CN111729660A - 一种具有co2响应性的磁性纳米材料及制备方法和应用 - Google Patents
一种具有co2响应性的磁性纳米材料及制备方法和应用 Download PDFInfo
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Abstract
本发明涉及一种具有CO2响应性的磁性纳米材料及制备方法和应用。本发明采用HNTs作为载体，赋予埃洛石优异磁性，并在其上仿生负载了绿色环保的聚多巴胺，利用迈克尔加成反应将含有巯基的CO2响应性聚合物聚甲基丙烯酸N,N‑二甲基氨基乙酯(PDMAEMA)接枝在负载了多巴胺的磁性埃洛石上。制备出一种具有CO2响应性的磁性纳米材料，从而实现对多种水包油和油包水乳液的高效分离，具有广阔的应用前景。
Description
技术领域
本发明涉及一种具有CO2响应性的磁性纳米材料及制备方法和应用，尤其涉及一种利用RAFT自由基聚合法制备的CO2响应性聚合物及其磁性纳米材料的制备方法，并用于乳化油的分离，属功能材料制备技术领域。
背景技术
随着人们消费水平的提升，人们的餐饮、旅游、出行会导致大量污水产生，势必会导致生活中含油污水的日益增多。若未能及时处理，不慎排入外界环境则会对水体，动植物，土壤造成极大污染和破坏。另外像美国墨西哥湾石油泄露事件也引起了严重的环境污染，海域内大量鱼类因为原油沾附在鱼鳃上而窒息死亡。原油泄露形成的油膜也大大影响海洋浮游生物生长，破坏海洋生态平衡。其中乳化油污水因其油滴主要以乳化形式存在，尺寸小、稳定性强，难以通过离心或气浮等方式实现油水分离，使得油水分离难度大大增加，想要进一步降低废水中的含油量也变得相当困难。通常在复杂水环境中水包油乳液和油包水乳液同时存在，具有单一固定润湿性能的材料越来越难以满足分离条件。因此如何制备出既可以分离水包油乳液也可以分离油包水乳液的材料尤为关键。
随着纳米技术、界面化学和高分子科学的发展，许多对油和水具有特殊润湿性的“智能”界面材料被不断开发出来。其中，基于刺激响应大分子体系的“智能”表面可以通过外界我们所熟知的刺激源调控表面润湿性，进而用于可控油/水“开-关”。目前，基于刺激响应聚合物界面材料的研究主要围绕传统的温度、光照、pH、磁场等刺激响应大分子体系。但是一些物理刺激比如高能量的紫外光在一定程度上会损害材料；通过加酸加碱调节体系pH时，不仅会造成盐的积累，还会稀释溶液，影响体系的循环可逆性。因此，需要利用更加温和的刺激源，开发环境友好性的界面材料用于调控油/水“开-关”。CO2刺激响应聚合物因为调控过程仅仅涉及CO2及N2等惰性气体，避免了副产物的产生以及体系的污染。并且聚合物性质能够发生可逆性变化，这样一种绿色开关控制的刺激响应聚合物在乳化油分离领域有潜在的应用。已有CO2响应聚合物在膜以及气凝胶上的应用，但是存在膜的易污染和气凝胶的易堵塞问题，并且只能分离油水混合物以及分离种类单一的乳化油。
发明内容
针对上述现有技术存在的不足，本发明的目的在于克服现有技术中存在的技术缺陷，解决传统CO2刺激响应材料选择性低、聚合过程难于控制、分离效率低等问题，使得制备的CO2响应纳米材料的可以分离多种含有不同表面活性剂的乳液以及分离效率大幅提升。
