CN112063005B - 一种用于富集多氯联苯的分子印迹整体针式萃取装置的制备方法 - Google Patents
一种用于富集多氯联苯的分子印迹整体针式萃取装置的制备方法 Download PDFInfo
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Abstract
本发明公开了一种用于富集多氯联苯的分子印迹整体针式萃取装置的制备方法,属于有机复合材料技术领域。本发明制备方法,以3,4‑二氯苯基乙酸为模板分子,溶解于甲苯和乙腈的混合液,以甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸酯为交联剂,偶氮二异丁晴为引发剂,经过原位聚合法制得分子印迹聚合物;通过填充的方式将涂敷分子印迹聚合物的预处理纤维填充到不锈钢针内,制得分子印迹整体针式萃取装置。本发明制备的分子印迹整体针式萃取装置通透性良好,机械强度好,选择性高,富集能力强,使用方便;可以特异性吸附复杂样品中的多氯联苯。本发明方法简单,原料易得,纤维数目可调,在分析化学吸附和富集领域具有广阔的应用前景。
Description
技术领域
本发明涉及有机复合材料技术领域,更具体的说是涉及一种用于富集多氯联苯的分子印迹整体针式萃取装置的制备方法。
背景技术
随着我国国民经济的增长,人们的环保意识越来越高,挥发性有机物污染问题日渐突出。研究空气和水中挥发性有机物的污染特性,监测环境空气和水中挥发性有机污染物的主要种类及背景浓度是至关重要的问题。多氯联苯(Polychlorinated biphenyl,PCBs)是一类广泛存在于水环境中的挥发性有机污染物。挥发性有机化合物通常是痕量的,为了提高分析的灵敏度,样品前处理中的富集技术非常必要。
针式萃取(needle trap extraction,NTE)是近年来开发的一种新型样品前处理技术,尤其以分子印迹聚合物(Molecularly imprinted polymer,MIP)为吸附介质的NTE技术,可以有效进行复杂环境中挥发性有机物及半挥发性有机物的浓缩和富集。MIP具有选择性高,稳定性好,吸附能力强,可以特异性识别目标分子等优点,在样品前处理技术中具有重要的开发潜力。将这两种技术完美的结合,就发展成了先进的分子印迹整体针式萃取装置。
因此,一种用于富集多氯联苯的分子印迹整体针式萃取装置的制备方法是本领域技术人员亟需解决的问题。
发明内容
有鉴于此,本发明提供了一种用于富集多氯联苯的分子印迹整体针式萃取装置的制备方法,先对纤维进行改性,再使分子印迹聚合物附着于纤维表面形成整体柱,进一步将具有分子印迹聚合物涂层的纤维穿入不锈钢针中老化即可得到涂层均匀稳定,耐高温,且萃取效率高的萃取装置。
为了实现上述目的,本发明采用如下技术方案:
一种用于富集多氯联苯的分子印迹整体针式萃取装置的制备方法,包括如下步骤:
(1)纤维预处理:将纤维用丙酮,甲醇清洗,0.1M盐酸浸泡1h后用0.1M NaCl浸泡1h,使表面产生羟基,超纯水清洗,吹干,然后用10%甲基三甲氧基硅烷室温下硅化2-3h,然后用甲醇清洗,吹干备用;
(2)分子印迹聚合物的制备:将3,4-二氯苯基乙酸2-2.5mmol,溶解于20-40mL甲苯和乙腈的1:1混合液中,加入20-40mmol甲基丙烯酸,100-140mmol乙二醇二甲基丙烯酸酯,250-300mg偶氮二异丁晴,经过原位聚合法制得分子印迹聚合物;
(3)将步骤(1)经过预处理的纤维纵向穿入毛细管中,然后将步骤(2)制备好的分子印迹聚合物注入毛细管中,氮吹脱氧5-10min后密封,60℃聚合18-24h形成分子印迹纤维整体柱;
(4)将步骤(3)制备得到的分子印迹纤维整体柱用过量的甲醇、乙酸和超纯水按4:1:1的比例组成的混合溶液洗脱,直到检测不到模板分子,然后将洗脱模板分子的纤维纵向穿入不锈钢针中,在270-290℃氮气保护下加热20-40min,得到分子印迹整体针式萃取装置。
对纤维进行预处理,除去纤维表面的聚酰亚胺保护层和其他杂质,使纤维表面产生羟基,然后对其进行硅化使其表面产生硅羟基,为后续分子印迹聚合物的反应提供基础。
以3,4-二氯苯基乙酸为模板分子,溶解于30mL甲苯和乙腈的1:1混合液中,以甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸酯为交联剂,偶氮二异丁晴为引发剂,经过原位聚合法制得分子印迹聚合物,所形成的聚合涂层具有高选择性,高特异性识别的优点,富集能力强,萃取效率高。
