CN115792009A - Method for determining aldehyde ketone volatile organic compounds in automotive interior parts - Google Patents
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Abstract
A method for determining aldehyde ketone volatile organic compounds in automotive interior parts relates to the technical field of accurate analysis and detection, solves the problem that acrolein and acetone are difficult to separate, and comprises the following steps: performing qualitative and quantitative analysis on each aldehyde ketone compound in the mixed standard substance solution by using an ultra-high performance liquid chromatograph and a mass spectrometer; injecting the aldehyde ketone compound mixed standard solution with different concentrations into an ultra-high performance liquid chromatograph to fit a standard working curve equation of each aldehyde ketone compound; collecting aldehyde ketone components by using a DNPH (deoxyribose nucleic acid) column to obtain a sample solution to be detected; and (3) placing the sample to be detected in an ultra-high performance liquid chromatograph to obtain a chromatogram corresponding to the sample solution, and performing analysis calculation to obtain the concentration of each aldehyde ketone compound in the sample to be detected according to the chromatogram, the qualitative analysis result and the quantitative analysis result corresponding to the sample solution and a standard working curve equation. The method realizes the separation of the acrolein and the acetone, and can quickly, accurately and sensitively perform quantitative detection.
Description
Technical Field
The invention belongs to the field of accurate analysis and detection, and particularly relates to a method for determining aldehyde ketone volatile organic compounds in automotive interior parts.
Background
With the overall and rapid development of the automobile industry, china now becomes a world major automobile manufacturing country. In recent years, the holding quantity of motor vehicles and the holding quantity of all people in China are increased rapidly, the environment pollution is brought to people while the transportation convenience and the comfortable life are brought to people, and the problem of the quality of air in a vehicle increasingly becomes the focus of attention of consumers. Pollutants in the air in the vehicle are mainly harmful substances such as VOC (volatile organic compounds) released by automotive interior materials, including volatile organic substances such as alkanes, alkenes, aromatic hydrocarbons, aldehydes or ketones, and the like, and the harmful substances are easy to gather in a relatively narrow and closed space in the vehicle, when reaching a certain concentration, people feel headache, nausea and the like in a short time, and in severe cases, twitch occurs, and the liver, kidney, brain and nervous system of people can be injured, so that the physical health of passengers is seriously harmed.
Automotive interior VOCs are widely available, and generally comprise three aspects: the release of toxic and harmful substances remained in the organic parts and the decorative materials inside the automobile, the entry of pollutants outside the automobile and the entry of toxic substances discharged by the automobile. Among them, the release of harmful substances remaining in plastic materials, surface covering materials, adhesives, and cushioning interior materials of automotive upholsteries is the most important source. In order to make the air quality in the vehicle meet the standard requirement, the VOC emission of the interior materials and parts of the vehicle is detected and controlled, and different detection means are provided for detecting different organic compounds in different vehicle enterprises. At present, the method for determining the aldehyde ketone compounds in automotive interior parts in China mainly comprises a photometric method, a Gas Chromatography (GC), a gas chromatography-mass spectrometry (GC-MS), a High Performance Liquid Chromatography (HPLC), and a high performance liquid chromatography-mass spectrometry (HPLC-MS), wherein the HPLC is a main method for analyzing the aldehyde ketone compounds due to high sensitivity and good selectivity. However, the existing method can not meet the requirements completely because of more types of aldehyde ketone compounds, similar structures and very close molecular weights.
At present, HJ/T400-2007 Standard of method for sampling and determining volatile organic compounds and aldehyde ketone substances in vehicles is applied to determination of aldehyde ketone compounds in air in vehicles in China. In appendix C of the standard, the liquid chromatography adopted for the detection of aldehyde and ketone has certain defects in the separation of aldehyde and ketone compounds, so that the conditions that acrolein and acetone cannot be effectively separated exist, and the result given by the standard is acrolein + acetone, but the content of the acrolein is not more than 0.05mg/mL specified in the judgment standard GB/T27630' evaluation guidance for air quality in passenger vehicles issued by the national ministry of environmental protection. The content of acetone is not limited, and misjudgment is easily caused. In order to achieve accurate quantification of acetone and acrolein, many researchers have focused on the separation of the pair of difficult-to-separate substances, acetone and acrolein.
Therefore, a method for measuring the aldehyde ketone volatile organic compounds in the automotive interior parts, which realizes separation of acrolein and acetone from the aspect of detection, is needed.
Disclosure of Invention
Aiming at the defects in the existing method, the invention provides a method for measuring aldehyde ketone volatile organic compounds in automotive interior parts.