埃洛石(HNTs)因为其存在广泛，价格低廉，并且具有较大的长径比和比表面积在许多领域都有广泛应用。HNTs外表面的羟基含量较低，与水分子相互作用较弱，其表面相对疏水。在纳米管之间，其纵横比适当的管形态减小了管之间的接触面积，因此，HNTs可以均匀地分散在聚合物中，所以本发明采用HNTs作为载体。另外我们赋予埃洛石优异磁性，并在其上仿生负载了绿色环保的聚多巴胺，利用迈克尔加成反应将含有巯基的CO2响应性聚合物聚甲基丙烯酸N,N-二甲基氨基乙酯(PDMAEMA)接枝在负载了多巴胺的磁性埃洛石上。制备出一种具有CO2响应性的磁性纳米材料，从而实现对多种水包油和油包水乳液的高效分离，具有广阔的应用前景。
本发明采用的技术方案如下，本发明由三步反应完成：
1、不同分子量的PDMAEMA-SH的合成(现有技术)：
采用RAFT自由基聚合法，将不同比例的RAFT链转移剂苄基三硫代碳酸酯基丙酸(BSPA)和甲基丙烯酸N,N-二甲基氨基乙酯(DMAEMA)用1，4-二氧六环溶解，用AIBN引发聚合，得到不同分子量的聚甲基丙烯酸N,N-二甲基氨基乙酯(PDMAEMA)。然后在常温氮气保护下加入制备好的PDMAEMA，用正丁胺进行还原，得到PDMAEMA-SH。
进一步地，所述不同比例的RAFT链转移剂苄基三硫代碳酸酯基丙酸(BSPA)和甲基丙烯酸N,N-二甲基氨基乙酯(DMAEMA)指RFAT链转移剂与DMAEMA之间的摩尔比为1：40～1：400，优选1：200。
所述不同分子量的PDMAEMA指5K～30K分子量的PDMAEMA，优选30K。
2、负载多巴胺的磁性埃洛石(MHNTs@PDA)的制备(现有技术)：
将埃洛石与九水硝酸铁均匀分散在乙二醇中，并在N2氛围中400℃的高温下煅烧4h，得到负载Fe3O4纳米颗粒的磁性埃洛石。然后将得到的磁性埃洛石分散在15mM Tris缓冲液(pH8.5)的盐酸多巴胺(2mg/ml)溶液中。去离子水洗涤干燥得到负载多巴胺的磁性埃洛石。
3、将上述合成的不同分子量的PDMAEMA-SH溶解于乙醇溶液中，再将负载多巴胺的磁性埃洛石超声分散在乙醇中半小时，再将PDMAEMA-SH乙醇溶液加入到含有埃洛石的乙醇溶液中(PDMAEMA-SH与埃洛石的质量比为3:1)，机械搅拌24小时。用乙醇和去离子水充分洗涤，干燥得到MHNTs@PDA@PDMAEMA磁性纳米材料。
4、称取负载了CO2响应聚合物的磁性埃洛石20mg，置于水包油或油包水乳液中,通入20分钟CO2或N2，用磁铁吸附分离，取上层清澈液体进行测试，此纳米复合材料的分离效率高于99％。
本实验使用的水包油乳液中水和油的体积比为99：1，并添加阴离子表面活性剂十二烷基硫酸钠和非离子表面活性剂吐温80，每mL水包油乳液分别添加1mg十二烷基硫酸钠和吐温80；同样地，油包水乳液中，油和水的体积比为1：99，添加非离子型表面活性剂司盘80，每mL油包水乳液添加1mg司盘80。
利用RAFT自由基聚合制备得到PDMAEMA，然后还原得到PDMAEMA-SH，再与负载了多巴胺的磁性埃洛石进行亲核反应，得到磁性埃洛石@多巴胺@PDMAEMA，用乙醇水洗涤多次，30℃下真空干燥。制备的纳米材料具有CO2响应性，可用于乳化油分离。
本发明采用的技术方案是：
步骤1、制备磁性埃洛石(现有技术)：将埃洛石超声均匀分散在乙醇中，然后加入九水硝酸铁，超声，然后在室温下搅拌，90℃下真空干燥得橙色粉末。将所得固体粉末用乙二醇浸渍，然后放入管式炉中通N2在400℃的高温煅烧4h。高温煅烧所得产物用乙醇洗涤，干燥。
