Method for detecting benzene series and isooctanol in organic polymer and application of method

Abstract

The invention provides a method for detecting benzene series and isooctanol in an organic polymer and application thereof, the detection method comprises the following steps: (1) crushing a sample to be detected, and then mixing with an organic solvent to obtain a test solution; (2) performing GC-MS detection on the test solution, and calculating the concentration of the benzene series and the isooctanol according to a detection result in combination with the standard curve; the benzene series comprises any one or a combination of at least two of methylbenzene, ethylbenzene, p-xylene, m-xylene, isopropyl benzene, o-xylene, propyl benzene, styrene, benzaldehyde or acetophenone. The detection method provided by the invention can be used for simultaneously detecting various benzene series and isooctanol in the organic polymer, and is high in accuracy and high in sensitivity.

Description

Technical Field

[0001] The invention belongs to the field of organic matter detection, and specifically relates to a detection method for benzene series and isooctyl alcohol in an organic polymer and an application thereof, and especially relates to a detection method for benzene series and isooctyl alcohol in an organic polymer with high accuracy and an application thereof. Background Art

[0002] BTEX is a general term for benzene derivatives. BTEX in a broad sense includes all aromatic compounds. Many BTEX are toxic to organisms and can cause direct harm to human health. At present, there are no relevant national standards for electronic and electrical products. The existing determination is carried out by thermal desorption gas chromatography-mass spectrometry, and the calibration curve is drawn using Tenax adsorption calibration substances. The substance is heated to a certain temperature to release the adsorbed compounds, and the airflow is collected in a thin tube in the thermal desorber, which is usually called a focusing trap or cold trap. By heating the focusing cold trap, the analyte is released again and injected into the GC. This method has some disadvantages: when preparing calibration curves for multiple substances at the same time during the analysis process, there are cases where the calibration substances penetrate, decompose and desorb in the adsorbent, and some BTEX cannot be effectively adsorbed, resulting in inaccurate quantification; the BTEX content of some materials is too high, which is easy to cause detector saturation and damage the detector. Saturation affects the accuracy of the results and requires re-determination, which is inconvenient to operate and affects work efficiency.

[0003] CN201911380302.5 discloses a method for detecting benzene pollutants in the air. The detection method can completely separate the three isomers of xylene, namely, p-xylene, m-xylene and o-xylene, and can simultaneously detect benzene, toluene, ethylbenzene, p-xylene, m-xylene, o-xylene and styrene. It has good chromatographic separation effect and high detection efficiency, and can simultaneously realize the detection of occupational disease hazard factors in the workplace, indoor air quality and atmospheric environment hazard factors in residential areas.

[0004] CN201510820006.8 discloses a method for detecting benzene series in dairy products, the method comprising the steps of: adding v1 ml of acetonitrile to a container containing m grams of a sample to be tested, sealing the container, and the volume of the sealed container is v ml; wherein m / v1 is 8-12, and v / m is 3-5. The invention also provides a method for detecting benzene series in dairy products after pre-treating the dairy products to be tested using the above method. After pre-treating the dairy products to be tested using the pre-treatment method of the invention, the benzene series in the dairy products are detected, with high accuracy, sensitivity and precision, and a low detection limit.

[0005] CN201410428564.5 discloses a method for detecting benzene series and total volatile organic compounds, and the steps are as follows: (1) using an activated carbon sampling tube to enrich the benzene series and total volatile organic compounds in ambient air or indoor air; (2) taking out two sections of samples in the activated carbon sampling tube respectively, adding carbon disulfide, and desorbing with benzene-free carbon disulfide; (3) gas chromatography analysis; (4) calculation: after gas chromatography analysis, the peak area of ​​each substance is obtained, and then substituted into the calibration curve to calculate the concentration of each substance in the sample. The method for detecting benzene series and total volatile organic compounds of the invention is suitable for the determination of benzene series and TVOC in ambient air and indoor air, does not require pretreatment, and can be analyzed multiple times in one sampling. The TVOC omits the thermal desorption analysis step and is replaced by the direct injection method of carbon disulfide analysis. Under the premise of ensuring the safety factor of the detection, the detection time is shortened, and only the desorption time of carbon disulfide is increased, the detection cost is reduced, and the analysis data is more accurate.

[0006] CN202110519912.X discloses a method for determining benzene series in water, comprising the following steps: placing a sample in a sealed headspace bottle, at a certain temperature and pressure, the volatile components in the sample in the headspace bottle volatilize to the liquid headspace, generating vapor pressure, when the gas-liquid two phases reach thermodynamic dynamic equilibrium, within a certain concentration range, the concentration of benzene series in the gas phase is proportional to the concentration in the water phase, and then the gas phase is quantitatively extracted and separated by gas chromatography, and detected by a hydrogen flame ionization detector. Before sampling, the pH value of the sample is determined, and according to the pH value determination result, an appropriate amount of hydrochloric acid solution is added to the sampling bottle. The beneficial effects achieved by the invention are: in view of the defects of the existing determination of benzene series in water, the headspace / gas chromatography method is adopted. This standard is applicable to the determination of 8 kinds of benzene series, such as benzene, toluene, ethylbenzene, p-xylene, m-xylene, o-xylene, isopropylbenzene and styrene in surface water, groundwater, domestic sewage and industrial wastewater.

