CN105906759A - 一种功能聚合物微球及其合成制备方法和用途 - Google Patents

一种功能聚合物微球及其合成制备方法和用途 Download PDF

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CN105906759A
CN105906759A CN201610511611.1A CN201610511611A CN105906759A CN 105906759 A CN105906759 A CN 105906759A CN 201610511611 A CN201610511611 A CN 201610511611A CN 105906759 A CN105906759 A CN 105906759A
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焦扬
杨亚玲
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YUNNAN JIANNIU BIOLOGICAL TECHNOLOGY Co Ltd
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Abstract

一种功能聚合物微球及其合成制备方法和用途，属有机合成及检测技术领域。以具有双齿配体的5‑氨基‑1,10‑邻菲罗啉为功能配体进行合成而得到的功能聚合物微球。制备方法包括：(1)甲基丙烯酸缩水甘油酯/甲基丙烯酸甲酯交联微球的制备；(2)功能聚合物微球的合成制备。用途是作为茶叶样品中的镍离子、铁离子、铅离子及锌离子中的一种或多种的固相萃取剂。由于5‑氨基‑1,10‑邻菲罗啉易与镍离子、铁离子、铅离子及锌离子形成配合物，作为这些金属离子的固相萃取剂，选择性高、比表面积大、pH使用范围宽、通用性强、吸附容量大、稳定性好、机械强度高、制备简单，可选择性识别和富集复杂样品中的目标物，在复杂样品分析中具有良好的应用前景。

