CN110713609A - 一种基于Janus纳米材料制备自修复水凝胶的方法 - Google Patents
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Abstract
本发明公开了一种氧化石墨烯基Janus纳米复合材料制备自修复水凝胶的方法,首先通过用氧化石墨烯与丙烯酸在一定温度下反应一定时间,制得表面功能化的纳米片(GO@AA),然后利用Pickering乳液模板制得在GO@AA两面分别接枝了聚吡咯和聚甲基丙烯酸二甲氨基乙酯的Janus纳米材料,将其应用于制备聚丙烯酸基纳米复合水凝胶。所得Janus纳米复合水凝胶具有自主、快速修复能力且具有较高机械强度,在人体运动检测领域具有潜在的运用前景。
Description
技术领域
本发明通过利用Pickering乳液模板法成功制备了一种功能性Janus纳米片,然后将其应用于制备聚丙烯酸基纳米复合水凝胶,属于功能高分子领域。
背景技术
导电水凝胶以其优异的电子性能、可调的机械性能和显著的生物特性,作为柔性可穿戴应变传感器的新兴材料而得到了广泛的研究。其良好的机械强度和机电性能是决定其应用的因素。良好的自愈性能可以显著提高水凝胶的耐用性,延长其使用寿命。迄今为止,研究者们通过物理或动态化学键合成了多种自愈合水凝胶。根据自修复机制,自修复水凝胶主要包括物理自修复和化学自修复水凝胶,主要利用氢键、疏水缔合作用、主客体识别作用、离子键作用、亚胺键等作用进行自修复。纳米复合自修复水凝胶的快速自愈性能有助于反复恢复传感器的机电性能,避免在大变形时性能下降。
Janus粒子是一种胶体结构,其表面或体块具有不对称的物理和化学性质。不同的材料以不同的形态、不同的化学性质、物理性质和表面性质在同一粒子中组合,令其在化学、应用光学、传感、生物医学和催化领域具有多种多样的应用。因此,基于Janus的自修复水凝胶材料非常有研究价值。
近几十年来,人们开发了许多制备Janus粒子的方法,主要包括掩蔽法、表面保护法、微流体法、相分离法、种子乳液聚合法和自组装法等。以固体颗粒代替分子表面活性剂的Pickering乳液作为一种掩蔽技术,引起了人们极大的兴趣。本发明通过Pickering乳液模板制备Janus GO,制备一种基于Janus GO的自修复水凝胶材料。
本发明首先制备表面功能化的纳米片(GO@AA),并与甲苯、蒸馏水混合匀浆形成Pickering乳液,通过水包油的形态,将疏水聚合物聚吡咯(PPy)接枝在GO纳米片一侧,再将亲水聚合物聚甲基丙烯酸二甲氨基乙酯(PDMAEMA)接枝在GO另一侧,由此制备出Janus GO,最后将其参与制备自修复水凝胶。该方法为自修复水凝胶的制备提供了一种新方法,其良好的机械强度与强大的机电性能可令其在检测人体运动情况监测方向有较好的应用前景。
发明内容
本发明专利的目的在于提供一种通过Pickering乳液制备Janus GO自修复水凝胶的方法。
为达到上述目的,本发明具体技术方案是:
(1)将氧化石墨烯(GO)与丙烯酸(AA)在一定条件下发生酯化反应制备表面功能化的纳米片(GO@AA),包括:GO、AA、4-二甲氨基吡啶(DMAP)、二甲基甲酰胺(DMF)、二环己基碳二亚胺(DCC)在一定的温度和搅拌速度下反应一定时间,进行离心、冷冻干燥;其中,按质量比,GO:AA:DMAP:DMF:DCC = 0.1~1:0.1~1:0.005~0.05:1~10:0.1~2;
所述反应温度:10~50摄氏度,
所述搅拌速度:100~500转/分,
所述反应时间:12~36小时;
