CN117659347A - 一种高疏水导电聚氨酯复合材料及其制备方法和应用 - Google Patents
一种高疏水导电聚氨酯复合材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及有机材料技术领域,具体公开了一种高疏水导电聚氨酯复合材料及其制备方法和应用,高疏水导电聚氨酯复合材料是以导电聚氨酯复合材料为基底,在所述基底上引入羟基化聚二甲基硅氧烷,得到高疏水导电聚氨酯复合材料。本发明通过简单、新颖的方法制备了复合材料,所得复合材料有利于提高在潮湿环境中的使用寿命,有望在机器人皮肤、健康监测等领域有广阔的应用前景。
Description
技术领域
本发明属于有机材料领域,研究了一种高疏水导电聚氨酯复合材料及其制备方法和应用。
背景技术
传统的可穿戴传感器,通常由刚性制成材料,如金属或半导体,是硬的,不灵活的,难以满足穿戴。然而,柔性传感器因其重量轻,尺寸小,身体舒适。已经引起了人们的广泛关注。由于聚氨酯(PU)自身良好的柔性成为了目前柔性材料的最佳选择之一。然而,聚氨酯长时间的使用会导致其损坏,且在许多恶劣情况下,可能导致聚氨酯失效无法发挥它的作用。为了解决这一问题,“自我修复”材料的研究***式增长彻底改变我们使用聚合物的方式。为了赋予聚氨酯自我修复的能力,有许多不同的物理和化学方法。其中动态键的结合可允许聚氨酯的流动和键的重组,从而避免了聚氨酯材料的后续损坏。这一方法成为当前自修复研究的主要焦点。
然而,由于聚氨酯自身的绝缘性无法成为了导电复合材料,因此,掺杂导电材料使聚氨酯成为导电复合材料成为了研究热点,导电填料材料常用的有碳纳米管、石墨烯、金属纳米线等材料。填充在弹性基体中的导电纳米材料相互接触形成使自由电子易于移动并导电的电网络。这些导电材料重量轻,耐腐蚀,可以很容易地适应满足特定应用程序的需求。因此,在某些应用中,它们可以取代金属。
然而,导电聚氨酯复合材料长期处于潮湿环境后会逐渐分解,这是因为导电聚氨酯往往是亲水性的,导致其无法在液体或潮湿环境中工作。为了解决这一难题,制备高疏水导电复合材料成为了研究热点。偶联剂作为高分子复合材料的一种添加剂,在氢键的作用下,无机物与有机物之间发生的化学反应在无机-有机界面中形成“桥梁”,使两者紧密结合。从而改善了无机-有机相的相容性和界面结合。本文利用羟基化聚二甲基硅氧烷填料对导电聚氨酯进行改性,制备了低填料含量的高疏水导电复合材料。这种高疏水多功能导电聚氨酯在可穿戴设备、健康监测、传感器等领域具有潜在的应用前景。
发明内容
本发明提供了一种通过简单新颖的方法即可制备出高疏水可导电的聚氨酯复合材料。
本发明采用的技术方案是:一种高疏水导电聚氨酯复合材料,是以导电聚氨酯复合材料为基底,在所述基底上引入羟基化聚二甲基硅氧烷,得到高疏水复合材料。
上述的一种高疏水导电聚氨酯复合材料,是以羟基化聚二甲基硅氧烷与导电聚氨酯间形成氢键为特征的结构。
上述的一种高疏水导电聚氨酯复合材料的制备方法,包括如下步骤:取聚乙二醇、羟基化聚二甲基硅氧烷、二月桂酸二丁基锡和二苯基甲烷二异氰酸酯,剧烈搅拌后,加入前驱体硼酸酯;继续反应后,加入1,1’-((3-(二甲基氨基)丙基)氮烷二基)二(丙-2-醇),反应后,加入碳纳米管和石墨烯纳米片,反应,反应过程中加入适量的N,N-二甲基乙酰胺,反应结束后,将所得反应物倒入模具中,放入鼓风干燥箱中进行一次干燥,最后放入真空干燥箱中进行二次干燥,得目标产物。
上述的制备方法,所述的剧烈搅拌是在N2气保护下,80℃剧烈搅拌2h。
