CN114002348A - Method for detecting content of terephthalonitrile or isophthalonitrile and application thereof - Google Patents
Method for detecting content of terephthalonitrile or isophthalonitrile and application thereof Download PDFInfo
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- CN114002348A CN114002348A CN202111256071.4A CN202111256071A CN114002348A CN 114002348 A CN114002348 A CN 114002348A CN 202111256071 A CN202111256071 A CN 202111256071A CN 114002348 A CN114002348 A CN 114002348A
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- terephthalonitrile
- isophthalonitrile
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- LAQPNDIUHRHNCV-UHFFFAOYSA-N isophthalonitrile Chemical compound N#CC1=CC=CC(C#N)=C1 LAQPNDIUHRHNCV-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 64
- 238000001514 detection method Methods 0.000 claims abstract description 91
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000000523 sample Substances 0.000 claims abstract description 83
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- 239000012159 carrier gas Substances 0.000 claims description 12
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 4
- 239000012965 benzophenone Substances 0.000 description 4
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 3
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- TXRVDQMSXQKAPG-UHFFFAOYSA-N 2,3,5,6-tetrachlorobenzene-1,4-dicarbonitrile Chemical compound ClC1=C(Cl)C(C#N)=C(Cl)C(Cl)=C1C#N TXRVDQMSXQKAPG-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
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- BKFXSOCDAQACQM-UHFFFAOYSA-N 3-chlorophthalic acid Chemical compound OC(=O)C1=CC=CC(Cl)=C1C(O)=O BKFXSOCDAQACQM-UHFFFAOYSA-N 0.000 description 1
- 206010008132 Cerebral thrombosis Diseases 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005747 Chlorothalonil Substances 0.000 description 1
- 201000001429 Intracranial Thrombosis Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
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- 229910052801 chlorine Inorganic materials 0.000 description 1
- CRQQGFGUEAVUIL-UHFFFAOYSA-N chlorothalonil Chemical compound ClC1=C(Cl)C(C#N)=C(Cl)C(C#N)=C1Cl CRQQGFGUEAVUIL-UHFFFAOYSA-N 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
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- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
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Images
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/86—Signal analysis
- G01N30/8675—Evaluation, i.e. decoding of the signal into analytical information
- G01N30/8679—Target compound analysis, i.e. whereby a limited number of peaks is analysed
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N2030/042—Standards
- G01N2030/045—Standards internal
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/065—Preparation using different phases to separate parts of sample
Abstract
The invention relates to a method for detecting the content of terephthalonitrile or isophthalonitrile and application thereof, wherein the method for detecting the content of terephthalonitrile or isophthalonitrile comprises the following steps: and respectively carrying out gas chromatography detection on a standard sample and a sample of the object to be detected and a standard sample solution and a sample solution prepared from an internal standard substance, and calculating according to a detection result to obtain the content of the object to be detected, wherein the object to be detected comprises terephthalonitrile or isophthalonitrile. The method creatively uses the naphthalene as an internal standard substance, and is favorable for quick detection and accurate quantification of the terephthalonitrile or the isophthalonitrile. The detection method provided by the invention has the advantages of high analysis speed, good separation effect, good repeatability, high accuracy, simplicity, convenience and economy, and has important application value in the aspect of pesticide detection or medicine detection.
Description
Technical Field
The invention belongs to the field of analytical chemistry, and particularly relates to a gas chromatography detection method for the content of terephthalonitrile or isophthalonitrile and application thereof, in particular to a rapid and accurate gas chromatography detection method for the content of terephthalonitrile or isophthalonitrile and application thereof.
Background
Terephthalonitrile, white needle crystals or powder, insoluble in water, slightly soluble in ethanol, acetone and hot ether, soluble in hot benzene and hot acetic acid. Terephthalonitrile is an important organic intermediate, can synthesize a series of fine chemical products, and is widely applied to the fields of pesticides, medicines, dyes, spices and resins. The p-xylylenediamine prepared by the hydrogenation of the terephthalonitrile is an important raw material of polyamide and is also an epoxy resin curing agent with excellent performance; the tetrachloroterephthalonitrile prepared by the reaction of the tetrachloroterephthalonitrile with chlorine can be used for synthesizing herbicide chlorophthalic acid, pyrethroid insecticides and medicines for treating cerebral thrombosis; the terephthalic acid obtained by hydrolysis can be used for producing polyester resin, polyester fiber, films, insulating paint, engineering plastics, plasticizers and the like. Isophthalonitrile, white needle crystals or powder, dissolved in benzene, ether, hot ethanol and chloroform, slightly soluble in water. The m-phthalonitrile is also an important organic intermediate, and m-xylylenediamine prepared by hydrogenation is an epoxy resin curing agent with excellent performance and can also be used as other fine chemical raw materials; the pesticide chlorothalonil prepared by chlorination reaction has the advantages of high efficiency, broad spectrum, low toxicity and low residue. Due to the wide application of the terephthalonitrile and the isophthalonitrile, the demand of high-quality terephthalonitrile and isophthalonitrile in domestic and foreign markets is increased year by year in recent years, and the simple, rapid and accurate content detection method has important significance for improving the quality of terephthalonitrile and isophthalonitrile products, promoting market trade and efficient and high-quality production of downstream medicines, pesticides and other products.
