CN106188437B - A kind of method that Pickering emulsion polymerizations prepare metal organic frame particle trace adsorbent - Google Patents
A kind of method that Pickering emulsion polymerizations prepare metal organic frame particle trace adsorbent Download PDFInfo
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Abstract
A kind of Pickering emulsion polymerizations of the present invention prepare the preparation method of metal organic frame particle trace adsorbent, belong to technical field of environment function material preparation.Dopamine and methyl methacrylate are reacted first, generate dopamine methacrylic acid amino, and then prepares the metal-organic framework material (BA MOF) of phenyl boric acid type；Then it is prepared after lotion imprinted polymer microballoon carries out a series of processing by emulsion polymerization and obtains adsorbent, and adsorbent is used for Selective recognition and the separation of BA MOF.The lotion imprinted polymer microballoon of preparation has preferable thermal stability, and higher adsorption capacity has acid and base effect can be with the metal-organic framework material of acid-base value reversible adsorption/release function phenyl boric acid type modification, special high Selective recognition performance.
Description
Technical field
The present invention relates to a kind of method that Pickering emulsion polymerizations prepare metal organic frame particle trace adsorbent,
Belong to technical field of environment function material preparation.
Background technology
In recent years, as three-dimensional porous structure, it was generally made metal-organic framework material (MOFs) with metal ion
For tie point, other organic ligands are as support framework structure.Metal-organic framework material is using more and more extensive row such as biology
Engineering is catalyzed engineering, separation absorption engineering.A large amount of pollution and economic loss are caused to environment, therefore is timely handled back
Receiving MOFs seems of crucial importance.Since the size and group of metal-organic framework material differ and the environmental system that recycles also phase
When complexity, therefore efficient selective identification separation pollutant MOFs be that there is great meaning.
Molecular imprinting technology is to prepare the three-dimensional material with identity hole.Pass through the spy of function monomer and template molecule
Property row identification reach demand.There is molecular imprinting technology many advantages such as active site to embed too deep, mass transfer and charge transfer
Kinetic rate it is slow, the attached dynamic performance of absorption-desorption is bad etc..Pickering lotions are a kind of liquid with drop
Form, which exists, to be made of water phase and oil phase and is stablized by stable particle without the lotion by surfactant.
Pickering lotions are applied to a large amount of food, medicine and cosmetics etc..The preparation of Pickering lotions generally has
Following flow in water phase or the stable particle of middle introducing function monomer and modified, and is formed surely by violent stirring
Fixed lotion.Then caused by initiator and polymerize, obtain W/O O/W lotion microballoons.
Therefore this work is to prepare molecularly imprinted polymer by Pickering emulsion technologies, by synthetic emulsion mistake
Cis-form dihydroxy structures alone is added in journey, then adds the metal-organic framework material of stable particle phenyl boric acid type to stablize
Lotion.The metal-organic framework material of stable particle phenyl boric acid type is identified and adsorbed by boron affinity interaction.
Invention content
The present invention prepares the metal organic frame material of phenyl boric acid type by molecular imprinting technology and Pickering emulsion technologies
The imprinted polymer of material.The polymer of dopamine and methyl methacrylate is synthesized first, is made with dopamine methacrylic acid amino
For function monomer.Then synthesis BA-MOF is as stable particle.It is distilled water solution in water phase, oil phase is styrene (St), is gathered
Ethylene glycol two (methacrylic acid) ester (PEGDMA), divinylbenzene (DVB), toluene (Toluene), 2,2'- azo, two isobutyl
Nitrile (AIBN).Then stable Pickering lotions are formed.The microballoon methanol acetic acid (v that this polymerization obtains:V, 11:1) it is molten
Liquid elution removes BA-MOF and passes through the affine dissociation in acid condition of boron.Microballoon after this elution can form BA-
The specific hole that MOF is stayed, this imprinted polymer can be used for specificity recycling BA-MOF.
