A method for determining tertiary butylated triphenyl phosphate in consumer goods

Abstract

This application provides a method for determining tert-butylated triphenyl thiophosphate in consumer products, comprising the steps of: sampling; adding a first volume of a first reagent to the sample and sonicating at a first specified temperature for a first specified time to obtain an extract; adding a second volume of a second reagent to the extract and sonicating at a second specified temperature for a second specified time, filtering to obtain a test solution; and placing the test solution in a gas chromatography-mass spectrometry (GC-MS) instrument for qualitative and quantitative analysis. The analytical parameters of the GC-MS instrument are as follows: column: DB-5HT; carrier gas flow rate: 1.2 ml / min; injection volume: 1 μL; injection port temperature: 280℃; column oven temperature: 100℃ held for 0 min; temperature ramped at 20℃ / min to 280℃ and held for 0 min; temperature ramped at 35℃ / min to 325℃ and held for 8 min; added ions: 342, 383, 439, 495. The optimized method conditions and parameters of this application enable accurate determination of the tert-butylated triphenyl thiophosphate content in consumer products.

Description

Technical Field

[0001] This application relates to the field of chemical testing technology for consumer products, and in particular to a method for determining tert-butylated triphenyl thiophosphate in consumer products. Background Technology

[0002] Tert-butylated triphenyl thiophosphate is an industrial product mainly used as a lubricant additive to improve the performance of lubricants under extreme conditions and enhance their oxidation resistance. In addition, this substance can also be added to daily consumer products as a flame retardant and plasticizer.

[0003] According to research by the European Chemicals Agency (ECHA), this substance is difficult to decompose in nature and accumulates rapidly in organisms, exhibiting significant toxicity to aquatic plants and animals. Therefore, the EU designated it a Substance of Very High Concern (SVHC) on January 23, 2025, and included it in its control measures. It is foreseeable that this substance may be subject to control by more countries and regions in the future.

[0004] However, tert-butylated triphenyl thiophosphate is a complex mixture, and there is currently no reliable method for its determination. Summary of the Invention

[0005] In view of the aforementioned problems, this application is made in order to provide a method for determining tert-butylated triphenyl thiophosphate in consumer products that overcomes or at least partially solves the aforementioned problems.

[0006] A method for determining tert-butylated triphenyl thiophosphate in a consumer product includes the following steps:

[0007] sampling;

[0008] A first volume of a first reagent is added to the sample, and the sample is sonicated at a first specified temperature for a first specified time to obtain an extract.

[0009] A second volume of the second reagent is added to the extract, and the mixture is sonicated at a second specified temperature for a second specified time. After filtration, the test solution is obtained.

[0010] The test solution was placed in a gas chromatography-mass spectrometry system for qualitative and quantitative analysis.

[0011] The analytical parameters of the gas chromatography-mass spectrometry system include:

[0012] Column: DB-5HT; Carrier gas flow rate: 1.2 ml / min; Injection volume: 1 μL; Injector temperature: 280℃;

[0013] Column oven temperature: 100℃ held for 0 min; 20℃ / min to 280℃ held for 0 min; 35℃ / min to 325℃ held for 8 min;

[0014] Addition ions: 342, 383, 439, 495.

[0015] Furthermore, the sampling step includes:

[0016] Cut the sample into small pieces and weigh 1g ± 0.05g of the homogenized sample into a test tube.

[0017] Further, the step of adding a second volume of the second reagent to the extract includes:

[0018] First, place the extract in a shaker for 28-32 minutes, then add a second volume of the second reagent to the extract.

[0019] Furthermore, the first volume is 10 ml ± 0.1 ml.

[0020] Furthermore, the second volume is 20 ml.

[0021] Furthermore, both the first specified temperature and the second specified temperature are 65℃-75℃.

[0022] Furthermore, both the first specified time and the second specified time are 28min-32min.

[0023] Furthermore, the first reagent is tetrahydrofuran.

[0024] Furthermore, the second reagent is acetonitrile.

[0025] Furthermore, the step of placing the test solution in a gas chromatography-mass spectrometry (GC-MS) instrument for qualitative and quantitative detection and analysis includes:

[0026] The response values ​​of the four representative ions of the tert-butylated triphenyl thiophosphate standard were summed, and a standard curve was established based on the summation result.

[0027] The response values ​​of the four representative ions of the sample are summed and compared with the standard curve for quantitative analysis.

