CN108276589B - 一种改性环糊精聚合物水凝胶的制备方法与应用 - Google Patents
一种改性环糊精聚合物水凝胶的制备方法与应用 Download PDFInfo
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Abstract
本发明涉及污水处理技术领域，为解决现有的水凝胶大多只能处理单一污染物，效率低、应用范围小的问题，本发明提出了一种改性环糊精聚合物水凝胶的制备方法与应用，以β‑环糊精为原料，利用对甲苯磺酰氯对其进行选择性磺酰化得到对甲苯磺酰基‑β‑环糊精，再经硫脲取代得到巯基接枝β‑环糊精，经过悬浮乳液聚合法制得新型双功能聚合物水凝胶。本发明所制备的水凝胶可应用于苯酚与重金属离子共存的复杂污水体系。可以高效同步吸附苯酚与重金属离子两类污染物，应用范围广、吸附效率高。
Description
技术领域
本发明涉及污水处理技术领域，具体涉及一种同步识别吸附污水体系中分子/离子污染物的改性环糊精聚合物水凝胶的制备方法与应用。
背景技术
随着工业化、城市化的发展，工业及生活废水的大量排放造成了严重的水体污染，直接威胁到动植物的生长以及人类的身体健康与生存环境，污水治理得到空前重视。有机污染物与重金属离子是污水中最重要的成分，目前处理此类污染物的方法有膜分离法、吸附法、化学法、生物法等，上述方法大多仅针对单一污染物，且成本高、效率低、耗时长。因此，高效的污水处理技术成为当前的关注热点，特别是处理多污染物共存的复杂污水体系是目前研发的前沿。其中，同时含苯酚和重金属离子的污水是较常见的复杂污水体系，对于处理含酚及重金属离子废水，吸附仍然是主流技术之一，关键是吸附材料的选择。水凝胶具有良好的水渗透性、吸附性、生物相容性及降解性，能够同时感知和响应环境变化的刺激，是一种良好的环境友好型吸附材料。
目前已有许多专利涉及水凝胶材料吸附污染物的研究。例如，专利号为CN103877953A的专利公开了一种利用聚乙烯醇、壳聚糖、羧甲基纤维素钠、氧化石墨烯、海藻酸钠制得的用于吸附重金属离子的水凝胶。专利号为CN104941584B的专利公开了一种SiO2/C复合材料吸附重金属离子，其制备方法为：(1)淀粉均匀凝胶分散体系的制备。(2)淀粉/二氧化硅复合材料的制备。(3)SiO2/C复合材料的制备。由此可见，现有的水凝胶大多只能处理单一污染物，效率低、应用范围小。因此，开展高效同步吸附多种污染物的新型水凝胶研究极有必要。
发明内容
为解决现有的水凝胶大多只能处理单一污染物，效率低、应用范围小的问题，本发明提出了一种改性环糊精聚合物水凝胶的制备方法与应用，可以高效同步吸附苯酚与重金属离子两类污染物，应用范围广、吸附效率高。
本发明是通过以下技术方案实现的：一种改性环糊精聚合物水凝胶的制备方法为以下步骤：
(1)将β-环糊精与对甲苯磺酰氯在氢氧化钠溶液A混合，0～5℃水浴搅拌反应3～5h，结束后减压抽滤，调节滤液pH至6.0～8.0，0～5℃结晶8～12h，减压抽滤，去离子水重结晶后40～50℃真空干燥，得到中间体对甲苯磺酰基-B-环糊精；
采用β-环糊精为原料，β-环糊精是多糖化合物，具有良好的生物降解性、应用范围广、生产成本低等优点。
所述的β-环糊精与对甲苯磺酰氯的摩尔比为1∶3～1∶6。
