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CN108559107B - 一种具有电磁屏蔽功能的石墨烯纳米片/离子液体封端的水性聚氨酯复合乳液的制备方法 - Google Patents

一种具有电磁屏蔽功能的石墨烯纳米片/离子液体封端的水性聚氨酯复合乳液的制备方法 Download PDF

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CN108559107B
CN108559107B CN201810401498.0A CN201810401498A CN108559107B CN 108559107 B CN108559107 B CN 108559107B CN 201810401498 A CN201810401498 A CN 201810401498A CN 108559107 B CN108559107 B CN 108559107B
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徐佩
桑国龙
丁运生
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Hefei University of Technology
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Abstract

本发明公开了一种具有电磁屏蔽功能的石墨烯纳米片/离子液体封端的水性聚氨酯复合乳液的制备方法，采用氨基咪唑基离子液体对聚氨酯预聚体进行封端，利用离子液体与石墨烯纳米片之间的阳离子‑π相互作用，提高石墨烯纳米片在聚氨酯中的分散性和相容性，离子液体和石墨烯纳米片协同赋予材料优异的电磁屏蔽性能。本发明修饰的石墨烯纳米片在水性聚氨酯复合乳液中分散均匀且具有良好的稳定性，并且低石墨烯纳米片含量的聚氨酯纳米复合材料具有优异的电磁屏蔽性能。

Description

一种具有电磁屏蔽功能的石墨烯纳米片/离子液体封端的水 性聚氨酯复合乳液的制备方法
技术领域
本发明涉及具有电磁屏蔽功能的水性聚氨酯复合乳液的制备方法，具体涉及一种具有电磁屏蔽功能的石墨烯纳米片/离子液体封端的水性聚氨酯复合乳液的制备方法。
背景技术
随着信息技术的不断发展，电磁波在生产和生活中的应用领域也不断扩大，同时也带来了一些负面的影响，尤其是电磁辐射所造成的电磁污染和电磁干扰，不但会对电子仪器、设备造成干扰和损坏，而且会造成电磁信息的泄露，甚至还会污染环境，危害人类的健康。近年来，电子通讯设备不断向小型化、轻量化和高性能化发展，电磁屏蔽材料各项性能的要求也越来越严苛，传统的碳系导电填料/溶剂型复合乳液成膜的电磁屏蔽材料已很难同时满足环境友好，低成本，屏蔽效能高等要求，因而，研发环境友好，低成本，屏蔽效能高的水性复合乳液，是满足新发展需求下电磁屏蔽材料严苛要求的有效途径，具有巨大的竞争优势和广泛的应用前景。
聚氨酯即聚氨基甲酸酯，是主链上含有重复氨基甲酸酯基团的化合物的统称。一般由有机二异氰酸酯与二羟基或多羟基化合物聚加成得到。以水为分散介质的水性聚氨酯体系，具有无污染、零挥发性有机物排放、安全可靠、性能优异等特点。作为碳系导电填料，石墨烯纳米片是一种新型的二维纳米碳材料，具有极其优异的导电、力学和热稳定性能，这些优异的性能使得石墨烯纳米片在与高分子材料形成复合材料后具备了应用于电磁屏蔽材料的可能性。然而石墨烯纳米片自身具有很强的聚集作用，在水性聚氨酯体系中很难均匀分散，限制了其应用范围和性能，采用共价键修饰将聚合物或共聚物接枝到石墨烯纳米片表面进行改性是一种常用的对石墨烯纳米片化学改性的方法，但是会破坏其表面结构和导电性能，并且化学改性方法步骤多、相对效率低。