A method for determining the content of flame retardant FRC-2 in textiles and foams

Abstract

The invention relates to a method for determining the content of flame retardant FRC-2 in textiles and foams, comprising the following steps: 1) sample pretreatment: crushing a textile sample or a foam sample to a size not exceeding 2mm×2mm×2mm, mixing evenly, putting the sample into a clean and dry ziplock bag, sealing and storing the ziplock bag for standby use; 2) sample extraction: weighing the sample obtained in step 1), ultrasonically extracting the sample with an 85% methanol-water solution, and obtaining a sample extraction solution; 3) determining the concentration of flame retardant FRC-2 in the obtained sample extraction solution by liquid chromatography-mass spectrometry; 4) calculating the content of flame retardant FRC-2 in the sample according to the concentration of flame retardant FRC-2 in the obtained sample extraction solution; compared with the prior art, the determination method of the invention is fast and simple, and can realize accurate determination of the content of flame retardant FRC-2 in textiles and foams, thereby solving the problem of lack of a method for detecting the content of flame retardant FRC-2.

Description

[Technical field]

[0001] The invention belongs to the technical field of analytical chemistry, in particular to a method for determining the content of flame retardant FRC-2 in textiles and foam. [Background Technology]

[0002] Fires in textile materials threaten human life and property safety, and flame retardant science and technology came into being. Flame retardants are special chemical additives used to improve the combustion performance of combustible and flammable materials. After being processed by flame retardants, materials can effectively prevent, delay or terminate the spread of flames when attacked by external fire sources, thereby achieving the effect of flame retardancy. Flame retardants can be divided into halogen, inorganic, nitrogen, phosphorus, etc. Although traditional halogen flame retardants have good flame retardant effects, they produce a lot of smoke when burning and produce a lot of toxic gases, causing secondary pollution; although inorganic flame retardants overcome the above shortcomings, the amount of addition is large, which seriously deteriorates the performance of the material. With the continuous improvement of people's awareness of environmental protection and their own safety, people's requirements for flame retardants should not only meet the requirements of flame retardancy, but also meet the requirements of halogen-free, high efficiency, low toxicity, and no deterioration of raw material performance. In recent years, high-performance flame retardants have become a hot topic of research.

[0003] Flame retardant FRC-2 is a new type of organic phosphorus and nitrogen flame retardant. Its thermal degradation products promote the dehydration of cellulose into carbon, which greatly reduces the combustibles and achieves the flame retardant effect. It has the characteristics of environmental friendliness, thermal stability, low toxicity, low smoke, low price, etc., showing excellent application effects and widely used as a flame retardant processing aid. Flame retardants containing nitrogen and phosphorus elements, represented by flame retardant FRC-2, have developed rapidly in recent years because they are in line with the development trend of flame retardants. Flame retardant FRC-2 is widely used in textiles, foam and other products at home and abroad, but as a new flame retardant, its safety data is still incomplete. Adding a large amount of it to household items has certain safety hazards. Foreign countries have gradually paid attention to the limit requirements and content detection of flame retardant FRC-2.

[0004] At present, there is no detection method for the content of flame retardant FRC-2 in textiles and foams at home and abroad. Flame retardant FRC-2 has a large polarity, is easily soluble in water, and is almost insoluble in organic solvents such as toluene and acetone. Conventional flame retardant detection methods are obviously not applicable. Therefore, it is urgent to establish a detection method for the content of flame retardant FRC-2 in textiles and foams. [Summary of the invention]

[0005] The purpose of the present invention is to solve the above-mentioned shortcomings and provide a method for determining the content of flame retardant FRC-2 in textiles and foams. The determination method is fast and simple, and can accurately determine the content of flame retardant FRC-2 in textiles and foams, solving the problem of no method for detecting the content of flame retardant FRC-2.

