CN106046363A - 一类含四甲氧基芴结构高可溶性聚芳酰胺及其制备方法 - Google Patents
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Abstract
本发明提供了一类含四甲氧基芴结构高可溶性聚芳酰胺,其制备方法为:将等物质量的含四甲氧基芴基结构的芳香二胺单体和商品化芳香二酸单体加入有机溶剂中,于180~200℃搅拌反应8‑12h后,结束反应,进一步沉降、洗涤和干燥,即可得到纤维状的含四甲氧基芴结构高可溶性聚芳酰胺聚合物。该类聚芳酰胺在特定溶剂中的溶解度可达20wt%以上,具有优异的成膜性,所制聚合物薄膜在气体分离膜领域具有重要的应用价值。
Description
技术领域
本发明属高性能芳香型聚合物及其制备领域,特别涉及一类含四甲氧基芴结构高可溶性聚芳酰胺聚合物及其制备方法。
背景技术
膜分离是近年来迅猛发展的一类分离新技术。膜分离技术由于兼有分离、浓缩、纯化和精制的功能,又有高效、节能、环保、分子级过滤及过滤过程简单、易于控制等特征,因此,已广泛应用于食品、医药、生物、环保、化工、冶金、能源、石油、水处理、电子、仿生等领域,产生了巨大的经济效益和社会效益,已成为当今分离科学中最重要的手段之一。膜分离材料是膜分离技术的核心关键,相对无机膜分离材料,高分子有机膜分离材料制备工艺更简单、分子结构易于设计改性、材料易于回收利用等优点,受到研究者们的关注。
聚芳酰胺是一类分子结构中含有酰胺基团的芳香型高性能聚合物,在气体分离膜和反渗透膜领域具有重要的应用价值。但常规的聚芳酰胺聚合物由于存在强的氢键作用和较高的结晶度,通常表现出难熔难溶、难以加工等问题。此外,聚芳酰胺制备中,由于聚合物溶解性差,通常需要采用高温高压下的熔融缩聚,制备工艺能耗高。基于分子设计改性,采用溶液缩聚制备可溶性聚芳酰胺,并进一步引入特殊分子结构改善聚芳酰胺膜分离材料的性能,具有重要的研究价值。本发明专利开发了一类含有四甲氧基芴结构高可溶性聚芳酰胺聚合物,通过在聚合物分子主链中同时引入大自由体积的四甲氧基芴结构和柔性的双醚键,有效改善了聚合物在特定溶剂中的溶解性和成膜性,并进一步提高聚芳酰胺的膜分离性能。
发明内容
本发明专利旨在改善传统聚芳酰胺溶解成膜性,并进一步提高聚合物膜的分离性能,采用了一种相对简易的合成制备方法,提供了一类含有四甲氧基芴结构高可溶性聚芳酰胺;通过在聚合物分子主链中同时引入大自由体积的四甲氧基芴结构和柔性的双醚键,有效改善了聚合物在特定溶剂中的溶解性和成膜性,并进一步提高聚芳酰胺的膜分离性能。所制聚芳酰胺膜分离材料,在气体分离膜领域具有重要的应用价值。
本发明提供了一类含有四甲氧基芴结构高可溶性聚芳酰胺,其结构式为:
其中分别为 重复结构单元n=40~80。
本发明还提供了一种上述含四甲氧基结构高可溶性聚芳酰胺聚合物的制备方法,具体步骤为:
氮气保护下,将等物质量的含四甲氧基芴基结构芳香二胺单体和商品化芳香二酸单体加入有机溶剂中,室温下搅拌均匀后,升温至180~200℃搅拌反应8-12h后,结束反应,进一步沉降、洗涤和干燥,即可得到纤维状的含四甲氧基芴结构高可溶性聚芳酰胺聚合物。
其中,所述的含四甲氧基芴结构芳香二胺单体为9,9-双[3,3’,5,5’-四甲氧基-4-(4-胺基-苯氧基)苯基]芴;所述的商品化芳香二酸单体为对苯二甲酸、间苯二甲酸、4,4’-二苯醚二酸、2,2-双(4-羧基苯基)六氟丙烷或4,4’-二苯砜二酸中的一种。
所述溶剂为多聚磷酸,其用量为二胺单体和二酸单体质量的5-10倍。
本发明的含四甲氧基芴结构高可溶性聚芳酰胺聚合物的具体合成路线如下:
本发明的有益效果是:
(1)本发明提供了一类含四甲氧基芴结构高可溶性聚芳酰胺及其制备方法,其合成制备工艺简单,利于工业化放大生产;
(2)以本发明提供的含四甲氧基芴结构高可溶性聚芳酰胺聚合物,在N-甲基吡咯烷酮、N,N-二甲基乙酰胺、N,N-二甲基甲酰胺、二甲基亚砜等特定溶剂中具有高的溶解度(溶解度可达20wt%),可方便地利用其溶液涂膜得到聚合物薄膜;所制聚合物薄膜具有良好的气体分
离性能,在气体分离膜领域具有重要的应用价值。
