CN105854838A - 一种选择性吸附剂磺化聚(苯乙烯-马来酸酐)纳米微球的制备方法及其用途 - Google Patents
一种选择性吸附剂磺化聚(苯乙烯-马来酸酐)纳米微球的制备方法及其用途 Download PDFInfo
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Abstract
本发明公开了一种选择性吸附剂磺化聚(苯乙烯‑马来酸酐)纳米微球的制备方法及其用途,采用沉淀聚合法制备交替型聚(苯乙烯‑马来酸酐)纳米微球;再将得到的聚(苯乙烯‑马来酸酐)纳米微球用浓硫酸进行磺化,得到磺化的聚(苯乙烯‑马来酸酐),即目标产物。本发明所得产物中引入了磺酸基团,使其微球表面的电荷密度增加;本发明所得磺化8h的产物相比于未磺化的聚(苯乙烯‑马来酸酐)纳米微球对亚甲基蓝的吸附量有了显著的提高;本发明所得产物对亚甲基蓝、罗丹明B、甲基橙和刚果红的吸附研究表明磺化聚(苯乙烯‑马来酸酐)纳米微球对阳离子染料具有选择性吸附作用。
Description
一、技术领域
本发明涉及一种纳米微球的制备方法,具体的说是一种选择性吸附剂磺化聚(苯乙烯-马来酸酐)纳米微球的制备方法及其用途,属于功能材料领域。
二、背景技术
近年来,合成染料在纺织、造纸、食品、制药和化妆等制造业中的应用越来越多,大量染料废水对环境的污染也越来越严重,合理有效的处理染料废水逐渐演变成一个全球性的问题。合成染料因含有复杂的苯环结构而在光、热、氧化剂等条件下仍然稳定难以降解,一旦这些染料分解成有毒、致突变和致癌的物质,将会对水生态系统和人类的健康产生极大的危害和威胁。在过去的几年里,人们开发应用了很多方法来处理废水中的染料,主要处理技术有絮凝、膜分离、离子交换、过滤、化学氧化、电解、微生物降解、光催化降解和吸附等。其中,吸附法因成本低、效率高等优势而被广泛应用于废水处理中。目前,传统的吸附剂主要有活性炭、粘土、金属氧化物、凝胶和多糖等,但是这些吸附剂存在的问题是吸附量小、难以降解等,例如,专利号为201510647899.0(授权公号为CN 105251466 A)的中国发明专利《一种磁性壳聚糖木质素磺酸盐氧化石墨烯吸附剂的制备方法及用途》,以制备的磁性壳聚糖木质素磺酸盐氧化石墨烯作为吸附剂对亚甲基蓝进行吸附,发现当吸附剂用量为10mg、亚甲基蓝的浓度为200ppm时,其吸附量为252mg/g;专利号为201510513765.X(授权公号为CN 105126743 A)的中国发明专利《一种磁性粘土吸附材料的制备及回收方法》,将制备的磁性粘土作为吸附剂,发现当吸附剂用量为10mg、亚甲基蓝的浓度为20ppm时,其最高吸附量为89.62mg/g;专利号为201510251702.1(授权公号为CN 105080499 A)的中国发明专利《一种亚甲基蓝染料吸附剂及其制备和使用方法》,将桂圆壳粉作为吸附剂,发现当吸附剂用量为50mg、亚甲基蓝的浓度为150ppm时,其最高吸附量为116.65mg/g。因此,寻求一种具有生物相容性和生物可降解性的高效吸附剂显得尤为重要。
三、发明内容
本发明旨在提供一种选择性吸附剂磺化聚(苯乙烯-马来酸酐)纳米微球的制备方法及其用途,以提高对阳离子有机染料的选择性吸附性能。
本发明选择性吸附剂磺化聚(苯乙烯-马来酸酐)纳米微球的制备方法,包括如下步骤:
步骤1,采用沉淀聚合法制备聚(苯乙烯-马来酸酐)纳米微球
将1.47g的马来酸酐单体和0.03g的引发剂加入盛有20mL反应介质的三口烧瓶中,超声分散均匀后,于室温下通氮气30分钟,缓慢升温至80℃,然后将1.56g苯乙烯单体和200μL交联剂溶解在10mL反应介质中,以3~5d/s的速度滴入三口烧瓶中,在氮气氛围中于80℃反应5h,反应结束后离心,并用乙醇清洗,于35℃真空干燥24h,得到聚(苯乙烯-马来酸酐)纳米微球,备用。步骤1中将容易均聚的苯乙烯逐滴加入到马来酸酐和偶氮二异丁腈的混合溶液里,更易制备交替型的聚(苯乙烯-马来酸酐)。
