CN115286517A - 一种二胺单体及其合成的热塑性聚酰亚胺 - Google Patents
一种二胺单体及其合成的热塑性聚酰亚胺 Download PDFInfo
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- C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
- C07C211/55—Diphenylamines
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Abstract
本发明涉及一种二胺单体及其合成的热塑性聚酰亚胺，其结构如式所示。该单体以N原子相连接，氮原子上可连接不同官能团。本发明提供了一种课设计性的二胺单体结构及其与二酐合成的聚酰亚胺材料。通过引入杂原子，提高聚酰亚胺分子柔顺性。
其中该二胺单体结构如下所示：进一步地，R由不同官能团等组成，具体结构如下所示。R可为：烷烃链、烯烃链、炔烃链、
等结构。通过本发明所制备的二胺单体，与4,4'‑二氨基二苯醚二胺、1,2,4,5‑均苯四甲酸二酐单体通过一定配比缩聚制备聚酰亚胺薄膜。
Description
技术领域
本发明属于有机高分子特种工程材料技术领域，具体涉及一种二胺单体及其合成的热塑性聚酰亚胺。
背景技术
聚酰亚胺(Polyimide，简称PI)是一种优良的几种少数耐高温聚合物材料之一，由于其苯环共轭堆砌导致普遍能忍耐400℃的高温，常用于高温环境，并且其尺寸稳定性、机械性能也不低，因此备受关注。然而，在实际生产中，由于玻璃化转变温度Tg与融化温度Tm相差不大，因此难以加工，对实际生产造成很大困扰。因此本发明针对该问题，从单体结构出发，设计了一种柔性二胺单体，通过掺杂加入4,4'-二氨基二苯醚二胺、1,2,4,5-均苯四甲酸二酐所制备的聚酰亚胺中，制备本征型共聚聚酰亚胺，在不降低或少量降低耐热性的前提下，提高分子链柔顺性，制备热塑性聚酰亚胺材料，满足我国现代化生产需求。
发明内容
为了克服现有技术的不足，本发明的首要目的在于提供一种新二胺单体。
本发明的另一目的在于提供上述二胺单体的合成方法。
本发明的再一目的在于提供一种上述二胺单体制备的聚酰亚胺。
本发明的第四个目的在于提供一种用上述二胺单体制备聚酰亚胺的方法。
本发明的首要目的通过以下技术方案来实现：
一种二胺单体，结构主要以杂原子N与联苯形式构成，带有微量杂原子，提高分子柔顺性，该二胺单体的主体结构如下式I所示：
进一步地，本发明的单体中R由不同结构组成，其中具体形式如下所述。
进一步地，R可为烷烃链、烯烃链、炔烃链、
等结构组成。
下面提供制备上述单体种类的其中一种单体结构的方法，其特征在于，该单体名称为N4'-(3'-氨基-[1,1'-联苯]-4-基)-N4'-丁基-[1,1'-联苯]-3,4'-二胺(N4'-(3'-amino-[1,1'-biphenyl]-4-yl)-N4'-butyl-[1,1'-biphenyl]-3,4'-diamine)，具体步骤如下所述：
(1)合成4-溴-N-(4-溴苯基)-N-丁基苯胺(4-bromo-N-(4-bromophenyl)-N-butylaniline)：在反应容器中加入N,N二甲基甲酰胺(DMF)、磁力搅拌子、氢氧化钠、双(4-溴苯基)胺(bis(4-bromophenyl)amine)。待溶质完全溶解后逐滴加入1-碘丁烷。常温搅拌24-36小时后，加入去离子水倒入分液器中，充分震荡后分离水层。加入二氯甲烷萃取油层，取有机层旋蒸出溶剂得粘稠有机混合物。利用硅胶层析柱分离提纯得4-溴-N-(4-溴苯基)-N-丁基苯胺。
