Extraction method and application of acrylate monomers in a high-content film-forming agent product

Abstract

This invention discloses a method and application for extracting acrylate monomers from high-content film-forming agent products. The extraction method includes: simultaneously extracting 2-hydroxyethyl methacrylate and dimethylhexyldicarbamate (HEMA) from the high-content film-forming agent product using an organic solvent to obtain a product extract; wherein the high-content film-forming agent product includes oily nail polish and / or nail gel; and the organic solvent includes tetrahydrofuran and n-hexane. This invention uses organic solvents to extract products containing film-forming agents such as vinylcaprolactam / VP / dimethylaminoethyl methacrylate copolymer, acrylic resin and dimethylsiloxane copolymer, and acrylic copolymer, enabling simultaneous extraction of HEMA and dimethylhexyldicarbamate (HEMA) from products containing film-forming agents and nitrocellulose; it also solves the defects of easy column contamination and column pressure rise in subsequent detection.

Description

Technical Field

[0001] This invention belongs to the field of extraction and analysis technology, specifically relating to a method and application for extracting acrylate monomers from high-content film-forming agent products. Background Technology

[0002] Hydroxyethyl methacrylate (HEMA) and di-HEMA trimethylhexanedicarbamate (Di-HEMATMHDC) are common polyacrylate monomers used in plastics, coatings, adhesives, textiles, and medical fields. These monomers are sensitizing and a common trigger for allergic contact dermatitis (ACD). HEMA and Di-HEMATMHDC are generally added as film-forming agents to nail products. The European Union Scientific Committee on Consumer Safety (SCCS) believes that the sensitization risk in nail products may be related to uncured (incompletely reacted), unpolymerized reactive monomers HEMA and Di-HEMATMHDC. Currently, with the continuous development of the beauty industry, the demand for nail products is showing a sustained and rapid upward trend, and more and more nail products with different functions are emerging. Most of these nail products contain (meth)acrylate monomers, posing sensitization risks to nail consumers and nail technicians. Related data shows that in Leeds, UK, the allergy rate to (meth)acrylates tripled between 2008 and 2014. In Portugal, nail-related (meth)acrylate-induced allergic reactions (ACD) account for 76% of all acrylate-related ACD symptoms. The European Union Scientific Committee on Consumer Safety (SCCS) opinion (SCCS / 1592 / 17) on the sensitizing safety of cosmetic ingredients HEMA and Di-HEMA™ HDC lists numerous positive allergy cases of HEMA and Di-HEMA™ HDC since 1986. Currently, there are no explicit regulations in China regarding HEMA and Di-HEMA™ HDC in nail products, nor are there relevant testing methods. Therefore, it is necessary to establish testing technologies for HEMA and Di-HEMA™ HDC in nail products.

[0003] Currently, most domestic and international research on the detection of acrylate monomers focuses on soil, atmosphere, food contact materials, dental materials, and resin coatings, with no relevant research on detection methods for acrylate monomers in nail products. Zhao Jinyao, Zhang Qinjun, and others used gas chromatography-mass spectrometry (GC-MS) to separate acrylate monomers; however, the boiling points of these acrylate compounds are relatively low, with Di-HEMATMHDC having a boiling point above 300℃, making it difficult to vaporize by heating. Furthermore, the compounds contain numerous double bonds, making them prone to self-polymerization under high temperatures, significantly affecting peak shape and recovery rate. Therefore, GC-MS is not suitable for their detection. Currently, different types of nail polish generally require corresponding pretreatment procedures. For example, oil-based nail polish often contains nitrocellulose, which significantly affects the chromatographic column. Nitrocellulose, which is poorly soluble in water, easily precipitates in a water-methanol mobile phase, causing unstable column pressure. Nail polish gel, as a UV-curing system that aids in film formation, mainly consists of various macromolecular excipients (acrylate copolymers, acrylate / hydroxy ester acrylate copolymers). These excipients are generally readily soluble in organic solvents but poorly soluble in water. Literature typically describes adding excess water to the methanol / acetonitrile extraction solvent to increase the polarity of the extract system and remove impurities from these excipients. However, due to the low solubility of di-HEMA trimethylhexyldicarbamate (Di-HEMATMHDC) in water, adding excess water will also cause Di-HEMA trimethylhexyldicarbamate (Di-HEMATMHDC) to precipitate from the extract, thus affecting subsequent detection. Therefore, developing a method suitable for extracting hydroxyethyl 2-methacrylate and di-HEMA trimethylhexyldicarbamate from nail polish products and applicable to chromatographic detection is an urgent problem to be solved. Summary of the Invention

[0004] The main objective of this invention is to provide a method for extracting acrylate monomers from high-content film-forming agent products and its application, so as to overcome the shortcomings of the prior art.

