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CN109354649A - A kind of preparation method and application of pyraclostrobin molecularly imprinted polymer - Google Patents

A kind of preparation method and application of pyraclostrobin molecularly imprinted polymer Download PDF

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Publication number
CN109354649A
CN109354649A CN201811314731.8A CN201811314731A CN109354649A CN 109354649 A CN109354649 A CN 109354649A CN 201811314731 A CN201811314731 A CN 201811314731A CN 109354649 A CN109354649 A CN 109354649A
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pyraclostrobin
kresoxim
methyl
preparation
molecularly imprinted
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CN109354649B (en
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贾明宏
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Henan Chentong Biotechnology Co Ltd
Beijing University of Agriculture
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Henan Chentong Biotechnology Co Ltd
Beijing University of Agriculture
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/12—Esters of phenols or saturated alcohols
    • C08F222/14—Esters having no free carboxylic acid groups, e.g. dialkyl maleates or fumarates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J20/28014—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 form
    • B01J20/28016—Particle form
    • B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2335/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
    • C08J2335/04—Homopolymers or copolymers of nitriles

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Abstract

The present invention relates to compound extraction and field is isolated and purified, in particular to a kind of preparation method and applications of kresoxim-methyl class molecularly imprinted polymer.The preparation method is using kresoxim-methyl and pyraclostrobin as template molecule, using methacrylic acid as function monomer, using trimethylol-propane trimethacrylate as crosslinking agent carry out polymerization reaction, then remove the template molecule in unpolymerized function monomer, crosslinking agent and polymer to get.Kresoxim-methyl class molecularly imprinted polymer is prepared by precipitation polymerization method, the molecularly imprinted polymer, which can be realized, carries out specific recognition to kresoxim-methyl, pyraclostrobin, to realize separation, enrichment and purifying to kresoxim-methyl, pyraclostrobin, purification method is provided for the residue detection of kresoxim-methyl, pyraclostrobin in environment and agricultural product.

Description

A kind of preparation method and applications of kresoxim-methyl class molecularly imprinted polymer
Technical field
The present invention relates to compound extraction and field is isolated and purified, in particular to a kind of kresoxim-methyl class molecular engram The preparation method and applications of polymer.
Background technique
Methoxy acrylic bactericide is found on the basis of natural products 'beta '-methoxy acrylic acid ester.Pass through To methoxy acrylic bactericide in-depth study, it is found that the mechanism of action of such fungicide is by interfering disease fungus Respiration and play bactericidal effect, it is a kind of fungal cytochrome bc1 respiration inhibitor.Due to methoxy acrylate The continuous increase of class fungicide usage amount, the continuous increase of residual quantity, the residue problem of this kind of fungicide cause whole world various countries The attention of regulatory authorities, multiple countries and linked groups define the residue limits of this kind of fungicide.
Higher methoxy acrylic bactericide-the ether of an activity was developed in BASF AG's exploitation in 1989 Bacterium ester (Kresoxim-methyl), kresoxim-methyl were also commercialized in 1996, european patent number EP0253213.Kresoxim-methyl is again Name kresoxim-methyl, benzene oxygen polyester, imines bacterium, chemical name (E) -2- methoxyimino-[2- (o-methyl-benzene oxygroup methyl) benzene Base] methyl acetate.
Pyraclostrobin is methoxy acrylic sterilization with pyrrazole structure of the Bath company in research and development in 1993 Agent, and listed in registration in 2001.Its broad-spectrum is widely used in by basidiomycetes, Fungi Imperfecti, sac fungus and oomycetes etc. almost Disease caused by all types of fungal pathogens.It is mainly used for preventing and treating wheat powdery mildew, rust, leaf rust of barley, grape Powdery mildew, downy mildew, the black leaf cecospora spot of banana, tomato morning, late blight etc..
Molecular engram is one and is based on molecular level, can be formed in the polymer matrix to template molecule or template analog High-end technology with specific identification ability site.Molecularly imprinted polymer (MIPs) is that one kind forms three around template molecule The material of dimension space polymer after template molecule is eluted, leaves the specific hole of template molecule, is formed to template molecule Specific adsorption material.Molecular imprinting technology has evolved to certain level, all has made great progress in all respects.But at present MIPs is the single template of trace mostly, only has to template itself highly selective, therefore limits the use of MIPs.
