A method for detecting residual low-boiling harmful components in POE materials

Abstract

The present invention provides a method for detecting residual low-boiling harmful components in a POE material, including: A) preparing a standard curve solution from a mixed standard solution; mixing the standard curve solution and the internal standard solution, placing them in a static headspace sampler, using HS-GC-MS for detection, and using the internal standard method to draw a mass-peak area standard curve of residual low-boiling harmful components; B) taking a POE sample to be tested and mixing the internal standard solution, placing them in a static headspace sampler, using HS-GC-MS for detection, and calculating the content of each residual low-boiling harmful component according to the peak area of ​​each harmful component combined with the mass-peak area standard curve of the residual low-boiling harmful component. The detection method provided by the present invention does not require pre-treatment of the sample to be tested, thereby achieving simple, rapid and accurate quantitative analysis of the residual low-boiling harmful components in the POE material, with good precision and high recovery.

Description

Technical Field

[0001] The invention relates to the technical field of analytical chemistry, and in particular to a method for detecting residual low-boiling harmful components in a POE material. Background Art

[0002] POE refers to polyolefin elastomers (Polyolefin Elastomer) formed by copolymerization of ethylene and α-olefins such as ethylene-octene copolymer, ethylene-butene copolymer and ethylene-hexene copolymer. General POE refers to ethylene-octene copolymer, that is, vinyl copolymer with octene mass fraction greater than 35% (less than 20% is a plastomer). POE has the following structural characteristics: (1) The soft chain curling structure of octene and the crystalline ethylene chain as physical crosslinking points make it have both excellent toughness and good processability; (2) The relative molecular weight distribution is narrow, it has good compatibility with polyolefins and has better fluidity; (3) There is no unsaturated double bond, and the weather resistance is better than other elastomers; (4) Strong shear sensitivity and melt strength can achieve high extrusion and increase production; (5) Good fluidity can improve the dispersion effect of fillers and also improve the welding strength of products. These structural characteristics of POE determine that it has more excellent performance. Compared with other elastomers such as EPR, EPDM, and SBS, POE has the advantages of better dispersibility, better affinity, higher transparency, excellent weather resistance, stronger toughness and plasticity, lighter weight, and lower price. Therefore, POE has been widely used in medical packaging materials, auto parts, wires and cables, daily necessities, toys, etc.

[0003] Due to the complexity of organic reactions, residual small molecule monomers or residual solvents are inevitably present in the production process of POE products. The presence of these residual low-boiling components seriously affects the application quality of POE materials. Given that there is no report on the analysis method for the residual low-boiling harmful components in POE materials, in order to accurately and effectively monitor the residual low-boiling harmful components in POE materials to guide the optimization of production processes, it is urgent to establish a quantitative analysis method with high accuracy, good reproducibility, high precision, simplicity and high efficiency to achieve quantitative analysis of residual low-boiling harmful components in POE materials. Summary of the invention

[0004] In view of this, the technical problem to be solved by the present invention is to provide a method for detecting residual low-boiling harmful components in POE materials. The method of the present invention is stable, accurate and reliable.

[0005] The present invention provides a method for detecting residual low-boiling harmful components in a POE material, comprising:

[0006] A) Prepare the standard curve solution by mixing the standard solution;

[0007] The standard curve solution and the internal standard solution are mixed, placed in a static headspace sampler, and detected by HS-GC-MS. The mass-peak area standard curve of the residual low-boiling harmful components is drawn by the internal standard method;

[0008] B) taking the POE sample to be measured and mixing it with the internal standard solution, placing it in a static headspace sampler, adopting HS-GC-MS to detect, and calculating the content of each residual low-boiling harmful component according to the peak area of ​​each harmful component in combination with the mass-peak area standard curve of the residual low-boiling harmful component;

[0009] Selection of chromatographic columns: HP-PONA (50m×0.20mm×0.50μm), VF-WAXms (60m*0.25mm*0.50um) and HP-5MS (60m*0.25mm*0.25um) capillary chromatographic columns were selected respectively, and the standard solution and internal standard solution were used for testing and comparative analysis. The analysis results showed that HP-PONA and VF-WAXms can completely separate all the components to be tested, and the separation effect is very good; when the HP-5MS column is used for analysis and testing, benzene and cyclohexane completely overlap and cannot be separated. Therefore, HP-PONA or VF-WAXms chromatographic columns are preferred.

[0010] Because the POE sample to be tested contains some residual isomers of 1-octene, in order to prevent the isomers of 1-octene in the sample from overlapping with other components to be tested and interfering with the analysis, the solid chromatographic column needs to be subjected to optimal selection experimental analysis. HP-PONA (50m×0.20mm×0.50μm) and VF-WAXms (60m*0.25mm*0.25um) capillary chromatographic columns were selected respectively, and the POE sample to be tested and the internal standard solution were used for test and comparative analysis. The analysis results showed that VF-WAXms could not effectively separate the isomers of 1-octene from the internal standard isopropanol completely, while the HP-PONA capillary chromatographic column had the best separation effect. The most preferred chromatographic column of the present invention is the HP-PONA capillary chromatographic column.

[0011] The chromatographic column of the HS-GC-MS uses dimethylpolysiloxane as the stationary phase.

[0012] Preferably, the chromatographic column of the HS-GC-MS is HP-PONA; the specifications of the chromatographic column are: 50m×200μm×0.50μm.

[0013] Preferably, the injection port temperature of the HS-GC-MS is 220° C. to 260° C.; the carrier gas is helium; the carrier gas flow rate is 0.6 to 1.0 mL / min; the split ratio is (5 to 10): 1; and the injection method is headspace injection.

[0014] Selection of chromatographic program heating conditions: using an initial temperature of 50-100°C, heating to 300°C at a rate of (25-30)°C / min, and maintaining for 5-6 minutes. Under this heating program, benzene and cyclohexane cannot be effectively separated, and styrene and o-xylene cannot be effectively separated. After multiple experiments using different heating programs, the optimal chromatographic heating conditions were finally determined.

