CN109251449B - 一种复合水凝胶及其制备方法和应用 - Google Patents
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Abstract
本发明公开了一种复合水凝胶及其制备方法和应用。首先将聚乙烯醇(PVA)、羧甲基纤维素钠(CMC)及单体吡咯(Py)共混合后,以戊二醛作为交联剂,在酸性条件下,制备得到包埋有CMC及Py的聚乙烯醇单网络水凝胶,随后在低温下,将所得单网络水凝胶浸泡于适宜浓度的FeCl3溶液中,制得聚吡咯/羧甲基纤维素钠‑Fe3+/聚乙烯醇(PPy/CMC‑Fe3+/PVA)双网络复合水凝胶。本发明将上述复合水凝胶应用于应变传感贴片中,最终得到具有高力学强度、弹性、导电性及应变敏感性的复合水凝胶应变传感贴片。本发明开辟了聚吡咯在水凝胶中原位合成的新途径,为水凝胶应变传感器应用于可穿戴领域提供了新思路和新方法。
Description
技术领域
本发明涉及一种复合水凝胶及其制备方法和应用,具体涉及一种采用原位氧化法制备掺杂有导电材料(聚吡咯)的双网络结构复合水凝胶的制备方法,及将该具有高力学强度、弹性、导电性及应变敏感性的复合水凝胶应用于应变传感贴片的方法。
背景技术
传感器作为可穿戴设备的核心组件,其功能化决定了可穿戴设备的发展。应变传感器具有随机械形变可重复变化的电学特性以及类似人体皮肤触觉的传感灵敏度,有望应用于生物力学研究、人体健康监测、嵌入治疗传感。聚合物水凝胶作为一种由大量水分和三维聚合物网络构成的物质,具有类似生物软组织的柔软性,而且还展现出优于传统聚合物的延展性、自修复能力和自恢复性,成为可穿戴或可嵌入设备的理想柔软基体材料。导电水凝胶作为一类新型材料,在健康监测体系领域具有潜在应用价值。目前已有的导电水凝胶均无法兼具优异的导电性及优良的力学性能,而解决这一问题的途径之一就是建立起化学和物理交联网络之间的平衡。 (Y. J. Liu, W. T. Cao, M. G. Ma, P. B. Wan, AcsAppl Mater Interfaces, 2017 , 9 (30))。 将可观的机械性能和高传感灵敏度整合到一起,设计出一款可伸缩、弹性、应变敏感的水凝胶作为可穿戴传感器仍然存在挑战。
发明内容
本发明旨在提供一种复合水凝胶及其制备方法及应用。相比已有的水凝胶应变传感贴片,本发明提供了一种集成可导电、弹性和应变敏感的双网络结构复合水凝胶,并将其发展为多功能可穿戴式应变传感器,从而实现快速、准确地监测手指关节运动、呼吸方式的变化以及不同运动状态下的轻微脉搏。
本发明提供了一种具有导电性能的双网络水凝胶及其应用于应变传感贴片的方法。该方法不仅制备过程操作简便,节约成本,更重要的是,在制备过程中,Fe3+既可作为羧甲基纤维素钠(CMC)分子链间的配位交联剂,同时还可以作为吡咯单体被氧化过程中的氧化剂及掺杂剂,从而使聚吡咯缓慢掺杂于双网络水凝胶内,最终得到具有高力学强度、弹性、导电性及应变敏感性的复合水凝胶应变传感贴片。
本发明提供了一种复合水凝胶,包括以下重量配比的原料:
聚乙烯醇:40%~72%
羧甲基纤维素钠: 5%~35%
吡咯:4%~25%
戊二醛:0.5%~2.5%
FeCl3:1.5%~4.5%。
