CN115128195A - LC-MS/MS detection method for pesticide and veterinary drug residues in animal oil and vegetable oil - Google Patents
LC-MS/MS detection method for pesticide and veterinary drug residues in animal oil and vegetable oil Download PDFInfo
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- CN115128195A CN115128195A CN202211058741.6A CN202211058741A CN115128195A CN 115128195 A CN115128195 A CN 115128195A CN 202211058741 A CN202211058741 A CN 202211058741A CN 115128195 A CN115128195 A CN 115128195A
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
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Abstract
The invention relates to an LC-MS/MS detection method for pesticide and veterinary drug residues in animal oil and vegetable oil, which comprises the following steps: (S1) extracting: mixing an animal oil and/or vegetable oil sample with a buffer solution, adding an extraction solvent, a water removing agent and a salting-out agent after shaking, centrifuging after vortex shaking, and taking a supernatant for purification; (S2) purification: mixing the liquid to be purified obtained in the step (S1) with a purifying agent, performing vortex oscillation, centrifuging, taking supernatant, drying with nitrogen, redissolving, and filtering to obtain a liquid to be detected; the purifying agent is an amino-functionalized covalent organic framework material which is formed by orderly arranging a honeycomb porous structure and has a three-dimensional loose porous nanosphere structure; (S3) mass spectrometric detection: measuring (S2) the solution to be measured by liquid chromatography-tandem mass spectrometry; and quantifying by using an external standard method to obtain the content of the veterinary and agricultural medicines. The detection method has good detection effect on the pesticide and veterinary drug residues in most of animal oil and vegetable oil.
Description
Technical Field
The invention relates to the field of food safety, in particular to an LC-MS/MS detection method for pesticide and veterinary drug residues in animal oil and vegetable oil.
Background
The grease is an indispensable nutrient substance for the human body to maintain normal activities of life. Contains essential fatty acids which can not be synthesized by human body, participates in phospholipid synthesis, and can be combined with cholesterol to prevent arteriosclerosis, hypercholesterolemia and hyperlipidemia, and the essential fatty acids can only be obtained from food. The added grease can not only increase the flavor of the food, but also improve the mouthfeel. Therefore, with the continuous improvement of living standard, people can not eat animal oil and vegetable oil in life. During the cultivation of animals and plants, various pesticides and veterinary drugs are generally used to ensure the health of animals and plants in order to prevent diseases. Meanwhile, after animals eat feed containing pesticide residues, the pesticide in the organisms can be enriched. After eating the vegetable oil and the animal oil with pesticide and veterinary drug residues, human bodies can have serious influence on health.
At present, few researches are carried out on analysis methods of pesticide and veterinary drug residues in animal oil and vegetable oil, and the main focus is on animal muscle tissues and samples such as vegetables and fruits. The problem of pesticide residues in animal and vegetable oil samples is easily overlooked by people. The two samples have complex components and high fat content, which seriously affects the detection of pesticides and veterinary drugs, and how to effectively remove fat is the premise and difficulty for obtaining accurate determination results. The prior pretreatment method mainly adopts n-hexane and/or freezing method for degreasing, which not only has large usage amount of organic solvent, but also has long operation time and unsatisfactory purification effect.
The main pretreatment methods for removing oil include solid-phase extraction, liquid-liquid extraction and gel permeation chromatography for removing fat. However, the above method consumes a large amount of organic solvent, is not time-consuming, complicated to operate, and is not suitable for practical application and commercial production. More importantly, in fat-rich foods, lipophilic analytes are also lost due to non-specific adsorption, resulting in insufficient sensitivity of detection. In fat-rich foods, with many fats and free fatty acids, different carbon chain lengths, it is not practical to develop porous materials that cover the full size of the lipid. QuEChERS (Quick, Easy, Cheap, Effective, Rugged, Safe) is widely regarded by researchers because of its simplicity and rapidity of operation. QuEChERS is a novel food sample pretreatment method which is based on matrix solid phase dispersion, extracts components to be detected through extraction and purification and simultaneously removes redundant impurities. Has the advantages of rapidness, simplicity, low price, high efficiency, reliability and safety. However, there is a lack of suitable materials suitable for effective treatment of fats and oils in animal fats and vegetable oils.
The inventor's prior patent CN202210989648.0 discloses an amino ligand substituted covalent organic framework material as QuEChERS purifying agent, which can effectively remove grease in various foods and provide technical support for sample pretreatment. The invention is based on the novel covalent organic framework material with functional group amino, is used for adsorbing and removing animal oil and vegetable oil in food samples, and efficiently and accurately detects pesticide and veterinary drug residues in the animal oil and the vegetable oil.
Disclosure of Invention
The invention aims to solve the problem that an effective method for detecting pesticide and veterinary drug residues in animal oil and vegetable oil is lacked in the prior art, and provides an LC-MS/MS detection method for replacing covalent organic framework materials with amino ligands as a QuEChERS purifying agent and detecting pesticide and veterinary drug residues in animal oil and vegetable oil.
The invention realizes the aim through the following technical scheme:
an LC-MS/MS detection method for pesticide and veterinary drug residues in animal oil and vegetable oil comprises the following steps:
(S1) extracting: mixing an animal oil and/or vegetable oil sample with a buffer solution, adding an extraction solvent, a water removing agent and a salting-out agent after shaking, centrifuging after vortex shaking, and taking a supernatant for purification;
(S2) purification: and (S1) mixing the liquid to be purified obtained in the step (S1) with a purifying agent, carrying out vortex oscillation and centrifugation, taking supernatant, drying by nitrogen, redissolving and filtering to obtain the liquid to be detected.
(S3) mass spectrometric detection: performing separation and measurement on the liquid to be measured (S2) by liquid chromatography-tandem mass spectrometry (LC-MS/MS); quantifying by an external standard method to obtain the content of the veterinary drug;
in the step (S2), the purifying agent is an amino functionalized covalent organic framework material, is formed by orderly arranging a honeycomb porous structure, has a three-dimensional loose porous nanosphere structure, simultaneously has macropores and mesopores, and has an average particle size of 500-1000 nm; the amino-functionalized covalent organic framework material is prepared by taking diamine and polyaldehyde as monomers, polymerizing the monomers in the presence of micelles formed by quaternary ammonium salt cationic surfactant to obtain three-dimensional nanospheres, adding excessive polyamine to replace the diamine with and modify amino functional groups through Building Block Exchange (BBE), and finally washing the quaternary ammonium salt cationic surfactant to obtain the amino-functionalized covalent organic framework material.
