Detection method of picloram and triclopyr butoxyethyl ester compound herbicide

Abstract

The invention discloses a detection method of a picloram and triclopyr butoxyethyl ester compound herbicide, which comprises the following steps: S1, sample pretreatment: taking picloram to prepare a standard sample 1, taking triclopyr butoxyethyl ester to prepare a standard sample 2 for later use, and taking a sample to be detected to dilute for later use; s2, preparing a mobile phase: mixing an organic solvent and water to prepare the mobile phase; s3, the standard sample 1, the diluted to-be-detected sample and the standard sample 2 are injected into the high performance liquid chromatograph according to the sequence, and liquid chromatography detection is carried out by adopting a gradient elution program. According to the method, picloram and triclopyr butoxyethyl ester can be stably peaked, errors in calculation of the peak area proportion of the two components caused by too large or too small peak area are avoided, picloram and triclopyr butoxyethyl ester can be separated in a short time, and the detection efficiency is improved.

Description

Technical Field

[0001] The invention relates to the field of measurement and testing, and in particular to a method for detecting a compound herbicide of picloram and triclopyr butoxyethyl ester. Background Art

[0002] The compound herbicide of picloram and butoxyethyl triclopyra has a good weed control effect on plants, but picloram and butoxyethyl triclopyra have a certain instability after mixing, so after the finished product is produced, the active ingredients need to be tested to ensure the efficacy. However, the solvents, emulsifiers, dispersants, etc. in the finished medicine will interfere with the detection of the active ingredients. The traditional detection method is to detect picloram and butoxyethyl triclopyra separately, and the detection efficiency is low. Therefore, it is very important to develop a method that can detect picloram and butoxyethyl triclopyra simultaneously.

[0003] Chinese invention patent CN103308641A discloses a method for determining three amide herbicides in tobacco and tobacco products by high performance liquid chromatography-tandem mass spectrometry, which extracts pesticide residues by matrix dispersed solid phase extraction, and directly determines the pesticide residues in tobacco and tobacco products by liquid chromatography-tandem mass spectrometry. The pretreatment process is simple and fast, which can reduce the interference of impurities such as pigments in tobacco, but it needs to be detected in series with mass spectrometry. CN117434181A discloses a method for detecting herbicides and their metabolites in grains and oils, which uses acidic acetonitrile as an extractant and inorganic salts as dehydration and salting out, and performs qualitative and quantitative detection and analysis of pesticide metabolite residues in grains by dispersed solid phase extraction purification-high performance liquid chromatography-tandem mass spectrometry, but the steps are cumbersome and the process is complicated. Summary of the invention

[0004] In order to develop a method for simultaneously detecting picloram and butoxyethyl triclopyrazone, the first aspect of the present invention provides a method for detecting a compound herbicide of picloram (also known as amiloride) and butoxyethyl triclopyrazone, comprising the following steps:

[0005] S1: sample pretreatment, prepare standard sample 1 with piclopidine, prepare standard sample 2 with triclopyr butoxyethyl ester for later use, and dilute the sample to be tested for later use;

[0006] S2 prepares the mobile phase, mixing the organic solvent and water to prepare the mobile phase;

[0007] S3 injects the standard sample 1, the diluted sample to be tested twice, and the standard sample 2 into the high performance liquid chromatograph in this order. The high performance liquid chromatograph uses the mobile phase configured by S2 to perform liquid chromatography detection under the gradient elution program.

[0008] As a preferred embodiment, the high performance liquid chromatograph is Agilent 1260II; VWD detector.

[0009] As a preferred embodiment, the compound herbicide of picloram and butoxyethyl triclopyrazone is an emulsifiable concentrate, the original drug concentration of picloram in the compound herbicide is 100-500 g / L; the original drug concentration of butoxyethyl triclopyrazone in the compound herbicide is 100-300 g / L.

[0010] As a preferred embodiment, the original drug concentration of chlorpyrifos in the compound herbicide is 300 g / L; the original drug concentration of triclopyr butoxyethyl in the compound herbicide is 100 g / L.

