Synthesis And Properties Of Amino-functionalized Conjugated Microporous Polymers

A series of amine-functionalized conjugated microporous polymers(CMPs) were synthesized via palladium-catalyzed Sonogashira-Hagihara crosscoupling polycondensation of three amine-functionalized monomers,bis(4-bromophenyl)amine, N,N-bis(4-bromobenzyl)amine and 2,4,6-tribromoaniline with 1,3,5-triethynylbenzene in different solvent systems. The morphology, chemical composition, thermal stability, pore properties, surface wettability of prepared conjugated microporous polymers were characterized. Meanwhile the adsorption properties for CO2, heavy metal ions, iodine and dyes of the as-prepared conjugated microporous polymers were studied.The Fourier transform infrared spectra(FTIR) and 13 C CP/magic angle spinning(MAS) nuclear magnetic resonance(NMR) measurements indicated that the as-prepared amine-functionalized conjugated microporous polymers were composed by benzene ring, carbon-carbon triple bond. The SEM and N2-adsorption/desorption experiments show that the morphology, BET surface areas and pore properties of the amine-functionalized conjugated microporous polymers are great influenced by the choice of polymerization solvent. In this paper we have synthesized a series of amine-functionalized conjugated microporous polymers with tubular, sphere and amorphous morphologies. Among them the amorphous NCMP-I possesses the highest BET surface areas of 945 m2 g-1. The thermogravimetric analysis indicated that the amine-functionalized conjugated microporous polymers are thermally stable, almost all of CMPs have thermal decomposition temperature above 300 o C.On the basis of their abundant pore structures and unique surfcce wettability, we have studied the adsorption properties for CO2, heavy metal ions, iodine and dyes and the properties of constructing of superhydrophobic surface of the as-prepared conjugated microporous polymers were studied. Our results, in this paper, show that the as-prepared conjugated microporous polymers have a good performance for adsorption of CO2, heavy metal ions, dyes and iodine of which the NCMP-I shows higest CO2 and heavy metal ions(Ni(II)) adsorption capacity of 85 mg g-1 and 384 mg g-1. The iodine and dyes adsorption experiments show that the CMP-3 have good adsorption performance for both iodine, rhodamine B and methyl orange. The adsorption capacity of iodine, rhodamine B and methyl orange for CMP-3 was 218 mg g-1、269 mg g-1 and 198 mg g-1. The as-prepared CMP-based stainless steel mesh and the CMP-2-coated PDMS film shows good superhydrophobic which have potential applications of oil/water and self-cleaning fields.A series of amine-functionalized conjugated microporous polymers(CMPs) were synthesized by varying the solvents and monomers in the polymerization process and explored the impacts of reaction conditions on the resulted conjugated microporous polymers which may provide a new idea for the controllable synthesis and special applications of conjugated microporous polymers.