CN110655601B - 一种丙烯酸吸附树脂及其紫外光聚合制备方法和应用 - Google Patents
一种丙烯酸吸附树脂及其紫外光聚合制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种丙烯酸吸附树脂及其紫外光聚合制备方法和应用,属于吸附材料制备技术领域,所述丙烯酸吸附树脂以甲基丙烯酸为功能单体、二甲基丙烯酸乙二醇酯为交联剂、并加入光引发剂、致孔剂和溶剂,通过在紫外光固化制备得到;将得到的丙烯酸吸附树脂应用于去除水体中阳离子染料亚甲基蓝,丙烯酸吸附树脂对亚甲基蓝的平衡吸附量超过650mg/g。本发明采用紫外光固化的方法操作简便、固化速度快、产率高、反应条件温和、绿色环保,成本低,在材料制备方面有较大的发展前景;除此之外,将得到的丙烯酸吸附树脂应用在环境污染处理和环境修复领域具有广泛的应用前景。
Description
技术领域
本发明属于吸附材料制备技术领域,尤其是一种丙烯酸吸附树脂及其紫外光聚合制备方法和应用。
背景技术
丙烯酸系吸附树脂是含有酯基的多孔共聚体,是以丙烯酸系单体与多功能基交联剂在致孔剂、分散剂存在下,进行引发交联,不经功能基化而制成的吸附树脂,其表面疏水部分和亲水部分共存。丙烯酸系吸附树脂具有亲水性强,易湿润,化学稳定性高、机械强度好、耐高压等特性。丙烯酸系吸附树脂既可用于从极性溶剂中吸附非极性溶质,也可用于从非极性溶剂中吸附一定极性的溶质。
紫外光聚合技术是指以紫外光为能源,在紫外光的照射下,光引发剂分解产生自由基,从而引发具有反应性基团的液体快速固化聚合为固体产物的过程。相比于传统的热引发聚合,紫外光引发的制备方法具备耗能低、操作简易、固化速度快、产率高和绿色环保的优点。
随着我国纺丝、皮革、造纸等行业的快速发展,染料废水的排放量也日益增多。其中,亚甲基蓝就属于常见的染料,亚甲基蓝由于含有复杂的芳香结构使其非常稳定而不容易被去除,所以会产生大量有毒的甚至致癌的污染物,给人类和水生生物带来了严重的危害,处理亚甲基蓝染料废水的方法包括光催化降解、吸附、化学氧化和膜过滤等。其中,吸附法因操作简易,绿色环保,成本低廉而成为主要的处理技术。
申请号为201410798813.X的中国发明专利,具有亲水性的丙烯酸酯类吸附树脂的制备及在处理苯酚废水中的应用,具体公开了以丙烯酸酯和合碳碳双键的磺酸钠盐为单体,乙二醇二甲基丙烯酸酯为交联剂,采用一步法合成了具有亲水性的丙烯酸酯类吸附树脂,增强了其与水环境中合苯酚污染物的有效接触,提高该类树脂对苯酚的处理能力。但吸附效果难以满足现有需求。
综上所述,现在需要研究一种紫外光引发的丙烯酸吸附树脂及其制备的方法,同时采用该丙烯酸吸附树脂在去除水体中阳离子染料亚甲基蓝的应用。
发明内容
为解决上述问题,本发明提供一种丙烯酸吸附树脂及其紫外光聚合制备方法和应用,紫外光固化的方法操作简便、固化速度快、产率高、反应条件温和、绿色环保,成本低,在材料制备方面有较大的发展前景,除此之外,将得到的丙烯酸吸附树脂应用在环境污染处理和环境修复领域具有广泛的应用前景。
为实现上述目的,本发明提供的方案如下:
一种丙烯酸吸附树脂,所述丙烯酸吸附树脂以甲基丙烯酸为功能单体、二甲基丙烯酸乙二醇酯为交联剂,并加入光引发剂、致孔剂和溶剂,通过在紫外光固化制备得到,所述丙烯酸吸附树脂的比表面积为45-556m2/g;其中,
所述致孔剂为:甲苯、正庚烷、乙酸乙酯、环己烷和辛醇的一种或几种的混合;
