A method for determining (meth)acrylate compounds in textiles

Abstract

This invention discloses a method for determining (meth)acrylate compounds in textiles, comprising the following steps: (1) placing an accurately weighed textile sample to be tested in a reactor, adding an extractant for ultrasonic extraction to obtain an extract; (2) injecting the above extract into a gas chromatograph-mass spectrometer to determine the (meth)acrylate compounds and their peak areas, and calculating the content of (meth)acrylate compounds in the textile sample to be tested according to the standard curve equation. This invention employs ultrasonic extraction-gas chromatography-mass spectrometry to simultaneously and accurately detect 12 (meth)acrylate compounds in textiles. The method is simple to operate, the detection process can be easily automated, and it has high sensitivity. Within the concentration range of 0.50–10.00 mg / L, the linear correlation coefficient is above 0.998, the detection limit is in the range of 0.09 mg / kg–2.41 mg / kg, the quantitation limit is in the range of 0.32 mg / kg–7.44 mg / kg, the spiked recovery rate is 87.71%–99.43%, and the relative standard deviation (RSD) is 1.07%–2.81%, demonstrating good accuracy and reproducibility.

Description

Technical Field

[0001] This invention belongs to the field of detection technology, specifically relating to a method for determining (meth)acrylate compounds in textiles. Background Technology

[0002] (Meth)acrylate compounds are widely used in textile processing, such as as crosslinking agents, coating monomers, or functional modifiers. They are mostly in polymer form, where polymerization primarily involves crosslinking through covalent or ionic bonds (in-situ polymerization) to transform liquid substances into solid or gel states. This process may result in incompletely reacted, non-polymerized monomers remaining in the polymer, known as residual monomers. Generally, current technology cannot achieve 100% complete polymerization under ideal conditions. While the polymer itself is harmless, the (meth)acrylate residues in the polymer are harmful, not only significantly reducing product quality but also polluting the environment and endangering human health.

[0003] Most (meth)acrylates have low boiling points, are highly volatile, and possess a strong, pungent odor and toxicity, even exhibiting reproductive toxicity. Small residues can produce a strong unpleasant odor, degrade air quality, and harm human health. Experiments have shown that even a small amount inhaled by a mouse (109 g / m³) can cause significant damage. 3 Methyl acrylate can cause poisoning, and inhalation for 17 minutes can produce embryotoxicity (days 6-15 of gestation), leading to muscle and bone structure disorders. Currently, ethyl acrylate (EA) is classified as a Group 2B carcinogen by the International Agency for Research on Cancer (IARC). Miller et al., using SD rats as research subjects, observed in animal experiments that EA inhalation can induce thyroid endocrine disorders, stimulate pituitary TS secretion, and thereby stimulate and induce thyroid tumors (follicular adenomas and follicular adenocarcinomas).

[0004] On January 1, 2009, the EU REACH Regulation officially entered the full registration phase. According to REACH regulations, polymer products exported from China to the EU face registration for monomers and additives, and declaration and authorization for substances of very high concern. Therefore, it is necessary to establish detection methods for (meth)acrylate residues in textiles as soon as possible to ensure the safe use of related products, respond to the EU REACH Regulation in a timely and effective manner, and promote the sustained growth of my country's textile export trade.

[0005] my country's standard GB 9685-2016, "Standard for the Use of Additives in Food Contact Materials and Articles," clearly stipulates the production usage and maximum residue limits of (meth)acrylates in packaging materials: the residue level of (meth)acrylates in food packaging materials must not exceed 6 mg / kg. Currently, the International Agency for Research on Cancer (IARC) of the World Health Organization (WHO) has listed some acrylates as carcinogens, such as acrylic acid, methyl acrylate, ethyl acrylate, and 2-ethylhexyl acrylate.

[0006] Residues of (meth)acrylates in textiles can cause skin allergies, nausea, fatigue, and even cancer. International textile environmental certification standards... The Blue Label Certification (BSSL) Consumer Safety Limits List (v13.0) provides the restrictions and corresponding safety limits for (meth)acrylates in textiles, as shown in Table 1:

[0007] Table 1. List of BSSL Consumer Safety Limits for Acrylic Esters

[0008]

[0009] Note: A represents infant and toddler textile products; B represents textile products that come into direct contact with the skin; C represents textile products that do not come into direct contact with the skin.

[0010] In conclusion, there is an urgent need to develop an efficient, accurate, and simple method for determining (meth)acrylate residues in textiles to meet the increasingly stringent requirements for textile quality and safety testing. Summary of the Invention

[0011] The purpose of this invention is to address the aforementioned problems in the prior art by exploring a method for determining the 12 (meth)acrylate compounds included in the BSSL using gas chromatography-mass spectrometry (GC-MS). Through experiments, the pretreatment method was determined, and the optimal instrumental analysis conditions were explored. Under these optimal detection conditions, method verification experiments were conducted, including linear correlation, detection limit, and precision tests, as well as the detection of actual samples. Ultimately, a precise and efficient method for determining (meth)acrylate compounds in textiles was obtained.

[0012] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0013] A method for determining (meth)acrylate compounds in textiles, comprising the following steps:

[0014] (1) Place the accurately weighed textile sample to be tested into a reactor, add the extractant and perform ultrasonic extraction to obtain the extract;

[0015] (2) Inject the above extract into a gas chromatograph-mass spectrometer to determine the (meth)acrylate compounds and their peak areas, and calculate the content of (meth)acrylate compounds in the textile sample to be tested according to the standard curve equation.

[0016] The present invention is further configured such that the (meth)acrylate compounds include methyl acrylate, ethyl acrylate, butyl acrylate, tert-butyl acrylate, octadecyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, 2-ethylhexyl acrylate, 2-phenoxyethyl acrylate, and 2-methoxyethyl acrylate.

