CN100486667C - 一种制备聚醚砜酮固相微萃取纤维头的方法 - Google Patents
一种制备聚醚砜酮固相微萃取纤维头的方法 Download PDFInfo
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Abstract
本发明涉及固相微萃取，具体地说是一种制备聚醚砜酮固相微萃取纤维头的方法，取聚醚砜酮用溶剂溶解，配成浓度重量体积为5-30%的高聚物溶液，离心5-10分钟；将纤维针放入高聚物溶液中，然后取出立即放入去离子水凝固浴中，浸泡12-24小时，取出在室温下干燥；将干燥后的纤维针在氮气保护下60-100℃恒温10-50分钟，然后升温到220-290℃老化1-6小时，得产品。本发明优点为：方法简单，产品质量好，应用范围广。
Description
技术领域
本发明涉及固相微萃取，具体地说是一种应用沉浸相转换技术制备聚醚砜酮固相微萃取纤维头的方法。
背景技术
固相微萃取是20世纪90年代初发展的样品预处理技术。美国Supelco公司看好它的应用前景，于1993年推出了商品化的固相微萃取装置。与其他的样品制备技术相比，固相微萃取法具有操作简单方便，分析时间短，样品需要量小，无需萃取溶剂，重现性好，特别适合现场分析等优点。固相微萃取技术的原理是被测组分被吸附(吸收)而分配到涂层内，达到富集作用。萃取的选择性主要取决于萃取固定相材料的性能，按照分析物易被与其极性相似的固定相所萃取的原则，选择极性、中等极性或非极性萃取固定相。萃取固定相还需要有合适的表面结构，保证分析物在其中有较快的吸附速度，能在短时间内达到吸附平衡，并在热解吸时能迅速脱离固定相涂层，而不会造成峰展宽，由于分析物是在高温下被解析，所以涂层还必须具有大的表面积和良好的热稳定性。极性化合物广泛存在于环境、食品及生物样品中，例如环境中酚类、硝基苯类污染物，食品中的农残以及一些生物样品中的药物。固相微萃取技术用于这些极性样品的前处理，有一定局限性，主要是因为可选择的极性萃取相的种类较少限制了它的应用。目前，大部分的商品化涂层是通过物理作用粘合到萃取头表面，所以它们的稳定性比较差。利用溶胶-凝胶法制备的有机硅涂层虽然稳定性有所提高，但是此类涂层只能在一定的PH范围内使用，所以对其应用产生一定的限制。随着合成工业的发展，出现了许多机械性能好、耐溶剂、耐酸碱和耐高温的极性高聚物材料。利用这些高性能的高聚物材料作为固定相，可以制作出高性能的复膜萃取纤维头用于样品的前处理。
发明内容
本发明的目的在于采用沉浸相转换法制备以聚醚砜酮高聚物材料为固定相的萃取纤维头。该技术制备的萃取固定相具有海绵状多孔结构和耐高温，耐溶剂及使用寿命长的特点。同时可以选择不锈钢等材料作为萃取纤维材料，增强纤维头的物理强度。
为实现上述目的，本发明通过一个相转换的物理过程将高聚物涂敷在纤维外表面，制作成萃取纤维头用于样品的前处理过程。本方法包括配置高聚物溶液、在凝胶浴中固化和老化三个步骤。具体为：
一种制备聚醚砜酮固相微萃取纤维头的方法，
1)取聚醚砜酮用溶剂溶解，配成浓度重量体积为5—30％的高聚物溶液，离心5—10分钟；
2)将纤维针放入高聚物溶液中，然后取出立即放入去离子水凝固浴中，浸泡12—24小时，取出在室温下干燥；高聚物涂层的厚度可以通过调节高聚物溶液的浓度实现；选择去离子水作为凝固浴，与溶剂进行交换，使高聚物转变成固体。
3)将干燥后的纤维针在氮气保护下60-100℃恒温10—50分钟，然后升温到220—290℃老化1—6小时，得产品。
所述溶剂可为氮甲基吡咯烷酮或浓硫酸；纤维针可为玻璃、石英或不锈钢纤维；纤维针应用前应进行预处理，具体为，先用甲醇清洗，然后用去离子水冲洗干净，在60-120℃条件下烘干。
所述聚醚砜酮的具体名称为含二氮杂萘酮结构的聚芳醚砜酮，具有耐高温、耐酸碱和机械强度高的特点。
本发明具有如下优点：
1.产品质量好。本发明为沉浸相转换技术制作聚醚砜酮固相微萃取纤维头的方法，具体的说，利用沉浸相转换技术，使涂在玻璃、石英或不锈钢等金属材料表面的高聚物溶液固化形成一层高聚物多孔膜。该膜有良好的机械强度，耐受有机溶剂和水，在惰性气氛环境下能耐温290℃而无流失。制备的纤维涂层具有海绵状多孔结构和耐高温，耐溶剂及使用寿命长的特点。
2.应用范围广。本发明所制备的复膜萃取纤维头能萃取富集经过匀质化处理的环境样品或食品中微量及痕量挥发类和半挥发类物质，特别是极性组分的预富集，可应用于极性样品的预富集，如硝基苯类爆炸物、酚类物质、食品中的农残及其他极性化合物，并可与气相色谱和液相色谱联用进行分析。
3.方法简单。本发明具有简单、快速且重复性好的特点。沉浸相转换技术与传统萃取头的制作方法(如溶胶-凝胶法)不同，本发明只发生物理相转换过程，无化学过程发生，因此制作过程简单且易于控制。室温干燥后在氮气保护下高温老化，去掉残留的溶剂和非溶剂。同时高聚物多孔膜在高温老化过程中会有轻微收缩，这种作用可使其紧固的包裹在纤维外表面。