At present, no national or industrial standard method exists for detecting the content of the terephthalonitrile or the isophthalonitrile, related reports of journals at home and abroad are few, and the most common methods of production enterprises and users are a liquid chromatography and a gas chromatography area percentage method. When the liquid chromatography is used for detection, the following defects exist: firstly, because the liquid-phase ultraviolet detector is suitable for detecting low-concentration solution, when the content of the main component is measured, a sample needs to be diluted for multiple times and the volume is constant to prepare a test solution with proper concentration, the operation is troublesome, and the use amount of an organic solvent is large; secondly, terephthalonitrile and isophthalonitrile are a pair of isomers which are difficult to separate from each other, in order to separate the terephthalonitrile and the isophthalonitrile better, harmful reagents such as acetonitrile and methanol are used as mobile phases, the usage amount of organic reagents is large, the environmental hazard is large, and the analysis time is long; in addition, when the liquid chromatography area percentage method is adopted for quantification, the impurity components in the sample are more, and the response values of the components under the same wavelength are greatly different, so that the error of the quantification result is larger. When gas chromatography is used for detection, the following defects currently exist: firstly, due to the non-ideal selection of chromatographic columns and chromatographic separation conditions, the isophthalonitrile and the terephthalonitrile are difficult to be completely separated, so that the quantitative accuracy is influenced; secondly, components which are not detected by the gas chromatography exist in the sample, and the difference of response values of impurity components is large, so that the quantitative error of the area percentage method is large; in addition, a few studies use an internal standard method for quantification, but because the selection of an internal standard substance is not ideal, the detection time is long, and the detection repeatability is poor due to the interference of impurity components of the sample to different degrees.
Therefore, how to provide a method for detecting the content of terephthalonitrile or isophthalonitrile, which has the advantages of good separation effect, good repeatability, high quantitative accuracy, high detection speed, simplicity, convenience and economy, becomes a problem to be solved in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for detecting the content of terephthalonitrile or isophthalonitrile and application thereof. The detection method has the advantages of high analysis speed, good separation effect, good repeatability, high accuracy, simplicity, convenience and economy, and has important application value in the aspects of pesticide detection or medicine detection.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for detecting the content of terephthalonitrile or isophthalonitrile, wherein the method comprises the following steps: and respectively carrying out gas chromatography detection on a standard sample and a sample of the object to be detected and a standard sample solution and a sample solution prepared from an internal standard substance, and calculating according to the detection result to obtain the content of the object to be detected.
The substance to be measured comprises terephthalonitrile or isophthalonitrile.
The internal standard comprises naphthalene.
The invention provides a gas chromatography internal standard quantitative method, which can be used for detecting the content of terephthalonitrile and the content of isophthalonitrile. The method creatively uses the naphthalene as the internal standard substance, compared with other internal standard substances, on one hand, the naphthalene has ideal separation degree with the terephthalonitrile or the isophthalonitrile, and in the gas chromatography detection, the naphthalene generates a peak in front of the terephthalonitrile or the isophthalonitrile and is not interfered by any impurity in a sample, thereby being beneficial to the rapid detection and accurate quantification of the terephthalonitrile or the isophthalonitrile. More importantly, the naphthalene peaks in front of the terephthalonitrile or the isophthalonitrile, so the detection can be completed in only 9min, and the detection can be completed in more than 20min by using acetophenone, diethyl phthalate and the like which are commonly used in the prior art as internal standard substances. In a word, the detection method provided by the invention greatly shortens the gas chromatography analysis time, has high analysis speed and high detection precision and accuracy, and can be applied to medicine detection or pesticide detection.
Preferably, the preparation method of the standard sample solution and the sample solution comprises the following steps:
(1) dissolving and diluting the internal standard substance by using a solvent, and performing constant volume to obtain an internal standard solution;
(2) dissolving a standard sample of an object to be detected by using an internal standard solution to obtain a standard sample solution; and dissolving the sample of the object to be detected by using the internal standard solution to obtain the sample solution.
Preferably, the solvent of step (1) comprises acetonitrile.
Compared with other solvents, the acetonitrile has good solubility to naphthalene, terephthalonitrile and isophthalonitrile as internal standard substances, and has a proper boiling point. The acetonitrile is used as a solvent, so that the prepared internal standard solution, the prepared external standard solution and the prepared sample solution can stably exist at normal temperature, and the accuracy of the detection of the content of the terephthalonitrile or the isophthalonitrile can be improved.
Preferably, the concentration of the internal standard solution in the step (1) is 8-12 mg/mL.
Preferably, the concentration of the standard sample of the object to be detected in the standard sample solution in the step (2) is 8-12 mg/mL.
Preferably, the concentration of the sample to be detected in the sample solution in the step (2) is 8-12 mg/mL.
The specific value of 8-12mg/mL can be selected from 8.0mg/mL, 8.5mg/mL, 9.0mg/mL, 10mg/mL, 10.5mg/mL, 11.0mg/mL, 11.5mg/mL or 12mg/mL, and other specific values within the numerical range can be selected at will, and are not repeated herein.
The selection of the specific concentration range can lead the concentration of the object to be detected in the standard sample solution to be consistent with that of the object to be detected in the sample solution, and simultaneously lead the chromatographic response value of the object to be detected to be close to that of the internal standard substance, thus improving the accuracy of quantification. And weighing errors can be caused by too low concentration of the solution, the sample is difficult to dissolve due to too high concentration of the solution, and the accuracy of quantification and the stability of the method are influenced due to poor stability of the solution.
