CN107353365A - The preparation method and applications of imidaclothiz molecular blotting polymer microsphere - Google Patents
The preparation method and applications of imidaclothiz molecular blotting polymer microsphere Download PDFInfo
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Abstract
The invention belongs to molecularly imprinted polymer technical field, more particularly to a kind of preparation method of imidaclothiz molecular blotting polymer microsphere, comprise the following steps：α methacrylic acids, imidaclothiz are dissolved in solvent, ultrasound, crosslinking agent is then added, is filled with nitrogen deoxygenation, sealing, prepolymerization, then prepolymer is transferred in polymer reactor, add column layer chromatography silicone rubber and initiator, fully vibration, is filled with nitrogen deoxygenation, then seals again；Mixture after sealing is reacted in thermostatic control oscillator vibration, is cooled down, is placed in refrigerator, adds excessive hydrofluoric acid, is stirred, is filtered, washing, dry solid sediment；By solid sediment mixed solvent surname extraction, until washing lotion high performance liquid chromatography GC-MS can not detect imidaclothiz molecule, stop washing, dry to constant weight.Filler using the imidaclothiz molecular blotting polymer microsphere as SPE posts, for imidaclothiz residues of pesticides situation in monitoring tealeaves, ensure that quality and safety of tea provides technical support.
Description
Technical field
The invention belongs to molecularly imprinted polymer technical field, more particularly to a kind of imidaclothiz molecular blotting polymer microsphere
Preparation method and applications.
Background technology
Imidaclothiz (Imidaclothiz, CAS 105843-36-5, its molecular structural formula are shown below), is a kind of work
Anabasine systemic insecticide for nAChR ligands.Early stage, foreign countries predominantly stayed in reality to the thing Quality Research
Test the room stage, Jiangshan Pesticides ＆ Chemical Co., Ltd., Nantong is taken the lead in its commercialization at home, and chlorine is obtained in October, 2002
Thiophene quinoline active compound and the registration of 10% wettable powder.At present, 10% imidaclothiz wettable agent is registered as on tea tree, controlling object is
Smaller green leaf hopper.
Imidaclothiz molecular structural formula
In June, 2017, national health State Family Planning Commission, the Ministry of Agriculture combine issue national food safety standard with Shi Yao general bureaus《GB
2763-2016 Pesticide MRLs》, China's Pesticide maximum residue limit figureofmerit is by by existing 3650
Increase to 4140, increase 490 newly, but imidaclothiz maximum residual in tealeaves is still the 3mg/kg to limit the quantity temporarily, be exactly because
Not yet to formulate corresponding country or the recommendatory detection method standard of industry.At present on imidaclothiz residues detection side in document
The report of method is simultaneously few.Due to the presence of N- nitroguanidines so that imidaclothiz is volatile, has thermal instability, is not suitable for using gas
Phase chromatogram is analyzed.At present in about crop in the detection method research of imidaclothiz, mainly using dichloromethane, acetic acid second
Ester, the extraction of n-hexane equal solvent, qualitative, quantitative is carried out with liquid chromatogram-UV-detector or liquid chromatography mass combined instrument, but
It is that traditional analysis method clean-up effect is bad, easy contaminated liquid matter combined instrument containing a large amount of uncertain chaff interferences in tealeaves,
And the complex matrices in tealeaves produce interference under UV-detector to imidaclothiz, easily cause false positive results.
In recent years, the detection technique research of imidaclothiz makes some progress, but these methods in actual applications
Common drawback is complex pretreatment, cumbersome, and time-consuming and with high costs.Although at present for imidaclothiz pre-treatment more using solid
Mutually extraction (SPE) technology, although post is wide in variety, lacks high selectivity, easily extract the chaff interference coexisted together, it is right
In the extremely low sample of analytical concentration, enrichment times are limited, do not reach testing requirements.
In view of this, it is necessory to provide a kind of preparation method of imidaclothiz molecular blotting polymer microsphere, molecular engram
Polymer (Molecularly Imprinted Polymers, MIPs) has stronger molecule distinguishability, has antibody-like
Specificity, high selectivity, high intensity the advantages that, be highly suitable as the filler of imidaclothiz molecular adsorbent.By the imidaclothiz
Filler of the molecular blotting polymer microsphere as SPE posts, can be made high selectivity, it is accurate, quick, stably, reliable diuril
Quinoline pre-treatment solid-phase extraction column, for imidaclothiz residues of pesticides situation in monitoring tealeaves, ensure that quality and safety of tea provides technology branch
Hold.