本发明提供了上述复合水凝胶的制备方法,首先将聚乙烯醇、羧甲基纤维素钠(CMC)及单体吡咯(Py)共混合后,以戊二醛作为交联剂,在酸性条件下,制备得到包埋有CMC及Py的聚乙烯醇单网络水凝胶,随后在低温下,将所得单网络水凝胶浸泡于适宜浓度的FeCl3溶液中,制得聚吡咯/羧甲基纤维素钠-Fe3+/聚乙烯醇(PPy/CMC-Fe3+/PVA)双网络复合水凝胶。上述制备方法,具体包括以下步骤:
(1)包埋有CMC及单体Py的聚乙烯醇单网络水凝胶的制备:将PVA和CMC溶解于90℃-100℃的二次蒸馏水中,磁力搅拌使二者混合均匀,给混合溶液中缓慢滴加(20μL/min)稀盐酸,调节pH为2.0-5.0,随后加入一定浓度的吡咯溶液并于氮气氛围下搅拌30min,待溶液混合均匀后加入一定浓度的戊二醛水溶液,搅拌均匀,将混合溶液倒入水凝胶预制模具中,在水浴条件下反应30~90min,得到包埋有CMC及单体py的聚乙烯醇单网络水凝胶;
(2)PPy/CMC-Fe3+/PVA双网络复合水凝胶的制备:将步骤(1)中制备所得包埋有CMC及单体py的聚乙烯醇单网络水凝胶浸泡到适宜浓度的三氯化铁溶液中,保持低温(0℃)状态浸泡数小时;在此过程中,Fe3+既能同步与CMC分子链间发生络合交联,从而得到CMC-Fe3+的第二层高分子网络结构,也是聚吡咯形成的氧化剂及掺杂剂,最终得到掺杂有PPy的Ppy/CMC-Fe3+/PVA双网络复合水凝胶。
上述的制备方法,步骤(1)中,PVA溶液的浓度为0.10~0.15g/mL,CMC溶液的浓度为0.03~0.07g/mL,戊二醛溶液的浓度为4.0~6.0mg/mL,Py溶液的浓度为0.2~1.0mol/L,HCl溶液的溶度为10%~15%(体积百分比)。其中,PVA溶液、CMC溶液、戊二醛溶液与Py溶液的体积比为15:8:0.5:1~25:15:1.0:1。
上述的制备方法,步骤(1)中,水浴的温度控制在40~70℃。
上述的制备方法,步骤(2)中,所用FeCl3溶液的浓度为0.6mo/L-3.0mol/L,控制溶液中Fe3+与水凝胶中Py的物质的量之比为1:2~1:4。
上述的制备方法,步骤(2)中,所述单网络水凝胶浸泡到FeCl3溶液中保持0~4℃的低温环境,且浸泡时间为18~24h。
上述的制备方法,步骤(2)所得的双网络复合水凝胶浸泡于去离子水中24~48h。期间每隔6h换一次水,以去除水凝胶网络内未反应的FeCl3。
本发明提供了上述复合水凝胶在应变传感贴片中的应用。
将复合水凝胶用于制备具有导电性能的双网络水凝胶应变传感贴片,包括以下步骤:将所得复合水凝胶裁成长为1cm、宽为0.5cm的小片,以黏性塑料薄膜为载体,将其黏附在塑料薄膜上,然后在复合水凝胶的左右两侧距离边缘约3mm处的下方分别埋置直径为3mm左右的铜导线两根,并在复合水凝胶与铜导线的交界处用铜箔胶带纸固定完全,制备得到具有导电性能的双网络水凝胶应变传感贴片。
本发明的有益效果:
1)本发明通过结合化学交联与动态配位键合,在保证水凝胶的力学稳定性和导电性的基础上,将其发展为双网络水凝胶应变传感贴片。
2)本发明基于原位氧化合成,制备的水凝胶应变传感器具有导电性、高弹性、高韧性、高应变敏感度等优势,开辟了聚吡咯在水凝胶中原位合成的新途径,为水凝胶应变传感器应用于可穿戴领域提供了新思路和新方法。
