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Herein, two sulfhydryl‐functionalized polymers, namely, EDT‐HCPS and TMPMP‐HCPS, were synthesized according to the Friedel‐Craft s alkylation and nucleophilic substitution, and they were used to adsorb Pd2+ and Ag+ from aqueous solution. The Friedel‐Crafts alkylation offered the polymers with hyper‐cross‐linking frameworks composed of plentiful rigid methylene. The nucleophilic substitution brought abundant functional SH groups (the sulfur contents were 12.6 and 9.4 wt%, respectively) to the polymers. The adsorption results showed that the capacities of Pd2+ and Ag+ on EDT‐HCPS were larger than TMPMP‐HCPS, and the higher quantities of functional SH groups and the porosity played a beneficial role. The equilibrium data can be characterized by the Langmuir model, and the maximum capacities of Pd2+ and Ag+ on EDT‐HCPS at 308 K were predicted to be 383.92 and 212.93 mg g−1, respectively. The produced polymers represented superior adsorption selectivity, reproducibility, and reusability, demonstrating their excellent performance for the adsorption of Pd2+ and Ag+, and analysis of the adsorption mechanism demonstrated that the SH groups played a major role due to the strong chemical complexation of the functional SH with Pd2+/Ag+. [ABSTRACT FROM AUTHOR]

The heterogeneous antioxidant, namely, PS-2, 6-DTBP, was easily synthesized from chloromethylated polystyrene (CMPS) with 2, 6-di-tert-butylphenol by a simple one-step Friedel–Crafts reaction. As compared with CMPS (78 m2/g and 34.8 nm, respectively), the Brunauer–Emmett–Teller (BET) surface area (SBET) of PS-2, 6-DTBP was greatly increased to 623 m2/g, while the average pore size was sharply reduced to 7.0 nm. The antioxidative property of PS-2, 6-DTBP was extensively evaluated by the scavenging activity of superoxide and 2, 2-diphenyl-1-picrylhydrazyl radical (DPPH·) in inhibiting oxidation of benzaldehyde, and the results indicated that 2,6-di-tert-butylphenol loaded on PS-2, 6-DTBP had excellent capability in scavenging O2−· and DPPH·, and effectively inhibited the oxidation of benzaldehyde. As a heterogeneous antioxidant with free radical scavenger, PS-2, 6-DTBP can be conveniently separated from the liquid phase and is environment friendly, showing promising potential in solid antioxidant field. [ABSTRACT FROM AUTHOR]

Herein, the one‐pot Friedel‐Crafts reaction was performed for polydivinylbenzene and 1,2‐dichloroethane, tetrachloride, and cyanuric chloride were used as the external cross‐linking agents to fill the mesopores of polydivinylbenzene. The results indicated that methylene, carbonyl, and triazine ring filled the mesopores of polydivinylbenzene as the rigid cross‐linking bridges successfully and the Brunauer‐Emmett‐Teller surface area and total pore volume of the resultant post‐cross‐linked polymers were greatly increased and the pore size distribution was readily tuned. Importantly, using cyanuric chloride as the cross‐linking agent produced abundant micropores with considerable micropore area and micropore volume, and the pore size distribution had an obvious transfer from mainly distributed mesopores to predominated micropores. The equilibrium adsorption revealed that the resulting polymer PDVB‐CC using cyanuric chloride as the post‐cross‐linking agent exhibited the best adsorption to phenol with the maximum capacity (qmax) of 448.5 mg/g while the least adsorption to Congo red (qmax: 128.5 mg/g). The kinetic adsorption demonstrated that PDVB‐CC needed the least time to the equilibrium while more than 300 min was required for the adsorption of Congo red attaining the equilibrium due to the much difficult diffusion of Congo red in the micropores. [ABSTRACT FROM AUTHOR]

