CN102070739A - Method for preparing cyhalothrin molecular imprinting polymer microspheres - Google Patents

Method for preparing cyhalothrin molecular imprinting polymer microspheres Download PDF

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CN102070739A
CN102070739A CN2010105686565A CN201010568656A CN102070739A CN 102070739 A CN102070739 A CN 102070739A CN 2010105686565 A CN2010105686565 A CN 2010105686565A CN 201010568656 A CN201010568656 A CN 201010568656A CN 102070739 A CN102070739 A CN 102070739A
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cyhalothrin
lambda
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梁晓
郭逸蓉
王阳阳
桂文君
刘毅华
朱国念
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Zhejiang University ZJU
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Abstract

The invention discloses a method for preparing cyhalothrin molecular imprinting polymer microspheres, which comprises the following steps of: 1) dissolving cyhalothrin and functional monomer serving as template molecules into a pore forming solvent; 2) adding cross linker and initiator into the obtained solution, introducing nitrogen to remove oxygen and sealing, and then placing the solution in an oscillator for heating reaction; 3) centrifuging the obtained reaction product, and re-dispersing the collected polymer in an extract in a volume ratio of methanol to acetic acid of 8.5-9.5: 1; 4) ultrasonically extracting the polymer suspension, centrifuging, and repeatedly washing and centrifuging the obtained sediment in turn; and 5) washing the template molecule-free polymer obtained in the step 4) to be neutral by using methanol, performing suction-filtration, and performing vacuum drying to obtain the cyhalothrin molecular imprinting polymer microspheres. The polymer microspheres obtained by the method have good selective identification function and high bonding capacity for the cyhalothrin.

Description

The preparation method of lambda-cyhalothrin molecular blotting polymer microsphere
Technical field
The present invention relates to a kind of method that directly prepares the lambda-cyhalothrin molecular blotting polymer microsphere by the precipitator method.
Background technology
(commodity are called cyhalothrin to lambda-cyhalothrin, lambda-cyhalothrin) be (S)-alcohol-(Z)-1R-cis-acid with (R)-alcohol-(Z)-1S-cis-acid[1: 1] mixture, it is as typical s-generation pyrethroid pesticide, have that insecticidal action is fast, the lasting period is long, the characteristics of efficient, low toxicity and low residue, is that one of principal item of mite is killed in current domestic and international farming, forestry deinsectization.It to be to tag and stomach poison function, perviousness is arranged and does not have systemic action, can prevent and treat lepidopteran, Hemiptera, Coleoptera and mite pest effectively, but to the high poison of hydrocoles such as fishes and shrimps, silkworm and honeybee.Some toxicity reports about lambda-cyhalothrin are also arranged so far, as there are some researches show that lambda-cyhalothrin might cause the sexual function imbalance of male rat; Also have scholar's latest find lambda-cyhalothrin to have the potential neurotoxicity.Because the long-term of lambda-cyhalothrin is extensive use of, its residue problem in agricultural-food and environment is subjected to people's attention day by day.The main detection method of this medicine is a vapor-phase chromatography at present, though method sensitivity is higher, the sample pre-treatments step is more, wastes time and energy relatively, especially the retention analysis in the complex matrices sample.Therefore, this just need seek determinand is had the pre-treatment purifying method of highly selective.
Molecular imprinting has been considered to prepare the effective means of highly selective separating medium.As new functional macromolecule material, and molecularly imprinted polymer (molecularly imprinted polymer, MIP) with the separating or analyze medium and compare of routine, its outstanding advantage is that separated object or analyte are had higher selectivity and affinity; Compare with biological active materials, have easy to prepare, better tolerance again, characteristics such as can reuse.So far, the agricultural chemicals MIPs of report mainly concentrates on triazines and sulfonylurea herbicide both at home and abroad, also has the MIPs of some organophosphorus insecticides, but very few for the synthetic report of pyrethroid pesticide MIPs.And agricultural chemicals MIPs adopts traditional mass polymerization preparation mostly at present, and this is that experimental implementation is simple because this method condition is easy to control; But its shortcoming is also obvious, mainly is that the bulk polymer post-processing operation is tediously long, loaded down with trivial details, and the circulation of template wash-out is many, the cycle is long, and it is irregular to pulverize the gained coating of particles, causes all once relatively poor of bonding properties, and this has just limited to the application prospect of this method.
