CN111019356B - 压力敏感型多孔导电橡胶及其制备方法 - Google Patents

压力敏感型多孔导电橡胶及其制备方法 Download PDF

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CN111019356B
CN111019356B CN201911328130.7A CN201911328130A CN111019356B CN 111019356 B CN111019356 B CN 111019356B CN 201911328130 A CN201911328130 A CN 201911328130A CN 111019356 B CN111019356 B CN 111019356B
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赵妍
李秉洋
王鹏飞
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Foshan National Defense Science And Technology Industrial Technology Achievement Industrialization Application And Promotion Center
China Academy of Space Technology CAST
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Abstract

本发明公开了一种压力敏感型多孔导电橡胶的制备方法，包括如下步骤：在真空搅拌机内加入半成品胶A组分100重量份，然后分批加入抑制剂0.001～0.0015重量份、硫化剂B组分10重量份、交联剂3～8重量份、纳米填料、白炭黑25～40重量份、结构控制剂2.5～5重量份、导电填料100～180重量份，在真空环境下搅拌2h以上，使得各个组分均匀混合；然后将催化剂0.007～0.01重量份、增塑剂8～12重量份分批加入胶料内，在真空搅拌机内混合30min以上；然后进行预硫化、超临界发泡、硫化。本发明解决了现有技术中压力敏感导电橡胶材料泡孔尺寸和分布不均，导热性、稳定性、力学性能、恢复性均有待提高等问题。

Description

压力敏感型多孔导电橡胶及其制备方法
技术领域
本发明涉及高分子材料技术领域，特别涉及一种压力敏感型多孔导电橡胶及其制备方法。
背景技术
导电橡胶是一种固化或干燥后具有一定导电性能的胶黏剂,它通常以基体树脂和导电填料即导电粒子为主要组成成分,通过基体树脂的粘接作用把导电粒子结合在一起,形成导电通路,实现被粘材料的导电连接。导电橡胶属于复合型导电高分子材料的一种，高分子材料本身不具有导电性，但在加工成型时通过加入导电填料，如炭黑、金属粉末箔等，利用分散复合、层基复合、表面复合等方法，使制品具有导电性。
导电橡胶不仅具有橡胶的高弹性、易加工成型、重量轻、体积小等特点，还有与金属相似的导电性能，以及高分子材料的许多优异特性。随着电子工业材料的迅猛发展，导电高分子材料应用日益广泛，是抗静电产品和抗电磁屏蔽装置的良好功能复合材料。除此之外，目前利用导电橡胶的力敏或温敏效应开发出了各种电子键用材料、触感元件、温敏和力敏传感器材料。使导电橡胶的应用范围不断扩大。
压力敏感导电橡胶是一种特殊的导电橡胶，同样是在绝缘的高分子材料中加入导电材料形成的。这种复合材料不仅具有与人的皮肤类似的柔软粘弹性，而且材料的导电性是随着外力的变化而变化的，具有一定的压力敏感特性，也就是说这种压力敏感导电橡胶的电阻值与外力之间存在一定的函数关系。可根据电阻阻值的变化来检测外加的触觉力信息。这样就可满足具有类似于人体皮肤那样弹性的触觉敏感功能材料的需求。已有日本东京电气通信大学Sh imojo,M等人利用缝合了导线的压力敏感导电橡胶制备新型的一维触觉传感器；日本的科学家Yoj i Yamada等在硅橡胶内埋入柔性光纤研究多维触觉传感器及其结构，利用硅橡胶变形产生的压力作用于传感器单元上，达到测量多维力的目的；合肥智能机械研究所提出一种基于导电橡胶的三维力触觉传感器，利用导电橡胶做覆层材料，内部布有触觉传感阵列。目前所研究的多维触觉传感器仍存在着诸多的问题，如造价昂贵、信号处理复杂、柔性差、不适合大面积测量、制作工艺要求高等诸多问题，研究者仍在积极寻找新材料，新原理，设计传感器，力图设计出高性能，高柔性，高可靠性的传感器，使触觉传感器尽快走入实用阶段