In the preparation process of the purifying agent, the quaternary ammonium salt cationic surfactant is used as a structure directing agent to form a micelle containing a hydrophobic chain, the added monomer diamine and the added polybasic aldehyde are polymerized around an alkane chain of the micelle under the action of the hydrophobic chain to form a loose and porous nanosphere structure with a three-dimensional structure, and if the quaternary ammonium salt cationic surfactant does not exist, the monomer polymerization can only obtain a two-dimensional structure. The resulting covalent organic framework is then used to introduce functional amino groups by adding an excess of polyamino compounds. The prepared amino functionalized covalent organic framework material presents a loose and porous spherical shape, has an average size of about 700 nm and has mesoporous/macroporous channels. The introduction of the cationic surface activity of the quaternary ammonium salt obviously increases the specific surface area of the material, and is beneficial to the promotion of the mass transfer rate in the adsorption process.
Further, the pesticide detected by the detection method comprises acetamiprid, acetochlor, alachlor, aldicarb sulfone, ametoctradin, ametryn, amisulbrom, anilofos, atrazine, abamectin, bafenphos, azoxystrobin, benalaxyl, bendiocarb, bensulfuron-methyl, benzovindiflupyr, benate, bifenox, bitertanol, boscalid, bromuconazole, bupirimate, buprofezin, butralin, cadusafos, menadiol, carbofuran, 3-hydroxy carbofuran, chlorbenzuron, chlordimeform, fenvinphos, oxamyl, chlorpyrifos, chlorsulfuron, chlortoluron, cyclofenozide, clomazine, clomazone, coumaphos, cyanazine, cyantraniliprole, cyhalodiamide, cyprodin, cyprodinil, metosulam, thiophosphoryl methyl sulfone, phoxim-methyl, systemic, Phorate, fenprophos, fenpropathrin, fenoxaprop-S-oxide, diazinon, diclorotriazol, diclofenofos, diethofencarb, difenoconazole, diflubenzuron, diflufenican, pipindomethacin, dimethenamid, dimethoate, dimethomorph, dimoxystrobin, diniconazole, ethoprophos, oxydisulfuron, diuron, phenthoate, emamectin benzoate, enestrobin, epoxiconazole, ethion, ethirimol, ethofumesate, fenamiphos, etridiazolone, famoxadone, fenamidone, fenphos, fenamiphos, fenfurazone, fenfursultone, fenfurazophos-ethyl, fenobuconazole, fenbucarb-fenbucarb, fenobucarb, fenobucfenfuram, fenobuconazole, fenoxanil, fenobuconazole, fenoxycarb, fenobuconazole, fenobucarb, fenoxycarb, fenobucarb, fenoxycarb, Oxofenphosone, fenthion sulfone, fenthion sulfoxide, fenvalerate, flonicamid, florasulam, fluazifop-p-butyl, flufenacet, flumetsulam, flumorph, fluopicolide, fluopyram, flurtamone, flusilazole, metamifop, flutolanil, flutriafol, fluvalinate, fluxapyroxamid, fon, forchlorfenuron, fosthiazate, furametphos, heptenophos, hexaconazole, hexaflumuron, hexazinone, hexythiazox, imazalil, imidacloprid, indoxacarb, ipconazole, iprobenfos, valocarb, clofenphos, isocrotophos, isoxaphos-methyl, isoprocarb, isoprothiolane, isoproturon, isoprothiolane, metamifop, mandipropa, fenflurazone, fenpropachtin, fenfluramine, metam, metamifop, isophorp, metamifop, isophoron, isophorp, isophoron, isoproxb, isophos, isophoron, isoproxb, isophos, isoproxb, isophos, isoproxb, isophos, isoproxb, isophos, isoprozachlor, isophos, isoproxil, isophos, isoprox, isoproxil, isophoron, isophos, isoprox, isophoron, isophos, isophoron, isoproxil, isophos, isophoron, Metconazole, methamidophos, methiocarb, methoxyfenozide, metolachlor, metolcarb, metrafenone, metribuzin, metsulfuron-methyl, metoclopramide, monocrotophos, myclobutanil, alachlor, nitenpyram, novaluron, omethoate, oxadiazon, oxadixyl, oxamyl oxime, oxaziclomefone, demeton-methyl, paclobutrazol, parathion, penconazole, pencycuron, penflufenapyr, penoxsulam, penthiopyrad, pyraclostrobin, betanin, phenthoate, phorate sulfoxide, fenthion, thiocyclam, thiophosphoryl methyl, phosmet, phosphamidon, phoxim, picoxystrobin, synergistic ether, pirimicarb, demethylpirimicarb, pirimiphos-methyl, prochlor, profenofos, propaphos, prometryn, propyzacarb, propyzamide, propathrin, propyzamide, propathrin, propathyrifos, propachlor, propathyribac, propathyrifos, propachlor, propach, Propoxur, propaquizamide, prosulfocarb, pyraflufen, pyraclostrobin, pyraoxystrobin, pyribenzoxim, pyridaphenthion, pyrimethanil, pyrisoxazole, quinalphos, quizalofop, rotenone, saflufenacil, cyproconazole, silthiopham, simazine, simetryn, spinetoram J, spinetoram L, spinosad A, spinosad D, spirodiclofen, spirotetramat-keto-hydroxy, spirotetramat-mono-hydroxy, sulfentrazone, sulfotep, tebuconazole, tebufenozide, buthiuron, terbufothiofos, terbufos sulfoxide, terbutazole, tetraconazole, thiabendazole, thiacloprid, thiamethoxam, thifensulfuron-methyl, thifenphos, tolfenpyrad, triazamate, triallate, trifloxystrobin, flutriafolpet, fluazinaxathifluazid, fluazinam, triadimenol, pyraclostrobin, fluazid, thifluazid, thiflufen, thifluazid, thifluzamide, thiflutriafola, thiflufen, thiflutriafolk, thifenchol, thifenpyroxas, thifenchol, thifenpyroxas, thiflutrian, thiflutriafol, thiflutrian, thifenchol, thiflutrian, thifluzamide, thiflutrian, thifluzamide, thiflutrian, thifluzamide, thiflutrian, One or more of triflumuron, aphidifop, zoxamide, benazolin, fenthion, fensulfolane, prochloraz-deaminated imidazole, prochloraz-deimidazole carboxamido, propisochlor, pyrethrin II, pyrimorph, spiromesifen, terbufos, triflumizole metabolite FM-6-1, uniconazole, cyazofamid and pyraclostrobin; veterinary drugs detected by the detection method comprise