CN110093034A - 改性的聚酰胺酸及其制备方法、复合膜层的制备方法 - Google Patents

改性的聚酰胺酸及其制备方法、复合膜层的制备方法 Download PDF

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CN110093034A
CN110093034A CN201910445906.7A CN201910445906A CN110093034A CN 110093034 A CN110093034 A CN 110093034A CN 201910445906 A CN201910445906 A CN 201910445906A CN 110093034 A CN110093034 A CN 110093034A
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polyamic acid
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汪亚民
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Wuhan China Star Optoelectronics Semiconductor Display Technology Co Ltd
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Abstract

本发明提供了一种改性的聚酰胺酸及其制备方法、复合膜层的制备方法。所述改性的聚酰胺酸包括聚酰胺酸和聚偏氟乙烯。所述改性的聚酰胺酸通过引入具有良好的热稳定性、高的介电常数，和优良的压电和铁电性能的聚偏氟乙烯，从而提高聚酰胺酸的介电常数，增强其结构可调节性。

Description

改性的聚酰胺酸及其制备方法、复合膜层的制备方法
技术领域
本发明涉及显示面板衬底材料领域，特别是一种改性的聚酰胺酸及其制备方法、复合膜层的制备方法。
背景技术
通常，聚酰亚胺(Polyimide，PI)薄膜是由聚酰亚胺制成的，而聚酰亚胺是指一种高耐热树脂，所述树脂由芳香族二酐和芳香族二胺或芳香族二异氰酸酯经溶液聚合制成聚酰胺酸衍生物后，在高温下经环闭合反应及脱水从而酰亚胺化而制成。
在这种聚酰亚胺的制备中可以使用的芳香族二酐可以包括均苯四甲酸二酐(PMDA)或联苯四甲酸二酐(BPDA)等，而可以使用的芳香族二胺可以包括二氨基二苯醚(ODA)、对苯二胺(p-PDA)、间苯二胺(m-PDA)、二氨基二苯基甲烷(Methylenedianiline，MDA)、二氨基苯基六氟丙烷(HFDA)等。
聚酰亚胺是指主链上含有酰亚胺环的一类聚合物，其是一种不溶不熔的超高耐热性树脂，在耐热氧化性、耐热性、抗辐射性、低温特性、耐化学性等方面都表现优良，因此被广泛应用于包括汽车、航空、宇宙飞船等的尖端耐热材料，以及如绝缘涂层、绝缘膜、半导体、TFT-LCD的电极保护膜等电子材料的多种领域。
近年来关于其在柔性可印刷线路板、液晶显示及光伏领域也获得了极大的深入研究和广泛应用。而在柔性印刷线路板、液晶显示及光伏领域的应用也对聚酰亚胺薄膜的理化性能提出了新的更高的要求：(1)极低的介电常数，以避免介电损失所带来的功耗。(2)极低的热膨胀系数(CET)，以避免在温度改变时聚酰亚胺薄膜因膨胀或收缩与基底剥离。(3)极低的吸湿性，以避免吸湿对电学器件的电学性能产生不良影响。
常规的聚酰亚胺材料常常具有较密集的刚性结构以及很强的分子间相互作用，而纯PI目前已经很少用于生产，因为各方面的性能很难达到综合性能的标准，诸如，纯的PI的介电常数较低(1.7-2.0之间)，这样会限制于在某些领域应用，比如在存储和显示等领域需求的PI具有高介电常数、低介质损耗材料，从而实现高存储能力，优良的柔性等，同时期因为结构可调节性很强，目前制备增强复合型聚酰亚胺成为应用领域越来越关注的事。
发明内容
本发明的目的是提供一种改性的聚酰胺酸及其制备方法、复合膜层的制备方法，以解决现有技术中，聚酰亚胺材料介电常数过低、介质损耗过高，由所述聚酰亚胺材料所制备的复膜层柔性不佳等问题。
为实现上述目的，本发明提供一种改性的聚酰胺酸，其组分按质量分数包括：聚酰胺酸40％-95％，聚偏氟乙烯5％-60％。
