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KINETICS AND CATALYSIS · 2024 · IF 1.3

Crosslinked Cation Exchange Resin with -SO3H Groups as an Efficient Solid Catalyst for the Ketalization of Ethyl Acetoacetate with Glycols

Chen Bo-Jiang,Wu Jian-Ping,Rukhsana,Xiang Fei-Yong,Shen Yong-Miao,Liang Xue-Zheng

Abstract A highly efficient protocol was developed for the synthesis of fructone spice from the ketalization of ethyl acetoacetate with ethylene glycol utilizing the sulfonated polydivinylbenzene (PDVB-SO 3 H) solid acid catalyst. A comparative analysis revealed that PDVB-SO 3 H exhibited better catalytic activity and reusability than conventional H 2 SO 4 and p -toluene sulfonic acid. The impact of reaction conditions, including temperature, reaction time, catalyst dosage, and molar ratio of reactants, was extensively investigated in order to optimize the reaction parameters. The results revealed the remarkable catalytic efficiency of PDVB-SO 3 H in synthesizing apple ester flavor, achieving a conversion rate exceeding 99% under reflux conditions with a ketone to alcohol ratio of 1.5. Furthermore, PDVB-SO 3 H solid acid demonstrated its versatility by enhancing the synthesis of a variety of fruit ketone flavors with high conversion rates. Notably, the catalyst displayed excellent recyclability, remaining active for up to six cycles without any noticeable decline in performance. Therefore, PDVB-SO 3 H solid acid exhibits immense potential for utilization in the chemical industry.

研究领域: 有机化学 · 食品科学
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Journal of Water Process Engineering · 2024 · IF 6.3

Synthesis of polyacrylate-divinylbenzene hydroxamic resins and its gallium adsorption performance in sulfuric acid solution

Yujie Li,Xiangxiang Chen,Bao Guo,Zilin Dai,Zhenxing Kong,Fangxu Li,Juhua Ou

In this study, the adsorption behavior of gallium ions on a synthesized hydroxamic acid resin from sulfuric acid solution was investigated, aiming to recover Ga directly from pressure leaching solution in zinc hydrometallurgical plant. Hydroxamic acid chelating resin (HA-PDR) was prepared by introducing hydroxamic acid groups into the pre-made polyacrylate resin (PDR) with methyl ester group through hydroxylamine reaction. Polyacrylate-divinylbenzene hydroxamic resins with a nitrogen content of up to 3.85 % were obtained at a divinylbenzene (DVB) content of 13 % and an optimal raw material ratio of NH 2 OH·HCl: NaOH: −CH 3  = 4:4.5:1 (molar ratio). The obtained materials was characterized using FTIR, XPS and SEM to verify the successful introduction of hydroxamic acid groups. The results of adsorption experiments showed that the adsorption capacity of 27.65 mg/g could be obtained with a chemical, multilayered, and heterogeneous adsorption process , and film diffusion and intra-particle diffusion rate controlled mainly the adsorption efficiency. It has been proven that polyacrylate-divinylbenzene hydroxamic resins has extremely high adsorption selectivity for gallium in sulfuric acid solution, and the desorption effect is obvious, which can be applied promisingly in the industrial development of gallium extraction technology from zinc leaching residue in sulfuric acid system.

研究领域: 化学工程 · 材料科学 · 环境工程
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JOURNAL OF CHROMATOGRAPHY A · 2017 · IF 3.981

The high efficient separation of divinylbenzene and ethylvinylbenzene isomers using high performance liquid chromatography with Fe-based MILs packed columns

