阅读说明：本技术 一种纺织品的pfoa检测方法 (PFOA (Perfluorooctanoic acid) detection method for textile ) 是由 卢霜 廖爱铃 宫玉琢 于 2021-01-27 设计创作，主要内容包括：本发明涉及一种去除纺织品PFOA的方法,1)根据织物重量配制工作液,按浴比为1.0:15.0～25.0,配制工作液；2)在室温下将织物加入工作液中,并以2～3℃/min的速度将工作液升温至80～100℃,再保温30～60 min,排液；3)用80℃热水将织物洗两次,每次洗10 min,然后以冷水洗一次；工作液配方包括：除油剂DM-1130：3.0～6.0 g/L,H-2O-2：5.0～10.0 g/L,纯碱：0～2.0 g/L。本发明去除PFOA的方法比较简单,对纺织品的颜色和性能不产生影响,其推广应用意义巨大。(The invention relates to a method for removing PFOA (Perfluorooctanoic acid) of a textile, which comprises the following steps of 1) preparing working solution according to the weight of the textile, wherein the bath ratio is 1.0: 15.0-25.0; 2) adding the fabric into the working solution at room temperature, heating the working solution to 80-100 ℃ at the speed of 2-3 ℃/min, preserving heat for 30-60 min, and discharging liquid; 3) washing the fabric twice with 80 deg.C hot water for 10 min each time, and washing once with cold water; the formula of the working solution comprises: oil removal agent DM-1130: 3.0 to 6.0 g/L, H 2 O 2 : 5.0-10.0 g/L, soda: 0 to 2.0 g/L. The method for removing the PFOA is simple, does not influence the color and the performance of the textile, and has great significance in popularization and application.)

1. A PFOA detection method of a textile is characterized by comprising the following steps:

1) preparing a standard solution: preparing PFOA standard solution with the mass concentration of 1, 5, 10 and 50 mug/mL and PFDA internal standard solution with the mass concentration of 10 mug/mL by using methanol to fix the volume of chemically pure PFOA and PFDA;

2) measuring a marked line: diluting the standard solution obtained in the step 1) into solutions of 20, 40, 80, 160, 400 and 800 mu g/L, adding 2mL of each solution into a 10mL centrifuge tube, dropwise adding 10 drops of acetyl chloride, then placing the centrifuge tube into a water bath at 55 ℃, and performing auxiliary oscillation derivatization for 55min by using an ultrasonic instrument; after the solution is cooled, adding 2mL of deionized water and 5mL of normal hexane for oscillation extraction, standing, collecting an upper-layer normal hexane organic phase, immediately taking 1 mu L of the organic phase, and analyzing by GC-MS sample injection, wherein the result is calculated by an internal standard curve method;

3) drawing a standard curve: and (3) taking the peak area ratio of the PFOA to-be-detected substance methyl ester and the PFDA internal standard substance methyl ester as a horizontal coordinate, taking the mass ratio of the PFOA to-be-detected substance and the PFDA internal standard substance as a vertical coordinate, drawing a working curve, and obtaining: y is 1.0671X-0.0487, and the linear correlation coefficient R2 is 0.9998, which shows that the peak area and the mass concentration have good linear relation in the concentration range of 20-800 mug/L;

4) sample extraction, derivatization and analytical calculation: accurately weighing 2.5 + -0.0002 g of cloth sample, and cutting into 1cm²And (3) putting the left and right small blocks into a micro-extraction tank, adding 50mL of a mixture of 1: 1, putting the methanol aqueous solution with the pH value of 9-10 into a microwave extractor, and extracting for 50min at 70 ℃ by using microwaves of 200W; transferring the extracted sample to a culture dish, heating to evaporate the solvent, and evaporating to be nearly dry; carefully transferring the extract into a 10mL derivatization test tube by using 2mL methanol, adding 1mL of PFDA internal standard solution, dripping 5-10 drops of acetyl chloride, then putting the test tube into a water bath at 55 ℃, and performing assisted oscillation derivatization for 55min by using an ultrasonic instrument; after the solution is cooled, 2mL of deionized water and 5mL of normal hexane are added for oscillation extraction, after standing, an upper-layer normal hexane organic phase is collected, 1 mu L of the organic phase is immediately taken and subjected to sample injection analysis by GC-MS, and the result is calculated by an internal standard curve method.