(2)合成N4'-(3'-氨基-[1,1'-联苯]-4-基)-N4'-丁基-[1,1'-联苯]-3,4’-二胺：在带有搅拌装置和冷凝管的容器中加入甲苯、4-溴-N-(4-溴苯基)-N-丁基苯胺、乙醇、碳酸钠水溶液、3-氨基苯硼酸、四(三苯基膦)钯(0)催化剂，通入惰性气体排出空气后在油浴(70-80℃)条件下冷凝回流，反应24-36小时。反应完成后倒入萃取容器，加入去离子水萃取有机层，再加入二氯甲烷萃取。后将所得有机层旋蒸出有机溶剂得有机混合物，再经中性氧化铝层析柱分离提纯得N4'-(3'-氨基-[1,1'-联苯]-4-基)-N4'-丁基-[1,1'-联苯]-3,4’-二胺单体。
具体合成过程分子式如下所示：
进一步地，步骤(1)中1-碘丁烷的用量为双(4-溴苯基)胺的1.5-3倍，保证反应完全。
进一步地，步骤(2)中3-氨基苯硼酸用量为4-溴-N-(4-溴苯基)-N-丁基苯胺单体的2-3.5倍，且层析柱发所用溶剂为乙酸乙酯与石油醚混合溶剂。
由上述制备得的N4'-(3'-氨基-[1,1'-联苯]-4-基)-N4'-丁基-[1,1'-联苯]-3,4’-二胺单体所制备的共聚聚酰亚胺，其特征在于，包括如下步骤：
(1)在装有DMAc溶剂的带搅拌装置的容器中加入本发明制备的N4'-(3'-氨基-[1,1'-联苯]-4-基)-N4'-丁基-[1,1'-联苯]-3,4’-二胺与4,4'-二氨基二苯醚二胺单体，待其完全溶解后在二十分钟内逐步加入1,2,4,5-均苯四甲酸二酐，直到溶液粘度提升，调低转速至100转/分钟以下，搅拌1-2小时后停止。
(2)将所得聚酰胺酸浆料进行减压抽气，消除卷入的空气，直至无气泡产生后进行涂布操作，将浆料均匀涂膜在玻璃基材上，后置于90-110℃、250-360℃烘箱中进行亚胺化，制备聚酰亚胺薄膜，具体反应方程式如下所述：
进一步地，步骤(1)中1,2,4,5-均苯四甲酸二酐加入时，搅拌装置转速在250-360转/分钟。
进一步地，步骤(2)中亚胺化过程是通过程序升温，温度从250-360℃，
进一步地，步骤(2)所制备的N4'-(3'-氨基-[1,1'-联苯]-4-基)-N4'-丁基-[1,1'-联苯]-3,4’-二胺单体，是带有短支链的杂链柔性结构，常温下为粘稠固态状，具有一定反应活性。
通过上诉所得共聚聚酰亚胺，具有以下分子链节结构式：
本发明所制备的本征型共聚聚酰亚胺具有以下优点：
1.分子链中引入杂原子且带有柔性支链，整体上改善了柔顺性；
2.主体结构还是以联苯-酰亚胺环结构为主，其耐热性能不会因为杂原子的引入而降低；
3.短支链具有一定柔性，带有自由体积，能降低堆砌密度，有助于分子链间柔性提高。
为使本发明具体实施方式的目的和技术方案更加清楚，下面将结合本发明的具体实施方式的实施实例，对本发明具体实施方式的技术方案进行清楚、完整地描述。显然，所描述的具体实施方式是本发明的一部分具体实施方式，而不是全部的具体实施方式。基于所描述的本发明的具体实施方式，本领域普通技术人员在无需创造性劳动的前提下所制备的所有其它具体实施方式，都属于本发明保护的范围。
附图说明
图1为本发明合成的二胺的核磁共振氢谱。
具体实施方案
下面通过具体实施例对本发明作进一步的说明，但这些具体实施方案不以任何方式限制本发明的保护范围。
实施例1
将等当量的1-碘丁烷缓慢加入溶解在碱性DMF溶剂中的双(4-溴苯基)胺中，常温搅拌24小时，加入去离子水静置分层分液。分液得出油层，加入硅胶吸附，经过旋转蒸发器除去溶剂后经层析柱分离出纯净的4-溴-N-(4-溴苯基)-N-丁基苯胺。
将上述所得物质，以摩尔比1:3的配比加入3-氨基苯硼酸，溶于除水的甲苯中，加入适量乙醇与2摩尔每升的碳酸钠水溶液。通氮气洗二十分钟后加入催化剂，并升温至78℃冷凝回流24小时，制备得N4'-(3'-氨基-[1,1'-联苯]-4-基)-N4'-丁基-[1,1'-联苯]-3,4’-二胺。
将本发明制备出的二胺与4,4'-二氨基二苯醚二胺，按照等当量摩尔比与1,2,4,5-均苯四甲酸二酐缩聚得到共聚得聚酰亚胺。经TMA测试得知其玻璃化转变温度明显降低。