The technical solution adopted by the present invention is：
(1) preparation of dopamine methacrylic acid amino (PDA-MA)：
Dopamine hydrochloride is added in the aqueous solution comprising Boratex and sodium bicarbonate, stirs 2h, it then will be dissolved with first
The tetrahydrofuran solution of base methyl acrylate drips to dropwise to be added in above-mentioned aqueous solution, and nitrogen protection is lower at 25 DEG C reacts
Organic phase is extracted with ethyl acetate in 16h after reaction, then rotary evaporation again, then with n-hexane dissolution and is vigorously stirred
Until a large amount of precipitation is generated, 60 DEG C of drying of finally centrifugation and vacuum.
(2) preparation of the metal-organic framework material BA-MOF of phenyl boric acid type：
By crome metal, 3,5- dicarboxyl phenyl boric acids, trimesic acid and distilled water are added in reaction kettle, stir 1-4h,
Hydrofluoric acid is added, is stirred for half an hour, baking oven is then placed in and 72h is reacted at 120-240 DEG C, be cooled to after reaction
Room temperature impregnates 2h, centrifugation, then with 1mol L with dimethylformamide (DMF)-1Sodium hydroxide solution impregnates 2h, centrifuges again,
Distillation washing 3 times, 100 DEG C of vacuum dryings are for 24 hours.
(3) lotion trace metal organic frame adsorbent is prepared
First, the metal-organic framework material (BA-MOF) of water phase phenyl boric acid type as made from step (2) and distilled water group
Into oil phase is by styrene (St), polyethylene glycol two (methacrylic acid) ester (PEGDMA), divinylbenzene (DVB), toluene
(Toluene), dopamine methacrylic acid amino (PDA-MA) made from step (1), 2,2'- azodiisobutyronitriles (AIBN) group
Into being vigorously stirred in 500rpm and form stable lotion after five minutes；
Then, under air-proof condition, water-bath polymerisation is carried out；
Finally, vacuum drying finally cleans 3 times with methanol and acetic acid mixed solution, then vacuum drying again.
Wherein in step (1), the methyl methacrylate, Dopamine hydrochloride, Boratex, sodium bicarbonate and water ratio
Example be：4~5mL：4~6g：9~11g：3~5g：90~110mL.
Wherein in step (1), the ratio of the methyl methacrylate and tetrahydrofuran is：4~5mL：20~30mL.
Wherein in step (1), the ratio of the methyl methacrylate, ethyl acetate and n-hexane is：4~5mL：40
~100mL：200~500mL.
Wherein in step (2), the crome metal, 3,5- dicarboxyl phenyl boric acids, trimesic acid, hydrofluoric acid, distilled water
Ratio be：40~60mg：20~30mg：100~150mg：5-10uL：4-6mL.
Wherein in step (2), the crome metal, dimethylformamide, the ratio of sodium hydroxide is：40~60mg：20
~40mL：10~30mL.
Wherein in step (3), the ratio of (BA-MOF) and distilled water in the water phase are：10~20mg：4~7mL.
Wherein in step (3), the styrene (St) in the 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 isobutyronitrile (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), the ratio of the methanol acetic acid mixed solution and dopamine methacrylic acid amino is：20~
50mL：10~20mg.
In step (3), the temperature of the water-bath polymerisation is 70 DEG C, polymerization time 12-48h；Vacuum drying
Temperature is 60 DEG C.
In the methanol acetic acid mixed solution, the volume ratio of methanol acetic acid is 1:1.
The technological merit of the present invention：
The product identifies recycling metal-organic framework material by preparing single trace lotion microballoon.Wherein, emulsion material
There is shape recognition, secondly lotion microballoon has cis-form dihydroxy structure recognition site；Materials chemistry stability is good simultaneously
Good, also there is material pH response functions can simplify adsorption/desorption operation in addition.
Description of the drawings
Fig. 1 is the metal-organic framework material (A1, A2, A3) of phenyl boric acid type that is prepared in embodiment 1 and without phenyl boric acid
The metal-organic framework material (B1, B2, B3) of type.
Fig. 2 is the lotion imprinted polymer microballoon (A1) prepared in embodiment 1, the lotion imprinted polymer microballoon after elution
(B1, B2), then the microballoon (C1, C2, C3) after adsorbing.
Fig. 3 is the nuclear-magnetism figure of dopamine methacrylic acid amino prepared in embodiment 1.