所述溶剂为:乙醇、乙酸乙酯、丙酮的一种或几种的混合;
所述光引发剂为:安息香、安息香二甲醚、(2,4,6-三甲基苯甲酰基)二苯基氧化膦、2-甲基-1-[4-甲硫基苯基]-2-吗琳基-1-丙酮、1-羟基-环己基-苯基甲酮、2-羟基-2-甲基-1-苯基-1-丙酮的一种或几种的混合;
所述的丙烯酸吸附树脂的结构式为:
进一步地,所述的功能单体甲基丙烯酸为溶液总质量的16%~88%,交联剂二甲基丙烯酸乙二醇酯为功能单体质量的0.02%~115%,致孔剂为功能单体质量的5%-150%,溶剂为功能单体质量的20%~100%,光引发剂为功能单体质量的0.5%~6%。
本发明提供所述丙烯酸吸附树脂的制备方法,包括如下步骤:
(1)将功能单体甲基丙烯酸、交联剂二甲基丙烯酸乙二醇酯、光引发剂、致孔剂溶解于溶剂中,室温下进行磁力搅拌6-12小时;
(2)在距离溶液体系8cm~25cm处,采用紫外光引发固化,再将所得产物进行抽滤分离,得到固形物即为粗品;
(3)将所述粗品用乙醇溶液进行索氏提取后,放于温度为50-80℃的真空环境下干燥处理后,密封保存,即得到所述丙烯酸吸附树脂。
进一步地,在步骤(2)中,所述紫外光引发固化过程中,采用紫外光功率为36~1000W,光照固化时间为0.2~12小时。
进一步地,在步骤(3)中,所述索氏提取的时间为48~96小时。
进一步地,在步骤(3)中,所述真空干燥的时间为12~48小时。
进一步地,在步骤(3)中,所述真空干燥后将所得物质经过研磨处理,并研磨至通过80-200目标准筛。
本发明提供所述丙烯酸吸附树脂的应用,是将丙烯酸吸附树脂用于去除水体中阳离子染料。
进一步地,所述阳离子染料为亚甲基蓝、碱性品红、罗丹明B、孔雀绿、中性红任一种。
进一步地,将丙烯酸吸附树脂应用于去除水体中阳离子染料亚甲基蓝,丙烯酸吸附树脂对亚甲基蓝的平衡吸附量超过650mg/g。
本发明所用原料:甲基丙烯酸(MAA),二甲基丙烯酸乙二醇酯(EGDMA),安息香、安息香二甲醚、(2,4,6-三甲基苯甲酰基)二苯基氧化膦、2-甲基-1-[4-甲硫基苯基]-2-吗琳基-1-丙酮、1-羟基-环己基-苯基甲酮、2-羟基-2-甲基-1-苯基-1-丙酮、溶剂乙醇、乙酸乙酯、丙酮,甲苯、正庚烷、乙酸乙酯、环己烷和辛醇等均购自国内外化学原料公司,并没有经过继续提纯而是直接使用的。
本发明具有以下有益效果:
1.本发明采用的紫外光引发聚合,相比传统的热引发聚合,具有操作简便,节约能源,固化速度快,产率高,绿色环保等特点。采用紫外光技术制备出的丙烯酸吸附树脂,不仅固化速率快,并且性能优异,可通过其功能性基团-COOH和交联形成的网状结构对水体中的亚甲基蓝进行有效去除,能在很大程度上提高吸附效率。
2.利用本发明制备方法获得的丙烯酸吸附树脂能对阳离子染料亚甲基蓝进行有效吸附,吸附效果明显;平衡吸附量超过650mg/g。
附图说明
附图1为本发明的制得丙烯酸吸附树脂的电镜扫描图。
附图2为本发明的制得丙烯酸吸附树脂的化学结构示意图。
附图3为本发明的紫外光固化装置图。
附图4为本发明的制备的丙烯酸吸附树脂的红外光谱图。
附图5为本发明的制备的丙烯酸吸附树脂的热重分析图;图中1为聚甲基丙烯酸、即PMAA,2为交联后的聚(甲基丙烯酸-二甲基丙烯酸乙二醇酯)、即Poly(MAA-co-EGDMA)。
具体实施方式
下面结合实施例对本发明作进一步的描述:
本发明的丙烯酸吸附树脂的制备方法实施例:
实施例1
称取5g甲基丙烯酸,0.8g二甲基丙烯酸乙二醇酯,1.5g正庚烷,0.05g的光引发剂安息香二甲醚溶解于装有2.5g乙醇的玻璃瓶中,室温下磁力搅拌6h,在距离溶液体系18cm处,使用功率为1000W的紫外灯进行光照0.2小时,将所得产物进行抽滤,分离出的固体产物用乙醇进行索氏提取48h,于温度60℃真空干燥24h,之后进行研磨过100目标准筛,密封备用。
实施例2
称取5g甲基丙烯酸,1.2g二甲基丙烯酸乙二醇酯,1g甲苯,0.1g的光引发剂安息香溶解于装有2.5g乙酸乙酯的玻璃瓶中,室温下磁力搅拌10h,在距离溶液体系25cm处,使用功率为1000的紫外灯进行光照1小时,将所得产物进行抽滤,分离出的固体产物用乙醇进行索氏提取96h,50℃真空干燥48h,之后进行研磨过100目标准筛,密封备用。
实施例3
称取5g甲基丙烯酸,2.6g二甲基丙烯酸乙二醇酯,2g环己烷,0.05g的光引发剂(2,4,6-三甲基苯甲酰基)二苯基氧化膦溶解于装有5g乙醇的玻璃瓶中,室温下磁力搅拌12h,在距离溶液体系8cm处,使用功率为500W的紫外灯进行光照10小时,将所得产物进行抽滤,分离出的固体产物用乙醇进行索氏提取60h,80℃真空干燥12h,之后进行研磨过80目标准筛,密封备用。
实施例4
称取5g甲基丙烯酸,4.2g二甲基丙烯酸乙二醇酯,3g乙酸乙酯,0.1g的光引发剂2-甲基-1-[4-甲硫基苯基]-2-吗琳基-1-丙酮溶解于装有5g丙酮的玻璃瓶中,室温下磁力搅拌8h,在距离溶液体系12cm处,使用功率为36W的紫外灯进行光照12小时,将所得产物进行抽滤,分离出的固体产物用乙醇进行索氏提取80h,60℃真空干燥24h,之后进行研磨过200目标准筛,密封备用。
实施例5
称取5g甲基丙烯酸,0.01g二甲基丙烯酸乙二醇酯,4g辛醇,0.2g的光引发剂2-羟基-2-甲基-1-苯基-1-丙酮溶解于装有3g乙醇的玻璃瓶中,室温下磁力搅拌8h,在距离溶液体系16cm处,使用功率为90W的紫外灯进行光照6h,将所得产物进行抽滤,分离出的固体产物用乙醇进行索氏提取72h,50℃真空干燥36h,之后进行研磨过120目标准筛,密封备用。
实施例6
称取5g甲基丙烯酸,3g二甲基丙烯酸乙二醇酯,4g致孔剂,0.15g的光引发剂溶解于装有3g溶剂的玻璃瓶中,室温下磁力搅拌4h,在距离溶液体系20cm处,使用功率为150W的紫外灯进行光照4h,将所得产物进行抽滤,分离出的固体产物用乙醇进行索氏提取72h,50℃真空干燥36h,之后进行研磨过160目标准筛,密封备用;
其中,致孔剂是乙酸乙酯、环己烷和辛醇混合得到的组合物;
溶剂是乙醇、乙酸乙酯、丙酮混合得到的组合物;
光引发剂是安息香二甲醚、(2,4,6-三甲基苯甲酰基)二苯基氧化膦混合得到的组合物。
丙烯酸吸附树脂的理化性能检测:
1、对实施例1中所得的丙烯酸吸附树脂进行如下形貌和理化性能测试:
1.1采用SUPRA 55Sapphire型场发射扫描电子显微镜SEM观测其表面形貌(图1);
1.2对丙烯酸吸附树脂进行红外光谱分析(图4);
1.3对聚甲基丙烯酸(即PMAA),交联后的聚(甲基丙烯酸-二甲基丙烯酸乙二醇酯)、即2-Poly(MAA-co-EGDMA)进行热重分析(图5);
2结果分析:
2.1在图1可看出树脂外观呈不规则球状,且球状表面具有褶皱的特点,此外,可看出有孔隙存在于树脂中,这些结构都为吸附过程的进行提供良好的扩散通道。
