CN104877062A - Method for preparing hierarchical pore foam material by using high-internal-phase emulsion template and using interface grafting method - Google Patents

Method for preparing hierarchical pore foam material by using high-internal-phase emulsion template and using interface grafting method Download PDF

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CN104877062A
CN104877062A CN201510228101.9A CN201510228101A CN104877062A CN 104877062 A CN104877062 A CN 104877062A CN 201510228101 A CN201510228101 A CN 201510228101A CN 104877062 A CN104877062 A CN 104877062A
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nanoparticle
mesoporous sio
mesoporous
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deionized water
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CN104877062B (en
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才洪美
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TAIZHOU ENTRY-EXIT INSPECTION AND QUARANTINE BUREAU
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TAIZHOU ENTRY-EXIT INSPECTION AND QUARANTINE BUREAU
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Abstract

The invention provides a method for preparing hierarchical pore foam material by using a high-internal-phase emulsion template and using an interface grafting method. An oil phase of high-internal-phase emulsion is stabilized by using Hypermer2296, the oil phase contains a polymeric monomer glycidyl methacrylate, a crosslinking agent divinyl benzene, a solvent toluene and an initiator azodiisobutyronitrile, and an aqueous phase is a potassium sulphate aqueous solution. After the oil phase and the aqueous phase are mixed, the obtained mixture is prepared into stable water-in-oil emulsion by stirring, and the stable water-in-oil emulsion is subjected to thermal induced polymerization so as to obtain a macroporous foam polymer; and then, mesoporous nanoparticles are grafted onto the macroporous foam material, so that a hierarchical porous material is obtained. The product has the characteristics of two kinds of materials, i.e. macropore and mesopore, wherein the mesopore can effectively increase the specific surface area of the material, thereby increasing the adsorption capacity of the material; and a large amount of carboxy groups on the surface of the material facilitate the adsorption of trifluoro-cypermethrin and cupric ions, so that the adsorption effect is obviously enhanced.

Description

High Internal Phase Emulsion template and interface crosslinking legal system are for the method for multi-stage porous foam materials
Technical field
The present invention relates to a kind of method adopting High Internal Phase Emulsion polymerization and interface crosslinking medium hole nano particles to prepare high-ratio surface macroporous adsorbent, belong to environment-friendly function technical field of material.
Background technology
In recent years due to the develop rapidly of industrial or agricultural, environmental pollution is very serious.As agriculture aspect, the abuse of pyrethroid has threatened the health of the mankind gradually.The chemical structure of this quasi-chrysanthemum ester to natural compounds is revised, and makes it have more stability and maintains insecticidal activity.Although pyrethrin is a kind of to target pest rapid paralysis and the neurotoxin knocked down fast, some medical researchers find that it may have the impact of developmental character neurotoxicity and immunotoxicity on the mankind.And this kind of agricultural chemicals finds in surface water, soil, organism, food.As industrial aspect, various metal ion pollution is very serious, and especially cupric ion pollutes.Cupric ion easily causes biological dispirited, headache, nausea and vomiting etc.Further, studies have found that chrysanthemum ester and metal ion are present in waste water jointly, perhaps its acting in conjunction increases the harm to biology.Therefore, the control of environmental pollution more and more receives the concern of the mankind with improving.
In several years of past, large pore material is paid close attention to widely and is applied to numerous areas because of its significant anti-pressure ability, such as catalyzer, organizational project, absorption and be separated etc.The method preparing this large pore material is exactly that this method is simple and efficient by being formed to carry out stable High Internal Phase Emulsion to produce with tensio-active agent, and emulsion-stabilizing, macropore and connecting pore can be regulated by the amount of water oil ratio and linking agent.In recent years, the method for mesoporous material grafting large pore material was generally applied, it can in and the advantage of bi-material reach better adsorption effect or adsorb two or more objects.Therefore, the waste water that mesoporous grafting large pore material coexists for absorption chrysanthemum ester and metal ion is good selection.
At present, the mesoporous or large pore material that most sorbent material is single often.Although, the large advantages of good adsorption effect of mesoporous material specific surface area, because its Kong Tai little have impact on mass-transfer efficiency.But large pore material specific surface area is little, loading capacity is not too high, but its obvious advantage is exactly that mass transfer is fast.Therefore, mesoporous material grafting large pore material can make up respective deficiency, accelerates mass-transfer efficiency to a certain extent, also improves loading capacity.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art part, by what improve namely method is hydrolyzed alkyl silicate and the method for condensing in alcohol carrys out synthesizing mesoporous silicon dioxide nanoparticle, and uses butanedioic anhydride modification to make surface containing a large amount of carboxylic groups.Obtained macropore glycidyl methacrylate material subsequently, it is potassium sulfate solution in aqueous phase, oil phase is glycidyl methacrylate (GMA), Vinylstyrene (DVB), toluene, 2,2'-Diisopropyl azodicarboxylate (AIBN) and tensio-active agent 2296 form stable High Internal Phase Emulsion, obtain porous foam sorbent material by radical polymerization.Finally, mesoporous successful grafting large pore material and multilevel hole material (HPFs), and absorption sorbent material being applied to the lambda-cyhalothrin (CL) in the aqueous solution and cupric ion be separated.
