CN114181531A - 用于制备致动器件的离子聚合物、致动器件及其制备方法 - Google Patents
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Abstract
本发明公开一种用于制备致动器件的离子聚合物、致动器件及其制备方法,属于功能材料技术领域。该用于制备致动器件的离子聚合物,由离子化聚硅氧烷与金属盐溶于第一溶剂中得到铸膜液,之后干燥制得所述离子聚合物;所述离子化聚硅氧烷与所述金属盐的质量比为1:(2‑11);所述铸膜液中的固含量为30%‑50%。该致动器件的制备方法,包括以下步骤:将电极材料置于第二溶剂中,经分散形成电极层铸膜液;在上述离子聚合物形成的电解质层的上下两面涂覆所述电极层铸膜液,之后干燥形成所述致动器件。制得的致动器件在低电场作用下,具有较高的响应应变和应力。
Description
技术领域
本发明涉及功能材料技术领域,具体涉及一种用于制备致动器件的离子聚合物、致动器件及其制备方法。
背景技术
随着人工智能、自动化技术的不断发展,智能响应材料受到越来越多的关注。智能响应材料因其可受到外界刺激如光、热、电(场)、pH、磁场等做出形状变化,而当外界刺激撤除时,其形变可恢复。据此,可应用于如人工肌肉、电子皮肤、微控开关、智能监测等领域。对于智能响应材料,其响应效率对其在智能应用领域有着重要意义,比如过载保护、温湿检测等需要材料在较短时间产生快速的响应,以便达到监测、警报的目的。又比如在人工肌肉、电子皮肤、人工心脏等需要材料拥有良好的柔韧性,可有效的完成形变的响应及恢复,达到仿生目的。
传统有机硅,又称聚二甲基硅氧烷(PDMS)具有优异的柔性、低弹性模量、光学透明性以及生理惰性,目前已经在日化、医药等领域被广泛应用。但是由于PDMS低极性、低表面张力,疏水表面等导致其在智能材料领域应用受限。如材料间相容性差、粘接力弱、附着力低等缺点,特别是在电致制动器制备上,通常需要外加上千伏电场以完成其介电驱动,且形变响应弱而缓慢。如何获得低电压下具有高相应应变和应力的致动器件是现有技术的难题。
发明内容
为降低驱动电压,致动器必须选择合适的材料,而聚电解质是必须且具有选择性的,高离子电导率以及高柔性赋予致动器高效的制动响应以及形变位移,此外聚电解质的韧性及强度可保障致动器的使用效果及使用寿命。
本发明的目的在于克服上述技术不足,提供一种用于制备致动器件的离子聚合物、致动器件及其制备方法,解决现有技术中如何获得低电压下具有较高的相应应变和应力的致动器件的技术问题。
为达到上述技术目的,本发明的技术方案提供一种用于制备致动器件的离子聚合物、致动器件及其制备方法。
本发明提出一种用于制备致动器件的离子聚合物,由离子化聚硅氧烷与金属盐溶于第一溶剂中得到铸膜液,之后干燥制得所述离子聚合物;所述离子化聚硅氧烷与所述金属盐的质量比为1:(2-11);所述铸膜液中的固含量为30%-50%。
进一步地,所述离子化聚硅氧烷的离子化程度为25%-100%。
进一步地,所述金属盐为锆盐、钙盐、铜盐、铁盐和锌盐中的一种或者多种。
进一步地,所述锆盐为氯氧化锆,所述钙盐为氯化钙,所述铜盐为氯化铜,所述铁盐为氯化铁,所述锌盐为氯化锌。
进一步地,所述第一溶剂为水、甲醇、冰醋酸和四氢呋喃中的一种或者多种。
此外,本发明还提出一种致动器件,包括上述离子聚合物形成的电解质层、以及涂敷于所述电解质层上下两面的电极层。
