CN113788908B - 一种利用空间调整策略提高光固化离子凝胶电导率和灵敏度的方法 - Google Patents

一种利用空间调整策略提高光固化离子凝胶电导率和灵敏度的方法 Download PDF

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CN113788908B
CN113788908B CN202111211470.9A CN202111211470A CN113788908B CN 113788908 B CN113788908 B CN 113788908B CN 202111211470 A CN202111211470 A CN 202111211470A CN 113788908 B CN113788908 B CN 113788908B
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何勇
张超
姚淼
聂俊
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Beijing University of Chemical Technology
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Abstract

离子凝胶的高电导率和作为传感器的高灵敏度一直是巨大的挑战。本发明提出了一种空间调整策略，在不改变离子凝胶内化合物类型和比例的情况下，通过减少空间阻碍来提高电导率和灵敏度。在离子凝胶制备过程中添加可去除的空间预占位剂减少了聚合物链的缠结，从而改善聚合物网络的流动性。凝胶成型后除去空间预占位剂，获得的自由体积可以促进离子的移动和聚合物的迁移。通过这种方式，成功地提高了离子凝胶的电导率和灵敏度，同时保持了其良好的透明性、拉伸性、稳定性和机电性能，如快速的响应速度和良好的重复性。这种简单有效的策略对化学结构没有特殊要求，因此在各种系统中具有广泛的适用性，为柔性传感器的发展开辟了一条新的途径。

