CN115570859A - 一种可循环再生的高强韧复合水凝胶及其制备方法和应用 - Google Patents
一种可循环再生的高强韧复合水凝胶及其制备方法和应用 Download PDFInfo
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Abstract
本发明公开了一种可循环再生的高强韧复合水凝胶的制备方法:将CPO、ANF的水分散液和PVA水溶液复合形成均匀的浆液,通过无机离子聚合和自组装制备各向同性的复合薄膜;将复合薄膜浸于水中达到溶胀平衡、定向拉伸至薄膜内部结构重组和再次浸于水中达到溶胀平衡,获得分级有序结构的水凝胶薄膜;将获得的水凝胶薄膜经过层层堆垛,采用胶水进行层间粘接,施加瞬时压缩应力后干燥,再次浸于水中达到溶胀平衡,获得高强韧体相水凝胶,作为可循环再生的高强韧复合水凝胶。该水凝胶可以实现高强与高韧的平衡,并具有可循环再生的特点,且可以应用在制备软体机器人材料或生物组织工程材料领域上的非疾病诊断和治疗上。
Description
技术领域
本发明属于高强韧软材料技术领域,特别涉及一种可循环再生的高强韧复合水凝胶及其制备方法和应用。
背景技术
水凝胶是在水环境中由三维交联聚合物网络构成的一类软材料,在能源(水凝胶电解质/电极)、环境(水净化/收集)、生物医学(软组织修复/替代、药物加载/释放)、结构工程材料(智能可穿戴电子、软体机器人)等领域得到了广泛的研究。水凝胶的纳米结构和力学性能对其应用至关重要。例如,天然肌肉组织(一种生物水凝胶)是由丰富的水(70~80wt%)和胶原纤维等组成,它具有优异的拉伸强度和高承载能力,能够为生物体提供结构支撑。其优异的力学性能源于其高度集成和各向异性的分级有序结构。相比之下,普通合成的单一聚合物水凝胶由于简单的各向同性结构,强度和韧性相对较低。因此,在单一水凝胶网络中引入双网络或纳米增强相,构建复合水凝胶,并在水凝胶内部引入多重相互作用(如离子/共价交联、氢键等)和复杂的分级结构,以提高力学性能得到了广泛的研究。然而,高强和高韧通常是相互冲突的,在水凝胶中同时实现这两者一直是一个巨大的挑战。
受肌肉水凝胶的分级有序结构和纳米复合水凝胶内部多重分子相互作用的启发,具有各向异性分级结构的高强韧纳米复合水凝胶受到了广泛的关注与研究。在纳米复合水凝胶中施加电磁场、温度场或应力场,通常会形成分级有序结构。其中,预应力诱导结构取向策略因其操作简单已广泛应用于各向异性纳米复合水凝胶的制备。但是,由于预应力不能均匀地作用于大尺寸三维体相水凝胶,这严重限制了其应用。此外,高强韧的复合水凝胶通常是化学交联的,尤其是共价交联的水凝胶,一旦形成,其中的共价键就很难断裂,因此所制备的水凝胶很难自发降解和回收再利用。随着未来水凝胶的广泛研究和大规模应用,水凝胶的终端产品无疑会造成资源的浪费和环境的污染,不利于绿色经济和循环经济的发展。
近年来,超小无机离子纳米材料因小尺寸效应在构建超韧纳米复合材料方面显示出巨大的潜力。如公开号为CN110669231A的中国专利申请公开了一种高强韧仿生肌肉水凝胶材料,所述高强韧仿生肌肉水凝胶材料包括10~40wt%的磷酸钙纳米簇和60~90wt%的有机物,所述有机物包括PVA和海藻酸钠,所述PVA和海藻酸钠的质量比为8:1~3:1。该发明还公开了一种高强韧仿生肌肉水凝胶材料的制备方法和在软体机器人或生物组织工程领域上的应用。该发明提供的仿生肌肉水凝胶材料具有高强度和高韧性;提供的制备方法为构建具有分级有序结构的有机-无机复合水凝胶提出了新的制备策略,所制备的类肌肉水凝胶在软体机器人,生物组织工程领域具有巨大的应用前景。但由于构成类肌肉水凝胶的有机组分PVA和海藻酸钠均为柔性的长链分子聚合物,通过与磷酸钙纳米簇复合仅能在分子和纳米尺度上构成有机分子链与无机纳米线的两相有序组装;此外,类肌肉水凝胶内部的海藻酸钠分子与磷酸钙通过离子键结合在一起,在酸性条件下仍然会存在海藻酸钙分子,因而无法实现类肌肉水凝胶的可逆循环再生,这严重限制了水凝胶的回收与再利用。