上述的制备方法,所述的一次干燥是80℃鼓风干燥箱中干燥48h,所述的二次干燥是80℃真空干燥箱中干燥48h。
上述的制备方法,所述前驱体硼酸酯的制备方法,包括如下步骤:将1,4-苯二硼酸和3-硫基-1,2丙二醇溶解于四氢呋喃中,加入无水硫酸镁,室温下搅拌24h后,过滤,于所得滤液中,滴加正己烷,所得浑浊液在55℃下旋蒸,得前驱体硼酸酯。
上述的制备方法,前驱体硼酸酯:1,1’-((3-(二甲基氨基)丙基)氮烷二基)二(丙-2-醇)=1:2。
上述的制备方法,原料固定按摩尔比,硬段:软段=3:1,所述的硬段是二苯基甲烷二异氰酸酯、软段是聚乙二醇和羟基化聚二甲基硅氧烷。
上述的高疏水导电聚氨酯复合材料在机器人可穿戴皮肤中的应用。
本发明的有益效果是:
1、本发明,将导电聚氨酯复合材料作为基底,引入羟基化聚二甲基硅氧烷,得到了高疏水导电聚氨酯复合材料,具有普适性。
2、本发明,所制备的高疏水复合材料在可穿戴皮肤器件中具有高疏水性、导电性和拉伸性。
3、本发明,所制备的高疏水复合材料在可穿戴皮肤器件方面具有很好的应用前景。
4、本发明,制备的高疏水复合材料可自愈、可拉伸、可导电、可回收、可疏水、可形状记忆等。在可穿戴电子器件中的有非常大的利用价值。
5、本发明,以导电聚氨酯复合材料为基体,以羟基化聚二甲基硅氧烷为疏水填料,通过羟基化聚二甲基硅氧烷与导电聚氨酯间的氢键作用,开发了一种高疏水性的复合材料。由于采用简便的混合法,所得复合材料易于制备和应用。
附图说明
图1是实施例1制备的前驱体硼酸酯的核磁共振氢谱图。
图2是实施例1前驱体硼酸酯的红外光谱;
图3是实施例1制备的高疏水导电聚氨酯复合材料PU-PDMS0.2的接触角图。
图4是实施例1制备的高疏水导电聚氨酯复合材料导电图。
具体实施方式
实施例1对照组复合材料(PU-P0)
制备方法如下:
1、前驱体硼酸酯的合成:
将3g 1,4-苯二硼酸和4g 3-硫基-1,2丙二醇溶解于50mL超干四氢呋喃中,加入10g无水硫酸镁,室温下搅拌24h后,过滤,得到淡黄色液体。将淡黄色液体倒入250mL的圆底烧瓶中,并滴加50mL正己烷进行沉淀。将所得浑浊液在55℃下旋蒸,得到白色粉末状固体,即为前驱体硼酸酯。
2、对照组复合材料的制备:
将8.1mmol聚乙二醇10000倒入三颈烧瓶和1g二月桂酸二丁基锡,加入2.7mmol二苯基甲烷二异氰酸酯,N2气保护下,80℃剧烈搅拌2h。然后,加入1.8mmol前驱体硼酸酯,继续反应2h。然后,加入3.6mmol 1,1’-((3-(二甲基氨基)丙基)氮烷二基)二(丙-2-醇),再继续反应2h,加入聚氨酯重量3%的碳纳米管和石墨烯纳米片,(其中碳纳米管和石墨烯纳米片为1:1混合),继续反应2h,反应过程中适当加入除水的N,N-二甲基乙酰胺,待反应结束后,将所得反应物倒入模具中,放入80℃鼓风干燥箱中48h,烘去大部分溶剂,最后放入80℃真空干燥箱中干燥48h,得到厚度约为1mm的膜,即为对照组复合材料,命名为PU-P0。
实施例2高疏水复合材料(PU-P0.2)
制备方法如下:
1、前驱体硼酸酯的合成:同实施例1
2、高疏水复合材料的制备:
将2.16mmol聚乙二醇10000、1g二月桂酸二丁基锡和0.54mmol的聚二甲基硅氧烷1000倒入三颈烧瓶,加入8.1mmol二苯基甲烷二异氰酸酯,N2气保护下,80℃剧烈搅拌2h。然后,加入1.8mmol前驱体硼酸酯,继续反应2h。然后,加入3.6mmol的1,1’-((3-(二甲基氨基)丙基)氮烷二基)二(丙-2-醇),再继续反应2h,加入聚氨酯重量3%的碳纳米管和石墨烯纳米片,(其中碳纳米管和石墨烯纳米片质量比为1:1混合),继续反应2h,反应过程适当加入除水的N,N-二甲基乙酰胺,待反应结束后,将所得反应物倒入模具中,放入80℃鼓风干燥箱中48h,烘去大部分溶剂,最后放入80℃真空干燥箱中干燥48h,得到厚度约为1mm的膜,即为高疏水复合材料,命名为PU-P0.2。