The content of the invention
An object of the present invention is：In view of the shortcomings of the prior art, a kind of imidaclothiz molecular engram polymerization is provided
The preparation method of thing microballoon, molecularly imprinted polymer (Molecularly Imprinted Polymers, MIPs) have stronger
Molecule distinguishability, there is the specificity, high selectivity, high intensity of antibody-like, be highly suitable as imidaclothiz point
The filler of sub- adsorbent.Filler using the imidaclothiz molecular blotting polymer microsphere as SPE posts, can be made high selectivity,
Accurately, quickly, stably, reliable imidaclothiz pre-treatment solid-phase extraction column, for monitoring tealeaves in imidaclothiz residues of pesticides situation, protect
Hinder quality and safety of tea and technical support is provided.
In order to achieve the above object, the present invention adopts the following technical scheme that：
The preparation method of imidaclothiz molecular blotting polymer microsphere, including at least following steps：
The first step, by α-methacrylic acid, imidaclothiz according to (5-10):1 mol ratio is dissolved in solvent, ultrasound, then
Crosslinking agent is added, is filled with nitrogen deoxygenation, is sealed, prepolymerization 8h-16h at 0-4 DEG C, then prepolymer is transferred to the polymerization of plastics cylindricality
In reactor, column layer chromatography silicone rubber and initiator, fully vibration are added, nitrogen deoxygenation is filled with again, then seals；
Second step, the mixture after sealing is reacted into 10h-30h in thermostatic control oscillator vibration at 60 DEG C -80 DEG C, cooled down,
Mixture is placed in 8h-18h in the refrigerator that temperature is 0-4 DEG C, taken out, and adds excessive hydrofluoric acid, stirs 8h- at room temperature
20h, filtering, is washed with deionized water and methanol respectively, is dried, is obtained solid sediment；
3rd step, solid sediment acetic acid, the mixed solvent surname extraction of methanol that second step is obtained, until washing lotion
Imidaclothiz molecule can not be detected with high performance liquid chromatography GC-MS, stops washing, is remained with methanol washing precipitate
Acetic acid, then dried in air dry oven under conditions of 30 DEG C -50 DEG C to constant weight, produce the polymerization of imidaclothiz molecular engram
Thing microballoon.
The a kind of of preparation method as imidaclothiz molecular blotting polymer microsphere of the present invention improves, in the first step, diuril
The amount of the material of quinoline and the volume ratio of solvent are 1mmol:(60-100)mL；Crosslinking agent and the ratio of the amount of the material of imidaclothiz molecule
For (40-60):1；The mass ratio of column layer chromatography silicone rubber and imidaclothiz is (100-500):1；α-methacrylic acid and crosslinking agent
The amount sum of material and the mass ratio of initiator are (100-200) mmol:1g.
The a kind of of preparation method as imidaclothiz molecular blotting polymer microsphere of the present invention improves, described in the first step
Solvent is acetonitrile.
The a kind of of preparation method as imidaclothiz molecular blotting polymer microsphere of the present invention improves, described in the first step
Crosslinking agent is ethylene glycol dimethacrylate.
The a kind of of preparation method as imidaclothiz molecular blotting polymer microsphere of the present invention improves, described in the first step
Initiator is azodiisobutyronitrile.
The a kind of of preparation method as imidaclothiz molecular blotting polymer microsphere of the present invention improves, and the mixing of the 3rd step is molten
Acetic acid, methanol volume ratio are 1 in agent:(8-15).
The a kind of of preparation method as imidaclothiz molecular blotting polymer microsphere of the present invention improves, and the polymerization of plastics cylindricality is anti-
The material for answering device is polypropylene.
The a kind of of preparation method as imidaclothiz molecular blotting polymer microsphere of the present invention improves, column layer chromatography silicone rubber
Average pore size is 20A ° -20000A °.
