CN104371279B - 含石墨烯的复合材料及其制备方法和应用 - Google Patents

含石墨烯的复合材料及其制备方法和应用 Download PDF

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CN104371279B
CN104371279B CN201410640645.1A CN201410640645A CN104371279B CN 104371279 B CN104371279 B CN 104371279B CN 201410640645 A CN201410640645 A CN 201410640645A CN 104371279 B CN104371279 B CN 104371279B
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graphene
composite
functional material
poly
conductive channels
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CN104371279A (zh
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周超
陈思浩
楼建中
陈志昌
徐刚
杨春宇
朱同贺
王继虎
邢晨晨
包鸣
包一鸣
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Shanghai University of Engineering Science
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Priority to US15/526,427 priority patent/US10351677B2/en
Priority to PCT/CN2014/001167 priority patent/WO2016090523A1/zh
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Abstract

本发明公开了一种含石墨烯的复合材料及其制备方法和应用，所述含石墨烯的复合材料，其组分包括具有双导电通道的复合功能材料和聚合物基体。具有双导电通道的复合功能材料，为磺化石墨烯表面接枝导电聚合物聚3,4‑(乙撑二氧噻吩)，其结构通式如式1所示。具有双导电通道的复合功能材料和含石墨烯的复合材料，可以用于制备压阻响应材料或者是抗静电、电磁屏蔽材料等，具有优异压阻响应和压阻重复性以及电磁屏蔽效应；本发明操作简单易行，可以大规模生产，其压阻性能优异，具有非常灵敏的压阻响应，渗阈值仅为0.5Wt％；不仅可以维持聚合物原有的性能，更能够形成一种不稳定的导电网络体系，有利于提高压阻响应的灵敏性。

Description

含石墨烯的复合材料及其制备方法和应用
技术领域
本发明涉及一种含石墨烯的复合材料及其制备方法和应用。
背景技术
石墨烯(Graphene)是由单层碳原子构成的具有六边形蜂窝状结构的二维晶体。理想的石墨烯结构是平面六边形点阵，可以看作是一层被剥离的石墨分子，每个碳原子均为sp2杂化，并贡献剩余一个p轨道上的电子形成大π键，π电子可以自由移动，赋予石墨烯良好的导电性。二维石墨烯结构可以看是形成所有sp2杂化碳质材料的基本组成单元。石墨烯中碳-碳键长约为0.143nm，每个晶格内有三个σ键，链接十分牢固，形成了稳定的六边形状。单层石墨烯厚度仅为0.35nm，约为头发丝直径的二十万分之一。
