CN106188437A - A kind of method that metal organic frame particle trace adsorbent is prepared in Pickering emulsion polymerization - Google Patents
A kind of method that metal organic frame particle trace adsorbent is prepared in Pickering emulsion polymerization Download PDFInfo
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Abstract
The preparation method of metal organic frame particle trace adsorbent is prepared in the present invention a kind of Pickering emulsion polymerization, belongs to technical field of environment function material preparation.First dopamine and methyl methacrylate are reacted, generate dopamine methacrylic acid amino, and then prepare the metal-organic framework material (BA MOF) of phenylboric acid type；Then obtain adsorbent after carrying out a series of process by emulsion polymerization preparation emulsion imprinted polymer microsphere, and adsorbent is used for Selective recognition and the separation of BA MOF.The emulsion imprinted polymer microsphere of preparation has preferable heat stability, higher adsorption capacity, has the metal-organic framework material that acid and base effect can be modified, special high Selective recognition performance with acid-base value reversible adsorption/release function phenylboric acid type.
Description
Technical field
The present invention relates to a kind of method that metal organic frame particle trace adsorbent is prepared in Pickering emulsion polymerization,
Belong to technical field of environment function material preparation.
Background technology
In recent years, metal-organic framework material (MOFs) was as three-dimensional loose structure, and it is typically made with metal ion
For junction point, other organic ligands are as support framework structure.Metal-organic framework material application more and more extensively row are as biological
Engineering, is catalyzed engineering, separates absorption engineering.Environment is caused substantial amounts of pollution and economic loss, processes back the most timely
Receive MOFs and seem of crucial importance.The environmental system also phase differing due to size and the group of metal-organic framework material and reclaiming
When complexity, therefore efficient selective identification separation pollutant MOFs is to have great meaning.
Molecular imprinting is the three-dimensional material prepared and have identity hole.By function monomer and the spy of template molecule
Property row identification reaches demand.Molecular imprinting has a lot of advantage such as avtive spot and embedded deeply, mass transfer and charge transfer
Kinetic rate slow, the attached dynamic performance of absorption-desorption is the best.Pickering emulsion is that a kind of liquid is with drop
Form exist be made up of aqueous phase and oil phase and stablized by stable particle and without by the emulsion of surfactant.
Pickering emulsion is applied to the aspects such as a large amount of food, medicine and cosmetics.The preparation of Pickering emulsion typically has
Following flow process, at aqueous phase or middle introducing function monomer and the stable particle of modified, and is formed surely by violent stirring
Fixed emulsion.Then cause polymerization by initiator, obtain W/O or O/W emulsion microsphere.
Therefore this work is to prepare molecularly imprinted polymer by Pickering emulsion technology, by synthetic emulsion mistake
Adding cis-form dihydroxy structures alone in journey, the metal-organic framework material then adding stable particle phenylboric acid type is stablized
Emulsion.It is identified and adsorbs the metal-organic framework material of stable particle phenylboric acid type by boron affinity interaction.
Summary of the invention
The present invention prepares the metal organic frame material of phenylboric acid type by molecular imprinting and Pickering emulsion technology
The imprinted polymer of material.First synthesis dopamine and the polymer of methyl methacrylate, makees with dopamine methacrylic acid amino
For function monomer.Then synthesis BA-MOF is as stable particle.Being distilled water solution in aqueous phase, oil phase is styrene (St), poly-
Ethylene glycol bisthioglycolate (methacrylic acid) ester (PEGDMA), divinylbenzene (DVB), toluene (Toluene), 2,2'-azo two isobutyls
Nitrile (AIBN).Then stable Pickering emulsion is formed.Microsphere methanol acetic acid (v:v, 11:1) that this polymerization obtains is molten
Liquid eluting removes BA-MOF by the affine dissociation in acid condition of boron.Microsphere after this eluting just can form BA-
The specificity hole that MOF stays, this imprinted polymer can be used to specificity and reclaims BA-MOF.