Preferably, the stationary phase of the chromatographic column in the gas chromatography detection is 50% phenyl-methyl polysiloxane, for example, the types are DB-17, OV-17, HP-17, 007-17, SP-2250, RSL-300, and the like, and other types of chromatographic columns with the same stationary phase can be selected, which is not described in detail herein.
The selection of the chromatographic column stationary phase is a key choice for effectively separating the terephthalonitrile and the isophthalonitrile, and compared with other stationary phases, the specific chromatographic column stationary phase can shorten the analysis time on the premise of effectively separating the terephthalonitrile and the isophthalonitrile.
Preferably, the column temperature change process in the gas chromatography detection is as follows: the initial temperature of the column is 160-175 ℃, the initial temperature holding time of the column is 4-6min, the temperature is raised to the final temperature of 250-260 ℃ at the temperature raising rate of 30-40 ℃/min, and the final temperature holding time of the column is 3-5 min.
Specific values in the range of 160 ℃ and 175 ℃ are, for example, 160 ℃, 161 ℃, 162 ℃, 163 ℃, 164 ℃, 165 ℃, 166 ℃, 167 ℃, 168 ℃, 169 ℃, 170 ℃, 171 ℃, 172 ℃, 173 ℃, 174 ℃, 175 ℃ and the like.
The specific value of the above 4-6min is 4min, 4.2min, 4.5min, 4.7min, 5min, 5.2min, 5.5min, 5.7min, 6min, etc.
The specific value of 30-40 deg.C/min can be selected from 30 deg.C/min, 31 deg.C/min, 32 deg.C/min, 33 deg.C/min, 34 deg.C/min, 35 deg.C/min, 36 deg.C/min, 37 deg.C/min, 38 deg.C/min, 39 deg.C/min, 40 deg.C/min, etc.
The specific value in the temperature range of 250 ℃ and 260 ℃ can be selected from 250 ℃, 251 ℃, 252 ℃, 253 ℃, 254 ℃, 255 ℃, 256 ℃, 257 ℃, 258 ℃, 259 ℃, 260 ℃ and the like.
The specific value of 3-5min can be selected from 3min, 3.2min, 3.5min, 3.7min, 4min, 4.2min, 4.5min, 4.7min, 5min, etc.
Other specific point values within the above numerical ranges can be selected, and are not described in detail herein.
Preferably, the carrier gas in the gas chromatography detection comprises nitrogen.
Preferably, the flow rate of the carrier gas is 1.5-3.5mL/min, such as 1.5mL/min, 1.7mL/min, 2.0mL/min, 2.2mL/min, 2.5mL/min, 2.7mL/min, 3.0mL/min, 3.2mL/min, 3.5mL/min, and the like, and other specific points in the numerical range can be selected, which is not described in detail herein.
The combination of the column temperature change process and the specific parameters in the carrier gas flow rate can ensure that the gas chromatography has good peak shape, good separation effect, more accurate result and high detection speed.
Preferably, the temperature of the gasification chamber in the gas chromatography detection is 260-.
Preferably, the temperature of the detection chamber in the gas chromatography detection is 280-300 ℃, such as 280 ℃, 282 ℃, 285 ℃, 287 ℃, 290 ℃, 292 ℃, 295 ℃, 297 ℃, 300 ℃ and the like, and other specific values in the value range can be selected, which is not described herein again.
Preferably, the split ratio in the gas chromatography detection is 20:1-50:1, such as 20:1, 22:1, 25:1, 27:1, 30:1, 32:1, 35:1, 37:1, 40:1, 42:1, 45:1, 47:1, 50:1, and the like, and other specific points in the numerical range can be selected, which is not described in detail herein.
Preferably, the sample amount in the gas chromatography detection is 0.5-2.0 μ L, such as 0.5 μ L, 0.6 μ L, 0.7 μ L, 0.8 μ L, 0.9 μ L, 1.0 μ L, 1.1 μ L, 1.2 μ L, 1.3 μ L, 1.4 μ L, 1.5 μ L, 1.6 μ L, 1.7 μ L, 1.8 μ L, 1.9 μ L, 2.0 μ L, etc., and other specific values in the value range can be selected, which is not repeated herein.
The combination of the specific parameters enables the amount of sample entering the column to be controlled, resulting in more accurate detection.
In a second aspect, the invention provides an application of the method for detecting the content of terephthalonitrile or isophthalonitrile in pesticide detection or medicine detection.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a gas chromatography internal standard quantitative method, which can be used for detecting the content of terephthalonitrile and the content of isophthalonitrile. The method creatively uses the naphthalene as the internal standard substance, compared with other internal standard substances, on one hand, the naphthalene has ideal separation degree with the terephthalonitrile or the isophthalonitrile, and in the gas chromatography detection, the naphthalene generates a peak in front of the terephthalonitrile or the isophthalonitrile and is not interfered by any impurity in a sample, thereby being beneficial to the rapid detection and accurate quantification of the terephthalonitrile or the isophthalonitrile. More importantly, the naphthalene peaks in front of the terephthalonitrile or the isophthalonitrile, so the detection can be completed in only 9min, and the detection can be completed in more than 20min by using the common benzophenone, diethyl phthalate and the like in the prior art as internal standard substances. In a word, the detection method provided by the invention greatly shortens the gas chromatography analysis time, has high analysis speed and high detection precision and accuracy, and can be applied to medicine detection or pesticide detection.
