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1.
The chelation behavior of poly(2‐hydroxy‐4‐acryloyloxybenzophenone) [poly(2H4ABP) or polymer I ] obtained through the free‐radical polymerization of 2‐hydroxy‐4‐acryloyloxybenzophenone monomer and for crosslinked polymers prepared from the monomer and known amounts of the crosslinker divinylbenzene (DVB) [4 mol % of DVB for polymer II, 8 mol % of DVB for polymer III, and 16 mol 16% of DVB for polymer IV ] toward the divalent metal ions Cu2+, Ni2+, Zn2+, and Pb2+ in aqueous solution was studied by a batch equilibration technique as a function of contact time and pH. The effect of the crosslinker, DVB, was also studied. The metal‐ion uptake of the polymers was determined with atomic absorption spectroscopy, and the highest uptake was achieved at pH 7.0 for polymers I, II, III, and IV. The selectivity and binding capacity of the resins toward the investigated divalent metal ions are discussed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008  相似文献   

2.
Metal ion desorbed crosslinked N,N‐bis(2‐aminoethyl)polyacrylamides showed enhanced specificity for the desorbed metal ion, and these polymers selectively rebind the desorbed metal ion from a mixture of metal ions. For this, polyacrylamide with 8 mol % divinylbenzene (DVB) and N,N′‐methylene‐bisacrylamide (NNMBA) crosslinking were prepared by solution polymerization. Diethylenetriamino functions were incorporated into the polymers by polymer analogous reactions. The complexing ability of the amino polymers were investigated toward various transition metal ions like Co(II), Ni(II), Cu(II), and Zn(II). Polymeric ligand and metal complexes were characterized by various spectral methods. The removal of the metal ion from the polymer matrix resulted in a memory for the desorbed metal ion. On rebinding, these polymers specifically rebind the desorbed metal ion and from a mixture of metal ions, it showed selectivity to the desorbed metal ion. Thus, the Cu(II) desorbed polymer specifically and selectively rebind Cu(II) ion from a mixture of Cu(II) and other metal ion. This selectivity is higher in the rigid DVB‐crosslinked system, resulting from the high rigidity of the crosslinked matrix compared to the semirigid NNMBA‐crosslinked system. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008  相似文献   

3.
The adsorption behavior of Cu(II) ions onto poly(2‐hydroxy‐4‐acryloyloxybenzophenone), polymer I, and onto poly(2‐hydroxy‐4‐acryloyloxybenzophenone) crosslinked with different amounts of divinylbenzene (DVB), polymers II, III, and IV, in aqueous solutions was investigated using batch adsorption experiments as a function of contact time, pH, and temperature. The amount of metal ion uptake of the polymers was determined by using atomic absorption spectrometry (AAS) and the highest uptake was achieved at pH 7.0 and by using perchlorate as an ionic strength adjuster for polymers I, II, III, and IV. Results revealed that the adsorption capacity (qe and Qm) of Cu(II) ions decreases with increasing crosslinking due to the decrease of chelation sites. In addition, the rate of adsorption (k2) of Cu(II) ions decreases with the increase of crosslinking because it becomes more difficult for Cu(II) ions to diffuse into the chelation sites. The isothermal behavior and the kinetics of adsorption of Cu(II) ions on these polymers with respect to the initial mass of the polymer and temperature were also investigated. The experimental data of the adsorption process was found to correlate well with the Langmuir isotherm model. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

4.
《分离科学与技术》2012,47(5):535-546
Abstract

The kinetics of the adsorption of uranium from seawater by humic acids fixed onto a polymer matrix was measured in a fluidized bed as a function of the grain size of the adsorbent and the flow velocity of the seawater. The adsorption rate was found to be governed by the diffusion of the uranium ions through the hydrodynamic surface layer of the adsorbent which is always formed in laminar flows of liquids. The measured rate constants are interpreted in terms of effective diffusion coefficients of 3.6 × 10?5 cm2/s for uranyl ions and 1.8 × 10?5 cm2/s for tricarbonatouranate ions in the surface layer. As a consequence of this kinetic behavior, the geometry of the adsorbent as well as the velocity of the water flow are relevant parameters for the amount of adsorbent needed for a projected extraction rate. This conclusion applies to all adsorption processes where diffusion through the hydrodynamic layer is the rate-determining kinetic step.  相似文献   