High Internal Phase Emulsion template of the present invention and interface crosslinking legal system, for the method for multi-stage porous foam materials, comprise the steps:
(1) mesoporous SiO 2the synthesis of nanoparticle and modification:
Mesoporous SiO 2the synthesis of nanoparticle is obtained by ammonia catalytic hydrolysis tetraethyl orthosilicate; First, cetyl trimethylammonium bromide, Neutral ammonium fluoride join in deionized water; Subsequently, when being raised to 80 DEG C to temperature, tetraethyl orthosilicate dropwise adds, and stirs after 1-2 hour, and collected by centrifugation product also removes tensio-active agent cetyl trimethylammonium bromide with the 24h that refluxes at ethanol, hydrochloric acid mixed solution 90 DEG C, and backflow cleaning is carried out repeatedly repeatedly; Finally, collected by centrifugation and repeatedly cleaning several times with deionized water and ethanol, mesoporous SiO2 nanoparticle dry 48h at 50-60 DEG C of preparation;
The mesoporous SiO2 nanoparticle of amination; First, mesoporous SiO 2nanoparticle dispersion is in toluene solution, evenly ultrasonic; Then, aminopropyl triethoxysilane dropwise add and under nitrogen protection 120 DEG C backflow 24 hours; Finally, collected by centrifugation product also cleans several times repeatedly with deionized water and ethanol, the mesoporous SiO of amination of preparation 2nanoparticle is dry 48h at 50-60 DEG C;
Carboxylated mesoporous SiO 2nanoparticle; The mesoporous SiO of amination 2nanoparticle dispersion in DMF solution, and adds a certain amount of Succinic anhydried, under 30 DEG C of conditions, react 12h, and finally, collected by centrifugation product also cleans several times repeatedly with deionized water and ethanol, the carboxylated mesoporous SiO of preparation 2nanoparticle is dry 48h at 50-60 DEG C;
(2) synthesis of macropore glycidyl methacrylate foam materials
Polymerization single polymerization monomer glycidyl methacrylate, cross-linker divinylbenzene, is distributed in solvent toluene, then adds initiator Diisopropyl azodicarboxylate, adds tensio-active agent (Hypermer 2296) after being uniformly mixed.Dropwise add potassium sulfate solution under agitation, etc. emulsion formed and stable after, above-mentioned emulsion is poured in ampere bottle, 24h is reacted at 60-70 DEG C, after having reacted, carry out surname extraction 12h with acetone soln and remove organic solvent, put into 50 DEG C of baking ovens and dry;
(3) carboxylated mesoporous SiO 2nano particle grafting macroporous acrylic glycidyl ester foam materials:
Carboxylated mesoporous SiO 2nanoparticle, macroporous acrylic glycidyl ester foam materials, calcium chloride is distributed to organic solvent N, in dinethylformamide solution, 24h is carried out at being grafted to 45 DEG C, this reaction process is carried out repeatedly repeatedly, and finally, graft materials is collected and by washing with alcohol repeatedly and under 50-65 DEG C of condition dry a day;
Preferably,
In described step (1), prepare mesoporous SiO 2in nanoparticle process, the ratio of cetyl trimethylammonium bromide, Neutral ammonium fluoride, deionized water and tetraethyl orthosilicate is (0.45-0.50): 0.75:(120-130): 2.25 (g/g/ml/ml).
In described step (1), prepare mesoporous SiO 2in nanoparticle process, the ratio of ethanol, hydrochloric acid is 100:2 (ml:ml).
In described step (1), the mesoporous SiO of amination 2in nanoparticle process, mesoporous SiO 2the ratio of nanoparticle, aminopropyl triethoxysilane, toluene is 1:(1.0-1.5): 10 (g/ml/ml).
In described step (1), carboxylated mesoporous SiO 2in nanoparticle process, mesoporous amination SiO 2the ratio of nanoparticle, Succinic anhydried, DMF is 0.1:(1.0-1.8): 30 (g/g/ml).
In step (2), the ratio of glycidyl acrylate, Vinylstyrene, toluene, Diisopropyl azodicarboxylate, tensio-active agent Hypermer 2296, potassium sulfate solution is (0.6-0.7): (0.7-1): 1:0.02:(0.4-0.6): (11-13) (ml/ml/ml/g/ml/ml).
In step (2), in potassium sulfate solution, the ratio of potassium sulfate and deionized water is 0.55:45 (g/ml).
In step (3), carboxylated mesoporous SiO 2the ratio of nanoparticle, macroporous acrylic glycidyl ester foam materials, calcium chloride, DMF is (0.1-0.2): 0.3:0.15:10 (g/g/g/ml).
In the present invention, the change of content in mesoporous silicon oxide preparation process, just change the size of mesoporous particle, when 0.50g cetyl trimethylammonium bromide adds fashionable, mesoporous particle diminishes (80nm), otherwise when 0.40g cetyl trimethylammonium bromide adds fashionable, mesoporous particle becomes large (150nm); In modifying process, the increase of Succinic anhydried amount may make mesoporous silicon aperture diminish, and reduces specific surface area on the contrary, is unfavorable for absorption; Preparing in macropore glycidyl methacrylate process, the consumption changed between monomer makes large pore material mechanical degradation, and macropore, connecting hole are not obvious, thus adsorption effect may be made to be deteriorated.
Of the present invention have following technique effect: this product, in conjunction with High Internal Phase Emulsion and interface crosslinking technology, has both length concurrently, has macropore and mesoporous performance and have good absorption to lambda-cyhalothrin (CL) and cupric ion.Nonionogenic tenside (Hypermer 2296) is used to carry out stable emulsion in experiment, stability of emulsion is improved greatly, and mesoporous carboxylated silicon-dioxide is grafted on macropore methyl propenoic acid glycidyl fat material, increase the specific surface area of material, further enhancing the performance of sorbent material.
Accompanying drawing explanation
Fig. 1 is the different magnification (a) 200 times (b) 600 times of High Internal Phase Emulsion and 1000 times (c) of preparation in embodiment 1.
Fig. 2 is the sub-MSNs of (a) mesoporous silicon dioxide nano particle in embodiment 1, (b) amination mesoporous silicon dioxide nano particle, the infrared spectrum of the sub-CMSNs of (c) carboxylated mesoporous silicon dioxide nano particle, (d) poly (glycidyl methacrylate) MPGMA and (e) multilevel hole material HPFs.