[0005] To achieve the aforementioned objectives, the technical solution adopted by this invention includes:

[0006] This invention provides a method for extracting acrylate monomers from a high-content film-forming agent product, comprising:

[0007] 2-hydroxyethyl methacrylate and diHEMA methylhexyldicarbamate in a high-content film-forming agent product are extracted simultaneously using an organic solvent to obtain a product extract, thereby achieving the simultaneous extraction of 2-hydroxyethyl methacrylate and diHEMA methylhexyldicarbamate.

[0008] The high-content film-forming agent products include oil-based nail polish and / or nail gel; the organic solvents include tetrahydrofuran and n-hexane.

[0009] This invention also provides a method for determining acrylate monomers in a high-content film-forming agent product, comprising:

[0010] An organic solvent is used to extract acrylate monomers from a high-content film-forming agent product to obtain a product extract. The high-content film-forming agent product includes oily nail polish and / or nail gel. The organic solvent includes tetrahydrofuran and n-hexane. The acrylate monomers include 2-hydroxyethyl methacrylate and diHEMA methylhexyl dicarboxylate.

[0011] Using 2-hydroxyethyl methacrylate and diHEMA methylhexyldicarbamate as standard substances, standard working curves for 2-hydroxyethyl methacrylate and diHEMA methylhexyldicarbamate were established by liquid chromatography.

[0012] Furthermore, the product extract was analyzed using liquid chromatography and compared with the standard working curve to simultaneously determine the content of hydroxyethyl 2-methacrylate and diHEMA methylhexyldicarbamate in the nail polish product.

[0013] This invention also provides a method for identifying acrylate monomers in a high-content film-forming agent product, which includes: using liquid chromatography-mass spectrometry to identify the components of the aforementioned product extract.

[0014] The invention allows for the confirmation of results using liquid chromatography-mass spectrometry to rule out the possibility of other components interfering with the determination of the target analyte.

[0015] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0016] (1) The acrylate monomer extraction method provided by the present invention can simultaneously extract and rapidly determine 2-hydroxyethyl methacrylate and dimethylhexyldicarbamate in high-content film-forming agent products in the presence of vinylcaprolactam / VP / dimethylaminoethyl methacrylate copolymer, acrylic resin and dimethylsiloxane copolymer, acrylic copolymer and nitrocellulose. Furthermore, when used for liquid chromatography detection, it can solve the defects of easy column contamination and column pressure rise, thereby achieving simultaneous and accurate measurement of 2-hydroxyethyl methacrylate and dimethylhexyldicarbamate.

[0017] (2) This invention targets high-content film-forming agent products, such as nail products. For nail polishes with different solvent and matrix compositions, different pretreatment operations are adopted to remove impurities while ensuring the recovery efficiency of compounds 2-hydroxyethyl methacrylate (HEMA) and di-HEMA trimethylhexyl dicarboxylate (Di-HEMA TMHDC). The detection limit of 2-hydroxyethyl methacrylate (HEMA) in oily nail polish is 50 mg / kg, and the detection limit of di-HEMA trimethylhexyl dicarboxylate (Di-HEMA TMHDC) is 100 mg / kg.

[0018] (3) The determination method provided by this invention provides a standard technical specification for the detection of sensitizing monomers in film-forming agents, which can be applied to daily testing work, the business order of the nail product market, and the protection of personal safety. Attached Figure Description

[0019] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0020] Figure 1 This is a calibration curve of 2-hydroxyethyl methacrylate (HEMA) in a typical embodiment of the present invention;

[0021] Figure 2 This is a calibration curve of di-HEMA trimethylhexyl dicarboxylate (Di-HEMATMHDC) in a typical embodiment of the present invention.