xylazine, azaperone, pindolol, alprenolol, propranolol, oxprenolol, metoprolol, cananolol, bisoprolol, betaxolol, eszolam, penbutolol, oxazepam, diazepam, nitrazepam, acetylkitasamycin, salinomycin, monensin, sulfadiazine, trimethoprim, ethopabate, sulfamethazine, sulfadimidine, sulfamethoxazole, sulfamethazine, sulfathiazole, sulfamazole, sulfacetamide, sulfadiazine, sulfapyridine, sulfaguanidine monohydrate, sulfaquinoxaline, sulfadimethoxine, sulfadimidine, metronidazole, isopropazole, 6-nitrobenzimidazole, thiodazole, sulfadiazine, sulfadimidine, metronidazole, 6-nitrobenzimidazole, and the like, 5-chloro-1-methyl-4-nitroimidazole, 2-hydroxydinitroimidazole, dimezole, 2-methyl-5-nitroimidazole, 4-nitroimidazole, kitasamycin, nalidixic acid, oxolinic acid, flumequine, roxithromycin, virginiamycin S1, rifampin, midecamycin, telithromycin B, azithromycin, oleandomycin, virginiamycin M1, tylosin tartrate, tilmicosin, spiramycin, acetanilide, benzocaine, ditomidine, levamisole, lidocaine, flurbiprofen, fenbufen, diphenhydramine, clenbuterol, antazoline, clomezanone, chlorpheniramine, clotrimazole, doxepin, anastrozole, diclofenac, fluconazole, ketotiferin, bifonazole, kresoxim-methyl, clomipramine, flufenamipramine, fluazurin, fludioxonil, clotrimazole, clomipramine, fluazinaxapride, clomipramine, clotrimazole, clomipramine, clomipron, clotrimazole, clomipron, cloropin, clomipron, clorophan, clomipron, clorophan, clomipron, clomipramine, clomipron, clorophane, clomipron, clorophan, clomipron, cloropin, clorophan, clorophane, and so, clorophane, clomipramine, clorophane, and so, Gliclazide, citalopram, danazol, griseofulvin, bromhexine, doxaprost, econazole, betamethasone, phenothiazine, glyburide, 2- (4-thiazolyl) benzimidazole, levamisole, 2-amino-5-propanesulfonylbenzimidazole, oxibendazole, ketoprofen, 2-aminofluoropyridazole, albendazole sulfoxide, N-acetaminosulfone, fenbendazole sulfone, phenylguanidine, cimaterol, ceterole, clenbuterol, chlorpropaline, clenbuterol, tobuterol, clenbuterol, brombutol, clenbuterol, bambuterol, maprotide, cyproheptadine, methylynone, progesterone, megestrol acetate, androstenedione, danazol, mestanolol, betamethasone, canrenone, closasone, testosterone propionate, medroxyprogesterone, ketonurone, fludroxyverine, glitazone, sulindac, fludroxyverine, fludroxymedroxide, fludroxyverine, fludroxymedroxide, fludroxyverine, fluben, fludroxyverine, fluniben, fluben, and other, fluben, and other, One or more of chlormadinone, acetylsalicylic acid and doramectin.
Further, in the step (S1), the animal oil includes one or more of lard, beef tallow, mutton tallow, fish oil, bone marrow, fat meat, fish liver oil, etc.; the vegetable oil comprises one or more of soybean oil, rapeseed oil, palm oil, olive oil, peanut oil, sunflower seed oil and the like; the buffer solution is 0.1-0.3M of Na 2 EDTA-Mclvaine, acetic acid-sodium acetate, citric acid-sodium citrate and sodium citrate-disodium hydrogen citrate; the extraction solvent is at least one of acetonitrile, methanol, formic acid water, acetic acid acetonitrile and acetic acid methanol; the proportion of the sample containing the animal oil and/or the vegetable oil, the buffer solution and the extraction solvent is 1 g: 1-2 mL: 3-5 mL; the mass ratio of the animal oil and/or vegetable oil sample to the water removing agent to the salting-out agent is 1: 10-15: 0.3-0.6; the water removing agent is selected from anhydrous sodium sulfate and/or anhydrous magnesium sulfate; the salting-out agent is selected from at least one of sodium chloride, sodium acetate, ammonium acetate and sodium citrate; the operation of centrifugation after vortex oscillation is vortex oscillation for 1-5 min, and centrifugation for 10-30 min at 0-4 ℃ and 8000-.
Further, in the step (S2), the volume-to-mass ratio of the liquid to be purified to the purifying agent is 1 mL: 15-25 mg; the centrifugation after vortex oscillation is that the vortex oscillation time is 30-60 s, and then the centrifugation is carried out for 5-15min under the conditions of 0-4 ℃, 14000-; the redissolving solvent is methanol/water with the volume ratio of 1-2:1-2, and the filtration adopts a 0.22 mu m organic phase filter membrane.
Further, in the step (S3), the liquid chromatography is ultra high performance liquid chromatography (UPLC), and for the detection of the pesticide, ACQUITY UPLC HST 3 (2.1 mm × 100 mm, 1.8 μm) is adopted; the mobile phase adopted by the ultra-high performance liquid chromatography is as follows: 1-2 mM ammonium formate +0.01-0.02% (v/v) formic acid solution (A) and 1-2 mM ammonium formate +0.01-0.02% (v/v) formic acid in methanol solution (B); gradient elution procedure is 3% B (0-1.0 min), 3% -15% B (1.0-1.5 min), 15% -50% B (1.5-2.5 min), 50% -70% B (2.5-18.0 min), 70% -98% B (18.0-23.0 min), 98% B (23.0-27.0 min), 98% -3% B (27.0-27.1 min), 3% B (27.1-30.0 min); the flow rate is 0.1-0.3 mL/min; the column temperature is 40-45 ℃, and the sample injection amount is 2-4 mu L;
for the detection of veterinary drugs, ACQUITY UPLC BEH C18 (2.1 mm. times.100 mm, 1.7 μm) was used; the mobile phase adopted by the ultra-high performance liquid chromatography is as follows: 0.2-0.5 mM ammonium fluoride +0.1-0.2% (v/v) formic acid water (a) and acetonitrile/methanol (v/v = 1/1) (B); flow rate: 0.3 mL/min; gradient elution procedure is 3% B (0-2.0 min), 3% -15% B (2.0-5.0 min), 15% B (5.0-10.0 min), 15% -30% B (10.0-15.0 min), 30% -50% B (15.0-20.0 min), 50% -100% B (20.0-24.0 min), 100% B (24.0-28.0 min)), 3% B (28.5-29.0 min); the flow rate is 0.1-0.3 mL/min; the column temperature is 40-45 ℃, and the sample injection amount is 1-3 mu L.