(2)通过Pickering乳液在GO纳米片内侧接枝聚吡咯(PPy),制备纳米材料(GO@PPyJanus NS);包括:上述反应所得的GO@AA、蒸馏水(H2O)、甲苯、吡咯和三氯化铁在一定的温度和搅拌速度下反应一定时间,离心、冷冻干燥;其中,按质量比,GO@AA:蒸馏水:甲苯:吡咯:三氯化铁= 0.1~1:100~1000:20~200:0.1~10:0.01~0.5;
所述反应温度:25摄氏度,
所述搅拌速度:100~500转/分,
所述反应时间:30~120分钟;
(3)将上述反应所得GO@PPy Janus NS在过硫酸钾(KPS)溶液环境下接枝聚甲基丙烯酸二甲氨基乙酯(PDMAEMA),制备Janus纳米复合材料(GO@PPy/PDMAEMA Janus NS);包括:GO@PPy Janus NS、KPS和甲基丙烯酸二甲氨基乙酯(DMAEMA)在一定的温度和搅拌速度下反应一定时间,离心、冷冻干燥;其中,按质量比,GO@PPy Janus NS:KPS:DMAEMA = 0.1~1:0.01~0.1:0.001~0.01;
所述反应温度:20~100摄氏度,
所述搅拌速度:100~500转/分,
所述反应时间:1~3小时;
(4)将(3)中所得GO@PPy/PDMAEMA Janus NS与AA、H2O、KPS、六水三氯化铁(FeCl3·6H2O)在一定温度下反应一定时间制得自修复水凝胶;其中,按质量比,AA:H2O:FeCl3·6H2O:KPS:GO@PPy/PDMAEMA Janus NS = 1:1~10:0.1~10:1~10:1~10;
所述反应温度:20~45摄氏度,
所述反应时间:1~5小时;
应用上述体系可合成Janus纳米材料,并参与制备具有自修复功能的水凝胶。
因此,本发明要求保护制备自修复水凝胶的方法。包括以下步骤:
(1)按照权利要求1所述配方配制体系;
(2)将所制得的纳米材料加入聚丙烯酸(PAA)水凝胶中制备自修复水凝胶的方法;
由于上述技术方案运用,本发明与现有技术相比具有下列优点:
本发明利用Pickering乳液制备Janus纳米复合自修复水凝胶,该复合水凝胶在室温下能自主、快速自动愈合,同时具有较高的材料机械强度和机械性能,可用于可穿戴电子设备的研发。
具体实施方式
下面结合典型实施案例对本发明作进一步描述,但本发明并不限于以下实施案例。所述方法如无特殊说明均为常规方法。所述原材料如无特别说明均能从公开商业途径而得。
实施例一:制备表面功能化的纳米片(GO@AA)
将0.5克GO,0.325毫升AA和0.025克DMAP与25毫升DMF混合,用N2吹扫,冷却至0摄氏度。将0.55克DCC溶解在5毫升DMF中并在10分钟内滴加到该溶液中,然后在25摄氏度下搅拌24小时,离心并冷冻干燥。
实施例二:利用Pickering乳液接枝聚吡咯制备Janus纳米材料(GO@PPy JanusNS)
取50毫克的GO@AA加入到含有50毫升蒸馏水的烧杯中,超声震荡溶解30分钟左右,使之均匀分散在水中。将10毫升的甲苯和0.5毫升的吡咯混合后加入烧杯中,用匀浆机将其乳化,直到静止不分层为止(约为10分钟),再机械搅拌10分钟,转速300转/分。称取10毫克FeCl3,加入烧瓶中,继续搅拌30分钟。
实施例三:制备Janus纳米复合材料(GO@PPy/PDMAEMA Janus NS)
将0.5毫升DMAEMA和5.0毫升KPS水溶液(0.0066克/毫升)加入上述Pickering乳液中,并置于60摄氏度油浴中2小时。将最终的Pickering乳液在室温下冷却,离心并用乙醇洗涤,最后冷冻干燥。
实施例四:制备自修复水凝胶
将1毫升AA、2毫升去离子水、1毫升KPS、0.8毫升FeCl3·6H2O和不同量的Janus纳米材料GO@PPy/PDMAEMA Janus NS制备聚丙烯酸水凝胶,将水凝胶倒入模具中,置于35摄氏度烘箱中干燥。以聚合物的加入量作为变量设置对照试验。通过对所制水凝胶的自修复性能进行表征,探究聚合物的最佳用量。