[0017] The present invention is further configured such that, in step (1), the extractant is ethyl acetate.

[0018] The present invention is further configured such that, in step (1), the mass-to-volume ratio of the textile sample to be tested and the extractant is 1g:10-20mL.

[0019] The present invention is further configured such that, in step (1), the ultrasonic extraction conditions are: extraction temperature of 40-50℃, extraction time of 30-40min, and extraction power of 400-500W.

[0020] The present invention is further configured such that, in step (1), after ultrasonic extraction, an SPE solid phase extraction column is used to purify the extract.

[0021] The present invention is further configured such that the instrument conditions of the gas chromatography-mass spectrometry instrument are:

[0022] The chromatographic column was a DB-WAX column; the carrier gas was helium (purity ≥99.999%); the carrier gas flow rate was 0.8–1.1 mL / min; the injection port temperature was 100–200℃; the temperature program was as follows: initial temperature 25–40℃, hold for 10 min, then increase to 100℃ at a rate of 20℃ / min, hold for 8 min, then increase to 250℃ at a rate of 40℃ / min, and hold for 8 min; the GC-MS interface temperature was 200–250℃.

[0023] The ionization method was EI; the ionization energy was 40–60 eV; the ion source temperature was 170–250 °C; and the mass spectrometry scan was performed in SIM mode.

[0024] The present invention is further configured such that the retention time and characteristic ions of the (meth)acrylate compounds are shown in the table below:

[0025]

[0026]

[0027] The present invention is further configured such that the generation of the standard curve equation includes the following steps:

[0028] S1: Accurately weigh an appropriate amount of the (meth)acrylate compound standard to be tested, dissolve it in ethyl acetate, make up to volume, and then dilute it to prepare a series of gradient mixed standard working solutions;

[0029] S2: Inject the gradient mixed standard working solution into a gas chromatograph-mass spectrometer to determine the (meth)acrylate compounds to be tested and their peak areas. Plot a standard working curve with concentration as the abscissa and the peak area of ​​(meth)acrylate compounds as the ordinate, and calculate the standard curve equation.

[0030] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0031] This invention employs ultrasonic extraction-gas chromatography-mass spectrometry to simultaneously and accurately detect 12 (meth)acrylate compounds in textiles. The method is simple to operate, easily automated, and highly sensitive, exhibiting linear correlation coefficients above 0.998 within a concentration range of 0.50–10.00 mg / L. The limits of detection range from 0.09 mg / kg to 2.41 mg / kg, the limits of quantitation from 0.32 mg / kg to 7.44 mg / kg, and the recoveries range from 87.71% to 99.43%, with relative standard deviations (RSDs) of 1.07% to 2.81%, demonstrating good accuracy and reproducibility. Attached Figure Description

[0032] Figure 1 These are extraction effect diagrams for different extractants.

[0033] Figures 2a-2g These are chromatograms obtained using different extraction solvents.

[0034] Figure 3 This is a graph showing the extraction effect of different extractants on actual positive samples.

[0035] Figure 4 a-4c is a graph showing the effect of extractant dosage on the extraction effect of (meth)acrylate on spiked textiles of different materials.

[0036] Figure 5 a-5d are graphs showing the extraction effects of (meth)acrylate on spiked textiles of different materials and actual positive samples at different extraction temperatures.

[0037] Figure 6 a-6d are graphs showing the extraction effects of (meth)acrylate on spiked textiles of different materials and actual positive samples at different extraction times.

[0038] Figure 7 a-7d are graphs showing the extraction effects of (meth)acrylate on spiked textiles of different materials and actual positive samples at different extraction powers.

[0039] Figures 8a-8e These are chromatograms of the detection of (meth)acrylates using different chromatographic columns.

[0040] Figure 9 This is a graph showing the effect of inlet temperature on the detection of (meth)acrylates.

[0041] Figure 10 This is a graph showing the effect of the initial heating temperature on the detection of (meth)acrylates.

[0042] Figure 11 This is a graph showing the effect of heating rate on the detection of (meth)acrylates.

[0043] Figure 12 This is a graph showing the effect of termination temperature on the detection of (meth)acrylates.

[0044] Figure 13 This is a graph showing the effect of carrier gas flow rate on the detection of (meth)acrylates.

[0045] Figure 14 This is a graph showing the effect of ion source temperature on the detection of (meth)acrylates.

[0046] Figure 15 This is a GC-MS chromatogram for the detection of (meth)acrylates. Detailed Implementation

[0047] The technical solution of the present invention will be clearly and thoroughly described below with reference to the accompanying drawings and specific embodiments. It should be understood that the following embodiments are only some embodiments of the present invention, and other embodiments obtained by those skilled in the art without creative effort should be covered within the protection scope of the present invention.

[0048] The materials used in the following examples are all commercially available products. Unless otherwise specified, the experimental conditions were performed according to the manufacturer's recommendations or conventional experimental conditions in the field.

[0049] (1) Preparation of standard stock solutions and mixed standard working solutions:

[0050] Accurately weigh 0.2 g of each of the 12 (meth)acrylate compound standards, dissolve them separately in ethyl acetate, and then transfer them to 10 mL volumetric flasks. Dilute to the mark to obtain a standard stock solution with a concentration of 2000 mg / L. According to the experimental design requirements, pipette equal volumes of each (meth)acrylate standard stock solution into the same brown volumetric flask protected from light, and dilute to the mark with ethyl acetate to prepare the required concentration; this is the mixed standard working solution. The mixed standard working solution should be prepared fresh before use.

