CN114736399B - 高弹性羧甲基壳聚糖/酸化碳纳米管复合水凝胶及其制备方法 - Google Patents
高弹性羧甲基壳聚糖/酸化碳纳米管复合水凝胶及其制备方法 Download PDFInfo
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Abstract
本发明属于高分子凝胶及吸附分离技术领域,公开一种高弹性羧甲基壳聚糖/酸化碳纳米管复合水凝胶及其制备方法。采用一锅法,以羧甲基壳聚糖为原料,与亚氨基二乙酸和酸化多壁碳纳米管通过酰胺化反应交联,得到三维交联多孔水凝胶。本发明工艺简单,反应条件温和。所得水凝胶力学性能优异,能够承受自身78倍以上的重量,且在受力后弹性形变可完全恢复。该水凝胶结构稳定,在吸附锶离子后,通过洗脱可实现多次循环使用,在吸附分离领域具有良好的应用前景。
Description
技术领域
本发明属于高分子凝胶及吸附分离技术领域,具体涉及一种高弹性羧甲基壳聚糖/酸化碳纳米管复合水凝胶及其制备方法。
背景技术
壳聚糖水凝胶在吸附分离方面有重要应用。壳聚糖本身含有羟基、氨基、羧基等活性基团,易于进行化学接枝、交联、复合等改性,利于其与多种有机分子和金属离子产生化学作用。但壳聚糖难溶于水,一般需在强酸性条件下进行改性。
羧甲基壳聚糖是壳聚糖的羧甲基化衍生物。其具有与壳聚糖相似的化学性质,但水溶性优异,在进行改性时操作简单,改性分子选择范围广,因而在进行吸附材料合成时具有明显优势。目前,以羧甲基壳聚糖为基体制备的吸附材料力学性能通常都较弱,实用性不高,主要表现为承受压力时易碎。并且,吸附反应通常于水中进行,导致凝胶在吸水溶胀后脆性增加,机械性能更为脆弱,这非常不利于其回收利用。如CN110483662A公开了一种羧甲基壳聚糖交联凝胶,这类水凝胶一般力学性能不佳,很难承受实际应用中的各种外力。因而增强羧甲基壳聚糖凝胶的机械性能,对于其实际应用极为重要。
发明内容
针对上述问题,本发明提供一种高弹性羧甲基壳聚糖/酸化碳纳米管复合水凝胶的制备方法。将羧甲基壳聚糖通过缩合反应与亚氨基二乙酸及酸化多壁碳纳米管共价交联,利用酸化多壁碳纳米管的机械增强作用,及反应后形成的大量氢键增加材料弹性,得到高弹性三维交联多孔结构凝胶。
本发明涉及的高弹性羧甲基壳聚糖/酸化碳纳米管复合水凝胶,其制备方法包括如下步骤:
(1)将亚氨基二乙酸溶于水中,用NaOH溶液将其调至中性。
(2)在步骤(1)的亚氨基二乙酸溶液中加入酸化多壁碳纳米管和羧甲基壳聚糖,搅拌均匀。
步骤(2)中,羧甲基壳聚糖与酸化多壁碳纳米管的质量比为(20-100):1。
步骤(2)中,羧甲基壳聚糖与亚氨基二乙酸的摩尔比为(1-5):1。
(3)将酰胺化反应用缩合剂加入步骤(2)的混合溶液中,室温下搅拌均匀。
步骤(3)中缩合剂总量与亚氨基二乙酸的摩尔比至少为1:1。
进一步的,缩合剂为酰胺化反应常用缩合剂,可选为1-(3-二甲氨基丙基)-3-乙基碳二亚胺(EDC)、1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐(EDC·HCl)、二环己基碳二亚胺(DCC)中的任意一种或几种与4-二甲氨基吡啶(DMAP)、N-羟基琥珀酰亚胺(NHS)、1-羟基苯并三唑(HOBT)中的任意一种或几种的联用,优选为EDC与NHS联用,联用时EDC与NHS的摩尔比为1:1。
(4)将步骤(3)中的混合溶液转移到模具中在室温下固化,一般60min可固化。
本发明限定羧甲基壳聚糖与亚氨基二乙酸摩尔比为(1-5):1,在此比例范围内可以得到力学性能优良的高弹性羧甲基壳聚糖/酸化碳纳米管复合水凝胶,如果低于1:1,水凝胶孔隙率和机械强度均较低,如果高于5:1则弹性不佳。