本发明中还提供一种改性的聚酰胺酸的制备方法，包括：提供聚偏氟乙烯，将所述聚偏氟乙烯和所述聚酰胺酸混合得到改性的聚酰胺酸。其中，在改性的聚酰胺酸中，所述聚酰胺酸质量分数为40％-95％，所述聚偏氟乙烯质量分数为5％-60％。
进一步地，在所述提供聚偏氟乙烯步骤前还包括：
将第一化合物、第二化合物分别使用溶解剂溶解后，置于反应容器中混合并充分反应得到反应液。其中，所述第一化合物中具有二胺基团，所述第二化合物中具有二酐基团。
将所述反应液在真空环境中进行抽滤，得到聚酰胺酸。
进一步地，所述第一化合物和所述第二化合物的摩尔比为1:0.7-1。
进一步地，所述第一化合物由苯胺和苯甲酸缩合而成。
进一步地，所述第二化合物的分子结构式中包括以下结构中的一种：
进一步地，所述溶解剂为N,N－二甲基己酰胺与N-甲基吡咯烷酮的混合物。其中，所述N,N－二甲基己酰胺与所述N-甲基吡咯烷酮体积比为1：0.5-5。
进一步地，所述将偏氟乙烯和所述聚酰胺酸混合步骤中包括：将所述聚偏氟乙烯使用溶解剂溶解后与所述聚酰胺酸通过机械共混法充分混合，得到所述改性的聚酰胺酸。
本发明中还提供一种复合膜层的制备方法，包括：
提供如上所述的改性的聚酰胺酸。
将所述改性的聚酰胺酸涂布后进行干燥交联固化，得到所述复合膜层。
本发明中还提供一种显示装置，包括衬底，所述衬底所用材料为上所述的改性的聚酰胺酸。
本发明的优点是：本发明的一种改性的聚酰胺酸通过引入具有良好的热稳定性、高的介电常数，和优良的压电和铁电性能的聚偏氟乙烯，从而提高聚酰胺酸的介电常数，增强其结构可调节性。同时，所述改性的聚酰胺酸的制备方法的工艺步骤简单，易操作。并且，由所述改性的聚酰亚胺所制得的复合膜层具有高存储能力和优良的柔性。
附图说明
为了更清楚地说明本发明实施例中的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本发明实施例中改性的聚酰胺酸制备方法的制备流程图；
图2为本发明实施例中复合膜层制备方法的制备流程图；
图3为本发明实施例中不同的质量分数聚偏氟乙烯的复合膜层的介电损耗与随频率的变化关系示意图。
具体实施方式
以下结合说明书附图详细说明本发明的优选实施例，以向本领域中的技术人员完整介绍本发明的技术内容，以举例证明本发明可以实施，使得本发明公开的技术内容更加清楚，使得本领域的技术人员更容易理解如何实施本发明。然而本发明可以通过许多不同形式的实施例来得以体现，本发明的保护范围并非仅限于文中提到的实施例，下文实施例的说明并非用来限制本发明的范围。
本发明的说明书和权利要求书以及上述附图中的术语“第一”、“第二”、“第三”等(如果存在)是用于区别类似的对象，而不必用于描述特定的顺序或先后次序。应当理解，这样描述的对象在适当情况下可以互换。
本发明说明书中使用的术语仅用来描述特定实施方式，而并不意图显示本发明的概念。除非上下文中有明确不同的意义，否则，以单数形式使用的表达涵盖复数形式的表达。在本发明说明书中，应理解，诸如“包括”、“具有”以及“含有”等术语意图说明存在本发明说明书中揭示的特征、数字、步骤、动作或其组合的可能性，而并不意图排除可存在或可添加一个或多个其他特征、数字、步骤、动作或其组合的可能性。
上下文有明确的相反提示，否则本文中所述的所有方法的步骤都可以按任何适当次序加以执行。本发明的改变并不限于描述的步骤顺序。除非另外主张，否则使用本文中所提供的任何以及所有实例或示例性语言(例如，“例如”)都仅仅为了更好地说明本发明的概念，而并非对本发明的概念的范围加以限制。在不脱离精神和范围的情况下，所属领域的技术人员将易于明白多种修改和适应。
本发明实施例中提供一种改性的聚酰胺酸，所述聚酰亚胺中包括10％的聚酰胺酸以及90％的聚偏氟乙烯。其中，所述聚偏氟乙烯的结构式为：
本发明实施例还提供一种改性的聚酰胺酸的制备方法，其制备流程如图1所示，具体制备步骤如下：
步骤S11)合成聚酰胺酸：称取第一化合物和溶解剂加入到反应容器中，并将所述反应容器转移至机械揽拌器上，启动机械揽拌器，进行搅拌。然后，称取第二化合物同样溶解在相同的溶解剂中，并逐滴加至所述反应容器中。所述第一化合物和所述第二化合物混合后，其混合溶液在室温下揽拌24小时-96小时，使其充分溶解并反应，得到反应液，所述反应液中具有所述聚酰胺酸。
其中，所述第一化合物中具有二胺基团，所述第二化合物中具有二酐基团，所述第一化合物和所述第二化合的摩尔比为1:0.7-1。并且，所述第二化合物的分子结构式中包括以下结构中的一种：