[0007] However, the detection objects of the above methods are different from those in the present application, and it is not possible to effectively detect organic polymers in electronic and electrical products. Therefore, how to provide a method for accurately and effectively detecting benzene series of organic polymers in electronic and electrical products has become an urgent problem to be solved. Summary of the invention

[0008] In view of the deficiencies of the prior art, the object of the present invention is to provide a method for detecting benzene series and isooctyl alcohol in an organic polymer and its application, and in particular to provide a method for detecting benzene series and isooctyl alcohol in an organic polymer with high accuracy and its application. The detection method provided by the present invention can simultaneously detect multiple benzene series and isooctyl alcohol in an organic polymer with high accuracy and high sensitivity.

[0009] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0010] In one aspect, the present invention provides a method for detecting benzene series and isooctyl alcohol in an organic polymer, the detection method comprising the following steps:

[0011] (1) crushing the sample to be tested, and then mixing it with an organic solvent to obtain a test solution;

[0012] (2) The test solution is subjected to GC-MS (gas chromatography-mass spectrometry) detection, and the concentrations of benzene series and isooctyl alcohol are calculated based on the test results and the standard curve.

[0013] The benzene series includes any one of toluene, ethylbenzene, p-xylene, m-xylene, isopropylbenzene, o-xylene, propylbenzene, styrene, benzaldehyde or acetophenone, or a combination of at least two thereof.

[0014] The specific method can effectively detect benzene series and isooctyl alcohol in organic polymers simultaneously with high detection accuracy and sensitivity.

[0015] Preferably, the benzene series substances are toluene, ethylbenzene, p-xylene, m-xylene, isopropylbenzene, o-xylene, propylbenzene, styrene, benzaldehyde and acetophenone.

[0016] The detection method provided by the present invention can detect the above ten benzene series and isooctyl alcohol at the same time, and has excellent technical effect.

[0017] Preferably, the organic solvent in step (1) comprises any one of dichloromethane, acetone, ethanol or carbon disulfide, or a combination of at least two thereof.

[0018] Preferably, the organic solvent in step (1) is a combination of dichloromethane and acetone.

[0019] The above-mentioned specific solvent selection can further improve the accuracy of detection compared with other solvents.

[0020] Preferably, the liquid-to-solid ratio of the sample to be tested to the organic solvent in step (1) is (15-25) mg / mL, for example 15 mg / mL, 16 mg / mL, 17 mg / mL, 18 mg / mL, 19 mg / mL, 20 mg / mL, 21 mg / mL, 22 mg / mL, 23 mg / mL, 24 mg / mL or 25 mg / mL, but is not limited to the above-listed values, and other values ​​not listed within the above numerical range are equally applicable.

[0021] Preferably, after mixing with the organic solvent in step (1), the mixed solution is shaken to obtain a supernatant.

[0022] If the organic polymer is not completely dissolved during mixing, it can be treated through the above-mentioned shaking process so that the benzene series and isooctyl alcohol in the sample can be dissolved in the solvent as much as possible.

[0023] Preferably, the particle size of the sample to be tested after crushing in step (1) is 1-2 mm, for example, 1 mm, 1.1 mm, 1.2 mm, 1.3 mm, 1.4 mm, 1.5 mm, 1.6 mm, 1.7 mm, 1.8 mm, 1.9 mm or 2 mm, but is not limited to the values ​​listed above, and other values ​​not listed within the above numerical range are also applicable.

[0024] Preferably, the temperature raising program of the GC-MS in step (2) is: maintaining at 35-44°C for 0.8-1.2 min, then heating to 80-100°C at a rate of 8-12°C / min and maintaining for 21.5-2.5 min, then heating to 180-200°C at a rate of 18-22°C / min.

[0025] The present invention can detect ten benzene series and isooctyl alcohol simultaneously by adopting the above-mentioned specific temperature rising program, thus avoiding misjudgment caused by missed detection.

[0026] Preferably, the GC-MS chromatographic column in step (2) comprises a DB-WAX chromatographic column.

