Solid-State Chemical Transformations to Enhance Gas Capture in Benzoxazine-Linked Conjugated Microporous Polymers

Abstract

We describe the first examples of benzoxazine (BZ)linked tetraphenylethylene (TPE)-and pyrene (Py)-containing conjugated microporous organic polymers (CMPs)TPE-TPE-BZ and Py-TPE-BZ, respectivelyhaving high surface areas and pore volumes, prepared through multistep syntheses (Schiff base, reduction, Mannich, and Sonogashira−Hagihara coupling), and their solid-state transformations through ring-opening polymerizations (ROPs) to give BZ linkages have never been reported previously. The chemical structures and, particularly, the presence of BZ units in the TPE-TPE-BZ and Py-TPE-BZ CMPs were confirmed through Fourier transform infrared and solid-state nuclear magnetic resonance spectroscopic analyses. The TEP-TPE-BZ CMP had a high BET specific surface area and a high total pore volume (325 m 2 g −1 and 0.69 cm 3 g −1 , respectively). Because BZ units can undergo ROP through simple thermal treatment without the need for a curing agent or catalyst, the CMPs readily underwent one-step chemical transformations in the solid state to form new CMPs featuring phenolic OH and Mannich bridges as functional groups capable of forming strong intermolecular hydrogen bonds and/or acid/base interactions with molecules of CO 2 gas to enhance the gas uptake ability.

Ultrastable Covalent Triazine Organic Framework Based on Anthracene Moiety as Platform for High-Performance Carbon Dioxide Adsorption and Supercapacitors

“…The cause for this massive demand is the variety of natural resources that supply raw materials to support industrialization and urbanization in our modern era [ 1 , 2 , 3 , 4 , 5 ]. This trend has raised major concerns about the availability of natural resources for future generations, which might lead to disaster in terms of global warming and a shortage of energy supplies [ 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 ]. To address these issues, researchers across the world have devoted themselves to finding clean and sustainable electrical energy storage devices.…”

Metal Complexes of the Porphyrin-Functionalized Polybenzoxazine

“…The thermal ring-opening polymerizations (ROPs) of BZ monomers result in highly cross-linked structures, formed as a result of Mannich condensations of phenolic and formaldehyde derivatives with primary amines [ 7 , 8 , 9 , 10 , 11 , 12 , 13 ]. Because strong inter- and intramolecular hydrogen bonds exist after the thermal ROP of BZ units, formed among the tertiary amino and phenolic units in the Mannich bridges, the polymerization products can possess low dielectric constants, low surface free energies, low degrees of shrinkage, and high thermal stabilities and char yields [ 14 , 15 , 16 , 17 , 18 , 19 , 20 ]. Flexibility in molecular design—by varying the structures of the phenolic and amino groups—has allowed the introduction of a range of functional groups (e.g., allyl, propargyl, crown ether) [ 21 , 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 ] or inorganic nanomaterials (such as polyhedral oligomeric silsesquioxane, graphene, carbon nanotube) [ 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 ] into the BZ matrix.…”

Microporous Carbon and Carbon/Metal Composite Materials Derived from Bio-Benzoxazine-Linked Precursor for CO2 Capture and Energy Storage Applications

“…We attribute the higher CO 2 uptake for PCMC to its higher surface area (1110 m 2 g –1 ) and abundance of micropores that provided suitable spaces for CO 2 uptake. Furthermore, because of its high surface area and large pores, the CO 2 adsorption of our PCMC was excellent when compared with that of other previously reported porous materials, including poly(TPE-TPE-BZ), poly(Py-TPE-BZ), BPOP-1, the BZ-linked material BoxPOP-1, the ferrocene-containing material Fc-CMP-1, A6CMP-3, CTF-HUST-3, the triphenylamine-based polymer PTPA-3, CTHP-3, and COF-102 [ 66 , 67 , 68 , 69 , 70 , 71 , 72 , 73 , 74 ].…”