In view of this, the present invention is specifically proposed.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of kresoxim-methyl class molecularly imprinted polymer, manufactured kresoxim-methyl Class molecular blotting polymer microsphere and using the kresoxim-methyl class molecular blotting polymer microsphere as solid made of packing material Phase extraction column prepares kresoxim-methyl class molecular engram by precipitation polymerization method using kresoxim-methyl and pyraclostrobin as template molecule Polymer, the molecularly imprinted polymer, which can be realized, carries out specific recognition to kresoxim-methyl, pyraclostrobin, thus realization pair Kresoxim-methyl, the separation of pyraclostrobin, enrichment and purifying are the residual of kresoxim-methyl, pyraclostrobin in environment and agricultural product Detection provides purification method.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
A kind of preparation method of kresoxim-methyl class molecularly imprinted polymer, using kresoxim-methyl and pyraclostrobin as template molecule, Using methacrylic acid as function monomer, polymerization reaction is carried out by crosslinking agent of trimethylol-propane trimethacrylate, then remove Go the template molecule in unpolymerized function monomer, crosslinking agent and polymer to get.
The kresoxim-methyl class molecular engram that a kind of preparation method of above-mentioned kresoxim-methyl class molecularly imprinted polymer is prepared is poly- Close object microballoon.
A kind of solid-phase extraction column, using above-mentioned kresoxim-methyl class molecular blotting polymer microsphere as filler.
Compared with prior art, the invention has the benefit that the present invention uses double-template molecule by precipitation polymerization method Kresoxim-methyl class molecularly imprinted polymer is synthesized, kresoxim-methyl and pyraclostrobin are had good selectivity.Its molecular imprinting is poly- Conjunction object microballon partial size is smaller, and specific surface is big, and adsorption capacity is strong.The kresoxim-methyl class molecularly imprinted polymer that the present invention synthesizes is as solid The filler of phase extraction column can be applied to the trace kresoxim-methyl of environment and food and the high selection separation and concentration of pyraclostrobin.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is the kresoxim-methyl equilibrium adsorption curve of the kresoxim-methyl class molecular blotting polymer microsphere in experimental example 2 of the present invention Figure；
Fig. 2 is the pyraclostrobin equilibrium adsorption of the kresoxim-methyl class molecular blotting polymer microsphere in experimental example 2 of the present invention Curve graph.
Specific embodiment
The purpose of the present invention is to provide a kind of preparation methods of kresoxim-methyl class molecularly imprinted polymer, manufactured kresoxim-methyl Class molecular blotting polymer microsphere and using the kresoxim-methyl class molecular blotting polymer microsphere as solid made of packing material Phase extraction column prepares kresoxim-methyl class molecular engram by precipitation polymerization method using kresoxim-methyl and pyraclostrobin as template molecule Polymer, the molecularly imprinted polymer, which can be realized, carries out specific recognition to kresoxim-methyl, pyraclostrobin, thus realization pair Kresoxim-methyl, the separation of pyraclostrobin, enrichment and purifying are the residual of kresoxim-methyl, pyraclostrobin in environment and agricultural product Detection provides purification method.
A kind of preparation method of kresoxim-methyl class molecularly imprinted polymer, using kresoxim-methyl and pyraclostrobin as template molecule, Using methacrylic acid as function monomer, polymerization reaction is carried out by crosslinking agent of trimethylol-propane trimethacrylate, then remove Go the template molecule in unpolymerized function monomer, crosslinking agent and polymer to get.
For the present invention by selecting to be template molecule to kresoxim-methyl and pyraclostrobin, having synthesized has height " class " special Property, molecularly imprinted polymers selective microballoon (MIP), while the detection to kresoxim-methyl and pyraclostrobin can be achieved in.
The selection of function monomer has a significant impact for the absorption property of molecularly imprinted polymer, needs according to template molecule Structure and fundamental property selected.The present invention has selected methacrylic acid as function monomer, can extraordinary raising conjunction Recognition reaction of the object to template molecule.
In order to make the imprinted polymer generated that there is certain spacial framework and stable binding site, molecular engram The degree of cross linking that polymer requires is very high.Trimethylol-propane trimethacrylate (TRIM) preferred for this invention has higher The degree of cross linking (70~90%), and in pre-polymer solution have good dissolubility.
In some embodiments, the structure of the kresoxim-methyl class molecularly imprinted polymer is microballoon；The grain of the microballoon Diameter≤50 μm.
In some embodiments, the specific surface area of the microballoon is greater than 8m2/g。
Partial size, specific surface area size and its absorption property of molecularly imprinted polymer have close ties, it is directly affected Absorption property and recognition capability of the adsorbent material to target analytes.The specific surface area of adsorbent material is bigger under normal conditions, hole The smaller adsorbance of diameter is bigger.