所述引发剂为偶氮二异丁腈;
所述交联剂为二乙烯基苯;
所述反应介质为直链烷烃,优选为正丁酸乙酯;
步骤2,制备磺化聚(苯乙烯-马来酸酐)纳米微球
取步骤1制备的聚(苯乙烯-马来酸酐)纳米微球0.4g,加入到盛有4mL质量浓度98%的浓硫酸的单口烧瓶中,超声分散均匀,于40℃磁力搅拌2-15h,通过改变磺化时间来控制聚(苯乙烯-马来酸酐)的磺化度,磺化反应结束后,用去离子水洗涤至离心所得上清液为中性,于35℃真空干燥24h,得到磺化聚(苯乙烯-马来酸酐)纳米微球。
本发明选择性吸附剂磺化聚(苯乙烯-马来酸酐)纳米微球的用途,作为阳离子有机染料的选择性吸附剂。
所述阳离子有机染料包括亚甲基蓝、罗丹明B。
本发明选择性吸附剂磺化聚(苯乙烯-马来酸酐)纳米微球作为阳离子有机染料的选择性吸附剂的吸附过程如下:
将20mg磺化聚(苯乙烯-马来酸酐)纳米微球分散于盛有100mL浓度为100ppm的中性亚甲基蓝溶液的锥形瓶中,将锥形瓶置于25℃、150r/min的恒温水浴振荡箱中震荡,吸附24h后达到平衡。分别在预设的时间内取0.5mL的亚甲基蓝溶液,稀释10倍至5mL,用紫外-可见分光光度计测其在645nm处的吸光度,根据染料浓度-吸光度的标准曲线计算吸附剂的平衡吸附量。
聚(苯乙烯-马来酸酐)是一种无毒、无刺激、生物相容和生物降解的合成交替型共聚物,可通过对聚(苯乙烯-马来酸酐)进行一定的改性从而引入表面活性基团,使其具有更高的反应性。
为了提高聚(苯乙烯-马来酸酐)在水中的分散性,首先采用浓硫酸对聚(苯乙烯-马来酸酐)纳米微球进行磺化得到磺化聚(苯乙烯-马来酸酐)纳米微球,磺化聚(苯乙烯-马来酸酐)表面带有大量的亲水性磺酸基团。由于吸附过程主要受电荷相互作用的影响,因此,磺化时间等因素必然会大大影响磺化聚(苯乙烯-马来酸酐)对染料的吸附。考虑到磺酸基团带有的大量负电荷,磺化聚(苯乙烯-马来酸酐)应是一种极好的阳离子染料吸附剂。
尽管聚(苯乙烯-马来酸酐)纳米微球的报导很多,但是很少有应用于吸附有机染料的研究,也很少有通过改性来提高其对有机染料的吸附量的报导。
本发明的有益效果体现在:
1、本发明制备的磺化聚(苯乙烯-马来酸酐)纳米微球,具有良好的生物相容性和生物可降解性。
2、本发明制备的磺化聚(苯乙烯-马来酸酐)纳米微球对有机染料的吸附量相比于未磺化的聚(苯乙烯-马来酸酐)有了显著的提高,且对阳离子有机染料具有选择性吸附性能。
四、附图说明
图1为本发明实施例1所制备的交替型聚(苯乙烯-马来酸酐)的核磁共振碳谱(13C NMR)图;
图2为本发明实施例1所制备的交替型聚(苯乙烯-马来酸酐)(a)和磺化8小时的聚(苯乙烯-马来酸酐)(b)的红外谱(FT-IR)图;
图3为本发明实施例1制备的交替型聚(苯乙烯-马来酸酐)(a)和磺化8小时的聚(苯乙烯-马来酸酐)(b)对有机染料亚甲基蓝的吸附曲线图;
图4为本发明实施例1制备的交替型聚(苯乙烯-马来酸酐)(a)和磺化8小时的聚(苯乙烯-马来酸酐)(b)对有机染料亚甲基蓝吸附量随pH的变化曲线;
图5为本发明实施例1制备的交替型聚(苯乙烯-马来酸酐)和磺化8小时的聚(苯乙烯-马来酸酐)对有机染料亚甲基蓝、罗丹明B、甲基橙、刚果红的吸附柱状图(a)和吸附前后的光学照片(b)。
五、具体实施方式
实施例1:
本实施例首先按如下步骤制备有机染料吸附剂交替型聚(苯乙烯-马来酸酐)和磺化聚(苯乙烯-马来酸酐)纳米微球:
1、制备交替型聚(苯乙烯-马来酸酐)纳米微球