The imidaclothiz molecular blotting polymer microsphere prepared present invention also offers a kind of method using the present invention is answered
With：Filler using imidaclothiz molecular blotting polymer microsphere as SPE posts, for detecting the imidaclothiz agricultural chemicals of trace.
Relative to prior art, the imidaclothiz molecular blotting polymer microsphere grain shape obtained using the inventive method is advised
Then, size is homogeneous, by using the column layer chromatography silicone rubber of different size size, can reach and change the polymerization of imidaclothiz molecular engram
The purpose of the specific surface area of thing microballoon, so as to improve the adsorptivity of imidaclothiz molecular blotting polymer microsphere, imidaclothiz molecule
Hole in imprinted polymer bead surface structure is advantageous to the enrichment of imidaclothiz.In addition, molecularly imprinted polymer
(Molecularly Imprinted Polymers, MIPs) has stronger molecule distinguishability, has the special of antibody-like
The advantages that property, high selectivity, high intensity, it is highly suitable as the filler of imidaclothiz molecular adsorbent.The imidaclothiz molecule is printed
Filler of the mark polymer microballoon as SPE posts, high selectivity, accurate, quick, stably, locate before reliable imidaclothiz can be made
Solid-phase extraction column is managed, for imidaclothiz residues of pesticides situation in monitoring tealeaves, ensures that quality and safety of tea provides technical support.Practice
Show, during filler of the imidaclothiz molecular blotting polymer microsphere obtained using the inventive method as SPE posts, imidaclothiz it is flat
The equal rate of recovery is 95.61%.
Brief description of the drawings
Fig. 1 is that the ESEM of 5000 times of the gained imidaclothiz molecular blotting polymer microsphere of the embodiment of the present invention 1 amplification shows
Micro- photo.
Fig. 2 is that the single microballoon of the gained imidaclothiz molecular blotting polymer microsphere of the embodiment of the present invention 1 amplifies 20000 times
ESEM microphoto.
Embodiment
Embodiment 1
A kind of preparation method of imidaclothiz molecular blotting polymer microsphere is present embodiments provided, including at least following step
Suddenly：
The first step, by α-methacrylic acid, imidaclothiz according to 7:1 mol ratio is dissolved in solvent acetonitrile, wherein, imidaclothiz
The amount of material and the volume ratio of solvent be 1mmol:80mL, then add crosslinking agent ethylene glycol dimethacrylate, crosslinking
The mol ratio of agent and imidaclothiz is 45:1, then the ultrasonic 5min under conditions of power is 65W, is filled with nitrogen deoxygenation, seals, 0-
Prepolymerization 12h at 4 DEG C, then prepolymer is transferred in polypropylene plastics cylindricality polymer reactor, add column layer chromatography silicone rubber and
The amount sum of the material of initiator, α-methacrylic acid and crosslinking agent and the mass ratio of initiator azodiisobutyronitrile are
130mmol:The mass ratio of 1g, column layer chromatography silicone rubber and imidaclothiz is 500:1, the average pore size of column layer chromatography silicone rubber is
2000A °, fully vibration, are filled with nitrogen deoxygenation, then seal again；
Second step, the mixture after sealing is reacted into 24h in thermostatic control oscillator vibration at 65 DEG C, cooled down, by mixture
18h in the refrigerator that temperature is 2 DEG C is placed in, is taken out, and adds excessive hydrofluoric acid, at room temperature magnetic agitation 12h, is filtered, respectively
Washed twice with deionized water and methanol, dry, obtain solid sediment；
3rd step, the solid sediment acetic acid that second step is obtained, mixed solvent (acetic acid, the methanol volume ratio of methanol
For 1:9) surname extraction, until washing lotion high performance liquid chromatography GC-MS can not detect imidaclothiz molecule, washing is stopped,
With the acetic acid remained in methanol washing precipitate, then dry to constant weight, produce under conditions of 40 DEG C in air dry oven
Imidaclothiz molecular blotting polymer microsphere.
