The influence of the diluent system on the porous structure formation of copolymers based on 2‐vinylpyridine and divinylbenzene. Diluent system. III. heptane/methylethylketone

The effects of the diluent mixture's composition and crosslinking degree [divinylbenzene (DVB)] on the porous characteristics of the anion‐exchange resins based on 2‐vinylpyridine (2VP) and DVB, synthesized by suspension polymerization, in the presence of a diluent mixture constituted of heptane (HEP) and methyl ethyl ketone (MEK) at different proportions, were evaluated. The resins were characterized by mercury porosimetry, nitrogen adsorption (Brunauer–Emmett–Teller (BET) method surface area determination), apparent density, and swelling in methanol. The optical appearance of the copolymer beads was examined by optical microscopy. It was found that the development of porosity was attained whenever the content of methyl ethyl ketone in the diluent mixture was increased for all DVB contents employed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 666–669, 2004     

Modification of porous copolymers network based on acrylonitrile

Summary The preparation of a chelating ion-exchange network based on acrylonitrile was carried out by chemical modification with hydroxylamine. The beads of resin were synthesized by aqueous suspension copolymerization of acrylonitrile (AN), styrene (STY) and divinylbenzene (DVB). The influence of diluent used in the suspension polymerization on the structure of the resulting copolymers was evaluated. The diluents employed were heptane (HEP), toluene (TOL) and anisole (ANI). It was found that the AN incorporation into copolymer structure was dependent on the diluent used. Conversion of nitrile groups into the amidoxime was conducted by treatment with hydroxylamine under alkaline solution. The resins were characterized by apparent density, surface area, average pore diameter, elemental analysis (CHN), FTIR and optical microscopy. Based on the results obtained, it was possible to control the porosity by diluent employed in the synthesis and to modify chemically a resin containing nitrile groups by hydroxylamine reaction. Received: 6 October 2001/Revised version: 2 April 2002/ Accepted: 11 April 2002     

Recovery of uranium from seawater V. Preparation and properties of the macroreticular chelating resins containing amidoxime and other functional groups

We have synthesized macroreticular chelating resins containing amidoxime groups from acrylonitrile (AN)-divinylbenzene (DVB)-alkyl acrylate, alkyl methacrylate, or vinylpyridine (VPy) copolymer beads. It was found that the chelating resin (RNMH)-containing amidoxime groups prepared from AN-DVB-methyl acrylate (MA) indicated the highest adsorption ability for uranium in seawater. Hydroxamic acid and carboxylic groups in addition to amidoxime groups were formed during the reaction of the copolymer beads with a methanol solution of hydroxylamine. The adsorption ability for uranium was greatly influenced by the physical pore structure (macropore) and the pore structure formed by the swelling(micropore). RNMH (RNMH10-10) prepared with 10 mol% of DVB and 10 mol% of MA had the highest adsorption ability and physical stability for uranium. On the other hand, improved adsorption ability for uranium was not observed in the case of the macroporous resins (RNPyH) prepared by the copolymerization of VPy as the basic component. After seawater was passed through the column packed with RNMH10-10 at a space velocity (SV) of 180 h^?1 (up-flow) for 10 days, the amount of uranium adsorbed on the resin was about 100 mg/dm³-R and 260 mg/kg-R.     

Water‐swellable hydrophobic porous copolymer resins based on divinylbenzene and acrylonitrile. II. Pore structure and adsorption behavior

By using purified divinylbenzene (DVB, 98.8%) or technical DVB (79.3%), the hydrophobic, but water‐wettable or swellable porous copolymer resins based on DVB and acrylonitrile (AN) could be prepared with a wide range of pore structures under certain conditions. The specific surface area for the resulting AN/DVB resin, with an AN/DVB ratio of 40/60 (by mole), could reach a value of 704 m²/g, while such a resin is still water wettable or swellable by direct contact with water. The adsorption behavior of the AN/DVB resins was investigated by focusing on the comparison between the resins with and without prewetting, using caffeine and phenol as model adsorbates. Adsorption behavior of the AN/DVB resins, without prewetting, correlates well with the wetting ability of the resins in water, suggesting that a well water‐wettable hydrophobic porous AN/DVB resin could be directly applied, in a dry state, to the adsorption in an aqueous medium, almost without diminishing the ability of the resin to adsorb the solutes. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2050–2056, 2004     

Water‐swellable hydrophobic porous copolymer resins based on divinylbenzene and acrylonitrile. I. Water‐swelling behavior