A method for measuring aldehyde ketone volatile organic compounds in automotive interior parts comprises the following steps:
preparing various aldehyde ketone compound mixed standard substance solutions with different concentrations, wherein the aldehyde ketone compound mixed standard substance solution contains acetone and acrolein;
secondly, performing qualitative and quantitative analysis on each aldehyde ketone compound in the aldehyde ketone compound mixed standard substance solution by using an ultra-high performance liquid chromatograph and a triple quadrupole mass spectrometer;
step three, injecting the aldehyde ketone compound mixed standard substance solutions with different concentrations into an ultra-high performance liquid chromatograph respectively to measure the quantitative ion chromatographic peak area average value of each aldehyde ketone compound, and fitting according to the measurement result to obtain a standard working curve equation of each aldehyde ketone compound;
selecting a plastic and/or foam product with a certain volume on the automotive interior trim part, and collecting aldehyde ketone components in the plastic and/or foam product by using a DNPH pillar to obtain a sample solution to be detected;
and fifthly, placing the sample to be detected in an ultra-high performance liquid chromatograph to obtain a chromatogram corresponding to the sample solution, and performing analysis calculation according to the chromatogram corresponding to the sample solution, the qualitative and quantitative analysis results in the step two and the standard working curve equation obtained in the step three to obtain the types of the aldehyde-ketone compounds in the sample to be detected and the concentration of each aldehyde-ketone compound in the sample to be detected.
The beneficial effects of the invention are:
compared with the prior art, the invention has the beneficial effects that:
the method optimizes the liquid phase method, realizes the complete separation of acetone and acrolein, realizes the rapid, accurate and sensitive quantitative detection of various volatile aldehyde ketone compounds in the automotive interior parts, can eliminate the occurrence of false positive results in the detection process, improves the accuracy of the detection result, has low detection limit on the aldehyde ketone compounds, and has high correlation coefficient r value of a standard working curve equation;
the aldehyde-ketone compound is lack of easily ionized groups and chromophoric groups, so that the detection of a mass spectrometry method and a liquid phase method is difficult, and the method improves the detection sensitivity by performing derivatization reaction on the aldehyde-ketone compound and DNPH in the pretreatment process to introduce the easily ionized groups and the chromophoric groups;
the method can effectively reduce the background interference, minimizes the influence of the sample matrix by accurately extracting the ion pair information of the target compound, and provides an accurate way for the detection of related samples;
the method has the advantages of high sensitivity, good precision, nearly one hundred percent recovery rate and accuracy and reliability, and can accurately determine and measure the content of each aldehyde ketone compound and provide data basis for the detection of aldehyde ketone volatile compounds in the automobile by combining the discussion of the method and a specific test application and detection mode, so the method can be popularized and applied in the field of automobile parts.
Drawings
FIG. 1 is a flow chart of a method for measuring aldehyde ketone volatile organic compounds in automotive interior parts;
FIG. 2 is a condition parameter diagram of a liquid chromatograph and a triple quadrupole tandem mass spectrometer;
FIG. 3 is a graph of various parameters under mass spectrometric monitoring of 16 aldehydes and ketones;
FIG. 4 is a standard graph of 16 aldone compounds;
FIG. 5 is a quantitative ion chromatogram (20 ng/ml) of 16 kinds of aldehyde ketone compounds;
FIG. 6 is an enlarged view of the quantitative ion chromatogram of 20ng/ml acrolein and acetonide;
FIG. 7 is a schematic diagram showing detection limits and quantification limits of 16 kinds of aldone compounds;
FIG. 8 is RSD values of retention time and relative peak area of 16 kinds of aldehyde-ketone compounds;
FIG. 9 is a total ion flow graph of each compound for a spiked sample (100 ng/mL);
FIG. 10 shows the recovery rates of 16 aldehydes and ketones;
FIG. 11 is a total ion flow diagram of sample 1;
FIG. 12 is a sample 2 total ion flow diagram;
FIG. 13 shows the information on the detection of 16 aldonic compounds in sample 1;
FIG. 14 shows the information on the detection of 16 aldonic compounds in sample 2.
Detailed description of the preferred embodiments
The invention is described in detail below with reference to the accompanying drawings.