非共价键改性可以在克服石墨烯纳米片聚集作用的同时，保持其各项优异性能，是一种工艺简单，效果良好的改性方法。离子液体是指在室温或室温附近完全呈液态的由阴、阳离子组成的有机物质，具有热和化学稳定性好、不易挥发和极性强等优良性质。与石墨烯纳米片修饰的其他方法相比，利用离子液体的包覆作用有着明显的优点：一是离子液体和石墨烯纳米片之间是一种特殊的强阳离子-π强物理相互作用力，对石墨烯纳米片表面有效改性而不破坏其共轭结构，保持石墨烯纳米片本身优异的物理性能；二是这种方法不使用剧烈的化学方法，不会造成石墨烯纳米片的断裂、降低石墨烯纳米片的尺寸；三是这种修饰石墨烯纳米片的方法步骤少，因而简单易行，而且相对效率高。
发明内容
本发明的目的是克服现有技术的不足，提供一种具有电磁屏蔽功能的石墨烯纳米片/离子液体封端的水性聚氨酯复合乳液的制备方法。本发明制备的水性聚氨酯复合乳液不仅具有良好的电磁屏蔽性能，而且制备方法环境友好、工艺简单。离子液体修饰的石墨烯纳米片在水性聚氨酯复合乳液中分散均匀且具有良好的稳定性，并且低石墨烯纳米片含量的聚氨酯纳米复合材料具有优异的电磁屏蔽性能。
本发明具有电磁屏蔽功能的石墨烯纳米片/离子液体封端的水性聚氨酯复合乳液的制备方法，是采用氨基咪唑基离子液体对聚氨酯预聚体进行封端，利用离子液体与石墨烯纳米片之间的阳离子-π相互作用，提高石墨烯纳米片在聚氨酯中的分散性和相容性，离子液体和石墨烯纳米片协同赋予材料优异的电磁屏蔽性能。
本发明具有电磁屏蔽功能的石墨烯纳米片/离子液体封端的水性聚氨酯复合乳液的制备方法，包括如下步骤：
步骤1：将聚醚多元醇和环氧树脂加入三口烧瓶混合，在真空度0.08-0.10MPa、温度80-110℃的条件下脱水1-2小时，然后加入二异氰酸酯单体，在60-90℃下搅拌反应1-2小时，进一步加入亲水扩链剂、催化剂和扩链剂，加入适量丙酮降低粘度，在60-90℃下反应1-4小时，获得异氰酸酯基封端的聚氨酯预聚体；
步骤2：向步骤1所得异氰酸酯基封端的聚氨酯预聚体中加入氨基咪唑基离子液体对聚氨酯链段进行封端，在70-90℃下反应得到离子液体封端的聚氨酯预聚体；
步骤3：将步骤2所得反应液降至室温后用三乙胺中和，然后进一步加入石墨烯纳米片和去离子水，在高速剪切下使石墨烯分散均匀，减压脱除丙酮溶剂，最后得到石墨烯纳米片/离子液体封端的水性聚氨酯复合乳液。
步骤1中，各原料配比按质量份数构成如下：
Figure BDA0001645826940000021
步骤1中，所述聚醚多元醇为聚四氢呋喃二醇、聚丙二醇或聚己内酯二醇。
步骤1中，所述环氧树脂为双酚A型环氧树脂E-51、E-44或EP-828。
步骤1中，所述二异氰酸酯单体为甲苯二异氰酸酯、异佛尔酮二异氰酸酯或六亚甲基二异氰酸酯。
步骤1中，所述扩链剂为1，4-丁二醇、1，6-己二醇、1，6-己二胺或二羟甲基环己烷；所述亲水扩链剂为二羟甲基丙酸；所述催化剂为二月桂酸二丁基锡。
步骤2中，离子液体封端的聚氨酯预聚体中氨基咪唑基离子液体的质量百分含量为1-4％；步骤2中氨基咪唑基离子液体与步骤3中石墨烯纳米片的质量比为1：1-2。
步骤2中，氨基咪唑基离子液体为1-胺丙基-3-甲基咪唑溴盐、1-胺丙基-3-甲基咪唑四氟硼酸盐、1-胺丙基-3-甲基咪唑六氟磷酸盐、1-胺乙基-3-甲基咪唑溴盐、1-胺乙基-3-甲基咪唑四氟硼酸盐、1-胺乙基-3-甲基咪唑六氟磷酸盐中的一种或几种任意配比的组合。
步骤3中，各原料的添加量按质量份数构成如下：
离子液体封端的聚氨酯预聚体100份
石墨烯纳米片2-8份
去离子水100-300份。