In some embodiments, the kresoxim-methyl, pyraclostrobin, methacrylic acid, trimethylol propane trimethyl Acrylate, trimethylol-propane trimethacrylate molar ratio be (0.8~1.2): (0.8~1.2): (4~8): (20 ~40).In some embodiments, molar ratio is also an option that (0.9~1.1): (0.9~1.1): (4~6): (25~45), 1: 1:6:30 etc..
In some embodiments, the polymerization reaction carries out in the reaction system that acetonitrile-methylbenzene is solvent；The second The volume ratio of acetonitrile and toluene is (6~8): (2~4) in nitrile-toluene.In some embodiments, volume ratio can also be 7:3 Deng.
The effect of the practical also act as solvents of pore-foaming agent.The selection of solvent plays an important role in molecular engram preparation, It is very big to the morphology influence of intermolecular active force and MD, and play a part of pore-foaming agent.The solvent generally selected to have with Lower 3 conditions: 1), template molecule and function monomer can be dissolved；2) big recirculation hole can, be formed；3), to template molecule and function Interaction interference between monomer is small.It is suitable generally to be selected according to active force type possible between microsphere and function monomer The polarity of polar solvent, solvent is bigger, also bigger to the interference of molecular recognition, and adsorption rate is lower.The present invention is used Acetonitrile-methylbenzene polarity it is moderate, dielectric constant is low, while also very good to the dissolubility of several reactants.
In some embodiments, the kresoxim-methyl, the pyraclostrobin, the methacrylic acid are added to described 2~3h is stood after being uniformly dissolved in acetonitrile-methylbenzene to form template molecule-function monomer complex.
In some embodiments, the trimethylol-propane trimethacrylate and the template molecule-function list When body complex carries out polymerization reaction, being additionally added 2,2'- azodiisobutyronitrile is initiator.
It is mostly radical initiation reaction in molecular engram polymerization reaction, therefore initiator initiation need to be added in reaction and gather Reaction is closed, the present invention preferably 2,2'- azodiisobutyronitrile (AIBN) is used as initiator.2,2'- azodiisobutyronitrile is oil-soluble Azo initiator, azo-initiator stable reaction is first order reaction, without side reaction, relatively good control.
In some embodiments, the polymerization reaction carries out under anaerobic, 65 DEG C~75 DEG C reaction 20h~28h. In some embodiments, oxygen free condition can also be 68 DEG C of reaction 26h, 70 DEG C of reactions for 24 hours etc..
In some embodiments, the method for forming the oxygen free condition include: lead under the conditions of ice-water bath nitrogen 10~ 15min.In some embodiments, the time of the logical nitrogen can also be 12min, 13min etc..
In some embodiments, the template removed in unpolymerized function monomer, crosslinking agent and polymer point The method of son includes then centrifugation carries out Soxhlet extraction with acetic acid and methanol mixed solution.
In some embodiments, the condition of the centrifugation is 5~10min of centrifugation under the conditions of 2000~4000r/min.? In some embodiments, the condition of the centrifugation can also be 10min, 3000r/min are centrifuged under the conditions of 2000r/min under the conditions of from 5min etc. is centrifuged under the conditions of the heart 8min, 4000r/min.
In some embodiments, the volume ratio of the acetic acid and methanol is 1:(8~10).In some embodiments, institute Stating volume ratio can also be 1:8.5,1:9 etc..
It in some embodiments, further include methanol elution after the Soxhlet extraction.
Another aspect of the present invention also resides in the preparation method preparation for providing and stating a kind of kresoxim-methyl class molecularly imprinted polymer Obtained kresoxim-methyl class molecular blotting polymer microsphere.
Another aspect of the present invention, which also resides in, provides a kind of solid-phase extraction column, poly- with above-mentioned kresoxim-methyl class molecular engram Conjunction object microballoon is filler.
In some embodiments, the kresoxim-methyl class molecular blotting polymer microsphere is as chromatograph packing material.
Kresoxim-methyl class molecularly imprinted polymer prepared by the present invention has specific adsorption to kresoxim-methyl and pyrazoles Fluoxastrobin Effect, can be used as the filler of Solid Phase Extraction, in environment and food kresoxim-methyl and pyrazoles Fluoxastrobin separated and be enriched with, tie Close chromatographic detection method (HPLC method), in environment and food kresoxim-methyl and pyrazoles Fluoxastrobin residual check.It can also make Detection at chromatograph packing material, for trace kresoxim-methyl and pyrazoles Fluoxastrobin.
