CN108033452A - 一种磁性介孔氧化硅分子印迹聚合物及其制备方法和应用 - Google Patents
一种磁性介孔氧化硅分子印迹聚合物及其制备方法和应用 Download PDFInfo
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- CN108033452A CN108033452A CN201711194278.7A CN201711194278A CN108033452A CN 108033452 A CN108033452 A CN 108033452A CN 201711194278 A CN201711194278 A CN 201711194278A CN 108033452 A CN108033452 A CN 108033452A
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Abstract
本发明公开了一种磁性介孔氧化硅分子印迹聚合物及其制备方法，包括：一锅法制备介孔氧化硅分子印迹聚合物和介孔印迹材料介孔孔道内四氧化三铁的原位合成，得到磁性介孔氧化硅分子印迹聚合物，用于快速、高选择性分离环境样品中的双酚A。本发明的制备方法操作简单，原材料廉价易得，可获得磁性介孔结构的印迹材料，适用于环境复杂样品中双酚A的高选择性、快速分离。
Description
技术领域
本发明属于分子印迹聚合物领域，具体涉及一种磁性介孔氧化硅分子印迹聚合物及其制备方法和应用。
背景技术
分子印迹技术(MIT)是一种制备对目标分子具有特异亲和性和识别能力的高分子聚合物材料的技术。分子印迹技术的原理如下：当模板分子与不同功能单体进行接触时会形成不同类型的作用点，然后通过交联聚合过程将这些作用“记忆”下来。用适当的洗脱剂去除模板分子后，在聚合物结构中就会形成与模板分子在空间结构上非常匹配的印迹孔穴，而这些印迹孔穴就会具有多重作用点能够选择性的识别印迹分子及其结构类似物。在进行分子印迹的过程中模板分子和功能单体之间的作用形式主要有五种，分别是(i)非共价作用，(ii)静电作用/离子作用，(iii)共价作用，(iv)半共价作用和(v)金属螯合作用。但概括来讲，分子印迹方法主要包括共价型印迹法、非共价型印迹法、共价-非共价杂化型印迹法及金属螯合印迹法这四种。
由传统方法制备的分子印迹聚合物(MIPs)因高度交联而具有对目标分子萃取困难、吸附容量低和动力学性能差等缺点。在载体材料的表面印迹目标分子是近年来新兴的一种印迹技术。印迹活性位点由于被控制在载体材料表面，因此，所得MIPs的吸附容量和动力学性能可大大改善，从而在污水处理、色谱分离、手性物质拆分、仿生传感器和固相萃取等领域展现出良好的应用前景。介孔氧化硅基材料具有比表面积大、修饰简便、稳定性好、机械强度高等优势，非常适合用做表面分子印迹聚合物(SMIPs)的载体材料。
双酚A(BPA)作为一种典型的环境雌激素又称为内分泌干扰物，是近年来人们关注的焦点。BPA可通过直接接触或食物链等途径进入生物体内进而干扰生物体内天然激素的合成、分泌、代谢等过程，导致生物体许多功能的紊乱，因此对生物体具有较强的毒害作用。目前，BPA的去除方法主要有吸附分离法、细菌和真菌降解法、化学氧化法、溶剂萃取法等。这些方法各有优点，但也存在很多局限性。如液-液萃取技术大量使用到有机溶剂会产生二次污染；化学氧化过程操作比较复杂、成本费用较高；膜分离技术存在膜的堵塞等问题。而吸附技术因其操作简单、富集效率高和成本低廉被广泛地应用。活性炭是最常见的吸附剂，但是它的吸附分离存在选择性差，吸附容量小，达到平衡的时间长等不足。因此，迫切需要开发一类新型的成本低廉、高选择性分离双酚A的吸附剂材料。
发明内容
本发明提供了一种磁性介孔氧化硅分子印迹聚合物及其制备方法，该方法操作简单方便，所得磁性介孔氧化硅分子印迹聚合物选择性分离效果好，原材料廉价易得。
本发明采用的技术方案如下：
一种磁性介孔氧化硅分子印迹聚合物的制备方法，包括如下步骤：