Fig. 3 is the sub-MSNs of (a) mesoporous silicon dioxide nano particle in embodiment 1, (b) amination mesoporous silicon dioxide nano particle, the sub-CMSNs of (c) carboxylated mesoporous silicon dioxide nano particle, the x-ray photoelectron energy spectrogram of the transmission electron microscope picture that (d) amplifies CMSNs and the sub-CMSNs of carboxylated mesoporous silicon dioxide nano particle.
Fig. 4 is poly (glycidyl methacrylate) MPGMA (a) in embodiment 1, MPGMA abscess junction (b), MPGMA connecting hole (c), multilevel hole material (d), the scanning electron microscope (SEM) photograph of multilevel hole material abscess junction (e) and multilevel hole material connecting hole (f).
Fig. 5 is poly (glycidyl methacrylate) MPGMA (a) in embodiment 1, multilevel hole material mesoporous particle (b) of grafting, the mesoporous particle (c) of multilevel hole material secondary grafting, the energy dispersion spectrogram of multilevel hole material three mesoporous particles (d) of grafting and the content form of three kinds of elements.
Fig. 6 is TGA (solid line) and DTG (dotted line) curve of CMSNs (a), MPGMA (b) in embodiment 1, HPFs (c).
Fig. 7 is the amplification picture of embodiment 2 step 2 poly (glycidyl methacrylate) MPGMA and abscess.Its pattern is disproportionate because change polymerization single polymerization monomer and dosage of crosslinking agent and aqueous phase, thus makes polymeric foam mechanical property not strong.
Fig. 8 is the amplification picture of step 2 poly (glycidyl methacrylate) MPGMA and abscess in embodiment 3.Change polymerization single polymerization monomer and dosage of crosslinking agent in example 3 step 2, possible itself and aqueous phase are disproportionate, thus make polymeric foam mechanical property not strong.
Embodiment
Below in conjunction with accompanying drawing, the present invention is further described.
Absorption property analysis test method concrete steps in the examples below comprise as follows:
One, Static Adsorption test
Certain density for 10ml lambda-cyhalothrin (cupric ion) solution is joined in colorimetric cylinder, add 10mg HPFs sorbent material respectively, be placed in 15 DEG C, 25 DEG C, 35 DEG C waters bath with thermostatic control and leave standstill certain hour, investigate the starting point concentration of lambda-cyhalothrin (cupric ion) in test soln and differing temps to the impact of adsorbent lambda-cyhalothrin (cupric ion); After saturated adsorption, sorbent material is centrifugal and use polyvinylidene fluoride microporous film collecting by filtration, lambda-cyhalothrin (cupric ion) the concentration UV spectrum of not adsorbing, and calculates loading capacity (Q according to result e, mg/g):
Q e = ( C 0 - C e ) V W
Wherein C 0and C (mg/L) e(mg/L) be the concentration of adsorbing front and back lambda-cyhalothrin (cupric ion) respectively, W (g) is adsorbent amount, and V (mL) is test fluid volume.
Two, static mixing adsorption test
By (the 0mg/l of three kinds of different concns, 25mg/l, 50mg/l) cupric ion (lambda-cyhalothrin) joins in a series of lambda-cyhalothrin (cupric ion) solution, above-mentioned solution 10ml is gone to add 10mgHPFs sorbent material respectively, be placed in 15 DEG C of waters bath with thermostatic control and leave standstill certain hour, investigate the impact on adsorbent lambda-cyhalothrin (cupric ion) under the condition of the starting point concentration of lambda-cyhalothrin (cupric ion) and the cupric ion (betacyfluthrin) of different concns in test soln.The concentration UV spectrum of the lambda-cyhalothrin (cupric ion) do not adsorbed is measured and calculates, and formula as above.
Below in conjunction with concrete embodiment, the present invention will be further described.
Embodiment 1
(1) mesoporous SiO 2the synthesis of nanoparticle and modification:
Mesoporous SiO 2the synthesis of nanoparticle is obtained by ammonia catalytic hydrolysis tetraethyl orthosilicate; First, 0.4550g cetyl trimethylammonium bromide, 0.7500g Neutral ammonium fluoride join in 125ml deionized water; Subsequently, when being raised to 80 DEG C to temperature, 2.25ml tetraethyl orthosilicate dropwise adds, and stirs after 2 hours, and collected by centrifugation product also removes tensio-active agent with the 24h that refluxes at 100ml ethanol, 2ml hydrochloric acid mixed solution 90 DEG C, and backflow cleaning carries out 3 times repeatedly; Finally, collected by centrifugation and repeatedly cleaning several times with deionized water and ethanol, the mesoporous SiO of preparation 2nanoparticle is dry 48h at 50-60 DEG C;
The mesoporous SiO of amination 2nanoparticle; First, the mesoporous SiO of 1.0g 2nanoparticle dispersion is in 10ml toluene solution, evenly ultrasonic; Then, 1.17ml aminopropyl triethoxysilane dropwise add and under nitrogen protection 120 DEG C backflow 24 hours; Finally, collected by centrifugation product also cleans several times repeatedly with deionized water and ethanol, the mesoporous SiO of preparation 2nanoparticle is dry 48h at 50-60 DEG C;
Carboxylated mesoporous SiO 2nanoparticle; The mesoporous SiO of 0.1g amination 2nanoparticle dispersion in 30ml DMF solution, and adds 1.0g Succinic anhydried, under 30 DEG C of conditions, react 12h.Finally, collected by centrifugation product also cleans several times repeatedly with deionized water and ethanol, the mesoporous SiO of preparation 2nanoparticle is dry 48h at 50-60 DEG C;
(2) synthesis of macropore glycidyl methacrylate foam materials:
Polymerization single polymerization monomer 0.7ml glycidyl methacrylate, linking agent 1.0ml Vinylstyrene, be distributed in solvent 1ml toluene, then add initiator 0.02g Diisopropyl azodicarboxylate, after being uniformly mixed, add 0.4ml tensio-active agent (Hypermer 2296).Dropwise add 11.25ml potassium sulfate solution under agitation, formed and the stable rear 5min that continues to stir etc. emulsion, above-mentioned emulsion is poured in ampere bottle, at 60-70 DEG C, react 24h.After having reacted, carry out surname extraction 12h with acetone soln and remove organic solvent, put into 50 DEG C of baking ovens and dry.In this step, in potassium sulfate solution, the ratio of potassium sulfate and deionized water is 0.55:45 (g/ml).