Sha Chen,Xiao-Xin Li,Lun Shu,P. Somsundaran,Jian-Rong Li

The baseline separation of divinylbenzene (DVB) and ethylvinylbenzene (EVB) isomers was achieved using HPLC with MIL-53(Fe) and MIL-100(Fe) packed columns respectively when hexane/dichloromethane (100:0) used as mobile phase, at flow rate of 0.5   mL   min −1 , room temperature, and monitored with a UV detector at 254   nm. The two Fe-based MILs packed columns showed different separated performances, analytes had short retention time on MIL-100(Fe) compared to MIL-53(Fe), but selectivity of DVB isomers (m-DVB and p-DVB) was lower, which was mainly due to the differences of the pore size and structure of MILs. Moreover, the results of calculated thermodynamic parameters showed that the separation of DVB and EVB isomers was not only controlled by enthalpy change (ΔH), but also controlled by entropy change (ΔS). The head-to-tail stacking was the main reason for the separation according to the mechanism of the DVB and EVB isomers on Fe-based MILs packed columns.

CAS / MDL: 100-21-0 554-95-0
研究领域: 分析化学 · 材料科学
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SEPARATION AND PURIFICATION TECHNOLOGY · 2021 · IF 7.312

Ion-binding ameliorates the organic solvents nanofiltration performance of poly (butyl acrylamide-co-divinylbenzene) composites

Muntadher M. Alwan Almijbilee,Yifei Wang,Mao Peng,Aiqun Kong,Jinli Zhang,Wei Li

A new nanofiltration composite membrane poly (butyl acrylamide-co-divinylbenzene) (poly-TaDb) was synthesized via a facile photopolymerization on polyetherimide using the monomers of n- tert -butyl acrylamide and divinylbenzene, and evaluated the separation performance in organic solutions. The unique poly-TaDb toplayer has a feature of branch structure containing regularly distributed oxygen and nitrogen groups that work as the interacting sites with metal ions (Fe 3+ , Zn 2+ , and Cu 2+ ), as reflected by the characterizations of ATR-FTIR, XPS, AFM, etc. Without the metal ion treatment, the optimal poly-TaDb membrane shows the permeance of 31, 17, 20.4 L m −2 h −1 MPa −1 respectively for organic solutions of tetrahydrofuran (THF), methanol (MeOH) and acetonitrile (ACN), with the rejection rates higher than 90% toward EB dye (879.8 g.mol −1 ). After interacting with these metal ions, the obtained Fe-binding poly-TaDb membranes possess higher permeance, with the THF, MeOH, and ACN permeance enhanced respectively to 113, 35, and 24.2 L m −2 h −1 MPa −1 , meanwhile maintaining high dye rejection rate. While the Cu- and Zn-binding membranes show much higher permeance but lower dye rejection rate. Density functional theory (DFT) calculations disclose that the void size of the toplayer network increases in the order of: the pristine (11.40 Å) < Fe-binding (11.54 Å) < Zn-binding (11.60 Å) < Cu-binding membrane (11.63 Å). It is the suitable void size and charge density distribution in the toplayer network of Fe-binding membrane. that results in the superior nanofiltration performance. This work provides a facile route to explore new polymeric network materials for highly effective separation performance in organic solvents.

研究领域: 材料科学 · 环境工程 · 化学工程
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Crystals · 2025 ·Vol. 15 ·期 1 ·82 · IF 2.4

Development and Assessment of a Water-Based Drilling Fluid Tackifier with Salt and High-Temperature Resistance

Yue Gao,Xiaobo Wang,Yun Cheng,Xuan Qi,Hao Yan

A high-temperature-resistant copolymer thickener (DT) was synthesized through free radical polymerization, utilizing monomers such as N-vinylformamide (NVF), divinylbenzene (DVB), and acrylamide (AM) as the primary raw materials. The polymer system’s structure was characterized using FTIR and 1H NMR, while its thermal properties were analyzed through thermogravimetric analysis. The viscosity changes of the polymers were evaluated before and after high-temperature aging at various temperatures. The results indicated that the viscosity retention rate of the thickener DT in the base slurry at 240 °C and 15% NaCl was 87.1%. Additionally, it exhibited varying anti-aging cycles between 200 °C and 240 °C. In a slurry with 25% NaCl, the viscosity retention rate reached 130% at 200 °C. High-temperature and high-pressure rheological tests demonstrated that drilling fluids containing DT exhibit consistent rheological behavior within the temperature range of 150 °C to 180 °C, which aids in stabilizing the viscosity and strength of drilling fluids at elevated temperatures.

