Detection method for rapidly determining content of twenty-two flame retardants in consumer goods

Abstract

The invention relates to the technical field of consumer goods detection, and discloses a detection method for rapidly determining the content of twenty-two flame retardants in consumer goods, which comprises the following steps: S1, preparing a liquid sample; s2, putting a solid sample to be detected into a reaction tube, and adding a liquid sample; step S3, extracting; and S4, analyzing the sample solution by adopting a liquid chromatograph-mass spectrometer. The method can simultaneously detect the content of twenty-two organic flame retardants, utilizes ultrasonic extraction and LCMSMS analysis, makes up the disadvantages of gas chromatography, can rapidly determine the content of twenty-two organic flame retardants, is simple in operation and short in analysis time, and has very high test efficiency. According to the method, the repeatability is 0.3%-3.8%, the reproducibility is 1.3%-2.7%, the detection limit of the method is as low as 0.02 mg / kg, and the method completely meets the control requirements of all countries and the test requirements of customers.

Description

Technical Field

[0001] The present invention relates to the technical field of consumer product testing, and in particular to a method for rapidly determining the contents of twenty-two flame retardants in consumer products. Background Art

[0002] Organic flame retardants are a type of additive that can make synthetic materials flame retardant and self-extinguishing and have plasticizing functions. They are mainly classified into phosphorus flame retardants and bromine flame retardants. They are widely used in foams, plastics, textiles, furniture and building materials, and electronic products. However, organic flame retardants are mostly used as additives rather than reacting with materials. Therefore, they are easily released into the surrounding environment through wear, volatilization, etc., causing environmental pollution. Some flame retardants can induce DNA breaks in cells and increase the risk of genetic diseases such as cancer due to their high persistence, bioaccumulation, biomagnification, and long-distance migration. In addition, they may also have toxic effects on the nervous system and immune system, affect the development and function of the nervous system, inhibit the function of the immune system, and cause impaired immune response. For example, TBBPA (tetrabromobisphenol A) has endocrine toxicity and carcinogenicity; HBCDD (hexabromocyclododecane) has neurotoxicity, etc.

[0003] In the US CHCC children's safety product program, 22 organic flame retardants are included in the control list, with a limit of 30 mg / kg; so far, the European Chemicals Agency (ECHA) has included 15 organic flame retardants in the list of substances of very high concern, and their content must not exceed 0.1wt%; the current POPs Convention also has limited use of organic flame retardants, such as hexabromocyclododecane and decabromodiphenyl ether; the list of organic flame retardants controlled by each country is shown in the table below.

[0004]

[0005]

[0006] Considering the control of various countries and regions and the demand for export of consumer products, it is particularly important to develop a detection method that can simultaneously determine the content of these 22 organic flame retardants in products. At present, most of the tests for flame retardants are gas chromatography, such as the GC-MS test used in GB / T 24279.1-2018. However, for some flame retardants with high boiling points (such as HBCDD), gas chromatography cannot fully detect them, and bromine-containing flame retardants will have secondary decomposition at high temperatures at the injection port (such as TBBPA / TRIS). This makes it impossible to accurately quantify during the test process, resulting in low test efficiency and the need for repeated testing. At present, there is no literature, information or standard method to use LC-MS / MS to provide a detection method for these 22 organic flame retardants in consumer products. Summary of the invention

[0007] The purpose of the present invention is to provide a new testing method, which can simultaneously and quickly and efficiently detect twenty-two flame retardants in consumer products, and conduct accurate qualitative and quantitative analysis.

[0008] To achieve the above object, the present invention provides the following technical solutions:

[0009] A method for rapidly determining the content of twenty-two flame retardants in consumer products comprises the following steps:

[0010] Step S1: preparing standard working solutions of twenty-two organic flame retardants to obtain liquid samples;

[0011] Step S2: placing the solid sample to be tested in a reaction tube and adding the liquid sample;

[0012] Step S3: extraction, adding toluene solvent to the reaction tube, ultrasonic extraction to obtain a primary extract, adding an equal amount of toluene solvent again, ultrasonic extraction to obtain a secondary extract, combining the extracts to obtain an extract, evaporating and concentrating the extract until the residue is nearly dry, dissolving the residue with acetonitrile, filtering through an organic filter membrane to obtain a sample solution;

[0013] Step S4 uses liquid chromatography-mass spectrometry to analyze the sample solution, and the analysis conditions are:

[0014] Ionization mode: electrospray (ESI) positive / negative ion; chromatographic column: ACQUI TY UPLC BEH C18 150X2.1mm1.7um or equivalent chromatographic column; mobile phase: A: 5mmo l / L ammonium acetate aqueous solution B: 1% tetrahydrofuran acetonitrile; gradient elution program; mass spectrometry parameters: capillary voltage: -2.5kV (negative mode) / +3.2kV ​​(positive mode), ion source temperature: 150°C, desolvation gas temperature: 300°C, desolvation flow rate: 800L / Hr, cone flow rate: 20L / Hr;

[0015] The twenty-two flame retardants are TCEP, TCPP, TDCPP, TEPA, TRIS, V6, MDPP, DBPP, TMP, TEP, TBP, BDBPP, TBEP, TEHP, ToCP, TmCP, TpCP, TBBPA, HBCDD, IPIPP, OPOP and TPP.

[0016] Specifically, the selection of extraction method: the main extraction methods of flame retardants are ultrasonic extraction, oscillation extraction and Soxhlet extraction. Therefore, by comparing the extraction efficiency of these three methods, the experiment found that the extraction efficiency of ultrasonic extraction and Soxhlet extraction is higher than that of oscillation extraction, and the extraction efficiency of the two is equivalent, but the operation steps of Soxhlet extraction are cumbersome and time-consuming, which cannot meet the needs of rapid detection. At the same time, ultrasonic extraction has the advantages of easy operation, short extraction time, and large amount of samples that can be processed at the same time. Therefore, ultrasonic extraction is adopted as the extraction method of this patent.

[0017] Specifically, the selection of ultrasonic extraction solvent: organic flame retardants are easily soluble in organic solvents. The extraction efficiency of five organic solvents, including toluene, ethyl acetate, n-hexane, dichloromethane and acetone, was compared. The extraction efficiency of acetone, ethyl acetate, n-hexane and dichloromethane relative to toluene was 85.2%, 71.2%, 62.5% and 30.5%, respectively. The results showed that the recovery rate of toluene solution was higher than that of other extraction solvents. Therefore, toluene was selected as the extraction agent.

[0018] Specifically, optimization of ultrasonic extraction conditions:

[0019] (1) The ultrasonic temperature of ultrasonic extraction was optimized. The control variable method was used to set four ultrasonic extraction temperatures of 40°C, 50°C, 60°C, and 70°C. Blank matrix was spiked and the extraction recoveries were compared. It was found that the overall extraction efficiency at 60°C and 70°C was higher than that at 40°C and 50°C. The overall extraction efficiency at 70°C was lower than that at 60°C. The experimental analysis showed that ultrasonic extraction involved the intervention of ultrasonic energy and used a higher extraction temperature, which caused the loss of the target. Therefore, 60°C was selected as the ultrasonic extraction temperature.

[0020] (2) The extraction time of ultrasonic extraction was optimized. The control variable method was used to set four ultrasonic extraction times of 30 min, 45 min, 60 min, and 90 min. The blank matrix was spiked and the extraction recoveries were compared. It was found that the overall recoveries of 60 min and 90 min were equivalent and higher than those of 30 min and 45 min. Based on the requirements of high-throughput testing, 60 min was finally selected as the ultrasonic extraction time.

[0021] Specifically, the optimization of color spectrum conditions:

[0022] (1) Selection of liquid mobile phase: The liquid chromatography conditions of UPLC-MS / MS were optimized. The ionization modes of the twenty-two components in this patent were both positive and negative. Seven mobile phase systems were compared, including water-acetonitrile, water-methanol, 5 mmol / L ammonium acetate aqueous solution-acetonitrile, 5 mmol / L ammonium acetate aqueous solution-methanol, 10 mmol / L ammonium acetate aqueous solution-acetonitrile, 5 mmol / L ammonium acetate aqueous solution-acetonitrile, and 5 mmol / L ammonium acetate aqueous solution-1% tetrahydrofuran acetonitrile. It was found that the ammonium acetate system had better separation than other systems, better ionization efficiency of the target components, and higher response. The separation and peak shape were better with increasing concentration of ammonium acetate. However, the isomers of HBCDD were not completely separated. Therefore, 1% tetrahydrofuran was added to enhance its elution ability and improve the separation. All substances were effectively separated using 5 mmol / L ammonium acetate aqueous solution-1% tetrahydrofuran acetonitrile. Considering the damage of the salt system to the instrument hardware, 5 mmol / L ammonium acetate was used. 1 / L ammonium acetate aqueous solution-1% tetrahydrofuran acetonitrile was used as the mobile phase to elute the target, which could obtain a good peak shape and improved separation. Finally, 5mmo l / L ammonium acetate aqueous solution-1% tetrahydrofuran acetonitrile was used as the mobile phase.