Drawings
FIG. 1 is a GC plot of the first standard solution of example 1, wherein 1-naphthalene; 2-terephthalonitrile.
FIG. 2 is a GC graph of a first sample solution of example 1, in which 1-naphthalene; 2-terephthalonitrile.
FIG. 3 is a GC plot of a second sample solution of example 1, wherein 1-naphthalene; 2-terephthalonitrile.
FIG. 4 is a GC plot of a second sample solution of example 1, wherein 1-naphthalene; 2-terephthalonitrile.
FIG. 5 is a graph showing a standard curve of terephthalonitrile.
FIG. 6 is a GC plot of the first standard solution of example 6, wherein 1-naphthalene; 2-isophthalonitrile.
FIG. 7 is a GC graph of a first sample solution of example 6 in which 1-naphthalene; 2-isophthalonitrile.
FIG. 8 is a GC plot of a second sample solution of example 6, in which 1-naphthalene; 2-isophthalonitrile.
FIG. 9 is a GC plot of a second sample solution of example 6, wherein 1-naphthalene; 2-isophthalonitrile.
FIG. 10 is a standard curve of isophthalonitrile.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The apparatus used in the following examples and comparative examples was: the gas chromatograph is Agilent GC 7890B and is provided with a FID detector; sample injector: 10 mu L of the solution; balance: METTLER TOLEDO, model number ME 204/02. The mass fraction of the terephthalonitrile standard described in the examples and comparative examples was 99.3%, the mass fraction of the isophthalonitrile standard was 99.2%, and the terephthalonitrile and isophthalonitrile samples were obtained from Jiangsu, New river Agrochemical Co., Ltd, and other materials and reagents were commercially available without specific description.
Example 1
The embodiment provides a method for detecting the content of terephthalonitrile, which comprises the following steps:
(1) weighing 2.0g (accurate to 0.0001g) of naphthalene, placing the naphthalene in a 250mL volumetric flask, adding an appropriate amount of acetonitrile to dissolve and dilute the naphthalene to a scale, and shaking up to obtain an internal standard solution.
(2) Weighing 0.10g (accurate to 0.0001g) of terephthalonitrile standard sample, placing the terephthalonitrile standard sample into a glass bottle with a plug, adding 10mL of internal standard solution into a 10mL pipette, shaking the mixture in ultrasonic waves (40kHz) for 10min to completely dissolve the internal standard solution, cooling the mixture to room temperature, and shaking the mixture uniformly to obtain the standard sample solution.
(3) Grinding a terephthalonitrile sample into fine powder and uniformly mixing. Weighing 0.10g (accurate to 0.0001g) of terephthalonitrile sample, placing the sample in a glass bottle with a plug, adding 10mL of internal standard solution by using a 10mL pipette, shaking the sample in ultrasonic waves for 10min to completely dissolve the internal standard solution, cooling the sample to room temperature, and shaking the sample uniformly to obtain a sample solution.
(4) Injecting the standard sample solution into a gas chromatograph for detection until the relative peak area change of two adjacent pairs of phthalonitrile and an internal standard substance is less than 1.0%, and then measuring according to the sequence of the standard sample solution, the sample solution and the standard sample solution, wherein the chromatographic conditions are set as follows:
the type of the chromatographic column is DB-17, the stationary phase is 50 percent phenyl-methyl polysiloxane, the length of the chromatographic column is 30m, the inner diameter is 0.25mm, and the film thickness is 0.5 mu m; the temperature change process of the chromatographic column comprises the following steps: the initial temperature of the column is kept at 170 ℃ for 4min, the temperature is increased to 260 ℃ at the heating rate of 40 ℃/min, the temperature is kept for 3min, the temperature of the gasification chamber is 270 ℃, the temperature of the detection chamber is 300 ℃, the carrier gas is high-purity nitrogen, the flow rate is 2.0mL/min, the split ratio is 30:1, and the sample injection amount is 1.0 mu L.
FIGS. 1-4 are GC plots of the first, second and second standard solutions, respectively, wherein 1 is naphthalene; 2-terephthalonitrile.
Example 2
The embodiment provides a method for detecting the content of terephthalonitrile, which comprises the following steps:
(1) weighing 3.0g (accurate to 0.0001g) of naphthalene, placing the naphthalene in a 250mL volumetric flask, adding a proper amount of anhydrous acetonitrile to dissolve and dilute the naphthalene to a scale, and shaking up to obtain an internal standard solution.
(2) Weighing 0.12g (accurate to 0.0001g) of terephthalonitrile standard sample, placing the standard sample in a glass bottle with a plug, adding 10mL of internal standard solution into a 10mL pipette, shaking the internal standard solution in ultrasonic waves (frequency of 40kHz) for 10min to completely dissolve the internal standard solution, cooling the internal standard solution to room temperature, and shaking the internal standard solution uniformly to obtain the standard sample solution.