Kresoxim-methyl class molecularly imprinted polymer of the invention can simultaneously specificity identification kresoxim-methyl and pyrazoles Fluoxastrobin, inhale Attached ability is strong, is remarkably improved kresoxim-methyl and pyrazoles Fluoxastrobin detection sensitivity and detection efficiency, has biggish popularization and application Value.
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is It can be with conventional products that are commercially available.
The preparation of 1 molecularly imprinted polymer of embodiment
1. 0.8mmol kresoxim-methyl, 1.2mmol pyraclostrobin, 8mmol function list is added in 100mL ground glass stoppered bottle Body methacrylic acid and 75mL acetonitrile-methylbenzene solution (7:3, v/v), are stored at room temperature 2h；
2. 20mmol trimethylol-propane trimethacrylate and 50mg 2 is added, 2` azodiisobutyronitrile, ultrasound is mixed It is even, high pure nitrogen 10min is then led under the conditions of ice-water bath, is sealed with ground glass stopper, 28h polymerize anti-in 65 DEG C of water-baths It answers；
3. being centrifuged 10min after being cooled to room temperature, under the conditions of 3000r/min obtains precipitation polymers, with acetic acid and methanol body Product carries out Soxhlet extraction, extraction time 20h than the mixed solution for being 1:9, and temperature is 80 DEG C；
It is eluted 4. being vibrated with methanol, the solidifying pearl of the polymer finally obtained is placed in vacuum drying oven and is dried under vacuum to perseverance for 60 DEG C Weight obtains kresoxim-methyl class molecular blotting polymer microsphere and coagulates pearl powder.
The preparation of 2 molecularly imprinted polymer of embodiment
1. 1mmol kresoxim-methyl, 0.8mmol pyraclostrobin, 4mmol function monomer is added in 100mL ground glass stoppered bottle Methacrylic acid and 65mL acetonitrile-methylbenzene solution (7:3, v/v), are stored at room temperature 2.5h；
2. 40mmol trimethylol-propane trimethacrylate and 45mg 2 is added, 2` azodiisobutyronitrile, ultrasound is mixed It is even, high pure nitrogen 15min is then led under the conditions of ice-water bath, is sealed with ground glass stopper, carries out polymerizeing for 24 hours in 72 DEG C of water-baths anti- It answers；
3. being centrifuged 8min after being cooled to room temperature, under the conditions of 2000r/min obtains precipitation polymers, with acetic acid and methanol volume Soxhlet extraction is carried out than the mixed solution for 1:8, extraction time is that for 24 hours, temperature is 85 DEG C；
It is eluted 4. being vibrated with methanol, the solidifying pearl of the polymer finally obtained is placed in vacuum drying oven and is dried under vacuum to perseverance for 60 DEG C Weight obtains kresoxim-methyl class molecular blotting polymer microsphere and coagulates pearl powder.
The preparation of 3 molecularly imprinted polymer of embodiment
1. 1mmol kresoxim-methyl, 1mmol pyraclostrobin, 6mmol function monomer first is added in 100mL ground glass stoppered bottle Base acrylic acid and 70mL acetonitrile-methylbenzene solution (7:3, v/v), are stored at room temperature 3h；
2. 30mmol trimethylol-propane trimethacrylate and 55mg 2 is added, 2` azodiisobutyronitrile, ultrasound is mixed It is even, high pure nitrogen 12min is then led under the conditions of ice-water bath, is sealed with ground glass stopper, 20h polymerize anti-in 68 DEG C of water-baths It answers；
3. being centrifuged 5min after being cooled to room temperature, under the conditions of 4000r/min obtains precipitation polymers, with acetic acid and methanol volume Soxhlet extraction, extraction time 26h are carried out than the mixed solution for 1:10, temperature is 85 DEG C；
It is eluted 4. being vibrated with methanol, the solidifying pearl of the polymer finally obtained is placed in vacuum drying oven and is dried under vacuum to perseverance for 60 DEG C Weight obtains kresoxim-methyl class molecular blotting polymer microsphere and coagulates pearl powder.
The preparation of 4 molecular engram extraction column of embodiment
1. having taken solid-phase extraction column, it is packed into one piece of sieve plate；
It is prepared 2. each 50mg of molecularly imprinted polymer powder that Examples 1 to 3 is prepared is separately added into 1mL methanol At suspension, suspension is added in the empty solid-phase extraction column, while once with methanol rinses, vacuum is drained；
3. being packed into other one piece of sieve plate, compacting；
4. 2mL methanol is added into column again, vacuum is drained.
