CN114894930B

CN114894930B - Method for detecting alkylphenol ethoxylate content in textile by high performance liquid chromatography

Info

Publication number: CN114894930B
Application number: CN202210470364.0A
Authority: CN
Inventors: 谢云龙; 陶亚娟; 吕超; 方洁玮; 聂家缘; 傅景旺; 徐铭伟; 张微; 周英杰; 陈巧仙; 郑绍辉; 鲍中梁; 陆茹启琦; 马楠楠
Original assignee: Lanxi Institute Of Product And Commodity Quality Inspection; Zhejiang Normal University CJNU
Current assignee: Lanxi Institute Of Product And Commodity Quality Inspection; Zhejiang Normal University CJNU
Priority date: 2022-04-28
Filing date: 2022-04-28
Publication date: 2023-10-20
Anticipated expiration: 2042-04-28
Also published as: CN114894930A

Abstract

The application discloses a method for detecting alkylphenol ethoxylate content in textiles by using high performance liquid chromatography, which comprises the following steps: (S1) carrying out ultrasonic treatment on a mixture containing a sample to be detected and a solvent I, and filtering to obtain a washing liquid I; (S2) carrying out ultrasonic treatment on the mixture containing the sample to be detected and the solvent II after the filtration in the step (S1), and filtering to obtain a washing liquid II; (S3) carrying out microwave extraction on the mixture I containing the sample to be detected after the filtration in the step (S2) and the extractant I, and separating to obtain a washing liquid III; (S4) carrying out microwave extraction on the mixture II containing the sample to be detected after the separation in the step (S3) and the extractant II, and separating to obtain a washing liquor IV; (S5) measuring a mixture containing the washing reagent I, the washing reagent II, the washing reagent III and the washing reagent IV by high performance liquid chromatography. The method has the characteristics of accuracy, rapidness and high sensitivity; meanwhile, the recovery rate, the precision and the detection limit reach the national standard detection level.

Description

Method for detecting alkylphenol ethoxylate content in textile by high performance liquid chromatography

Technical Field

The application relates to a method for detecting alkylphenol ethoxylate content in textile by high performance liquid chromatography, belonging to the field of determination methods of alkylphenol ethoxylate substances in textile.

Background

Alkylphenol ethoxylates (APEO) are an important class of nonionic surfactants, have superior washing, wetting, dispersing, emulsifying and penetrating properties compared with other surfactants, and are widely used in textile printing and dyeing assistants to be applied to textile printing and finishing, and the main commercial products are nonylphenol ethoxylates (NPEO) and octylphenol ethoxylates (opoo). APEO is stable in nature, slowly degraded in the environment and easily aggregated to generate toxicity, and degradation products of Nonylphenol (NP), octylphenol (OP) and short-chain NP1EO, NP2EO and NP3EO are more durable in the environment and more toxic, wherein part of metabolites have environmental hormone-like properties and easily disturb endocrine functions of wild living beings and human beings, so that the degradation products are forbidden and limited by various countries and tissues.

The textile component system is complex, and besides APEO, various dyes, auxiliary agents, salts, lipids and other substances are contained, and the impurities can increase interference, reduce the detection sensitivity of the instrument and cause pollution to the instrument, so that a reasonable extraction method is needed to be adopted for pretreatment of a sample before detection and analysis, and target compounds APEO and the like are extracted from a medium. Thus, research on methods for detecting APEO in textiles is largely divided into two major parts, instrumental detection and pretreatment of samples. The currently mature APEO detection methods include gas chromatography-mass spectrometry (GC-MS), high Performance Liquid Chromatography (HPLC), high performance liquid-nuclear magnetic resonance (HPLC-NMR), high performance liquid chromatography-mass spectrometry (HPLC-MS), LC-MS/MS, and the like. The extraction treatment method of the APEO mainly comprises Soxhlet extraction, liquid-liquid extraction, microwave-assisted extraction, reflux extraction, ultrasonic extraction, solid phase microextraction and the like. The extraction time required by Soxhlet extraction and reflux extraction is long; the liquid-liquid extraction has larger solvent requirement and complex operation; the capacity of solid phase extraction is low and the adsorbent is easily clogged. The ultrasonic extraction has the characteristics of rapidness, high efficiency and economy, and the microwave-assisted extraction method also has the advantages of simple operation, high extraction efficiency, good reproducibility and the like. For application research of detecting APEO content in textiles, only pure extraction is generally performed on the textiles, and no deep research is made on how to realize the condition of maximum extraction efficiency by utilizing ultrasonic extraction and microwave extraction.

Disclosure of Invention

According to one aspect of the application, a method for detecting alkylphenol ethoxylate content in textiles by high performance liquid chromatography is provided, which comprises the steps of performing textile pretreatment by designing proper extraction conditions by using a microwave digestion instrument, so as to maximize extraction efficiency; the method is accurate, quick and high in sensitivity; with reference to the existing detection method (ultrasonic and rotary steaming) and the indexes of recovery rate and precision (RSD), the method has the detection limit, recovery rate and precision reaching the national standard detection level, recovery rate range of 90-105%, precision of 0.65-4.20%, detection limit of 0.7896 mg/kg-0.9832 mg/kg, and the whole pretreatment and analysis process time can be controlled within 30min (the working curve time is removed), thus greatly shortening the pretreatment time and saving the solvent.

A method for detecting alkylphenol ethoxylate content in textiles by high performance liquid chromatography comprises the following steps:

(S1) carrying out ultrasonic treatment on a mixture containing a sample to be detected and a solvent I, and filtering to obtain a washing liquid I;

(S2) carrying out ultrasonic treatment on the mixture containing the sample to be detected and the solvent II after the filtration in the step (S1), and filtering to obtain a washing liquid II;

(S3) carrying out microwave extraction I on the mixture containing the sample to be detected after the filtration in the step (S2) and the extractant I, and separating to obtain a washing liquid III;

(S4) carrying out microwave extraction on the mixture II containing the sample to be detected after the separation in the step (S3) and the extractant II, and separating to obtain a washing liquor IV;

(S5) measuring a mixture containing the washing reagent I, the washing reagent II, the washing reagent III, and the washing reagent IV by high performance liquid chromatography.

Optionally, the solvent I, the solvent II, the extractant I and the extractant II are independently selected from at least one of methanol, dichloromethane, tert-butyl methyl ether, acetone and petroleum ether.

Optionally, the textile is selected from one of woven fabric, cotton fabric, knitted fabric and chemical fiber.

Optionally, the solid-to-liquid ratio of the sample to be tested in (S1) to (S4) to the solvent I, the solvent ii, the extractant I, and the extractant ii corresponding thereto is independently selected from 10mL/g to 20mL/g.

Optionally, the solid-to-liquid ratio of the sample to be tested in (S1) to (S4) to the solvent I, the solvent ii, the extractant I, the extractant ii corresponding thereto is independently selected from any value or range of values between any two of 10mL/g, 12mL/g, 14mL/g, 16mL/g, 18mL/g, 20mL/g.