本发明限定羧甲基壳聚糖与酸化多壁碳纳米管的质量比为(20-100):1,在此比例范围内可以得到力学性能优良的高弹性羧甲基壳聚糖/酸化碳纳米管复合水凝胶,如果低于此范围,水凝胶脆性较高易破裂,如果高于此范围,水凝胶弹性模量较低。
本发明涉及的反应机理为:利用羧甲基壳聚糖的氨基和亚氨基二乙酸、酸化多壁碳纳米管的羧基反应生成酰胺键,其中,亚氨基二乙酸和酸化多壁碳纳米管均起到交联作用,生成的大量酰胺基团之间形成了多重氢键,因而极大提高了弹性。
相比于现有技术,本发明技术方案的优点在于:
(1)本发明使用一锅法,反应条件温和,通过缩合反应形成三维网络结构凝胶。
(2)本发明制备的羧甲基壳聚糖水凝胶具有优异的弹性和韧性,可以承受自身重量78倍的压力,且多次压缩循环形变可完全恢复,有利于使用时操作和延长寿命。
本发明制备的高弹性羧甲基壳聚糖/酸化碳纳米管复合水凝胶有优良的吸附性能,且多次使用吸附容量无明显下降。
附图说明
图1为本发明制备水凝胶涉及的反应机理示意图。
图2为本发明实施例1制备的高弹性羧甲基壳聚糖/酸化碳纳米管复合水凝胶(图中的弹性水凝胶)的红外光谱图。
图3为本发明实施例1制备的高弹性羧甲基壳聚糖/酸化碳纳米管复合水凝胶的SEM图。
图4为本发明对比例1制备的水凝胶SEM图。
图5为本发明实施例1制备的高弹性羧甲基壳聚糖/酸化碳纳米管复合水凝胶的力学性能展示图。
图6为本发明对比例3制备的水凝胶压缩曲线图。
图7为本发明实施例1制备的高弹性羧甲基壳聚糖/酸化碳纳米管复合水凝胶的循环压缩曲线图。
图8为本发明实施例1制备的高弹性羧甲基壳聚糖/酸化碳纳米管复合水凝胶对Sr2+吸附-解吸的剩余吸附量变化图。
具体实施方式
本发明不局限于下列具体实施方式,本领域一般技术人员根据本发明公开的内容,可以采用其他多种具体实施方式实施本发明的,或者凡是采用本发明的设计结构和思路,做简单变化或更改的,都落入本发明的保护范围。需要说明的是,在不冲突的情况下,本发明中的实施例及实施例中的特征可以相互组合。
以下结合具体实施例对本发明进行进一步的阐述,下述实施例中所用的材料、试剂均可从商业途径获得。
实施例1
(1)称取0.5g亚氨基二乙酸,加入20mL去离子水中,搅拌均匀,调节pH值至7-9。
(2)称取0.0328g酸化多壁碳纳米管,加入到步骤(1)的亚氨基二乙酸溶液中,搅拌均匀,得混合溶液。
(3)称取3.28g羧甲基壳聚糖,加入到步骤(2)的混合液中,搅拌均匀,得到新的混合液。
(4)向步骤(3)的混合溶液中加入0.72gEDC·HCl和0.44gNHS,搅拌均匀,转移至模具中,室温固化1h。
其中图5为实施例1制备的高弹性羧甲基壳聚糖/酸化碳纳米管复合水凝胶的力学性能展示图,图7为实施例1制备的高弹性羧甲基壳聚糖/酸化碳纳米管复合水凝胶的循环压缩曲线,从图5及图7中可以看出水凝胶具有优异的弹性。
实施例1制备的高弹性羧甲基壳聚糖/酸化碳纳米管复合水凝胶采用静态吸附法进行对Sr2+吸附后,用NaOH洗脱法解吸附,再次吸附,循环5次,得到的吸附量变化图,如图8所示,从中可见,多次使用后吸附性能没有明显下降。
实施例2
(1)称取0.5g亚氨基二乙酸,加入20mL去离子水中,搅拌均匀,调节pH值至7-9。
(2)称取0.0328g酸化多壁碳纳米管,加入到步骤(1)的亚氨基二乙酸溶液中,搅拌均匀,得混合溶液。
(3)称取2.46g羧甲基壳聚糖,加入到步骤(2)的混合液中,搅拌均匀,得到新的混合液。
(4)向步骤(3)的混合溶液中加入0.72gEDC·HCl和0.44gNHS,搅拌均匀,转移至模具中,室温固化1h。
实施例3
(1)称取0.5g亚氨基二乙酸,加入20mL去离子水中,搅拌均匀,调节pH值至7-9。
(2)称取0.0656g酸化多壁碳纳米管,加入到步骤(1)的亚氨基二乙酸溶液中,搅拌均匀,得混合溶液。
(3)称取3.28g羧甲基壳聚糖,加入到步骤(2)的混合液中,搅拌均匀,得到新的混合液。
