CN112225908B - 一种光交联水凝胶及其制备方法与应用 - Google Patents
一种光交联水凝胶及其制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种光交联水凝胶及其制备方法与应用,具体是一种光交联聚乙烯醇‑苯乙烯基吡啶盐缩合物(PVA‑SbQ)/金属有机框架(MOF)/聚丙烯酰胺复合水凝胶及其制备方法,应用于染料吸附。第一步,将MOF分散于PVA‑SbQ水溶液或者在用MOF前驱体在PVA‑SbQ水溶液中原位生成MOF,采用光交联技术制备光交联的PVA‑SbQ/MOF复合水凝胶,形成第一重网络;第二步,将PVA‑SbQ/MOF复合水凝胶浸泡到含有单体AM、交联剂MBAA、光引发剂的水溶液中,吸附饱和后,再次在紫外光照射下引发聚合形成交联互穿的第二重网络结构。采用光聚合手段制备具有互穿网络结构的聚合物/MOF复合水凝胶,环保高效,而且有效克服了聚合物/无机填料复合过程中无机粒子沉降,实现MOF在聚合物网络中的均匀分散。
Description
技术领域
本发明属于染料废水处理技术领域,具体涉及一种光交联水凝胶及其制备方法与应用,尤其是一种互穿网络水凝胶制备技术。
背景技术
染料废水是水体的主要污染源之一,染料废水的处理多采用物理吸附法、生物法、化学氧化法、絮凝和膜分离等方法。其中,吸附法作为一种重要的物理化学方法,不引入新的污染物,能从废水中富集分离有机污染物,实现废物资源化,具有吸附效果好、操作简便、适用范围广等特点,在染料废水污染治理的实际工作中得到了广泛的使用。吸附法是染料废水处理的首选方法,活性炭是主要的吸附剂,但是活性炭再生困难,易产生二次污染。近年来,粉煤灰、介孔炭材料、生物吸附剂等处理染料废水均取得了较好的效果,但这些吸附剂仍然存在无选择性、再生困难或吸附容量低等问题,因此寻找一种新型高效的吸附剂成为处理染料废水的关键。
金属有机骨架(MOFs)是金属离子与有机配体连接而成的一种多孔网状结构材料,由于具有孔隙率高且孔道大小可调、比表面积大、有特殊的金属位点以及结构多样等特点,在气体吸附分离、光电催化、离子交换、生物活性和分子识别等领域展现出广阔的应用前景。近几年来,许多研究者将MOFs作为吸附剂对液相中的染料进行吸附,取得了较好的吸附效果。但MOFs 作为吸附剂处理成本较高,吸附剂固液分离能力较差,限制了其实际应用。
水凝胶作为具有三维交联网络结构的柔性聚合材料,因其具有良好的水渗透性、刺激响应性、环境友好和生物相容性,并可根据需求引入不同功能性的螯合基团,已广泛应用于农林、园艺、医学诊疗、生物传感、水体净化和吸附分离等领域。同时,水凝胶聚合物网络内部存在大量亲水性官能团,使其具有良好的溶胀度而并不溶于水,极大提高了水凝胶作为吸附材料的固液分离能力,并简化了污水净化的后续处理程序,为解决水体中有机染料污染问题提供了有效途径。制备MOF/聚合物水凝胶复合材料用于染料吸附将同时具备高的吸附容量和良好的固液分离能力。但是传统制备MOF/聚合物水凝胶复合材料多采用热交联固化的方法,固化速度慢,容易造成MOF在聚合物基体中的分散不均匀,同时,单重聚合物网络形成的凝胶强度较弱。
互穿聚合物网络是指由两种或两种以上的交联聚合物网络互相穿插而形成的三维网络结构,相类似,互穿网络水凝胶指的是网络结构由两个或多个聚合物网络相互贯穿而形成的水凝胶材料。与单一网络相比,互穿网络水凝胶不仅能够增强凝胶强度,而且能够将两种网络的性能适当地结合在一起,赋予至一个凝胶体系当中,而不破坏各自网络的性能,因而具有相当的优势。
光交联技术作为一种新型的交联技术,以低能耗的紫外光作为辐射源,具有操作简便,环保快捷,成本低等优点。