[0027] On the other hand, the present invention also provides the use of the above-mentioned method for detecting benzene series and isooctyl alcohol in organic polymers in the detection of electronic and electrical products.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] (1) The present invention provides a method for detecting benzene series and isooctyl alcohol in an organic polymer, which can effectively detect benzene series and isooctyl alcohol in an organic polymer simultaneously, with high detection accuracy and high sensitivity;

[0030] (2) The detection method provided by the present invention can simultaneously detect ten kinds of benzene series including toluene, ethylbenzene, p-xylene, m-xylene, isopropylbenzene, o-xylene, propylbenzene, styrene, benzaldehyde and acetophenone as well as isooctyl alcohol, and has excellent technical effects;

[0031] (3) The present invention can further improve the accuracy of detection by selecting a specific solvent compared with other solvents;

[0032] (4) The present invention can detect ten benzene series and isooctyl alcohol simultaneously by adopting a specific temperature rising program, thus avoiding misjudgment caused by missed detection. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 This is a graph of the detection results in Example 1, wherein peaks 1-11 are toluene, ethylbenzene, p-xylene, m-xylene, isopropylbenzene, o-xylene, propylbenzene, styrene, isooctyl alcohol, benzaldehyde, and acetophenone, respectively. DETAILED DESCRIPTION

[0034] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0035] Example 1

[0036] This embodiment provides a method for detecting benzene series and isooctyl alcohol in an organic polymer, and the specific steps are as follows:

[0037] The sample to be tested was ground, crushed and sieved to obtain particles with a particle size between 1 and 2 mm; then 100 mg of the particle sample was placed in a 10 mL centrifuge tube, 3 mL of dichloromethane and 2 mL of acetone were added to dissolve, and then GC-MS detection was performed under the following conditions:

[0038] Instrument: Shimadzu GC-MS 2010SE;

[0039] Chromatographic column: DB-WAX, specification: 30m×0.25mm×0.25μm;

[0040] Carrier gas: high purity helium above 99.999%;

[0041] Inlet temperature 250 °C, split ratio 1:50, column flow 1.03 mL / min;

[0042] Heating program: 35 °C for 1 min, then increase the temperature to 80 °C at 10 °C / min and hold for 2 min, then increase the temperature to 180 °C at 20 °C / min;

[0043] Mass spectrometry conditions: ion source temperature 230°C, SIM (selected ion monitoring) mode, qualitative and quantitative parameters are as follows:

[0044] name Retention time Quantitative ion Qualifier ions Toluene 4.435 91 91,92,65 Ethylbenzene 5.790 91 91,106,65, p-Xylene 5.915 91 91,106,105 Meta-Xylene 6.025 91 91,106,105 Cumene 6.625 105 105,120,77 o-Xylene 6.835 91 91,106,105 Propylbenzene 7.362 91 91,120,92 Styrene 8.301 104 104,78,103 2-Ethylhexyl alcohol 11.131 57 57,43,41, Benzaldehyde 11.490 106 106,105,77 Acetophenone 12.485 105 105,77,120

[0045] The above method was used to test the sample (mixed standard solution, in which the concentrations of toluene, ethylbenzene, p-xylene, m-xylene, isopropylbenzene, o-xylene, propylbenzene, styrene, benzaldehyde, acetophenone and isooctyl alcohol were 2 mg / L respectively). Figure 1 As shown (wherein peaks 1-11 are toluene, ethylbenzene, p-xylene, m-xylene, isopropylbenzene, o-xylene, propylbenzene, styrene, isooctyl alcohol, benzaldehyde, and acetophenone, respectively).

[0046] According to the results and the standard curve, the contents of toluene, ethylbenzene, p-xylene, m-xylene, isopropylbenzene, o-xylene, propylbenzene, styrene, benzaldehyde, acetophenone and isooctyl alcohol in the samples to be tested were calculated.

[0047] The standard curve preparation method is as follows:

[0048] Toluene, ethylbenzene, p-xylene, m-xylene, isopropylbenzene, o-xylene, propylbenzene, styrene, benzaldehyde, acetophenone and isooctyl alcohol standards were diluted, and five points were selected within the concentration range of 0.1 mg / L-2 mg / L. The standard curve of each compound was calculated according to the solution concentration (x) and the quantitative ion response value (y). 2 All are greater than 0.995, and the results are as follows:

[0049] Toluene y=446.575804x+29800.588723 Ethylbenzene y=611.980058x+7101.155887 p-Xylene y=477.550240x+6242.217247 Meta-Xylene y=487.456692x+13737.114428 Cumene y=611.332023x+2304.862355 o-Xylene y=505.607239x+7733.298507 Propylbenzene y=762.739544x+1747.346600 Styrene y=384.862148x+1504.767828 2-Ethylhexyl alcohol y=344.831269x+3185.835821 Benzaldehyde y=167.291692x+1739.114428 Acetophenone y=458.426227x+3786.867330

[0050] Example 2

[0051] This embodiment provides a method for detecting benzene series and isooctyl alcohol in an organic polymer. The specific steps are the same as those in Embodiment 1 except that dichloromethane is not included and the reduced portion is allocated to acetone.