2.2在图4中3000cm-1~3600cm-1之间出现的宽峰是由于甲基丙烯酸中羧基的O-H拉伸所致,2987cm-1和2946cm-1处为-CH3和CH2中C-H的伸缩对称吸收峰,1705cm-1附近较强的吸收峰为甲基丙烯酸和二甲基丙烯酸乙二醇酯的C=O的伸缩振动峰,而位于1269cm-1和1155cm-1处的是二甲基丙烯酸乙二醇酯的C-O-C伸缩振动吸收峰;说明本发明制备所得丙烯酸树脂上具有多种官能团结构,有助于提升吸附性能。
2.3在图5在低于100℃阶段的失重为PMAA和Poly(MAA-co-EGDMA)中水的重量,重量损失分别为2.1%和1.5%;在100℃之后,发现PAMM的第二阶段的失重在150℃,而Poly(MAA-co-EGDMA)在200℃之后才失重,说明交联后的Poly(MAA-co-EGDMA)热稳定性更高。
进一步的,对实施例2-6所制备得到的丙烯酸吸附树脂进行与实施例1制备的丙烯酸吸附树脂进行相同的表征,实施例2-6制备得到的丙烯酸吸附树脂的表征结果与实施例1高度吻合,说明了所制备的产品重现性极好。
本发明制备的丙烯酸吸附树脂应用于亚甲基蓝的吸附实施例:
实施例7
准确配制50mL浓度为180mg/L的亚甲基蓝溶液,调节pH=8,称取质量为0.01g的实施例1制作得到的丙烯酸吸附树脂,在298K下恒温震荡12h,取上层清液,通过紫外光分光光度计对吸附后的溶液进行测定;
根据公式(1)计算丙烯酸树脂的吸附量。
式中,qe(mg/g)是平衡吸附容量;C0和Ce(mg/L)分别是溶液的初始浓度和平衡浓度;W(g)是吸附剂的质量;V(L)是溶液的体积。
测定结果为:对亚甲基蓝的吸附量为720mg/g。
实施例8
配制浓度为250mg/L的亚甲基蓝溶液50mL于锥形瓶中,调节pH=8,加入0.01g的实施例2制作得到的丙烯酸吸附树脂,在298K下恒温震荡12h,取上层清液,通过紫外光分光光度计对吸附后的溶液进行测定。测定结果为:对亚甲基蓝的吸附量为760mg/g。
实施例9
准确配制一系列不同浓度的亚甲基蓝溶液各50mL于锥形瓶中,调节溶液的pH=8,分别加入0.01g的实施例4制作得到的丙烯酸吸附树脂,分别在298K、308K、318K下恒温震荡12h,取上层清液,通过紫外光分光光度计对吸附后的溶液进行测定。测定结果为:在298K、308K、318K时,树脂对亚甲基蓝的最大吸附量分别为791mg/g、725mg/g、676mg/g,说明树脂对亚甲基蓝的吸附是放热反应。
实施例10
配制浓度为200mg/L的亚甲基蓝溶液50mL于锥形瓶中,调节pH=8,加入0.016g的实施例3制作得到的丙烯酸吸附树脂,在298K下恒温震荡24h,取上层清液,通过紫外光分光光度计对吸附后的溶液进行测定。测定结果为:对亚甲基蓝的吸附量为736mg/g。
本发明制备的丙烯酸吸附树脂应用于阳离子染料的吸附实验:
采用实施例7的吸附方法依次用于去除水中阳离子染料,区别在于将亚甲基蓝溶液分别替换为等浓度的甲基紫、碱性品红、罗丹明B、孔雀绿、中性红溶液;对阳离子染料的吸附量测定结果如表1。
表1吸附量结果
由表1可知,本发明制得的丙烯酸吸附树脂对亚甲基蓝、碱性品红、罗丹明B、孔雀绿、中性红几种阳离子染料均有较好的吸附性能。