到目前为止，石墨烯被发现具有许多新奇而独特的物理现象，例如无质量的狄拉克费米子、量子霍尔效应、室温磁效应以及在室温下自旋依赖的输运。更重要的是，独特结构的石墨烯具有多重的优异性能，较小的质量密度(2.2g/cm3)，极大的比表面积(～2630m2/g)，极高的本征迁移率(＞104cm2/Vs超过商用硅片10倍)而电阻率只约10-6Ω.cm，为目前世界上电阻率最小的材料、突出的导热性能(3000W/m-1K-1,是金刚石的3倍)和力学性能(杨氏模量高达1.0TPa，是钢的100多倍),石墨烯中电子的运动速度超过了在其他金属单体或是半导体中的运动速度，能够达到光速的1/300。石墨是矿物质中最软的，其莫氏硬度只有1～2级，但被分离成一个碳原子厚度的石墨烯后，性能则发生突变，其硬度比莫氏硬度10级的金刚石还高，高达130GPa的强度，却又拥有很好的韧性，可任意弯曲。并且几近透明，在很宽的波段内光吸收只有2.3％。因其室温导电速度最快、力学强度最大、导热能力最强等性能，石墨烯在纳米电子器件、光电子器件、传感器、超级电容器、能量存储、燃料电池集成电路、晶体管、场效应管等方面具有重要潜在应用。
可通过溶融共混、溶液共混、也可通过溶液插层等方法将有机分子引入石墨的片层之间，然后原位生长制备石墨烯/高分子材料复合材料。由于石墨烯具有高强度、高导电性、高透光性、高硬度、高阻隔性、室温量子霍尔效应等一系列优异的性能，而且其原料(石墨、烃类等)充足，价格低廉。因此具有很广泛的用途。将石墨烯作为添加相应用于高分子材料之中制备复合材料是目前制备高性能、多功能、智能化复合材料研究的重点。而高分子材料中直接添加石墨烯，其性能往往达不到实际生产期望的要求，所以需对其进行进一步的功能化改性和结构设计才能达到功能化和智能化的目标。
多功能、智能化聚合物复合材料中，压力-电阻响应复合材料的制备技术中，多用炭黑、碳纳米管、和普通的石墨烯作为填料。但存在一系列的问题，如：以炭黑为填料的压阻复合材料低敏感度、高填充量、重复性不佳；以碳纳米管为填料的压阻复合材料虽然具有较高的压阻敏感度以及较低的填充量，但是这种优异的压阻特性很难在循环测试中得到理想的重复。也有用石墨烯作为填料，并且用烷基化来改善导电填料和聚合物基体间的结合从而达到压阻响应的目的。这只是简单地解决了界面的结合问题，但是没有从根本和源头解决界面的结合和压阻响应的问题。因此，我们我们先将石墨烯表面进行磺化接枝，然后再采用原位聚合的方法通过氢键结合上聚3,4-(乙撑二氧噻吩)，从而制备得到一种石墨烯-导电聚合物的复合材料。此种材料可单独作为压阻材料，也可和聚合物复合形成压阻材料。
目前，研究石墨烯高分子多功能、智能化复合材料主要有以下几种：申请日为：2012.05.10，申请号为：201210144498.X，公开号为：CN 102173145 A，公开日期为：2012.09.19，专利名称为：“一种表面改性石墨烯聚合物基压阻复合材料及其制备方法”，以烷基化石墨烯作为填料，和硅橡胶复合制备一种压阻响应材料。
申请日为：2011.12.15，申请号为：201110419526.X，授权公告号为：CN102558772B，授权日期为：2013.03.06，专利名称为：“一种聚3,4-(乙撑二氧噻吩)/磺化石墨烯复合水凝胶及其制备方法”，以聚3,4-(乙撑二氧噻吩)、聚苯乙烯磺酸钠、磺化石墨烯作为单组份，然后混合形成复合水凝胶，用以改善电性能和力学强度。
申请日为：2014.02.18，申请号为：201410055227.6，申请公布号为：CN103824615A，申请公布日期为：2014.05.28，专利名称为：“气相聚合聚3,4-乙撑二氧噻吩和石墨烯叠层柔性透明电极的方法”，以聚3,4-(乙撑二氧噻吩)薄膜和石墨烯薄膜通过叠层的方式制备复合薄膜，用以提高导电率和柔软性。