A method for measuring aldehyde ketone volatile organic compounds in automotive interior parts, as shown in figure 1, comprises the following steps:
preparing various aldehyde ketone compound mixed standard substance solutions with different concentrations, wherein the aldehyde ketone compound mixed standard substance solution contains acetone and acrolein;
secondly, performing qualitative and quantitative analysis on each aldehyde ketone compound in the aldehyde ketone compound mixed standard substance solution by using an ultra-high performance liquid chromatograph and a triple quadrupole mass spectrometer;
injecting a mixed standard solution of aldehyde ketone compounds with a certain concentration into an ultra-high performance liquid chromatograph, detecting all aldehyde ketone compounds separated from the ultra-high performance liquid chromatograph by a triple quadrupole mass spectrometer, obtaining ion peak areas and retention time according to the number of characteristic ion pairs of each aldehyde ketone compound and the peak emergence sequence of each aldehyde ketone compound collected by the triple quadrupole mass spectrometer, and carrying out qualitative and quantitative analysis on each aldehyde ketone compound through the qualitative ion peak areas and the quantitative ion peak areas of each aldehyde ketone compound;
step three, injecting the aldehyde ketone compound mixed standard substance solutions with different concentrations into an ultra-high performance liquid chromatograph respectively to measure the quantitative ion chromatographic peak area average value of each aldehyde ketone compound, and fitting according to the measurement result to obtain a standard working curve equation of each aldehyde ketone compound;
selecting a plastic and/or foam product with a certain volume on the automotive interior trim part, and collecting aldehyde ketone components in the plastic and/or foam product by using a DNPH pillar to obtain a sample solution to be detected;
the method specifically comprises the following steps: selecting a plastic or foam product with a certain volume on an automotive interior part, filling nitrogen into a sampling bag, putting the sampling bag into an oven for balancing, connecting the sampling bag with a sampler through a DNPH pillar after balancing, collecting a certain amount of gas in the sampling bag at a certain speed by the sampler, adsorbing aldehyde-ketone components in the gas by the DNPH pillar in the process, reversely eluting the DNPH pillar with acetonitrile and collecting eluent, carrying out ultrasonic treatment on the eluent, then fixing the volume with the acetonitrile, and filtering the eluent to obtain a sample solution to be measured;
and fifthly, placing the sample to be detected in an ultra-high performance liquid chromatograph to obtain a chromatogram corresponding to the sample solution, and analyzing and calculating the types of the aldehyde-ketone compounds in the sample to be detected and the concentration of each aldehyde-ketone compound contained in the sample to be detected according to the chromatogram corresponding to the sample solution, the qualitative and quantitative analysis results in the step two and the standard working curve equation obtained in the step three.
The following provides a detailed description of the specific steps of the method for measuring aldehyde ketone volatile organic compounds in automotive interior parts according to the present invention.
The instrument selects ULC510 ultra-high performance liquid chromatograph (specifically provided with a binary ultra-high pressure infusion pump, an ultra-high pressure automatic sample injector and a column oven), EXPEC5210 triple quadrupole tandem mass spectrometer, a sampler (QC-6H), a Tedlar sampling bag (10L) and a DNPH solid phase extraction column (200mg, 3 mL), high-purity nitrogen (the purity phi is not less than 99.999%), and phenylhydrazone mixture liquid (M-1004-10X), the reagents used in the method are analytically pure, and the water is primary water specified in GB/T6682.
Preparing a mixed standard solution: the phenylhydrazone mixture standard solution is used for obtaining aldehyde ketone compound mixed standard solution, the phenylhydrazone mixture standard stock solution is moved into a 10mL volumetric flask, acetonitrile is used for diluting and fixing the volume, and a series of 16 aldehyde ketone compound mixed standard solutions (such as 1ng/mL, 2ng/mL, 5ng/mL, 10ng/mL, 20ng/mL, 50ng/mL, 100ng/mL and 200 ng/mL) with a series of concentrations are obtained (based on aldehyde ketone content).
The method comprises the steps of collecting samples by adopting a bag method, selecting plastic and/or foam products with a certain volume on the automotive upholstery, putting the foam products and/or the plastic products cut into a certain volume into a 10L sampling bag, quantitatively filling 4L of high-purity nitrogen, and then placing the sampling bag in an oven for balancing, wherein the temperature of the oven is 65 ℃, and the balancing time is 2 hours. The sampling bag is connected with a sampler through a DNPH small column (CleanertDNPH aldehyde ketone gas sampling small column), and gas in the sampling bag is collected at the speed of 500mL/min for 4min, so that 2L of gas is collected. The aldehyde ketone component in the gas was adsorbed by the DNPH column. And reversely eluting the DNPH small column by using 5mL of acetonitrile, collecting eluent by using a 5mL volumetric flask, putting the volumetric flask into an ultrasonic processor, carrying out ultrasonic treatment at 23 ℃ for 5min, and then carrying out volume fixing by using the acetonitrile. The eluate was filtered through a 0.45 μm filter for further use.
The condition parameters of the liquid chromatograph LC and the triple quadrupole tandem mass spectrometer MS as shown in fig. 2 were used.
Chromatographic conditions of the liquid chromatograph:
liquid chromatography column conditions: waters BEHC18 (2.1 x 100mm,1.7 um), i.e. inner diameter 2.1mm, length 100mm, particle size 1.7 μm; mobile phase A:1mmol/mol ammonium acetate/water solution; mobile phase B: acetonitrile; the flow rate is 0.5mL/min; column temperature: 40 ℃; and (3) sample introduction mode: partial loop sample injection; sample introduction volume: 10uL; operating time: and (5) 25min.
Gradient elution procedure: 0-1 min:100% by weight of A; 1-19 min:100% A-0%A; 19-20 min:0% A,100% B; 20-20.5 min:0%A-100% a; 20.5-25 min:100% by weight of A.
