CN111501327A - pH敏感型纳米纤维水凝胶毡及其制备方法 - Google Patents
pH敏感型纳米纤维水凝胶毡及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种pH敏感型纳米纤维水凝胶毡及其制备方法,涉及响应型纳米水凝胶材料技术领域。本发明提供的一种pH敏感型纳米纤维水凝胶毡及其制备方法,通过采用聚天冬氨酸的中间体聚琥珀酰亚胺和聚丙烯腈溶于溶剂中进行静电纺丝,得到聚琥珀酰亚胺/聚丙烯腈纳米纤维毡;再分别用热交联法对聚琥珀酰亚胺/聚丙烯腈纳米纤维毡中聚丙烯腈组分进行交联,用交联剂对聚琥珀亚酰胺组分进行交联;将交联后的聚琥珀酰亚胺/聚丙烯腈纳米纤维毡进行水解,洗涤干燥,得到pH敏感型纳米纤维水凝胶毡。本发明提供的纳米水凝胶毡在具备较强pH敏感性的同时、兼具较强机械性能和吸水性能,且溶胀速率高,在药物缓释、传感器、驱动器等领域具有广泛的应用前景。
Description
技术领域
本发明涉及响应型纳米水凝胶材料技术领域,特别涉及一种pH敏感型纳米纤维水凝胶毡及其制备方法。
背景技术
材料的智能化是现代高技术新材料发展的重要方向之一,响应型水凝胶作为一种智能软材料,不仅具有与生物组织相似的“软、湿”特性,而且在外界环境刺激,比如pH、温度、电场、光等作用下,会产生溶胀或收缩行为,因此在智能机器人、微流体阀门、生物医学、传感器等领域具有巨大的应用前景。近些年来,响应型水凝胶的应用取得了较大进展。然而,传统水凝胶响应速度慢,通常需要数分钟甚至数小时才能完成响应行为,严重阻碍了响应型水凝胶的应用。因此,构建具有快速响应特性的水凝胶具有重要意义。
近些年来,静电纺丝技术因可制备直径较小的纳米纤维、方法简单、工艺可控等优点,在水凝胶制备领域得到应用。静电纺纳米纤维膜内部丰富的贯穿孔洞结构形成水分子扩散通道,可大大提高水凝胶的响应速度。目前,关于静电纺丝法构建温度、pH、电场等刺激响应型纳米纤维水凝胶毡的研究已有报道。
在实现本发明的过程中,发明人发现相关技术至少存在以下问题:
纳米纤维水凝胶毡由纳米纤维沉积而成,现有技术制备得到的纳米纤维水凝胶毡中,纳米纤维之间抱合力弱且纳米纤维内高分子分子链取向度差,导致纳米纤维水凝胶毡的机械性能普遍较差,尤其是其发生溶胀后机械性能进一步减弱。
发明内容
针对相关技术存在的上述问题,本发明提供了一种pH敏感型纳米纤维水凝胶毡及其制备方法,通过制备工艺的改进,采用聚丙烯腈与聚琥珀酰亚胺进行溶液共混,经静电纺丝成型得到复合纳米纤维膜,再将复合纳米纤维膜进行热处理,使聚丙烯腈交联,然后将复合纳米纤维膜置于交联剂中对聚琥珀酰亚胺交联;最后将两组分中未交联部分水解,得到pH敏感型纳米纤维水凝胶毡,得到的pH敏感型纳米纤维水凝胶毡机械性能较高,且兼具较快的pH响应速度。本发明的技术方案如下:
根据本发明实施例的第一个方面,提供一种pH敏感型纳米纤维水凝胶毡的制备方法,其特征在于,所述方法包括:
(1)将聚琥珀酰亚胺、聚丙烯腈按预设质量比共同溶于溶剂后,搅拌并静止脱泡得到纺丝液,再将所述纺丝液加入溶液存储装置中,施加高压电进行静电纺丝,制备得到聚琥珀酰亚胺/聚丙烯腈纳米纤维毡;
(2) 将所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡置于150-300℃的加热装置内加热0.4-4h,使得所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡中的聚丙烯腈组分发生热交联,然后再将所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡置于交联剂中,使得所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡中的聚丙烯腈组分发生交联剂交联;
(3)将交联后的所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡进行水解,再使用去离子水洗涤至中性,冷冻干燥处理后制得pH敏感型纳米纤维水凝胶毡。
在一个优选的实施例中,所述聚琥珀酰亚胺与所述聚丙烯腈的质量比为1:99-99:1。
在一个优选的实施例中,所述溶剂为二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜中的至少一种。
在一个优选的实施例中,所述加热装置内气体为空气或氮气。
在一个优选的实施例中,所述交联剂为二胺类化合物,交联剂交联工序采用的方式为蒸汽交联或溶液交联。
在一个优选的实施例中,所述交联剂为乙二胺或己二胺。
在一个优选的实施例中,所述将交联后的所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡进行水解,包括:
将交联后的所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡置于碱性溶液中加热水解;或,