[0011] As a preferred embodiment, the concentration of chlorpyrifos in the standard sample 1 is 0.3-0.8 g / L, and the concentration of triclopyrazone butoxyethyl in the standard sample 2 is 0.3-0.8 g / L.

[0012] As a preferred embodiment, the concentration of chlorpyrifos in the standard sample 1 is 0.5 g / L, and the concentration of butoxyethyl triclopyrazone in the standard sample 2 is 0.5 g / L.

[0013] As a preferred embodiment, the concentration of the diluted sample to be tested is 1-3 g / L.

[0014] As a preferred embodiment, the concentration of the diluted sample to be tested is 2 g / L.

[0015] The inventor found in the experimental process that the compounded emulsifiable concentrate herbicide of amiloride and butoxyethyl triclopyrazone is unstable in efficacy after actual mixing, and the actual content of amiloride and butoxyethyl triclopyrazone in the emulsifiable concentrate herbicide needs to be detected when leaving the factory to achieve the prescribed efficacy. The inventor found in the actual detection process that in the compounded product of amiloride and butoxyethyl triclopyrazone, the content of amiloride is high, and the concentration of the sample to be tested needs to be controlled to 2g / L, so that amiloride and butoxyethyl triclopyrazone can achieve stable peaking, and avoid the peak area being too large or too small to cause the peak area ratio calculation of the two components to have errors.

[0016] As a preferred embodiment, the diluent for diluting the sample to be tested is methanol.

[0017] The inventors found during the experiment that when methanol was used as the diluent, the sample to be tested was in a clear state, while when acetonitrile was used as the diluent, the sample to be tested was in a turbid state, and the dissolution was uneven, which would affect the accuracy of subsequent detection.

[0018] As a preferred embodiment, the volume ratio of organic solvent to water in the mobile phase is (30-90): (70-10); the organic solvent is methanol or acetonitrile; the mobile phase is adjusted to pH 2-4 using phosphoric acid. Preferably, the mobile phase is adjusted to pH 3 using phosphoric acid.

[0019] Preferably, the organic solvent is methanol.

[0020] The inventors found during the experiment that it is also necessary to control the mobile phase to a mixture of methanol and water and adjust the pH to 3 with phosphoric acid so that the sample can be stably dissolved. If an acetonitrile aqueous solution is used for injection, the compounded emulsifiable concentrate herbicide will become turbid, affecting the accuracy of detection. The reason may be that the solubility of amloprotinic acid and butoxyethyl triclopyrazone is different. When diluting the sample, it is necessary to coordinate the dissolution effects of the two components to avoid turbidity caused by insufficient dissolution of a single component, which affects the peak accuracy of liquid chromatography.

[0021] As a preferred embodiment, the chromatographic column in the high performance liquid chromatograph is selected from Agilent EclipsePlus C 18 5μm 4.6×150mm column, Agilent Poroshell 120EC-C 18 4μm4.6×100mm chromatographic column, Agilent Eclipse XDB-C 18 At least one of the 5μm 4.6×150mm chromatography columns.

[0022] As a preferred embodiment, the high performance liquid chromatograph is Agilent Eclipse Plus C 18 For a 5μm 4.6×150mm chromatographic column, the gradient elution procedure was as follows: 0.00min, methanol-water ratio was 50:50; 5.00min, methanol-water ratio was 50:50; 5.50min, methanol-water ratio was 90:10; 14.00min, methanol-water ratio was 90:10; 14.50min, methanol-water ratio was 50:50; and then run for 5min.

[0023] As a preferred embodiment, the high performance liquid chromatograph adopts Agilent Eclipse XDB-C 18 For a 5μm 4.6×150mm chromatographic column, the gradient elution procedure was as follows: 0.00min, methanol to water ratio was 50:50; 5.00min, methanol to water ratio was 50:50; 5.50min, methanol to water ratio was 90:10; 16.50min, methanol to water ratio was 90:10; 17.00min, methanol to water ratio was 50:50; and then run for 5min.