Mass spectrum conditions:
the operation mode is an ESI ion source negative mode (ESI electrospray ionization and ESI negative ion mode); the atomized gas flow is 1.6L/min, the desolvation gas flow is 7L/min, the temperature is 300 ℃, the back blowing gas flow is 1.5L/min, the high pressure of a capillary tube is 3.8kV, the taper hole voltage parameter is 50V, the collision energy is 1-22V, the desolvation gas temperature is 300 ℃, and the collision gas flow is 0.5mL/min (5.37 e-3 Torr). The monitoring mode is multi-reaction monitoring (MRM), and parameters such as ion pair monitoring and collision voltage (CE) of each compound are shown in fig. 3. To improve the detection sensitivity, each compound can be monitored in stages according to the retention time.
Drawing 10 mu L of standard working solution with each concentration, injecting into a liquid chromatograph to record signals, taking the average area of quantitative ion chromatographic peaks (ion peaks or ion chromatographic peaks) of each target as a vertical coordinate (Y), taking the mass concentration (X) of the standard solution of the target as a horizontal coordinate, taking a weight coefficient of 1/X (namely the weight of Y value of each mass concentration is the same), and fitting by an external standard method (linear one-time fitting by the external standard method) to obtain a standard curve diagram 4 of 16 aldehyde ketone compounds, wherein the diagrams (4.1) to (4.16) respectively represent a standard curve of formaldehyde-DNPH, a standard curve of acetaldehyde-DNPH, a standard curve of acrolein-DNPH, a standard curve of acetone-DNPH, a standard curve of propionaldehyde-DNPH, a standard curve of crotonaldehyde-DNPH, a standard curve of methylacrolein-DNPH, a standard curve of butanone-DNPH, a standard curve of butyraldehyde-DNPH, a standard curve of benzaldehyde-DNPH, a standard curve of cyclohexanone-DNPH, a standard curve of benzaldehyde-DNPH, a standard curve of benzaldehyde-DNPH, a standard PH, a standard curve of DNPH, a standard PH of DNPH, a standard curve of benzaldehyde-DNPH, a standard PH, a standard curve of DNPH, a standard PH of o-PH, a standard PH of benzaldehyde-PH, aThe line, the standard curve for m-methylbenzaldehyde-DNPH, and the standard curve for hexanal-DNPH were fitted with 7 concentrations, i.e., through 7 points. The standard working curve equation of formaldehyde is: y is 1 ＝8002.7326x 1 -2698.5247，y 1 Quantitative ion chromatogram peak area average, x, representing formaldehyde 1 Represents the concentration of a standard working solution containing formaldehyde; the standard working curve equation for acetaldehyde is: y is 2 ＝13692.0725x 2 -4364.8090，y 2 Represents the mean value of the area of the quantitative ion chromatogram peak of acetaldehyde, x 2 Represents the concentration of a standard working solution containing acetaldehyde; the standard working curve equation for acrolein is: y is 3 ＝7293.1109x 3 -3448.6799，y 3 Means for quantitative ion chromatogram peak area average, x of acrolein 3 Represents the concentration of a standard working solution containing acrolein; the standard working curve equation for acetone is: y is 4 ＝10405.9449x 4 -2913.6042，y 4 Denotes the average value of the peak areas of the quantitative ion chromatograms for acetone, x 4 Represents the concentration of a standard working solution containing acetone; the standard working curve equation for propionaldehyde is: y is 5 ＝10826.0506x 5 -3429.1090，y 5 Represents the average of the quantitative ion chromatographic peak areas, x, of propionaldehyde 5 Represents the concentration of a standard working solution containing propionaldehyde; the standard working curve equation of crotonaldehyde is as follows: y is 6 ＝10402.5020x 6 -2476.6564，y 6 Represents the average value of the quantitative ion chromatographic peak area, x, of crotonaldehyde 6 Representing the concentration of a standard working solution containing crotonaldehyde; the standard working curve equation of methacrolein is: y is 7 ＝9665.0297x 7 -3469.6454，y 7 Denotes the mean value of the quantitative ion chromatographic peak areas, x, of methacrolein 7 Represents the concentration of a standard working solution containing methacrolein; the standard working curve equation of butanone is as follows: y is 8 ＝14080.9095x 8 -2619.7646，y 8 Quantitative ion chromatogram peak area average value, x, representing butanone 8 Represents the concentration of a standard working solution containing butanone; the standard working curve equation for butyraldehyde is: y is 9 ＝11018.9814x 9 -2479.9440，y 9 Representing butyraldehydeQuantification of the mean ion chromatographic peak area, x 9 Representing the concentration of a standard working solution containing butyraldehyde; the standard working curve equation of benzaldehyde is as follows: y is 10 ＝15100.2953x 10 -3208.3120，y 10 Represents the average value of the quantitative ion chromatographic peak area, x, of benzaldehyde 10 Represents the concentration of a standard working solution containing benzaldehyde; the standard working curve equation for cyclohexanone is: y