[0023] (2) Selection of liquid chromatography columns: Since the twenty-two organic flame retardants exist as isomers or have the same parent ions and fragment ions, certain requirements are placed on the separation effect. The separation effects of three chromatographic columns, ACQUI TY UPLC BEH C8 (2.1*50mm*1.7um), ACQUI TY UPLC BEH C18 (2.1*50mm*1.7um), and UPLC HSS T3 (2.1*50mm*1.8um), on the twenty-two organic flame retardants were compared. The results showed that the separation effect of ACQUI TY UPLC BEH C18 was better than that of the other two chromatographic columns. When ACQUI TY UPLC BEH C18 with a length of 100 mm and 150 mm were used for comparison, it was found that when the 150 mm column was used for separation, the twenty-two compounds were well separated, with high sensitivity and good peak shape. Therefore, ACQUI TY UPLC BEH C18 (2.1*150mm*1.7um) column was selected as the analytical column.

[0024] Specifically, the method was determined to be applicable to sample types: four sample matrices in the consumer goods field, namely textiles, plastics, paints and coatings, were selected, and matrix blank and spike recovery tests were performed on the samples according to the test method. The sample matrix blank had no interference with the target, and the spike recovery and precision were good.

[0025] A positive sample (HBCDD) was selected for comparison, and GCMS and LCMSMS were used for comparison. The GCMS analysis procedure was long, and secondary cleavage occurred in HBCDD, making it impossible to accurately quantify. The LCMSMS analysis time was short and could accurately determine the quality and quantification.

[0026] Preferably, the preparation method of the liquid sample in step S1 is:

[0027] S11. Prepare 22 organic flame retardant stock solutions with a concentration of 1000 mg / L: weigh 0.01 g (accurate to 0.1 mg) of 22 organic flame retardant standards respectively, dissolve them with toluene, transfer them to a 10 mL brown volumetric flask, and dilute to the mark with toluene;

[0028] S12. Prepare a 10 mg / L mixed intermediate solution of 22 kinds of organic flame retardants: use a pipette to transfer 0.1 mL of each of the 22 organic flame retardant stock solutions to a 10 mL brown volumetric flask, and dilute to the mark with acetonitrile to prepare a 10 mg / L mixed standard intermediate solution of 22 kinds of organic flame retardants;

[0029] S13. Prepare standard curve working solutions of twenty-two kinds of organic flame retardants. Transfer 0.01ml, 0.02ml, 0.05ml, 0.1ml and 0.2ml of the ten preservative intermediate solutions into five 10ml brown volumetric flasks, dilute to the scale with acetonitrile, and prepare twenty-two kinds of organic flame retardant standard working solutions with concentrations of 0.01mg / L, 0.02mg / L, 0.05mg / L, 0.1mg / L and 0.2mg / L, respectively.

[0030] Preferably, the solid sample described in step S2 is specifically prepared by: taking 5-10 g of a representative solid sample with clean and uncontaminated stainless steel scissors, cutting the sample into small cubes of about 2×2 mm or crushing the sample with a grinder, and mixing the sample evenly, weighing 1 g of the sample, and placing it in a clean 40 ml threaded reaction tube.

[0031] Preferably, the liquid sample in step S1 is repeatedly shaken 3-5 times to mix well, and 1 g of the liquid sample is weighed with a clean and uncontaminated pipette and placed in the reaction tube in step S2.

[0032] Preferably, the extraction in step S3 is specifically as follows: adding 20 mL of toluene to the reaction tube, extracting in an ultrasonic generator at 60±2°C for 40 min, collecting the extract in a 100 mL concentration bottle, adding another 20 mL of toluene to the reaction tube, extracting in an ultrasonic generator at 60±2°C for 20 min, combining the extracts and collecting them in a 100 mL concentration bottle; concentrating with a rotary evaporator at 60°C until the residue is nearly dry, taking 2 mL of acetonitrile to dissolve the residue, and filtering through an organic filter membrane to obtain a sample solution.