3)本发明的应变响应导电特性的水凝胶制备过程中,一方面,羧甲基纤维素钠上的羧基与Fe3+配位形成具有导电能力的“芯-皮”结构网络,另一方面,水凝胶网络中包埋的聚吡咯也具有很强的导电能力,因此该复合水凝胶具有良好的应变响应导电特性。
附图说明
图1是PPy/CMC-Fe3+/PVA复合水凝胶的高分辨扫描电子显微镜(HRSEM)下照片。照片的放大倍数为2000倍。
图2是PPy/CMC-Fe3+/PVA复合水凝胶作为应变传感贴片应用于监测人体运动前后脉搏跳动次数。
图3是不同吡咯浓度下制备所得PPy/CMC-Fe3+/PVA复合水凝胶的断裂强度。吡咯浓度分别为(a)0mol/L,(b)0.2mol/L,(c)0.4mol/L,(d)0.6mol/L,(e)0.8mol/L,(f)1.0mol/L。
图4是不同吡咯浓度下制备所得PPy/CMC-Fe3+/PVA复合水凝胶的含水率。吡咯浓度分别为(a)0mol/L,(b)0.2mol/L,(c)0.4mol/L,(d)0.6mol/L,(e)0.8mol/L,(f)1.0mol/L。
具体实施方式
下面通过实施例来进一步说明本发明,但不局限于以下实施例。
实施例1:
一种具有导电性能的双网络水凝胶应变传感贴片的制备方法,其具体制备过程包括如下步骤:
①包埋有CMC及单体Py的聚乙烯醇单网络水凝胶的制备:将浓度为0.1g/mL的PVA溶液(10.5mL)和浓度为0.04g/mL的CMC溶液(5.5mL)混合,并保持溶液温度为95℃,磁力搅拌使二者混合均匀,给混合溶液中滴加浓度为20%的HCl溶液100μL,调节pH为4.0,随后加入浓度为0.5mol/L的吡咯(Py)溶液0.5mL并搅拌30min,待溶液混合均匀后加入浓度为4.0mg/mL的戊二醛水溶液(0.38 mL),搅拌均匀,将混合溶液倒入模具中,水浴60℃反应50min,得到包埋有CMC及单体Py的聚乙烯醇单网络水凝胶;
②PPy/CMC-Fe3+/PVA复合水凝胶的制备:将步骤①中制备所得包埋有CMC及单体Py的聚乙烯醇单网络水凝胶浸泡到浓度为2.0 mol/L的三氯化铁(FeCl3)溶液中,保持低温(0℃)状态反应24h,随后将该复合水凝胶浸泡于去离子水中48h,期间每隔6h换一次水,从而去除水凝胶网络内未反应的FeCl3。
③具有导电性能的双网络水凝胶应变传感贴片的制备:将步骤②制备所得复合水凝胶裁成长、宽分别为1cm、0.5cm的小片,以自制黏性塑料薄膜为载体,将其黏附在塑料薄膜上,并在复合水凝胶的左右两侧的下方分别埋置直径为3mm左右的铜导线两根,并在复合水凝胶与铜导线的交界处用铜箔胶带纸固定完全,从而制备得到具有导电性能的双网络水凝胶应变传感贴片。
步骤②所得复合水凝胶的微观形貌如图1所示;图1是PPy/CMC-Fe3+/PVA复合水凝胶的高分辨扫描电子显微镜(HRSEM)照片。图中显示:因聚吡咯的存在,该复合水凝胶的网络结构更加致密,孔洞大小均一程度高。
将步骤③所得双网络水凝胶应变传感贴片应用于志愿者运动前后的脉搏监测。图2是PPy/CMC-Fe3+/PVA复合水凝胶作为应变传感贴片佩戴于志愿者手臂的脉搏跳动最明显处,应用于监测人体运动前、后脉搏跳动次数。运动前志愿者的心率约为80次/min,运动后志愿者的心率约为120次/min,图中显示,当志愿者佩戴由该复合水凝胶制备所得的应变传感贴片后,可从该应变传感贴片的电阻变化率监测到志愿者的脉搏跳动变化情况,表明该水凝胶可作为柔性可穿戴传感贴片,应用于健康监护领域。