[0015] Preferably, the programmed temperature rise of the HS-GC-MS is: the initial temperature is 35°C to 50°C, the temperature is raised to 80°C at a rate of (5-10)°C / min, the temperature is then raised to 125°C at a rate of 1.5°C / min, and finally the temperature is raised to 200°C at a rate of (10-25)°C / min, and maintained for 5-6 minutes.

[0016] Preferably, the mass spectrometry conditions of the HS-GC-MS are:

[0017] The ionization source is an EI source; the electron energy is 70 eV; the ion source temperature is 200°C to 280°C; the quadrupole temperature is 150°C to 180°C; the transmission line temperature is 260 to 280°C; the filament current is 3 to 8uA; the scanning mode is: full scanning mode, the scanning range is: 30amu to 600amu.

[0018] Preferably, the headspace conditions are:

[0019] The heating temperature of the sample bottle is 100℃~150℃;

[0020] The equilibrium time is 30 to 50 minutes;

[0021] The transfer line temperature was 140°C; the quantitative loop temperature was 135°C.

[0022] Preferably, the mixed standard solution in step A) is a mixed standard solution of n-hexane, benzene, cyclohexane, toluene, 1-octene, ethylbenzene, p-xylene, styrene, o-xylene and methylcyclohexane.

[0023] Preferably, the internal standard solution is an isopropanol solution; the concentration of the isopropanol solution is 0.86 mg / mL.

[0024] Preferably, the POE sample to be tested is a crude product, a granular product, a block product, a film product or a competitive product obtained in the POE production process; the size of the POE sample to be tested is fragments or particles of 0.20 cm*0.20 cm.

[0025] Preferably, the mass-peak area standard curve of the residual low-boiling harmful components is specifically:

[0026] The regression equation of the internal standard curve of n-hexane is: Y=3.4337X; the regression equation of the internal standard curve of benzene is: Y=6.1323X; the regression equation of the internal standard curve of cyclohexane is: Y=4.5485X; the regression equation of the internal standard curve of methylcyclohexane is: Y=4.8723X; the regression equation of the internal standard curve of toluene is: Y=5.0952X; the regression equation of the internal standard curve of 1-octene is: Y=3.5610X ; The regression equation of the internal standard curve of ethylbenzene is obtained: Y=5.6770X; the internal standard curve of p-xylene is obtained: Y=5.5064X; the internal standard curve of styrene is obtained: Y=4.1853X; the internal standard curve of o-xylene is obtained: Y=4.9181X; wherein Y is the peak area ratio, that is, the ratio of the peak area of ​​the corresponding residual low-boiling harmful components to the peak area of ​​the internal standard isopropanol; X is the mass ratio, that is, the ratio of the mass of the corresponding residual low-boiling harmful components to the mass of the internal standard isopropanol.

[0027] Compared with the prior art, the present invention provides a method for detecting residual low-boiling harmful components in POE materials, including: A) preparing a standard curve solution from a mixed standard solution; mixing the standard curve solution and the internal standard solution, placing them in a static headspace sampler, using HS-GC-MS for detection, and using the internal standard method to draw a mass-peak area standard curve of residual low-boiling harmful components; B) taking a POE sample to be tested and mixing the internal standard solution, placing them in a static headspace sampler, using HS-GC-MS for detection, and calculating the content of each residual low-boiling harmful component according to the peak area of ​​each harmful component combined with the mass-peak area standard curve of the residual low-boiling harmful component; the chromatographic column of the HS-GC-MS is dimethylpolysiloxane as the stationary phase. The present invention can accurately quantitatively analyze the residual low-boiling harmful components in the POE material by performing high-resolution gas-gas analysis on the residual low-boiling harmful components and performing mass spectrometry analysis on each mass spectrum peak. The detection method provided by the present invention does not require pretreatment of the sample to be tested, thereby achieving simple, rapid and accurate quantitative analysis of the residual low-boiling harmful components in the POE material, with good precision and high recovery rate. The method has high accuracy, good reproducibility, high precision, simple and easy operation, and greatly shortens the analysis time. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 is the standard curve of ten low boiling components of the present invention;

[0029] Figure 2 is the total ion current chromatogram of the sample in Example 1 of the present invention;

[0030] Figure 3 This is the total ion current chromatogram of the sample of Comparative Example 1 of the present invention. DETAILED DESCRIPTION

[0031] The present invention provides a method for detecting residual low-boiling harmful components in POE materials. Those skilled in the art can refer to the content of this article and appropriately improve the process parameters to achieve it. It should be particularly noted that all similar replacements and modifications are obvious to those skilled in the art, and they all belong to the scope of protection of the present invention. The method and application of the present invention have been described through preferred embodiments, and relevant personnel can obviously modify or appropriately change and combine the method and application of this article without departing from the content, spirit and scope of the present invention to implement and apply the technology of the present invention.

[0032] The present invention provides a method for detecting residual low-boiling harmful components in a POE material, comprising:

[0033] A) Prepare the standard curve solution by mixing the standard solution;

[0034] The standard curve solution and the internal standard solution are mixed, placed in a static headspace sampler, and detected by HS-GC-MS. The mass-peak area standard curve of the residual low-boiling harmful components is drawn by the internal standard method;

[0035] B) taking the POE sample to be measured and mixing it with the internal standard solution, placing it in a static headspace sampler, adopting HS-GC-MS to detect, and calculating the content of each residual low-boiling harmful component according to the peak area of ​​each harmful component in combination with the mass-peak area standard curve of the residual low-boiling harmful component;

[0036] The chromatographic column of the HS-GC-MS uses dimethylpolysiloxane as the stationary phase.