步骤3中，所述石墨烯纳米片具有超大的形状比(直径/厚度比，直径5-10μm，厚度3-10nm)，比表面积31.657m2/g，电导率500-1000S/cm。
将本发明制备的石墨烯纳米片/离子液体封端的水性聚氨酯复合乳液倒入聚四氟乙烯模具中，先室内静置24h以上，再放入真空干燥箱控温40-70℃，干燥24h成膜，制得电磁屏蔽聚氨酯复合材料，最后放入干燥器中备用。
本发明的有益效果体现在：
本发明针对石墨烯纳米片分散性较差和化学改性方法的缺陷，首先利用功能化咪唑基离子液体和石墨烯纳米片之间特殊的阳离子-π相互作用，提高石墨烯纳米片在聚氨酯基体中的分散性；其次采用氨基咪唑基离子液体对聚氨酯预聚体进行封端，获得离子液体封端的聚氨酯预聚物，提高石墨烯纳米片在聚氨酯基体中的相容性。利用离子液体和石墨烯纳米片协同赋予聚氨酯纳米复合材料优异的电磁屏蔽性能。本发明制备方法，相对于现有技术，简单高效且不破坏石墨烯纳米片结构，保持其本身优异的物理性能，有低成本和良好分散性的特点，在制备石墨烯纳米片/水性聚氨酯复合乳液方面具有良好的应用前景。
附图说明
图1为复合材料断面的扫描电子显微镜照片。从图1中可以看出，氨基咪唑基离子液体修饰石墨烯纳米片均匀分布在聚氨酯基体中。
在本实施例制备的复合材料的矢量网络分析仪测量仪测试样品的电磁屏蔽性能。电磁屏蔽性能测试如图2所示。
具体实施方式
下面结合实施例对本说明做进一步描述，下列实施例并不用限制本发明的实施范围。
实施例1：
本实施例中具有电磁屏蔽功能的石墨烯纳米片/离子液体封端的水性聚氨酯复合乳液的制备方法如下：
1、将50g聚丙二醇和5.7g环氧树脂E-44加入500ml三口烧瓶中，在真空度0.10MPa、温度110℃的条件下脱水1.5小时，然后加入41.7g异佛尔酮二异氰酸酯，在70℃下搅拌反应2小时，进一步加入12.5g亲水扩链剂二羟甲基丙酸，0.3g催化剂二月桂酸二丁基锡和1.38g1,4-丁二醇，并加入22.8g丙酮降低粘度，在70℃下反应4小时，获得异氰酸酯基封端的聚氨酯预聚体；
2、向步骤1所得异氰酸酯基封端的聚氨酯预聚体中加入2.3g1-胺丙基-3-甲基咪唑四氟硼酸盐离子液体，在70℃下反应得到离子液体封端的聚氨酯预聚体；
3、将步骤2所得反应液降至室温，在700r/min的高速剪切分散下加入5g三乙胺中和3min，然后进一步加入4.6g石墨烯纳米片和230g去离子水，搅拌分散30min，然后减压脱除丙酮溶剂，得到石墨烯纳米片/离子液体封端的水性聚氨酯复合乳液。
其中，所述水性聚氨酯复合乳液各组分按重量份的构成为：
离子液体封端的聚氨酯预聚体 100份
石墨烯纳米片 4份
去离子水 200份。
离子液体封端的聚氨酯预聚体中氨基咪唑基离子液体质量百分含量为2％，功能化咪唑基离子液体与石墨烯纳米片质量比为1：2。石墨烯纳米片(直径/厚度比，直径5-10μm，厚度3-10nm，)比表面积31.657m2/g，电导率500-1000S/cm。功能化咪唑基离子液体为1-胺丙基-3-甲基咪唑四氟硼酸。
图1为复合材料断面的扫描电子显微镜照片。从图2中可以看出，氨基咪唑离子液体修饰石墨烯纳米片均匀分布在聚氨酯基体中。
在本实施例制备的复合材料的矢量网络分析仪测量仪测试样品(厚度2mm)的电磁屏蔽性能。电磁屏蔽性能测试如图2所示。
实施例2：
本实施例中具有电磁屏蔽功能的石墨烯纳米片/离子液体封端的水性聚氨酯复合乳液的制备方法如下：
1、将50g聚四氢呋喃二醇和4.6g环氧树脂E-51加入500ml三口烧瓶中，在真空度0.10MPa、温度110℃的条件下脱水1.5小时，然后加入31.8g六亚甲基二异氰酸酯，在70℃下搅拌反应2小时，进一步加入12.5g亲水扩链剂二羟甲基丙酸，0.3g催化剂二月桂酸二丁基锡和1.38g1,6-己二醇，并加入20.1g丙酮降低粘度，在70℃下反应4小时，获得异氰酸酯基封端的聚氨酯预聚体；