步骤2、制备磁性埃洛石@多巴胺(现有技术)：在去离子水中加入三羟基氨基甲烷，待其完全溶解后用稀盐酸调节PH至8.5，得缓冲溶液。随后往缓冲溶液中加入一定比例的磁性埃洛石粉末，乙醇和多巴胺，室温搅拌后抽滤。所得粉末用去离子水洗涤3次，然后40℃真空干燥，得多巴胺改性的磁性埃洛石粉末。
步骤3、制备PDMAEMA(现有技术)：先取DMAEMA，RAFT链转移剂溶于干燥过的1，4-二氧六环中，待各组分完全溶解后，向体系中加入AIBN之后密封。进行抽真空-通氮气三次，再将体系移至预热80℃油浴中，反应18h。
步骤4、制备PDMAEMA-SH(现有技术)：将合成的PDMAEMA溶解于THF中，加入磁力搅拌转子搅拌，常温下加入正丁胺反应4h。
步骤5、制备磁性埃洛石@多巴胺@PDMAEMA：将磁性埃洛石@多巴胺超声分散于乙醇中30min，将PDMAEMA-SH用乙醇溶解后加入到磁性埃洛石@多巴胺中，室温搅拌24h。
步骤1中，埃洛石、九水硝酸铁和乙醇的比例为6g：4g：120mL。
步骤2中，三羟基氨基甲烷、去离子水、磁性埃洛石、乙醇和多巴胺的比例为1.5mmol：300ml：6.0g：10ml：0.3g。
步骤3中，所述的RAFT链转移剂与AIBN的比例为10mol：1mol，RAFT链转移剂和甲基丙烯酸N,N-二甲基氨基乙酯的摩尔比为1：40～1：400。
步骤4中，正丁胺与PDMAEMA的摩尔比为50：1。
步骤5中，PDMAEMA-SH在乙醇中的浓度为0.3g/ml，磁性埃洛石@多巴胺与PDMAEMA-SH的质量比为3：1；超声分散的时间为30min。
本发明的有益效果在于：
(1)制得一种可以利用CO2刺激响应的新型磁性纳米材料，可以高效分离多种水包油以及油包水乳液。
(2)采用绿色环保的CO2作为刺激源，分离时无二次污染和副产物产生，能耗低。
(3)赋予埃洛石优异的超顺磁性，可以利用外加磁场的作用对复合材料进行分离和收集，使得乳化油分离时分离速度更快且可以多次循环使用。
(4)发明制备方法成熟稳定、反应过程简单、操作方便、能耗低、易于处理、无二次污染。
附图说明
图1是水包油/油包水乳液在N2/CO2中分离示意图。(a-d)为水包油乳液在显微镜下的油滴图片，通入N2后显微镜下无油滴显示，乳液由浑浊变为澄清。
图1(e-h)为油包水乳液在显微镜下的油滴图片，通入CO2后显微镜下无水滴显示，乳液由浑浊变为澄清。
具体实施方式
下面结合具体实施例对本发明作进一步描述：
实施例1：
(1)制备磁性埃洛石：加入3g埃洛石，超声均匀分散在60ml乙醇中。然后加入2g九水硝酸铁，超声，然后在室温下搅拌，90℃下真空干燥得橙色粉末。将所得固体粉末用乙二醇浸渍，然后放入管式炉中通N2在400℃的高温煅烧4h。高温煅烧所得产物用乙醇充分洗涤，干燥；
(2)制备磁性埃洛石@多巴胺：在150ml去离子水中加入0.0909g(0.75mmol)三羟基氨基甲烷。待其完全溶解后用稀盐酸调节PH至8.5，得缓冲溶液。随后往缓冲溶液中加入3g磁性埃洛石粉末，5ml乙醇和0.15g多巴胺，室温搅拌后抽滤。所得粉末用去离子水洗涤3次，然后40℃真空干燥，得多巴胺改性的磁性埃洛石粉末；
