Hypercrosslinked Polymers Research Articles

A novel crosslinker for synthesizing hypercrosslinked ionic polymers containing activating groups as efficient catalysts for the CO2 cycloaddition reaction

A novel crosslinker for synthesizing hypercrosslinked ionic polymers with high ionic content, high specific surface area and hydroxyl activating group as efficient heterogeneous catalysts for CO2 cycloaddition at atmospheric pressure.

Efficient adsorption of methyl orange and methyl blue dyes by a novel triptycene-based hyper-crosslinked porous polymer.

It is still a great challenge to develop new materials for the highly efficient entrapment of organic dyes from aqueous solution. Herein, a novel triptycene-based hyper-crosslinked porous polymer (TPP–PP) was designed and synthesized by a simple Friedel–Crafts reaction. The obtained polymer TPP–PP has a high surface area, abundant pore structure and stable thermal performance. Due to the above characteristics, TPP–PP has good adsorption performance for anionic methyl orange solution (MO) and cationic methyl blue solution (MB). Under the optimal experiment conditions, the TPP–PP showed an excellent adsorption capacity for MO (220.82 mg g−1) and MB (159.80 mg g−1), respectively. The adsorption kinetics fitted the pseudo-second-order model. The adsorption of MO by TPP–PP reaches equilibrium within 180 minutes, and the adsorption of MB reaches equilibrium within 150 minutes. The adsorption behavior was not only spontaneous but also endothermic in reality. At the same time, TPP–PP also has good reusability. After 5 cycles of experiments, the removal rate of MO and MB by TPP–PP can still reach more than 80%. Thus, the Friedel–Crafts reaction crosslinked method might be a promising approach for the synthesis of novel material for the highly efficient extraction of dye wastewater.

One-pot route to fine-tuned hypercrosslinked polymer solid acid catalysts

A simple route to highly sulfonated hypercrosslinked polymers: low-cost and tunable heterogeneous catalysts.

Metal-free, atom and redox-economical construction of C–C bonds enabled by oligofluorene-containing hypercrosslinked polymers

A metal-free, atom and redox-economical approach for the assembly of C–C bonds has been developed using oligofluorene-based hypercrosslinked polymers as the recoverable and reusable photocatalysts under visible-light irradiation.

Synthesis and post-polymerization functionalization of a tosylated hyper-crosslinked polymer for fast and efficient removal of organic pollutants in water

The synthesis and post-synthetic modification of a novel tosylate-functionalized hyper-crosslinked polymer (HCP) for the purpose of water remediation are reported.

Carbonate-based hyper-cross-linked polymers with pendant versatile electron-withdrawing functional groups for CO2adsorption and separation

The simple and highly efficient preparation of porous hyper-cross-linked polymers (HCPs) with high surface area and manifold functionalities for high-performance CO2uptake and selective separation has drawn significant attention in the past decade.

Gas sorption and selectivity study of N,N,N′,N′-tetraphenyl-1,4-phenylenediamine based microporous hyper-crosslinked polymers