Further, in the amino functionalized covalent organic framework material, the quaternary ammonium salt cationic surfactant is Cetyl Trimethyl Ammonium Bromide (CTAB), the diamine is 1, 4-Phenylenediamine (PA), the polyaldehyde is 1, 3, 5-tris (p-formylphenyl) benzene (TFPB), and the polyamine is diaminobenzidine (BD-NH) 2 ) The resulting amino-functionalized covalent organic framework material was named CTAB @ TFBD-NH 2 (ii) a The molar ratio of the quaternary ammonium salt cationic surfactant to the diamine to the polyaldehyde is 0.8-1.2: 1.5-2.0: 1.0-1.2: 10-15.
The CTAB/TFBD-NH prepared by the invention 2 The nanosphere has a suitable mesoporous pore diameter (34.9A-46.1A) and a functional group (free amino group) to remove lipid, and has a good removal effect on lipid in animal and vegetable oil.
Further, the amino-functionalized covalent organic framework material provided by the invention is a loose and porous three-dimensional porous nanosphere structure with mesopores and macropores, the average diameter is 500-1000nm, preferably 700-800 nm, and the specific surface area (BET) is 400-600 m 2 (ii)/g, the mesoporous pore diameter is from 20 to 50A, preferably from 30 to 50A; the pore diameter of the macropores is 50-300 nm, preferably 50-200 nm.
The resulting amino-functionalized covalent organic framework material has an ordered arrangement of high crystallinity, consisting of an ordered arrangement of cellular porous structures having pore diameters from 34.9 a to 46.1 a.
Further, the preparation method of the amino functionalized covalent organic framework material comprises the following steps:
(P1) adding a solution in which diamine, polyaldehyde and a catalyst are dissolved into a quaternary ammonium salt cationic surfactant aqueous solution, carrying out ultrasonic treatment on the mixture, carrying out circulating freeze-pumping, carrying out high-temperature reaction, and cooling to room temperature for later use after the reaction is finished;
(P2) adding a solution of polyamine and a catalyst into the system obtained in the step (P1), performing ultrasonic treatment on the mixture, performing circulating freeze-pumping, heating for reaction, and centrifuging, extracting and drying the product to obtain the catalyst.
Further, in the step (P1), the concentration of the quaternary ammonium salt cationic surfactant in the aqueous solution of quaternary ammonium salt cationic surfactant is 0.05 to 0.10 mol/L, at which a micelle having a suitable size is formed. Preferably, the concentration of the quaternary ammonium salt cationic surfactant is 0.06-0.08 mol/L.
In the step (P1), a solution of diamine, polyaldehyde and catalyst is dissolved, and in the step (S2), the solution of polyamine is dissolved in at least one solvent selected from the group consisting of 1, 4-dioxane, n-butanol, o-dichlorobenzene, 1, 3, 5-trimethylbenzene, benzene, toluene and xylene, preferably 1, 4-dioxane and 1, 3, 5-trimethylbenzene in a volume ratio of 1-2: 1-2.
The catalyst is acetic acid, and in the step (P1), the amount of the catalyst is 1-2 times, preferably 1.5-1.7 times that of the monomer substances; in step (P2), the catalyst is used in an amount of 0.1 to 0.2 times, preferably 0.12 to 0.15 times the amount of the polyamine substance.
Further, in the step (P1), (P2), the number of times of freezing and pumping cycles is 3 to 5; the operation of circulating freeze-thaw is well known in the art, i.e., circulating freeze-thaw-vacuum-thaw; in one embodiment of the invention, the circulating freezing and pumping is to put the glass tube filled with the mixture into liquid nitrogen for freezing, and vacuumize in the thawing process, wherein the vacuum degree is 0.1-10 kPa; the ultrasonic treatment time is 10-30 min, and the materials are uniformly mixed.
Further, in the step (P1), the high-temperature reaction temperature is 100 ℃ and 150 ℃, and the reaction time is 2-4 days; in the step (S2), the reaction temperature is heated to 30-60 ℃ and the reaction time is 2-4 days.
Further, in the step (P2), the post-treatment is to remove the solvent by centrifugation after the reaction is finished, wash, perform soxhlet extraction, and perform vacuum drying to obtain the product; the washing solvent is selected from water, ethanol, and acetone; the solvent for Soxhlet extraction is at least one of acetone, 1, 4-dioxane and tetrahydrofuran.
The purifying agent used by the invention is an amino functionalized covalent organic framework material, and is a three-dimensional nanosphere with macropores/mesopores, the average diameter is 500-1000nm, preferably 700-800 nm, and the specific surface area (BET) is 400-600 m 2 The specific surface area is increased by about 10 times compared to the polymer obtained in the absence of micelles, which is due to the loose and porous structure of the three-dimensional, loose nanospheres obtained in the presence of micelles, the larger specific surface area providing more reaction sites and active adsorption sites.
Drawings
FIG. 1 is a schematic representation of the LC-MS/MS detection method for veterinary drug residues in animal and vegetable oils of the present invention;
FIG. 2 is a diagram of the synthesis of amino-functionalized covalent organic framework material CTAB @ TFBD-NH of the present invention 2 A schematic diagram of (a);
FIG. 3 shows TFBD-NH obtained in preparation example 2 CTAB @ TFPA and CTAB @ TFBD-NH 2 HRTEM images and SEM images of (g);
FIG. 4 shows TFPA, CTAB/TFPA, TFBD-NH obtained in example 1 2 And CTAB/TFBD-NH 2 Nitrogen adsorption-desorption isotherms.