Hydrophobic porous copolymer resins based on divinylbenzene (DVB) and acrylonitrile (AN) could be prepared as directly swellable in water by using purified DVB (98.8%) and technical DVB (79.3%) in the presence of 1,2‐dichloroethane as porogen. Compared with the resins based on DVB and methyl acrylate (MA/DVB resins), the AN/DVB resins thus obtained are water‐swellable over a wider range of copolymer compositions, and the swelling ability of the AN/DVB resins in water was further confirmed by investigating the water‐swelling behavior of the AN/DVB resins undergoing solvent treatment. The copolymer composition (AN and DVB contents) of the resins and the property of the porogen affect the water‐swellable behavior of the AN/DVB resins profoundly. The results in this paper provide additional evidence to support the hypothesis that the swelling ability of a hydrophobic porous copolymer in water originates from the existence of the inner stresses in the strained polymer network of the resins and the weak interaction between polymer and water that is negligible in the case of a conventional hydrophobic polymer. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2041–2049, 2004     

1，3-丙二醇发酵液脱盐用离子交换树脂的筛选

研究了用离子交换树脂处理1,3-丙二醇发酵液,选用6种阳离子交换树脂和3种阴离子交换树脂,以交换容量、电导率和再生时间为指标,考察了树脂的脱盐效果。结果表明：阳离子交换树脂中的D001-cc对1,3-丙二醇发酵液的处理效果最好,150mL树脂的平均交换容量达到240mL,电导率能降到2250gS／cm,再生时间7h;3种阴离子交换树脂中,D301R的去盐效果最好。     

Application of concentrated emulsion polymerization for preparation of ion‐exchange chromatography columns

Concentrated inverse emulsion polymerization was used for making chromatography columns [based on crosslinked polystyrene divinylbenzene (PS–DVB)] with pore sizes less than 10 μm. For application of these columns in ion‐exchange chromatography, the sulfonation process was performed by concentrated sulfuric acid. According to X‐ray fluorescence analysis and ASTM D2187‐94 standard test method, the total capacity of resins (sulfonated PS–DVB) increased with increasing time. To obtain high‐capacity resins, the sulfonation process was carried out over two steps. The optimum sulfonation time for the first and second sulfonation steps was 24 and 48 h, respectively. By increasing the DVB content, the capacity of resins passed through a maximum; thus the optimum amount of DVB, as crosslinking agent in the sulfonation process, was 22.5%. The structure of columns was analyzed by scanning electron microscopy (SEM). SEM evaluations showed that the porous structure of PS–DVB resin was maintained intact after the sulfonation steps. According to DSC–thermal gravimetry thermograms, it was confirmed that the residual monomer concentration after polymerization process was negligible. Also, the PS–DVB resins exhibit thermal stability up to 300°C and this quantity would increase with increasing amount of DVB weight percentage. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2973–2979, 2004     

Characterization of macroporous 1‐vinyl‐2‐pyrrolidone copolymers obtained by suspension polymerization

Radical suspension copolymerization of 1‐vinyl‐2‐pyrrolidone (VP) with three different cross‐linkers: divinylbenzene (DVB), trimethylolpropane trimethacrylate (TRIM), and di(methacryloxymethyl) naphthalene (DMN) was used to prepare macroporous microspheres. During the copolymerization, the mixture of toluene and n‐dodecane as a pore‐forming diluent was used. All samples were characterized in terms of particle size and distribution, nitrogen content, specific surface area total pore volume, and pore size distribution. It was found that specific surface area of the obtained beads is strongly dependent on the diluent system and the type of cross‐linker and achieves value from 27 to 845 m²/g. To determine the influence of chemical structure of cross‐linkers on the selectivity and polarity of the copolymers, inverse gas chromatography was applied. In addition, VP–DVB and VP–DMN copolymers were modified by sulfonation into cation‐exchangers with cation exchange capacity equal 1.98 and 2.31 mmol/g, respectively. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Diametric swelling and hydrophilic characteristics of fibrous acrylic ion exchanger

In our previous works, modified acrylic fiber samples with highly ion‐exchange ability were described. These fibers contain suitable functional groups such as amidoxime, amid, and amine groups in their molecular chains. In this work, swelling in fiber diameter and hydrophilic properties of the modified acrylic fiber samples, as important parameters affecting on ion‐exchange efficiency, were investigated. The results showed that all modification treatments gave rise to diameter swelling ratio, but this does not mean that sample with highest swelling ratio in all cases can result in highest ability to ion‐exchange. In other words, the relation between them was complicated, and several factors such as the kind and the size of ion adsorbent and crosslinking ability of chemical reagent were used for modification interfere in ion‐exchange phenomena.The results of moisture adsorption indicate that incorporating functional groups by modification treatments enhance moisture adsorption in which samples with higher ion‐exchange ability possess higher hydrophilic property. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis,Characterization, and Evaluation of Gel‐Type Poly(4‐Vinylpyridine) Resins for Plutonium Sorption