发明内容
本发明的目的在于提供一种可循环再生的高强韧复合水凝胶及其制备方法,可以实现高强与高韧的平衡,并具有可循环再生的特点;本发明还提供了可循环再生的高强韧复合水凝胶在制备软体机器人材料或生物组织工程材料领域上的非疾病诊断和治疗上的应用。
本发明提供如下技术方案:
一种可循环再生的高强韧复合水凝胶的制备方法,所述制备方法包括:
(1)将磷酸钙寡聚体CPO、芳纶纳米纤维ANF的水分散液和聚乙烯醇PVA水溶液复合形成均匀的浆液,通过无机离子聚合和自组装制备各向同性的复合薄膜;
(2)将复合薄膜浸于水中达到溶胀平衡、定向拉伸至薄膜内部结构重组和再次浸于水中达到溶胀平衡,获得分级有序结构的水凝胶薄膜;
(3)将步骤(2)制备的单层的水凝胶薄膜经过层层堆垛,采用胶水进行层间粘接,施加瞬时压缩应力后干燥,再次浸于水中达到溶胀平衡,获得高强韧体相水凝胶,作为可循环再生的高强韧复合水凝胶(又称之为高强韧纳米复合水凝胶)。
本发明的技术构思在于:
以PVA水溶液构建有机主网络,使用具有超小尺寸的CPO作为无机增强相,具有高强高模高刚度的ANF作为有机增强相,与PVA水溶液复合形成均匀的浆液,通过无机离子聚合和自组装首先制备各向同性的复合薄膜。其中,CPO在PVA/ANF复合网络中原位聚合,形成一维超细羟基磷灰石纳米线(HLs)。随后将获得的复合薄膜在水中湿拉伸至一定的应变,使得薄膜内部结构重组(薄膜内部三个一维组分(一维PVA分子链、一维ANF和一维HLs)有序组装成为纳米纤维)。这些纳米纤维进一步定向组装成为宏观尺度上的水凝胶纤维网络。
其中,PVA构成复合薄膜的有机主网络结构。CPO在形成复合薄膜的过程中,通过无机离子聚合逐渐转变为结晶的HLs,并与ANF和PVA分子链以氢键结合在一起。同时在ANF与PVA之间也会形成氢键,最终在PVA分子链、ANF和HLs之间形成分子间多重氢键。
基于CPO诱导的有机-无机整合和协同增韧与预应力诱导的结构取向策略使得所制备的水凝胶薄膜在分子尺度上拥有多重氢键作用,在纳米到宏观尺度上,拥有分级有序的纤维网络结构,所以该水凝胶在宏观上表现出优异的机械性能。
为了进一步获得更大尺寸的三维体相水凝胶,可通过层层组装与层间交联的策略,即将获得的水凝胶薄膜沿着取向层层堆垛,层与层之间通过胶水粘接在一起,然后施加瞬时应力,加强层间交联。最后,将获得的三维体相板材经自然干燥,再次浸于水中达到吸水平衡,获得大尺寸的高强韧的三维体相水凝胶。
在步骤(1)中,所述CPO的制备方法为:将三乙胺作为稳定剂、将钙盐作为钙源、磷酸作为磷源加入到有机溶剂中生成CPO;所述有机溶剂中钙盐的浓度为0.001~0.1mol L-1,保持钙磷摩尔比在1~2,三乙胺的浓度为0.02~1mol L-1。
所述有机溶剂为乙醇,乙二醇,丙三醇等有机溶剂以及其混合溶剂。钙盐溶液与磷酸反应会产生CPO。反应温度在25℃左右,首先制备具有超小尺寸(~1nm)的CPO,作为无机增强相。
优选的,钙盐的浓度为0.02~0.05mol L-1,保持钙磷摩尔比在1~1.67,三乙胺的浓度为0.2~0.5mol L-1。
在步骤(1)中,所述CPO的粒径为0.5~2.0nm。
在步骤(1)中,所述ANF的制备方法为:以凯夫拉纤维为原料,以氢氧化钾KOH的二甲基亚砜DMSO饱和溶液作为溶剂,进行去质子化,实现宏观纤维的剥离,获得ANF;其中凯夫拉纤维与KOH的质量比为0.2~2:1,DMSO与KOH的质量比为1000~100:1。
其中,ANF作为有机增强相。