[0037] The present invention performs high-resolution gas chromatography-mass spectrometry analysis on the residual low-boiling harmful components and performs mass spectrometry analysis on each mass spectrum peak, thereby being able to accurately quantitatively analyze the residual low-boiling harmful components in the POE material. The detection method provided by the present invention does not require pretreatment of the sample to be tested, thereby achieving simple, rapid and accurate quantitative analysis of the residual low-boiling harmful components in the POE material, with good precision and high recovery rate. The method has high accuracy, good reproducibility, high precision, simple and easy operation, and greatly shortens the analysis time.

[0038] The method for detecting residual low-boiling harmful components in POE materials provided by the present invention first prepares a standard curve solution from a mixed standard solution.

[0039] Among them, the ten low-boiling components used to prepare the mixed standard solution are all commercially available standard substances.

[0040] The mixed standard solution of the present invention is a mixed standard solution of n-hexane, benzene, cyclohexane, toluene, 1-octene, ethylbenzene, p-xylene, styrene, o-xylene and methylcyclohexane.

[0041] The present invention selects N-methylpyrrolidone (NMP) with a relatively high boiling point as a solvent, so that the low-boiling component to be measured can be absolutely separated from the solvent, thereby avoiding interference of the solvent on the test of the low-boiling component to be measured.

[0042] The standard curve solution can preferably be prepared as follows:

[0043] First, prepare the mother solution of the mixed standard solution. Accurately weigh: 8.7 mg of n-hexane, 5.2 mg of benzene, 9.9 mg of cyclohexane, 7.3 mg of toluene, 22.0 mg of 1-octene, 6.6 mg of ethylbenzene, 6.7 mg of p-xylene, 7.0 mg of styrene, 7.3 mg of o-xylene, and 14.7 mg of methylcyclohexane in a 10 ml volumetric flask, and dissolve them to the mark with NMP; then accurately transfer 5.00 ml of the mother solution of the mixed standard solution to a 50 ml volumetric flask, dissolve them to the mark with NMP, and obtain the standard curve solution to be tested.

[0044] The standard curve solution and the internal standard solution were mixed and placed in a static headspace sampler. The samples were detected by HS-GC-MS. The mass-peak area standard curve of the residual low-boiling harmful components was drawn by the internal standard method.

[0045] The internal standard solution of the present invention is an isopropanol solution; the concentration of the isopropanol solution is preferably 0.86 mg / mL. Prepare the internal standard solution: accurately weigh 0.0860 g of isopropanol in a 100 ml volumetric flask, and dilute to the mark with NMP.

[0046] The standard curve solution is added with the internal standard solution and then subjected to high-resolution gas chromatography-mass spectrometry. The injection method is preferably static headspace injection analysis; the gas chromatography-mass spectrometry instrument is preferably Agilent 7250GC-QTOF.

[0047] Preferred gas phase conditions for high resolution gas chromatography-mass spectrometry include:

[0048] The temperature of the injection port is preferably 220°C to 260°C, more preferably 230-260°C, and even more preferably 250°C; the split ratio is preferably (5-10):1, and most preferably 5:1; injection method: headspace injection.

[0049] The chromatographic column of the HS-GC-MS is based on dimethylpolysiloxane as the stationary phase; preferably, the chromatographic column of the HS-GC-MS is preferably HP-PONA or HP-5, and more preferably HP-PONA. The specifications of the chromatographic column are: 50m×200μm×0.50μm.

[0050] The carrier gas is helium; the carrier gas flow rate is preferably (0.6-1.0) mL / min, more preferably (0.7-0.9) mL / min, and even more preferably 0.8 mL / min.

[0051] The programmed temperature is specifically as follows: the column box temperature is initially 35°C to 50°C, then heated to 80°C at a rate of (5-10)°C / min, then heated to 125°C at a rate of 1.5°C / min, and finally heated to 200°C at a rate of (10-25)°C / min, and maintained for 5-6min; more preferably: the initial temperature is 50°C, then heated to 80°C at a rate of 10°C / min, then heated to 125°C at a rate of 1.5°C / min, and finally heated to 200°C at a rate of 25°C / min, and maintained for 5min.

[0052] The mass spectrometry conditions of HS-GC-MS of the present invention are:

[0053] The ionization source is an EI source; the electron energy is 70eV; the ion source temperature is preferably 200°C to 280°C, more preferably 200°C to 250°C; more preferably 200°C to 230°C; the quadrupole temperature is preferably 150°C to 180°C, more preferably 150°C to 170°C, more preferably 150°C to 160°C; the transmission line temperature is preferably 260°C to 280°C, more preferably 265°C to 280°C, more preferably 270°C to 280°C; the filament current is preferably 3 to 8uA, more preferably 4 to 7uA, more preferably 5 to 6uA.

[0054] Scan mode: full scan mode, scan range: 30amu~600amu.

[0055] The quantitative characteristic ions of the present invention are: isopropanol m / z=45.0333; n-hexane m / z=57.0698; benzene m / z=78.0463; cyclohexane m / z=56.0620; methylcyclohexane m / z=83.0852; toluene m / z=91.0541; 1-octene m / z=55.0541; ethylbenzene m / z=91.0541; p-xylene m / z=91.0541; styrene m / z=104.0618; o-xylene m / z=91.0541.

[0056] The headspace conditions of the present invention are:

[0057] In the static head space sampler, the heating temperature of the sample bottle is preferably 100°C to 150°C, more preferably 110°C to 140°C, and more preferably 120°C to 130°C; the equilibration time of the static head space sampler is preferably 30 to 50 min, more preferably 30 to 40 min, and more preferably 30 min; the transmission line temperature is 140°C; and the quantitative loop temperature is 135°C.

