CN114544800B - Method for detecting methoxy acrylic acid ester bactericide by molecular sieve series solid phase extraction - Google Patents
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Abstract
The invention provides a method for detecting methoxy acrylic acid ester bactericides by molecular sieve series solid phase extraction, which specifically comprises the following steps: 1) Synthesizing amino-functionalized SBA-15 molecular sieve powder; 2) Preparing a series solid phase extraction column; 3) Sample collection and pretreatment; 4) And detecting the sample by gas chromatography tandem mass spectrometry. The invention firstly carries out serial solid phase extraction on the amination SBA-15 and the PSA powder, provides a method reference for detecting the residue of methoxy acrylic acid ester bactericides in a laboratory, provides an important theoretical basis for safe production and consumption of agricultural products and formulation and revision of the maximum residue limit, and provides a reference for safe use of the pesticides and residue conditions in the environment; the method has the advantages of simple and quick operation, less reagent consumption, good purification effect, high method sensitivity and the like, and is suitable for detection and analysis of methoxy acrylic acid ester bactericides in complex matrix samples.
Description
Technical Field
The invention relates to a solid phase extraction detection method, in particular to a method for detecting methoxy acrylic acid ester bactericides by molecular sieve series solid phase extraction, belonging to the technical field of analytical chemistry.
Background
The methoxy acrylic acid ester bactericide is a novel agricultural bactericide which has great development potential and market activity after triazole bactericides in the world pesticide world, and is the component with the longest lasting period in the chemical protective bactericides. The bactericide has the characteristics of protection, treatment, eradication, permeation, no cancerogenic and mutagenic effects, and the like, can effectively prevent and treat diseases caused by fungi such as ascomycetes, basidiomycetes, fungi imperfecti, oomycetes and the like, has good systemic activity and wide bactericidal spectrum, has prevention and treatment effects on almost all fungal diseases, has a certain growth regulation effect besides bactericidal activity, has the advantages of broad-spectrum bactericidal property and low toxicity, has wide development prospect due to unique action mechanism, high environmental safety and ultrahigh activity, and is the most popular bactericide in the current pesticide market. However, as the application range of the methoxy acrylic acid ester bactericide on crops is wider and wider, the dosage is also increased, the safety of different components of the bactericide is also greatly different, and the residual risk of the bactericide in crops such as grains and the like and the environment can cause potential harm to human health.
The related research reports for detecting methoxy acrylic acid ester bactericides in China are few, the pretreatment method adopted at present mainly comprises a solid-phase extraction method, a rapid solvent extraction method, a solid-phase microextraction method, a QuEChERS method and the like, and the main instrument methods comprise Gas Chromatography (GC), gas chromatography mass spectrometry (GC-MS), gas chromatography tandem mass spectrometry (GC-MS/MS), liquid Chromatography (LC), liquid chromatography tandem mass spectrometry (LC-MS/MS) and the like. However, the pretreatment method has the advantages that the rapid solvent method has high reagent consumption when detecting and analyzing the methoxy acrylic acid ester bactericides in different matrixes such as grains, soil samples and the like, the QuEChERS has simple and convenient operation but low extraction efficiency, and the solid-phase microextraction method has poor stability, so that the establishment of a rapid, efficient and sensitive scheme system for detecting the methoxy acrylic acid ester bactericides in different matrixes is very necessary. The solid phase extraction method has the advantages of high recovery rate, stable performance and the like, and the method uses the aminated SBA-15 mesoporous molecular sieve as a solid phase extraction column filling material for the first time to purify a complex matrix and detect the content of 8 methoxy acrylic acid ester bactericides by combining GC-MS/MS.
Disclosure of Invention
The invention aims to solve the problems of the existing detection method of the methoxy acrylic acid ester bactericide, and provides a detection method of the methoxy acrylic acid ester bactericide in different matrixes of grain and soil samples, which is based on pretreatment of a serial solid phase extraction method of an amino-functionalized SBA-15 molecular sieve and a PSA material and detection analysis by a GC-MS/MS method.