The technical solution used in the present invention is:
(1) preparation of dopamine methacrylic acid amino (PDA-MA):
Dopamine hydrochloride is joined in the aqueous solution comprising sodium borate and sodium bicarbonate, stir 2h, then will be dissolved with first
The tetrahydrofuran solution of base acrylic acid methyl ester. dropwise drips to join in above-mentioned aqueous solution, the lower reaction of nitrogen protection at 25 DEG C
16h, reaction is extracted with ethyl acetate organic facies after terminating, rotary evaporation the most again, then with n-hexane dissolution and be stirred vigorously
Until producing substantial amounts of precipitation, finally centrifugal and 60 DEG C of vacuum drying.
(2) preparation of metal-organic framework material BA-MOF of phenylboric acid type:
By crome metal, 3,5-dicarboxyl phenylboric acids, trimesic acid and distilled water join in reactor, stir 1-4h,
Adding Fluohydric acid., be stirred for half an hour, be then placed in baking oven and react 72h at 120-240 DEG C, reaction is cooled to after terminating
Room temperature, soaks 2h with dimethylformamide (DMF), centrifugal, then uses 1mol L-1Sodium hydroxide solution immersion 2h, recentrifuge,
Distillation washing 3 times, 100 DEG C of vacuum drying 24h.
(3) emulsion trace metal organic frame adsorbent is prepared
First, aqueous phase is prepared by step (2) the metal-organic framework material (BA-MOF) of phenylboric acid type and distilled water group
Becoming, oil phase is by styrene (St), Polyethylene Glycol two (methacrylic acid) ester (PEGDMA), divinylbenzene (DVB), toluene
(Toluene), the dopamine methacrylic acid amino (PDA-MA) that step (1) prepares, 2,2'-azodiisobutyronitriles (AIBN) group
Become, after 500rpm is stirred vigorously 5 minutes, forms stable emulsion；
Then, under air-proof condition, carry out water-bath polyreaction；
Finally, vacuum drying, finally cleans 3 times with methanol and acetic acid mixed solution, vacuum drying the most again.
Wherein in step (1), described methyl methacrylate, the ratio of dopamine hydrochloride, sodium borate, sodium bicarbonate and water
Example is: 4～5mL:4～6g:9～11g:3～5g:90～110mL.
Wherein in step (1), described methyl methacrylate and the ratio of oxolane be: 4～5mL:20～30mL.
Wherein in step (1), the ratio of described methyl methacrylate, ethyl acetate and normal hexane is: 4～5mL:40
～100mL:200～500mL.
Wherein in step (2), described crome metal, 3,5-dicarboxyl phenylboric acids, trimesic acid, Fluohydric acid., distilled water
Ratio be: 40～60mg:20～30mg:100～150mg:5-10uL:4-6mL.
Wherein in step (2), described crome metal, dimethylformamide, the ratio of sodium hydroxide is: 40～60mg:20
～40mL:10～30mL.
Wherein in step (3), (BA-MOF) and the ratio of distilled water in described aqueous phase be: 10～20mg:4～7mL.
Wherein in step (3), the styrene (St) in described oil phase, Polyethylene Glycol two (methacrylic acid) ester
(PEGDMA), divinylbenzene (DVB), toluene (Toluene), dopamine methacrylic acid amino (PDA-MA), 2,2'-azos two
The ratio of isopropyl cyanide (AIBN) is: 0.1～0.3mL:0.4～0.8mL:0.2～0.25mL:0.3～0.6mL:10～20mg:2
～4mg.
Wherein in step (3), described methanol acetic acid mixed solution and the ratio of dopamine methacrylic acid amino be: 20～
50mL:10～20mg.
In step (3), the temperature of described water-bath polyreaction is 70 DEG C, and polymerization time is 12-48h；Vacuum drying
Temperature is 60 DEG C.
In described methanol acetic acid mixed solution, the volume ratio of methanol acetic acid is 1:1.
The technological merit of the present invention:
This product identifies recovery metal-organic framework material by the single trace emulsion microsphere of preparation.Wherein, emulsion material
Having shape recognition function, secondly emulsion microsphere has cis-form dihydroxy structure recognition site；Materials chemistry stability is good simultaneously
Good, material also has pH response function and can simplify adsorption/desorption operation in addition.