Detailed Description
All reagents were purchased from commercial suppliers and used without further purification.
Preparation example 2 Synthesis of CTAB @ TFBD-NH
The preparation method is described in patent CN202210989648.0, and comprises the following steps:
cetyl trimethyl ammonium bromide (CTAB, 32.8 mg, 0.09 mmol) was placed in a Schlenk tube, 1.3 mL of ultrapure water was added for ultrasonic dissolution, glacial acetic acid (0.6 mL, 6 mol/L), 1, 4-benzenediAmine (PA, 16.3 mg, 0.15 mmol) and 1, 4-dioxane (1.5 mL) and the mixture was stored in a refrigerator to prevent oxidation of the PA. A solution containing 1, 3, 5-tris (p-formylphenyl) benzene (TFPB, 39.0 mg, 0.1 mmol) was added as a solvent mixture of 1.5 mL1, 4-dioxane and 3 mL1, 3, 5-trimethylbenzene. The mixture is treated by ultrasonic for 10min to be mixed evenly, liquid nitrogen freezing-methanol unfreezing circulation degassing is carried out for three times, the mixture is heated for three days at 120 ℃ under the vacuum condition, and after the mixture is cooled to the room temperature, a polymer which takes CTAB as a structure directing agent and PA and TFPB as monomers is obtained and is called CTAB @ TFPA. Subjecting Schlenk tube containing CTAB @ TFPA to ultrasonic treatment for 10min, and adding diaminobenzidine (BD-NH) 2 321.4 mg, 1.5 mmol), 1, 4-dioxane (2.0 mL), 1, 3, 5-trimethylbenzene (1.0 mL) and 6M acetic acid (0.3 mL), the mixture was sonicated for 10min, degassed by three liquid nitrogen freeze-methanol thaw cycles, heated at 40 ℃ for three days under vacuum sealed conditions to give a dark red precipitate, centrifuged to remove the solvent, washed with ultrapure water, extracted with THF in a Soxhlet extractor, then vacuum dried at 120 ℃ for 12 h to give an amino functionalized covalent organic framework material, named CTAB @ TFBD-NH 2 . The synthetic scheme is shown in figure 2.
To further illustrate the synthetic routes of the present invention, and to study and explain the morphological changes of the amino-functionalized covalent organic framework materials of the three-dimensional structures of the present invention. The invention also carries out the following synthesis:
synthesis of TFPA:
to a 20 mL Schlenk tube were added PA (16.3 mg, 0.15 mmol) and TFPB (39.0 mg, 0.1 mmol), 1, 4-dioxane (3.0 mL), 1, 3, 5-trimethylbenzene (3.0 mL), and 6M acetic acid (0.6 mL). The mixture was sonicated for 10 minutes to obtain a homogeneous dispersion, degassed by three liquid nitrogen freeze-pump-methanol thaw cycles, sealed under vacuum and heated at 120 ℃ for three days. The yellow precipitate obtained was centrifuged to remove the solvent, Soxhlet extracted in THF for two days, then dried under vacuum at 120 ℃ for 12 h.
2 Synthesis of TFBD-NH by BBE:
to a 20 mL Schlenk tube were added PA (16.3 mg, 0.15 mmol) and TFPB (39.0 mg, 0.1 mmol), 1, 4-dioxane (3.0 mL), 1, 3, 5-trimethylbenzene (3.0 mL), and 6M acetic acid (0.6 mL). The mixture was sonicated for 10 minutes to obtain a homogeneous dispersion, degassed by three liquid nitrogen freeze-pump-methanol thaw cycles, sealed under vacuum and heated at 120 ℃ for three days. After cooling to Room Temperature (RT), Schlenk tubes containing TFPA were sonicated for 10 minutes. Then, BD-NH was added to the mixture 2 (321.4 mg, 1.5 mmol), 1, 4-dioxane (1.5 mL), 1, 3, 5-trimethylbenzene (1.5 mL), and 6M acetic acid (0.3 mL). The mixture was sonicated for an additional 10 minutes, degassed by three liquid nitrogen freeze-pump-methanol thaw cycles, sealed under vacuum and heated at 40 ℃ for three days. The dark red precipitate obtained was centrifuged to remove the solvent, Soxhlet extracted in THF for two days, then dried under vacuum at 120 ℃ for 12 h.
FIG. 3 shows the resulting TFBD-NH 2 CTAB @ TFPA and CTAB @ TFBD-NH 2 HRTEM image and SEM image of (A) in FIG. 3 is TFBD-NH 2 Fig. 3 (B) is an enlarged image of a selected region of fig. 3 (a), and fig. 3 (C) is a crystal structure observed by vertical projection of fig. 3 (B). As can be seen, TFBD-NH 2 Having an ordered arrangement of high crystallinity, a honeycomb-like porous structure can be observed under a high-resolution electron microscope ((C) of fig. 3). Porous Structure indicates TFBD-NH 2 The pitch of (C) was about 4 nm, which is very consistent with the simulated structure model of fig. 3, in which the pitch of (C) was 4.14 nm. FIG. 3 (D) is an SEM image of CTAB/TFPA, and FIG. 3 (E) is CTAB @ TFBD-NH 2 Fig. 3 (F) is a partially enlarged view of a selected region of fig. 3 (E). As can be seen, CTAB/TFPA and CTAB/TFBD-NH were added after initial CTAB addition in the material synthesis 2 The material has a loose and porous 3D spherical shape, the average size is about 700 nm, and the material has obvious macroporous channels.
FIG. 4 is TFPA, CTAB/TFPA、TFBD-NH 2 And CTAB/TFBD-NH 2 Nitrogen adsorption-desorption isotherm. TFPA and TFBD-NH 2 Respectively BET surface areas of 56 m 2 G and 43 m 2 (ii) in terms of/g. However, CTAB/TFPA and CTAB/TFBD-NH 2 The BET surface area is respectively increased by about ten times to 563 m 2 (g and 455 m) 2 /g, which can be attributed to CTAB/TFPA and CTAB/TFBD-NH 2 A porous and porous structure.