所述氢氧化钠溶液A的摩尔浓度为为0.3～0.5mol/L。氢氧化钠溶液作为溶剂，使用量为使溶质溶解的量。氢氧化钠溶液A浓度过高或过低都会使产率降低。
(2)将对甲苯磺酰基-β-环糊精与硫脲在乙醇水溶液混合，60～70℃回流反应24～48h，收集液旋转蒸发得到固体，加入氢氧化钠溶液B，50～60℃回流反应3～5h，调节滤液pH至2.0～3.0，去离子水重结晶后40～50℃真空干燥，得到巯基接枝β-环糊精单体；
所述对甲苯磺酰基-β-环糊精与硫脲的质量比为1∶1～2。
所述乙醇水溶液的质量浓度为80％～95％。乙醇溶液作为溶剂，使用量为使溶质溶解的量。
氢氧化钠溶液B的质量浓度为10～20％。使用量为使溶质溶解的量，氢氧化钠溶液B的使用是为了制造碱性环境。
(3)将巯基接枝β-环糊精单体溶于去离子水中，氮气保护搅拌10～20分钟，加入交联剂与引发剂，氮气保护搅拌10分钟后40～60℃水浴反应3～4h，取出产物并将其置于去离子水中浸泡3～5天，50～60℃烘干，得到改性环糊精聚合物水凝胶。
所述巯基接枝β-环糊精单体与交联剂的质量比为2～10∶1，交联剂选自N，N-亚甲基双丙烯酰胺、环氧氯丙烷、异氰酸酯中的一种。
所述交联剂与引发剂的质量比为2～3∶1，引发剂选自过硫酸钾、过硫酸铵中的一种。
上述步骤中选用盐酸溶液调节pH，更优选为10％盐酸溶液。
本发明所制备的改性环糊精聚合物水凝胶通过环糊精的包合作用、双硫键网状结构与重金属离子强烈的亲和作用实现高效同步吸附苯酚与重金属离子两类污染物，能克服已有水凝胶材料处理对象单一的缺陷，应用范围广、吸附效率高，可广泛应用于养殖场废水、化工厂废水等污水体系，具有良好的发展前景。
与现有技术相比，本发明的有益效果是：本发明工艺过程简单、操作方便、成本经济，制得的水凝胶具有良好的同步吸附性能，具有广泛的应用前景。
附图说明
图1为对甲苯磺酰基-β-环糊精红外光谱图；
图2为巯基接枝β-环糊精单体红外光谱图；
图3为本发明改性环糊精聚合物水凝胶的扫描电镜图。
具体实施方式
下面通过实施例对本发明作进一步详细说明，实施例中所用原料均可市购或采用常规方法制备。以下实施例旨在说明本发明而不是在对本发明的进一步限定。
实施例1
(1)将8g(相当于0.007mol)β-环糊精与250mL 0.45mol/L氢氧化钠溶液混合，3℃水浴搅拌反应5h，每隔1h加入1.1g(0.005mol)对甲苯磺酰氯，总共加入0.025mol，反应结束后减压抽滤，10％盐酸溶液调节滤液pH至7.0，3℃结晶10h，减压抽滤，去离子水重结晶后50℃真空干燥，得到中间体对甲苯磺酰基-β-环糊精，红外光谱图如图1所示。
(2)将4g对甲苯磺酰基-β-环糊精、4.4g硫脲、200mL95％乙醇水溶液混合，70℃回流反应24h，加入150mL20％氢氧化钠溶液，50℃回流反应5h，10％盐酸溶液调节滤液pH至2.0，去离子水重结晶后50℃真空干燥，得到巯基接枝β-环糊精单体，红外光谱图如图2所示。
(3)将0.2g巯基接枝β-环糊精单体溶于20mL去离子水中，氮气保护搅拌10分钟，加入0.08g，交联剂N，N-亚甲基双丙烯酰胺与0.04g引发剂过硫酸钾，氮气保护搅拌10分钟后40℃水浴反应4h，取出产物置于去离子水中浸泡一周，50℃烘干，得到一种改性环糊精聚合物水凝胶1，扫描电镜图如图3所示。