Abstract

Three different cross‐linked (4, 8, and 12%) gel‐type strong‐base poly(4‐vinylpyridine) resins (PVP) have been synthesized and characterized by elemental analysis, IR, exchange capacity, and moisture content. The uptake of plutonium and uranium was measured as a function of nitric acid concentration using all the three PVP resins. Plutonium sorption and elution kinetics experiments were also performed on all three PVP resins and compared with the benchmark, a gel‐type quarternary ammonium type anion‐exchange resin. The plutonium sorption rate decreases with the increase in cross‐linkage of the resin. All the three PVP resins exhibit better elution kinetics compared to the benchmark. The results on kinetic experiments performed on all three‐gel‐type resins indicated 8% gel‐type PVP resin with 50–100 mesh as a better candidate for plutonium processing or purification. Radiation degradation studies were carried out on the 8% PVP resin by gamma irradiation up to 200 MRad. The irradiated resins were characterized by IR, TGA, and SEM.

The exchange capacity, moisture content, and plutonium uptake were also evaluated for the irradiated PVP resins in comparison with the benchmark. The results indicated a better radiation stability for PVP resin over the benchmark.     

Evaluation of New Anion Exchange Resins for Plutonium Processing

Abstract

This paper presents the results of studies comparing the performance of two new anion exchange resins for plutonium processing with the well proven and widely used benchmark, Dowex 1X4 resin. In this connection, the experiments on distribution ratio measurement of plutonium as a function of nitric acid concentration, Pu(IV) sorption kinetics, chemical, thermal, and radiation degradation of the two commercially available anion exchange resins namely, Tulsion A‐PSL 4 and Tulsion A‐PSL 6 have been studied, vis‐à‐vis the benchmark. Tulsion A‐PSL 6 was found to have higher plutonium sorption capacity and polymer matrix stability as well as better kinetics of sorption than the other two resins, while Tulsion A‐PSL 4 and Dowex 1X4 were found to have comparable sorption capacity, kinetics, and resistance to chemical and radiation degradation. The small‐scale evaluation of these new anion exchange resins shows that they can be used for the purification and concentration of plutonium.     

强酸树脂催化双-三羟甲基丙烷丙烯酸酯合成

以双-三羟甲基丙烷和丙烯酸为原料,以强酸性离子交换树脂作为催化剂合成了双-三羟甲基丙烷丙烯酸酯。研究了影响反应的因素和催化剂的重复使用性能。结果表明,NKC-9型阳离子交换树脂具有良好的催化活性,在醇酸摩尔比为4.5∶1、催化剂用量占酸醇总质量的7%、搅拌转速400 r/min、0.5%阻聚剂以及30%带水剂苯、100℃回流分水6.0 h,最高酯化率可达92.2%;并且该树脂的催化性能比较稳定,重复使用5次,其酯化率仍在88%以上。     

The mixed-bed ion exchange performance at ultralow concentrations 1. Variable feed concentration and incomplete mixing of resins

Experimental data were obtained to evaluate the performance of mixed-bed ion exchange for the cases of variable feed concentration and incomplete mixing of anion and cation resins observed in large scale industrial units. For variable feed concentration, step changes in feed concentration were arbitrarily introduced into a test column. For incomplete mixing, only anion resin was loaded in the upper 20% of the column and more cation resin in the lower portion. Feed concentrations of 5.0× 10⁻⁵−2.0×10^-4 M NaCl were used for the experiments, with flow rates of 0.665-7.0 ml/sec. The effluent from the column was collected periodically and analyzed using on-line/off-line ion chromatography. The step changes in feed concentration affect the breakthrough times of sodium and chloride. Sodium breakthrough curve is more sensitive to the step changes than chloride breakthrough curve. With the same volumes of cation and anion resins, incomplete mixing of resins increases the cation exchange rate slightly and decreases the anion exchange rate slightly. As the cation resin volume increases, the effect of the incomplete mixing of resins decreases. The breakthrough curves of both ions, plotted as the ratio of effluent to the influent concentration versus run time in hour, give some detailed results about the effects of the conditions.     

