CN102554263B - 有机分散性Cu/Fe3O4复合纳米微粒的制备方法 - Google Patents
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Abstract
本发明涉及一种有机分散性Cu/Fe3O4复合纳米微粒的制备方法,该方法包括如下步骤:将含有氨水的水合肼水溶液加入到铜盐水溶液中反应1~30min;再加入二价铁盐和三价铁盐的混合水溶液反应10~60min,最后加入溶有修饰剂的非极性或弱极性有机溶剂反应10~120min,静置分离,取有机相,浓缩后即得;所述铜盐、水合肼、二价铁盐和修饰剂的摩尔比为1:1-10:0.1-1:0.25-2,氨水与水合肼的摩尔比为4.4-11:1,三价铁盐与二价铁盐的摩尔比为2:1。该方法工艺简单,原料廉价易得,成本低,制得的纳米微粒颗粒粒径小,分散性及稳定性好,适合大规模的工业生产。
Description
技术领域
本发明属于新型功能纳米材料制备技术领域,具体涉及一种有机分散性Cu/Fe3O4磁性复合纳米微粒的制备方法。
背景技术
软金属铜纳米微粒因具有比表面积大、量子尺寸效应、宏观量子隧道效应等特性,而被广泛应用于催化、电子、磁学,光学,热学,涂料、润滑等领域,例如应用于高效催化剂、导电浆料、以及润滑油添加剂等。近年来关于铜纳米微粒的制备、性能及应用的研究倍受关注。中国专利200610165009.3公开了一种采用超重力技术制备纳米铜润滑油添加剂的方法,其利用旋转填充床的相间传递强化作用和微观混合的特性,先将铜盐和还原液在超重力反应器中进行还原,然后再将馏出液和修饰剂在反应釜中反应对其进行修饰,最后减压蒸馏得到表面修饰的棕红色油状液体,即纳米铜润滑油添加剂。这种方法具有反应速度快,产物重复性好,产品质量高,收率高等优点,但是所采用的仪器比较苛刻,对生产设备要求比较高。高愈尊等人在专利96105280.5中采用络合还原的方法,用活性金属粉末作还原剂来制备铜纳米微粒,该方法在反应完成后因活性金属粉还原剂不易洗净,可能会影响到纳米铜粉的纯度。此外,还有采用等离子体法、电辐射法、机械化学法、热分解法或溶剂热法等来制备铜纳米微粒。其中,等离子体法设备简单、易操作、生产速度快,但是能耗大,高温下电极易于融化而污染产物。辐射合成法虽然制备工艺简单、粒度易控、产率高,但所获得的产物处于离散胶体状态,收集非常困难,不易规模化。机械化学方法虽然工艺简单,可以制备其他常规方法难以制备的高熔点金属、金属陶瓷复合材料等,但是其缺点是晶体不均匀,在球磨过程中易引入杂质。热分解法相对于其它方法更快速、经济,但实现所要求温度比较高,并且对粒径和形貌的控制技术还不成熟,距离工业生产还相差甚远。溶剂热法使用压力装置,对装置材料要求高,条件相对苛刻,不易扩大生产。
近年来,制备铜纳米微粒较活跃的方法是液相还原法。专利CN1188700A公开了一种采用连二亚硫酸钠在水与有机物质的混合溶剂中还原二价铜离子的方法。专利CN1381328A公开了一种在较高温度和压力下,用氢还原铜盐制备铜纳米微粒的方法。现有的这些液相还原方法虽然能制得几十到几百纳米的金属微粒,但是由于表面未得到充分的改性,仍无法解决制备出的纳米微粒在空气中稳定性差,及在有机介质中的分散性不好等问题,难于广泛应用。
发明内容
本发明的目的在于提供一种有机分散性Cu/Fe3O4复合纳米微粒的制备方法,制得的纳米微粒颗粒粒径小,分散性及稳定性好。
为实现上述目的,本发明采用如下技术方案:
一种有机分散性Cu/Fe3O4复合纳米微粒的制备方法,其包括如下步骤:将含有氨水的水合肼水溶液加入到铜盐水溶液中反应1~30min;再加入二价铁盐和三价铁盐的混合水溶液反应10~60min,最后加入溶有修饰剂的非极性或弱极性有机溶剂反应10~120min,静置分离,取有机相,浓缩后即得。反应温度控制在20-80℃之间为宜。
所述铜盐与水合肼、二价铁盐、修饰剂的摩尔比为1∶1-10∶0.1-1∶0.25-2,氨水与水合肼水溶液的摩尔比为4.4-11∶1,三价铁盐与二价铁盐的摩尔比为2∶1。氨水的质量分数以25-28%为宜,水合肼水溶液质量分数以50-85%为宜,铜盐水溶液的摩尔浓度以0.2-0.7mol/l为宜。
具体的,所述铜盐优选为硫酸铜、氯化铜、硝酸铜和乙酸铜等可溶于水的铜盐中的一种或两种以上。
所述二价铁盐优选为硫酸亚铁、氯化亚铁、硝酸亚铁、乙酸亚铁中的一种或两种以上;所述三价铁盐优选为硫酸铁、氯化铁、硝酸铁、乙酸铁中的一种或两种以上。
所述修饰剂可以是碳链在C6-C40之间的有机羧酸和/或有机胺。如有机羧酸可以是饱和、不饱和、直链、支链或含芳香烃基团中的一种或两种以上的混合物。修饰剂优选碳链在C10-C20之间的有机羧酸和/或有机胺。
所述非极性或弱极性有机溶剂为碳原子数不小于5的烷烃、环烷烃、芳香烃和氯代烃中的一种或两种以上的混合物。此外有机溶剂还可以是饱和烷烃混合物,如石油醚(戊烷和己烷的混合物)等。
本发明方法利用四氧化三铁容易被表面修饰剂修饰的特性,通过液相还原的方法制备得到Cu/Fe3O4复合纳米微粒,解决了金属纳米微粒很难被不含硫、磷修饰剂修饰的难题。该方法主要分为两大步骤:1)制备铜溶胶:将含有氨水的水合肼水溶液一次性加入到铜盐水溶液中,在磁力搅拌下反应得到淡黄色透明的铜溶胶。2)将二价和三价铁盐水溶液加入到铜溶胶中,反应一段时间后加入溶有修饰剂的有机溶剂,反应后经分离得到粘稠状、表面修饰的油溶性的四氧化三铁包覆铜纳米微粒。所制得的产品在有机溶剂中具有良好的分散性;在空气中具有良好的氧化稳定性。此处良好的分散性指产品以1%的质量浓度分散在所述非极性或弱极性有机溶剂中,180天内无沉降发生。良好的氧化稳定性指产品以1%的质量浓度分散在所述非极性或弱极性有机溶剂中,180天内无任何颜色变化。
本发明方法采用四氧化三铁包覆技术与液相还原相结合的方法,解决了液相还原法中铜纳米微粒表面不容易修饰的问题,所得纳米微粒颗粒粒径小(2-15nm之间)且粒径均一,分散性及稳定性好。该方法具有工艺设备简单、绿色环保、原料廉价易得、成本低,产物的产率高等特点,通过控制反应温度条件(20-80℃)能得到粒径可控的复合纳米微粒,适合大规模工业化生产。一般情况下,在较低温度所得纳米微粒的粒径特别小;而在较高温度下制得的纳米微粒粒径较大。如在室温反应时得到复合纳米微粒粒径为2nm;在60℃反应时得到的复合纳米微粒粒径为15nm。该方法所得纳米微粒分散于基础油中,在空气中可以长期稳定存在,具有广泛的工业应用前景。此外所得复合纳米微粒具有磁性,使用后比较容易回收,对环境友好。
附图说明:
图1为实施例1制得的油酸、油胺修饰的Cu/Fe3O4纳米微粒的透射电镜图;
图2为实施例1制得的油酸、油胺修饰的Cu/Fe3O4纳米微粒分散于PAO中的光学图片;
图3为实施例1制得的油酸、油胺修饰的Cu/Fe3O4纳米微粒的磁性试验结果;
图4为实施例2制得的油酸、油胺修饰的Cu/Fe3O4纳米微粒的透射电镜图;
图5为实施例2制得的油酸、油胺修饰的Cu/Fe3O4纳米微粒分散于PAO中的光学图片。
具体实施方式
为了更好地理解本发明,以下通过优选实施例对本发明方法作进一步的详细说明,但本发明的保护范围并不局限于此。