is 11 ＝48416.2895x 11 -6238.8088，y 11 Means for quantitative ion chromatographic peak area average, x, of cyclohexanone 11 Represents the concentration of a standard working solution containing cyclohexanone; the standard working curve equation of valeraldehyde is as follows: y is 12 ＝28931.1192x 12 -4822.9038，y 12 Quantitative ion chromatogram peak area average, x, representing valeraldehyde 12 Represents the concentration of a standard working solution containing valeraldehyde; the standard working curve equation of p-tolualdehyde is as follows: y is 13 ＝11442.0836x 13 -1225.5610，y 13 Represents the average value of the quantitative ion chromatographic peak areas, x, of p-tolualdehyde 13 Represents the concentration of a standard working solution containing p-tolualdehyde; the standard working curve equation of o-tolualdehyde is as follows: y is 14 ＝11829.7395x 14 -3375.1592，y 14 Represents the average value of the quantitative ion chromatographic peak areas, x, of o-tolualdehyde 14 Represents the concentration of a standard working solution of o-tolualdehyde; the standard working curve equation of the m-methylbenzaldehyde is as follows: y is 15 ＝10971.2834x 15 -1396.1719，y 15 Means for quantitative ion chromatogram peak area average value, x, of m-tolualdehyde 15 Represents the concentration of a standard working solution containing m-methylbenzaldehyde; the standard working curve equation for hexanal is: y is 16 ＝49258.1944x 16 -2760.5760，y 16 Means for quantitative ion chromatogram peak area average, x of hexanal 16 Denotes the concentration of the standard working solution containing hexanal, r 1 To r 16 The fitting accuracy from formaldehyde to hexanal is respectively corresponded one by one. The correlation coefficients of the 16 aldehyde ketone compounds are all larger than 0.990, and the linear relation of a standard curve in the range of 0-200ng/mL is good. Quantitative ion chromatography overlay chart of 16 aldehyde ketone compounds in 20ng/ml standard solutionAs shown in FIG. 5 (there is some overlap between the curves for some of the aldonic compounds), it can be seen that the retention times of acrolein and acetone are 10.7min and 11.05min, respectively (FIG. 6), which can be quantified separately, and the method realizes complete separation of the pair of hardly separable substances, acetone and acrolein.
The limit of quantitation was calculated as S/N =10 and the limit of detection was calculated as S/N =3, with S representing the peak height and N representing the baseline noise, as shown in fig. 7. The detection limit of each compound is 0.0018-0.0081 ng/mL, the quantification limit is 0.058-0.27ng/mL, and the method is suitable for measuring volatile organic compounds, namely aldehyde ketone, in low-concentration automotive upholsteries and can fully meet the requirements of monitoring aldehyde ketone compounds in the evaluation guidelines of the quality of air in passenger vehicles.
Preparing 16 aldehyde ketone mixed control solutions with the concentrations of 5ng/mL and 20ng/mL, continuously injecting samples for 6 times respectively, and investigating the repeatability of retention time and peak area, wherein the result is shown in figure 8, and the repeatability of 5 ng/mL: the retention time and the RSD value of the relative peak area are respectively between 0.07 percent and 0.13 percent and between 1.15 percent and 3.21 percent. Reproducibility 20 ng/ml: the retention time and the RSD value of the relative peak area are respectively between 0.09% and 0.16% and between 1.56% and 2.89%. It was found that the retention time and the relative peak area RSD of all the compounds were 3.21% or less, and the precision was good.
Taking a blank sample, adding a certain amount of aldehyde ketone compound standard substance, and pretreating with the preparation method of the test solution. And the standard adding concentration of the aldehyde ketone compounds in the blank sample matrix after pretreatment is 100ng/mL, substituting the peak area of the aldehyde ketone compounds into a standard working curve to obtain a calculated concentration, and taking the ratio of the calculated concentration to the standard adding concentration as the recovery rate. The range of the standard recovery rate of 16 targets in the standard sample is 78.5% -96.3%, the total ion flow diagram is shown in figures 9 and 10, and the precision and the accuracy can meet the measurement requirement.
The method of the invention is adopted to carry out qualitative and quantitative determination on 16 aldehyde ketone compounds released by a plastic sample 1 and a foam material sample 2 of a certain automobile interior trim part, and the total ion flow diagram is shown in figures 11 and 12. As can be seen from the results of the measurements in FIGS. 13 and 14, 16 targets were detected in both samples, with the average concentrations ranging from 1.880 to 499.061ng/mL and 2.761 to 1067.371ng/mL, respectively, and the highest concentrations of both formaldehyde and acetaldehyde, wherein the concentration of formaldehyde in the foam was higher than 1.00. Mu.g/mL.