上述虽然结合附图对本发明的具体实施方式进行了描述,但并非对发明保护范围的限制,所属领域技术人员应该明白,在本发明的技术方案的基础上,本领域技术人员不需要付出创造性劳动即可做出的各种修改或变形仍在本发明的保护范围内。
Claims (9)
1.一种丙烯酸吸附树脂,其特征在于,所述丙烯酸吸附树脂以甲基丙烯酸为功能单体、二甲基丙烯酸乙二醇酯为交联剂,并加入光引发剂、致孔剂和溶剂,通过在紫外光固化制备得到,所述丙烯酸吸附树脂的比表面积为45-556m2/g;其中,
所述的功能单体甲基丙烯酸为溶液总质量的16%~88%,交联剂二甲基丙烯酸乙二醇酯为功能单体质量的0.02%~115%;
所述致孔剂为:正庚烷、乙酸乙酯、环己烷和辛醇的一种或几种的混合;
所述溶剂为:乙醇、乙酸乙酯、丙酮的一种或几种的混合;
所述光引发剂为:安息香、安息香二甲醚、2-甲基-1-(4-甲硫基苯基)-2-吗啉基-1-丙酮、1-羟基-环己基-苯基甲酮、2-羟基-2-甲基-1-苯基-1-丙酮的一种或几种的混合;
所述的丙烯酸吸附树脂的结构式为:
2.根据权利要求1所述丙烯酸吸附树脂,其特征在于,致孔剂为功能单体质量的5%-150%,溶剂为功能单体质量的20%~100%,光引发剂为功能单体质量的0.5%~6%。
3.一种如权利要求1-2任一项所述丙烯酸吸附树脂的制备方法,其特征在于,包括如下步骤:
(1)将功能单体甲基丙烯酸、交联剂二甲基丙烯酸乙二醇酯、光引发剂、致孔剂溶解于溶剂中,室温下进行磁力搅拌6-12小时;
(2)在距离溶液体系8cm~25cm处,采用紫外光引发固化,再将所得产物进行抽滤分离,得到固形物即为粗品;所述紫外光引发固化是采用紫外光功率为36~1000W进行光照固化时间为0.2~12小时;
(3)将所述粗品用乙醇溶液进行索氏提取后,放于温度为50-80℃的真空环境下干燥处理后,密封保存,即得到所述丙烯酸吸附树脂。
4.根据权利要求3所述丙烯酸吸附树脂的制备方法,其特征在于,在步骤(3)中,所述索氏提取的时间为48~96小时。
5.根据权利要求3所述丙烯酸吸附树脂的制备方法,其特征在于,在步骤(3)中,所述真空干燥的时间为12~48小时。
6.根据权利要求3所述丙烯酸吸附树脂的制备方法,其特征在于,在步骤(3)中,所述真空干燥后将所得物质经过研磨处理,并研磨至通过80-200目标准筛。
7.一种如权利要求1-2任一项所述丙烯酸吸附树脂的应用,其特征在于,是将丙烯酸吸附树脂用于去除水体中阳离子染料。
8.根据权利要求7所述丙烯酸吸附树脂的应用,其特征在于,所述阳离子染料为亚甲基蓝、碱性品红、罗丹明B、孔雀绿、中性红任一种。
9.根据权利要求7所述丙烯酸吸附树脂的应用,其特征在于,将丙烯酸吸附树脂应用于去除水体中阳离子染料亚甲基蓝,丙烯酸吸附树脂对亚甲基蓝的平衡吸附量超过650mg/g。
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丙烯酸系吸附树脂研究进展;杨维本 等;《材料科学与工程学报》;20051031;第23卷(第5期);618-620,628 * |
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甲基丙烯酸基质的毛细管电色谱整体柱的制备与应用;左国强 等;《分析化学》;20080930;第36卷(第9期);1233-1237 * |
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