(3) carboxylated mesoporous SiO 2nano particle grafting macroporous acrylic glycidyl ester foam materials:
The carboxylated mesoporous SiO of 0.1g 2nanoparticle, 0.3g macroporous acrylic glycidyl ester foam materials, 0.15g calcium chloride is distributed in organic solvent 10ml DMF solution, carries out 24h at being grafted to 45 DEG C.This reaction process is carried out repeatedly repeatedly, and finally, graft materials is collected and by washing with alcohol repeatedly and under 50-65 DEG C of condition dry a day.
2, absorption property analytical test
(1) get 10ml starting point concentration be respectively 10,30,50,80, lambda-cyhalothrin (cupric ion) solution of 100mg/L joins in colorimetric cylinder, add multilevel hole material sorbent material prepared by aforesaid method in 10mg embodiment 1 respectively, test fluid is placed on 15 DEG C, 25 DEG C, after leaving standstill 12h in the water-bath of 35 DEG C, supernatant liquid collecting by filtration, lambda-cyhalothrin molecule (cupric ion) the concentration ultraviolet-visible pectrophotometer do not adsorbed measures, and calculates loading capacity according to result.
Result shows: the saturated adsorption capacity during absorption 15 DEG C of multilevel hole material sorbent material to trifluoro Cypermethrin is 80.11mg/g, and saturated adsorption capacity when 25 DEG C is 67.10mg/g, and saturated adsorption capacity when 35 DEG C is 49.16mg/g.Along with temperature raises, adsorbent deleterious; The saturated adsorption capacity during absorption 15 DEG C of multilevel hole material sorbent material to cupric ion is 82.86mg/g, and saturated adsorption capacity when 25 DEG C is 72.91mg/g, and saturated adsorption capacity when 35 DEG C is 61.53mg/g.Along with temperature raises, adsorbent deleterious.
(2) getting lambda-cyhalothrin (cupric ion) solution that 10ml starting point concentration is 100mg/L joins in colorimetric cylinder, add multi-stage porous sorbent material prepared by aforesaid method in 10mg embodiment 1 respectively, test fluid is placed in the water-bath of 15 DEG C and leaves standstill 5,10,20,30,60,90,120,240,360,480, after 720min, supernatant liquid is through centrifugal and use polyvinylidene fluoride microporous film collecting by filtration, the lambda-cyhalothrin molecular conecentration ultraviolet-visible pectrophotometer do not adsorbed measures, and calculates loading capacity according to result.
Result shows: in 120min, reached 81.82% of equilibrium adsorption capacity during multilevel hole material adsorbent lambda-cyhalothrin, reaches adsorption equilibrium gradually subsequently after absorption 480-720min; In 90min, reach 86.81% of equilibrium adsorption capacity during multilevel hole material adsorbent cupric ion, after absorption 480-720min, reach adsorption equilibrium gradually subsequently.
(3) by (0mg/l of three kinds of different concns, 25mg/l, 50mg/l) cupric ion (lambda-cyhalothrin) joins in a series of lambda-cyhalothrin (cupric ion) solution, above-mentioned solution 10ml is gone to add 10mg HPFs sorbent material respectively, be placed in 15 DEG C of waters bath with thermostatic control and leave standstill certain hour, investigate the impact on adsorbent lambda-cyhalothrin (cupric ion) under the condition of the starting point concentration of lambda-cyhalothrin (cupric ion) and the cupric ion (betacyfluthrin) of different concns in test soln.The concentration UV spectrum of the lambda-cyhalothrin (cupric ion) do not adsorbed is measured and calculates.
Result shows: multilevel hole material sorbent material to trifluoro Cypermethrin be adsorbed on three differences coexist lower 15 DEG C of concentration time saturated adsorption capacity be 74.99mg/g, 89.59mg/g, 104.1mg/g.Along with the copper ion concentration added raises, the adsorption effect of sorbent material to trifluoro Cypermethrin improves; Multilevel hole material sorbent material to cupric ion be adsorbed on three differences coexist lower 15 DEG C of concentration time saturated adsorption capacity be 76.56mg/g, 83.55mg/g, 84.53mg/g.Along with the trifluoro Cypermethrin concentration added raises, the adsorption effect of sorbent material to trifluoro Cypermethrin improves.
3, the physicochemical property of material characterizes
(1) pass through amplification 200 times, 600 times according to the method for embodiment 1 by the High Internal Phase Emulsion stirring preparation, 1000 times of observations obtain a result emulsion droplet obviously, emulsion-stabilizing.As shown in Figure 1.
(2) the sub-MSNs of (a) mesoporous silicon dioxide nano particle in embodiment 1 is tested, (b) amination mesoporous silicon dioxide nano particle, the sub-CMSNs of (c) carboxylated mesoporous silicon dioxide nano particle, d the infrared spectrum of () poly (glycidyl methacrylate) MPGMA and (e) multilevel hole material HPFs, result as shown in Figure 2.470,800 and 1100cm -1the symmetrical stretching vibration of corresponding is Si – O – Si, antisymmetric stretching vibration and flexural vibration.1633cm -1for-NH 2vibration absorption peak, 1733cm -1that the characteristic absorption band of-COOH represents the carboxylated success of mesoporous silicon.In d infrared line, 910cm-1 is the charateristic avsorption band of epoxide group.Occur in e spectral line 470,800 and 1100cm -1absorption peak shows that mesoporous silicon dioxide nano particle is successfully grafted on large pore material.
