Matesanz-Niño Laura, Cuellas David, Aguilar-Lugo Carla, Palacio Laura, González-Ortega Alfonso, de la Campa José G, Álvarez Cristina, Lozano Ángel E
Department of Macromolecular Chemistry, Institute of Polymer Science and Technology, ICTP-CSIC, Juan de la Cierva 3, E-28006 Madrid, Spain.
SMAP, UA-UVA_CSIC, Research Unit associated to CSIC, Faculty of Science, University of Valladolid, Paseo Belén 11, E-47011 Valladolid, Spain.
Polymers (Basel). 2023 Mar 7;15(6):1333. doi: 10.3390/polym15061333.
An optimized synthesis of the monomer 2,2'3,3'-biphenyltetracarboxylic dianhydride, iBPDA, was performed to obtain high molecular weight polymers. This monomer has a contorted structure that produces a non-linear shape, hindering the packing of the polymer chain. Aromatic polyimides of high molecular weight were obtained by reaction with the commercial diamine 2,2-bis(4-aminophenyl) hexafluoropropane, 6FpDA, which is a very common monomer in gas separation applications. This diamine has hexafluoroisopropylidine groups which introduce rigidity in the chains, hindering efficient packing. The thermal treatment of the polymers processed as dense membranes had two targets: on the one hand, to achieve the complete elimination of the solvent used, which could remain occluded in the polymeric matrix, and on the other hand to ensure the complete cycloimidization of the polymer. A thermal treatment exceeding the glass transition temperature was performed to ensure the maximum degree of imidization at 350 °C. The good mechanical properties of these materials allow for their use in high-pressure gas purification applications. Moreover, models of the polymers exhibited an Arrhenius-like behavior characteristic of secondary relaxations, normally associated with local motions of the molecular chain. The gas productivity of these membranes was high.
为了获得高分子量聚合物,对单体2,2',3,3'-联苯四甲酸二酐(iBPDA)进行了优化合成。该单体具有扭曲的结构,会产生非线性形状,阻碍聚合物链的堆积。通过与商业二胺2,2-双(4-氨基苯基)六氟丙烷(6FpDA)反应获得了高分子量的芳香族聚酰亚胺,6FpDA是气体分离应用中非常常见的单体。这种二胺具有六氟异亚丙基基团,会在链中引入刚性,阻碍有效堆积。对加工成致密膜的聚合物进行热处理有两个目标:一方面,要完全去除可能残留在聚合物基质中的所用溶剂,另一方面要确保聚合物完全环化。进行了超过玻璃化转变温度的热处理,以确保在350°C时达到最大程度的亚胺化。这些材料良好的机械性能使其可用于高压气体净化应用。此外,聚合物模型表现出类似阿仑尼乌斯的行为,这是二级弛豫的特征,通常与分子链的局部运动有关。这些膜的气体生产率很高。