The development of functionalized hyper-cross-linked resins (HCLRs) with high Brunauer-Emmett-Teller (BET) surface area (S BET) is of great importance. Herein, a kind of anisole-modified HCLRs was fabricated by two successive Friedel-Crafts reactions and it was used for the adsorption of aniline from aqueous solution. The resultant HCLRs owned high S BET and plentiful oxygen (O), with the values of 650 m2/g and 7.6 wt% respectively. The adsorption experiments indicated that the adsorption of aniline on the prepared HCLRs was efficient with the maximum capacity of 200.6 mg/g at 308 K, and both of the S BET and the introduced O were beneficial for the adsorption. Additionally, the as-prepared HCLRs had a good reusability without obvious capacity loss after five adsorption-desorption cycles. [ABSTRACT FROM AUTHOR]

Abstract: A series of novel hyper-cross-linked resins were synthesized from macroporous cross-linked chloromethylated poly(styrene-co-divinylbenzene) by adding different dosage of hydroquinone in Friedel-Crafts reaction. The results of the pore structures revealed that the prepared resins possessed micropores, mesopores and macropores, and the chloromethyl groups and the uploaded hydroquinone were partly oxidized according to the results of Fourier-transformed infrared ray spectra. Among these hydroquinone modified resins, HJ-Y06 resin held the largest adsorption capacity for β-naphthol, and its adsorption capacity was comparable with XAD-4 while much larger than X-5. The adsorption kinetics could be characterized by pseudo-second-order rate equation and intra-particle diffusion model was the rate-limiting step at the initial process. The adsorption was favorable at solution pH lower than 6.5. The adsorption isotherms could be fitted by Langmuir model and the adsorption was an endothermic process. Hydrogen bonding between formaldehyde carbonyl and quinone carbonyl groups on HJ-Y06 and phenolic hydroxyl groups of β-naphthol was the main driving force for the adsorption. [Copyright &y& Elsevier]

Abstract: A kind of phenolic hydroxyl group modified hyper-cross-linked polymeric adsorbent HJ-02 was prepared from macroporous crosslinked chloromethylated styrene-divinylbenzene copolymers by Friedel–Crafts post-cross-linked reaction and esterified reaction. Its chemical structure and pore structure were characterized by chemical analysis, infrared spectroscopy, and N2 adsorption–desorption experiments. It was thereafter applied to adsorb p-aminobenzoic acid in aqueous solution for its potential application in separation and purification. The p-aminobenzoic acid aqueous solution, pH unadjusted, was the optimum for the adsorption and the salinity posed a positive effect. The adsorption dynamic curves obeyed the pseudo-second-order rate equation and the adsorption was controlled by an intraparticle diffusion model. The adsorption enthalpy was calculated to be negative and decreased with the increase of the p-aminobenzoic acid uptake. The surface character of HJ-02 resin was described with function of the adsorption enthalpy by Do’s model and the result indicated that it exhibited surface energy heterogeneity. [Copyright &y& Elsevier]

Abstract: Chloromethylated styrene-divinylbenzene copolymers were post-crosslinked through Fredel–Crafts alkylation reaction and a water-compatible hypercrosslinked resin HJ-1 was developed successfully. It can be wetted directly by water and can be used without any wetting process. It was applied to remove p-nitrophenol in aqueous solution in comparison with the commercial Amberlite XAD-4 resin. Their adsorption behaviors for p-nitrophenol were conducted and it was found the adsorption dynamics obeyed the pseudo-second-order rate equation and the intra-particle diffusion was the rate-limiting step. The adsorption isotherms can be correlated to Freundlich isotherm and the adsorption capacity onto HJ-1 resin was much larger than XAD-4. The maximum adsorption capacity of p-nitrophenol for HJ-1 resin was measured to be 179.4 mg/g with the equilibrium concentration at 178.9 mg/l and the maximum removal percentage was predicted to be 98.3%. The adsorption thermodynamic parameters were calculated and the adsorption was mainly driven by enthalpy change. The micropore structure, the size matching between the pore diameter of HJ-1 resin and the molecular size of p-nitrophenol, and polarity matching between the formaldehyde carbonyl groups of HJ-1 resin and p-nitrophenol bring the larger adsorption capacity and higher adsorption affinity. [Copyright &y& Elsevier]