Fig. 4 is the metal-organic framework material a crossed without process phenyl boric acid type prepared in embodiment 1, by phenyl boric acid
The metal-organic framework material b and the infrared figure of lotion imprinted polymer microballoon c that type is crossed.
Fig. 5 is the BA-MOF (a) for preparing in embodiment 1, the Raman spectrogram of MOF (b), MIPs (c).
Fig. 6 is the BA-MOF (a) for preparing in embodiment 1, the X-ray diffraction spectrogram of MOF (b), MIPs (c).
Fig. 7 is the adsorption capacity in the one-component solution of different MOF for MIPs.
Fig. 8 is the adsorption capacity in the bi-component of different MOF or three component solution for MIPs.
Fig. 9 is Dynamic Adsorption curves of the MIPs to BA-MOF.
Specific embodiment
Recognition performance evaluation carries out by the following method in the specific embodiment of the invention：It is complete using Staticadsorption experiment
Into.The metal-organic framework material solution of the certain density phenyl boric acid types of 10ml is added in the centrifuge tube of 10mL, adds in one
Quantitative trace adsorbent is placed in 25 DEG C of constant temperature waters and stands several hours, the metal organic frame of phenyl boric acid type after absorption
Material content is measured with ultraviolet-uisible spectrophotometer, and calculates adsorption capacity according to result；Select several structures and property
Similar metal organic frame class compound, such as ZIF-8, Cu-MOF etc. are used as competitive Adsorption object, participate in the knowledge of research MIPs
Other performance.
With reference to specific implementation example, the present invention will be further described.
Embodiment 1：
(1) preparation of dopamine methacrylic acid amino (PDA-MA)
The Boratex and 3g of 9g is included in the reaction solution of the distilled water for the ready 90mL that 4g Dopamine hydrochlorides add in
Sodium bicarbonate in stir 2h, secondly in the tetrahydrofuran of 20mL that is dissolved in advance of methyl methacrylate of 4mL then by by
It drips to and is added in above-mentioned solution.Then this reaction reacts 16h at 25 DEG C under nitrogen protection.Finally use organic phase quilt
The ethyl acetate extraction of 40mL, then rotary evaporation again.Then it with the n-hexane dissolution of 200mL and is vigorously stirred until generating big
The precipitation of amount, 60 DEG C of drying of finally centrifugation and vacuum.
(2) preparation of the metal-organic framework material of phenyl boric acid type
The crome metal of 40mg, 3, the 5- dicarboxyl phenyl boric acids of 20mg, the trimesic acid of 100mg and the distilled water of 4mL add
Enter into reaction kettle, stir 1h, then 5 microlitres of hydrofluoric acid joins, and is then stirred for half an hour, is finally putting into baking oven
72h is reacted at 120 DEG C.It is then cooled to room temperature, is then centrifuged for and impregnates 2h with the DMF of 20mL, then again with 10mL's
1mol L-1Sodium hydroxide solution impregnates 2h, finally centrifuges, then is washed 3 times with distillation.Finally dried for 24 hours at 100 DEG C of vacuum.
(3) lotion trace metal organic frame adsorbent is prepared
First, water phase is made of the metal-organic framework material (BA-MOF) of the distilled water of 4mL and the phenyl boric 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, 2, the 2'- azos of 2mg
Bis-isobutyronitrile (AIBN) forms.It is vigorously stirred in 500rpm and forms stable lotion after five minutes, 70 DEG C of water are put into after then sealing
The lower polymerization 12h of bath.It finally dries, is cleaned 3 times with methanol and acetic acid mixed solution, then 60 DEG C of vacuum are dried again at 60 DEG C of vacuum
It is dry.
Embodiment 2：
(1) preparation of dopamine methacrylic acid amino (PDA-MA)
5g Dopamine hydrochlorides add in ready 100mL distilled water reaction solution in comprising 10g Boratex and
2h is stirred in the sodium bicarbonate of 4g, in the tetrahydrofuran of 25mL that secondly methyl methacrylate of 4.7mL is dissolved in advance then
It is dripped to and is added in above-mentioned solution dropwise.Then this reaction reacts 16h at 25 DEG C under nitrogen protection.Finally with organic
It is mutually extracted by the ethyl acetate of 50mL, then rotary evaporation again.Then with the n-hexane dissolution of 250mL and be vigorously stirred until production
Raw a large amount of precipitation, 60 DEG C of drying of finally centrifugation and vacuum.