Optionally, the time of the ultrasonic I and the ultrasonic II is 1 min-10 min.

Optionally, the time of the ultrasound I, the ultrasound ii is independently selected from any value or range of values between any two of 1min, 3min, 5min, 7min, 10min.

Optionally, the time of the microwave extraction I and the time of the microwave extraction II are both 10 min-15 min.

Optionally, the time of the microwave extraction I, the microwave extraction ii is independently selected from any value or range of values between any two of 10min, 11min, 12min, 13min, 14min, 15min.

Optionally, the temperature of the microwave extraction I and the microwave extraction II is 40-60 ℃.

Alternatively, the temperatures of the microwave extraction I and the microwave extraction II are independently selected from any value or range of values between any two of 40 ℃, 42 ℃, 44 ℃, 48 ℃, 52 ℃, 54 ℃, 58 ℃, 60 ℃.

Optionally, in step (S5), mixing, then fixing the volume, and filtering.

Optionally, the recovery rate of alkylphenol ethoxylates is 90-105%.

Optionally, the precision of the method is 0.65% -4.20%.

Alternatively, the detection limit of the high performance liquid chromatography is 0.7896 mg/kg-0.9832 mg/kg.

According to the method for measuring alkylphenol ethoxylates in the textile, the sample is a uniformly mixed sample which is sheared to a size of less than about 1cm, 10mL of methanol solvent is added to each gram of sample for each extraction, the microwave extraction temperature is 50 ℃, the ultrasonic cleaning time is 2min each time, and the microwave extraction time is 10min each time. The pretreatment of the method is carried out for 4 times, namely two times of ultrasonic extraction and two times of microwave extraction, 10ml of extractant is added in each time of extraction, bi Guolv washing liquid is extracted each time, four times of methanol washing liquid are combined, the volume is fixed to 50ml/g sample, and finally chromatographic analysis is carried out.

The conditions for detecting the sample solution by the high performance liquid chromatograph are as follows: chromatographic column: ecosil C18 (4.6X150 mm,3.0 μm); chromatographic column temperature: 30 ℃; mobile phase: methanol-acetonitrile-water ternary system (V/v=81/13/6), isocratic elution; detection wavelength: 227nm; flow rate: 1.0mL/min; sample injection amount: 10. Mu.L; a detector: an ultraviolet visible absorption detector.

The method comprises the following steps:

(1) Preparing a standard solution:

a) Standard stock solution: appropriate amounts of OP, NP, OPEO and NPEO were weighed accurately, respectively, and a single-component standard stock solution at a concentration of 10mg/mL (1000 ppm) was prepared with methanol.

b) Standard working solution: and respectively taking a proper amount of volumes of OP, NP, OPEO and NPEO standard stock solutions, placing the stock solutions into a volumetric flask, diluting the stock solutions with methanol, and respectively preparing standard working solutions with required concentrations.

(2) Sample preparation: a sample of the textile was cut into pieces of about 1cm x 1cm or less and mixed. 1g of the sheared sample was weighed, placed in a container, 10ml of methanol was added, and the mixture was ultrasonically cleaned for 2 minutes, and the solvent was collected and repeated 2 times. Then performing microwave extraction, placing the mixture in a sample tank, adding an extracting agent, shaking uniformly, and performing microwave extraction under the following extraction conditions: the extractant is methanol at 50deg.C for 10min. And after the extraction is finished and the temperature and the pressure are reduced to normal temperature and normal pressure, opening a tank to separate the extractant from the sample, and collecting the solvent. The microwave extraction was repeated 2 times for 10 minutes each time with 10ml extractant. The filtrates were combined and fixed to a volume of 50ml with methanol. 2ml of the extract was collected by a sample tube, filtered through a 0.22 μm organic filter, and subjected to liquid chromatography.

(3) Preparation of a standard curve: and (3) taking standard working solutions with different concentrations, injecting the standard working solutions into a high performance liquid chromatograph, measuring the peak area, taking the sample injection amount as an abscissa and the peak area value as an ordinate, and drawing a standard working curve.

(4) And (3) detection: and (3) the sample solution enters a high performance liquid chromatograph to be measured, the chromatographic peak area is recorded, and the content of alkylphenol ethoxylates is calculated by an external standard method. If the concentration of alkylphenol ethoxylates in the sample exceeds the measurement range, the concentration can be measured after dilution with methanol, and the dilution factor (5-fold) can be multiplied when calculated.

The application has the beneficial effects that:

1) The method provided by the application has the characteristics of accuracy, rapidness and high sensitivity; the detection limit, recovery rate and precision of the method reach the national standard detection level, wherein the recovery rate is in the range of 90-105%, the precision is 0.65-4.16%, the detection limit is xx mg/kg-xx mg/kg, and the time of the whole pretreatment and analysis process can be controlled within 30min (the time for eliminating the formulated working curve), so that the pretreatment time is greatly shortened, and the solvent is saved.

2) Compared with the ultrasonic and rotary steaming method in the national standard GB-T23222-2018, the method provided by the application has the advantages that the operation is simple, the detection time is greatly shortened compared with the national standard GB-T23222-2018, the detection requirement of APEO in textiles can be met, and the method has important significance for guaranteeing the development of textile industry in China.

Drawings

FIG. 1 is a flow chart of experimental operation of the present application.

FIG. 2 is a graph of APEO standard operation of the present application.

FIG. 3 is a chromatogram of alkylphenol and alkylphenol ethoxylates of the present application.

FIG. 4 is a chromatogram of alkylphenol and alkylphenol ethoxylate of example 1 of the present application.

FIG. 5 is a chromatogram of alkylphenol and alkylphenol ethoxylate of example 2 of the present application.

Detailed Description

The present application is described in detail below with reference to examples, but the present application is not limited to these examples.

Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.

The precision of the application: the detection method of the present application repeatedly measures the relative standard deviation of the recovery rate obtained for the same sample.

The detection limit of the application: the textile is extracted and detected according to the requirement of the analysis method, and can be distinguished from the lowest detection concentration of noise, wherein the response value corresponding to the detection limit is three times of the noise.

The instruments used in the examples of the application are shown in the following table:

the analysis method in the embodiment of the application is as follows:

reversed phase high performance liquid chromatography analysis was performed using high performance liquid chromatograph LC 20A.

The contents of alkylphenols and alkylphenol ethoxylates in the examples of the present application were calculated as follows:

Calculating the contents of alkylphenols and alkylphenol polyoxyethylene ethers in the sample according to the formula (1)

Wherein:

x-the content of the analyte in the sample in milligrams per kilogram (mg/kg);

c-the concentration of the analyte in milligrams per liter (mg/L) in the sample solution obtained from the standard working curve;

c ₀ -the concentration of the test substance in milligrams per liter (mg/L) in blank test solutions obtained from a standard working curve;

v-final constant volume of sample solution in milliliters (mL);

m-the mass of the sample represented by the final sample solution in grams (g).