Two hyper-cross-linked polymers (HCPs) were readily prepared through one-pot Friedel-Crafts reaction using methylene and carbonyl as the rigid cross-linking bridges. Unexpectedly, the methylene cross-linked PDV-pc-1 (686 m2/g and 0.37 cm3/g, respectively) owned a little higher Brunauer-Emmett-Teller surface area and pore volume than the carbonyl cross-linked PDV-pc-2 (635 m2/g and 0.33 cm3/g, respectively), while PDV-pc-2 had a higher CO2 uptake (86 mg/g) than PDV-pc-1 (64 mg/g), the introduced carbonyl groups and the better microporosity were the main reasons. Specially, the CO2 uptake had a good linear correlation with the ultramicropores (d < 1.0 nm) (R2 = 0.998). In particular, the CO2 uptake of the direct carbonized PDVC-2 (57 mg/g) was almost identical to the KOH-activated carbonized PDVC-KOH (62 mg/g) at 0.15 bar in spite of its much lower Brunauer-Emmett-Teller surface area, proving that PDVC-2 had a good prospect of CO2 capture from harsh flue gas conditions. [ABSTRACT FROM AUTHOR]

Graphical abstract Abstract Pyrrole, furan, and thiophene modified hyper-cross-linked polymers (HCPs) were prepared in one-pot method by two successive Friedel-Crafts reactions, and they were assessed by phenol adsorption from aqueous solution. The results indicated that the three chemically modified polymers had lower Brunauer-Emmett-Teller surface area and pore volume than the common HCPs, while the phenol adsorption on the pyrrole and thiophene modified polymers was relatively enhanced due to the introduction of the heteroatoms on the surface. Notably, the enthalpy changes of HCP-Py, HCP-Fu, and HCP-Th were greater than the HCPs, and the introduced heteroatoms provide greater interaction with phenol through dipole-dipole interaction. More importantly, the kinetic adsorption revealed that the required equilibrium time on the three chemically modified polymers (about 45 min) was shorter than the HCPs (about 75 min), and the pseudo-second-order rate equation described the kinetic data very well. The micropore diffusion model was suitable for characterizing the adsorption on the HCPs, but it could not account for the kinetic data on the chemically modified polymers. [ABSTRACT FROM AUTHOR]

Herein, octaphenylcyclotetrasiloxane was used as the substrate, cyanuric chloride was applied as the cross-linker, and a series of novel hyper-cross-linked polymers with organic-inorganic hybrid framework and spherical morphology was fabricated by a typical Friedel-Crafts reaction. These polymers were used as the excellent precursors for the synthesis of N-doped porous carbons. After KOH-activation carbonization, the spherical morphology of the polymers was retained while the porosity was significantly enhanced. Interestingly, the Brunauer-Emmett-Teller surface area ( S BET ), total pore volume ( V total ), micropore volume ( V micro ), and V micro /V total of the carbons could be finely tuned in the range of 237–2058 m 2 /g, 0.12–1.08 cm 3 /g, 0.10–0.93 cm 3 /g, and 79.4–88.5%, respectively, and the microporosity was distinctly improved as the carbonization temperature increased. These carbons owned decent CO 2 uptake (80–263 mg/g), HCP2b-K700 had the highest CO 2 uptake of 263 mg/g at 273 K and 1.0 bar and it arrived at 590 mg/g at 298 K and 10 bar. These carbons had moderate isosteric heat of adsorption (20.3–41.8 kJ/mol) and acceptable CO 2 /N 2 selectivity (IAST: 10.8–43.7). The porous carbons developed therein had high surface area and outstanding microporosity, endowed them with promising application prospect in CO 2 capture and sequestration. [ABSTRACT FROM AUTHOR]