[0033] Preferably, in step S4, the gradient elution procedure is specifically:

[0034]

[0035] Preferably, the detection ion pairs and collision energies (ion pairs, cone voltage and collision energy) of the twenty-two flame retardants are specifically:

[0036]

[0037]

[0038]

[0039] Preferably, in step S4, the detection instrument used is Waters Acquity HCl ass+Xevo TQD or equivalent equipment, the detection method adopted is multiple reaction ion monitoring (MRM), and the injection volume is 5uL.

[0040] Technical effects and advantages of the present invention:

[0041] 1. Previously, there was a lack of detection methods for the simultaneous detection of these 22 organic flame retardants. This method uses ultrasonic extraction and LCMSMS analysis to make up for the shortcomings of gas chromatography analysis. It can quickly determine the content of 22 flame retardants. It is simple to operate and has a short analysis time, and has a high test efficiency.

[0042] 2. The repeatability of this method is 0.3%-3.8%, the reproducibility is 1.3%-2.7%, and the detection limit is as low as 0.02 mg / kg, which fully meets the control requirements of various countries and the testing requirements of customers.

[0043] 3. The present invention uses ultrasonic extraction to extract samples and liquid chromatography-mass spectrometry to analyze samples. Ultrasonic extraction is a mature extraction technology that uses the strong cavitation effect, mechanical vibration, disturbance effect, high acceleration, emulsification, diffusion, crushing and stirring effects generated by ultrasonic radiation pressure to increase the frequency and speed of molecular motion of substances and the penetration of solvents, thereby accelerating the entry of target components into solvents and promoting extraction. It has the advantages of simple operation and high extraction efficiency.

[0044] 4. The liquid chromatography-mass spectrometry has a strong separation capability. The sample is separated once on the chromatographic column and then screened twice at the mass spectrometer end by parent ions and daughter ions in the form of ion pairs. The qualitative analysis results are reliable. The detection limit is low and the MS has high sensitivity. The ESI spray ion focused ionization technology is used to increase the electric field density while increasing the atomization temperature, which significantly improves the ionization efficiency and effectively shields the matrix interference. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 It is the chromatogram of the present invention.

[0046] Figure 2 It is a curve diagram of TBBPA of the present invention.

[0047] Figure 3 It is a curve diagram of HBCDD of the present invention.

[0048] Figure 4 It is a graph of TRIS of the present invention.

[0049] Figure 5 This is a curve diagram of V6 of the present invention.

[0050] Figure 6 It is a curve diagram of TEHP of the present invention.

[0051] Figure 7 It is a curve diagram of TDCPP of the present invention.

[0052] Figure 8 It is a curve diagram of OPOP of the present invention.

[0053] Fig. 9 It is a graph of TCPP of the present invention.

[0054] Fig.10 It is a curve diagram of TCEP of the present invention.

[0055] Fig.11 It is a graph of TEP of the present invention.

[0056] Fig.12 It is a curve diagram of TEPA of the present invention.

[0057] Fig.13 It is a graph of TMP of the present invention.

[0058] Fig.14 It is a curve diagram of BDBPP of the present invention.

[0059] Fig.15 It is a graph of IPIPP of the present invention.

[0060] Fig.16 It is a curve diagram of DBPP of the present invention.

[0061] Fig.17 It is a curve diagram of TBEP of the present invention.

[0062] Fig.18 It is a curve diagram of MDPP of the present invention.

[0063] Fig.19 It is a curve diagram of TpCP of the present invention.

[0064] Fig. 20 It is a curve diagram of TmCP of the present invention.

[0065] Fig.21 It is a curve diagram of ToCP of the present invention.

[0066] Fig. 22 It is a curve diagram of TBP of the present invention.

[0067] Fig.23 This is a graph of TPP of the present invention. DETAILED DESCRIPTION

[0068] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0069] Embodiment: A method for rapidly determining the content of twenty-two flame retardants in consumer products comprises the following steps:

[0070] Step S1: prepare standard working solutions of twenty-two organic flame retardants to obtain liquid samples.

