CN115282945B - 含磺酸基的聚酰亚胺树脂粉末作为固相萃取材料的应用 - Google Patents
含磺酸基的聚酰亚胺树脂粉末作为固相萃取材料的应用 Download PDFInfo
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- CN115282945B CN115282945B CN202210833775.1A CN202210833775A CN115282945B CN 115282945 B CN115282945 B CN 115282945B CN 202210833775 A CN202210833775 A CN 202210833775A CN 115282945 B CN115282945 B CN 115282945B
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Classifications
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- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
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- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
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Abstract
本发明提供含磺酸基的聚酰亚胺树脂粉末作为固相萃取材料应用于不同类型极性物质以及多种金属元素的选择性吸附和脱附,并且可在高温高压条件下,以及酸性环境中实现吸附和脱附。该固相萃取材料可制备成固相萃取柱,同时可采用洗脱技术实现该固相萃取柱的再生利用。
Description
技术领域
本发明属于分析化学技术领域,尤其涉及含磺酸基的聚酰亚胺树脂粉末作为固相萃取材料的应用。
背景技术
食品是人类社会赖以生存和发展的最基本的物质条件,食品安全一直是关乎人民生活稳定和国家长治久安的重大问题。食品安全事故引发了人们对食品安全的高度重视,以及对食品安全检测问题的高度关注。由于食源性样品来源广泛,基质复杂,干扰因素多,对检测结果影响很大。为了消除这些干扰,有必要对样品进行提取和净化。
对食品检测技术发展影响最大的问题之一是样品的前处理技术。在所有的前处理技术中,溶剂萃取是最常用的化合物提取方法,但是在提取过程中,复杂的基体物质不可避免地成为共萃取物进入萃取剂中,造成高浓度基体物质对分析仪器的污染和对分析结果的干扰。为了减少高浓度基体物质对分析仪器的污染和对分析结果的干扰,需要采用净化步骤减少污染,减轻干扰。常用的净化方法包括固相萃取(SPE),液液萃取和凝胶色谱(GPC)等,使用液液萃取和凝胶色谱 (GPC)进行净化时在减少基体干扰的同时却增加了试剂的用量,并有可能影响目标化合物的回收率,影响高通量分析。为了满足高效快速的市场化分析测试要求,发展省时高效、环境友好的样品前处理新技术,固相萃取技术已成为分析化学研究的热点领域之一。
极性化合物是目前食品行业中使用种类较多,数量较大的一类物质,包括各种药物、添加剂和污染物,例如含氮的碱性极性化合物、含羧基的酸性极性化合物和各类无机污染物等。常见的含氮极性化合物包括克伦特罗、莱克多巴胺、沙丁胺醇等受体激动剂类药物,诺氟沙星、环丙沙星、沙拉沙星、恩诺沙星等喹诺酮类药物,链霉素、双氢链霉素、卡那霉素等氨基糖苷类药物,磺胺类药物,三聚氰胺这类非法添加剂等。常见的酸性极性化合物主要有苯甲酸、水杨酸、双水杨酸酯、哌替啶酸、去甲基哌替啶酸、巴比妥酸、5-苯基巴比妥、一氯乙酸、二氯乙酸、苯磺酸等有机酸类物质。常见的无机污染物包括铅、镉、汞、砷等金属元素和硝酸根、亚硝酸根等无机阴离子。