One of the most important parameters to design porous polymeric materials for gas storage and separation is to discover appropriate linker. Determining the effect of linker, in fixed core, over the selectivity and adsorption has been great challenge. Here, three different N,N,N′,N′-tetraphenyl-1,4-phenylenediamines (TPPA) based microporous hyper-crosslinked polymers synthesized by the Friedel-Craft reactions. Hypercrosslinked polymer, TPPA-DMM, was obtained from dimethoxymethane (DMM) and hypercrosslinked-covalent polymer, TPPA-DMB, from dimethoxybenzene (DMB) in presence of FeCl3. TPPA-CC, covalent triazine polymer was synthesized from cyanuric chloride (CC) via AlCl3 as the catalyst. After the careful characterization of these microporous structures with different analytical and spectral analyses, the gas uptake (for CO2, CH4, O2, CO, and H2) and selectivity properties (for CO2/N2, CO2/O2, for CO2/CO and CO2/CH4) were comparatively investigated at pipe gas temperatures and up to 1 bar. The high BET specific surface areas ranging from 742 to 883 m2/g with ultramicropore characters (0.53–0.58 nm), high chemical stability in different solvents even in concentrated acid and thermal stability (up to 450 °C) promised that these materials can be used in pipe gas processes. By changing the linkers on the core, materials have high gas uptake properties reaching 12.98 wt% for CO2 uptake, 1.57 wt% for CH4 uptake, 1.06 wt% for CO uptake at 1 bar/273 K and also reaching 1.28 wt% for H2 uptake at 1 bar/77 K. In addition, the unusual N2 phobic character down to 0.2 wt% and O2 phobic character down to 0.3 wt% were observed. The selectivity was calculated by using the ideal adsorbed solution theory (IAST). The selectivities were found reaching 80.4 for CO2/N2, 8.5 for CO2/CH4, 30.1 for CO2/CO and 39.1 for CO2/O2. These calculations show that the obtained polymers can be used in post combustion processes which needs high pressures and temperatures. The selectivities of the synthesized materials for the gas sorptions changed drastically by switching the linkers in all three materials. Interestingly, IAST calculations from single to dual gas, in the different ratios, showed that selectivities were almost the same for each polymer within itself at same temperature. To date, these are the first reported discoveries for the porous organic polymers in the literature.

Synergistic Catalysis of Hypercrosslinked Ionic Polymers with Multi-Ionic Sites for Conversion of Co2 to Cyclic Carbonates

Synergistic Catalysis of Hypercrosslinked Ionic Polymers with Multi-Ionic Sites for Conversion of Co2 to Cyclic Carbonates

A robust ethane-selective hypercrosslinked porous organic adsorbent with high ethane capacity

A hypercrosslinked polymer adsorbent exhibits record high C2H6 capacity, excellent recyclability, and superior structural stability.

The influence of the size of aromatic monomers on the structure and catalytic activity of polymer solid acids

High activity hyper-crosslinked polymer solid acids (HCPSAs) were prepared from different aromatic monomers, and the structure was regulated by selecting the type and size of aromatic monomers.

Hard Carbons Derived from Phenyl Hyper-Crosslinked Polymers for Lithium-Ion Batteries

Hard Carbons Derived from Phenyl Hyper-Crosslinked Polymers for Lithium-Ion Batteries

Correction: s-Tetrazine-functionalized hyper-crosslinked polymers for efficient photocatalytic synthesis of benzimidazoles

Correction for ‘s-Tetrazine-functionalized hyper-crosslinked polymers for efficient photocatalytic synthesis of benzimidazoles’ by Wan-Kai An et al., Green Chem., 2021, 23, 1292–1299, https://doi.org/10.1039/d0gc03719b.

Determination of Synthetic Estrogens in Milk by a Novel Hyper-Crosslinked Polymer Spme Coupled with Hplc-Ms

Determination of Synthetic Estrogens in Milk by a Novel Hyper-Crosslinked Polymer Spme Coupled with Hplc-Ms

A metal-free hydroxyl functionalized quaternary phosphine type ionic liquid polymer for cycloaddition of CO2 and epoxides.

Quaternary phosphine type hypercrosslinked polymer catalysts were successfully prepared using the Friedel-Crafts alkylation reactions, which benefit from the synergistic effects between the Brønsted acidity of the hydroxyl group and nucleophilicity of the Br- group as well as the CO2 capture of the ionic liquids. The as-obtained metal-free catalysts facilitate the cycloaddition and synthesis of high value-added fine chemicals.