压力敏感导电橡胶作为一种新型的高分子导电复合材料，以其优良的特性和潜在的应用价值正受到广泛的关注和研究，已有中国专利申请号为201610351838.4、发明名称为“具有压敏特性的多孔导电高分子材料的制备方法及其应用”，具体公开了一种具有压敏特性的多孔导电高分子复合材料的制备方法，包括如下步骤：a)制备悬浮液；b)单向冷冻c)低温低压干燥。本发明制备的具有压敏特性的多孔导电高分子复合材料具有优异的稳定性和回复性，可用于制备轻质高分子基应变传感器。但现有技术中制备的压力敏感导电橡胶材料仍然存在泡孔尺寸不均、分布不均；工艺复杂的问题；以及导热性、稳定性、力学性能、恢复性等均有待进一步提高；并且高填料率得到了高导电率但却具有低阻尼性的问题有待解决。
发明内容
本发明的目的在于提供一种压力敏感型多孔导电橡胶及其制备方法，解决现有技术中压力敏感导电橡胶材料泡孔尺寸和分布不均，导热性、稳定性、力学性能、恢复性均有待提高，以及现有制备工艺复杂等问题。
本发明的技术方案如下：一种压力敏感型多孔导电橡胶的制备方法，包括如下步骤：
(1)在真空搅拌机内加入半成品胶A组分100重量份，然后分批加入抑制剂0.001～0.0015重量份、硫化剂B组分10重量份、交联剂3～8重量份、纳米填料、白炭黑25～40重量份、结构控制剂2.5～5重量份、导电填料100～180重量份，在真空环境下搅拌2h以上，使得各个组分均匀混合；然后将催化剂0.007～0.01重量份、增塑剂8～12重量份分批加入胶料内，在真空搅拌机内混合30min以上；
(2)将步骤(1)混合均匀后的胶料进行预硫化；
(3)将步骤(2)的样品放入高压反应釜中进行超临界发泡；
(4)将步骤(3)获得的样品进行硫化，去除小分子。
优选的，所述步骤(2)中的预硫化为：将胶料放入垫有PET膜的模具内，放入平板硫化机中，控制温度为110～130℃、压力为10～20MPa，持续10～15min。
优选的，所述步骤(3)超临界发泡为：升温至所需温度160℃，待温度稳定后，充入低压CO2将容器中的空气置换干净，随后增压至预设压力值，饱和溶胀0.5～2h后瞬间泄压，取出样品，在室温条件下静置20min。
优选的，所述步骤(4)中的硫化为：将步骤(3)的发泡样品放入平板硫化机中，将温度控制在165～170℃、压力为10～20MPa，持续5～15min。
优选的，所述半成品胶A组分为乙烯基聚二甲基硅氧烷；所述硫化剂B组分为甲基含氢硅氧烷。
优选的，所述抑制剂为炔醇、所述交联剂为甲基硅烷、所述白炭黑为气相白炭黑、所述结构控制剂为羟基硅油、所述导电填料为碳纳米管或银包玻璃纤维或银包铜颗粒、所述催化剂为铂金催化剂、增塑剂为1，2-丙二醇。
本发明的另一个技术方案如下：一种压力敏感型多孔导电橡胶，由上述制备方法制得。
本发明还提供一个技术方案：压力敏感型多孔导电橡胶的应用，用于制备柔性压力传感器、压敏元件及压力测试用设备。
本发明提供的压力敏感型多孔导电橡胶的制备方法，将各组分材料分批加入到真空搅拌机内混合，特定条件处理后混合均匀，经预硫化和硫化后得到压力敏感型多孔导电橡胶材料。本发明方法工艺流程简单、易操作，原料成本低、易获得，本方法制得的压力敏感型多孔导电橡胶材料具有可压缩性以及良好的回弹性；材料孔径分布以及孔尺寸具有可调性；质量轻；压力传感灵敏度高，响应时间短，可达10ms。
附图说明
图1为本发明实施例1和2的SEM图；
图2为本发明实施例1和2的压缩性能测试图；
图3为本发明实施例1的负压阻性测试图；
图4为本发明。
具体实施方式
下面结合实施例对本发明进一步详细说明，但本发明的保护范围不仅限于这些实施例。以下实施例中对所有原料的来源并没有特殊的限制，所用的原料均为市售。
本发明提供一种压力敏感型多孔导电橡胶的制备方法，包括如下步骤：
(1)在真空搅拌机内加入半成品胶A组分100重量份，然后分批加入抑制剂0.001～0.0015重量份、硫化剂B组分10重量份、交联剂3～8重量份、纳米填料、白炭黑25～40重量份、结构控制剂2.5～5重量份、导电填料100～180重量份，在真空环境下搅拌2h以上，使得各个组分均匀混合；然后将催化剂0.007～0.01重量份、增塑剂8～12重量份分批加入胶料内，在真空搅拌机内混合30min以上，提高胶料的可塑性；
(2)将步骤(1)混合均匀后的胶料进行预硫化：将胶料放入垫有PET膜的模具内，放入平板硫化机中，控制温度为110～130℃、压力为10～20MPa，持续10～15min；
