CN111458434A - Method for testing hydrazine and alkylamine compounds in derivatization mode - Google Patents
Method for testing hydrazine and alkylamine compounds in derivatization mode Download PDFInfo
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- CN111458434A CN111458434A CN202010302512.9A CN202010302512A CN111458434A CN 111458434 A CN111458434 A CN 111458434A CN 202010302512 A CN202010302512 A CN 202010302512A CN 111458434 A CN111458434 A CN 111458434A
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- G01N30/8675—Evaluation, i.e. decoding of the signal into analytical information
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- G—PHYSICS
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- 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
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- G01N2030/062—Preparation extracting sample from raw material
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Abstract
The invention provides a method for testing hydrazine and alkylamine compounds in a derivatization mode, wherein ketones are simultaneously used as a solvent and a derivatization reagent for sample extraction, acid or acid anhydride is used as a promoter of derivatization reaction, hydrazine, alkylamine and ketone react to generate a compound with a specific structure, and the compound can be separated and quantified by a gas chromatograph-mass spectrometer. The testing method of the invention can realize the simultaneous extraction and derivatization of the sample, and solves the technical problems of quantitative interference phenomenon in a colorimetric method, poor chromatographic peak shape in direct testing of a gas chromatograph, incapability of detecting by a liquid chromatograph and the like.
Description
Technical Field
The invention relates to the field of methods for testing hydrazine and alkylamine compounds, in particular to a method for testing hydrazine and alkylamine compounds in a derivatization mode.
Background
Hydrazine is also called hydrazine, which is a commonly used raw material in industry and is widely used in the industries of electroplating, polymers, pharmacy, water treatment agents and the like. Hydrazine is a strong reducing agent, is used in the electroplating industry, and is used for plating metal films on mirror silver plating, plastics and glass. Hydrazine is a monomeric starting material for polymers used in the manufacture of polyamides and epoxy resins. Hydrazine is also used in the production of pharmaceuticals and other chemical raw materials, such as semicarbazide, isoniazid, nitrofurazone, and chlorothalonil. Hydrazine is also used as rocket fuels, imaging agents, antioxidants, and the like.
Hydrazine is a colorless oily liquid with the pungent odor of ammonia. Inhalation of hydrazine vapor presents symptoms of headache, dizziness, nausea, vomiting, diarrhea, eye and upper respiratory tract irritation. The inhalation of high concentration steam rapidly causes central nervous system symptoms, firstly arouse, such as restlessness and tetany, and rapidly enter a suppression state. Oral intoxication causes frequent nausea, vomiting, diarrhea, followed by temporary central respiratory depression, cardiac rhythm disturbances and central nervous system symptoms. Prolonged exposure can cause neurasthenia, liver damage, and skin damage.
An alkylamine compound is an alkyl compound having an amine structure. Methylamine, ethylamine, ethylenediamine, triethylamine, propylenediamine and the like belong to alkylamine compounds. The compounds with the structure are colorless liquids, have the smell of ammonia and have irritation. The toxicity is lower as the number of carbons at the alkyl end is larger. The alkylamine compounds are mainly used for the production of pesticides, dyes, rubber accelerators, surfactants, antioxidants, ion exchange resins, polymers, aircraft fuels, solvents, detergents, lubricants, metallurgical beneficiation agents, cosmetics and pharmaceuticals.
Hydrazine and alkylamine compounds present in everyday contact items can be toxic to humans slowly, and hydrazine and alkylamine compounds present in the environment can also be toxic to terrestrial and aquatic organisms.
At present, the standard of occupational health is available, and the standard GBZ/T300 series is tested for ethylamine, ethylenediamine, cyclohexylamine, trimethylamine, diethylamine, triethylamine and the like in the air of a workplace; the method is characterized by comprising the following steps of (1) having an environmental standard, namely a test standard HJ 674 for hydrazine and methylhydrazine in water in an ecological environment, and a test standard GB/T14377 for triethylamine in water; there are test standards for triethylamine and tri-n-butylamine GB 31604.37 in food contact polymer materials.