Technical Field

The invention relates to the technical field of textile finishing, in particular to a PFOA (Perfluorooctanoic acid) detection method for removing textiles.

Background

Perfluorooctanoic acid is a generic term for a class of synthetic chemicals, which generally includes perfluorooctanoic acid and perfluorooctanoate species. Among the most widely used perfluorooctanoic acids are the ammonium salts thereof, namely ammonium perfluorooctanoate, abbreviated as PFOA in english. Perfluorooctanoic acid (PFOA), its salts and related compounds are widely used in the field of various consumer products, such as the surface treatment of waterproof coatings for textiles and antifouling coatings for clothing, textiles and carpets, and also as surfactants for defoaming. STANDARD 100by OEKO-TEX 2015 edition uniformly reduces the PFOA limit for all classes of textiles to <1.0 μ g/m 2. The purpose of such strict ban is to prevent the further production of such chemical substances, perfluorooctanoic acid (PFOA) and its salts and related compounds contain extremely stable fluorocarbon bonds, so that such substances have strong chemical stability, surface activity, excellent thermal stability and hydrophobic and oleophobic properties. Once the PFOA of the textile exceeds the limit value, the closing can not be detected through the outlet, thereby causing economic loss. Of course, such chemicals are generally not used any more in the production process, but because the chemicals are used in many fields once and PFOA exceeding limit values occasionally occur, PFOA disqualification is still detected on part of the textile. In order to reduce economic losses, a simple, operable fabric PFOA detection method is of great importance.

Disclosure of Invention

The invention aims to solve the technical problem of providing a PFOA detection method of a textile so as to overcome the defects of the prior art.

The technical scheme for solving the technical problem is as follows: a detection method of a textile PFOA comprises the following steps:

1) preparing a standard solution: preparing PFOA standard solution with the mass concentration of 1, 5, 10 and 50 mug/mL and PFDA internal standard solution with the mass concentration of 10 mug/mL by using methanol to fix the volume of chemically pure PFOA and PFDA;

2) measuring a marked line: diluting the standard solution obtained in the step 1) into solutions of 20, 40, 80, 160, 400 and 800 mu g/L, adding 2mL of each solution into a 10mL centrifuge tube, dropwise adding 10 drops of acetyl chloride, then placing the centrifuge tube into a water bath at 55 ℃, and performing auxiliary oscillation derivatization for 55min by using an ultrasonic instrument; after the solution is cooled, adding 2mL of deionized water and 5mL of normal hexane for oscillation extraction, standing, collecting an upper-layer normal hexane organic phase, immediately taking 1 mu L of the organic phase, and analyzing by GC-MS sample injection, wherein the result is calculated by an internal standard curve method;

3) drawing a standard curve: and (3) taking the peak area ratio of the PFOA to-be-detected substance methyl ester and the PFDA internal standard substance methyl ester as a horizontal coordinate, taking the mass ratio of the PFOA to-be-detected substance and the PFDA internal standard substance as a vertical coordinate, drawing a working curve, and obtaining: y is 1.0671X-0.0487, and the linear correlation coefficient R2 is 0.9998, which shows that the peak area and the mass concentration have good linear relation in the concentration range of 20-800 mug/L;

4) sample extraction, derivatization and analytical calculation: accurately weighing 2.5 +/-0.0002 g of cloth sample,cut into 1cm²And (3) putting the left and right small blocks into a micro-extraction tank, adding 50mL of a mixture of 1: 1, putting the methanol aqueous solution with the pH value of 9-10 into a microwave extractor, and extracting for 50min at 70 ℃ by using microwaves of 200W; transferring the extracted sample to a culture dish, heating to evaporate the solvent, and evaporating to be nearly dry; carefully transferring the extract into a 10mL derivatization test tube by using 2mL methanol, adding 1mL of PFDA internal standard solution, dripping 5-10 drops of acetyl chloride, then putting the test tube into a water bath at 55 ℃, and performing assisted oscillation derivatization for 55min by using an ultrasonic instrument; after the solution is cooled, 2mL of deionized water and 5mL of normal hexane are added for oscillation extraction, after standing, an upper-layer normal hexane organic phase is collected, 1 mu L of the organic phase is immediately taken and subjected to sample injection analysis by GC-MS, and the result is calculated by an internal standard curve method.

