CN110330645A - 一种含苯并咪唑结构可溶性聚酰亚胺及其制备方法 - Google Patents
一种含苯并咪唑结构可溶性聚酰亚胺及其制备方法 Download PDFInfo
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- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
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Abstract
本发明公开了一种含苯并咪唑结构的可溶性聚酰亚胺及其制备方法,所述聚酰亚胺由含苯并咪唑结构二胺单体和不同芳香二酐单体,在N N‑二甲基甲酰胺中,以吡啶为催化剂,通过一步法缩聚反应制备得到。所得聚酰亚胺不仅展现出良好的溶解性,同时还具备优异的热稳定性及机械性能。
Description
技术领域
本发明涉及聚酰亚胺技术领域,具体涉及一类含苯并咪唑结构可溶性聚酰亚胺及其制备方法。
背景技术
芳香族聚酰亚胺由于具有良好的热稳定性、力学性能和电性能,被广泛的应用于复合材料、涂料和微电子材料等领域。此外,由于聚酰亚胺具有优异的抗化学腐蚀性和黏附性,已被作为液晶分子的定向剂广泛应用于液晶显示器(1iquid crystal display,LCD)领域。但是常规的聚酰亚胺在许多有机溶剂中不溶解,且具有较高的熔融温度,因此在成型加工方面限制了它的许多应用。大多数聚酰亚胺的制备都是通过聚酰胺酸前驱体在热亚胺化或化学亚胺化的作用下完成。而热亚胺化过程中,加热温度通常在250℃~300℃之间,且伴随着小分子水的放出,当将其用于微电子行业时,容易引起基板材料的破坏.同时,聚酰胺酸的储存稳定性也较差.难以长期保存,且后处理较麻烦。因此,开发能用常规方法加工,且能保持高耐热性和良好机械性能的聚酰亚胺成为具有挑战性的研究课题。
为了解决这些问题,可溶性聚酰亚胺的开发成为近几年研究的热点。许多研究者通过在聚酰亚胺主链中引入柔性基团,脂肪结构,不对称取代基或是大的侧基以及共聚的方法以改善其溶解性能。但是这些方法在提高聚酰亚胺的同时也会导致聚酰亚胺热性能及力学性能的下降。
基于上述背景,本发明采用一种含苯并咪唑结构二胺单体与各种商品化芳香二酐单体制备了一系列含大侧基的新型聚酰亚胺树脂,该类聚酰亚胺树脂不仅保持了传统聚酰亚胺良好的耐热性能(Tg>280℃),同时还具备优异的溶解性,可以在较低的温度(室温~80℃)下加工成型。
发明内容
本发明提供一种含苯并咪唑结构可溶性聚酰亚胺及其制备方法,旨在使得保持其特点不变的前提下,可以在较低的温度(室温~80℃)下加工成型。
为实现上述目的,本发明提供如下技术方案:一种可溶性聚酰亚胺,其特征在于,所述可溶性聚酰亚胺包含苯并咪唑结构同时具有如下重复结构单元:
其中:10<n<1000。
优选的,所述的重复结构单元中Ar选自如下化学结构单元中的一种或几种:
一种可溶性聚酰亚胺的制备方法,其特征在于,其具体合成方法如下:在N N-二甲基甲酰胺中,以吡啶为催化剂,由含苯并咪唑结构二胺和芳香二酐通过一步法缩聚反应生成所述的可溶性聚酰亚胺。
优选的,所述2含苯并咪唑结构二胺和芳香二酐的摩尔比为1:0.95~1.05。
优选的,其特征在于,具体步骤如下:
(1)将N N-二甲基甲酰胺溶、吡啶、含苯并咪唑结构二胺和芳香二酐加入反应器中,在室温和氮气保护下,搅拌反应得到透明聚酰胺酸溶液;