进一步地,本发明还提出一种上述致动器件的制备方法,包括以下步骤:将电极材料置于第二溶剂中,经分散形成电极层铸膜液;在上述离子聚合物形成的电解质层的上下两面涂覆所述电极层铸膜液,之后干燥形成所述致动器件。
进一步地,所述电极材料为碳纳米管和/或碳纳米管衍生物;所述碳纳米管衍生物优选为酸化碳纳米管。
进一步地,所述第二溶剂为水、甲醇、冰醋酸和四氢呋喃中的一种或者多种。
进一步地,所述电极层铸膜液的固含量为10%-20%。
与现有技术相比,本发明的有益效果包括:按照配比,由离子化程度可控的聚硅氧烷与金属盐溶于第一溶剂中得到铸膜液,之后干燥制得所述性能及强度可调的离子聚合物,该离子聚合物用于制备致动器件,制得的致动器件在低电场作用下,具有较高的响应应变和应力,该致动器在较小驱动电压(1-5V)下,获得较大的形变弯曲,且这种弯曲形变是可逆响应的。
附图说明
图1是本发明具体实施方式提出的致动器件的结构示意图。
附图标记说明:1、电解质层;2、电极层。
具体实施方式
本具体实施方式提供了一种用于制备致动器件的离子聚合物,由离子化聚硅氧烷与金属盐溶于第一溶剂中得到铸膜液,之后干燥制得所述离子聚合物;所述离子化聚硅氧烷与所述金属盐的质量比为1:(2-11);所述铸膜液的固含量为30%-50%;所述离子化聚硅氧烷的离子化程度为25%-100%;所述金属盐为锆盐、钙盐、铜盐、铁盐和锌盐中的一种或者多种;所述锆盐为氯氧化锆,所述钙盐为氯化钙,所述铜盐为氯化铜,所述铁盐为氯化铁,所述锌盐为氯化锌;所述第一溶剂为水、甲醇、冰醋酸和四氢呋喃中的一种或者多种。
本具体实施方式还包括一种致动器件,如图1所示,包括上述离子聚合物形成的电解质层1、以及涂敷于所述电解质层上下两面的电极层2。
本具体实施方式还包括一种上述致动器件的制备方法,包括以下步骤:将电极材料置于第二溶剂中,经分散形成电极层铸膜液;在上述离子聚合物形成的电解质层的上下两面涂覆所述电极层铸膜液,之后干燥形成所述致动器件;进一步地,所述电极材料为碳纳米管和/或碳纳米管衍生物;所述碳纳米管衍生物优选为酸化碳纳米管;所述第二溶剂优选为水、甲醇、冰醋酸和四氢呋喃中的一种或者多种;所述电极层铸膜液固含量为10%-20%。
本发明将环硅氧烷单体开环聚合及点击反应后接枝上离子基团;再将离子化的聚硅氧烷与金属离子络合形成电活性高分子络合物膜;最后在电活性络合物膜材料两表面负载电极层、形成三明治结构的致动器件。
为此,本发明选取甲基乙烯基环硅氧烷作为单体合成聚甲基乙烯基硅氧烷(PMVS),再经过巯烯加成点击反应完成PMVS的改性。
进一步的,所述点击反应中,离子改性剂为巯基化合物,更进一步的,可选为巯基乙磺酸钠、巯基丙磺酸钠或其他烷基链段可调控巯基磺酸盐。
在本发明中,几乎每个高分子链接中硅原子连接有一个乙烯基官能团,通过高效的点击反应,仅需改变原料的比例,PMVS离子化程度可以在0~100%范围精准调节,且得到的离子化PMVS的离子电导率、柔性、极性同样可以精准调控。
进一步的,络合物膜由金属离子(M)与离子化PMVS络合形成;更进一步的,M可选为钙、铜、铁、锌、锆等;更进一步的,二者络合摩尔比例为SO3 -:M=1:0.01~0.1。
在本申请中,PMVS提供稳定的柔性,通过与金属离子络合,改变金属离子用量,实现交联度可控,膜材料兼具强韧性和高力学强度;此外,络合物仅在室温条件下即可进行,合成条件简便快捷。