实施例1
一种有机分散性Cu/Fe3O4复合纳米微粒的制备方法,其包括如下步骤:
1)取4ml浓度为0.5mol/l的CuSO4水溶液用蒸馏水稀释至50ml得溶液A;
2)取6ml质量分数为25-28%的氨水(分析纯,购自洛阳昊华化学试剂有限公司)与0.8ml质量分数为80%的水合肼水溶液混合后,用蒸馏水稀释至50ml得溶液B;
3)取1ml浓度1mol/l FeCl3和0.25ml浓度2mol/l FeCl2混合后用蒸馏水稀释至30ml得溶液C;将2mmol油胺和2mmol油酸溶于100ml石油醚中得溶液D;
4)将溶液A转入500ml的三颈烧瓶中,在常温、搅拌条件下将溶液B加入到溶液A中反应2min(此时溶液为透明的淡黄色溶液),再逐滴加入溶液C,反应30min溶液逐渐变为红棕色悬浊液,最后一次性加入溶液D反应1h,反应结束后将溶液体系转移到分液漏斗中静置分层,溶液分两层(上层棕黑色有机层,下层无色水层),取上层有机层旋蒸得棕红色粘稠状液体产品。
所得产品粒径均匀(见图1),平均粒径约为2nm;其溶解于PAO(聚α烯烃)(在PAO中质量分数为1wt%),静置30天后的光学照片见图2,由图2可看出其在基础油中具有良好的分散性。为了验证四氧化三铁是否包覆在铜纳米微粒上及包覆后是否具有磁性,进行如下试验:对其母液进行磁铁吸引,如图3所示,从图3可看出在磁铁的吸引下物质全部被吸引到有磁铁的一边(图3中,左侧为磁铁),其余为澄清透明的溶液,说明铜纳米微粒全部被四氧化三铁所包覆,并且包覆后具有较强的磁性。
实施例2
一种有机分散性Cu/Fe3O4复合纳米微粒的制备方法,其包括如下步骤:
1)取4ml浓度为0.5mol/l的CuSO4水溶液用蒸馏水稀释至50ml得溶液A;
2)取6ml质量分数为25-28%的氨水与0.8ml质量分数为80%的水合肼水溶液混合后,用蒸馏水稀释至50ml得溶液B;
3)取1ml浓度1mol/l FeCl3和0.25ml浓度2mol/l FeCl2混合后用蒸馏水稀释至30ml得溶液C;将2mmol油胺和2mmol油酸溶于100ml石油醚中得溶液D;
4)将溶液A转入500ml的三颈烧瓶中,在60℃、搅拌条件下将溶液B加入到溶液A中反应2min(此时溶液为透明的淡黄色溶液),再逐滴加入溶液C,反应30min溶液逐渐变为红棕色悬浊液,最后一次性加入溶液D反应1h,反应结束后将溶液体系转移到分液漏斗中静置分层,溶液分两层(上层棕黑色有机层,下层无色水层),取上层有机层旋蒸得棕黑色粘稠状液体产品。
所得产品粒径均匀(见图4),平均粒径约为15nm;其溶解于PAO(聚α烯烃)(在PAO中质量分数为1wt%),静置30天后的光学照片见图5,由图5可看出其在基础油中具有良好的分散性。
实施例3
一种有机分散性Cu/Fe3O4复合纳米微粒的制备方法,其包括如下步骤:
1)取4ml浓度为0.25mol/l的乙酸铜水溶液用蒸馏水稀释至50ml得溶液A;
2)取3ml质量分数为25-28%的氨水与0.7ml质量分数为50%的水合肼水溶液混合后,用蒸馏水稀释至50ml得溶液B;
3)取0.5ml浓度1mol/l Fe(NO3)3和0.125ml浓度2mol/l Fe(NO3)2混合后用蒸馏水稀释至30ml得溶液C;将1mmol正辛胺和1mmol油酸溶于100ml氯仿中得溶液D;
4)将溶液A转入500ml的三颈烧瓶中,在45℃、搅拌条件下将溶液B加入到溶液A中反应2min(此时溶液为透明的浅黄色溶液),再逐滴加入溶液C,反应30min溶液逐渐变为暗红棕色悬浊液,最后一次性加入溶液D反应1h,反应结束后将溶液体系转移到分液漏斗中静置分层,溶液分两层(上层无色水层,下层棕黄色有机层),取下层有机层旋蒸得棕黄色粘稠状液体产品。