The calculation result is kept to the last two bits of the decimal point.

In the embodiment of the application, the recovery rate of Nonylphenol Polyoxyethylene Ether (NPEO) and Octylphenol Polyoxyethylene Ether (OPEO) and degradation products of Nonylphenol (NP) and Octylphenol (OP) are calculated as follows:

recovery = (addition of standard sample measurement value-sample measurement value)/(addition of standard amount×100%).

Example 1

Determination of alkylphenol ethoxylate content in cotton-type fabrics

Blank marking treatment: a cotton type textile sample is taken and sheared into a plurality of complete sample blocks with the weight of 1g (+ -0.01 g). Placing in a microwave sample kettle for microwave extraction, adding 10mL of methanol extractant, performing microwave treatment for 10min for 2 times, discarding washing liquid after digestion, naturally airing after extraction for two times, and performing adsorption treatment of standard solution. 1mL of OP standard solution with the concentration of 10mg/L is dripped, and the sample is dried by a blower (cold air), so that the phenomenon that liquid drops on the surface of the sample are splashed due to too high air speed is avoided.

Pretreatment and chromatographic analysis: cutting the labeled sample, placing in a container, adding 10ml of methanol, ultrasonically cleaning for 2min, collecting the washing liquid, and repeating for 2 times. And performing microwave extraction, namely placing filter residues after decantation of the filtrate into a sample tank, adding an extractant, shaking uniformly, and performing microwave extraction. The extraction conditions are as follows: the extractant is methanol at 50deg.C for 10min. And after the extraction is finished and the temperature and the pressure are reduced to normal temperature and normal pressure, opening a tank to separate the extractant from the sample, and collecting the solvent. The microwave extraction was repeated 2 times for 10 minutes each time with 10ml extractant. The filtrates were combined and fixed to a volume of 50ml with methanol. 2ml of the extract was removed by a sample tube, filtered through a 0.22 μm organic filter and subjected to liquid chromatography. The obtained chromatographic behavior patterns are clear, and specific APEO content can be obtained by referring to the working curve. The average recovery in this case was 98.5%, RSD was 3.12%, pretreatment was carried out for 24min, and 50mL of methanol was consumed.

Example 2

Determination of alkylphenol ethoxylate content in knitted fabric

Blank marking treatment: samples of knitted textiles were taken and sheared into complete 1g (+ -0.01 g) swatches. Placing in a microwave sample kettle for microwave extraction, adding 10mL of methanol extractant, performing microwave treatment for 10min for 2 times, discarding washing liquid after digestion, naturally airing after extraction for two times, and performing adsorption treatment of standard solution. 1mL of NP standard solution with the concentration of 10mg/L is dripped, and the sample is dried by a blower (cold air), so that the splash of liquid drops on the surface of the sample cloth due to the too high wind speed is avoided.

Pretreatment and chromatographic analysis: cutting the labeled sample, placing in a container, adding 10ml of methanol, ultrasonically cleaning for 2min, collecting the washing liquid, and repeating for 2 times. And performing microwave extraction, namely placing filter residues after decantation of the filtrate into a sample tank, adding an extractant, shaking uniformly, and performing microwave extraction. The extraction conditions are as follows: the extractant is methanol at 50deg.C for 10min. And after the extraction is finished and the temperature and the pressure are reduced to normal temperature and normal pressure, opening a tank to separate the extractant from the sample, and collecting the solvent. The microwave extraction was repeated 2 times for 10 minutes each time with 10ml extractant. The filtrates were combined and fixed to a volume of 50ml with methanol. 2ml of the extract was removed by a sample tube, filtered through a 0.22 μm organic filter and subjected to liquid chromatography. The obtained chromatographic behavior patterns are clear, and specific APEO content can be obtained by referring to the working curve. The average recovery in this case was 96.3%, RSD was 2.68%, and pretreatment was carried out for 24min with 50mL of methanol consumption.

Example 3

Determination of alkylphenol ethoxylate content in woven cloth

Blank marking treatment: taking a tatted fabric skin sample, and cutting the tatted fabric skin sample into a plurality of complete sample blocks with the weight of 1g (+ -0.01 g). Placing in a microwave sample kettle for microwave extraction, adding 10mL of dichloromethane extractant, performing microwave treatment for 10min once, repeating for 2 times, discarding washing liquid after digestion, performing natural drying after extraction twice, and performing adsorption treatment of standard solution. 1mL of OPEO standard solution with the concentration of 10mg/L is added dropwise, and the mixture is dried by a blower (cold air), and the air speed is carefully prevented from being too high so that liquid drops on the surface of the sample cloth splash.

Pretreatment and chromatographic analysis: the labeled sample was crushed and placed in a container, 10ml of methylene chloride was added, the ultrasonic washing was performed for 2 minutes, and the washing solution was collected and repeated 2 times. And performing microwave extraction, namely placing filter residues after decantation of the filtrate into a sample tank, adding an extractant, shaking uniformly, and performing microwave extraction. The extraction conditions are as follows: the extractant is dichloromethane, the temperature is 50 ℃ and the time is 10min. And after the extraction is finished and the temperature and the pressure are reduced to normal temperature and normal pressure, opening a tank to separate the extractant from the sample, and collecting the solvent. The microwave extraction was repeated 2 times for 10 minutes each time with 10ml extractant. The filtrates were combined and the volume was fixed to 50ml with dichloromethane. 2ml of the extract was removed by a sample tube, filtered through a 0.22 μm organic filter and subjected to liquid chromatography. The obtained chromatographic behavior patterns are clear, and specific APEO content can be obtained by referring to the working curve. The average recovery in this case was 101.2%, RSD 4.06%, pretreatment 24min, and consumption of 50mL of methylene chloride.

Example 4

Determination of alkylphenol ethoxylate content in braided fabric

Blank marking treatment: samples of the braid were taken and cut into complete 1g (+ -0.01 g) swatches. Placing in a microwave sample kettle for microwave extraction, adding 10mL of tert-butyl methyl ether extractant, performing microwave treatment for 10min once, repeating for 2 times, discarding washing liquid after digestion, performing natural drying after extraction twice, and performing adsorption treatment of standard solution. 1mL of NPEO standard solution with the concentration of 10mg/L is dripped, and the sample is dried by a blower (cold air), so that the liquid drops on the surface of the sample are prevented from splashing due to too high air speed.