According to the literature, compare with mass polymerization, the MIPs microballoon of some template molecule that the employing precipitation polymerization prepares also has the specific recognition performance of bigger binding capacity and Geng Gao.As Q.Z.Feng, L.X.Zhao, B.L.Chu, et al., Synthesis and binding site characteristics of 2,4,6-trichlorophenol-imprinted polymers.Analytical and Bioanalytical Chemistry 392 (2008) 1419-1429. (2,4, the preparation of 6-Trichlorophenol molecularly imprinted polymer and binding site feature thereof are analyzed and the bioanalysis chemistry).But for concrete template molecule, how the research for preparing corresponding MIPs by the precipitator method still need be carried out one by one.And at present, do not see the research report that directly prepares lambda-cyhalothrin MIPs microballoon with the precipitation polymerization single stage method as yet in external.
Summary of the invention
Problems such as the technical problem to be solved in the present invention provides a kind of preparation method of lambda-cyhalothrin molecular blotting polymer microsphere, and irregular and bonding properties is not good enough with the imprinted polymer particle that solves the preparation of traditional mass polymerization; Adopt the polymer microballoon of the inventive method gained that lambda-cyhalothrin is had good selectivity recognition function and bigger binding capacity, can be as sorbing material at lambda-cyhalothrin and analog thereof.
In order to solve the problems of the technologies described above, the invention provides a kind of preparation method of lambda-cyhalothrin molecular blotting polymer microsphere, may further comprise the steps successively:
1), will be dissolved in the porogenic solvents as the lambda-cyhalothrin and the function monomer of template molecule, leave standstill 1~4h under the room temperature, lysate; The mol ratio of function monomer and lambda-cyhalothrin is 3~5: 1, and the porogenic solvents volume is 80~120ml: 1mmol with the ratio of lambda-cyhalothrin mole;
2), in the lysate of step 1) gained, add linking agent and initiator, behind the mixing mixed solution; With mixed solution sealing after letting nitrogen in and deoxidizing is handled, place vibrator to be heated to 45~65 ℃ then, reaction 22~26h under the rotating speed of 30~50rpm; The mol ratio of linking agent and function monomer is 4.5~5.5: 1, and the consumption of initiator is 1.8~2.2% of a polymerisable double bonds total moles;
That is the consumption of initiator=(the mole number * 2 of the mole number+linking agent of function monomer) * (1.8%~2.2%);
The polymerisable double bonds total moles is that translation gets according to foreign language document " With respect to the total number of moles of polymerizable double bonds ".Function monomer of the present invention only contains a two key, and linking agent of the present invention contains two two keys; Therefore the consumption of initiator is 1.8~2.2% of a polymerisable double bonds total moles;
3), with step 2) reaction product of gained is centrifugal, collects the polymkeric substance of white precipitate; Polymkeric substance is scattered in methyl alcohol/acetate=8.5~9.5 again: in the extracting solution of 1 volume ratio (v/v), get polymer slurry;
4), with centrifugal after the polymer slurry ultrasonic extraction, the precipitation of gained is washed repeatedly successively with centrifugal, in the centrifuged supernatant of final gained, do not detect lambda-cyhalothrin till, final gained be precipitated as the polymkeric substance that does not contain template molecule; Washing used washings is methyl alcohol/acetate=8.5~9.5: 1 volume ratio (v/v) mixed solvent;
5), the polymkeric substance that does not contain template molecule of step 4) gained is washed till neutrality with methyl alcohol, suction filtration final vacuum drying obtains the lambda-cyhalothrin molecular blotting polymer microsphere.
Improvement as the preparation method of lambda-cyhalothrin molecular blotting polymer microsphere of the present invention: function monomer can be selected methacrylic acid (MAA), vinylformic acid (AA), 2-hydroxyethyl-methacrylate (HEMA), Methacrylamide (MAAM) or acrylamide (AAM) or the like for use; Porogenic solvents can be selected acetonitrile/toluene=2.5~3.5 for use: the mixed solvent of 1 (v/v); Linking agent can be selected for use divinylbenzene (DVB); Initiator can be selected Diisopropyl azodicarboxylate (AIBN) or 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABDV) or the like for use.
Further improvement as the preparation method of lambda-cyhalothrin molecular blotting polymer microsphere of the present invention: earlier mixed solution is carried out ultrasonic degas 8~12min step 2), place logical nitrogen bubbling deoxygenation 8~12min on 0~4 ℃ of ice-water bath then.
