CN110713565B - 一种超支化pei修饰的磁性二氧化硅分子印迹聚合物的制备方法 - Google Patents
一种超支化pei修饰的磁性二氧化硅分子印迹聚合物的制备方法 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000003756 stirring Methods 0.000 claims abstract description 45
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- 239000000843 powder Substances 0.000 claims abstract description 13
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 11
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Abstract
本发明涉及印迹聚合物技术领域,公开了一种超支化PEI修饰的磁性二氧化硅分子印迹聚合物的制备方法。包括以下步骤:1)将四氧化三铁粉末加入无水乙醇中搅拌混合形成溶胶状混合液,滴加正硅酸乙酯,陈化;2)烷基化处理得烷基化二氧化硅包覆四氧化三铁颗粒;3)将烷基化二氧化硅包覆四氧化三铁颗粒加入超支化聚乙烯亚胺溶液得超支化聚乙烯亚胺接枝二氧化硅颗粒;4)加入甲基丙烯酸单体交联反应,即得。以二氧化硅包覆四氧化三铁微球为载体,功能单体甲基丙烯酸在载体表面发生交联形成球状印迹聚合物微球,具有高比表面积,增多与模板分子结合位点。
Description
技术领域
本发明涉及印迹聚合物技术领域,尤其是涉及一种超支化PEI修饰的磁性二氧化硅分子印迹聚合物的制备方法。
背景技术
分子印迹聚合物又称为分子烙印技术,属于高分子化学、材料科学、生物化学、分析化学等之间的一个交叉学科领域。分子印迹技术是为获得在空间结构和结合点位上与某一分子完全匹配的聚合物的实验制备技术。分子印迹聚合物是指以目标分子为模板分子,将具有结构互补功能化聚合物单体通过共价键或非共价键的方式与模板分子结合,加入交联剂进行聚合反应,反应完成后将模板分子提取出来形成一种有固定空穴大小和形状及有确定排列功能团的交联高聚物。分子印迹技术至所以发展如此迅速,主要是因为它具有预定性、识别性和实用性。分子印迹聚合物及时将模板分子与功能单体通过共价、非共价或金属协同作用形成预聚合物,在交联剂的作用下功能单体发生聚合,将模板分子固定在聚合物中,最后脱除模板分子,即聚合物材料上留下与模板分子在大小、形状和官能团的方向上都互补的空穴结构。空穴不仅保留了与模板分子化学结构互补的官能团的有序排列,也维持了它的整个空间构象,所以当材料再次遇到模板分子时,可发生特异性的结合。现有技术中通常使用交联剂对功能单体进行交联形成印迹聚合物,形成的印迹聚合物固体颗粒的表面与印迹分子结合,使用大量印迹聚合物与印迹分子只能形成少量的结合位点,印迹聚合物分子的利用率较低。如中国专利公开号CN105348429公开了一种分子印迹聚合物,将聚乙烯醇与水搅拌溶解,加入抗坏血酸和丙烯酰胺的水溶液,再滴加乙二醇二甲基丙烯酸酯和偶氮二异丁腈的甲苯溶液,得到印迹聚合物,此技术方案中制备得到的印迹聚合物的利用率较低。
发明内容
本发明是为了克服现有技术印迹聚合物利用率低的问题,提供一种超支化PEI修饰的磁性二氧化硅分子印迹聚合物的制备方法。
为了实现上述目的,本发明采用以下技术方案:超支化PEI修饰的磁性二氧化硅分子印迹聚合物的制备方法,包括以下步骤:
1)将四氧化三铁粉末加入无水乙醇中搅拌混合形成溶胶状混合液,向混合液中加入氨水,搅拌混合均匀,滴加正硅酸乙酯,进行陈化3-6h,经过离心过滤,洗涤,干燥得二氧化硅包覆四氧化三铁颗粒;