Recovery of uranium from seawater. VI. Uranium adsorption ability and stability of macroporous chelating resin containing amidoxime groups prepared by the simultaneous use of divinylbenzene and ethyleneglycol dimethacrylate as crosslinking reagent

Macroporous chelating resins (RNH-DVB-1G) containing amidoxime groups with various degrees of crosslinking were synthesized by varying the amount of divinylbenzene (DVB) and ethyleneglycol dimethacrylate (1G). It was confirmed that the content of amidoxime group decreased with an increase in the degree of crosslinking. On the other hand, the amount of amidoxime group hydrolyzed by acid treatment showed a tendency to decrease with an increase in degree of crosslinking. From the measurement of specific surface area and pore size distribution, it was found that the macropore of RNH-DVB-1G with the same degree of crosslinking was remarkably affected by the composition of crosslinking reagent (DVB and 1G). The RNH-DVB-1G prepared in the present work were applied to the recovery of uranium from seawater. It was found that the uranium adsorption ability of RNH-DVB-1G with the same degree of crosslinking was remarkably affected by the proportion of DVB and 1G, although each RNH-DVB-1G had the same content of amidoxime group. In the case of RNH-DVB-1G prepared with 25 mol% of crosslinking reagent, the resin prepared with 10 mol% of DVB and 15 mol% of 1G showed the high adsorption ability for uranium in seawater. These results indicate that the simultaneous use of DVB and 1G contributes to the formation of effective macropore and micropore for recovery of uranium from seawater and the increase of chemical and physical stability.     

Elasticity of ion‐exchange resin beads in solvent mixtures

The effect of the solvent composition on the elasticity of strong and weak cation‐ and anion‐exchange resin beads was studied. Poly(styrene‐co‐divinylbenzene) resins containing sulfonic acid or quaternary ammonium groups and an acrylic acid resin crosslinked with divinylbenzene were immersed in water, NaCl solutions, or aqueous alcohol solutions and the shear modulus was measured with a uniaxial compression method. The elastic data were compared with the swelling properties. In pure water the shear moduli increased when the crosslink density, counterion valence, counterion size, and functional group size increased. Two additional phenomena in the elastic behavior were observed when the swelling degree of the resins was changed by the addition of alcohol or salt. A decrease of the modulus was observed when moving from the fully swollen state to a less swollen state, and a steep upturn of the modulus took place at a characteristic swelling region. The depth of the minimum and the location of the transition from the rubbery to the glassy state depended on the characteristics of the resins. The finite expansibility of the polymer chains and the glass transition explained these findings. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1256–1264, 2001     

The condensate polishing performance of powdered ion-exchange resins

The coating properties and ion-exchange performance of powdered ion-exchange resins were examined in a small test facility. Satisfactory resin coatings were obtained with cation : anion resin ratios in the range 1 : 1 to 3 : 1, but a 9 : 1 resin ratio resulted in a high pressure drop across the coating. The “settled resin volume” proved to be a reliable guide to the coating performance of resin slurries. The ion-exchange capacity of the cation resin increased from 2.5 to 2.8 equiv./kg as the sodium concentration in the influent decreased from 49 to 0.5 mg 1^?1. Within the ranges examined, resin ratio, resin loading and flowrate had no significant effect on cation capacity. The ion-exchange capacity of the anion resin for chloride ions was 2.2 to 2.3 equiv/kg at ambient temperature but exposure of the resin for four days at 80 °C reduced the capacity to 1.6 equiv./kg; four days at 90 °C reduced the capacity to less than 1 equiv./kg. The thermal stability of the powdered anion resin was markedly less than that quoted elsewhere for anion bead resin. The stability of the floc was also investigated.     

Recovery of uranium from sea water. IV. Influence of crosslinking reagent of the uranium adsorption of macroreticular chelating resin containing amidoxime groups

