材料，其特征在于：所述功能材料的结构式如下：
Figure FDA0003547501140000011
三蝶烯骨架上有两个相同侧链，侧链结构由维生素E单元、琥珀酰基和聚乙二醇单元构成，三蝶烯骨架两个侧链的聚乙二醇单元的n值相同，n≥1；
所述功能材料的相对分子质量2108～5308。
2.一种如权利要求1所述的三蝶烯类功能材料的制备方法，其特征在于：所述制备方法步骤如下：
(1)在保护气体的保护下，将TPGS与三乙胺溶于有机溶剂，在20℃～30℃下搅拌，加入对甲苯磺酰氯，反应时间大于等于24h，得到反应产物，分离纯化，得到TPGS对甲苯磺酸酯；
保护气体为氮气或惰性气体；
有机溶剂为二氯甲烷或三氯甲烷；
(2)将三蝶烯对苯二氢醌、TPGS对甲苯磺酸酯和碳酸钾溶于乙腈中，加热回流，反应时间大于等于24h，冷却，收集产物，分离纯化，得到三蝶烯类功能材料。
3.根据权利要求2所述的一种三蝶烯类功能材料的制备方法，其特征在于：步骤(1)中：所述保护气体为氮气；
TPGS与三乙胺的摩尔比为1:26～1:58；
甲苯磺酰氯与TPGS的摩尔比为1.5:1～2:1；
反应温度为25℃；
反应时间为24h～28h；
采用硅胶柱进行分离纯化；
步骤(2)中：三蝶烯对苯二氢醌、TPGS对甲苯磺酸酯与碳酸钾的摩尔比为1:x:y，x≥2，y≥4；
反应时间为24h～28h；
冷却时间为0.5h～1h；
采用硅胶柱进行分离纯化。
4.根据权利要求2中所述的一种三蝶烯类功能材料的制备方法，其特征在于：所述三蝶烯对苯二氢醌采用以下方法制备得到：
将三蝶烯对苯二醌溶解于冰醋酸溶剂中，加热回流大于等于1h，在反应过程中，加入与三蝶烯对苯二醌等摩尔量的氢溴酸，继续反应，反应时间大于等于1h，冷却，收集产物，制得TP-2OH。
5.根据权利要求4所述的一种三蝶烯类功能材料的制备方法，其特征在于：
加热回流1h～2h；
继续反应时间为1h～2h；
冷却时间为0.5h～1h；
所述三蝶烯对苯二醌采用以下方法制备得到：
将蒽与对苯醌溶解于有机溶剂中，加热回流大于等于3h，冷却，收集产物，分离纯化，制得三蝶烯对苯二醌。
6.根据权利要求5所述的一种三蝶烯类功能材料的制备方法，其特征在于：蒽与对苯醌的摩尔比为1:1～1:2；
有机溶剂为沸点为135℃～145℃的有机溶剂；
加热回流3h～4h；
冷却时间为0.5h～1h。
7.根据权利要求6所述的一种三蝶烯类功能材料的制备方法，其特征在于：有机溶剂为二甲苯。
8.一种如权利要求1所述的三蝶烯类功能材料的应用，其特征在于：将所述功能材料作为气相色谱固定相用于气相色谱分析。
9.根据权利要求8所述的一种三蝶烯类功能材料的应用，其特征在于：将所述功能材料涂渍到毛细管柱内壁上，制成毛细管柱，用于气相色谱分析。
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