发明内容
技术问题:
针对现有技术中存在的问题,本发明的目的在于提供一种光交联水凝胶及其制备方法与应用,具体为一种光交联PVA-SbQ/MOF/PAM互穿网络水凝胶及其制备方法与应用,以解决现有技术中填料在聚合物中分散不均匀、聚合物凝胶固化速度慢、凝胶强度低等问题。
技术方案:
一种光交联PVA-SbQ/MOF/PAM互穿网络复合水凝胶,用于染料吸附,其制备方法,包括以下步骤:
(1)PVA-SbQ/MOF混合分散液的制备:将已制备好的MOF分散在质量分数为 6%-15%PVA-SbQ水溶液中,超声分散均匀,配置成PVA-SbQ/MOF悬浮液;或者将MOF前驱体溶解在6%-15%PVA-SbQ水溶液中,原位反应生成PVA-SbQ/MOF悬浮液;
(2)光交联PVA-SbQ/MOF复合水凝胶的制备:将所得的PVA-SbQ/MOF悬浮液倒入到直径25mm、厚3mm的圆形聚四氟乙烯模具中,在紫外光照射下,SbQ基团发生二聚交联,形成第一重网络,即可得到光交联PVA-SbQ/MOF复合水凝胶;
(3)光交联PVA-SbQ/MOF/PAM互穿网络水凝胶的制备:
PAM前驱体溶液的制备:称取计量的单体丙烯酰胺、交联剂、光引发剂溶解在去离子水中,交联剂为亚甲基双丙烯酰胺;所得PAM前驱体溶液中,丙烯酰胺的物质的量浓度为1-5mol/L,交联剂的量为丙烯酰胺摩尔数的0.4%-0.8%、光引发剂的质量占丙烯酰胺与交联剂总质量的0.01%-0.1%;
将步骤(2)中所得PVA-SbQ/MOF复合水凝胶浸泡在PAM前驱体溶液中,浸泡3天达到吸附平衡;取出吸附了PAM前驱体溶液的PVA-SbQ/MOF水凝胶,再次进行紫外光照射,丙烯酰胺聚合交联得到第二重网络,即可得到PVA-SbQ/MOF/PAM互穿网络水凝胶,将其浸泡在水中24h,期间每隔6h更换一次水,洗去未反应的单体。
进一步的,所述步骤(1)中的MOF是IRMOF系列、ZIF系列、MIL系列、UiO系列、 PCN系列等中的一种,可以是提前制备好的MOF粉末,也可以是用MOF前驱体单体在 PVA-SbQ水溶液中原位生成;所述的MOF占PVA-SbQ的质量分数为5-20%,即MOF与 PVA-SbQ的质量比为1:5~20。
进一步的,所述步骤(2)中的紫外光照射采用50-100W/cm2的紫外灯,照射时间为5-10min。
进一步的,所述步骤(3)中的光引发剂选自二茂铁类光引发剂、卤化银类光引发剂、联苯甲酰类光引发剂或有机氧化磷类光引发剂中的一种。
进一步的,所述步骤(3)中的紫外光照射采用100W/cm2的紫外灯,照射时间为10min。
本发明的另一目的是提供了上述制备方法制得的光交联PVA-SbQ/MOF/PAM互穿网络水凝胶吸附剂。
本发明的另一目的是提供光交联水凝胶在染料吸附中的应用,尤其是在刚果红染料吸附中的应用。
有益效果:
与现有技术相比,本发明具有以下有益效果:
(1)本发明采用光交联制备PVA-SbQ/MOF/PAM水凝胶具有绿色快捷、MOF在聚合物网络中分散均匀的优点。
(2)本发明的PVA-SbQ/MOF/PAM水凝胶通过形成两重网络结构互穿缠结,提高了水凝胶的机械性能。
(3)本发明的PVA-SbQ/MOF/PAM水凝胶用于染料吸附具有高的吸附容量。
附图说明
图1是实施例1所得PVA-SbQ/MOF/PAM互穿网络水凝胶吸水前后示意图;
图2是对比例1所得PVA-SbQ/ZIF-8水凝胶吸水前后示意图;
图3是对比例2所得PVA-SbQ水凝胶吸水前后示意图;
图4是对比例3所得PVA-SbQ/PAM互穿网络水凝胶吸水前后示意图。
图5是对比例4所得PAM水凝胶吸水前后示意图。