CAS / MDL: 64-17-5 67-64-1 865-49-6
研究领域: 化学工程 · 材料科学
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TALANTA · 2016 · IF 4.035

Octadecylamine-modified poly (glycidylmethacrylate-divinylbenzene) stationary phase for HPLC determination of N-nitrosamines

Junwei Liu,Yong Wang,Weixia Li,Peimin Zhang,Nani Wang,Shuchao Wu,Yan Zhu

Poly (glycidylmethacrylate-divinylbenzene) (Poly (GMA-DVB)) microspheres were prepared by the two-staged swelling and polymerization method, and modified with octadecylamine (ODA) to obtain ODA-poly (GMA-DVB) stationary phase for HPLC. The new material was characterized by scanning electron microscope, nitrogen adsorption-desorption measurement, Fourier transform infrared spectrum , elemental analysis and thermogravimetric analysis . The results showed that poly (GMA-DVB) microspheres had good monodispersity, porosity and ball shapes. The diameters and specific surface area of the microspheres were about 6   µm and 396   m 2   g −1 , respectively. ODA-poly (GMA-DVB) stationary phase had good thermal stability. Furthermore, the chromatographic performance of the stationary phase was illustrated by separating n-alkylbenzenes, mono-substituted benzenes and N -nitrosamines. Auxiliary quantum chemistry calculation was also carried out to evaluate the interaction mechanism. According to the evaluation, ODA-poly (GMA-DVB) stationary phase exhibited good hydrophobicity and hydrophobic selectivity, strong stereo-selectivity, polar interaction and π-π interaction. The multi-interaction mechanisms could very likely guarantee its excellent chromatographic performance for the analysis of complex samples. Finally, the column was successfully applied in the determination of N -nitrosamines in pickles sample.

CAS / MDL: 124-30-1
研究领域: 分析化学 · 材料科学
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Journal of Physical Chemistry C · 2019 · IF 4.309

Chemiluminescence as a New Indicator for Monitoring Hydroxylated Intermediates in Persulfate-Based Advanced Oxidation Processes

Zenghe Li,Xuejie Chen,Xu Teng,Chao Lu

The formation of hydroxylated intermediates is the first step in the persulfate-based advanced oxidation processes (AOPs) and depends directly on the oxidation degree of recalcitrant pollutants. Therefore, the monitoring of hydroxylated intermediates plays a vital role in persulfate-based AOPs for evaluating the oxidation degree and understanding the degradation mechanism. In this work, based on the attractive amplification of luminol chemiluminescence (CL) signals by hydroxylated intermediates, we developed a rapid, sensitive, and simple CL-based method to monitor hydroxylated intermediate (i.e., 3,5-diethyl-1,4-benzenediol) generated in persulfate-based AOPs of 1,2-divinylbenzene (DVB). The possible mechanism of the proposed CL system was that hydroxylated intermediates could be oxidized by persulfate in alkaline solution to form superoxide anion radicals and thus lead to an increase in the luminol CL. Finally, the proposed CL system was successfully applied in monitoring hydroxylated intermediates generated during persulfate-based AOPs under different degradation conditions, whose validity and reliability were verified by liquid chromatography–mass spectrometry (LC-MS) and Fourier-transform infrared spectroscopy (FT-IR). The generality of the proposed CL system was verified by monitoring hydroxylated intermediates generated in persulfate-based AOPs of methylbenzene and benzoic acid. These results suggested that this present CL system provided a promising indicator for monitoring hydroxylated intermediates in persulfate-based AOPs.

