CN114854151B - 水下损伤自报警自修复材料及其制备方法与应用 - Google Patents
水下损伤自报警自修复材料及其制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种水下损伤自报警自修复材料及其制备方法与应用，包括：芯层和疏水保护层，疏水保护层包裹于芯层的外部；芯层，包括叠加设置的A层和B层，A层包括相互混合的离子液体、含氟聚合物以及可与水反应生成双氧水的物质；所述B层包括相互混合的过氧草酸酯、染料、含氟聚合物和离子液体；疏水保护层为由含氟聚合物和离子液体耦合形成的薄膜；所述含氟聚合物均能够与离子液体耦合，所述染料为可化学发光的染料。该材料在损伤后可以通过级联反应调节的化学发光实现损伤后的自发报警。此外，离子液体的引入也可以为材料赋予水下自愈合能力，优异导电性能和传感性能。
Description
技术领域
本发明属于高分子领域，特别涉及一种水下损伤自报警自修复材料及其制备方法与应用。
背景技术
这里的陈述仅提供与本发明相关的背景技术，而不必然地构成现有技术。
现有的部分合成材料虽然具有一定的自修复功能，但是在自修复体系中，大多需要人为让受损面接触以使其修复，这就需要人们能够及时发现损伤位置。因此，对于材料损伤后自报警性能的研究也非常重要。
常用的损伤自报警方法为两种，一种是使用释放颜色指示剂，另一种是在材料中添加荧光探针。但是，添加释放颜色指示剂无法实现材料在黑暗条件下的损伤自报警。而添加香豆素或AIE分子等荧光探针去实现黑暗条件下的损伤自报警时，严重依赖于外部紫外光源。
发明内容
针对现有技术存在的不足，本发明的目的是提供一种水下损伤自报警自修复材料及其制备方法与应用。所构建的材料具有分级结构，在损伤后材料内部的反应性物质与水发生反应诱导级联反应的发生，从而实现材料损伤后的自发报警。
为了实现上述目的，本发明是通过如下的技术方案来实现：
第一方面，本发明提供了一种水下损伤自报警自修复材料，包括：芯层和疏水保护层，疏水保护层包裹于芯层的外部；
芯层，包括叠加设置的A层和B层，A层包括相互混合的离子液体、含氟聚合物以及可与水反应生成双氧水的物质；
所述B层包括相互混合的过氧草酸酯、染料、含氟聚合物和离子液体；
疏水保护层为由含氟聚合物和离子液体耦合形成的薄膜；
所述含氟聚合物均能够与离子液体耦合，所述染料为可化学发光的染料。
第二方面，本发明提供所述水下损伤自报警自修复材料的制备方法，包括如下步骤：
将可与水反应生成双氧水的物质、含氟聚合物、离子液体和有机溶剂混合均匀，旋蒸后烘干，热压成膜，制备得到A层；
将过氧草酸酯、染料、含氟聚合物、离子液体和有机溶剂混合均匀，旋蒸后烘干，热压成膜，制备得到B层；
将A层和B层叠加设置；
将含氟聚合物与离子液体混合耦合制备得到的材料包裹A层和B层的叠合层，形成疏水保护层，即得。
第三方面，本发明提供所述水下损伤自报警自修复材料在离子皮肤，应变传感器等离子电子学领域有潜在的应用。
上述本发明的一种或多种实施例取得的有益效果如下：
(1)本发明中材料损伤后的自报警是通过级联反应调节的化学发光实现的，损伤后即可自发报警，不依赖于外部光源。
(2)离子液体的引入，不仅可以与含氟聚合物产生离子-偶极相互作用，还可以为材料赋予导电性能，从而制备出集自报警能力、水下自愈合能力、优异导电性能和传感性能于一体的多功能材料。
附图说明
构成本发明的一部分的说明书附图用来提供对本发明的进一步理解，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。
图1是本发明实施例1所制备材料的结构示意图。
图2为本发明中实施例1所制备材料损伤后自报警和自愈合图。
图3为本发明中所制备材料的电化学阻抗谱图(a)及不同应变下的相对电阻变化(b)。
具体实施方式
应该指出，以下详细说明都是例示性的，旨在对本发明提供进一步的说明。除非另有指明，本发明使用的所有技术和科学术语具有与本发明所属技术领域的普通技术人员通常理解的相同含义。
第一方面，本发明提供了一种水下损伤自报警自修复材料，包括：芯层和疏水保护层，疏水保护层包裹于芯层的外部；
芯层，包括叠加设置的A层和B层，A层包括相互混合的离子液体、含氟聚合物以及可与水反应生成双氧水的物质；