2、向步骤1所得异氰酸酯基封端的聚氨酯预聚体中加入3.2g1-羟乙基-3-甲基咪唑四氟硼酸盐离子液体，在70℃下反应得到离子液体封端的聚氨酯预聚体；
3、将步骤2所得反应液降至室温，在700r/min的高速剪切分散下加入5g三乙胺中和3min，然后进一步加入4.13g石墨烯纳米片和206.7g去离子水，搅拌分散30min，然后减压脱除丙酮溶剂，得到石墨烯纳米片/离子液体封端的水性聚氨酯复合乳液。
其中，所述水性聚氨酯复合乳液各组分按重量份的构成为：
离子液体封端的聚氨酯分散体 100份
石墨烯纳米片 4份
去离子水 200份。
离子液体封端的聚氨酯预聚体中氨基咪唑基离子液体质量百分含量为3％，功能化咪唑基离子液体与石墨烯纳米片质量比为3：4。石墨烯纳米片(直径/厚度比，直径5-10μm，厚度3-10nm，)比表面积31.657m2/g，电导率500-1000S/cm。功能化咪唑基离子液体为1-胺丙基-3-甲基咪唑四氟硼酸。
在本实施例制备的复合材料的矢量网络分析仪测量仪测试样品(厚度2mm)的电磁屏蔽性能。电磁屏蔽性能测试如图2所示。
实施例3：
本实施例中具有电磁屏蔽功能的石墨烯纳米片/离子液体封端的水性聚氨酯复合乳液的制备方法如下：
1、将50g聚己内酯二醇和5.1g环氧树脂EP-828加入500ml三口烧瓶中，在真空度0.10MPa、温度110℃的条件下脱水1.5小时，然后加入31.3g甲苯二异氰酸酯，在70℃下搅拌反应2小时，进一步加入12.5g亲水扩链剂二羟甲基丙酸，0.3g催化剂二月桂酸二丁基锡和1.38g1,6-己二胺，并加入21.0g丙酮降低粘度，在70℃下反应4小时，获得异氰酸酯基封端的聚氨酯预聚体；
2、向步骤1所得异氰酸酯基封端的聚氨酯预聚体中加入4.19g1-胺丙基-3-甲基咪唑溴盐离子液体，在70℃下反应得到离子液体封端的聚氨酯预聚体；
3、将步骤2所得反应液降至室温，在700r/min的高速剪切分散下加入5g三乙胺中和3min，然后进一步加入4.27g石墨烯纳米片和210g去离子水，搅拌分散30min，然后减压脱除丙酮溶剂，得到石墨烯纳米片/离子液体封端的水性聚氨酯复合乳液。
其中，各主要组分按重量份的构成为：
离子液体封端的聚氨酯分散体 100份
石墨烯纳米片 4份
去离子水 200份。
离子液体封端的聚氨酯预聚体中氨基咪唑基离子液体质量百分含量为4％，功能化咪唑基离子液体与石墨烯纳米片质量比为1：1。石墨烯纳米片(直径/厚度比，直径5-10μm，厚度3-10nm，)比表面积31.657m2/g，电导率500-1000S/cm。功能化咪唑基离子液体为1-胺丙基-3-甲基咪唑溴盐。
在本实施例制备的复合材料的矢量网络分析仪测量仪测试样品(厚度2mm)的电磁屏蔽性能。电磁屏蔽性能测试如图2所示。
对比例：未加离子液体修饰的石墨烯纳米片
本实施例按实施例1相同方法制备具有电磁屏蔽功能的石墨烯纳米片/水性聚氨酯复合乳液，区别在于不使用氨基咪唑基离子液体对石墨烯纳米片进行改性，制成石墨烯纳米片/水性聚氨酯复合乳液。在本实施例制备的复合材料的矢量网络分析仪测量仪测试样品的电磁屏蔽性能。电磁屏蔽性能测试如图2所示。
将50g聚丙二醇和5.7g环氧树脂E-44加入500ml三口烧瓶中，在真空度0.10MPa、温度110℃的条件下脱水1.5小时，然后加入39.9g异佛尔酮二异氰酸酯，在70℃下搅拌反应2小时，进一步加入12.5g亲水扩链剂二羟甲基丙酸，0.3g催化剂二月桂酸二丁基锡和1.38g1,4-丁二醇，并加入22.3g丙酮降低粘度，在70℃下反应4小时，获得羟基封端的聚氨酯预聚体；将反应液降至室温，在700r/min的高速剪切分散下，加入5g三乙胺中和3min，加4.39g石墨烯纳米片和220g去离子水，搅拌分散30min，即得石墨烯纳米片/离子液体封端的水性聚氨酯复合乳液。