优选的,凯夫拉纤维与KOH的质量比为0.5~1,DMSO与KOH的质量比为500~200。反应温度在25℃左右,通过机械搅拌直至获得暗红色粘稠的ANF溶液,随后用去离子水进行溶剂交换,获得ANF。
在步骤(1)中,所述无机相CPO与有机相PVA/ANF的投料比为5~40wt%:60~95wt%;且PVA与ANF的投料比为6:1。
其中,使用CPO,与ANF水分散液(浓度为0.1~0.5wt%),PVA水溶液(浓度为1~10wt%)复合形成均匀的浆液,此过程中可以通过调节CPO的加入量(5~40wt%)获得不同强度,韧性的复合薄膜。
优选的,PVA水溶液的浓度为1~5wt%。
在步骤(2)中,定向拉伸至应变50~150%。其中,浸于水中5~60min。优选的,定向拉伸至应变50~100%。
在步骤(3)中,瞬时压缩应力为5~20kPa。优选的,瞬时压缩应力为5~10kPa。
在步骤(3)中,所述胶水为PVA水溶液与CPO混合而得到的乳液,乳液中CPO的质量百分比在10~35wt%。
所述高强韧复合水凝胶依次通过酸解脱矿、水中加热溶解获得均匀的分散液、加入CPO进行二次无机离子聚合和自组装,实现水凝胶的可逆循环再生。
由于构成水凝胶的三组分是通过氢键作用连接在一起的,因此,通过酸解脱矿,加热溶解再分散以及随后的二次无机离子聚合,能够实现水凝胶的可逆循环再生。
具体为:将水凝胶薄膜浸入pH=3.0的盐酸溶液,薄膜内的磷酸钙矿物则会溶解;随后,将残余的有机薄膜相在去离子水中清洗几遍,再次放入100℃沸水中加热溶解,获得均匀的分散液;最后再加入CPO(5~40wt%)进行二次无机离子聚合和自组装,实现水凝胶的可逆循环再生。
本发明还提供了一种上述制备方法得到的可循环再生的高强韧复合水凝胶。
本发明还提供了一种上述可循环再生的高强韧复合水凝胶在制备软体机器人材料或生物组织工程材料领域上的非疾病诊断和治疗上的应用。
与现有技术相比,本发明通过在一维PVA分子链和一维ANF组成的聚合物复合网络中进行CPO的原位无机离子聚合制备了一种高强韧的纳米复合水凝胶。为了实现高强与高韧的平衡,本发明将ANF作为有机增强相引入PVA水凝胶基质中,首先构建了PVA/ANF复合网络。然后,CPO作为无机增强相在PVA/ANF复合网络中原位聚合,形成一维超细HLs。有机PVA/ANF和无机HLs从分子尺度到宏观尺度形成完整的结构,成为独立的PVA/ANF/HL(PAHL)薄膜。随后,对获得的PAHL薄膜在水中湿拉伸至应变100%,构建分级有序的纤维结构。由于CPO诱导的有机-无机整合和协同增韧,以及预应力诱导的分级有序纤维结构,PAHL水凝胶膜具有优异的拉伸强度(24.15±1.12MPa)和韧性(15.68±1.78MJ m-3),远远超过绝大多数的单一聚合物水凝胶、双/多网络水凝胶和纳米复合水凝胶。通过层层组装和层间交联策略,本发明进一步制备出具有优异力学性能和显著能量吸收/耗散能力的大尺寸三维体相水凝胶。
此外,由于所制备的纳米复合水凝胶具有物理交联特性,且水凝胶内部的无机矿物单元可以在弱酸性条件下溶解,通过在PVA/ANF复合网络中进行CPO的二次聚合,很容易实现水凝胶的可逆循环再生,为水凝胶的可持续大规模生产和应用奠定了基础。本发明提供的基于CPO和ANF协同韧化的高强韧复合水凝胶在软体机器人,生物组织工程领域等具有重要的应用前景。
附图说明
图1为实施例制备的高强韧复合水凝胶干燥后内部的扫描电子显微镜图像(左)和透射电子显微镜图像(右)。
图2为实施例制备的高强韧复合水凝胶薄膜在水中的光学照片(左)和冷冻干燥之后内部的扫描电子显微镜图像(右)。
图3为实施例制备的高强韧复合水凝胶薄膜表现出优异的柔韧性(可卷曲、扭拧、打结、提拉重物)和承载能力(提拉重物,抗冲击)。
图4为实施例制备的高强韧复合水凝胶薄膜的拉伸应力-应变曲线。
图5为实施例制备的高强韧复合水凝胶薄膜的循环拉伸应力-应变曲线。