CAS / MDL: 3317-61-1
研究领域: 环境化学 · 分析化学 · 水处理
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JOURNAL OF CHROMATOGRAPHY A · 2021 · IF 4.759

Preparation of a polymer-based weak cation exchanger for ion chromatography via atom transfer radical polymerization

Xuefang Liu,Shuangshuang Pang,Feifang Zhang,Zongying Li,Bingcheng Yang

A novel polymer-based weak cation exchanger (WCX) for ion chromatography has been described. It was prepared by grafting tert-butyl acrylate and maleic anhydride onto the surface of poly(glycidyl methacrylate-divinylbenzene) microspheres via atom transfer radical polymerization, followed by hydrolytic treatment to produce acrylic and maleic acid groups. The obtained WCX showed better separation and higher selectivity for model cations relative to solely acrylic or maleic acid. Simultaneous separation of alkali and alkaline earth cations (including NH 4 + ) was achieved in a single isocratic run under suppressed mode, and ion exchange was found to dominate the separation process. Its utility was demonstrated for determination of several cations in a beer sample and the recovery was ranging from 98.4 to 109.9%.

研究领域: 分析化学 · 高分子科学 · 离子色谱
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Advanced Science · 2024 · IF 14.3

Recyclable Robust Plastic Scintillation Resin Achieving the Exceptional Separation and Detection of Technetium-99

Tonghuan Liu,Yichen Hu,Junqiang Yang,Kesheng Hu,Bei Qi,Yun Zhou,Juan Tong,Man Wang,Liang Huang,Keliang Shi,Xiaolin Hou

Rapid detection and absorption of 99 TcO 4 ⁻ contamination in the environment are critical due to its high radioactivity, long half-life, and significant environmental mobility. Resins have been demonstrated effective bifunctional properties for both the detection and separation of 99 TcO 4 ⁻ . However, the poor stability of these compounds limits their practical application. Here, a chemical grafting strategy is presented to synthesize ultra-stable plastic scintillation resin, in which 4-vinylpyridine and divinylbenzene are cross-linked as matrix polymer to withstand extreme conditions and a fluorophore “shield” to convert beta radiation into detectable signals. As expected, the as-obtained resin exhibits a high adsorption capacity of 549.2 mg g ⁻¹ for 99 TcO 4 ⁻ with a rapid kinetic response of just 10 min as well as superior selectivity at 1000 times excess of interfering ions and full reusability. Moreover, it showed remarkable stability under 800 kGy, 3.0 mol L −1 HNO 3 or 2.5 L solution continuous leaching, consistently maintaining high separation and detection efficiency after recycling 10 times. This strategy paves a new way to develop stable resin for the rapid capture and accurate measurement of 99 TcO 4 ⁻ , which owns great potential for practical application.

研究领域: 环境科学 · 核化学 · 材料科学
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CHINESE JOURNAL OF CHEMICAL ENGINEERING · 2024 · IF 3.7

B-COPNA resin formation from ethylene tar light fractions: Process development and mechanical exploration by molecular simulation

Hongyan Shen,Lingrui Cui,Xingguo Wei,Yuanqin Zhang,Lian Cen,Jun Xu,Fahai Cao

Efficient utilization strategy of ethylene tar (ET), the main by-product of ethylene cracking unit, is urgently required to meet demands for modern petrochemical industry. On the other hand, condensed polynuclear aromatic resin of moderate condensation degree (B-COPNA) is a widely used carbon material due to its superb processability, the production of which is however seriously limited by high cost of raw materials. Under such context, an interesting strategy was proposed in this study for producing B-COPNA resin using crosslinked light fractions of ethylene tar (ETLF, boiling point < 260 °C) facilitated by molecular simulation. 1,4-Benzenedimethanol (PXG) was first selected as the crosslinking agent according to the findings of molecular simulation. The effects of operating conditions, including reaction temperature, crosslinking agent and catalyst content, on the softening point and yield of B-COPNA resin products were then investigated to optimize the process. The reaction mechanism of resin production was studied by analyzing the molecular structure and transition state of ETLF and crosslinking agent. It was shown that PXG exhibited a superior capacity of withdrawing electrons and higher electrophilic reactivity than other crosslinking agents. In addition to the highest yield and greatest heat properties, PXG-prepared resin contained most condensed aromatics. The corresponding optimized conditions of resin preparation were 180 °C, 1:1.9 (PXG:ETLF) and 3% (mass) of catalyst content with a resin yield of 78.57%. It was the electrophilic substitution reaction occurred between the ETLF and crosslinking agent molecules that was responsible for the resin formation according to the experimental characterization and molecular simulation. Hence, it was confirmed that the proposed strategy and demonstrated process can achieve a clean and high value-added utilization of ETLF via B-COPNA resin preparation, bringing huge economic value to the current petrochemical industry.

