CN106964322A - A kind of preparation method of boric acid functionalization porous adsorbent - Google Patents
A kind of preparation method of boric acid functionalization porous adsorbent Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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Abstract
The present invention relates to a kind of preparation method of boric acid functionalization porous adsorbent, belong to medicine functional material preparing technical field；The method comprises the steps of firstly, preparing the nano-particle BA MSNs of boric acid functionalization, then using GMA as monomer, divinylbenzene is crosslinking agent, azodiisobutyronitrile is initiator, and formation Pickering High Internal Phase Emulsions after surfactant Hypermer 2296 is stirred are added, the porous resin of boric acid functionalization is obtained after thermal-initiated polymerization；B N complexes are introduced by the method for rear modification again, the porous adsorbent of boric acid functionalization are prepared, and use it for the adsorbing separation under neutrallty condition to cyanidenon；Adsorbent prepared by the present invention has the loose structure of UNICOM, and Penetration ration is high, and adsorption capacity is high, and environment-friendly, recycling rate of waterused is strong；And it can in neutral conditions be adsorbed, reduce secondary pollution and the oxidation of cyanidenon.
Description
Technical field
The present invention relates to a kind of preparation method of boric acid functionalization porous adsorbent, category medicine functional material technology of preparing neck
Domain.
Background technology
Flavone compound containing cis-form dihydroxy functional group, such as cyanidenon（LTL）, due to its oxidation resistance,
Antitumaous effect, anti-inflammatory and antiallergic activity are increasingly attracted attention in recent years, and separation cyanidenon is extracted from natural plants
It is the main source of its current industrial applications.Organic solvent extractionprocess is that extraction cyanidenon is the most frequently used from native compound
Method, still, organic solvent extractionprocess usually requires to use substantial amounts of organic solvent, and environmental pollution is big, low separation efficiency.Cause
This, the adsorbing separation for developing new sorbing material for cyanidenon is very urgent.Due to easy to operate, pollute few, energy consumption
Low advantage, the adsorbing separation that cyanidenon is used for based on porous adsorption resin is a kind of effective adsorption method.
Pickering High Internal Phase Emulsion templates are to produce the preferable method of porous adsorption resin, the porous tree of preparation
Fat has good permeability and enough mechanical performances, and this is extremely important in actual applications, and is replaced using solid particle
Emulsifying agent stablizes Pickering High Internal Phase Emulsions, reduces the consumption of emulsifying agent, has saved synthesis cost, environmentally friendly.
Boron affinity interaction, which has proven to a kind of very effective mode of action, is used for cis-form dihydroxy compound
Separation, boric acid can form five yuan reversible or hexa-atomic boron cyclic ester, Pan etc. with cis-form dihydroxy compound in an aqueous medium
（Pan, J. M.,Huang, X. B., Gao, L., Peng, Y. X., Liu, S. C., Gu. R. X.
Experimental investigation of a natural favonoid adsorption on macroporous
polymers with ontrinsic cis-diol moieties recognition function: static and
dynamic methods.Chem. Eng. J.2017, 312, 263-274.）Prepared by High Internal Phase Emulsion template
The macroporous polymer of boric acid functionalization is used for the adsorbing separation of cyanidenon.However, these traditional boric acid functionalization are porous
Adsorbent usually requires to realize to the separation of LTL efficient absorption in alkalescence condition, but LTL easy quilts in the basic conditions
Oxidation, and the discharge of alkalescence/acidic aqueous solution can cause secondary environmental pollution.Can be in neutrality it is therefore desirable to research and develop preparation
Under the conditions of to LTL have compared with high separating efficiency boric acid functionalization porous adsorbent.
Therefore, this work is prepared containing many of B-N complexes by Pickering High Internal Phase Emulsion templates
Hole adsorbent（PGM-Pickering-BN）Cyanidenon is adsorbed for Selective Separation in neutral conditions（LTL）.
The content of the invention
It is an object of the invention to overcome existing boric acid functionalization adsorbent to need in the basic conditions to reach LTL
The shortcoming of higher adsorption efficiency, and the boric acid functionalization porous adsorbent under a kind of neutrallty condition with higher adsorption efficiency is provided
And preparation method thereof.