Accompanying drawing explanation
Fig. 1 is the metal-organic framework material (A1, A2, A3) of the phenylboric acid type of preparation in embodiment 1 and does not has phenylboric acid
The metal-organic framework material (B1, B2, B3) of type.
Fig. 2 is emulsion imprinted polymer microsphere (A1) of preparation, the emulsion imprinted polymer microsphere after eluting in embodiment 1
Microsphere (C1, C2, C3) after (B1, B2), then absorption.
Fig. 3 is the nuclear-magnetism figure of the dopamine methacrylic acid amino of preparation in embodiment 1.
Fig. 4 is metal-organic framework material a do not crossed through phenylboric acid type of preparation in embodiment 1, through phenylboric acid
Metal-organic framework material b that type is crossed and the infrared figure of emulsion imprinted polymer microsphere c.
Fig. 5 is the Raman spectrogram of the BA-MOF (a), MOF (b), MIPs (c) of preparation in embodiment 1.
Fig. 6 is the X-ray diffraction spectrogram of the BA-MOF (a), MOF (b), MIPs (c) of preparation in embodiment 1.
Fig. 7 be MIPs be the adsorption capacity in the one-component solution of different MOF.
Fig. 8 be MIPs be the adsorption capacity in the bi-component or three component solution of different MOF.
Fig. 9 is the MIPs dynamic adsorption curve to BA-MOF.
Detailed description of the invention
In the specific embodiment of the invention, recognition performance evaluation is carried out by the following method: utilize Staticadsorption experiment complete
Become.The metal-organic framework material solution of certain density for 10ml phenylboric acid type is joined in the centrifuge tube of 10mL, add one
Quantitative trace adsorbent, is placed in 25 DEG C of constant temperature waters and stands some hours, the metal organic frame of phenylboric acid type after absorption
Material content ultraviolet-uisible spectrophotometer measures, and calculates adsorption capacity according to result；Select several structure and character
Similar metal organic frame compounds, such as ZIF-8, Cu-MOF etc., as competitive Adsorption thing, participate in the knowledge of research MIPs
Other performance.
Below in conjunction with being embodied as example, the present invention will be further described.
Embodiment 1:
(1) preparation of dopamine methacrylic acid amino (PDA-MA)
The reaction solution of the distilled water of the ready 90mL that 4g dopamine hydrochloride adds comprises sodium borate and the 3g of 9g
Sodium bicarbonate in stir 2h, secondly in the oxolane of the 20mL that the methyl methacrylate of 4mL is dissolved in advance then by by
Drip to join in above-mentioned solution.Then this reaction reacts 16h under nitrogen protection at 25 DEG C.Finally use organic facies quilt
The ethyl acetate extraction of 40mL, rotary evaporation the most again.Then with the n-hexane dissolution of 200mL and be stirred vigorously until producing big
The precipitation of amount, finally centrifugal and 60 DEG C of vacuum drying.
(2) preparation of the metal-organic framework material of phenylboric acid type
The crome metal of 40mg, the 3 of 20mg, 5-dicarboxyl phenylboric acid, the trimesic acid of 100mg and the distilled water of 4mL add
Entering in reactor, stir 1h, then the Fluohydric acid. of 5 microlitres joins, and is then stirred for half an hour, being finally putting into baking oven
72h is reacted at 120 DEG C.Then it is cooled to room temperature, is then centrifuged for and soaks 2h with the DMF of 20mL, the most again with 10mL's
1mol L-1Sodium hydroxide solution soaks 2h, is finally centrifuged, then washes 3 times with distillation.Last drying 24h at 100 DEG C of vacuum.
(3) emulsion trace metal organic frame adsorbent is prepared
First, aqueous phase is made up of the metal-organic framework material (BA-MOF) of the distilled water of 4mL and the phenylboric acid type of 10mg,
Oil phase is by the ethylene (St) of 0.1mL, Polyethylene Glycol two (methacrylic acid) ester (PEGDMA) of 0.4mL, the divinyl of 0.2mL
Benzene (DVB), the toluene (Toluene) of 0.3mL, the dopamine methacrylic acid amino (PDA-MA) of 10mg, the 2 of 2mg, 2'-azo
Bis-isobutyronitrile (AIBN) forms.After 500rpm is stirred vigorously 5 minutes, forms stable emulsion, after then sealing, puts into 70 DEG C of water
It is polymerized 12h under bath.Last drying at 60 DEG C of vacuum, cleans 3 times with methanol and acetic acid mixed solution, and 60 DEG C of vacuum are dried the most again
Dry.