(4)向步骤(3)的混合溶液中加入0.72gEDC·HCl和0.44gNHS,搅拌均匀,转移至模具中,室温固化1h。
对比例1
对比例1与实施例1相比,区别在于:羧甲基壳聚糖与亚氨基二乙酸的摩尔比不在(1-5):1范围内。
(1)称取0.5g亚氨基二乙酸,加入20mL去离子水中,搅拌均匀,调节pH值至7-9。
(2)称取0.0328g酸化多壁碳纳米管,加入到步骤(1)的亚氨基二乙酸溶液中,搅拌均匀,得混合溶液。
(3)称取0.5g羧甲基壳聚糖,加入到步骤(2)的混合液中,搅拌均匀,得到新的混合液。
(4)向步骤(3)的混合溶液中加入0.72gEDC·HCl和0.44gNHS,搅拌均匀,转移至模具中,室温固化1h。
对比例1由于羧甲基壳聚糖与亚氨基二乙酸摩尔比低于1:1,从图4的SEM图中可以看出得到的水凝胶孔隙较少,且该水凝胶较软易碎,难以满足实际应用要求。
对比例2
对比例2与实施例1相比,区别在于:羧甲基壳聚糖与亚氨基二乙酸的摩尔比不在(1-5):1范围内。
(1)称取0.5g亚氨基二乙酸,加入20mL去离子水中,搅拌均匀,调节pH值至7-9。
(2)称取0.0328g酸化多壁碳纳米管,加入到步骤(1)的亚氨基二乙酸溶液中,搅拌均匀,得混合溶液。
(3)称取6.56g羧甲基壳聚糖,加入到步骤(2)的混合液中,搅拌均匀,得到新的混合液。
(4)向步骤(3)的混合溶液中加入0.72gEDC·HCl和0.44gNHS,搅拌均匀,转移至模具中,室温固化1h。
对比例1由于羧甲基壳聚糖与亚氨基二乙酸摩尔比高于5:1,得到的水凝胶孔隙较少,硬度较高但受力易破碎,难以满足实际应用要求。
对比例3
对比例3与实施例1相比,区别在于:制备过程中不加酸化多壁碳纳米管。
(1)称取0.5g亚氨基二乙酸,加入20mL去离子水中,搅拌均匀,调节pH值至7-9。
(3)称取3.28g羧甲基壳聚糖,加入到步骤(1)的混合液中,搅拌均匀,得到新的混合液。
(4)向步骤(3)的混合溶液中加入0.72gEDC·HCl和0.44gNHS,搅拌均匀,转移至模具中,室温固化1h。
对比例3由于原料中没有加酸化多壁碳纳米管,得到的水凝胶力学性能不佳,在图6的压缩曲线中可看出,凝胶弹性模量低,且在应变较小时已被压碎,难以满足实际应用要求。
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。
Claims (4)
1.一种高弹性羧甲基壳聚糖/酸化碳纳米管复合水凝胶的制备方法,其特征在于,包括以下步骤:将亚氨基二乙酸溶于水中,用NaOH调至中性,加入酸化多壁碳纳米管和羧甲基壳聚糖,搅拌均匀后加入缩合剂,继续搅拌均匀后将混合液转移到模具中固化,得到高弹性羧甲基壳聚糖/酸化碳纳米管复合水凝胶;羧甲基壳聚糖与亚氨基二乙酸的摩尔比为(1-5):1,羧甲基壳聚糖与酸化多壁碳纳米管的质量比为(20-100):1;
缩合剂总量与亚氨基二乙酸的摩尔比至少为1:1。
2.根据权利要求1所述的高弹性羧甲基壳聚糖/酸化碳纳米管复合水凝胶的制备方法,其特征在于,缩合剂为1-(3-二甲氨基丙基)-3-乙基碳二亚胺、1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐、二环己基碳二亚胺中的任意一种与4-二甲氨基吡啶、N-羟基琥珀酰亚胺、1-羟基苯并三唑中的任意一种的联用,联用时两种缩合剂的摩尔比为1:1。
3.根据权利要求1所述的高弹性羧甲基壳聚糖/酸化碳纳米管复合水凝胶的制备方法,其特征在于,固化温度为室温,固化时间至少为60min。
4.如权利要求1至3中任一项所述的高弹性羧甲基壳聚糖/酸化碳纳米管复合水凝胶的制备方法制得的复合水凝胶。
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