碳纳米管具有优异的导电性、良好的成膜性和一定的柔韧性,与电活性络合物膜复合后得到的致动器件的柔性不会受到影响,且电极导电性得到有效提升;特别是酸化碳纳米管可有效保障材料间的相容性。
需要说明的是,本申请中固含量是指铸膜液中的液体挥发后剩余的固体与铸膜液总质量的百分比。
形变ε计算公式如下:
其中,l为材料长度,d为材料厚度,δ为形变位移。
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合附图及实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
需要说明的是,下述实施例中的离子化聚甲基乙烯基硅氧烷用Ix-PMVS表示,其中x表示PMVS的离子化程度,以百分比计算,例如当x为10时,则表示离子化程度为10%。
实施例1
本实施例提出一种致动器件,由以下步骤制得:
将单壁碳纳米管置于四氢呋喃中,经过高速分散形成均匀的电极层铸膜液,铸膜液中固含量为10%;
将I100-PMVS,氯氧化锆按质量比1:8溶解于水中,得到络合物铸膜液,铸膜液中固含量为30%;
将络合物铸膜液干燥成络合物膜(即为离子聚合物形成的电解质层)后,将电极层铸膜液依次涂敷在络合物膜两面,干燥后得到致动器件。经过拉伸实验测得致动器件的断裂强度为1.6MPa,经过交流阻抗测得络合物膜的离子电导率为8.7×10-5S/cm。将制备的致动器件置于2V直流电压,经过10s,达到1.5%最大驱动形变,反向施加2V直流电压,经过12s回到初始形变,再经过9s,反向达到1.3%最大驱动形变。
实施例2
本实施例提出一种致动器件,由以下步骤制得:
将酸化单壁碳纳米管置于甲醇中,经过高速分散形成均匀的电极层铸膜液,铸膜液中固含量为20%;
将I50-PMVS,氯化钙按质量比1:11溶解于体积比为1:1的水和甲醇溶液中,得到络合物铸膜液,铸膜液中固含量为50%;
将络合物铸膜液干燥成络合物膜(即为离子聚合物形成的电解质层)后,将电极层铸膜液依次涂敷在络合物膜两面,干燥后得到致动器件。经过拉伸实验测得致动器件断裂强度为2.1MPa,经过交流阻抗测得络合物膜的离子电导率为3.6×10-5S/cm。将制备的制动器件置于2V直流电压,经过15s,达到1.1%最大驱动形变,反向施加2V直流电压,经过17s回到初始形变,再经过12s,反向达到1.2%最大驱动形变。
实施例3
本实施例提出一种致动器件,由以下步骤制得:
将多壁碳纳米管置于水中,经过高速分散形成均匀的电极层铸膜液,铸膜液中固含量为10%;
将I75-PMVS,氯化铜按质量比1:7溶解于水中,得到络合物铸膜液,铸膜液中固含量为50%;
将络合物铸膜液干燥成络合物膜(即为离子聚合物形成的电解质层)后,将电极层铸膜液依次涂敷在络合物膜两面,干燥后得到致动器件。经过拉伸实验测得致动器件的断裂强度为1.4MPa,经过交流阻抗测得络合物铸膜离子电导率为4.2×10-5S/cm。将制备的致动器件置于2V直流电压,经过11s,达到0.9%最大驱动形变,反向施加2V直流电压,经过15s回到初始形变,再经过12s,反向达到1.1%最大驱动形变。
实施例4
本实施例提出一种致动器件,由以下步骤制得:
将单壁碳纳米管置于冰醋酸中,经过高速分散形成均匀的电极层铸膜液,铸膜液中固含量为20%。
将I25-PMVS,氯化铁按质量比1:3溶解于体积比为1:1的冰醋酸与甲醇混合溶液中,得到络合物铸膜液,铸膜液中固含量为30%。