[0058] The peak area of ​​each quantitative characteristic ion of high-resolution mass spectrometry analysis was recorded, and the mass-peak area standard curve of the residual low-boiling harmful components was obtained by the internal standard method. The regression equation of the internal standard curve of n-hexane was obtained: Y=3.4337X; the regression equation of the internal standard curve of benzene was obtained: Y=6.1323X; the regression equation of the internal standard curve of cyclohexane was obtained: Y=4.5485X; the regression equation of the internal standard curve of methylcyclohexane was obtained: Y=4.8723X; the regression equation of the internal standard curve of toluene was obtained: Y=5.0952X; 1 -The regression equation of the internal standard curve of octene is: Y=3.5610X; the regression equation of the internal standard curve of ethylbenzene is: Y=5.6770X; the internal standard curve of p-xylene is: Y=5.5064X; the internal standard curve of styrene is: Y=4.1853X; the internal standard curve of o-xylene is: Y=4.9181X; wherein Y is the peak area ratio, that is, the ratio of the peak area of ​​the corresponding residual low-boiling harmful components to the peak area of ​​the internal standard isopropanol; X is the mass ratio, that is, the ratio of the mass of the corresponding residual low-boiling harmful components to the mass of the internal standard isopropanol.

[0059] The POE sample to be tested was mixed with the internal standard solution, placed in a static headspace injector, and detected by HS-GC-MS. The content of each residual low-boiling harmful component was calculated based on the peak area of ​​each harmful component and the mass-peak area standard curve of the residual low-boiling harmful component.

[0060] The preferred method is as follows: take an appropriate amount of the POE sample to be tested into a headspace bottle, add an appropriate amount of internal standard solution, cover and seal it, place it in a static headspace injector, perform static headspace-gas-mass analysis, record the peak area of ​​each quantitative characteristic ion, and obtain the content of the residual low-boiling harmful components in the POE sample to be tested according to the mass-peak area standard curve of the residual low-boiling harmful components.

[0061] The POE sample to be tested in the present invention is a crude product, a granular product, a block product, a film product or a competitive product obtained in the POE production process.

[0062] The size of the POE sample to be tested is 0.20cm*0.20cm fragments or particles. That is, in order to ensure that the low-boiling organic components in the POE product or competitor's product can be effectively detected, the produced POE block solid or POE film is cut into 0.20cm*0.20cm fragments with scissors or extruded into uniform particles of corresponding size with granulation equipment, so as to facilitate better analysis.

[0063] Take the POE fragments or particle samples to be tested, add an appropriate amount of internal standard solution, and perform high-resolution gas chromatography-mass spectrometry; the high-resolution gas chromatography-mass spectrometry conditions are the same as described above and will not be repeated here.

[0064] The peak area of ​​each quantitative characteristic ion of high-resolution mass spectrometry analysis is recorded, and the content of the residual low-boiling harmful components in the POE sample to be tested is obtained according to the mass-peak area standard curve of the residual low-boiling harmful components.

[0065] The present invention adopts a static headspace sampling method for analysis, which avoids cumbersome pre-treatment processes, saves reagents, is simple and easy to operate, saves time, and is fast and efficient.

[0066] The present invention establishes for the first time a quantitative method for determining residual low-boiling harmful components in POE materials by a high-resolution gas chromatography-mass spectrometry internal standard quantitative method. This method realizes accurate, rapid and efficient analysis of the content of residual low-boiling harmful components in POE materials, and provides strong analytical technical support for effectively monitoring the content of residual low-boiling harmful components in POE materials to guide the optimization of production processes.

[0067] The present invention provides a method for detecting residual low-boiling harmful components in POE materials, comprising: A) preparing a standard curve solution from a mixed standard solution; mixing the standard curve solution and the internal standard solution, placing them in a static headspace sampler, using HS-GC-MS for detection, and using the internal standard method to draw a mass-peak area standard curve of residual low-boiling harmful components; B) taking a POE sample to be tested and mixing the internal standard solution, placing them in a static headspace sampler, using HS-GC-MS for detection, and calculating the content of each residual low-boiling harmful component according to the peak area of ​​each harmful component combined with the mass-peak area standard curve of the residual low-boiling harmful component; the chromatographic column of the HS-GC-MS is dimethylpolysiloxane as a stationary phase. The present invention performs high-resolution gas chromatography-mass spectrometry analysis on the residual low-boiling harmful components and performs mass spectrometry analysis on each mass spectrum peak, thereby being able to accurately quantitatively analyze the residual low-boiling harmful components in the POE material. The detection method provided by the present invention does not require pre-treatment of the sample to be tested, thereby realizing simple, rapid and accurate quantitative analysis of the residual low-boiling harmful components in the POE material, with good precision and high recovery rate. This method has high accuracy, good reproducibility, high precision, simple operation, and greatly shortens the analysis time.

[0068] In order to further illustrate the present invention, a method for detecting residual low-boiling harmful components in a POE material provided by the present invention is described in detail below in conjunction with examples.

[0069] Example 1

[0070] There is a batch of 1,000 kg of newly produced POE block products in the production workshop, and the content of residual low-boiling harmful components in the POE material needs to be tested.

[0071] The gas phase conditions used in the high-resolution gas chromatography-mass spectrometry analysis were as follows: injection port: 250°C; split ratio 5:1; column flow rate: 0.8 ml / min; column box temperature: initial temperature 50°C, heated to 80°C at a rate of 10°C / min, then heated to 125°C at a rate of 1.5°C / min, and finally heated to 200°C at a rate of 25°C / min, and maintained for 5 min; chromatographic column: Agilent 19091S-001, HP-PONA, chromatographic column specifications: 50m×200μm×0.50μm (temperature range -60~325 / 350°C); static headspace injector conditions were as follows: heating box: 130°C; quantitative loop: 135°C; transfer line: 140°C; GC cycle time: 55min; equilibrium time: 30min, and the injection volume was 1 ml each time under these instrument conditions.

