CN105753067B - 一种超顺磁氧化铁微球的粒径调控方法 - Google Patents
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Abstract
本发明属于超顺磁氧化铁微球的制备领域,具体涉及一种超顺磁氧化铁微球的粒径调控方法。在多元醇法制备超顺磁氧化铁微球的过程中,通过加入离子液体,改变体系极性,调节所得微球的粒径大小,同时保持组成微球的晶粒度大小不变,实现单一调节;制得粒径为60‑250 nm,晶粒度为5.5 ±0.3 nm的超顺磁氧化铁微球。该方法操作简便,实用性强。
Description
技术领域
本发明属于超顺磁氧化铁微球的制备领域,具体涉及一种超顺磁氧化铁微球的粒径调控方法。
背景技术
超顺磁氧化铁微球在蛋白核酸纯化、免疫检测、磁分离、纳米载药等领域具有广泛的应用。超顺磁氧化铁微球的磁性、水分散性等性能与其粒径大小有关,其合成的关键是微球直径的控制,开发简单、可精确调节微球粒径的合成技术有重要的价值。
超顺磁氧化铁微球的制备主要有微乳液法和多元醇法。微乳液法是分两步法构建微球,先通过高温热分解法合成油溶性的超顺磁氧化铁纳米粒子,然后用水包油型微乳液法组装成微球,微球粒径大小可通过微乳液胶束大小来控制,该方法较复杂。多元醇方法可以一步法合成超顺磁微球,微球大小和组成微球的晶粒大小可同时控制,该方法合成超顺磁氧化铁微球的工艺已经比较成熟。Ge等(Angew. Chem. Int. Ed. 2007, 46, 4342–4345)人把三氯化铁和聚丙烯酸溶解在二乙二醇中,加热到220℃,然后注入氢氧化钠溶液可以生成超顺磁Fe3O4微球,微球粒径可以通过改变氢氧化钠用量来控制,但是该方法不容易重复。Xuan等(Chem. Mater. 2009, 21, 5079–5087)以三氯化铁为前驱体,乙二醇为溶剂,通过调节丙烯酸钠和乙酸钠的比例,可以调节微球大小和组成微球的晶粒度大小。本专利第一发明人在先前的专利中(一种超顺磁Fe3O4微球的制备方法,ZL201310224500.9),以三氯化铁为前驱体,聚丙烯酸为稳定剂,通过调节乙二醇和3-氨基丙醇的比例可同时改变微球的粒径和组成微球的晶粒大小。保持组成微球的晶粒度大小不变,单一的调节Fe3O4微球粒径大小还存在困难,本发明在先前发明的基础上,加入离子液体来调节其微球大小,同时保持组成微球的晶粒度不变。
发明内容
本发明的目的在于提供一种超顺磁氧化铁微球的粒径调控方法,该方法可以通过控制加入离子液体的量来调节微球粒径大小,同时保持组成微球的晶粒度大小不变,微球的形貌可通过透射电镜观察和扫描电镜观察。
为实现上述发明目的,本发明的技术方案为:
一种超顺磁氧化铁微球的粒径调控方法,在多元醇法制备超顺磁氧化铁微球的过程中,通过加入离子液体调节微球的粒径大小,制得粒径为60-250 nm,晶粒度为5.5 ±0.3nm的超顺磁氧化铁微球。
所述离子液体包括咪唑类、吡啶类、季铵类、季鏻类、吡咯烷类和哌啶类中的一种。
所述超顺磁氧化铁微球的粒径调控方法,其特征在于:具体步骤为:
1)将三氯化铁和聚丙烯酸固体溶解在乙二醇中,形成透明的溶液;
2)在搅拌下,将3-氨基丙醇逐滴加入步骤1)所得溶液中,混合均匀;
3)将离子液体加入步骤2)所得溶液中,混合均匀;
4)将步骤3)所得溶液转入高压反应釜中,密闭,控制温度180-220℃,反应3-24小时,冷却至室温,产物倒入水中,磁铁辅助洗涤除去杂质,经真空干燥得固体产物。
