Determination of trimethylolpropane triacrylate and dipentaerythritol hexaacrylate in plastics and coatings

Abstract

The present application provides a method for determining trimethylolpropane triacrylate and dipentaerythritol hexaacrylate in plastics and coatings, specifically comprising: pre-treating the analyte; specifically, adding a first volume of a first reagent to the analyte, ultrasonically extracting the analyte at a first temperature for a first time to obtain a first mixed solution, adding a second volume of a second reagent to the first mixed solution, filtering to obtain a second mixed solution; sampling the second mixed solution to obtain a sample test solution; and performing qualitative and quantitative analysis on the sample test solution using a gas chromatography-mass spectrometer. The method uses gas chromatography-mass spectrometry to determine the content of trimethylolpropane triacrylate and dipentaerythritol hexaacrylate in consumer products, optimizes the conditions and parameters of the method, fills the gap in the national standard method, has a low detection limit, is simple to operate, and the equipment used is easily available, making it highly scalable.

Description

Technical Field

[0001] The present application relates to the technical field of analytical chemistry, in particular to a method for determining trimethylolpropane triacrylate and dipentaerythritol hexaacrylate in plastics and coatings. Background Art

[0002] Trimethylolpropane triacrylate (TMPTA) and dipentaerythritol hexaacrylate (DPHA) are both common multifunctional acrylate monomers, which are widely used as cross-linkers and active diluents in acrylate coating formulas. However, due to the limitations of the coating curing process, these monomer substances cannot be completely polymerized during the curing process and produce monomer residues. In recent years, with the increasing requirements for product safety, the hazards of residual monomer substances have also received widespread attention. Among them, trimethylolpropane triacrylate and two other acrylate monomer substances were identified as carcinogens by California, USA in December 2021 and are subject to control. However, there is currently no reliable method to measure the content of these two substances. Summary of the Invention

[0003] In view of the above problems, the present application is proposed to provide a method for determining trimethylolpropane triacrylate and dipentaerythritol hexaacrylate in plastics and coatings to overcome or at least partially solve the above problems, comprising:

[0004] A method for determining trimethylolpropane triacrylate and dipentaerythritol hexaacrylate in plastics and coatings comprises the following steps:

[0005] Pre-treating the analyte; specifically, adding a first volume of a first reagent to the analyte, ultrasonically extracting the analyte at a first temperature for a first time to obtain a first mixed solution, adding a second volume of a second reagent to the first mixed solution, and filtering to obtain a second mixed solution;

[0006] Sampling the second mixed solution to obtain a sample test solution;

[0007] The sample solution is subjected to qualitative and quantitative analysis by gas chromatography-mass spectrometry.

[0008] Furthermore, the method further includes processing the object to be tested into pieces no larger than 3 mm×3 mm.

[0009] Furthermore, the first volume is 20 times the volume of the object to be detected.

[0010] Furthermore, the first reagent is tetrahydrofuran.

[0011] Furthermore, the first temperature is 60-80°C.

[0012] Furthermore, the first duration is 25-40 minutes.

[0013] Furthermore, the second reagent is acetonitrile.

[0014] Furthermore, the second volume is the volume of the first mixed liquid.

[0015] Furthermore, the chromatographic column model is DB-5HT.

[0016] Furthermore, the temperature rise curve of the gas chromatography-mass spectrometry instrument is as follows: the starting temperature is 50° C., maintained for 1 minute, increased to 200° C. at 20° C. / min, then increased to 320° C. at 30° C. / min, and maintained for 2 minutes.

[0017] This application has the following advantages:

[0018] In the embodiments of the present application, the blank of the prior art in which the content of trimethylolpropane triacrylate and dipentaerythritol hexaacrylate is not determined is filled. The present application provides a method for determining trimethylolpropane triacrylate and dipentaerythritol hexaacrylate in plastics and coatings, specifically: pre-treating the analyte; specifically, adding a first volume of a first reagent to the analyte, ultrasonically extracting the analyte at a first temperature for a first time to obtain a first mixed solution, adding a second volume of a second reagent to the first mixed solution, filtering to obtain a second mixed solution; sampling the second mixed solution to obtain a sample test solution; and performing qualitative and quantitative analysis on the sample test solution by gas chromatography-mass spectrometry. The content of trimethylolpropane triacrylate and dipentaerythritol hexaacrylate in consumer goods is determined using gas chromatography-mass spectrometry (GC-MS) mass spectrometry, optimizing the conditions and parameters of the method, filling the gap in the national standard method, and the method has a low detection limit, is simple to operate, and the equipment used is easily available, making it highly scalable. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] In order to more clearly illustrate the technical solution of the present application, the following is a brief introduction to the drawings required for the description of the present application. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without any creative work.