The invention has the beneficial effects that: the invention can quickly and accurately detect the PFOA on the textile.

The precision of the test method is less than 3% relative to the standard deviation RSD, and the precision is satisfactory when the three PFOA mass concentration levels are subjected to 5-time parallel measurement. And taking another 7 parts of blank sample without PFOA, extracting, deriving and analyzing sample injection according to the test method, and calculating according to 3 times of signal-to-noise ratio to obtain the detection limit of the test method of 5 mu g/L.

Detailed Description

The following detailed description of embodiments of the invention is intended to be illustrative, but not limiting, of the invention and is intended to be exemplary and explanatory only.

PFOA detection:

extracting trace perfluorooctanoic acid (PFOA) in the textile by a microwave extraction method, and quantitatively detecting by a gas chromatography-mass spectrometer (GC-MS).

Firstly, preparing a standard solution: the chemically pure PFOA and PFDA are prepared into PFOA standard solutions with the mass concentrations of 1, 5, 10 and 50 mug/mL and PFDA internal standard solutions with the mass concentrations of 10 mug/mL respectively by methanol constant volume.

Further reticle measurement: and diluting the standard solution into solutions of 20, 40, 80, 160, 400 and 800 mu g/L, adding 2mL of the solutions into a 10mL centrifuge tube, dropwise adding 10 drops of acetyl chloride, putting the centrifuge tube into a water bath at 55 ℃, and performing auxiliary oscillation derivatization for 55min by using an ultrasonic instrument. After the solution is cooled, 2mL of deionized water and 5mL of normal hexane are added for oscillation extraction, after standing, an upper-layer normal hexane organic phase is collected, 1 mu L of the organic phase is immediately taken and subjected to sample injection analysis by GC-MS, and the result is calculated by an internal standard curve method.

Further drawing a standard curve: drawing a working curve by taking the peak area ratio of the methyl ester of the object to be measured (PFOA) and the methyl ester of the internal standard substance (PFDA) as a horizontal coordinate and the mass ratio of the PFOA of the object to be measured (PFOA) and the PFDA of the internal standard substance (PFDA) as a vertical coordinate to obtain: y is 1.0671X-0.0487 and the linear correlation coefficient R2 is 0.9998, indicating that the peak area has a good linear relationship with mass concentration in the concentration range of 20-800 μ g/L.

Further sample extraction, derivatization and analytical calculation: accurately weighing 2.5 +/-0.0002 g of cloth sample (if the conversion is mu g/m2, the mass of 1m2 cloth sample needs to be accurately weighed and converted), cutting into small pieces of about 1cm2, placing the small pieces into a micro-extraction tank, adding 50mL 1: 1 (pH value is 9-10), placing into a microwave extractor, and extracting at 70 deg.C for 50min under microwave of 200W. The extracted sample is transferred to a culture dish, heated to evaporate the solvent, and evaporated to be nearly dry. Carefully transferring the extract into a 10mL derivatization test tube by using 2mL methanol, adding 1mL (400 mu g/L) of PFDA internal standard solution, dripping 5-10 drops of acetyl chloride, putting the test tube into a water bath at 55 ℃, and performing assisted oscillation derivatization for 55min by using an ultrasonic instrument. After the solution is cooled, 2mL of deionized water and 5mL of normal hexane are added for oscillation extraction, after standing, an upper-layer normal hexane organic phase is collected, 1 mu L of the organic phase is immediately taken and subjected to sample injection analysis by GC-MS, and the result is calculated by an internal standard curve method.

Removing the PFOA on the fabric:

khaki polyester-wool blended woven double-layer composite fabric:

oil removal agent DM-1130: 5.0g/L of the total weight of the mixture,

H₂O₂：6.0g/L，

according to the bath ratio of 1.0: 20.0, preparing working solution;

adding the fabric into the working solution, placing into a vibration dyeing machine, heating to 80 deg.C at 2 deg.C/min from room temperature, maintaining for 30min, directly discharging liquid, washing with hot water at 80 deg.C twice, 5min each time, and washing with water at room temperature for 1 time. The test results of the detection method of the present invention are shown in the following table 1:

TABLE 1 EXAMPLE 1 comparison of PFOA CONTENT before and after removing polyester-wool blended woven double-layer composite cloth

	Original cloth	The washed fabric of the invention
			PFOA(μg/m2)	65	0.75

The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.