所述B层包括相互混合的过氧草酸酯、染料、含氟聚合物和离子液体；
疏水保护层为由含氟聚合物和离子液体耦合形成的薄膜；
所述含氟聚合物均能够与离子液体耦合，所述染料为可化学发光的染料。
该材料在水下损伤后，疏水保护层破裂，使可与水反应生成H2O2的物质会暴露出来首先与水反应生成H2O2，之后H2O2与过氧草酸酯反应生成双氧基中间体，双氧基中间体极其不稳定，它会将能量传递给染料，使其发光，从而实现材料受损后的自报警。此外，由于材料内部离子液体和含氟聚合物之间存在的离子-偶极相互作用，还可以实现水下修复。
离子液体的引入，不仅可以与含氟聚合物产生离子-偶极相互作用，还可以为材料赋予导电性能，从而制备出集自报警能力、水下自愈合能力、优异导电性能和传感性能于一体的多功能材料。
在一些实施例中，所述的能够溶解含氟聚合物的有机溶剂为丙酮或DMF。
在一些实施例中，所述可与水反应生成双氧水的物质为CaO2或NaO2。
在一些实施例中，所述含氟聚合物为P(VDF-HFP)，所述离子液体为疏水离子液体。
优选的，所述离子液体为EMITFSI或[Emim]PF6。
优选的，A层中，离子液体、含氟聚合物和可与水反应生成双氧水的物质的质量比为0.5～1:1:0.1～0.3。
优选的，A层的厚度为0.1mm～2mm。
在一些实施例中，所述过氧草酸酯为CPPO、DNPO或TCPO。
在一些实施例中，所述染料为DPA、BPEA、ST、罗丹明B或吖啶橙。
优选的，B层中，过氧草酸酯、染料、含氟聚合物和离子液体的质量比为0.1～0.3:0.001～0.01:1:0.5～1。
优选的，B层的厚度为0.1mm～2mm。
在一些实施例中，疏水保护层中，含氟聚合物和离子液体的质量比为1:0.5～1。
优选的，疏水保护层的厚度为0.1mm～2mm。
第二方面，本发明提供所述水下损伤自报警自修复材料的制备方法，包括如下步骤：
将可与水反应生成双氧水的物质、含氟聚合物、离子液体和有机溶剂混合均匀，旋蒸后烘干，热压成膜，制备得到A层；
将过氧草酸酯、染料、含氟聚合物、离子液体和有机溶剂混合均匀，旋蒸后烘干，热压成膜，制备得到B层；
将A层和B层叠加设置；
将含氟聚合物与离子液体混合耦合制备得到的材料包裹A层和B层的叠合层，形成疏水保护层，即得。
第三方面，本发明提供所述水下损伤自报警自修复材料在离子皮肤，应变传感器等离子电子学领域有潜在的应用。
术语解释：
DMF：N,N-二甲基甲酰胺；
P(VDF-HFP)：聚偏氟乙烯-六氟丙烯；
EMITFSI或[EMI]+[TFSI]-：1-乙基-3-甲基咪唑双三氟甲磺酰亚胺盐；
[Emim]PF6：1-乙基-3-甲基咪唑六氟磷酸盐；
CaO2：过氧化钙；
NaO2：过氧化钠；
H2O2：过氧化氢；
DNPO：双(2，4-二硝基苯基)草酸酯；
CPPO：双(2,4,5–三氯水杨酸正戊酯)草酸酯；
TCPO：双(2，4，6-三氯苯基)草酸酯；
DPA：9,10-二苯基蒽；
BPEA：9,10-双苯乙炔基蒽；
ST：藏红T。
下面结合附图和实施例对本发明作进一步说明。
实施例1
A膜的制备方法：将P(VDF-HFP)(10g)和EMITFSI(8g)室温溶解于丙酮中，得到均一溶液后再加入CaO2(2g)。旋蒸，烘干，压缩成型得到A膜。
B膜的制备方法：将P(VDF-HFP)(10g)和EMITFSI(8g)室温溶解于丙酮中，得到均一溶液后再加入DNPO(2g)与DPA(0.003g)。旋蒸，烘干，压缩成型得到B膜。
疏水透明薄膜的制备方法：将P(VDF-HFP)(10g)和EMITFSI(8g)室温溶解于丙酮中，得到均一溶液。之后旋蒸，烘干，压缩成型得到疏水透明薄膜。
将A膜与B膜先组装成一个整体，再用疏水透明薄膜将其严密包裹起来，得到最终材料，其结构如图1所示。
如图2所示，当材料未损伤时，不会引发级联反应，材料不会发光。当材料在水下损伤后，由于A膜中的CaO2会暴露出来首先与水反应生成H2O2，之后H2O2与DNPO反应生成双氧基中间体，双氧基中间体极其不稳定，它会将能量传递给发光染料DPA，使其发光，从而实现材料受损后的自发报警。此外，将受损断面贴合到一起，还可以实现损伤后修复。