The technical solution of the invention is as follows: a method for detecting methoxy acrylic acid ester bactericide by molecular sieve series solid phase extraction specifically comprises the following steps:
1) Synthesis of amino-functionalized SBA-15 molecular sieve powder
Weighing 5g of SBA-15 molecular sieve powder into a round bottom distillation flask, adding 100mL of toluene into the flask, and stirring the mixture for 30min; 20mL of 3-aminopropyl triethylsilane is added dropwise, and the mixture is stirred and refluxed for 6 hours at 110 ℃ in a constant temperature magnetic stirrer, and then stirred for 12 hours at room temperature; and washing with absolute ethyl alcohol for multiple times, filtering to obtain white powder, and vacuum drying at 65 ℃ for 12 hours to obtain amino-functionalized SBA-15 molecular sieve powder.
2) Preparation of series solid phase extraction column
21 mL polypropylene solid phase extraction columns are connected in series up and down to serve as a purification device, 100mg of PSA powder is filled in the lower layer solid phase extraction column, 300mg of amino functional SBA-15 molecular sieve powder prepared in the step 1) is filled in the upper layer solid phase extraction column, and both the upper layer and the lower layer are fixedly compacted by a 1mL hydrophobic sieve plate.
3) Sample collection and pretreatment
Collecting 40 parts of just-matured rice and corresponding soil samples from rice planting areas in different areas respectively, wherein each sample is not less than 500g; weighing 100g of uniformly mixed rice sample, shelling by a sheller, grinding, sieving for later use, and storing in a refrigerator at the temperature of minus 20 ℃; grinding and sieving soil for later use, and storing in a refrigerator at the temperature of minus 20 ℃.
Weighing 10g of ground rice or soil sample, putting the ground rice or soil sample into a 50mL centrifuge tube, adding 15mL of acetonitrile and 5g of NaCl, carrying out ultrasonic extraction for 20min, carrying out freeze centrifugation for 5min at 8000r/min, transferring supernatant into a nitrogen blowing bottle, adding 10mL of acetonitrile for repeated extraction once, merging the supernatant, carrying out nitrogen blowing concentration in a nitrogen blowing instrument at 40 ℃ until the supernatant is nearly dry, carrying out redissolution by using 2mL of 1:1 cyclohexane-ethyl acetate solution, and purifying;
activating the solid phase extraction column manufactured in the step 2) by 3mL of 1:1 cyclohexane-ethyl acetate solution, loading, collecting filtrate, eluting for multiple times by using 5mL of 1:1 cyclohexane-ethyl acetate solution, collecting eluent, concentrating, fixing the volume by using 1mL of cyclohexane-ethyl acetate solution, and passing through a 0.22um PTFE filter membrane to be detected.
4) Gas chromatography tandem mass spectrometry detection sample
The gas phase conditions are specifically as follows: sample injection is carried out at 300 ℃ without diversion, sample injection is carried out at high pressure for 1min, the flow control mode is linear speed, the linear speed is 40.2cm/sec, and the column flow rate is 1.2mL/min; the Rtx-5MS chromatographic column is kept at 70 ℃ for 1min, is kept at a temperature of between 15 ℃ and 280 ℃ for 2min, is kept at a temperature of between 30 ℃ and 300 ℃ for 10min, and the sample injection amount is 1uL.
The mass spectrum conditions are specifically as follows: EI ion source 230 ℃, interface temperature 280 ℃, solvent delay 3min, detector voltage 0.6kV relative to tuning voltage, and time-division multiple reaction selection monitoring mode.
Compared with the prior art, the invention has the advantages that:
1) The method firstly carries out serial solid phase extraction on the amination SBA-15 and the PSA powder, provides a method reference for detecting the residue of methoxy acrylic acid ester bactericides in a laboratory, provides an important theoretical basis for safe production and consumption of agricultural products and formulation and revision of the maximum residue limit, and provides a reference for safe use of the pesticides and residue conditions in the environment; 2) The method has the advantages of simple and quick operation, less reagent consumption, good purification effect, high method sensitivity and the like, and is suitable for detection and analysis of methoxy acrylic acid ester bactericides in complex matrix samples.
Drawings
FIG. 1 is a schematic diagram of a series of solid phase extraction columns in accordance with an embodiment of the present invention.
FIG. 2 is a MRM mass spectrum of 8 methacrylate fungicides.
FIG. 3 is a line graph of the effect of the mass of amino SBA-15 on the recovery of the addition mark.
