CN113831734A - 一种抗静电聚酰亚胺/石墨烯复合薄膜及其制备方法 - Google Patents
一种抗静电聚酰亚胺/石墨烯复合薄膜及其制备方法 Download PDFInfo
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- 238000000034 method Methods 0.000 claims description 10
- ZPSUIVIDQHHIFH-UHFFFAOYSA-N 3-(trifluoromethyl)-4-[2-(trifluoromethyl)phenyl]benzene-1,2-diamine Chemical group FC(F)(F)C1=C(N)C(N)=CC=C1C1=CC=CC=C1C(F)(F)F ZPSUIVIDQHHIFH-UHFFFAOYSA-N 0.000 claims description 8
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 claims description 8
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 claims description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 claims description 3
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- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- WOSVXXBNNCUXMT-UHFFFAOYSA-N cyclopentane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)C1C(O)=O WOSVXXBNNCUXMT-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
本发明提出了一种抗静电聚酰亚胺/石墨烯复合薄膜及其制备方法,所述抗静电聚酰亚胺/石墨烯复合薄膜的制备方法包括:将氧化石墨烯与二氯亚砜进行超声反应,得到酰氯化石墨烯;将所得酰氯化石墨烯与二胺、二酐进行缩聚反应,得到聚酰胺酸;将所得聚酰胺酸涂布成膜后,加热进行亚胺化反应,得到所述抗静电聚酰亚胺/石墨烯复合薄膜。本发明提出的一种抗静电聚酰亚胺/石墨烯复合薄膜及其制备方法,通过使石墨烯均匀分散于聚酰亚胺中,极大地改善了聚酰亚胺薄膜的抗静电性能同时,也不影响其整体绝缘性能和力学性能。
Description
技术领域
本发明涉及抗静电材料技术领域,尤其涉及一种抗静电聚酰亚胺/石墨烯复合薄膜及其制备方法。
背景技术
OLED作为第三代显示技术,相较于LCD技术,实现了显示屏超薄、柔性可折叠设计,同时具备发光亮度高、对比度高、色彩鲜明、响应速度快、能耗低等优点,已逐渐登陆显示领域。
OLED显示面板包括呈阵列式排布的多个正常发光像素、及包围该呈阵列式排布的多个正常发光像素的至少一圈的虚拟像素(Dummy Pixel),虚拟像素中OLED的阴极与正常发光像素中OLED的阴极相连,虚拟像素中OLED的阳极与正常发光像素中OLED的阳极一样,与对应的驱动薄膜晶体管相连。然而,外部静电的流入导致OLED驱动不良,结果可能发生诸如瑕疵的图像质量劣化。
为了使静电的影响最小化,OLED显示面板通常包括设置在其表面上的抗静电基材。聚酰亚胺薄膜具有良好的机械性能、介电性能以及热稳定性,已广泛使用于OLED的基底材料。然而普通的聚酰亚胺薄膜易产生静电积累,若不及时清除,极易引起电子元件的击穿、损毁甚至会造成燃烧、爆炸等事故。因此对聚酰亚胺薄膜进行抗静电改性具有十分重大的意义。
CN102516574A公布了一种三层抗静电聚酰亚胺薄膜的制备方法,先合成聚酰亚胺前体树脂溶液以及抗静电聚酰亚胺前体聚合物,再将两种树脂溶液在流延板上依次涂覆成膜。但是此法制得薄膜的厚度受限制且调节困难,而且抗静电的性能提高的同时会显著降低薄膜的力学性能。
