CN113549242B - 一种用于水体净化的类海绵结构凝胶及其制备和应用 - Google Patents
一种用于水体净化的类海绵结构凝胶及其制备和应用 Download PDFInfo
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Abstract
本发明涉及一种用于水净化的类海绵结构水/油复合凝胶的制备方法和应用,包括以下步骤:(1)将成胶组分、有机溶剂以及可溶性造孔剂加入水中,搅拌至完全溶解成为透明均一的溶液,得到凝胶前驱液;(2)将步骤(1)得到的凝胶前驱液进行固化成胶,制备得到含有特殊孔道结构的水凝胶;(3)挤压步骤(2)制备得到的水凝胶,放入污水中吸附至饱和,再通过挤压出水分实现污水净化。本发明制备过程简单高效,材料廉价易得,具有更高机械强度和吸水率,可根据不同的环境和***使用要求,灵活的调节形态和尺寸而不影响其性能,即使是在极端环境中,也能维持体系在短时间内保持温度稳定,在应对火灾等灾害时具有重要意义。
Description
技术领域
本发明涉及一种水/油复合凝胶材料,尤其是涉及一种用于水体净化的类海绵结构凝胶及其制备和应用。
背景技术
水体质量一直是人们关注最多的环境问题,但近年来随着经济社会的发展和工业化的扩张,越来越多的水域正受到不同程度、不同方式的污染。水污染已经成为全世界必须处理的主要问题之一。水体污染物主要有油、有机物、重金属离子及染料分子等,它们严重破坏了生态***和水环境的平衡,因此对水污染物进行有效处理至关重要。现有的水污染处理方法主要有吸附法、絮凝沉淀法、生物降解法等,这种方法通过使用吸附剂如活性炭、普鲁士蓝、活性氧化铝等吸附相关杂质。但这类吸附剂吸附能力低、再生能力差,通量低且饱和后容易产生二次污染,难以适应连续净化处理等要求,从而限制了其的大规模应用。
水凝胶作为一种具有3D孔道网络结构的材料,具有表观密度低、比表面积大、成本低、化学稳定的优点,已经被用于水污染处理中,以去除油污、有机物和大分子染料。同时,水凝胶丰富的化学组成和内部大量的空间结构,使其可以被改性和进一步修饰,从而被赋予更多功能。通常用于水净化的水凝胶主要分为:水凝胶球珠、水凝胶膜和水凝胶纳米复合材料。它们基于不同的化学性质,利用静电作用、螯合作用、离子交换、疏水作用、截留分离中的一种或多种,实现对污染物的去除。
此外,水凝胶强大的吸水能力也使得其具备作为净水材料的条件,而强大的吸水性也造就了水凝胶的柔韧性、延展性和多孔性,使得水凝胶能被塑形制备成各种器件需要的形貌和尺寸,且能够对周围环境如pH、温度等做出响应,从而使得水凝胶能够很好的适应于各种极端环境,极大的拓宽了净水材料的应用范围。
但是,水凝胶材料在净水中也存在一些问题,其中最主要的就是机械性能与吸水能力的矛盾。吸水性能较好的水凝胶,其机械强度并不高,尤其是在吸水溶胀饱和后,其压缩模量通常只有几千帕到十几千帕,远远无法满足高通量的水净化要求,且多数水凝胶净水材料都为一次性产品,吸水挤压净化后就无法二次使用。这不仅造成了资源的浪费和成本的提升,也降低了水净化工作的效率。
发明内容
本发明的目的就是为了克服上述现有缺陷而提供一种用于水体净化的类海绵结构凝胶及其制备和应用。
本发明的目的可以通过以下技术方案来实现:
一种用于水体净化的类海绵结构凝胶的制备方法,包括以下步骤:
(1)将成胶组分、有机溶剂和可溶性造孔剂加入水中,搅拌至完全溶解成为透明均一的溶液,得到凝胶前驱液;
(2)将步骤(1)得到的凝胶前驱液进行聚合成胶,制备得到具有特殊孔道结构的类海绵水凝胶;