研究领域: 化学工程 · 材料科学 · 石油化学
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MOLECULES · 2025 ·Vol. 30 ·期 1 ·166 · IF 4.6

Anisotropic Microparticles with a Controllable Structure via Soap-Free Seeded Emulsion Polymerization

Yanping Duan,Xia Zhao,Xiang Nan,Zhifeng Sun,Xiaoyun Lei,Wei Wang,Hong Hao,Jianfang Li

Anisotropic particles have a wide range of applications in materials science such as emulsion stabilization, oil–water separation, and catalysis due to their asymmetric structure and properties. Nevertheless, designing and synthesizing large quantities of anisotropic particles with controlled morphologies continue to present considerable challenges. In this study, we successfully synthesized anisotropic microspheres using a soap-free seed emulsion polymerization method. This approach combines the benefits of seed emulsion polymerization with emulsion interfacial polymerization. By varying the concentrations of dissolved polymeric monomers, 3-methacryloyloxypropyltrimethoxysilane (MPS), and the initiator of potassium persulfate (KPS), different shapes of bowl, cap, and three-sided concave particles were obtained in surfactant-free aqueous solutions, simplifying the post-treatment process. The cap particles are Janus particles with good emulsion stability to toluene/water emulsions over 30 days. The catalytic degradation of 4-nitrophenol (4-NP) was investigated after loading silver nanoparticles on the surface of the particles by in situ deposition. The anisotropic particles obtained in this work have potential applications in emulsion stabilization and catalysis.

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LANGMUIR · 2024 · IF 3.7

Anisotropic Magnetic Polymeric Particles with a Controllable Structure via Seeded Emulsion Polymerization

Qianrui Xu,Yingrui Nie,Diyan Wu,Jiatong Li,Jiaxin Zeng,Zhi-Fei Wang,Yong Jiang

Magnetic polymer composites have been widely utilized in potential applications in material science, such as reduction of dyes, immunodiagnostics, biomedicals, and magnetically controllable photonic crystals owing to large surface areas, fast separation, and recyclable performance. In this work, anisotropic magnetic particles were prepared by seeded emulsion polymerization, with morphologies of “Fe3O4-shell”, “hemisphere-like”, “raspberry-like”, “multiple lobes-like”, and “sandwich-like”. Poly(styrene/divinylbenzene/mono-2-(methacryloxy)ethyl succinate)@ Fe3O4 (P(St/DVB/MMES)@Fe3O4) were the seed microspheres, and P(St/DVB/MMES)@Fe3O4@polymer particles are achieved by seeded emulsion polymerizations. The morphology of the particles depends on polymerization conditions (monomer ratios and surfactant), particle properties, and so on. Then, the minimum surface free energy change principles were used to predict the equilibrium morphologies of the magnetic polymer composites. Through theory, the model gives the correct tendency and good agreement with the equilibrium morphology which was in tandem with TEM results. Lastly, after in situ surface deposition of Ag nanoparticles, magnetic composite particles with sandwich-like morphology were applied for the catalytic degradation of 4-nitrophenol (4-NP) reacting with NaBH4. The apparent rate coefficient is 0.0069 s–1, and it can keep mainly about 80% efficiency in catalysis after five cycles.

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