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CN-121994968-A - Headspace-gas chromatography detection method of 1, 3-butadiene in automotive interior material

CN121994968ACN 121994968 ACN121994968 ACN 121994968ACN-121994968-A

Abstract

The application discloses a headspace-gas chromatography detection method of 1, 3-butadiene in an automotive interior material, which comprises the following steps of 1) crushing a sample into fine particles, freezing and embrittling the fine particles by liquid nitrogen, crushing the fine particles at a low temperature, 2) weighing the crushed sample which is recovered to room temperature, putting the crushed sample into a headspace bottle, rapidly sealing the headspace bottle, and carrying out gas chromatography detection by a headspace sample injection mode. The application establishes a1, 3-butadiene detection method with simple pretreatment, high sensitivity and accurate quantification by optimizing headspace sampling conditions, instrument parameters and chromatographic column selection based on headspace-gas chromatography technology. And the method is precisely determined to be positioned on a specific and complex substrate of an automobile interior material. Compared with the prior art, the method has the advantages of simple and convenient operation and high detection speed, can effectively avoid the problems of incomplete dissolution, difficult sample introduction and the like, is suitable for measuring actual samples, and provides a reliable technical means for detecting the residual quantity of the 1, 3-butadiene in the automotive interior material.

Inventors

  • XI WENFEI
  • LIU YOUSHENG
  • LIN HONGYI
  • XU JIAHUI

Assignees

  • 奇瑞汽车股份有限公司

Dates

Publication Date
20260508
Application Date
20260311

Claims (10)

  1. 1. A headspace-gas chromatography detection method of 1, 3-butadiene in an automotive interior material is characterized by comprising the following steps: 1) Crushing a sample into fine particles, freezing by liquid nitrogen, embrittling, and crushing at a low temperature; 2) Weighing a crushed sample which is restored to room temperature, putting the crushed sample into a headspace bottle, rapidly sealing the headspace bottle, and performing gas chromatography detection in a headspace sample injection mode; wherein, headspace sampling conditions include: a) The balancing time is 15-60min; b) The heating temperature of the head space is 70-95 ℃; c) The pressurizing pressure is 80 kPa-150 kPa; d) The pressurizing time is 0.5 min-5.0 min; e) Sampling time is 0.02 min-0.1 min; f) The needle pulling time is 0.02 min-0.15 min; g) GC analysis cycle time 25 min-50 min; h) The temperature of the transmission line is 80-110 ℃; i) The temperature of the sampling needle is 80-110 ℃; j) Carrier gas 20.0 psi-35.0 psi; the gas chromatography conditions included: a) The chromatographic column is HP-INNOWax Polyethylene Glycol or equivalent polarity chromatographic column, the column length is 30m, the inner diameter is 250 μm, and the film thickness is 0.25 μm; b) The column temperature program is that 80-85 ℃ is kept for 10-12 min,8-10 ℃ per min is raised to 120-125 ℃ and kept for 10-12 min; c) The temperature of the sample inlet is 220 ℃; d) Detector temperature 250 ℃; e) The flow rate of carrier gas nitrogen is 60-65mL/min; f) The flow rate of hydrogen is 40mL/min; g) The air flow rate is 400mL/min; h) Tail blowing flow rate is 100-105kPa; i) detector-Hydrogen flame ionization detector, detector temperature was set at 250 ℃.
  2. 2. The headspace-gas chromatography detection method of 1, 3-butadiene according to claim 1, wherein in step 1), liquid nitrogen is continuously added during the pulverization process to ensure that the pulverization is performed at low temperature.
  3. 3. The headspace-gas chromatography detection method of 1, 3-butadiene according to claim 1 or 2, wherein in step 1), the crushed sample particle size is less than 1mm.
  4. 4. The headspace-gas chromatography detection method of 1, 3-butadiene according to claim 1, wherein in step 2), a solvent for dissolving the sample is further added to the headspace bottle before sealing.
  5. 5. The headspace-gas chromatography detection method of 1, 3-butadiene according to claim 1, wherein in step 2), after said sealing, further comprising injecting an internal standard solution into the headspace bottle for a blank.
  6. 6. The headspace-gas chromatography detection method of 1, 3-butadiene according to any one of claims 1-5, wherein in step 2), the headspace sampling conditions comprise: a) The balancing time is 30min; b) Furnace temperature is 80 ℃; c) The pressure is 100kPa; d) The pressurizing time is 2 min; e) Sample injection time is 0.04 min; f) The needle pulling time is 0.1 min; g) The GC analysis cycle time is 35 min; h) The temperature of the transmission line is 85 ℃; i) The temperature of the sampling needle is 85 ℃; j) Carrier gas 25.0 psi.
  7. 7. The method for detecting 1, 3-butadiene by headspace-gas chromatography according to any of claims 1-6, further comprising step 3) of performing qualitative analysis according to retention time of standard substance, and performing quantitative analysis in combination with the drawn standard curve.
  8. 8. The method for detecting 1, 3-butadiene by headspace-gas chromatography according to claim 7, wherein the qualitative determination comprises quantifying a peak area under a hydrogen flame ionization detector according to a retention time of 1, 3-butadiene, and wherein n-pentane, 1, 4-difluorobenzene or D6-benzene is selected as an internal standard when an internal standard is used, and the retention time and response signal of the internal standard are used to perform relative quantitative correction on 1, 3-butadiene.
  9. 9. The headspace-gas chromatography detection method of 1, 3-butadiene according to claim 7 or 8, wherein the drawing of the standard curve comprises dissolving a certain amount of 1, 3-butadiene standard and an internal standard in a solvent and fixing the volume to prepare a series of standard working solutions containing internal standard with fixed concentration, configuring 1, 3-butadiene into a series of concentrations, placing each standard working solution into a headspace bottle in a headspace sample injection mode, heating and balancing under the set balance temperature and time condition, extracting gas on the liquid for gas chromatography analysis, recording chromatographic peak areas of 1, 3-butadiene and the internal standard under each concentration, and drawing an internal standard calibration curve by taking the content of 1, 3-butadiene as an abscissa and taking the ratio of the peak area of 1, 3-butadiene to the peak area of the internal standard as an ordinate.
  10. 10. The headspace-gas chromatography detection method of 1, 3-butadiene according to claim 9, wherein the range of concentrations of 1, 3-butadiene is 0.2 μg, 0.4 μg, 0.6 μg, 0.8 μg and 1.0 μg, respectively.