(3)挤压步骤(2)制备得到的水凝胶中的水分,即得到可吸收污水的类海绵水凝胶。
优选的,步骤(1)中:所述成胶组分为单体聚合体系。
优选的,所述单体聚合体系含有单体、交联剂、有机/水复合溶剂、造孔剂和紫外光引发剂,所述单体为丙烯酸酯类单体或丙烯酸类单体,所述交联剂为聚乙二醇(二醇)二丙烯酸酯(PEGDA),所述有机溶剂为丙三醇或乙二醇类可水溶性有机物,所述造孔剂为苯并呋喃酮类等大分子化合物与无机盐的混合物,所述紫外光引发剂为2,2-二乙氧基苯乙酮(DEAP)。
优选的,所述单体为丙烯酸酯、甲基丙烯酸酯、丙烯酸-2-羟乙酯(HEA)、甲基丙烯酸-2-羟乙酯(HEMA)中的一种或多种。
优选的,所述单体的添加量为有机/水复合溶剂总重量的20%~50%,所述交联剂的添加量为单体总重量的0.1%~1%,所述紫外光引发剂的添加量为单体总重量的0.1%~1%。
优选的,当成胶组分为单体聚合体系时,步骤(2)中的成胶方式为:将凝胶前驱液置于光强为25~30mW/cm2的紫外灯下辐射,反应时间为20~45min;
优选的,步骤(1)中:所述复合溶剂为去离子水、丙三醇、乙二醇、乙醇、二甲基亚砜中的一种或多种。
优选的,步骤(1)中:可溶性造孔剂为3,3-二(4-羟苯基)-3H-异苯并呋喃酮、花苷素、花青素中的一种或多种与碳酸钠、碳酸氢钠、硫酸钠、磷酸钠、磷酸二氢钠、二磷酸氢钠中的一种或多种的复合。
优选的,所述可溶性造孔剂的添加量为水总重量的0.1%-0.5%。
优选的,步骤(1)中:搅拌温度为20-40℃,搅拌时间为5-10min。
一种类海绵结构的复合水凝胶在水净化***中的应用。
本发明中的工艺条件为最合适的制备条件。搅拌是为了单体、溶剂和添加剂的快速溶解;添加造孔剂是为了对水凝胶的空岛结构进行控制调节,添加剂含量越高,凝胶孔道越大,但净水效率越低;光照强度与反应时间对应,光照强度过低会延长所需的反应时间;光照长度与反应程度对应,过短的时长会降低反应的聚合程度,从而影响机械性能;反应物添加量会影响最终得到的净水凝胶的性能,尤其是其吸附性能,如单体或交联剂含量过低会降低净水凝胶的机械强度,甚至导致成胶不成形,单体或交联剂含量过高则会造成凝胶网络过于致密,无法实现净水效果。
本发明通过使用造孔剂等添加剂对一种具有两亲性的单体的水凝胶网络结构进行调节,得到了一种在常温常压下具有类海绵结构、能够用于水净化的水/油复合凝胶。其中,复合凝胶含有交联的高分子凝胶基体材料,有机/水按一定比例构成的复合溶剂;高分子凝胶基体可通过单体聚合或高分子物理交联形成三维空间网状结构,造孔剂填充在网络结构空隙中,实现对网络结构的调节。
本发明是一种新型的制备净水复合凝胶的方法,首先通将适量的造孔剂和复合溶剂添加在前驱液中,在前驱液成胶后降温形成特殊的高分子链构象和网络结构,得到具有机械性能优异、可重复使用的类海绵结构的复合凝胶。
该方法工艺简单,可控性强,容易操作。该方法制得的类海绵结构复合凝胶具有超高机械强度,能够循环使用1000次以上,是纯水凝胶的几千倍。此外,由于复合凝胶单体分子具有两亲性,复合溶剂和适量的造孔剂能使其结构具有良好的可调节性,不需要引入其它添加剂物或操作手段,即可作为有效可靠的吸附材料应用于水资源净化中。在单体聚合的过程中,会使高分子链段的构象随着体系设计转变为合适的形态,降低对水的亲合程度,从而提高凝胶材料的吸附能力,使水处理的效率更高。
另外,由于所选用的单体结构具有良好的生物相容性、温度响应性和离子效应,因此通过设计凝胶孔道的结构能够使得该类海绵复合凝胶能够用于生物大分子的分离如:细菌、蛋白等。此外,该复合凝胶优良的结构性能和两亲性使得其可以作为药物载体,进行体内药物的可控释放。
