Tailoring Pore Structure and Properties of Functionalized Porous Polymers by Cyclotrimerization

Abstract

Porous polymers were prepared by cyclotrimerization reaction in molten p-toluenesulfonic acid. Their properties could be tailored by functionalization of the aromatic diacetyl monomers. Thus, a range of homo-and copolymers based on hydrogen-, amine-, or nitro-functionalized 4,4′-diacetylbiphenyl derivatives and 1,4-diacetylbenzene was synthesized. The pores size could be tuned from mainly microporous to hierarchical micro-and mesoporous or even hierarchical micro-and macroporous. BET surface areas up to 720 m 2 /g and total pore volumes up to 1.76 cm 3 /g were achieved. The formation of different pore types was related to the solvent−monomer/polymer interactions, which is shown by 15 N solid state MAS NMR spectroscopy and SEM. Other physical properties such as surface polarity and thermal stability were influenced by the different monomers as well.

A new route to phosphonium polymer network solids via cyclotrimerization

“…Due to the non‐porous structure of P1 revealed by N 2 sorption, the water uptake is only 10.63%. This number is comparable with the values reported by Kaskel (12 ± 3%), which indicates weak interaction with water …”

“…A similar situation was observed by the Kaskel group when they used different monomers bearing diacetyl group to synthesize polymers. They found that monomers bearing amino groups tend to have nonporous structure because the amino groups were protonated to form ammonium moieties during synthesis, leading to a better solubility in molten p ‐toluenesulfonic acid through ion pair formation . The phosphonium moieties in a growing sample of P1 similarly improve its solubility in the highly polar PTSA versus neutral organic monomers.…”

“…Organic network solids support an ever‐expanding field of research due to their broad applications in gas storage/separation and catalysis . Much effort has been devoted to the development of polymer scaffolds bearing diverse functional units to have precise control of physical (pore size, surface area) and chemical properties (polar or ionic) . Compared with traditional organic frameworks, ionic hypercrosslinked polymers, specifically those involving ionic liquids as monomers, have attracted growing attention.…”

Porous imine-based networks with protonated imine linkages for carbon dioxide separation from mixtures with nitrogen and methane

“…The signal at À336 ppm in PIN1 and PIN2 is consistent with the protonation of unreacted amine groups to NH 3 + under acidic conditions. 58 On account of the structural equality of the networks PIN1 and PIN1_2, we assume the inuence of DMSO as the solvent, in particular its decomposition products, in creating such acidic environments. It is known that DMSO is not stable for long periods of heating at high temperatures, which leads to decomposition products such as formaldehyde, dimethyl sulde, bis-methylthiomethane and methyl disulde.…”

Prefunctionalized Porous Organic Polymers: Effective Supports of Surface Palladium Nanoparticles for the Enhancement of Catalytic Performances in Dehalogenation

“…As a new class of important porous materials, porous organic polymers (POPs) have captured widespread interest in gas storage and separation, sensing, proton conductivity, drug delivery, and catalysis . It has been demonstrated that the structures and porous properties of POPs could be elegantly tuned through selecting building units with different linking groups . In addition, the modular nature of the synthesis of POPs has allowed the incorporation of various functionalities for a specific purpose .…”