发明内容
基于背景技术存在的技术问题,本发明提出了一种抗静电聚酰亚胺/石墨烯复合薄膜及其制备方法,通过使石墨烯均匀分散于聚酰亚胺中,极大地改善了聚酰亚胺薄膜的抗静电性能同时,也不影响其整体绝缘性能和力学性能。
本发明提出的一种抗静电聚酰亚胺/石墨烯复合薄膜的制备方法,包括如下步骤:
S1、将氧化石墨烯与二氯亚砜进行超声反应,得到酰氯化石墨烯;
S2、将所得酰氯化石墨烯与二胺、二酐进行缩聚反应,得到聚酰胺酸;
S3、将所得聚酰胺酸涂布成膜后,加热进行亚胺化反应,得到所述抗静电聚酰亚胺/石墨烯复合薄膜。
优选地,所述二胺包括含氟取代的二胺;
优选地,所述含氟取代的二胺为2,2'-二(三氟甲基)二氨基联苯。
优选地,所述二酐包括芳香族二酐和脂环族二酐;
优选地,所述芳香族二酐为4,4'-(六氟异丙烯)二酞酸酐、4,4'-氧双邻苯二甲酸酐、3,3',4,4'-二苯甲酮四甲酸二酐或3,3',4,4'-联苯四羧酸二酐中的至少一种;
优选地,所述脂环族二酐为1,2,3,4-环丁烷四羧酸二酐或1,2,4,5-环戊烷四羧酸二酐中的至少一种。
优选地,所述二胺、二酐的摩尔比为1:0.8-1.1;
优选地,所述酰氯化石墨烯的用量是二胺、二酐总量的1-20wt%。
优选地,所述超声反应的温度为70-90℃,时间为10-16h。
优选地,所述氧化石墨烯是采用Hummers法制备得到。
优选地,所述加热进行亚胺化反应包括:先升温至80-120℃,保温30-60min,再升温至180-220℃,保温30-60min,最后升温到340-380℃,保温30-60min。
本发明还提出一种抗静电聚酰亚胺/石墨烯复合薄膜,其是上述抗静电聚酰亚胺/石墨烯复合薄膜的制备方法制备得到。
本发明还提出一种上述抗静电聚酰亚胺/石墨烯复合薄膜在OLED显示器中的应用。
本发明所述抗静电聚酰亚胺/石墨烯复合薄膜中,通过采用原位聚合法添加导电填料—石墨烯,酰氯化石墨烯可以作为酰化原料,与二胺、二酐一起进行缩聚反应,从而使得石墨烯可以很好的分散在聚酰胺酸溶液中,形成稳定的悬浮液,由此所得的复合薄膜表面电阻率可降至抗静电范围,并保持较高的体积电阻率,有效避免导电填料加入对聚酰亚胺薄膜绝缘性能的影响。
与此同时,通过将石墨烯参与缩聚反应后所得的聚酰亚胺膜,克服了传统将石墨烯与聚酰胺酸直接混合造成的将石墨烯分散性差的缺陷,获得了一种力学性能还有所改进的聚酰亚胺薄膜。
具体实施方式
下面,通过具体实施例对本发明的技术方案进行详细说明,但是应该明确提出这些实施例用于举例说明,但是不解释为限制本发明的范围。
实施例1
一种抗静电聚酰亚胺/石墨烯复合薄膜及其制备方法,包括如下步骤:
(1)、将1g天然鳞片石墨和1g硝酸钠加入100mL浓硫酸中混匀,搅拌条件下再缓慢加入10g KMnO4,0℃下搅拌反应2h后,加入体积浓度为3%的H2O2还原过量的KMnO4直至溶液变为金黄色,再将所得悬浮液过滤、洗涤并真空脱水干燥,得到氧化石墨烯;将所得氧化石墨烯加入100mL的二氯亚砜中,室温下超声反应3h,再升温至80℃反应15h,降至室温后,过滤,去离子水洗涤,室温真空干燥,得到酰氯化石墨烯;
(2)、将1g酰氯化石墨烯加入85gN,N’-二甲基甲酰胺(DMF)溶剂中超声分散均匀,再加入4.4g 4,4'-(六氟异丙烯)二酞酸酐、2.0g 1,2,3,4-环丁烷四羧酸二酐以及7.0g 2,2'-二(三氟甲基)二氨基联苯,室温下搅拌反应6h,得到聚酰胺酸溶液;
(3)、将所得聚酰胺酸溶液涂布在玻璃板上,将该玻璃板放置于干燥箱中,升温至100℃,干燥45min,升温至200℃,干燥45min,升温至360℃,干燥50min,降温至25℃后取出,即得到所述抗静电聚酰亚胺/石墨烯复合薄膜,该聚酰亚胺/石墨烯复合薄膜的厚度为20μm。
实施例2
一种抗静电聚酰亚胺/石墨烯复合薄膜及其制备方法,包括如下步骤:
(1)、将1g天然鳞片石墨和1g硝酸钠加入100mL浓硫酸中混匀,搅拌条件下再缓慢加入10g KMnO4,0℃下搅拌反应2h后,加入体积浓度为3%的H2O2还原过量的KMnO4直至溶液变为金黄色,再将所得悬浮液过滤、洗涤并真空脱水干燥,得到氧化石墨烯;将所得氧化石墨烯加入100mL的二氯亚砜中,室温下超声反应3h,再升温至80℃反应15h,降至室温后,过滤,去离子水洗涤,室温真空干燥,得到酰氯化石墨烯;
(2)、将2.5g酰氯化石墨烯加入100gN,N’-二甲基甲酰胺(DMF)溶剂中超声分散均匀,再加入4.4g 4,4'-(六氟异丙烯)二酞酸酐、2.0g 1,2,3,4-环丁烷四羧酸二酐以及7.0g2,2'-二(三氟甲基)二氨基联苯,室温下搅拌反应6h,得到聚酰胺酸溶液;
(3)、将所得聚酰胺酸溶液涂布在玻璃板上,将该玻璃板放置于干燥箱中,升温至80℃,干燥60min,升温至220℃,干燥30min,升温至340℃,干燥60min,降温至25℃后取出,即得到所述抗静电聚酰亚胺/石墨烯复合薄膜,该聚酰亚胺/石墨烯复合薄膜的厚度为20μm。
实施例3
一种抗静电聚酰亚胺/石墨烯复合薄膜及其制备方法,包括如下步骤:
(1)、将1g天然鳞片石墨和1g硝酸钠加入100mL浓硫酸中混匀,搅拌条件下再缓慢加入10g KMnO4,0℃下搅拌反应2h后,加入体积浓度为3%的H2O2还原过量的KMnO4直至溶液变为金黄色,再将所得悬浮液过滤、洗涤并真空脱水干燥,得到氧化石墨烯;将所得氧化石墨烯加入100mL的二氯亚砜中,室温下超声反应3h,再升温至80℃反应15h,降至室温后,过滤,去离子水洗涤,室温真空干燥,得到酰氯化石墨烯;
(2)、将0.2g酰氯化石墨烯加入70g N,N’-二甲基甲酰胺(DMF)溶剂中超声分散均匀,再加入4.4g 4,4'-(六氟异丙烯)二酞酸酐、2.0g 1,2,3,4-环丁烷四羧酸二酐以及7.0g2,2'-二(三氟甲基)二氨基联苯,室温下搅拌反应6h,得到聚酰胺酸溶液;
(3)、将所得聚酰胺酸溶液涂布在玻璃板上,将该玻璃板放置于干燥箱中,升温至120℃,干燥30min,升温至180℃,干燥60min,升温至380℃,干燥30min,降温至25℃后取出,即得到所述抗静电聚酰亚胺/石墨烯复合薄膜,该聚酰亚胺/石墨烯复合薄膜的厚度为20μm。
实施例4
一种抗静电聚酰亚胺/石墨烯复合薄膜及其制备方法,包括如下步骤:
(1)、将1g天然鳞片石墨和1g硝酸钠加入100mL浓硫酸中混匀,搅拌条件下再缓慢加入10g KMnO4,0℃下搅拌反应2h后,加入体积浓度为3%的H2O2还原过量的KMnO4直至溶液变为金黄色,再将所得悬浮液过滤、洗涤并真空脱水干燥,得到氧化石墨烯;将所得氧化石墨烯加入100mL的二氯亚砜中,室温下超声反应3h,再升温至80℃反应15h,降至室温后,过滤,去离子水洗涤,室温真空干燥,得到酰氯化石墨烯;
(2)、将1g酰氯化石墨烯加入85gN,N’-二甲基甲酰胺(DMF)溶剂中超声分散均匀,再加入3.1g 4,4'-氧双邻苯二甲酸酐、2.0g 1,2,3,4-环丁烷四羧酸二酐以及7.0g 2,2'-二(三氟甲基)二氨基联苯,室温下搅拌反应6h,得到聚酰胺酸溶液;
(3)、将所得聚酰胺酸溶液涂布在玻璃板上,将该玻璃板放置于干燥箱中,升温至100℃,干燥45min,升温至200℃,干燥45min,升温至360℃,干燥50min,降温至25℃后取出,即得到所述抗静电聚酰亚胺/石墨烯复合薄膜,该聚酰亚胺/石墨烯复合薄膜的厚度为20μm。
实施例5
一种抗静电聚酰亚胺/石墨烯复合薄膜及其制备方法,包括如下步骤:
(1)、将1g天然鳞片石墨和1g硝酸钠加入100mL浓硫酸中混匀,搅拌条件下再缓慢加入10g KMnO4,0℃下搅拌反应2h后,加入体积浓度为3%的H2O2还原过量的KMnO4直至溶液变为金黄色,再将所得悬浮液过滤、洗涤并真空脱水干燥,得到氧化石墨烯;将所得氧化石墨烯加入100mL的二氯亚砜中,室温下超声反应3h,再升温至80℃反应15h,降至室温后,过滤,去离子水洗涤,室温真空干燥,得到酰氯化石墨烯;
(2)、将1g酰氯化石墨烯加入85gN,N’-二甲基甲酰胺(DMF)溶剂中超声分散均匀,再加入3.0g 3,3',4,4'-联苯四羧酸二酐、2.0g 1,2,3,4-环丁烷四羧酸二酐以及7.0g 2,2'-二(三氟甲基)二氨基联苯,室温下搅拌反应6h,得到聚酰胺酸溶液;