实施例4
一种有机分散性Cu/Fe3O4复合纳米微粒的制备方法,其包括如下步骤:
1)取6ml浓度为0.5mol/l的CuCl2水溶液用蒸馏水稀释至50ml得溶液A;
2)取6ml质量分数为25-28%的氨水与1.6ml质量分数为50%的水合肼水溶液混合后,用蒸馏水稀释至50ml得溶液B;
3)取1ml浓度1mol/l Fe(SO4)3和0.25ml浓度2mol/l Fe(SO4)2混合后用蒸馏水稀释至30ml得溶液C;将0.5mmol油胺和0.5mmol硬脂酸溶于100ml氯仿中得溶液D;
4)将溶液A转入500ml的三颈烧瓶中,在45℃搅拌条件下将溶液B加入到溶液A中反应2min(此时溶液为透明的淡黄色溶液),再逐滴加入溶液C,反应30min溶液逐渐变为棕色悬浊液,最后一次性加入溶液D反应1h,反应结束后将溶液体系转移到分液漏斗中静置分层,溶液分两层(上层无色水层,下层棕色有机层),取下层有机层旋蒸得棕色粘稠状液体产品。
实施例5
一种有机分散性Cu/Fe3O4复合纳米微粒的制备方法,其包括如下步骤:
1)取4ml浓度为0.5mol/l的Cu(NO3)2水溶液用蒸馏水稀释至50ml得溶液A;
2)取6ml质量分数为25-28%的氨水与1.2ml质量分数为50%的水合肼水溶液混合后,用蒸馏水稀释至50ml得溶液B;
3)取2ml浓度1mol/l FeCl3和0.5ml浓度2mol/l FeCl2混合后用蒸馏水稀释至30ml得溶液C;将1mmol正辛胺和1mmol十四酸溶于100ml石油醚中得溶液D;
4)将溶液A转入500ml的三颈烧瓶中,在常温、搅拌条件下将溶液B加入到溶液A中反应2min(此时溶液为透明的淡黄色溶液),再逐滴加入溶液C,反应60min溶液逐渐变为深棕色悬浊液,最后一次性加入溶液D反应1h,反应结束后将溶液体系转移到分液漏斗中静置分层,溶液分两层(上层深棕色有机层,下层无色水层),取上层有机层旋蒸得棕色粘稠状液体产品。
Claims (4)
1.一种有机分散性Cu/Fe3O4复合纳米微粒的制备方法,其特征在于,包括如下步骤:将含有氨水的水合肼水溶液加入到铜盐水溶液中反应1~30min;再加入二价铁盐和三价铁盐的混合水溶液反应10~60min,最后加入溶有修饰剂的非极性或弱极性有机溶剂反应10~120min,静置分离,取有机相,浓缩后即得;所述铜盐与水合肼、二价铁盐、修饰剂的摩尔比为1:1-10:0.1-1:0. 25-2,氨水与水合肼的摩尔比为4.4-11:1,三价铁盐与二价铁盐的摩尔比为2:1;所述修饰剂为碳链在C6―C40之间的有机羧酸和/或有机胺;所述非极性或弱极性有机溶剂为碳原子数不小于5的烷烃、环烷烃、芳香烃和氯代烃中的一种或两种以上的混合物。
2.如权利要求1所述有机分散性Cu/Fe3O4复合纳米微粒的制备方法,其特征在于,所述铜盐为硫酸铜、氯化铜、硝酸铜和乙酸铜中的一种或两种以上。
3.如权利要求1所述有机分散性Cu/Fe3O4复合纳米微粒的制备方法,其特征在于,所述二价铁盐为硫酸亚铁、氯化亚铁、硝酸亚铁、乙酸亚铁中的一种或两种以上;所述三价铁盐为硫酸铁、氯化铁、硝酸铁、乙酸铁中的一种或两种以上。
4.如权利要求1所述有机分散性Cu/Fe3O4复合纳米微粒的制备方法,其特征在于,所述修饰剂为碳链在C10―C20之间的有机羧酸和/或有机胺。
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