Embodiment 2:
(1) preparation of dopamine methacrylic acid amino (PDA-MA)
5g dopamine hydrochloride add ready 100mL distilled water reaction solution in comprise 10g sodium borate and
The sodium bicarbonate of 4g stirs 2h, secondly in the oxolane of the 25mL that the methyl methacrylate of 4.7mL is dissolved in advance then
Dropwise dripped to join in above-mentioned solution.Then this reaction reacts 16h under nitrogen protection at 25 DEG C.Finally with organic
Extracted by the ethyl acetate of 50mL, the most again rotary evaporation.Then with the n-hexane dissolution of 250mL and be stirred vigorously until producing
Raw substantial amounts of precipitation, finally centrifugal and 60 DEG C of vacuum drying.
(2) preparation of the metal-organic framework material of phenylboric acid type
The crome metal of 52mg, the 3 of 28.54mg, 5-dicarboxyl phenylboric acid, the trimesic acid of 112.6mg and the steaming of 4.8mL
Distilled water joins in reactor, stirs 2h, and then the Fluohydric acid. of 7.8 microlitres joins, and is then stirred for half an hour, finally
Put into baking oven at 200 DEG C, react 72h.Then it is cooled to room temperature, is then centrifuged for and soaks 2 hours with the DMF of 30mL, the most again
With the 1mol L of 20mL-1Sodium hydroxide solution soaks 2h, is finally centrifuged, then with distillation washing 3 times, finally at 100 DEG C of vacuum
Dry 24h.
(3) emulsion trace metal organic frame adsorbent is prepared
First, aqueous phase is made up of the metal-organic framework material (BA-MOF) of the distilled water of 5mL and the phenylboric acid type of 15mg,
Oil phase is by the ethylene (St) of 0.2mL, Polyethylene Glycol two (methacrylic acid) ester (PEGDMA) of 0.5mL, the divinyl of 0.22mL
Base benzene (DVB), the toluene (Toluene) of 0.4mL, the dopamine methacrylic acid amino (PDA-MA) of 15mg, the 2 of 3mg, 2'-is even
Nitrogen bis-isobutyronitrile (AIBN) forms.After 500rpm is stirred vigorously 5 minutes, forms stable emulsion, after then sealing, puts into 70 DEG C
24h it is polymerized under water-bath.Last drying at 60 DEG C of vacuum, cleans 3 times with methanol and acetic acid mixed solution, 60 DEG C of vacuum the most again
Dry.
Embodiment 3:
(1) preparation of dopamine methacrylic acid amino (PDA-MA)
6g dopamine hydrochloride add ready 110mL distilled water reaction solution in comprise 11g sodium borate and
The sodium bicarbonate of 5g stirs 2h, secondly in the oxolane of the 50mL that the methyl methacrylate of 5mL is dissolved in advance then by
Dropwise drip to join in above-mentioned solution.Then this reaction reacts 16h under nitrogen protection at 25 DEG C.Finally use organic facies
Extracted by the ethyl acetate of 100mL, the most again rotary evaporation.Then with the n-hexane dissolution of 500mL and be stirred vigorously until producing
Raw substantial amounts of precipitation, finally centrifugal and 60 DEG C of vacuum drying.
(2) preparation of the metal-organic framework material of phenylboric acid type
The crome metal of 60mg, the 3 of 30mg, 5-dicarboxyl phenylboric acid, the trimesic acid of 150mg and the distilled water of 7mL add
Entering in reactor, stir 4h, then the Fluohydric acid. of 10 microlitres joins, and is then stirred for half an hour, being finally putting into baking
Case reacts 72h at 220 DEG C.Then it is cooled to room temperature, is then centrifuged for and soaks 2h with the DMF of 40mL, the most again with 30mL's
1mol L-1Sodium hydroxide solution soaks 2h, is finally centrifuged, then washes 3 times with distillation.Last drying 24h at 100 DEG C of vacuum.