(3)将步骤(2)的样品放入高压反应釜中进行超临界发泡：升温至所需温度160℃，待温度稳定后，充入低压CO2将容器中的空气置换干净，随后增压至预设压力值，饱和溶胀0.5～2h后瞬间泄压，取出样品，在室温条件下静置20min，使得胶料形成均匀致密的孔洞，并促进结构控制剂与导电填料之间发生更有效的作用，保证导电性能的稳定性；
(4)将步骤(3)获得的样品进行硫化：将步骤(3)的发泡样品放入平板硫化机中，将温度控制在165～170℃、压力为10～20MPa，持续5～15min，除去橡胶内的其他未反应完的小分子物质，以保证导电橡胶的力学稳定性以及使用寿命。
实施例1
本实施例提供一种压力敏感型多孔导电橡胶的制备方法，包括如下步骤：
(1)基胶与填料混合：
按下表1的组分和用量，在真空搅拌机内加入半成品胶A组分，然后分批加入抑制剂、硫化机B组分、交联剂、纳米填料、白炭黑和结构控制剂、导电填料，在真空环境下搅拌2h以上，使得各个组分均匀混合；将催化剂、增塑剂分批加入胶料内，在真空搅拌机内混合30min以上，提高胶料的可塑性。
表1：本实施例1的组分列表
Figure BDA0002328903780000051
Figure BDA0002328903780000061
(2)预硫化：
将混合均匀的胶料放入垫有PET膜的模具内，放入平板硫化机，控制温度、压力及时间(120℃，10MPa，15min)进行预硫化。
(3)超临界发泡：
将样品放入高压反应釜中，升温至所需温度(160℃)，待温度稳定后，充入低压CO2将容器中的空气置换干净。随后增压至预设压力值，饱和溶胀0.5～2h后瞬间泄压。取出样品，在室温条件下静置20min。
(4)硫化：
将发泡样品在平板硫化机中(170℃，20MPa)，硫化8min。
实施例2
本实施例提供一种压力敏感型多孔导电橡胶的制备方法，包括如下步骤：
(1)基胶与填料混合：
按下表2的组分及用量，在真空搅拌机内加入半成品胶A组分，然后分批加入抑制剂、硫化机B组分、交联剂、纳米填料、白炭黑和结构控制剂、导电填料，在真空环境下搅拌2h以上，使得各个组分均匀混合。将催化剂、增塑剂分批加入胶料内，在真空搅拌机内混合30min以上，提高胶料的可塑性。
表2：本实施例2的组分列表
Figure BDA0002328903780000071
(2)预硫化：
将混合均匀的胶料放入垫有PET膜的模具内，放入平板硫化机，控制温度、压力及时间(120℃，10MPa，10min)进行预硫化。
(3)超临界发泡：
将样品放入高压反应釜中，升温至所需温度(160℃)，待温度稳定后，充入低压CO2将容器中的空气置换干净。随后增压至预设压力值，饱和溶胀0.5～2h后瞬间泄压。取出样品，在室温条件下静置20min。
(4)硫化：
将发泡样品在平板硫化机中(170℃，20MPa)，硫化8min。
对本发明实施例1和实施例2制得的样品进行下述测试：
(1)微观形貌：
硅橡胶泡沫样品首先在液氮中冷冻淬断，并将断面喷金，采用日本日立公司SU8010型高分辨场发射扫描电镜对多孔硅橡胶材料进行表征。参见图1，示出了实施例1及实施例2的SEM图，图中可见实施例1样品的泡孔尺寸较实施例2样品的泡孔尺寸小。实施例1中控制预硫化时间较实施例2长，使得实施例1样品基胶强度增大，泡孔成核和泡孔生长都受到限制；实施例2预硫化时间较短，其基胶强度相对实施例1的样品较弱，难以固定泡孔结构，泡孔容易合并或塌陷。从而通过控制预硫化时间来调节材料孔径分布以及孔尺寸。
(2)力学性能：
测试设备为电子万用试验机(美特斯/CMT6103)，力学性能中的拉伸强度和断裂伸长率的根据GB/T528-2009将导电橡胶制成哑铃状，试样狭窄平行部位长约35mm，宽6mm，试样总长115mm，厚度为2mm。测试多孔硅橡胶材料的压缩变形，样品为圆柱形，高约为12mm，直径28mm。测试结果如图2和下表3所示：
表3：实施例1和实施例2的拉伸性能和断裂伸长率
样品 拉伸性能 断裂伸长率
实施例1 3.6 370％
实施例2 2.5 210％
由表1和图2可知，本发明实施例1和实施例2的样品拉伸性能、断裂伸长率均明显高于现有技术的产品，其中实施例1的拉伸性能、断裂伸长率以及压缩性能还要高于实施例2，这也是通过预硫化时间控制的长短不同而使得实施例1的基体强度提高，进而拉伸强度和断裂伸长率逐渐增加，可见本发明中预硫化过程是影响泡沫拉伸性能的重要因素，通过调整预硫化条件来调节聚合物基体强度及多孔泡沫的拉伸强度。在相同应力作用下，实施例2的孔径、变形量大于实施例1，实施例1的压缩能力高于实施例2.