FIG. 4 is a line graph of the effect of PSA mass on the normalized recovery.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings. Examples of the embodiments are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to like or similar elements throughout or elements having like or similar functionality. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
The following disclosure provides many different embodiments, or examples, for implementing different features of the invention. In order to simplify the present disclosure, specific example implementation steps are described below. They are, of course, merely examples and are not intended to limit the invention. Furthermore, the present invention may repeat reference numerals and/or letters in the various examples, which are for the purpose of brevity and clarity, and which do not themselves indicate the relationship between the various embodiments and/or arrangements discussed. In addition, the present invention provides examples of various specific processes and materials, but one of ordinary skill in the art will recognize the application of other processes and/or the use of other materials.
In the description of the present specification, the description with reference to the terms "present example," "specific example," or "some examples," etc., means that a particular feature material or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular feature materials or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The embodiment provides a method for detecting methoxy acrylic acid ester bactericides by molecular sieve series solid phase extraction, which comprises the following specific operation steps:
1) Instrument and reagent
The instrument model and reagent type used in this example are specifically as follows:
instrument: TQ-8040 gas mass spectrometer (Shimadzu corporation, japan); rtx-5MS column (30 m. Times.0.25 mm. Times.0.25 μm); full-automatic nitrogen blowing instrument (horizons, usa); constant temperature sonicator (Jiangsu, kunshan ultrasonic instruments Co., ltd.); refrigerated centrifuge (thermo scientific, usa); VORTEX1 VORTEX mixer (Germany Ai Ka), DF-101s constant temperature magnetic stirrer (Shanghai Libang West instruments and technologies Co., shanghai), 1mL series solid phase extraction column and fittings (Hangzhou micron Pi technologies Co., hangzhou).
Reagent: acetone, cyclohexane, sodium chloride, acetonitrile, ethyl acetate (all of the above reagents were analytically pure, purchased from merck, germany), 3-aminopropyl triethylsilane (Shanghai Ala Biotechnology Co., ltd., shanghai), SBA-15 mesoporous molecular sieve material (Nanfeng nanomaterials Co., ltd., nanjing), PSA (N-propylethylenediamine) solid phase adsorbent powder (particle size 40 μm-60 μm, tianjin Bona Ai Jieer Co.).
8 samples of commonly used methoxy acrylate based bactericides, including: the picoxystrobin, the E-phenoxymycylamine, the kresoxim-methyl, the pyriminostrobin, the trifloxystrobin, the fluoxastrobin and the azoxystrobin are all standard solutions with the concentration of 1000mg/mL, the standard mixed stock solution with the concentration of 1000mg/L is diluted by acetone, and the standard mixed stock solution is gradually diluted by a matrix to prepare a mixed standard series with the concentration of 50, 100, 500, 1000, 2000 and 4000 mug/L of the fluoxastrobin and the azoxystrobin and the concentration of other components of 25, 50, 100, 250, 500, 1000 and 2000 mug/L. The relevant physical and chemical parameters of the 8 methoxy acrylic bactericide are shown in table 1.
Table 18 physicochemical Properties of methoxy acrylic acid ester based Bactericide
2) Synthesis of amino-functionalized SBA-15 molecular sieve powder and preparation of solid phase extraction column thereof
Weighing 5g of SBA-15 molecular sieve powder into a round bottom distillation flask, adding 100mL of toluene into the flask, and stirring the mixture for 30min; 20mL of 3-aminopropyl triethylsilane (APTES) is added dropwise, the mixture is stirred and refluxed for 6 hours at the temperature of 110 ℃ by a constant-temperature magnetic stirrer, the mixture is stirred for 12 hours at the room temperature, then the mixture is washed with absolute ethyl alcohol for multiple times, white powder is obtained by filtration, and then vacuum drying (at the temperature of 65 ℃ for 12 hours) is carried out, thus obtaining the amino-functional SBA-15 molecular sieve powder.
The solid phase extraction columns with 2 pieces of 1mL polypropylene as materials are connected in series up and down to serve as a purification device, the upper end of the solid phase extraction column is provided with a luer female port, the lower end of the solid phase extraction column is provided with a luer male port, 100mg of PSA powder is filled in the lower layer of the solid phase extraction column, 300mg of amino-functionalized SBA-15 molecular sieve powder is filled in the upper layer of the solid phase extraction column, and the upper layer and the lower layer are both fixedly compacted by using 1mL of hydrophobic sieve plates, so that positive pressure purification is facilitated. The structure of the tandem solid phase extraction column is shown in figure 1.
