Deformation of styrene—divinylbenzene copolymers and hypercrosslinked polystyrenes during solvent adsorption and desorption

An automated procedure was developed for monitoring fast changes in the size of spherical samples of polymers during their contact with a solvent or drying. The kinetics of bulk deformation in these processes was studied for a series of cross-linked polymers, viz., gel-type and porous styrene—divinylbenzene copolymers and poly(divinylbenzenes), and hypercrosslinked polystyrenes. Gel, macroporous, and hypercrosslinked polystyrenes are substantially different in the rate, mechanism, and degree of swelling, which is associated with the principal differences in their physical structures. An unusual effect of a sharp decrease followed by a temporary increase in the volume of porous polystyrene and poly(divinylbenzene) materials were observed during desorption (evaporation) of organic solvents. Water desorption is accompanied by an excessive bulk compression of porous granules giving rise to negative deformations, which gradually relax to the state equilibrium for the dry polymer. The results of dynamic desorption porometry (for water desorption) are indicative of a bimodal size distribution of micropores in hypercrosslinked polystyrene. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 467–476, March, 2007.     

Influence of heat treatment conditions on the porosity changes of sulfonated styrene/divinylbenzene copolymers

Sulfonic cation exchangers with two ion exchange group concentrations (0.5 and 2.4 mmol/g, samples A and B, respectively) were obtained by sulfonation of a porous styrene (S) and divinylbenzene (DVB) copolymer with chlorosulfonic acid. Strong thermal decomposition of the sulfonated copolymer A, accompanied by significant changes in its porous structure, starts at ca. 400°C. The char has no sulfonic groups. After heat treatment at 400°C in steam, a sorbent was obtained (yield 65%) that shows higher phenol sorption than the untreated sample when related to the bed volume. The chlorosulfonic derivatives of the initial copolymer were less thermally resistant than the sulfonic ones obtained by hydrolysis. Pyrolysis of the cation exchanger B, in its H+ and Ca²⁺ forms, was carried out at 900°C (yield of both chars close to 30%). By subsequent steam activation at 800°C to a 50% burn-off of the char, sorbents with well-developed, but distinctly different, porous structures were obtained. The activated char from the sulfonated copolymer in its hydrogen form was highly microporous and indicated an effective surface area of 1180 m²/g. However, because of a low contribution of mesopores, its ability to adsorb phenol from the liquid phase was not very high. The activated char from the calcium-doped copolymer, indicating a smaller surface area (580 m²/g) but characterized by a well-developed mesoporosity, was a better sorbent for phenol. © 1994 John Wiley & Sons, Inc.     

Synthesis of monodisperse poly(chloromethylstyrene-co-divinylbenzene) beads and their application in separation of biopolymers

The monodisperse, porous poly(chloromethylstyrene-co-divinylbenzene) beads of 7.9 microm were prepared by a single-step swelling and polymerization method. The seed particles prepared by dispersion polymerization exhibited good absorption of the monomer phase. Based on this media, a weak cation-exchange (WCX) stationary phase for HPLC was synthesized by a new chemically modified method. The prepared resin has advantages of biopolymer separation, high column efficiency, low column backpressure, high protein mass recovery, and good resolution for proteins. The dynamic protein-loading capacity of the synthesized WCX packings was 18.2 mg/g. Five proteins were separated in 3.0 min using the synthesized WCX stationary phase. The experimental results show that the obtained WCX resin has very weak hydrophobicity. The WCX resin was also used for the rapid separation and purification of lysozyme from egg white in 5.0 min with only one step. The purity and specific bioactivity of the purified lysozyme were found to be more than 93% and 70 245 U/mg, respectively.     

计算机Monte Carlo法模拟自由基交联共聚网络结构的增长

本文成功地用MonteCarlo方法模拟了以画面方式表示的苯乙烯-二乙烯苯交联共聚反应中大分子链增长、支化及交联的进化情况，并给出了相应的转化率，以定量模型的方式描述了该类反应。     

Highly crosslinked micron-range polymer microspheres by dispersion polymerization of divinylbenzene

Narrow disperse microparticles are formed by dispersion polymerization of commercial divinylbenzene in acetonitrile or ethanol solution in the presence of 2,2′-azobis(2-methylpropionitrile) initiator and polyvinylpyrrolidone stabilizer. The particles have average diameters between 1 and 9 μm depending on monomer concentration, solvent, and temperature. While the smaller particles are relatively smooth, surface texture increases with diameter to give popcorn shapes at 9 μm diameter. High crosslinker concentration is shown to be essential for particle formation. © 1993 John Wiley & Sons, Inc.     