与现有技术相比,本发明具有以下有益效果:
(1)与传统的净水凝胶相比,本发明制备的类海绵结构水/油复合凝胶由于结构的特殊性能,因此具有更高的机械强度、吸附能力和可靠性,在水处理净化的应用上更高效、安全;
(2)与活性炭类吸附净水材料相比,本发明制备的类海绵结构水/油复合凝胶具有更多可调节的孔道结构,能够实现对目标分子量的污染物的定向吸附和处理,可以使材料获得更优的水处理性能和更多的功能;
(3)该复合凝胶可吸水/挤出的结构特点,使其能够长期稳定重复使用。其溶胀稳定性使得其在用于水处理设备时,能够有较高的水环境耐受性,保证了安全性和稳定性;
(4)由于在单体聚合过程中,分子链的构象转变,使得分子在一定温度下发生相分离,因此具有温度响应性,通过调节结构配比,可以用于粗略的估计废水温度并进行预处理,拓宽水处理设备的温度窗口,使其在低温下依然能正常工作;
(5)类海绵结构水/油复合凝胶可有净化废水中的污染物,特别是大分子染料和苯系物,同时自身不会造成环境污染;
(6)本发明的制备工艺简单,原料廉价易得。
附图说明
图1为实施例1的类海绵结构水/油复合凝胶的实物图;
图2为实施例1的类海绵结构水/油复合凝胶的扫描电子显微镜图;
图3为实施例1的类海绵结构水/油复合凝胶成胶过程中的流变图;
图4为实施例1的类海绵结构水/油复合凝胶的压缩曲线图;
图5为实施例1的类海绵结构水/油复合凝胶的循环压缩使用图;
图6为实施例1的类海绵结构水/油复合凝胶对大分子染料(罗丹明为例)的净化情况;
图7为实施例1的类海绵结构水/油复合凝胶针对大分子染料(罗丹明为例)的可循环使用情况;
图8为实施例1的类海绵结构水/油复合凝胶对苯系物(苯酚为例)的净化情况;
图9为实施例1的类海绵结构水/油复合凝胶在水中的溶胀稳定性。
具体实施方式
下面结合附图和具体实施例对本发明进行详细说明。
实施例1
将0.3g甲基丙烯酸-2-羟乙酯(HEMA),0.35mg丙三醇(Gly),1μL 2,2-二乙氧基苯乙酮(DEAP),5mg碳酸钠溶液(2%wt,含有0.02%3,3-二(4-羟苯基)-3H-异苯并呋喃酮)加入到0.35mL蒸馏水中,在室温下下搅拌5min,形成含透明均一的前驱液。在25℃条件下,将前驱液加以紫外光辐射,光照强度约25mW/cm2,反应25min制得具有合适孔径的类海绵结构水/油复合凝胶。所得复合凝胶的压缩模量为3.35MPa。
如图1所示,本实施例的类海绵结构水/油复合凝胶具有良好的使用性和使用后的恢复性。图2为其扫描电子显微镜图像,显示出凝胶中有明显且较为均一的孔道结构,且孔径在20~30μm。图3为类海绵结构水/油复合凝胶在成胶过程中的流变曲线,反应出该体系有效的形成凝胶结构。图4、5为类海绵结构水/油复合凝胶的力学性能图像,结果显示本实施例的复合凝胶具有优越的力学性能且能够实现1000次以上的循环使用。
本实施例的类海绵结构水/油复合凝胶,对于大分子污染物(罗丹明为例)在进化4次后,净化率能够达到98%以上(图6);对于相同浓度大分子污染物(罗丹明为例),本实施例的类海绵结构水/油复合凝胶可以使用10次以上(图7)。对于苯系物(苯酚)也有较为优异的净化能力(图8)。
图9显示出本实施例的类海绵结构水/油复合凝胶,在水中具有很高的稳定性,几乎不发生溶胀,并能够长期保持良好的形貌。
实施例2