以上的研究仍然没有能给同时解决界面结合性的问题和提升导电率、机械强度、柔性等问题。
发明内容
本发明的目的在于提供一种含石墨烯的复合材料及其制备方法和应用，以克服现有技术存在的缺陷。
本发明首先涉及一种具有双导电通道的复合功能材料，为磺化石墨烯表面接枝导电聚合物聚3,4-(乙撑二氧噻吩)，其结构通式如式1所示：
其中：为聚合度，n＝100～8000的整数。
磺化石墨烯和聚3,4-(乙撑二氧噻吩)的质量比为1:1～1:100，优选的，磺化石墨烯和聚3,4-(乙撑二氧噻吩)的质量比为1:3～1:10；
所述磺化石墨烯是石墨烯经过4-苯胺磺酸及其衍生物接枝而得到的，接枝率为1％～80％；
所述磺化石墨烯的制备方法，可参见Guixia Zhao.et al.Sulfonated Graphenefor PersistentAromatic Pollutant Management.Adv.Mater.2011,23,3959-3963.文献报道的方法，推荐的方法，包括如下步骤：
(1)将羧基化石墨烯分散在水中，得到1～10mg/ml的羧基化石墨烯溶液A；
(2)将4-苯胺磺酸溶解在水中，得到10～20mg/ml的溶液B；
(3)将溶液A与溶液B按体积比为2:3～2:5的比例混合，滴加1-3滴二月桂酸二丁基锡作为催化剂，并在90～95℃加热回流反应8～10小时，降低体系温度至85～90℃，接着向反应体系中加入水合肼，恒温反应2～3小时，得到磺化石墨烯；
所述水合肼的加入量为1ml/1g～2ml/1g羧基化石墨烯；
催化剂的重量用量为溶液A与溶液B总体积的0.1～0.3％；
式1所示的化合物，可单独成型，作为具有双导电通道的复合功能材料；
本发明还涉及一种含石墨烯的复合材料，其组分包括所述具有双导电通道的复合功能材料与聚合物基体；
优选的，所述含石墨烯的复合材料中，所述具有双导电通道的复合功能材料与所述聚合物基体的重量比为0.1:100～20:100，优选的，聚合物基体的重量比为1:100～10:100；
所述聚合物基体选自聚烯烃类聚合物、聚酯类聚合物、橡胶类聚合物或聚甲醛、聚砜、聚乳酸；
所述聚烯烃类聚合物优选聚乙烯、聚丙烯、聚苯乙烯或聚偏二氯乙烯等；
所述聚酯类聚合物优选聚对苯二甲酸乙二醇酯或聚碳酸酯等聚酯类聚合物
所述橡胶类聚合物优选硅橡胶；
所述的具有双导电通道的复合功能材料的制备方法，包括如下步骤：
(1)将所述的磺化石墨烯溶解在水中，得到浓度为1～20mg/ml的磺化石墨烯溶液；
(2)然后加入3,4-(乙撑二氧噻吩)；
3,4-(乙撑二氧噻吩与磺化石墨烯的质量比为1:1～100:1，优选的为3:1～10:1；
再加入重量浓度为5～30％的过硫酸钠(Na2S2O8)溶液，过硫酸钠的重量用量为磺化石墨烯的10～60％；然后在室温下反应4-8小时，然后从反应产物中收集聚3,4-(乙撑二氧噻吩)-石墨烯复合浆料浓缩，得到聚3,4-(乙撑二氧噻吩)-石墨烯复合浆料，即为具有双导电通道的复合功能材料浆料；
所述的收集方法，如蒸发浓缩等；
将浆料直接固化成型的步骤，即可得到聚3,4-(乙撑二氧噻吩)-石墨烯复合功能材料，即所述的具有双导电通道的复合功能材料；
术语“固化”方法如下：
将上述复合功能材料浆料装入成型的模具中，然后放入真空干燥箱中40-80℃氛围下干燥12-24h，最后获得所述的含石墨烯的复合功能材料。
或者：
包括如下步骤：
将所述的浆料与聚合物基体共混，包括溶融共混或者是溶液共混，然后通过溶剂挥发固化工艺或者外加固化剂等固化工艺处理得到的共混体系，最后获得所述含石墨烯的复合材料。
或者：
还包括如下步骤：
将所述的浆料涂布于聚合物基材、金属基材、无机材料基材或织物基材等的表面，然后在真空环境中固化成型，固化温度为40-80℃，形成功能复合膜，涂布厚度0.1um～10mm，涂布功能膜A和聚合物膜B的组成结构可以是B-A，B-A-B，A-B-A等形式组装，获得所述含石墨烯的复合材料。