3) Sample collection and processing
40 parts of just-matured rice and corresponding soil samples are respectively collected from rice planting sites in different areas, and each sample is not less than 500g. Weighing 100g of rice samples which are uniformly mixed, unshelling by a unshelling machine, grinding, sieving for later use, and storing in a refrigerator at the temperature of minus 20 ℃; grinding and sieving soil for later use, and storing in a refrigerator at the temperature of minus 20 ℃.
Weighing 10g of ground rice or soil sample, putting into a 50mL centrifuge tube, adding 15mL of acetonitrile, extracting with 5g of NaCl by ultrasonic for 20min, freezing and centrifuging at 8000r/min for 5min, transferring supernatant into a nitrogen blowing bottle, adding 10mL of acetonitrile for repeated extraction, merging the supernatant, concentrating to near dryness by nitrogen blowing in a nitrogen blowing instrument at 40 ℃, redissolving with 2mL of 1:1 cyclohexane-ethyl acetate solution, and purifying.
Activating the solid phase extraction column manufactured in the step 2) by 3mL of 1:1 cyclohexane-ethyl acetate solution, loading, collecting filtrate, eluting for multiple times by using 5mL of 1:1 cyclohexane-ethyl acetate solution, collecting eluent, concentrating, fixing the volume by using 1mL cyclohexane-ethyl acetate solution, and passing through a 0.22um PTFE filter membrane to be detected.
4) Gas chromatography tandem mass spectrometry (GC-MS/MS) detects gas conditions: sample injection is carried out at 300 ℃ without diversion, sample injection is carried out at high pressure for 1min, the flow control mode is linear speed, the linear speed is 40.2cm/sec, and the column flow rate is 1.2mL/min; rtx-5MS chromatographic column is kept at 70 ℃ for 1min, 15 ℃/min is raised to 280 ℃ for 2min, 30 ℃/min is raised to 300 ℃ for 10min, and the sample injection amount is 1uL
Mass spectrometry conditions: EI ion source 230 ℃, interface temperature 280 ℃, solvent delay 3min, detector voltage 0.6kV relative to tuning voltage, time-division multiple reaction selection monitoring mode (MRM).
In consideration of the influence of various conditions on the detection result, in the embodiment, the gas chromatography-mass spectrometry condition, the purification condition and the matrix effect related to the detection method are optimized, the optimal experimental condition is determined, the linearity and the detection limit of the method, the recovery rate and the precision are calculated, and the detection effect is verified through actual sample detection.
1. Gas chromatography-mass spectrometry condition optimization
And (3) carrying out total ion flow diagram scanning on 8 methoxy acrylic acid ester bactericides under the mode that an electron bombardment ion source is an EI source, respectively finding precursor ions of 8 methoxy acrylic acid ester compounds, setting collision energy of 3-45 eV, carrying out product ion scanning on the selected precursor ions, selecting proper quantitative ion pairs and qualitative ion pairs according to a secondary mass spectrum, and referring to table 2, wherein relevant detection parameters and optimization conditions are shown in the table 2, and MRM mass spectrograms of the optimized 8 methoxy acrylic acid ester bactericides are shown in the table 2, wherein 1-8 respectively represent compounds corresponding to serial numbers in the table 2.
Table 28 mass spectrum detection parameter table for methoxy acrylic acid ester germicides
2. Purification condition optimization
The SBA-15 mesoporous molecular sieve has the advantages of high specific surface area, uniform main pore canal size, large pore wall thickness, large pore diameter and the like, and has potential application prospects in the fields of adsorption and separation, biology, nano materials and the like. In the embodiment, SBA-15 is aminated, and the nano molecular sieve has high adsorption performance and impurity removing capability of amino groups, so that the nano molecular sieve has stronger adsorption and purification capability on methoxy acrylic compounds; wherein PSA can effectively remove fatty acid, organic acid, polar pigment, saccharide and other interferents in grains and soil, so that the dosage of the amination SBA-15 and the PSA becomes a key for improving recovery rate and removing matrix interference.