The main detection methods of hydrazine and alkylamine compounds include colorimetric method, gas chromatography and gas chromatography. However, the above method has the following disadvantages: the colorimetric method is used for developing color in a water matrix, and the detection of daily necessities is carried out by crushing a sample and dissolving the sample by using an organic solvent, so that hydrazine and alkylamine are released into an organic solution and cannot be converted into water without damage again. The existing gas chromatography is usually a sample introduction test after purification and concentration of extract liquor, a flame ionization detector or a mass spectrum detector is adopted for quantification, hydrazine and alkylamine are difficult to form chromatographic peaks with high reproducibility and symmetry due to strong polarity under the chromatographic condition, no response or serious tailing phenomenon is usually generated, and even if the hydrazine and alkylamine can reach the detector, the hydrazine and alkylamine usually form ions with the mass number lower than 50amu under electron bombardment when the mass spectrum detector is used, so that the quantitative stability is seriously reduced. Amine and alkylamine compounds have strong polarity, cannot be retained on a liquid chromatographic column, cannot form stable and symmetrical chromatographic peaks, and cannot be detected by using a liquid chromatograph.
The methods can not accurately and efficiently detect the amine and various alkyl compounds.
Disclosure of Invention
The method aims to solve the technical problems that the prior colorimetric method for testing hydrazine and alkylamine compounds has complex pretreatment, uses a large amount of reagents, has sample solution and matrix interference, cannot effectively separate the strong polar compounds such as hydrazine and alkylamine compounds by using a gas chromatography, cannot keep the strong polar compounds by using a liquid chromatography and the like. The invention provides a method for testing hydrazine and alkylamine compounds in a derivatization mode, which can accurately and efficiently detect amine and various alkyl compounds, and the specific scheme is as follows:
A. using ketone organic solvent as sample extraction solvent and as sample derivatization reagent;
B. using a derivatization reaction promoter;
C. extracting and derivatizing a sample in an ultrasonic extraction mode;
D. and testing the product of the sample and the ketone organic solvent derivatization by using a gas chromatography-mass spectrometer, and obtaining the test result of the hydrazine and the alkylamine compound in the sample through quantitative conversion.
In a preferred embodiment of the present invention, the ketone organic solvent is one of acetone, butanone, pentanone, and hexanone.
As a preferred embodiment of the present invention, the ketone-based organic solvent is used in an amount of 5 to 50m L.
In a preferred embodiment of the present invention, the derivatization reaction accelerator is an organic carboxylic acid or organic acid anhydride solvent.
In a preferred embodiment of the present invention, the organic acid or the organic acid anhydride is one of formic acid, acetic acid, propionic acid, acetic anhydride and propionic anhydride, and the organic acid or the organic acid anhydride is mixed with the ketone organic solvent in advance and then used, and the content of the derivatization reaction accelerator is 0.1 to 10% by volume of the ketone organic solvent.
In a preferred embodiment of the present invention, the conditions of the ultrasonic extraction method are as follows: the ultrasonic power is 200-600W, the water temperature of the ultrasonic pool is 40-90 ℃, and the ultrasonic extraction and derivatization time is 15-60 min.
As a preferred embodiment of the invention, the mass number detected by the mass spectrometer of the gas chromatograph-mass spectrometer is in the range of 50-1000 amu.
The invention has the advantages that:
1. the traditional color development method has serious color interference, the color development method has color interference, accurate quantification cannot be realized, more reagents are used in the color development method, the operation is complex, the consumed time is long, and the labor intensity of technical personnel is high. The invention uses a derivatization method, the derivatization product is qualitative by using a fixed ion ratio, mass spectrum interference does not exist, the target substance reaction specificity is high, the reacted substance is stable and easy to detect, the invention can simultaneously complete the steps of sample extraction and derivatization by using a small amount of organic solvent, the operation is simple, the consumed time is short, and the labor intensity is low.
2. In the traditional liquid chromatography method, hydrazine and most alkylamine compounds generally flow out along with a mobile phase, and even if signal response exists, reproducible symmetrical chromatographic peaks cannot appear, so that difficulty is brought to chromatographic quantification. The invention uses the gas chromatograph-mass spectrometer, does not generate a large amount of waste organic solvent due to the use of a liquid chromatograph, and does not generate chromatographic peaks which are difficult to quantify.
3. In the traditional gas chromatography, hydrazine and alkylamine compounds belong to strong polar compounds, so that the chromatographic peak intensity is low, the tailing is serious, and irreversible damage is caused to a chromatographic column. The invention uses a gas chromatography method, tests substances after derivatization reaction, has reduced polarity, improved stability, is friendly to chromatographic column, prolongs the service life of the chromatographic column, and the substances after derivatization reaction form ions with larger mass number in a mass spectrum detector, thereby improving the quantitative stability and reducing the use cost of the instrument.
Drawings
FIG. 1 is a blank chromatogram of a hydrazine-acetone derivative in example one of the present invention.
FIG. 2 is a blank chromatogram of an ethylenediamine-acetone derivative according to example one of the present invention.
