CN106543719B - 一种柔性发光聚酰亚胺膜及其制备方法和应用 - Google Patents
一种柔性发光聚酰亚胺膜及其制备方法和应用 Download PDFInfo
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
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- RICKKZXCGCSLIU-UHFFFAOYSA-N 2-[2-[carboxymethyl-[[3-hydroxy-5-(hydroxymethyl)-2-methylpyridin-4-yl]methyl]amino]ethyl-[[3-hydroxy-5-(hydroxymethyl)-2-methylpyridin-4-yl]methyl]amino]acetic acid Chemical compound CC1=NC=C(CO)C(CN(CCN(CC(O)=O)CC=2C(=C(C)N=CC=2CO)O)CC(O)=O)=C1O RICKKZXCGCSLIU-UHFFFAOYSA-N 0.000 description 4
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- -1 4- (p-tolyl) -4H-1,2,4-triazole-3,5- Diyl Chemical group 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- JQFNNKKJVDIDNM-UHFFFAOYSA-N 4-[5-(4-aminophenyl)-4-(4-tritylphenyl)-1,2,4-triazol-3-yl]aniline Chemical compound Nc1ccc(cc1)-c1nnc(-c2ccc(N)cc2)n1-c1ccc(cc1)C(c1ccccc1)(c1ccccc1)c1ccccc1 JQFNNKKJVDIDNM-UHFFFAOYSA-N 0.000 description 1
- NJQGWNKJMSCDMV-UHFFFAOYSA-N 4-[5-(4-aminophenyl)-4-[4-[4-(2,2-diphenylethenyl)phenyl]phenyl]-1,2,4-triazol-3-yl]aniline Chemical compound C1=CC=C(C=C1)C(=CC2=CC=C(C=C2)C3=CC=C(C=C3)N4C(=NN=C4C5=CC=C(C=C5)N)C6=CC=C(C=C6)N)C7=CC=CC=C7 NJQGWNKJMSCDMV-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
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- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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Abstract
本发明公开了一种柔性发光聚酰亚胺膜及其制备方法和应用。本发明的聚酰亚胺材料采用具有含强吸电子结构1,2,4‑三氮唑的芳香二胺与各种二酐为原料,反应得到聚酰胺酸溶液后酰亚胺化和涂布制备得到。本发明的柔性聚酰亚胺膜不仅具有高的光致发光效率,而且具有高的玻璃化转变温度和热稳定性、优异的力学性能等,适用于制备光致发光产品和柔性电致发光器件中的发光层材料。
Description
技术领域
本发明涉及材料科学领域,特别是一类柔性发光聚酰亚胺膜及其制备方法和应用。
技术背景
聚酰亚胺是主链上含有酰亚胺环的一类高性能聚合物,具有高力学强度、耐高低温、耐化学腐蚀、良好的尺寸稳定性和介电性能等优点,在航天航空、微电子器件、液晶显示等领域具有广泛的应用。另一方面,随着显示技术的进步,有机发光二极管(OrganicLight-Emitting Diode,OLED)以其主动发光、全彩色显示、低功耗、低启动电压、高亮度、快速响应、宽视角、加工工艺简单及低成本等优点,成为近十年来有机光电领域的研究热点之一。相对于有机小分子发光材料,聚合物发光材料可通过旋涂、喷墨打印、浸渍等多种低成本技术大面积成膜,做成结构简单的柔性器件,并且发光聚合物一般具有大共轭的电子结构,可通过分子结构设计对其发光颜色进行调节。因此,在未来的柔性可印刷显示领域,基于聚合物发光材料的有机发光二极管(Polymer Light-Emitting Diode,PLED)将成为研究的重点。但是,聚合物发光材料的制备、纯化过程复杂,彩色化难且寿命短,这些都成为制约其在PLED领域应用的瓶颈。特别是PLED器件的制作过程中,这些有机材料会出现氧化和光降解等化学变化,同时由于其高温下尺寸不稳定及其易结晶等性质,严重影响器件的稳定性和寿命。因此,具有优异热稳定性能的聚酰亚胺材料可克服普通有机材料的上述缺点,从而成为下一代PLED发光材料的优秀候选对象。