将交联后的所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡置于酸性溶液中加热水解,再置于碱性溶液中常温水解。
在一个优选的实施例中,静电纺丝工序的参数包括:注射泵推进速度为0.3-0.4mL/h,电压为15-18kV,纺丝距离为18cm。
根据本发明实施例的第二个方面,提供一种pH敏感型纳米纤维水凝胶毡,其特征在于,所述pH敏感型纳米纤维水凝胶毡由上述任意所述的pH敏感型纳米纤维水凝胶毡的制备方法制备得到,所述pH敏感型纳米纤维水凝胶毡具备网络互穿结构。
与现有技术相比,本发明提供的一种pH敏感型纳米纤维水凝胶毡及其制备方法具有以下优点:
本发明提供的一种pH敏感型纳米纤维水凝胶毡及其制备方法,通过采用聚天冬氨酸的中间体聚琥珀酰亚胺和聚丙烯腈溶于溶剂中进行静电纺丝,得到聚琥珀酰亚胺/聚丙烯腈纳米纤维毡;再分别用热交联法对聚琥珀酰亚胺/聚丙烯腈纳米纤维毡中聚丙烯腈组分进行交联,用交联剂对聚琥珀亚酰胺组分进行交联;将交联后的聚琥珀酰亚胺/聚丙烯腈纳米纤维毡进行水解,洗涤干燥,得到pH敏感型纳米纤维水凝胶毡。本发明提供的纳米水凝胶毡在具备较强pH敏感性的同时、兼具较强机械性能和吸水性能,且溶胀速率高,在药物缓释、智能开关、传感器、驱动器等领域具有广泛的应用前景。
附图说明
此处的附图被并入说明书中并构成本说明书的一部分,示出了符合本发明的实施例,并于说明书一起用于解释本发明的原理。
图1是根据一示例性实施例示出的一种pH敏感型纳米纤维水凝胶毡的制备方法的方法流程图。
图2是根据一示例性实施例示出的一种pH敏感型纳米纤维水凝胶毡的扫描电子显微镜照片。
图3是一种现有技术通过静电纺制备得到的聚琥珀酰亚胺/聚天冬氨酸纳米纤维毡的扫描电子显微镜照片。
具体实施方式
为了更清楚地说明本发明实施例中的技术方案,下面将对实施例描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1是根据一示例性实施例示出的一种pH敏感型纳米纤维水凝胶毡的制备方法的方法流程图,如图1所示,该pH敏感型纳米纤维水凝胶毡的制备方法包括:
步骤1:将聚琥珀酰亚胺、聚丙烯腈按预设质量比共同溶于溶剂后,搅拌并静止脱泡得到纺丝液,再将所述纺丝液加入溶液存储装置中,施加高压电进行静电纺丝,制备得到聚琥珀酰亚胺/聚丙烯腈纳米纤维毡。
步骤2 :将所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡置于150-300℃的加热装置内加热0.4-4h,使得所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡中的聚丙烯腈组分发生热交联,然后再将所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡置于交联剂中,使得所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡中的聚丙烯腈组分发生交联剂交联。
需要说明的是,本发明选用聚琥珀酰亚胺和聚丙烯腈作为静电纺原料,其中,聚丙烯腈为pH响应型聚丙烯腈基水凝胶前体,经过热处理交联后可形成网络,也可水解生成pH响应基团羧基;聚琥珀酰亚胺为聚天冬氨酸类水凝胶前体,可通过化学交联形成网络,也可水解生成pH响应基团羧基。
步骤3:将交联后的所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡进行水解,再使用去离子水洗涤至中性,冷冻干燥处理后制得pH敏感型纳米纤维水凝胶毡。
本发明通过双交联的手段,使得最终制得的pH敏感型纳米纤维水凝胶毡具备网络互穿结构,从而极大提高了聚琥珀酰亚胺/聚丙烯腈纳米纤维毡的机械性能,且选用的两种材料经交联水解后均具有pH响应性能,因此在增加聚琥珀酰亚胺/聚丙烯腈纳米纤维毡机械性能的同时,仍具有较快的pH响应速度。
在一个优选的实施例中,所述聚琥珀酰亚胺与所述聚丙烯腈的质量比为1:99-99:1。
在一个优选的实施例中,所述溶剂为二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜中的至少一种。
在一个优选的实施例中,所述加热装置内气体为空气或氮气。
在一个优选的实施例中,所述交联剂为二胺类化合物,交联剂交联工序采用的方式为蒸汽交联或溶液交联。
在一个优选的实施例中,所述交联剂为乙二胺或己二胺。
在一个优选的实施例中,所述将交联后的所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡进行水解,包括:
将交联后的所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡置于碱性溶液中加热水解;或,
将交联后的所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡置于酸性溶液中加热水解,再置于碱性溶液中常温水解。
在一个优选的实施例中,静电纺丝工序的参数包括:注射泵推进速度为0.3-0.4mL/h,电压为15-18kV,纺丝距离为18cm。