所述的具有双导电通道的复合功能材料，可以用于制备压阻响应材料或者是抗静电、电磁屏蔽材料等，试验证明，其具有优异压阻响应和压阻重复性以及电磁屏蔽效应；
本发明操作简单易行，可以大规模的生产磺化石墨烯。由于表面接枝上了磺酸基团，可以有效的降低石墨烯的表面能，使石墨烯可以较高浓度的分散在去离子水中；另一方面也为和下一步的导电聚合物接枝提供了官能基团，进一步加强石墨烯和聚合物的结合性和相容性；从而制备出双导电通道的复合功能材料。
由于双导电通道的存在，复合功能材料的压阻性能格外优异；纯导电聚合物-功能化石墨烯-聚合物复合功能材料具有非常灵敏的压阻响应，而导电聚合物-功能化石墨烯-聚合物复合功能材料中渗阈值仅为0.5Wt％；低于经过同样表面改性的碳纳米管复合材料渗阈值1.2Wt％以及石墨烯复合材料渗阈值0.7Wt％。较低的添加量不仅可以维持聚合物原有的性能，更能够形成一种不稳定的导电网络体系，有利于提高压阻响应的灵敏性。
由于聚3,4-(乙撑二氧噻吩)-石墨烯复合浆料可以单独固化成型，也可和其他材料结合形成电阻响应的功能材料，有非常广泛的应用领域。
由于石墨烯巨大的比表面积以及接枝上的聚3,4-(乙撑二氧噻吩)两者之间的协同同作用，使最重的复合功能材料具有优异的压阻重复性。同样条件下碳纳米管或者单纯的石墨烯复合材料内部的导电网络搭建完全跟不上外力的变化，优异的压阻性能自然是无法重复展现。
本发明所提供的制备方法，工艺简单，操作方便，不需要大型加工设备，有利于实现大规模、低成本生产此种复合功能材料。
附图说明
图1磺化石墨烯透镜照片。
图2聚3,4-(乙撑二氧噻吩-石墨烯复合功能材料红外光谱图。
图3聚3,4-(乙撑二氧噻吩-石墨烯复合材料SEM。
图4实施例4-6导电聚合物-石墨烯-聚合物复合功能材料电阻率和功能组分含量曲线。
图5实施例4中导电聚合物-石墨烯-聚合物复合功能材料电阻在压力作用下的变化趋势。
具体实施方式
以下通过具体实施例对本发明进行更详细的说明。实施例仅是对本发明的一种说明，而不构成对本发明的限制。实施例是实际应用例子，对于本领域的专业技术人员很容易掌握并验证。如果在本发明的基础上做出某种改变，那么其实质并不超出本发明的范围。
实施例1
1)磺化石墨烯的制备
将羧基化石墨烯分散在去离子水中，超声分散2小时，制备得到10mg/ml的羧基化石墨烯溶液，以便后续使用；
将4-苯胺磺酸溶解在去离子水中，制备得到20mg/ml的溶液，以便后续使用；
将上述得到的两种溶液按体积比2:3混合，滴加1-3滴二月桂酸二丁基锡作为催化剂，并在95℃加热回流反应10小时，降低体系温度至90℃，接着向混合反应体系中加入水合肼，恒温反应2小时，其中，水合肼的加入量与羧基化石墨烯的比例为1.0ml:0.8g。最后得到磺化石墨烯，并对其进行了结构形貌和表面基团的表针分析，结果如图1，图1可以看出磺化石墨烯是很薄的片层结构；接枝率为40％；
2)导电聚合物-功能化石墨烯复合材料制备
首先称取步骤1)得到的磺化石墨烯100mg溶解在100ml的去离子水中，得到浓度为1mg/ml的磺化石墨烯溶液；之后向溶液中加入5g 3,4-(乙撑二氧噻吩)单体，再加入一定量的过硫酸钠(Na2S2O8)溶液作为引发剂；然后将上述混合溶液在室温下反应4小时，旋转蒸馏，浓缩，最终得到聚3,4-(乙撑二氧噻吩)-石墨烯复合浆料，其红外图谱见图2。磺化石墨烯和聚3,4-(乙撑二氧噻吩)的质量比为3:1；n＝400；
图2中1190cm-1处为磺酸基团的特征峰，1228cm-1处为C-O-C的伸缩振动峰，此处主要是3,4-(乙撑二氧噻吩)中的C-O-C结构，1540cm-1处为C-N面内弯曲的特征峰，1720cm-1附近为酯基中C＝O的伸缩振动峰。