(2)将步骤(1)所得聚酰胺酸溶液升温至80℃~120℃反应12~24h,得到可溶性聚酰亚胺溶液;
(3)将步骤(2)所得聚酰亚胺溶液冷却至室温后,倒入一定量的沉淀剂中,沉淀出聚酰亚胺,然后分离干燥。
优选的,其特征在于,所述的含苯并咪唑结构二胺单体为如下结构式所示:
优选的,所述的芳香二酐选自4,4’-(六氟异亚丙基)二酞酸酐、3,3,4,4-二苯基砜四羧酸二酸酐、3,3’,4,4’–联苯四羧酸二酐、3,3’,4,4’-二苯醚四羧酸二酐、双酚A型二醚二酐中的一种。
优选的,步骤(1)中聚酰胺酸溶液的固含量为10wt%~20wt%。
优选的,步骤(2)中,聚酰胺酸溶液升温至80℃~120℃的过程为一步升温或程序升温反与现有技术相比,本发明的特点在于:采用三乙酰丙酮铝为成孔剂,三乙酰丙酮铝在180℃以上时会升华,而聚酰胺酸热酰亚胺化的温度远大于180℃,因此在聚酰胺酸热酰亚胺化转变为聚酰亚胺的过程中,三乙酰丙酮铝就会升华,在聚酰亚胺基体中留下孔洞。和传统的成孔方法相比,本技术不需要额外的成孔步骤,简化工艺,降低成本,对环境无污染。
附图说明
图1为发明化学结构图;
具体实施方式
以下对本发明的优选实施例进行说明,应当理解,此处所描述的优选实施例仅用于说明和解释本发明,并不用于限定本发明。
实施例1(PI-1的合成):
本实施例的PI-1的制备原理和过程如下:
在氮气保护下,将224.3mg(1.0mmol)含苯并咪唑结构二胺单体加入100ml三口圆底烧瓶中,然后依次加入9mLN,N-二甲基甲酰胺和444.2mg(1.0mmol)4,4’-(六氟异亚丙基)二酞酸酐,滴入两滴吡啶,于常温下搅拌反应12h,生成聚酰胺酸溶液,再升温至120℃反应15h。反应液冷却至室温后,加入20mL氯仿稀释,再缓慢倾倒入300ml快速搅拌的甲醇中,析出白色纤维状固体。经抽滤并在150℃真空干燥24h得到PI-1树脂。在70℃下,将一定量PI-1树脂溶于N N-二甲基甲酰胺中(固含量为6wt%),然后在洁净的玻璃片(3×6cm2)上浇铸成膜。最后在150℃下真空干燥12h,可得淡黄色PI-1薄膜。
实施例2(PI-2的合成):
在氮气保护下,将224.3mg(1.0mmol)含苯并咪唑结构二胺单体加入100ml三口圆底烧瓶中,然后依次加入10mlN,N-二甲基甲酰胺和358.3mg(1.0mmol)3,3,4,4-二苯基砜四羧酸二酸酐,滴入三滴吡啶,于常温下搅拌反应12h,生成聚酰胺酸溶液,再升温至120℃反应15h。反应液冷却至室温后,加入20ml氯仿稀释,再缓慢倾倒入300ml快速搅拌的甲醇中,析出白色纤维状固体。经抽滤并在150℃真空干燥24h得到PI-2树脂。在70℃下,将一定量PI-2树脂溶于N N-二甲基甲酰胺中(固含量为6wt%),然后在洁净的玻璃片(3×6cm2)上浇铸成膜。最后在150℃下真空干燥12h,可得淡黄色PI-2薄膜。
实施例三(PI-3的合成):
在氮气保护下,将224.3mg(1.0mmol)含苯并咪唑结构二胺单体加入100ml三口圆底烧瓶中,然后依次加入12mlN,N-二甲基甲酰胺和294.2mg(1.0mmol)3,3’,4,4’–联苯四羧酸二酐,滴入四滴吡啶,于常温下搅拌反应12h,生成聚酰胺酸溶液,再升温至140℃反应20h。反应液冷却至室温后,加入20ml氯仿稀释,再缓慢倾倒入300ml快速搅拌的甲醇中,析出白色纤维状固体。经抽滤并在150℃真空干燥24h得到PI-3树脂。在70℃下,将一定量PI-3树脂溶于N N-二甲基甲酰胺中(固含量为6wt%),然后在洁净的玻璃片(3×6cm2)上浇铸成膜。最后在150℃下真空干燥12h,可得棕色PI-3薄膜。