[0020] Figure 1 This is a flowchart of the steps of a method for determining trimethylolpropane triacrylate and dipentaerythritol hexaacrylate in plastics and coatings provided in one embodiment of the present application;

[0021] Figure 2 This is a chromatogram of dipentaerythritol hexaacrylate provided in one embodiment of the present application;

[0022] Figure 3 This is a chromatogram of trimethylolpropane triacrylate provided in one embodiment of the present invention. DETAILED DESCRIPTION

[0023] To make the objectives, features, and advantages of this application more readily apparent, the present application is further described below in conjunction with the accompanying drawings and specific embodiments. It is apparent that the embodiments described are only a portion of the embodiments of this application, not all of them. All other embodiments derived by persons of ordinary skill in the art based on the embodiments in this application without inventive effort are also within the scope of protection of this application.

[0024] By analyzing the existing technology, the inventors found that after certain pretreatment of the analyte, by studying the instrument parameters and improving the instrument method, gas chromatography-mass spectrometry can be used to accurately determine the content of trimethylolpropane triacrylate and dipentaerythritol hexaacrylate in plastics and coatings.

[0025] Reference Figure 1 , shows a method for determining trimethylolpropane triacrylate and dipentaerythritol hexaacrylate in a plastic and a coating provided in one embodiment of the present application:

[0026] The method comprises:

[0027] S110, pre-treating the analyte; specifically, adding a first volume of a first reagent to the analyte, ultrasonically extracting the analyte at a first temperature for a first time to obtain a first mixed solution, adding a second volume of a second reagent to the first mixed solution, and filtering to obtain a second mixed solution;

[0028] S120, sampling the second mixed solution to obtain a sample test solution;

[0029] S130, performing qualitative and quantitative analysis on the sample solution by gas chromatography-mass spectrometry.

[0030] In the embodiments of the present application, the blank of the prior art in which the content of trimethylolpropane triacrylate and dipentaerythritol hexaacrylate is not determined is filled. The present application provides a method for determining trimethylolpropane triacrylate and dipentaerythritol hexaacrylate in plastics and coatings, specifically: pre-treating the analyte; specifically, adding a first volume of a first reagent to the analyte, ultrasonically extracting the analyte at a first temperature for a first time to obtain a first mixed solution, adding a second volume of a second reagent to the first mixed solution, filtering to obtain a second mixed solution; sampling the second mixed solution to obtain a sample test solution; and performing qualitative and quantitative analysis on the sample test solution by gas chromatography-mass spectrometry. The content of trimethylolpropane triacrylate and dipentaerythritol hexaacrylate in consumer goods is determined using gas chromatography-mass spectrometry (GC-MS) mass spectrometry, optimizing the conditions and parameters of the method, filling the gap in the national standard method, and the method has a low detection limit, is simple to operate, and the equipment used is easily available, making it highly scalable.

[0031] Next, the determination method of trimethylolpropane triacrylate and dipentaerythritol hexaacrylate in the plastic and the coating in this exemplary embodiment will be further described.

[0032] As described in step S110, the object to be tested is pre-treated; specifically, a first volume of a first reagent is added to the object to be tested, ultrasonic extraction is performed at a first temperature for a first time to obtain a first mixed solution, a second volume of a second reagent is added to the first mixed solution, and the mixture is filtered to obtain a second mixed solution.

[0033] In one embodiment of the present invention, the specific process of step S110 of "pre-treating the object to be tested; specifically, adding a first volume of a first reagent to the object to be tested, ultrasonically extracting at a first temperature for a first time to obtain a first mixed liquid, adding a second volume of a second reagent to the first mixed liquid, filtering, and obtaining a second mixed liquid" can be further explained in combination with the following description.

[0034] As described in the following steps, the object to be tested is processed into pieces no larger than 3 mm×3 mm.

[0035] As described in the following steps, the first volume is 20 times the volume of the object to be tested.

[0036] As described in the following steps, the first reagent is tetrahydrofuran.

[0037] As described in the following steps, the first temperature is 60-80°C.

[0038] As described in the following steps, the first duration is 25-40 minutes.

[0039] As described in the following steps, the second reagent is acetonitrile.

[0040] As described in the following steps, the second volume is the volume of the first mixed solution.

[0041] In a specific implementation, the coating sample was cut into pieces smaller than 3 mm × 3 mm, 0.5 g of the sample was added to 10 mL of tetrahydrofuran, and ultrasonic extraction was performed at 70° C. for 30 min. 13 mL of acetonitrile was then added for precipitation and purification, and the sample mixture was obtained by filtration.