[0024] As a preferred embodiment, the high performance liquid chromatograph adopts Agilent Poroshell 120EC-C 18 For a 4μm 4.6×100mm chromatographic column, the gradient elution procedure was as follows: 0.00min, methanol to water ratio was 30:70; 5.00min, methanol to water ratio was 30:70; 5.50min, methanol to water ratio was 90:10; 12.50min, methanol to water ratio was 90:10; 13.00min, methanol to water ratio was 30:70; and then run for 5min.

[0025] The inventors used gradient elution to separate amiloride and triclopyraclostrobin in the experiment, which accelerated the analysis speed. 18 The chromatographic column combination of 0.00min alcohol-water ratio of 30:70; 5.00min alcohol-water ratio of 30:70; 5.50min alcohol-water ratio of 90:10; 12.50min alcohol-water ratio of 90:10; 13.00min alcohol-water ratio of 30:70 can achieve rapid separation of amiloride and butoxyethyl triclopyrazone, with good separation from impurity peaks, clear peak shape and accurate data.

[0026] As a preferred embodiment, the calculation formula of the mass fraction X of chlorpyrifos in the sample to be tested is as follows:

[0027] Where:

[0028] A1—average value of the peak area of ​​picloram in standard solution 1;

[0029] A2—the average area of ​​picroclatam in the sample to be tested;

[0030] m1—mass of picloram standard solution 1, g;

[0031] m2—mass of the picloram sample to be tested, g;

[0032] P—mass fraction of atromycin in standard solution 1, %.

[0033] As a preferred embodiment, the calculation formula for the mass fraction X of butoxyethyl triclopyraclostrobin in the sample to be tested is as follows:

[0034] Where:

[0035] A1—average peak area of ​​butyloxyethyl triclopyraclostrobin in standard solution 2;

[0036] A2—the average area of ​​butyloxyethyl triclopyraclostrobin in the sample to be tested;

[0037] m1—the mass of triclopyr butoxyethyl ester standard solution 2, g;

[0038] m2—the mass of the triclopyr butoxyethyl ester sample to be tested, g;

[0039] P—mass fraction of butoxyethyl triclopyraclostrobin in standard solution 2, %.

[0040] The second aspect of the present invention provides an application of a method for detecting a compound herbicide of picloram and triclopyr, which is applied to the detection of a compound herbicide of picloram and triclopyr in the form of an emulsifiable concentrate.

[0041] Compared with the prior art, the present invention has the following beneficial effects:

[0042] (1) In the method for detecting the compound herbicide of piclopitol and triclopyrazone, the concentration of the sample to be tested is 2 g / L, so that the peaks of amiloride and triclopyrazone are stably eluted, and errors in the calculation of the peak area ratio of the two components due to excessively large or small peak areas are avoided.

[0043] (2) In the method for detecting the compound herbicide of piclopitol and triclopyr butoxyethyl ester of the present invention, the mobile phase is controlled to be a mixture of methanol and water, and the pH is adjusted to 3 with phosphoric acid, so that the injected sample can be stably dissolved and the problem of inaccurate detection caused by uneven dissolution can be avoided.

[0044] (3) The detection method of the compound herbicide of piclopitol and triclopyrazone-butyloxyethyl ester of the present invention uses a gradient elution method to separate amiloride and triclopyrazone-butyloxyethyl ester, thereby accelerating the analysis speed.

[0045] (4) The detection method of the compound herbicide of picloram and triclopyr butyloxyethyl ester described in the present invention is carried out using Agilent Eclipse XDB-C 18 The 5μm 4.6×150mm chromatographic column with a suitable gradient elution program can separate piclopidine and triclopyr butoxyethyl ester in a short time, thus improving the detection efficiency.

