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Rapid Synthesis of Polyimide Precursors by Solution Polymerization Using Continuous-flow Microreactors
Chemical Engineering Journal ( IF 13.3 ) Pub Date : 2020-05-06 , DOI: 10.1016/j.cej.2020.125361
Wenhua Xu , Yuanhai Su , Minjing Shang , Xueming Lu , Qinghua Lu

Preparation method is of importance for development and application of polymers. Herein, we proposed a continuous-flow strategy for the preparation of polyimide precursors through solution polymerization in microreactors for the first time. The polymerization time was significantly reduced from several hours in a batch reactor to twenty minutes in a microreactor. Lower temperature, more appropriate molar ratio of monomers and longer residence time in the polymerization process resulted in poly(amic acid)s with higher molecular weights. Moreover, the relationship between the molecular weight and the residence time was used to discuss the polymerization kinetics. Meanwhile, the rapid preparation of poly(amic acid)s from pyromellitic dianhydride (PMDA), 4,4’-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), benzophenone-3,3’,4,4’- tetracarboxylic dianhydride (BTDA), 4,4’ - oxydiphthalic dianhydride (ODPA), or cyclobutane tetracarboxylic dianhydride (CBDA) was achieved in the microreactor. In particular, the number-average molecular weight of the PAA prepared by BTDA and 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether (6FODA) reached 36.3 kg / mol at the polymerization time of 19.6 minutes. This work demonstrated that microreactors would provide a promising and efficient pathway to prepare polyimide precursors with high molecular weights.



中文翻译:

使用连续流微反应器通过溶液聚合快速合成聚酰亚胺前体

制备方法对聚合物的开发和应用具有重要意义。在本文中,我们首次提出了一种通过在微反应器中进行溶液聚合制备聚酰亚胺前体的连续流策略。聚合时间从间歇式反应器中的几小时显着减少到微反应器中的二十分钟。较低的温度,更合适的单体摩尔比和更长的在聚合过程中的停留时间导致具有较高分子量的聚(酰胺酸)。此外,使用分子量和停留时间之间的关系来讨论聚合动力学。同时,由均苯四甲酸二酐(PMDA),4,4'-(六氟异亚丙基)二邻苯二甲酸酐(6FDA),二苯甲酮3,3',4,在微反应器中获得了4'-四羧酸二酐(BTDA),4,4'-氧二邻苯二甲酸二酐(ODPA)或环丁烷四羧酸二酐(CBDA)。特别地,在19.6分钟的聚合时间,由BTDA和2,2'-双(三氟甲基)-4,4'-二氨基二苯醚(6FODA)制备的PAA的数均分子量达到36.3kg / mol。这项工作表明,微反应器将为制备高分子量的聚酰亚胺前体提供有希望的有效途径。3kg / mol,在19.6分钟的聚合时间。这项工作表明,微反应器将为制备高分子量的聚酰亚胺前体提供有希望的有效途径。3kg / mol,在19.6分钟的聚合时间。这项工作表明,微反应器将为制备高分子量的聚酰亚胺前体提供有希望的有效途径。

更新日期:2020-05-06
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