[0071] The preparation method of the liquid sample in step S1 of this embodiment is:

[0072] S11. Prepare 22 organic flame retardant stock solutions with a concentration of 1000 mg / L: weigh 0.01 g (accurate to 0.1 mg) of 22 organic flame retardant standards respectively, dissolve them with toluene, transfer them to a 10 mL brown volumetric flask, and dilute to the mark with toluene;

[0073] S12. Prepare a 10 mg / L mixed intermediate solution of 22 kinds of organic flame retardants: use a pipette to transfer 0.1 mL of each of the 22 organic flame retardant stock solutions to a 10 mL brown volumetric flask, and dilute to the mark with acetonitrile to prepare a 10 mg / L mixed standard intermediate solution of 22 kinds of organic flame retardants;

[0074] S13. Prepare standard curve working solutions of twenty-two kinds of organic flame retardants. Transfer 0.01ml, 0.02ml, 0.05ml, 0.1ml and 0.2ml of the ten preservative intermediate solutions into five 10ml brown volumetric flasks, dilute to the scale with acetonitrile, and prepare twenty-two kinds of organic flame retardant standard working solutions with concentrations of 0.01mg / L, 0.02mg / L, 0.05mg / L, 0.1mg / L and 0.2mg / L, respectively.

[0075] Step S2: placing the solid sample to be tested in a reaction tube and adding the liquid sample.

[0076] The solid sample described in step S2 of this embodiment is specifically prepared by taking 5-10 g of a representative solid sample with clean and uncontaminated stainless steel scissors, cutting the sample into small cubes of about 2×2 mm or crushing the sample with a grinder, and mixing the sample evenly, weighing 1 g of the sample, and placing it in a clean 40 ml threaded reaction tube.

[0077] In this embodiment, the liquid sample in step S1 is shaken repeatedly for 3-5 times to make it evenly mixed, and 1 g of the liquid sample is weighed with a clean and uncontaminated pipette and placed in the reaction tube in step S2.

[0078] Step S3 is extraction, adding toluene solvent to the reaction tube, ultrasonic extraction to obtain a primary extract, adding an equal amount of toluene solvent again, ultrasonic extraction to obtain a secondary extract, combining the extracts to obtain an extract, evaporating and concentrating the extract until the residue is nearly dry, dissolving the residue with acetonitrile, filtering through an organic filter membrane, and obtaining a sample solution.

[0079] In this embodiment, the extraction in step S3 is specifically as follows: adding 20 mL of toluene to the reaction tube, extracting in an ultrasonic generator at 60±2°C for 40 min, collecting the extract in a 100 mL concentration bottle, adding another 20 mL of toluene to the reaction tube, extracting in an ultrasonic generator at 60±2°C for 20 min, combining the extracts and collecting them in a 100 mL concentration bottle; concentrating at 60°C with a rotary evaporator until the residue is nearly dry, taking 2 mL of acetonitrile to dissolve the residue, filtering through an organic filter membrane, and obtaining a sample solution.

[0080] Step S4 uses liquid chromatography-mass spectrometry to analyze the sample solution, and the analysis conditions are:

[0081] The detection instrument used is Waters Acquity HCl ass+Xevo TQD or equivalent equipment

[0082] Ionization method: electrospray (ESI) positive / negative ion

[0083] The detection method is multiple reaction ion monitoring (MRM)

[0084] The injection volume is 5uL

[0085] Chromatographic column: ACQUI TY UPLC BEH C18 150X2.1mm 1.7um or equivalent

[0086] Mobile phase: A: 5 mmol / L ammonium acetate aqueous solution B: 1% tetrahydrofuran acetonitrile

[0087] Gradient elution program

[0088] Mass spectrometry parameters: capillary voltage: -2.5 kV (negative mode) / +3.2 kV (positive mode), ion source temperature: 150 °C, desolvation gas temperature: 300 °C, desolvation flow rate: 800 L / Hr, cone flow rate: 20 L / Hr;

[0089] The twenty-two flame retardants are TCEP, TCPP, TDCPP, TEPA, TRIS, V6, MDPP, DBPP, TMP, TEP, TBP, BDBPP, TBEP, TEHP, ToCP, TmCP, TpCP, TBBPA, HBCDD, IPIPP, OPOP and TPP.