2)将3-(2,3-环氧丙氧)丙基三甲氧基硅烷加入甲苯溶剂中搅拌溶解,向溶液中加入二氧化硅包覆四氧化三铁颗粒,加热反应得烷基化二氧化硅包覆四氧化三铁颗粒;
3)将超支化聚乙烯亚胺加入去离子水中搅拌溶解得超支化聚乙烯亚胺溶液,将烷基化二氧化硅包覆四氧化三铁颗粒加入超支化聚乙烯亚胺溶液中,加热反应得超支化聚乙烯亚胺接枝二氧化硅颗粒;
4)将超支化聚乙烯亚胺接枝二氧化硅颗粒、紫杉醇、甲基丙烯酸单体加入丙酮溶剂中搅拌溶解,加入乙二醇二甲基丙烯酸酯和偶氮二异丁腈,搅拌反应40-60min,磁性分离后经过索氏抽提洗净模板分子,干燥,即得。
本发明以四氧化三铁的印迹聚合物的磁核,外加磁场便能分离出将印迹聚合物,操作简单方便;正硅酸乙酯水解生成二氧化硅纳米颗粒,二氧化硅纳米颗粒沉积在四氧化三铁的表面,形成二氧化硅包覆四氧化三铁微球,能够避免四氧化三铁粉末发生团聚,然后进行烷基化处理,将3-(2,3-环氧丙氧)丙基三甲氧基硅烷接枝到二氧化硅壳层上,由于二氧化硅表面具有机较多的羟基,容易与3-(2,3-环氧丙氧)丙基三甲氧基硅烷发生接枝;超支化聚乙烯亚胺与3-(2,3-环氧丙氧)丙基三甲氧基硅烷发生开环反应,从而将超支化聚乙烯亚胺接枝到二氧化硅壳层,由于超支化聚乙烯亚胺具有独特的空间结构和丰富的氨基基团,可以为功能单体提供附着位点,增强印迹效率。功能单体甲基丙烯酸在交联剂乙二醇二甲基丙烯酸酯和引发剂偶氮二异丁腈的作用下在超支化聚乙烯亚胺层表面发生交联反应,将模板分子紫杉醇固定在功能单体交联形成的聚合物中,超支化聚乙烯亚胺上的氨基与紫杉醇形成氢键,从而使模板分子紫杉醇不容易从印迹聚合物上脱离,最后脱除模板分子,即聚合物材料上留下与模板分子在大小、形状和官能团的方向上都互补的空穴结构,形成的空穴结构与紫杉醇具有较强的结合能力,从而使印迹聚合物具有较强的从其他组分中分离紫杉醇的能力。本发明以二氧化硅包覆四氧化三铁微球为载体,功能单体甲基丙烯酸在载体表面发生交联形成球状印迹聚合物微球,具有高比表面积,增多与模板分子结合位点。由于印迹聚合物内部为二氧化硅包覆四氧化三铁微球,能够减少印迹聚合物的用量。
作为优选,所述步骤1)中四氧化三铁粉末与无水乙醇的质量体积比为1g/80-100mL。
作为优选,所述步骤1)中四氧化三铁粉末与正硅酸乙酯的质量比为1:0.3-0.6。
作为优选,所述步骤2)中反应温度为40-50℃,反应时间为30-50min。
作为优选,所述步骤3)中超支化聚乙烯亚胺溶液浓度为2-5wt%。
作为优选,所述步骤3)中反应温度为35-40℃,反应时间为40-60min。
作为优选,所述步骤4)中超支化聚乙烯亚胺接枝二氧化硅颗粒、紫杉醇、甲基丙烯酸单体的质量比为1:0.1-0.2:0.3-0.5。
因此,本发明具有如下有益效果:本发明以二氧化硅包覆四氧化三铁微球为载体,功能单体甲基丙烯酸在载体表面发生交联形成球状印迹聚合物微球,具有高比表面积,增多与模板分子结合位点。由于印迹聚合物内部为二氧化硅包覆四氧化三铁微球,能够减少印迹聚合物的用量。
具体实施方式
下面通过具体实施例,对本发明的技术方案做进一步说明。
本发明中,若非特指,所采用的原料和设备等均可从市场购得或是本领域常用的,实施例中的方法,如无特别说明,均为本领域的常规方法。
实施例1
超支化PEI修饰的磁性二氧化硅分子印迹聚合物的制备方法,包括以下步骤:
1)将2g四氧化三铁粉末加入180mL无水乙醇中搅拌混合形成溶胶状混合液,向混合液中加入10mL质量浓度为25%的氨水,搅拌混合均匀,滴加0.8g正硅酸乙酯,进行陈化4h,经过离心过滤,洗涤,干燥得二氧化硅包覆四氧化三铁颗粒;
2)将2g 3-(2,3-环氧丙氧)丙基三甲氧基硅烷加入100mL甲苯溶剂中搅拌溶解,向溶液中加入步骤1)中得到的二氧化硅包覆四氧化三铁颗粒,加热至45℃反应40min,得烷基化二氧化硅包覆四氧化三铁颗粒;