[0046] (5) The detection method of the compound herbicide of picloram and triclopyr butyloxyethyl ester of the present invention can simultaneously realize qualitative and quantitative detection of picloram and triclopyr butyloxyethyl ester, and the detection is time-saving, labor-saving, reagent-saving and energy-saving. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] Figure 1 It is the liquid chromatogram of Example 3;

[0048] Figure 2 It is the liquid chromatogram of Example 4;

[0049] Figure 3 It is the liquid chromatogram of Example 8;

[0050] Figure 4 This is the liquid chromatogram of Example 10. DETAILED DESCRIPTION

[0051] Example A

[0052] Example 1

[0053] A method for detecting a compound herbicide of picloram and triclopyr butoxyethyl ester comprises the following steps:

[0054] S1: sample pretreatment, prepare standard sample 1 with piclopidine, prepare standard sample 2 with triclopyr butoxyethyl ester for later use, and dilute the sample to be tested for later use;

[0055] S2 prepares the mobile phase, mixing the organic solvent and water to prepare the mobile phase;

[0056] S3: Inject the standard sample 1, the diluted sample to be tested twice, and the standard sample 2 into the high performance liquid chromatograph in this order, and perform liquid chromatography detection using a gradient elution program.

[0057] The high performance liquid chromatograph is Agilent 1260II; VWD detector.

[0058] The original drug concentration of chlorpyrifos in the compound herbicide is 300 g / L; the original drug concentration of triclopyr butoxyethyl in the compound herbicide is 100 g / L.

[0059] The concentration of chlorpyrifos in the standard sample 1 is 0.5 g / L, and the concentration of butoxyethyl triclopyrazone in the standard sample 2 is 0.5 g / L.

[0060] The concentration of the sample to be tested after dilution is 2 g / L. The diluent for diluting the sample to be tested is methanol.

[0061] The diluted sample to be tested

[0062] The mobile phase was methanol and water, and the pH was adjusted to 3 using phosphoric acid.

[0063] The chromatographic column in the high performance liquid chromatograph is an Agilent Eclipse Plus C18 5μm 4.6×150mm chromatographic column. The gradient elution procedure is as follows:

[0064] 0.00min, the ratio of methanol to water was 50:50; 5.00min, the ratio of methanol to water was 50:50; 5.50min, the ratio of methanol to water was 70:30; 25.00min, the ratio of methanol to water was 70:30; 25.50min, the ratio of methanol to water was 50:50; and then run for 5min.

[0065] Flow rate: 1.000mL / min; Detection wavelength: 230nm; Injection volume: 5μL

[0066] Under this condition, the retention time of chloranil in the sample is 2.324min. The peak of butoxyethyl triclopyr has not appeared until the end of the run. Then the ratio of methanol to water is adjusted to 70:30. The peak of butoxyethyl triclopyr has not appeared at 49min. At 49min, the ratio of methanol to water is adjusted to 80:20. At 55min, the ratio of methanol to water is adjusted to 90:10. The peak of butoxyethyl triclopyr appears at 58.325min. The detection efficiency is low. The detection time is long.

[0067] Example 2

[0068] A method for detecting a compound herbicide of picloram and triclopyr butoxyethyl ester, the specific implementation method is the same as that of Example 1, except that the procedure of gradient elution is as follows:

[0069] 0.00min, the ratio of methanol to water was 50:50; 5.00min, the ratio of methanol to water was 50:50; 5.50min, the ratio of methanol to water was 80:20; 31.00min, the ratio of methanol to water was 80:20; 31.50min, the ratio of methanol to water was 50:50; then run for 5min.

[0070] Under this condition, the retention time of chlorpyrifos in the sample is 2.318min, and the retention time of clopyrifos butoxyethyl is 29.073min. The peak shape of chlorpyrifos is not very good with a slight tailing, while the peak shape of clopyrifos butoxyethyl is very good.