Application example
1.UHPLC-MS/MS working conditions:
for the pesticide-based standard, liquid chromatography analysis was performed using a Waters Acquity Ultra Performance LC high Performance liquid chromatograph. The analytes were chromatographed using an ACQUITY UPLC HSS T3 (2.1 mm. times.100 mm, 1.8 μm) column. The column temperature was 40 ℃ and the sample size was 2. mu.L. Mobile phase: 2 mM ammonium formate +0.01% (v/v) formic acid water (A) and 2 mM ammonium formate +0.01% (v/v) formic acid methanol (B); flow rate: 0.3 mL/min. The gradient elution procedure is 3% B (0-1.0 min), 3% -15% B (1.0-1.5 min), 15% -50% B (1.5-2.5 min), 50% -70% B (2.5-18.0 min), 70% -98% B (18.0-23.0 min), 98% B (23.0-27.0 min), 98% -3% B (27.0-27.1 min), 3% B (27.1-30.0 min). The total cycle time for each sample was 30.0 min.
Mass spectrometry was performed using a Waters Xevo TQ-S triple quadrupole mass spectrometer and operated in Multiple Reaction Monitoring mode (MRM). The main parameters are as follows, ion source: electrospray ion source (ESI); an ionization mode: a positive ion mode; ion source temperature: 350 ℃.
For the veterinary drug standards, liquid chromatography analysis was performed using a Waters Acquity Ultra Performance LC high Performance liquid chromatograph. The analytes were chromatographed using an ACQUITY UPLC BEH C18 (2.1 mm. times.100 mm, 1.7 μm) chromatography column. The column temperature was 40 ℃ and the amount of sample was 3. mu.L. Mobile phase: 0.5 mM ammonium fluoride +0.1% (v/v) formic acid water (a) and acetonitrile/methanol (v/v = 1/1) (B); flow rate: 0.3 mL/min. The gradient elution procedure is 3% B (0-2.0 min), 3% -15% B (2.0-5.0 min), 15% B (5.0-10.0 min), 15% -30% B (10.0-15.0 min), 30% -50% B (15.0-20.0 min), 50% -100% B (20.0-24.0 min), 100% B (24.0-28.0 min), 100% -3% B (28.0-28.5 min), 3% B (28.5-29.0 min). The total cycle time for each sample was 29.0 min.
Mass spectrometry was performed using a Waters Xevo TQ-XS triple quadrupole mass spectrometer and operated in Multiple Reaction Monitoring mode (MRM). The main parameters are as follows, ion source: electrospray ion source (ESI); an ionization mode: a positive ion mode; ion source temperature: 400 ℃.
2. UPLC-MS/MS detection of pesticide and veterinary drug residues in animal oil and vegetable oil
(S1) extracting: 2 g animal oil/vegetable oil samples were mixed with 2mL 0.1M Na 2 Mixing EDTA-Mclvaine buffer solution, adding 10 mL acetonitrile, 20 g anhydrous sodium sulfate and 1g sodium chloride after 1 min vortex oscillation, carrying out vortex oscillation for 1 min, centrifuging at 8000 rpm and 4 ℃ for 10min, and taking 1mL of supernatant to be purified.
(S2) purification: and (2) mixing the liquid to be purified obtained in the step (1) with a purifying agent, and centrifuging for 10min at 14000 rpm after vortexing for 60 s. Take 0.5 mL of supernatant and blow dry with 0.5 mL of methanol/water = 50: and (5) redissolving by 50, and filtering by a filter membrane of 0.22 mu m to obtain a solution to be detected.
(S3) mass spectrometric detection: separating and measuring the solution to be measured in the step (2) by UPLC-MS/MS; and quantifying by using an external standard method to obtain the content of the veterinary drug.
3. The experimental results are as follows:
to evaluate the full recovery performance of the material, the accuracy and precision of the method was evaluated by a recovery experiment at an addition level of 100 ppb (n = 3). The test tests carried out on 277 pesticides and 135 veterinary drugs, combined 412 pesticide and veterinary drug residues. The test results are shown in Table 1. Where recovery and Relative Standard Deviation (RSD) represent the accuracy and precision of the process, respectively. For the animal oil sample, among 412 kinds of agricultural and veterinary medicines, the recovery rate of 378 kinds is more than 50%; for the animal oil sample, 398 recovery rates out of 412 veterinary drugs were greater than 50%. Although the recovery rate of part of the veterinary drugs is low, all compounds can be detected, and the qualitative requirement of non-directional screening is met. In the animal oil and vegetable oil samples, the relative standard deviation of the 412 kinds of veterinary drugs is 0.18-19.79% and 0.43-20.18%, respectively, which shows that the method has high precision.
Table 1412 agricultural and veterinary medicine information and standard recovery rate (100 mug/mL)
The LC-MS/MS detection method has a good detection effect on most of pesticide and veterinary drug residues (100 mug/mL) in the animal oil and the plant oil. Recovery rates for small quantities of veterinary drugs, particularly some veterinary drugs such as thiabendazole, tolfenpyrad, tricyclazole, triflumizole, cananolol, sulfamethizole, glyburide, brombuterol, are less than ideal, probably due to their size and CTAB/TFBD-NH 2 The pore size of the nanospheres is similar to that of CTAB/TFBD-NH 2 The amino groups on the nanospheres have strong hydrogen bonding interaction. Therefore, some other functional modifications may be made in the future to avoid this risk.
Claims (10)
1. An LC-MS/MS detection method for pesticide and veterinary drug residues in animal oil and vegetable oil is characterized by comprising the following steps:
(S1) extracting: mixing an animal oil and/or vegetable oil sample with a buffer solution, adding an extraction solvent, a water removing agent and a salting-out agent after shaking, centrifuging after vortex shaking, taking supernate, and purifying;
(S2) purification: mixing the liquid to be purified obtained in the step (S1) with a purifying agent, performing vortex oscillation, centrifuging, taking supernatant, drying with nitrogen, redissolving, and filtering to obtain a liquid to be detected;
(S3) mass spectrometric detection: performing separation and measurement on the (S2) to-be-measured solution by liquid chromatography-tandem mass spectrometry; quantifying by an external standard method to obtain the content of the veterinary drug;
in the step (S2), the purifying agent is an amino functionalized covalent organic framework material which is formed by orderly arranging a honeycomb porous structure, has a three-dimensional loose porous nanosphere structure, simultaneously has macropores and mesopores, and has an average particle size of 500-1000 nm; the amino-functionalized covalent organic framework material is prepared by taking diamine and polyaldehyde as monomers, polymerizing the monomers in the presence of micelles formed by quaternary ammonium salt cationic surfactant to obtain three-dimensional nanospheres, adding excessive polyamine to replace the diamine by building block exchange and modify the diamine with amino functional groups, and finally washing the quaternary ammonium salt cationic surfactant off.