3)将超支化聚乙烯亚胺加入去离子水中搅拌溶解得浓度为3wt%的超支化聚乙烯亚胺溶液,将步骤2)得到的烷基化二氧化硅包覆四氧化三铁颗粒加入超支化聚乙烯亚胺溶液中,加热至40℃反应40min,得超支化聚乙烯亚胺接枝二氧化硅颗粒;
4)将3g超支化聚乙烯亚胺接枝二氧化硅颗粒、0.4g紫杉醇、1.2g甲基丙烯酸单体加入200mL丙酮溶剂中搅拌溶解,加入1g乙二醇二甲基丙烯酸酯和0.2g偶氮二异丁腈,搅拌反应50min,磁性分离后经过索氏抽提洗净模板分子,干燥,即得。
实施例2
超支化PEI修饰的磁性二氧化硅分子印迹聚合物的制备方法,包括以下步骤:
1)将2g四氧化三铁粉末加入180mL无水乙醇中搅拌混合形成溶胶状混合液,向混合液中加入10mL质量浓度为25%的氨水,搅拌混合均匀,滴加1g正硅酸乙酯,进行陈化5h,经过离心过滤,洗涤,干燥得二氧化硅包覆四氧化三铁颗粒;
2)将2g 3-(2,3-环氧丙氧)丙基三甲氧基硅烷加入100mL甲苯溶剂中搅拌溶解,向溶液中加入步骤1)中得到的二氧化硅包覆四氧化三铁颗粒,加热至50℃反应30min,得烷基化二氧化硅包覆四氧化三铁颗粒;
3)将超支化聚乙烯亚胺加入去离子水中搅拌溶解得浓度为4wt%的超支化聚乙烯亚胺溶液,将步骤2)得到的烷基化二氧化硅包覆四氧化三铁颗粒加入超支化聚乙烯亚胺溶液中,加热至40℃反应40min,得超支化聚乙烯亚胺接枝二氧化硅颗粒;
4)将3g超支化聚乙烯亚胺接枝二氧化硅颗粒、0.5g紫杉醇、1.3g甲基丙烯酸单体加入200mL丙酮溶剂中搅拌溶解,加入1g乙二醇二甲基丙烯酸酯和0.2g偶氮二异丁腈,搅拌反应60min,磁性分离后经过索氏抽提洗净模板分子,干燥,即得。
实施例3
超支化PEI修饰的磁性二氧化硅分子印迹聚合物的制备方法,包括以下步骤:
1)将2g四氧化三铁粉末加入160mL无水乙醇中搅拌混合形成溶胶状混合液,向混合液中加入10mL质量浓度为25%的氨水,搅拌混合均匀,滴加0.7g正硅酸乙酯,进行陈化4h,经过离心过滤,洗涤,干燥得二氧化硅包覆四氧化三铁颗粒;
2)将2g 3-(2,3-环氧丙氧)丙基三甲氧基硅烷加入100mL甲苯溶剂中搅拌溶解,向溶液中加入步骤1)中得到的二氧化硅包覆四氧化三铁颗粒,加热至40℃反应50min,得烷基化二氧化硅包覆四氧化三铁颗粒;
3)将超支化聚乙烯亚胺加入去离子水中搅拌溶解得浓度为2.5wt%的超支化聚乙烯亚胺溶液,将步骤2)得到的烷基化二氧化硅包覆四氧化三铁颗粒加入超支化聚乙烯亚胺溶液中,加热至35℃反应60min,得超支化聚乙烯亚胺接枝二氧化硅颗粒;
4)将3g超支化聚乙烯亚胺接枝二氧化硅颗粒、0.4g紫杉醇、1g甲基丙烯酸单体加入200mL丙酮溶剂中搅拌溶解,加入1g乙二醇二甲基丙烯酸酯和0.2g偶氮二异丁腈,搅拌反应40min,磁性分离后经过索氏抽提洗净模板分子,干燥,即得。
实施例4
超支化PEI修饰的磁性二氧化硅分子印迹聚合物的制备方法,包括以下步骤:
1)将2g四氧化三铁粉末加入200mL无水乙醇中搅拌混合形成溶胶状混合液,向混合液中加入10mL质量浓度为25%的氨水,搅拌混合均匀,滴加1.2g正硅酸乙酯,进行陈化6h,经过离心过滤,洗涤,干燥得二氧化硅包覆四氧化三铁颗粒;
2)将2g 3-(2,3-环氧丙氧)丙基三甲氧基硅烷加入100mL甲苯溶剂中搅拌溶解,向溶液中加入步骤1)中得到的二氧化硅包覆四氧化三铁颗粒,加热至50℃反应50min,得烷基化二氧化硅包覆四氧化三铁颗粒;
3)将超支化聚乙烯亚胺加入去离子水中搅拌溶解得浓度为5wt%的超支化聚乙烯亚胺溶液,将步骤2)得到的烷基化二氧化硅包覆四氧化三铁颗粒加入超支化聚乙烯亚胺溶液中,加热至40℃反应60min,得超支化聚乙烯亚胺接枝二氧化硅颗粒;