The O-containing hyper-cross-linked polymers were synthesized from phenol (2-naphthol) and formaldehyde dimethyl acetal by a simple one-step Friedel-Crafts reaction, they were subsequently carbonized using KOH as the activating agent, and their adsorption to CO 2 was carefully tested. The results indicated that these samples had a high Brunauer-Emmett-Teller surface area (up to 2241 m 2 /g), pore volume (up to 1.20 cm 3 /g), CO 2 uptake (up to 6.3 mmol/g at 273 K and 1.0 bar), and CO 2 /N 2 selectivity (up to 96 for the HCPs, and 22.5 for the porous carbon). In particular, the CO 2 adsorption was highly dependent on the ultramicropore volume (pore width<0.7 nm), while the CO 2 /N 2 selectivity mainly relied on the oxygen content and the ultramicropore structure. [ABSTRACT FROM AUTHOR]

• The porogens influenced the pore structure of the hyper-cross-linked polymers. • The Friedel-Crafts reaction induced steep increased for the S BET and V total of the polymers. • Hierarchical micro/mesoporous distribution was shown for the polymers using o-xylene as the porogen. • Microporous distribution was present for the polymers using paraffin as the porogen. • The porogens affected the phenol and rhodamine B adsorption of the hyper-cross-linked polymers. The porogens are the key components in the polymerization process, they do not participate in the polymerization reaction, but play a very important role in the pore structure of the synthetic polymers. Herein, o- xylene and paraffin were applied as the porogens and three acrylate-functionalized hyper-cross-linked polymers were fabricated according to the suspension polymerization and Friedel-Crafts reaction. The Brunauer-Emmett-Teller (BET) surface area (S BET) and pore volume (V total) of the initial copolymers were nearly zero, while the Friedel-Crafts reaction resulted in a steep increase of the S BET and V total. In particular, the resultant polymer, namely, HCP-PDVE-(Xy), using o- xylene as the porogen had the greatest S BET and V total (1126 m2/g and 0.958 cm3/g, respectively), while the S BET and V total of HCP-PDVE-(Lp) using paraffin as the porogen were the lowest (487 m2/g and 0.299 cm3/g, respectively). Meanwhile, HCP-PDVE-(Xy + Lp) using 50 % of o- xylene and 50 % of paraffin as the mixed porogens possessed the intermediate data. More importantly, HCP-PDVE-(Xy) had the hierarchical micro- and meso-porous distribution, while predominant micro-pores were distributed for HCP-PDVE-(Lp) and HCP-PDVE-(Xy + Lp). The equilibrium adsorption indicated that HCP-PDVE-(Xy + Lp) exhibited the largest equilibrium capacity (q e) to phenol while HCP-PDVE-(Xy) owned the largest q e to Rhodamine B. The phenol adsorption was subjected to the micro-pore filling mechanism while the high S BET , V total and the hierarchical micro-/meso-pores were favorable for the adsorption of Rhodamine B. The kinetic adsorption revealed that HCP-PDVE-(Lp) and HCP-PDVE-(Xy + Lp) (20 min) required much less time than HCP-PDVE-(Xy) (50 min) to reach the equilibrium for the phenol adsorption, and the micro-pore diffusion model characterized the kinetic data very well. The dynamic adsorption indicated that the dynamic capacity of phenol adsorbed on HCP-PDVE-(Xy + Lp) was 160.2 mg/g, very close to the q e (163.6 mg/g) in the equilibrium adsorption. [ABSTRACT FROM AUTHOR]

Due to the p-π conjugative effect between the nitrogen atom of the amide and the carbonyl, the amide carbonyl has much low reactivity and the Schiff base reaction between the amide and amine usually did not take place, but after the amide was polymerized, it's quite different. Herein, benzene-1,3,5-triyltris((9H-carbazol-9-yl) methanone) (HTCZ) is not able to have the Schiff base reaction with melamine. Surprisingly, after HTCZ was polymerized according to the Friedel-Crafts reaction, the resultant polymer PHTCZ-1 performed the Schiff base reaction with melamine successfully, and a kind of novel N-rich porous organic polymers, namely, PHTCZ-1-MA was successfully synthesized. Moreover, PHTCZ-1-MA owned much higher Brunauer-Emmett-Teller surface area (613 m2·g−1) and pore volume (0.57 cm3·g−1) with very high nitrogen content (42.39 wt%). The theoretical calculation showed that the positive charge of the carbonyl carbon increased by 18% after the polymerization, which greatly improved the reactivity of the carbonyl. Because of this amazing change, PHTCZ-1-MA was proven to be an excellent adsorbent for CO 2 capture (180 mg·g−1 at 273 K and 1.0 bar) and mercury(II) adsorption (335 mg·g−1 at 273 K). This study makes the impossibility possible and provides a unique synthesis strategy for the fabrication of a kind of N-rich porous organic polymers. [ABSTRACT FROM AUTHOR]

