Microporous Cyanate Resins: Synthesis, Porous Structure, and Correlations with Gas and Vapor Adsorptions

Abstract

Three silicon and nitrogen-centered cyanate monomers tetrakis(4-cyanatophenyl)silane, tetrakis(4-cyanatobiphenyl)silane, and tris(4-cyanatobiphenyl)amine were designed and synthesized, which were then polymerized via thermal cyclotrimerization reaction to create highly porous cyanate resin networks with systematically varied nodes and linking struts. The chemical structures of monomers and polymers were confirmed by 1 H NMR, FTIR, solid-state 13 C CP/MAS NMR spectra, and elemental analysis. The products are amorphous with 5% weight-loss temperatures over 428 °C. The results based on N 2 and CO 2 adsorption isotherms show that the pores in these polymers mainly locate in the microporous region, and the BET surface areas are up to 960 m 2 g −1 , which is the highest value for the porous cyanate resin reported to date. The nitrogen-and oxygen-rich characteristics of cyanate resins lead to the networks strong affinity for CO 2 and thereby high CO 2 adsorption capacity of 11.1 wt % at 273 K and 1.0 bar. The adsorption behaviors of H 2 , CO 2 , benzene, n-hexane, and water vapors were investigated by correlating with the chemical composition and porosity parameters of the networks as well as the physicochemical nature of adsorbates.

Tuning the adsorption and fluorescence properties of aminal‐linked porous organic polymers through N‐heterocyclic group decoration

“…As shown in Figure 1 and Table 1, NAPOP-1 comprises the smallest micropore with a size less than 3.9 Å, which is beneficial to the selective capture of CO 2 because of its small kinetic diameter. 32 NAPOP-4 comprises the micropore larger than 10 Å. In addition, macropores with a size varying from 20 to 200 Å were observed for all NAPOPs, with a notable pore volume contribution.…”

“…39,40 NAPOPs have large N content and small pore size and thus are preferred for CO 2 adsorption owing to strong dipole-quadruple interaction as well as size selectivity. 32,40 The adsorption selectivity of NAPOPs were evaluated at 273 K toward an imaginary mixture of CO 2 and N 2 with a molar ratio of 15:85, using the ideal adsorbed solution theory (IAST) 41 based on the single adsorption data. As shown in Figure 3(a), NAPOPs display different CO 2 /N 2 adsorption selectivity in an increasing order of NAPOP-2<NAPOP-4<NAPOP-3<NAPOP-1.…”

Metallophthalocyanine‐Based Conjugated Microporous Polymers as Highly Efficient Photosensitizers for Singlet Oxygen Generation

“…[15] Moreover,t he apparent rise at high relative pressure suggests their macroporosity as aresult of the loose stacking of nanoparticles.The Brunauer-Emmett-Teller (BET) surface areas are evaluated to be 540, 510, 600, and 610 m 2 g À1 for CoPc-CMP,NiPc-CMP, CuPc-CMP,and ZnPc-CMP,respectively (see Figure S7 in the Supporting Information). These values are comparable with other phthalocyanine-based porous organic polymers, [16] such as Pc-PBBAC OF (PBBA = phenylenebis(boronic acid), 450 m 2 g À1 ), [16a] NiPc-COF (624 m 2 g À1 ), [16b] and CoPc20 network-PIM (PIM = polymer of intrinsic microporosity, 610 m 2 g À1 ).…”

Advances in Porous Organic Polymers for Efficient Water Capture

“…Cyanate resins exhibit good thermals tability, permittivity,a nd mechanical properties,b ut they are knownf or their low moisture adsorption characteristics. Wang et al [57] transformed cyanate resins into triazine-containing polymers throught hermalcyclotrimerization reactions. Each of the nitrile functionalized monomers-namely,t etrakis(4-cyanatophenyl) silane, tetrakis(4-cyanatobiphenyl) silane, and tris(4-cyanatobiphenyl) amine-was subjected to thermalc yclotrimerization by using nonylphenol as ac atalystt oo btain crosslinked cyanate resin polymers (CE-1, CE-2, CE-3).…”