4)将3g超支化聚乙烯亚胺接枝二氧化硅颗粒、0.6g紫杉醇、1.5g甲基丙烯酸单体加入200mL丙酮溶剂中搅拌溶解,加入1g乙二醇二甲基丙烯酸酯和0.2g偶氮二异丁腈,搅拌反应60min,磁性分离后经过索氏抽提洗净模板分子,干燥,即得。
实施例5
超支化PEI修饰的磁性二氧化硅分子印迹聚合物的制备方法,包括以下步骤:
1)将2g四氧化三铁粉末加入160mL无水乙醇中搅拌混合形成溶胶状混合液,向混合液中加入10mL质量浓度为25%的氨水,搅拌混合均匀,滴加0.6g正硅酸乙酯,进行陈化3h,经过离心过滤,洗涤,干燥得二氧化硅包覆四氧化三铁颗粒;
2)将2g 3-(2,3-环氧丙氧)丙基三甲氧基硅烷加入100mL甲苯溶剂中搅拌溶解,向溶液中加入步骤1)中得到的二氧化硅包覆四氧化三铁颗粒,加热至40℃反应30min,得烷基化二氧化硅包覆四氧化三铁颗粒;
3)将超支化聚乙烯亚胺加入去离子水中搅拌溶解得浓度为2wt%的超支化聚乙烯亚胺溶液,将步骤2)得到的烷基化二氧化硅包覆四氧化三铁颗粒加入超支化聚乙烯亚胺溶液中,加热至35℃反应40min,得超支化聚乙烯亚胺接枝二氧化硅颗粒;
4)将3g超支化聚乙烯亚胺接枝二氧化硅颗粒、0.3g紫杉醇、0.9g甲基丙烯酸单体加入200mL丙酮溶剂中搅拌溶解,加入1g乙二醇二甲基丙烯酸酯和0.2g偶氮二异丁腈,搅拌反应40min,磁性分离后经过索氏抽提洗净模板分子,干燥,即得。
试验测试:
分别选取10mg实施例1-5得到的印迹聚合物,置于初始浓度为0.125mg/mL的紫杉醇溶液中,常温搅拌12h,进行高效液相色谱测试,得到印迹聚合物的吸附效率如下:
以上所述,仅是本发明的较佳实施例而已,并非对本发明作任何形式上的限制,虽然本发明已以较佳实施例揭露如上,然而并非用以限定本发明,任何熟悉本专业的技术人员,在不脱离本发明技术方案范围内,当可利用上述揭示的技术内容作出些许更动或修饰为等同变化的等效实施例,但凡是未脱离本发明技术方案内容,依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰,均仍属于本发明技术方案的范围内。
Claims (7)
1.一种超支化PEI修饰的磁性二氧化硅分子印迹聚合物的制备方法,其特征在于,包括以下步骤:
1)将四氧化三铁粉末加入无水乙醇中搅拌混合形成溶胶状混合液,向混合液中加入氨水,搅拌混合均匀,滴加正硅酸乙酯,进行陈化3-6h,经过离心过滤,洗涤,干燥得二氧化硅包覆四氧化三铁颗粒;
2)将3-(2,3-环氧丙氧)丙基三甲氧基硅烷加入甲苯溶剂中搅拌溶解,向溶液中加入二氧化硅包覆四氧化三铁颗粒,加热反应得烷基化二氧化硅包覆四氧化三铁颗粒;
3)将超支化聚乙烯亚胺加入去离子水中搅拌溶解得超支化聚乙烯亚胺溶液,将烷基化二氧化硅包覆四氧化三铁颗粒加入超支化聚乙烯亚胺溶液中,加热反应得超支化聚乙烯亚胺接枝二氧化硅颗粒;
4)将超支化聚乙烯亚胺接枝二氧化硅颗粒、紫杉醇、甲基丙烯酸单体加入丙酮溶剂中搅拌溶解,加入乙二醇二甲基丙烯酸酯和偶氮二异丁腈,搅拌反应40-60min,磁性分离后经过索氏抽提洗净模板分子,干燥,即得。
2.根据权利要求1所述的一种超支化PEI修饰的磁性二氧化硅分子印迹聚合物的制备方法,其特征在于,所述步骤1)中四氧化三铁粉末与无水乙醇的质量体积比为1g/80-100mL。
3.根据权利要求1所述的一种超支化PEI修饰的磁性二氧化硅分子印迹聚合物的制备方法,其特征在于,所述步骤1)中四氧化三铁粉末与正硅酸乙酯的质量比为1:0.3-0.6。
4.根据权利要求1所述的一种超支化PEI修饰的磁性二氧化硅分子印迹聚合物的制备方法,其特征在于,所述步骤2)中反应温度为40-50℃,反应时间为30-50min。
5.根据权利要求1所述的一种超支化PEI修饰的磁性二氧化硅分子印迹聚合物的制备方法,其特征在于,所述步骤3)中超支化聚乙烯亚胺溶液浓度为2-5wt%。