[0022] Figure 3 This is a chromatogram of a mixed standard solution of hydroxyethyl 2-methacrylate and diHEMA methylhexyldicarbamate in a typical embodiment of the present invention;

[0023] Figure 4 This is the detection wavelength obtained by diode array scanning in a typical embodiment of the present invention;

[0024] Figures 5a-5b This is the column pressure graph of the methyl methacrylate product extracted with tetrahydrofuran and n-hexane, methanol and water in Comparative Example 1 of this invention during chromatographic detection. Detailed Implementation

[0025] In view of the deficiencies of the prior art, the inventors of this invention, through long-term research and extensive practice, have proposed the technical solution of this invention. This invention provides a method for extracting and purifying 2-hydroxyethyl methacrylate and di-HEMA methylhexyl dicarboxylate (Di-HEMA) ester from a high-content film-forming agent product (the product contains vinylcaprolactam / VP / dimethylaminoethyl methacrylate copolymer, acrylic resin and dimethylsiloxane copolymer, acrylic copolymer, and nitrocellulose). Different extraction methods are selected according to different nail polish formulations. In particular, for oily nail polish, tetrahydrofuran is used for dissolution, and n-hexane is used for precipitation of nitrocellulose and other impurities in the nail polish gel. Oil-based nail polish contains high levels of film-forming agents such as acrylate copolymers and nitrocellulose. Nail gel polish, as an auxiliary film-forming UV-curing system, mainly consists of various macromolecular excipients (acrylate copolymers, acrylate / hydroxy ester acrylate copolymers). These excipients are generally readily soluble in organic solvents, and the analyte Di-HEMA is poorly soluble in water. Therefore, using conventional methods for detecting organic matter in cosmetics, such as methanol dissolution followed by liquid chromatography analysis, presents significant challenges, and the chromatographic column is highly susceptible to contamination, leading to a pressure rise that prevents further analysis. The method provided by this invention effectively solves this problem.

[0026] The technical solution of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0027] First, it should be noted that 2-hydroxyethyl methacrylate (HEMA) and di-HEMA trimethylhexyl dicarboxylate (Di-HEMATMHDC) in this invention are two different film-forming monomers, both of which belong to acrylate monomers.

[0028] Specifically, as one aspect of the technical solution of this invention, the method for extracting acrylate monomers from a high-content film-forming agent product includes:

[0029] 2-hydroxyethyl methacrylate and diHEMA methylhexyldicarbamate in a high-content film-forming agent product are extracted simultaneously using an organic solvent to obtain a product extract, thereby achieving the simultaneous extraction of 2-hydroxyethyl methacrylate and diHEMA methylhexyldicarbamate.

[0030] The high-content film-forming agent products include oil-based nail polish and / or nail gel; the organic solvents include tetrahydrofuran and n-hexane; and the acrylate monomers include hydroxyethyl 2-methacrylate and diHEMA methylhexyl dicarboxylate.

[0031] In some more specific implementations, the extraction method specifically includes: mixing and dispersing oily nail polish with tetrahydrofuran, centrifuging, then mixing and dispersing the obtained supernatant with n-hexane, extracting, centrifuging, and filtering to obtain the product extract.

[0032] Furthermore, the volume ratio of hexane to tetrahydrofuran is greater than or equal to 2.

[0033] Furthermore, the centrifugation is performed at a centrifugation rate of 10,000 r / min for a centrifugation time of 5–10 min.

[0034] In some more specific implementation schemes, the extraction method specifically includes: mixing and dispersing nail polish gel with tetrahydrofuran and n-hexane, followed by centrifugation and filtration to obtain the product extract.

[0035] Furthermore, the volume ratio of hexane to tetrahydrofuran is greater than or equal to 2.

[0036] Furthermore, the centrifugation is performed at a centrifugation rate of 10,000 r / min for a centrifugation time of 5–10 min.

[0037] In some more specific implementation schemes, when the nail polish product extract was spiked for recovery testing, the average recovery rate of 2-hydroxyethyl methacrylate was 88.8% to 101.6%, and the precision was ≤3.04%.

[0038] In some more specific implementation schemes, when the nail polish product extract was spiked for recovery testing, the average recovery rate of dimethylhexyldicarbamate (HEMA) was 88.8%–101.6%, and the precision was ≤3.04%.

[0039] In some more specific embodiments, the content of the film-forming agent in the high-content film-forming agent product is 10-90 wt%.