5.
Amidoxime polymers crosslinked with tetraethylene glycol dimethacrylate (40 wt%) and with differing water contents were prepared by poly(acrylonitrile) treatment in various quantities of toluene with hydroxylamine. Adsorption rates of uranium on the amidoxime polymers from seawater were examined in relation to their porosity. The amidoxime polymer prepared from poly(acrylonitrile) in an increasing quantity of toluene exhibits a significantly increasing water content. On the basis of mercury intrusion measurements, the increasing water content was revealed to be predominantly owing to the enhancement of porosity. The adsorption rate of uranium from seawater increased steadily with an increase of porosity, suggesting the dependence of the adsorption rate on a diffusion process of uranium into the pore domain.  相似文献   

6.
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.  相似文献   

7.
Wastes of foam polystyrene were dissolved in styrene and copolymerized with DVB and the final product was sulfonated with H2SO4 (group B). Group A of cross-linked polystyrene was synthesized using styrene and divinylbenzene (DVB) in the presence of n-heptane (macroporous ion exchangers) and then was sulfonated with H2SO4. The chemical structure of the cross-linked polymers before and after sulfonation was determined by infrared spectroscopy. The ion-exchange capacity was higher for the polymers of group A. The poresize distribution for polymers of group A was determined and the average pore diameter (4V/A) of 39.9 nm for a representative polymer resulted. The degree of swelling of the polymers and their adsorption for methylene blue and alizarin yellow were also determined. The degree of swelling in toluene is decreased by increasing the ratio of DVB in the initial mixture and by sulfonation. The adsorption of methylene blue and alizarin yellow is strongly increased by the sulfonated polymers in comparison with the unsulfonated. As far as group B is concerned, the adsorption of alizarin yellow on the sulfonated polymers, which have higher cross-linking and lower sulfonation, increased more, especially at the initial time. The networks of both groups examined are different. The polystyrene wastes were incorporated into the whole network to an extent of 15–35%. Such investigations could contribute to the utilization of wastes of polystyrene in the direction of sorbents and especially if the polystrene wastes are contaminated with other polymers. © 1995 John Wiley & Sons, Inc.  相似文献   

8.
A novel metal ion imprinted polymer was prepared by the surface molecular imprinting technique. Trimethylolpropane trimethacrylate (TRIM), zinc ions, and 1,12-dodecanediol-O,O′-diphenyl phosphonic acid (DDDPA) were used as the matrix-forming monomer, imprint molecule, and functional monomer, respectively. We have prepared Zn(II)-imprinted microspheres utilizing water-in-oil-in-water emulsions, which are spherically well defined and uniform. TRIM comprises of three polymerizable groups that serve to align the recognition sites produced on the polymer surface with better template effect. We conducted diagnostic zinc adsorption tests by using the Zn(II)-imprinted and unimprinted polymers in order to make an assessment on the effectiveness of TRIM-based and divinylbenzene-based imprinted polymers. The template effect of the TRIM-based polymer was enhanced by the high rigidity of the polymer matrix compared to that of the imprinted polymer whose matrix is divinylbenzene. In addition, the adsorption equilibrium constant was evaluated on the basis of the Langmuir analysis for the adsorption data. The method to prepare metal-imprinted microspheres on the surface of polymers crosslinked by TRIM is easy, and the adsorbent produced can be readily used without subsequent grinding or sieving. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1223–1230, 1999  相似文献   