Synthesis of an Ethylenediamine-Modified Hypercrosslinked Polymer and its Preliminary Study for Antipyrine and Pamabrom Extraction

Emerging contaminants (EC) are naturally occurring or synthetic chemicals that may enter the environment and cause adverse effects to aquatic and human health. EC consist of pharmaceuticals, pesticides, organic chemicals and personal care products that present in water sources at low concentrations (μg/L), hence, they are not widely monitored in the environment. Pharmaceuticals contain biologically-active components that pollute water courses. These generally originate from human waste or the uncontrolled release of residues from chemical plants. The removal of pharmaceutical compounds from water can be carried out using polymeric materials with high specific surface areas and good selectivity due to the presence of accessible active functional groups. In the present work, the synthesis and characterizations of microspheres, acrylonitrile-co-divinylbenzene-80-co-vinylbenzylchloride(AN-co-DVB-80-co-VBC) terpolymers with weak-anion-exchange (WAX) character and high porosity have been successfully carried out. The polymeric microspheres were synthesized by precipitation polymerization and subsequently hypercrosslinked (HXL) via a Friedel-Crafts reaction. The HXL terpolymer was then chemically modified with 1,2-ethylenediamine (EDA) to incorporate diamine functional groups, which improved the selectivity of the HXL microspheres towards polar compounds. Fourier Transform-Infrared (FT-IR) spectra of the EDA-modified HXL terpolymer showed that the nitrile groups derived from AN units were utilized due to the presence of diamine groups along the polymeric chains, indicating that the chemical modification was successful. The microanalysis showed that the chlorine content of the polymer was significantly decreased after hypercrosslinking, indicating that the reaction was successful. The nitrogen content increased after chemical modification with EDA, indicating successful chemical modification of the microspheres. The polymers were in the form of spherical monodisperse polymer microspheres with mean particle diameters of ~7.00 μm. The highest observed specific surface areas (SSAs) of the HXL terpolymer and EDA-modified HXL terpolymer were 2,274 m²/g and 503 m²/g, respectively. The microspheres were utilized to extract the pharmaceutical compounds antipyrine and pamabrom from aqueous solution using the dispersive solid phase extraction (DSPE) method. The extraction analysis was carried out by Gas Chromatography–Mass Spectrometry (GC-MS). The influence of adsorbent dosage, extraction time and elution time were studied to evaluate the performance of the adsorbent in the extraction of antipyrine and pamabrom from aqueous solution. It can be concluded that EDA-modified HXL poly(AN-co-DVB-80-co-VBC) was more favourable towards the extraction of antipyrine, which had a maximum extraction efficiency (EE%) of 95%, compared to that of pamabrom (maximum EE% of 54%).

Construction of hypercrosslinked polymers with styrene-based copolymer precursor for adsorption of rare earth elements

Adsorption and separation of rare earth elements (REEs) are of significant importance due to their unique properties and low supply of these elements. Porous hypercrosslinked polymers (HCPs) are currently an important category of polymer adsorbents and attracting great interest because of their merits including high surface area, moderate synthetic conditions and various building blocks. Herein, for the first time, we constructed HCPs with copolymers precursors and applied to the adsorption of REEs. Styrene (S) and glycidyl methacrylate-iminodiacetic acid (GMA-IDA) were polymerized by a facile reversible addition-fragmentation chain transfer process, and GMA-IDA-co-PS copolymers were employed as precursors to construct HCPs. The adsorption behavior of REEs was investigated in detail with Tb3+ as a representative. The separation of light, medium and heavy REEs was also studied. It is the first attempt that copolymers were employed to the preparation of HCPs and used in the area of REEs adsorption, which can serve as a foundation for further design and application of various HCPs in the field of adsorption.