(3)负压阻性与压敏性：
将直径28mm长度12mm的圆柱形样品，两端用银胶粘合铜片放置于电子万用试验机(美特斯/CMT6103)试样台上，将数字万用表(DMM4050)与铜片连接测试电阻。压头加载压力，压缩到一定应变后再解除压力，如此循环，记录时间-电阻曲线。
图3示出了对实施例1样品测试负压阻性的结果，对实施例1样品施加压力，其体积电阻率大幅下降，随着施加压力的增大，其导电率明显提高。可见，本发明的多孔导电橡胶，在一定压力下，其孔结构被压缩，导电颗粒间距离迅速减小，形成了三维的导电通路，其导电性能提高，明显优于现有技术材料。
图4示出了对实施例1样品测试压敏性能的结果，可知，本发明多孔导电橡胶具有良好的稳定性以及回复性，在经过40次循环之后为初始值的98.4％，说明材料精确度高，且使用寿命长。
通过上述实施例可知，本发明方法制得的压力敏感型多孔导电橡胶，具有可压缩性以及良好的回弹性；材料孔径分布以及孔尺寸具有可调性；质量轻；压力传感灵敏度高，响应时间短，可达10ms。可应用于制备柔性压力传感器、压敏元件，以及应用于压力测试场所。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (4)

1.一种压力敏感型多孔导电橡胶的制备方法，其特征在于，包括如下步骤：
(1)在真空搅拌机内加入半成品胶A组分100重量份，然后分批加入抑制剂0.001～0.0015重量份、硫化剂B组分10重量份、交联剂3～8重量份、纳米填料、白炭黑25～40重量份、结构控制剂2.5～5重量份、导电填料100～180重量份，在真空环境下搅拌2h以上，使得各个组分均匀混合；然后将催化剂0.007～0.01重量份、增塑剂8～12重量份分批加入胶料内，在真空搅拌机内混合30min以上；
(2)将步骤(1)混合均匀后的胶料进行预硫化；
(3)将步骤(2)的样品放入高压反应釜中进行超临界发泡；
(4)将步骤(3)获得的样品进行硫化，去除小分子，其中
所述步骤(2)中的预硫化为：将胶料放入垫有PET膜的模具内，放入平板硫化机中，控制温度为110～130℃、压力为10～20MPa，持续15min，并且
其 中，所述步骤(3)超临界发泡为：升温至所需温度160℃，待温度稳定后，充入低压CO2将容器中的空气置换干净，随后增压至预设压力值，饱和溶胀0.5～2h后瞬间泄压，取出样品，在室温条件下静置20min，
所述步骤(4)中的硫化为：将步骤(3)的发泡样品放入平板硫化机中，将温度控制在165～170℃、压力为10～20MPa，持续5～15min，并且
所述半成品胶A组分为乙烯基聚二甲基硅氧烷；所述硫化剂B组分为甲基含氢硅氧烷。
2.根据权利要求1所述的制备方法，其特征在于，所述抑制剂为炔醇、所述交联剂为甲基硅烷、所述白炭黑为气相白炭黑、所述结构控制剂为羟基硅油、所述导电填料为碳纳米管或银包玻璃纤维或银包铜颗粒、所述催化剂为铂金催化剂、增塑剂为1，2-丙二醇。
3.一种压力敏感型多孔导电橡胶，其特征在于，根据权利要求1或2所述的制备方法制得。
4.权利要求3所述的压力敏感型多孔导电橡胶的应用，其特征在于，用于制备柔性压力传感器、压敏元件及压力测试用设备。
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