目前针对极性化合物的固相萃取材料含有的官能团较为单一,一类固相萃取柱针对一类化合物来进行萃取吸附,不能实现多种极性物质在不同条件下的吸附分离。同时吸附材料的重复使用次数有限,不能实现固相萃取材料的反复利用,增加了前处理成本。并且,目前的固相萃取材料大多是在聚苯乙烯、聚丙烯氰等高分子骨架上进行高分子化反应制得,耐温、耐酸碱、耐有机溶剂等性能一般。
发明内容
针对上述技术现状,本发明采用含磺酸基的聚酰亚胺树脂粉末作为固相萃取材料,可用于不同类型极性物质以及多种金属元素的选择性吸附和脱附,并且可在高温高压条件下,以及酸性环境中实现吸附和脱附。
所述含磺酸基的聚酰亚胺树脂粉末的制备方法如下:
在氮气保护下,将含有磺酸基团的二胺、三乙胺和间甲酚混合,搅拌溶解后加入不含磺酸基团的二胺、二酐和苯甲酸,将此混合物反应一段时间后稀释到一定浓度,然后倒入沉淀剂中得到粉末状的聚合物,过滤、洗涤、干燥后得到含磺酸基的聚酰亚胺树脂粉末。
所述含磺酸基团的二胺不限,可以是2,2’-二(磺酸基)-4,4’-二氨基二苯醚、 4,4'-二氨基-3.3'-联苯二磺酸等。
所述的不含磺酸基团的二胺不限,可以是4,4’-二氨基二苯醚等。
所述的二酐不限,可以是萘-1,4,5,8-四甲酸二酐、硫醚萘四甲酸二酐等。
作为优选,反应温度为180-220℃。
作为优选,反应时间为12-24小时。
作为优选,稀释后的浓度为5-15%,进一步优选为8-12%。
所述的沉淀剂不限,包括乙醇或丙酮等。作为优选,倒入沉淀剂中时搅拌转速为300-1000rpm。
所制备的含磺酸基的聚酰亚胺树脂粉末的粒径的D50在1-100微米,优选的粒径的D50在5-20微米。
所述的含磺酸基的聚酰亚胺树脂粉末具有耐高温、耐有机溶剂、耐强酸的特性,通过控制制备条件可实现材料粒径的控制,得到不同粒径的树脂粉末。该材料作为固相萃取材料能够用于不同类型极性物质(例如磺胺类物质等)和多种金属元素(例如汞元素、镧元素等)的选择性吸附和脱附,从而将液体样品中的目标化合物与干扰化合物分离,以达到富集、分离净化样品的目的。例如,可用于牛奶中的磺胺和汞吸附等。
作为一种实现方式,利用本发明的固相萃取材料制备固相萃取柱用于不同类型极性物质和多种金属元素的选择性吸附和脱附,并且可在强酸环境中和有机溶剂中长期使用。该固相萃取柱的制备方法如下:
取一侧装有筛板的固相萃取柱,加入一定量的所述固相萃取材料,再塞入另一个筛板,使固相萃取材料位于两个筛板之间,压紧待用。
当目标化合物为极性物质与金属元素时,利用上述方法制得的固相萃取柱在目标化合物检测中的应用方法如下:
(1)取一定量的样品上样,让样品进入固相萃取柱,目标化合物被吸附在固相萃取柱上;
(2)采用淋洗液将目标化合物自固相萃取柱洗脱下来,收集洗脱液,用于后续具体的分析测定。
所述步骤(2)中,洗脱后的固相萃取柱可以采用再生方法进行再生后重复使用。作为一种实现方式,所述的再生方法如下:
(1)对于吸附了金属元素的固相萃取柱,采用含有10%(m/v)硫脲的1 mol/L盐酸溶液作为脱附溶液进行脱附,脱附溶液体积为5~10倍填料体积;或者采用3mol/L的盐酸溶液浸泡所述固相萃取柱,过夜后清洗。
(2)对于吸附了有机物的固相萃取柱,采用含有10%(m/v)的0.1mol/L 的氢氧化钠的乙腈溶液作为脱附溶液进行洗脱,脱附溶液体积为5~10倍填料体积,随后用1mol/L的硫酸溶液洗脱1小时,最后用3倍填料体积的去离子水进行洗脱。
例如,对于吸附了磺胺类物质的固相萃取柱,洗脱后的固相萃取柱的再生方法优选如下:采用含有10%(m/v)的0.1mol/L的氢氧化钠的乙腈溶液进行洗脱,洗脱溶液体积为6倍填料体积,随后用1mol/L的硫酸溶液洗脱1小时,最后用3倍填料体积的去离子水进行洗脱。
所述步骤(2)中,的后续具体的色谱分析测定时候优选条件为:
液相色谱条件:Agilent Zorbax SB-C18色谱柱(250mm×4.6mm i.d.,5um);流速0.25mL/min;进样体积10uL;柱温40℃;流动相为0.1%甲酸-甲醇溶液 (A)和0.1%甲酸-水(B);洗脱梯度为:B初始浓度为95%,在7.5min内降至为 0,保持7.5min,再在0.5min内升至95%平衡2.5min。
质谱条件:采用电喷雾电离(ESI)源,正离子模式,离子源温度190℃;检测方式:多反应检测(MRM);雾化气流速:1.8L/min;质量数校准方法采用自动调谐优化电压。
又例如,对于吸附了汞的固相萃取柱,洗脱后的固相萃取柱的再生方法优选如下:用含有10%(m/v)硫脲的1mol/L盐酸溶液作为脱附溶液进行洗脱,脱附溶液体积为10倍填料体积;最后用3倍填料体积的去离子水进行洗脱。
当牛奶中的汞吸附在固相萃取柱上,经淋洗液洗脱收集后得到的洗脱液进行电感耦合等离子体质谱分析测定时,优选的条件为:
仪器操作条件:碰撞反应池,RF功率:1550W;等离子体气流速:15 L/min;载气流速:0.95L/min;补充气流速:0.25L/min,采样锥深度:8.0mm;雾化室温度:2℃;蠕动泵转速:0.1rps。
与现有技术相比,本发明采用含磺酸基的聚酰亚胺树脂粉末作为固相萃取材料,具有以下优点:
(1)该材料可以实现磺胺类物质等多种极性物质与汞等金属元素从干扰物质中的吸附分离。
(2)该材料具有耐高温高压、耐有机溶剂、耐强酸的特性,使其可以采用多种方式进行再生,例如采用有机溶剂和酸性溶液进行洗脱再生等。
(3)该材料耐高温,在280℃以下常压条件下热稳定性良好,在高压140℃条件下也可正常使用,因此可以用于在高温高压条件下极性物质和金属元素从干扰物质中的吸附分离;同时,该材料耐有机溶剂,可以用于酸性溶液中极性物质和金属元素从干扰物质中的吸附分离,如用于强酸性的工业废水等,从而填补了高温强酸环境中有机固相萃取材料的空白。
(4)该材料可应用于固相萃取柱中实现磺胺类物质等多种极性物质与汞等金属元素从干扰物质中的吸附分离,然后经过脱附、仪器分析测定这些物质的含量,实验证实磺胺类物质的检出限可达3ug/kg,定量限可达10ug/kg。
附图说明
图1是实施例2中10ng/mL磺胺甲噁唑的标准品谱图。
图2是实施例2中10ng/mL磺胺噻唑的标准品谱图。
图3是实施例2中10ng/mL磺胺氯哒嗪的标准品谱图。
图4是实施例2中含10ng/mL磺胺甲噁唑的牛奶样品的谱图。
图5是实施例2中含10ng/mL磺胺噻唑的牛奶样品的谱图。
图6是实施例2中含10ng/mL磺胺氯哒嗪的牛奶样品的谱图。
具体实施方式
下面结合实施例与附图对本发明进一步详细描述,需要指出的是,以下所述实施例旨在便于对本发明的理解,而对其不起任何限定作用。
实施例1:
本实施例中,固相萃取柱的制备如下:
(1)在氮气保护下,在三口瓶中加入2,2’-二(磺酸基)-4,4’-二氨基二苯醚(0.6524g,1.81mmol),三乙胺(0.5390g,5.33mmol)和8mL间甲酚,搅拌溶解后加入4,4’-二氨基二苯醚(0.2417g,1.21mmol),硫醚萘四甲酸二酐(1.2866g,3.02mmol)和苯甲酸(0.5522g,4.53mmol)。将此混合物在180℃反应20h。待混合物冷却到80℃时,稀释到浓度为11%后倒入500mL的丙酮中,倒入丙酮中时搅拌转速为500rpm,得到粉末状的聚合物。然后过滤,用丙酮洗三次后,在150 ℃真空烘箱中干燥24h,得到含磺酸基的聚酰亚胺树脂粉末,测定其粒径分布,得到D50在18微米。
(2)将步骤(1)得到的含磺酸基的聚酰亚胺树脂粉末作为固相萃取材料。取适合尺寸的一侧装有筛板的固体萃取柱,加入1.0g的固相萃取材料,再塞入另一个筛板,压紧,待用。
上述制得的固体萃取柱可以应用于牛奶中磺胺类物质的测定,具体的测定方法如下:
(1)准确量取5.0mL牛奶样品,让样品进入固体萃取柱,等到快要滴完后,加入5.0mL去离子水淋洗,去除部分干扰基质;
(2)用5.0mL含有10%(m/v)的0.1mol/L氢氧化钠的乙腈溶液(即,乙腈溶液中添加0.1mol/L的氢氧化钠溶液,100mL混合溶液中含有10g氢氧化钠溶液)将目标化合物洗脱下来,收集全部洗脱液,用于色谱分析测定;洗脱后的固相萃取柱可以采用再生方法进行再生后重复使用。
色谱分析测定中的仪器与试剂为:美国AB公司的液相色谱-串联四极杆线性离子阱质谱联用仪;涡旋振荡器;美国Cole-Parmer公司的超声波清洗器;离心管;德国Sartorius公司的pH计。
色谱分析测定方法为:将洗脱液用水定容至10.0mL,经0.22μm滤膜过滤后直接进入色谱分析仪器进行分析,液相色谱条件与质谱条件如下:
液相色谱条件为:Agilent Zorbax SB-C18色谱柱(250mm×4.6mm i.d., 5um);流速0.25mL/min;进样体积10uL;柱温40℃;流动相为0.1%甲酸-甲醇溶液(A)和0.1%甲酸-水(B);洗脱梯度为:B初始浓度为95%,在7.5 min内降至为0,保持7.5min,再在0.5min内升至95%平衡2.5min。
质谱条件:采用电喷雾电离(ESI)源,正离子模式,离子源温度190℃;检测方式:多反应检测(MRM);雾化气流速:1.8L/min;质量数校准方法采用自动调谐优化电压。
洗脱后的固相萃取柱的再生方法如下:
采用含有摩尔体积浓度为0.1mol/L的氢氧化钠的乙腈溶液进行洗脱,洗脱溶液体积为6倍填料体积,随后用1mol/L的硫酸溶液洗脱1小时,最后用3倍填料体积的去离子水进行淋洗,待用。
实施例2:
本实施中使用的材料来源以及纯度如下:
磺胺甲噁唑(Sulfamethoxazole,SMZ):纯度≥99.9%,购自Sigma公司;
磺胺噻唑(sulfathiazole,STZ):纯度≥99.9%,购自Sigma公司;
磺胺氯哒嗪(sulfachloropyridazine,SCP):纯度≥99.9%,购自Sigma公司;
乙腈:色谱纯,购自Fisher Scientific公司;
甲醇:色谱纯,购自Fisher Scientific公司;
NaOH溶液:pH=13;
氨水:分析纯;
盐酸:优级纯;
硫酸:优级纯;
实验用水:去离子水。
本实施例中,采用上述三种磺胺类标准物质:磺胺甲噁唑、磺胺噻唑、磺胺氯哒嗪,进行如下配置:
配制磺胺甲噁唑标准贮备溶液:准确称取磺胺甲噁唑标准品10mg,置于 10mL棕色容量瓶中,用乙腈使之完全溶解,并定容至刻度,摇匀,该溶液中磺胺甲噁唑的浓度为1.0mg/mL,置于-20℃冰箱内避光保存保存。
配制磺胺噻唑标准贮备溶液:准确称取磺胺噻唑标准品10mg,,置于 10mL棕色容量瓶中,用乙腈使之完全溶解,并定容至刻度,摇匀,该溶液中磺胺噻唑的浓度为1.0mg/mL,置于-20℃冰箱内避光保存保存。
配制磺胺氯哒嗪标准贮备溶液:准确称取磺胺氯哒嗪标准品10mg,置于 10mL棕色容量瓶中,用乙腈使之完全溶解,并定容至刻度,摇匀,该溶液中磺胺氯哒嗪的浓度为1.0mg/mL,置于-20℃冰箱内避光保存保存。
配制磺胺类标准工作液:分别取磺胺甲噁唑,磺胺噻唑,磺胺氯哒嗪标准贮备溶液各100uL于10mL容量瓶中,然后用乙腈定容,得到浓度为10mg/L的各标准储备液。将各标准储备液(10mg/L)用乙腈稀释配制成浓度分别为5,10, 20,50和100ng/mL的各标准工作液,进行LC-MS/MS分析测定,其中10 ng/mL的各标准工作液的色谱图如图1-3所示。以峰面积为纵坐标,浓度为横坐标(ng/mL)做标准曲线,从而得到相应的回归方程。三种磺胺类药物在5-100ng/mL范围内线性关系良好,回归方程及相关系数详见下表1。
表1:标准曲线和相关系数