Microporous triazine-based ionic hyper-crosslinked polymers for efficient and selective separation of H2S/CH4/N2

Ionic hyper-crosslinked polymers (IHCPs) are a class of unique porous organic polymers (POPs) that not only have high specific surface area and porosity, but also have abundant anionic and cationic sites. These characteristics make IHCPs potential excellent gas adsorbing materials. In this work, a series of microporous triazine-based IHCPs were prepared through Friedel-Crafts alkylation and quaternization reaction for selective separation of H2S/CH4/N2. The structure and textural properties of these IHCPs were characterized in detail by FTIR, 13C solid-state NMR, XPS, XRD, TGA, SEM, TEM, H2S-TPD and N2 adsorption–desorption experiments, respectively. The H2S adsorption capacity of IHCPs was up to 4.85 mmol∙g−1 at 25 °C and 1.0 bar, in which IHCPs-2 shows an appreciable IAST selectivity for H2S/CH4 and H2S/N2 (23.0 and 83.8 at 25 °C and 1.0 bar, respectively). Furthermore, the thermodynamics parameters of H2S absorption, including enthalpy change (ΔH°), entropy change (ΔS°), and Gibbs free energy (ΔG°), were also calculated from isothermal adsorption data, and the results showed that the adsorption process of H2S is exothermic and physical adsorption. This work demonstrated that the microporous triazine-based IHCPs can be used as a promising H2S adsorption material for selective separation of H2S/CH4/N2 mixed gas.

Porous carbon black-polymer composites for volatile organic compound adsorption and efficient microwave-assisted desorption

Adsorbents with high surface area, thermal stability and microwave absorption ability are highly desired for cyclic adsorption and microwave regeneration processes. However, most polymeric adsorbents are transparent to microwaves. Herein, porous hyper-crosslinked polymers (HCP) of (4,4′-bis((chloromethyl)-1,1′-biphenyl-benzyl chloride)) with different carbon black (CB) contents were synthesized via the Friedel-Crafts reaction. CB was selected as the filler due to its low cost and high dielectric loss and was embedded inside the polymer structure during polymerization. CB-containing composites showed enhanced thermal stability at elevated temperatures, and more than a 90-times increase in the dielectric loss factor, which is favorable for microwave regeneration. Nitrogen physisorption analysis by the Bruner-Emmett-Teller isotherms demonstrated that CB presence in the polymer structure nonlinearly decreases the surface area and total pore volume (by 38% and 26%, respectively at the highest CB load). Based on the characterization testing, 4 wt% of CB was found to be an optimum filler content, having the highest MW absorption and minimal effect on the adsorbent porosity. HCP with 4 wt% CB allowed a substantial increase in the desorption temperature and yielded more than a 450% enhancement in the desorption efficiency compared to HCP without CB.

Suzuki–Miyaura Cross-Coupling by a Pd–Schiff Base Complex Immobilized on a Hypercrosslinked Polymer

Key words palladium catalysis - hypercrosslinked polymer - Schiff bases - Suzuki–Miyaura reaction - cross-coupling

Evaluation of three sorbent‐phase extraction techniques based on hyper‐crosslinked polymer for the extraction of five endocrine disrupters in water

A series of low-cost hyper-crosslinked polymers were prepared by an easy one-step Friedel-Crafts reaction. The synthesized hyper-crosslinked polymers exhibited remarkably porous structure, large surface area, and hydroxyl groups, which can be employed as an ideal adsorbent material for novel sorbent-phase extraction techniques. Based on this, using hyper-crosslinked polymers as sorbent and coating, three novel extraction methods, including micro-solid-phase extraction, dispersive solid-phase extraction, and solid-phase microextraction, were explored and evaluated for simultaneous measurement of five endocrine-disrupting compounds (triclosan and bisphenol A, tetrabromobisphenol A, tetrabromobisphenol A bisallylether, and tetrabromobisphenol A bis(2,3-dibromopropyl ether)) in environment water prior to high-performance liquid chromatography-ultraviolet. The influence of experimental parameters on three extraction techniques such as extraction time, the amount of hyper-crosslinked polymers, extraction temperature, ionic strength, and desorption conditions were optimized. Three previously mentioned methods provided limits of detection ranging from 0.01 to 0.05 μg/L, and high recoveries (85-99%) with relative standard deviations of 1.7-5.6%. This study presented the merits and disadvantages of three proposed extraction methods and their potential for effective monitoring of hazardous pollutants in real water samples.