2. The detection method according to claim 1, wherein the pesticide to be detected comprises acetamiprid, acetochlor, alachlor, aldicarb, ametoctradin, ametryn, amisulbrom, anilofos, atrazine, abamectin, bazophos, azoxystrobin, benalaxyl, bendiocarb, bensulfuron methyl, benzovindiflupyr, fenbutate, bifenox, boscalid, bromacil, bromuconazole, bupirimate, buprofezin, butralin, cadusafos, carbaryl, carbendazim, carbofuran, 3-hydroxycarbicarb, chlorbenzuron, chlordimeform, fenpyrad, fenpyroxim, chlorpyrifos, chlorsulfuron, chlortoluron, chromafenozide, clofentrazine, clomazone, clothianidin, coumaphos, cyanazine, cyantraniliprole, cyflufen, cyflufenamidon, cyprodin, cyprodinil, cyprosulfan, cyproconazole, thifenpyrad, triazophos, pyraclostrobin, clofos, cyhalofos, etc, Methyl systemic phosphorus, methyl sulfone systemic phosphorus, disulfotoxin, phosphorus-S-sulfoxide, diazinon, phenicol, diclofen, fenoxaprop-P-ethyl, chlorothalofop-P-methyl, diethofencarb, difenoconazole, diflubenzuron, diflufenican, pipindoside, dimethenamid, dimethoate, dimethomorph, dimorpholine, ethofexamine, diniconazole, ethoprophos-P-ethyl, oxydisup-S-sulfoxide, diuron, thiophosphoryl, diphenofos, emamectin benzoate, enestroburin, epoxiconazole, ethion, ethirimol, ethofumesate, fenamiphos, etrifos, famoxadone, fenamidone, dimethomoxamine, fenamiphos, fenaminosulf, fenamiphos, fenaminobac-ethyl, fenpropathrin, fenpropidin, fenpyrazofen-ethyl, fenoxafen-ethyl, fenpyrazofenoxafen-ethyl, fenpyrazofen-ethyl, fenoxafen-ethyl, fenpyrazofenoxaprop-p-ethyl, fenpyrazofenoxapyrone, fenpyrazofenoxaprop-p-ethyl, fenugo-p-ethyl, fenugo-p-ethyl, fenugo-p-ethyl, fenpyr, fenugo-p-ethyl, fenugo-p-ethyl, fenpyr-p-methyl, fenpyr, Fenpyroximate, fenphos, fenprophos, fenthion sulfone, fenthion sulfoxide, fenvalerate, flonicamid, florasulam, fluazifop-p-butyl, flufenacet, flumetsulam, flumorphine, fluopicolide, flurtamone, flusilazole, metamitron, flutolanil, fluvalinate, fluvalicarb, fluxapyroxamid, fonofos, clopidogyne, fosthiazate, furametphos, heptenophos, hexaconazole, hexaflumuron, hexazinone, hexythiazox, imazalil, imidacloprid, indoxacarb, ipconazole, iprobenfos, iprovalicarb, clofos, isochlorofos, isofenphos, isoprocarb, isoprothiolane, isoproturon, isopyrazam, isoxaflutolon, linuron, malathion, propaferin, propyzamide, fenphos, fenpropamocarb, propamocarb, isoprothiolane, isoproturon, isoprothiolane, isoproxil, isoprothiolane, isoproturon, isoprox, isoproxil, isoproturon, isoproxil, isoprothiolane, isoproturon, isoproxil, isoproturon, isoproxil, isoproturon, isoproxil, isoprox, Metamifop, metamitron, pyraflufen, metconazole, methamidophos, methiocarb, methoxyfenozide, metolachlor, metolcarb, metrafenone, metribuzin, metsulfuron-methyl, metocloprid, monocrotophos, myclobutanil, alachlor, nitenpyram, novaluron, omethoate, oxadiargyl, oxadiazon, oxadixyl, oxamyl oxime, oxaziclomefone, endothos, paclobutrazol, parathion, penconazole, pencycuron, penflufenapyr, penoxsulam, penthiopyrad, fenaminostrobin, phenthol, fenpropathrin, phorate, metsul, metsulphos, thiocyclophos, thiophosphoryl-methyl, phos-methyl, phoxim, synergistic ether, pirimicarb-methyl, pirimibensulam, propamocarb, prochlorate, prochloraz, prophos, prochloraz, methidathion, bromacil, bencarb, bensulam, benazolin, fenphos, fenpyr, fenphos, fenpyr, fenphos, fenpyr, fenphos, fenpyr, fenphos, fenpyr, propamocarb, propanil, propoxur, propyzamide, propoxymidine, prosulfocarb, pyraclostrobin, pyraoxystrobin, pyribenzoxim, pyridaphenthion, quizalofop, rotenone, saflufenacil, sedaxane, silthiopham, silthiofam, simethiam, simazine, simetryn, spinetoram J, spinetoram L, spinosad A, spinosad D, spirodiclofen, spirotetramat-keto-hydroxy, spirotetramat-mono-hydroxy, sulfentrazone, fenpyrad, tebuconazole, tebufenozide, buthiuron, terbufos sulfoxide, terbuthylazine, tebufenoconazole, thiabendazole, thiacloprid, thiabendazole, thifensulfuron-methyl, thifenflurazon, tolfenpyrad, triadimefon, One or more of triallate, triazophos, tricyclazole, trifloxystrobin, triflumizole, triflumuron, aphidophos, zoxamide, benazolin, fensulfofop-methyl, prochloraz-deaminated imidazole, prochloraz-deimidazole carboxamido, propisochlor, pyrethrin II, pyrimorph, spiromesifen, terbufos, triflumizole metabolite FM-6-1, uniconazole, cyazofamid and pyraclostrobin;
the veterinary drug for detection comprises xylazine, azaperone, pindolol, alprenolol, propranolol, oxprenolol, metoprolol, cananolol, bisoprolol, betaxolol, eszolam, penbutolol, oxazepam, diazepam, acekitasamycin, salinomycin, monensin, sulfanitrone, trimethoprim, fexouba, sulfamethazine, phenacyl sulfonamide, sulfamethizole, sulfamethoxazole, sulfamethazine, sulfathiazole, sulfamethazole, sulfadiazine, sulfapyridine, sulfaguanidine monohydrate, sulfaquinoxaline, sulfadimethoxine, sulfadimidine, metronidazole, hydroxymetronidazole, metronidazole, isopropazole, 6-nitrobenzimidazole, 5-chloro-1-methyl-4-nitroimidazole, metoprolol, sulfadimidine, doxine, metronidazole, nitroimidazole, nitrobenzimidazole, nitroimidazole, and other compounds, 2-hydroxydiniconazole, dimeprazole, 2-methyl-5-nitroimidazole, 4-nitroimidazole, kitasamycin, nalidixic acid, oxolinic acid, flumequine, roxithromycin, virginiamycin S1, rifampin, medecamycin, telithromycin, tylosin B, azithromycin, oleandomycin, virginiamycin M1, tylosin