同时也对此种复合材料的表面形貌进行了表征，如图3所示。此浆料可直接固化成型得到聚3,4-(乙撑二氧噻吩)-石墨烯复合功能材料，也可与其他聚合物结合制备复合功能材料。
实施例2
1)磺化石墨烯的制备
首先称取一定量的羧基化石墨烯分散在去离子水中，超声分散4小时，制备得到10mg/ml的羧基化石墨烯溶液，以便后续使用；其次称取一定量的4-苯胺磺酸衍生物R-1溶解在去离子水中(可加热助溶解)，制备得到20mg/ml的溶液，以便后续使用；最后取上述得到的两种溶液按体积比2:3混合，滴加1-3滴二月桂酸二丁基锡作为催化剂，并在95℃加热回流反应10小时，降低体系温度至90℃，接着向混合反应体系中加入一定量的水合肼，恒温反应2小时。得到磺化石墨烯，其中所述水合肼的加入量与羧基化石墨烯的比例为1.2ml:1g。接枝率为60％；
2)导电聚合物-功能化石墨烯复合材料制备
首先称取步骤1)得到的磺化石墨烯300mg溶解在100ml去离子水中，得到浓度为3mg/ml的磺化石墨烯溶液；之后向溶液中加入50g 3,4-(乙撑二氧噻吩)单体，再加入一定量的过硫酸钠(Na2S2O8)溶液；然后将上述混合溶液在室温下反应6小时，旋转蒸馏，浓缩，最终得到聚3,4-(乙撑二氧噻吩)-石墨烯复合浆料。此浆料可直接固化成型得到聚3,4-(乙撑二氧噻吩)-石墨烯复合功能材料，也可与其他聚合物结合制备复合功能材料。磺化石墨烯和聚3,4-(乙撑二氧噻吩)的质量比为6:1；n＝1000。
实施例3
1)磺化石墨烯的制备
首先称取一定量的羧基化石墨烯分散在去离子水中，超声分散6小时，制备得到10mg/ml的羧基化石墨烯溶液，以便后续使用；其次称取一定量的4-苯胺磺酸衍生物R-2溶解在去离子水中(可加热助溶解)，制备得到20mg/ml的溶液，以便后续使用；最后取上述得到的两种溶液按体积比2:3混合，滴加1-3滴二月桂酸二丁基锡作为催化剂，并在95℃加热回流反应10小时，降低体系温度至90℃，接着向混合反应体系中加入一定量的水合肼，恒温反应2小时。得到磺化石墨烯，其中所述水合肼的加入量与羧基化石墨烯的比例为1.5ml:1g。接枝率为75％；
2)导电聚合物-功能化石墨烯复合材料制备
首先称取步骤1)得到的磺化石墨烯500mg溶解在100ml去离子水中，得到浓度为5mg/ml的磺化石墨烯溶液；之后向溶液中加入100g 3,4-(乙撑二氧噻吩)单体，再加入一定量的过硫酸钠(Na2S2O8)溶液；然后将上述混合溶液在室温下反应8小时，旋转蒸馏，浓缩，最终得到聚3,4-(乙撑二氧噻吩)-石墨烯复合浆料。此浆料可直接固化成型得到聚3,4-(乙撑二氧噻吩)-石墨烯复合功能材料，也可与其他聚合物结合制备复合功能材料。磺化石墨烯和聚3,4-(乙撑二氧噻吩)的质量比为10:1；n＝6000。
实施例4
导电聚合物-石墨烯-聚合物复合材料制备
取上述实施例1中制备得到的浓缩复合浆料1g与聚氨酯共混100g(溶液共混)制备功能复合材料，其中固含量质量比为0.1:100；经干燥固化处理，最终制备得到导电聚合物-功能化石墨烯-聚合物复合功能材料；然后结合实施例5、6对功能填料的含量与导电性能之间的关系也做了系列分析，如图4所示，此外也研究了此种复合功能材料对压力的响应程度，结果如图5所示。
结果表明，当聚3,4-(乙撑二氧噻吩)-石墨烯复合功能填料的固含量增加时，复合材料体积电阻急剧下降，当固含量质量比为0.5％时，达到渗阈值，并且当填料含量继续增加时，电阻变化趋于平缓；此外，图5中随着压力增加，电阻率变化值逐渐增大，并且趋向于线性变化。这说明制备得到的功能复合材料具有很好的电性能和压阻响应特性，可应用于传感材料领域和电磁屏蔽领域。
实施例5