9.
For the preparation of a heterogenized N,N′‐bis(acetylacetone)ethylenediamine cobalt(II) Schiff base complex, first crosslinked polymer beads were prepared by the suspension copolymerization of styrene (48.97 mmol, 5.1 g), allyl chloride (48.97 mmol, 3.746 g), and divinyl benzene (DVB; 1.75 mmol, 0.228 g) in the presence of azobisisobutyronitrile (0.9 × 10?3 mmol, 0.15 g) as an initiator at 23 ± 0.1°C under an inert atmosphere. The copolymerization of styrene, allyl chloride in the presence of gelatin (0.75 g), bentonite (2.0 g), and boric acid (2.5 g) produced beads of different crosslinked densities corresponding to the concentration of DVB in the reaction mixture. The amount of allyl chloride in the prepared beads varied from 5.40 to 7.40 mmol g?1 of beads with the amount of DVB varying from 2.0 to 0.8 mmol in the reaction mixture. A quadridentate Schiff base (acen) was prepared with ethylenediamine (5.0 mmol, 0.3 g) and acetylacetone (10.0 mmol, 1.0 g), and it was used to obtain a homogenized and heterogenized Co(II)(acen)2 complex. The extent and arrangement of the Schiff base (acen) in the crosslinked beads depended on the availability of DVB in the reaction mixture. The amount of DVB in the reaction mixture influenced the extent of cobalt(II) ion loading, the degree of swelling, the porosity, and the pore size in the prepared beads. The beads (type IV) prepared with 1.75 mmol (0.228 g) of DVB in the reaction mixture showed a degree of swelling of 9.65% and efficiencies of loading and complexation for cobalt(II) ions of 49.4 and 85%, respectively, in comparison with beads obtained at other concentrations of DVB in the reaction mixture. The structure of free and polymer‐supported Co(II)(acen)2 complexes was verified with IR, UV, and magnetic measurements, which suggested a square planar geometry for the complexes under both conditions. The catalytic activities of the homogenized and heterogenized Co(II)(acen)2 complexes were compared by the evaluation of the rate constant (k) for the decomposition of hydrogen peroxide. The heterogenized Co(II)(acen)2 complex showed a high catalytic activity for the decomposition of hydrogen peroxide (k = 2.02 × 10?4 s?1) in comparison with the homogenized Co(II)(acen)2 complex (k = 4.32 × 10?6 s?1). The energy of activation for the decomposition of hydrogen peroxide with the heterogenized Co(II)(acen)2 complex was low (38.52 kJ mol?1) in comparison with that for the homogenized complex (73.44 kJ mol?1). In both cases, the rate of decomposition of hydrogen peroxide was directly proportional to the concentration of hydrogen peroxide and cobalt(II) ions. On the basis of experimental observations, a rate expression for the decomposition of hydrogen peroxide was derived. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1398–1411, 2003  相似文献   

10.
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.  相似文献   

11.
A crosslinked amphiphilic copolymer [poly(ethylene glycol) (PEG)–poly(methyl methacrylate) (PMMA)–ethylene glycol dimethacrylate (EGDM)] composed of PMMA, PEG, and crosslinking units (EGDM) was synthesized by atom transfer radical polymerization to develop micelles as carriers for hydrophobic drugs. By adjusting the molar ratio of methyl methacrylate and EGDM, three block copolymer samples (P0, P1, and P2) were prepared. The measurement of gel permeation chromatography and 1H‐NMR indicated the formation of crosslinked structures for P1 and P2. Fluorescence spectroscopy measurement indicated that PEG–PMMA–EGDM could self‐assemble to form micelles, and the critical micelle concentration values of the crosslinked polymer were lower than those of linear ones. The prepared PEG–PMMA–EGDM micelles were used to load doxorubicin (DOX). The drug‐loading efficiencies of P1 and P2 were higher than that of P0 because the crosslinking units enhanced the micelles' stability. With increasing drug‐loading contents, DOX release from the micelles in vitro was decreased, and in the crosslinked formulations, the release rate was also slower. An in vitro release study indicated that DOX release from the micelles for the linear samples was faster than that for crosslinked micelles. The drug feeding amount increased and resulted in an increase in the drug‐loading content, and the loading efficiency decreased. These PEG–PMMA–EGDM micelles did not show toxicity in vitro and could reduce the cytotoxicity of DOX in the micelles; this suggested that they are good candidates as stable drug carriers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39623.  相似文献   