[0071] Example 3

[0072] A method for detecting a compound herbicide of picloram and triclopyr butoxyethyl ester, the specific implementation method is the same as that of Example 1, except that the procedure of gradient elution is as follows:

[0073] 0.00min, methanol-water ratio is 50:50; 5.00min, methanol-water ratio is 50:50; 5.50min, methanol-water ratio is 90:10; 14.00min, methanol-water ratio is 90:10; 14.50min, methanol-water ratio is 50:50; run for 5min. Liquid phase spectrum is shown in Figure 1 .

[0074] The theoretical concentration of the diluted sample to be tested is 30 wt % picloram+10 wt % butoxyethyl triclopyrazone.

[0075] According to the peak area of ​​the detection spectrum, the detection result was calculated by the formula: piclopidine: 29.8wt% triclopyr butoxyethyl ester: 10.1wt%.

[0076] Under this condition, the retention time of chlorpyrifos in the sample is 2.316min, and the separation degree from the two impurity peaks of 1.648min and 4.648min is very good. The retention time of triclopyr butoxyethyl is 12.809min, and the separation degree from the previous 14 impurity peaks is also very good. The elution time of the 14th impurity peak is 11.519min. The peak shape of chlorpyrifos is not very good, with a little tailing, while the peak shape of triclopyr butoxyethyl is very good.

[0077] Summary: Solution A uses Agilent Eclipse Plus C 18 In the case of a 5μm 4.6×150mm chromatographic column, the mobile phase methanol ratio of Example 1 is 70, which is too low, resulting in a late elution time of butoxyethyl triclopyr. The mobile phase methanol ratio of Example 2 is 80, and the elution time of butoxyethyl triclopyr is 29.073min, which is also too late. The mobile phase ratio of Example 3 is 90, and the elution time of butoxyethyl triclopyr is 12.809min, which is not long and has a good separation from the 14th impurity peak (peak time is 11.519min), and the effect is the best.

[0078] Example B

[0079] Example 4

[0080] A method for detecting a compound herbicide of picloram and triclopyr butoxyethyl ester, the specific implementation method is the same as that of Example 1, except that the chromatographic column in the high performance liquid chromatograph is Agilent Eclipse XDB-C 18 5μm 4.6×150mm chromatographic column. The gradient elution procedure is as follows:

[0081] 0.00min, methanol-water ratio is 50:50; 5.00min, methanol-water ratio is 50:50; 5.50min, methanol-water ratio is 90:10; 16.50min, methanol-water ratio is 90:10; 17.00min, methanol-water ratio is 50:50; run for 5min. Liquid phase spectrum is shown in Figure 2 .

[0082] The theoretical concentration of the diluted sample to be tested is 30 wt % picloram+10 wt % butoxyethyl triclopyrazone.

[0083] According to the peak area of ​​the detection spectrum, the detection result was calculated by the formula: piclopidine: 30wt% triclopyr butoxyethyl ester: 10wt%.

[0084] The length and inner diameter of the chromatographic column of Example B are the same as those of Example A, so a ratio of 90:10 of methanol and water is directly selected. Under this condition, the retention time of chlorpyrifos in the sample is 2.347 min, and the separation degree from the three impurity peaks of 1.600 min, 2.020 min and 5.729 min is very good. The retention time of triclopyr butoxyethyl ester is 15.724 min, and the separation degree from the previous 14 impurity peaks is also very good. The elution time of the 14th impurity peak is 13.644 min. The peak shapes of chlorpyrifos and triclopyr butoxyethyl ester under this chromatographic column are very good.

[0085] Example C

[0086] Example 5

[0087] A method for detecting a compound herbicide of picloram and triclopyr butoxyethyl ester, the specific implementation method is the same as that of Example 1, except that the chromatographic column in the high performance liquid chromatograph is Agilent Poroshell 120EC-C 18 4μm4.6×100mm chromatographic column, the gradient elution procedure is as follows:

[0088] 0.00min, the ratio of methanol to water was 50:50; 5.00min, the ratio of methanol to water was 50:50; 5.50min, the ratio of methanol to water was 90:10; 16.50min, the ratio of methanol to water was 90:10; 17.00min, the ratio of methanol to water was 50:50; and then run for 5min.