Pretreatment and chromatographic analysis: cutting the marked sample, placing in a container, adding 10ml of tert-butyl methyl ether, ultrasonically cleaning for 2min, collecting the washing liquid, and repeating for 2 times. And performing microwave extraction, namely placing filter residues after decantation of the filtrate into a sample tank, adding an extractant, shaking uniformly, and performing microwave extraction. The extraction conditions are as follows: the extractant is tert-butyl methyl ether, and the temperature is 50 ℃ and the time is 10min. And after the extraction is finished and the temperature and the pressure are reduced to normal temperature and normal pressure, opening a tank to separate the extractant from the sample, and collecting the solvent. The microwave extraction was repeated 2 times for 10 minutes each time with 10ml extractant. The filtrates were combined and the volume was fixed to 50ml with t-butyl methyl ether. 2ml of the extract was removed by a sample tube, filtered through a 0.22 μm organic filter and subjected to liquid chromatography. The obtained chromatographic behavior patterns are clear, and specific APEO content can be obtained by referring to the working curve. The average recovery rate in this example was 93.9%, RSD was 3.63%, and pretreatment was carried out for 24 minutes, consuming 50mL of t-butyl methyl ether.

Example 5

Determination of alkylphenol ethoxylate content in cotton-type fabrics

Blank marking treatment: a cotton type textile sample is taken and sheared into a plurality of complete sample blocks with the weight of 1g (+ -0.01 g). Placing in a microwave sample kettle for microwave extraction, adding 10mL of methanol extractant, performing microwave treatment for 10min for 2 times, discarding washing liquid after digestion, naturally airing after extraction for two times, and performing adsorption treatment of standard solution. 1mL of OP standard solution with the concentration of 20mg/L is dripped, and the sample is dried by a blower (cold air), so that the phenomenon that liquid drops on the surface of the sample are splashed due to too high air speed is avoided.

Pretreatment and chromatographic analysis: cutting the labeled sample, placing in a container, adding 10ml of methanol, ultrasonically cleaning for 2min, collecting the washing liquid, and repeating for 2 times. And performing microwave extraction, namely placing filter residues after decantation of the filtrate into a sample tank, adding an extractant, shaking uniformly, and performing microwave extraction. The extraction conditions are as follows: the extractant is methanol at 50deg.C for 10min. And after the extraction is finished and the temperature and the pressure are reduced to normal temperature and normal pressure, opening a tank to separate the extractant from the sample, and collecting the solvent. The microwave extraction was repeated 2 times for 10 minutes each time with 10ml extractant. The filtrates were combined and fixed to a volume of 50ml with methanol. 2ml of the extract was removed by a sample tube, filtered through a 0.22 μm organic filter and subjected to liquid chromatography. The obtained chromatographic behavior patterns are clear, and specific APEO content can be obtained by referring to the working curve. The average recovery in this case was 96.7%, RSD 1.68%, pretreatment 24min, consumption of 50mL of methanol.

Example 6

Determination of alkylphenol ethoxylate content in knitted fabric

Blank marking treatment: samples of knitted textiles were taken and sheared into complete 1g (+ -0.01 g) swatches. Placing in a microwave sample kettle for microwave extraction, adding 10mL of methanol extractant, performing microwave treatment for 10min for 2 times, discarding washing liquid after digestion, naturally airing after extraction for two times, and performing adsorption treatment of standard solution. 1mL of NP standard solution with the concentration of 20mg/L is dripped, and the sample is dried by a blower (cold air), so that the phenomenon that liquid drops on the surface of the sample are splashed due to too high air speed is avoided.

Pretreatment and chromatographic analysis: cutting the labeled sample, placing in a container, adding 10ml of methanol, ultrasonically cleaning for 2min, collecting the washing liquid, and repeating for 2 times. And performing microwave extraction, namely placing filter residues after decantation of the filtrate into a sample tank, adding an extractant, shaking uniformly, and performing microwave extraction. The extraction conditions are as follows: the extractant is methanol at 50deg.C for 10min. And after the extraction is finished and the temperature and the pressure are reduced to normal temperature and normal pressure, opening a tank to separate the extractant from the sample, and collecting the solvent. The microwave extraction was repeated 2 times for 10 minutes each time with 10ml extractant. The filtrates were combined and fixed to a volume of 50ml with methanol. 2ml of the extract was removed by a sample tube, filtered through a 0.22 μm organic filter and subjected to liquid chromatography. The obtained chromatographic behavior patterns are clear, and specific APEO content can be obtained by referring to the working curve. The average recovery in this case was 103.9%, RSD 3.45%, pretreatment 24min, and methanol consumption 50mL.

Example 7

Determination of alkylphenol ethoxylate content in woven cloth

Blank marking treatment: taking a tatted fabric skin sample, and cutting the tatted fabric skin sample into a plurality of complete sample blocks with the weight of 1g (+ -0.01 g). Placing in a microwave sample kettle for microwave extraction, adding 10mL of dichloromethane extractant, performing microwave treatment for 10min once, repeating for 2 times, discarding washing liquid after digestion, performing natural drying after extraction twice, and performing adsorption treatment of standard solution. 1mL of OPEO standard solution with the concentration of 20mg/L is added dropwise, and the mixture is dried by a blower (cold air), and the air speed is carefully prevented from being too high so that liquid drops on the surface of the sample cloth splash.

Pretreatment and chromatographic analysis: the labeled sample was crushed and placed in a container, 10ml of methylene chloride was added, the ultrasonic washing was performed for 2 minutes, and the washing solution was collected and repeated 2 times. And performing microwave extraction, namely placing filter residues after decantation of the filtrate into a sample tank, adding an extractant, shaking uniformly, and performing microwave extraction. The extraction conditions are as follows: the extractant is dichloromethane, the temperature is 50 ℃ and the time is 10min. And after the extraction is finished and the temperature and the pressure are reduced to normal temperature and normal pressure, opening a tank to separate the extractant from the sample, and collecting the solvent. The microwave extraction was repeated 2 times for 10 minutes each time with 10ml extractant. The filtrates were combined and the volume was fixed to 50ml with dichloromethane. 2ml of the extract was removed by a sample tube, filtered through a 0.22 μm organic filter and subjected to liquid chromatography. The obtained chromatographic behavior patterns are clear, and specific APEO content can be obtained by referring to the working curve. The average recovery in this case was 97.5%, RSD 1.72%, pretreatment 24min, and consumption of 50mL of methylene chloride.

Example 8

Determination of alkylphenol ethoxylate content in braided fabric

Blank marking treatment: samples of the braid were taken and cut into complete 1g (+ -0.01 g) swatches. Placing in a microwave sample kettle for microwave extraction, adding 10mL of tert-butyl methyl ether extractant, performing microwave treatment for 10min once, repeating for 2 times, discarding washing liquid after digestion, performing natural drying after extraction twice, and performing adsorption treatment of standard solution. 1mL of NPEO standard solution with the concentration of 20mg/L is dripped, and the sample is dried by a blower (cold air), so that the liquid drops on the surface of the sample are prevented from splashing due to too high air speed.