以下表1为本发明所制备的共聚聚酰亚胺的TMA测试所得的Tg结果
| 样品 | ODA/PMDA | 10％混 | 20％混 | 30％混 | 40％混 |
| Tg | 399 | 370 | 351 | 342 | 330 |
以上结合具体实施例，对本发明技术方案的具体实施方式进行了进一步描述，此具体实施方案是为了对本技术方案的详细描述，而不是为了限制本技术方案。以上所述的具体实施方案，仅仅是对本发明的优选实施方式进行描述，并非对本发明的技术构思和保护范围进行限定，在不脱离本发明设计构思的前提下，本领域普通技术人员对本技术方案作出的各种变型和改进，均应落入本发明的保护范围。
Claims (7)
1.一种二胺单体，其结构主要以N原子连接的苯环为主体，其特征在于，该二胺单体分子结构式如下式I所示：
2.根据权利要求1所述的二胺单体，其特征在于，结构式中R为烷烃、烯烃、炔烃、
等其中一种结构。
3.一种制备权利要求1所述单体结构的方法，其特征在于，该单体名称为N4'-(3'-氨基-[1,1'-联苯]-4-基)-N4'-丁基-[1,1'-联苯]-3,4'-二胺(N4'-(3'-amino-[1,1'-biphenyl]-4-yl)-N4'-butyl-[1,1'-biphenyl]-3,4'-diamine)，具体合成步骤如下所述：
(1)将1.5摩尔当量的1-溴丁烷加入含有双(4-溴苯基)胺(bis(4-bromophenyl)amine)的碱性DMF溶剂中搅拌反应，反应温度为40-50℃，反应时间为12-16小时，经萃取、柱层析法提纯得4-溴-N-(4-溴苯基)-N-丁基苯胺(4-bromo-N-(4-bromophenyl)-N-butylaniline)，其结构式如下：
(2)将上述制备的4-溴-N-(4-溴苯基)-N-丁基苯胺化合物放入含有碳酸钠水溶液、无水乙醇、甲苯、3-氨基苯硼酸的容器中加热回流反应，时间为24-36小时、反应温度为70-80℃；后经萃取与柱层析分离提纯得到单体N4'-(3'-氨基-[1,1'-联苯]-4-基)-N4'-丁基-[1,1'-联苯]-3,4’-二胺(N4'-(3'-amino-[1,1'-biphenyl]-4-yl)-N4'-butyl-[1,1'-biphenyl]-3,4'-diamine)，其结构式如下：
4.根据权利要求3所述的N4'-(3'-氨基-[1,1'-联苯]-4-基)-N4'-丁基-[1,1'-联苯]-3,4’-二胺的制备方法，其特征在于，1-碘丁烷的用量是双(4-溴苯基)胺的1.5倍，加入氢氧化钠使得溶剂呈碱性；其中还包括如下步骤：加入去离子水、二氯甲烷后充分震荡后萃取得混合物，再经柱层析法分离出4-溴-N-(4-溴苯基)-N-丁基苯胺单体；其柱层析法所用流动相为二氯甲烷与石油醚混合溶剂。
5.根据权利要求书3所述的N4'-(3'-氨基-[1,1'-联苯]-4-基)-N4'-丁基-[1,1'-联苯]-3,4’-二胺单体的制备中，其特征在于，3-氨基苯硼酸的用量(摩尔量)为4-溴-N-(4-溴苯基)-N-丁基苯胺单体的2.4-3倍；碳酸钠水溶液与无水乙醇的用量(摩尔量)为3-氨基苯硼酸的2倍；流动相是用乙酸乙酯与石油醚混合溶剂；固定相是中性氧化铝。
6.单体N4'-(3'-氨基-[1,1'-联苯]-4-基)-N4'-丁基-[1,1'-联苯]-3,4’-二胺与4,4'-二氨基二苯醚二胺、1,2,4,5-均苯四甲酸二酐制备的共聚制备的聚酰亚胺，其特征在于，聚酰亚胺分子主链上有N杂原子，柔顺性提高，且带有一定长度短支链，其共聚聚酰亚胺结构式如下所示：
7.本发明所制备的N4'-(3'-氨基-[1,1'-联苯]-4-基)-N4'-丁基-[1,1'-联苯]-3,4’-二胺单体，进一步制备得的聚酰亚胺，其特征在于，所述的具有侧链基团的杂链共聚聚酰亚胺化合物的制备方法包括如下步骤：