[0090] In this embodiment, the gradient elution procedure is specifically as follows:

[0091]

[0092]

[0093] In this embodiment, the detection ion pairs and collision energies (ion pairs, cone voltage and collision energy) of the twenty-two flame retardants are specifically:

[0094]

[0095]

[0096] Recovery rate and repeatability experiment: In the consumer goods field, four sample matrices, textiles, plastics, paints, and coatings, were used for matrix blank and spike recovery tests according to the test method. The sample matrix blank had no interference with the target. The experimental results showed that the spike recovery rate and precision were good, the repeatability was 0.3%-3.8%, the reproducibility was 1.3%-2.7%, and the method detection limit was as low as 0.02mg / kg, which fully met the control requirements of various countries and the testing requirements of the market.

[0097] 1. Recovery rate and repeatability test of blank textile samples spiked (0.02 mg / kg):

[0098]

[0099]

[0100]

[0101] 2. Recovery rate and repeatability experiment of plastic blank sample spiked (0.2 mg / kg):

[0102]

[0103]

[0104]

[0105] 3. Recovery rate and repeatability experiment of paint sample spiked (5.0 mg / kg):

[0106]

[0107]

[0108]

[0109] 4. Recovery and repeatability of paint sample spike (10.0 mg / kg)

[0110]

[0111]

[0112] Results and Discussion:

[0113] Specifically, the selection of extraction method: the main extraction methods of flame retardants are ultrasonic extraction, oscillation extraction and Soxhlet extraction. Therefore, by comparing the extraction efficiency of these three methods, the experiment found that the extraction efficiency of ultrasonic extraction and Soxhlet extraction is higher than that of oscillation extraction, and the extraction efficiency of the two is equivalent, but the operation steps of Soxhlet extraction are cumbersome and time-consuming, which cannot meet the needs of rapid detection. At the same time, ultrasonic extraction has the advantages of easy operation, short extraction time, and large amount of samples that can be processed at the same time. Therefore, ultrasonic extraction is adopted as the extraction method of this patent.

[0114] Specifically, the selection of ultrasonic extraction solvent: organic flame retardants are easily soluble in organic solvents. The extraction efficiency of five organic solvents, including toluene, ethyl acetate, n-hexane, dichloromethane and acetone, was compared. The extraction efficiency of acetone, ethyl acetate, n-hexane and dichloromethane relative to toluene was 85.2%, 71.2%, 62.5% and 30.5%, respectively. The results showed that the recovery rate of toluene solution was higher than that of other extraction solvents. Therefore, toluene was selected as the extraction agent.

[0115] Specifically, optimization of ultrasonic extraction conditions:

[0116] (1) The ultrasonic temperature of ultrasonic extraction was optimized. The control variable method was used to set four ultrasonic extraction temperatures of 40°C, 50°C, 60°C, and 70°C. Blank matrix was spiked and the extraction recoveries were compared. It was found that the overall extraction efficiency at 60°C and 70°C was higher than that at 40°C and 50°C. The overall extraction efficiency at 70°C was lower than that at 60°C. The experimental analysis showed that ultrasonic extraction involved the intervention of ultrasonic energy and used a higher extraction temperature, which caused the loss of the target. Therefore, 60°C was selected as the ultrasonic extraction temperature.

[0117] (2) The extraction time of ultrasonic extraction was optimized. The control variable method was used to set four ultrasonic extraction times of 30 min, 45 min, 60 min, and 90 min. The blank matrix was spiked and the extraction recoveries were compared. It was found that the overall recoveries of 60 min and 90 min were equivalent and higher than those of 30 min and 45 min. Based on the requirements of high-throughput testing, 60 min was finally selected as the ultrasonic extraction time.

[0118] Specifically, optimization of chromatographic conditions: (1) Selection of liquid mobile phase: The liquid chromatography conditions of UPLC-MS / MS were optimized. The ionization modes of the twenty-two components in this patent were both positive and negative ion modes. The ionization modes of water-acetonitrile, water-methanol, 5 mmol / L ammonium acetate aqueous solution-acetonitrile, 5 mmol / L ammonium acetate aqueous solution-methanol, 10 mmol / L ammonium acetate aqueous solution-acetonitrile, 5 mmol / L ammonium acetate aqueous solution-acetonitrile, 5 mmol / L ammonium acetate aqueous solution-methanol, 1 / L ammonium acetate aqueous solution-1% tetrahydrofuran acetonitrile 7 mobile phase systems, it was found that the ammonium acetate system had better separation than other systems, better ionization efficiency of the target components, and higher responses. The separation and peak shape were better with the increase of ammonium acetate concentration, but the isomers of HBCDD were not completely separated, so 1% tetrahydrofuran was added to enhance its elution ability and improve the separation. All substances were effectively separated using 5mmol / L ammonium acetate aqueous solution-1% tetrahydrofuran acetonitrile. Considering the damage of the salt system to the instrument hardware, 5mmo l / L ammonium acetate aqueous solution-1% tetrahydrofuran acetonitrile was used as the mobile phase to elute the target, which could obtain a good peak shape and improved separation. Finally, 5mmo l / L ammonium acetate aqueous solution-1% tetrahydrofuran acetonitrile was used as the mobile phase.