(3) emulsion trace metal organic frame adsorbent is prepared
First, aqueous phase is made up of the metal-organic framework material (BA-MOF) of the distilled water of 6mL and the phenylboric acid type of 20mg,
Oil phase is by the ethylene (St) of 0.3mL, Polyethylene Glycol two (methacrylic acid) ester (PEGDMA) of 0.8mL, the divinyl of 0.25mL
Base benzene (DVB), the toluene (Toluene) of 0.6mL, the dopamine methacrylic acid amino (PDA-MA) of 20mg, the 2 of 4mg, 2'-is even
Nitrogen bis-isobutyronitrile (AIBN) forms.After 500rpm is stirred vigorously 5 minutes, forms stable emulsion, after then sealing, puts into 70 DEG C
48h it is polymerized under water-bath.Last drying at 60 DEG C of vacuum, cleans 3 times with methanol and acetic acid mixed solution, 60 DEG C of vacuum the most again
Dry.
Test example 1: the metal organic frame compounds selecting ZIF-8, Cu-MOF to be competitive Adsorption, is respectively configured above
The aqueous solution of 2 kinds of metal organic frame compounds, the concentration of every kind of competitive adsorbate is all 30mg/l, takes what 10ml configured
Solution joins in centrifuge tube, the MIPs adsorbent being separately added in 10mg embodiment 1, and test fluid is placed in the water-bath of 25 DEG C
Standing 8.0h respectively, after time of repose completes, supernatant high speed centrifugation separates and collects, and unadsorbed various competition metals have
Machine frame compounds concentration ultraviolet spectrophotometer measures, and such as Fig. 7, result shows, MIPs is to BA-MOFs, ZIF-8, Cu-
The adsorption capacity of MOFs is respectively 43.24mg/g, 6.52mg/g, 3.52mg/g.Show that BA-MOFs is had by MIPs the most single-minded
Identity, adsorption capacity is higher than other metal organic frame compounds.
Test example 2: the metal organic frame compounds selecting ZIF-8, Cu-MOF to be competitive Adsorption is competitive Adsorption
Phenolic compound.It is respectively configured LTL and the binary of three kinds of competition phenolic compounds and the mixed solution of ternary, every kind of hydroxy kind
Concentration is all 30mg/l, takes the mixed solution that 10ml configures and joins in centrifuge tube, is separately added in 10mg embodiment 1
MIPs adsorbent, is placed on test fluid in the water-bath of 30 DEG C and stands 8.0h respectively, and after time of repose completes, the supernatant is at a high speed
Centrifugation is collected, and unadsorbed BA-MOF concentration ultraviolet spectrophotometer measures, and such as Fig. 8, result shows, at binary system
In in the presence of other chaff interference ZIF-8, Cu-MOF MIPs the adsorption capacity of BA-MOFs is respectively 41.4mg/g, 38.2mg/
g.In ternary system, in the presence of other chaff interference ZIF-8, Cu-MOF, MIPs is 35.6mg/ to the adsorption capacity of BA-MOFs
g。
Test example 3: selecting different factor pH, temperature, flowing velocity, concentration comes what bar of dynamic adsorption is being done in systematic analysis
Part MIPs can optimal adsorption BA-MOFs.The MIPs adsorbent added in 10mg embodiment 1 is 6 at pH, under conditions of 7,8, then
Do different temperatures (25 DEG C, 35 DEG C, 45 DEG C), be concentration (the 10mg L of different BA-MOF with this understanding-1,17.5mg L-1,
25mg L-1), this outer control different in flow rate (1mL min-1,2mL min-1,3mL min-1) adsorb BA-MOFs.Such as Fig. 9, can
PH is affected with draw various factors > temperature > concentration > flowing velocity.Through the analysis of system, at 45 DEG C, pH is 8.0 concentration
For 25mg L-1Flow velocity is 1.23mL min-1Time be optimal adsorption condition adsorb BA-MOFs.