(3) Grinding a terephthalonitrile sample into fine powder and uniformly mixing. Weighing 0.12g (accurate to 0.0001g) of terephthalonitrile sample, placing the sample in a glass bottle with a plug, adding 10mL of internal standard solution by using a 10mL pipette, shaking the sample in ultrasonic waves (the frequency is 40kHz) for 10min to completely dissolve the internal standard solution, cooling the sample to room temperature, and shaking the sample uniformly to obtain a sample solution.
(4) Injecting the standard sample solution into a gas chromatograph for detection until the relative peak area change of two adjacent pairs of phthalonitrile and an internal standard substance is less than 1.0%, and then measuring according to the sequence of the standard sample solution, the sample solution and the standard sample solution, wherein the chromatographic conditions are set as follows:
the type of the chromatographic column is 007-17, and the stationary phase of the chromatographic column is 50% of phenyl-methyl polysiloxane; the temperature change process of the chromatographic column comprises the following steps: keeping the initial temperature of the column at 160 ℃ for 5min, raising the temperature to the final temperature of the column at 250 ℃ at the heating rate of 40 ℃/min, keeping the temperature for 5min, keeping the temperature of the gasification chamber at 260 ℃, keeping the temperature of the detection chamber at 280 ℃, taking high-purity nitrogen as carrier gas, keeping the flow rate at 1.5mL/min, keeping the split ratio at 20:1 and keeping the sample injection amount at 1.0 mu L.
Example 3
The embodiment provides a method for detecting the content of terephthalonitrile, which comprises the following steps:
(1) weighing 2.5g (accurate to 0.0001g) of naphthalene, placing the naphthalene in a 250mL volumetric flask, adding an appropriate amount of acetonitrile to dissolve and dilute the naphthalene to a scale, and shaking up to obtain an internal standard solution.
(2) Weighing 0.09g (accurate to 0.0001g) of terephthalonitrile standard sample, placing the terephthalonitrile standard sample into a glass bottle with a plug, adding 10mL of internal standard solution into a 10mL pipette, shaking the mixture in ultrasonic waves (40kHz) for 10min to completely dissolve the internal standard solution, cooling the mixture to room temperature, and shaking the mixture uniformly to obtain the standard sample solution.
(3) Grinding a terephthalonitrile sample into fine powder and uniformly mixing. Weighing 0.09g (accurate to 0.0001g) of terephthalonitrile sample, placing the sample in a glass bottle with a plug, adding 10mL of internal standard solution by using a 10mL pipette, shaking the sample in ultrasonic waves (40kHz) for 10min to completely dissolve the internal standard solution, cooling the sample to room temperature, and shaking the sample uniformly.
(4) Injecting the standard sample solution into a gas chromatograph for detection until the relative peak area change of two adjacent pairs of phthalonitrile and an internal standard substance is less than 1.0%, and then measuring according to the sequence of the standard sample solution, the sample solution and the standard sample solution, wherein the chromatographic conditions are set as follows:
the type of the chromatographic column is OV-17, and the stationary phase of the chromatographic column is 50 percent phenyl-methyl polysiloxane; the temperature change process of the chromatographic column comprises the following steps: maintaining the initial temperature of the column at 175 ℃ for 4min, increasing the temperature to the final temperature of the column at 255 ℃ at the temperature rise rate of 35 ℃/min, and maintaining for 4 min; the temperature of the gasification chamber is 265 ℃, the temperature of the detection chamber is 290 ℃, the carrier gas is high-purity nitrogen, the flow rate is 2.5mL/min, the split ratio is 50:1, and the sample injection amount is 1.0 mu L.
Example 4
This example provides a method for detecting the content of terephthalonitrile, which is different from example 1 only in that the chromatographic conditions are set as follows:
the temperature change process of the chromatographic column comprises the following steps: maintaining the initial temperature of the column at 172 deg.C for 5min, increasing the temperature to the final temperature of the column at 255 deg.C at a rate of 32 deg.C/min, and maintaining for 4 min; the temperature of the gasification chamber is 290 ℃, the temperature of the detection chamber is 300 ℃, the carrier gas is high-purity nitrogen, the flow rate is 2.5mL/min, the split ratio is 35:1, and the sample injection amount is 1.0 mu L.
Example 5
This example provides a method for detecting the content of terephthalonitrile, which is different from example 1 only in that the chromatographic conditions are set as follows:
the temperature change process of the chromatographic column comprises the following steps: keeping the initial temperature of the column at 162 ℃ for 6min, increasing the temperature to the final temperature of the column at 250 ℃ at a heating rate of 38 ℃/min, and keeping the temperature for 5 min; the temperature of the gasification chamber is 265 ℃, the temperature of the detection chamber is 285 ℃, the carrier gas is high-purity nitrogen, the flow rate is 3.0mL/min, the split ratio is 40:1, and the sample injection amount is 1.0 mu L.
Examples 6 to 10
Examples 6 to 10 provide methods for detecting the contents of five kinds of isophthalonitrile, which are different from examples 1 to 5 only in that "terephthalonitrile" as a sample is replaced with "isophthalonitrile", and other conditions are as in examples 1 to 5, respectively.
FIGS. 6-9 are GC plots of the first primary standard solution, the first primary sample solution, the second secondary sample solution, and the second standard solution, respectively, of example 6, wherein 1 is naphthalene; 2-isophthalonitrile.