采用沉淀聚合法制备聚(苯乙烯-马来酸酐)纳米微球。具体方法如下:将1.47g的马来酸酐单体和0.03g的引发剂偶氮二异丁腈加入盛有20mL正丁酸乙酯的三口烧瓶中,超声分散均匀后,于室温下通氮气30分钟,缓慢升温至80℃,然后将1.56g的苯乙烯单体和200μL的二乙烯基苯溶解在10mL正丁酸乙酯中,以3~5d/s的速度缓慢滴入三口烧瓶,通氮气水浴反应5h,将得到的产品离心收集,并用乙醇清洗三次,于35℃真空干燥24h,备用。
图1为本实施例所得交替型聚(苯乙烯-马来酸酐)的核磁共振碳谱(13C NMR)图。从图1中可以看出在化学位移δ=141.5×10-6,146×10-6及145~147.5×10-6处没有任何特征吸收峰出现,表明产物的结构里没有St-St-Ma,Ma-St-St和St-St-St链段,化学位移δ=(137~139)×10-6处为苯环上季碳(C7)的特征峰,此特征吸收峰对应聚(苯乙烯-马来酸酐)的交替结构(St-Ma-St),说明具有严格交替结构的交替型聚(苯乙烯-马来酸酐)纳米微球被成功的制备出来。
2、制备磺化8小时的聚(苯乙烯-马来酸酐)纳米微球
取步骤1制备的聚(苯乙烯-马来酸酐)纳米微球0.4g,加入到盛有4mL浓硫酸的单口烧瓶中,超声分散均匀,于40℃磁力搅拌8小时。磺化反应结束后,用去离子水洗涤数次直至离心所得上清液为中性,将得到的磺化聚(苯乙烯-马来酸酐)纳米微球于35℃真空干燥24h,备用。
图2为本发明实施例1所制备的交替型聚(苯乙烯-马来酸酐)(a)和磺化8小时的聚(苯乙烯-马来酸酐)(b)的红外谱(FT-IR)图。从,2中可以看出,相比于从图2(a),图2(b)在1009、1034、1125和1172cm-1处出现了新的特征吸收峰,1034cm-1的特征峰为碳硫键的振动峰,1009、1125和1172cm-1的特征峰归属于磺化8小时的聚(苯乙烯-马来酸酐)苯环上磺酸基团-SO3H的O=S=O的伸缩振动,由于-SO3H的影响,1632cm-1处的吸收峰移动至1599cm-1,结果表明磺化之后磺酸基团已成功修饰到磺化8小时的聚(苯乙烯-马来酸酐)纳米微球上。
为验证本实施例所得聚(苯乙烯-马来酸酐)和磺化8小时的聚(苯乙烯-马来酸酐)对有机染料亚甲基蓝具有良好的吸附作用,作如下测试:
聚(苯乙烯-马来酸酐)和磺化8小时的聚(苯乙烯-马来酸酐)各20mg分别置于盛有100mL,浓度为100ppm的中性亚甲基蓝溶液的锥形瓶中。将锥形瓶置于25℃,150r/min的恒温水浴振荡箱中进行吸附实验。分别在预设的时间内取0.5mL的亚甲基蓝溶液,稀释10倍至5mL,用紫外-可见分光光度计测其在645nm处的吸光度,根据染料浓度-吸光度的标准曲线计算吸附剂对各染料的平衡吸附量。
图3为本发明实施例1所制备的交替型聚(苯乙烯-马来酸酐)(a)和磺化8小时的聚(苯乙烯-马来酸酐)(b)对有机染料亚甲基蓝的吸附曲线图。从图3中可以看出,磺化8小时的聚(苯乙烯-马来酸酐)对亚甲基蓝的吸附量为520.39mg/g,未磺化的聚(苯乙烯-马来酸酐)对亚甲基蓝的吸附量为179.11mg/g,说明磺化之后聚(苯乙烯-马来酸酐)对亚甲基蓝的吸附量有了明显的提高;在吸附开始的前30分钟吸附量增加最快,表明聚(苯乙烯-马来酸酐)和磺化8小时的聚(苯乙烯-马来酸酐)对亚甲基蓝的吸附作用是一个快速发生的过程。
为验证溶液pH对本实施例所得聚(苯乙烯-马来酸酐)和磺化8小时的聚(苯乙烯-马来酸酐)吸附染料的影响,作如下测试:
聚(苯乙烯-马来酸酐)和磺化8小时的聚(苯乙烯-马来酸酐)各20mg分别置于盛有100mL,浓度为100ppm,pH分别为2、4、6、8、10的亚甲基蓝溶液的锥形瓶中。将锥形瓶置于25℃,150r/min的恒温水浴振荡箱中进行吸附实验。24小时后吸附达到平衡,用紫外-可见分光光度计测其在645nm处的吸光度,根据染料浓度-吸光度的标准曲线计算吸附剂对各染料的平衡吸附量。