Macroreticular chelating resins (RNH) containing amidoxime groups with various degrees of crosslinking were synthesized by using various amounts of ethyleneglycol dimethacrylate (1G), dimethyleneglycol dimethacrylate (2G), triethyleneglycol dimethacrylate (3G), tetraethyleneglycol dimethacrylate (4G), and nanoethyleneglycol dimethacrylate (9G) as crosslinking reagent. The effect of crosslinking reagents on the pore structure, ion exchange capacity, swelling ratio, and adsorption ability for uranium of RNH was investigated. RNH (RNH–1G) prepared by using 1G were showed to have macroreticular structures by the measure of specific surface area. RNH–1G had the high adsorption ability and physical stability. Though RNH (RNH–4G) obtained by using 4G have little macroreticular structure (macropore), these resins showed the high adsorption ability for uranium by the treatment with 0.1 mol dm^?3 NaOH at 30°C for 15 h (alkali treatment). These results suggest that the formation of not only the favorable macropore but also the micropore is important for the effective recovery of uranium in sea water, whereas RNH–4G was defined to be low physical and chemical stability. For the preparation of RNH which have effective pore structure for the recovery of uranium, chemical, and physical stability, the simultaneous use of divinylbenzene (DVB) and 1G or 4G as crosslinking reagent was examined (abbreviated as RNH–DVB–1G and RNH–DVB–4G). The specific surface area of RNH–DVB–1G increased with an increase of 1G used. These RNH–DVB–1G have been shown the high adsorption ability for uranium. On the other hand, the specific surface area and adsorption ability for uranium of RNH–DVB–4G decreased with an increase of 4G used. Repeated use did not cause the deterioration of both RNH–DVB–1G and RNH–DVB–4G. This result suggests that the simultaneous use of DVB and 1G or 4G contributed the improvement of chemical and physical stability. In particular, RNH–DVB–1G has the effective macropore and micropore for the recovery of uranium.     

Preparation and characterization of EVAL hollow fiber membrane adsorbents filled with cation exchange resins

EVAL hollow fiber membrane adsorbents filled with powder D061-type cation exchange resin were prepared through dry-wet spinning process, using hydrophilic copolymer EVAL as the fiber substrate. The microstructures of the membrane adsorbents were observed, and the pure water fluxes, BSA rejection, and static adsorption capacities of membrane adsorbents for BSA were measured. The effect of the resin-filled content on membrane performance has been discussed. The results showed that EVAL hollow fiber membrane adsorbents filled with D061-type cation exchange resins had good adsorption capacity, and the adsorption capacity increased with the quantity of the resin-filled content. The static protein adsorption capacity was 77.14 mg BSA/g membrane adsorbents when D061 resin loading content was 65% at pH 4.5.     

Adsorption and separation of rhenium(VII) using N‐methylimidazolium functionalized strong basic anion exchange resin

BACKGROUND: Rhenium is a rare and valuable metal coexisting with molybdenum in molybdenite and sulfide copper ores and is hard to separate. Methods such as solvent extraction, ion exchange, adsorption, precipitation, etc. have been used to separate and purify Re(VII), and resin ion exchange has been widely investigated and used owing to its convenient operation and relatively low‐cost. The main challenge comes from the preparation of resins having high performance and stability. In an earlier study, an N‐methylimidazolium functionalized strong basic anion exchange resin was successfully synthesized and used for Cr(IV) extraction. This paper, reports on further synthesis and application of this resin for adsorption and separation of Re(VII) and Mo(VI), especially from copper arsenic filter cake. RESULTS: At pH 6.25, Re(VII) and Mo(VI) can be effectively separated with the N‐methylimidazolium functionalized strong basic anion exchange resin, giving a Re(VII) recovery of up to 93.3%, but only 5.1% for Mo(VI). When using the copper arsenic filter cake sample 89.1% Re(VII) recovery was achieved. CONCLUSION: The N‐methylimidazolium functionalized strong basic anion exchange resin exhibited high selectivity and recovery for Re(VII) in a mixed system. © 2012 Society of Chemical Industry     

Influence of solubility parameter difference between monomer and porogen on structures of poly (acrylonitrile–styrene-divinylbenzene) resins

In this work, the acrylonitrile (AN)-styrene (St)-divinylbenzene (DVB) resin was synthesized via suspension polymerization in the presence of inert porogens as diluent. The relationship of the solubility parameter (SP) of the materials and the porous properties of the resin was investigated. These porous spherical resin particles (0.25–0.84 mm) can be used as precursors of amidoxime resin which has a high metal ion chelating efficiency. The results showed that the porous properties (surface area and mean pore width) of the resin changed with variation in the compatibility between monomers and porogens. According to the the BET theory to N₂ sorption and scanning electron microscopy (SEM), the specific surface area of the obtained beads was strongly dependent on the compatibility of the components of the system and achieved values from 3.3 to 66.8 m²/g. The surface area of the terpolymer beads was found to rise with a decrease in the content of acrylonitrile or an increase in the SP of the porogens. However, the variation of the pore size was just the opposite. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46979.