Example 11
The present embodiment provides a method for detecting terephthalonitrile content, which is different from embodiment 1 only in that the temperature change process of the chromatographic column is changed to: keeping the initial temperature of the column at 180 ℃ for 3min, increasing the temperature to the final temperature of the column at 270 ℃ at a temperature rise rate of 45 ℃/min, and keeping the temperature for 2min, wherein other conditions are unchanged.
Example 12
The present embodiment provides a method for detecting terephthalonitrile content, which is different from embodiment 1 only in that the temperature change process of the chromatographic column is changed to: keeping the initial temperature of the column at 150 ℃ for 7min, increasing the temperature to the final temperature of the column at 230 ℃ at the heating rate of 20 ℃/min, and keeping the temperature for 1min, wherein other conditions are unchanged.
Example 13
This example provides a method for detecting the content of terephthalonitrile, which is different from example 1 only in that "0.10 g of terephthalonitrile standard sample" in step (2) is replaced with "0.06 g of terephthalonitrile standard sample", and "0.10 g of terephthalonitrile sample" in step (3) is replaced with "0.06 g of terephthalonitrile sample", and other conditions are not changed.
Example 14
This example provides a method for detecting the content of terephthalonitrile, which is different from example 1 only in that "0.10 g of terephthalonitrile standard sample" in step (2) is replaced with "0.15 g of terephthalonitrile standard sample", and "0.10 g of terephthalonitrile sample" in step (3) is replaced with "0.15 g of terephthalonitrile sample", and other conditions are not changed.
Example 15
This example provides a method for detecting the content of terephthalonitrile, which is different from example 1 only in that "acetonitrile" in step (1) is replaced by "acetone", and other conditions are not changed.
Example 16
This example provides a method for detecting the content of terephthalonitrile, which is different from example 1 only in that a DB-17 column is replaced by a DB-5 column (the stationary phase is 5% phenyl-methyl polysiloxane), and other conditions are not changed.
Example 17
This example provides a method for detecting the content of terephthalonitrile, which is different from example 1 only in that the DB-17 column is replaced by a DB-1 column (the stationary phase is 100% methyl polysiloxane), and the other conditions are not changed.
Examples 18 to 24
Examples 18 to 24 provide methods for measuring the contents of seven kinds of isophthalonitrile, which are different from examples 11 to 17 only in that "terephthalonitrile" as a specimen was replaced with "isophthalonitrile", and other conditions were as in examples 11 to 17, respectively.
Comparative example 1
This comparative example provides a method for measuring the content of terephthalonitrile, which is different from example 1 only in that "naphthalene" in step (1) is replaced with "diethyl phthalate", and other conditions are not changed.
Comparative example 2
This comparative example provides a method for measuring the content of terephthalonitrile, which is different from example 1 only in that "naphthalene" in step (1) is replaced with "benzophenone", and other conditions are not changed.
Comparative examples 3 to 4
Comparative examples 3 to 4 provide two methods for measuring the content of isophthalonitrile, which are different from comparative examples 1 to 2 only in that "terephthalonitrile" as a sample to be measured is replaced with "isophthalonitrile", and other conditions are respectively referred to comparative examples 1 to 2.
The detection results in the above examples and comparative examples were calculated as follows:
calculating the content of the substance to be measured in the sample according to a gas chromatography internal standard method formula:
in the formula:
ω1-the mass fraction of the test substance in the sample, expressed in%;
r2-average value of peak area ratio of the object to be measured and the internal standard substance in the sample solution;
m1-mass of the standard in grams (g);
omega is the mass fraction of the object to be measured in the standard sample, and is expressed by percent;
r1-average value of peak area ratio of the object to be measured and the internal standard substance in the standard sample solution;
m2the mass of the sample in grams (g).
Each of the above examples and comparative examples was measured 5 times in parallel.
Test example 1
Precision and robustness testing:
the content of the terephthalonitrile sample was measured by the terephthalonitrile content measuring method provided in examples 1 to 5, 11 to 17, and comparative examples 1 and 2, and the content of the isophthalonitrile sample was measured by the isophthalonitrile content measuring method provided in examples 6 to 10, 18 to 24, and comparative examples 3 and 4. The results are shown in Table 1.
TABLE 1
The results show that: firstly, the influence of changing the experimental conditions in a certain range on the test result is small, which shows that the test method provided by the invention has high stability. Secondly, the standard deviation and the coefficient of variation of the embodiments 1 to 24 are less than 0.8%, which shows that the detection method provided by the embodiments 1 to 24 has high precision and meets the detection requirement of the content of the terephthalonitrile or the isophthalonitrile. The standard deviation and the coefficient of variation of the samples of examples 1 to 10 are less than 0.3%, which indicates that the precision of the detection methods provided by examples 1 to 10 is higher than that of other samples. And the standard deviation and the coefficient of variation of the comparative examples 1 to 4 are more than 1 percent, so that the detection requirement of the content of the terephthalonitrile or the isophthalonitrile is difficult to meet. The detailed analysis is as follows:
as can be seen from comparison between example 1 and examples 11 and 12 (or between example 6 and examples 18 and 19), the temperature change process of the column has a great influence on the measurement result, wherein excessively high or excessively low initial temperature and final temperature, and excessively fast temperature change both affect the separation of the components to be measured from impurities, and excessively slow temperature change causes slow analysis speed and retention of high-boiling components in the column.