为了更好地说明本发明提供的pH敏感型纳米纤维水凝胶毡及其制备方法所带来的有益效果,示出下述实施例1~3进行说明:
实施例1
(1):将0.45g聚琥珀酰亚胺、1.05g聚丙烯腈共同溶于8.5g二甲基甲酰胺后,搅拌并静止脱泡得到纺丝液,再将所述纺丝液加入溶液存储装置中,施加高压电进行静电纺丝,制备得到聚琥珀酰亚胺/聚丙烯腈纳米纤维毡,静电纺丝工序采用的注射泵推进速度为0.4mL/h,电压为15kV,纺丝距离为18cm。
(2) :将所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡置于230℃的马弗炉内加热2h,使得所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡中的聚丙烯腈组分发生热交联,然后再将所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡置于乙二胺蒸汽中18h,使得所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡中的聚丙烯腈组分发生交联剂交联,所述马弗炉内气体为空气。
(3):将交联后的所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡浸入氢氧化钠溶液中,于80℃下水解20min后,采用去离子水洗涤至中性,冷冻干燥处理后制得pH敏感型纳米纤维水凝胶毡。
实施例2
(1):将2.2g聚琥珀酰亚胺、0.8g聚丙烯腈共同溶于7g二甲基甲酰胺后,搅拌并静止脱泡得到纺丝液,再将所述纺丝液加入溶液存储装置中,施加高压电进行静电纺丝,制备得到聚琥珀酰亚胺/聚丙烯腈纳米纤维毡,静电纺丝工序采用的注射泵推进速度为0.3mL/h,电压为18kV,纺丝距离为18cm。
(2) :将所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡置于250℃的马弗炉内加热1h,使得所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡中的聚丙烯腈组分发生热交联,然后再将所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡置于0.3mol/L的乙二胺水溶液中,使得所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡中的聚丙烯腈组分发生交联剂交联,所述马弗炉内气体为氮气。
(3):将交联后的所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡浸入10%的硫酸溶液中,于60℃下水解6h,再置于1mol/L的氢氧化钠溶液中中和10min,采用去离子水洗涤至中性,冷冻干燥处理后制得pH敏感型纳米纤维水凝胶毡。
实施例3
(1):将3g聚琥珀酰亚胺、0.2g聚丙烯腈共同溶于7g二甲基亚砜后,搅拌并静止脱泡得到纺丝液,再将所述纺丝液加入溶液存储装置中,施加高压电进行静电纺丝,制备得到聚琥珀酰亚胺/聚丙烯腈纳米纤维毡,静电纺丝工序采用的注射泵推进速度为0.3mL/h,电压为18kV,纺丝距离为18cm。
(2) :将所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡置于200℃的马弗炉内加热2h,使得所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡中的聚丙烯腈组分发生热交联,然后再将所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡置于0.6mol/L的己二胺溶液中,于60℃下交联1h,使得所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡中的聚丙烯腈组分发生交联剂交联,所述马弗炉内气体为空气。
(3):将交联后的所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡浸入氢氧化钠溶液中,于60℃下水解30min后,采用去离子水洗涤至中性,冷冻干燥处理后制得pH敏感型纳米纤维水凝胶毡。
对上述实施例1-3制备得到的各个pH敏感型纳米纤维水凝胶毡进行性能测试,测试得到的各项性能测试参考数据如表一所示。
其中,实施例1-3提供的pH敏感型纳米纤维水凝胶毡性能数据表如表一所示:
测试项目 | 实施例1 | 实施例2 | 实施例3 | 现有纳米纤维水凝胶毡 |
干态断裂强度(MPa) | 1.21 | 1.03 | 0.78 | 0.33 |
湿态断裂强度(MPa) | 0.49 | 0.39 | 0.33 | ≤0.02 |
吸水倍率(g/g) | 30 | 40 | 54 | 55 |
表一
通过上述表一的数据可知,本发明实施例提供的pH敏感型纳米纤维水凝胶毡,除了具备较强pH敏感性能的同时,无论在干态断裂强度还是湿态断裂强度上均强于现有纳米纤维水凝胶毡,且吸水倍率与现有纳米纤维水凝胶毡相仿。显然,本发明提供的pH敏感型纳米纤维水凝胶毡的适用环境较现有纳米纤维水凝胶毡更加广泛。