(3) the sub-MSNs of (a) mesoporous silicon dioxide nano particle in embodiment 1 is tested, (b) amination mesoporous silicon dioxide nano particle, the sub-CMSNs of (c) carboxylated mesoporous silicon dioxide nano particle, d transmission electron microscope picture that () amplifies CMSNs, result shows, the mean diameter of mesoporous silicon dioxide nano particle that embodiment 1 obtains is at 100 ran, and aperture is at about 3nm.Result shows, modification makes mesoporous silicon dioxide nano particle sub-aperture diminish, and the bright carboxylated mesoporous silicon oxide success of X-ray diffraction power spectrum graphs in d figure.Result as shown in Figure 3.
(4) scanning electron microscope (SEM) photograph before and after embodiment 1 intermediary hole Nano particles of silicon dioxide grafting macropore poly (glycidyl methacrylate) is tested.Result shows, macropore diameter probably at 10-40 micron, the general 1.5-3 micron of connecting hole.After the mesoporous particle of grafting, material obviously becomes coarse, and photographs mesoporous silicon dioxide nano particle of a large amount of load on surface.Result as shown in Figure 4.
(5) the grafting situation of material is analyzed, from ultimate analysis, macropore poly (glycidyl methacrylate) did not observe element silicon before not having grafting, along with the increase of grafting number of times, surface carbon oxygen element content reduces, and the content of element silicon raises.Result as shown in Figure 5.
(6) CMSNs (a), MPGMA (b) in embodiment 1 is tested, the TGA (solid line) of HPFs (c) and DTG (dotted line) curve.Result shows, the CMSNs rate of weight loss that embodiment 1 obtains be 10.48%, MPGMA rate of weight loss is 96.34%, HPFs rate of weight loss is 69.31%.MPGMA probably has exothermic peak 435.8 DEG C time.Result as shown in Figure 6.
Embodiment 2
(1) mesoporous SiO 2the synthesis of nanoparticle and modification:
Mesoporous SiO 2the synthesis of nanoparticle is obtained by ammonia catalytic hydrolysis tetraethyl orthosilicate; First, 0.4500g cetyl trimethylammonium bromide, 0.7500g Neutral ammonium fluoride join in 120ml deionized water; Subsequently, when being raised to 80 DEG C to temperature, 2.25ml tetraethyl orthosilicate dropwise adds, and stirs after 2 hours, and collected by centrifugation product also removes tensio-active agent with the 24h that refluxes at 100ml ethanol, 2ml hydrochloric acid mixed solution 90 DEG C, and backflow cleaning carries out 3 times repeatedly; Finally, collected by centrifugation and repeatedly cleaning several times with deionized water and ethanol, the mesoporous SiO of preparation 2nanoparticle is dry 48h at 50-60 DEG C;
The mesoporous SiO of amination 2nanoparticle; First, the mesoporous SiO of 1.0g 2nanoparticle dispersion is in 10ml toluene solution, evenly ultrasonic; Then, 1.0ml aminopropyl triethoxysilane dropwise add and under nitrogen protection 120 DEG C backflow 24 hours; Finally, collected by centrifugation product also cleans several times repeatedly with deionized water and ethanol, the mesoporous SiO of preparation 2nanoparticle is dry 48h at 50-60 DEG C;
Carboxylated mesoporous SiO 2nanoparticle; The mesoporous SiO of 0.1g amination 2nanoparticle dispersion in 30ml DMF solution, and adds 1.5g Succinic anhydried, under 30 DEG C of conditions, react 12h.Finally, collected by centrifugation product also cleans several times repeatedly with deionized water and ethanol, the mesoporous SiO of preparation 2nanoparticle is dry 48h at 50-60 DEG C;
(2) synthesis of macropore glycidyl methacrylate foam materials:
Polymerization single polymerization monomer 0.6ml glycidyl methacrylate, linking agent 0.7ml Vinylstyrene, be distributed in solvent 1ml toluene, then add initiator 0.02g Diisopropyl azodicarboxylate, after being uniformly mixed, add 0.5ml tensio-active agent (Hypermer 2296).Dropwise add 11ml potassium sulfate solution under agitation, formed and the stable rear 5min that continues to stir etc. emulsion, above-mentioned emulsion is poured in ampere bottle, at 60-70 DEG C, react 24h.After having reacted, carry out surname extraction 12h with acetone soln and remove organic solvent, put into 50 DEG C of baking ovens and dry.In this step, in potassium sulfate solution, the ratio of potassium sulfate and deionized water is 0.55:45 (g/ml).
(3) carboxylated mesoporous SiO 2nano particle grafting macroporous acrylic glycidyl ester foam materials:
The carboxylated mesoporous SiO of 0.15g 2nanoparticle, 0.3g macroporous acrylic glycidyl ester foam materials, 0.15g calcium chloride is distributed in organic solvent 10ml DMF solution, carries out 24h at being grafted to 45 DEG C.This reaction process is carried out repeatedly repeatedly, and finally, graft materials is collected and by washing with alcohol repeatedly and under 50-65 DEG C of condition dry a day.
2, absorption property analytical test
(1) get 10ml starting point concentration be respectively 10,30,50,80, lambda-cyhalothrin (cupric ion) solution of 100mg/L joins in colorimetric cylinder, add multilevel hole material sorbent material prepared by aforesaid method in 10mg embodiment 1 respectively, test fluid is placed on 15 DEG C, 25 DEG C, after leaving standstill 12h in the water-bath of 35 DEG C, supernatant liquid collecting by filtration, lambda-cyhalothrin molecule (cupric ion) the concentration ultraviolet-visible pectrophotometer do not adsorbed measures, and calculates loading capacity according to result.