[0072] The mass spectrometry conditions used for high-resolution mass spectrometry analysis were: ion source: EI; ion source temperature: 200°C; transfer line: 280°C; quadrupole temperature: 150°C;

[0073] Agilent 7250GC-QTOF high-resolution gas chromatography-mass spectrometry was used for detection and internal standard quantitative analysis. The specific steps included:

[0074] (1) Preparation of standard curve solution: First, prepare the mixed standard solution mother solution. Accurately weigh the following: 8.7 mg of n-hexane, 5.2 mg of benzene, 9.9 mg of cyclohexane, 7.3 mg of toluene, 22.0 mg of 1-octene, 6.6 mg of ethylbenzene, 6.7 mg of p-xylene, 7.0 mg of styrene, 7.3 mg of o-xylene, and 14.7 mg of methylcyclohexane in a 10 ml volumetric flask, and dissolve them in NMP to the mark. Then, accurately transfer 5.00 ml of the mixed standard solution mother solution to a 50 ml volumetric flask, dissolve them in NMP to the mark, and obtain the standard curve solution to be tested.

[0075] (2) Prepare internal standard solution: Accurately weigh 0.0860 g of isopropanol into a 100 ml volumetric flask and dilute to the mark with NMP.

[0076] (3) Accurately pipette 0.10 ml of the standard curve solution to be tested into a headspace bottle, and accurately pipette 50.0 ul of the internal standard solution, seal it with a cap, and place it in a static headspace injector for high-resolution gas chromatography-mass spectrometry. Record the peak area of ​​each quantitative characteristic ion, and use the internal standard method to draw a mass-peak area standard curve of the residual low-boiling harmful components, such as Figure 1As shown, the regression equation of the internal standard curve of n-hexane is obtained: Y = 3.4337X; the regression equation of the internal standard curve of benzene is obtained: Y = 6.1323X; the regression equation of the internal standard curve of cyclohexane is obtained: Y = 4.5485X; the regression equation of the internal standard curve of methylcyclohexane is obtained: Y = 4.8723X; the regression equation of the internal standard curve of toluene is obtained: Y = 5.0952X; the regression equation of the internal standard curve of 1-octene is obtained: Y = 3.561 0X; the regression equation of the internal standard curve of ethylbenzene is obtained: Y=5.6770X; the internal standard curve of p-xylene is obtained: Y=5.5064X; the internal standard curve of styrene is obtained: Y=4.1853X; the internal standard curve of o-xylene is obtained: Y=4.9181X; wherein y is the peak area ratio, that is, the ratio of the peak area of ​​the residual low-boiling harmful components to the peak area of ​​the internal standard isopropanol; x is the mass ratio, that is, the ratio of the mass of the residual low-boiling harmful components to the mass of the internal standard isopropanol.

[0077] (4) Take the POE block solid and cut it into 0.20 cm*0.20 cm fragments with scissors, accurately weigh 1.5010 g of the POE fragment sample to be tested, add 50.0 ul of the internal standard solution, seal it with a cover, place it in a static headspace sampler, perform static headspace-high resolution gas chromatography-mass spectrometry, record the peak area of ​​each quantitative characteristic ion, and obtain the content of the residual low-boiling harmful components in the POE block product to be tested according to the mass-peak area standard curve of the residual low-boiling harmful components in step (3).

[0078] (5) Calculation of the content of residual low-boiling harmful components in POE bulk products

[0079] The mass content of n-hexane is: C = 43Y / 3.4337m 样 ;

[0080] The mass content of benzene is: C = 43Y / 6.1323m 样 ;

[0081] The mass content of cyclohexane is: C = 43Y / 4.5485m 样 ;

[0082] The mass content of methylcyclohexane is: C = 43Y / 4.8723m 样 ;

[0083] The mass content of toluene is: C = 43Y / 5.0952m 样 ;

[0084] The mass content of 1-octene is: C = 43Y / 3.5610m 样 ;

[0085] The mass content of ethylbenzene is: C = 43Y / 5.6770m 样 ;

[0086] The mass content of paraxylene is: C = 43Y / 5.5064m 样 ;

[0087] The mass content of styrene is: C = 43Y / 4.1853m 样 ;

[0088] The mass content of o-xylene is: C = 43Y / 4.9181m 样 ;

[0089] Where, C is the mass content of the residual low-boiling harmful components in the POE sample to be tested, mg / kg; Y is the peak area ratio, that is, the ratio of the peak area of ​​the residual low-boiling harmful components to the peak area of ​​the internal standard isopropanol; m 样 is the mass of the POE sample to be tested, g.

[0090] After calculation, the mass content of each residual low-boiling harmful component in the POE block product to be tested is shown in Table 1. Figure 2 This is the total ion current chromatogram of the sample in Example 1 of the present invention.

[0091] Table 1

[0092]

[0093] Example 2

[0094] There is a batch of 800 kg of POE crude block products in the production workshop, and the content of residual low-boiling harmful components in the POE crude block products needs to be tested.

[0095] The gas phase conditions used for high-resolution gas chromatography-mass spectrometry are as follows: injection port: 250°C; split ratio 5:1; column flow rate: 0.8 ml / min; column box temperature: initial temperature 50°C, heating to 80°C at a rate of 10°C / min, then heating to 125°C at a rate of 1.5°C / min, and finally heating to 200°C at a rate of 25°C / min, and maintaining for 5 min; chromatographic column: Agilent 19091S-001, HP-PONA, chromatographic column specifications: 50m×200μm×0.50μm (temperature range -60~325 / 350°C); static headspace injector conditions are as follows:

[0096] Heating box: 130℃; quantitative loop: 135℃; transfer line: 140℃; GC cycle time: 55min; equilibrium time: 30min. Under this instrument condition, the injection volume is 1ml each time.