The method comprises the steps of firstly, preparing the medium hole nano particles for obtaining boric acid functionalization（BA-MSNs）, and as
The stable particle of Pickering High Internal Phase Emulsions；Secondly, with GMA（GMA）For monomer, divinyl
Benzene（DVB）For crosslinking agent, azodiisobutyronitrile（AIBN）For initiator, BA-MSNs is stable particle, and toluene is solvent supersonic point
Continuous phase is formed after dissipating, and adds the deionized water solution that contain a certain amount of surfactant Hypermer 2296 as dividing
Dephasing, forms Pickering High Internal Phase Emulsions, the porous resin of boric acid functionalization is obtained after thermal-initiated polymerization after stirring（PGM-
Pickering.Finally, 1,6- hexamethylene diamines and APBA are dissolved in tetrahydrofuran（THF）In and be thermally formed B-N ligand compounds
Thing, is subsequently added the boric acid functionalization porous resin obtained after PGM-Pickering, reaction containing B-N ligand compounds（PGM-
Pickering-BN）, and use it for the adsorbing separation of the cyanidenon under neutrallty condition.
Specifically, the technical solution adopted by the present invention is：
（1）The medium hole nano particles of boric acid functionalization（BA-MSNs）Preparation：
First, reference method（J. Tan, H.F. Wang, X.P. Yan. Discrimination of Saccharides
with a Fluorescent Molecular Imprinting Sensor Array Based on Phenylboronic
Acid Functionalized Mesoporous Silica. Anal. Chem. 2009, 81, 5273-5280.）Synthesis
The silane coupler of phenyl boric acid coupling（APBA-GPTES）：By 1.37g 3- amino phenyl boric acids and 2.36g 3- glycidyl ether oxygens
Base propyl-triethoxysilicane is added in 25mL round-bottomed flask, is then slowly added to 10mL tetrahydrofurans, and be passed through nitrogen
Except oxygen 15min, then 12h is reacted at 25 DEG C.Mixed solution is finally removed into liquid by rotary evaporation, and will be obtained
Brown oil material is dissolved in 10mL methanol solutions, has both obtained the APBA-GPTES solution that concentration is 1.0 mmol/mL.
Then, by 0.2-0.4g cetyl trimethylammonium bromides, 0.05-0.15g sodium hydroxides be dissolved in 150mL go from
In sub- water, then heating stirring instills 1.0-1.5mL tetraethyl orthosilicates and 50-150 μ L APBA- dropwise to 70-80 DEG C
GPTES solution, is persistently stirred after 1-3h, is centrifuged and is washed precipitation with ethanol 5 times.Finally, by the product of acquisition 50
Vacuum drying can obtain the medium hole nano particles of boric acid functionalization at DEG C（BA-MSNs）.
（2）Porous polymethyl glycidyl acrylate resin（PGM-Pickering）Preparation：
First, by GMA（GMA）, divinylbenzene（DVB）, toluene, azodiisobutyronitrile（AIBN）
And BA-MSNs is according to 1.0 mL：0.5-1.5 mL：1.0-2.0 mL： 0.01-0.02 g：0.05-0.15 g::::Mixing
Afterwards, add in round-bottomed flask and ultrasonic disperse formation continuous phase.16mL is then contained into 50-150 μ L emulsifying agents Hypermer
2296 deionized water solution is added dropwise, and low whipping speed is mechanical agitation 10min formation W/O under 500-700rpm
Type Pickering High Internal Phase Emulsions, then polymerize 12 h, and product acetone is passed through into Soxhlet by emulsion at 60-70 DEG C
Extract washing 24h and remove unreacted monomer, be finally dried in vacuo at 50 DEG C.
（3）Boric acid functionalization porous adsorbent containing B-N complexes（PGM-Pickering-BN）Preparation：
By 0.31-0.51g 1,6- hexamethylene diamines and 0.4-0.6g 3- amino phenyl boric acids are dissolved in 60mL tetrahydrofurans, then molten
Liquid is heated to 40 DEG C under agitation, and continues 1h to form B-N complexes.Then by 0.2-0.4g PGM-
Pickering is added in above-mentioned solution and stirred at 70-90 DEG C, condensing reflux 12h.Product is finally washed 3 with ethanol
It is secondary, and 50 DEG C of vacuum drying obtain final product PGM-Pickering-BN.