(2) preparation of the metal-organic framework material of phenyl boric acid type
The crome metal of 52mg, 3, the 5- dicarboxyl phenyl boric acids of 28.54mg, the steaming of the trimesic acid and 4.8mL of 112.6mg
Distilled water is added in reaction kettle, stirs 2h, and then 7.8 microlitres of hydrofluoric acid joins, and is then stirred for half an hour, finally
It is put into baking oven and reacts 72h at 200 DEG C.It is then cooled to room temperature, is then centrifuged for and is impregnated 2 hours with the DMF of 30mL, Ran Houzai
With the 1mol L of 20mL-1Sodium hydroxide solution impregnates 2h, finally centrifuges, then is washed 3 times with distillation, finally at 100 DEG C of vacuum
Drying is for 24 hours.
(3) lotion trace metal organic frame adsorbent is prepared
First, water phase is made of the metal-organic framework material (BA-MOF) of the distilled water of 5mL and the phenyl boric 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, 2, the 2'- of 3mg are even
Nitrogen bis-isobutyronitrile (AIBN) forms.It is vigorously stirred in 500rpm and forms stable lotion after five minutes, 70 DEG C are put into after then sealing
It polymerize for 24 hours under water-bath.It is finally dried at 60 DEG C of vacuum, 3 times is cleaned with methanol and acetic acid mixed solution, then 60 DEG C of vacuum again
Drying.
Embodiment 3：
(1) preparation of dopamine methacrylic acid amino (PDA-MA)
6g Dopamine hydrochlorides add in ready 110mL distilled water reaction solution in comprising 11g Boratex and
2h is stirred in the sodium bicarbonate of 5g, secondly in the tetrahydrofuran of 50mL that is dissolved in advance of methyl methacrylate of 5mL and then quilt
It drips to and is added in above-mentioned solution dropwise.Then this reaction reacts 16h at 25 DEG C under nitrogen protection.Finally use organic phase
It is extracted by the ethyl acetate of 100mL, then rotary evaporation again.Then with the n-hexane dissolution of 500mL and be vigorously stirred until production
Raw a large amount of precipitation, 60 DEG C of drying of finally centrifugation and vacuum.
(2) preparation of the metal-organic framework material of phenyl boric acid type
The crome metal of 60mg, 3, the 5- dicarboxyl phenyl boric acids of 30mg, the trimesic acid of 150mg and the distilled water of 7mL add
Enter into reaction kettle, stir 4h, then 10 microlitres of hydrofluoric acid joins, and is then stirred for half an hour, is finally putting into baking
Case reacts 72h at 220 DEG C.It is then cooled to room temperature, is then centrifuged for and impregnates 2h with the DMF of 40mL, then again with 30mL's
1mol L-1Sodium hydroxide solution impregnates 2h, finally centrifuges, then is washed 3 times with distillation.Finally dried for 24 hours at 100 DEG C of vacuum.
(3) lotion trace metal organic frame adsorbent is prepared
First, water phase is made of the metal-organic framework material (BA-MOF) of the distilled water of 6mL and the phenyl boric 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, 2, the 2'- of 4mg are even
Nitrogen bis-isobutyronitrile (AIBN) forms.It is vigorously stirred in 500rpm and forms stable lotion after five minutes, 70 DEG C are put into after then sealing
It polymerize 48h under water-bath.It is finally dried at 60 DEG C of vacuum, 3 times is cleaned with methanol and acetic acid mixed solution, then 60 DEG C of vacuum again
Drying.