实施例2
(1)将8g(相当于0.007mol)β-环糊精与250mL 0.6mol/L氢氧化钠溶液混合，0℃水浴搅拌反应5h，每隔1h加入2.2g(0.01mol)对甲苯磺酰氯，共加入0.040mol，反应结束后减压抽滤，10％盐酸溶液调节滤液pH至6.0，0℃结晶12h，减压抽滤，去离子水重结晶后40℃真空干燥，得到中间体对甲苯磺酰基-β-环糊精，红外光谱图如图1所示。
(2)将4g对甲苯磺酰基-β-环糊精、4g硫脲、200mL 90％乙醇水溶液混合，65℃回流反应36h，加入150mL15％氢氧化钠溶液，50℃回流反应4h，10％盐酸溶液调节滤液pH至3.0，去离子水重结晶后50℃真空干燥，得到巯基接枝β-环糊精单体，红外光谱图如图2所示。
(3)将0.2g巯基接枝β-环糊精单体溶于20mL去离子水中，氮气保护搅拌20分钟，加入0.04g交联剂环氧氯丙烷与0.02g引发剂过硫酸钾，氮气保护搅拌20分钟后50℃水浴反应4h，取出产物置于去离子水中浸泡一周，60℃烘干，的奥一种改性环糊精聚合物水凝胶2，红外光谱图如图1所示，扫描电镜图如图3所示。
实施例3
(1)将8g(相当于0.007mol)，β-环糊精与250mL 0.8mol/L氢氧化钠溶液混合，5℃水浴搅拌反应3h，每隔1h加入2.2g(0.01mol)对甲苯磺酰氯，共加入0.03mol，反应结束后减压抽滤，10％盐酸溶液调节滤液pH至8.0，5℃结晶8h，减压抽滤，去离子水重结晶后45℃真空干燥，得到中间体对甲苯磺酰基-B-环糊精，红外光谱图如图1所示。
(2)将4g对甲苯磺酰基-β-环糊精、8g硫脲、200mL 80％乙醇水溶液混合，60℃回流反应48h，加入150mL 10％氢氧化钠溶液，60℃回流反应3h，10％盐酸溶液调节滤液pH至3.0，去离子水重结晶后40℃真空干燥，得到巯基接枝β-环糊精单体，红外光谱图如图2所示。
(3)将0.2g巯基接枝β-环糊精单体溶于20mL去离子水中，氮气保护搅拌10分钟，加入0.02g交联剂异氰酸酯与0.008g引发剂过硫酸铵，氮气保护搅拌10分钟后60℃水浴反应3h，取出产物置于去离子水中浸泡一周，50℃烘干，得到一种改性环糊精聚合物水凝胶3，扫描电镜图如图3所示。
测试例
实施例1-3制得的水凝胶吸附性能表如表1所示：
表1
本发明所制备的同步识别吸附分子/离子污染物的新型聚合物水凝胶经实例测试可得，其对苯酚及其他金属离子污染物具有较好的吸附性能，其中在金属离子污染物中，新型聚合物水凝胶对Pb2+的吸附性能最佳。同理，本发明制备的新型材料也可对其他目标污染物进行功能性吸附，在此不作一一列举。
Claims (3)
1.一种改性环糊精聚合物水凝胶的制备方法，其特征在于，所述的制备方法为以下步骤：
（1）将8g β-环糊精与250mL 0.45mol/L氢氧化钠溶液混合，3℃水浴搅拌反应5h，每隔1h加入1.1g对甲苯磺酰氯，总共加入0.025mol，反应结束后减压抽滤，10%盐酸溶液调节滤液pH至7.0，3℃结晶10h，减压抽滤，去离子水重结晶后50℃真空干燥，得到中间体对甲苯磺酰基-β-环糊精；
（2）将4g对甲苯磺酰基-β-环糊精、4.4g硫脲、200mL 95wt%乙醇水溶液混合，70℃回流反应24h，加入150mL 20wt% 氢氧化钠溶液，50℃回流反应5h，10%盐酸溶液调节滤液pH至2.0，去离子水重结晶后50℃真空干燥，得到巯基接枝β-环糊精单体；