[0089] Under this condition, the retention time of chlorpyrifos in the sample is 1.559 min. There is a bulge in front of the peak, which obviously contains impurities. The retention time of triclopyr butoxyethyl ester is 11.842 min.

[0090] Example 6

[0091] A method for detecting a compound herbicide of picloram and triclopyr butoxyethyl ester, the specific implementation method is the same as that of Example 5, except that the procedure of gradient elution is as follows:

[0092] 0.00min, the ratio of methanol to water was 40:60; 5.00min, the ratio of methanol to water was 40:60; 5.50min, the ratio of methanol to water was 80:20; 16.50min, the ratio of methanol to water was 80:20; 17.00min, the ratio of methanol to water was 40:60; and then run for 5min.

[0093] Under this condition, the retention time of chlorpyrifos in the sample is 2.002min, and there is an impurity 1.624min before the peak. The peak shape of chlorpyrifos is not good with tailing in front of the peak, and the impurity is in the package. Triclopyr butoxyethyl acetate did not produce a peak under this condition. At 30min, methanol and water were adjusted to 90:10, and triclopyr butoxyethyl acetate produced a peak at 32.3min.

[0094] Example 7

[0095] A method for detecting a compound herbicide of picloram and triclopyr butoxyethyl ester, the specific implementation method is the same as that of Example 5, except that the procedure of gradient elution is as follows:

[0096] 0.00min, the ratio of methanol to water was 30:70; 5.00min, the ratio of methanol to water was 30:70; 5.50min, the ratio of methanol to water was 80:20; 35.00min, the ratio of methanol to water was 80:20; 35.50min, the ratio of methanol to water was 30:70; and then run for 5min.

[0097] Under this condition, the retention time of chlorpyrifos in the sample is 2.841min, and the separation degree from the three impurity peaks such as 2.030min is very good. The retention time of triclopyr butoxyethyl ester is 25.941min, and the separation degree from the previous 13 impurity peaks is also very good. The elution time of the 13th impurity peak is 15.840min. The peak shapes of chlorpyrifos and triclopyr butoxyethyl ester are very good.

[0098] Example 8

[0099] A method for detecting a compound herbicide of picloram and triclopyr butoxyethyl ester, the specific implementation method is the same as that of Example 5, except that the procedure of gradient elution is as follows:

[0100] 0.00min, the ratio of methanol to water was 30:70; 5.00min, the ratio of methanol to water was 30:70; 5.50min, the ratio of methanol to water was 90:10; 12.50min, the ratio of methanol to water was 90:10; 13.00min, the ratio of methanol to water was 30:70; and then run for 5min.

[0101] Under this condition, the retention time of chlorpyrifos in the sample is 2.821min, and the separation degree from the impurity peak of 2.019min is very good. The retention time of triclopyr butoxyethyl ester is 11.828min, and the separation degree from the first 14 impurity peaks is also very good. The elution time of the 14th impurity peak is 11.558min, and the separation degree between triclopyr butoxyethyl ester and this impurity peak is >1.5. The peak shapes of chlorpyrifos and triclopyr butoxyethyl ester are very good. See the liquid chromatography Figure 3 .

[0102] The theoretical concentration of the diluted sample to be tested is 30 wt % picloram+10 wt % butoxyethyl triclopyrazone.

[0103] According to the peak area of ​​the detection spectrum, the detection result was calculated by the formula: piclopidine: 30wt% triclopyr butoxyethyl ester: 10.1wt%.