将0.3g甲基丙烯酸-2-羟乙酯(HEMA),0.4mg丙三醇(Gly),1μL 2,2-二乙氧基苯乙酮(DEAP),5mg碳酸钠溶液(2%wt,含有0.02%3,3-二(4-羟苯基)-3H-异苯并呋喃酮)加入到0.6mL蒸馏水中,在室温下下搅拌5min,形成含透明均一的前驱液。在25℃条件下,将前驱液加以紫外光辐射,光照强度约25mW/cm2,反应25min制得具有合适孔径的类海绵结构水/油复合凝胶。所得复合凝胶的压缩模量为4.72MPa。
实施例3
将0.2g甲基丙烯酸-2-羟乙酯(HEMA),0.4mg丙三醇(Gly),1μL 2,2-二乙氧基苯乙酮(DEAP),5mg碳酸钠溶液(2%wt,含有0.02%3,3-二(4-羟苯基)-3H-异苯并呋喃酮)加入到0.6mL蒸馏水中,在室温下下搅拌5min,形成含透明均一的前驱液。在25℃条件下,将前驱液加以紫外光辐射,光照强度约25mW/cm2,反应25min制得具有合适孔径的类海绵结构水/油复合凝胶。所得复合凝胶的压缩模量为0.27MPa,对于大分子污染物(罗丹明为例)的1次净化率为74%。
实施例4
将0.4g甲基丙烯酸-2-羟乙酯(HEMA),0.4mg丙三醇(Gly),1μL 2,2-二乙氧基苯乙酮(DEAP),5mg碳酸钠溶液(2%wt,含有0.02%3,3-二(4-羟苯基)-3H-异苯并呋喃酮)加入到0.6mL蒸馏水中,在室温下下搅拌5min,形成含透明均一的前驱液。在25℃条件下,将前驱液加以紫外光辐射,光照强度约25mW/cm2,反应25min制得具有合适孔径的类海绵结构水/油复合凝胶。所得复合凝胶的压缩模量为5.61MPa,对于大分子污染物(罗丹明为例)的1次净化率为10%。
实施例5
将0.3g甲基丙烯酸-2-羟乙酯(HEMA),0.4mg丙三醇(Gly),1μL 2,2-二乙氧基苯乙酮(DEAP),5mg硫酸钠溶液(2%wt,含有0.02%3,3-二(4-羟苯基)-3H-异苯并呋喃酮)加入到0.6mL蒸馏水中,在室温下下搅拌5min,形成含透明均一的前驱液。在25℃条件下,将前驱液加以紫外光辐射,光照强度约25mW/cm2,反应25min制得具有合适孔径的类海绵结构水/油复合凝胶。所得复合凝胶的压缩模量为2.21MPa,对于大分子污染物(罗丹明为例)的1次净化率为60.3%。
实施例6
将0.3g甲基丙烯酸-2-羟乙酯(HEMA),0.4mg丙三醇(Gly),1μL 2,2-二乙氧基苯乙酮(DEAP),5mg氯化钠溶液(2%wt,含有0.02%3,3-二(4-羟苯基)-3H-异苯并呋喃酮)加入到0.6mL蒸馏水中,在室温下下搅拌5min,形成含透明均一的前驱液。在25℃条件下,将前驱液加以紫外光辐射,光照强度约25mW/cm2,反应25min制得具有合适孔径的类海绵结构水/油复合凝胶。所得复合凝胶的压缩模量为2.77MPa,对于大分子污染物(罗丹明为例)的1次净化率为63.5%。
实施例7
将0.3g丙烯酸-2-羟乙酯(HEA),0.4mg丙三醇(Gly),1μL 2,2-二乙氧基苯乙酮(DEAP),5mg碳酸钠溶液(2%wt,含有0.02%3,3-二(4-羟苯基)-3H-异苯并呋喃酮)加入到0.6mL蒸馏水中,在室温下下搅拌5min,形成含透明均一的前驱液。在25℃条件下,将前驱液加以紫外光辐射,光照强度约25mW/cm2,反应25min制得具有合适孔径的类海绵结构水/油复合凝胶。所得复合凝胶的压缩模量为3.31MPa,对于大分子污染物(罗丹明为例)的1次净化率为12.6%。
实施例8