As seen from Figure 1, using the imidaclothiz drug molecule imprinted polymer microballoon obtained by the method for the present embodiment
Grain shape rule, size is homogeneous, the specific surface area of imidaclothiz drug molecule imprinted polymer microballoon is added, so as to improve
The adsorptivity of imidaclothiz drug molecule imprinted polymer microballoon.As shown in Figure 2 in imidaclothiz drug molecule imprinted polymer microballoon
There is hole in surface texture, this hole is advantageous to the enrichment of imidaclothiz agricultural chemicals in trace detection imidaclothiz.
Embodiment 2
A kind of preparation method of imidaclothiz molecular blotting polymer microsphere is present embodiments provided, including at least following step
Suddenly：
The first step, by α-methacrylic acid, imidaclothiz according to 9:1 mol ratio is dissolved in solvent acetonitrile, wherein, imidaclothiz
The amount of material and the volume ratio of solvent be 1mmol:70mL, then add crosslinking agent ethylene glycol dimethacrylate, crosslinking
The mol ratio of agent and imidaclothiz is 55:1, then the ultrasonic 3min under conditions of power is 70W, is filled with nitrogen deoxygenation, seals, 0-
Prepolymerization 18h at 4 DEG C, then prepolymer is transferred in polypropylene plastics cylindricality polymer reactor, add column layer chromatography silicone rubber and
The amount sum of the material of initiator, α-methacrylic acid and crosslinking agent and the mass ratio of initiator azodiisobutyronitrile are
150mmol:The mass ratio of 1g, column layer chromatography silicone rubber and imidaclothiz is 400:1, the average pore size of column layer chromatography silicone rubber is
5000A °, fully vibration, are filled with nitrogen deoxygenation, then seal again；
Second step, the mixture after sealing is reacted into 14h in thermostatic control oscillator vibration at 75 DEG C, cooled down, by mixture
16h in the refrigerator that temperature is 3 DEG C is placed in, is taken out, and adds excessive hydrofluoric acid, at room temperature magnetic agitation 15h, is filtered, respectively
Washed twice with deionized water and methanol, dry, obtain solid sediment；
3rd step, the solid sediment acetic acid that second step is obtained, mixed solvent (acetic acid, the methanol volume ratio of methanol
For 1:12) surname extraction, until washing lotion high performance liquid chromatography GC-MS can not detect imidaclothiz molecule, stop washing
Wash, with the acetic acid remained in methanol washing precipitate, then dried in air dry oven under conditions of 45 DEG C to constant weight, i.e.,
Obtain imidaclothiz molecular blotting polymer microsphere.
Embodiment 3
A kind of preparation method of imidaclothiz molecular blotting polymer microsphere is present embodiments provided, including at least following step
Suddenly：
The first step, by α-methacrylic acid, imidaclothiz according to 6:1 mol ratio is dissolved in solvent acetonitrile, wherein, imidaclothiz
The amount of material and the volume ratio of solvent be 1mmol:90mL, then add crosslinking agent ethylene glycol dimethacrylate, crosslinking
The mol ratio of agent and imidaclothiz is 58:1, then the ultrasonic 4min under conditions of power is 75W, is filled with nitrogen deoxygenation, seals, 0-
Prepolymerization 10h at 4 DEG C, then prepolymer is transferred in polypropylene plastics cylindricality polymer reactor, add column layer chromatography silicone rubber and
The amount sum of the material of initiator, α-methacrylic acid and crosslinking agent and the mass ratio of initiator azodiisobutyronitrile are
180mmol:The mass ratio of 1g, column layer chromatography silicone rubber and imidaclothiz is 300:1, the average pore size of column layer chromatography silicone rubber is 100A °,
Fully vibration, is filled with nitrogen deoxygenation, then seals again；
Second step, the mixture after sealing is reacted into 18h in thermostatic control oscillator vibration at 65 DEG C, cooled down, by mixture
14h in the refrigerator that temperature is 0 DEG C is placed in, is taken out, and adds excessive hydrofluoric acid, at room temperature magnetic agitation 16h, is filtered, respectively
Washed twice with deionized water and methanol, dry, obtain solid sediment；
3rd step, the solid sediment acetic acid that second step is obtained, mixed solvent (acetic acid, the methanol volume ratio of methanol
For 1:14) surname extraction, until washing lotion high performance liquid chromatography GC-MS can not detect imidaclothiz molecule, stop washing
Wash, with the acetic acid remained in methanol washing precipitate, then dried in air dry oven under conditions of 50 DEG C to constant weight, i.e.,
Obtain imidaclothiz molecular blotting polymer microsphere.