[0104] Summary: Example C uses Agilent Poroshell 120EC-C 18 In the case of a 4 μm 4.6×100 mm chromatographic column, the ratio of methanol to water in Example 5 was 50:50, which was too high at the beginning, resulting in poor separation between picloram and the impurity peak. The ratio of methanol to water in Example 6 was 40:60, which was still too high, resulting in poor separation between picloram and the impurity peak. The ratio of methanol to water was 80:10, which was too low, resulting in no peak of butoxyethyl triclopyr within the running time. The ratio of methanol to water in Example 7 was 30:70 at the beginning, resulting in good separation between picloram and the impurity peak. The ratio of methanol to water was 80:10, which was too low. The elution time of oxyethyl ester is 25.941min, which is not short and has good separation from the 13th impurity peak (peak time is 15.840min). In Example 8, the mobile phase is initially prepared with a methanol to water ratio of 3:70, and the separation between piclopidine and the impurity peak is very good. Later, the methanol to water ratio is 90:10, and the elution time of butoxyethyl triclopyr is 11.828min, which is just right and has good separation from the 14th impurity peak (peak time is 11.558min). Therefore, the mobile phase ratio of Example 7 under the chromatographic column of Example C is the most preferred.

[0105] Example D

[0106] Example 9

[0107] A method for detecting a compound herbicide of picloram and triclopyr butoxyethyl ester, the specific implementation method is the same as that of Example 1, except that the chromatographic column in the high performance liquid chromatograph is Agilent ZORBAX SB-C 18 5μm 4.6×250mm chromatographic column, the gradient elution procedure is as follows:

[0108] At 0.00min, the ratio of methanol to water was 55:45; at 5.00min, the ratio of methanol to water was 55:45; at 5.50min, the ratio of methanol to water was 90:10; at 19.50min, the ratio of methanol to water was 90:10; at 20.00min, the ratio of methanol to water was 55:45; and then the mixture was run for 5min.

[0109] Under this condition, the retention time of chlorpyrifos in the sample is 3.709min, and the retention time of triclopyr butoxyethyl ester is 17.076min. The peak of chlorpyrifos is severely tailed.

[0110] Example 10

[0111] A method for detecting a compound herbicide of picloram and triclopyr butoxyethyl ester, the specific implementation method is the same as that of Example 9, except that the procedure of gradient elution is as follows:

[0112] 0.00min, the ratio of methanol to water was 55:45; 8.00min, the ratio of methanol to water was 55:45; 8.50min, the ratio of methanol to water was 90:10; 21.00min, the ratio of methanol to water was 90:10; 21.50min, the ratio of methanol to water was 55:45; and then run for 5min.

[0113] Under this condition, the retention time of chlorpyrifos in the sample is 3.720min, and the retention time of triclopyr butoxyethyl is 20.061min. The peak shape of chlorpyrifos is not very good and the tailing is serious. The last peak of 13 impurity peaks is 17.676min, which is well separated from triclopyr butoxyethyl. Figure 4 .

[0114] The theoretical concentration of the diluted sample to be tested is 30 wt % picloram+10 wt % butoxyethyl triclopyrazone.

[0115] According to the peak area of ​​the detection spectrum, the detection result was calculated by the formula: piclopidine: 29.5wt% triclopyr butoxyethyl ester: 9.9wt%.

[0116] Summary: Solution D uses Agilent ZORBAX SB-C 18 In the case of a 5 μm 4.6×250 mm chromatographic column, the picloram peaks of the mobile phases of Example 8 and Example 9 were severely tailed, and neither was the most preferred.

[0117] Example E

[0118] Embodiment 11

[0119] A method for detecting a compound herbicide of picloram and triclopyr butoxyethyl ester, the specific implementation method is the same as that of Example 1, except that the chromatographic column in the high performance liquid chromatograph is Fenome Luna C 18 5μm 4.6×250mm chromatographic column, the mobile phase was as follows: methanol: water ratio was 50:50.

[0120] Under this condition, the retention time of chlorpyrifos in the sample is 5.252min, and the chlorpyrifos peak has severe tailing.