Comparing example 1 with examples 13 and 14 (or example 6 with examples 20 and 21), it can be seen that the weighing range has a large influence on the results, that too little weighing results in a large relative error in weighing, and that too much weighing results in a difficult dissolution of the sample and a poor solution stability.
Comparing example 1 with example 15 (or example 6 with example 22), it can be seen that the selection of the solvent has an influence on the test results, the boiling point of acetonitrile is appropriate, the sample has appropriate solubility, and the solution stability is better when acetonitrile is selected as the solvent.
As can be seen from comparison between example 1 and example 16 and example 17 (or between example 6 and examples 23 and 24), the stationary phase of the column has a large influence on the test results, and the difficult-to-separate components, namely, terephthalonitrile and isophthalonitrile, in the sample can be completely separated by selecting a column having a stationary phase of 50% phenyl-methyl polysiloxane.
As can be seen from comparison between example 1 and comparative examples 1 and 2 (or between example 6 and comparative examples 3 and 4), the selection of the internal standard substance has great influence on the test results, and the invention selects naphthalene as the internal standard substance has the advantages that on one hand, the naphthalene has ideal separation degree with terephthalonitrile or isophthalonitrile, and in the gas chromatography detection, the naphthalene generates peaks in front of the terephthalonitrile or isophthalonitrile without being interfered by any impurities in the sample, thereby being beneficial to the rapid detection and accurate quantification of the terephthalonitrile or the isophthalonitrile. More importantly, the naphthalene peaks in front of the terephthalonitrile or the isophthalonitrile, so the detection can be completed in only 9min, and the detection can be completed in more than 20min by using the common benzophenone, diethyl phthalate and the like in the prior art as internal standard substances. In a word, the naphthalene is selected as the internal standard substance, so that the precision of the analysis result is improved, and the analysis speed is greatly improved.
Test example 2
And (3) testing accuracy:
a standard sample of terephthalonitrile with a known accurate content of 99.3% was measured using the method for measuring the content of terephthalonitrile provided in examples 1 to 5 and 11 to 17. A standard sample of known isophthalonitrile having an accurate content of 99.2% was measured by the isophthalonitrile content measuring method provided in examples 6-10 and 18-24. The results are shown in Table 2.
TABLE 2
The results show that: the absolute value of the relative error of the measurement results of the examples 1 to 24 is less than or equal to 0.5%, which shows that the detection method provided by the examples 1 to 24 has high accuracy and meets the detection requirement of the content of the terephthalonitrile or the isophthalonitrile. The absolute value of the relative error of the measurement results of examples 1 to 10 is 0.2% or less, which shows that the detection methods provided by examples 1 to 10 have higher accuracy than other examples. Comparative examples 1 to 4, however, did not give any more accuracy evaluation because the precision of the process was not satisfactory.
Test example 3
Drawing a standard curve:
respectively weighing terephthalonitrile marks with different qualitiesThe standards were prepared as the standard solutions according to the preparation method of the standard solutions in the embodiment to obtain terephthalonitrile standard solutions with concentrations of 0.00421g/mL, 0.00889g/mL, 0.01027g/mL, 0.01332g/mL and 0.01548g/mL, respectively, and the samples were injected according to the chromatographic conditions in example 1, and the results were measured and calculated. Drawing a standard curve by taking the content ratio of the terephthalonitrile to the internal standard substance as an abscissa and the peak area ratio as an ordinate to obtain a regression equation of Y-9.4815X-0.000752 and a correlation coefficient R2The standard curve is shown in fig. 5, 1.0000.
Different masses of isophthalonitrile standard are respectively weighed, isophthalonitrile standard solutions with the concentrations of 0.00512g/mL, 0.00788g/mL, 0.00969g/mL, 0.01268g/mL and 0.01646g/mL are respectively prepared according to the preparation method of the standard solution in the embodiment, and sample injection is carried out according to the chromatographic conditions in the example 1, and the result is measured and calculated. Drawing a standard curve by taking the content ratio of the m-phthalonitrile to the internal standard substance as an abscissa and the peak area ratio as an ordinate to obtain a regression equation of Y9.4800X +0.000108 and a correlation coefficient R2The standard curve is shown in fig. 10, 1.0000.
The results show that: the method for detecting the content of the terephthalonitrile or the isophthalonitrile provided by the invention has a wide linear range, and the component concentration of the substance to be detected has a good linear relation with the peak area measured by the gas chromatography.
In conclusion, the invention provides a gas chromatography internal standard quantitative method, which can be used for detecting the content of terephthalonitrile and the content of isophthalonitrile. The method creatively uses the naphthalene as the internal standard substance, compared with other internal standard substances, on one hand, the naphthalene has ideal separation degree with the terephthalonitrile or the isophthalonitrile, and in the gas chromatography detection, the naphthalene generates a peak in front of the terephthalonitrile or the isophthalonitrile and is not interfered by any impurity in a sample, thereby being beneficial to the rapid detection and accurate quantification of the terephthalonitrile or the isophthalonitrile. More importantly, the naphthalene peaks in front of the terephthalonitrile or the isophthalonitrile, so the detection can be completed in only 9min, and the detection can be completed in more than 20min by using the common benzophenone, diethyl phthalate and the like in the prior art as internal standard substances. In a word, the detection method provided by the invention greatly shortens the gas chromatography analysis time, has high analysis speed and high detection precision and accuracy, and can be applied to medicine detection or pesticide detection.