具体实施方式
根据下述实施例,可以更好的理解本发明。然而,本领域的技术人员容易理解,实施例所描述的具体的物料配比、工艺条件及其结果仅用于说明本发明,而不应当也不会限制权利要求书中所详细描述的本发明。
实施例
实施例1
(1)制备PVA-SbQ/MOF悬浮液:将ZIF-8(MOF可以是IRMOF系列、ZIF系列、MIL 系列、UiO系列、PCN系列等中的一种)分散在质量分数为10%的PVA-SbQ水溶液中,ZIF-8 与PVA-SbQ的质量比为1:10,超声分散均匀,配置成PVA-SbQ/MOF悬浮液;
(2)制备光交联PVA-SbQ/MOF复合水凝胶:PVA-SbQ/MOF混合分散液倒入到直径25mm,厚3mm的圆形聚四氟乙烯模具中,采用100W/cm2的紫外灯,在紫外光下照射5min,SbQ基团发生二聚交联,形成第一重网络,得到光交联PVA-SbQ/ZIF-8复合水凝胶;
(3)制备光交联PVA-SbQ/MOF/PAM互穿网络水凝胶:将所得PVA-SbQ/ZIF-8复合水凝胶浸泡在含有丙烯酰胺(AM)、亚甲基双丙烯酰胺(MBAA)和光引发剂的混合溶液中,混合液中丙烯酰胺的物质的量浓度为2.0mol/L,亚甲基双丙烯酰胺的量为丙烯酰胺摩尔数的0.6%、光引发剂的质量占丙烯酰胺与交联剂总质量的0.05%,光引发剂为联苯甲酰(光引发剂可以是二茂铁类光引发剂、卤化银类光引发剂、联苯甲酰类光引发剂或有机氧化磷类光引发剂中的一种)。浸泡3天达到吸附平衡后,取出吸附了PAM前驱体的PVA-SbQ/ZIF-8水凝胶,再次进行紫外光照射,采用100W/cm2的紫外灯,照射10min,丙烯酰胺聚合交联得到第二重网络,即可得到PVA-SbQ/ZIF-8/PAM互穿网络水凝胶,将其浸泡在水中24h,期间每隔6h更换一次水,洗去未反应的单体。所得PVA-SbQ/MOF/PAM互穿网络水凝胶吸水前后的数码照片如图1 所示。
实施例2
步骤(2)中,采用100W/cm2的紫外灯,在紫外光下照射10min,得到光交联PVA-SbQ/ZIF-8 复合水凝胶。其余过程同实施例1。
实施例3
步骤(2)中,采用100W/cm2的紫外灯,在紫外光下照射15min,得到光交联PVA-SbQ/ZIF-8 复合水凝胶。其余过程同实施例1。
实施例4
步骤(2)中,采用50W/cm2的紫外灯,在紫外光下照射10min,得到光交联PVA-SbQ/ZIF-8 复合水凝胶。其余过程同实施例1。
实施例5
步骤(2)中,采用150W/cm2的紫外灯,在紫外光下照射10min,得到光交联PVA-SbQ/ZIF-8 复合水凝胶。其余过程同实施例1。
实施例6
步骤(1)中,ZIF-8与PVA-SbQ的质量比为1:20,其余过程同实施例1。
实施例7
步骤(1)中,ZIF-8与PVA-SbQ的质量比为3:20,其余过程同实施例1。
实施例8
步骤(1)中,ZIF-8与PVA-SbQ的质量比为1:5,其余过程同实施例1。
实施例9
步骤(3)中,混合液中丙烯酰胺的物质的量浓度为1.0mol/L,其余过程同实施例1。
实施例10
步骤(3)中,混合液中丙烯酰胺的物质的量浓度为4.0mol/L,其余过程同实施例1。
实施例11
步骤(3)中,混合液中丙烯酰胺的物质的量浓度为5.0mol/L,其余过程同实施例1。
实施例12
步骤(3)中,亚甲基双丙烯酰胺的量为丙烯酰胺摩尔数的0.4%,其余过程同实施例1。
实施例13
步骤(3)中,亚甲基双丙烯酰胺的量为丙烯酰胺摩尔数的0.8%,其余过程同实施例1。
实施例14
步骤(3)中,光引发剂的质量占丙烯酰胺与交联剂总质量的0.01%,其余过程同实施例1。
实施例15