聚合物涂层形成后进行加温老化可进一步保证聚合物纤维涂层在纤维表面的结合牢固程度,防止萃取过程涂层脱落影响萃取效率,并且具有耐高温的特点。
进一步,步骤(1)所述纤维为Zylon纤维。
进一步,步骤(3)60℃聚合24h形成分子印迹纤维整体柱。
进一步,步骤(4)在270℃氮气保护下加热30min。
进一步,步骤(4)所述不锈钢针为标准21G,长度5cm,耐高温300℃以上。
经由上述的技术方案可知,与现有技术相比,本发明公开提供了一种用于富集多氯联苯的分子印迹整体针式萃取装置的制备方法,具有以下有益效果:
(1)本发明与现有的分子印迹技术相比,未使用目标物为模板分子,而是使用与模板分子结构相同的化合物为模板,合成了分子印迹聚合物材料,使用此技术合成的材料选择性高,通透性好,可以选择性富集多种多氯联苯,解决了分子印迹材料单一性识别的缺点;
(2)本发明方法简单,原料易得,无需任何溶剂,符合绿色化学理念,且纤维数目可调,涂层厚度可调,具有较高的萃取效率,可应用于分析化学领域水样品中痕量挥发性有机物的快速萃取;
(3)将针式萃取装置与分子印迹技术结合,既有效改善了固相微萃取纤维易碎,涂层易脱落的缺点,同时也继承了分子印迹技术特异性识别,选择性高的优点,所制备的装置可以高效的实现水样中多氯联苯的萃取。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据提供的附图获得其他的附图。
图1附图为本发明实施例1萃取装置富集多氯联苯的气相检测图;
图2附图为本发明实施例2萃取装置富集多氯联苯的气相检测图;
图3附图为本发明实施例3萃取装置富集多氯联苯的气相检测图;
图4附图为本发明对比例萃取装置富集多氯联苯的气相检测图。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
一种用于富集多氯联苯的分子印迹整体针式萃取装置的制备方法,包括以下步骤:
(1)将Zylon纤维用丙酮,甲醇清洗,0.1M盐酸浸泡1h后用0.1MNaCl浸泡1h,使表面产生羟基,超纯水清洗,吹干,然后用10%甲基三甲氧基硅烷室温下硅化3h,然后用甲醇清洗,吹干备用;
(2)2.2mmol 3,4-二氯苯基乙酸溶解于30mL甲苯和乙腈的1:1混合液中,加入30mmol甲基丙烯酸,120mmol乙二醇二甲基丙烯酸酯为交联剂,280mg偶氮二异丁晴为引发剂,经过原位聚合法制得分子印迹聚合物;
(3)将步骤(1)预处理的纤维纵向穿入毛细管中,然后将步骤(2)制备好的分子印迹聚合物注入毛细管中,氮吹脱氧10min后密封,60℃聚合24h形成分子印迹纤维整体柱;
(4)将分子印迹纤维整体柱用过量的甲醇、乙酸和超纯水(4:1:1)的混合溶液洗脱,直到检测不到模板分子,然后将洗脱模板分子的纤维纵向穿入不锈钢针中,在270℃氮气保护下加热30min得到分子印迹整体针式萃取装置。
实施例2
一种用于富集多氯联苯的分子印迹整体针式萃取装置的制备方法,包括以下步骤:
(1)将Zylon纤维用丙酮,甲醇清洗,0.1M盐酸浸泡1h后用0.1MNaCl浸泡1h,使表面产生羟基,超纯水清洗,吹干,然后用10%甲基三甲氧基硅烷室温下硅化3h,然后用甲醇清洗,吹干备用;
(2)2.5mmol 3,4-二氯苯基乙酸溶解于40mL甲苯和乙腈的1:1混合液中,加入40mmol甲基丙烯酸,140mmol乙二醇二甲基丙烯酸酯为交联剂,300mg偶氮二异丁晴为引发剂,经过原位聚合法制得分子印迹聚合物;
(3)将步骤(1)预处理的纤维纵向穿入毛细管中,然后将步骤(2)制备好的分子印迹聚合物注入毛细管中,氮吹脱氧10min后密封,60℃聚合24h形成分子印迹纤维整体柱;
(4)将分子印迹纤维整体柱用过量的甲醇、乙酸和超纯水(4:1:1)的混合溶液洗脱,直到检测不到模板分子,然后将洗脱模板分子的纤维纵向穿入不锈钢针中,在290℃氮气保护下加热40min得到分子印迹整体针式萃取装置。
实施例3
一种用于富集多氯联苯的分子印迹整体针式萃取装置的制备方法,包括以下步骤:
(1)将Zylon纤维用丙酮,甲醇清洗,0.1M盐酸浸泡1h后用0.1MNaCl浸泡1h,使表面产生羟基,超纯水清洗,吹干,然后用10%甲基三甲氧基硅烷室温下硅化2h,然后用甲醇清洗,吹干备用;
(2)2mmol 3,4-二氯苯基乙酸溶解于20mL甲苯和乙腈的1:1混合液中,加入20mmol甲基丙烯酸,100mmol乙二醇二甲基丙烯酸酯为交联剂,250mg偶氮二异丁晴为引发剂,经过原位聚合法制得分子印迹聚合物;