(1)以双酚A-3-异氰丙基三乙氧基硅烷复合物(BPA-ICPIES)和正硅酸乙酯(TEOS)为共同硅源，聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物(P123)为介孔模板剂，经水热反应后，洗脱模板分子双酚A(BPA)，最后去除介孔模板剂P123，得介孔氧化硅分子印迹聚合物(MIMSP)；
(2)将MIMSP用γ-(2,3-环氧丙氧)丙基三甲氧基硅烷(GLYMO)进行功能化修饰，得介孔孔道内带有环氧基的中间体A；再与高氯酸反应，得带有双羟基的中间体B；
(3)将中间体B加入溶有FeCl2·4H2O和FeCl3·6H2O的甲醇水溶液，经超声分散后升温，加入氨水进行反应，得到所述的磁性介孔氧化硅分子印迹聚合物(m-MIMSP)。
本发明采用一锅法制备介孔氧化硅分子印迹聚合物，并在该介孔氧化硅分子印迹聚合物的介孔孔道内原位合成四氧化三铁，得到磁性介孔氧化硅分子印迹聚合物，本发明的制备方法操作简单，原材料廉价易得，可获得磁性介孔结构的印迹材料。
步骤(1)中，所述的双酚A-3-异氰丙基三乙氧基硅烷复合物的制备方法如下：将双酚A和3-异氰丙基三乙氧基硅烷(ICPTES)以摩尔比为1：1.5～3混合置于四氢呋喃中，在90～110℃下反应18～24h即得；其中，每mmol双酚A加入2～5mL四氢呋喃。
优选地，步骤(1)中，所述聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物、双酚A-3-异氰丙基三乙氧基硅烷复合物和正硅酸乙酯的投加摩尔比为：1.5～2：30～40。
优选地，步骤(1)中，采用二甲亚砜和水的混合液洗脱模板分子双酚A，其中，二甲亚砜和水的体积比为4～6：1。
优选地，步骤(1)中，采用甲醇和水的混合液去除介孔模板剂P123，其中，甲醇和水的体积比4～6：1。
所述的介孔氧化硅分子印迹聚合物的比表面积为600～700m2/g，孔径为4～6nm，孔容为0.7～0.8cm3/g。
步骤(2)中，γ-(2,3-环氧丙氧)丙基三甲氧基硅烷和介孔氧化硅分子印迹聚合物的投加比例为0.5～1.5mL：100mg。
所述中间体A的制备包括：将MIMSP溶于溶剂中，加入γ-(2,3-环氧丙氧)丙基三甲氧基硅烷后，在20～40℃下反应18～24h；其中，溶剂为乙醇。
所述中间体B的制备包括：将中间体A分散于10％～20％的高氯酸水溶液中，在20～40℃下反应18～24h；其中，中间体A和高氯酸水溶液的投加比例为100mg:8～12mL。
步骤(3)中，FeCl2·4H2O和FeCl3·6H2O的投加摩尔比为1：1～4，升温至75～85℃滴加氨水，每100mg中间体B加入1～2mL氨水，加毕，继续搅拌1～2h。
所述的甲醇水溶液由甲醇和水以体积比为1：4～6混合得到。
本发明还提供了一种由上述方法制备得到的磁性介孔氧化硅分子印迹聚合物。
所述的磁性介孔氧化硅分子印迹聚合物的比表面积为300～400m2/g，孔径为6～8nm，孔容为0.4～0.6cm3/g。
本发明的另一目的是提供所述的磁性介孔氧化硅分子印迹聚合物在去除水体中双酚A中的应用，m-MIMSP能从水体中高效选择性分离双酚A，加标回收率达到95.6％到106.2％之间。
相对于现有技术，本发明方法的优点在于：
(1)本发明的制备方法操作简单，原材料廉价易得，获得磁性分子印迹材料的途径简便，并且磁性印迹材料具有较好磁饱和强度可通过外部磁场快速分离免去离心等复杂分离过程；
(2)在介孔氧化硅表面进行印迹过程，合成的印迹材料同样具有较大比表面积，传质速率快，表面印迹活性位点暴露多，选择性能高，具有高选择性快速分离实际样品中双酚A的潜力。
附图说明
图1为本发明磁性介孔氧化硅分子印迹聚合物的制备流程图；
图2为实施例1制备的BPA-ICPTES，实施例2制备的MIMSP，对比例1制备的NIMSP，实施例4制备的m-MIMSP，对比例2制备的m-NIMSP的红外光谱图；
图3为实施例2制备的MIMSP和实施例4制备的m-MIMSP的XRD图谱；
图4为印迹材料的扫描电镜、透射电镜以及能谱图，其中，(a)MIMSP的扫描电镜照片；(b)MIMSP的透射电镜照片；(c)m-MIMSP的扫描电镜照片；(d)m-MIMSP的透射电镜照片；(e)m-MIMSP的EDS能谱图；