步骤(3)中,光引发剂的质量占丙烯酰胺与交联剂总质量的0.1%,其余过程同实施例1。
对比例
对比例1
参照实施例1得到的光交联PVA-SbQ/ZIF-8复合水凝胶。
(1)制备PVA-SbQ/MOF悬浮液:将ZIF-8(MOF可以是IRMOF系列、ZIF系列、MIL 系列、UiO系列、PCN系列等中的一种)分散在质量分数为10%的PVA-SbQ水溶液中,ZIF-8 与PVA-SbQ的质量比为1:10,超声分散均匀,配置成PVA-SbQ/MOF悬浮液;
(2)制备光交联PVA-SbQ/MOF复合水凝胶:PVA-SbQ/MOF混合分散液倒入到直径25mm,厚3mm的圆形聚四氟乙烯模具中,采用100W/cm2的紫外灯,在紫外光下照射5min,得到光交联PVA-SbQ/ZIF-8复合水凝胶。所得PVA-SbQ/ZIF-8水凝胶吸水前后的数码照片如图2所示。
对比例2
制备光交联PVA-SbQ水凝胶,制备方法为:质量分数为10%的PVA-SbQ水溶液,倒入到直径25mm,厚3mm的圆形聚四氟乙烯模具中,采用100W/cm2的紫外灯,在紫外光下照射5min,得到光交联PVA-SbQ水凝胶。所得PVA-SbQ水凝胶吸水前后的数码照片如图3所示。
对比例3
制备光交联PVA-SbQ/PAM互穿网络水凝胶,制备方法为:质量分数为10%的PVA-SbQ 水溶液,倒入到直径25mm,厚3mm的圆形聚四氟乙烯模具中,采用100W/cm2的紫外灯,在紫外光下照射5min,得到光交联PVA-SbQ水凝胶;将所得PVA-SbQ水凝胶浸泡在含有丙烯酰胺(AM)、亚甲基双丙烯酰胺(MBAA)和光引发剂的混合溶液中,混合液中丙烯酰胺的物质的量浓度为2.0mol/L,亚甲基双丙烯酰胺的量为丙烯酰胺摩尔数的0.6%、光引发剂的质量占丙烯酰胺与交联剂总质量的0.05%,光引发剂为联苯甲酰(光引发剂可以是二茂铁类光引发剂、卤化银类光引发剂、联苯甲酰类光引发剂或有机氧化磷类光引发剂中的一种)。浸泡3天达到吸附平衡后,取出吸附了PAM前驱体的PVA-SbQ/ZIF-8水凝胶,再次进行紫外光照射,采用 100W/cm2的紫外灯,照射10min,丙烯酰胺聚合交联得到第二重网络,即可得到PVA-SbQ/ ZIF-8/PAM互穿网络水凝胶,将其浸泡在水中24h,期间每隔6h更换一次水,洗去未反应的单体。所得PVA-SbQ/PAM互穿网络水凝胶吸水前后的数码照片如图4所示。
对比例4
制备光聚合交联PAM水凝胶,制备方法为:配置丙烯酰胺(AM)、亚甲基双丙烯酰胺(MBAA) 和光引发剂的混合溶液,丙烯酰胺的物质的量浓度为2.0mol/L,亚甲基双丙烯酰胺的量为丙烯酰胺摩尔数的0.6%、光引发剂的质量占丙烯酰胺与交联剂总质量的0.05%,光引发剂为联苯甲酰(光引发剂可以是二茂铁类光引发剂、卤化银类光引发剂、联苯甲酰类光引发剂或有机氧化磷类光引发剂中的一种)。浸泡3天达到吸附平衡后,取出吸附了PAM前驱体的PVA-SbQ/ ZIF-8水凝胶,再次进行紫外光照射,采用100W/cm2的紫外灯,照射10min,丙烯酰胺聚合交联得到第二重网络,即可得到PVA-SbQ/ZIF-8/PAM互穿网络水凝胶,将其浸泡在水中24h,期间每隔6h更换一次水,洗去未反应的单体。所得PAM水凝胶吸水前后的数码照片如图5 所示。
实施例和对比例的结果分析
以上实施例中的性能测试方法参照如下:
(1)力学强度测试方法:将水凝胶裁成哑铃型样条,规格为长l=15±2mm,宽b=4±0.2 mm,厚h=2.0±0.2mm.将裁好的哑铃型样条在室温下进行拉伸试验,本实验采用KDIII-5型微机控制电子万能试验机,按国家标准GB1040-79,由测试可以得到试样的拉伸强度。