Pretreatment and chromatographic analysis: cutting the marked sample, placing in a container, adding 10ml of tert-butyl methyl ether, ultrasonically cleaning for 2min, collecting the washing liquid, and repeating for 2 times. And performing microwave extraction, namely placing filter residues after decantation of the filtrate into a sample tank, adding an extractant, shaking uniformly, and performing microwave extraction. The extraction conditions are as follows: the extractant is tert-butyl methyl ether, and the temperature is 50 ℃ and the time is 10min. And after the extraction is finished and the temperature and the pressure are reduced to normal temperature and normal pressure, opening a tank to separate the extractant from the sample, and collecting the solvent. The microwave extraction was repeated 2 times for 10 minutes each time with 10ml extractant. The filtrates were combined and the volume was fixed to 50ml with t-butyl methyl ether. 2ml of the extract was removed by a sample tube, filtered through a 0.22 μm organic filter and subjected to liquid chromatography. The obtained chromatographic behavior patterns are clear, and specific APEO content can be obtained by referring to the working curve. The average recovery rate of this example was 93.2%, RSD was 3.26%, and pretreatment was carried out for 24min with 50mL of t-butyl methyl ether consumed.

Example 9

Determination of alkylphenol ethoxylate content in cotton-type fabrics

Blank marking treatment: a cotton type textile sample is taken and sheared into a plurality of complete sample blocks with the weight of 1g (+ -0.01 g). Placing in a microwave sample kettle for microwave extraction, adding 10mL of methanol extractant, performing microwave treatment for 10min for 2 times, discarding washing liquid after digestion, naturally airing after extraction for two times, and performing adsorption treatment of standard solution. 1mL of OP standard solution with the concentration of 40mg/L is dripped, and the sample is dried by a blower (cold air), so that the phenomenon that liquid drops on the surface of the sample are splashed due to too high air speed is avoided.

Pretreatment and chromatographic analysis: cutting the labeled sample, placing in a container, adding 10ml of methanol, ultrasonically cleaning for 2min, collecting the washing liquid, and repeating for 2 times. And performing microwave extraction, namely placing filter residues after decantation of the filtrate into a sample tank, adding an extractant, shaking uniformly, and performing microwave extraction. The extraction conditions are as follows: the extractant is methanol at 50deg.C for 10min. And after the extraction is finished and the temperature and the pressure are reduced to normal temperature and normal pressure, opening a tank to separate the extractant from the sample, and collecting the solvent. The microwave extraction was repeated 2 times for 10 minutes each time with 10ml extractant. The filtrates were combined and fixed to a volume of 50ml with methanol. 2ml of the extract was removed by a sample tube, filtered through a 0.22 μm organic filter and subjected to liquid chromatography. The obtained chromatographic behavior patterns are clear, and specific APEO content can be obtained by referring to the working curve. The average recovery in this case was 95.7%, RSD 3.64%, pretreatment 24min, and methanol consumption 50mL.

Example 10

Determination of alkylphenol ethoxylate content in knitted fabric

Blank marking treatment: samples of knitted textiles were taken and sheared into complete 1g (+ -0.01 g) swatches. Placing in a microwave sample kettle for microwave extraction, adding 10mL of methanol extractant, performing microwave treatment for 10min for 2 times, discarding washing liquid after digestion, naturally airing after extraction for two times, and performing adsorption treatment of standard solution. 1mL of NP standard solution with the concentration of 40mg/L is dripped, and the sample is dried by a blower (cold air), so that the phenomenon that liquid drops on the surface of the sample are splashed due to too high air speed is avoided.

Pretreatment and chromatographic analysis: cutting the labeled sample, placing in a container, adding 10ml of methanol, ultrasonically cleaning for 2min, collecting the washing liquid, and repeating for 2 times. And performing microwave extraction, namely placing filter residues after decantation of the filtrate into a sample tank, adding an extractant, shaking uniformly, and performing microwave extraction. The extraction conditions are as follows: the extractant is methanol at 50deg.C for 10min. And after the extraction is finished and the temperature and the pressure are reduced to normal temperature and normal pressure, opening a tank to separate the extractant from the sample, and collecting the solvent. The microwave extraction was repeated 2 times for 10 minutes each time with 10ml extractant. The filtrates were combined and fixed to a volume of 50ml with methanol. 2ml of the extract was removed by a sample tube, filtered through a 0.22 μm organic filter and subjected to liquid chromatography. The obtained chromatographic behavior patterns are clear, and specific APEO content can be obtained by referring to the working curve. The average recovery in this case was 91.8%, RSD 3.41%, pretreatment 24min, and methanol consumption 50mL.

Example 11

Determination of alkylphenol ethoxylate content in woven cloth

Blank marking treatment: taking a tatted fabric skin sample, and cutting the tatted fabric skin sample into a plurality of complete sample blocks with the weight of 1g (+ -0.01 g). Placing in a microwave sample kettle for microwave extraction, adding 10mL of dichloromethane extractant, performing microwave treatment for 10min once, repeating for 2 times, discarding washing liquid after digestion, performing natural drying after extraction twice, and performing adsorption treatment of standard solution. 1mL of OPEO standard solution with the concentration of 40mg/L is added dropwise, and the mixture is dried by a blower (cold air), and the air speed is carefully prevented from being too high so that liquid drops on the surface of the sample cloth splash.

Pretreatment and chromatographic analysis: the labeled sample was crushed and placed in a container, 10ml of methylene chloride was added, the ultrasonic washing was performed for 2 minutes, and the washing solution was collected and repeated 2 times. And performing microwave extraction, namely placing filter residues after decantation of the filtrate into a sample tank, adding an extractant, shaking uniformly, and performing microwave extraction. The extraction conditions are as follows: the extractant is dichloromethane, the temperature is 50 ℃ and the time is 10min. And after the extraction is finished and the temperature and the pressure are reduced to normal temperature and normal pressure, opening a tank to separate the extractant from the sample, and collecting the solvent. The microwave extraction was repeated 2 times for 10 minutes each time with 10ml extractant. The filtrates were combined and the volume was fixed to 50ml with dichloromethane. 2ml of the extract was removed by a sample tube, filtered through a 0.22 μm organic filter and subjected to liquid chromatography. The obtained chromatographic behavior patterns are clear, and specific APEO content can be obtained by referring to the working curve. The average recovery in this case was 97.6%, RSD was 2.92%, and pretreatment was carried out for 24min, consuming 50mL of methylene chloride.

Example 12

Determination of alkylphenol ethoxylate content in braided fabric

Blank marking treatment: samples of the braid were taken and cut into complete 1g (+ -0.01 g) swatches. Placing in a microwave sample kettle for microwave extraction, adding 10mL of tert-butyl methyl ether extractant, performing microwave treatment for 10min once, repeating for 2 times, discarding washing liquid after digestion, performing natural drying after extraction twice, and performing adsorption treatment of standard solution. 1mL of NPEO standard solution with the concentration of 40mg/L is dripped, and the sample is dried by a blower (cold air), so that the liquid drops on the surface of the sample are prevented from splashing due to too high air speed.