当材料在无水条件下损伤后，由于A膜中的CaO2暴露出来后无水参与反应，无法生成H2O2，不会引发级联反应，所以无法实现材料受损后的自发报警。
实施例2
A膜的制备方法：将P(VDF-HFP)(10g)和EMITFSI(5g)室温溶解于丙酮中，得到均一溶液后再加入CaO2(2g)。旋蒸，烘干，压缩成型得到A膜。
B膜的制备方法：将P(VDF-HFP)(10g)和EMITFSI(5g)室温溶解于丙酮中，得到均一溶液后再加入DNPO(3g)与BPEA(0.001g)。旋蒸，烘干，压缩成型得到B膜。
疏水透明薄膜的制备方法：将P(VDF-HFP)(10g)和EMITFSI(5g)室温溶解于丙酮中，得到均一溶液。之后旋蒸，烘干，压缩成型得到疏水透明薄膜。
将A膜与B膜先组装成一个整体，再用疏水透明薄膜将其严密包裹起来，得到最终材料。
实施例3
A膜的制备方法：将P(VDF-HFP)(10g)和EMITFSI(10g)室温溶解于丙酮中，得到均一溶液后再加入CaO2(2g)。旋蒸，烘干，压缩成型得到A膜。
B膜的制备方法：将P(VDF-HFP)(10g)和EMITFSI(10g)室温溶解于丙酮中，得到均一溶液后再加入TCPO(1g)与吖啶橙(0.01g)。旋蒸，烘干，压缩成型得到B膜。
疏水透明薄膜的制备方法：将P(VDF-HFP)(10g)和EMITFSI(10g)室温溶解于丙酮中，得到均一溶液。之后旋蒸，烘干，压缩成型得到疏水透明薄膜。
将A膜与B膜先组装成一个整体，再用疏水透明薄膜将其严密包裹起来，得到最终材料。
对比例1
相对于实施例1的区别在于：省略A膜，只将B膜用透明薄膜严密的包裹起来，从而得到最终材料。
当材料在水下损伤后，由于没有A膜的参与无法生成H2O2，不会引发级联反应，所以无法实现材料受损后的自发报警。
对比例2
相对于实施例1的区别在于：将A膜与不含DNPO的B膜先组装成一个整体，再用透明薄膜将其严密的包裹起来，得到最终的材料。
当材料在水下损伤后，A膜中的CaO2会首先暴露出来与水反应生成H2O2，但是没有DNPO的参与，不会进行后续的级联反应，所以无法实现材料受损后的自发报警。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (5)
1.一种水下损伤自报警自修复材料，其特征在于：包括：芯层和疏水保护层，疏水保护层包裹于芯层的外部；
芯层，包括叠加设置的A层和B层，A层包括相互混合的离子液体、含氟聚合物以及可与水反应生成双氧水的物质；
所述B层包括相互混合的过氧草酸酯、染料、含氟聚合物和离子液体；
疏水保护层为由含氟聚合物和离子液体耦合形成的薄膜；
所述含氟聚合物均能够与离子液体耦合，所述染料为可化学发光的染料；
所述可与水反应生成双氧水的物质为CaO2或NaO2；
所述含氟聚合物为P(VDF-HFP)，所述离子液体为EMITFSI或[Emim]PF6；
所述过氧草酸酯为CPPO、DNPO或TCPO；
所述染料为DPA、BPEA、ST、罗丹明B或吖啶橙；
A层中，离子液体、含氟聚合物和可与水反应生成双氧水的物质的质量比为0.5~1:1:0.1~0.3；
B层中，过氧草酸酯、染料、含氟聚合物和离子液体的质量比为0.1~0.3:0.001~0.01:1:0.5~1；
疏水保护层中，含氟聚合物和离子液体的质量比为1:0.5~1。
2.权利要求1所述水下损伤自报警自修复材料的制备方法，其特征在于：包括如下步骤：
将可与水反应生成双氧水的物质、含氟聚合物、离子液体和有机溶剂混合均匀，旋蒸后烘干，热压成膜，制备得到A层；
将过氧草酸酯、染料、含氟聚合物、离子液体和有机溶剂混合均匀，旋蒸后烘干，热压成膜，制备得到B层；
将A层和B层叠加设置；
将含氟聚合物与离子液体混合耦合制备得到的材料包裹A层和B层的叠合层，形成疏水保护层，即得。
3.权利要求2所述的水下损伤自报警自修复材料的制备方法，其特征在于：所述有机溶剂为丙酮或DMF。
4.权利要求1所述一种水下损伤自报警自修复材料在离子电子学领域的应用。
5.权利要求1所述的水下损伤自报警自修复材料在离子皮肤，应变传感器的应用。
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