(3)制备PDMAEMA：先取(1.57g，10mmol)DMAEMA，RAFT链转移剂(91.16mg，0.25mmol)溶于干燥过的1，4-二氧六环(3ml)中。待各组分完全溶解后，向体系中加入AIBN(4.1mg，0.025mmol)之后密封。进行抽真空-通氮气三次，再将体系移至预热80℃油浴中，反应18h；
(4)制备PDMAEMA-SH：将合成的PDMAEMA溶解于适量THF中，常温下加入正丁胺(1.27ml)反应4h；
(5)制备磁性埃洛石@多巴胺@PDMAEMA：将磁性埃洛石@多巴胺(3.0g)超声分散于乙醇中30min，将一定量的PDMAEMA-SH(1.0g)用乙醇溶解后加入到磁性埃洛石@多巴胺中，室温搅拌24h；
实施例2：
(1)制备磁性埃洛石：加入3.0g埃洛石，超声均匀分散在60ml乙醇中。然后加入2.0g九水硝酸铁，超声。然后在室温下搅拌，90℃下真空干燥得橙色粉末。将所得固体粉末用乙二醇浸渍，然后放入管式炉中通N2在400℃的高温煅烧4h。高温煅烧所得产物用乙醇充分洗涤，干燥；
(2)制备磁性埃洛石@多巴胺：在150ml去离子水中加入0.0909g(0.75mmol)三羟基氨基甲烷。待其完全溶解后用稀盐酸调节PH至8.5，得缓冲溶液。随后往缓冲溶液中加入3.0g磁性埃洛石粉末，5ml乙醇和0.15g多巴胺，室温搅拌后抽滤。所得粉末用去离子水洗涤3次，然后40℃真空干燥，得多巴胺改性的磁性埃洛石粉末；
(3)制备PDMAEMA：先取(2.36g，15mmol)DMAEMA，RAFT链转移剂(91.16mg，0.25mmol)溶于干燥过的1，4-二氧六环(3ml)中。待各组分完全溶解后，向体系中加入AIBN(4.1mg，0.025mmol)之后密封。进行抽真空-通氮气三次，再将体系移至预热80℃油浴中，反应18h；
(4)制备PDMAEMA-SH：将合成的PDMAEMA溶解于适量THF中，常温下加入正丁胺(1.5ml)反应4h；
(5)制备磁性埃洛石@多巴胺@PDMAEMA：将磁性埃洛石@多巴胺(3.0g)超声分散于乙醇中30min，将PDMAEMA-SH(1.0g)用乙醇溶解后加入磁性埃洛石中，室温搅拌24h。
实施例3：
(1)制备磁性埃洛石：加入3.0g埃洛石，超声均匀分散在60ml乙醇中。然后加入2.0g九水硝酸铁，超声。在室温下搅拌，90℃下真空干燥得橙色粉末。将所得固体粉末用乙二醇浸渍，然后放入管式炉中通N2在400℃高温煅烧4h。高温煅烧所得产物用乙醇充分洗涤，干燥；
(2)制备磁性埃洛石@多巴胺：在150ml去离子水中加入0.0909g(0.75mmol)三羟基氨基甲烷。待其完全溶解后用稀盐酸调节PH至8.5，得缓冲溶液。随后往缓冲溶液中加入3.0g磁性埃洛石粉末，5ml乙醇和0.15g多巴胺，室温搅拌后抽滤。所得粉末用去离子水洗涤3次，然后40℃真空干燥，得多巴胺改性的磁性埃洛石粉末；
(3)制备PDMAEMA：先取(3.14g，20mmol)DMAEMA，RAFT链转移剂(91.16mg，0.25mmol)溶于干燥过的1，4-二氧六环(3ml)中。待各组分完全溶解后，向体系中加入AIBN(4.1mg，0.025mmol)之后密封。进行抽真空-通氮气三次，再将体系移至预热80℃油浴中，反应18h；