Test example 1：Select the metal organic frame class compound of ZIF-8, Cu-MOF for competitive Adsorption, be respectively configured more than
The aqueous solution of 2 kinds of metal organic frame class compounds, the concentration of each competitive adsorbate is all 30mg/l, takes what 10ml had been configured
Solution is added in centrifuge tube, and the MIPs adsorbents being separately added into 10mg embodiments 1 are placed on test fluid in 25 DEG C of water-bath
Stand 8.0h respectively, after the completion of time of repose, supernatant liquor is collected with being centrifuged at a high speed, and unadsorbed various competition metals have
Machine frame class compound concentration is measured with ultraviolet specrophotometer, such as Fig. 7, the results showed that, MIPs is to BA-MOFs, ZIF-8, Cu-
The adsorption capacity of MOFs is respectively 43.24mg/g, 6.52mg/g, 3.52mg/g.It is significant single-minded to show that MIPs has BA-MOFs
Identity, adsorption capacity are higher than other metal organic frame class compounds.
Test example 2：It for the metal organic frame class compound of competitive Adsorption is competitive Adsorption to select ZIF-8, Cu-MOF
Phenolic compound.LTL and the mixed solution of three kinds of binary for competing phenolic compound and ternary is respectively configured, each hydroxy kind
Concentration is all 30mg/l, and the mixed solution that 10ml has been configured is taken to be added in centrifuge tube, is separately added into 10mg embodiments 1
MIPs adsorbents are placed on test fluid in 30 DEG C of water-bath and stand 8.0h respectively, and after the completion of time of repose, supernatant liquor is at a high speed
It centrifuges and collects, unadsorbed BA-MOF concentration is measured with ultraviolet specrophotometer, such as Fig. 8, the results showed that, in binary system
In other chaff interferent ZIF-8, Cu-MOF there are when MIPs be respectively 41.4mg/g, 38.2mg/ to the adsorption capacity of BA-MOFs
g.In ternary system other chaff interferent ZIF-8, Cu-MOF there are when MIPs be 35.6mg/ to the adsorption capacity of BA-MOFs
g。
Test example 3：Select different factor pH, temperature, flowing velocity, concentration comes Dynamic Adsorption what item is being done in network analysis
Part MIPs being capable of optimal adsorption BA-MOFs.The MIPs adsorbents in 10mg embodiments 1 are added under conditions of pH is 6,7,8, then
Different temperatures (25 DEG C, 35 DEG C, 45 DEG C) is done, is concentration (the 10mg L of different BA-MOF on this condition-1,17.5mg L-1,
25mg L-1), (1mL min different in flow rate are controlled in addition-1,2mL min-1,3mL min-1) adsorb BA-MOFs.It, can such as Fig. 9
To obtain the influence pH of various factors>Temperature>Concentration>Flowing velocity.By the analysis of system, pH is 8.0 concentration at 45 DEG C
For 25mg L-1Flow velocity is 1.23mL min-1When for optimal adsorption condition adsorb BA-MOFs.
Fig. 1 is the metal-organic framework material (A1, A2, A3) of phenyl boric acid type that is prepared in embodiment 1 and without phenyl boric acid
The metal-organic framework material (B1, B2, B3) of type.As can be drawn from Figure 1, the metal organic frame material crossed by phenyl boric acid type
The average diameter of material reaches 1um.
Fig. 2 is the lotion imprinted polymer microballoon (A1) prepared in embodiment 1, the lotion imprinted polymer microballoon after elution
(B1, B2), then the microballoon (C1, C2, C3) after adsorbing.As can be drawn from Figure 2, A1 figures have thick shell, by elution
Later, shell comes off, and obtains B1, B2, using absorption BA-MOF, obtains figure C1, C2, C3, finds many BA-MOF more
Grain.
Fig. 3 is the nuclear-magnetism figure of dopamine methacrylic acid amino prepared in embodiment 1, as can be drawn from Figure 3, dopamine
It has successfully been reacted with methyl methacrylate, has generated dopamine methacrylic acid amino.
Fig. 4 is to be prepared in embodiment 1 without the metal-organic framework material a that crosses by phenyl boric acid type and by phenyl boric acid
The metal-organic framework material b and the infrared figure of lotion imprinted polymer microballoon c that type is crossed, as can be drawn from Figure 4 by benzene boron
The metal-organic framework material that acid type is crossed is in 1348cm-1There is a peak, illustrate that boric acid is successfully modified to surface,
3700cm-1There is a peak, illustrate to be successfully formed polymer microballoon.