附图说明
图1是实施例1中,含四甲氧基芴结构高可溶性聚芳酰胺聚合物的1H NMR图谱(其中芳香二酸单体为4,4’-二苯醚二酸)。
具体实施方式
实施例1
在装有氮气保护和冷凝管的100ml干燥三口烧瓶中,分别加入6.5273g(10mmol)的9,9-双[3,3’,5,5’-四甲氧基-4-(4-胺基-苯氧基)苯基]芴、2.5823g(10mmol)的芳香二酸单体(以4,4’-二苯醚二酸为例)和46g多聚磷酸,室温下搅拌均匀后,升温至200℃搅拌反应8h后,降温结束反应,将产物倒入乙醇中沉降,并进一步用热水洗涤三遍、过滤、烘干,即可得到含四甲氧基芴结构高可溶性聚芳酰胺聚合物,产率为99%;1H NMR(DMSO,400MHz)如附图1所示。
实施例2
在装有氮气保护和冷凝管的100ml干燥三口烧瓶中,分别加入6.5273g(10mmol)的9,9-双[3,3’,5,5’-四甲氧基-4-(4-胺基-苯氧基)苯基]芴、3.9225g(10mmol)的芳香二酸单体(以2,2-双(4-羧基苯基)六氟丙烷为例)和104g多聚磷酸,室温下搅拌均匀后,升温至180℃搅拌反应12h后,降温结束反应,将产物倒入乙醇中沉降,并进一步用热水洗涤三遍、过滤、烘干,即可得到含四甲氧基芴结构高可溶性聚芳酰胺聚合物,产率为99%。
Claims (4)
1.一类含四甲氧基芴结构高可溶性聚芳酰胺,其特征在于:所述的聚芳酰胺二胺结构单元中同时含有四甲氧基芴和双醚键结构,其结构式为
其中分别为 重复结构单元n=40~80。
2.如权利要求1所述的含四甲氧基芴结构高可溶性聚芳酰胺的制备方法,其特征在于:所述制备方法的步骤为
氮气保护下,将等物质量的含四甲氧基芴基结构芳香二胺单体和商品化芳香二酸单体加入有机溶剂中,室温下搅拌均匀后,升温至180~200℃搅拌反应8-12h后,结束反应,进一步沉降、洗涤和干燥,即可得到纤维状的含四甲氧基芴结构高可溶性聚芳酰胺聚合物。
3.如权利要求2所述的含四甲氧基芴结构高可溶性聚芳酰胺的制备方法,其特征在于:步骤中所述的含四甲氧基芴结构芳香二胺单体为9,9-双[3,3’,5,5’-四甲氧基-4-(4-胺基-苯氧基)苯基]芴;所述的商品化芳香二酸单体为对苯二甲酸、间苯二甲酸、4,4’-二苯醚二酸、2,2-双(4-羧基苯基)六氟丙烷或4,4’-二苯砜二酸中的一种。
4.如权利要求2所述的含四甲氧基芴结构高可溶性聚芳酰胺的制备方法,其特征在于:步骤中所述的溶剂为多聚磷酸,其用量为二胺单体和二酸单体质量的5-10倍。
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CN114349649A (zh) * | 2021-04-26 | 2022-04-15 | 镇江微电智能科技有限公司 | 两种同时含甲氧基芴和甲基结构的芳香二胺单体及其制备方法 |
KR20230028633A (ko) * | 2021-08-19 | 2023-03-02 | 이근수 | 플루오렌계 유기 화합물, 이를 포함하는 유기막 및 응용 |
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Application publication date: 20161026 Assignee: Senbiao Technology Services (Shandong) Co.,Ltd. Assignor: CHANGZHOU University Contract record no.: X2023980051006 Denomination of invention: A class of highly soluble polyarylamides containing tetramethoxyfluorene structure and their preparation method Granted publication date: 20190125 License type: Common License Record date: 20231209 |