Embodiment 4
A kind of preparation method of imidaclothiz molecular blotting polymer microsphere is present embodiments provided, including at least following step
Suddenly：
The first step, by α-methacrylic acid, imidaclothiz according to 7.5:1 mol ratio is dissolved in solvent acetonitrile, wherein, diuril
The amount of the material of quinoline and the volume ratio of solvent are 1mmol:75mL, crosslinking agent ethylene glycol dimethacrylate is then added, handed over
The mol ratio for joining agent and imidaclothiz is 42:1, then the ultrasonic 6min under conditions of power is 75W, is filled with nitrogen deoxygenation, seals,
Prepolymerization 9h at 0-4 DEG C, then prepolymer is transferred in polypropylene plastics cylindricality polymer reactor, add column layer chromatography silicone rubber and
The amount sum of the material of initiator, α-methacrylic acid and crosslinking agent and the mass ratio of initiator azodiisobutyronitrile are
110mmol:The mass ratio of 1g, column layer chromatography silicone rubber and imidaclothiz is 200:1, the average pore size of column layer chromatography silicone rubber is
1000A °, fully vibration, are filled with nitrogen deoxygenation, then seal again；
Second step, the mixture after sealing is reacted into 25h in thermostatic control oscillator vibration at 68 DEG C, cooled down, by mixture
12h in the refrigerator that temperature is 4 DEG C is placed in, is taken out, and adds excessive hydrofluoric acid, at room temperature magnetic agitation 11h, is filtered, respectively
Washed twice with deionized water and methanol, dry, obtain solid sediment；
3rd step, the solid sediment acetic acid that second step is obtained, mixed solvent (acetic acid, the methanol volume ratio of methanol
For 1:13) surname extraction, until washing lotion high performance liquid chromatography GC-MS can not detect imidaclothiz molecule, stop washing
Wash, with the acetic acid remained in methanol washing precipitate, then dried in air dry oven under conditions of 35 DEG C to constant weight, i.e.,
Obtain imidaclothiz molecular blotting polymer microsphere.
Embodiment 5
A kind of preparation method of imidaclothiz molecular blotting polymer microsphere is present embodiments provided, including at least following step
Suddenly：
The first step, by α-methacrylic acid, imidaclothiz according to 8.5:1 mol ratio is dissolved in solvent acetonitrile, wherein, diuril
The amount of the material of quinoline and the volume ratio of solvent are 1mmol:95mL, crosslinking agent ethylene glycol dimethacrylate is then added, handed over
The mol ratio for joining agent and imidaclothiz is 53:1, then the ultrasonic 3min under conditions of power is 85W, is filled with nitrogen deoxygenation, seals,
Prepolymerization 9h at 0-4 DEG C, then prepolymer is transferred in polypropylene plastics cylindricality polymer reactor, add column layer chromatography silicone rubber and
The amount sum of the material of initiator, α-methacrylic acid and crosslinking agent and the mass ratio of initiator azodiisobutyronitrile are
170mmol:The mass ratio of 1g, column layer chromatography silicone rubber and imidaclothiz is 100:1, the average pore size of column layer chromatography silicone rubber is
12000A °, fully vibration, are filled with nitrogen deoxygenation, then seal again；
Second step, the mixture after sealing is reacted into 22h in thermostatic control oscillator vibration at 78 DEG C, cooled down, by mixture
8h in the refrigerator that temperature is 1 DEG C is placed in, is taken out, and adds excessive hydrofluoric acid, at room temperature magnetic agitation 13h, filtering, is used respectively
Deionized water and methanol wash twice, and dry, obtain solid sediment；
3rd step, the solid sediment acetic acid that second step is obtained, mixed solvent (acetic acid, the methanol volume ratio of methanol
For 1:15) surname extraction, until washing lotion high performance liquid chromatography GC-MS can not detect imidaclothiz molecule, stop washing
Wash, with the acetic acid remained in methanol washing precipitate, then dried in air dry oven under conditions of 38 DEG C to constant weight, i.e.,
Obtain imidaclothiz molecular blotting polymer microsphere.