Therefore, when two materials are synthesized to purify cereal and soil matrixes, single factor experiments are respectively carried out on the addition amounts of the amination SBA-15 and the PSA, the optimal use amount of the blank matrix is selected by taking the addition standard recovery rate of the blank matrix as an index, the use amounts of the amino functionalization SBA-15 and the PSA are taken as the abscissa, and a line graph is drawn by taking the recovery rate as the ordinate, as shown in figures 3 and 4; as is clear from the figure, when the amount of amino SBA-15 added was 300mg and the amount of PSA added was 100mg, the recovery rate of 8 bactericides in rice and soil was good.
3. Matrix effect
Matrix Effect (ME) refers to the effect of other components on the accuracy and reproducibility of quantitative analysis during sample processing, in addition to the target compound. ME is calculated using equation (1):
k in m For the slope of the matrix-matched calibration curve, k is the slope of the solvent calibration curve.
Extracting blank rice and soil matrix solution by referring to the sample collecting and processing process of the step 3). Preparing working solutions with the same concentration by using acetone and blank matrix solution respectively, and analyzing and measuring according to the detection conditions of the gas chromatography-tandem mass spectrometry in the step 4). And drawing a matrix matching calibration curve and a solvent calibration curve by taking the concentration as an abscissa and the peak area as an ordinate, calculating a matrix effect, and finally calculating an ME value of 1.21-1.89 to indicate the existence of the matrix effect. Therefore, a matrix matching calibration curve external standard method is adopted to quantitatively analyze the sample, so that the influence of matrix effect on experimental results is reduced.
4. The method comprises the steps of calculating linearity and detection limit, preparing 8 standard series of methoxy acrylic compounds by using rice and a soil blank matrix, measuring for 6 times under the optimal experimental condition, and taking an average value as a standard curve; when the concentration ranges of the fluoroether fungus ester and the azoxystrobin are 50-4000 mug/L and the concentration ranges of other components are 25-2000 mug/L, a standard curve is drawn by taking the concentration (mug/L) of the compound as an abscissa and the peak area of the target compound as an ordinate, and the correlation coefficient and the linear range are calculated. The linear relation of 8 compounds is good through calculation, and the correlation coefficient is in the range of 0.9969-0.9998. The minimum limit of detection of this method was calculated from the 3-fold signal to noise ratio (S/N) of the minimum standard concentration, and the minimum limit of detection of 8 compounds was in the range of 1.0 to 3.5. Mu.g/kg, as shown in Table 3.
TABLE 3 Linear coefficient, detection limit and quantitative limit
| Compounds of formula (I) | Linear equation | Correlation coefficient (R) | Linear range (μg/L) | Detection limit (mug/Kg) | Quantitative limit (mug/Kg) |
| Picoxystrobin | Y＝67.24x+1213.7 | 0.9992 | 25-2000 | 2.0 | 6 |
| E-phenoxyl bacteria amine | Y＝41.90x-188.9 | 0.9997 | 25-2000 | 2.5 | 7.5 |
| Kresoxim-methyl | Y＝38.10x+649.9 | 0.9996 | 25-2000 | 2.0 | 6 |
| Pyrimoxastrobin | Y＝169.6x-108.4 | 0.9993 | 25-2000 | 1.0 | 3 |
| Trifloxystrobin | Y＝19.28x-88.3 | 0.9995 | 25-2000 | 2.5 | 7.5 |
| Dimoxystrobin | Y＝188.9x-1731 | 0.9998 | 25-2000 | 1.0 | 3 |
| Fluopicolide | Y＝15.6x+295.4 | 0.9984 | 50-4000 | 3.5 | 10 |
| Azoxystrobin | Y＝14.46x-790.8 | 0.9969 | 50-4000 | 3.5 | 10 |
5. Recovery and precision calculation of the method
The rice and soil samples without 8 methoxy acrylic acid ester bactericides are taken, three samples with different standard adding levels of 10, 50 and 100 mug/Kg are respectively prepared, the sample collection and treatment process in the step 3) is referred to for treatment, each level is subjected to 6 parallel experiments, the recovery rate and precision are calculated, the recovery rate is finally calculated to be 71.0-102%, the RSD is calculated to be 1.99-4.98%, the accuracy and precision are good, and the detection analysis of the methoxy acrylic acid ester bactericides in the grain and soil samples can be satisfied. The results of the standard recovery and precision experiments are shown in Table 4.