[0051] The 12 (meth)acrylate compounds mentioned above include methyl acrylate (MAE), ethyl acrylate (EA), butyl acrylate (BA), tert-butyl acrylate (TBA), octadecyl acrylate (OA), methyl methacrylate (MMA), ethyl methacrylate (EM), butyl methacrylate (BM), hydroxyethyl methacrylate (HM), 2-ethylhexyl acrylate (2-EA), 2-phenoxyethyl acrylate (2-PA), and 2-methoxyethyl acrylate (EMEA).

[0052] (2) Preparation of spiked textiles:

[0053] Accurately weigh 1.00g of blank lining fabrics of different materials such as cotton, wool, polyester, and nylon, cut them into pieces smaller than 0.5cm × 0.5cm, place them in a 50mL sealable screw-top sample bottle, add 100uL of 100mg / L mixed standard working solution to the cut blank lining fabric, seal the bottle tightly, and let it stand for 15 minutes.

[0054] Example 1: Screening of Sample Pretreatment Methods

[0055] 1.1 Selection of Extractant

[0056] Experiments were conducted using extractants with different solubilities. Seven samples of spiked textiles of different materials (cotton, wool, and polyester) were weighed, with each sample containing 10 mg / kg of the mixed standard substance. These samples were placed in 50 mL screw-top sample vials, and N,N-dimethylformyl, methyl tert-butyl ether, methanol, dichloromethane, acetonitrile, ethyl acetate, and n-hexane were added respectively. After sonication at 45℃ for 35 min, 1 mL of the extract was measured, filtered through a filtration filter, and then placed in a 2 mL injection vial. GC-MS analysis was performed. Three parallel experiments were set up, and the average value was calculated. Simultaneously, 100 μL of a 100 mg / L mixed standard stock solution was added to the screw-top sample vial, along with the same volume of extractant but without the lining fabric, to conduct a control experiment to calculate the extraction rate.

[0057] Meanwhile, a representative polyacrylate waterproof coating fabric synthesized with octadecyl acrylate as a monomer was selected as the actual positive sample for simultaneous extraction experiments: 1g of the actual positive sample was weighed, cut into small fragments of 0.5cm×0.5cm, placed in a 50mL sealable screw-top sample bottle, and extracted with extractants of different solubilities under the same extraction conditions. After extraction, the peak area was detected by GC-MS. Three sets of parallel experiments were conducted, and the average value of the results was calculated.

[0058] Figure 1 Extraction effects of different extractants used to label textiles; Figures 2a-2g Chromatograms for detection using different extractants; Figure 3 The extraction effects of different extractants on actual positive samples.

[0059] First, from Figure 1 It can be seen that all extractants can extract three relatively typical substances: hydroxyethyl methacrylate (HM), 2-phenoxyethyl acrylate (2-PA), and octadecyl acrylate (OA). Ethyl acetate solvent exhibits higher extraction rates for these three acrylates than the other six solvents and demonstrates a certain degree of universality. Furthermore, from... Figures 2a-2g It can be seen that ethyl acetate can extract all substances, and has the highest peak area, indicating the best extraction effect; finally, by Figure 3 It can be seen that in the verification of waterproof coated fabrics containing octadecyl acrylate, which can be extracted in all extraction solvents, ethyl acetate still has the highest peak area. Considering that ethyl acetate has low toxicity, low price, and similar polarity to acrylates, ethyl acetate was chosen as the extraction reagent for sample pretreatment.

[0060] 1.2 Investigation of Extraction Methods

[0061] Weigh 1.0g of each of three spiked textile samples (cotton, wool, and polyester), with a mixed standard substance content of 10mg / kg on each type of spiked textile. Place each sample in a 50mL screw-top sample bottle and add 10mL of chromatographic grade ethyl acetate. Extract each type of spiked textile sample using ultrasonic extraction, Soxhlet extraction, and shaking extraction, respectively. After extraction, measure 1mL of the extract, filter it through a filtration filter, and place it in a 2mL injection bottle for GC-MS analysis. Perform three parallel experiments for each extraction method and take the average value. Simultaneously, add 100μL of a 100mg / L mixed standard stock solution to the screw-top sample bottle, and add the same volume of extractant without the lining fabric for a control experiment to calculate the extraction rate.

[0062] Meanwhile, a representative polyacrylate waterproof coating fabric synthesized with octadecyl acrylate as a monomer was selected as the actual positive sample for simultaneous extraction experiments: 1g of the actual positive sample was weighed, cut into 0.5cm×0.5cm fragments, placed in a 50mL sealable screw-top sample bottle, and the extraction experiments of the above different extraction methods were carried out. After extraction, the peak area was detected by GC-MS. Three sets of parallel experiments were carried out, and the average value of the results was calculated. The extraction rates of different extraction methods are shown in Table 2.

[0063] Table 2 Extraction rates of different extraction methods (n=3)

[0064]

[0065] Table 2 shows that both Soxhlet extraction and ultrasonic extraction have higher extraction rates than mechanical oscillation extraction. However, considering the long extraction time (generally over 6 hours) and cumbersome extraction steps of Soxhlet extraction, as well as the large amount of organic reagents required, the rapid and efficient ultrasonic extraction method was chosen. Furthermore, after ultrasonic extraction, an SPE solid-phase extraction column can be used to further purify and extract (meth)acrylate compounds from textiles.