图4为本发明实施例1所制备的交替型聚(苯乙烯-马来酸酐)(a)和磺化8小时的聚(苯乙烯-马来酸酐)(b)对有机染料亚甲基蓝吸附量随pH的变化曲线。从图中可以看出,随着pH的增大,聚(苯乙烯-马来酸酐)和磺化8小时的聚(苯乙烯-马来酸酐)对有机染料亚甲基蓝吸附量逐渐增大,表明碱性环境下更有利于聚(苯乙烯-马来酸酐)和磺化8小时的聚(苯乙烯-马来酸酐)对有机染料亚甲基蓝的吸附。
为验证本实施例所得聚(苯乙烯-马来酸酐)和磺化8小时的聚(苯乙烯-马来酸酐)对阳离子有机染料具有选择性吸附作用,作如下测试:
聚(苯乙烯-马来酸酐)和磺化8小时的聚(苯乙烯-马来酸酐)各20mg分别置于盛有100mL,浓度为100ppm的中性亚甲基蓝、罗丹明B、甲基橙、刚果红溶液的锥形瓶中。将锥形瓶置于25℃,150r/min的恒温水浴振荡箱中进行吸附实验。24小时后吸附达到平衡,用紫外-可见分光光度计测其在645nm处的吸光度,根据染料浓度-吸光度的标准曲线计算吸附剂对各染料的平衡吸附量。
图5为本发明实施例1制备的交替型聚(苯乙烯-马来酸酐)和磺化8小时的聚(苯乙烯-马来酸酐)对有机染料亚甲基蓝、罗丹明B、甲基橙、刚果红的吸附柱状图(a)和吸附前后的光学照片(b)。从图中可以看出,聚(苯乙烯-马来酸酐)和磺化8小时的聚(苯乙烯-马来酸酐)对有机染料亚甲基蓝、罗丹明B的吸附量远远大于对甲基橙、刚果红的吸附量,表明聚(苯乙烯-马来酸酐)和磺化8小时的聚(苯乙烯-马来酸酐)对阳离子有机染料具有选择性吸附作用。
实施例2:
本实施例按实施例1相同的方式制备聚(苯乙烯-马来酸酐)和磺化聚(苯乙烯-马来酸酐),区别仅在于步骤2中磺化时间为2小时。
经表征,本实施例所得的磺化2小时的聚(苯乙烯-马来酸酐)对亚甲基蓝的吸附量为348.00mg/g。
实施例3:
本实施例按实施例1相同的方式制备聚(苯乙烯-马来酸酐)和磺化聚(苯乙烯-马来酸酐),区别仅在于步骤2中磺化时间为5小时。
经表征,本实施例所得的磺化5小时的聚(苯乙烯-马来酸酐)对亚甲基蓝的吸附量为486.83mg/g。
实施例4:
本实施例按实施例1相同的方式制备聚(苯乙烯-马来酸酐)和磺化聚(苯乙烯-马来酸酐),区别仅在于步骤2中磺化时间为12小时。
经表征,本实施例所得的磺化12小时的聚(苯乙烯-马来酸酐)对亚甲基蓝的吸附量为479.09mg/g。
实施例5:
本实施例按实施例1相同的方式制备聚(苯乙烯-马来酸酐)和磺化聚(苯乙烯-马来酸酐),区别仅在于步骤2中磺化时间为15小时。
经表征,本实施例所得的磺化15小时的聚(苯乙烯-马来酸酐)对亚甲基蓝的吸附量为289.12mg/g。
Claims (7)
1.一种选择性吸附剂磺化聚(苯乙烯-马来酸酐)纳米微球的制备方法,其特征在于包括如下步骤:
步骤1,采用沉淀聚合法制备聚(苯乙烯-马来酸酐)纳米微球
将1.47g的马来酸酐单体和0.03g的引发剂加入盛有20mL反应介质的三口烧瓶中,超声分散均匀后,于室温下通氮气30分钟,缓慢升温至80℃,然后将1.56g苯乙烯单体和200μL交联剂溶解在10mL反应介质中,以3~5d/s的速度滴入三口烧瓶中,在氮气氛围中于80℃反应5h,反应结束后离心,并用乙醇清洗,于35℃真空干燥24h,得到聚(苯乙烯-马来酸酐)纳米微球;
步骤2,制备磺化聚(苯乙烯-马来酸酐)纳米微球
取步骤1制备的聚(苯乙烯-马来酸酐)纳米微球0.4g,加入到盛有4mL质量浓度为98%的硫酸溶液的单口烧瓶中,超声分散均匀,于40℃磁力搅拌2-15h,通过改变磺化时间来控制聚(苯乙烯-马来酸酐)的磺化度,磺化反应结束后,用去离子水洗涤至离心所得上清液为中性,于35℃真空干燥24h,得到磺化聚(苯乙烯-马来酸酐)纳米微球。