其中，所述水性聚氨酯复合乳液各组分按重量份的构成为：
聚氨酯分散体 100份
石墨烯纳米片 4份
去离子水 200份
其中，石墨烯纳米片(直径/厚度比，直径5-10μm，厚度3-10nm，)比表面积31.657m2/g，电导率500-1000S/cm。在本实施例制备的复合材料的矢量网络分析仪测量仪测试样品(厚度2mm)的电磁屏蔽性能。电磁屏蔽性能测试如图2所示。
从图2中可以看出，石墨烯含量固定，随着离子液体增多，复合材料的电磁屏蔽性能随着氨基咪唑离子液体修饰石墨烯纳米片添加量的增大而增大。

Claims (7)

1.一种具有电磁屏蔽功能的石墨烯纳米片/离子液体封端的水性聚氨酯复合乳液的制备方法，其特征在于：采用氨基咪唑基离子液体对聚氨酯预聚体进行封端，利用离子液体与石墨烯纳米片之间的阳离子-π相互作用，提高石墨烯纳米片在聚氨酯中的分散性和相容性，离子液体和石墨烯纳米片协同赋予材料优异的电磁屏蔽性能；包括如下步骤：
步骤1：将聚醚多元醇和环氧树脂加入三口烧瓶混合，在真空度0.08-0.10MPa、温度80-110℃的条件下脱水1-2小时，然后加入二异氰酸酯单体，在60-90℃下搅拌反应1-2小时，进一步加入亲水扩链剂、催化剂、扩链剂以及丙酮，在60-90℃下反应1-4小时，获得异氰酸酯基封端的聚氨酯预聚体；
步骤2：向步骤1所得异氰酸酯基封端的聚氨酯预聚体中加入氨基咪唑基离子液体对聚氨酯链段进行封端，在70-90℃下反应得到离子液体封端的聚氨酯预聚体；
步骤3：将步骤2所得反应液降至室温后用三乙胺中和，然后进一步加入石墨烯纳米片和去离子水，在高速剪切下使石墨烯分散均匀，减压脱除丙酮溶剂，最后得到石墨烯纳米片/离子液体封端的水性聚氨酯复合乳液；
步骤1中，各原料配比按质量份数构成如下：
Figure FDA0002570819730000011
步骤1中，所述扩链剂为1，4-丁二醇、1，6-己二醇、1，6-己二胺或二羟甲基环己烷；所述亲水扩链剂为二羟甲基丙酸；所述催化剂为二月桂酸二丁基锡。
2.根据权利要求1所述的制备方法，其特征在于：
步骤1中，所述聚醚多元醇为聚四氢呋喃二醇、聚丙二醇或聚己内酯二醇；所述环氧树脂为双酚A型环氧树脂E-51、E-44或EP-828；所述二异氰酸酯单体为甲苯二异氰酸酯、异佛尔酮二异氰酸酯或六亚甲基二异氰酸酯。
3.根据权利要求1所述的制备方法，其特征在于：
步骤2中，离子液体封端的聚氨酯预聚体中氨基咪唑基离子液体的质量百分含量为1-4％。
4.根据权利要求1或3所述的制备方法，其特征在于：
步骤2中，氨基咪唑基离子液体为1-胺丙基-3-甲基咪唑溴盐、1-胺丙基-3-甲基咪唑四氟硼酸盐、1-胺丙基-3-甲基咪唑六氟磷酸盐、1-胺乙基-3-甲基咪唑溴盐、1-胺乙基-3-甲基咪唑四氟硼酸盐、1-胺乙基-3-甲基咪唑六氟磷酸盐中的一种或几种任意配比的组合。
5.根据权利要求1所述的制备方法，其特征在于：
步骤3中，各原料的添加量按质量份数构成如下：
离子液体封端的聚氨酯预聚体 100份
石墨烯纳米片 2-8份
去离子水 100-300份。
6.根据权利要求1、3或5所述的制备方法，其特征在于：
步骤2中氨基咪唑基离子液体与步骤3中石墨烯纳米片的质量比为1：1-2。
7.根据权利要求1所述的制备方法，其特征在于：
步骤3中，所述石墨烯纳米片的直径5-10μm，厚度3-10nm，比表面积31.657m2/g，电导率500-1000S/cm。
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