[0040] The main innovation of this invention lies in the development of a method for extracting and purifying 2-hydroxyethyl methacrylate and di-HEMA (di-HEMA) methylhexyl dicarboxylate from high-content film-forming agent products (containing a large amount of polypropylene copolymer). Different extraction methods are selected according to different nail polish formulations, especially for oily nail polish, using tetrahydrofuran for dissolution and n-hexane for precipitation of nitrocellulose and other impurities in the gel polish. (Oily nail polish contains a high content of acrylate copolymers and nitrocellulose, etc. Nail polish gel, as an auxiliary film-forming UV curing system, mainly consists of various macromolecular excipients (acrylate copolymers, acrylate / hydroxy ester acrylate copolymers). These excipients are usually readily soluble in organic solvents, and the analyte Di-HEMA is poorly soluble in water. Therefore, using the common method for detecting organic matter in cosmetics—dissolving in methanol followed by liquid chromatography—is very difficult, and the chromatographic column is easily contaminated, causing the column pressure to rise and become unsustainable. The method provided by this invention effectively solves this problem, and is simple and provides reliable results.)

[0041] Another aspect of the present invention provides a method for determining acrylate monomers in a high-content film-forming agent product, comprising:

[0042] An organic solvent is used to extract acrylate monomers from a high-content film-forming agent product to obtain a product extract. The high-content film-forming agent product includes oily nail polish and / or nail gel. The organic solvent includes tetrahydrofuran and n-hexane. The acrylate monomers include 2-hydroxyethyl methacrylate and diHEMA methylhexyl dicarboxylate.

[0043] Using 2-hydroxyethyl methacrylate and diHEMA methylhexyldicarbamate as standard substances, standard working curves for 2-hydroxyethyl methacrylate and diHEMA methylhexyldicarbamate were established by liquid chromatography.

[0044] Furthermore, the product extract was analyzed using liquid chromatography and compared with the standard working curve to simultaneously determine the content of hydroxyethyl 2-methacrylate and diHEMA methylhexyldicarbamate in the nail polish product.

[0045] In some more specific implementations, the determination method specifically includes: mixing and dispersing oily nail polish with tetrahydrofuran, centrifuging, then mixing and dispersing the obtained supernatant with n-hexane, extracting, centrifuging, and filtering to obtain the product extract.

[0046] Furthermore, the volume ratio of hexane to tetrahydrofuran is greater than or equal to 2.

[0047] Furthermore, the centrifugation is performed at a centrifugation rate of 10,000 r / min for a centrifugation time of 5–10 min.

[0048] In some more specific implementation schemes, the determination method specifically includes: mixing and dispersing nail polish with tetrahydrofuran and n-hexane, followed by centrifugation and filtration to obtain a product extract.

[0049] Furthermore, the volume ratio of hexane to tetrahydrofuran is greater than or equal to 2.

[0050] Furthermore, the centrifugation is performed at a centrifugation rate of 10,000 r / min for a centrifugation time of 5–10 min.

[0051] In some more specific embodiments, the determination method specifically includes: preparing a series of mixed standard solutions of 2-hydroxyethyl methacrylate and diHEMA methylhexyldicarbamate at different concentrations using 2-hydroxyethyl methacrylate and diHEMA methylhexyldicarbamate as standard substances; then analyzing the mixed standard solutions using a liquid chromatography apparatus to establish a standard working curve for 2-hydroxyethyl methacrylate and diHEMA methylhexyldicarbamate; wherein the correlation coefficient R of the standard working curve is... 2 ≥0.999.

[0052] In some more specific implementations, the detection limit for hydroxyethyl 2-methacrylate is 50 mg / kg and the detection limit for diHEMA methylhexyldicarbamate is 100 mg / kg.

[0053] In some more specific implementations, the standard working curve of the 2-hydroxyethyl methacrylate is y = 9563.737x + 16700.93.

[0054] In some more specific embodiments, the standard working curve of the methylhexyl dicarboxylic acid diHEMA ester is y = 1880.470x + 8080.425.

[0055] In some more specific implementations, the parameters used in the liquid chromatography apparatus include: column temperature of 30°C; mobile phase A is water, mobile phase B is methanol, flow rate is 1.0 mL / min, injection volume is 5 μL, and detection wavelength is 210 nm.