（3）将0.2g巯基接枝β-环糊精单体溶于20mL去离子水中，氮气保护搅拌10分钟，加入0.08g，交联剂N,N-亚甲基双丙烯酰胺与0.04g引发剂过硫酸钾，氮气保护搅拌10分钟后40℃水浴反应4h，取出产物置于去离子水中浸泡一周，50℃烘干，得到一种改性环糊精聚合物水凝胶；
改性环糊精聚合物水凝胶的吸附能力，苯酚为38mg/g，Cu2+为43mg/g，Pb2+为79mg/g，Fe3 +为38mg/g，Hg2+为51mg/g。
2.一种改性环糊精聚合物水凝胶的制备方法，其特征在于，所述的制备方法为以下步骤：
（1）将8g β-环糊精与250mL 0.6mol/L氢氧化钠溶液混合，0℃水浴搅拌反应5h，每隔1h加入2.2g对甲苯磺酰氯，共加入0.040mol，反应结束后减压抽滤，10%盐酸溶液调节滤液pH至6.0，0℃结晶12h，减压抽滤，去离子水重结晶后40℃真空干燥，得到中间体对甲苯磺酰基-β-环糊精；
（2）将4g对甲苯磺酰基-β-环糊精、4g硫脲、200mL 90wt%乙醇水溶液混合，65℃回流反应36h，加入150mL 15wt% 氢氧化钠溶液，50℃回流反应4h，10%盐酸溶液调节滤液pH至3.0，去离子水重结晶后50℃真空干燥，得到巯基接枝β-环糊精单体；
（3）将0.2g巯基接枝β-环糊精单体溶于20mL去离子水中，氮气保护搅拌20分钟，加入0.04g交联剂环氧氯丙烷与0.02g引发剂过硫酸钾，氮气保护搅拌20分钟后50℃水浴反应4h，取出产物置于去离子水中浸泡一周，60℃烘干，得到一种改性环糊精聚合物水凝胶，
改性环糊精聚合物水凝胶的吸附能力，苯酚为36mg/g，Cu2+为44mg/g，Pb2+为81mg/g，Fe3 +为36mg/g，Hg2+为49mg/g。
3.一种改性环糊精聚合物水凝胶的制备方法，其特征在于，所述的制备方法为以下步骤：
（1）将8g β-环糊精与250mL 0.8mol/L氢氧化钠溶液混合，5℃水浴搅拌反应3h，每隔1h加入2.2g对甲苯磺酰氯，共加入0.03mol，反应结束后减压抽滤，10%盐酸溶液调节滤液pH至8.0，5℃结晶8h，减压抽滤，去离子水重结晶后45℃真空干燥，得到中间体对甲苯磺酰基-β-环糊精；
（2）将4g对甲苯磺酰基-β-环糊精、8g硫脲、200mL 80wt%乙醇水溶液混合，60℃回流反应48h，加入150mL 10wt% 氢氧化钠溶液，60℃回流反应3h，10%盐酸溶液调节滤液pH至3.0，去离子水重结晶后40℃真空干燥，得到巯基接枝β-环糊精单体；
（3）将0.2g巯基接枝β-环糊精单体溶于20mL去离子水中，氮气保护搅拌10分钟，加入0.02g交联剂异氰酸酯与0.008g引发剂过硫酸铵，氮气保护搅拌10分钟后60℃水浴反应3h，取出产物置于去离子水中浸泡一周，50℃烘干，得到一种改性环糊精聚合物水凝胶；
改性环糊精聚合物水凝胶的吸附能力，苯酚为40mg/g，Cu2+为47mg/g，Pb2+为85mg/g，Fe3 +为40mg/g，Hg2+为55mg/g。
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