[0006] In order to achieve the above purpose, a method for determining the content of flame retardant FRC-2 in textiles and foams is designed, comprising the following steps:

[0007] 1) Sample pretreatment: crush the textile sample or foam sample to a size not exceeding 2mm×2mm×2mm, mix evenly, put it into a clean and dry ziplock bag, seal it and store it for later use;

[0008] 2) Sample extraction: weigh the sample obtained in step 1), and extract it with 85% methanol-water solution by ultrasonic wave to obtain a sample extraction solution;

[0009] 3) Determine the concentration of the flame retardant FRC-2 in the sample extraction solution obtained in step 2) by liquid chromatography-mass spectrometry; in this step, weigh an appropriate amount of sample into a glass screw bottle, add 85% methanol-water solution, tighten the lid and perform ultrasonic extraction, take 0.5 mL of the extract after cooling, dilute it to 1 mL with 85% methanol-water, filter it through a 0.2 μm PTFE organic phase filter membrane and wait for determination;

[0010] 4) According to the concentration of the flame retardant FRC-2 in the sample extraction solution obtained in step 3), the content of the flame retardant FRC-2 in the sample is calculated.

[0011] Furthermore, in step 1), for textile samples, scissors are used to cut them into pieces with a size not exceeding 2mm×2mm×2mm; for foam samples, a grinder is used to crush them into pieces with a size not exceeding 2mm×2mm×2mm.

[0012] Further, in step 2), 0.5 g of sample was weighed into a 40 mL glass screw-cap bottle, 25 mL of 85% methanol-water was added, and the lid was tightened and ultrasonic extraction was performed at 60° C. for 60 min. During the ultrasonic process, attention was paid to and the temperature was controlled; after cooling to room temperature, 0.5 mL of the extract was taken, diluted to 1 mL with 85% methanol-water, filtered through a 0.2 μm PTFE organic phase filter membrane, and then waited for determination.

[0013] Further, in step 3), the measurement conditions of the liquid chromatography-mass spectrometer are:

[0014] 1) The liquid chromatography column used was an XDB-C18 column with a column length of 15 cm, an inner diameter of 2.1 mm, and a particle size of 3.5 μm;

[0015] 2) The liquid chromatography column temperature was set to 30°C;

[0016] 3) Injection volume: 5 μL;

[0017] 4) Flow rate: 0.3 mL / min;

[0018] 5) Mobile phase: 10 mmol / L ammonium acetate solution and acetonitrile;

[0019] 6) Mobile phase gradient:

[0020] Time min 10mmol / L ammonium acetate solution% Acetonitrile% 0 95 5 3 95 5 3.5 5 95 29 5 95 29.1 95 5 35 95 5

[0021] 7) Mass spectrometry parameters are shown in the table below:

[0022] Ion source type Electrospray ion source Capillary voltage 3000V Drying gas temperature 330℃ Drying air flow rate 12L / min Atomizing gas pressure 35psi Scanning method Selected ion monitoring, positive mode Selected ions 165.0m / z Fragmentation voltage 100V .

[0023] Furthermore, in step 4), the concentration of the flame retardant FRC-2 in the sample extraction solution is converted to the content of the flame retardant FRC-2 in the sample, and the external standard method is used for quantification according to the solvent calibration curve, and the minimum quantitative concentration is 50 mg / kg.

[0024] Furthermore, before step 4), qualitative and quantitative steps are also included; wherein, qualitative: by comparing the retention time of the sample peak and the standard peak, and comparing the full scan mass spectrum of the sample peak and the full scan mass spectrum of the standard substance, whether the flame retardant FRC-2 is detected in the sample; quantitative: quantitatively using the solvent calibration curve external standard method.

[0025] Compared with the prior art, the present invention provides a method for determining the flame retardant FRC-2 in textiles and foams by using an organic solvent for extraction and a liquid chromatography-mass spectrometer. The method is not only fast and simple, but also can accurately determine the content of the flame retardant FRC-2 in the textiles and foams. The minimum quantitative concentration is 50 mg / kg, which solves the problem of no method for detecting the content of the flame retardant FRC-2. The method fully meets the requirements for monitoring the content of the flame retardant FRC-2 in textiles and foams, and is worthy of popularization and application. [Drawings]

[0026] Figure 1 This is a TIC chromatogram obtained by using liquid chromatography-mass spectrometry to detect the content of flame retardant FRC-2 in cotton cloth in Example 2 of the present invention. [Specific implementation method]

[0027] The invention provides a method for determining the content of flame retardant FRC-2 in textiles and foams. The determination principle is that the flame retardant FRC-2 in the sample is extracted with 85% methanol-water, and then the content of the flame retardant FRC-2 in the sample is determined by liquid chromatography-mass spectrometry.