Further improvement as the preparation method of lambda-cyhalothrin molecular blotting polymer microsphere of the present invention: adopt HPLC method or GC method to detect whether contain lambda-cyhalothrin in the centrifuged supernatant in the step 4).
Adopt the inventive method preparation and be a kind of micron-sized lambda-cyhalothrin molecularly imprinted polymer (lambda-cyhalothrin MIPs) microballoon.
Preparation method of the present invention is easy and simple to handle, reaction conditions is easily controlled, the particle diameter of prepared lambda-cyhalothrin MIPs is about 1-8 μ m, the microballoon homogeneity is better, can be as sorbing material at lambda-cyhalothrin and analog thereof, and be expected to satisfy multiple demands of applications, as solid phase extraction column, chromatographic column and chemical sensor etc.; Therefore the lambda-cyhalothrin molecular blotting polymer microsphere of gained of the present invention has application prospect characteristics widely.
Description of drawings
Below in conjunction with accompanying drawing the specific embodiment of the present invention is described in further detail.
Fig. 1 is the sem photograph of the lambda-cyhalothrin MIP1 of embodiment 1 gained;
Fig. 2 is the sem photograph of the lambda-cyhalothrin MIP2 of embodiment 2 gained;
Fig. 3 is the sem photograph of the lambda-cyhalothrin MIP3 of embodiment 3 gained.
Embodiment
Below embodiments of the invention are elaborated.Wherein, for the lambda-cyhalothrin Determination on content, high density adopts high performance liquid chromatography (HPLC), and lower concentration adopts vapor-phase chromatography (GC).
The HPLC condition: C18 chromatographic column (4.6mm * 150mm * 5 μ m) is a moving phase with acetonitrile/water=90/10 (v/v), and flow velocity 1mL/min, sample size are 20 μ L, and the detection wavelength is 278nm.(limit of detection LOD) is 0.1 μ g/mL to the method minimum detectability.
GC condition: capillary chromatographic column HP-5 (30m * 0.53mm * 0.88 μ m); The injection port gasification temperature is 250 ℃; Electron capture detector (ECD) temperature is 300 ℃; Column temperature heating schedule----starting temperature is 80 ℃ of maintenance 1min, and the speed with 30 ℃/min rises to 220 ℃ then, keeps 0min, and the speed with 10 ℃/min rises to 260 ℃ again, keeps 15min; Sample size is 1 μ L (a not split stream sampling); The make-up gas flow is 30mL/min; Column cap is pressed and is 0.4kg/cm2.Method minimum detectability LOD is 0.005 μ g/mL.
The preparation method of embodiment 1, a kind of lambda-cyhalothrin molecular blotting polymer microsphere, carry out following steps successively:
Take by weighing lambda-cyhalothrin (as template molecule) 0.5mmol and place the 150mL round-bottomed flask, with 50mL acetonitrile/toluene=3: 1 (v/v) dissolving, add 2mmol vinylformic acid (AA) again after, 1h is left standstill in mixing vibration back under room temperature.Add linking agent DVB 10mmol and initiator A IBN 0.44mmol mixing then, get mixed solution.Earlier, place logical nitrogen bubbling deoxygenation 10min on the 0-4 ℃ of ice-water bath again with mixed solution ultrasonic (ultrasonic frequency is 40KHz) degassing 10min, strict seal be placed on constant temperature oscillator reaction 24h (60 ℃, 50rpm).After reaction stops, centrifugal (10000rpm 15min) collects the sedimentary polymkeric substance that is white in color, the polymkeric substance of this white precipitate is scattered in again in the extracting solution of methyl alcohol/acetate=9: 1 (v/v) of 50mL, polymer slurry.That is, the mixed solvent with methyl alcohol/acetate=9: 1 (v/v) extracts template molecule.
(ultrasonic frequency is 40KHz with the polymer slurry ultrasonic extraction, 25 ℃, 30min) centrifugal (the 10000rpm in back, 15min), the precipitation of gained is washed repeatedly successively with centrifugal, do not detect lambda-cyhalothrin in the centrifuged supernatant of final gained till (HPLC method or GC method), the precipitation of final centrifugal gained is the polymkeric substance that does not contain template molecule.Washing used washings is methyl alcohol/acetate=9: 1 (v/v) mixed solvents.