Adsorbent prepared by the present invention contains substantial amounts of macropore and connecting hole, and good penetrability, porosity are high, exists a large amount of
Recognition site, adsorption capacity is big, and adsorbing separation can be carried out in neutral conditions
Compared with prior art, beneficial effects of the present invention are embodied in following aspect
At present, the main source that separation cyanidenon is its industrial applications is extracted from natural plants, and organic solvent is extracted
Method is the extraction cyanidenon most common method from native compound, and still, organic solvent extractionprocess is usually required using big
The organic solvent of amount, environmental pollution is big, low separation efficiency；Therefore the method comprises the steps of firstly, preparing the nanoparticle for having obtained boric acid functionalization
Sub- BA-MSNs, and as the stable particle of Pickering High Internal Phase Emulsions, then with GMA
（GMA）For monomer, divinylbenzene（DVB）For crosslinking agent, azodiisobutyronitrile（AIBN）For initiator, and add a small amount of table
Pickering High Internal Phase Emulsions are formed after face activating agent Hypermer 2296 stirring, boric acid function is obtained after thermal-initiated polymerization
The porous resin of change（PGM-Pickering）, B-N complexes are introduced finally by the method for rear modification, are prepared
The porous adsorbent of boric acid functionalization（PGM-Pickering-BN）, have studied suctions of the PGM-Pickering-BN to cyanidenon
Attached behavior and mechanism, and probed into the influence that pH value adsorbs cyanidenon to adsorbent, boric acid functionalization prepared by the present invention
The maximum adsorption capacity of porous adsorbent be 158.5 μm of ol/g, and can reach adsorption equilibrium in 3h, then modify
The B-N complexes of introducing are also beneficial to absorption in neutral conditions to cyanidenon, reduce secondary pollution.
The present invention, as stable particle, reduces the consumption of emulsifying agent first using the nano-particle of boric acid functionalization, saves
About synthesis cost, environmentally friendly, and uses the nano-particle of modified to be used as the steady of Pickering High Internal Phase Emulsion templates
Particle is determined so that adsorbent has more recognition sites, improves adsorption capacity.Boron affinity interaction is usually required in alkaline bar
Stronger effect could be produced under part to cyanidenon, and B-N complexes are introduced by rear modification, is effectively realized
To the absorption of cyanidenon under neutrallty condition, reduce caused by the discharge of alkalescence/acidic aqueous solution secondary environmental pollution and solve
The shortcoming that cyanidenon of having determined can be oxidized in the basic conditions, rear modification introduces B-N complexes to promote neutrallty condition
The absorption of lower cyanidenon not yet appears in the newspapers；Also, the porous adsorbent of the boric acid functionalization prepared is compared to organic solvent
Extraction, pollution subenvironment is friendly, it is easy to separate, and reusing is high, with more binding site, and adsorption capacity is big, and
And effective absorption can be realized to cyanidenon in neutral conditions.
Brief description of the drawings
Fig. 1 is the boric acid functional nanoparticle for preparing in embodiment 1（BA-MSNs）Transmission electron microscope picture.Figure a is BA-
MSNs TEM figures, figure b amplifies 4 times of TEM figures for figure a.
Fig. 2 is the porous absorption of the boric acid functionalization containing different amounts of BA-MSNs prepared in embodiment 1,2,3
Agent PGM-Pickering-BN scanning electron microscope (SEM) photograph.Scheme a：0.00g；Scheme b：0.05g；Scheme c:0.10g；Scheme d：0.15g.
Fig. 3 is the BA-MSNs for preparing in embodiment 1（a）, PGM（b）, PGM-Pickering（c）, PGM-BN
（d）And PGM-Pickering-BN（e）Infrared spectrogram.
Fig. 4 is the BA-MSNs for preparing in embodiment 1（a）, PGM-Pickering（b）, PGM-Pickering-
BN （c）XPS spectrum figure.
Embodiment
To make those skilled in the art be better understood from the technical scheme, with reference to specific embodiments and the drawings to this hair
Bright more preferable elaboration.
Recognition performance evaluation is carried out by the following method in the specific embodiment of the invention：It is complete using Staticadsorption experiment
Into.The certain density LTL of 10mL are added in centrifuge tube, the porous adsorbent PGM- of a certain amount of boric acid functionalization is added
Pickering-BN, is placed on 25oLTL contents ultraviolet-uisible spectrophotometer after some hours, absorption is stood in C constant temperature waters
Determine, and adsorption capacity is calculated according to result；The LTL solution 10mL of the different pH value of same concentrations is added in centrifuge tube, plus
Enter same amount of PGM-Pickering-BN adsorbents, 25oC constant temperature is stood after identical hour in waters, uses UV, visible light light splitting
The final LTL contents of photometric determination, and the influence that pH value is adsorbed to LTL is studied with this.