The analytical method of the liquid chromatogram-triple quadrupole mass spectrometry can simultaneously detect 16 volatile organic compounds of aldehydes and ketones in the automotive interior. The linearity, detection limit, precision, sensitivity and the like of the method are examined, and the result shows that: the 16 aldehyde ketone compounds have good linear relation within the mass concentration range of 0-200ng/mL, and the correlation coefficients are all larger than 0.996; the detection limit and the lower limit of quantification of the method for calculating the standard solution of 2ng/mL according to S/N =10 and S/N =3 are respectively 0.0018-0.0081 ng/mL and 0.0058-0.270 ng/mL; the range of the standard recovery rate of 16 targets in the standard sample (100 ng/mg) is 78.5-96.3%; the retention time of 5ng/mg standard reference substance and the Relative Standard Deviation (RSDs) of the relative peak area are between 0.07-0.13% and 1.15-3.21%, the retention time of 20ng/mg standard reference substance and the relative standard deviation of the relative peak area are between 0.09-0.16% and 1.56-2.89%, and the precision of the method is within 2.89%; the retention time of the acrolein and the acetone is 10.7min and 11.05min respectively, and the acrolein and the acetone can be quantified respectively, so that the separation of the substances which are difficult to separate, namely the acetone and the acrolein, is realized. The method has the advantages of high sensitivity, low detection limit and accuracy and reliability. In actual samples such as foam, plastic and the like applied to automotive upholsteries, 16 targets can be detected completely, and the average concentration is respectively between 1.880-499.061ng/mg and 2.761-1067.301 ng/mg. The method can be used for quickly, accurately and sensitively quantitatively detecting various aldehyde ketone compounds in the automotive interior trim parts. Therefore, by combining the method, the content of the aldehyde ketone can be determined, and a data basis can be provided for the detection of the aldehyde ketone volatile compound in the automobile through a specific test detection mode. The invention can be popularized and used in the field of automobile part production and circulation.
The invention establishes a method for determining volatile aldehyde ketone organic matters in automotive interior parts by using an ultra-high performance liquid chromatography-triple quadrupole mass spectrometry method, and realizes rapid, accurate and sensitive quantitative detection of various volatile aldehyde ketone compounds in the automotive interior parts. Provides a clear basis for solving the detection of aldehyde ketone volatile compounds in the automobile.
In conclusion, the high performance liquid chromatography-mass spectrometry combined detection method is established for simultaneously measuring various aldehyde ketone compounds in the automotive interior parts, and accurate relative molecular mass is extracted, so that separation of acrolein and acetone which are substances difficult to separate is realized from the aspect of detection, and the high performance liquid chromatography-mass spectrometry combined detection method has important significance in achieving a good separation effect.
Compared with the prior art, the invention has the beneficial effects that:
the method is characterized in that a UPLC-MS/MS method is used for detecting volatile aldehyde ketone organic compounds in automobile interior parts for the first time, and the method is verified according to the national standard GB/T27417-2017 qualification chemical analysis method confirmation and verification guide, the detection limit of 16 aldehyde ketone compounds is far lower than the limit value requirement in the national standard GB/T27630-2011 passenger vehicle interior air quality evaluation guide, the 16 aldehyde ketone compounds are good in linearity in the detection range, the correlation coefficient R value is larger than 0.996, and the method precision is within 3.21%.
The method optimizes the liquid phase method, realizes three pairs of isomers of propionaldehyde and acetone, crotonaldehyde and methylacrolein, butyraldehyde and butanone, completely separates the completely same compounds by the detection ions, can eliminate the occurrence of false positive results in the detection process, and improves the accuracy of the detection results.
The aldehyde ketone compound is lack of easily ionized groups and chromophoric groups, so that the detection of a mass spectrometry method and a liquid phase method is difficult.
The method can effectively reduce the background interference, minimizes the influence of the sample matrix by accurately extracting the ion pair information of the target compound, and provides an accurate way for the detection of related samples.
The method has the advantages of high sensitivity, good precision, nearly one hundred percent recovery rate and accuracy and reliability, and can accurately determine and measure the content of each aldehyde ketone compound and provide data basis for the detection of aldehyde ketone volatile compounds in the automobile by combining the discussion of the method and a specific test application and detection mode, so the method can be popularized and applied in the field of automobile parts.
The invention establishes a method for measuring the aldehyde ketone volatile organic compounds in the automotive interior parts, realizes the separation of acrolein and acetone from the aspect of detection by extracting accurate relative molecular mass, has important significance for achieving good separation effect, realizes the rapid, accurate and sensitive quantitative detection of various volatile aldehyde ketone compounds in the automotive interior parts, and provides clear basis for solving the problem of detection of the aldehyde ketone volatile organic compounds in the automobile.
The above description is only a preferred example of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like of the present invention shall be included in the protection scope of the present invention.