(4)制备PDMAEMA-SH：将合成的PDMAEMA溶解于适量THF中，常温下加入正丁胺(1.52ml)反应4h；
(5)制备磁性埃洛石@多巴胺@PDMAEMA：将磁性埃洛石@多巴胺超声分散于乙醇中30min，将PDMAEMA-SH(1.0g)用乙醇溶解后加入磁性埃洛石(3.0g)中，室温搅拌24h。
Claims (8)
1.一种具有CO2响应性的磁性纳米材料的制备方法，其特征在于，将磁性埃洛石@多巴胺超声分散于乙醇中，将PDMAEMA-SH用乙醇溶解后加入到磁性埃洛石@多巴胺中，室温搅拌24h，得到具有CO2响应性的磁性纳米材料。
2.如权利要求1所述的一种具有CO2响应性的磁性纳米材料的制备方法，其特征在于，PDMAEMA-SH在乙醇溶解后的浓度为0.3g/ml，磁性埃洛石@多巴胺与PDMAEMA-SH的质量比为3：1；超声分散的时间为30min。
3.如权利要求1所述的一种具有CO2响应性的磁性纳米材料的制备方法，其特征在于，所述磁性埃洛石@多巴胺的制备方法为：在去离子水中加入三羟基氨基甲烷，待其完全溶解后用稀盐酸调节PH至8.5，得缓冲溶液，随后往缓冲溶液中加入一定比例的磁性埃洛石粉末，乙醇和多巴胺，室温搅拌后抽滤，所得粉末用去离子水洗涤3次，然后40℃真空干燥，得多巴胺改性的磁性埃洛石粉末；三羟基氨基甲烷、去离子水、磁性埃洛石、乙醇和多巴胺的比例为1.5mmol：300ml：6.0g：10ml：0.3g。
4.如权利要求1所述的一种具有CO2响应性的磁性纳米材料的制备方法，其特征在于，所述PDMAEMA-SH的制备方法为：将PDMAEMA溶解于THF中，加入磁力搅拌转子搅拌，常温下加入正丁胺反应4h；正丁胺与PDMAEMA的摩尔比为50：1。
5.如权利要求4所述的一种具有CO2响应性的磁性纳米材料的制备方法，其特征在于，所述PDMAEMA的制备方法为：先取DMAEMA，RAFT链转移剂溶于干燥过的1，4-二氧六环中，待各组分完全溶解后，向体系中加入AIBN之后密封，进行抽真空-通氮气三次，再将体系移至预热80℃油浴中，反应18h；所述的RAFT链转移剂与AIBN的比例为10mol：1mol，RAFT链转移剂和甲基丙烯酸N,N-二甲基氨基乙酯的摩尔比为1：40～1：400；PDMAEMA指5K～30K分子量的PDMAEMA。
6.如权利要求5所述的一种具有CO2响应性的磁性纳米材料的制备方法，其特征在于，RAFT链转移剂和甲基丙烯酸N,N-二甲基氨基乙酯的摩尔比为1：200；PDMAEMA指30K分子量的PDMAEMA。
7.如权利要求1所述方法制备的一种具有CO2响应性的磁性纳米材料的用途，其特征在于，用于分离多种含有不同表面活性剂的乳液。
8.如权利要求7所述的用途，其特征在于，乳液为水包油或油包水乳液，水包油乳液中水和油的体积比为99：1，并添加阴离子表面活性剂十二烷基硫酸钠和非离子表面活性剂吐温80，每mL水包油乳液分别添加1mg十二烷基硫酸钠和吐温80；同样地，油包水乳液中，油和水的体积比为1：99，添加非离子型表面活性剂司盘80，每mL油包水乳液添加1mg司盘80；称取具有CO2响应性的磁性纳米材料20mg，置于水包油或油包水乳液中，通入20分钟CO2或N2，用磁铁吸附分离，取上层清澈液体进行测试。
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