(3)将步骤(1)预处理的纤维纵向穿入毛细管中,然后将步骤(2)制备好的分子印迹聚合物注入毛细管中,氮吹脱氧5min后密封,60℃聚合18h形成分子印迹纤维整体柱;
(4)将分子印迹纤维整体柱用过量的甲醇、乙酸和超纯水(4:1:1)的混合溶液洗脱,直到检测不到模板分子,然后将洗脱模板分子的纤维纵向穿入不锈钢针中,在280℃氮气保护下加热20min得到分子印迹整体针式萃取装置。
对比例
一种用于富集多氯联苯的分子印迹整体针式萃取装置的制备方法,包括以下步骤:
(1)将Zylon纤维用丙酮,甲醇清洗,0.1M盐酸浸泡1h后用0.1MNaCl浸泡1h,使表面产生羟基,超纯水清洗,吹干,然后用10%甲基三甲氧基硅烷室温下硅化1h,然后用甲醇清洗,吹干备用;
(2)2mmol 3,4-二氯苯基乙酸溶解于20mL甲苯和乙腈的1:1混合液中,加入15mmol甲基丙烯酸,100mmol乙二醇二甲基丙烯酸酯为交联剂,200mg偶氮二异丁晴为引发剂,经过原位聚合法制得分子印迹聚合物;
(3)将步骤(1)预处理的纤维纵向穿入毛细管中,然后将步骤(2)制备好的分子印迹聚合物注入毛细管中,氮吹脱氧5min后密封,60℃聚合12h形成分子印迹纤维整体柱;
(4)将分子印迹纤维整体柱用过量的甲醇、乙酸和超纯水(4:1:1)的混合溶液洗脱,直到检测不到模板分子,然后将洗脱模板分子的纤维纵向穿入不锈钢针中,在250℃氮气保护下加热20min得到分子印迹整体针式萃取装置。
用上述实施例1-3及对比例制得的萃取装置对200μg/L的多氯联苯样品(PCB28、PCB52、PCB118、PCB153、PCB180)进行顶空萃取。配制1g/L多氯联苯丙酮溶液,加标到10mL超纯水中配制成200μg/L的多氯联苯样品溶液。将装有样品溶液的棕色小瓶放入80℃的恒温加热磁力搅拌水浴锅搅拌15min,然后针式萃取装置连接真空气体采样泵插入瓶内置于瓶口下方2-3cm的位置。用真空气体采样泵缓慢的匀速的抽取瓶内顶空气体,顶空萃取30min,萃取完成。最后将针式萃取装置连接注射器抽取足量的氮气然后插入气相色谱进样口,在氮气辅助下热解吸进而实现多氯联苯的定量定性分析。色谱图见图1-4。由图1-4可知,实施例1-3萃取效果明显优于对比例。
对所公开的实施例的上述说明,使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的,本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下,在其它实施例中实现。因此,本发明将不会被限制于本文所示的这些实施例,而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。
Claims (4)
1.一种用于富集多氯联苯的分子印迹整体针式萃取装置的制备方法,其特征在于,包括如下步骤:
(1)纤维预处理:将纤维用丙酮,甲醇清洗,0.1 M盐酸浸泡1 h后用0.1 M NaCl浸泡1h,使表面产生羟基,超纯水清洗,吹干,然后用10%甲基三甲氧基硅烷室温下硅化2-3 h,然后用甲醇清洗,吹干备用;
(2)分子印迹聚合物的制备:将3,4-二氯苯基乙酸2-2.5mmol,溶解于20-40 mL甲苯和乙腈的1:1混合液中,加入20-40 mmol甲基丙烯酸,100-140 mmol乙二醇二甲基丙烯酸酯,250-300 mg偶氮二异丁晴,经过原位聚合法制得分子印迹聚合物;
(3)将步骤(1)经过预处理的纤维纵向穿入毛细管中,然后将步骤(2)制备好的分子印迹聚合物注入毛细管中,氮吹脱氧5-10min后密封,60℃聚合18-24 h形成分子印迹纤维整体柱;
(4)将步骤(3)制备得到的分子印迹纤维整体柱用过量的甲醇、乙酸和超纯水按4:1:1的比例组成的混合溶液洗脱,直到检测不到模板分子,然后将洗脱模板分子的纤维纵向穿入不锈钢针中,在270-290℃氮气保护下加热20-40min,得到分子印迹整体针式萃取装置;
步骤(1)所述纤维为Zylon纤维。
2.根据权利要求1所述的一种用于富集多氯联苯的分子印迹整体针式萃取装置的制备方法,其特征在于,步骤(3)60℃聚合24 h形成分子印迹纤维整体柱。
3.根据权利要求1所述的一种用于富集多氯联苯的分子印迹整体针式萃取装置的制备方法,其特征在于,步骤(4)在270℃氮气保护下加热30min。
4.根据权利要求1所述的一种用于富集多氯联苯的分子印迹整体针式萃取装置的制备方法,其特征在于,步骤(4)所述不锈钢针为标准21G,长度5cm,耐高温300℃以上。
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