Fig. 5 is the BA-MOF (a) for preparing in embodiment 1, the Raman spectrogram of MOF (b), MIPs (c), can be with from 5 figures
Obtain BA-MOF and MIPs in 189cm-1There are one characteristic peaks, show that there are phenyl boric acid function monomers in BA-MOF and MIPs；
Fig. 6 is the BA-MOF (a) prepared in embodiment 1, and the X-ray diffraction spectrogram of MOF (b), MIPs (c) can from Fig. 6
To obtain, there is apparent crystal form to occur at 45 degree, therefore BA-MOF successfully modifies upper boric acid and metal organic frame
Materials synthesis work(.
Fig. 7 is the adsorption capacity in the one-component solution of different MOF, as can be drawn from Figure 7, BA- for MIPs
The adsorption capacity of MOF is maximum, and showing MIPs, successfully synthesis can be with specific recognition BA-MOF.
Fig. 8 is the adsorption capacity in the bi-component of different MOF or three component solution for MIPs, can be with from Fig. 8
Obtain, MIPs can in multiple component solution specific adsorption BA-MOF.
Fig. 9 for MIPs to the Dynamic Adsorption curve of BA-MOF, investigated pH-value (a, b), temperature (c, d), concentration respectively
(e, f), the influence of flow velocity (g, h).As can be drawn from Figure 9 to the size pH of absorption BA-MOF influence factors>Temperature>Concentration>
Flowing velocity.When pH is 8.0 a concentration of 25mg L at 45 DEG C-1Flow velocity is 1.23mL min-1When for optimal adsorption condition adsorb
BA-MOFs。
Claims (9)
1. a kind of method that Pickering emulsion polymerizations prepare metal organic frame particle trace adsorbent, which is characterized in that packet
Include following steps：
(1) dopamine methacrylic acid amino PDA-MA is prepared, it is spare；
(2) the metal-organic framework material BA-MOF of phenyl boric acid type is prepared, it is spare；
By crome metal, 3,5- dicarboxyl phenyl boric acids, trimesic acid and distilled water are added in reaction kettle, stir 1-4h, then add
Enter hydrofluoric acid, be stirred for half an hour, be then placed in baking oven and 72h is reacted at 120-240 DEG C, be cooled to room after reaction
Temperature impregnates 2h, centrifugation, then with 1mol L with dimethylformamide (DMF)-1Sodium hydroxide solution impregnates 2h, centrifuges again,
Distillation washing 3 times, 100 DEG C of vacuum dryings are for 24 hours；
(3) lotion trace metal organic frame adsorbent is prepared：
First, the water phase metal-organic framework material BA-MOF of phenyl boric acid type and distilled water made from step (2) forms, oil phase
By styrene, polyethylene glycol two (methacrylic acid) ester, divinylbenzene, toluene, dopamine metering system made from step (1)
Acid amide PDA-MA, 2,2'- azodiisobutyronitriles composition, is vigorously stirred in 500rpm and forms stable lotion after five minutes；
Then, under air-proof condition, water-bath polymerisation is carried out；
Finally, vacuum drying finally cleans 3 times with methanol and acetic acid mixed solution, then vacuum drying again.
2. a kind of Pickering emulsion polymerizations according to claim 1 prepare metal organic frame particle trace adsorbent
Method, which is characterized in that the method for preparing dopamine methacrylic acid amino PDA-MA described in step (1) is：Hydrochloric acid is more
Bar amine is added in the aqueous solution comprising Boratex and sodium bicarbonate, stirs 2h, then will be dissolved with the four of methyl methacrylate
Hydrogen tetrahydrofuran solution drips to dropwise to be added in above-mentioned aqueous solution, and the lower reaction 16h of nitrogen protection, uses second after reaction at 25 DEG C
Acetoacetic ester extracts organic phase, then rotary evaporation again, then with n-hexane dissolution and is vigorously stirred until generate a large amount of precipitation,
60 DEG C of drying of finally centrifugation and vacuum.
3. a kind of Pickering emulsion polymerizations according to claim 2 prepare metal organic frame particle trace adsorbent
Method, which is characterized in that the methyl methacrylate, Dopamine hydrochloride, Boratex, sodium bicarbonate and water ratio
For：4~5mL：4~6g：9~11g：3~5g：90~110mL；The methyl methacrylate and the ratio of tetrahydrofuran
For：4~5mL：20~30mL；The ratio of the methyl methacrylate, ethyl acetate and n-hexane is：4~5mL：40~
100mL：200~500mL.