Fig. 1 is the metal-organic framework material (A1, A2, A3) of the phenylboric acid type of preparation in embodiment 1 and does not has phenylboric acid
The metal-organic framework material (B1, B2, B3) of type.As can be drawn from Figure 1, the metal organic frame material crossed through phenylboric acid type
The average diameter of material reaches 1um.
Fig. 2 is emulsion imprinted polymer microsphere (A1) of preparation, the emulsion imprinted polymer microsphere after eluting in embodiment 1
Microsphere (C1, C2, C3) after (B1, B2), then absorption.As can be drawn from Figure 2, A1 figure has thick shell, through eluting
Afterwards, shell comes off, and obtains B1, B2, then through absorption BA-MOF, obtains figure C1, C2, C3, finds many a lot of BA-MOF
Grain.
Fig. 3 is the nuclear-magnetism figure of the dopamine methacrylic acid amino of preparation in embodiment 1, as can be drawn from Figure 3, dopamine
The most successfully react with methyl methacrylate, generate dopamine methacrylic acid amino.
Fig. 4 is metal-organic framework material a do not crossed through phenylboric acid type of preparation in embodiment 1 and through phenylboric acid
Metal-organic framework material b that type is crossed and the infrared figure of emulsion imprinted polymer microsphere c, as can be drawn from Figure 4 through benzene boron
The metal-organic framework material that acid type is crossed is at 1348cm-1One peak occurs, illustrates that boric acid the most successfully modifies surface,
3700cm-1One peak occurs, illustrates to be successfully formed polymer microballoon.
Fig. 5 is the Raman spectrogram of the BA-MOF (a), MOF (b), MIPs (c) of preparation in embodiment 1, permissible from 5 figures
Show that BA-MOF and MIPs is at 189cm-1There is a characteristic peak, show BA-MOF and MIPs exists phenylboric acid function monomer；
Fig. 6 is the X-ray diffraction spectrogram of the BA-MOF (a), MOF (b), MIPs (c) of preparation in embodiment 1, can from Fig. 6
To draw, having obvious crystal formation to occur at 45 degree, therefore BA-MOF the most successfully modifies boric acid and metal organic frame
Materials synthesis merit.
Fig. 7 be MIPs be the adsorption capacity in the one-component solution of different MOF, as can be drawn from Figure 7, BA-
The adsorption capacity of MOF is maximum, and showing that MIPs the most successfully synthesizes can be with specific recognition BA-MOF.
Fig. 8 be MIPs be the adsorption capacity in the bi-component or three component solution of different MOF, permissible from Fig. 8
Draw, MIPs can in many heavy components solution specific adsorption BA-MOF.
Fig. 9 is the MIPs dynamic adsorption curve to BA-MOF, has investigated pH-value (a, b), temperature (c, d), concentration respectively
(e, f), the impact of flow velocity (g, h).Size pH to absorption BA-MOF influence factor as can be drawn from Figure 9 > temperature > concentration >
Flowing velocity.When at 45 DEG C pH be 8.0 concentration be 25mg L-1Flow velocity is 1.23mL min-1Time be optimal adsorption condition absorption
BA-MOFs。
Claims (10)
1. the method that metal organic frame particle trace adsorbent is prepared in a Pickering emulsion polymerization, it is characterised in that bag
Include following steps:
(1) dopamine methacrylic acid amino PDA-MA is prepared, standby；
(2) metal-organic framework material BA-MOF of phenylboric acid type is prepared, standby；
(3) emulsion trace metal organic frame adsorbent is prepared:
First, metal-organic framework material BA-MOF and the distilled water of the phenylboric acid type that aqueous phase is prepared by step (2) form, oil phase
By styrene, Polyethylene Glycol two (methacrylic acid) ester, divinylbenzene, toluene, the dopamine metering system that step (1) prepares
Acid amide PDA-MA, 2,2'-azodiisobutyronitrile compositions, after 500rpm is stirred vigorously 5 minutes, form stable emulsion；
Then, under air-proof condition, carry out water-bath polyreaction；
Finally, vacuum drying, finally cleans 3 times with methanol and acetic acid mixed solution, vacuum drying the most again.
