Preparation of phenolic hydroxyl-modified hyper-crosslinked polymers and their adsorption performance towards small molecular aromatic amines

Abstract

Herein, three phenolic hydroxyl-modified hyper-crosslinked polymers were synthesized according to two-step Friedel-Crafts alkylation, and they were applied to adsorb small aromatic amines in aqueous and organic solvents. The first low-temperature Friedel-Crafts at 313 K introduced massive phenolic –OH to the intermediates, then the second high-temperature Friedel-Crafts at 353 K, also known as post-crosslinking reaction, brought a hyper-crosslinked skeleton composed of plentiful rigid methylene bridges to the target products, greatly enhancing the Brunauer-Emmett-Teller (BET) surface area (SBET) and total pore volume (Vtotal) of the polymers. In aqueous solution, the HCPS-BNAP-FDA had great potential for efficient adsorption of aniline and p-nitroaniline (p-NANL), and the Langmuir model predicted that their maximum capacities (qmax) were 209.25 mg/g and 277.30 mg/g, respectively. In cyclohexane solution, the qmax of aniline on HCPS-BNAP-FDA was predicted to be 202.38 mg/g. The removal aniline in aqueous solution could exceed 95 % when the original concentration was less than 200 mg/L, and the final concentration was 0.12 mg/L, much lower than the emission limit of China (GB 4287–2012, China). The polymer with 1,4-bis(chloromethyl)benzene (DCX) as crosslinking agent had the highest SBET (1282 m2/g) and the best adsorption performance for aniline (qmax, 258.73 mg/g). The adsorption mechanism demonstrated that the grafting of phenolic –OH groups improved the adsorption performance, as the possible hydrogen bonds and acid-base interactions. The micropores added via post-crosslinking also achieved a significant increase in adsorption capacity, that is, the pore filling adsorption mechanism.