在本发明实施例中，所述第一化合物是由活性的苯胺和封端的苯甲酸缩合而成，其分子结构式为：这类化合物的共同特点在于使用苯胺形成聚合苯胺，同时使用苯甲酸作为封端试剂可以制备出以苯胺封端的二胺基团。因为苯胺具有优良的电化学可逆性，所以所述第一化合物中的二胺基团具有电活性。
在本发明实施例中，所述第二化合物为1,2,4,5-环己烷四羧酸二酐，其分子结构式为：
步骤S11中的制备流程式如式1所示：
步骤S12)抽滤所述反应液：搅拌结束后撤去机械揽拌器，将所述反应容器置于真空环境中进行抽滤，再将通过抽滤得到的溶液用真空泵抽气1小时，除去所述反应液中的气泡。然后，将抽气过后的反应液置于室温下静置2小时-4小时，使所述反应液中的气泡进一步减少，直到中无肉眼可见的气泡。最后所得到的溶液中具有所需的聚酰胺酸。
步骤S13)提供聚偏氟乙烯：称取聚偏氟乙烯，然后使用溶解剂进行溶解，溶解后的溶液浓度为1mmol/L。聚偏氟乙烯是一种具有良好的热稳定性，能够进行诸多羧酸和醇类聚合物的改性，因为其具有较高的介电常数，和优良的压电和铁电性能，本发明实施例中引入所述聚偏氟乙烯的目的在于引入电负性最强的F原子，从而提高聚酰胺酸的介电常数。
步骤S14)混合聚酰胺酸和聚偏氟乙烯：首先，将溶解后的聚偏氟乙烯溶液和步骤S12中得到的聚酰胺酸溶液分别按照质量比例称取对应质量，其中，所述聚酰胺酸质量分数为40％-95％，所述聚偏氟乙烯质量分数为5％-60％。然后，将所述聚偏氟乙烯溶液加入到所述聚酰胺酸溶液中进行机械搅拌5小时-9小时，得到聚酰胺酸/聚偏氟乙烯混合溶液，所述聚酰胺酸/聚偏氟乙烯混合溶液中具有改性的聚酰胺酸。
在本发明实施例中，所使用到的溶解剂为N,N－二甲基己酰胺与N-甲基吡咯烷酮的混合物。其中，所述N,N－二甲基己酰胺与所述N-甲基吡咯烷酮体积比为1：0.5-5。
在本发明实施例中还提供一种复合膜层的制备方法，所述复合膜层制备方法所制得的复合膜层为聚酰亚胺/聚偏氟乙烯复合膜层，其制备流程如图2所示，其制备步骤为：
步骤S21)涂布混合溶液：提供一基板，并将从所述改性的聚酰胺酸的制备方法中制得的具有改性的聚酰胺酸的聚酰胺酸/聚偏氟乙烯混合溶液均匀的涂布在所述基板上。
步骤S22)烘干混合溶液：将涂布有聚酰胺酸/聚偏氟乙烯混合溶液的基板放入使用柔性膜厚烘机中，在温度1℃-500℃的环境内进行烘烤，将所述基板上聚酰胺酸/聚偏氟乙烯混合溶液干燥交联固化，得到所述复合膜层。
本发明实施例中还提供一种显示装置，所述显示装置中具有衬底，所述衬底所用的材料为本发明实施例中所提供的改性的聚酰胺酸，所述衬底为本发明实施例中提供的复合膜层制备方法中所制得的聚酰亚胺/聚偏氟乙烯复合膜层。
如图3所示，在本发明实施例中，将聚偏氟乙烯质量分数为10％、30％和50％的聚酰亚胺/聚偏氟乙烯复合膜层的介电常数进行表征，得到在频率为50Hz的情况下，10％、30％及50％的聚偏氟乙烯含量的聚酰亚胺/聚偏氟乙烯复合膜层的介电常数分别为4.5、5.3和4.6，是普通纯聚酰亚胺的介电常数的2-3倍，证明加入的聚偏氟乙烯能够显著提高材料的介电性能，同时说明了聚酰亚胺与聚偏氟乙烯之间形成了良好的C-F-C键，但当聚偏氟乙烯的含量超过30％，多余的聚偏氟乙烯会在聚酰亚胺的表面形成聚集，从而抑制了聚酰亚胺的极化作用，进而降低了介电常数。
在本发明实施例中，还对所述聚酰亚胺/聚偏氟乙烯复合膜层测试了拉伸性能，可以得出其最大伸长率能达到20％，同时最大拉伸力可以达到412MPa，其拥有优良的柔性，耐弯折。
本发明实施例中所提供的改性的聚酰胺酸通过引入具有良好的热稳定性、高的介电常数，和优良的压电和铁电性能的聚偏氟乙烯，从而提高聚酰胺酸的介电常数，增强其结构可调节性。同时，所述改性的聚酰胺酸的制备方法的工艺步骤简单，易操作。并且，由所述改性的聚酰亚胺所制得的复合膜层具有高存储能力和优良的柔性。
虽然在本文中参照了特定的实施方式来描述本发明，但是应该理解的是，这些实施例仅仅是本发明的原理和应用的示例。因此应该理解的是，可以对示例性的实施例进行许多修改，并且可以设计出其他的布置，只要不偏离所附权利要求所限定的本发明的精神和范围。应该理解的是，可以通过不同于原始权利要求所描述的方式来结合不同的从属权利要求和本文中所述的特征。还可以理解的是，结合单独实施例所描述的特征可以使用在其他所述实施例中。