(2)溶胀吸水实验计算溶胀率:
精确称取2.000g干凝胶(W0)放入对应的小烧杯中,分别倒入25ml水,每隔1h取出水凝胶准确称取质量(W1)并记录,按式(1-1)计算水凝胶的溶胀率(SR):
式中W0——干凝胶质量,g;W1——溶胀后水凝胶的质量,g。
(3)以刚果红为例进行吸附试验对比,计算吸附量:
将制备得到的PVA-SbQ/MOF/PAM水凝胶切成小颗粒,置于冰箱中冷冻48h后,采用真空冷冻干燥机中冷冻干燥48h,得到PVA-SbQ/MOF/PAM复合干凝胶。称取0.100g干凝胶加入到200ml烧杯中,分别向试管中加入100ml浓度为200mg/ml的刚果红溶液。设定温度为25℃、 pH=7、转速为300rpm,在恒温水浴振荡器中吸附24小时,离心分离后测试上清液的吸光度,根据公式(2)分别计算不同吸附剂对甲基橙的吸附量Qe。
其中,C0为刚果红的初始浓度(mg/ml),Ce为吸附后刚果红的浓度(mg/ml),V为刚果红溶液的体积(ml),m为吸附剂即干凝胶的质量(g)。
对比例和实施例的力学强度、溶胀率、吸附容量进行比较,结果分别为表1所示。从表1 可以看出,本发明方法的工艺流程中,主要的工艺参数为:步骤(1)中ZIF-8与PVA-SbQ的质量比、步骤(2)中紫外灯照射的辐照剂量及时间、步骤(3)中PAM前驱体的浓度。各项参数的对比分析结果如下:
(一)实施例中各工艺参数的比较
1)实施例1、2、3相比较,实施例1、4、5相比较,验证了紫外灯照射的时间及辐照强度对水凝胶的性能影响,可以看出,水凝胶的性能随紫外灯照射的时间及辐照强度的增加是先提高后降低的,紫外灯照射的最佳条件是:采用100W/cm2的紫外灯,在紫外光下照射10min。这可能是因为该实验条件下,交联程度高,形成紧密的网络结构,有利于水凝胶吸附性能的提高。
2)实施例1、6、7、8及对比例3相比较:ZIF-8对水凝胶的影响极其添加量的确定
首先,实施例1、对比例3相比较,对比了无ZIF-8的光交联PVA-SbQ/PAM水凝胶,与实施例1根据本发明方法得到PVA-SbQ/ZIF-8/PAM水凝胶两种水凝胶的性能,可以看出,有了MOF的加成作用,实施例1所得的PVA-SbQ/ZIF-8/PAM水凝胶的性能均得到大大提升,验证了ZIF-8的添加对水凝胶的性能提高的有效性。这可能是因为ZIF-8有序的微孔结构,使其具有大的比表面积,与聚合物网络相比,吸附性能更高。
另外实施例1、6、7、8比较了ZIF-8与PVA-SbQ的质量比对水凝胶的性能影响,可以看出,水凝胶的性能中,强度随ZIF-8与PVA-SbQ的质量比增加呈现出先升高后降低的趋势,ZIF-8作为一种纳米填料可以增强复合水凝胶,但当含量太高时,由于部分聚集会造成一定程度的强度降低。水凝胶的溶胀率和吸附容量随ZIF-8与PVA-SbQ的质量比增加呈现逐渐增大的趋势,即ZIF-8与PVA-SbQ的质量比越大越有利于复合水凝胶吸附性能的提高。这可能是因为ZIF-8作为一种有序多孔材料具有大的比表面积,吸附主要发生在ZIF-8中,能显著提高吸附容量。综合得出,ZIF-8与PVA-SbQ的质量比的最佳条件是:ZIF-8与PVA-SbQ的质量比为3:20。
3)实施例1、9、10、11相比较,验证了PAM前驱体混合液中单体AM丙烯酰胺的物质的量浓度对水凝胶的性能影响,可以看出,水凝胶的性能中,除了强度随丙烯酰胺的物质的量浓度增加呈现出先增后稍有减小的趋势以外,溶胀率、吸附容量与丙烯酰胺的物质的量浓度呈正相关,综合得出,丙烯酰胺的物质的量浓度的最佳条件是:混合液中丙烯酰胺的物质的量浓度为4.0mol/L。这可能是因为增加丙烯酰胺的量可以形成更多的聚合物网络,有利于吸附性能的提高。