Pretreatment and chromatographic analysis: cutting the marked sample, placing in a container, adding 10ml of tert-butyl methyl ether, ultrasonically cleaning for 2min, collecting the washing liquid, and repeating for 2 times. And performing microwave extraction, namely placing filter residues after decantation of the filtrate into a sample tank, adding an extractant, shaking uniformly, and performing microwave extraction. The extraction conditions are as follows: the extractant is tert-butyl methyl ether, and the temperature is 50 ℃ and the time is 10min. And after the extraction is finished and the temperature and the pressure are reduced to normal temperature and normal pressure, opening a tank to separate the extractant from the sample, and collecting the solvent. The microwave extraction was repeated 2 times for 10 minutes each time with 10ml extractant. The filtrates were combined and the volume was fixed to 50ml with t-butyl methyl ether. 2ml of the extract was removed by a sample tube, filtered through a 0.22 μm organic filter and subjected to liquid chromatography. The obtained chromatographic behavior patterns are clear, and specific APEO content can be obtained by referring to the working curve. The average recovery rate of this example was 93.5%, RSD was 3.95%, and pretreatment was carried out for 24min with 50mL of t-butyl methyl ether consumed.

Table 1: linear relationship between alkylphenol and alkylphenol polyoxyethylene standard solution

Comparative example 1

2 times of microwave extraction and 2 times of ultrasonic extraction

Blank marking treatment: samples of knitted textiles were taken and sheared into complete 1g (+ -0.01 g) swatches. Placing in a microwave sample kettle for microwave extraction, adding 10mL of methanol extractant, performing microwave treatment for 10min for 2 times, discarding washing liquid after digestion, naturally airing after extraction for two times, and performing adsorption treatment of standard solution. 1mL of OP standard solution with the concentration of 10mg/L is dripped, and the sample is dried by a blower (cold air), so that the phenomenon that liquid drops on the surface of the sample are splashed due to too high air speed is avoided.

Pretreatment and chromatographic analysis: cutting the marked sample, placing in a sample kettle, performing microwave extraction, adding an extractant, shaking uniformly, and performing microwave extraction. The extraction conditions are as follows: the extractant is methanol at 50deg.C for 10min. The procedure was repeated twice. And after the extraction is finished and the temperature and the pressure are reduced to normal temperature and normal pressure, opening a tank to separate the extractant from the sample, and collecting the solvent. The filter residue was transferred to another vessel, 10mL of methanol was added, and ultrasonic extraction was performed for 2 min/time, and repeated twice. The four extracted filtrates were combined and the vessel was rinsed with methanol and the volume was fixed to 50ml with a wash solution. 2ml of the extract was removed by a sample tube, filtered through a 0.22 μm organic filter and subjected to liquid chromatography. The obtained chromatogram is clear in interval, and specific APEO content can be obtained by referring to a working curve. The average recovery of this example was 83.3%, RSD 4.31%, pretreatment 24min, and methanol consumption 50mL.

Comparative example 2

1 microwave extraction, 2 ultrasonic extraction and 1 centrifugation

Blank marking treatment: taking a knitted fabric sample, and cutting the knitted fabric sample into a plurality of complete sample blocks with the weight of 1g (+ -0.01 g). Placing in a microwave sample kettle for microwave extraction, adding 10mL of methanol extractant, performing microwave treatment for 10min for 2 times, discarding washing liquid after digestion, naturally airing after extraction for two times, and performing adsorption treatment of standard solution. 1mL of OP standard solution with the concentration of 10mg/L is dripped, and the sample is dried by a blower (cold air), so that the phenomenon that liquid drops on the surface of the sample are splashed due to too high air speed is avoided.

Pretreatment and chromatographic analysis: cutting the marked sample, placing in a sample kettle, performing microwave extraction, adding an extractant, shaking uniformly, and performing microwave extraction. The extraction conditions are as follows: the extractant is methanol at 50deg.C for 10min. And after the extraction is finished and the temperature and the pressure are reduced to normal temperature and normal pressure, opening a tank to separate the extractant from the sample, and collecting the solvent. The filter residue was transferred to another vessel, 10mL of methanol was added, and ultrasonic extraction was performed for 2 min/time, and repeated twice. And finally, carrying out centrifugal treatment, transferring filter residues to a centrifugal tube, adding 10mL of methanol, putting into the centrifugal tube for operation, and keeping the rotating speed at 8000r/min for 2min. The four filtrates were combined and the vessel was rinsed with methanol and the volume was fixed to 50ml with a wash solution. 2ml of the extract was removed by a sample tube, filtered through a 0.22 μm organic filter and subjected to liquid chromatography. The obtained chromatogram is clear in interval, and specific APEO content can be obtained by referring to a working curve. The average recovery in this case was 77.1%, RSD 4.62%, pretreatment 24min, consumption of 50mL of methanol.

Comparative example 3

1 time microwave extraction and 2 times ultrasonic extraction

Pretreatment and chromatographic analysis: cutting the marked sample, placing in a sample kettle, performing microwave extraction, adding an extractant, shaking uniformly, and performing microwave extraction. The extraction conditions are as follows: the extractant is methanol at 50deg.C for 10min. And after the extraction is finished and the temperature and the pressure are reduced to normal temperature and normal pressure, opening a tank to separate the extractant from the sample, and collecting the solvent. The filter residue was transferred to another vessel, 10mL of methanol was added, and ultrasonic extraction was performed for 2 min/time, and repeated twice. The filtrates from the three extractions were combined and the vessel was rinsed with methanol and the volume was fixed to 50ml with a wash solution. 2ml of the extract was removed by a sample tube, filtered through a 0.22 μm organic filter and subjected to liquid chromatography. The obtained chromatogram is clear in interval, and specific APEO content can be obtained by referring to a working curve. The average recovery in this case was 74.3%, RSD 3.96%, pretreatment 14min, and methanol consumption 50mL.

Comparative example 4

1 time microwave extraction+3 times ultrasonic extraction

Blank marking treatment: taking a knitted fabric sample, and cutting the knitted fabric sample into a plurality of complete sample blocks with the weight of 1g (+ -0.01 g). Placing in a microwave sample kettle for microwave extraction, adding 10mL of methanol extractant, performing microwave treatment for 10min for 2 times, discarding washing liquid after digestion, naturally airing after extraction for two times, and performing adsorption treatment of standard solution. 1mL of OP standard solution with the concentration of 40mg/L is dripped, and the sample is dried by a blower (cold air), so that the phenomenon that liquid drops on the surface of the sample are splashed due to too high air speed is avoided.