Description

Headspace-gas chromatography detection method of 1, 3-butadiene in automotive interior material Technical Field The application relates to the technical field of compound detection, in particular to a headspace-gas chromatography detection method of 1, 3-butadiene in an automotive interior material. Background 1, 3-Butadiene is an important industrial chemical, and is widely used for synthetic rubber and plastics, and is commonly used in high polymer materials such as polybutadiene rubber, acrylonitrile-butadiene-styrene copolymer (ABS), styrene Butadiene Rubber (SBR) and the like used for automotive interior materials. During the processing of the material, part of the 1, 3-butadiene monomer may be decomposed at high temperature, and during the use, the 1, 3-butadiene monomer which is not fully reacted may exist in the finished product and be slowly released in the closed space of the vehicle, and enter the human body through the contact of the respiratory tract or the skin, so that the potential health risk exists. According to the "carcinogen list" published by the world health organization International cancer research Institute (IARC) 2017, 1, 3-butadiene is classified as a class of carcinogens whose long-term exposure is closely related to blood system diseases such as leukemia. Therefore, the method for accurately measuring the residual quantity of the 1, 3-butadiene in the automotive interior material has important significance for guaranteeing the health of drivers and passengers and improving the air quality in the automobile. At present, the detection of Volatile Organic Compounds (VOC) or aldehyde ketone substances in a vehicle is mostly focused on conventional projects such as Volatile Organic Compounds (VOC) or aldehyde ketone substances, and a large amount of high molecular materials such as ABS, ABS+PC and the like containing ABS components are used in the vehicle, so that the products are easy to have 1, 3-butadiene residues, and the special or rapid detection method for the highly toxic and carcinogenic substances such as 1, 3-butadiene is not perfect. The existing partial detection standard refers to the analysis means of food contact materials, and the headspace or liquid phase sample injection mode is adopted for analysis after the solvent is dissolved. However, the automotive interior material has complex components and often contains a large amount of filler, plasticizer, flame retardant and cross-linked structure, and the sample injection conditions and instrument conditions used in the conventional method are difficult to completely dissolve the sample, so that the release of the target is insufficient and the recovery rate is low. In addition, automotive interior materials are complex in composition and various in the type of volatile organic compounds which are pyrolyzed or released, including various interferents such as acrylonitrile, ethylbenzene, styrene, isoprene, and n-hexane. The chromatographic column in the traditional method has poor separation effect on the compounds with similar boiling points, and is easy to cause co-elution or peak overlapping of 1, 3-butadiene and adjacent peaks, thereby affecting qualitative accuracy and quantitative accuracy. At present, no special standard method for detecting 1, 3-butadiene in automotive interior plastics exists at home and abroad. The national standard GB 31604.12-2016 food safety national standard food contact material and determination of determination and migration quantity of 1, 3-butadiene in products make a specification on the method for testing 1, 3-butadiene in food contact materials and products. When the standard is directly applied to detection of the 1, 3-butadiene with extremely high volatility and extremely low content in the automotive interior plastic, the problems of insufficient sensitivity, serious matrix interference, poor quantitative accuracy and the like exist. In the national standard, a special chromatographic column and a detection program are needed for detecting the 1, 3-butadiene, so that the universality is poor and the detection cost is high. Disclosure of Invention In view of the above, the main object of the present invention is to establish a headspace-gas chromatography detection method for 1, 3-butadiene in an automotive interior material, so as to realize efficient and reliable measurement of the residual amount of 1, 3-butadiene in the automotive interior material. In order to achieve the above object, the present application provides a headspace-gas chromatography detection method of 1, 3-butadiene in an automotive interior material, comprising the steps of: 1) Crushing a sample into fine particles, freezing by liquid nitrogen, embrittling, and crushing at a low temperature; 2) Weighing a crushed sample which is restored to room temperature, putting the crushed sample into a headspace bottle, rapidly sealing the headspace bottle, and performing gas chromatography detection in a headspace