Table 4 standard recovery and precision experiments (n=6)
6. Actual sample detection
Detecting 40 parts of collected rice and soil samples by using the established method, wherein 8 parts of fluoroether bacteria ester is detected in the rice, and the content range is 0.021-0.133 mg/Kg; 1 part of trifloxystrobin is detected, and the content is 0.035mg/Kg; the content of the 5 parts of the fluoroether fungus esters in the soil sample is 0.014-0.089mg/Kg, and the content of the 2 parts of picoxystrobin is 0.045mg/Kg and 0.018 mg/Kg respectively.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (4)
1. A method for detecting methoxy acrylic acid ester bactericide by molecular sieve tandem solid phase extraction is characterized by comprising the following steps:
1) Synthesizing amino-functionalized SBA-15 molecular sieve powder;
2) Preparing a series solid phase extraction column;
3) Sample collection and pretreatment;
4) Detecting a sample by gas chromatography tandem mass spectrometry;
the preparation of the series solid phase extraction column in step 2) specifically comprises the following steps: taking 21 mL polypropylene solid-phase extraction columns which are connected in series up and down as a purification device, filling 100mg of PSA powder into a lower layer solid-phase extraction column, filling 300mg of amino-functional SBA-15 molecular sieve powder prepared in the step 1) into an upper layer solid-phase extraction column, and fixing and compacting the upper layer and the lower layer by using 1mL hydrophobic sieve plates;
the step 3) of sample collection and pretreatment specifically comprises the following steps:
weighing 10g of ground rice or soil sample, putting the ground rice or soil sample into a 50mL centrifuge tube, adding 15mL of acetonitrile and 5g of NaCl, carrying out ultrasonic extraction for 20min, carrying out freeze centrifugation for 5min at 8000r/min, transferring supernatant into a nitrogen blowing bottle, adding 10mL of acetonitrile for repeated extraction once, merging the supernatant, carrying out nitrogen blowing concentration in a nitrogen blowing instrument at 40 ℃ until the supernatant is nearly dry, carrying out redissolution by using 2mL of 1:1 cyclohexane-ethyl acetate solution, and purifying;
activating the solid phase extraction column manufactured in the step 2) by 3mL of 1:1 cyclohexane-ethyl acetate solution, loading, collecting filtrate, eluting for multiple times by using 5mL of 1:1 cyclohexane-ethyl acetate solution, collecting eluent, concentrating, fixing the volume by using 1mL of cyclohexane-ethyl acetate solution, and passing through a 0.22um PTFE filter membrane to be detected.
2. The method for detecting methoxy acrylic acid ester bactericide by molecular sieve series solid phase extraction according to claim 1, wherein the synthesis of the amino-functionalized SBA-15 molecular sieve powder in the step 1) specifically comprises the following steps: weighing 5g of SBA-15 molecular sieve powder into a round bottom distillation flask, adding 100mL of toluene into the flask, and stirring the mixture for 30min; 20mL of 3-aminopropyl triethylsilane is added dropwise, and the mixture is stirred and refluxed for 6 hours at 110 ℃ in a constant temperature magnetic stirrer, and then stirred for 12 hours at room temperature; and washing with absolute ethyl alcohol for multiple times, filtering to obtain white powder, and vacuum drying at 65 ℃ for 12 hours to obtain amino-functionalized SBA-15 molecular sieve powder.
3. The method for detecting methoxy acrylic acid ester bactericide by molecular sieve tandem solid phase extraction according to claim 1, wherein the gas phase conditions of the step 4) gas chromatography tandem mass spectrometry detection sample are as follows: sample injection is carried out at 300 ℃ without diversion, sample injection is carried out at high pressure for 1min, the flow control mode is linear speed, the linear speed is 40.2cm/sec, and the column flow rate is 1.2mL/min; the Rtx-5MS chromatographic column is kept at 70 ℃ for 1min, is kept at a temperature of between 15 ℃ and 280 ℃ for 2min, is kept at a temperature of between 30 ℃ and 300 ℃ for 10min, and the sample injection amount is 1uL.
4. The method for detecting methoxy acrylic acid ester bactericide by molecular sieve tandem solid phase extraction according to claim 1, wherein the mass spectrometry conditions of the detection sample by the gas chromatography tandem mass spectrometry of the step 4) are as follows: EI ion source 230 ℃, interface temperature 280 ℃, solvent delay 3min, detector voltage 0.6kV relative to tuning voltage, and time-division multiple reaction selection monitoring mode.
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