[0056] Furthermore, the mobile phase program allows diHEMA methylhexyldicarbamate to elute at a peak in a shorter time.

[0057] The detection wavelength of 210nm used in this invention is the most suitable detection wavelength, such as... Figure 4As shown, the detection wavelength obtained by diode array scanning is 210nm. Below 210nm, it is affected by methanol interference, and above 210nm, the peak height gradually decreases. Therefore, 210nm is the most suitable detection wavelength.

[0058] In some more specific implementations, the determination method further includes: when analyzing the product extract using a liquid chromatography apparatus, if the concentration of 2-hydroxyethyl methacrylate or diHEMA methylhexyldicarbamate in the product extract exceeds the detection range of the standard working curve, the product extract is diluted with methanol before further testing and analysis.

[0059] In some more specific embodiments, the present invention provides a method for detecting 2-hydroxyethyl methacrylate and diHEMA trimethylhexyl dicarboxylate in oily nail polish (mainly composed of ethyl acetate / butyl acetate and nitrocellulose) and gel nail polish (mainly composed of acrylic (ester) copolymers and hydroxy (ester) acrylic (ester) copolymers), the detection steps of which include:

[0060] Step 1: Sample Pretreatment

[0061] 1. Oil-based nail polish

[0062] Weigh 0.2g of oily nail polish into a 50mL centrifuge tube, add 5mL of tetrahydrofuran, vortex to disperse, centrifuge the extract at 10000r / min for 5min, take the supernatant, add 10mL of n-hexane, vortex to disperse, centrifuge at 10000r / min for 5min, and filter the supernatant through a membrane for analysis.

[0063] 2. Gel nail polish

[0064] Weigh 0.2g of nail polish into a 50mL centrifuge tube, add 5mL of tetrahydrofuran and 10mL of n-hexane, vortex to disperse, and centrifuge at 10000r / min for 5min.

[0065] When the content of the analyte in the sample is high, take 1 mL of the supernatant into a 50 mL colorimetric tube, dilute to the mark with methanol, shake well, and filter the diluted solution through a membrane for testing.

[0066] Step 2: Prepare the standard working curve

[0067] Standard solutions of 2-hydroxyethyl methacrylate (HEMA) and di-HEMA trimethylhexyl dicarboxylate (Di-HEMATMHDC) with concentrations of 2 μg / mL, 10 μg / mL, 20 μg / mL, 50 μg / mL, 80 μg / mL, 200 μg / mL, and 400 μg / mL were prepared and analyzed by liquid chromatography to obtain standard curves for 2-hydroxyethyl methacrylate (HEMA) and di-HEMA trimethylhexyl dicarboxylate (Di-HEMATMHDC).

[0068] The calibration curve for hydroxyethyl methacrylate (HEMA) is shown below. Figure 1 As shown, the standard curve is: y = 9563.737x + 16700.93, R0 2 The value is 0.9996; the calibration curve for di-HEMA trimethylhexyl dicarboxylate (Di-HEMA TMHDC) is shown below. Figure 2 As shown, the standard curve is: y = 1880.470x + 8080.425, R0 2 It is 0.9996.

[0069] The standard solution concentrations in this invention exhibit good linearity within the ranges of 2 μg / mL, 10 μg / mL, 20 μg / mL, 50 μg / mL, 80 μg / mL, 200 μg / mL, and 400 μg / mL. The detection limits for the two film-forming agents in oily nail polish are 50 mg / kg, and the quantitation limits are 100 mg / kg.

[0070] Spiked recovery tests were conducted on three types of nail polish. The average recoveries of the two film-forming agents at three spiking levels (50 μg, 200 μg, and 4000 μg, n=6) were 88.8%–101.6%, with a precision ≤3.04%.

[0071] Step 3: Measurement

[0072] The conditions for liquid chromatography are as follows: Column: C18 column (250 mm × 4.6 mm × 5 m), or equivalent column; mobile phase A: water, mobile phase B: methanol; flow rate: 1.0 mL / min; detection wavelength: 210 nm; column temperature: 30 ℃; injection volume: 5 μL.