[0042] As described in step S120, sampling is performed to obtain a sample solution.

[0043] It should be noted that for routine sampling operations, 1 mL of sample solution is generally taken.

[0044] As described in step S130, the sample solution is subjected to qualitative analysis and quantitative analysis by gas chromatography-mass spectrometry.

[0045] Instrument parameters are: Instrument: Gas chromatography-mass spectrometry (GC-MS)

[0046] Chromatographic column: DB-5HT;

[0047] Heating curve: starting temperature 50 degrees, hold for 1 minute, increase to 200 degrees at 20 degrees per minute, then increase to 320 degrees at 30 degrees per minute, hold for 2 minutes;

[0048] Inlet temperature: 280 degrees;

[0049] Injection volume: 1 μL;

[0050] Shunt mode: pulse without shunt;

[0051] Data analysis: The external standard method was used for quantitative calculation; the quantitative and qualitative ions are shown in Table 1.

[0052]

[0053] Table 1

[0054] Main technical parameters:

[0055] Linear range (mg / L): 0.1, 0.5, 1, 5; correlation coefficient R 2 =0.998

[0056] like Figure 2 Shown is the chromatogram of dipentaerythritol hexaacrylate;

[0057] like Figure 3 Shown is the chromatogram of trimethylolpropane triacrylate.

[0058] In one specific implementation, a coating sample is tested.

[0059] Cut the layer sample into pieces smaller than 3 mm × 3 mm, take 0.5 g of sample and add 10 mL of tetrahydrofuran, add 40 μl of a 1000 mg / L mixed standard stock solution of the two substances, perform ultrasonic extraction at 70°C for 30 min, then add 13 mL of acetonitrile for precipitation and purification, and filter to obtain the sample mixture; measure on the machine, chromatographic column: DB-5HT; heating curve: starting temperature 50°C, hold for 1 minute, increase to 200°C at 20°C / min, then increase to 320°C at 30°C / min, and hold for 2 minutes; injection port temperature: 280°C; injection volume: 1 μL; split mode: pulsed without splitting.

[0060] Spike recovery:

[0061] The recovery rate of dipentaerythritol hexaacrylate was 92%;

[0062] The recovery rate of trimethylolpropane triacrylate was 103%.

[0063] Linearity and minimum detection limit:

[0064] Linear range (mg / L): 0.1, 0.5, 1, 5; correlation coefficient R 2 =0.998.

[0065] Minimum detection limit: 10mg / kg.

[0066] Although preferred embodiments of the present invention have been described, those skilled in the art may make additional changes and modifications to these embodiments once they become aware of the basic inventive concepts. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and all changes and modifications that fall within the scope of the embodiments of the present invention.

[0067] Finally, it should be noted that, in this document, relational terms such as first and second, etc., are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the terms "comprises," "comprising," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or terminal device that includes a series of elements includes not only those elements, but also other elements not explicitly listed, or elements inherent to such process, method, article, or terminal device. In the absence of further limitations, an element defined by the phrase "comprising a ..." does not exclude the presence of additional identical elements in the process, method, article, or terminal device that includes the element.

[0068] The above is a detailed introduction to the method for determining trimethylolpropane triacrylate and dipentaerythritol hexaacrylate in plastics and coatings provided by the present application. Specific examples are used herein to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only intended to help understand the method and core concept of the present application. At the same time, for those skilled in the art, according to the concept of the present application, there may be changes in the specific implementation method and application scope. In summary, the content of this specification should not be understood as limiting the present application.

Claims

1. A method for determining trimethylolpropane triacrylate and dipentaerythritol hexaacrylate in plastics and coatings, characterized in that: Including steps: Pre-treating the analyte; specifically, adding 10 ml of tetrahydrofuran to 0.5 g of the analyte, ultrasonically extracting at 60-80° C. for 25-40 min to obtain a first mixed solution, adding an equal volume of acetonitrile to the first mixed solution, and filtering to obtain a second mixed solution; Sampling the second mixed solution to obtain a sample test solution; The sample solution was subjected to qualitative and quantitative analysis by gas chromatography-mass spectrometry; the instrument parameters were as follows: instrument: gas chromatography-mass spectrometry (GC-MS); chromatographic column: DB-5HT; heating curve: starting temperature 50°C, held for 1 min, increased to 200°C at 20°C / min, then increased to 320°C at 30°C / min, held for 2 min; injection port temperature: 280°C; injection volume: 1 μL; split mode: pulsed without splitting.

2. The measuring method according to claim 1, wherein The method further includes processing the object to be tested into pieces no larger than 3 mm×3 mm.

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