[0066] 1.3 Investigation into the volume of extractant

[0067] Weigh 1.0g of each of four spiked textile samples (cotton, wool, and polyester), with a mixed standard substance content of 10mg / kg on each spiked fabric. Place each sample in a 50mL screw-top sample bottle and add (5, 10, 15, and 20)mL of chromatographic grade ethyl acetate, respectively. Sonicate at 45℃ for 35min. After sonication, measure 1mL of the extract, filter through a filtration filter, and place it in a 2mL injection bottle for GC-MS analysis. Perform three parallel experiments and calculate the average value. Simultaneously, add 100μL of 100mg / L mixed standard stock solution to the screw-top sample bottle, and add (5, 10, 15, and 20)mL of extractant without the lining fabric for a control experiment to calculate the extraction rate.

[0068] Figure 4 a-4c represents the extraction rates of (meth)acrylates from spiked textiles of different materials under different amounts of extractant. Figure 4 a represents cotton fabric. Figure 4 b represents wool fabric. Figure 4 c represents polyester fiber.

[0069] As shown in the figure, the extraction rate initially increases and then stabilizes with increasing extraction reagent dosage. The lowest extraction rate is observed when the extraction reagent dosage is 5 mL, mainly because the amount of extractant is too small to completely submerge 1.0 g of the test fabric, thus failing to extract all (meth)acrylates from the fabric. However, the spiked recoveries of acrylates are similar when the extractant dosage is 10 mL, 15 mL, and 20 mL. Therefore, a mass-to-volume ratio of 1 g to 10–20 mL for the textile sample and extractant should be selected.

[0070] 1.4 Investigation of Extraction Temperature

[0071] In ultrasonic extraction, extraction temperature is one of the most important factors affecting the extraction results. The extractant used in this experiment had a boiling point of 77℃, and the temperature in the detection chamber was 25℃. Ultrasonic extraction requires the extraction temperature to be lower than the boiling point of the selected extractant. Therefore, the effect of extraction temperature on the extraction results was investigated within the temperature range of 30–50℃.

[0072] Five 1.0g samples of spiked textiles of different materials (cotton, wool, and polyester) were weighed out, with each sample containing 10mg / kg of the mixed standard substance. The samples were placed in 50mL screw-top sample vials, and 10mL of chromatographic grade ethyl acetate was added. The samples were then sonicated for 35min at different extraction temperatures (30℃, 35℃, 40℃, 45℃, and 50℃). After sonication, 1mL of the extract was filtered through a filtration filter and placed in a 2mL injection vial for GC-MS analysis. Three parallel experiments were performed, and the average value was calculated. Simultaneously, 100μL of a 100mg / L mixed standard stock solution was added to each screw-top sample vial, and 10mL of the extractant was added without any lining fabric for analysis, serving as a control experiment to calculate the extraction rate.

[0073] Meanwhile, a representative polyacrylate waterproof coating fabric synthesized with octadecyl acrylate as the monomer was selected as the actual positive sample for simultaneous extraction experiments: 1g of the actual positive sample was weighed, cut into 0.5cm×0.5cm fragments, placed in a 50mL sealable screw-top sample bottle, and 10mL of chromatographic grade ethyl acetate was added. The same extraction method was used, and extraction was carried out at different extraction temperatures (30℃, 35℃, 40℃, 45℃, 50℃). After extraction, the peak area was detected by GC-MS. Three sets of parallel experiments were carried out, and the average value of the results was calculated.

[0074] Figure 5 a-5d represent the extraction rates of (meth)acrylates at different extraction temperatures for spiked textiles and actual positive samples of different materials. Figure 5 'a' represents cotton fabric. Figure 5 b represents wool fabric. Figure 5 c represents polyester fiber. Figure 5 d represents the actual positive sample.

[0075] As shown in the figure, with increasing extraction temperature, intermolecular thermal motion intensifies. Under the action of the extractant, (meth)acrylate monomers desorb from the fabric and enter the extraction solution. When the temperature rises to 45℃, the (meth)acrylate on the fabric is almost completely desorbed, reaching equilibrium. Further increasing the extraction temperature no longer improves the extraction effect. Therefore, in ultrasonic extraction, the extraction temperature should be selected between 40 and 50℃.

[0076] 1.5 Investigation into Extraction Time

[0077] Five 1.0g samples of spiked textiles of different materials (cotton, wool, and polyester) were weighed out, with each sample containing 10mg / kg of the mixed standard substance. The samples were placed in 50mL screw-top sample vials, and 10mL of chromatographic grade ethyl acetate was added. The samples were then ultrasonically extracted at 45℃ for 20min, 25min, 30min, 35min, and 40min. After ultrasonic extraction, the white residue was filtered out, and 1mL of the extract was placed in a 2mL injection vial for GC-MS analysis. Three parallel experiments were performed, and the average value was calculated. Simultaneously, 100μL of a 100mg / L mixed standard stock solution was added to each screw-top sample vial, and 10mL of the extractant was added without the lining fabric for analysis, serving as a control experiment to calculate the extraction rate.

[0078] Meanwhile, a representative polyacrylate waterproof coating fabric synthesized with octadecyl acrylate as the monomer was selected as the actual positive sample for simultaneous extraction experiments: 1g of the actual positive sample was weighed, cut into 0.5cm×0.5cm fragments, placed in a 50mL sealable screw-top sample bottle, and 10mL of chromatographic grade ethyl acetate was added. The same extraction method was used, and ultrasonic extraction was performed at 45℃ for 20min, 25min, 30min, 35min, and 40min, respectively. After extraction, the peak area was detected by GC-MS. Three sets of parallel experiments were performed, and the average value of the results was calculated.

[0079] Figure 6 a-6d represent the extraction rates of (meth)acrylates in spiked textiles and actual positive samples of different materials at different extraction times. Figure 6 'a' represents cotton fabric. Figure 6 b represents wool fabric. Figure 6 c represents polyester fiber. Figure 6 d represents the actual positive sample.