FIG. 3 is a chromatogram of standard working solutions of hydrazine derivative products at various concentrations, superimposed in example one of the present invention.
FIG. 4 is a chromatogram after the standard working solution of ethylenediamine-derived product of each concentration is overlapped in example one of the present invention.
FIG. 5 is a chromatogram of a test plastic sample (hydrazine-acetone derivative) according to a first embodiment of the present invention.
FIG. 6 is a chromatogram of a sample of a test plastic (ethylenediamine-acetone derivative) according to a first embodiment of the present invention.
FIG. 7 is a structural formula of diacetone hydrazone, a derivative of hydrazine and acetone, in accordance with an embodiment of the present invention.
FIG. 8 shows the structural formula of the derivatives of ethylenediamine and acetone, N1, N2-bis (1-methylethylidene) -1, 2-ethylenediamine, in the first embodiment of the present invention.
Note: in the chromatograms of fig. 1-6: the abscissa represents retention time, and the ordinate represents response intensity.
Detailed Description
The application scheme is further described below with reference to the accompanying drawings:
example one
A method for testing hydrazine and alkylamine compounds in a derivatization manner, comprising the steps of:
A. using ketone organic solvent as sample extraction solvent and as sample derivatization reagent;
B. using a derivatization reaction promoter;
C. extracting and derivatizing a sample in an ultrasonic extraction mode;
D. and testing the product of the sample and the ketone organic solvent derivatization by using a gas chromatography-mass spectrometer, and obtaining the test result of the hydrazine and the alkylamine compound in the sample through quantitative conversion.
The ketone organic solvent in this example is acetone, the derivatization reaction promoter is acetic acid, and the acetic acid is mixed with acetone for use, and accounts for 0.1% of the acetone by volume.
The specific operation is as follows:
weighing 1g of the crushed plastic sample into a glass container with a cover.
And (II) preparing an acetone solution containing 0.1% of acetic acid as a sample extraction solvent (extraction liquid) and a derivatization solution, and adding 10m L of the solution into the sample.
And (III) starting the ultrasonic extraction instrument, stabilizing the water temperature to 60 ℃, putting the sample into an ultrasonic pool, performing ultrasonic extraction for 30min, taking out and filtering.
(IV) instrumental testing
Equipment: gas chromatography mass spectrometer;
a chromatographic column: DB-624(60m 0.32mm 1.8 um);
column flow rate: 1 ml/min;
sample introduction mode: using a non-shunting liner tube and non-shunting sample injection;
shunting time: 1 min;
sample inlet temperature: 250 ℃;
transmission line temperature: 250 ℃;
detector temperature: 230 ℃;
column temperature: 50 deg.C (keeping for 1min), and increasing to 240 deg.C (keeping for 5min) at 15 deg.C/min;
the injection volume is 1 mu L;
and a mass spectrum detector, setting a scanning mode of 50-1000amu mass number for qualitative analysis, setting hydrazine-acetone derivative quantitative ions as 56amu, reference ions as 97amu and 112amu, and ethylenediamine-acetone derivative quantitative ions as 70amu and reference ions as 84amu and 125 amu.
(V) drawing of blank chromatogram
And (4) determining the blank solution collected in the pretreatment by a gas chromatography-mass spectrometer according to the determination conditions. As shown in fig. 1 and 2, are blank chromatograms of hydrazine and ethylenediamine.
(VI) drawing of Standard Curve
The hydrazine-acetone derivative and the ethylenediamine-acetone derivative are used in the test, an acetone solution containing 0.1% acetic acid is used for preparing a 1000 mg/L stock solution, the stock solution is sequentially diluted to a working solution, the concentration of the working solution is 0, 0.25, 0.5, 1.25, 2.5, 5 and 10 mg/L, the solution is filled into a glass container, the standard product is derivatized according to the sample extraction conditions, after the solution is taken out, the sample is sequentially injected from low concentration to high concentration for testing, the peak area response value of a target object is plotted against the concentration, a standard working curve of the hydrazine-acetone derivative and the ethylenediamine-acetone derivative is established according to the test result and the theoretical concentration of the working solution, as shown in figures 3 and 4, the curve peak value is 0, 0.25, 0.5, 1.25, 2.5, 5 and 10 mg/L from low to high, a standard working solution regression equation of the hydrazine-acetone derivative and the ethylenediamine-acetone derivative is obtained, the concentration of the hydrazine-acetone derivative is in the range of 0.25-10 mg/L, the concentration (X) and the linear relationship of the ethylenediamine-acetone derivative is more than the linear equation of the Y + E.06, the linear relationship of the linear acetone derivative is more than the equation of the linear equation of.