Claims (10)
1. A method for measuring aldehyde ketone volatile organic compounds in automotive interior parts is characterized by comprising the following steps:
preparing various aldehyde ketone compound mixed standard substance solutions with different concentrations, wherein the aldehyde ketone compound mixed standard substance solution contains acetone and acrolein;
performing qualitative and quantitative analysis on each aldehyde ketone compound in the aldehyde ketone compound mixed standard substance solution by using an ultra-high performance liquid chromatograph and a triple quadrupole mass spectrometer;
step three, injecting the aldehyde ketone compound mixed standard substance solutions with different concentrations into an ultra-high performance liquid chromatograph respectively to measure the quantitative ion chromatographic peak area average value of each aldehyde ketone compound, and fitting according to the measurement result to obtain a standard working curve equation of each aldehyde ketone compound;
selecting a plastic and/or foam product with a certain volume on the automotive interior trim part, and collecting aldehyde ketone components in the plastic and/or foam product by using a DNPH pillar to obtain a sample solution to be detected;
and fifthly, placing the sample to be detected in an ultra-high performance liquid chromatograph to obtain a chromatogram corresponding to the sample solution, and performing analysis calculation according to the chromatogram corresponding to the sample solution, the qualitative and quantitative analysis results in the step two and the standard working curve equation obtained in the step three to obtain the types of the aldehyde-ketone compounds in the sample to be detected and the concentration of each aldehyde-ketone compound in the sample to be detected.
2. The method for determining the aldehyde ketone volatile organic compounds in the automotive interior part according to claim 1, wherein the second step is specifically as follows: injecting the aldehyde ketone compound mixed standard solution with a certain concentration into an ultra-high performance liquid chromatograph, detecting all aldehyde ketone compounds separated from the ultra-high performance liquid chromatograph by a triple quadrupole mass spectrometer, obtaining ion peak areas and retention time according to the number of characteristic ion pairs of each aldehyde ketone compound and the appearance sequence of each aldehyde ketone compound collected by the triple quadrupole mass spectrometer, and carrying out qualitative and quantitative analysis on each aldehyde ketone compound through the qualitative ion peak area and the quantitative ion peak area of each aldehyde ketone compound.
3. The method for determining the aldehyde ketone volatile organic compounds in the automotive interior part according to claim 1, wherein the fourth step is specifically as follows: selecting plastic and/or foam products with a certain volume on an automotive interior part, filling nitrogen into a sampling bag, putting the sampling bag into an oven for balancing, connecting the sampling bag with a sampler through a DNPH pillar after balancing, collecting a certain amount of gas in the sampling bag at a certain speed by the sampler, adsorbing aldehyde-ketone components in the gas by the DNPH pillar in the process, reversely eluting the DNPH pillar with acetonitrile and collecting eluent, carrying out ultrasonic treatment on the eluent, then fixing the volume with the acetonitrile, and filtering the eluent to obtain a sample solution to be measured.
4. The method for detecting the aldone volatile organic compounds in the automotive interior, according to claim 3, wherein the volume of the sampling bag filled with nitrogen is 4L, the temperature of the oven is 65 ℃, the equilibration time is 2h, the sampler collects the gas in the sampling bag at the speed of 500mL/min for 4min, the acetonitrile of the reverse elution DNPH small column is 5mL, and the filtration is the filtration with a 0.45 μm filter membrane.
5. The method for measuring the aldehyde ketone volatile organic compounds in the automotive interior part according to claim 1, wherein the concentrations of the aldehyde ketone compound mixed standard solution comprise: 1ng/mL, 2ng/mL, 5ng/mL, 10ng/mL, 20ng/mL, 50ng/mL, 100ng/mL.
6. The method for measuring the aldehyde ketone volatile organic compounds in the automotive interior part according to claim 1, wherein the chromatographic conditions of the ultra-high performance liquid chromatograph are as follows:
chromatographic column conditions: waters BEH C18, 2.1mm internal diameter, 100mm length, 1.7 μm particle size; mobile phase A:1mmol/mol ammonium acetate/water solution; mobile phase B: acetonitrile; the flow rate is 0.5mL/min; column temperature: 40 ℃; and (3) sample introduction mode: partial loop sample introduction; sample introduction volume: 10uL; operating time: and (5) 25min.
Gradient elution procedure: 0-1 min:100% by weight of A; 1-19 min:100% A-0%A; 19-20 min:0% A,100% B; 20-20.5 min:0%A-100% a; 20.5-25 min:100% by weight of A.
7. The method for determining the aldehyde ketone volatile organic compounds in the automotive interior part according to claim 1, wherein the mass spectrum conditions of the triple quadrupole mass spectrometer are as follows: ESI ion source negative mode; the atomized gas flow is 1.6L/min, the desolventizing gas flow is 7L/min, the temperature is 300 ℃, the back blowing gas flow is 1.5L/min, the high pressure of the capillary tube is 3.8kV, the taper hole voltage parameter is 50V, and the collision energy is 1-22V.