[0080] As shown in the figure, the extraction time is positively correlated with the extraction rate when the extraction time is between 20 and 35 minutes. After 35 minutes, the extraction rate tends to reach equilibrium with increasing time. Therefore, in ultrasonic extraction, the extraction time should be selected between 30 and 40 minutes.

[0081] 1.6 Investigation of Extraction Power

[0082] Five samples of spiked textiles of different materials (cotton, wool, and polyester) were weighed, with a mixed standard substance content of 10 mg / kg on each spiked fabric. These samples were placed in 50 mL screw-top sample vials, and 10 mL of chromatographic grade ethyl acetate was added. The samples were then ultrasonically extracted at 45°C for 35 min at ultrasonic extraction powers of 300 W, 350 W, 400 W, 450 W, and 500 W. After ultrasonic extraction, 1 mL of the extracted solution was filtered and placed in a 2 mL injection vial for GC-MS analysis. Three parallel experiments were performed, and the average value was calculated. Simultaneously, 100 μL of a 100 mg / L mixed standard stock solution was added to a screw-top sample vial, and 10 mL of the extractant was added without a lining fabric for analysis, serving as a control experiment to calculate the extraction rate.

[0083] Meanwhile, a representative polyacrylate waterproof coating fabric synthesized with octadecyl acrylate as the monomer was selected as the actual positive sample for simultaneous extraction experiments: 1g of the actual positive sample was weighed, cut into 0.5cm×0.5cm fragments, placed in a 50mL sealable screw-top sample bottle, and 10mL of chromatographic grade ethyl acetate was added. The same extraction method was used, and ultrasonic extraction was performed at 45℃ for 35min. The ultrasonic extraction powers were 300W, 350W, 400W, 450W, and 500W, respectively. After extraction, the peak area was detected by GC-MS. Three parallel experiments were performed, and the average value of the results was calculated.

[0084] Figure 7 a-7d represent the extraction rates of (meth)acrylates in spiked textiles and actual positive samples of different materials at different extraction powers. Figure 7 'a' represents cotton fabric. Figure 7 b represents wool fabric. Figure 7 c represents polyester fiber. Figure 7 d represents the actual positive sample.

[0085] As shown in the figure, within the extraction power range of 300W to 450W, the extraction rate and peak area of ​​(meth)acrylate continuously increase with the increase of ultrasonic extraction power, and then gradually tend to reach equilibrium. However, considering that the maximum power of the ultrasonic extractor in the actual experiment is 500W, and that ethyl acetate and the target substance 2-methoxyethyl acrylate have low boiling points, when the ultrasonic power is too high, the thermal effect of the ultrasound will generate a large amount of heat, causing the ultrasonic water bath temperature to change and rise, which in turn will raise the temperature of the analyte and extraction reagent in the test tube. Therefore, the extraction power is selected to be 400-500W.

[0086] Example 2: Investigation of GC-MS Instrument Conditions

[0087] 2.1 Selection of chromatographic column

[0088] In gas chromatography, analytes of different polarities are separated by adsorption and desorption on the stationary phase within the chromatographic column. The selection of the stationary phase is crucial, considering not only the polarity of the analytes and the stationary phase but also the resolution and column efficiency during the chromatographic analysis. This experiment determined a wide variety of (meth)acrylates, with significant differences in polarity and boiling points among them; therefore, selecting a suitable chromatographic column was paramount.

[0089] This experiment selected five gas chromatography columns with different polarities: DB-5 column (weakly polar column), DB-17 column (medium polar column), DB-35 column (weakly-medium polar column), DB-624 column (medium polar capillary column), and DB-WAX column (strongly polar column). Under the same detection conditions (injector temperature 200℃, temperature program: initial temperature 40℃, hold for 10 min, increase to 100℃ at 20℃ / min and hold for 8 min, finally increase to 250℃ at 40℃ / min and hold for 8 min, carrier gas is helium (purity ≥99.999%), carrier gas flow rate is 1 mL / min, gas chromatography-mass spectrometry interface temperature is 250℃, ionization mode is EI; ionization energy is 60 eV, mass spectrometry scan is SIM mode, ion source temperature is 230℃, transfer line temperature is 250℃), a 50 mg / L mixed standard working solution was detected, and the peak shape, resolution and response value of different chromatographic columns were observed. Figures 8a-8e Chromatograms for detection using different chromatographic columns.

[0090] As can be seen from the figure, the peak elution patterns of different columns vary. The DB-17 column eluted earlier, with only 5 substances eluting. The DB-5 column had a low response value and eluted too early, which could potentially overlap with the solvent peak, resulting in only 6 substances eluting and affecting the experimental analysis. The DB-624 column failed to elute methyl acrylate and octadecyl acrylate. The DB-35 column failed to elute methyl acrylate and exhibited baseline instability. When the DB-WAX column was selected, all 12 substances eluted, and the elution times did not interfere with each other. The high response value better met the experimental detection requirements, so the DB-WAX column was chosen.

[0091] 2.2 Investigation of Inlet Temperature

[0092] In gas chromatography-mass spectrometry (GC-MS), the injection port temperature is a significant factor affecting the final detection results. Generally, the injection port temperature should be higher than the boiling point of the analyte (octadecyl acrylate boils at 400℃, while other acrylate analytes boil below 150℃). However, considering the need to ensure the instrument's lifespan (the column's maximum temperature is only 260℃), a minimum temperature of 160℃ was chosen, and six different temperatures between 160 and 260℃ were used to explore the conditions.