6.根据权利要求1所述的一种超支化PEI修饰的磁性二氧化硅分子印迹聚合物的制备方法,其特征在于,所述步骤3)中反应温度为35-40℃,反应时间为40-60min。
7.根据权利要求1所述的一种超支化PEI修饰的磁性二氧化硅分子印迹聚合物的制备方法,其特征在于,所述步骤4)中超支化聚乙烯亚胺接枝二氧化硅颗粒、紫杉醇、甲基丙烯酸单体的质量比为1:0.1-0.2:0.3-0.5。
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101423612A (zh) * | 2008-12-04 | 2009-05-06 | 中北大学 | 一种硅胶表面酚类分子印迹聚合物的制备方法 |
WO2010085851A1 (en) * | 2009-01-29 | 2010-08-05 | Commonwealth Scientific And Industrial Research Organisation | Molecularly imprinted polymers |
CN102417558A (zh) * | 2011-11-21 | 2012-04-18 | 嘉兴学院 | 一种分离莠去津的磁性分子印记聚合物及其制备方法 |
CN105884985A (zh) * | 2016-05-13 | 2016-08-24 | 华南农业大学 | 一种磁性镉离子印迹聚合物及其制备方法 |
-
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101423612A (zh) * | 2008-12-04 | 2009-05-06 | 中北大学 | 一种硅胶表面酚类分子印迹聚合物的制备方法 |
WO2010085851A1 (en) * | 2009-01-29 | 2010-08-05 | Commonwealth Scientific And Industrial Research Organisation | Molecularly imprinted polymers |
CN102417558A (zh) * | 2011-11-21 | 2012-04-18 | 嘉兴学院 | 一种分离莠去津的磁性分子印记聚合物及其制备方法 |
CN105884985A (zh) * | 2016-05-13 | 2016-08-24 | 华南农业大学 | 一种磁性镉离子印迹聚合物及其制备方法 |
Non-Patent Citations (3)
Title |
---|
Efficient adsorption of Pb(II) from aqueous solutions using aminopropyltriethoxysilane-modified magnetic attapulgite@chitosan (APTS-Fe3O4/APT@CS) composite hydrogel beads;Liang Xuexue et al.;《International Journal of Biological Macromolecules》;20190705;第137卷;第741-750页 * |
Thermal-responsive ion-imprinted polymer based;Liu Yan et al.;《Colloid Polym Sci》;20140919;第293卷(第1期);第109-123页 * |
硅胶表面铜(Ⅱ)离子印迹聚乙烯亚胺的制备及结合特性研究;安富强等;《高分子学报》;20070430(第4期);第366-373页 * |
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