[0119] (2) Selection of liquid chromatography columns: Since the twenty-two organic flame retardants exist as isomers or have the same parent ions and fragment ions, certain requirements are placed on the separation effect. The separation effects of three chromatographic columns, ACQUI TY UPLC BEH C8 (2.1*50mm*1.7um), ACQUI TY UPLC BEH C18 (2.1*50mm*1.7um), and UPLC HSS T3 (2.1*50mm*1.8um), on the twenty-two organic flame retardants were compared. The results showed that the separation effect of ACQUI TY UPLC BEH C18 was better than that of the other two chromatographic columns. When ACQUI TY UPLC BEH C18 with a length of 100 mm and 150 mm were used for comparison, it was found that when the 150 mm column was used for separation, the twenty-two compounds were well separated, with high sensitivity and good peak shape. Therefore, ACQUI TY UPLC BEH C18 (2.1*150mm*1.7um) column was selected as the analytical column.

[0120] Specifically, the method was determined to be applicable to sample types: four sample matrices in the consumer goods field, namely textiles, plastics, paints and coatings, were selected, and matrix blank and spike recovery tests were performed on the samples according to the test method. The sample matrix blank had no interference with the target, and the spike recovery and precision were good.

[0121] A positive sample (HBCDD) was selected for comparison, and GCMS and LCMSMS were used for comparison. The GCMS analysis procedure was long, and secondary cleavage occurred in HBCDD, making it impossible to accurately quantify. The LCMSMS analysis time was short and could accurately determine the quality and quantification.

[0122] from Figure 1 It can be seen from the chromatogram that after various conditions are optimized, the actual chromatogram can be obtained and each substance can be effectively separated. Figures 2 to 23 The corresponding curves of the twenty-two flame retardants can also prove that the curves of the 22 flame retardants in the present application are linear within the concentration range of the curves, and can be used for accurate quantification in actual tests.

[0123] The present invention adopts ultrasonic extraction method to extract samples, and liquid chromatography-mass spectrometry is used to analyze samples. Ultrasonic extraction method is to use the strong cavitation effect, mechanical vibration, disturbance effect, high acceleration, emulsification, diffusion, crushing and stirring effect generated by ultrasonic radiation pressure to increase the frequency and speed of material molecular movement, increase the penetration of solvent, thereby accelerating the target component to enter the solvent, and has the advantages of simple operation and high extraction efficiency.

[0124] The liquid chromatography-mass spectrometry instrument has a strong separation capability. The sample is separated once on the chromatographic column and then screened twice at the mass spectrometer end by parent ions and daughter ions in the form of ion pairs. The qualitative analysis results are reliable. The detection limit is low and the MS has high sensitivity. The ESI spray ion focused ionization technology is used to increase the electric field density while increasing the atomization temperature, which significantly improves the ionization efficiency and effectively shields the matrix interference.