Description

一种功能聚合物微球及其合成制备方法和用途
技术领域
本发明属于有机合成及检测技术领域，具体涉及一种功能聚合物微球、其制备方法并将该微球用于重金属离子的固相萃取。
背景技术
固相萃取SPE是由液固萃取和柱液相色谱技术相结合发展而来的一种样品预处理技术，主要用于液体样品中组分的分离、纯化和浓缩，是一种可靠性高和实用的现代分离技术。与传统液液萃取相比，固相萃取具有萃取时间短、回收率高、富集倍数大以及有机试剂消耗少等优点。固相萃取填料的性质决定了其应用价值，新型填料的开发和应用是固相萃取技术的重要研究课题。和硅胶类固相萃取填料相比，高分子聚合物类固相萃取填料具有更多的优点，发展前景也更可观。目前，商品化的高分子聚合物类固相萃取填料主要是以聚苯乙烯/二乙烯苯为基质的、未经改性的非极性吸附材料，以及通过某种官能团改性后的吸附材料。未经改性的填料主要是反相保留模式。改性后的填料具有亲脂和功能性基团特性或由于极性官能团的引入而增加对极性物质保留的水浸润性，使其对极性非极性化合物具有较均衡的吸附作用。粒径分布均匀的球形填料的固相萃取小柱内部结构均匀，能够保证样品流量均一、萃取效率高、重复性好。
发明内容
本发明的目的在于提供一种功能聚合物微球及其合成制备方法和用途。
本发明产品的特征在于：以具有双齿配体的5-氨基-1,10-邻菲罗啉为功能配体进行合成而得到的功能聚合物微球。
本发明功能聚合物微球的合成制备方法包括以下步骤：
(1)甲基丙烯酸缩水甘油酯/甲基丙烯酸甲酯交联微球的制备：
将聚合抑制剂和稳定剂溶于去离子水中，室温搅拌，混合均匀作为水相，聚合抑制剂为硫酸钠、氯化钠中的一种，稳定剂为聚乙烯醇、羧甲基纤维素中的一种，聚合抑制剂与稳定剂的重量比为1∶3～5，聚合抑制剂和稳定剂与去离子水重量体积比为1∶20～30；
将交联剂和聚合物单体相混合，室温搅拌，混溶均匀后作为油相，交联剂为二乙烯基苯，聚合物单体为二丙烯酸缩水甘油酯与甲基丙烯酸甲酯的等体积混合物，交联剂与聚合物单体的体积比为1∶4～5；
将油相加入到水相中，搅拌使两相充分分散，加入引发剂，引发剂为过氧化苯甲酰、过氧化甲乙酮、偶氮二异丁腈中的一种，引发剂与聚合物单体的重量比为1∶50～100；
在氮气保护下，于74～76℃恒温反应2.4～2.6h后，升温至84～86℃再反应2.4～2.6h，制得半透明状甲基丙烯酸缩水甘油酯/甲基丙烯酸甲酯交联微球，备用；
所述搅拌的速度最好均为为500～2000rpm，搅拌的时间最好均为2～10min；
(2)功能聚合物微球的合成制备：将步骤(1)制备的交联微球加入到N,N－二甲基甲酰胺中，交联微球与N,N－二甲基甲酰胺的重量体积比克/毫升为1∶15～30，浸泡23～25小时优选24小时，使微球充分溶胀，然后加入0.5～1％5-氨基-1,10-邻菲罗啉的N,N－二甲基甲酰胺，通氮气除氧9～11min，置于油浴中，搅拌条件下油浴加热于98～102℃反应68～76h，反应结束后，依次用N,N－二甲基甲酰胺、去离子水、丙酮和乙醚分别洗涤3～5次，真空干燥即得功能聚合物微球。真空干燥温度优选40℃。
本发明功能聚合物微球的用途是作为茶叶样品中的镍离子、铁离子、铅离子及锌离子中的一种或多种的固相萃取剂。
本发明以具有双齿配体的5-氨基-1,10-邻菲罗啉为功能配体，进行功能聚合物微球的合成，由于5-氨基-1,10-邻菲罗啉易与镍离子、铁离子、铅离子及锌离子形成配合物，合成的功能聚合物微球作为这些金属离子的固相萃取剂，具有选择性高、比表面积大、pH使用范围宽、通用性强、吸附容量大、稳定性好、机械强度高、制备简单等特点，可选择性识别和富集复杂样品中的目标物，因此在复杂样品分析中具有良好的应用前景。
本发明的优点在于：
1.采用悬浮聚合法制备的5-氨基-1,10-邻菲罗啉功能化的甲基丙烯酸缩水甘油酯/甲基丙烯酸甲酯的高分子聚合微球具有合成工艺简单、反应条件温和、易控制、合成效率高。
2.以能化的高分子聚合微球作为重金属离子的固相萃取具有选择性好、吸附容量大、重现性高、富集倍数大的优点。
3.合成的功能化高分子聚合微球不会像硅胶键合后会有残余硅羟基，对分析可能带来次级相互作用的影响，作为一种新型的固相萃取剂，具有广泛的应用前景。
具体实施方式
下面结合实施例对本发明作进一步地说明，但本发明的保护范围并不限于此。
实施例1
(1)交联微球甲基丙烯酸缩水甘油酯(GMA)/甲基丙烯酸甲酯(MMA)的制备：将2g NaCl及2g聚乙烯醇(PVA)溶于100mL去离子水中，1000rpm转速下室温搅拌5min，构成连续相水相；将4mL GMA、4mL MMA与2mL 二乙烯基苯(DVB)混溶，800rpm转速下室温搅拌7min，构成分散相油相；将油相加入到水相中，1000rpm转速下室温搅拌5min，使两相充分分散；加入0.1g过氧化苯甲酰作为引发剂，在氮气保护下，于75℃恒温反应2.5h后，升温至85℃再反应2.5h，制得的半透明状GMA/MMA交联微球，备用；
(2)功能聚合物微球的制备：取1g步骤(1)制备的GMA/MMA交联微球加入到20mL的N,N－二甲基甲酰胺(DMF)中，浸泡24h，使微球充分溶胀，加入20mL溶有0.20g 5-氨基-1,10-邻菲罗啉(5-Aphen)的DMF溶液，通氮气除氧10min，置于油浴中，1000rpm转速下油浴加热100℃搅拌反应72h。反应结束后，依次用DMF、去离子水、丙酮和乙醚分别洗涤5次，40℃真空干燥24h，即得GMA-MMA-DVB-5-Aphen功能聚合物微球。
(3)制备的功能聚合物微球用作茶叶中重金属镍离子、铁离子、铅离子及锌离子的固相萃取。采用GMA-MMA-DVB-5-Aphen聚合物微球填料装填固相萃取柱，采用通常的装填，上样，以及淋洗步骤，以2mol/L硝酸为洗脱剂，结合火焰原子吸收光谱法进行茶叶中Fe(II),Ni(II),Pb(II)and Zn(II)测定，其检测限分别为0.2，0.7，1.6和2.1ng/mL，富集倍数达160倍，最大吸附量分别为60.6(±1.8)mg,32.2(±1.4)mg,20.8(±1.7)mg和38.6(±1.8)mg of Fe(II),Ni(II),Pb(II)和Zn(II)/g GMA-MMA-DVB-5-Aphen功能聚合物微球，检测结果见表1。同时进行了仅用GMA-MMA-DVB聚合物微球填料装填固相萃取柱进行相同茶叶样品中Fe(II),Ni(II),Pb(II)and Zn(II)的固相萃取，结合火焰原子吸收光谱法测定，其检测限分别为0.8，1.5，5.3和3.2ng/mL，最大吸附量分别为54.1(±3.1)mg,30.9(±2.6)mg,16.2(±4.3)mg和36.1(±3.8)mg of Fe(II),Ni(II),Pb(II)和Zn(II)/g GMA-MMA-DVB聚合物微球。通过对比，功能聚合物微球与聚合物微球进行的固相萃取相比，无论在检测限、最大吸附量还是重现性上都有很大优势。
实施例2
(1)交联微球甲基丙烯酸缩水甘油酯(GMA)/甲基丙烯酸甲酯(MMA)的制备：将2g Na2SO4及2g羧甲基纤维素溶于120mL去离子水中，500rpm转速下室温搅拌10min，构成连续相水相；将5mL GMA、5mL MMA与2mL二乙烯基苯(DVB)混溶，1000rpm转速下室温搅拌5min，构成分散相油相；将油相加入到水相中，800rpm转速下室温搅拌6min，使两相充分分散；加入0.12g过氧化甲乙酮作为引发剂，在氮气保护下，于75℃恒温反应2.5h后，升温至85℃再反应2.5h，制得的半透明状GMA/MMA交联微球，备用；
(2)功能聚合物微球的制备：取1g步骤(1)制备的GMA/MMA交联微球加入到30mL的N,N－二甲基甲酰胺(DMF)中，浸泡24h，使微球充分溶胀，加入20mL溶有0.10g 5-氨基-1,10-邻菲罗啉(5-Aphen)的DMF溶液，通氮气除氧10min，置于油浴中，1000rpm转速下油浴加热100℃搅拌反应72h。反应 结束后，依次用DMF、去离子水、丙酮和乙醚分别洗涤3次，40℃真空干燥24h，即得GMA-MMA-DVB-5-Aphen功能聚合物微球。
(3)制备的功能聚合物微球用作茶叶中重金属镍离子、铁离子、铅离子及锌离子的固相萃取。同实施例1。
实施例3
(1)交联微球甲基丙烯酸缩水甘油酯(GMA)/甲基丙烯酸甲酯(MMA)的制备：将2g Na2SO4及2g PVA溶于80mL去离子水中，600rpm转速下室温搅拌8min，构成连续相水相；将3mL GMA、3mL MMA与2mL二乙烯基苯(DVB)混溶，1000rpm转速下室温搅拌5min，构成分散相油相；将油相加入到水相中，800rpm转速下室温搅拌6min，使两相充分分散；加入0.1g偶氮二异丁腈作为引发剂，在氮气保护下，于75℃恒温反应2.5h后，升温至85℃再反应2.5h，制得的半透明状GMA/MMA交联微球，备用；
(2)功能聚合物微球的制备：取1g步骤(1)制备的GMA/MMA交联微球加入到15mL的N,N－二甲基甲酰胺(DMF)中，浸泡24h，使微球充分溶胀，加入20mL溶有0.15g 5-氨基-1,10-邻菲罗啉(5-Aphen)的DMF溶液，通氮气除氧10min，置于油浴中，1000rpm转速下油浴加热100℃搅拌反应72h。反应结束后，依次用DMF、去离子水、丙酮和乙醚分别洗涤4次，40℃真空干燥24h，即得GMA-MMA-DVB-5-Aphen功能聚合物微球。
(3)制备的功能聚合物微球用作茶叶中重金属镍离子、铁离子、铅离子及锌离子的固相萃取。同实施例1。
表1茶叶样品中重金属含量(n＝3，μg/g)
a为3次测定平均值±相对标准偏差。