The partial size and specific surface area of 1 kresoxim-methyl class molecular blotting polymer microsphere of experimental example
Using laser particle analyzer to kresoxim-methyl class molecular blotting polymer microsphere particle size prepared by Examples 1 to 3 And specific surface area is analyzed.100mg polymer is weighed, 95% ethyl alcohol of 10mL is added, ultrasonic 5min carries out partial size and ratio The detection of surface area.Carry out parallel laboratory test three times.
The average grain diameter and specific surface area of 1 kresoxim-methyl class molecular blotting polymer microsphere of table
As can be seen from Table 1, using kresoxim-methyl class molecular blotting polymer microsphere prepared by the embodiment of the present invention 1~3 Average grain diameter less than 50 μm, and have biggish specific surface area.
Equilibrium adsorption experiment of the 2 kresoxim-methyl class molecular blotting polymer microsphere of experimental example to template molecule
The kresoxim-methyl equilibrium adsorption experiment of 2.1 kresoxim-methyl class molecular blotting polymer microspheres
Polymer microballoon that 20mg Examples 1 to 3 is prepared is accurately weighed in vial of the 10mL with screw lid, point It Jia Ru not 0.2,0.5,1,1.5,2,2.5,3mg/mL kresoxim-methyl solution of 2mL.12h is stood in 25 DEG C of water-baths, is taken after centrifugation Clearly, using chromatography (HPLC method) measurement supernatant in template molecule kresoxim-methyl concentration, using formula Q=(Ci-Cf) xV/m into Row calculates,
Wherein Ci: the initial concentration (mg/mL) of kresoxim-methyl in solution；
Cf: reach the concentration (mg/mL) of kresoxim-methyl in solution after adsorption equilibrium；
V: the volume (mL) of solution；
M: polymer quality (mg)
Experimental result is shown in Fig. 1.The results show that the kresoxim-methyl class molecularly imprinted polymer that the embodiment of the present invention is prepared is micro- Ball has preferable suction-operated for kresoxim-methyl, and maximal absorptive capacity can reach the adsorbable about 180mg kresoxim-methyl of every gram of polymer.
The pyraclostrobin equilibrium adsorption experiment of 2.2 kresoxim-methyl class molecular blotting polymer microspheres
Polymer microballoon that 20mg Examples 1 to 3 is prepared is accurately weighed in vial of the 10mL with screw lid, point It Jia Ru not 20,40,80,120,160,200,250,300mg/L pyrazoles Fluoxastrobin solution of 2mL.12h is stood in 25 DEG C of water-baths, Supernatant is taken after centrifugation, using the concentration of chromatography (HPLC method) measurement template molecule pyraclostrobin, utilizes formula Q=(Ci- Cf) xV/m is calculated,
Wherein Ci: the initial concentration (mg/L) of pyraclostrobin in solution；
Cf: reach the concentration (mg/L) of pyraclostrobin in solution after adsorption equilibrium；
V: the volume (mL) of solution；
M: polymer quality (mg)
Experimental result is shown in Fig. 2.The results show that the kresoxim-methyl class molecularly imprinted polymer that the embodiment of the present invention is prepared is micro- Ball has preferable suction-operated for pyraclostrobin, and maximal absorptive capacity can reach the adsorbable about 130mg pyrazoles of every gram of polymer Kresoxim-methyl.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent Present invention has been described in detail with reference to the aforementioned embodiments for pipe, but those skilled in the art should understand that: its It is still possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features It is equivalently replaced；And these are modified or replaceed, various embodiments of the present invention skill that it does not separate the essence of the corresponding technical solution The range of art scheme.