Again the above-mentioned polymkeric substance that does not contain template molecule is washed till neutrality with methyl alcohol, the dry 24h of suction filtration final vacuum (50 ℃) obtains the lambda-cyhalothrin molecular blotting polymer microsphere of solid powdery, about 1.39g, called after MIP1.
Simultaneously, all the other steps are identical with the preparation method of the MIP1 of the foregoing description 1 except that not adding the template molecule for corresponding non-imprinted polymer (NIP1) synthetic, must NIP1.The synthesizing formula and the name of concrete polymkeric substance see Table 1.
The electron-microscope scanning figure (SEM) of the MIP1 microballoon of embodiment 1 gained sees Fig. 1.
Measure the particle meso-position radius of polymkeric substance MIP1 and NIP1 respectively with the laser particle size distribution instrument, the results are shown in Table 2; Specific surface area and porosity with lacunarity analysis instrument mensuration polymkeric substance MIP1 and NIP1 the results are shown in Table 2.From the result, this base polymer (comprising MIP1 and NIP1) is spherical basically, and specific surface area is bigger, and the volume of contained micropore is also bigger, helps its absorption to lambda-cyhalothrin.
The synthesizing formula of the lambda-cyhalothrin MIPs/NIPs of table 1 precipitation polymerization preparation
Figure BSA00000368825600041
Specific surface area and the lacunarity analysis of the lambda-cyhalothrin MIPs/NIPs of table 2 precipitation polymerization preparation
Figure BSA00000368825600051
The preparation method of embodiment 2, a kind of lambda-cyhalothrin molecular blotting polymer microsphere, carry out following steps successively:
Take by weighing lambda-cyhalothrin 0.5mmol and place the 150mL round-bottomed flask, with 50mL acetonitrile/toluene=3: 1 (v/v) dissolving, add 2mmol 2-hydroxyethyl-methacrylate (HEMA) again after, leave standstill 1h after the mixing vibration.Add linking agent DVB 10mmol and initiator A IBN 0.44mmol mixing then, get mixed solution.Earlier, place logical nitrogen bubbling deoxygenation 10min on the 0-4 ℃ of ice-water bath again with mixed solution ultrasonic degas 10min, strict seal be placed on constant temperature oscillator reaction 24h (60 ℃, 50rpm).After reaction stops, centrifugal (10000rpm 15min) collects the sedimentary polymkeric substance that is white in color, the polymkeric substance of this white precipitate is scattered in again in the extracting solution of methyl alcohol/acetate=9: 1 (v/v) of 50mL, polymer slurry.That is, the mixed solvent with methyl alcohol/acetate=9: 1 (v/v) extracts template molecule.
(ultrasonic frequency is 40KHz with the polymer slurry ultrasonic extraction, 25 ℃, 30min) centrifugal (the 10000rpm in back, 15min), precipitation to gained is washed and centrifugal (10000rpm repeatedly successively, 15min), in the centrifuged supernatant of final gained, do not detect lambda-cyhalothrin till (HPLC method or GC method), the precipitation of final centrifugal gained is the polymkeric substance that does not contain template molecule.Washing used washings is methyl alcohol/acetate=9: 1 (v/v) mixed solvents.
Again the above-mentioned polymkeric substance that will not contain template molecule is washed till neutrality with methyl alcohol, the dry 24h of suction filtration final vacuum (50 ℃) obtains the lambda-cyhalothrin molecular blotting polymer microsphere of solid powdery, about 1.77g, called after MIP2.
Simultaneously, all the other steps are identical with the preparation method of the foregoing description 2 described MIP2 except that not adding the template molecule for corresponding non-imprinted polymer (NIP2) synthetic, must NIP2.The synthesizing formula and the name of concrete polymkeric substance see Table 1.
The electron-microscope scanning figure (SEM) of the MIP2 microballoon of embodiment 2 gained sees Fig. 2.
Measure the particle meso-position radius of polymkeric substance MIP2 and NIP2 respectively with the laser particle size distribution instrument, the results are shown in Table 2; Specific surface area and porosity with lacunarity analysis instrument mensuration polymkeric substance MIP2 and NIP2 the results are shown in Table 2.From the result, be spherical on this polymer-based, specific surface area is bigger, and the volume of contained micropore is also bigger, helps its absorption to lambda-cyhalothrin.