Claims (5)

1.一种功能聚合物微球，其特征在于为以具有双齿配体的5-氨基-1,10-邻菲罗啉为功能配体进行合成而得到的功能聚合物微球。
2.如权利要求1所述的功能聚合物微球的合成制备方法，其特征在于包括以下步骤：
(1)甲基丙烯酸缩水甘油酯/甲基丙烯酸甲酯交联微球的制备：
将聚合抑制剂和稳定剂溶于去离子水中，室温搅拌，混合均匀作为水相，聚合抑制剂为硫酸钠、氯化钠中的一种，稳定剂为聚乙烯醇、羧甲基纤维素中的一种，聚合抑制剂与稳定剂的重量比为1∶3～5，聚合抑制剂和稳定剂与去离子水重量体积比为1∶20～30；
将交联剂和聚合物单体相混合，室温搅拌，混溶均匀后作为油相，交联剂为二乙烯基苯，聚合物单体为二丙烯酸缩水甘油酯与甲基丙烯酸甲酯的等体积混合物，交联剂与聚合物单体的体积比为1∶4～5；
将油相加入到水相中，搅拌使两相充分分散，加入引发剂，引发剂为过氧化苯甲酰、过氧化甲乙酮、偶氮二异丁腈中的一种，引发剂与聚合物单体的重量比为1∶50～100；
在氮气保护下，于74～76℃恒温反应2.4～2.6h后，升温至84～86℃再反应2.4～2.6h，制得半透明状甲基丙烯酸缩水甘油酯/甲基丙烯酸甲酯交联微球，备用；
(2)功能聚合物微球的合成制备：将步骤(1)制备的交联微球加入到N,N－二甲基甲酰胺中，交联微球与N,N－二甲基甲酰胺的重量体积比克/毫升为1∶15～30，浸泡23～25h，使微球充分溶胀，然后加入0.5～1％5-氨基-1,10-邻菲罗啉的N,N－二甲基甲酰胺，通氮气除氧9～11min，置于油浴中，搅拌条件下油浴加热于98～102℃反应68～76h，反应结束后，依次用N,N－二甲基甲酰胺、去离子水、丙酮和乙醚分别洗涤3～5次，真空干燥即得功能聚合物微球。
3.如权利要求2所述的功能聚合物微球的合成制备方法，其特征在于步骤(1)所述搅拌的速度均为500～2000rpm，搅拌的时间均为2～10min。
4.如权利要求2所述的功能聚合物微球的合成制备方法，其特征在于步骤(2)所说浸泡的时间为24h，真空干燥的温度为40℃。
5.如权利要求1所述的功能聚合物微球的用途是作为茶叶样品中的镍离子、铁离子、铅离子及锌离子中的一种或多种的固相萃取剂。
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