[0093] A 20 mg / L mixed standard working solution of (meth)acrylate was prepared. A DB-WAX gas chromatograph column was used. The temperature program was the same as that in "(1) Selection of chromatographic column" above, except for the injection port temperature. Under the condition that other instrument conditions remained unchanged, the injection port temperature of the gas chromatograph was set to 160℃, 180℃, 200℃, 220℃ and 240℃ respectively. The peak area and resolution of (meth)acrylate at different temperatures were detected to determine the optimal injection port temperature. Figure 9 The effect of different injection port temperatures on the detection of (meth)acrylates.

[0094] from Figure 9 It can be seen that as the injection port temperature increases, the peak area of ​​the detected (meth)acrylate gradually increases. However, after reaching 200℃, the peak area of ​​the (meth)acrylate gradually decreases with further increases in temperature. Therefore, the injection port temperature should be selected between 180 and 200℃, preferably 200℃.

[0095] 2.3 Investigation of Heating Program

[0096] There are two types of temperature programs: single-stage linear temperature programming and multi-stage linear temperature programming. Single-stage temperature programming is generally used for homologues with a wide boiling point range, while multi-stage temperature programming is used when different types of compounds are present. A good temperature program can effectively separate the target substances and is the basis for qualitative and quantitative analysis of the analytes. In this embodiment, a suitable temperature program is explored by optimizing the initial temperature, heating rate, and termination temperature.

[0097] (1) Optimization of initial temperature: Prepare a 20 mg / L mixed standard working solution of (meth)acrylate. Use a DB-WAX gas chromatographic column. Except for the initial temperature, the temperature program is the same as the setting in "2.1 Selection of Column" above. Under the condition that other instrument conditions remain unchanged, the initial temperature is set to 35℃, 40℃, 60℃ and 80℃ respectively. The peak area and resolution of (meth)acrylate at different temperatures are measured to determine the optimal initial temperature. The different initial temperature programs are shown in Table 3.

[0098] Table 3 Heating programs at different initial temperatures

[0099]

[0100] The initial temperature must ensure complete separation of the target components while also considering the timeliness of the analysis; the analysis time should not be too long. If the initial temperature of the gas chromatography column is too high, it will not only decrease the resolution of the target substances, shorten the retention time, and narrow and heighten the chromatographic peaks, but also affect the elution of early substances due to the rapid initial temperature rise. Conversely, if the initial temperature is too low, the resolution will increase, but the analysis time will be prolonged. Therefore, this experiment mainly considers both retention time and peak area to explore the optimal initial temperature of the gas chromatography column. The results are as follows: Figure 10 As shown.

[0101] from Figure 10 As can be seen, initial temperatures of 60℃ and 80℃ were too high, affecting peak elution and resulting in only three substances with retention times exceeding 20 minutes eluting. Initial temperatures of 35℃ and 40℃ resulted in better peak elution and higher separation of the target substances. However, the peak area at 35℃ was relatively low, and baseline instability occurred in the later stages of detection. Therefore, the optimal initial temperature for (meth)acrylate detection is 35–40℃, preferably 40℃.

[0102] (2) Optimization of heating rate: Prepare a 20 mg / L mixed standard working solution of acrylate. Use a DB-WAX gas chromatographic column. Except for the heating rate, the heating program is the same as the setting in "2.1 Selection of Column" above. Under the condition that other instrument conditions remain unchanged, set a multi-stage linear heating program with different heating rates. Measure the peak area and resolution of (meth)acrylate at different rates and determine the optimal heating program. The different heating rate programs are shown in Table 4.

[0103] Table 4 Heating programs at different heating rates

[0104]

[0105] A faster heating rate in gas chromatography can shorten analysis time, but it also reduces resolution. A lower heating rate increases resolution and prolongs analysis time for high-boiling-point components, leading to peak broadening. Both excessively fast and slow heating rates affect peak elution and thus experimental results. Therefore, this experiment primarily considered both retention time and peak area, determining the heating rate of four (meth)acrylates at different heating rates to investigate the effects of the gas chromatography column. The results are as follows: Figure 11 As shown.

[0106] from Figure 11 As can be seen, heating rates of 10℃ / min and 20℃ / min are too slow, causing hydroxyethyl methacrylate, 2-phenoxyethyl acrylate, and octadecyl acrylate, which have longer retention times, to fail to elute. When the heating rate is 80℃ / min, it is too fast, causing the overall peak elution time of the target analytes to be advanced, and the overall peak area to decrease compared to 40℃ / min, resulting in baseline instability in the later stages of detection. Therefore, considering all factors, the heating procedure for (meth)acrylate detection was chosen to first heat to 100℃ at a rate of 20℃ / min, and then to 250℃ at a rate of 40℃ / min.

[0107] (3) Optimization of termination temperature: Prepare a 20 mg / L mixed standard working solution of (meth)acrylate. Use a DB-WAX gas chromatographic column. Except for the termination temperature, the temperature program is the same as the setting in "2.1 Selection of Column" above. Under the condition that other instrument conditions remain unchanged, the termination temperature is set to 150℃, 200℃ and 250℃ respectively. The peak area and resolution of (meth)acrylate at different temperatures are measured to determine the optimal termination temperature. The termination temperature program is shown in Table 5.

[0108] Table 5 Heating programs with different termination temperatures

[0109]

[0110]

[0111] The selection of the termination temperature should balance the highest boiling point of the component and the highest operating temperature of the stationary phase. This experiment, while ensuring the full efficiency of the DB-WAX column, mainly considered both retention time and peak area, and determined (meth)acrylates at three different termination temperatures to explore the termination temperature of the temperature program. The results are as follows: Figure 12 As shown.