为了提高聚酰亚胺的发光强度,提升聚酰亚胺的光致发光效率,一般采用在聚合物主链或侧链中引入有机共轭发色基团。如US 5677417、JP 2008297354等。但由于主链间、侧基间或主链与侧基间还存在较强的相互作用,电荷转移络合物的数量得不到减少,电荷转移效应仍较强,因此以此方法得到的聚酰亚胺材料的发光效率没有较大地提高;另外,过于庞大的发色基团的引入,一般在一定程度上降低聚酰亚胺的综合性能,如耐热性、玻璃化转变温度、尺寸稳定性及力学性能等,从而限制其进一步的应用。另一些提高聚酰亚胺发光效率的方法为采用脂环族单体合成半芳香族或非芳香族聚酰亚胺。如CN1371932、JP2005320393等。然而,由于这些材料芳香族发色团部分的基团过于平面化,较严重的基团堆叠作用仍然存在,导致聚酰亚胺的光致发光效率提升不大。
发明内容
本发明的目的是提供一种柔性发光聚酰亚胺膜,其具有高的光致发光效率,以及高的玻璃化转变温度、热稳定性和优异的力学性能。
本发明的另一目的在于提供上述柔性发光聚酰亚胺膜的制备方法,其制备工艺简单且多样,条件要求低,适于工业生产。
本发明还有一个目的在于提供上述柔性发光聚酰亚胺膜的应用,其用途广泛,适用于制备光致发光产品、柔性电致发光器件和各种光学设备中的发光层材料。
本发明的目的是这样实现的:一种柔性发光聚酰亚胺膜,其特征在于分子结构通式为:
其中:n和m表示聚合度,n/m=1/99~100/0,X和W为四价的芳香族烃基,Z为二价的芳香族烃基,Y为以下结构通式所示:
其中,Ar为芳香族取代基。
所述的Ar优选自下列结构式中的任何一种:
所述的X和W相同或不同,选自以下四价的芳香族烃基结构通式中的一种或一种以上:
所述的Z为二价的芳香族烃基,优选自以下结构通式中的任何一种:
上述柔性发光聚酰亚胺膜的制备方法,包括以下步骤:在氮气或氩气气氛中,将含Y或者Y和Z结构的二胺与含X或者X和W结构的二酐按摩尔比为1:(0.9~1.1)溶在非质子极性有机溶剂中,在-10~40℃搅拌反应0.5~72小时,得到聚酰亚胺溶液,然后进行脱水酰亚胺化和涂布得到聚酰亚胺膜。
本发明所提供的柔性发光聚酰亚胺膜,不仅具有高的光致发光效率,且具有高的玻璃化转变温度和热稳定性、优异的力学性能,同时其制备工艺简单且多样,条件要求低,因而适于工业生产。本发明所公开的聚酰亚胺材料适用于制备光致发光产品、柔性电致发光器件和各种光学设备中的发光层材料。
附图说明
图1是本发明实施例中四种聚酰亚胺膜的红外光谱图。从图中可以看到,在1717cm-1和1777cm-1处出现了酰亚胺环上羰基的对称和非对称伸缩振动吸收峰。
具体实施方式
本发明是一种柔性发光聚酰亚胺膜,适用于制备光致发光产品、柔性电致发光器件和各种光学设备中的发光层材料。其分子结构通式为:
其中:n和m表示聚合度,n/m=1/99~100/0,X和W为四价的芳香族烃基,Z为二价的芳香族烃基,Y为以下结构通式所示基团:
其中,Ar为芳香族取代基,优选自下列结构式中的任何一种:
X和W相同或不同,选自以下四价的芳香族烃基结构通式中的一种或一种以上:
Z为二价的芳香族烃基,优选自以下结构通式中的任何一种:
制备时,在氮气或氩气气氛中,将含Y或者Y和Z结构的二胺与含X或者X和W结构的二酐按摩尔比为1:(0.9~1.1)溶在非质子极性有机溶剂中,在-10~40℃搅拌反应0.5~72小时,得到聚酰亚胺溶液,然后进行脱水酰亚胺化和涂布得到聚酰亚胺膜。优选的,含Y或者Y和Z结构的二胺与含X或者X和W结构的二酐总质量占反应物料总质量的2~50%。所述的非质子极性有机溶剂优选N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、二甲基砜、环丁砜、1,4-二氧六环、间甲酚、四氢呋喃中的一种或两种以上的混合物。