Embodiment 1：
（1）The medium hole nano particles of boric acid functionalization（BA-MSNs）Preparation：
First, 1.37g 3- amino phenyl boric acids and 2.36g 3- glycydoxies triethoxysilane are added into 25mL
Round-bottomed flask in, 10mL tetrahydrofurans are then slowly added to, and be passed through nitrogen except oxygen 15min, then 25oIt is anti-under C
Answer 12h.Mixed solution is finally removed into liquid by rotary evaporation, and obtained brown oil material is dissolved in 10mL methanol
In solution, that is, concentration is obtained for 1.0 mmol mL-1APBA-GPTES solution.
Then, by 0.3g cetyl trimethylammonium bromides, 0.1g sodium hydroxides are dissolved in 150mL deionized waters, plus
Thermal agitation is to 75oC, then instills 1.25mL tetraethyl orthosilicates and 100 μ L APBA-GPTES solution, persistently stirs 2h dropwise
Afterwards, centrifuge and wash precipitation with ethanol 5 times.Finally, by the product of acquisition 50oVacuum drying can obtain boric acid under C
The medium hole nano particles of functionalization（BA-MSNs）.
（2）Porous polymethyl glycidyl acrylate resin（PGM-Pickering）Preparation：
First, by 1.0mL GMAs（GMA）With 1.0mL divinylbenzenes（DVB）, 1.5mL toluene,
0.015g azodiisobutyronitriles（AIBN）And after 0.10g BA-MSNs mixing, add in round-bottomed flask and ultrasonic disperse shape
Into continuous phase.Then the 16mL deionized water solutions for containing 100 μ L emulsifying agents Hypermer 2296 are added dropwise, and
Low whipping speed is mechanical agitation 10min formation w/o type Pickering High Internal Phase Emulsions under 600rpm, and then emulsion exists
65oIt polymerize 12 h under C, and product is washed into 24h with acetone by surname extraction and remove unreacted monomer, finally 50oUnder C
It is dried under vacuum to constant weight.
（3）Boric acid functionalization porous adsorbent containing B-N complexes（PGM-Pickering-BN）Preparation：
First, by 0.41g 1,6- hexamethylene diamines and 0.5g 3- amino phenyl boric acids are dissolved in 60mL tetrahydrofurans, and subsequent solution exists
40 are heated under stirringoC, and continue 1h to form B-N complexes.Then 0.3g PGM-Pickering are added
Enter in above-mentioned solution and 80oStirred under C, condensing reflux 12h.Product is finally washed into 3 times, and 50 with ethanoloC vacuum
It is dried to obtain final product PGM-Pickering-BN.
Fig. 1 is the boric acid functional nanoparticle for preparing in embodiment 1（BA-MSNs）Transmission electron microscope picture.Figure a is BA-
MSNs TEM figures, figure b schemes for figure a amplification TEM.Can be with the boric acid functionalized nano grain of preparation visible in detail from figure
Sub- even size distribution, particle size about 200nm, and with meso-hole structure, show that BA-MSNs is successfully prepared.Implement
The boric acid functional nanoparticle prepared in example 1 has clearly meso-hole structure, bigger than surface, and surface has abundant boronate
Group, the stable particle for Pickering High Internal Phase Emulsions can provide more adsorption sites for final product, improve absorption
Capacity.
Fig. 3 is the BA-MSNs for preparing in embodiment 1（a）, PGM（b）, PGM-Pickering（c）, PGM-BN
（d）And PGM-Pickering-BN（e）Infrared spectrogram.Correlation curve, it is observed that 1618 in curve a, c, d, e
cm-1With 1454 cm-1In the presence of strong absworption peak, respectively N-H flexural vibrations and C-N stretching vibration, show to be successfully introduced into
B-N complexes or BA-MSNs nano-particles.And curve a, c, e are in 1095 cm-1There is the flexible of Si-O and shake in place
It is dynamic, show there is BA-MSNs on last porous adsorbent surface, and the porous adsorbent PGM- of boric acid functionalization
Pickering-BN is successfully prepared.