[0125] Finally, it should be noted that the above is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, it is still possible for those skilled in the art to modify the technical solutions described in the aforementioned embodiments, or to make equivalent substitutions for some of the technical features therein. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for rapidly determining the content of twenty-two flame retardants in consumer products, characterized in that: The following steps are involved: Step S1: preparing standard working solutions of twenty-two organic flame retardants to obtain liquid samples; Step S2: placing the solid sample to be tested in a reaction tube and adding the liquid sample; Step S3: extraction, adding toluene solvent to the reaction tube, ultrasonic extraction to obtain a primary extract, adding an equal amount of toluene solvent again, ultrasonic extraction to obtain a secondary extract, combining the extracts to obtain an extract, evaporating and concentrating the extract until the residue is nearly dry, dissolving the residue with acetonitrile, filtering through an organic filter membrane to obtain a sample solution; Step S4 uses liquid chromatography-mass spectrometry to analyze the sample solution, and the analysis conditions are: Ionization method: electrospray (ESI) positive / negative ion Chromatographic column: ACQUITY UPLC BEH C18 150X2.1mm 1.7um or equivalent Mobile phase: A: 5mmol / L ammonium acetate aqueous solution B: 1% tetrahydrofuran acetonitrile Gradient elution program Mass spectrometry parameters: capillary voltage: -2.5 kV (negative mode) / +3.2 kV (positive mode), ion source temperature: 150 °C, desolvation gas temperature: 300 °C, desolvation flow rate: 800 L / Hr, cone flow rate: 20 L / Hr; The twenty-two flame retardants are TCEP, TCPP, TDCPP, TEPA, TRIS, V6, MDPP, DBPP, TMP, TEP, TBP, BDBPP, TBEP, TEHP, ToCP, TmCP, TpCP, TBBPA, HBCDD, IPIPP, OPOP and TPP.

2. A method for rapidly determining the content of twenty-two flame retardants in consumer products according to claim 1, characterized in that: The preparation method of the liquid sample in step S1 is: S11. Prepare 22 organic flame retardant stock solutions with a concentration of 1000 mg / L: weigh 0.01 g of 22 organic flame retardant standards respectively, dissolve them in toluene, transfer them to a 10 mL brown volumetric flask, and dilute to the mark with toluene; S12. Prepare a 10 mg / L mixed intermediate solution of 22 kinds of organic flame retardants: use a pipette to transfer 0.1 mL of each of the 22 organic flame retardant stock solutions to a 10 mL brown volumetric flask, and dilute to the mark with acetonitrile to prepare a 10 mg / L mixed standard intermediate solution of 22 kinds of organic flame retardants; S13. Prepare standard curve working solutions of twenty-two kinds of organic flame retardants. Transfer 0.01ml, 0.02ml, 0.05ml, 0.1ml and 0.2ml of the ten preservative intermediate solutions into five 10ml brown volumetric flasks, dilute to the scale with acetonitrile, and prepare twenty-two kinds of organic flame retardant standard working solutions with concentrations of 0.01mg / L, 0.02mg / L, 0.05mg / L, 0.1mg / L and 0.2mg / L, respectively.

3. A method for rapidly determining the content of twenty-two flame retardants in consumer products according to claim 1, characterized in that: The solid sample described in step S2 is specifically prepared by taking 5-10 g of the solid sample with stainless steel scissors, cutting the sample into small cubes of about 2×2 mm or crushing the sample with a grinder, and mixing the sample evenly, weighing 1 g of the sample, and placing it in a clean 40 ml threaded reaction tube.

4. A method for rapidly determining the content of twenty-two flame retardants in consumer products according to claim 1, characterized in that: First, repeatedly shake the liquid sample in step S1 for 3-5 times to mix well, weigh 1 g of the liquid sample with a pipette, and place it in the reaction tube in step S2.

5. The method for rapidly determining the content of twenty-two flame retardants in consumer products according to claim 1, characterized in that: The extraction in step S3 is specifically as follows: adding 20 mL of toluene to the reaction tube, extracting in an ultrasonic generator at 60±2° C. for 40 min, collecting the extract in a 100 mL concentration bottle, adding another 20 mL of toluene to the reaction tube, extracting in an ultrasonic generator at 60±2° C. for 20 min, combining the extracts and collecting them in a 100 mL concentration bottle; concentrating at 60° C. with a rotary evaporator until the residue is nearly dry, taking 2 mL of acetonitrile to dissolve the residue, and filtering through an organic filter membrane to obtain a sample solution.

6. A method for rapidly determining the content of twenty-two flame retardants in consumer products according to claim 1, characterized in that: In step S4, the gradient elution procedure is specifically as follows: 。 7. A method for rapidly determining the content of twenty-two flame retardants in consumer products according to claim 1, characterized in that: The ion pairs, cone voltages and collision energies of the twenty-two flame retardants are specifically:

8. The method for rapidly determining the content of twenty-two flame retardants in consumer products according to claim 1, characterized in that: In step S4, the detection instrument used is Waters Acquity H Class+Xevo TQD or equivalent equipment, the detection method adopted is multiple reaction ion detection (MRM), and the injection volume is 5uL.

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