Description

一种利用空间调整策略提高光固化离子凝胶电导率和灵敏度 的方法
技术领域
本发明涉及基于离子液体凝胶的传感器材料领域，尤其涉及一种提高离子凝胶电导率和灵敏度的通用策略，主要应用在柔性传感器方面。
背景技术
近年来，柔性/可拉伸电子设备在前沿领域显示出良好的应用前景，如柔性传感器、电子皮肤、人机交互界面和柔性电池等。柔性传感器是指可在一定范围内变形的电子设备，与传统电子设备相比，它具有更大的灵活性，在一定程度上能够适应不同的工作环境。电子皮肤是一种具有皮肤功能的人工电子材料，通过将柔性电子设备的机械变形转换为电信号来模拟人体皮肤以体验外部刺激（压力、温度、湿度）。
离子凝胶由离子液体溶胀的聚合物网络组成，具有良好的拉伸性和透明性。同时，离子凝胶保留了离子液体的固有特性，如高离子电导率（~1mS/cm）、低挥发性、热稳定性和化学稳定性、宽电化学窗口和不易燃性，并显示出优于水凝胶的显著优势。
高导电性和高灵敏度的离子凝胶是研究人员一直追求的目标。通常通过选择电导率较高的离子液体或增加离子液体的含量来提高电导率，这就需要离子液体在交联聚合物网络中具有高相容性和高容量，因此就存在液体泄漏的风险以及选择离子液体和聚合物类型的困难。而离子凝胶的灵敏度与变形过程中聚合物链和离子液体的重排速度有关，目前仅通过改变聚合物和离子液体的类型来调整。
除了离子液体的类型和含量外，离子液体和聚合物网络在凝胶中的运动能力也是决定电导率和灵敏度的关键因素，可以通过聚合物网络的空间障碍来控制。空间阻碍程度由空间密度和缠结程度决定，较低的空间密度和较低的缠结程度会导致较高的运动能力。如果可以降低聚合物网络的空间障碍程度，从而提高聚合物网络的流动性和离子液体在离子凝胶中的移动能力，那么可以得到具有更高电导率和灵敏度的离子凝胶。
发明内容
本发明的目的在于提供一种提高离子凝胶电导率和灵敏度的通用且简便的空间调整策略。在制备离子凝胶时，在溶液中加入惰性且可去除的空间预占位剂，以预先占据一定的空间。已有研究表明聚合过程中单体的浓度会影响聚合物网络的缠结程度。当凝胶从更高浓度的溶液中聚合时，更容易发生缠结。因此，在本策略中，稀释单体的额外溶剂将减少网络形成过程中聚合物的缠结，从而使聚合物网络更具流动性。离子凝胶形成后，去除空间预占位剂后释放的空间在离子凝胶中形成自由体积，然后离子液体和部分聚合物链段将自发地移动到这些自由空间中以平均空间密度，从而获得更高的运动能力。
在发明中选择相容性较好的离子液体和单体来制备离子凝胶，选择的空间预占位剂与离子液体及聚合物具有良好的相容性和适当的挥发性。选择合适的交联剂以及1 wt%的2-羟基-2-甲基1-苯基-1-丙酮（1173）作为光引发剂，采用一锅法通过光聚合制备了无离子液体渗漏的透明离子凝胶。在制备期间加入一定体积比（空间预占位剂/溶液）的空间预占位剂，最终在离子凝胶形成后移除。
随着聚合物网络状态的变化，离子凝胶的电导率发生变化（在空间调整后离子液体获得了更多的自由体积，这有利于离子迁移，实现了离子凝胶电导率的提高。
通过空间调整，离子凝胶拉伸性能显著的提高。聚合物网络和离子液体在拉伸过程中会同时重排，因此离子凝胶拉伸性能的改善主要取决于空间调整后聚合物链之间物理缠结的减少，聚合物链之间物理缠结的减少意味着分子链有更好的流动性，从而实现更高的断裂伸长率。空间调整后，由于聚合物分子链之间的缠结的减少和空间密度的调整，聚合物链和离子液体的重排速度加快，与未经过空间调整的凝胶相比，化学成分和比例没有任何变化的情况下，由空间调整后的离子凝胶制备的传感器具有更高的灵敏度。
具体实施方式
实施例1
1)将摩尔比为1:0.46的丙烯酸丁酯和1-丁基-3-甲基咪唑双(三氟甲烷磺酰)亚胺盐混合均匀。
2)将1173（相对于单体的1 wt%）和1,6-己二醇二丙烯酸酯（相对于单体的0.6mol%）溶解在溶液中。
3)添加5/8体积比（乙醇/溶液）的乙醇作为空间预占位剂到溶液中，并对溶液进行5分钟的超声处理。
4)将溶液转移到由夹有硅胶垫片的一对玻璃板制成的模具中，然后用强度为80mW/cm2和波长为365 nm的紫外光照射300 s。
5)将离子凝胶置于60 ℃的真空烘箱中6小时以除去乙醇。离子凝胶的性能如表1所示。
实施例2
所用单体和离子液体为丙烯酸乙酯和1-乙基-3-甲基咪唑双(三氟甲烷磺酰)亚胺盐（摩尔比为1:0.5）。交联剂为乙二醇二甲基丙烯酸酯（相对于单体的0.8 mol%），空间预占位剂为丙酮，真空烘箱的温度为40 ℃。其它实验步骤与实施例1相同。离子凝胶的性能如表1所示。
实施例3
所用单体和离子液体为丙烯酸羟丙酯和1-丁基-3-甲基咪唑三氟甲烷磺酸盐（摩尔比为1:0.4）。交联剂为三丙二醇二丙烯酸酯（相对于单体的0.8 mol%），空间预占位剂为甲醇，真空烘箱的温度为50 ℃。其它实验步骤与实施例1相同。离子凝胶的性能如表1所示。
实施例4
所用单体和离子液体换为丙烯酸六氟丁酯和N-乙基吡啶双(三氟甲烷磺酰)亚胺盐（摩尔比为1:0.45）。交联剂为双季戊四醇六丙烯酸酯（相对于单体的1 mol%），空间预占位剂为乙酸乙酯，真空烘箱的温度为65 ℃。其它实验步骤与实施例1相同。离子凝胶的性能如表1所示。
实施例5
所用单体和离子液体换为丙烯酸和1-乙基-3-甲基咪唑氯盐（摩尔比为1:0.38）。交联剂为三羟甲基丙烷三丙烯酸酯（相对于单体的0.6 mol%），空间预占位剂为乙醚，真空烘箱的温度为30 ℃。其它实验步骤与实施例1相同。离子凝胶的性能如表1所示。
实施例6
所用单体和离子液体换为丙烯酸二甲氨基乙酯，丙烯酸丁酯和三丁基甲基铵双(三氟甲烷磺酰)亚胺盐（摩尔比为1:1:0.8）。交联剂为季戊四醇四丙烯酸酯（相对于单体的0.8 mol%），空间预占位剂为二氯甲烷，真空烘箱的温度为35 ℃。其它实验步骤与实施例1相同。离子凝胶的性能如表1所示。
实施例7
所用单体和离子液体换为丙烯酸羟乙酯，丙烯酸羟丙酯和1-乙基-3-甲基咪唑四氟硼酸盐（摩尔比为1:0.9:0.9）。交联剂为季戊四醇三丙烯酸酯（相对于单体的1 mol%），空间预占位剂为异丙醇，真空烘箱的温度为60 ℃。其它实验步骤与实施例1相同。离子凝胶的性能如表1所示。
实施例8
所用的单体和离子液体换为丙烯酸正辛酯，丙烯酸和1-辛基-3-甲基咪唑双(三氟甲烷磺酰)亚胺盐（摩尔比为1:0.5:0.85）。交联剂为双季戊四醇六丙烯酸酯（相对于单体的0.8 mol%），空间预占位剂为乙醇，真空烘箱的温度为60 ℃。其它实验步骤与实施例1相同。离子凝胶的性能如表1所示。
实施例9
所用单体和离子液体换为丙烯酸丁酯，丙烯酸，丙烯酸乙酯和1-丁基-3-甲基咪唑六氟磷酸盐（摩尔比为1:0.5:0.5:0.9）。交联剂为三丙二醇二丙烯酸酯（相对于单体的0.6mol%），空间预占位剂为丙酮，真空烘箱的温度为40 ℃。其它实验步骤与实施例1相同。离子凝胶的性能如表1所示。
实施例10
所用单体和离子液体换丙烯酸乙酯，丙烯酸羟乙酯，丙烯酸二甲氨基乙酯和1-乙基-3-甲基咪唑二腈胺盐（摩尔比为1:0.6:1:1）。交联剂为乙二醇二甲基丙烯酸酯（相对于单体的1 mol%），空间预占位剂为丁酮，真空烘箱的温度为60 ℃。其它实验步骤与实施例1相同。离子凝胶的性能如表1所示。
实施例11
所用单体和离子液体换丙烯酸羟丙酯，丙烯酸羟乙酯，丙烯酸六氟丁酯和1-丙基-3-甲基咪唑四氟硼酸盐（摩尔比为1:0.6:0.8:0.85）。交联剂为季戊四醇三丙烯酸酯（相对于单体的0.8 mol%），空间预占位剂为二氯甲烷，真空烘箱的温度为35 ℃。其它实验步骤与实施例1相同。离子凝胶的性能如表1所示。
实施例12
所用单体和离子液体换丙烯酸，丙烯酸羟乙酯，丙烯酸羟丙酯和1-乙基-3-甲基咪唑对甲基苯磺酸盐（摩尔比为1:1:0.5:0.9）。交联剂为乙二醇二甲基丙烯酸酯（相对于单体的0.1 mol%），空间预占位剂为甲醇，真空烘箱的温度为50 ℃。其它实验步骤与实施例1相同。离子凝胶的性能如表1所示。
表1 各实施例中空间调整后的离子凝胶与未经空间调整的离子凝胶的性能对比
Figure 191021DEST_PATH_IMAGE002
注：对比值为具有与实施例相同单体，交联剂，离子液体，光引发剂组成，通过相同制备过程，但是不加入空间预占位剂体系的测量值。