聚酰胺酸溶液脱水酰亚胺化得到聚酰亚胺的方法可以为热酰亚胺化或化学酰亚胺化。热酰亚胺化的步骤为:将聚酰胺酸溶液刮涂在洁净的玻璃、铜、铝、铁、铅或硅材质基板上,再将基板置于烘箱中,程序升温进行热酰亚胺化,优选升温程序为:于室温升温至50~180℃后恒温,整个过程为10~240分钟;然后再升温至180~250℃后恒温,整个过程为10~240分钟;最后升温至250~380℃后恒温,整个过程10~360分钟;冷却后可得到聚酰亚胺膜。化学酰亚胺化法的步骤为:在聚酰胺酸溶液中加入脱水剂,然后升温搅拌,并在30~200℃的温度下搅拌0.5~72小时,冷却至室温后倒入甲醇、乙醇或丙酮中得到沉淀,过滤干燥后得到聚酰亚胺粉体;将聚酰亚胺粉体溶于N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、间甲酚或四氢呋喃中,待其完全溶解后,将聚酰亚胺溶液刮涂在洁净的玻璃、铜、铝、铁、铅或硅材质基板上,再将基板置于烘箱中,加热至70~300℃干燥除去溶剂,冷却后可得到聚酰亚胺膜。上述脱水剂优选吡啶/乙酸酐、三乙胺/乙酸酐或乙酸钠/乙酸酐。
下面给出实例以对本发明作更详细的说明,有必要指出的是以下实施例不能解释为对发明保护范围的限制。该领域的技术熟练人员根据上述发明内容对本发明作出的一些非本质的改进和调整,仍应属于本发明的保护范围。
实施例1
室温下,将3.4142g(0.01mol)4,4'-(4-(p-tolyl)-4H-1,2,4-triazole-3,5-diyl)dianiline和43ml的N,N-二甲基甲酰胺加入至100ml三口烧瓶中,通入氩气。待搅拌完全溶解后,加入3.1022g(0.01mol)3,3',4,4'-二苯醚四甲酸二酐,室温下继续搅拌反应8小时,获得均相、透明、粘稠的聚酰胺酸溶液。将所得的聚酰胺酸溶液刮涂在洁净的玻璃板上,再将玻璃板置于真空烘箱中,于真空下按升温程序升温:室温升温至100℃后恒温,整个过程为60分钟;然后再升温至200℃后恒温,整个过程为60分钟;最后升温至300℃后恒温,整个过程60分钟;冷却后可得到聚酰亚胺膜PI1。该柔性聚酰亚胺膜厚度约为35μm,绝对荧光量子产率为7%,其荧光最强峰对应的波长为540nm,5%的热失重温度为467℃,玻璃化转变温度为321℃(by DMA)。聚酰亚胺膜的红外光谱图如图1的PI1所示。
本实施例中的柔性发光聚酰亚胺膜的分子结构式如下:
实施例2
室温下,将5.8172g(0.01mol)
4,4'-(4-(4'-(2,2-diphenylvinyl)-[1,1'-biphenyl]-4-yl)-4H-1,2,4-triazole-3,5-diyl)dianiline和68ml的N,N-二甲基甲酰胺加入至100ml三口烧瓶中,通入氩气。待搅拌完全溶解后,加入4.4424g(0.01mol)4,4'-六氟异丙基邻苯二甲酸酐,室温下继续搅拌反应12小时,获得均相、透明、粘稠的聚酰胺酸溶液。在所得的聚酰胺酸溶液中加入含有5ml乙酸酐和2.5ml吡啶的混合溶液,室温下搅拌24小时后,将聚酰亚胺溶液缓慢倾入1L甲醇中,得到纤维状或球状沉淀,过滤出沉淀后置于烘箱中烘干。再将所得固体溶解于N,N-二甲基甲酰胺中,刮涂在洁净的玻璃板上,并置于真空烘箱中,升温至100℃干燥2小时,再升温至200℃干燥2小时,冷却后得到聚酰亚胺膜PI2。该柔性聚酰亚胺膜厚度约为30μm,绝对荧光量子产率为1.3%,其荧光最强峰对应的波长为530nm,5%的热失重温度为507℃,玻璃化转变温度(byDSC)为281℃。聚酰亚胺膜的红外光谱图如图1中的PI2所示。
本实施例中的柔性发光聚酰亚胺的分子结构式如下:
实施例3
室温下,将5.6971g(0.01mol)
4,4'-(4-(4-tritylphenyl)-4H-1,2,4-triazole-3,5-diyl)dianiline和58ml的N,N-二甲基甲酰胺加入至100ml三口烧瓶中,通入氩气。待搅拌完全溶解后,加入3.1022g(0.01mol)3,3',4,4'-二苯醚四甲酸二酐,室温下继续搅拌反应8小时,获得均相、透明、粘稠的聚酰胺酸溶液。按实施例1中的方法将聚酰胺酸进行热酰亚胺化,得到聚酰亚胺膜PI3。该聚酰亚胺膜厚度约为35μm,绝对荧光量子产率为10%,其荧光最强峰对应的波长为536nm,5%的热失重温度为491℃,玻璃化转变温度为310℃(by DMA)。聚酰亚胺膜的红外光谱图如图1的PI3所示。
本实施例中的柔性发光聚酰亚胺的分子结构式如下:
实施例4
0℃下,将5.8172g(0.01mol)
