Synthesis and Direct Observation of Molecules of 2D Polymers: With High Molecular Weights, Large Areas, Small Micropores, Solubility, Membrane Forming Ability, and High Oxygen Permselectivity

Abstract If ideal 2D polymer (2DP) macromolecules with small pores that are similar in size to gas molecules, large areas, small thickness, and excellent membrane‐forming ability are synthesized, ultimate gas separation membranes would be obtained. However, as far it is known, such ideal well‐characterized 2DP macromolecules are not isolated. In this study, an ideal 2DP macromolecule is synthesized by using the successive three reactions (Glaser coupling, SCAT reaction, and the introduction of octyl groups), in which the conjugated framework structure is maintained, from a fully conjugated 1D polymer. Because this exfoliated 2DP is soluble, the macromolecular structure can be fully characterized by ¹H‐NMR, GPC, SEM, AFM, and its dense membrane with no defects can be fabricated by the solvent cast method. This soluble 2DP macromolecule has very small micropores (6.0 Å) inside the macromolecule, a large area (30 × 68 nm by SEM and AFM), high molecular weight (Mn = 2.80 × 10⁵ by GPC), and a small thickness (4.4 Å by AFM). This membrane shows the highest oxygen permselectivity exceeding Robeson's upper line because of the high molecular sieving effect of the controlled small micropores.