图6为实施例制备的高强韧大尺寸体相纳米复合水凝胶材料,且所制备的水凝胶条同样具有优异的柔韧性(弯曲,扭拧)和承载能力。
图7为实施例制备的高强韧复合水凝胶薄膜经过酸解脱矿,加热溶解在分散,以及随后的二次无机离子聚合实现水凝胶薄膜的可逆循环再生过程的各阶段光学照片。
图8为实施例制备的再生高强韧复合水凝胶薄膜的拉伸应力-应变曲线。
图9为制备可循环再生的高强韧复合水凝胶的工艺流程和水凝胶内部分级有序的结构示意图。
具体实施方式
如图9所示,为制备可循环再生的高强韧复合水凝胶的工艺流程,及其内部的网络结构。使用CPO和ANF分别作为无机增强相和有机增强相,与PVA水溶液复合,通过无机离子聚合和自组装策略制备复合薄膜,随后将薄膜浸于去离子水中5~60min,定向拉伸至应变50~150%,内部结构发生重组,从无序的网状结构转变为有序排列的纤维网络结构,且HLs在PVA分子链和ANF的带动下形成有序排列的晶体阵列。
制备CPO:配制氯化钙的乙醇溶液,5.88g二水合氯化钙溶于0.80L无水乙醇中,加入110.90mL三乙胺,搅拌30min,随后加入磷酸的乙醇溶液(2.09mL磷酸溶于80mL乙醇),剧烈搅拌12h,通过离心获得白色凝胶,用乙醇清洗三遍,离心,再分散于乙醇中,制备浓度为10mg mL-1的CPO。
制备ANF:首先配制KOH的DMSO溶液,即将5.00g KOH加入1.00L DMSO中形成饱和溶液,随后将5.00g凯夫拉纤维用剪刀剪成碎屑,并转移至KOH的DMSO饱和溶液中,经机械搅拌直至凯夫拉纤维完全溶解形成暗红色粘稠的溶液,然后转移至3.00L烧杯中,加入2.00L沸水,进行溶剂交换,使得ANF析出,然后用去离子水清洗三遍,获得ANF纳米纤维的水分散液(0.5wt%)。
制备可循环再生的高强韧复合水凝胶薄膜:
(1)取60g浓度为0.5wt%的ANF分散液加入60g浓度为3.0wt%的PVA水溶液,剧烈搅拌30min,形成均匀的分散液。取120mL浓度为10mg mL-1的CPO置于离心管中,6000rpm离心5min,倒掉上清液,将获得的CPO凝胶加入到上述分散液中,剧烈搅拌3h,最后将均匀的浆液转移至12cm×12cm的培养皿中,室温干燥,最后从培养皿中剥离,获得干燥的复合薄膜。
(2)将薄膜浸于水中5~60min,达到溶胀平衡,取出后定向拉伸至应变100%即获得水凝胶薄膜。
(3)将单层水凝胶薄膜通过层层铺展,层与层之间通过特制的胶水(胶水制备:取30mL浓度为10mg mL-1的CPO置于离心管中,6000rpm离心5min,倒掉上清液,将获得的CPO凝胶加入到30g PVA水溶液(3.0wt%)中,搅拌均匀并挥发出部分水分,成为具有一定粘度和流动性的胶水)粘接在一起,随后用10kPa的瞬时压缩应力作用于粘接好的层状薄膜体相复合材料,使得层与层之间得到紧密连接。随后经自然干燥后,再次浸于水中达到溶胀平衡,获得大尺寸高强韧的三维体相水凝胶。
如图1所示,本实施例所制备的复合水凝胶薄膜,内部结构高度有序,超细HLs与PVA分子链,ANF高度整合在一起,形成复合纳米纤维。
如图2所示,本实施例制备的复合纳米纤维经有序组装成为宏观的水凝胶薄膜。
如图3所示,本实施例制备的水凝胶薄膜拥有优异的韧性,可以任意卷曲,打结;同时表现出优异的承载和抗冲击能力。
如图4所示,本实施例制备的水凝胶薄膜的拉伸强度为24.15±1.12MPa,韧性为15.68±1.78MJ m-3,弹性模量为18.56±7.13MPa。
如图5所示,在循环应力作用下,本实施例制备的水凝胶薄膜表现出优异的机械稳定性。
如图6所示,本实施例通过层层组装与层间交联,可制备出大尺寸体相水凝胶材料,所制备的水凝胶条同样具有卷曲,扭拧,打结,承载的能力。