实施例四(PI-4的合成):
在氮气保护下,将224.3mg(1.0mmol)含苯并咪唑结构二胺单体加入100ml三口圆底烧瓶中,然后依次加入10mlN,N-二甲基甲酰胺和310.2mg(1.0mmol)3,3’,4,4’-二苯醚四羧酸二酐,滴入四滴吡啶,于常温下搅拌反应12h,生成聚酰胺酸溶液,再升温至110℃反应18h。反应液冷却至室温后,加入20ml氯仿稀释,再缓慢倾倒入300ml快速搅拌的甲醇中,析出白色纤维状固体。经抽滤并在150℃真空干燥24h得到PI-3树脂。在70℃下,将一定量PI-3树脂溶于N N-二甲基甲酰胺中(固含量为6wt%),然后在洁净的玻璃片(3×6cm2)上浇铸成膜。最后在150℃下真空干燥12h,可得黄棕色PI-3薄膜。
对实施例一1至4的聚酰亚胺薄膜成品进行性能和溶解性测试,结果如下:
注:++表示室温下完全溶解,+-表示室温下部分溶解,--完全不溶。
经过测试数据证明本发明制备的聚酰亚胺大都可以在较低温度下(室温)溶于多数溶剂当中,且所有实例中聚酰亚胺都展现出较好的力学性能和耐热性能。
在本发明及上述实施例的教导下,本领域技术人员很容易预见到,本发明所列举或例举的各原料或其等同替换物、各加工方法或其等同替换物都能实现本发明,以及各原料和加工方法的参数上下限取值、区间值都能实现本发明,在此不一一列举实施例。
Claims (9)
1.一种可溶性聚酰亚胺,其特征在于,所述可溶性聚酰亚胺包含苯并咪唑结构同时具有如下重复结构单元:
其中:10<n<1000。
2.根据权利要求1所述的可溶性聚酰亚胺,其特征在于,所述的重复结构单元中Ar选自如下化学结构单元中的一种或几种:
3.一种权利要求1或2中任一项所述可溶性聚酰亚胺的制备方法,其特征在于,其具体合成方法如下:在N N-二甲基甲酰胺中,以吡啶为催化剂,由含苯并咪唑结构二胺和芳香二酐通过一步法缩聚反应生成所述的可溶性聚酰亚胺。
4.根据权利要求3所述可溶性聚酰亚胺的制备方法,所述2含苯并咪唑结构二胺和芳香二酐的摩尔比为1:0.95~1.05。
5.根据权利要求3所述的可溶性聚酰亚胺的制备方法,其特征在于,具体步骤如下:
(1)将N N-二甲基甲酰胺溶、吡啶、含苯并咪唑结构二胺和芳香二酐加入反应器中,在室温和氮气保护下,搅拌反应得到透明聚酰胺酸溶液;
(2)将步骤(1)所得聚酰胺酸溶液升温至80℃~120℃反应12~24h,得到可溶性聚酰亚胺溶液;
(3)将步骤(2)所得聚酰亚胺溶液冷却至室温后,倒入一定量的沉淀剂中,沉淀出聚酰亚胺,然后分离干燥。
6.根据权利要求3或4或5所述的溶性聚酰亚胺的制备方法,其特征在于,所述的含苯并咪唑结构二胺单体为如下结构式所示:
7.根据权利要求3或4或5所述可溶性聚酰亚胺的制备方法,其特征在于,所述的芳香二酐选自4,4’-(六氟异亚丙基)二酞酸酐、3,3,4,4-二苯基砜四羧酸二酸酐、3,3’,4,4’–联苯四羧酸二酐、3,3’,4,4’-二苯醚四羧酸二酐、双酚A型二醚二酐中的一种。
8.根据权利要求5所述可溶性聚酰亚胺的制备方法,其特征在于,步骤(1)中聚酰胺酸溶液的固含量为10wt%~20wt%。
9.根据权利要求5所述可溶性聚酰亚胺的制备方法,其特征在于,步骤(2)中,聚酰胺酸溶液升温至80℃~120℃的过程为一步升温或程序升温反应过程。
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