实施例3高疏水复合材料(PU-P0.4)
1、前驱体硼酸酯的合成:同实施例1
2、高疏水复合材料的制备:
将1.62mmol聚乙二醇10000、1g二月桂酸二丁基锡和1.08mmol的聚二甲基硅氧烷1000倒入三颈烧瓶,加入8.1mmol二苯基甲烷二异氰酸酯,N2气保护下,80℃剧烈搅拌2h。然后,加入1.8mmol前驱体硼酸酯,继续反应2h。然后,加入3.6mmol 1,1’-((3-(二甲基氨基)丙基)氮烷二基)二(丙-2-醇),再继续反应2h,加入聚氨酯重量3%的碳纳米管和石墨烯纳米片,(其中碳纳米管和石墨烯纳米片质量比为1:1混合),继续反应2h,反应过程中适当加入除水的N,N-二甲基乙酰胺,待反应结束后,将所得反应物倒入模具中,放入80℃鼓风干燥箱中48h,烘去大部分溶剂,最后放入80℃真空干燥箱中干燥48h,得到厚度约为1mm的膜,即为高疏水复合材料,命名为PU-P0.4。
实施例4高疏水导电聚氨酯复合材料(PU-P0.6)
1、前驱体硼酸酯的合成:同实施例1
2、高疏水复合材料的制备:
将1.08mmol聚乙二醇10000、1g二月桂酸二丁基锡和1.62mmol的聚二甲基硅氧烷1000倒入三颈烧瓶,加入8.1mmol二苯基甲烷二异氰酸酯,N2气保护下,80℃剧烈搅拌2h。然后,加入1.8mmol前驱体硼酸酯,继续反应2h。然后,加入3.6mmol 1,1’-((3-(二甲基氨基)丙基)氮烷二基)二(丙-2-醇),再继续反应2h,加入聚氨酯重量3%的碳纳米管和石墨烯纳米片,(其中碳纳米管和石墨烯纳米片质量比为1:1混合),继续反应2h,反应过程中适当加入除水的N,N-二甲基乙酰胺,待反应结束后,将所得反应物倒入聚模具中,放入80℃鼓风干燥箱中48h,烘去大部分溶剂,最后放入80℃真空干燥箱中干燥48h,得到厚度约为1mm的膜,即为高疏水复合材料,命名为PU-P0.6。
实施例5高疏水导电聚氨酯复合材料(PU-P0.8)
1、前驱体硼酸酯的合成:同实施例1
2、高疏水复合材料的制备:
将0.54mmol聚乙二醇10000、1g二月桂酸二丁基锡和2.16mmol的聚二甲基硅氧烷1000倒入三颈烧瓶,加入8.1mmol二苯基甲烷二异氰酸酯,N2气保护下,80℃剧烈搅拌2h。然后,加入1.8mmol前驱体硼酸酯,继续反应2h。然后,加入3.6mmol 1,1’-((3-(二甲基氨基)丙基)氮烷二基)二(丙-2-醇),再继续反应2h,加入聚氨酯重量3%的碳纳米管和石墨烯纳米片,(其中碳纳米管和石墨烯纳米片为1:1混合),继续反应2h,反应过程中适当加入除水的N,N-二甲基乙酰胺,待反应结束后,将所得反应物倒入模具中,放入80℃鼓风干燥箱中48h,烘去大部分溶剂,最后放入80℃真空干燥箱中干燥48h,得到厚度约为1mm的膜,即为高疏水复合材料,命名为PU-P0.8。
实施例6高疏水导电聚氨酯复合材料(PU-P1)
制备方法如下:
1、前驱体硼酸酯的合成:同实施例1
2、高疏水复合材料的制备:
将2.7mmol的聚二甲基硅氧烷1000倒入三颈烧瓶和1g二月桂酸二丁基锡,加入8.1mmol二苯基甲烷二异氰酸酯,N2气保护下,80℃剧烈搅拌2h。然后,加入1.8mmol前驱体硼酸酯,继续反应2h。然后,加入3.6mmol 1,1’-((3-(二甲基氨基)丙基)氮烷二基)二(丙-2-醇),再继续反应2h,加入聚氨酯重量3%的碳纳米管和石墨烯纳米片,(其中碳纳米管和石墨烯纳米片为1:1混合),继续反应2h,反应过程中适当加入除水的N,N-二甲基乙酰胺,待反应结束后,将所得反应物倒入模具中,放入80℃鼓风干燥箱中48h,烘去大部分溶剂,最后放入80℃真空干燥箱中干燥48h,得到厚度约为1mm的膜,即为高疏水复合材料,命名为PU-P1。
图1-2是前驱体硼酸酯的核磁共振氢谱和红外光谱图。图2中2656cm-1处为-SH的特征吸收峰,1364cm-1为B-C键伸缩振动特征峰,1099cm-1为B-O键伸缩振动特征峰,654cm-1为硼螺环特征吸收峰。红外及核磁证明成功合成了含有硼酸酯结构的前驱体。
图3是高疏水导电聚氨酯复合材料PU-P0.2的接触角图。当羟基化聚二甲基硅氧烷的填充量仅为软段的20%时,其接触角就可高达132.6°。可见所制备的聚氨酯具有优异的疏水性。
图4是高疏水导电聚氨酯复合材料导电实验。以实施例2制备的高疏水导电聚氨酯复合材料构筑对应电路。如图4所示,将含有高疏水导电复合材料的PU-P0.2样品与电路图形成闭合电路,小灯泡亮起;当将复合膜剪断后,小灯泡熄灭,将剪断后的复合膜置于80℃下2h,当复合膜自修复后,再次连接到闭合电路中,小灯泡再次亮起,以上结果说明制备的高疏水导电复合材料具有良好的导电性和自愈性。其在可穿戴设备与传感器等领域具备开发的潜力。
经过以上检测,说明本发明高疏水复合材料在可穿戴领域有较为理想的应用前景。
Claims (9)
1.一种高疏水导电聚氨酯复合材料,其特征在于,是以导电聚氨酯复合材料为基底,在所述基底上引入羟基化聚二甲基硅氧烷,得到高疏水复合材料。
2.根据权利要求1所述的一种高疏水导电聚氨酯复合材料,其特征在于,是以羟基化聚二甲基硅氧烷与导电聚氨酯间形成氢键为特征的结构。
3.权利要求1所述的一种高疏水导电聚氨酯复合材料的制备方法,其特征在于,包括如下步骤:取聚乙二醇、羟基化聚二甲基硅氧烷、二月桂酸二丁基锡和二苯基甲烷二异氰酸酯,剧烈搅拌后,加入前驱体硼酸酯;继续反应后,加入1,1,-((3-(二甲基氨基)丙基)氮烷二基)二(丙-2-醇),反应后,加入碳纳米管和石墨烯纳米片,反应,反应过程中加入适量的N,N-二甲基乙酰胺,反应结束后,将所得反应物倒入模具中,放入鼓风干燥箱中进行一次干燥,最后放入真空干燥箱中进行二次干燥,得目标产物。
4.根据权利要求3所述的制备方法,其特征在于,所述的剧烈搅拌是在N2气保护下,80℃剧烈搅拌2h。
5.根据权利要求3所述的制备方法,其特征在于,所述的一次干燥是80℃鼓风干燥箱中干燥48h,所述的二次干燥是80℃真空干燥箱中干燥48h。
6.根据权利要求3所述的制备方法,其特征在于,所述前驱体硼酸酯的制备方法,包括如下步骤:将1,4-苯二硼酸和3-硫基-1,2丙二醇溶解于四氢呋喃中,加入无水硫酸镁,室温下搅拌24h后,过滤,于所得滤液中,滴加正己烷,所得浑浊液在55℃下旋蒸,得前驱体硼酸酯。
7.根据权利要求3所述的制备方法,其特征在于,前驱体硼酸酯:1,1,-((3-(二甲基氨基)丙基)氮烷二基)二(丙-2-醇)=1:2。
8.根据权利要求3所述的制备方法,其特征在于,原料固定按摩尔比,硬段:软段=3:1,所述的硬段是二苯基甲烷二异氰酸酯、软段是聚乙二醇和羟基化聚二甲基硅氧烷。
9.权利要求1所述的高疏水导电聚氨酯复合材料在机器人可穿戴皮肤中的应用。
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