Metal organic frame particle trace adsorbent is prepared in a kind of Pickering emulsion polymerization the most according to claim 1
Method, it is characterised in that the method preparing dopamine methacrylic acid amino PDA-MA described in step (1) is: hydrochloric acid is many
Bar amine joins in the aqueous solution comprising sodium borate and sodium bicarbonate, stirs 2h, then by dissolved with the four of methyl methacrylate
Hydrogen tetrahydrofuran solution dropwise drips to join in above-mentioned aqueous solution, reacts 16h at 25 DEG C under nitrogen protection, and reaction uses second after terminating
Acetoacetic ester extraction organic facies, the most again rotary evaporation, then with n-hexane dissolution and be stirred vigorously until producing substantial amounts of precipitation,
Finally centrifugal also 60 DEG C of vacuum drying.
Metal organic frame particle trace adsorbent is prepared in a kind of Pickering emulsion polymerization the most according to claim 2
Method, it is characterised in that described methyl methacrylate, the ratio of dopamine hydrochloride, sodium borate, sodium bicarbonate and water
For: 4～5mL:4～6g:9～11g:3～5g:90～110mL；Described methyl methacrylate and the ratio of oxolane
For: 4～5mL:20～30mL；The ratio of described methyl methacrylate, ethyl acetate and normal hexane is: 4～5mL:40～
100mL:200～500mL.
Metal organic frame particle trace adsorbent is prepared in a kind of Pickering emulsion polymerization the most according to claim 1
Method, it is characterised in that the method for metal-organic framework material BA-MOF preparing phenylboric acid type described in step (2) is:
By crome metal, 3,5-dicarboxyl phenylboric acids, trimesic acid and distilled water join in reactor, stir 1-4h, add hydrogen
Fluoric acid, is stirred for half an hour, is then placed in baking oven and reacts 72h at 120-240 DEG C, and reaction is cooled to room temperature after terminating, and uses
Dimethylformamide (DMF) soaks 2h, centrifugal, then soaks 2h, recentrifuge, distilled water with 1mol L-1 sodium hydroxide solution
Wash 3 times, 100 DEG C of vacuum drying 24h.
Metal organic frame particle trace adsorbent is prepared in a kind of Pickering emulsion polymerization the most according to claim 4
Method, it is characterised in that described crome metal, 3,5-dicarboxyl phenylboric acids, trimesic acid, Fluohydric acid., the ratio of distilled water
Example is: 40～60mg:20～30mg:100～150mg:5-10uL:4-6mL；Described crome metal, dimethylformamide, hydrogen-oxygen
The ratio changing sodium is: 40～60mg:20～40mL:10～30mL.
Metal organic frame particle trace adsorbent is prepared in a kind of Pickering emulsion polymerization the most according to claim 1
Method, it is characterised in that in step (3), (BA-MOF) and the ratio of distilled water in described aqueous phase be: 10～20mg:4～
7mL。
Metal organic frame particle trace adsorbent is prepared in a kind of Pickering emulsion polymerization the most according to claim 1
Method, it is characterised in that in step (3), the styrene in described oil phase, Polyethylene Glycol two (methacrylic acid) ester, diethyl
Alkenyl benzene, toluene, dopamine methacrylic acid amino PDA-MA, the ratio of 2,2'-azodiisobutyronitriles is: 0.1～0.3mL:0.4
～0.8mL:0.2～0.25mL:0.3～0.6mL:10～20mg:2～4mg.
Metal organic frame particle trace adsorbent is prepared in a kind of Pickering emulsion polymerization the most according to claim 1
Method, it is characterised in that in step (3), described methanol acetic acid mixed solution and dopamine methacrylic acid amino PDA-MA
Ratio be: 20～50mL:10～20mg.
Metal organic frame particle trace adsorbent is prepared in a kind of Pickering emulsion polymerization the most according to claim 1
Method, it is characterised in that in step (3), the temperature of described water-bath polyreaction is 70 DEG C, and polymerization time is 12-48h.
Metal organic frame particle trace adsorbent is prepared in a kind of Pickering emulsion polymerization the most according to claim 1
Method, it is characterised in that the temperature of described vacuum drying is 60 DEG C；In described methanol acetic acid mixed solution, methanol acetic acid
Volume ratio is 1:1.
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