[0097] The mass spectrometry conditions used for high-resolution mass spectrometry analysis were: ion source: EI; ion source temperature: 200°C; transfer line: 280°C; quadrupole temperature: 150°C;

[0098] Agilent 7250GC-QTOF high-resolution gas chromatography-mass spectrometry was used for detection and internal standard quantitative analysis. The specific steps included:

[0099] (1) Preparation of standard curve solution: First, prepare the mixed standard solution mother solution. Accurately weigh the following: 8.7 mg of n-hexane, 5.2 mg of benzene, 9.9 mg of cyclohexane, 7.3 mg of toluene, 22.0 mg of 1-octene, 6.6 mg of ethylbenzene, 6.7 mg of p-xylene, 7.0 mg of styrene, 7.3 mg of o-xylene, and 14.7 mg of methylcyclohexane in a 10 ml volumetric flask, and dissolve them in NMP to the mark. Then, accurately transfer 5.00 ml of the mixed standard solution mother solution to a 50 ml volumetric flask, dissolve them in NMP to the mark, and obtain the standard curve solution to be tested.

[0100] (2) Prepare internal standard solution: Accurately weigh 0.0860 g of isopropanol into a 100 ml volumetric flask and dilute to the mark with NMP.

[0101] (3) Accurately pipette 0.10 ml of the standard curve solution to be tested into a headspace bottle, and accurately pipette 50.0 ul of the internal standard solution, seal it with a cap, and place it in a static headspace injector for high-resolution gas chromatography-mass spectrometry. Record the peak area of ​​each quantitative characteristic ion, and use the internal standard method to draw a mass-peak area standard curve of the residual low-boiling harmful components, such as Figure 1 As shown, the regression equation of the internal standard curve of n-hexane is obtained: Y = 3.4337X; the regression equation of the internal standard curve of benzene is obtained: Y = 6.1323X; the regression equation of the internal standard curve of cyclohexane is obtained: Y = 4.5485X; the regression equation of the internal standard curve of methylcyclohexane is obtained: Y = 4.8723X; the regression equation of the internal standard curve of toluene is obtained: Y = 5.0952X; the regression equation of the internal standard curve of 1-octene is obtained: Y = 3.561 0X; the regression equation of the internal standard curve of ethylbenzene is obtained: Y=5.6770X; the internal standard curve of p-xylene is obtained: Y=5.5064X; the internal standard curve of styrene is obtained: Y=4.1853X; the internal standard curve of o-xylene is obtained: Y=4.9181X; wherein y is the peak area ratio, that is, the ratio of the peak area of ​​the residual low-boiling harmful components to the peak area of ​​the internal standard isopropanol; x is the mass ratio, that is, the ratio of the mass of the residual low-boiling harmful components to the mass of the internal standard isopropanol.

[0102] (4) Take the crude POE block product and cut it into 0.20 cm*0.20 cm fragments with scissors, accurately weigh 1.5010 g of the POE fragment sample to be tested, add 50.0 ul of the internal standard solution, seal it with a cover, place it in a static headspace sampler, perform static headspace-high resolution gas chromatography-mass spectrometry, record the peak area of ​​each quantitative characteristic ion, and obtain the content of the residual low-boiling harmful components in the POE block product to be tested according to the mass-peak area standard curve of the residual low-boiling harmful components in step (3).

[0103] (5) Calculation of the content of residual low-boiling harmful components in POE crude block product

[0104] The mass content of n-hexane is: C = 43Y / 3.4337m 样 ;

[0105] The mass content of benzene is: C = 43Y / 6.1323m 样 ;

[0106] The mass content of cyclohexane is: C = 43Y / 4.5485m 样 ;

[0107] The mass content of methylcyclohexane is: C = 43Y / 4.8723m 样 ;

[0108] The mass content of toluene is: C = 43Y / 5.0952m 样 ;

[0109] The mass content of 1-octene is: C = 43Y / 3.5610m 样 ;

[0110] The mass content of ethylbenzene is: C = 43Y / 5.6770m 样 ;

[0111] The mass content of paraxylene is: C = 43Y / 5.5064m 样 ;

[0112] The mass content of styrene is: C = 43Y / 4.1853m 样 ;

[0113] The mass content of o-xylene is: C = 43Y / 4.9181m 样 ;

[0114] Wherein, C is the mass content of residual low-boiling harmful components in the POE sample to be tested, mg / kg; Y is the peak area ratio, that is, the ratio of the peak area corresponding to the residual low-boiling harmful components to the peak area of ​​the internal standard isopropanol; m is the mass of the POE sample to be tested, g.

[0115] After calculation, the mass content of each residual low-boiling harmful component in the crude POE block product to be tested is shown in Table 2.

[0116] Table 2

[0117]

[0118] Example 3

[0119] There is a batch of 500 kg of POE film products in the production workshop, and the content of residual low-boiling harmful components in the POE film products needs to be tested.

[0120] The gas phase conditions used for high-resolution gas chromatography-mass spectrometry are as follows: injection port: 250°C; split ratio 5:1; column flow rate: 0.8 ml / min; column box temperature: initial temperature 50°C, heating to 80°C at a rate of 10°C / min, then heating to 125°C at a rate of 1.5°C / min, and finally heating to 200°C at a rate of 25°C / min, and maintaining for 5 min; chromatographic column: Agilent 19091S-001, HP-PONA, chromatographic column specifications: 50m×200μm×0.50μm (temperature range -60~325 / 350°C); static headspace injector conditions are as follows:

[0121] Heating box: 130℃; quantitative loop: 135℃; transfer line: 140℃; GC cycle time: 55min; equilibrium time: 30min. Under this instrument condition, the injection volume is 1ml each time.