Determination of Naphthalenesulfonate Isomers in Industrial Effluents and River Water by Solid‐Phase Extraction and Capillary Zone Electrophoresis

This work presents a method to separate polar naphthalenesulfonate (NS) isomers by capillary zone electrophoresis (CZE) with ultraviolet detection in industrial effluents and river water samples. The method involves extraction of samples by a polystyrene‐divinylbenzene copolymer (PS‐DVB) solid‐phase extraction (SPE) cartridge. The most effective CZE separation conditions were obtained in 20 mM borate buffer with 30% acetonitrile at pH 9.0 and 30 °C. The method proposed herein provides a high precision and sensitivity for NS isomers, to quantitation at ≤ 1.0 μg/L in 200 mL of the water samples. Recovery of the NS isomers in spiked water samples ranged from 73% to 87% while RSD ranging from 5.6 to 9.7%. The analysis of industrial effluents and river water samples was performed and naphthalene‐2‐sulfonate was found as a major pollutant. The difficulties in quantitating and identifying analytes in complex environmental samples can be resolved by using an internal standard response factor to calculate concentrations and relative migration times for peak confirmation.     

Comparison of octadecyl-bonded silica and styrene-divinylbenzene copolymer sorbents for trace enrichment purposes fundamental aspects II. Linear chromatographic behaviour of the extracting supports

Summary Two reversed-phase LC systems were investigated by frontal analysis for the determination of linear chromatographic conditions, as defined according to the isotherm concept. The Partisil ODS-3 bonded silica and the PRP-1 polystyrene-divinylbenzene resin were used as stationary phases together withtrans-2-hexen-al as test solute and methanol-water mixtures as mobile phases. Particular attention was paid to the respective influence of the two main parameters which may cause sorbent overloading, that is, the capacity factor (k′) and the solute concentration in the mobile phase (C_m). Provided that k′C_m≤10⁻² M, linear chromatographic behaviour was observed for both sorbents, the maximum capacities of which were found greater than 1mmolg⁻¹.     

Sensitive monitoring of penicillin antibiotics in milk and honey treated by stir bar sorptive extraction based on monolith and LC‐electrospray MS detection

In the present study, a convenient and sensitive method for determination of six penicillin antibiotics (amoxicillin, ampicillin, penicillin G, oxacillin, cloxacillin, and dicloxacillin) in milk and honey samples was developed. Milk and honey samples were diluted with water, then directly treated by stir bar sorptive extraction based on poly (vinylimidazole‐divinylbenzene) monolithic material as coating. The analytes were analyzed by LC/ESI‐ MS/MS. Several extraction parameters including extraction and desorption time, pH value, and ionic strength in sample matrix were investigated in detail. Under the optimized extraction conditions, the calculated detection limits for the target compounds were as low as 0.23–2.66 ng/kg in milk and 0.18–1.42 ng/kg in honey, respectively. Good linearity was obtained for analytes with the correlation coefficients (R²) above 0.997. Excellent method reproducibility was achieved in terms of intraday and interday precisions, indicated by the RSDs of <5.0 and <10.0%, respectively. Finally, the proposed method was successfully applied to the determination of penicillin antibiotics residues in different milk and honey samples.     

高内相乳液法制备整体柱及其分离性能研究

建立了高内相乳液(HIPE)法制备以甲基丙烯酸十二烷酯为功能单体(LMA),二乙烯基苯(DVB)为交联剂的新型毛细管电色谱整体柱。polyHIPE整体柱利用扫描电镜与BET进行了表征,表明了制备的整体柱具有较大的孔径与较好的比表面积,更好的通透性,可更好地满足高效快速分离分析的需要。实验中K2S2O8不仅可以作为引发剂,同时加热后残基能为固定相提供电渗流。优化表面活性剂span80含量、W/O比例对整体柱制备的影响,以硫脲与苯系物为目标化合物考察了整体柱的分离性能与效果。该方法用实际水样品苯系物分析,取得良好的效果。     

Plasma brominated polymer particles as grafting substrate for thiol‐terminated telomers

A combined surface activation and “grafting to” strategy was developed to convert divinylbenzene particles into weak cation exchangers suitable for protein separation. The initial activation step was based on plasma modification with bromoform, which rendered the particles amenable to further reaction with nucleophiles by introducing Br to a surface content of 11.2 atom‐%, as determined by X‐ray photoelectron spectroscopy. Grafting of thiol‐terminated glydicyl methacrylate telomers to freshly plasma activated surfaces was accomplished without the use of added initiator, and the grafting was verified both by reduction in bromine content and the appearance of sulfur‐carbon linkages, showing that the surface grafts were covalently bonded. Following grafting the attached glydicyl methacrylate telomer tentacles were further modified by a two‐step procedure involving hydrolysis to 2,3‐hydroxypropyl groups and conversion of hydroxyl groups to carboxylate functionality by succinic anhydride. The final material was capable of baseline separating four model proteins in 3 min by gradient cation exchange chromatography in a fully aqueous eluent.