实施例2:
一种具有导电性能的双网络水凝胶应变传感贴片的制备方法,其具体制备过程包括如下步骤:
①包埋有CMC及单体Py的聚乙烯醇单网络水凝胶的制备:将浓度为0.15g/mL的PVA溶液(10.5mL)和浓度为0.05g/mL的CMC溶液(5.5mL)混合,并保持溶液温度为95℃,磁力搅拌使二者混合均匀,给混合溶液中滴加浓度为20%的HCl溶液200μL,调节pH为4.0,随后加入浓度为1.0mol/L的吡咯(Py)溶液0.5mL并搅拌30min,待溶液混合均匀后加入浓度为5.0mg/mL的戊二醛水溶液(0.38 mL),搅拌均匀,将混合溶液倒入模具中,水浴60℃反应50min,得到包埋有CMC及单体Py的聚乙烯醇单网络水凝胶;
②PPy/CMC-Fe3+/PVA复合水凝胶的制备:将步骤①中制备所得包埋有CMC及单体Py的聚乙烯醇单网络水凝胶浸泡到浓度为3.0 mol/L的三氯化铁(FeCl3)溶液中,保持低温(0℃)状态反应24h,随后将该复合水凝胶浸泡于去离子水中48h,期间每隔6h换一次水,从而去除水凝胶网络内未反应的FeCl3;
③具有导电性能的双网络水凝胶应变传感贴片的制备:将步骤②制备所得复合水凝胶裁成长、宽分别为1cm、0.5cm的小片,以自制黏性塑料薄膜为载体,将其黏附在塑料薄膜上,并在复合水凝胶的左右两侧的下方分别埋置直径为3mm左右的铜导线两根,并在复合水凝胶与铜导线的交界处用铜箔胶带纸固定完全,从而制备得到具有导电性能的双网络水凝胶应变传感贴片。
实施例3:
制备工艺过程同实施例1,本实施例提供了不同吡咯浓度下制备的PPy/CMC-Fe3+/PVA复合水凝胶,并对其性能进行了检测,如图3、图4所示。吡咯浓度分别为0mol/L,0.2mol/L, 0.4mol/L,0.6mol/L,0.8mol/L,1.0mol/L。
用Instron3343测定制备所得的PPy/CMC-Fe3+/PVA复合水凝胶的力学性能(Instron3343:美国,加载速率:30mm/min)。用Keithley 2400数字源表测定制备所得的聚吡咯/羧甲基纤维素钠-Fe3+/PVA复合水凝胶在不同应变及实际应用条件下的电阻(R),并将其换算为电阻的改变率(R-R0/R0×100%)。
图3是所用吡咯浓度分别为0mol/L,0.2mol/L, 0.4mol/L,0.6mol/L,0.8mol/L和1.0mol/L条件下制备所得PPy/CMC-Fe3+/PVA复合水凝胶的断裂强度。图中显示,随着制备过程中所用单体吡咯含量的增加,该复合水凝胶的断裂强度呈现先增加后减小的趋势,且当吡咯单体的浓度为0.4mol/L时,该复合水凝胶的断裂强度值最大,约为220kPa。
图4是所用吡咯浓度分别为0mol/L,0.2mol/L, 0.4mol/L,0.6mol/L,0.8mol/L和1.0mol/L条件下制备所得PPy/CMC-Fe3+/PVA复合水凝胶的含水率。图中显示,随着制备过程中所用单体吡咯含量的增加,该复合水凝胶的含水率也呈现先增加后减小的趋势,且当吡咯单体浓度为0.4 mol/L时,该复合水凝胶的含水率值最大,约为92%。
Claims (9)
1.一种复合水凝胶,其特征在于:包括以下重量配比的原料:
聚乙烯醇:40%~72%
羧甲基纤维素钠:5%~35%