[0028] This application has the following advantages:

[0029] In the embodiments of this application, the gap in the prior art regarding the determination of tert-butylated triphenyl thiophosphate content in consumer products is filled. A method for determining tert-butylated triphenyl thiophosphate in consumer products includes the following steps: sampling; adding a first volume of a first reagent to the sample and sonicating at a first specified temperature for a first specified time to obtain an extract; adding a second volume of a second reagent to the extract and sonicating at a second specified temperature for a second specified time, filtering to obtain a test solution; and placing the test solution in a gas chromatography-mass spectrometry (GC-MS) instrument for qualitative and quantitative analysis. The analytical parameters of the GC-MS instrument are as follows: column: DB-5HT; carrier gas flow rate: 1.2 ml / min; injection volume: 1 μL; injection port temperature: 280°C; column oven temperature: 100°C held for 0 min; temperature increased to 280°C at 20°C / min and held for 0 min; temperature increased to 325°C at 35°C / min and held for 8 min; added ions: 342, 383, 439, 495. Based on the material structure and composition of tert-butylated triphenyl thiophosphate, this application pre-processes it and then performs qualitative and quantitative analysis using gas chromatography-mass spectrometry. By optimizing the conditions and parameters of the method, it can accurately determine tert-butylated triphenyl thiophosphate in consumer products, filling the gap in national standard methods. The method has a low detection limit, is simple to operate, and the equipment used is readily available, making it highly scalable. Attached Figure Description

[0030] To more clearly illustrate the technical solution of this application, the drawings used in the description of this application will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0031] Figure 1 This is a flowchart of the steps for determining tert-butylated triphenyl thiophosphate in a consumer product according to an embodiment of this application;

[0032] Figure 2 This is the full spectrum of tert-butylated triphenyl thiophosphate provided in the embodiments of this application;

[0033] Figure 3 This is a chromatogram of tert-butylated triphenyl thiophosphate provided in the embodiments of this application under selective ion mode. Detailed Implementation

[0034] To make the objectives, features, and advantages of this application more apparent and understandable, the application will be further described in detail below with reference to the accompanying drawings and specific embodiments. Obviously, the described embodiments are only some, not all, of the embodiments of this application. All other embodiments obtained by those skilled in the art based on the embodiments of this application without inventive effort are within the scope of protection of this application.

[0035] Reference Figure 1 The flowchart illustrates the steps of a method for determining tert-butylated triphenyl thiophosphate in a consumer product according to an embodiment of this application.

[0036] The detection method includes:

[0037] S110, Sampling;

[0038] S120. Add a first volume of the first reagent to the sample and sonicate at a first specified temperature for a first specified time to obtain an extract;

[0039] S130. Add a second volume of the second reagent to the extract, sonicate at a second specified temperature for a second specified time, and filter to obtain the test solution for use.

[0040] S140. Place the test solution into a gas chromatography-mass spectrometry system for qualitative and quantitative detection and analysis.

[0041] The analytical parameters of the gas chromatography-mass spectrometry (GC-MS) instrument are as follows:

[0042] Column: DB-5HT; Carrier gas flow rate: 1.2 ml / min; Injection volume: 1 μL; Injector temperature: 280℃;

[0043] Column oven temperature: 100℃ held for 0 min; 20℃ / min to 280℃ held for 0 min; 35℃ / min to 325℃ held for 8 min;

[0044] Addition ions: 342, 383, 439, 495.

[0045] In the embodiments of this application, the gap in the prior art regarding the determination of tert-butylated triphenyl thiophosphate content in consumer products is filled. A method for determining tert-butylated triphenyl thiophosphate in consumer products includes the following steps: sampling; adding a first volume of a first reagent to the sample and sonicating at a first specified temperature for a first specified time to obtain an extract; adding a second volume of a second reagent to the extract and sonicating at a second specified temperature for a second specified time, filtering to obtain a test solution; and placing the test solution in a gas chromatography-mass spectrometry (GC-MS) instrument for qualitative and quantitative analysis. The analytical parameters of the GC-MS instrument are as follows: column: DB-5HT; carrier gas flow rate: 1.2 ml / min; injection volume: 1 μL; injection port temperature: 280°C; column oven temperature: 100°C held for 0 min; temperature increased to 280°C at 20°C / min and held for 0 min; temperature increased to 325°C at 35°C / min and held for 8 min; added ions: 342, 383, 439, 495. Based on the material structure and composition of tert-butylated triphenyl thiophosphate, this application pre-processes it and then performs qualitative and quantitative analysis using gas chromatography-mass spectrometry. By optimizing the conditions and parameters of the method, it can accurately determine tert-butylated triphenyl thiophosphate in consumer products, filling the gap in national standard methods. The method has a low detection limit, is simple to operate, and the equipment used is readily available, making it highly scalable.

[0046] The following will further describe a method for determining tert-butylated triphenyl thiophosphate in a consumer product according to an exemplary embodiment of this invention.

[0047] As described in step S110, sampling is generally one of the important steps to extract a small amount of target substance from the target object for testing. It is an effective way to obtain various data from the target object without affecting its main properties. The amount of the analyte extracted needs to be sufficient for 3-5 tests. The sampling area selection process for the analyte during sampling should be random.