tartrate, tilmicosin, spiramycin, acetanilide, benzocaine, ditetramidine, levamisole, lidocaine, flurbiprofen, fenbufen, diphenhydramine, clenbuterol, antazolirtilin, clomazone, chlorpheniramine, clotrimazole, cyproheptadine, anastrozole, diclofenac, fluconazole, ketotifen, bifonazole, kresoxim-methyl, clomipramine, gliclazide, citalopram, danazol, griseofulvin, bromhexine, doxazon, doxam, and, Econazole, betamethasone, phenothiazine, glyburide, 2- (4-thiazolyl) benzimidazole, levamisole, 2-amino-5-propanesulfonyl benzimidazole, oxibendazole, ketoprofen, 2-aminofluoropyridazole, albendazole sulfoxide, N-acetaminosulfone, fenbendazole sulfone, phenylguanidine, cimaterol, clenbuterol, clorpropyramine, clorprenaline, clenbuterol, tulobuterol, one or more of clenbuterol, brombutolol, cromopant, bambuterol, maprotide, cyproheptadine, methylethynone, progesterone, megestrol acetate, androstenedione, danazol, meperidol, betamethasone, canrenone, cloisonne, testosterone propionate, methyltestosterone, medroxyprogesterone, chlormadrogesterone, acetylsalicylic acid, doramectin.
3. The detection method according to claim 1, wherein in the step (S1), the animal oil comprises one or more of lard, beef tallow, mutton tallow, fish oil, bone marrow, fat meat, fish liver oil, etc.; the vegetable oil comprises one or more of soybean oil, rapeseed oil, palm oil, olive oil, peanut oil, sunflower seed oil and the like.
4. The detection method according to claim 1, wherein in the step (S1), the buffer solution is Na 2 EDTA-Mclvaine, acetic acid-sodium acetate, citric acid-sodium citrate and sodium citrate-disodium hydrogen citrate, wherein the concentration is 0.1-0.3M; the extraction solvent is at least one selected from acetonitrile, methanol, formic acid water, acetic acid acetonitrile and acetic acid methanol; the proportion of the animal oil and/or vegetable oil containing sample, the buffer solution and the extraction solvent is 1 g: 1-2 mL: 3-5 mL; quality of animal oil and/or vegetable oil sample, water scavenger and salting-out agentThe quantity ratio is 1: 10-15: 0.3-0.6; the water removing agent is selected from anhydrous sodium sulfate and/or anhydrous magnesium sulfate; the salting-out agent is at least one selected from sodium chloride, sodium acetate, ammonium acetate and sodium citrate.
5. The detection method according to claim 1, wherein in the step (S2), the volume-to-mass ratio of the liquid to be purified to the purifying agent is 1 mL: 15-25 mg.
6. The detection method according to claim 1, wherein the amino-functionalized covalent organic framework material is obtained by using cetyltrimethylammonium bromide as the quaternary ammonium salt cationic surfactant, 1, 4-phenylenediamine as the diamine, 1, 3, 5-tri (p-formylphenyl) benzene as the polyaldehyde, and diaminobenzidine as the polyamine, and is named CTAB @ TFBD-NH 2 (ii) a The quaternary ammonium salt cationic surfactant, diamine and polybasic aldehyde are added, wherein the molar ratio of the polybasic amine is 0.8-1.2: 1.5-2.0: 1.0-1.2: 10-15.
7. The detection method as claimed in claim 6, wherein the amino-functionalized covalent organic framework material has a porous three-dimensional porous nanosphere structure with mesopores and macropores, an average diameter of 500-1000nm, and a specific surface area of 400-600 m 2 The diameter of the mesopores is between 20 and 50A, and the diameter of the macropores is between 50 and 300 nm.
8. The detection method according to claim 7, wherein the amino functionalized covalent organic framework material has an average diameter of 700-800 nm, a mesoporous pore diameter of 30-50A, and a macroporous pore diameter of 50-200 nm.
9. The detection method according to claim 1, wherein the amino-functionalized covalent organic framework material is prepared by a method comprising the following steps:
(P1) adding a solution in which diamine, polyaldehyde and a catalyst are dissolved into a quaternary ammonium salt cationic surfactant aqueous solution, carrying out ultrasonic treatment on the mixture, carrying out circulating freeze-pumping, carrying out high-temperature reaction, and cooling to room temperature after the reaction is finished for later use;
(P2) adding a solution of polyamine and a catalyst into the system obtained in the step (S1), performing ultrasonic treatment on the mixture, performing circulating freeze-pumping, performing heating reaction, and centrifuging, extracting and drying the product to obtain the catalyst.
10. The detection method according to claim 9, wherein the concentration of the quaternary ammonium salt cationic surfactant in the aqueous solution of the quaternary ammonium salt cationic surfactant in step (P1) is 0.05 to 0.10 mol/L; the catalyst is acetic acid, and in the step (S1), the amount of the catalyst is 1-2 times of the amount of the monomer substances; in the step (S2), the amount of the catalyst is 0.1 to 0.2 times of the amount of the polyamine substance; in the step (P1), (P2), the number of times of circulating freeze-pumping is 3-5 times;
and/or, in the step (P1), the high-temperature reaction temperature is 100 ℃ and 150 ℃, and the reaction time is 2-4 days; in the step (S2), the reaction temperature is heated to 30-60 ℃ and the reaction time is 2-4 days.
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