如图7所示,本实施例制备的高强韧复合水凝胶经过酸解脱矿,加热溶解在分散,以及随后的二次无机离子聚合,可以实现水凝胶薄膜的可逆循环再生。具体方法为:取3g干凝胶碎片(水凝胶碎片置于80℃干燥箱中直至完全干燥)转移至100mL盐酸水溶液(pH=3.0)30min后取出,反复用去离子水清洗去除残余的酸,然后转移至30mL去离子水中,加热沸腾,并剧烈搅拌,直至凝胶碎片完全打碎并形成均匀的分散液。随后补充蒸发掉的水,直至30mL,再次加入CPO(100mL,10mg mL-1)并搅拌均匀,形成均匀的浆液,然后在干燥过程中实现CPO的二次无机离子聚合,形成各向同性的再生水凝胶薄膜,为了获得分级有序的纳米复合结构,再次将再生水凝胶薄膜浸于水中5~60min,达到溶胀平衡,取出后定向拉伸至应变100%即获得再生分级有序水凝胶薄膜。
如图8所示,再生水凝胶的拉伸强度,弹性模量和韧性分别为23.21±2.59MPa,17.28±5.94MPa和14.76±3.67MJ m-3,与原始水凝胶基本一致。
Claims (10)
1.一种可循环再生的高强韧复合水凝胶的制备方法,其特征在于,所述制备方法包括:
(1)将磷酸钙寡聚体CPO、芳纶纳米纤维ANF的水分散液和聚乙烯醇PVA水溶液复合形成均匀的浆液,通过无机离子聚合和自组装制备各向同性的复合薄膜;
(2)将复合薄膜浸于水中达到溶胀平衡、定向拉伸至薄膜内部结构重组和再次浸于水中达到溶胀平衡,获得分级有序结构的水凝胶薄膜;
(3)将步骤(2)制备的水凝胶薄膜经过层层堆垛,采用胶水进行层间粘接,施加瞬时压缩应力后干燥,再次浸于水中达到溶胀平衡,获得高强韧体相水凝胶,作为可循环再生的高强韧复合水凝胶。
2.根据权利要求1所述的可循环再生的高强韧复合水凝胶的制备方法,其特征在于,在步骤(1)中,所述CPO的制备方法为:将三乙胺作为稳定剂、将钙盐作为钙源、磷酸作为磷源加入到有机溶剂中生成CPO;所述有机溶剂中钙盐的浓度为0.001~0.1mol L-1,保持钙磷摩尔比在1~2,三乙胺的浓度为0.02~1mol L-1;所述CPO的粒径为0.5~2.0nm。
3.根据权利要求1所述的可循环再生的高强韧复合水凝胶的制备方法,其特征在于,在步骤(1)中,所述ANF的制备方法为:以凯夫拉纤维为原料,以氢氧化钾KOH的二甲基亚砜DMSO饱和溶液作为溶剂,进行去质子化,实现宏观纤维的剥离,获得ANF;其中凯夫拉纤维与KOH的质量比为0.2~2:1,DMSO与KOH的质量比为1000~100:1。
4.根据权利要求1所述的可循环再生的高强韧复合水凝胶的制备方法,其特征在于,在步骤(1)中,所述无机相CPO与有机相PVA/ANF的投料比为5~40wt%:60~95wt%;且PVA与ANF的投料比为6:1。
5.根据权利要求1所述的可循环再生的高强韧复合水凝胶的制备方法,其特征在于,在步骤(2)中,定向拉伸至应变50~150%。
6.根据权利要求1所述的可循环再生的高强韧复合水凝胶的制备方法,其特征在于,在步骤(3)中,瞬时压缩应力为5~20kPa。
7.根据权利要求1所述的可循环再生的高强韧复合水凝胶的制备方法,其特征在于,在步骤(3)中,所述胶水为PVA水溶液与CPO混合而得到的乳液,乳液中CPO的质量百分比在10~35wt%。
8.根据权利要求1所述的可循环再生的高强韧复合水凝胶的制备方法,其特征在于,所述高强韧复合水凝胶依次通过酸解脱矿、水中加热溶解获得均匀的分散液、加入CPO进行二次无机离子聚合和自组装,实现水凝胶的可逆循环再生。
9.一种权利要求1-8任一所述的制备方法得到的可循环再生的高强韧复合水凝胶。
10.一种权利要求9所述的可循环再生的高强韧复合水凝胶在制备软体机器人材料或生物组织工程材料领域上的非疾病诊断和治疗上的应用。
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