图5为(a)MIMSP和m-MIMSP的吸附-脱附等温曲线；(b)MIMSP和m-MIMSP的粒径分布曲线图；
图6为印迹材料的XPS能谱图，其中，(a)MIMSP和m-MINSP的全谱图；(b)MIMSP的C1s谱图；(c)MIMSP的O1s谱图；(d)m-MIMSP的Fe2p谱图；(e)m-MIMSP的C1s谱图；(f)m-MIMSP的O1s谱图；
图7为(a)悬浮在水中(右)和在外加磁场作用下分离(左)m-MIMSP的照片；(b)m-MIMSP和m-NIMSP在298K的磁滞回线；
图8为m-MIMSP和m-NIMSP的吸附动力学研究，其中，(a)动力学曲线；(b)不同时间下的印迹因子；(c)一级动力学拟合；(d)二级动力学拟合；
图9为m-MIMSP的吸附等温线和吸附选择性，其中，(a)吸附等温线及Langmuir等温模型拟合；(b)双酚A结构类似物：4,4’-二羟基联苯、乙烯雌酚、对苯二酚；(c)吸附选择性；(d)选择性吸附过程示意图；
图10为m-MIMSP处理混合溶液的高效液相色谱图，其中，(a)m-MIMSP处理前的混合溶液；(b)m-MIMSP处理后的溶液；(c)m-MIMSP吸附混合溶液后的解吸液。
具体实施方式
本发明磁性介孔氧化硅分子印迹聚合物的制备流程如图1所示。
实施例1
将BPA(2.751g，12mmol)和ICPTES(5.97mL，24mmol)溶于45mL四氢呋喃(THF)中，在氮气保护下于100℃搅拌24h，用旋转蒸发仪把溶剂蒸干，得到油状液体即为BPA-ICPTES；
从图2的红外光谱中可以看出在BPA-ICPTES中3400cm-1附近的特征峰归属于苯环的特征峰，1720cm-1的特征吸收峰归属于ICPTES上C＝O的特征峰，这些都说明成功制备了BPA-ICPTES。
实施例2
(1)将P123(8.4g)，NaCl(24.4g)，去离子水(69.6g)和2mol/LHCl(208.8g)混合均匀直至完全溶解。
(2)取上述混合溶液44g置于平底烧瓶中，加入0.347g BPA-ICPTES和1.80g TEOS，室温下混合均匀剧烈搅拌24h后，将溶液转移到反应釜中，80℃水热反应24h。
(3)产物离心分离，用无水乙醇洗涤20h。
(4)用二甲亚砜:水＝5:1(体积比)的混合溶液洗脱模板BPA，在160℃下回流8h，用甲醇:水＝4:1(体积比)的混合溶液洗脱P123，得介孔氧化硅分子印迹聚合物(MIMSP)。
对比例1
(1)将P123(8.4g)，NaCl(24.4g)，去离子水(69.6g)和2mol/LHCl(208.8g)混合均匀直至完全溶解。
(2)取上述混合溶液44g置于平底烧瓶中，加入0.236g ICPTES和1.80g TEOS，室温下混合均匀剧烈搅拌24h后，将溶液转移到反应釜中，80℃水热反应24h。
(3)产物离心分离，用无水乙醇洗涤20h。
(4)用甲醇:水＝4:1(体积比)的混合溶液洗脱P123，得介孔氧化硅非分子印迹聚合物(NIMSP)。
实施例3
(1)准确称取200mg按照实施例2的方法制备的MIMSP溶于100mL无水乙醇中，加入1.0mLγ-(2,3-环氧丙氧)丙基三甲氧基硅烷，通入氮气去除氧气，反应物在30℃条件下搅拌24h，得到的产物用去离子水和无水乙醇交替洗涤，真空干燥，得介孔孔道内带有环氧基的中间体A。
(2)将200mg中间体A分散于20mL 15％的高氯酸水溶液中，在30℃条件下搅拌24h，得到的产物用去离子水和无水乙醇交替洗涤，真空干燥，得到介孔孔道内带有双羟基的中间体B。
实施例4
准确称取200mg中间体B溶于30mL甲醇:水＝1:4(体积比)的混合溶液中，加入FeCl2·4H2O(0.1mmol，19.9mg)和FeCl3·6H2O(0.2mmol，54.1mg)，超声分散，通入氮气去除氧气，当温度升至80℃时逐滴滴入3.0mL氨水溶液，剧烈搅拌下反应2h，反应结束后用磁铁进行分离，用无水乙醇和去离子水交替洗涤，真空干燥，即得磁性介孔氧化硅分子印迹聚合物(m-MIMSP)。
对比例2
采用对比例1制备的NIMSP为原料，重复实施例3～4的操作步骤，制得磁性介孔氧化硅非分子印迹聚合物(m-NIMSP)。