附图说明
图1为高聚物溶液在凝固浴中的相转换过程示意图；其中S为溶剂，NS为非溶剂，P为高聚物。
图2为空白色谱基线和萃取纤维头在290℃条件下解吸30分钟后的色谱基线；比较两图可以看出，在290℃高温下的解吸几乎不会造成涂层的流失，说明本发明制备的萃取纤维头具有大的表面积以及较高的热稳定性和机械强度。
图3为水样品中硝基苯类爆炸物的气相色谱图；其中1 Nitrobenzene；2.2-Nitrotoluene；3.4-Nitrotoluene；4.1，3-Dinitrobenzene；5.2，4-Dinitrotoluene；6.2，6-Dinitrotoluene(2，6-DNT)；7.2，4，6-Trinitrotoluene。
图4为顶空萃取水样品中酚类物质的气相色谱图；其中1.Phenol；2.2-Chlorophenol；3.2-Metholphenol；4.2-Nitrophenol；5.2，4-Dichlorophenol；6.2，4，6-Trichloropheno。
具体实施方式
以下结合具体的实施例对本发明的技术方案作进一步说明：
实施例1
取1g聚醚砜酮高聚物，将其溶解在5mL氮甲基吡咯烷酮中，配成浓度为20％的高聚物溶液。待高聚物充分溶解后，离心10分钟，去除杂质。将清洗干净的纤维放入高聚物溶液中，取出后立即放入去离子水凝固浴中，浸泡12小时，然后取出在室温下干燥。将纤维在氮气保护下，100℃恒温15分钟，然后升到250℃老化5小时。用此方法制备的萃取纤维头的高聚物涂层厚度为30μm。
实施例2
采用实施例1所得的萃取纤维头，对水中硝基苯类爆炸物进行萃取分析，所得气相色谱图为图3。样品浓度：2ng/mL；样品体积：30mL；萃取温度：40℃；萃取时间：30min；盐浓度：30％；搅拌速度：940rpm。
实例3
采用实施例1所得的萃取纤维头，对水中酚类物质采用顶空方式进行萃取分析，所得气相色谱图为图4。样品浓度：20ng/mL；样品体积：20mL；萃取温度：50℃；萃取时间：30min；盐浓度：30％；搅拌速度：940rpm。
Claims (4)
1.一种制备聚醚砜酮固相微萃取纤维头的方法，其特征在于：
1)取聚醚砜酮用溶剂溶解，配成浓度重量体积为5—30％的高聚物溶液，离心5—10分钟；
2)将纤维针放入高聚物溶液中，然后取出立即放入去离子水凝固浴中，浸泡12—24小时，取出在室温下干燥；
3)将干燥后的纤维针在氮气保护下60-100℃恒温10—50分钟，然后升温到220—290℃老化1—6小时，得到所述的聚醚砜酮固相微萃取纤维头。
2.按照权利要求1所述的方法，其特征在于：所述溶剂为氮甲基吡咯烷酮或浓硫酸。
3.按照权利要求1所述的方法，其特征在于：所述纤维针为玻璃、石英或不锈钢纤维。
4.按照权利要求1所述的方法，其特征在于：所述纤维针应用前应进行预处理，具体为，先用甲醇清洗，然后用去离子水冲洗干净，在60-120℃条件下烘干。
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|---|---|---|---|---|
| US6759126B1 (en) * | 1998-09-21 | 2004-07-06 | University Of South Florida | Solid phase microextraction fiber structure and method of making |
| DE10044044A1 (de) * | 2000-08-30 | 2002-03-21 | Ufz Leipzighalle Gmbh | Verfahren und Aufbereitungsgefäß zum Nachweis organischer Verbindungen in flüssigen Phasen |
| CN1299692A (zh) * | 2000-12-18 | 2001-06-20 | 武汉大学 | 羟基冠醚固相微萃取萃取头及其制备方法 |
| CN1438059A (zh) * | 2003-03-10 | 2003-08-27 | 武汉大学 | 一种固相微萃取萃取头及其制备方法 |
| US20060013981A1 (en) * | 2004-07-19 | 2006-01-19 | University Of South Florida | Polytetrahydrofuran-Based Coating for Capillary Microextraction |
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| CN101143272A (zh) | 2008-03-19 |
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