Claims

1. A method for detecting a compound herbicide of picloram and triclopyr butoxyethyl ester, characterized in that: The following steps are involved: S1: sample pretreatment, prepare standard sample 1 with piclopidine, prepare standard sample 2 with triclopyr butoxyethyl ester for later use, and dilute the sample to be tested for later use; S2 prepares the mobile phase, mixing the organic solvent and water to prepare the mobile phase; S3 injects the standard sample 1, the diluted sample to be tested, and the standard sample 2 into the high performance liquid chromatograph in the order of the standard sample 1. The high performance liquid chromatograph uses the mobile phase configured by S2 to perform liquid chromatography detection under the gradient elution program.

2. The method for detecting the compound herbicide of picloram and triclopyr butoxyethyl ester according to claim 1, characterized in that: The compound herbicide of picloram and butoxyethyl triclopyrazone is emulsifiable concentrate, the original drug concentration of picloram in the compound herbicide is 100-500 g / L; the original drug concentration of butoxyethyl triclopyrazone in the compound herbicide is 100-300 g / L.

3. The method for detecting the compound herbicide of picloram and triclopyr butoxyethyl ester according to claim 1, characterized in that: The concentration of chlorpyrifos in the standard sample 1 is 0.3-0.8 g / L, and the concentration of butoxyethyl triclopyrazone in the standard sample 2 is 0.3-0.8 g / L.

4. The method for detecting the compound herbicide of picloram and triclopyr butoxyethyl ester according to claim 1, characterized in that: The concentration of the diluted sample to be tested is 1-3 g / L.

5. The method for detecting the compound herbicide of picloram and triclopyr butoxyethyl ester according to claim 1, characterized in that: The volume ratio of the organic solvent to water in the mobile phase is (30-90): (70-10); the organic solvent is methanol or acetonitrile; and the mobile phase is adjusted to a pH of 2-4 using phosphoric acid.

6. The method for detecting the compound herbicide of picloram and triclopyr butoxyethyl ester according to claim 1, characterized in that: The chromatographic column in the high performance liquid chromatograph is selected from Agilent Eclipse Plus C 18 5μm 4.6×150mm column, Agilent Poroshell 120EC-C 18 4μm 4.6×100mm column, Agilent EclipseXDB-C 18 At least one of the 5μm 4.6×150mm chromatography columns.

7. The method for detecting the compound herbicide of picloram and triclopyr butoxyethyl ester according to claim 6, characterized in that: The high performance liquid chromatograph was Agilent Eclipse Plus C 18 For a 5μm 4.6×150mm chromatographic column, the gradient elution procedure was as follows: 0.00min, methanol-water ratio was 50:50; 5.00min, methanol-water ratio was 50:50; 5.50min, methanol-water ratio was 90:10; 14.00min, methanol-water ratio was 90:10; 14.50min, methanol-water ratio was 50:50; and then run for 5min.

8. The method for detecting the compound herbicide of picloram and triclopyr butoxyethyl ester according to claim 6, characterized in that: The high performance liquid chromatograph used was Agilent Eclipse XDB-C 18 For a 5μm 4.6×150mm chromatographic column, the gradient elution procedure was as follows: 0.00min, methanol-water ratio was 50:50; 5.00min, methanol-water ratio was 50:50; 5.50min, methanol-water ratio was 90:10; 16.50min, methanol-water ratio was 90:10; 17.00min, methanol-water ratio was 50:50; and then run for 5min.

9. The method for detecting the compound herbicide of picloram and triclopyr butoxyethyl ester according to claim 6, characterized in that: The high performance liquid chromatograph used was Agilent Poroshell 120EC-C 18 For a 4μm 4.6×100mm chromatographic column, the gradient elution procedure was as follows: 0.00min, methanol to water ratio was 30:70; 5.00min, methanol to water ratio was 30:70; 5.50min, methanol to water ratio was 90:10; 12.50min, methanol to water ratio was 90:10; 13.00min, methanol to water ratio was 30:70; and then run for 5min.

10. An application of the method for detecting the compound herbicide of picloram and triclopyr butoxyethyl ester according to any one of claims 1 to 9, characterized in that: It is used in the detection of compound herbicides of piclopitidine and triclopyr butoxyethyl ester in emulsifiable concentrate form.

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