Fig. 4 is the BA-MSNs for preparing in embodiment 1（a）, PGM-Pickering（b）, PGM-Pickering-
BN （c）XPS spectrum figure.O1s can be significantly observed from figure a（531.07 eV）, N1s（397.72 eV）, C1s
（282.86 eV）, B1s（189.76 eV）And Si2p（101.46）Absworption peak, surface successfully introduces boric acid base group
Medium hole nano particles surface is arrived.And b, c are schemed because BA-MSNs presence spectrogram absworption peak is similar, but can be with comparison diagram 3
Infrared spectrum shows that PGM-Pickering-BN is successfully prepared.
Embodiment 2：
（1）The medium hole nano particles of boric acid functionalization（BA-MSNs）Preparation：
First, 1.37g 3- amino phenyl boric acids and 2.36g 3- glycydoxies triethoxysilane are added into 25mL
Round-bottomed flask in, 10mL tetrahydrofurans are then slowly added to, and be passed through nitrogen except oxygen 15min, then 25oIt is anti-under C
Answer 12h.Mixed solution is finally removed into liquid by rotary evaporation, and obtained brown oil material is dissolved in 10mL methanol
In solution, that is, concentration is obtained for 1.0 mmol mL-1APBA-GPTES solution.
Then, by 0.2g cetyl trimethylammonium bromides, 0.05g sodium hydroxides are dissolved in 150mL deionized waters, plus
Thermal agitation is to 70oC, then instills 1.0mL tetraethyl orthosilicates and 50 μ L APBA-GPTES solution dropwise, persistently stirs after 1h,
Centrifuge and wash precipitation with ethanol 5 times.Finally, by the product of acquisition 50oVacuum drying can obtain boric acid work(under C
The medium hole nano particles of energyization（BA-MSNs）.
（2）Porous polymethyl glycidyl acrylate resin（PGM-Pickering）Preparation：
First, by 1.0mL GMAs（GMA）With 0.5mL divinylbenzenes（DVB）, 1.0mL toluene,
0.01g azodiisobutyronitriles（AIBN）And after 0.05g BA-MSNs mixing, add in round-bottomed flask and ultrasonic disperse is formed
Continuous phase.Then the 16mL deionized water solutions for containing 50 μ L emulsifying agents Hypermer 2296 are added dropwise, and stirring
It is mechanical agitation 10min formation w/o type Pickering High Internal Phase Emulsions under 500rpm to mix speed, then by emulsion 60oUnder C
It polymerize 12 h, and product is washed into 24h with acetone by surname extraction and remove unreacted monomer, finally 50oVacuum is done under C
It is dry to constant weight.
（3）Boric acid functionalization porous adsorbent containing B-N complexes（PGM-Pickering-BN）Preparation：
First, by 0.31g 1,6- hexamethylene diamines and 0.4g 3- amino phenyl boric acids are dissolved in 60mL tetrahydrofurans, and subsequent solution exists
40 are heated under stirringoC, and continue 1h to form B-N complexes.Then 0.2g PGM-Pickering are added
Enter in above-mentioned solution and 70oStirred under C, condensing reflux 12h.Product is finally washed into 3 times, and 50 with ethanoloC vacuum
It is dried to obtain final product PGM-Pickering-BN.
Embodiment 3：
（1）The medium hole nano particles of boric acid functionalization（BA-MSNs）Preparation：
First, 1.37g 3- amino phenyl boric acids and 2.36g 3- glycydoxies triethoxysilane are added into 25mL
Round-bottomed flask in, 10mL tetrahydrofurans are then slowly added to, and be passed through nitrogen except oxygen 15min, then 25oIt is anti-under C
Answer 12h.Mixed solution is finally removed into liquid by rotary evaporation, and obtained brown oil material is dissolved in 10mL methanol
In solution, that is, concentration is obtained for 1.0 mmol mL-1APBA-GPTES solution.
Then, by 0.4g cetyl trimethylammonium bromides, 0.15g sodium hydroxides are dissolved in 150mL deionized waters, plus
Thermal agitation is to 80oC, then instills 1.5mL tetraethyl orthosilicates and 150 μ L APBA-GPTES solution dropwise, persistently stirs after 3h,
Centrifuge and wash precipitation with ethanol 5 times.Finally, by the product of acquisition 50oVacuum drying can obtain boric acid work(under C
The medium hole nano particles of energyization（BA-MSNs）.