[Display omitted] • Phenolic hydroxyl modified hyper-crosslinked polymers were synthesized. • The polymers had high specific surface area with predominant microporosity. • The polymer was efficient for adsorption of berberine hydrochloride with the capacity of 505.42 mg/g. • The electrostatic interaction, hydrogen bonding, and π-π stacking were the primary driving forces. Phenolic hydroxyl modified hyper-crosslinked polymers were synthesized according to two consecutive Friedel-Crafts reactions. The first Friedel-Crafts reaction grafted plentiful phenolic hydroxyl on the polymers, and the second Friedel-Crafts reaction inserted abundant methylene in the polymer chains. The resulting polymers had relatively high Brunauer-Emmet-Teller (BET) surface area (S BET) and pore volume (V total). The adsorption experiments indicated that the intermediate polymer, namely, PS-CA (Polystyrene-Catechol), showed excellent adsorption for berberine hydrochloride (BBH) with the maximum capacity (q max) of 505.42 mg/g at 298 K, and the electrostatic interaction, π-π stacking and hydrogen bonding were the main driving forces. Anhydrous alcohol could desorb 75.36% of the adsorbed BBH from the polymer. On the other hand, the final polymers owned much higher adsorption of aniline and β-naphthylamine due to the micropore-filling. The dynamic adsorption used Chinese herbs Coptidis rhizoma solution present that the dynamic capacity was 248.70 mg/g dry resin. [ABSTRACT FROM AUTHOR]

[Display omitted] • Three phenolic hydroxyl-functionalized hyper-cross-linked polymers were produced. • These polymers contained abundant phenolic –OH (up to 17.95 wt%), high S BET and V total. • The polymers were promising for adsorptive removal of aniline with the q max of 210.9 mg/g. • Acid-base interaction and hydrogen bonding, especially the micropore-filling were the main driving forces. Herein, three phenolic hydroxyl-functionalized hyper-cross-linked polymers were synthesized according to two sequential Friedel-Crafts alkylation reactions at two different temperatures and they were used to adsorb aniline. The first reaction at 293 K brought abundant phenolic –OH (up to 17.95 wt%) to the intermediates, and the followed reaction at 353 K offered the resultant products with a hyper-cross-linked frameworks composed of plentiful rigid methylene bridges. The resulting polymers were promising for the adsorption of aniline, and the maximum capacities (q max) arrived at 210.9 mg/g. As the initial concentration of aniline was<100 mg/L, the adsorption efficiency reached>95 %, and the final concentration was lower than 0.1 mg/L, much lower than the emission concentration limit of aniline in China (1.0 mg/L). The adsorption mechanism discovered that acid-base interaction, electrostatic interaction and hydrogen bonding, especially the micropore-filling were important for the adsorption. [ABSTRACT FROM AUTHOR]

