CN110627969A - 一种利用Janus纳米材料制备自修复水凝胶的方法 - Google Patents
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Abstract
本发明公开了一种基于纤维素纳米晶表面改性制备的Janus纳米杂化材料,构筑自修复纳米复合水凝胶的方法,实现了由纤维素纳米晶基Janus纳米杂化材料制备聚丙烯酸基自修复纳米复合水凝胶。通过浓硫酸水解微晶纤维素制得CNCs;加入引发剂,使纤维素纳米晶与聚赖氨酸的聚合,制备纤维素纳米晶基复合物;进一步改性后成功制备纤维素纳米晶基Janus纳米杂化材料,以其为添加剂成功制备了一种纤维素纳米晶基Janus纳米杂化材料参与的自修复纳米复合水凝胶。
Description
技术领域
本发明基于纤维素纳米晶表面改性制备的Janus纳米杂化材料,成功设计了一种纳米复合自修复水凝胶,属于功能高分子领域。
背景技术
水凝胶是聚合物网络中柔软且高度水化的结构,水凝胶已被广泛应用于生物医学、制药等领域。大部分水凝胶具有易脆性,断裂应变小、延展性差等缺点,因而通过自我修复使他们在机械损伤和后恢复功能至关重要。在水凝胶的制备过程中引入纳米粒子作为纳米增强剂和多功能交联剂,所制备出的水凝胶具有较好的力学性能,在受到外力损伤后,表现出较强自我修复能力。
近年来,纳米复合自修复水凝胶的研究主要集中在无机纳米填料(例如二氧化硅、氧化石墨烯)或刚性聚合物纳米填料(例如纤维素纳米晶)。其中,纤维素纳米晶(CNCs)具有来源天然、机械强度高、生物相容性好、制备工艺简易等优点,此外,可对其表面进行表面修饰,如氧化、酯化、醚化或化合物接枝,因而能够对CNCNs进行表面改性并使其有效地结合到水凝胶基质中,这也使它成为近年来研究的热点。将基于CNCs制备的纳米杂化材料用于水凝胶的制备工艺中,所制得的水凝胶具有优越的力学性能。
Janus粒子包含两个具有不同表面化学性质的区域,与其它各向同性的纳米粒子相比,通常表现出不同的性质,因而具有较高的研究价值,近年来也常用做皮克林乳液的稳定剂。Pickering乳液是一种以胶体粒子为稳定剂稳定水油系统的乳液,其中负性纳米晶、孢子、细菌等被证明是Pickering乳液的高效稳定剂。相对于通常意义以表面活性剂分子稳定的乳液,Pickering乳液不易受温度、Ph值、盐浓度等因素的影响,具有更强的稳定性。皮克林乳液是一种常用的CNCs表面改性工艺,同时Pickering乳液也为制备Janus纳米粒子提供了一种新思路,例如,二氧化硅/氧化锌纳米粒子、聚丙烯酸酯/二氧化硅纳米粒子的制备。本专利以甲苯为油相,Tris-HCl缓冲溶液为水相,纤维素纳米晶基复合物为表面活性剂,成功制得具有两亲性的Janus纳米粒子。
表面引发聚合(SIP)是一种用于表面改性的极有效工具,在制备具有设计结构和性能的杂化材料方面有着广泛的应用。由于其活性自由基聚合特性,表面引发的原子转移自由基聚合(SI-ATRP)成为使用最为广泛的SIP方法之一。SI-ATRP已被广泛应用于材料改性。本实验利用浓硫酸水解微晶纤维素制得纤维素纳米晶(CNCs),利用SI-ATRP成功制备出一种纤维素纳米晶基复合物(CNCs@PLL)。通过Pickering乳液界面,借助氨基的亲水性,使聚多巴胺(PDA)对CNCs@PLL的水相一侧进行表面改性,制得具有两亲性的Janus纳米杂化材料。将该材料作为纳米增强剂添加到聚丙烯酸基水凝胶中,成功设计了一种由纤维素纳米晶基Janus纳米杂化材料制备的聚丙烯酸基自修复纳米复合水凝胶。此过程中加入的金属离子Fe3+与聚丙烯酸上的羧基形成离子键结构,构成的金属配位体网络极大地增强了其交联结构以及力学强度;聚多巴胺上存在大量的儿茶酚基团,其能够与Fe3+形成的可逆键合能力可赋予水凝胶优异的自修复性能。