The applicant states that the method for detecting the content of terephthalonitrile or isophthalonitrile and the application thereof according to the present invention are illustrated by the above examples, but the present invention is not limited to the above examples, i.e., it is not intended that the present invention is implemented by relying on the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
Claims (10)
1. A method for detecting the content of terephthalonitrile or isophthalonitrile is characterized by comprising the following steps: respectively carrying out gas chromatography detection on a standard sample solution and a sample solution prepared by a standard sample and a sample of an object to be detected and an internal standard substance, and calculating according to a detection result to obtain the content of the object to be detected;
the object to be detected comprises terephthalonitrile or isophthalonitrile;
the internal standard comprises naphthalene.
2. The method for detecting terephthalonitrile or isophthalonitrile as claimed in claim 1, wherein the preparation method of the standard sample solution and the sample solution comprises the steps of:
(1) dissolving and diluting the internal standard substance by using a solvent, and performing constant volume to obtain an internal standard solution;
(2) dissolving a standard sample of an object to be detected by using an internal standard solution to obtain a standard sample solution; and dissolving the sample of the object to be detected by using the internal standard solution to obtain the sample solution.
3. The method for detecting the terephthalonitrile or isophthalonitrile content as recited in claim 1 or 2, wherein the solvent in the step (1) includes acetonitrile;
preferably, the concentration of the internal standard solution in the step (1) is 8-12 mg/mL;
preferably, the concentration of the standard sample of the object to be detected in the standard sample solution in the step (2) is 8-12 mg/mL;
preferably, the concentration of the sample to be detected in the sample solution in the step (2) is 8-12 mg/mL.
4. The method for detecting the content of terephthalonitrile or isophthalonitrile as claimed in any one of claims 1 to 3, wherein the stationary phase of the chromatographic column in the gas chromatography detection is 50% phenyl-methyl polysiloxane.
5. The method for detecting the content of terephthalonitrile or isophthalonitrile as claimed in any one of claims 1 to 4, wherein the column temperature change flow in the gas chromatography detection is as follows: the initial temperature of the column is 160-175 ℃, the initial temperature holding time of the column is 4-6min, the temperature is raised to the final temperature of 250-260 ℃ at the temperature raising rate of 30-40 ℃/min, and the final temperature holding time of the column is 3-5 min.
6. The method for detecting the content of terephthalonitrile or isophthalonitrile as claimed in any one of claims 1 to 5, wherein the carrier gas in the gas chromatography detection comprises nitrogen;
preferably, the flow rate of the carrier gas is 1.5-3.5 mL/min.
7. The method for detecting the content of terephthalonitrile or isophthalonitrile as claimed in any one of claims 1 to 6, wherein the temperature of the gasification chamber in the gas chromatography detection is 260-300 ℃;
preferably, the temperature of the detection chamber in the gas chromatography detection is 280-300 ℃.
8. The method for detecting the content of terephthalonitrile or isophthalonitrile as claimed in any one of claims 1 to 7, wherein the split ratio in the gas chromatography detection is 20:1 to 50: 1;
preferably, the sample amount in the gas chromatography detection is 0.5-2.0 μ L.
9. The method for detecting the content of terephthalonitrile or isophthalonitrile as claimed in any one of claims 1 to 8, wherein the method for detecting the content of terephthalonitrile or isophthalonitrile comprises the steps of:
(1) dissolving and diluting the internal standard substance by using a solvent, and fixing the volume to obtain an internal standard solution with the concentration of 8-12 mg/mL;
the internal standard comprises naphthalene and the solvent comprises acetonitrile;
(2) dissolving a standard sample of an object to be detected by using an internal standard solution to obtain a standard sample solution with the concentration of the standard sample of the object to be detected being 8-12 mg/mL; dissolving a sample of the object to be detected by using an internal standard solution to obtain a sample solution with the concentration of the sample of the object to be detected being 8-12 mg/mL;
the object to be detected comprises terephthalonitrile or isophthalonitrile;
(3) taking 0.5-2.0 mu L of standard sample solution and 0.5-2.0 mu L of sample solution to respectively enter a gas chromatograph for detection, wherein the chromatographic conditions are as follows:
the stationary phase of the chromatographic column is 50% phenyl-methyl polysiloxane; the column temperature change process in the gas chromatography detection comprises the following steps: the initial temperature of the column is 160-175 ℃, the initial temperature holding time of the column is 4-6min, the temperature is raised to the final temperature of 250-260 ℃ at the temperature raising rate of 30-40 ℃/min, and the final temperature holding time of the column is 3-5 min; the carrier gas in the gas chromatography detection comprises nitrogen; the flow rate of the carrier gas is 1.5-3.5 mL/min; the temperature of the gasification chamber is 260-300 ℃; the temperature of the detection chamber is 280-300 ℃; the split ratio is 20:1-50: 1; the sample amount is 0.5-2.0 μ L.
10. The use of the method for detecting the terephthalonitrile or isophthalonitrile content as defined in any one of claims 1 to 9 for the detection of pesticides or medicines.
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| 詹益兴 等: "间苯二甲腈分析方法研究", 农药, no. 05, pages 31 - 33 * |
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