图2为实施例1制备的BPA-ICPTES，实施例2制备的MIMSP，对比例1制备的NIMSP，实施例4制备的m-MIMSP，对比例2制备的m-NIMSP的红外光谱图；
图3为实施例2制备的MIMSP和实施例4制备的m-MIMSP的XRD图谱，从图3可以看出，当在MIMSP介孔孔道内嫁接四氧化三铁后，m-MIMSP的XRD图谱中出现了四氧化三铁的特征峰(2θ＝30.2°,35.6°,43.3°,53.5°,57.2°)说明成功在MIMSP介孔孔道内嫁接四氧化三铁。
图4为印迹材料的扫描电镜、透射电镜以及能谱图，其中，(a)MIMSP的扫描电镜照片；(b)MIMSP的透射电镜照片；(c)m-MIMSP的扫描电镜照片；(d)m-MIMSP的透射电镜照片；(e)m-MIMSP的EDS能谱图。
图5为(a)MIMSP和m-MIMSP的吸附-脱附等温曲线；(b)MIMSP和m-MIMSP的粒径分布曲线图。
图6为印迹材料的XPS能谱图，其中，(a)MIMSP和m-MINSP的全谱图；(b)MIMSP的C1谱图s；(c)MIMSP的O1s谱图；(d)m-MIMSP的Fe2p谱图；(e)m-MIMSP的C1s谱图；(f)m-MIMSP的O1s谱图。
从图4(e)和图6(d)m-MIMSP的EDS能谱和XPS能谱图可以进一步看出四氧化三铁的存在。从图5中可以看出MIMSP和m-MIMSP都具有介孔结构，而m-MIMSP的比表面积明显变小，这是由于四氧化三铁在介孔孔道内生成导致。
图7为(a)悬浮在水中(右)和在外加磁场作用下分离(左)m-MIMSP的照片；(b)m-MIMSP和m-NIMSP在298K的磁滞回线；由图可知，m-MIMSP的磁饱和强度为4.8emu/g，可利用外部磁铁进行磁性分离。
实施例5
考察了制备的磁性介孔氧化硅分子印迹聚合物(m-MIMSP)的吸附动力学、吸附等温线以及吸附选择性，探讨了其吸附的动力学模型和等温线模型，最后将其用于实际水样中双酚A的高选择性分离。
吸附动力学实验：分别称取30mg m-MIMSP和m-NIMSP加入到8mL浓度为0.5mmol/L的BPA溶液中，通过测定不同吸附时间下的吸附容量来研究m-MIMSP和m-NIMSP的动力学模型。
等温吸附实验：分别称取30mg m-MIMSP和m-NIMSP加入到8mL无水乙醇：水(2：3，V：V)配制的不同浓度的BPA溶液中，吸附一定时间后，离心分离，上清液中的BPA浓度用高效液相色谱进行测定。
选择性吸附实验：选择乙烯雌酚(DES)、对苯二酚(HDQ)、4,4’-二羟基联苯(BP)作为竞争物质，配制BPA和竞争物质的混合溶液，混合溶液的初始浓度为0.5mmol/L，分别称取30mg m-MIMSP和m-NIMSP加入到8mL混合溶液中，吸附进行3h，离心分离，上层清液即为m-MIMSP处理后的溶液，用高效液相色谱测定上层清液中各物质的浓度。
解吸附实验：将吸附了BPA的m-MIMSP分散于二甲亚砜:水＝5:1(体积比)的混合溶液中，在160℃下回流8h洗脱模板BPA，磁分离，收集解吸液，计算解吸效率，实验结果表明解吸效率可达到94％以上。
图8为m-MIMSP和m-NIMSP的吸附动力学研究，其中，(a)动力学曲线；(b)不同时间下的印迹因子；(c)一级动力学拟合；(d)二级动力学拟合；从图8中可以看出m-MIMSP具有较快的吸附动力学，1h内吸附就能达到平衡，而印迹因子为4.8，从动力学曲线拟合情况可知，吸附过程复合二级动力学吸附模型，化学吸附是主要的吸附方式。
图9为m-MIMSP的吸附等温线和吸附选择性，其中，(a)吸附等温线及Langmuir等温模型拟合；(b)双酚A结构类似物：4,4'-二羟基联苯、乙烯雌酚、对苯二酚；(c)吸附选择性；(d)选择性吸附过程示意图；从图9可以看出m-MIMSP的吸附过程符合Langmuir等温吸附模型，属于单分子层吸附，并且m-MIMSP对双酚A具有非常好的吸附选择性，结构类似物的存在不影响吸附效果。