[0122] The mass spectrometry conditions used for high-resolution mass spectrometry analysis were: ion source: EI; ion source temperature: 200°C; transfer line: 280°C; quadrupole temperature: 150°C;

[0123] Agilent 7250GC-QTOF high-resolution gas chromatography-mass spectrometry was used for detection and internal standard quantitative analysis. The specific steps included:

[0124] (1) Preparation of standard curve solution: First, prepare the mixed standard solution mother solution. Accurately weigh the following: 8.7 mg of n-hexane, 5.2 mg of benzene, 9.9 mg of cyclohexane, 7.3 mg of toluene, 22.0 mg of 1-octene, 6.6 mg of ethylbenzene, 6.7 mg of p-xylene, 7.0 mg of styrene, 7.3 mg of o-xylene, and 14.7 mg of methylcyclohexane in a 10 ml volumetric flask, and dissolve them in NMP to the mark. Then, accurately transfer 5.00 ml of the mixed standard solution mother solution to a 50 ml volumetric flask, dissolve them in NMP to the mark, and obtain the standard curve solution to be tested.

[0125] (2) Prepare internal standard solution: Accurately weigh 0.0860 g of isopropanol into a 100 ml volumetric flask and dilute to the mark with NMP.

[0126] (3) Accurately pipette 0.10 ml of the standard curve solution to be tested into a headspace bottle, and accurately pipette 50.0 ul of the internal standard solution, seal it with a cap, and place it in a static headspace injector for high-resolution gas chromatography-mass spectrometry. Record the peak area of ​​each quantitative characteristic ion, and use the internal standard method to draw a mass-peak area standard curve of the residual low-boiling harmful components, such as Figure 1 As shown, the regression equation of the internal standard curve of n-hexane is obtained: Y = 3.4337X; the regression equation of the internal standard curve of benzene is obtained: Y = 6.1323X; the regression equation of the internal standard curve of cyclohexane is obtained: Y = 4.5485X; the regression equation of the internal standard curve of methylcyclohexane is obtained: Y = 4.8723X; the regression equation of the internal standard curve of toluene is obtained: Y = 5.0952X; the regression equation of the internal standard curve of 1-octene is obtained: Y = 3.561 0X; the regression equation of the internal standard curve of ethylbenzene is obtained: Y=5.6770X; the internal standard curve of p-xylene is obtained: Y=5.5064X; the internal standard curve of styrene is obtained: Y=4.1853X; the internal standard curve of o-xylene is obtained: Y=4.9181X; wherein y is the peak area ratio, that is, the ratio of the peak area of ​​the residual low-boiling harmful components to the peak area of ​​the internal standard isopropanol; x is the mass ratio, that is, the ratio of the mass of the residual low-boiling harmful components to the mass of the internal standard isopropanol.

[0127] (4) Take the POE film product and cut it into 0.20 cm*0.20 cm fragments with scissors, accurately weigh 1.5010 g of the POE fragment sample to be tested, add 50.0 ul of internal standard solution, seal it with a cover, place it in a static headspace sampler, perform static headspace-high resolution gas chromatography-mass spectrometry, record the peak area of ​​each quantitative characteristic ion, and obtain the content of residual low-boiling harmful components in the POE block product to be tested according to the mass-peak area standard curve of the residual low-boiling harmful components in step (3).

[0128] (5) Calculation of the content of residual low-boiling harmful components in POE film products

[0129] The mass content of n-hexane is: C = 43Y / 3.4337m 样 ;

[0130] The mass content of benzene is: C = 43Y / 6.1323m 样 ;

[0131] The mass content of cyclohexane is: C = 43Y / 4.5485m 样 ;

[0132] The mass content of methylcyclohexane is: C = 43Y / 4.8723m 样 ;

[0133] The mass content of toluene is: C = 43Y / 5.0952m 样 ;

[0134] The mass content of 1-octene is: C = 43Y / 3.5610m 样 ;

[0135] The mass content of ethylbenzene is: C = 43Y / 5.6770m 样 ;

[0136] The mass content of paraxylene is: C = 43Y / 5.5064m 样 ;

[0137] The mass content of styrene is: C = 43Y / 4.1853m 样 ;

[0138] The mass content of o-xylene is: C = 43Y / 4.9181m 样 ;

[0139] Wherein, C is the mass content of residual low-boiling harmful components in the POE sample to be tested, mg / kg; Y is the peak area ratio, that is, the ratio of the peak area corresponding to the residual low-boiling harmful components to the peak area of ​​the internal standard isopropanol; m is the mass of the POE sample to be tested, g.

[0140] After calculation, the mass content of each residual low-boiling harmful component in the POE film product to be tested is shown in Table 3.

[0141] Table 3

[0142]

[0143] Example 4

[0144] 1. Precision experiment

[0145] The sample in Example 1 was taken as the object of investigation, and 6 samples of different masses were weighed for measurement. The results are shown in Table 4. It can be seen from Table 4 that the RSD of the measurement results is less than 2.5%, indicating that the detection method described in the present invention has good precision.

[0146] Table 4 Precision test results

[0147]

[0148]

[0149] 2. Accuracy experiment

[0150] The sample in Example 3 was taken as the object of investigation. The sample was placed at 25°C and sampled and analyzed at 0h, 8h, 24h, 36h, 48h, and 72h respectively. The results are shown in Table 5. The RSD calculated from the results was less than 2.5%, indicating that the sample had good stability. Therefore, the detection method of the present invention has high accuracy.

[0151] Table 5 Stability test results

[0152]

[0153]

[0154] 3. Reproducibility experiment

[0155] The samples in Example 2 were taken as the objects of investigation, and different researchers in different laboratories carried out measurements on the same type of instrument. The results are shown in Table 6. It can be seen from Table 6 that the RSD of the two measurement results is less than 2.0%, indicating that the detection method described in the present invention has good reproducibility.