[0073] The gradient elution procedure is shown in Table 1:

[0074] Table 1 Gradient elution program for mobile phase

[0075] Time / min V(mobile phase A)% V(mobile phase B)% 0.0 65 35 8.0 65 35 9.0 20 80 15.0 20 80 15.1 65 35 23.0 65 35

[0076] Another aspect of the present invention provides a method for identifying acrylate monomers in a high-content film-forming agent product, comprising: identifying the components of the aforementioned product extract using liquid chromatography-mass spectrometry.

[0077] Specifically, the present invention can use liquid chromatography-mass spectrometry to confirm the results and rule out whether other components interfere with the determination of the target analyte.

[0078] Liquid chromatography conditions: Column: C18 column (3m, 150mm × 2.0mm), or equivalent column; Mobile phase A: methanol; Mobile phase B: water. Flow rate: 0.3mL / min; Column temperature: 30℃; Injection volume: 2μL.

[0079] The gradient elution program for the mobile phase is shown in Table 2:

[0080] Table 2 Positive ion gradient elution program

[0081] Time (min) A(％) B(％) 0.00 35 65 5.00 35 65 5.10 80 20 10.00 80 20 10.10 35 65 15.00 35 65

[0082] Mass spectrometry conditions: Ion source: Electrospray ionization (ESI); Monitoring mode: Positive ion multiple reaction monitoring (MRM); Monitoring ion pairs and related voltage parameters are set as shown in Table 3; Curtain gas flow rate: 25 μL / min; Collision gas flow rate: Medium ion source gas 1 flow rate: 50 μL / min; Ion source gas 2 flow rate: 50 μL / min; Ion source heating temperature: 500 °C; Ionization voltage: 4500 (positive ion mode)

[0083] Table 3. Mass Spectrometry Monitoring Ion Pairs and Related Voltage Parameter Settings

[0084]

[0085] The technical solution of the present invention will be further described in detail below with reference to several preferred embodiments and accompanying drawings. This embodiment is implemented on the premise of the technical solution of the invention, and provides detailed implementation methods and specific operation processes. However, the protection scope of the present invention is not limited to the following embodiments.

[0086] Unless otherwise specified, the experimental materials used in the examples below can be purchased from conventional biochemical reagent companies.

[0087] Currently, there are no domestic or international regulations regarding the limits of HEMA and Di-HEMA TMHDC additions in nail products. Only relevant human patch test data for HEMA and Di-HEMA TMHDC have been found. S. Rolls recommends using a 2% HEMA addition level as the benchmark for detecting allergic contact dermatitis (ACD) in British patients during patch testing. Patch tests related to Di-HEMA TMHDC are less common; the levels of Di-HEMA TMHDC added in several patch tests listed in SCCS / 1592 / 17 were 0.2%-0.6% and 2%, respectively. It is tentatively agreed that the sample content of 2% HEMA and 2% Di-HEMA TMHDC will be used as the basis for determining whether commercially available samples pose a risk of sensitization.

[0088] The steps for establishing a standard operating curve in the following embodiments are as follows:

[0089] Standard solutions of 2-hydroxyethyl methacrylate (HEMA) and di-HEMA trimethylhexyl dicarboxylate (Di-HEMA TMHDC) with concentrations of 2 μg / mL, 10 μg / mL, 20 μg / mL, 50 μg / mL, 80 μg / mL, 200 μg / mL, and 400 μg / mL were prepared and analyzed by liquid chromatography to obtain standard working curves for 2-hydroxyethyl methacrylate (HEMA) and di-HEMA trimethylhexyl dicarboxylate (Di-HEMATMHDC).

[0090] The calibration curve for hydroxyethyl methacrylate (HEMA) is shown below. Figure 1 As shown, the standard working curve is: y = 9563.737x + 16700.93, R0 2 The value is 0.9996; the calibration curve for di-HEMA trimethylhexyl dicarboxylate (Di-HEMATMHDC) is shown below. Figure 2 As shown, the standard working curve is: y = 1880.470x + 8080.425, R0 2 The chromatogram of a standard solution of hydroxyethyl 2-methacrylate (HEMA) and di-HEMA trimethylhexyl dicarboxylate (Di-HEMA TMHDC) is shown below. Figure 3 As shown.