图10为m-MIMSP处理混合溶液的高效液相色谱图，其中，(a)m-MIMSP处理前的混合溶液；(b)m-MIMSP处理后的溶液；(c)m-MIMSP吸附混合溶液后的解吸液；色谱条件：流动相甲醇：水＝70：30(v/v)，流速1.0mL/min，检测波长276nm，进样量20μL柱温25℃。从图10中可以看出，通过吸附解吸过程可以实现m-MIMSP对混合样品中双酚A的高选择性分离。
实际样品分析：将m-MIMSP用于实际水样(来自实验室自来水、河水以及工业废水)中BPA的检测，采用标准加入法对实际水样进行了分析。首先将水样进行高速离心处理，除去水样中的不溶性杂质，然后将得到的水样通过0.40μm的滤膜。称取30mg m-MIMSP加入到8mL处理后的水样中，吸附进行3h，离心分离，将吸附了BPA的m-MIMSP分散于二甲亚砜:水＝5:1(体积比)的混合溶液中，在160℃下回流8h将BPA解吸出来，通过磁分离，收集解吸液，解吸液中存留的BPA的含量用高效液相色谱进行测定；由于水样中BPA的含量较低，我们进行了加标回收实验，结果如表1所示，从表中数据可以看出，BPA的加标回收率在95.6％到106.2％之间，而相对标准偏差(RSD)在1.7％到3.8％之间，表明m-MIMSP可以用来高选择性的分离实际样品中的BPA。
表1实际水样中BPA测定
表中，ND代表没有检测到。
Claims (9)
1.一种磁性介孔氧化硅分子印迹聚合物的制备方法，其特征在于，包括如下步骤：
(1)以双酚A-3-异氰丙基三乙氧基硅烷复合物和正硅酸乙酯为共同硅源，聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物为介孔模板剂，经水热反应后，洗脱模板分子双酚A，最后去除介孔模板剂聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物，得介孔氧化硅分子印迹聚合物；
(2)将介孔氧化硅分子印迹聚合物用γ-(2,3-环氧丙氧)丙基三甲氧基硅烷进行功能化修饰，得介孔孔道内带有环氧基的中间体A；再与高氯酸反应，得带有双羟基的中间体B；
(3)将中间体B加入溶有FeCl2·4H2O和FeCl3·6H2O的甲醇水溶液，经超声分散后升温，加入氨水进行反应，得到所述的磁性介孔氧化硅分子印迹聚合物。
2.根据权利要求1所述的磁性介孔氧化硅分子印迹聚合物的制备方法，其特征在于，步骤(1)中，所述的双酚A-3-异氰丙基三乙氧基硅烷复合物的制备方法如下：将双酚A和3-异氰丙基三乙氧基硅烷以摩尔比为1：1.5～3混合置于四氢呋喃中，在90～110℃下反应18～24h即得。
3.根据权利要求1所述的磁性介孔氧化硅分子印迹聚合物的制备方法，其特征在于，步骤(1)中，所述聚环氧乙烷-聚环氧丙烷-聚环氧乙烷三嵌段共聚物、双酚A-3-异氰丙基三乙氧基硅烷复合物和正硅酸乙酯的投加摩尔比为1：1.5～2：30～40。
4.根据权利要求1所述的磁性介孔氧化硅分子印迹聚合物的制备方法，其特征在于，步骤(1)中，采用二甲亚砜和水的混合液洗脱模板分子双酚A，其中，二甲亚砜和水的体积比为4～6：1。
5.根据权利要求1所述的磁性介孔氧化硅分子印迹聚合物的制备方法，其特征在于，步骤(2)中，γ-(2,3-环氧丙氧)丙基三甲氧基硅烷和介孔氧化硅分子印迹聚合物的投加比例为0.5～1.5mL：100mg。
6.根据权利要求1所述的磁性介孔氧化硅分子印迹聚合物的制备方法，其特征在于，所述中间体B的制备包括：将中间体A分散于10％～20％的高氯酸水溶液中，在20～40℃下反应18～24h；其中，中间体A和高氯酸水溶液的投加比例为100mg:8～12mL。
7.根据权利要求1所述的磁性介孔氧化硅分子印迹聚合物的制备方法，其特征在于，步骤(3)中，FeCl2·4H2O和FeCl3·6H2O的投加摩尔比为1：1～4，升温至75～85℃滴加氨水，每100mg中间体B加入1～2mL氨水，加毕，继续搅拌1～2h。
8.一种磁性介孔氧化硅分子印迹聚合物，其特征在于，由权利要求1～7任一项所述的方法制备得到。
9.一种根据权利要求8所述的磁性介孔氧化硅分子印迹聚合物在去除水体中双酚A中的应用。
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