(VII) calculation of results
The hydrazine or ethylenediamine content in the sample is obtained by multiplying the hydrazine or ethylenediamine concentration in the extraction liquid by the volume of the extraction liquid divided by the weight of the sample, and the dilution ratio needs to be converted when the sample is diluted.
(VIII) recovery and precision
To a plastic sample containing no hydrazine or ethylenediamine, 0.25ml of a standard solution containing 100 mg/L of hydrazine or ethylenediamine was added for 10 runs, and the results of recovery and accuracy are shown in tables 1 and 2.
TABLE 1 hydrazine recovery and precision test results
TABLE 2 results of ethylenediamine recovery and precision tests
As can be seen from tables 1 and 2, the recovery rate of hydrazine is between 88.7% and 98.4%, and the recovery rate of ethylenediamine is between 89.1% and 98.6%, which indicates that the determination method provided by the invention has high accuracy, and the RSD of the sample test results is less than 5%, which indicates that the determination method has good repeatability.
The above preferred embodiments should be considered as examples of the embodiments of the present application, and technical deductions, substitutions, improvements and the like similar to, similar to or based on the embodiments of the present application should be considered as the protection scope of the present patent.
Claims (7)
1. A method for testing hydrazine and alkylamine compounds in a derivatization mode is characterized by comprising the following steps:
A. using ketone organic solvent as sample extraction solvent and as sample derivatization reagent;
B. using a derivatization reaction promoter;
C. extracting and derivatizing a sample in an ultrasonic extraction mode;
D. and testing the product of the sample and the ketone organic solvent derivatization by using a gas chromatography-mass spectrometer, and obtaining the test result of the hydrazine and the alkylamine compound in the sample through quantitative conversion.
2. The method for derivatizing test hydrazine and alkylamine compounds according to claim 1, wherein the ketone organic solvent is one of acetone, butanone, pentanone and hexanone.
3. The method for testing hydrazine and alkylamine compounds according to the derivatization manner of claim 2, wherein the ketone organic solvent is used in an amount of 5 to 50m L.
4. The method for testing hydrazine and alkylamine compounds according to the derivatization mode of claim 3, wherein the derivatization reaction promoter is an organic carboxylic acid or an organic acid anhydride solvent.
5. The method for testing hydrazine and alkylamine compounds according to claim 4, wherein the organic acid or organic acid anhydride is one of formic acid, acetic acid, propionic acid, acetic anhydride and propionic anhydride, and is mixed with the ketone organic solvent in advance for reuse, and the content of the derivatization reaction promoter is 0.1-10% by volume of the ketone organic solvent.
6. The method for testing hydrazine and alkylamine compounds according to the derivatization method of claim 1, wherein the ultrasonic extraction method is performed under the following conditions: the ultrasonic power is 200-600W, the water temperature of the ultrasonic pool is 40-90 ℃, and the ultrasonic extraction and derivatization time is 15-60 min.
7. The method for derivatizing a hydrazine and alkylamine compound according to claim 1, wherein the mass number detected by the mass spectrometer of the GC-MS is in the range of 50-1000 amu.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113884589A (en) * | 2021-09-15 | 2022-01-04 | 湖北省地质实验测试中心(国土资源部武汉矿产资源监督检测中心) | Method for measuring phenolic compounds in water |
Citations (1)
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| CN108645936A (en) * | 2018-08-09 | 2018-10-12 | 苏州科铭生物技术有限公司 | A kind of oxaloacetic acid content assaying method based on high performance liquid chromatography |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108645936A (en) * | 2018-08-09 | 2018-10-12 | 苏州科铭生物技术有限公司 | A kind of oxaloacetic acid content assaying method based on high performance liquid chromatography |
Non-Patent Citations (3)
| Title |
|---|
| MINGJIANG SUN 等: "A generic approach for the determination of trace hydrazine in drug substances using in situ derivatization-headspace GC–MS", 《JOURNAL OF PHARMACEUTICAL AND BIOMEDICAL ANALYSIS》 * |
| 侯倩倩 等: "衍生气相色谱法测定土壤中残留水合肼", 《化学推进剂与高分子材料》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113884589A (en) * | 2021-09-15 | 2022-01-04 | 湖北省地质实验测试中心(国土资源部武汉矿产资源监督检测中心) | Method for measuring phenolic compounds in water |
| CN113884589B (en) * | 2021-09-15 | 2023-12-26 | 湖北省地质实验测试中心(国土资源部武汉矿产资源监督检测中心) | Method for measuring phenolic compounds in water |
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