[0028] The present invention is further described below in conjunction with specific embodiments:

[0029] Example 1: Determination of the content of flame retardant FRC-2 in filling cotton

[0030] 1. Preparation of sample solution:

[0031] Crush the stuffing cotton with a grinder. The sample size should not exceed 2mm x 2mm x 2mm. Mix well, put into a clean and dry ziplock bag, and seal for later use. Weigh 0.5g of sample into a 40mL glass screw bottle, add 25mL 85% methanol-water, tighten the lid, and perform ultrasonic extraction at 60℃ for 60min. Pay attention to and control the temperature during the ultrasonic process; after cooling to room temperature, take 0.5mL of the extract and dilute it to 1mL with 85% methanol-water, filter it through a 0.2μm PTFE organic phase filter membrane, and wait for determination.

[0032] 2. Set instrument parameters:

[0033] 1) The liquid chromatography column used was an XDB-C18 column with a column length of 15 cm, an inner diameter of 2.1 mm, and a particle size of 3.5 μm;

[0034] 2) The liquid chromatography column temperature was set to 30°C;

[0035] 3) Injection volume: 5 μL;

[0036] 4) Flow rate: 0.3 mL / min;

[0037] 5) Mobile phase: 10 mmol / L ammonium acetate solution and acetonitrile;

[0038] 6) Mobile phase gradient:

[0039]

[0040]

[0041] 7) Mass spectrometry parameters are shown in the table below:

[0042] Ion source type Electrospray ion source Capillary voltage (V) 3000 Drying gas temperature (℃) 330 Drying gas flow rate (L / min) 12 Atomizing gas pressure (psi) 35 Scanning method Selected ion monitoring, positive mode Selected ion m / z 165.0 Fragmentation voltage(V) 100

[0043] 3. Qualitative and quantitative

[0044] 1) Qualitative

[0045] By comparing the retention time of the sample peak and the standard peak, and comparing the full scan mass spectrum of the sample peak with the full scan mass spectrum of the standard substance, it is determined whether the flame retardant FRC-2 is detected in the sample.

[0046] 2) Quantification

[0047] Quantification by external standard method using solvent calibration curve

[0048] 4. Calculation

[0049] According to the concentration of flame retardant FRC-2 in the sample extraction solution, the content of flame retardant FRC-2 in the sample is calculated. After testing, no flame retardant FRC-2 was detected in the filling cotton sample.

[0050] Example 2: Determination of flame retardant FRC-2 in cotton cloth

[0051] 1. Preparation of sample solution:

[0052] Crush the stuffing cotton with a grinder. The sample size should not exceed 2mm*2mm*2mm. Mix well and put it into a clean and dry ziplock bag. Seal it for later use. Weigh 0.5g of sample into a 40mL glass screw bottle, add 25mL 85% methanol-water, tighten the lid and perform ultrasonic extraction at 60℃ for 60min. After cooling, take 0.5mL of the extract and dilute it to 1mL with 85% methanol-water. Filter it through a 0.2μm PTFE organic phase filter membrane and wait for determination.

[0053] 2. Set instrument parameters:

[0054] 1) The liquid chromatography column used was an XDB-C18 column with a column length of 15 cm, an inner diameter of 2.1 mm, and a particle size of 3.5 μm;

[0055] 2) The liquid chromatography column temperature was set to 30°C;

[0056] 3) Injection volume: 5 μL;

[0057] 4) Flow rate: 0.3 mL / min;

[0058] 5) Mobile phase: 10 mmol / L ammonium acetate solution and acetonitrile;

[0059] 6) Mobile phase gradient:

[0060]

[0061] 7) Mass spectrometry parameters are shown in the table below:

[0062] Ion source type Electrospray ion source Capillary voltage (V) 3000 Drying gas temperature (℃) 330 Drying gas flow rate (L / min) 12 Atomizing gas pressure (psi) 35 Scanning method Selected ion monitoring, positive mode Selected ion m / z 165.0 Fragmentation voltage(V) 100

[0063] 3. Qualitative and quantitative

[0064] 1) Qualitative

[0065] By comparing the retention time of the sample peak with the standard peak, and comparing the full scan mass spectrum of the sample peak with the full scan mass spectrum of the standard substance, it is determined whether the flame retardant FRC-2 is detected in the sample.