12.
Reaction of Cu(BF4)2 salt with the polymer [NP(OC6H4C(O)C–OC6H5)2] n (1) in THF affords three new polymers gels containing varied copper (II) ions contents, (2), (3), and (4). The nature of the copper (II) ions in the gel (2)(4) was examined by IR spectroscopy, solid state 31P, 13C and 63Cu NMR spectroscopy and EPR spectroscopy. Despite the copper content, the gels were insulators as measured by complex impedance spectroscopy. SEM images show a uniform distribution of the Cu (II) ions and a most porous morphology than those without copper polymer. TEM images show the formation of small aggregates being smallest for, gel (2) of about 200 nm. All the data suggest the Cu2+ centers behave as a solid dilute into the polyphosphazenes.  相似文献   

13.
The copolymers of 4‐vinylpyridine (4VP), styrene (St) and divinylbenzene (DVB) with varied compositions, P(4VP‐St‐DVB), were synthesized by suspension polymerization using 2,2′‐azobisisobutyronitrile (AIBN) as an initiator. The insoluble (crosslinked) pyridinium‐type polymers in benzyl–pyridinium bromide form, which possess various macromolecular chain compositions, were prepared by the reaction of each P(4VP‐St‐DVB) with benzyl bromide (BzBr), respectively. By using different halohydrocarbon RX in the quaternization of P(4VP‐St‐DVB), the insoluble pyridinium‐type polymers with various pyridinium group structures were obtained. The structures of P(4VP‐St‐DVB) and its quaternized product Q‐P(4VP‐St‐DVB) were identified by FTIR. The 4VP content in each copolymer P(4VP‐St‐DVB) was measured by nonaqueous titration; and the pyridinium group content (Cq) in each Q‐P(4VP‐St‐DVB) sample was determined by means of the back titration manner in argentometry and/or the elemental analysis method, respectively. In addition, the particle structure and the surface morphology of the thus‐prepared polymer were observed using SEM. According to a series of experimental results, the preparation and characterization of insoluble pyridinium‐type polymers are analyzed and discussed. This work can prepare the ground for a study on the antibacterial activity of insoluble pyridinium‐type polymers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 668–675, 2000  相似文献   

14.
The authors have been investigating the adsorption and desorption dynamics of nonionic water soluble polymers on inorganic particles. The influence of the nature of polymers with and without associating hydrophobic end groups, the nature of adsorbents [TiO2, Al2O3 (neutral, acid and basic), and SiO2], polymer concentrations, linear velocity of fluids, and mutual diffusion of polymer molecules on the patterns of adsorption and desorption distribution of polymer concentrations are shown. The model polymer is a nonionic polyurethane polymer based on ethylene oxide. The polymer's structure is R-O-(DI-PEO)6-DI-O-R (R is C16H33, DI is isophorone diisocyanate, and PEO is CARBOWAXTM with a molecular weight of 8200). The phenomenological models of association and dissociation kinetics of associative polymers are suggested. The half-lives of clusters into adsorption and desorption layers are estimated. It is shown that heats of desorption of associative polymers are dependent essentially on heats of dissociation of clusters.  相似文献   

15.
Two novel chelating resins are prepared by anchoring diethylenetriamine bis‐ and mono‐furaldehyde Schiff bases onto the macroporous GMA‐DVB copolymer beads and utilized for the adsorption towards Cu(II), Co(II), Ni(II), and Zn(II). FTIR spectra show that Schiff base groups have been successfully introduced into the polymer matrix and the chelating resins can form complexes with the metal ions. The chelating resins show a higher adsorption capacity toward Cu(II). The conductivity method can be used for determining the adsorption kinetics of the resins towards metal ions. The results show that the adsorption rates towards Cu(II) are much higher than those towards other ions and pseudo second‐order and intraparticle diffusion models can be applied to treat the adsorption amount‐time data. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