导电聚合物-石墨烯-聚合物复合材料制备
取上述实施例2中制备得到的浓缩复合浆料10g与天然橡胶共混100g(直接共混)制备功能复合材料，其中固含量质量比为1:100；经干燥固化处理，最终制备得到导电聚合物-功能化石墨烯-聚合物复合功能材料。
实施例6
导电聚合物-石墨烯-聚合物复合材料制备
取上述实施例3中制备得到的浓缩复合浆料20g与聚苯乙烯共混100g(熔融共混)制备功能复合材料，其中固含量质量比为2:100；经干燥固化处理，最终制备得到导电聚合物-功能化石墨烯-聚合物复合功能材料；
实施例7
导电聚合物-石墨烯-聚合物复合材料制备
取上述实施例3中制备得到的浓缩复合浆料1g，将复合浆料涂布于聚合物基材的表面形成功能复合膜(不限于聚合物基材，也可以是金属基材、无机材料基材、织物基材等)，此实施例选用聚碳酸酯作为基材，涂布厚度(0.1um～10mm)，也可根据实际需求而定(不限于上述厚度)，涂布功能膜A和聚合物膜B的组装结构可以是B-A，B-A-B，A-B-A等形式组装，经干燥固化处理，最终得到导电聚合物-功能化石墨烯-聚合物复合功能材料。

Claims (11)

1.具有双导电通道的复合功能材料，其特征在于，为磺化石墨烯表面接枝导电聚合物聚3,4-(乙撑二氧噻吩)，其结构通式如式1所示：
其中：n为聚合度，n＝100～8000的整数。
2.根据权利要求1所述的具有双导电通道的复合功能材料，其特征在于，磺化石墨烯和聚3,4-(乙撑二氧噻吩)的质量比为1:1～1:100。
3.根据权利要求2所述的具有双导电通道的复合功能材料，其特征在于，磺化石墨烯和聚3,4-(乙撑二氧噻吩)的质量比为1:3～1:10。
4.一种含石墨烯的复合材料，其特征在于，其组分包括权利要求1～3任一项所述具有双导电通道的复合功能材料和聚合物基体。
5.根据权利要求4所述的含石墨烯的复合材料，其特征在于，所述含石墨烯的复合材料中，所述具有双导电通道的复合功能材料与所述聚合物基体的重量比为0.1:100～20:100。
6.根据权利要求4所述的含石墨烯的复合材料，其特征在于，具有双导电通道的复合功能材料与聚合物基体的重量比为1:100～10:100。
7.根据权利要求4所述的含石墨烯的复合材料，其特征在于，所述聚合物基体选自聚烯烃类聚合物、聚酯类聚合物、橡胶类聚合物或聚甲醛、聚砜。
8.根据权利要求7所述的含石墨烯的复合材料，其特征在于，所述聚烯烃类聚合物为聚乙烯、聚丙烯或聚苯乙烯；
所述聚酯类聚合物为聚对苯二甲酸乙二醇酯；
所述橡胶类聚合物为硅橡胶。
9.根据权利要求1～3任一项所述的具有双导电通道的复合功能材料的制备方法，其特征在于，包括如下步骤：
(1)将所述的磺化石墨烯溶解在水中，得到浓度为1～20mg/ml的磺化石墨烯溶液；
(2)然后加入3,4-(乙撑二氧噻吩)；
再加入重量浓度为5～30％的过硫酸钠(Na2S2O8)溶液，过硫酸钠的重量用量为磺化石墨烯的10～60％；然后在室温下反应4-8小时，然后从反应产物中收集聚3,4-(乙撑二氧噻吩)-石墨烯复合浆料浓缩，得到聚3,4-(乙撑二氧噻吩)-石墨烯复合浆料，即为具有双导电通道的复合功能材料浆料；
将浆料直接固化成型，即可得到聚3,4-(乙撑二氧噻吩)-石墨烯复合功能材料，即所述的具有双导电通道的复合功能材料。
10.根据权利要求9所述的方法，其特征在于，3,4-(乙撑二氧噻吩)与磺化石墨烯的质量比为1:1～100:1。
11.根据权利要求1～3任一项所述的具有双导电通道的复合功能材料或权利要求4～8任一项所述的含石墨烯的复合材料的应用，其特征在于，用于制备压阻响应材料或者抗静电或电磁屏蔽材料。
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