Claims (10)

1.一种改性的聚酰胺酸，其特征在于，其组分按质量分数包括：
聚酰胺酸 40％-95％；
聚偏氟乙烯 5％-60％。
2.一种改性的聚酰胺酸的制备方法，其特征在于，包括：
提供聚偏氟乙烯，将所述聚偏氟乙烯和所述聚酰胺酸混合得到改性的聚酰胺酸；
其中，在改性的聚酰胺酸中，所述聚酰胺酸质量分数为40％-95％；所述聚偏氟乙烯质量分数为5％-60％。
3.如权利要求2所述的改性的聚酰胺酸的制备方法，其特征在于，在所述提供聚偏氟乙烯步骤前还包括：
将第一化合物、第二化合物分别使用溶解剂溶解后，置于反应容器中混合并充分反应得到反应液，所述第一化合物中具有二胺基团；所述第二化合物中具有二酐基团；
将所述反应液在真空环境中进行抽滤，得到聚酰胺酸。
4.如权利要求3所述的改性的聚酰胺酸的制备方法，其特征在于，所述第一化合物和所述第二化合物的摩尔比为1:0.7-1。
5.如权利要求3所述的改性的聚酰胺酸的制备方法，其特征在于，所述第一化合物由苯胺和苯甲酸缩合而成。
6.如权利要求3所述的改性的极限氨酸的制备方法，其特征在于，所述第二化合物的分子结构式中包括以下结构中的一种：
7.如权利要求3所述的改性的聚酰胺酸的制备方法，其特征在于，所述溶解剂为N,N－二甲基己酰胺与N-甲基吡咯烷酮的混合物；其中所述N,N－二甲基己酰胺与所述N-甲基吡咯烷酮体积比为1：0.5-5。
8.如权利要求2所述的改性的聚酰胺酸的制备方法，其特征在于，所述将偏氟乙烯和所述聚酰胺酸混合步骤中包括：将所述聚偏氟乙烯使用溶解剂溶解后与所述聚酰胺酸通过机械共混法充分混合，得到所述改性的聚酰胺酸。
9.一种复合膜层的制备方法，其特征在于，包括：
提供如权利要求1所述的改性的聚酰胺酸；
将所述改性的聚酰胺酸涂布后进行干燥交联固化，得到所述复合膜层。
10.一种显示装置，其特征在于，包括衬底，所述衬底所用材料为权利要求1所述的改性的聚酰胺酸。
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