Comparative example 1
This comparative example is not added with the blank polymer microballoon of imidaclothiz microsphere, its preparation side using the preparation of silica gel method is sacrificed
Method is as follows：
The first step, 0.70mmol α-methacrylic acids are dissolved in 8mL acetonitriles, add ethyleneglycol dimethacrylate
Ester, under the conditions of power is 65W, ultrasonic 5min, fully vibration, sealed after obtaining mixture, then inflated with nitrogen deoxygenation, in 0-4 DEG C
Prepolymerization 12h, a certain proportion of initiator and silica gel are then added, vibrate, be filled with nitrogen, sealed；Wherein, α-methacrylic acid
It is 130mmol with the amount of the total material of ethylene glycol dimethacrylate and the mass ratio of azobisisobutyronitrile:1g.
Second step, the mixture after sealing is reacted into 24h in 65 DEG C of thermostatic control oscillator vibrations, is subsequently placed in cold in refrigerator
But, then the inward hydrofluoric acid and magneton of excessive addition, magnetic agitation 12h, filtering, washed respectively with deionized water and methanol respectively
Twice；
3rd step, the sediment acetic acid methanol volume ratio that second step is obtained are 1:9 solution surname extraction 12h, then use
Methanol washing removes the acetic acid remained in sediment, is then dried under conditions of 40 DEG C to constant weight, it is micro- to produce blank polymer
Ball.
The blank of the imidaclothiz molecular blotting polymer microsphere and the gained of comparative example 1 that weigh the gained of embodiment 1 to 5 respectively is gathered
Compound microballoon 200.00mg, then it is respectively placed in six ground conical flasks, then 5mL is separately added into six ground conical flasks
200mg/L imidaclothiz acetonitrile mixed standard solution, stands 12h, then filters at room temperature, by filtrate constant volume, using the U.S.
Waters company's T QD liquid chromatography mass instrument is tested filtrate, parallel determination 3 times, is averaged, and calculated equilibrium is inhaled respectively
The concentration of free imidaclothiz medicine in attached liquid, calculates the absorption of imidaclothiz molecularly imprinted polymer and blank polymer to imidaclothiz
(imidaclothiz molecular blotting polymer microsphere, blank polymer microballoon are filled out respectively as SPE posts for amount Q (mg/g) and the rate of recovery
Material), result of calculation such as table 1 (adsorbance contrast table) and table 2 (average recovery rate contrast table)：
Table 1：The suction of the imidaclothiz molecularly imprinted polymer of embodiment 1 to 5 and the blank polymer of comparative example 1 to imidaclothiz
Attached measurement test result.
| Group | Imidaclothiz adsorbance Q (mg/g) | Relative standard deviation RSD (%) |
| Embodiment 1 | 2.3332 | 3.7 |
| Embodiment 2 | 1.8270 | 7.8 |
| Embodiment 3 | 1.7544 | 9.2 |
| Embodiment 4 | 2.4598 | 7.3 |
| Embodiment 5 | 1.9032 | 7.8 |
| Comparative example 1 | 0.5329 | 9.1 |
Found out by table 1, suction of the imidaclothiz molecular blotting polymer microsphere prepared using the method for the present invention to imidaclothiz
Attached amount is higher than the adsorbance of blank polymer, i.e., the imidaclothiz molecular blotting polymer microsphere prepared using the method for the present invention
There can be higher absorption property to imidaclothiz.
Table 2：The imidaclothiz molecularly imprinted polymer of embodiment 1 to 5 and the blank polymer of comparative example 1 are put down to imidaclothiz
Equal rate of recovery test result.
| Polymer | Imidaclothiz average recovery rate (%) | Relative standard deviation (%) |
| Embodiment 1 | 95.61 | 3.2 |
| Embodiment 2 | 84.83 | 7.2 |
| Embodiment 3 | 79.66 | 9.4 |
| Embodiment 4 | 90.32 | 6.9 |
| Embodiment 5 | 85.08 | 8.2 |
| Comparative example 1 | 71.04 | 5.6 |
| C18 posts (55 μm, 70A) | 59.68 | 7.3 |
The imidaclothiz molecular blotting polymer microsphere found out by table 2 by the use of gained of the invention is used as SPE column packings, imidaclothiz
Average recovery rate be 95.61%, imidaclothiz molecular blotting polymer microsphere as SPE posts compared to C18 posts and blank polymerization
Thing microballoon is compared as NIP-SPE posts and the rate of recovery of imidaclothiz is greatly improved.