[0052] Example 3

[0053] This embodiment provides a method for detecting benzene series and isooctyl alcohol in an organic polymer. The specific steps are consistent with those of Embodiment 1 except that acetone is not included and a reduced portion is allocated to dichloromethane.

[0054] Example 4

[0055] This embodiment provides a method for detecting benzene series and isooctyl alcohol in an organic polymer. The specific steps are consistent with those of Embodiment 1 except that the temperature rising procedure is as follows.

[0056] Keep at 55℃ for 1 min, then increase the temperature to 80℃ at 10℃ / min and keep it for 2 min, then increase the temperature to 180℃ at 20℃ / min.

[0057] As a result, toluene and ethylbenzene could not be detected.

[0058] Precision and recovery:

[0059] The method of Example 1 was repeated 7 times, and three-level spike tests were performed in the samples at 100 μg / L, 500 μg / L, and 1000 μg / L. The results were as follows: RSDs were all lower than 10%, and recoveries were within 88.0%-102.4%, showing excellent results:

[0060]

[0061]

[0062] Detection Limit:

[0063] Weigh 0.1 g of sample, add a standard solution with a concentration of (100 μg / L), and test according to Example 1. Record the test results respectively, calculate the standard deviation of the concentration in the sample measured 10 times, take 3 times the standard deviation of the concentration in the sample as the detection limit, and 10 times the standard deviation as the quantitative limit. The quantitative limit is shown in the following table.

[0064]

[0065]

[0066] The methods of Examples 1 and 4 were used to test the EPS foam used in electronic and electrical products (repeated 3 times), and the results are as follows:

[0067]

[0068]

[0069]

[0070] In Example 1, due to the high contents of styrene and acetophenone, the precision RSD was below 15%, which met the precision requirement. By comparing the above results, it can be found that the present invention can simultaneously detect ten benzene series and isooctyl alcohol by selecting a specific heating program, thereby avoiding misjudgment caused by missed detection.

[0071] In addition, the recovery rate test of the method of Example 1-3 was carried out, and the theoretical spiked value was 500 μg / L. The results are as follows:

[0072]

[0073] It can also be found from the above results that the present invention can further improve the accuracy of detection by selecting a specific solvent.

[0074] The applicant declares that the present invention uses the above-mentioned embodiments to illustrate the detection method and application of benzene series and isooctyl alcohol in organic polymers of the present invention, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

[0075] The preferred embodiments of the present invention are described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0076] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

Claims

1. A method for detecting benzene series and isooctyl alcohol in an organic polymer, characterized in that: The detection method comprises the following steps: (1) crushing the sample to be tested, and then mixing it with an organic solvent to obtain a test solution; (2) The test solution is subjected to GC-MS detection, and the concentrations of benzene series and isooctyl alcohol are calculated based on the test results and the standard curve; The benzene series includes any one of toluene, ethylbenzene, p-xylene, m-xylene, isopropylbenzene, o-xylene, propylbenzene, styrene, benzaldehyde or acetophenone, or a combination of at least two thereof.

2. The detection method according to claim 1, characterized in that: The benzene series are toluene, ethylbenzene, p-xylene, m-xylene, isopropylbenzene, o-xylene, propylbenzene, styrene, benzaldehyde and acetophenone.

3. The detection method according to claim 1 or 2, characterized in that: The organic solvent in step (1) includes any one of dichloromethane, ethanol, acetone or carbon disulfide, or a combination of at least two of them.

4. The detection method according to any one of claims 1 to 3, characterized in that: The organic solvent in step (1) is a combination of dichloromethane and acetone.

5. The detection method according to any one of claims 1 to 4, characterized in that: The solid-liquid ratio of the sample to be tested to the organic solvent in step (1) is (15-25) mg / mL.

6. The detection method according to any one of claims 1 to 5, characterized in that: After the step (1) is mixed with the organic solvent, the mixed solution is shaken and the supernatant is collected.

7. The detection method according to any one of claims 1 to 6, characterized in that: The particle size of the sample to be tested after crushing in step (1) is 1-2 mm.

8. The detection method according to any one of claims 1 to 7, characterized in that: The temperature raising program of the GC-MS in step (2) is as follows: maintaining at 35-44°C for 0.8-1.2 min, then increasing the temperature to 80-100°C at a rate of 8-12°C / min and maintaining for 21.5-2.5 min, then increasing the temperature to 180-200°C at a rate of 18-22°C / min.

9. The detection method according to any one of claims 1 to 8, characterized in that: The chromatographic column of the GC-MS in step (2) comprises a DB-WAX chromatographic column.

10. Use of the method for detecting benzene series and isooctyl alcohol in an organic polymer according to any one of claims 1 to 9 in the detection of electronic and electrical products.

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