为了更好地说明本发明实施例提供的pH敏感型纳米纤维水凝胶毡,本发明实施例还示出本发明提供的一种pH敏感型纳米纤维水凝胶毡的扫描电子显微镜照片,放大倍数为5000倍,如图2所示。作为比较,本发明还示出现有技术通过静电纺制备得到的聚琥珀酰亚胺/聚天冬氨酸纳米纤维毡的扫描电子显微镜照片,放大倍数为5000倍,如图3所示。显然,图2所示pH敏感型纳米纤维水凝胶毡的纤维直径较粗,纤维直径在不同位置处的粗细较为均匀,因此具备优秀稳定的机械性能;而图3所示聚琥珀酰亚胺/聚天冬氨酸纳米纤维毡纤维直径较细,且纤维直径在不同位置处存在明显的粗细差异,因而机械性能较差,且容易发生断裂。
综上所述,本发明提供的一种pH敏感型纳米纤维水凝胶毡及其制备方法,通过采用聚天冬氨酸的中间体聚琥珀酰亚胺和聚丙烯腈溶于溶剂中进行静电纺丝,得到聚琥珀酰亚胺/聚丙烯腈纳米纤维毡;再分别用热交联法对聚琥珀酰亚胺/聚丙烯腈纳米纤维毡中聚丙烯腈组分进行交联,用交联剂对聚琥珀亚酰胺组分进行交联;将交联后的聚琥珀酰亚胺/聚丙烯腈纳米纤维毡进行水解,洗涤干燥,得到pH敏感型纳米纤维水凝胶毡。本发明提供的纳米水凝胶毡在具备较强pH敏感性的同时、兼具较强机械性能和吸水性能,且溶胀速率高,在药物缓释、智能开关、传感器、驱动器等领域具有广泛的应用前景。
虽然,前文已经用一般性说明、具体实施方式及试验,对本发明做了详尽的描述,但在本发明基础上,可以对之进行修改或改进,这对本领域技术人员而言是显而易见的。因此,在不偏离本发明精神的基础上所做的这些修改或改进,均属于本发明要求保护的范围。
本领域技术人员在考虑说明书及实践这里的发明的后,将容易想到本发明的其它实施方案。本发明旨在涵盖本发明的任何变型、用途或者适应性变化,这些变型、用途或者适应性变化遵循本发明的一般性原理并包括本发明未公开的本技术领域中的公知常识或惯用技术手段。应当理解的是,本发明并不局限于上面已经描述并在附图中示出的精确结构,并且可以在不脱离其范围进行各种修改和改变。
Claims (9)
1.一种pH敏感型纳米纤维水凝胶毡的制备方法,其特征在于,所述方法包括:
(1)将聚琥珀酰亚胺、聚丙烯腈按预设质量比共同溶于溶剂后,搅拌并静止脱泡得到纺丝液,再将所述纺丝液加入溶液存储装置中,施加高压电进行静电纺丝,制备得到聚琥珀酰亚胺/聚丙烯腈纳米纤维毡;
(2) 将所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡置于150-300℃的加热装置内加热0.4-4h,使得所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡中的聚丙烯腈组分发生热交联,然后再将所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡置于交联剂中,使得所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡中的聚丙烯腈组分发生交联剂交联;
(3)将交联后的所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡进行水解,再使用去离子水洗涤至中性,冷冻干燥处理后制得pH敏感型纳米纤维水凝胶毡。
2.根据权利要求1所述的方法,其特征在于,所述聚琥珀酰亚胺与所述聚丙烯腈的质量比为1:99-99:1。
3.根据权利要求1所述的方法,其特征在于,所述溶剂为二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜中的至少一种。
4.根据权利要求1所述的方法,其特征在于,所述加热装置内气体为空气或氮气。
5.根据权利要求1所述的方法,其特征在于,所述交联剂为二胺类化合物,交联剂交联工序采用的方式为蒸汽交联或溶液交联。
6.根据权利要求5所述的方法,其特征在于,所述交联剂为乙二胺或己二胺。
7.根据权利要求1所述的方法,其特征在于,所述将交联后的所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡进行水解,包括:
将交联后的所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡置于碱性溶液中加热水解;或,
将交联后的所述聚琥珀酰亚胺/聚丙烯腈纳米纤维毡置于酸性溶液中加热水解,再置于碱性溶液中常温水解。
8.根据权利要求1所述的方法,其特征在于,静电纺丝工序的参数包括:注射泵推进速度为0.3-0.4mL/h,电压为15-18kV,纺丝距离为18cm。
9.一种pH敏感型纳米纤维水凝胶毡,其特征在于,所述pH敏感型纳米纤维水凝胶毡由权利要求1-8任意所述的pH敏感型纳米纤维水凝胶毡的制备方法制备得到,所述pH敏感型纳米纤维水凝胶毡具备网络互穿结构。
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