[0091] Example 1

[0092] Seven different commercially available gel nail polishes (malortt gel nail polish, Zhiyou Zhencai functional gel nail polish, Meijia functional gel nail polish, Bole gel nail polish, UV adhesive gel nail polish, Goya gel nail polish G112, and GAOY Goya gel nail polish, and named them as samples 1 to 7 respectively) were selected. 0.2g of each sample was placed in a 50mL centrifuge tube, and 5mL of tetrahydrofuran and 10mL of n-hexane were added respectively. The mixture was vortexed and centrifuged at 10000r / min for 5min to obtain gel nail polish extract.

[0093] The nail gel extract was analyzed using liquid chromatography and compared with the aforementioned standard working curve to obtain the contents of hydroxyethyl 2-methacrylate (HEMA) and di-HEMA trimethylhexyl dicarboxylate (Di-HEMATMHDC) in the product, as shown in Table 4.

[0094] Table 4. HEMA, Di-HEMA, and TMHDC content in samples

[0095] compound Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6 Sample 7 HEMA 25％ 22％ 19％ 28％ 21％ 22％ 21％

[0096] Example 2

[0097] Spiked recovery tests were conducted on two types of nail polish (oil-based nail polish and gel nail polish), with corresponding sample pretreatments performed for each. For oil-based nail polish, 0.2 g of oil-based nail polish was weighed into a 50 mL centrifuge tube, 5 mL of tetrahydrofuran was added, and the mixture was vortexed. The extract was centrifuged at 10000 rpm for 5 min. The supernatant was collected, 10 mL of n-hexane was added, and the mixture was vortexed. The supernatant was then centrifuged at 10000 rpm for 5 min. The supernatant was filtered through a membrane for analysis.

[0098] Method for processing gel nail polish: Weigh 0.2g of gel nail polish into a 50mL centrifuge tube, add 5mL of tetrahydrofuran and 10mL of n-hexane, vortex to disperse, and centrifuge at 10000r / min for 5min.

[0099] The results showed that the average recoveries of the two film-forming agents at three spiking levels (50 μg, 200 μg, and 4000 μg, n=6) were 88.8%–101.6%, with a precision ≤3.04%. The spiked recoveries and precision of oil-based nail polish and gel nail polish are shown in the table below:

[0100] Table 5. Spike recoveries and precision of the two film-forming agents (n=6)

[0101]

[0102] Comparative Example 1

[0103] Seven samples identical to those in Example 1 were selected, and 0.2g of each sample was placed in a 50mL centrifuge tube. 8mL of methanol was added to disperse the samples, and the mixture was vortexed and centrifuged at 10000r / min for 5min to obtain the nail polish extract.

[0104] These nail polish extracts were analyzed using liquid chromatography in the same manner as in Example 1.

[0105] The nail polish gel extract obtained using the method in Example 1 exhibits stable column pressure during liquid chromatography detection, such as... Figure 5a As shown; however, the nail polish extract obtained using the method in Comparative Example 1 caused a rise in column pressure during liquid chromatography, making further detection impossible, such as... Figure 5b As shown.

[0106] Comparative Example 2

[0107] Seven samples identical to those in Example 1 were selected, with 0.2 g of each sample placed in 50 mL centrifuge tubes. 10 mL of tetrahydrofuran and 10 mL of n-hexane were added to each tube, and the samples were dispersed by vortexing. The tubes were then centrifuged at 10,000 r / min for 5 min. At this point, incomplete precipitation or no precipitation may occur, making effective extraction impossible.

[0108] Comparative Example 3

[0109] Seven samples identical to those in Example 1 were selected, and 0.2 g of each sample was placed in a 50 mL centrifuge tube. 15 mL of tetrahydrofuran was added to each tube, and the samples were vortexed and centrifuged at 10,000 r / min for 5 min to obtain nail polish extract.

[0110] Following the same procedure as in Example 1, these nail polish extracts were analyzed using a liquid chromatography apparatus. During liquid chromatography detection, the column pressure increased, indicating that the extraction could not be effectively purified.

[0111] Comparative Example 4

[0112] Seven samples identical to those in Example 1 were selected, and 0.2g of each sample was placed in a 50mL centrifuge tube. 15mL of n-hexane was added to each tube and the samples were vortexed for dispersion. It was found that the samples could not be completely dissolved or dispersed.