Result shows: the saturated adsorption capacity during absorption 15 DEG C of multilevel hole material sorbent material to trifluoro Cypermethrin is 76.35mg/g, and saturated adsorption capacity when 25 DEG C is 55.21mg/g, and saturated adsorption capacity when 35 DEG C is 39.14mg/g.Along with temperature raises, adsorbent deleterious; The saturated adsorption capacity during absorption 15 DEG C of multilevel hole material sorbent material to cupric ion is 80.26mg/g, and saturated adsorption capacity when 25 DEG C is 71.51mg/g, and saturated adsorption capacity when 35 DEG C is 55.53mg/g.Along with temperature raises, adsorbent deleterious.
(2) getting lambda-cyhalothrin (cupric ion) solution that 10ml starting point concentration is 100mg/L joins in colorimetric cylinder, add multi-stage porous sorbent material prepared by aforesaid method in 10mg embodiment 1 respectively, test fluid is placed in the water-bath of 15 DEG C and leaves standstill 5,10,20,30,60,90,120,240,360,480, after 720min, supernatant liquid is through centrifugal and use polyvinylidene fluoride microporous film collecting by filtration, the lambda-cyhalothrin molecular conecentration ultraviolet-visible pectrophotometer do not adsorbed measures, and calculates loading capacity according to result.
Result shows: in 120min, reached 75.36% of equilibrium adsorption capacity during multilevel hole material adsorbent lambda-cyhalothrin, reaches adsorption equilibrium gradually subsequently after absorption 480-720min; In 90min, reach 80.53% of equilibrium adsorption capacity during multilevel hole material adsorbent cupric ion, after absorption 480-720min, reach adsorption equilibrium gradually subsequently.
(3) by (0mg/l of three kinds of different concns, 25mg/l, 50mg/l) cupric ion (lambda-cyhalothrin) joins in a series of lambda-cyhalothrin (cupric ion) solution, above-mentioned solution 10ml is gone to add 10mg HPFs sorbent material respectively, be placed in 15 DEG C of waters bath with thermostatic control and leave standstill certain hour, investigate the impact on adsorbent lambda-cyhalothrin (cupric ion) under the condition of the starting point concentration of lambda-cyhalothrin (cupric ion) and the cupric ion (betacyfluthrin) of different concns in test soln.The concentration UV spectrum of the lambda-cyhalothrin (cupric ion) do not adsorbed is measured and calculates.
Result shows: multilevel hole material sorbent material to trifluoro Cypermethrin be adsorbed on three differences coexist lower 15 DEG C of concentration time saturated adsorption capacity be 62.12mg/g, 75.39mg/g, 90.21mg/g.Along with the copper ion concentration added raises, the adsorption effect of sorbent material to trifluoro Cypermethrin improves; Multilevel hole material sorbent material to cupric ion be adsorbed on three differences coexist lower 15 DEG C of concentration time saturated adsorption capacity be 70.51mg/g, 75.22mg/g, 85.14mg/g.Along with the trifluoro Cypermethrin concentration added raises, the adsorption effect of sorbent material to trifluoro Cypermethrin improves.
Embodiment 3
(1) mesoporous SiO 2the synthesis of nanoparticle and modification:
Mesoporous SiO 2the synthesis of nanoparticle is obtained by ammonia catalytic hydrolysis tetraethyl orthosilicate; First, 0.500g cetyl trimethylammonium bromide, 0.7500g Neutral ammonium fluoride join in 130ml deionized water; Subsequently, when being raised to 80 DEG C to temperature, 2.25ml tetraethyl orthosilicate dropwise adds, and stirs after 2 hours, and collected by centrifugation product also removes tensio-active agent with the 24h that refluxes at 100ml ethanol, 2ml hydrochloric acid mixed solution 90 DEG C, and backflow cleaning carries out 3 times repeatedly; Finally, collected by centrifugation and repeatedly cleaning several times with deionized water and ethanol, the mesoporous SiO of preparation 2nanoparticle is dry 48h at 50-60 DEG C;
The mesoporous SiO of amination 2nanoparticle; First, the mesoporous SiO of 1.0g 2nanoparticle dispersion is in 10ml toluene solution, evenly ultrasonic; Then, 1.5ml aminopropyl triethoxysilane dropwise add and under nitrogen protection 120 DEG C backflow 24 hours; Finally, collected by centrifugation product also cleans several times repeatedly with deionized water and ethanol, the mesoporous SiO of preparation 2nanoparticle is dry 48h at 50-60 DEG C;
Carboxylated mesoporous SiO 2nanoparticle; The mesoporous SiO of 0.1g amination 2nanoparticle dispersion in 30ml DMF solution, and adds 1.8g Succinic anhydried, under 30 DEG C of conditions, react 12h.Finally, collected by centrifugation product also cleans several times repeatedly with deionized water and ethanol, the mesoporous SiO of preparation 2nanoparticle is dry 48h at 50-60 DEG C;
(2) synthesis of macropore glycidyl methacrylate foam materials:
Polymerization single polymerization monomer 0.65ml glycidyl methacrylate, linking agent 0.8ml Vinylstyrene, be distributed in solvent 1ml toluene, then add initiator 0.02g Diisopropyl azodicarboxylate, after being uniformly mixed, add 0.6ml tensio-active agent (Hypermer 2296).Dropwise add 13ml potassium sulfate solution under agitation, formed and the stable rear 5min that continues to stir etc. emulsion, above-mentioned emulsion is poured in ampere bottle, at 60-70 DEG C, react 24h.After having reacted, carry out surname extraction 12h with acetone soln and remove organic solvent, put into 50 DEG C of baking ovens and dry.In this step, in potassium sulfate solution, the ratio of potassium sulfate and deionized water is 0.55:45 (g/ml).