[0048] As an example, the sample was cut into pieces, and 1g ± 0.05g of homogenized sample was weighed into a test tube.

[0049] As described in step S120, a first volume of a first reagent is added to the sample, and the sample is sonicated at a first specified temperature for a first specified time to obtain an extract. This is equivalent to pretreatment of the sample to be tested. Pretreatment generally involves steps such as purification and decontamination of the target substance before effective processing. In some special experiments, pretreatment steps may also include altering the properties of the substance. In this embodiment, ultrasonic treatment of the sample is preferred.

[0050] In this embodiment, the first reagent is tetrahydrofuran; the first volume is 10ml ± 0.1ml; the ultrasonic extraction conditions are: ultrasonic temperature 65℃-75℃, ultrasonic time 28min-32min.

[0051] As an example, 10 ml of tetrahydrofuran was added to the sample and ultrasonically extracted at 70 °C for 30 min to obtain the extract.

[0052] Tetrahydrofuran has good swelling or dissolving ability for most plastics and textiles, and the tert-butylated triphenyl thiophosphate of this application is easily soluble in tetrahydrofuran. Therefore, using tetrahydrofuran as a solvent for the sample to be tested can better dissolve the tert-butylated triphenyl thiophosphate, which can improve the sample extraction efficiency and extraction rate, thereby improving the accuracy of the test results.

[0053] As described in step S130, a second volume of the second reagent is added to the extract, and the mixture is sonicated at a second specified temperature for a second specified time. After filtration, the test solution is obtained.

[0054] Furthermore, before adding the second reagent, the extract is placed on a shaker and shaken for a certain period of time, preferably 28-32 minutes in this embodiment.

[0055] In this embodiment, the second reagent is acetonitrile; the second volume is 20 ml; the ultrasonic conditions for the second ultrasonic extraction are: ultrasonic temperature 65℃-75℃, ultrasonic time 28 min-32 min.

[0056] As an example, the extract was placed on a shaker for 30 minutes, then 20 ml of acetonitrile was added to the extract, and the mixture was sonicated at 70°C for 30 minutes. The mixture was then filtered to obtain the filtered test solution.

[0057] Adding acetonitrile can precipitate and purify the extract, removing dissolved consumer product matrices such as plastics and textile matrices from tetrahydrofuran. At the same time, it will not have much impact on tert-butylated triphenyl thiophosphate, thus preventing polymers from entering the instrument and protecting the equipment. Furthermore, filtration can improve the purity of the test solution, avoiding the influence of impurities and improving the accuracy of detection.

[0058] As described in step S140, the test solution is placed in a gas chromatography-mass spectrometry instrument for qualitative and quantitative detection and analysis.

[0059] The analytical parameters of the gas chromatography-mass spectrometry (GC-MS) instrument are as follows:

[0060] Column: DB-5HT; Carrier gas flow rate: 1.2 ml / min; Injection volume: 1 μL; Injector temperature: 280℃;

[0061] Column oven temperature: 100℃ held for 0 min; 20℃ / min to 280℃ held for 0 min; 35℃ / min to 325℃ held for 8 min;

[0062] Addition ions: 342, 383, 439, 495.

[0063] As an example, the response values ​​of the four representative ions of the tert-butylated triphenyl thiophosphate standard are summed, and a standard curve is established based on the summation result; the response values ​​of the four representative ions of the sample are summed and compared with the standard curve for quantitative analysis.

[0064] It should be noted that, because tert-butylated triphenyl thiophosphate is a multi-component mixture, its content cannot be directly calculated from the results of a single component. Through research, four representative components were isolated and selected from tert-butylated triphenyl thiophosphate, as shown below. Figure 2 And as shown in the table below.

[0065] Component 1 Triphenyl thiophosphate 342 Component 2 Triphenyl monotert-butyl phosphate (mixture) 383 Component 3 Di-tert-butyl triphenyl phosphate (mixture) 439 Component 4 Tri-tert-butyl thiophosphate (mixture) 495

[0066] In sample testing, representative ions of four components should be selected. The presence of at least two of the four representative components indicates the detection of tert-butylated triphenyl thiophosphate. For quantification, the response values ​​of the four representative ions in the sample should be summed, and the summed result should be compared with a standard curve for quantitative analysis.

[0067] The following are embodiments of the present invention:

[0068] Example

[0069] By conducting simulation experiments on typical sample materials and adding a quantitative amount of the target analyte to the simulation solution, the corresponding equipment is used for detection and analysis.

[0070] 1: Sample Description: Coating

[0071] 2: Spiking process:

[0072] Take 1g ± 0.01g of the sample, cut it into small pieces, and put it into a test tube. Add 150μL of 1000mg / L tert-butylated triphenyl thiophosphate standard stock solution. Then add 10mL of tetrahydrofuran to the test tube, extract by ultrasonication at 70 degrees for 30 minutes, shake on a shaker for 30 minutes, add 20mL of acetonitrile, and then sonicate at 70 degrees for 30 minutes. After filtration, perform qualitative and quantitative analysis using gas chromatography-mass spectrometry.