(1)在低湿度环境下，将二胺单体N4'-(3'-氨基-[1,1'-联苯]-4-基)-N4'-丁基-[1,1'-联苯]-3,4’-二胺、4,4'-二氨基二苯醚二胺放入DMAc溶剂中，充分搅拌至全部溶解，再在二十分钟内逐渐加入1,2,4,5-均苯四甲酸二酐，形成具有一定粘度的聚酰亚胺酸；所述使用的二胺单体结构如下：
所述使用的二酐单体结构式如下：
所述聚酰胺酸化合物具有下列结构式：
(2)所制备的聚酰亚胺酸就行涂覆在光滑的玻璃载体上，经90-105℃烘箱烘20分钟后，进行程序升温，温度范围从250℃至370℃；
(3)将(2)所得的聚酰亚胺薄膜揭下，所得聚酰亚胺薄膜具有如下结构
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002102756A2 (de) * | 2001-06-19 | 2002-12-27 | Merck Patent Gmbh | Polyimide mit cf2o-strukturelementen |
| CN102585843A (zh) * | 2011-01-05 | 2012-07-18 | Jnc株式会社 | 用以形成光配向用液晶配向膜的液晶配向剂、液晶配向膜及使用其的液晶显示元件 |
| CN103145581A (zh) * | 2013-02-27 | 2013-06-12 | 中山大学 | 一种含酰亚胺结构的芳香二胺化合物及其制备方法和应用 |
| CN105384933A (zh) * | 2015-12-25 | 2016-03-09 | 桂林电器科学研究院有限公司 | 一种低熔点热塑性聚酰亚胺树脂、含有该树脂的薄膜及制备方法 |
| CN108911992A (zh) * | 2018-07-31 | 2018-11-30 | 湖南工业大学 | 一种三胺单体及其制备方法和用途 |
-
2022
- 2022-06-01 CN CN202210617947.1A patent/CN115286517A/zh active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002102756A2 (de) * | 2001-06-19 | 2002-12-27 | Merck Patent Gmbh | Polyimide mit cf2o-strukturelementen |
| CN102585843A (zh) * | 2011-01-05 | 2012-07-18 | Jnc株式会社 | 用以形成光配向用液晶配向膜的液晶配向剂、液晶配向膜及使用其的液晶显示元件 |
| CN103145581A (zh) * | 2013-02-27 | 2013-06-12 | 中山大学 | 一种含酰亚胺结构的芳香二胺化合物及其制备方法和应用 |
| CN105384933A (zh) * | 2015-12-25 | 2016-03-09 | 桂林电器科学研究院有限公司 | 一种低熔点热塑性聚酰亚胺树脂、含有该树脂的薄膜及制备方法 |
| CN108911992A (zh) * | 2018-07-31 | 2018-11-30 | 湖南工业大学 | 一种三胺单体及其制备方法和用途 |
Non-Patent Citations (1)
| Title |
|---|
| 吴琦: "含侧基的高耐热可溶透明聚酰亚胺的合成及性能研究", 中国博士学位论文全文数据库工程科技Ⅰ辑, no. 1, 15 January 2022 (2022-01-15), pages 016 - 200 * |
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