2.根据权利要求1所述的制备方法,其特征在于:
步骤1中所述引发剂为偶氮二异丁腈。
3.根据权利要求1所述的制备方法,其特征在于:
步骤1中所述交联剂为二乙烯基苯。
4.根据权利要求1所述的制备方法,其特征在于:
步骤1中所述反应介质为直链烷烃。
5.根据权利要求1或4所述的制备方法,其特征在于:
步骤1中所述反应介质为正丁酸乙酯。
6.一种权利要求1制备的选择性吸附剂磺化聚(苯乙烯-马来酸酐)纳米微球的用途,其特征在于:作为阳离子有机染料的选择性吸附剂。
7.根据权利要求6所述的用途,其特征在于:
所述阳离子有机染料包括亚甲基蓝、罗丹明B。
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109806853A (zh) * | 2019-02-28 | 2019-05-28 | 天津科技大学 | 一种用于吸附碱性染料的阴离子型的支撑离子液体材料制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101422724A (zh) * | 2008-11-25 | 2009-05-06 | 华中师范大学 | 多孔吸附材料的制备方法及应用 |
CN102049242A (zh) * | 2011-01-08 | 2011-05-11 | 广州康盛生物科技有限公司 | 一种阴离子胆红素吸附树脂及其制备方法 |
CN105107474A (zh) * | 2015-08-03 | 2015-12-02 | 佛山市博新生物科技有限公司 | 一种用于血液净化的螯合型吸附剂及制备方法 |
-
2016
- 2016-04-13 CN CN201610231520.2A patent/CN105854838A/zh active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101422724A (zh) * | 2008-11-25 | 2009-05-06 | 华中师范大学 | 多孔吸附材料的制备方法及应用 |
CN102049242A (zh) * | 2011-01-08 | 2011-05-11 | 广州康盛生物科技有限公司 | 一种阴离子胆红素吸附树脂及其制备方法 |
CN105107474A (zh) * | 2015-08-03 | 2015-12-02 | 佛山市博新生物科技有限公司 | 一种用于血液净化的螯合型吸附剂及制备方法 |
Non-Patent Citations (1)
Title |
---|
YAPING LI ET AL.,: "Preparation and characterization of sulfonated poly(styrene-alt-maleic anhydride) and its selective removal ofcationic dyes", 《COLLOIDS AND SURFACES A: PHYSICOCHEM. ENG. ASPECTS》 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109806853A (zh) * | 2019-02-28 | 2019-05-28 | 天津科技大学 | 一种用于吸附碱性染料的阴离子型的支撑离子液体材料制备方法 |
CN109806853B (zh) * | 2019-02-28 | 2021-06-25 | 天津科技大学 | 一种用于吸附碱性染料的阴离子型的支撑离子液体材料制备方法 |
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