[0112] from Figure 12 As can be seen, when the termination temperature is 150℃, the peak area of ​​(meth)acrylates is low, and hydroxyethyl methacrylate and octadecyl acrylate do not elute. When the termination temperature is 200℃, the peak area of ​​(meth)acrylates is higher than that at 150℃, but 2-phenoxyethyl acrylate still does not elute. When the termination temperature is 250℃, all 12 (meth)acrylates show good separation and peak area. Therefore, 250℃ was chosen as the termination temperature for the (meth)acrylate detection temperature program.

[0113] Based on the above optimizations, the final temperature program for the gas chromatography column is determined as follows: initial temperature 40℃, hold for 10 min, then increase the temperature to 100℃ at a rate of 20℃ / min, hold for 8 min, then increase the temperature to 250℃ at a rate of 40℃ / min, and hold for 8 min.

[0114] 2.4 Investigation of Carrier Gas Flow Rate

[0115] In gas chromatography-mass spectrometry (GC-MS), different carrier gas flow rates have a significant impact on peak elution time and peak shape. A suitable carrier gas flow rate can improve column efficiency, reduce band broadening, and result in sharper, more symmetrical peaks.

[0116] In this experiment, a 20 mg / L mixed standard working solution of (meth)acrylate was prepared using a DB-WAX gas chromatographic column. The temperature program was the same as set in "2.1 Column Selection" above. With other instrument conditions unchanged, three parallel experiments were set up with a carrier gas flow rate ranging from 0.4 mL / min to 1.1 mL / min to determine the peak area and resolution of (meth)acrylate at different flow rates, thus identifying the optimal carrier gas flow rate. The effect of different carrier gas flow rates on the determination of the 20 mg / L mixed standard working solution of (meth)acrylate is as follows: Figure 13 As shown.

[0117] from Figure 13 It can be seen that as the carrier gas flow rate increases, the peak area of ​​(meth)acrylate first increases and then decreases. Therefore, a carrier gas flow rate of 0.8–1.1 mL / min is selected.

[0118] 2.5 Investigation into the temperature of the ion source

[0119] The primary function of an ion source is to bombard substances separated by gas chromatography into fragment ions, which are then detected for qualitative and quantitative analysis based on their relative molecular mass. Therefore, it is crucial to ensure complete bombardment of the chromatographically separated substances throughout the process. This requires preventing both excessively low ion source temperatures that could contaminate the ion source with bombarded fragment ions and excessively high temperatures that could lead to aging of the ion source ports.

[0120] To obtain the optimal ion source temperature, a 20 mg / L mixed standard working solution of (meth)acrylate was prepared. A DB-WAX gas chromatographic column was used, and the temperature program was the same as that set in "2.1 Column Selection" above. With other instrument conditions unchanged, the ion source temperature was set to 150℃, 170℃, 190℃, 210℃, 230℃, and 250℃ respectively. Three parallel experiments were set up to determine the peak area and resolution of (meth)acrylate at different temperatures and to determine the optimal ion source temperature.

[0121] The effect of different ion source temperatures on the determination of 20 mg / L (meth)acrylate mixed standard working solution is as follows: Figure 14 As shown.

[0122] Depend on Figure 14 It can be seen that when the ion source temperature is between 170℃ and 250℃, the peak areas of the corresponding (meth)acrylates are all high, with no significant difference.

[0123] 2.6 Retention time and characteristic ions

[0124] A 20 mg / L mixed standard working solution of (meth)acrylates was prepared and injected into a gas chromatography-mass spectrometry (GC-MS) instrument. The optimized instrument conditions described in Examples 2.1–2.5 above were used for detection. The retention times, characteristic ions, and corresponding gas chromatograms of the 12 (meth)acrylate target analytes were obtained, as shown in Tables 6 and 7. Figure 15 As shown. The optimal instrument conditions are as follows:

[0125] Select DB-WAX column; set the injection port temperature to 180℃; temperature program: initial temperature 40℃, hold for 10 min, increase to 100℃ at a rate of 20℃ / min, hold for 8 min, then increase to 250℃ at a rate of 40℃ / min and hold for 8 min; ion source temperature 230℃; carrier gas flow rate 1.0 mL / min.

[0126] Table 6 Retention time and characteristic ions of (meth)acrylates

[0127]

[0128] Example 3: Methodological Validation

[0129] 3.1 Linearity and Detection Limit

[0130] 1 mL of mixed standard working solutions of (meth)acrylates with concentration gradients of 0.5 mg / L, 1 mg / L, 2 mg / L, 5 mg / L, and 10 mg / L were respectively pipetted into 2 mL sample vials and then injected into a gas chromatography-mass spectrometry (GC-MS) instrument for detection. Gas chromatograms were obtained, and a standard curve was plotted with sample concentration on the x-axis and peak area on the y-axis. The GC-MS testing conditions were the same as described in "2.6 Retention Time and Characteristic Ions". The linear ranges, linear equations, and correlation coefficients of the 12 (meth)acrylates obtained are shown in Table 7 below.

[0131] Table 7. Linear range, linear equation, and correlation coefficient for 712 (meth)acrylates

[0132]

[0133] As shown in Table 7, this method exhibits good linearity in the concentration range of 0.50 mg / L to 10.00 mg / L. The linear correlation coefficients of the standard curves for the 12 target compounds are all above 0.998, which can meet the needs of actual testing.

[0134] Following the above method, the limits of detection and limits of quantitation for 12 (meth)acrylates were determined through low-concentration spiking tests, and the results are shown in Table 8.

[0135] Table 8 shows the detection limits and quantitation limits for 812 (meth)acrylates.

[0136]

[0137]

[0138] As shown in Table 8, the detection limit of this method is in the range of 0.09 mg / kg to 2.41 mg / kg, and the quantitation limit is in the range of 0.32 mg / kg to 7.44 mg / kg, which can meet the requirements of routine testing.

