One-Step, Room Temperature Synthesis of Well-Defined, Organo-Soluble Multifunctional Aromatic Polyimides

Abstract

Efficient and ambient synthesis of aromatic polyimides (PIs) from readily available starting materials remains a very challenging task in polymer chemistry. Herein, we report for the first time a robust, one-step synthesis of organo-soluble functional aromatic PIs. Room temperature, metal-free, superacid (TFSA)-catalyzed step polymerization of aryl-terminated diimides with carbonyl compounds (2,2,2-trifluoroacetophenone and indoline-2,3-dione (isatin)) afforded 14 high-molecular-weight, linear, film-forming PIs. The effect of structural variation of the dianhydride segment, the amount of catalyst, and monomer concentration were studied. The PIs were obtained in quantitative yields, with high thermal stabilities up to 525 °C and 55% weight residue at 800 °C under an inert atmosphere and number-average molecular weights (M n) in a range of 51–195 kg mol–1. Well-controlled proportions of the functional phenolic hydroxyl groups (at the ortho-position to the imide ring) and diaryloxindole reactive sites were introduced into macromolecules during polyimide syntheses, while pendent allyl and propargyl groups were formed by the chemical postpolymerization reactions. Subsequent modifications of the reactive sites using click-chemistry can afford multifunctional polymers with tunable properties. The thermal postpolymerization modification of polyhydroxyimides converts them into polybenzoxazoles (so-called thermally rearranged polymers).

High-Performance Polyimides Derived from Biomass: Design, Synthesis, and Properties

“…The general synthesis process for PIs is the polycondensation of dianhydride and diamine, in which the performance of PIs is determined by the structure of chosen monomers. , Therefore, rational design of bioderived monomers before polymerization could yield the specific green PIs. − Evidence of research results demonstrated that the introduction of aliphatic chains or the trifluoromethyl group (−CF 3 ) contributes to the transmittance of PIs. For instance, PIs prepared from modified monomers such as sorbitol, 4-aminocinnamic acid, and inositol show good performance in terms of transmittance. ,,, Additionally, some researchers disclosed that using monomers containing a benzene ring provide superior thermal stability, such as lignin-based and adenine-based PIs. ,, More recently, the designed monomers containing hydrogen bonding bring additional benefits in PIs, ,,, which with a bio-based content of 17.6% of modified furan-2,5-dicarboxylic acid showed excellent balance in superior physiochemical properties . Tremendous advancements have been achieved in the single performance of bio-based PIs via the above strategies.…”

“…The general synthesis process for PIs is the polycondensation of dianhydride and diamine, in which the performance of PIs is determined by the structure of chosen monomers. 24,25 Therefore, rational design of bioderived monomers before polymerization could yield the specific green PIs. 17−23 Evidence of research results demonstrated that the introduction of aliphatic chains or the trifluoromethyl group (−CF 3 ) contributes to the transmittance of PIs.…”

“…18,19,21,26 Additionally, some researchers disclosed that using monomers containing a benzene ring provide superior thermal stability, such as lignin-based and adenine-based PIs. 17,22,27 More recently, the designed monomers containing hydrogen bonding bring additional benefits in PIs, 3,10,23,25 which with a bio-based content of 17.6% of modified furan-2,5-dicarboxylic acid showed excellent balance in superior physiochemical properties. 23 Tremendous advancements have been achieved in the single performance of bio-based PIs via the above strategies.…”

Temporally Stable Supramolecular Polymeric Salts Enabling High‐Performance 3D All‐Aromatic Polyimide Lattices

“…Traditional polyimide synthesis for soluble poly(ether imides) (PEI) involves a single‐step poly(amic acid) formation and imidization in solution as opposed to the two‐step method typically for all‐aromatic PIs, which requires poly(amic acid) formation in solution with subsequent casting and chemical/thermal cyclodehydration. [ 9–13 ] In sharp contrast, earlier polyamide literature suggested an unconventional route for polyimide synthesis, termed polymerization of monomeric reagents (PMR). PMR employed supramolecular dicarboxylate‐diammonium interactions between aromatic diamines and the dialkylester from an aromatic tetracarboxylic acid.…”

Experimental Setup and Graphical User Interface for Zero-Length Column Chromatography

“…The number of new molecular sieves discovered every day has been increasing. Examples include: zeolites [1,2], metal-organic frameworks [3][4][5], mesoporous silicas [6], microporous carbons [7], polymers of intrinsic microporosity [8,9], and metal-organic framework with dual functionalities [1,4]. This rapid growth of the available molecular sieves imposes the challenge of understanding the sorption kinetics and equilibrium of a large number of adsorbates of industrial interest.…”