将0.3g甲基丙烯酸酯,0.4mg丙三醇(Gly),1μL 2,2-二乙氧基苯乙酮(DEAP),5mg碳酸钠溶液(2%wt,含有0.02%3,3-二(4-羟苯基)-3H-异苯并呋喃酮)加入到0.6mL蒸馏水中,在室温下下搅拌5min,形成含透明均一的前驱液。在25℃条件下,将前驱液加以紫外光辐射,光照强度约25mW/cm2,反应25min制得具有合适孔径的类海绵结构水/油复合凝胶。所得复合凝胶的压缩模量为1.13MPa,对于大分子污染物(罗丹明为例)的1次净化率为11.4%。
实施例9
将0.3g甲基丙烯酸-2-羟乙酯(HEMA),0.4mg乙二醇,1μL 2,2-二乙氧基苯乙酮(DEAP),5mg碳酸钠溶液(2%wt,含有0.02%3,3-二(4-羟苯基)-3H-异苯并呋喃酮)加入到0.6mL蒸馏水中,在室温下下搅拌5min,形成含透明均一的前驱液。在25℃条件下,将前驱液加以紫外光辐射,光照强度约25mW/cm2,反应25min制得具有合适孔径的类海绵结构水/油复合凝胶。所得复合凝胶的压缩模量为1.78MPa,对于大分子污染物(罗丹明为例)的1次净化率为12.1%。
实施例10
将0.3g甲基丙烯酸-2-羟乙酯(HEMA),0.4mg乙醇,1μL 2,2-二乙氧基苯乙酮(DEAP),5mg碳酸钠溶液(2%wt,含有0.02%3,3-二(4-羟苯基)-3H-异苯并呋喃酮)加入到0.6mL蒸馏水中,在室温下下搅拌5min,形成含透明均一的前驱液。在25℃条件下,将前驱液加以紫外光辐射,光照强度约25mW/cm2,反应25min制得具有合适孔径的类海绵结构水/油复合凝胶。所得复合凝胶的压缩模量为0.63MPa,对于大分子污染物(罗丹明为例)的1次净化率为1.3%。
实施例11
将0.3g甲基丙烯酸-2-羟乙酯(HEMA),0.4mg乙二醇,1μL 2,2-二乙氧基苯乙酮(DEAP),5mg硫酸钠溶液(2%wt,含有0.02%3,3-二(4-羟苯基)-3H-异苯并呋喃酮)加入到0.6mL蒸馏水中,在室温下下搅拌5min,形成含透明均一的前驱液。在25℃条件下,将前驱液加以紫外光辐射,光照强度约25mW/cm2,反应25min制得具有合适孔径的类海绵结构水/油复合凝胶。所得复合凝胶的压缩模量为0.99MPa,对于大分子污染物(罗丹明为例)的1次净化率为10.4%。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改,并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此,本发明不限于上述实施例,本领域技术人员根据本发明的揭示,不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。
Claims (3)
1.一种用于水体净化的类海绵结构凝胶的制备方法,其特征在于,包括:
将0.3 g甲基丙烯酸-2-羟乙酯、0.35 mg 丙三醇、1μL 2,2-二乙氧基苯乙酮、5 mg可溶性造孔剂溶液加入到0.35mL 蒸馏水中,在室温下下搅拌5 min,形成透明均一的前驱液;
在25℃条件下,将前驱液加以紫外光辐射,光照强度约25mW/cm2,反应25min制得类海绵结构水/油复合凝胶;
其中,所述的可溶性造孔剂溶液为2wt%的碳酸钠溶液,含有0.02% 3,3-二(4-羟苯基)-3H-异苯并呋喃酮。
2.一种用于水体净化的类海绵结构凝胶,采用如权利要求1所述的制备方法制备得到。
3.如权利要求2所述的一种用于水体净化的类海绵结构凝胶在水净化***中的应用。
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