8. The method for detecting aldehyde ketone volatile organic compounds in automotive interior parts according to claim 1, wherein the standard working curve equation is a linear equation.
9. The method according to claim 1, wherein the aldehyde ketone compound mixed standard solution further comprises formaldehyde, acetaldehyde, acetone, crotonaldehyde, methacrolein, butanone, butyraldehyde, valeraldehyde, cyclohexanone, benzaldehyde, o-tolualdehyde, m-tolualdehyde, p-tolualdehyde, and hexanal.
10. The method for determining the aldehyde ketone volatile organic compounds in the automotive interior part according to claim 9, wherein the standard working curve equation is specifically as follows: the standard working curve equation of formaldehyde is: y is 1 ＝8002.7326x 1 -2698.5247，y 1 Represents the average value of the peak areas of quantitative ion chromatograms of formaldehyde, x 1 Represents the concentration of a standard working solution containing formaldehyde; the standard working curve equation for acetaldehyde is: y is 2 ＝13692.0725x 2 -4364.8090，y 2 Represents the mean value of the area of the quantitative ion chromatogram peak of acetaldehyde, x 2 Represents the concentration of a standard working solution containing acetaldehyde; the standard working curve equation for acrolein is: y is 3 ＝7293.1109x 3 -3448.6799，y 3 Means for quantitative ion chromatogram peak area average, x of acrolein 3 Represents the concentration of a standard working solution containing acrolein; the standard working curve equation for acetone is: y is 4 ＝10405.9449x 4 -2913.6042，y 4 Means for quantitative ion chromatogram peak area average, x, of acetone 4 Represents the concentration of a standard working solution containing acetone; the standard working curve equation for propionaldehyde is: y is 5 ＝10826.0506x 5 -3429.1090，y 5 Quantitative ion chromatogram peak area average, x, representing propionaldehyde 5 Represents the concentration of a standard working solution containing propionaldehyde; the standard working curve equation of crotonaldehyde is as follows: y is 6 ＝10402.5020x 6 -2476.6564，y 6 Represents the average value of the quantitative ion chromatographic peak area, x, of crotonaldehyde 6 Representing the concentration of a standard working solution containing crotonaldehyde; the standard working curve equation of methacrolein is: y is 7 ＝9665.0297x 7 -3469.6454，y 7 Denotes the mean value of the quantitative ion chromatographic peak areas, x, of methacrolein 7 Represents the concentration of a standard working solution containing methacrolein; the standard working curve equation of butanone is as follows: y is 8 ＝14080.9095x 8 -2619.7646，y 8 Represents the average value of the peak area of the quantitative ion chromatogram of butanone, x 8 Represents the concentration of a standard working solution containing butanone; the standard working curve equation for butyraldehyde is: y is 9 ＝11018.9814x 9 -2479.9440，y 9 Denotes the quantitative ion chromatogram peak area average, x, of butyraldehyde 9 Representing the concentration of a standard working solution containing butyraldehyde; the standard working curve equation of benzaldehyde is as follows: y is 10 ＝15100.2953x 10 -3208.3120，y 10 Represents the average value of the quantitative ion chromatographic peak area, x, of benzaldehyde 10 Represents the concentration of a standard working solution containing benzaldehyde; the standard working curve equation for cyclohexanone is: y is 11 ＝48416.2895x 11 -6238.8088，y 11 Means for quantitative ion chromatographic peak area average, x, of cyclohexanone 11 Represents the concentration of a standard working solution containing cyclohexanone; the standard working curve equation of valeraldehyde is as follows: y is 12 ＝28931.1192x 12 -4822.9038，y 12 Quantitative ion chromatogram peak area average, x, representing valeraldehyde 12 Represents the concentration of a standard working solution containing valeraldehyde; the standard working curve equation of p-tolualdehyde is as follows: y is 13 ＝11442.0836x 13 -1225.5610，y 13 Quantitative ion chromatogram peak area average value, x, representing p-tolualdehyde 13 Represents the concentration of a standard working solution containing p-tolualdehyde; the standard working curve equation of o-tolualdehyde is: y is 14 ＝11829.7395x 14 -3375.1592，y 14 Represents the average value of the quantitative ion chromatographic peak areas, x, of o-tolualdehyde 14 Represents the concentration of a standard working solution of o-tolualdehyde; standard working curve of m-tolualdehydeThe equation is:
y 15 ＝10971.2834x 15 -1396.1719，y 15 means for quantitative ion chromatogram peak area average value, x, of m-tolualdehyde 15 Represents the concentration of a standard working solution containing m-methylbenzaldehyde; the standard working curve equation for hexanal is: y is 16 ＝49258.1944x 16 -2760.5760，y 16 Means for quantitative ion chromatogram peak area average, x of hexanal 16 The concentration of the standard working solution containing hexanal is indicated.
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