CN110215910A - 一种勃姆石改性吸附剂的制备方法 - Google Patents
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Abstract
本发明公开了一种勃姆石改性吸附剂的制备方法，属于复合材料领域。该制备方法包括两步：先用含有双键的有机酸对勃姆石进行酯化，得到含双键的酯化勃姆石；然后在水中加入引发剂、单体、少量交联剂、乳化剂及酯化勃姆石，对含双键的酯化勃姆石进行接枝聚合，即得到勃姆石改性吸附剂；该吸附剂能快速吸附水体中的杀虫剂、药物、内分泌干扰物、苯酚、氯仿及衍生物、油类物质等，具有吸附量大、吸附速率快、易于回收与再生等特点。
Description
技术领域
本发明涉及到复合材料领域，具体涉及到一种勃姆石改性吸附剂的制备方法。
背景技术
活性氧化铝是一种常用的吸附剂，为了提高其吸附能力，杜雯等采用氯化铜改性氧化铝以提高其吸附脱汞能力；也有采用氢氧化钠对氧化铝改性以提高去氟能力；也有采用钙、镁改性氧化铝以提高对氟和腐殖酸的去除能力；也有采用锰改性提高其对氟的去除能力；也有采用磷钨酸为改性剂、浸渍法制备负载型氧化铝，以吸附脱除焦化蜡油中氮化物，也有采用偶联剂(硅烷偶联剂、钛酸酯偶联剂、铝酸酯偶联剂)，通过醚化反应引入双键，然后进行接枝对氧化铝进行改性。
勃姆石(γ-Al00H)含有大量的羟基，本身具有一定吸附能力。近年，很多研究者对勃姆石的改性进行了大量的研究，如吴秀勇利用酯化反应辅助水热法制备勃姆石粉体：该申请(申请号：201220319265.4)将酯化反应生成的水，用于尿素的水解，进而在水热条件下，与铝盐发生反应，在获得酯化反应产品的同时，得到粒度小且均匀的勃姆石粉体；与此同时，水的消耗，还可以促进酯化反应的平衡移动，有利于缩短酯化反应时间，一个反应周期内，可以同时获得有机酯化产物和无机超细粉体，有利于能量的综合利用，节能效果明显；又如梁宇通过5-氨基-1,3,4-噻二唑-2-硫醇中巯基的活性与氯乙酸反应，制备端基为羧酸基团的缓蚀剂，然后通过酯化反应将缓蚀剂与勃姆石中的羟基键合，接枝到勃姆石的表面，制得pH敏感释放型缓蚀防锈填料。
勃姆石是亲水性物质，对水体中的杀虫剂、药物、内分泌干扰物、苯酚、氯仿及衍生物、油类物质等吸附能力弱，而疏水性的有机聚合物能吸附这些物质，但其存在密度小易上浮、且在水中难以润湿等问题；本发明通过将亲水勃姆石与疏水性的有机聚合物接枝到一起，可制备出密度可调、能快速润湿和快速吸附水体中的杀虫剂、药物、内分泌干扰物、苯酚、氯仿及衍生物、油类物质的一种新型勃姆石改性吸附剂。
发明内容
本发明的目的是针对背景技术提出的问题，设计出的一种勃姆石改性吸附剂的制备方法，该方法将勃姆石与含双键有机酸反应得到含双键酯化勃姆石，然后对含双键的酯化勃姆石进行接枝聚合，制备的勃姆石改性吸附剂能快速吸附水体中的杀虫剂、药物、内分泌干扰物、苯酚、氯仿及衍生物、油类物质等，具有吸附量大、吸附速率快、易于回收与再生等特点。
发明人经过大量试验和不懈努力，最终获得了如下的方案：
一种勃姆石改性吸附剂的制备方法,该制备方法包括如下步骤：
(1)勃姆石先加入水中或含一定量对苯二酚的水中或加入二甲苯中进行分散，然后加入含双键的有机酸进行酯化反应，得到含双键的酯化勃姆石，其酯化反应条件为：温度70-100℃下水溶液搅拌反应10-72小时或在二甲苯中(138-145℃)回流10-72小时；