16.
Hydrophobic, but water‐swellable, porous copolymer resins composed of divinylbenzene (DVB) and ethylene glycol dimethacrylate (EGDM) or ethylene glycol diacrylate (EGDA) were prepared by using purified DVB (98.8%) in the presence of toluene as porogen. The EGDM/DVB resins thus obtained, whose polarity was nearly identical to that of the resins based on DVB and methyl methacrylate (MMA) at the same DVB levels, were water‐swellable by direct contact with water up to a DVB content of 64%, whereas the latter did not swell in water at any DVB levels. EGDA is also hydrophobic, but with a polarity greater than that of EGDM. As a result, the EGDA/DVB resins were more water swellable than EGDM/DVB resins, and could also be prepared as water‐swellable materials by using technical DVB (79.3%), besides the use of the purified DVB. All these results were explained on the basis of the network rigidity (crosslinking density) and the polymer polarity of the resins that were formed in the presence of a well‐solvating porogenic solvent. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 997–1004, 2004  相似文献   

17.
《分离科学与技术》2012,47(11):2217-2227
Abstract

A separative elution of uranium from an amidoxime polymer which had been immersed in seawater was examined on its relation with the flow rate of acidic eluent. The elution with 0.5 M HC1 at S.V. ≤ 1 h?1 or with 1.0 M HCl at S.V. ≤ 3 h?1, which was started from the elution by 16.5 L/L p of 0.1 MHCl at S.V. ≤ 3 h?1, provided an eluate containing more than 80% of uranium adsorbed and separating from other metal ions except Fe(III) and Cu(II). The efficiency of uranium elution was hardly affected by the scale of the system employed. Acid consumption, which occurred predominantly in the elution with 0.1 M HCl, was ~1.4 mol/L p . The results suggest that this elution method is promising in the recovery of uranium from seawater.  相似文献   

18.
《分离科学与技术》2012,47(2-3):163-178
Abstract

A new type of adsorbent containing amidoxime groups for the recovery of uranium from seawater was synthesized by the radiation-induced graft polymerization of acrylonitrile onto polymeric fiber followed by amidoximation with hydroxylamine. When amidoxime groups were introduced superficially on the fiber, the amount of uranium adsorbed by the amidoxime groups was higher than that with the amidoxime groups introduced homogeneously in the fiber. The introduction of the poly(acrylic acid) chain and the increase in temperature and flow rate in the adsorption process were effective in increasing the amount of adsorbed uranium. Although alkali metals and alkaline earth metals were found in the adsorbent, the concentration factors for these metals were less than 1/103 of that for uranium. The present adsorbent had a high stability to various treatments such as contact with alkali and seawater.  相似文献   

19.
《分离科学与技术》2012,47(14):3109-3121
Abstract

We have studied a new method for the preparation of Th(IV)‐imprinted chitosan‐phthalate particles, which can considerably enhance the adsorption capacity and selectivity of thorium ions. In this study, chitosan‐phthalate was used as the complexing monomer, Th(IV) as template, epichlorohydrin as crosslinking agent. Initially, chitosan was modified with phthalic anhydrides and complex formation occured between carboxylic acid functional groups and Th(IV) ions. Secondly, particles were crosslinked with epichlorohydrin. After the removal of Th(IV) ions, thorium solid phase extraction (SPE) on the Th(IV) ion‐imprinted particles from aqueous solutions containing their different amounts, selectivity study of thorium versus other interfering metal ions mixture which are Fe3+, La3+, and Mn2+ and distribution and selectivity coefficients were reported here. A comparison of the selectivity coefficient of Th(IV)‐imprinted chitosan‐phthalate particles with the selectivity coefficient of non‐imprinted polymers showed that the imprinted matrix for Th(IV)/Fe(III), Th(IV)/La(III) and Th(IV)/Mn(II) was 8.35, 8.75 and 10.81 times greater than non‐imprinted matrix, respectively.  相似文献   

20.
《分离科学与技术》2012,47(16):2573-2586
ABSTRACT

This article introduces an investigation on the sorption power of two polyacrylamide-based chelating sorbents for uranium ion removal from aqueous solutions. The studied sorption parameters involved pH, contact time, initial uranium concentration, and polymer dosage. The results revealed that a maximum uptake percentage of 65.3 mg/g and 20.1 mg/g for polymers I and II, respectively, could be obtained at pH 4 with 120 min shaking time. Based on isotherm, kinetic, and thermodynamic studies, the sorption process of uranium on the chelating polymers is said to follow Langmuir isotherm model with pseudo second-order mechanism and exothermic nature.  相似文献   

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