Claims (3)

1.一种利用空间调整策略提高光固化离子凝胶电导率和灵敏度的方法，其特征在于，在制备离子凝胶时加入一种惰性且可去除的空间预占位剂，在应用光固化技术完成离子凝胶制备后将其去除，利用加入空间预占位剂导致的聚合物分子链缠结程度的降低和去除空间预占位剂导致的凝胶空间密度的降低来提高离子凝胶的电导率和灵敏度；离子凝胶制备过程为将离子液体，单体，交联剂，空间预占位剂，光引发剂混合均匀后通过紫外光固化形成凝胶，最后将空间预占位剂通过真空干燥的方法去除；所述空间预占位剂为挥发性小分子有机化合物，为甲醇，乙醇，异丙醇，丙酮，丁酮，乙醚，二氯甲烷，环己烷，乙酸乙酯中的一种或几种。
2.根据权利要求1所述的方法，其特征在于，所述凝胶为聚丙烯酸酯，通过单官能丙烯酸酯单体和丙烯酸酯交联剂的自由基交联反应制备； 单体为丙烯酸，丙烯酸乙酯，丙烯酸丁酯，丙烯酸正辛酯，丙烯酸羟丙酯，丙烯酸羟乙酯，丙烯酸二甲氨基乙酯，丙烯酸六氟丁酯中的1-3种，交联剂为乙二醇二甲基丙烯酸酯, 1,6-己二醇二丙烯酸酯，三丙二醇二丙烯酸酯，二丙二醇二丙烯酸酯，三羟甲基丙烷三丙烯酸酯，季戊四醇三丙烯酸酯，季戊四醇四丙烯酸酯，双季戊四醇六丙烯酸酯中的1-2种。
3.根据权利要求1所述的方法，其特征在于，所述离子液体的阳离子为带有不同烷基取代基的咪唑类、吡啶类、季铵类、季膦类、吡咯烷类和哌啶类中的一种，阴离子为氯，溴，碘，四氟硼酸，六氟磷酸，双三氟甲烷磺酰亚胺，三氟乙酸，三氟甲烷磺酸，对甲苯磺酸中的一种。
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5242491A (en) * 1989-10-23 1993-09-07 Massachusetts Institute Of Technology Photo-induced reversible, discontinuous volume changes in gels
CN108623826A (zh) * 2018-05-18 2018-10-09 北京大学 一种具有刺激响应性和自修复性的双网络离子凝胶
CN111848982A (zh) * 2020-06-29 2020-10-30 华南理工大学 一种自愈合导电离子凝胶及其制备方法与应用
CN113061266A (zh) * 2021-03-22 2021-07-02 北京大学 一种基于多重非共价交联作用的高强度离子凝胶

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5242491A (en) * 1989-10-23 1993-09-07 Massachusetts Institute Of Technology Photo-induced reversible, discontinuous volume changes in gels
CN108623826A (zh) * 2018-05-18 2018-10-09 北京大学 一种具有刺激响应性和自修复性的双网络离子凝胶
CN111848982A (zh) * 2020-06-29 2020-10-30 华南理工大学 一种自愈合导电离子凝胶及其制备方法与应用
CN113061266A (zh) * 2021-03-22 2021-07-02 北京大学 一种基于多重非共价交联作用的高强度离子凝胶

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