The announcement and teaching of book according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and changed.Therefore, the invention is not limited in embodiment disclosed and described above, to the present invention's
Some modifications and changes should also be as falling into the scope of the claims of the present invention.In addition, although used in this specification
Some specific terms, but these terms are merely for convenience of description, do not form any restrictions to the present invention.
Claims (9)
1. the preparation method of imidaclothiz molecular blotting polymer microsphere, it is characterised in that including at least following steps：
The first step, by α-methacrylic acid, imidaclothiz according to (5-10):1 mol ratio is dissolved in solvent, ultrasound, is then added
Crosslinking agent, nitrogen deoxygenation is filled with, sealed, prepolymerization 8h-16h at 0-4 DEG C, then prepolymer is transferred to plastics cylindricality polymerisation
In device, column layer chromatography silicone rubber and initiator, fully vibration are added, nitrogen deoxygenation is filled with again, then seals；
Second step, the mixture after sealing is reacted into 10h-30h in thermostatic control oscillator vibration at 60 DEG C -80 DEG C, cooled down, will be mixed
Compound is placed in 8h-18h in the refrigerator that temperature is 0-4 DEG C, takes out, and adds excessive hydrofluoric acid, stirs 8h-20h, mistake at room temperature
Filter, is washed with deionized water and methanol respectively, is dried, is obtained solid sediment；
3rd step, solid sediment acetic acid, the mixed solvent surname extraction of methanol that second step is obtained, until washing lotion is high
Effect liquid phase chromatogram GC-MS can not detect imidaclothiz molecule, stop washing, with the second remained in methanol washing precipitate
Acid, then dried in air dry oven under conditions of 30 DEG C -50 DEG C to constant weight, it is micro- to produce imidaclothiz molecularly imprinted polymer
Ball.
2. the preparation method of imidaclothiz molecular blotting polymer microsphere according to claim 1, it is characterised in that the first step
In, the amount of the material of imidaclothiz and the volume ratio of solvent are 1mmol:(60-100)mL；The material of crosslinking agent and imidaclothiz molecule
The ratio of amount be (40-60):1；The mass ratio of column layer chromatography silicone rubber and imidaclothiz is (100-500):1；α-methacrylic acid and
The amount sum of the material of crosslinking agent and the mass ratio of initiator are (100-200) mmol:1g.
3. the preparation method of imidaclothiz molecular blotting polymer microsphere according to claim 1, it is characterised in that the first step
Described in solvent be acetonitrile.
4. the preparation method of imidaclothiz molecular blotting polymer microsphere according to claim 1, it is characterised in that the first step
Described in crosslinking agent be ethylene glycol dimethacrylate.
5. the preparation method of imidaclothiz molecular blotting polymer microsphere according to claim 1, it is characterised in that the first step
Described in initiator be azodiisobutyronitrile.
6. the preparation method of imidaclothiz molecular blotting polymer microsphere according to claim 1, it is characterised in that the 3rd step
In the mixed solvent acetic acid, methanol volume ratio be 1:(8-15).
7. the preparation method of imidaclothiz molecular blotting polymer microsphere according to claim 1, it is characterised in that plastic column
The material of shape polymer reactor is polypropylene.
8. the preparation method of imidaclothiz molecular blotting polymer microsphere according to claim 1, it is characterised in that post is layer by layer
The average pore size for analysing silica gel is 20A ° -20000A °.
9. the application of imidaclothiz molecular blotting polymer microsphere prepared by a kind of claim 1, it is characterised in that by imidaclothiz point
Filler of the sub- imprinted polymer microballoon as SPE posts, for detecting the imidaclothiz agricultural chemicals of trace.
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| CN109593229A (en) * | 2018-11-30 | 2019-04-09 | 深圳市中鼎检测技术有限公司 | The preparation method and applications of diquat dibromide molecular blotting polymer microsphere |
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Application publication date: 20171117 |