基于智能材料设计理念,通过浓硫酸水解微晶纤维素制得CNCs,利用SI-ATRP技术实现其表面定向修饰后复合制备了自修复水凝胶。在制得CNCs的基础上,加入引发剂,引发纤维素纳米晶与聚赖氨酸的聚合。由甲苯、去离子水混合匀浆得到Pickering乳液,得到油包水的形态。借助于Pickering乳液界面,使CNCs@PLL的水相一侧接枝聚多巴胺,制得CNCs@PLL@PDA Janus纳米杂化材料,后将其引入水凝胶的制备工艺中,制备聚丙烯酸基自修复纳米复合水凝胶。所涉及的水凝胶具有较强的机械性能和优良的自修复性能,在智能、高机械性能水凝胶的设计合成中具有广泛的应用前景。
发明内容
本发明专利的目的在于提出一种利用Janus纳米材料制备自修复水凝胶的方法。为达到上述目的,本发明的具体技术方法如下:
(1)纤维素纳米晶基Janus纳米杂化材料的制备,首先,将纤维素纳米晶分散于去离子水中,向其中通入氮气25分钟,将过硫酸铵分散于聚赖氨酸中通入氮气5分钟。将后者倒入前者中,使纤维素纳米晶接枝聚赖氨酸(PLL),制备CNCs@PLL。包括:去离子水、纤维素纳米晶(CNCs)、引发剂过硫酸铵(APS,5mg/mL),聚赖氨酸(PLL,0.05g/mL)在适宜的温度下反应,其中,按质量比去离子水:纤维素纳米晶:引发剂:聚赖氨酸=1~10000:1~100:1~10:1~100,
其中,所用引发剂为过硫酸铵(APS),
所述反应温度为60℃,
所述反应时间为6~12h;
然后,在Tris-HCl缓冲溶液中(pH =8.5)将上述所得CNCs@PLL杂化材料的一侧接枝聚多巴胺,制备CNCs@PDA@PLL纳米杂化材料。去离子水、甲苯、盐酸多巴胺、CNCs@PLL在Tris-HCl缓冲溶液中反应一定时间。其特征在于,可以通过Pickering乳液模板对纤维素纳米晶基外侧接枝聚合物,其中,按质量比,Tris-HCl缓冲溶液:CNCs@PLL:盐酸多巴胺(DA):甲苯=1~10: 1~10:1:1~500
其中,所述反应温度:25~45℃,
所述反应时间:6~12h;
(2)基于CNCs@PDA@PLL纳米杂化材料构筑自修复纳米复合水凝胶
将所制备的CNCS@PDA@PLL与丙烯酸(AA),蒸馏水(H2O)、过硫酸钾(KPS)、六水三氯化铁(FeCl3.6H2O)、过硫酸钾(KPS),在一定温度下反应一段时间以制备具有自修复性能的纳米复合水凝胶。其中,按质量比,AA:FeCl3.6H2O:自由基引发剂:聚合物=1~1000: 1~10:1~10:1~10,
所述的反应温度:40~60℃,
所述反应时间:0.1~1h。
因此,本发明要求保护制备自修复纳米智能水凝胶的方法。主要包括以下步骤:
(1)按照权利要求1和2所述配方配制聚合体系;
(2)将所制得的聚合物加入聚丙烯酸(PAA)水凝胶中,得到以金属配位作用为自修复机理的纳米复合水凝胶。
借助于上述方法,本发明与现有技术相比具有下列优点:
本发明首次利用Pickering乳液模板制备纤维素纳米晶基Janus纳米杂化材料并制备出水凝胶。该自修复纳米复合水凝胶在室温下能自主、快速修复,同时在多项测试中显现出较高的材料机械强度和优越的力学性能。
具体实施方法
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:制备纤维素纳米晶(CNCs)