• The resulting polymers in this study showed high S BET (914 m2/g) and loaded controllable –NHCOCH 3 groups which were more effecient for the phenol adsorption. • The maximum capacity (q max) of HA10D was predicted to be 318.6 mg/g, larger than most of the data reported in the literature. • A novel synthetic strategy was developed based on two Friedel-Crafts reactions for the textural engineering of CMPS. • Dichloromethane was used for the introduction of plentiful methylene in the polymer chains. Chemically functionalized hyper-cross-linked polymers (HCLPs) with high Brunauer-Emmett-Teller (BET) surface area (S BET) and pore volume (V total) are efficient polymeric adsorbents for the adsorption of polar phenolic substances. Herein, chloromethylated polystyrene (CMPS) was used as the raw material and two consecutive Friedel-Crafts reactions were adopted to prepare the acylamino-functionalized HCLPs, and they were used to adsorb phenol in aqueous solution. In the first reaction, considerable acylamino groups were successfully loaded on the polymers, and the N and O contents were measured to be 1.03 wt% and 3.59 wt%, respectively. In particular, a great deal of rigid methylene joined the polymer chains in the second reaction as using dichloromethane as the novel external cross-linker, and hence acylamino-functionalized HCLPs with high S BET (up to 914 m2/g) and V total (up to 1.01 cm3/g) were prepared. The resulting HCLPs exhibited excellent adsorption of phenol, the fitted maximum capacity (q max) was measured to be 318.6 mg/g, and the adsorption reached the equilibrium within 120 min. The dynamic adsorption demonstrated that up to 79 BV (bed volume, 1 BV = 8 mL) of phenol could be removed at the initial concentration of 1000.5 mg/L and the dynamic capacity was scaled to be 316.1 mg/g, and ethanol could desorb phenol from the polymer column completely. The adsorption mechanism revealed that hydrogen bonding, π–π stacking, micropore-filling were the main driving forces for the adsorption. [ABSTRACT FROM AUTHOR]

[Display omitted] • This study synthesized a bifunctional ionic hyper-cross-linked polymer. • DHI-CSU-3-Br owns high S BET (1216 m2/g) and Br content (0.24 wt%), O content (9.11 wt%). • DHI-CSU-3-Br has good CO 2 capture capacity (134 mg/g, 273 K and 1.0 bar). • These DHI-CSU-Brs had a high CO 2 conversion property under mild conditions (70 ° C 0.1 MPa CO 2 in 4 h). A series of bifunctional ionic hyper-cross-linked polymers were synthesized by the Friedel-Crafts reaction and ionic post-functionalization. The as-prepared polymers had high Brunauer-Emmett-Teller surface areas (S BET , 623–1345 m2/g), considerable bifunctional ionic groups, namely bromide anions, and carboxyl groups. The polymer namely DHI-CSU-3-Br had a good CO 2 capture capacity (134 mg/g, 273 K, and 1.0 bar), moderate isotopic adsorption heat (28–38 kJ/mol), and excellent CO 2 cycloaddition ability. The catalytic experiments showed that 99% of propylene oxide was successfully converted to cyclic carbonate (70 °C, 0.1 MPa CO 2 , and 4 h). The catalytic activity of the polymer was easy to be recovered and it was repeatedly reused 5 times without significant reduction. This synthetic strategy for the preparation of the bifunctional ionic hyper-cross-linked polymers provided an alternative approach for CO 2 capture and catalytic conversion. [ABSTRACT FROM AUTHOR]

Abstract: We synthesized a series of gallic acid modified hyper-cross-linked resins named HJ-D11, HJ-D22, HJ-D44, HJ-D55 and HJ-D66 from macroporous chloromethylated styrene–divinylbenzene copolymer (PS) by adjusting the Friedel–Crafts reaction time from 1h to 6h and a further chemical modification by sodium gallate. These resins held different chemical structure (different uploading amounts of gallic acid on the surface) and different pore structure (different Brunauer–Emmett–Teller (BET) surface area and pore volume), which determined their different adsorption selectivity toward salicylic acid. HJ-D55 had the largest adsorption capacity toward salicylic acid and hence was employed as a specific adsorbent for adsorption equilibria and kinetics from aqueous solution. The isotherms were correlated by four linear Langmuir and a Freundlich equations and the Langmuir-II equation was shown to be the most suitable. The enthalpy ΔH, Gibb''s free energy ΔG and entropy ΔS were calculated to be negative. The kinetics was fitted by the pseudo-first-order and four linear pseudo-second-order rate equations and it was found that the pseudo-second-order rate equation-I was the best one for characterizing the kinetics. [Copyright &y& Elsevier]