[0113] Example 3

[0114] Commercially available oily nail polish was used as a sample. 0.2 g of the sample was placed in a 50 mL centrifuge tube, and 5 mL of tetrahydrofuran and 10 mL of n-hexane were added. The mixture was vortexed and centrifuged at 10000 r / min for 5 min to obtain the oily nail polish extract. It can be seen that the oily nail polish was successfully extracted. Following the same procedure as in Example 1, the oily nail polish extract was analyzed using liquid chromatography.

[0115] In addition, the inventors of this case also conducted experiments with other raw materials, process operations, and process conditions described in this specification, referring to the aforementioned embodiments, and obtained relatively ideal results in all cases.

[0116] It should be understood that the technical solutions of the present invention are not limited to the specific embodiments described above. Any technical modifications made to the technical solutions of the present invention without departing from the spirit and scope of the claims are within the scope of protection of the present invention.

Claims

1. A method for extracting acrylate monomers from a high-content film-forming agent product, characterized in that, include: Nail gel is mixed and dispersed with tetrahydrofuran and n-hexane, and then centrifuged and filtered to obtain nail product extract, thereby achieving simultaneous extraction of hydroxyethyl 2-methacrylate and diHEMA methylhexyldicarbamate. The volume ratio of n-hexane to tetrahydrofuran is 2. When the extract of the nail oil product was spiked for recovery testing, the average recovery rate of 2-hydroxyethyl methacrylate was 88.8%~101.6%, with a precision ≤3.04%; the average recovery rate of diHEMA methylhexyldicarbamate was 88.8%~101.6%, with a precision ≤3.04%.

2. The extraction method according to claim 1, characterized in that: The centrifugation was performed at a speed of 10,000 r / min for a time of 5 to 10 min.

3. The extraction method according to claim 1, characterized in that: The high-content film-forming agent product contains 10~90wt% of film-forming agent.

4. A method for determining acrylate monomers in a high-content film-forming agent product, characterized in that, include: Nail gel is mixed and dispersed with tetrahydrofuran and n-hexane, and then centrifuged and filtered to obtain nail product extract, thereby achieving simultaneous extraction of hydroxyethyl 2-methacrylate and diHEMA methylhexyldicarbamate; wherein the volume ratio of n-hexane to tetrahydrofuran is 2. Using 2-hydroxyethyl methacrylate and diHEMA methylhexyldicarbamate as standard substances, standard working curves for 2-hydroxyethyl methacrylate and diHEMA methylhexyldicarbamate were established by liquid chromatography. Furthermore, the extract of the nail polish product was analyzed using a liquid chromatography apparatus and compared with the standard working curve to simultaneously determine the content of hydroxyethyl 2-methacrylate and diHEMA methylhexyldicarbamate in the nail polish product.

5. The determination method according to claim 4, characterized in that, Specifically, it includes: The centrifugation was performed at a speed of 10,000 r / min for a time of 5 to 10 min.

6. The determination method according to claim 4, characterized in that, Specifically, it includes: Using hydroxyethyl methacrylate and diHEMA methylhexyldicarbamate as standard substances, a series of mixed standard solutions of hydroxyethyl methacrylate and diHEMA methylhexyldicarbamate at different concentrations were prepared. These mixed standard solutions were then analyzed using liquid chromatography to establish standard working curves for hydroxyethyl methacrylate and diHEMA methylhexyldicarbamate. The correlation coefficient R of the standard working curves is [not specified in the original text]. 2 ≥0.

999.

7. The determination method according to claim 4, characterized in that: The detection limit for hydroxyethyl 2-methacrylate in the assay method is 50 mg / kg, and the detection limit for diHEMA methylhexyldicarbamate is 100 mg / kg.

8. The determination method according to claim 4, characterized in that, The parameters used in the liquid chromatography apparatus include: column temperature of 30℃; mobile phase A is water, mobile phase B is methanol, flow rate is 1.0 mL / min, injection volume is 5 μL, and detection wavelength is 210 nm.

9. The determination method according to claim 4, characterized in that, Also includes: When analyzing the nail polish product extract using a liquid chromatography apparatus, if the concentration of 2-hydroxyethyl methacrylate or di(HEMA) methylhexyldicarbamate in the nail polish product extract exceeds the detection range of the standard working curve, the product extract is diluted with methanol before further testing and analysis.

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