The preparation method of embodiment 3, a kind of lambda-cyhalothrin molecular blotting polymer microsphere, carry out following steps successively:
Take by weighing lambda-cyhalothrin 0.5mmol and place the 150mL round-bottomed flask, with 50mL acetonitrile/toluene=3: 1 (v/v) dissolving, add 2mmol methacrylic acid (MAA) again after, leave standstill 1h after the mixing vibration.Add linking agent DVB10mmol and initiator A IBN 0.44mmol mixing then, get mixed solution.Earlier, place logical nitrogen bubbling deoxygenation 10min on the 0-4 ℃ of ice-water bath again with mixed solution ultrasonic degas 10min, strict seal be placed on constant temperature oscillator reaction 24h (60 ℃, 50rpm).After reaction stops, centrifugal (10000rpm 15min) collects the sedimentary polymkeric substance that is white in color, the polymkeric substance of this white precipitate is scattered in again in the extracting solution of methyl alcohol/acetate=9: 1 (v/v) of 50mL, polymer slurry.That is, the mixed solvent with methyl alcohol/acetate=9: 1 (v/v) extracts template molecule.
(ultrasonic frequency is 40KHz with the polymer slurry ultrasonic extraction, 25 ℃, 30min) centrifugal (the 10000rpm in back, 15min), precipitation to gained is washed and centrifugal (10000rpm repeatedly successively, 15min), in the centrifuged supernatant of final gained, do not detect lambda-cyhalothrin till (HPLC method or GC method), the precipitation of final centrifugal gained is the polymkeric substance that does not contain template molecule.Washing used washings is methyl alcohol/acetate=9: 1 (v/v) mixed solvents.
Again the above-mentioned polymkeric substance that does not contain template molecule is washed till neutrality with methyl alcohol, the dry 24h of suction filtration final vacuum (50 ℃) obtains the lambda-cyhalothrin molecular blotting polymer microsphere of solid powdery, about 1.58g, called after MIP3.
Simultaneously, corresponding non-imprinted polymer (NIP3) synthetic except that not adding the template molecule, all the other steps are identical with the preparation method of the foregoing description 3 described MIP3.The synthesizing formula and the name of concrete polymkeric substance see Table 1.
The electron-microscope scanning figure (SEM) of the MIP3 microballoon of embodiment 3 gained sees Fig. 3.
Measure the particle meso-position radius of polymkeric substance MIP3 and NIP3 respectively with the laser particle size distribution instrument, the results are shown in Table 2; Specific surface area and porosity with lacunarity analysis instrument mensuration polymkeric substance MIP3 and NIP3 the results are shown in Table 2.From the result, such polymer microballoon regular shape, specific surface area is bigger, and the volume of contained micropore is also bigger, helps its absorption to lambda-cyhalothrin.
Embodiment 4:
With spherical best MIP3 is test materials, carry out balance and investigate the bonding properties of this polymkeric substance: take by weighing imprinted polymer MIP3 and each 10mg of comparison polymer NIP3 thereof lambda-cyhalothrin in conjunction with test, put into the 1.5mL centrifuge tube respectively, adding 1mL lambda-cyhalothrin concentration is the hexane solution of 50ng/mL, sealing back shaken overnight (about 16h, 10 ℃) in quiet mixing tank, centrifugal then (10000rpm, 10min), draw an amount of supernatant and cross film (0.22 μ m organic membrane) back sample introduction.Measure the Cf C of lambda-cyhalothrin in the upper solution with the GC method FreeBefore and after the combination test, the change in concentration of lambda-cyhalothrin in the solution, the absolute bonding properties of calculating polymkeric substance is used in conjunction with per-cent Bound% and is weighed: Bound%=(C Total-C Free)/C Total* 100% (wherein, C Total: total interpolation concentration of target analytes; C Free: in conjunction with the Cf of target analytes in the supernatant of test back); Units of Account quality polymkeric substance is to the binding capacity Q=(C of template molecule then Total-C Free) * V/M (wherein, V: the solution of interpolation (being hexane solution) volume; M: the quality that takes by weighing polymkeric substance); Calculation of distribution coefficient (partition coefficient): K=Q/C again FreeAnd the trace factor (imprinting factor, IF): IF=K MIP/ K NIPFinally obtaining MIP3 is 41% to lambda-cyhalothrin in conjunction with per-cent, the Bound% of NIP3 is 34%, be that MIP3 is higher to the binding capacity of lambda-cyhalothrin than NIP3, IF is near 1.5, this explanation trace effect is better, and the imprinted polymer microballoon has embodied certain selectivity absorption to template molecule.