Claims (2)
1.一种基于Janus纳米材料制备自修复水凝胶的方法,其特征在于,主要分为以下两个步骤:
(1)制备氧化石墨烯基Janus纳米材料(GO@PPy/PDMAEMA Janus NS)
首先,将氧化石墨烯(GO)与丙烯酸(AA)在一定条件下发生酯化反应制备表面功能化的纳米片(GO@AA),包括:GO、AA、4-二甲氨基吡啶(DMAP)、二甲基甲酰胺(DMF)、二环己基碳二亚胺(DCC)在一定的温度和搅拌速度下反应一定时间,进行离心、冷冻干燥;其中,按质量比,GO:AA:DMAP:DMF:DCC=0.1~1:0.1~1:0.005~0.05:1~10:0.1~2;
所述反应温度:10~50摄氏度,
所述搅拌速度:100~500转/分,
所述反应时间:12~36小时;
其次,通过Pickering乳液在GO纳米片内侧接枝聚吡咯(PPy),制备纳米材料(GO@PPyJanus NS);包括:上述反应所得的GO@AA、蒸馏水(H2O)、甲苯、吡咯和三氯化铁在一定的温度和搅拌速度下反应一定时间,离心、冷冻干燥;其中,按质量比,GO@AA:蒸馏水:甲苯:吡咯:三氯化铁=0.1~1:100~1000:20~200:0.1~10:0.01~0.5;
所述反应温度:25摄氏度,
所述搅拌速度:100~500转/分,
所述反应时间:30~120分钟;
最后,将上述反应所得GO@PPy Janus NS在过硫酸钾(KPS)溶液环境下接枝聚甲基丙烯酸二甲氨基乙酯(PDMAEMA),制备Janus纳米复合材料(GO@PPy/PDMAEMA Janus NS);包括:GO@PPy Janus NS、KPS和甲基丙烯酸二甲氨基乙酯(DMAEMA)在一定的温度和搅拌速度下反应一定时间,离心、冷冻干燥;其中,按质量比,GO@PPy Janus NS:KPS:DMAEMA = 0.1~1:0.01~0.1:0.001~0.01;
所述反应温度:20~100摄氏度,
所述搅拌速度:100~500转/分,
所述反应时间:1~3小时;
(2)利用上述步骤(1)所制备的Janus纳米复合材料制备自修复水凝胶
将(1)中所得GO@PPy/PDMAEMA Janus NS与AA、H2O、KPS、六水三氯化铁(FeCl3·6H2O)在一定温度下反应一定时间制得自修复水凝胶;其中,按质量比,AA:H2O:FeCl3·6H2O:KPS:GO@PPy/PDMAEMA Janus NS = 1:1~10:0.1~10:1~10:1~10;
所述反应温度:20~45摄氏度,
所述反应时间:1~5小时。
2.利用上述制备工艺设计室温下具有自主、快速修复能力且具有较高机械强度的Janus纳米复合自修复水凝胶。
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CN116444745B (zh) * | 2023-04-14 | 2023-11-14 | 上海宇昂水性新材料科技股份有限公司 | 一种水性分散剂及其制备方法和应用 |
CN117820942A (zh) * | 2024-03-04 | 2024-04-05 | 成都虹润制漆有限公司 | 用于铁路桥梁钢结构的底、中、面复合涂料及其制备方法 |
CN117820942B (zh) * | 2024-03-04 | 2024-05-10 | 成都虹润制漆有限公司 | 用于铁路桥梁钢结构的底、中、面复合涂料及其制备方法 |
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