所述勃姆石与含双键有机酸的摩尔比为1:1-1:4；
所述含双键的有机酸为丙烯酸、甲基丙烯酸、丁烯二酸、苯乙烯磺酸、反式-苯乙烯乙酸(4-苯基-3-丁烯酸)中的任一种；
所述勃姆石在水中或含一定量对苯二酚的水中或二甲苯中的浓度为1-8wt％；
(2)在水中加入引发剂、单体、交联剂、乳化剂及酯化勃姆石，得到混合水溶液，在氮气保护、搅拌下对含双键的酯化勃姆石进行接枝聚合，其反应温度为60-80℃、反应时间3-15小时，然后经过离心、过滤、洗涤、真空干燥，即得到为勃姆石改性吸附剂；
所述水溶液中单体浓度为2-10wt％，引发剂添加量为单体的0.5-2wt％，交联剂用量为单体的1-5wt％，乳化剂在混合水溶液中的含量为0.05-2wt％，酯化勃姆石与单体的质量比为1:2-1:10；
所述的引发剂为过硫酸钾、过硫酸钠和过硫酸铵中的任一种；
所述的单体为甲基丙烯酸甲酯、甲基丙烯酸丁酯、甲基丙烯酸十二酯、苯乙烯中的一种或多种；
所述的交联剂为二乙烯基苯、丁二烯中的任一种或多种；
所述的乳化剂为span80、十二烷基硫酸钠、聚乙二醇辛基苯基醚中的一种或多种。
优选地，如上所述的一种勃姆石改性吸附剂的制备方法,所述步骤(2)中的酯化勃姆石也可为含酯化勃姆石的磁性聚合物微球。
本发明采用勃姆石与含双键有机酸反应的原理如下：勃姆石上含有大量羟基，与含双键有机酸中的羧基发生反应，脱水得到含双键的酯。
与现有技术相比，本发明的优点为：
1、通过勃姆石与含双键有机酸的酯化反应，将含双键的活泼单体通过共价键牢固地结合在勃姆石上，进而可以很方便地进行后续的接枝改性，从而克服疏水性吸附剂的润湿问题或亲水性吸附剂的水溶性等问题。
2、本发明制备的勃姆石改性吸附剂含有大量疏水连段，能快速吸附水体中的杀虫剂、药物、内分泌干扰物、苯酚、氯仿及衍生物、油类物质等，具有吸附量大、吸附速率快、易于回收与再生等特点。
附图说明
图1为勃姆石与丙烯酸反应的示意图。
具体实施例
以下结合附图对本发明实施例作进一步说明，为使本发明的目的、技术方案和优点更加清楚，下面本发明中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
一种勃姆石改性吸附剂的制备方法,该制备方法包括如下步骤：
(1)50克勃姆石(0.83mol)加入到800毫升蒸馏水中分散，并进行超声处理，5分钟后加入3克对苯二酚，然后在室温下缓慢加入甲基丙烯酸(154g，1.8mol)，在70℃搅拌下进行20小时的反应，固体产物用去离子水洗涤，最后在真空中50℃干燥20小时即得到酯化勃姆石；
(2)在450毫升水加30g单体(所述单体为甲基丙烯酸甲酯与苯乙烯按质量比为1:1混合而成)、8g span80、1.5g二乙烯基苯、10g酯化的勃姆石和0.20g过硫酸钾，通氮气10分钟，搅拌，在65℃下反应12小时，离心、过滤，然后依次用水、丙酮与己烷洗涤，在50℃下干燥即得到勃姆石改性吸附剂。
实施例2
一种勃姆石改性吸附剂的制备方法,该制备方法包括如下步骤：
(1)将10.0g勃姆石分散于250mL二甲苯中，然后缓慢加入49g丙烯酸，混合物在二甲苯138-145℃回流72小时，然后减压蒸馏去除二甲苯、用乙醚洗涤固体去除杂质，干燥后即得到白色酯化勃姆石粉末；