吡咯:4%~25%
戊二醛:0.5%~2.5%
FeCl3:1.5%~4.5%;
所述的复合水凝胶的制备方法:首先将聚乙烯醇、羧甲基纤维素钠及单体吡咯共混合后,以戊二醛作为交联剂,在酸性条件下,制备得到包埋有CMC及Py的聚乙烯醇单网络水凝胶,随后在低温下,将所得单网络水凝胶浸泡于FeCl3溶液中,制得聚吡咯/羧甲基纤维素钠-Fe3+/聚乙烯醇双网络复合水凝胶。
2.根据权利要求1所述的复合水凝胶的制备方法,其特征在于:包括以下步骤:
(1)制备包埋有CMC及单体Py的聚乙烯醇单网络水凝胶:
将PVA和CMC溶解于90℃-100℃的二次蒸馏水中,磁力搅拌使二者混合均匀,给混合溶液中缓慢滴加稀盐酸,调节pH为2.0-5.0,随后加入吡咯溶液并于氮气氛围下搅拌30min,待溶液混合均匀后加入戊二醛水溶液,搅拌均匀,将混合溶液倒入水凝胶预制模具中,在水浴条件下反应30~90min,得到包埋有CMC及单体py的聚乙烯醇单网络水凝胶;
(2)制备PPy/CMC-Fe3+/PVA双网络复合水凝胶:
将步骤(1)中制备所得包埋有CMC及单体Py的聚乙烯醇单网络水凝胶浸泡到三氯化铁溶液中,保持低温状态浸泡;在此过程中,Fe3+既能同步与CMC分子链间发生络合交联,从而得到CMC-Fe3+的第二层高分子网络结构,也是聚吡咯形成的氧化剂及掺杂剂,最终得到掺杂有聚吡咯PPy的PPy/CMC-Fe3+/PVA双网络复合水凝胶。
3.根据权利要求2所述的复合水凝胶的制备方法,其特征在于:步骤(1)中,PVA溶液的浓度为0.10~0.15g/mL,CMC溶液的浓度为0.03~0.07g/mL,戊二醛溶液的浓度为4.0~6.0mg/mL,Py溶液的浓度为0.2~1.0mol/L,其中,PVA溶液、CMC溶液、戊二醛溶液与Py溶液的体积比为15:8:0.5:1~25:15:1.0:1;稀盐酸的体积浓度为10%~15%;滴加速度为20μL/min。
4.根据权利要求2所述的复合水凝胶的制备方法,其特征在于:步骤(1)中,水浴的温度控制在40~70℃。
5.根据权利要求2所述的复合水凝胶的制备方法,其特征在于:步骤(2)中,所用三氯化铁溶液的浓度为0.6mo/L-3.0mol/L,控制溶液中Fe3+与水凝胶中Py的物质的量之比为1:2~1:4。
6.根据权利要求2所述的复合水凝胶的制备方法,其特征在于:步骤(2)中,所述单网络水凝胶浸泡到FeCl3溶液中保持0~4℃的低温环境,且浸泡时间为18~24h。
7.根据权利要求2所述的复合水凝胶的制备方法,其特征在于:步骤(2)所得的双网络复合水凝胶浸泡于去离子水中24~48h;期间每隔6h换一次水,以去除水凝胶网络内未反应的FeCl3。
8.一种权利要求1所述的复合水凝胶在应变传感贴片中的应用。
9.根据权利要求8所述的应用,其特征在于:将复合水凝胶用于制备具有导电性能的双网络水凝胶应变传感贴片,包括以下步骤:将所得复合水凝胶裁成长为1cm、宽为0.5cm的小片,以黏性塑料薄膜为载体,将其黏附在塑料薄膜上,然后在复合水凝胶的左右两侧距离边缘3mm处的下方分别埋置直径为3mm的铜导线两根,并在复合水凝胶与铜导线的交界处用铜箔胶带纸固定完全,制备得到具有导电性能的双网络水凝胶应变传感贴片。
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