Pretreatment and chromatographic analysis: cutting the marked sample, placing in a sample kettle, performing microwave extraction, adding an extractant, shaking uniformly, and performing microwave extraction. The extraction conditions are as follows: the extractant is methanol at 50deg.C for 10min. And after the extraction is finished and the temperature and the pressure are reduced to normal temperature and normal pressure, opening a tank to separate the extractant from the sample, and collecting the solvent. The filter residue was transferred to another vessel, 10mL of methanol was added, and ultrasonic extraction was performed for 2 min/time, and repeated three times. The four extracted filtrates were combined and the vessel was rinsed with methanol and the volume was fixed to 50ml with a wash solution. 2ml of the extract was removed by a sample tube, filtered through a 0.22 μm organic filter and subjected to liquid chromatography. The obtained chromatogram is clear in interval, and specific APEO content can be obtained by referring to a working curve. The average recovery in this case was 76.4%, RSD 3.9%, pretreatment 24min, consumption of 50mL of methanol.

Comparative example 5

1 time microwave extraction and 4 times ultrasonic extraction

Pretreatment and chromatographic analysis: cutting the marked sample, placing in a sample kettle, performing microwave extraction, adding an extractant, shaking uniformly, and performing microwave extraction. The extraction conditions are as follows: the extractant is methanol at 50deg.C for 10min. And after the extraction is finished and the temperature and the pressure are reduced to normal temperature and normal pressure, opening a tank to separate the extractant from the sample, and collecting the solvent. The residue was transferred to another vessel, 10mL of methanol was added, and ultrasonic extraction was performed for 2 min/time, and repeated four times. The five extracted filtrates were combined and the vessel was rinsed with methanol and the volume was fixed to 50ml with a wash solution. 2ml of the extract was removed by a sample tube, filtered through a 0.22 μm organic filter and subjected to liquid chromatography. The obtained chromatogram is clear in interval, and specific APEO content can be obtained by referring to a working curve. The average recovery of this example was 77.1%, RSD 3.65%, pretreatment 18min, consumption of 50mL of methanol.

Comparative example 6

1 time microwave extraction and 4 times ultrasonic extraction

Pretreatment and chromatographic analysis: cutting the marked sample, placing in a sample kettle, performing microwave extraction, adding an extractant, shaking uniformly, and performing microwave extraction. The extraction conditions are as follows: the extractant is methanol at 50deg.C for 10min. And after the extraction is finished and the temperature and the pressure are reduced to normal temperature and normal pressure, opening a tank to separate the extractant from the sample, and collecting the solvent. The residue was transferred to another vessel, 10mL of methanol was added, and ultrasonic extraction was performed for 2 min/time, and repeated four times. The five extracted filtrates were combined and the vessel was rinsed with methanol and the volume was fixed to 50ml with a wash solution. 2ml of the extract was removed by a sample tube, filtered through a 0.22 μm organic filter and subjected to liquid chromatography. The obtained chromatogram is clear in interval, and specific APEO content can be obtained by referring to a working curve. The average recovery of this example was 71.6%, RSD was 4.12%, and pretreatment was 18min, consuming 50mL of methanol.

Comparative example 7

3 times microwave extraction (12 min/time)

Pretreatment and chromatographic analysis: cutting the marked sample, placing in a sample kettle, performing microwave extraction, adding an extractant, shaking uniformly, and performing microwave extraction. The extraction conditions are as follows: the extractant is methanol at 50deg.C for 10min. Repeating the extraction for three times, cooling to normal temperature and normal pressure, opening the tank to separate the extractant from the sample, and collecting the solvent. The filtrates from the three extractions were combined and the vessel was rinsed with methanol and the volume was fixed to 50ml with a wash solution. 2ml of the extract was removed by a sample tube, filtered through a 0.22 μm organic filter and subjected to liquid chromatography. The obtained chromatogram is clear in interval, and specific APEO content can be obtained by referring to a working curve. The average recovery of this example was 91.3%, RSD 4.02%, pretreatment 36min, and methanol consumption 50mL.

Comparative example 8

3 times microwave extraction (20 min/time)

Pretreatment and chromatographic analysis: cutting the marked sample, placing in a sample kettle, performing microwave extraction, adding an extractant, shaking uniformly, and performing microwave extraction. The extraction conditions are as follows: the extractant is methanol at 50deg.C for 20min. Repeating the extraction for three times, cooling to normal temperature and normal pressure, opening the tank to separate the extractant from the sample, and collecting the solvent. The filtrates from the three extractions were combined and the vessel was rinsed with methanol and the volume was fixed to 50ml with a wash solution. 2ml of the extract was removed by a sample tube, filtered through a 0.22 μm organic filter and subjected to liquid chromatography. The obtained chromatographic behavior patterns are clear, and specific APEO content can be obtained by referring to the working curve. The average recovery in this case was 75.8%, RSD 4.57%, pretreatment 1h, consumption of 50mL of methanol.

Comparative example 9

Ultrasonic extraction and rotary evaporation concentration

Pretreatment and chromatographic analysis: the labeled sample was minced, placed in a 50mL centrifuge tube, 30mL of methanol was added, and the mixture was subjected to ultrasonic extraction (60 th.) at 70 th.) C for 5 min. Concentrating the extractive solution to near dryness at 40deg.C by rotary evaporator, accurately adding 2ml of methanol solution residue, and filtering with 0.22 μm filter membrane for reversed phase high performance liquid chromatography. Recovery was calculated against a standard working curve. The average recovery of this example was 85.3%, RSD 4.71%, pretreatment 1h, 30mL of methanol consumption.

Comparative example 10

Ultrasonic extraction and rotary evaporation concentration

Pretreatment and chromatographic analysis: the labeled sample was minced, placed in a 50mL centrifuge tube, 30mL of methanol was added, and the mixture was subjected to ultrasonic extraction (60 th.) at 70 th.) C for 5 min. Concentrating the extractive solution to near dryness at 40deg.C by rotary evaporator, accurately adding 2ml of methanol solution residue, and filtering with 0.22 μm filter membrane for reversed phase high performance liquid chromatography. Recovery was calculated against a standard working curve. The average recovery in this case was 75.6%, RSD 5.12%, pretreatment 1h, 30mL of methanol consumption.

Comparative example 11

Soxhlet extraction+ultrasonic extraction

Pretreatment and chromatographic analysis: the marked sample cloth is cut into fragments of about 5mm x 5mm, the sample is wrapped by filter paper, the sample is placed in a Soxhlet extractor, 150mL of methanol is added into a round bottom flask, the round bottom flask is placed in an electric heating sleeve, the flow rate is controlled to be 1-2 drops per second through the temperature of the heating sleeve and a condensing pump, and the sample is extracted for 3 hours. Then the ultrasonic extractor is preheated to 70 ℃, and the prepared sample is placed in a screw reactor and sealed. 10mL of methanol was added for ultrasonic extraction for 1h, the extracts were collected and the extracts were combined. Concentrating to near dryness by using a rotary evaporator, and accurately adding 2mL of methanol to dissolve the residue. The concentrate was filtered into a sample bottle with a 0.22um filter for instrumental analysis. Recovery was calculated against a standard working curve.