将络合物铸膜液干燥成络合物膜(即为离子聚合物形成的电解质层)后,将电极层铸膜液依次涂敷在络合物膜两面,干燥后得到致动器件。经过拉伸实验测得材料断裂强度为0.4MPa,经过交流阻抗测得络合物膜的离子电导率为2.7×10-7S/cm。将制备的致动器件置于5V直流电压,经过20s,达到1.4%最大驱动形变,反向施加5V直流电压,经过17s回到初始形变,再经过17s,反向达到1.3%最大驱动形变。
实施例5
本实施例提出一种致动器件,由以下步骤制得:
将单壁碳纳米管置于四氢呋喃中,经过高速分散形成均匀的电极层铸膜液,铸膜液中固含量为20%;
将I25-PMVS,氯化锌按质量比1:2溶解于水中,得到聚电解质层铸膜液,铸膜液中固含量为30%。
将络合物铸膜液干燥成络合物膜(即为离子聚合物形成的电解质层)后,将电极层铸膜液依次涂敷在络合物膜两面,干燥后得到致动器件。经过拉伸实验测得致动器件的断裂强度为0.5MPa,经过交流阻抗测得络合物膜离子电导率为1.1×10-6S/cm。将制备的制动器件置于5V直流电压,经过15s,达到1.1%最大驱动形变,反向施加5V直流电压,经过17s回到初始形变,再经过17s,反向达到0.8%最大驱动形变。
根据本发明的致动器件,可迅速对外界湿气刺激、电刺激产生有效响应,可广泛应用于电子皮肤、能量收集器、人造肌肉、智能监控等领域。
以上所述本发明的具体实施方式,并不构成对本发明保护范围的限定。任何根据本发明的技术构思所做出的各种其他相应的改变与变形,均应包含在本发明权利要求的保护范围内;另外如选用不同离子化官能团(羧酸类、咪唑类等)、不同的配位金属(K、Mg等)及配合其应用产生的如光热驱动、湿气驱动等都属于本申请的保护范围。
Claims (10)
1.一种用于制备致动器件的离子聚合物,其特征在于,由离子化聚硅氧烷与金属盐溶于第一溶剂中得到铸膜液,之后干燥制得所述离子聚合物;所述离子化聚硅氧烷与所述金属盐的质量比为1:(2-11);所述铸膜液中的固含量为30%-50%。
2.根据权利要求1所述的离子聚合物,其特征在于,所述离子化聚硅氧烷的离子化程度为25%-100%。
3.根据权利要求1所述的离子聚合物,其特征在于,所述金属盐为锆盐、钙盐、铜盐、铁盐和锌盐中的一种或者多种。
4.根据权利要求3所述的离子聚合物,其特征在于,所述锆盐为氯氧化锆,所述钙盐为氯化钙,所述铜盐为氯化铜,所述铁盐为氯化铁,所述锌盐为氯化锌。
5.根据权利要求1所述的离子聚合物,其特征在于,所述第一溶剂为水、甲醇、冰醋酸和四氢呋喃中的一种或者多种。
6.一种致动器件,其特征在于,包括权利要求1-5任一项所述的离子聚合物形成的电解质层、以及涂敷于所述电解质层上下两面的电极层。
7.一种权利要求6所述的致动器件的制备方法,其特征在于,包括以下步骤:将电极材料置于第二溶剂中,经分散形成电极层铸膜液;在权利要求1-5任一项所述的离子聚合物形成的电解质层的上下两面涂覆所述电极层铸膜液,之后干燥形成所述致动器件。
8.根据权利要求7所述的制备方法,其特征在于,所述电极材料为碳纳米管和/或碳纳米管衍生物;所述碳纳米管衍生物优选为酸化碳纳米管。
9.根据权利要求7所述的制备方法,其特征在于,所述第二溶剂为水、甲醇、冰醋酸和四氢呋喃中的一种或者多种。
10.根据权利要求7所述的制备方法,其特征在于,所述电极层铸膜液的固含量为10%-20%。
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