Simultaneously, close test with above-mentioned junction at equilibrium and investigate the absorption property of MIP3 the analogue of lambda-cyhalothrin.The result shows that MIP3 is 54% to the Bound% of fenvalerate, and MIP3 has reached 60% to the Bound% of Deltamethrin.This illustrates that this imprinted polymer can be as the sorbing material at lambda-cyhalothrin and analog thereof.
Embodiment 5: the MIP3 and the lambda-cyhalothrin MIP for preparing according to the prior art mass polymerization of precipitation polymerization preparation of the present invention are carried out performance relatively.The step of the synthetic lambda-cyhalothrin MIP of substance law is as follows: take by weighing lambda-cyhalothrin 0.5mmol and place Glass tubing, with the dissolving of 3ml acetonitrile, add 2mmol MAA again after, mixing vibration 1h.Add linking agent DVB 10mmol and initiator A IBN 0.25mmol mixing then.With mixed solution ultrasonic degas 5min, place logical nitrogen bubbling deoxygenation 5min on the 0-4 ℃ of ice-water bath more earlier, the strict seal reaction tubes heats 24h at 60 ℃ of gas baths then.React the taking-up bulk polymer that finishes, dry back is ground, is pulverized, and sieve (230-450 order) obtains the particulate matter of about 32-65 μ m.Removed fine particle with 50mL acetone sedimentation decant, and used 50mL methyl alcohol resuspended again, filter dried powder, be bundled into the sample bag with filter paper, the cable-styled extraction template molecule of the mixed solvent 48h (85 ℃ of heating in water bath) of methyl alcohol/acetate=9: 1 (v/v).Take out powder after extraction finishes, filter with pure methyl alcohol (50mL * 2) and remove acetate, last is all over filtering washing with the 50mL polymer solvent.The pressed powder vacuum-drying 24h (50 ℃) that obtains is stored in the dry vessel standby.Simultaneously, make blank with non-imprinted polymer, it is synthetic except that not adding the trace molecule, and all the other steps are identical with the above-mentioned method for preparing embodiment 5.Therefore, two kinds of polymkeric substance that obtain are called after MIP4 and NIP4 respectively.
The balance of carrying out is in conjunction with test (being equal to embodiment 4) then, and obtaining MIP4 is 7% to the Bound% of lambda-cyhalothrin, and the Bound% of NIP4 is 2%, is far smaller than among the embodiment 4 MIP3/NIP3 to the Bound% of lambda-cyhalothrin.It is higher to the binding capacity of lambda-cyhalothrin that these explanation precipitator method prepare imprinted polymer, and application prospect is wider.
At last, it is also to be noted that what more than enumerate only is several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.

Claims (7)

1. the preparation method of lambda-cyhalothrin molecular blotting polymer microsphere is characterized in that may further comprise the steps successively:
1), will be dissolved in the porogenic solvents as the lambda-cyhalothrin and the function monomer of template molecule, leave standstill 1~4h under the room temperature, lysate; The mol ratio of described function monomer and lambda-cyhalothrin is 3~5: 1, and described porogenic solvents volume is 80~120ml: 1mmol with the ratio of lambda-cyhalothrin mole;
2), in the lysate of step 1) gained, add linking agent and initiator, behind the mixing mixed solution; With the sealing after letting nitrogen in and deoxidizing is handled of described mixed solution, place vibrator to be heated to 45~65 ℃ then, reaction 22~26h under the rotating speed of 30~50rpm; The mol ratio of described linking agent and function monomer is 4.5~5.5: 1, and the consumption of initiator is 1.8~2.2% of a polymerisable double bonds total moles;
3), with step 2) reaction product of gained is centrifugal, collects the polymkeric substance of white precipitate; Described polymkeric substance is scattered in methyl alcohol/acetate=8.5~9.5 again: in the extracting solution of 1 volume ratio, get polymer slurry;
4), with centrifugal after the described polymer slurry ultrasonic extraction, the precipitation of gained is washed repeatedly successively with centrifugal, till in the centrifuged supernatant of final gained, not detecting lambda-cyhalothrin, final gained be precipitated as the polymkeric substance that does not contain template molecule; The used washings of described washing is methyl alcohol/acetate=8.5~9.5: 1 volume ratio mixed solvent;
5), the polymkeric substance that does not contain template molecule of step 4) gained is washed till neutrality with methyl alcohol, suction filtration final vacuum drying obtains the lambda-cyhalothrin molecular blotting polymer microsphere.