Claims (10)

1.一种醚菌酯类分子印迹聚合物的制备方法，其特征在于，以醚菌酯和吡唑醚菌酯为模板分子，以甲基丙烯酸为功能单体，以三羟甲基丙烷三甲基丙烯酸酯为交联剂进行聚合反应，再除去未聚合的功能单体、交联剂以及聚合物中的模板分子，即得。1. a preparation method of pyraclostrobin molecularly imprinted polymer, is characterized in that, with pyraclostrobin and pyraclostrobin as template molecule, with methacrylic acid as functional monomer, with trimethylolpropane trimethylolpropane The methacrylate is used as the cross-linking agent to carry out the polymerization reaction, and then the unpolymerized functional monomer, the cross-linking agent and the template molecules in the polymer are removed, that is, it is obtained. 2.根据权利要求1所述的制备方法，其特征在于，所述醚菌酯类分子印迹聚合物的结构为微球；所述微球的粒径≤50μm。2 . The preparation method according to claim 1 , wherein the structure of the pyraclostrobin-based molecularly imprinted polymer is a microsphere; the particle size of the microsphere is less than or equal to 50 μm. 3 . 3.根据权利要求1所述的制备方法，其特征在于，所述醚菌酯、吡唑醚菌酯、甲基丙烯酸、三羟甲基丙烷三甲基丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯的摩尔比为(0.8～1.2):(0.8～1.2):(4～8):(20～40)。3. preparation method according to claim 1 is characterized in that, described pyraclostrobin, pyraclostrobin, methacrylic acid, trimethylolpropane trimethacrylate, trimethylolpropane trimeth The molar ratio of the base acrylate is (0.8-1.2):(0.8-1.2):(4-8):(20-40). 4.根据权利要求1所述的制备方法，其特征在于，所述聚合反应在乙腈-甲苯为溶剂的反应体系中进行；所述乙腈-甲苯中乙腈和甲苯的体积比为(6～8)：(2～4)。4. preparation method according to claim 1, is characterized in that, described polymerization is carried out in the reaction system that acetonitrile-toluene is solvent; The volume ratio of acetonitrile and toluene in described acetonitrile-toluene is (6～8) : (2 to 4). 5.根据权利要求1所述的制备方法，其特征在于，将所述醚菌酯、所述吡唑醚菌酯、所述甲基丙烯酸加入到所述乙腈-甲苯中溶解均匀后静置2～3h以形成模板分子-功能单体配合物。5. preparation method according to claim 1, is characterized in that, adding described pyraclostrobin, described pyraclostrobin, described methacrylic acid in described acetonitrile-toluene to dissolve evenly and then stand for 2 ~3h to form the template molecule-functional monomer complex. 6.根据权利要求5所述的制备方法，其特征在于，所述三羟甲基丙烷三甲基丙烯酸酯与所述模板分子-功能单体配合物进行聚合反应时，还加入2,2'-偶氮二异丁腈为引发剂。6. preparation method according to claim 5, is characterized in that, when described trimethylolpropane trimethacrylate and described template molecule-functional monomer complex carry out polymerization reaction, also add 2,2' - Azobisisobutyronitrile is the initiator. 7.根据权利要求1～6任一项所述的制备方法，其特征在于，所述聚合反应在无氧条件下进行，65℃～75℃反应20h～28h；7. The preparation method according to any one of claims 1 to 6, wherein the polymerization reaction is carried out under anoxic conditions, and the reaction is carried out at 65°C to 75°C for 20h to 28h; 优选地，形成所述无氧条件的方法包括：在冰水浴条件下通氮气10～15min。Preferably, the method for forming the anaerobic condition comprises: passing nitrogen gas for 10-15 min under ice-water bath conditions. 8.根据权利要求1所述的制备方法，其特征在于，所述除去未聚合的功能单体、交联剂以及聚合物中的模板分子的方法包括离心然后用乙酸和甲醇混合溶液进行索氏提取；8. The preparation method according to claim 1, wherein the method for removing the unpolymerized functional monomer, the crosslinking agent and the template molecule in the polymer comprises centrifugation and then performing Soxhlet with a mixed solution of acetic acid and methanol extract; 优选地，所述离心的条件是2000～4000r/min条件下离心5～10min；Preferably, the centrifugation condition is 5-10 min under the condition of 2000-4000 r/min; 优选地，所述乙酸和甲醇的体积比为1:(8～10)；Preferably, the volume ratio of the acetic acid and methanol is 1:(8～10); 优选地，所述索氏提取后还包括甲醇洗脱。Preferably, methanol elution is also included after the Soxhlet extraction. 9.权利要求1～8任一项所述一种醚菌酯类分子印迹聚合物的制备方法制备得到的醚菌酯类分子印迹聚合物微球。9. The pyraclostrobin-based molecularly imprinted polymer microspheres prepared by the method for preparing a pyraclostrobin-based molecularly imprinted polymer according to any one of claims 1 to 8. 10.一种固相萃取柱，其以权利要求9所述的醚菌酯类分子印迹聚合物微球为填料。10. A solid-phase extraction column, which uses the pyraclostrobin-based molecularly imprinted polymer microspheres of claim 9 as fillers.
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