4)实施例1、12、13相比较,验证了PAM前驱体混合液中交联剂MBAA亚甲基双丙烯酰胺的量对水凝胶的性能影响,可以看出,水凝胶的性能随PAM前驱体混合液中亚甲基双丙烯酰胺的量先提高后降低,PAM前驱体混合液中亚甲基双丙烯酰胺的量的最佳条件是:亚甲基双丙烯酰胺的量为丙烯酰胺摩尔数的0.6%。这可能是因为适量的交联剂用量有助于提高交联程度,从而使得吸附性能提高。
5)实施例1、14、15相比较,验证了PAM前驱体混合液中光引发剂的质量对水凝胶的性能影响,可以看出,水凝胶的性能随PAM前驱体混合液中光引发剂的质量增加而先升高后降低,的最佳条件是:PAM前驱体混合液中光引发剂的质量占丙烯酰胺与交联剂总质量的0.05%。这可能是因为具有适宜的交联网络。
(二)实施例与对比例的比较
6)实施例1、对比例1相比较,对比了光交联PVA-SbQ/ZIF-8复合水凝胶有无吸附PAM 前驱体并进行二次光交联,两种情况下对水凝胶的性能影响,可以看出,光交联PVA-SbQ/ZIF-8 复合水凝胶在经过吸附PAM前驱体并进行二次光交联后,得到的PVA-SbQ/ZIF-8/PAM水凝胶的性能大大提高,尤其是力学强度和溶胀率提升数倍。这可能是因为PAM的引入形成互穿网络结构,有助于吸附性能的提升。
7)实施例1、对比例2相比较,对比了简单的光交联PVA-SbQ水凝胶,与实施例1根据本发明方法得到PVA-SbQ/ZIF-8/PAM水凝胶两种水凝胶的性能,可以看出,实施例1所得的PVA-SbQ/ZIF-8/PAM水凝胶的性能均得到大大提升。这可能是因为互穿网络结构的形成和具有较大比表面积ZIF-8的引入,均能够大幅提升复合材料的吸附性能。
8)同前述第2)点,实施例1、对比例3相比较,对比了无ZIF-8的光交联PVA-SbQ/PAM水凝胶,与实施例1根据本发明方法得到PVA-SbQ/ZIF-8/PAM水凝胶两种水凝胶的性能,可以看出,有了MOF的加成作用,实施例1所得的PVA-SbQ/ZIF-8/PAM水凝胶的性能均得到大大提升,验证了ZIF-8的添加对水凝胶的性能提高的有效性。这可能是因为ZIF-8有序的微孔结构,使其具有大的比表面积,与聚合物网络相比,吸附性能更高。
9)实施例1、对比例4相比较,对比了简单的光聚合交联PAM水凝胶,与实施例1根据本发明方法得到PVA-SbQ/ZIF-8/PAM水凝胶两种水凝胶的性能,可以看出,较之仅有PAM前驱体的光交联水凝胶,添加了光交联PVA-SbQ/PAM复合水凝胶后,实施例1所得的 PVA-SbQ/ZIF-8/PAM水凝胶的性能均得到大大提升。这可能是因为互穿网络结构的形成和具有较大比表面积ZIF-8的引入,均能够大幅提升复合材料的吸附性能。
综合对比例来看,与实施例1根据本发明方法得到PVA-SbQ/ZIF-8/PAM水凝胶相比,无论缺少了PVA-SbQ、ZIF-8、PAM中任何一个组分,最终的产品性能都会受到很大影响,其吸水前后的效果对比如图1-5所示。相较而言,实施例1即展示了本发明主要的优势在于:聚合物凝胶的引入有助于改善MOF机械强度低、吸附以后不易分离等问题;互穿网络结构的设计有助于提高凝胶网络的强度;采用光交联制备聚合物/MOF复合水凝胶,具有绿色快捷、MOF 在聚合物网络中分散均匀的优点;聚合物交联网络中引入MOF材料具有更大的比表面积,从而得到更高的吸附容量。这也充分说明了该三种成分之间存在相互协同增益效果。
表1对比例和实施例的力学强度、溶胀率、吸附容量结果
Claims (8)
1.一种光交联水凝胶的制备方法,其特征在于:包括以下步骤:
(1)PVA-SbQ/MOF悬浮液的制备:MOF分散在PVA-SbQ水溶液中,获得PVA-SbQ/MOF悬浮液,所述的MOF与PVA-SbQ的质量比为1:5~20,所述MOF为ZIF-8;
(2)光交联PVA-SbQ/MOF复合水凝胶的制备:所述PVA-SbQ/MOF悬浮液倒入聚四氟乙烯模具中,在紫外光照射下,SbQ基团发生二聚交联,形成第一重网络,得光交联PVA-SbQ/MOF复合水凝胶,所述的紫外光照射采用50-100W/cm2的紫外灯,照射时间为5-10min;
(3)光交联PVA-SbQ/MOF/PAM互穿网络水凝胶的制备:丙烯酰胺、交联剂、光引发剂溶解在去离子水中制备得到PAM前驱体溶液,所述PVA-SbQ/MOF复合水凝胶在所述PAM前驱体溶液中浸泡直至达到吸附平衡;取出吸附了PAM前驱体的PVA-SbQ/MOF水凝胶,再次进行紫外光照射,丙烯酰胺聚合交联得到第二重网络,得PVA-SbQ/MOF/PAM互穿网络水凝胶。
2.根据权利要求1所述的光交联水凝胶的制备方法,其特征在于:步骤(2)中,所述的紫外光照射采用100W/cm2的紫外灯,照射时间为10min。
3.根据权利要求1所述的光交联水凝胶的制备方法,其特征在于:步骤(3)中,所述的紫外光照射采用100W/cm2的紫外灯,照射时间为10min。
4.根据权利要求1所述的光交联水凝胶的制备方法,其特征在于:步骤(3)中,所述PAM前驱体溶液中,丙烯酰胺的物质的量浓度为1-5mol/L,交联剂的物质的量浓度为丙烯酰胺的物质的量浓度的0.4%-0.8%,光引发剂的质量占丙烯酰胺与交联剂总质量的0.01%-0.1%,所述交联剂为亚甲基双丙烯酰胺。
5.根据权利要求1所述的光交联水凝胶的制备方法,其特征在于:步骤(1)中,所述PVA-SbQ水溶液的质量浓度为6%-15%。
6.根据权利要求1所述的光交联水凝胶的制备方法,其特征在于,步骤(1)中,所述的PVA-SbQ/MOF悬浮液的制备方法为:MOF分散在PVA-SbQ水溶液中,通过超声分散均匀,配置成PVA-SbQ/MOF悬浮液;或者将MOF前驱体溶解在PVA-SbQ水溶液中,原位反应生成PVA-SbQ/MOF悬浮液。
7.根据权利要求1-6任一所述方法制备的光交联PVA-SbQ/MOF/PAM水凝胶。
8.根据权利要求7所述的PVA-SbQ/MOF/PAM水凝胶在染料吸附中的应用。
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Non-Patent Citations (3)
Title |
---|
High performance HKUST-1@PVA-co-PE/PVA hybrid hydrogel with enhanced selective adsorption;Zhu Qing,et al;《Composites Communications》;20180615;第10卷;摘要,第2.2节,第36页左栏第2段 * |
Methylene blue removal on nano-Fe3O4/poly(vinyl alcohol)/polyacrylamide hydrogel;Neeta Pandey,et al;《Emerging Materials Research》;20171221;第6卷(第2期);第2.3节 * |
紫外光聚合法制备 PVA-SbQ/透明质酸凝胶及其性能研究;艾玲等;《功能材料》;20111231;第42卷;第346页左栏最后1段 * |
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