[0156] Table 6 Reproducibility test results

[0157]

[0158]

[0159] 4. Spike recovery experiment

[0160] Accurately weigh 2 portions of POE samples with known residual low-boiling harmful components in two headspace injection vials, add known standard samples of ten components of different masses into the headspace vials, and then accurately transfer 50.0ul of internal standard solution, seal it with a cap, and place it in a static headspace injector for high-resolution gas chromatography-mass spectrometry. Record the peak area of ​​each quantitative characteristic ion, calculate the measured spiked amount from the peak area, and calculate its spiked recovery (see Table 7). As can be seen from Table 7, the target recovery rate measurement values ​​are all between 85% and 100%, which meets the requirements of daily analysis and detection.

[0161] Table 7 Spiked recovery experimental results

[0162]

[0163]

[0164] 5. Using the T test method, according to all the steps of sample analysis, the spiked samples were repeatedly measured 7 times, and the detection limits of this method are shown in Table 8 below. It can be seen from Table 8 that the detection limits of each target are between 0.13 and 0.27 mg / kg, which meets the analysis requirements for residual low-boiling harmful components in POE materials.

[0165] Table 8 Detection limit experimental results

[0166] Compound (mg / kg) n-Hexane 0.22 benzene 0.15 Cyclohexane 0.27 Methylcyclohexane 0.19 Toluene 0.16 1-Octene 0.13 Ethylbenzene 0.26 p-Xylene 0.24 Styrene 0.15 o-Xylene 0.23

[0167] It can be seen from the above precision, accuracy, reproducibility and spike recovery experiments that the method for detecting residual low-boiling harmful components in a POE material described in the present invention is convenient and feasible. The method adopts internal standard quantitative analysis, has high precision, good reproducibility, high accuracy, good repeatability, simple and easy operation, does not require any pretreatment of the sample, can realize direct and rapid detection of the sample, and greatly shortens the analysis time.

[0168] Comparative Example 1

[0169] Example of selection of chromatographic program heating conditions: Initial temperature 80℃, heating to 250℃ at a rate of 15℃ / min, maintaining for 15min, the spectrum is shown in Figure 3 , Figure 3 This is the total ion current chromatogram of the sample of Comparative Example 1 of the present invention. Figure 3 It can be seen that under this temperature program, the internal standard cannot be effectively separated from the residual low-boiling harmful components in the POE material.

[0170] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for detecting residual low-boiling harmful components in POE materials, comprising: A) Prepare the standard curve solution by mixing the standard solution; The mixed standard solution is a mixed standard solution of n-hexane, benzene, cyclohexane, toluene, 1-octene, ethylbenzene, p-xylene, styrene, o-xylene, and methylcyclohexane; The standard curve solution and the internal standard solution are mixed, placed in a static headspace sampler, and detected by HS-GC-MS. The mass-peak area standard curve of the residual low-boiling harmful components is drawn by the internal standard method; B) Mix the POE sample to be tested and the internal standard solution, place them in a static headspace injector, and detect them using HS-GC-MS. The content of each residual low-boiling harmful component is calculated based on the peak area of ​​each harmful component and the mass-peak area standard curve of the residual low-boiling harmful component; the internal standard solution is an isopropanol solution; the concentration of the isopropanol solution is 0.86 mg / mL; The chromatographic column of the HS-GC-MS is based on dimethylpolysiloxane as the stationary phase; the chromatographic column of the HS-GC-MS is HP-PONA or HP-5; The programmed temperature rise of the HS-GC-MS is as follows: the initial temperature is 35°C to 50°C, the temperature is raised to 80°C at a rate of (5-10)°C / min, the temperature is then raised to 125°C at a rate of 1.5°C / min, and finally the temperature is raised to 200°C at a rate of (10-25)°C / min, and maintained for 5-6 minutes; Scanning mode: full scan mode, scanning range: 30amu~600amu; The injection port temperature of the HS-GC-MS is 220°C to 260°C; The mass spectrometry conditions of the HS-GC-MS are: The ionization source is EI source; the electron energy is 70eV; the ion source temperature is 200℃~280℃; the quadrupole temperature is 150℃~180℃; the transmission line temperature is 260~280℃; the filament current is 3~8uA; the headspace conditions are: The heating temperature of the sample bottle is 100℃~150℃; The equilibrium time is 30 to 50 minutes; The transfer line temperature was 140°C; the quantitative loop temperature was 135°C.

2. The detection method according to claim 1, characterized in that: The specifications of the chromatographic column are: 50 m×200 μm×0.50 μm.

3. The detection method according to claim 1, characterized in that: The carrier gas of the HS-GC-MS is helium; the carrier gas flow rate is 0.6-1.0 mL / min; the split ratio is (5-10):1; and the injection method is headspace injection.

4. The detection method according to claim 1, characterized in that: The POE sample to be tested is a crude product, a granular product, a block product, a film product or a competitive product obtained in the POE production process; the size of the POE sample to be tested is fragments or particles of 0.20 cm*0.20 cm.

5. The detection method according to claim 1, characterized in that: The mass-peak area standard curve of the residual low-boiling harmful components is specifically: The regression equation of the internal standard curve of n-hexane is: Y=3.4337X; the regression equation of the internal standard curve of benzene is: Y=6.1323X; the regression equation of the internal standard curve of cyclohexane is: Y=4.5485X; the regression equation of the internal standard curve of methylcyclohexane is: Y=4.8723X; the regression equation of the internal standard curve of toluene is: Y=5.0952X; the regression equation of the internal standard curve of 1-octene is: Y=3.5610X ; The regression equation of the internal standard curve of ethylbenzene is obtained: Y=5.6770X; the internal standard curve of p-xylene is obtained: Y=5.5064X; the internal standard curve of styrene is obtained: Y=4.1853X; the internal standard curve of o-xylene is obtained: Y=4.9181X; where Y is the peak area ratio, that is, the ratio of the peak area of ​​the corresponding residual low-boiling harmful components to the peak area of ​​the internal standard isopropanol; X is the mass ratio, that is, the ratio of the mass of the corresponding residual low-boiling harmful components to the mass of the internal standard isopropanol.

Images