（2）Porous polymethyl glycidyl acrylate resin（PGM-Pickering）Preparation：
First, by 1.0mL GMAs（GMA）With 1.5mL divinylbenzenes（DVB）, 2.0mL toluene,
0.02g azodiisobutyronitriles（AIBN）And after 0.15g BA-MSNs mixing, add in round-bottomed flask and ultrasonic disperse is formed
Continuous phase.Then the 16mL deionized water solutions for containing 150 μ L emulsifying agents Hypermer 2296 are added dropwise, and
Mixing speed is mechanical agitation 10min formation w/o type Pickering High Internal Phase Emulsions under 700rpm, then by emulsion 70oC
12 h of lower polymerization, and product is washed into 24h removing unreacted monomers with acetone by surname extraction, finally 50oVacuum under C
Dry to constant weight.
（3）Boric acid functionalization porous adsorbent containing B-N complexes（PGM-Pickering-BN）Preparation：
First, by 0.51g 1,6- hexamethylene diamines and 0.6g 3- amino phenyl boric acids are dissolved in 60mL tetrahydrofurans, and subsequent solution exists
40 are heated under stirringoC, and continue 1h to form B-N complexes.Then 0.4g PGM-Pickering are added
Enter in above-mentioned solution and 90oStirred under C, condensing reflux 12h.Product is finally washed into 3 times, and 50 with ethanoloC vacuum
It is dried to obtain final product PGM-Pickering-BN.
Fig. 2 is the porous absorption of the boric acid functionalization containing different amounts of BA-MSNs prepared in embodiment 1,2,3
Agent PGM-Pickering-BN scanning electron microscope (SEM) photograph.Scheme a：0.05g；Scheme b：0.10g；Scheme c:0.15g.Make as we can see from the figure
Standby obtained PGM-Pickering-BN adsorbents have the open-celled structure of UNICOM, on surface it can clearly be seen that different amounts of work
For the BA-MSNs of stable particle, and pore size is reduced with BA-MSNs increase.
Test example 1：
The LTL solution that 10mL initial concentrations are respectively 5,10,15,20,25 mg/L is taken, LTL is dissolved in ethanol and the mixing of water is molten
In liquid,（Ethanol:Water=1:1, V/ V）It is added in centrifuge tube, is then respectively adding the boron prepared in 10mg embodiments 1
Test fluid, is placed on 25 by the porous adsorbent PGM-Pickering-BN of acid functionalizationoStood in C water-bath after 2h, upper strata is clear
Liquid is separated and collected with supercentrifuge, and unadsorbed LTL molecular concentrations are detected with ultraviolet-uisible spectrophotometer, and according to result
Adsorption capacity is calculated, is as a result shown, PGM-Pickering-BN maximum adsorption capacity is 158.5 μ when reaching adsorption equilibrium
Mol/g, PGM-Pickering-BN have higher adsorbance to cyanidenon, and using the nano-particle of boric acid functionalization
It can effectively increase recognition site as the stable particle of Pickering High Internal Phase Emulsions, improve adsorption efficiency.
Test example 2：
The luteolin solution for taking 10mL initial concentrations to be 20 mg/L is added in centrifuge tube, is separately added into 10mg embodiments 1
Boric acid functionalization porous adsorbent PGM-Pickering-BN, in the water bath with thermostatic control for test fluid being placed on 25 DEG C, exist respectively
5th, 15,30,60,120,240,360,480, taken out when 720 min；Adsorbent and solution are separated by centrifuging, filtered
LTL concentration ultraviolet specrophotometer in liquid is determined under 351nm wavelength, and probes into out adsorption mechanism according to result；As a result
Show, in initial 2h, PGM-Pickering-BN adsorption capacity quickly increases, and illustrates that cyanidenon can easily spread
Into porous adsorbent.After quick adsorption, due to the decline and the reduction of binding site quantity of LTL concentration, absorption speed
Rate drastically declines and balance is reached in 3.0 h.And may indicate that the absorption in whole process is by boron affinity interaction
Chemisorbed control.