步骤1)中三氯化铁的用量为0.05-2 mmol,聚丙烯酸的用量为1-6 mmol,乙二醇的用量为5-14 mL;步骤2)中3-氨基丙醇用量为1-10 mL。
步骤1)所述聚丙烯酸固体的分子量为2000。
乙二醇和3-氨基丙醇的体积之和优选为15 mL。
步骤3)离子液体的用量为1-30 μL。
本发明的有益效果在于:
本发明通过在多元醇法制备超顺磁微球的体系中加入少量离子液体即可在比较宽的范围内调节粒径大小,并可以保持晶粒度不变,单一的调节微球大小;操作简单、方便,实用性好。
附图说明
图1实施例1所得超顺磁微球的透射电镜照片;
图2实施例2所得超顺磁微球的透射电镜照片;
图3实施例3所得超顺磁微球的透射电镜照片;
图4 实施例4所得超顺磁微球的透射电镜照片;
图5 实施例1-4所得微球的X-射线衍射曲线;根据谢乐公式算出平均晶粒度为5.5±0.3 nm。
具体实施方式
为了使本发明所述的内容更加便于理解,下面结合具体实施方式对本发明所述的技术方案做进一步的说明,但是本发明不仅限于此。
实施例 1
分别称取0.14 g (2 mmol)聚丙烯酸和0.16 g (1 mmol)无水三氯化铁溶解在12mL乙二醇中,搅拌形成透明溶液,然后搅拌下逐滴加入3 mL 3-氨基丙醇,再加入20 μL离子液体1-乙基-3甲基咪唑四氟硼酸盐,混合均匀后移入具有聚四氟乙烯内衬的水热合成反应釜(20 mL),密封,于鼓风干燥箱中200℃恒温6 h,随炉冷却至室温,得黑色溶胶,加入水稀释,磁铁辅助洗涤除去杂质,真空干燥可得黑色粉末。
所得产物的电镜照片如图1所示,微球平均粒径为63 nm。
实施例 2
方法同实施例1,加入离子液体体积为10 μL,所得产物的电镜照片如图2所示,微球平均粒径为122 nm。
实施例 3
方法同实施例1,加入离子液体体积为5 μL,所得产物的电镜照片如图3所示,微球平均粒径为165 nm。
实施例 4
方法同实施例1,不加入离子液体,所得产物的电镜照片如图3所示,微球平均粒径为250 nm。
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (3)
1. 一种超顺磁氧化铁微球的粒径调控方法,其特征在于:在多元醇法制备超顺磁氧化铁微球的过程中,通过加入离子液体调节微球的粒径大小,制得粒径为60-250 nm,晶粒度为5.5 ±0.3 nm的超顺磁氧化铁微球;所述离子液体包括咪唑类、吡啶类、季铵类、季鏻类、吡咯烷类和哌啶类中的一种;具体步骤为:
1)将三氯化铁和聚丙烯酸固体溶解在乙二醇中,形成透明的溶液;
2)在搅拌下,将3-氨基丙醇逐滴加入步骤1)所得溶液中,混合均匀;
3)将离子液体加入步骤2)所得溶液中,混合均匀;
4)将步骤3)所得溶液转入高压反应釜中,密闭,控制温度180-220℃,反应3-24小时,冷却至室温,产物倒入水中,磁铁辅助洗涤除去杂质,经真空干燥得固体产物;步骤1)中三氯化铁的用量为0.05-2 mmol,聚丙烯酸的用量为1-6 mmol,乙二醇的用量为5-14 mL;步骤2)中3-氨基丙醇用量为1-10 mL;步骤3)离子液体的用量为1-30 μL。
2. 根据权利要求1所述超顺磁氧化铁微球的粒径调控方法,其特征在于:步骤1)中的乙二醇和步骤2)中的3-氨基丙醇的体积之和为15 mL。
3.根据权利要求1所述超顺磁氧化铁微球的粒径调控方法,其特征在于:步骤1)所述聚丙烯酸固体的分子量为2000。
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