(3)、将所得聚酰胺酸溶液涂布在玻璃板上,将该玻璃板放置于干燥箱中,升温至100℃,干燥45min,升温至200℃,干燥45min,升温至360℃,干燥50min,降温至25℃后取出,即得到所述抗静电聚酰亚胺/石墨烯复合薄膜,该聚酰亚胺/石墨烯复合薄膜的厚度为20μm。
对比例1
一种抗静电聚酰亚胺/石墨烯复合薄膜及其制备方法,包括如下步骤:
(1)、将1g天然鳞片石墨和1g硝酸钠加入100mL浓硫酸中混匀,搅拌条件下再缓慢加入10g KMnO4,0℃下搅拌反应2h后,加入体积浓度为3%的H2O2还原过量的KMnO4直至溶液变为金黄色,再将所得悬浮液过滤、洗涤并真空脱水干燥,得到氧化石墨烯;
(2)、将1g氧化石墨烯加入85gN,N’-二甲基甲酰胺(DMF)溶剂中超声分散均匀,再加入4.4g 4,4'-(六氟异丙烯)二酞酸酐、2.0g 1,2,3,4-环丁烷四羧酸二酐以及7.0g 2,2'-二(三氟甲基)二氨基联苯,室温下搅拌反应6h,得到聚酰胺酸溶液;
(3)、将所得聚酰胺酸溶液涂布在玻璃板上,将该玻璃板放置于干燥箱中,升温至100℃,干燥45min,升温至200℃,干燥45min,升温至360℃,干燥50min,降温至25℃后取出,即得到所述抗静电聚酰亚胺/石墨烯复合薄膜,该聚酰亚胺/石墨烯复合薄膜的厚度为20μm。
对上述实施例和对比例得到的聚酰亚胺/石墨烯复合薄膜的拉伸强度、弹性模量、表面电阻率以及体积电阻率进行测试
拉伸强度、弹性模量按照国家标准GB/T1040-2006进行测试;表面电阻率以及体积电阻率按照国家标准GB/T1410-2006测试进行测试
表1实施例和对比例获得的聚酰亚胺/石墨烯复合薄膜的性能测试结果
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。
Claims (9)
1.一种抗静电聚酰亚胺/石墨烯复合薄膜的制备方法,其特征在于,包括如下步骤:
S1、将氧化石墨烯与二氯亚砜进行超声反应,得到酰氯化石墨烯;
S2、将所得酰氯化石墨烯与二胺、二酐进行缩聚反应,得到聚酰胺酸;
S3、将所得聚酰胺酸涂布成膜后,加热进行亚胺化反应,得到所述抗静电聚酰亚胺/石墨烯复合薄膜。
2.根据权利要求1所述抗静电聚酰亚胺/石墨烯复合薄膜的制备方法,其特征在于,所述二胺包括含氟取代的二胺;
优选地,所述含氟取代的二胺为2,2'-二(三氟甲基)二氨基联苯。
3.根据权利要求1或2所述抗静电聚酰亚胺/石墨烯复合薄膜的制备方法,其特征在于,所述二酐包括芳香族二酐和脂环族二酐;
优选地,所述芳香族二酐为4,4'-(六氟异丙烯)二酞酸酐、4,4'-氧双邻苯二甲酸酐、3,3',4,4'-二苯甲酮四甲酸二酐或3,3',4,4'-联苯四羧酸二酐中的至少一种;
优选地,所述脂环族二酐为1,2,3,4-环丁烷四羧酸二酐或1,2,4,5-环戊烷四羧酸二酐中的至少一种。
4.根据权利要求1-3任一项所述抗静电聚酰亚胺/石墨烯复合薄膜的制备方法,其特征在于,所述二胺、二酐的摩尔比为1:0.8-1.1;
优选地,所述酰氯化石墨烯的用量是二胺、二酐总量的1-20wt%。
5.根据权利要求1-4任一项所述抗静电聚酰亚胺/石墨烯复合薄膜的制备方法,其特征在于,所述超声反应的温度为70-90℃,时间为10-16h。
6.根据权利要求1-5任一项所述抗静电聚酰亚胺/石墨烯复合薄膜的制备方法,其特征在于,所述氧化石墨烯是采用Hummers法制备得到。
7.根据权利要求1-6任一项所述抗静电聚酰亚胺/石墨烯复合薄膜的制备方法,其特征在于,所述加热进行亚胺化反应包括:先升温至80-120℃,保温30-60min,再升温至180-220℃,保温30-60min,最后升温到340-380℃,保温30-60min。
8.一种抗静电聚酰亚胺/石墨烯复合薄膜,其特征在于,其是权利要求1-7任一项所述抗静电聚酰亚胺/石墨烯复合薄膜的制备方法制备得到。
9.一种权利要求8所述抗静电聚酰亚胺/石墨烯复合薄膜在OLED显示器中的应用。
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