[0073] like Figure 2The chromatogram shown is that of tert-butylated triphenyl thiophosphate in this embodiment. The figure shows sharp chromatographic peaks for the four components, significantly higher than all nearby interfering peaks, indicating that this method can effectively separate the target substance from impurities and detect tert-butylated triphenyl thiophosphate. Figure 3 The image shows a chromatogram of tert-butylated triphenyl thiophosphate at a concentration of 10 mg / L in the selected ion mode of this application, which allows for a clearer view of the spectra of the four components in the four channels.

[0074] Meanwhile, the target peak in the standard curve exhibits good linearity, with linear ranges (mg / L) of 1, 2, 5, and 10; the linearity coefficient R0 is [missing value]. 2 The linear coefficient was 0.998, and the limit of detection (LOD) was calculated to be 50 mg / kg based on the linear minimum point, sample amount, and extraction volume. The EU SVHC regulatory limit is 1000 mg / kg, and this method's LOD of 50 mg / kg means it meets the regulatory requirements. A linear coefficient generally needs to be >0.995; the linear coefficient of 0.998 in this example also meets this requirement, indicating that the analytical method is feasible.

[0075] The above spiking process was repeated to conduct six independent standard spiking tests. The average value of the six test data was taken. The results showed that the average recovery rate was 102%, which is relatively high, indicating that the content of tert-butylated triphenyl thiophosphate in consumer products can be detected efficiently.

[0076] Although preferred embodiments of the present application have been described, those skilled in the art, upon learning the basic inventive concept, can make other changes and modifications to these embodiments. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments as well as all changes and modifications falling within the scope of the embodiments of the present application.

[0077] Finally, it should be noted that in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or terminal device that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or terminal device. Without further limitations, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or terminal device that includes said element.

[0078] The above provides a detailed description of the method for determining tert-butylated triphenyl thiophosphate in consumer products provided by this application. Specific examples have been used to illustrate the principles and implementation methods of this application. The descriptions of the above embodiments are only for the purpose of helping to understand the method and core ideas of this application. At the same time, for those skilled in the art, there will be changes in the specific implementation methods and application scope based on the ideas of this application. Therefore, the content of this specification should not be construed as a limitation of this application.

Claims

1. A method for determining tert-butylated triphenyl thiophosphate in consumer goods, characterized in that, Includes the following steps: sampling; A first volume of a first reagent is added to the sample, and the sample is sonicated at a first specified temperature for a first specified time to obtain an extract. A second volume of the second reagent is added to the extract, and the mixture is sonicated at a second specified temperature for a second specified time. After filtration, the test solution is obtained. The first reagent is tetrahydrofuran; The second reagent is acetonitrile; The test solution was subjected to qualitative and quantitative analysis using a gas chromatography-mass spectrometry (GC-MS) system, including: The response values ​​of the four representative ions of the tert-butylated triphenyl thiophosphate standard were summed, and a standard curve was established based on the summation result. The response values ​​of the four representative ions of the sample are summed and compared with the standard curve for quantitative analysis. The analytical parameters of the gas chromatography-mass spectrometry system include: Column: DB-5HT; Carrier gas flow rate: 1.2 ml / min; Injection volume: 1 μL; Injector temperature: 280℃; Column oven temperature: 100℃ held for 0 min; 20℃ / min to 280℃ held for 0 min; 35℃ / min to 325℃ held for 8 min; Addition ions: 342, 383, 439, 495.

2. The method for determining tert-butylated triphenyl thiophosphate in consumer goods according to claim 1, characterized in that, The sampling steps include: Cut the sample into small pieces and weigh 1g ± 0.05g of the homogenized sample into a test tube.

3. The method for determining tert-butylated triphenyl thiophosphate in consumer goods according to claim 1, characterized in that, The step of adding a second volume of the second reagent to the extract includes: First, place the extract in a shaker for 28-32 minutes, then add a second volume of the second reagent to the extract.

4. The method for determining tert-butylated triphenyl thiophosphate in consumer goods according to claim 3, characterized in that, The first volume is 10ml ± 0.1ml.

5. The method for determining tert-butylated triphenyl thiophosphate in consumer goods according to claim 4, characterized in that, The second volume is 20 ml.

6. The method for determining tert-butylated triphenyl thiophosphate in consumer goods according to claim 5, characterized in that, Both the first specified temperature and the second specified temperature are 65℃-75℃.

7. The method for determining tert-butylated triphenyl thiophosphate in consumer goods according to claim 6, characterized in that, The first specified time and the second specified time are both 28min-32min.

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