[0066] 2) Quantification

[0067] Quantification by external standard method using solvent calibration curve

[0068] 4. Calculation

[0069] According to the concentration of flame retardant FRC-2 in the sample extraction solution, the content of flame retardant FRC-2 in the sample is calculated.

[0070] After testing, the content of flame retardant FRC-2 in the cotton cloth sample was 75.36 mg / kg. Figure 1 As shown in FIG. 1 , the TIC chromatogram obtained by using liquid chromatography-mass spectrometry to detect the content of flame retardant FRC-2 in cotton cloth samples. As can be seen from the figure, the chromatographic peak at 4.585 min is the chromatographic peak of flame retardant FRC-2 in the cotton cloth extract solution, that is, the compound represented by the chromatographic peak at 4.584 min is flame retardant FRC-2.

[0071] The present invention is not limited to the above-mentioned embodiments, and any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principles of the present invention shall be equivalent replacement methods and shall be included in the protection scope of the present invention.

Claims

1. A method for determining the content of flame retardant FRC-2 in textiles and foams, characterized in that: The following steps are involved: 1) Sample pretreatment: crush the textile sample or foam sample to a size not exceeding 2mm×2mm×2mm, mix evenly, put it into a clean and dry ziplock bag, seal it and store it for later use; 2) Sample extraction: weigh the sample obtained in step 1), and extract it with 85% methanol-water solution by ultrasonic wave to obtain a sample extraction solution; 3) using liquid chromatography-mass spectrometry to determine the concentration of the flame retardant FRC-2 in the sample extraction solution obtained in step 2); 4) Calculating the content of the flame retardant FRC-2 in the sample according to the concentration of the flame retardant FRC-2 in the sample extraction solution obtained in step 3); In step 1), for textile samples, scissors are used to cut into pieces with a size not exceeding 2 mm×2 mm×2 mm; for foam samples, a grinder is used to crush into pieces with a size not exceeding 2 mm×2 mm×2 mm; In step 2), 0.5 g of sample was weighed into a 40 mL glass screw-cap bottle, 25 mL of 85% methanol-water was added, and the lid was tightened and ultrasonic extraction was performed at 60° C. for 60 min. During the ultrasonic process, attention was paid to and the temperature was controlled; after cooling to room temperature, 0.5 mL of the extract was taken, diluted to 1 mL with 85% methanol-water, filtered through a 0.2 μm PTFE organic phase filter membrane, and then waited for determination; In step 3), the measurement conditions of liquid chromatography-mass spectrometry are: 1) The liquid chromatography column used was an XDB-C18 column with a column length of 15 cm, an inner diameter of 2.1 mm, and a particle size of 3.5 μm; 2) The liquid chromatography column temperature was set to 30°C; 3) Injection volume: 5 μL; 4) Flow rate: 0.3 mL / min; 5) Mobile phase: 10 mmol / L ammonium acetate solution and acetonitrile; 6) Mobile phase gradient: 7) Mass spectrometry parameters are shown in the table below: In step 4), the concentration of flame retardant FRC-2 in the sample extraction solution is converted to the content of flame retardant FRC-2 in the sample, and the external standard method is used for quantification according to the solvent calibration curve, and the minimum quantitative concentration is 50 mg / kg.

2. The method for determining the content of flame retardant FRC-2 in textiles and foams according to claim 1, characterized in that: Before step 4), qualitative and quantitative steps are also included; wherein, qualitative: by comparing the retention time of the sample peak and the standard peak, and comparing the full scan mass spectrum of the sample peak and the full scan mass spectrum of the standard substance, whether the flame retardant FRC-2 is detected in the sample; quantitative: quantitatively using the solvent calibration curve external standard method.

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