采用在空白牛奶样品中添加上述制得的不同浓度的磺胺类标准工作液,得到包含磺胺类目标分析物的牛奶样品,进行LC-MS/MS分析测定,其中含10 ng/mL磺胺甲噁唑,磺胺噻唑,磺胺氯哒嗪的牛奶样品的色谱图如图4-6所示。利用实施例1中的固体萃取柱以及测定方法,对照上述标准曲线及回归方程,可实现该牛奶样品中的磺胺类目标化合物的含量测定。下表2是目标分析物在色谱上的保留时间,以及质谱上确证的定性离子对和定量离子对等。
表2:目标分析物在色谱上的保留时间,以及质谱上的定性离子对和定量离子对等
根据离子峰的3倍信噪比(S/N)为检出限(LOD),以10倍信噪比(S/N)为定量限(LOQ),得出磺胺类目标分析物的检出限为3ug/kg,定量限为10ug/kg。
精密度实验:
精确吸取50ng/mL三种磺胺类标准工作液适量,分别添加到5mL空白牛奶样品中,分别制得空白样品中分析物含量依次为5ng/mL,10ng/mL,15ng/mL的三种水平的空白添加试样,按上述的样品处理步骤进行处理,每一个添加浓度进行6个平行实验,连续进样三天,分别计算日内标准偏差和日间标准偏差。结果见下表3,日内和日间标准偏差均小于13.0%。
表3:三种磺胺类药物的日内标准偏差和日间标准偏差
回收率实验:
精确吸取50ng/mL三种磺胺类标准工作液适量,分别添加到5mL空白牛奶样品中,分别制得空白样品中分析物含量依次为5ng/mL,10ng/mL,15ng/mL的三种水平的空白添加试样,按上述的样品处理步骤进行处理,每一个添加浓度进行6个平行实验,以实际测得的浓度与添加浓度之比计算各个被测物质的方法回收率。结果见下表,三种磺胺类药物的平均回收率在63.5-89.9%之间,能够满足实验要求。
实施例3:
本实施例中,固相萃取柱的制备如下:
(1)在氮气保护下,在三口瓶中加入2,2’-二(磺酸基)-4,4’-二氨基二苯醚(0.7390g,2.05mmol),三乙胺(0.5390g,5.33mmol)和8mL间甲酚,搅拌溶解后加入4,4’-二氨基二苯醚(0.2060g,1.03mmol),萘-1,4,5,8-四甲酸二酐(0.8126g, 3.03mmol)和苯甲酸(0.5522g,4.53mmol)。将此混合物在180℃反应14h。待混合物冷却到80℃时,稀释到8%的浓度后,倒入500mL的丙酮中,倒入丙酮中时候,搅拌转速为1000rpm,得到粉末状的聚合物。然后过滤,用丙酮洗三次后,在150℃真空烘箱中干燥24h,得到含磺酸基的聚酰亚胺树脂粉末,测定其粒径分布,得到D50在9微米。
(2)将步骤(1)得到的含磺酸基的聚酰亚胺树脂粉末作为固相萃取材料。取适合尺寸的一侧装有筛板的固相萃取柱,加入1.0g的固相萃取材料,再塞入另一个筛板,压紧,待用。
上述制得的固体萃取柱可以应用于牛奶中汞的测定,具体的测定方法如下:
(1)准确量取5.0mL牛奶上样,让样品进入固相萃取柱,等到快要滴完后,加入5.0mL去离子水淋洗,去除部分干扰基质;
(2)用5.0mL3 mol/L的盐酸溶液将目标化合物洗脱下来,收集全部洗脱液,用于后续具体的仪器分析测定目标化合物含量;洗脱后的固相萃取柱可以采用再生方法进行再生后重复使用。
质谱分析测定方法为:将洗脱液用水定容至10.0mL,经0.22μm滤膜过滤后直接注入电感耦合等离子体质谱仪进行分析。本实施例中采用安捷伦型号8800 的电感耦合等离子体质谱仪。仪器操作条件:碰撞反应池,RF功率:1550W;等离子体气流速:15L/min;载气流速:0.95L/min;补充气流速:0.25L/min,采样锥深度:8.0mm;雾化室温度:2℃;蠕动泵转速:0.1rps。
洗脱后的固相萃取柱可以采用再生方法进行再生后重复使用。再生方法优选为:采用含有10%(m/v)硫脲的1mol/L盐酸溶液进行脱附,脱附溶液体积为10 倍填料体积;最后用3倍填料体积的去离子水进行淋洗。
实施例4:
本实施中使用的材料来源以及纯度如下:
汞标准溶液:浓度为1000mg/L,采购自国家钢铁材料测试中心钢铁研究总院;