Test example 3：
It is 20 mg/ L to take 10mL concentration respectively, and pH value is respectively 8.5,7.0,3.0 luteolin solution（Ethanol：Water V/V
=1:1）Add in centrifuge tube, the porous adsorbent PGM-Pickering- for the boric acid functionalization being subsequently added in 10mg embodiments 1
BN, 6h in 25 DEG C of water bath with thermostatic control is placed on by test fluid, and supernatant liquor is separated and collected with supercentrifuge, unadsorbed LTL points
Sub- concentration ultraviolet-uisible spectrophotometer, and the influence adsorbed according to outcome research pH value to LTL；As a result show, in alkalescence
Under the conditions of boric acid functionalization porous adsorbent there is preferable adsorbance, reach 47.21 μm of ol/g, in neutral conditions adsorbance
For 46.53 μm of ol/g, it is declined slightly but can be ignored compared to alkalescence, and is 7.129 μ in the adsorbance of acid condition
Mol/g, hence it is evident that less than alkalescence and the adsorbance of neutrallty condition.So the porous adsorbent PGM-Pickering- of boric acid functionalization
BN still has higher adsorbance in neutral conditions, can be used for the adsorbing separation of cyanidenon under neutrallty condition.
Claims (10)
1. a kind of boric acid functionalization porous adsorbent, it is characterised in that the adsorbent has the open-celled structure of UNICOM.
2. the preparation method of a kind of boric acid functionalization porous adsorbent described in claim 1, it is characterised in that according to following step
It is rapid to carry out：
The medium hole nano particles of boric acid functionalization（BA-MSNs）Preparation：
By cetyl trimethylammonium bromide, sodium hydroxide dissolving in deionized water, then heating stirring instills silicic acid dropwise
Tetra-ethyl ester and APBA-GPTES solution, after lasting stirring a period of time, centrifuge and wash precipitation with ethanol；By acquisition
Product vacuum is dried to obtain the medium hole nano particles of boric acid functionalization；
（2）Porous polymethyl glycidyl acrylate resin（PGM-Pickering）Preparation：
First, GMA, divinylbenzene, toluene, azodiisobutyronitrile and BA-MSNs are mixed
Afterwards, add in round-bottomed flask and ultrasonic disperse formation continuous phase；Then by containing emulsifying agent Hypermer 2296 go from
The sub- aqueous solution is added dropwise, and is formed under agitation after w/o type Pickering High Internal Phase Emulsions, emulsion polymerization, will produce
Thing washs removing unreacted monomer with acetone by surname extraction, is finally dried in vacuo；
（3）Boric acid functionalization porous adsorbent containing B-N complexes（PGM-Pickering-BN）Preparation：
1,6- hexamethylene diamines and 3- amino phenyl boric acids are dissolved in tetrahydrofuran, heat to form B-N coordinations under agitation
Compound；PGM-Pickering is added and stirred and evenly mixed afterwards, after condensing reflux reaction, product is washed with ethanol, vacuum is done
It is dry to obtain final product PGM-Pickering-BN.
3. method according to claim 2, it is characterised in that step（1）Described in cetyl trimethylammonium bromide
Mass ratio with sodium hydroxide is 0.2-0.4：0.05-0.15；The heating stirring temperature is to 70-80 DEG C.
4. method according to claim 2, it is characterised in that step（1）Described in tetraethyl orthosilicate, APBA-GPTES it is molten
The usage ratio of liquid and cetyl trimethylammonium bromide is 1.0-1.5mL：50-150µL：0.2-0.4g；The lasting stirring
1-3h。
5. method according to claim 2, it is characterised in that step（2）Described in methyl propenoic acid glycidyl
Ester, divinylbenzene, toluene, azodiisobutyronitrile with and BA-MSNs usage ratio be 1.0 mL：0.5-1.5 mL：1.0-
2.0 mL：0.01-0.02 g：0.05-0.15 g.
6. method according to claim 2, it is characterised in that step（2）Described in add contain emulsifying agent
Hypermer 2296 deionized water solution be 16mL deionized water solutions in contain 50-150 μ L emulsifying agents Hypermer
2296；
The mixing speed is 500-700rpm, stirs 10min；
The polymerisation be 60-70 DEG C at polymerize 12 h.
7. method according to claim 2, it is characterised in that step（3）Described in 1,6- hexamethylene diamines, 3- amino phenyl boric acids
Usage ratio with tetrahydrofuran is 0.31-0.51g：0.4-0.6g：60mL；
It is heated to be under the stirring condition and is heated to 40 DEG C, continues 1h.
8. method according to claim 2, it is characterised in that step（3）In
The PGM-Pickering of the addition is 0.2-0.4g；It is described to stir and evenly mix to stir at 70-90 DEG C；The backflow
Reaction time 12h.
9. application of the adsorbent in separation absorption cyanidenon described in claim 1.
10. application according to claim 9, it is characterised in that the application is inhaled for Selective Separation in neutral conditions
Attached cyanidenon.
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