[0139] 3.2 Recovery rate and precision

[0140] To demonstrate the universality of the detection method of this invention, standard lining fabrics of four different materials (cotton fiber, wool fiber, polyester fiber, and polyamide fiber) were weighed, and three different spiking amounts (5 mg / kg, 500 mg / kg, and 1000 mg / kg) within the range of 5 to 100 mg / kg were selected to prepare spiked textiles.

[0141] The spiked textile was placed in a reactor, and ethyl acetate, the extraction solvent, was added. The mass-to-volume ratio of the spiked textile to the extraction solvent was 1 g: 10 mL. The reactor was placed in an ultrasonic generator at 40 °C with an extraction power of 400 W for 30 min. The resulting extract was used as the test solution. The test solution was injected into a liquid chromatography-mass spectrometry (LC-MS) instrument for detection. The detection conditions for the LC-MS instrument were the same as those described in "2.6 Retention Time and Characteristic Ions". Six parallel experiments were performed for each group of experiments. The peak area was recorded, and the recovery rate and relative standard deviation (RSD) were calculated. The results are shown in Table 9 below.

[0142] Table 9. Recovery and relative standard deviation of (meth)acrylates by GC-MS (n=6)

[0143]

[0144]

[0145] The results showed that the recoveries of the 12 (meth)acrylates in cotton fabrics ranged from 87.71% to 94.90%, in wool fabrics from 88.89% to 96.10%, in polyester fibers from 93.69% to 99.43%, and in polyamide fibers from 93.59% to 99.03%.

[0146] The relative standard deviation (RSD) of this method for detecting (meth)acrylates in different textiles ranged from 1.07% to 2.81%, indicating that the ultrasonic extraction-gas chromatography-mass spectrometry method has good reproducibility and accuracy for the detection of (meth)acrylates in textiles.

[0147] Application Example 1

[0148] The determination of (meth)acrylate in a positive sample includes the following steps:

[0149] (1) Accurately weigh 1g of the positive sample to be tested, cut the sample into pieces no larger than 0.5cm×0.5cm, place them in the reactor, add 10mL of extraction solvent ethyl acetate, perform ultrasonic extraction, the extraction temperature is 40℃, the extraction time is 30min, the extraction power is 400W, and the resulting extract is the test solution.

[0150] (2) The standard working curve equation and the test conditions of the gas chromatography-mass spectrometry system are the same as those in “3.1 Linearity and Detection Limit”.

[0151] (3) Inject the test solution from step (1) into a gas chromatograph-mass spectrometer for detection. The test conditions are the same as in step (2) above. Measure the (meth)acrylate compounds and their peak areas, and calculate the analysis based on the standard curve equation.

[0152] The final measured content of octadecyl acrylate in the positive sample was 2.72 mg / kg, and the content of methyl methacrylate was 1.88 mg / kg. Other (meth)acrylates were not detected.

[0153] The above description is only a preferred embodiment of the present invention and does not limit the scope of protection of the present invention. Any equivalent structural or procedural transformations made based on the description and drawings of the present invention are similarly included within the scope of protection of the present invention.

Claims

1. A method for determining a (meth) acrylate compound in a textile, characterized by, Includes the following steps: (1) Place the accurately weighed textile sample to be tested in a reactor, add an extractant and perform ultrasonic extraction to obtain an extract; the extractant is ethyl acetate; (2) Inject the above extract into a gas chromatograph-mass spectrometer to determine the (meth)acrylate compounds and their peak areas, and calculate the content of (meth)acrylate compounds in the textile sample to be tested according to the standard curve equation. The (meth)acrylate compounds include methyl acrylate, ethyl acrylate, butyl acrylate, tert-butyl acrylate, octadecyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, 2-ethylhexyl acrylate, 2-phenoxyethyl acrylate, and 2-methoxyethyl acrylate. The instrument conditions for the gas chromatography-mass spectrometry (GC-MS) system are as follows: The chromatographic column was a DB-WAX column; the carrier gas was helium with a purity ≥99.999%; the carrier gas flow rate was 0.8~1.1 mL / min; the injection port temperature was 100~200℃; the temperature program was as follows: initial temperature 25~40℃, hold for 10 min, then increase to 100℃ at a rate of 20℃ / min, hold for 8 min, then increase to 250℃ at a rate of 40℃ / min, and hold for 8 min; the GC-MS interface temperature was 200~250℃. The ionization method was EI; the ionization energy was 40~60 eV; the ion source temperature was 170~250℃; and the mass spectrometry scan was in SIM mode.

2. The method according to claim 1, wherein In step (1), the mass-to-volume ratio of the textile sample to be tested and the extractant is 1g:10~20mL.

3. The method according to claim 1, wherein In step (1), the ultrasonic extraction conditions are: extraction temperature of 40~50℃, extraction time of 30~40min, and extraction power of 400~500W.

4. The method for determining a (meth) acrylate compound in a textile according to claim 1, characterized by, In step (1), after ultrasonic extraction, the extract is purified by using an SPE solid-phase extraction column.

5. The method according to claim 1, wherein The retention times and characteristic ions of the (meth)acrylate compounds are shown in the table below:

6. The method according to claim 1, wherein The creation of the standard curve equation includes the following steps: S1: Accurately weigh an appropriate amount of the (meth)acrylate compound standard to be tested, dissolve it in ethyl acetate, make up to volume, and then dilute it to prepare a series of gradient mixed standard working solutions. S2: Inject the gradient mixed standard working solution into a gas chromatograph-mass spectrometer to determine the (meth)acrylate compounds to be tested and their peak areas. Plot a standard working curve with concentration as the abscissa and the peak area of ​​(meth)acrylate compounds as the ordinate, and calculate the standard curve equation.

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