将98%的浓硫酸(126mL)缓慢加入盛有适量去离子水的烧杯中,搅拌冷却至室温,转移至250mL的容量瓶中定容。取微晶纤维素(3g)于500mL三口瓶中,加入65%的硫酸(250mL),在45℃下搅拌4h,后用大量去离子水洗涤至Ph值呈中性,离心、液氮处理后冷冻干燥。
实施例二:通过表面引发的ATRP合成纤维素纳米晶基复合物CNCs@PLL
现将纤维素纳米晶(0.5 g)和去离子水(50 mL)装入圆底烧瓶,通入氮气25min。然后将过硫酸铵(3mL)分散于聚赖氨酸(5mL)中,并通入氮气5min。将分散在PLL中的APS倒入前者中,在60℃下反应6h。后取出液体,进行离心,用去离子水洗涤三次,后进行液氮处理,将所得样品冷冻干燥。
实施例三:通过Pickering乳液模板制备纤维素纳米晶基Janus纳米杂化材料CNCs@PDA@PLL
将Tris-HCl缓冲液(10mL),盐酸多巴胺(10 mg),甲苯(3mL)加入匀浆瓶中,机械搅拌5min。在不设置温度的条件下反应8h。待反应完成后,将反应所得溶液离心,用乙醇洗涤三次、进行液氮处理。最后将所得到的CNCS@PDA@PLL冷冻干燥,以备后续使用。
实施例四:基于CNCs@PDA@PLL纳米杂化材料构筑自修复纳米复合水凝胶
将丙烯酸(2.5mL)、去离子水(5mL)、过硫酸钾(2.5mL)、六水合氯化铁FeCl3.6H2O(0.8mL)和实施例二中所制得的CNCs@PDA@PLL(5mg)置于玻璃瓶中,置于磁力搅拌器中,温度设置为60℃。后将水凝胶倒入模具中,在室温下放置一夜后,置于35℃固定成型。
Claims (2)
1.一种利用Janus纳米材料制备自修复水凝胶的方法,其特征在于,包括以下两个步骤:
(1)纤维素纳米晶基Janus纳米杂化材料的制备,首先,将纤维素纳米晶分散于去离子水中,向其中通入氮气25分钟,将过硫酸铵分散于聚赖氨酸中通入氮气5分钟,将后者倒入前者中,使纤维素纳米晶接枝聚赖氨酸(PLL),制备CNCs@PLL,包括:去离子水、纤维素纳米晶(CNCs)、引发剂过硫酸铵(APS,5mg/mL),聚赖氨酸(PLL,0.05g/mL)在适宜的温度下反应,其中,按质量比去离子水:纤维素纳米晶:引发剂:聚赖氨酸=1~10000:1~100:1~10:1~100,
其中,所用引发剂为过硫酸铵(APS),
所述反应温度为60℃,
所述反应时间为6~12h;
然后,在Tris-HCl缓冲溶液中(pH =8.5)将上述所得CNCs@PLL杂化材料的一侧接枝聚多巴胺,制备CNCs@PDA@PLL纳米杂化材料、去离子水、甲苯、盐酸多巴胺、CNCs@PLL在Tris-HCl缓冲溶液中反应一定时间,
其特征在于,可以通过Pickering乳液模板对纤维素纳米晶基外侧接枝聚合物,其中,按质量比,Tris-HCl缓冲溶液:CNCs@PLL:盐酸多巴胺(DA):甲苯=1~10: 1~10:1:1~500
其中,所述反应温度:25~45℃,
所述反应时间:6~12h;
(2)基于CNCs@PDA@PLL纳米杂化材料构筑自修复纳米复合水凝胶
将所制备的CNCS@PDA@PLL与丙烯酸(AA),蒸馏水(H2O)、过硫酸钾(KPS)、六水三氯化铁(FeCl3.6H2O)、过硫酸钾(KPS),在一定温度下反应一段时间以制备具有自修复性能的纳米智能水凝胶,
其中,按质量比,AA:FeCl3.6H2O:自由基引发剂:聚合物=1~1000: 1~10:1~10:1~10,
所述的反应温度:40~60℃,
所述反应时间:0.1~1h。
2.应用上述制备工艺制得的纤维素纳米晶基Janus纳米杂化材料制备的聚丙烯酸基自修复纳米复合水凝胶。
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