4. a kind of Pickering emulsion polymerizations according to claim 1 prepare metal organic frame particle trace adsorbent
Method, which is characterized in that in step (2), the crome metal, 3,5- dicarboxyl phenyl boric acids, trimesic acid, hydrofluoric acid,
The ratio of distilled water is：40~60mg：20~30mg：100~150mg：5-10uL：4-6mL；The crome metal, dimethyl
Formamide, the ratio of sodium hydroxide are：40~60mg：20~40mL：10~30mL.
5. a kind of Pickering emulsion polymerizations according to claim 1 prepare metal organic frame particle trace adsorbent
Method, which is characterized in that in step (3), the ratio of BA-MOF and distilled water in the water phase are：10~20mg：4~
7mL。
6. a kind of Pickering emulsion polymerizations according to claim 1 prepare metal organic frame particle trace adsorbent
Method, which is characterized in that in step (3), the styrene in the oil phase, polyethylene glycol two (methacrylic acid) ester, diethyl
Alkenyl benzene, toluene, dopamine methacrylic acid amino PDA-MA, the ratio of 2,2'- azodiisobutyronitriles are：0.1~0.3mL：0.4
~0.8mL：0.2~0.25mL：0.3~0.6mL：10~20mg：2~4mg.
7. a kind of Pickering emulsion polymerizations according to claim 1 prepare metal organic frame particle trace adsorbent
Method, which is characterized in that in step (3), the methanol acetic acid mixed solution and dopamine methacrylic acid amino PDA-MA
Ratio be：20~50mL：10~20mg.
8. a kind of Pickering emulsion polymerizations according to claim 1 prepare metal organic frame particle trace adsorbent
Method, which is characterized in that in step (3), the temperature of the water-bath polymerisation is 70 DEG C, polymerization time 12-48h.
9. a kind of Pickering emulsion polymerizations according to claim 1 prepare metal organic frame particle trace adsorbent
Method, which is characterized in that the temperature of the vacuum drying be 60 DEG C；In the methanol acetic acid mixed solution, methanol acetic acid
Volume ratio is 1:1.
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| CN106929912B (en) * | 2017-03-02 | 2019-02-19 | 山东师范大学 | One kind having multilayered structure metal organic frame nanocrystal and preparation method |
| CN106964322A (en) * | 2017-03-29 | 2017-07-21 | 江苏大学 | A kind of preparation method of boric acid functionalization porous adsorbent |
| CN107090059B (en) * | 2017-05-10 | 2018-12-25 | 中南大学 | A kind of preparation method of the molecular imprinted polymer on surface of water phase application |
| CN107353369B (en) * | 2017-07-10 | 2019-04-19 | 中国人民解放军军事医学科学院卫生学环境医学研究所 | A kind of photonic crystal sensor material and its preparation method and application |
| CN108031455B (en) * | 2017-12-21 | 2019-11-12 | 常州大学 | A kind of preparation method of hollow porous micro sphere adsorbent |
| CN109174013A (en) * | 2018-10-17 | 2019-01-11 | 五邑大学 | A kind of acid modified metal organic framework material and preparation method thereof |
| CN110813253B (en) * | 2019-11-22 | 2021-07-16 | 山东农业大学 | Preparation method and application of hydrophilic metal organic framework surface bisphenol A molecular imprinting high-selectivity nanocomposite |
| CN112023899A (en) * | 2020-07-09 | 2020-12-04 | 江苏大学 | Preparation method of hydrophilic flexible porous boron affinity imprinted hydrogel adsorbent |
| CN112657475B (en) * | 2020-12-02 | 2023-09-26 | 常州大学 | Boron affinity functionalized microsphere adsorbent and preparation method and application thereof |
| WO2022197778A1 (en) * | 2021-03-18 | 2022-09-22 | The University Of Akron | Catechol containing polymer emulsions and methods of preparation thereof |
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