(3) carboxylated mesoporous SiO 2nano particle grafting macroporous acrylic glycidyl ester foam materials:
The carboxylated mesoporous SiO of 0.20g 2nanoparticle, 0.3g macroporous acrylic glycidyl ester foam materials, 0.15g calcium chloride is distributed in organic solvent 10ml DMF solution, carries out 24h at being grafted to 45 DEG C.This reaction process is carried out repeatedly repeatedly, and finally, graft materials is collected and by washing with alcohol repeatedly and under 50-65 DEG C of condition dry a day.
2, absorption property analytical test
(1) get 10ml starting point concentration be respectively 10,30,50,80, lambda-cyhalothrin (cupric ion) solution of 100mg/L joins in colorimetric cylinder, add multilevel hole material sorbent material prepared by aforesaid method in 10mg embodiment 1 respectively, test fluid is placed on 15 DEG C, 25 DEG C, after leaving standstill 12h in the water-bath of 35 DEG C, supernatant liquid collecting by filtration, lambda-cyhalothrin molecule (cupric ion) the concentration ultraviolet-visible pectrophotometer do not adsorbed measures, and calculates loading capacity according to result.
Result shows: the saturated adsorption capacity during absorption 15 DEG C of multilevel hole material sorbent material to trifluoro Cypermethrin is 78.72mg/g, and saturated adsorption capacity when 25 DEG C is 60.85mg/g, and saturated adsorption capacity when 35 DEG C is 43.95mg/g.Along with temperature raises, adsorbent deleterious; The saturated adsorption capacity during absorption 15 DEG C of multilevel hole material sorbent material to cupric ion is 81.33mg/g, and saturated adsorption capacity when 25 DEG C is 73.86mg/g, and saturated adsorption capacity when 35 DEG C is 57.97mg/g.Along with temperature raises, adsorbent deleterious.
(2) getting lambda-cyhalothrin (cupric ion) solution that 10ml starting point concentration is 100mg/L joins in colorimetric cylinder, add multi-stage porous sorbent material prepared by aforesaid method in 10mg embodiment 1 respectively, test fluid is placed in the water-bath of 15 DEG C and leaves standstill 5,10,20,30,60,90,120,240,360,480, after 720min, supernatant liquid is through centrifugal and use polyvinylidene fluoride microporous film collecting by filtration, the lambda-cyhalothrin molecular conecentration ultraviolet-visible pectrophotometer do not adsorbed measures, and calculates loading capacity according to result.
Result shows: in 120min, reached 78.34% of equilibrium adsorption capacity during multilevel hole material adsorbent lambda-cyhalothrin, reaches adsorption equilibrium gradually subsequently after absorption 480-720min; In 90min, reach 79.22% of equilibrium adsorption capacity during multilevel hole material adsorbent cupric ion, after absorption 480-720min, reach adsorption equilibrium gradually subsequently.
(3) by (0mg/l of three kinds of different concns, 25mg/l, 50mg/l) cupric ion (lambda-cyhalothrin) joins in a series of lambda-cyhalothrin (cupric ion) solution, above-mentioned solution 10ml is gone to add 10mg HPFs sorbent material respectively, be placed in 15 DEG C of waters bath with thermostatic control and leave standstill certain hour, investigate the impact on adsorbent lambda-cyhalothrin (cupric ion) under the condition of the starting point concentration of lambda-cyhalothrin (cupric ion) and the cupric ion (betacyfluthrin) of different concns in test soln.The concentration UV spectrum of the lambda-cyhalothrin (cupric ion) do not adsorbed is measured and calculates.
Result shows: multilevel hole material sorbent material to trifluoro Cypermethrin be adsorbed on three differences coexist lower 15 DEG C of concentration time saturated adsorption capacity be 63.65mg/g, 73.98mg/g, 87.21mg/g.Along with the copper ion concentration added raises, the adsorption effect of sorbent material to trifluoro Cypermethrin improves; Multilevel hole material sorbent material to cupric ion be adsorbed on three differences coexist lower 15 DEG C of concentration time saturated adsorption capacity be 70.51mg/g, 75.22mg/g, 85.14mg/g.Along with the trifluoro Cypermethrin concentration added raises, the adsorption effect of sorbent material to trifluoro Cypermethrin improves.

Claims (8)

1. High Internal Phase Emulsion template and interface crosslinking legal system are for the method for multi-stage porous foam materials, it is characterized in that, comprise the steps:
(1) mesoporous SiO 2the synthesis of nanoparticle and modification:
Mesoporous SiO 2the synthesis of nanoparticle is obtained by ammonia catalytic hydrolysis tetraethyl orthosilicate; First, cetyl trimethylammonium bromide, Neutral ammonium fluoride join in deionized water; Subsequently, when being raised to 80 DEG C to temperature, tetraethyl orthosilicate dropwise adds, and stirs after 1-2 hour, and collected by centrifugation product also removes cetyl trimethylammonium bromide tensio-active agent with the 24h that refluxes at ethanol, hydrochloric acid mixed solution 90 DEG C, and backflow cleaning is carried out repeatedly repeatedly; Finally, collected by centrifugation and repeatedly cleaning several times with deionized water and ethanol, the mesoporous SiO of preparation 2nanoparticle is dry 48h at 50-60 DEG C;
The mesoporous SiO of amination 2nanoparticle; First, mesoporous SiO 2nanoparticle dispersion is in toluene solution, evenly ultrasonic; Then, aminopropyl triethoxysilane dropwise add and under nitrogen protection 120 DEG C backflow 24 hours; Finally, collected by centrifugation product also cleans several times repeatedly with deionized water and ethanol, the mesoporous SiO of amination of preparation 2nanoparticle is dry 48h at 50-60 DEG C;
Carboxylated mesoporous SiO 2nanoparticle; The mesoporous SiO of amination 2nanoparticle dispersion in DMF solution, and adds a certain amount of Succinic anhydried, under 30 DEG C of conditions, react 12h, and finally, collected by centrifugation product also cleans several times repeatedly with deionized water and ethanol, the carboxylated mesoporous SiO of preparation 2nanoparticle is dry 48h at 50-60 DEG C;
(2) synthesis of macropore glycidyl methacrylate foam materials
Polymerization single polymerization monomer glycidyl methacrylate, cross-linker divinylbenzene, is distributed in solvent toluene, then adds initiator Diisopropyl azodicarboxylate, tensio-active agent Hypermer 2296 is added after being uniformly mixed, dropwise add potassium sulfate solution under agitation, etc. emulsion formed and stable after, above-mentioned emulsion is poured in ampere bottle, 24h is reacted at 60-70 DEG C, after having reacted, carry out surname extraction 12h with acetone soln and remove organic solvent, put into 50 DEG C of baking ovens and dry;
(3) carboxylated mesoporous SiO 2nano particle grafting macroporous acrylic glycidyl ester foam materials:
Carboxylated mesoporous SiO 2nanoparticle, macroporous acrylic glycidyl ester foam materials, calcium chloride is distributed to organic solvent N, in dinethylformamide solution, 24h is carried out at being grafted to 45 DEG C, this reaction process is carried out repeatedly repeatedly, and finally, graft materials is collected and by washing with alcohol repeatedly and under 50-65 DEG C of condition dry a day.