The average recovery in this case was 87.4%, RSD 5.29%, pretreatment 4h, and methanol consumption 160mL.

Comparative example 12

Soxhlet extraction

Pretreatment and chromatographic analysis: cutting the marked sample cloth into fragments of about 5mm x 5mm, uniformly mixing, wrapping the sample with filter paper, placing the sample in a Soxhlet extractor, adding 160mL of methanol into a round bottom flask, placing the round bottom flask in an electric heating sleeve, controlling the flow rate to be 1-2 drops per second through the temperature of the heating sleeve and a condensing pump, and extracting for 6 hours. After extraction, the extract was collected, concentrated to near dryness by rotary evaporator, and 2mL of methanol was accurately added to dissolve the residue. The concentrate was filtered into a sample bottle with a 0.22um filter for instrumental analysis. Recovery was calculated against a standard working curve. The average recovery in this case was 94.1%, RSD 3.43%, pretreatment 6h, and methanol consumption 160mL.

Comparative example 13

Twice microwave extraction and vortex oscillation

Pretreatment and chromatographic analysis: the sample cloth after the addition of the marks is sheared to be about 5mm multiplied by 5mm, placed in an extraction tube, 15mL of methanol is added, the mixture is subjected to vortex oscillation for 2min, then microwave extraction is carried out, and after the mixture is cooled to room temperature, the extract is poured out. The second extraction was performed with 15mL of extraction solvent, each for 30min. Combining the extracts, rotationally evaporating the extracts to 2-3 mL, and fixing the volume to l 0mL by using an extraction solvent for analysis. If the concentration is too high, the analysis is performed after the appropriate dilution. Recovery was calculated against a standard working curve. The average recovery in this case was 88.7%, RSD 4.96%, pretreatment 1h, 30mL of methanol consumption.

Comparative example 14

1 ultrasonic extraction, 2 microwave extraction and 1 centrifugation

Pretreatment and chromatographic analysis: cutting the labeled sample, placing in a container, performing ultrasonic extraction, adding 10mL of methanol, shaking uniformly for 2min, and collecting the solvent. Transferring the filter residue to a microwave sample kettle, adding an extracting agent, shaking uniformly, and performing microwave extraction. The extraction conditions are as follows: the extractant is methanol at 50deg.C for 20min. The procedure was repeated twice. And finally, carrying out centrifugal treatment, namely transferring filter residues to a centrifugal tube, adding 10mL of methanol, putting into the centrifugal tube for operation, and keeping the rotating speed at 8000r/min for 2min. The four filtrates were combined and the vessel was rinsed with methanol and the volume was fixed to 50ml with a wash solution. 2ml of the extract was removed by a sample tube, filtered through a 0.22 μm organic filter and subjected to liquid chromatography. The obtained chromatographic behavior patterns are clear, and specific APEO content can be obtained by referring to the working curve. The average recovery of this example was 81.4%, RSD 3.94%, pretreatment 24min, and methanol consumption 50mL.

The extraction methods and specific data for examples 1-12 and comparative examples 1-14 are shown in the following table:

analytical example

According to GB/T23222-2018 determination of textile-surfactant, the partial recovery rate of alkylphenol and alkylphenol polyoxyethylene in reverse-phase high performance liquid chromatography is 80-110%, and the time is 1h. The pretreatment process of the method is controlled within 30mins, the whole pretreatment and analysis process time can be controlled within 40mins (the time for preparing the working curve is removed), the pretreatment time is greatly shortened, and the solvent is saved. The method for combining ultrasonic extraction and microwave extraction in the research test meets and is superior to the current national standard recovery rate requirement. Comparative examples 1, 2 and the method of the present invention demonstrate that the order of microwave and sonication cannot be changed, and that the microwave first causes target analyte cleavage resulting in a reduction in recovery from subsequent sonication or centrifugation. Comparative examples 3, 4, 5, 6 demonstrate that the increase in the number of sonications performed after microwave extraction does not increase much for higher recovery and lower for higher concentrations of sample. Comparative examples 7 and 8 show that the recovery rate obtained by the short-time multiple microwave extraction treatment is ideal, but the time efficiency is lower compared with the invention; the single long-time microwave treatment can lead to separation and cracking of target analytes, the recovery rate is obviously reduced, and comparison examples 9 and 10 with longer treatment time show that the recovery rate of the method of ultrasonic and rotary evaporation concentration at 70 ℃ is lower, the time is longer, and the feasibility is not high. Comparative examples 11 and 12 show that the soxhlet extraction has high extraction efficiency but long working time, and the required solvents are relatively large and are not suitable for practical detection. Comparative example 13 demonstrates that the long-term microwave extraction and vortex-induced concentration process yields are high, but the process is long, complex to operate, and not feasible. Comparison of example 14 with the present invention shows that the ultrasonic extraction efficiency can be maximized by performing microwave extraction after two times of ultrasonic treatment, and the recovery rate of the method of one ultrasonic treatment-two times of microwave treatment-one centrifugation is low.

While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.

Claims

1. The method for detecting the alkylphenol ethoxylate content in the textile by using the high performance liquid chromatography is characterized by comprising the following steps of:

(S3) carrying out microwave extraction on the mixture I containing the sample to be detected after the filtration in the step (S2) and the extractant I, and separating to obtain a washing liquid III;

(S5) measuring a mixture containing the washing reagent I, the washing reagent II, the washing reagent III and the washing reagent IV by high performance liquid chromatography;

The time of the ultrasonic I and the ultrasonic II is 1 min-10 min;

the time of the microwave extraction I and the time of the microwave extraction II are both 10 min-15 min.

2. The method according to claim 1, wherein the solvent i, the solvent ii, the extractant i, the extractant ii are independently selected from at least one of methanol, methylene chloride, tert-butyl methyl ether, acetone, petroleum ether.

3. The method of claim 1, wherein the textile is selected from one of a woven fabric, a cotton fabric, a knitted fabric, and a chemical fiber.

4. The method according to claim 1, wherein the solid-to-liquid ratio of the sample to be tested in (S1) to (S4) to the solvent i, the solvent ii, the extractant i, the extractant ii corresponding thereto is independently selected from 10mL/g to 20mL/g.

5. The process according to claim 1, wherein the temperature of the microwave extraction i and the microwave extraction ii are each 40 ℃ to 60 ℃.

6. The method according to claim 1, wherein in step (S5), the mixture is subjected to constant volume and filtration.

7. The method according to claim 1, wherein the alkylphenol ethoxylate recovery is 90% to 105%.

8. The method of claim 1, wherein the precision of the method is 0.65% to 4.20%.

9. The method according to claim 1, wherein the detection limit of the high performance liquid chromatography is 0.7896mg/kg to 0.9832mg/kg.