2. the preparation method of lambda-cyhalothrin molecular blotting polymer microsphere according to claim 1 is characterized in that: described function monomer is methacrylic acid, vinylformic acid, 2-hydroxyethyl-methacrylate, Methacrylamide or acrylamide.
3. the preparation method of lambda-cyhalothrin molecular blotting polymer microsphere according to claim 2 is characterized in that: described porogenic solvents is acetonitrile/toluene=2.5~3.5: the mixed solvent of 1 volume ratio.
4. the preparation method of lambda-cyhalothrin molecular blotting polymer microsphere according to claim 3 is characterized in that: described linking agent is to divinylbenzene.
5. the preparation method of lambda-cyhalothrin molecular blotting polymer microsphere according to claim 4 is characterized in that: described initiator is Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile).
6. the preparation method of lambda-cyhalothrin molecular blotting polymer microsphere according to claim 5 is characterized in that: earlier mixed solution is carried out ultrasonic degas 8~12min described step 2), place logical nitrogen bubbling deoxygenation 8~12min on 0~4 ℃ of ice-water bath then.
7. the preparation method of lambda-cyhalothrin molecular blotting polymer microsphere according to claim 6 is characterized in that: adopt HPLC method or GC method to detect whether contain lambda-cyhalothrin in the centrifuged supernatant in the described step 4).
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102432736A (en) * 2011-09-05 2012-05-02 薛巍 Method for preparing monodisperse molecularly imprinted polymer nano-microspheres
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1583804A (en) * 2004-06-10 2005-02-23 中国农业大学 Use and preparation of molecular track polymer of sulfonyl urea herbicide
CN101173058A (en) * 2007-10-11 2008-05-07 上海交通大学 Method for producing molecular engram polyalcohol microsphere and method for separating enrofloxacin thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1583804A (en) * 2004-06-10 2005-02-23 中国农业大学 Use and preparation of molecular track polymer of sulfonyl urea herbicide
CN101173058A (en) * 2007-10-11 2008-05-07 上海交通大学 Method for producing molecular engram polyalcohol microsphere and method for separating enrofloxacin thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
郭逸蓉: "计算机辅助设计拟除虫菊酯类农药分子印迹聚合物研制", 《中国博士学位论文》 *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102432736A (en) * 2011-09-05 2012-05-02 薛巍 Method for preparing monodisperse molecularly imprinted polymer nano-microspheres
CN102875730A (en) * 2012-10-17 2013-01-16 河南出入境检验检疫局检验检疫技术中心 Method for preparing pyrethroid fragment imprinted polymer
CN102875730B (en) * 2012-10-17 2014-10-22 河南出入境检验检疫局检验检疫技术中心 Method for preparing pyrethroid fragment imprinted polymer
CN103214615A (en) * 2013-04-09 2013-07-24 江苏大学 Preparation method of rare earth doped fluorescent imprinted polymer
CN103214615B (en) * 2013-04-09 2015-03-04 江苏大学 Preparation method of rare earth doped fluorescent imprinted polymer
CN103351449A (en) * 2013-04-11 2013-10-16 江苏大学 Method for preparing porous magnetic imprinting absorption agent through emulsion polymerization
CN103204966A (en) * 2013-04-11 2013-07-17 江苏大学 Method for preparing magnetic/hollow double-shell layer print adsorbent by emulsion polymerization
CN103351449B (en) * 2013-04-11 2015-08-26 江苏大学 The method of porous magnetic trace sorbent material is prepared in letex polymerization
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CN103739846B (en) * 2013-12-27 2016-04-06 江苏大学 A kind of preparation method of quantum dot fluorescence imprinted polymer
CN104761748A (en) * 2014-08-12 2015-07-08 河北科技大学 Preparation method and use of double-template molecular imprinting solid phase extraction membrane
CN104761748B (en) * 2014-08-12 2018-04-03 河北科技大学 The preparation method of double-template molecular engram solid phase extraction film and the application being film-made
CN104297043A (en) * 2014-09-29 2015-01-21 宁波大学 Method for extracting pyrethroid pesticide residues in complex samples by film
CN104297043B (en) * 2014-09-29 2017-07-04 宁波大学 The membrane extraction method of pyrethroid pesticide is remained in a kind of complex sample
CN105017463A (en) * 2015-08-14 2015-11-04 福州市产品质量检验所 Chrysanthemum ester molecularly imprinted polymer preparing method

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