2. method according to claim 1, is characterized in that, in described step (1), prepares mesoporous SiO 2in nanoparticle process, the ratio of cetyl trimethylammonium bromide, Neutral ammonium fluoride, deionized water and tetraethyl orthosilicate is (0.45-0.50): 0.75:(120-130): 2.25(g/g/ml/ml).
3. method according to claim 1, is characterized in that, in described step (1), prepares mesoporous SiO 2in nanoparticle process, the ratio of ethanol, hydrochloric acid is 100:2(ml:ml).
4. method according to claim 1, is characterized in that, in described step (1), and the mesoporous SiO of amination 2in nanoparticle process, mesoporous SiO 2the ratio of nanoparticle, aminopropyl triethoxysilane, toluene is 1:(1.0-1.5): 10(g/ml/ml).
5. method according to claim 1, is characterized in that, in described step (1), and carboxylated mesoporous SiO 2in nanoparticle process, mesoporous SiO 2the ratio of nanoparticle, Succinic anhydried, DMF is 0.1:(1.0-1.8): 30(g/g/ml).
6. method according to claim 1, it is characterized in that, in described step (2), the ratio of glycidyl acrylate, Vinylstyrene, toluene, Diisopropyl azodicarboxylate, tensio-active agent Hypermer 2296, potassium sulfate solution is (0.6-0.7): (0.7-1): 1:0.02:(0.4-0.6): (11-13) (ml/ml/ml/g/ml/ml).
7. method according to claim 1, is characterized in that, in described step (2), in potassium sulfate solution, the ratio of potassium sulfate and deionized water is 0.55:45(g/ml).
8. method according to claim 1, is characterized in that, in described step (3), and carboxylated mesoporous SiO 2the ratio of nanoparticle, macroporous acrylic glycidyl ester foam materials, calcium chloride, DMF is (0.1-0.2): 0.3:0.15:10(g/g/g/ml).
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105289540A (en) * 2015-11-11 2016-02-03 江苏大学 Method for preparing porous difunctional adsorption material
CN106076288A (en) * 2016-06-17 2016-11-09 江苏大学 A kind of preparation method of porous ion/molecularly imprinted polymer
CN106883336A (en) * 2016-12-13 2017-06-23 济南大学 A kind of preparation method of the fluorine-containing porous polymer material of controllable hole structure
CN108786649A (en) * 2018-07-17 2018-11-13 宁德师范学院 One kind is by mesoporous SiO2Stable Pickering lotions and preparation method thereof
CN110227435A (en) * 2019-06-26 2019-09-13 河海大学 Macroscopical 3D high porosity Hyposmolality nano catalytic material and preparation method thereof
CN113252588A (en) * 2021-05-11 2021-08-13 西南科技大学 Organic clay, preparation method thereof, and color development system and method for detecting hydroquinone
CN117861630A (en) * 2024-01-27 2024-04-12 杭州捷瑞智能装备股份有限公司 Preparation method of modified silica gel adsorbent

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2007284002A1 (en) * 2006-08-18 2008-02-21 Commonwealth Scientific And Industrial Research Organisation Polymeric coatings and methods for forming them
CN101348577A (en) * 2007-07-17 2009-01-21 中国科学院化学研究所 Porous integral medium, preparation and use thereof
CN102949728A (en) * 2012-12-12 2013-03-06 重庆大学 Meso-porous silicon nano-drug carrier with both reduction responsiveness and targeting ability and preparation method thereof
CN104013965A (en) * 2014-05-06 2014-09-03 重庆大学 Method for preparing meso-porous silicon nano medicine carrier with cell specificity target, reduction responsiveness and triple anticancer treatment effects

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2007284002A1 (en) * 2006-08-18 2008-02-21 Commonwealth Scientific And Industrial Research Organisation Polymeric coatings and methods for forming them
CN101348577A (en) * 2007-07-17 2009-01-21 中国科学院化学研究所 Porous integral medium, preparation and use thereof
CN102949728A (en) * 2012-12-12 2013-03-06 重庆大学 Meso-porous silicon nano-drug carrier with both reduction responsiveness and targeting ability and preparation method thereof
CN104013965A (en) * 2014-05-06 2014-09-03 重庆大学 Method for preparing meso-porous silicon nano medicine carrier with cell specificity target, reduction responsiveness and triple anticancer treatment effects

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
周婵等: "非对称环氧乙烷的区域选择性亲核开环反应", 《化学进展》 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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CN106076288B (en) * 2016-06-17 2018-06-26 江苏大学 A kind of preparation method of porous ion/molecularly imprinted polymer
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CN110227435B (en) * 2019-06-26 2021-06-01 河海大学 Macroscopic 3D high-porosity low-permeability nano catalytic material and preparation method thereof
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