4,4'-(4-(4'-(2,2-diphenylvinyl)-[1,1'-biphenyl]-4-yl)-4H-1,2,4-triazole-3,5-diyl)dianiline和59ml的N,N-二甲基甲酰胺加入至100ml三口烧瓶中,通入氩气。待搅拌完全溶解后,加入3.1022g(0.01mol)3,3',4,4'-二苯醚四甲酸二酐,室温下继续搅拌反应8小时,获得均相、透明、粘稠的聚酰胺酸溶液。按实施例1中的方法将聚酰胺酸进行热酰亚胺化,得到聚酰亚胺膜。该聚酰亚胺膜厚度约为30μm,绝对荧光量子产率为12%,其荧光最强峰对应的波长为524nm,5%的热失重温度为484℃,玻璃化转变温度为303℃(by DMA)。聚酰亚胺膜的红外光谱图如图1的PI4所示。
本实施例中的柔性发光聚酰亚胺的分子结构式如下:
实施例5
0℃下,将5.8172g(0.01mol)
4,4'-(4-(4'-(2,2-diphenylvinyl)-[1,1'-biphenyl]-4-yl)-4H-1,2,4-triazole-3,5-diyl)dianiline、2.1037g(0.01mol)4,4'-二氨基二环己基甲烷和120ml的N,N-二甲基甲酰胺加入至500ml三口烧瓶中,通入氩气。待搅拌完全溶解后,加入6.2044g(0.02mol)3,3',4,4'-二苯醚四甲酸二酐,室温下继续搅拌反应8小时,获得均相、透明、粘稠的聚酰胺酸溶液。按实施例1中的方法将聚酰胺酸进行热酰亚胺化,得到聚酰亚胺膜。
本实施例中的柔性发光聚酰亚胺的分子结构式如下(其中n/m=50/50):
Claims (8)
1.一种柔性发光聚酰亚胺膜,其分子结构通式如下:
其中:n和m表示聚合度,n/m=1/99~100/0,X和W为四价的芳香族烃基,Z为二价的芳香族烃基,Y为以下结构通式所示:
其中,Ar为芳香族取代基;
所述的Ar选自下列结构式中的任何一种:
所述的X和W相同或不同,选自以下四价的芳香族烃基结构通式中的一种或一种以上:
2.根据权利要求1所述的一种柔性发光聚酰亚胺膜,其特征在于:所述的Z为二价的芳香族烃基,选自以下结构通式中的任何一种:
3.权利要求1或2所述的一种柔性发光聚酰亚胺膜的制备方法,其特征在于:在氮气或氩气气氛中,将含Y或者Y和Z结构的二胺与含X或X和W结构的二酐按摩尔比为1:(0.9~1.1)溶在非质子极性有机溶剂中,在-10~40℃搅拌反应0.5~72小时,得到聚酰亚胺溶液,然后进行脱水酰亚胺化和涂布得到聚酰亚胺膜。
4.根据权利要求3所述的一种柔性发光聚酰亚胺膜的制备方法,其特征在于:含Y或者Y和Z结构的二胺与含X或者X和W结构的二酐总质量占反应物料总质量的2~50%。
5.根据权利要求3所述的一种柔性发光聚酰亚胺膜的制备方法,其特征在于:所述非质子极性有机溶剂选自N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、二甲基砜、环丁砜、1,4-二氧六环、间甲酚、四氢呋喃中的一种或两种以上的混合物。
6.根据权利要求3所述的一种柔性发光聚酰亚胺膜的制备方法,其特征在于:所述的酰亚胺化通过热酰亚胺化法或化学酰亚胺化法进行。
7.根据权利要求6所述的一种柔性发光聚酰亚胺膜的制备方法,其特征在于:所述热酰亚胺化法的步骤为:将聚酰胺酸溶液刮涂在洁净的玻璃、铜、铝、铁、铅或硅材质基板上,再将基板置于烘箱中,程序升温进行热酰亚胺化,升温程序为:于室温升温至50~180℃后恒温,整个过程为10~240分钟;然后再升温至180~250℃后恒温,整个过程为10~240分钟;最后升温至250~380℃后恒温,整个过程10~360分钟;冷却后可得到聚酰亚胺膜;所述化学酰亚胺化法的步骤为:在聚酰胺酸溶液中加入脱水剂,然后升温搅拌,并在30~200℃的温度下搅拌0.5~72小时,冷却至室温后倒入甲醇、乙醇或丙酮中得到沉淀,过滤干燥后得到聚酰亚胺粉体;将聚酰亚胺粉体溶于N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、间甲酚或四氢呋喃中,待其完全溶解后,将聚酰亚胺溶液刮涂在洁净的玻璃、铜、铝、铁、铅或硅材质基板上,再将基板置于烘箱中,加热至70~300℃干燥除去溶剂,冷却后可得到聚酰亚胺膜。
8.权利要求1或2所述的一种柔性发光聚酰亚胺膜应用于制备光致发光产品或柔性电致发光器件中的发光层材料。
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