(2)在450毫升水加50g单体(所述单体为甲基丙烯酸丁酯与苯乙烯按质量比为1:2混合而成)、0.25g十二烷基硫酸钠、1.0g二乙烯基苯和1.0g丁二烯、5g酯化的勃姆石和0.50g过硫酸钾搅拌，在80℃下反应5小时，离心、过滤，然后依次用水洗、丙酮和石油醚洗涤，在80℃下干燥得到勃姆石改性吸附剂。
实施例3
一种勃姆石改性吸附剂的制备方法,该制备方法包括如下步骤：
(1)取6.0g商业勃姆石，加250mL水分散后，再加11.6g丁烯二酸，搅拌加热在二甲苯中138-145℃回流24小时，过滤，乙醇洗涤，在80℃下干燥得到酯化勃姆石；
(2)用12g聚偏氟乙烯、5g四氧化三铁、5g酯化勃姆石和78g二甲亚砜在60℃搅拌12小时配成溶液，然后滴加到蒸馏水中凝胶24小时得到聚合物微球，沥干放入乙醇中浸泡1小时，空气中干燥得到含酯化勃姆石的磁性聚合物微球；
(3)在450毫升水加20g单体(所述单体为甲基丙烯酸丁酯与苯乙烯按质量比为1:1混合而成)、0.10g十二烷基硫酸钠和3g span80、0.5g二乙烯基苯、10g酯化的勃姆石微球和0.20g过硫酸钾，通氮气15分钟，搅拌，在72℃下反应5小时，离心过滤，然后依次用水洗、丙酮和石油醚洗涤，在80℃下干燥得到勃姆石改性磁性微球吸附剂。
我们对实施例1制备的样品，对其吸附性能进行了测定，具体见表1。
表1、勃姆石改性磁性微球吸附剂的吸附性能
Claims (2)
1.一种勃姆石改性吸附剂的制备方法,其特征在于：该制备方法包括如下步骤：
（1）勃姆石先加入水中或含一定量对苯二酚的水中或加入二甲苯中进行分散处理，然后加入含双键的有机酸进行酯化反应，得到含双键的酯化勃姆石，其酯化反应条件为：温度70-100℃下搅拌反应10-72小时或在二甲苯中138-145℃回流10-72小时；
所述勃姆石与含双键有机酸的摩尔比为1:1-1:4；
所述含双键的有机酸为丙烯酸、甲基丙烯酸、丁烯二酸、苯乙烯磺酸、反式-苯乙烯乙酸（4-苯基-3-丁烯酸）中的任一种；
所述勃姆石在水中或含一定量对苯二酚的水中或二甲苯中的浓度为1-8wt%；
（2）在水中加入引发剂、单体、交联剂、乳化剂及酯化勃姆石，得到混合水溶液，在氮气保护、搅拌下对含双键的酯化勃姆石进行接枝聚合，其反应温度为60-80℃、反应时间3-15小时，然后经过离心、过滤、洗涤、真空干燥，即得到为勃姆石改性吸附剂；
所述水溶液中单体浓度为2-10wt%，引发剂添加量为单体的0.5-2wt%，交联剂用量为单体的1-5wt%，乳化剂在混合水溶液中的含量为0.05-2wt%，酯化勃姆石与单体的质量比为1:2-1:10；
所述的引发剂为过硫酸钾、过硫酸钠和过硫酸铵中的任一种；
所述的单体为甲基丙烯酸甲酯、甲基丙烯酸丁酯、甲基丙烯酸十二酯、苯乙烯中的一种或多种；
所述的交联剂为二乙烯基苯、丁二烯中的任一种或多种；
所述的乳化剂为span80、十二烷基硫酸钠、聚乙二醇辛基苯基醚中的一种或多种。
2.如权利要求1所述的一种勃姆石改性吸附剂的制备方法,其特征在于：所述步骤（2）中的酯化勃姆石也可为含酯化勃姆石的磁性聚合物微球。
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