内标溶液:安捷伦的混合内标溶液;
氩气(Ar):液氩;
氦气(He):≥99.999%
由汞标准溶液稀释得到10mg/L的汞标准储备液,然后用(5+95)(v/v)硝酸溶液稀释配制成浓度分别为0.1,0.5,1.0,1.5和2.0ng/mL的汞标准工作液, ICP-MS分析测定。以汞元素与内标响应信号值的比值为纵坐标,汞元素浓度为横坐标(ng/mL)做标准曲线,从而得到相应的回归方程。汞元素在0.1~2.0 ng/mL线性范围内线性关系良好,相关系数达到0.998。
采用在空白牛奶样品中添加上述制得的不同浓度的汞标准工作液,得到包含汞目标分析物的牛奶样品。利用实施例3中的固体萃取柱以及测定方法可实现该牛奶样品中的汞目标化合物的含量测定。
以上所述的实施例对本发明的技术方案进行了详细说明,应理解的是以上所述仅为本发明的具体实施例,并不用于限制本发明,凡在本发明的原则范围内所做的任何修改、补充或类似方式替代等,均应包含在本发明的保护范围之内。
Claims (13)
1.采用含磺酸基的聚酰亚胺树脂粉末作为固相萃取材料的应用,其特征是:
所述含磺酸基的聚酰亚胺树脂粉末的制备方法如下:
在氮气保护下,将含有磺酸基团的二胺、三乙胺和间甲酚混合,搅拌溶解后加入不含磺酸基团的二胺、二酐和苯甲酸,将此混合物反应一段时间后稀释到一定浓度,然后倒入沉淀剂中得到粉末状的聚合物,过滤、洗涤、干燥后得到含磺酸基的聚酰亚胺树脂粉末;
所述固相萃取材料用于金属汞的吸附和脱附;
所述含磺酸基的聚酰亚胺树脂粉末的粒径的D50在1-100 微米;
所述固相萃取材料设置在固相萃取柱中;所述固相萃取柱的制备方法是:取一侧装有筛板的固相萃取柱,加入一定量的所述固相萃取材料,再塞入另一个筛板,使固相萃取材料位于两个筛板之间,压紧待用;
所述固相萃取柱在极性物质检测中的应用方法如下:
(1)取一定量的样品上样,让样品进入固相萃取柱,目标化合物被吸附在固相萃取柱上;
(2)采用淋洗液将目标化合物自固相萃取柱洗脱下来,收集洗脱液,用于色谱分析测定。
2.如权利要求1所述的应用,其特征是:所述含磺酸基团的二胺是2,2’-二(磺酸基)-4,4’-二氨基二苯醚、4,4'-二氨基-3.3'-联苯二磺酸中的一种或者两种。
3.如权利要求1所述的应用,其特征是:所述的不含磺酸基团的二胺是4,4’-二氨基二苯醚。
4.如权利要求1所述的应用,其特征是:所述的二酐是萘-1,4,5,8-四甲酸二酐、硫醚萘四甲酸二酐中的一种或者两种。
5.如权利要求1所述的应用,其特征是:反应温度为180-220℃。
6.如权利要求1所述的应用,其特征是:反应时间为12-24小时。
7.如权利要求1所述的应用,其特征是:稀释后的浓度为5-15%。
8.如权利要求7所述的应用,其特征是:稀释后的浓度为8-12%。
9.如权利要求1所述的应用,其特征是:所述的沉淀剂包括乙醇或丙酮。
10.如权利要求1所述的应用,其特征是:所制备的含磺酸基的聚酰亚胺树脂粉末的粒径的D50在5-20 微米。
11.如权利要求1所述的应用,其特征是:所述固相萃取材料用于在高温高压条件下的吸附和脱附,或者用于酸性溶液中的吸附和脱附。
12.如权利要求1所述的应用,其特征是:洗脱后的固相萃取柱采用再生方法进行再生后重复使用。
13.如权利要求12所述的应用,其特征是:对于吸附了金属元素的固相萃取柱,采用含有10%(m/v)硫脲的1 mol/L盐酸溶液进行脱附,脱附溶液体积为5~10倍填料体积;或者采用3 mol/L的盐酸溶液浸泡所述固相萃取柱,过夜后清洗;
对于吸附了有机物的固相萃取柱,采用含有10%(m/v)的0.1mol/L的氢氧化钠的乙腈溶液进行洗脱,洗脱溶液体积为5~10倍填料体积,随后用1mol/L的硫酸溶液洗脱1小时,最后用3倍填料体积的去离子水进行洗脱。
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