CN107917968A - A kind of method of azodicarbonamide content in high effective liquid chromatography for measuring leather - Google Patents
A kind of method of azodicarbonamide content in high effective liquid chromatography for measuring leather Download PDFInfo
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- CN107917968A CN107917968A CN201710227505.5A CN201710227505A CN107917968A CN 107917968 A CN107917968 A CN 107917968A CN 201710227505 A CN201710227505 A CN 201710227505A CN 107917968 A CN107917968 A CN 107917968A
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- azodicarbonamide
- solution
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- leather
- liquid chromatography
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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
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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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
Abstract
The invention discloses a kind of method of azodicarbonamide content in high effective liquid chromatography for measuring leather, it comprises the following steps：Step 1, prepares three kinds of samples, step 2, and three kinds of solution prepared by step 1 carry out high performance liquid chromatography measure under high-efficient liquid phase chromatogram condition.The present invention is not only able to control the content detection of azodicarbonamide in leather well, ensures that consumer's is healthy and safe, and pre-treatment is simple, can be used for azodicarbonamide content in accurate detection leather.
Description
Technical field
The present invention relates to a kind of method of azodicarbonamide content in high effective liquid chromatography for measuring leather.
Background technology
Azodicarbonamide abbreviation AC foaming agents or ADC foaming agents, suitable for various kinds of resin, such as PVC, PE, EVA, EPDM
, PS, PU, epoxy resin, natural and synthetic rubber etc., by hydrazine hydrate；Urea is condensed into intermediate biruea with sulfuric acid, then through oxygen
Change and obtain finished product, raw materials for production hydrazine hydrate has severe corrosive, and toxicity is very big.Energy attack glass, rubber, leather and cork etc..Steam
Gas and liquid can corrode skin, eyes, nose, larynx and mucous membrane etc., sufficient evidence show azodicarbonamide can induce asthma and
The generation of other respiratory symptoms.On December 19th, 2012 is put into the highest attention substance list SVHC of European Union's REACH annexes
In after, its require outlet foamed products in ADC residual must not exceed 1000ppm.
Azodicarbonamide is added into the processing technology of leather as a kind of good foaming agent, and there are media in foreign countries
Report, the more sensitive common people of tracheae, contact the excessive article containing azodicarbonamide, it is possible that asthma, allergy etc. are reacted.By
In current technique and technology, it is also difficult to control to the smooth content ensured in leather products to be no more than to limit, since azo two
After formamide is put into the highest attention substance list SVHC of European Union's REACH annexes, leather abroad was exported over the past two years
And its product requires and azodicarbonamide project must be detected.
But the key issue of supervision difficulty at present, is no detection method, ADC residues detecton phases in studies in China leather
The research of pass is considerably less, causes mainly due to the property of azodicarbonamide in itself, and one is due to its rapid decomposition at high temperature
Chemical property so that conventional quantitative instrument gas-chromatography (GC) and the chromatograph joint used instrument of gas phase (GC-MS, GC-MS-MS) can not
Use, second, the insoluble of itself causes general measure instrument LC-MS instrument (LC-MS, LC-MS-MS) and is excluded,
At the same time also so that the leeway of the mobile phase selection of liquid chromatogram greatly reduces, third, this compound is highly polar so that in reversed-phase column
On almost without reserve, bring great difficulty to detection.
The content of the invention
The present invention provides a kind of method of azodicarbonamide content in high effective liquid chromatography for measuring leather, it is not only
The content detection of azodicarbonamide in leather can be controlled well, ensure that consumer's is healthy and safe, and pre-treatment letter
List, can be used for azodicarbonamide content in accurate detection leather.
1. present invention employs following technical scheme：Azodicarbonamide contains in a kind of high effective liquid chromatography for measuring leather
The method of amount, it is characterized in that it comprises the following steps：
Step 1, prepares three kinds of samples
A, prepares blank solution：The leather of two formyl of no azo is taken, it is accurately weighed, add dimethyl sulfoxide (DMSO) 40mL, put 50mL appearances
Measuring bottle, ultrasonic extraction 30min, adds dimethyl sulfoxide (DMSO) constant volume after placing cooling, is blank sample with 0.45 μm of membrane filtration；
B, azodicarbonamide standard solution is prepared：Azodicarbonamide standard items are taken, it is accurately weighed, prepare the azo two of 2g/L
Formamide Standard Stock solutions, with 0.45 μm of membrane filtration, dilution, is standard solution；
C, test sample solution 1 is prepared：1.0g samples accurately are weighed, adds dimethyl sulfoxide (DMSO) 40mL, puts 50mL volumetric flasks, ultrasound carries
30min is taken, adds dimethyl sulfoxide (DMSO) constant volume after placing cooling, is test sample solution with 0.45 μm of membrane filtration；
Step 2, three kinds of solution prepared by step 1 carry out high performance liquid chromatography measure under high-efficient liquid phase chromatogram condition：
A, the 10 μ l of blank solution in accurate aspiration step one, are measured according to high-efficient liquid phase chromatogram condition, establish azo two
Formamide standard blank solution spectrogram；According to standard blank solution spectrogram, the two of azodicarbonamide standard blank solution
Methyl sulfoxide appearance time is 9.135min；
B, the 10 μ l of azodicarbonamide standard solution in accurate aspiration step one, are surveyed according to high-efficient liquid phase chromatogram condition
It is fixed, obtain azodicarbonamide standard solution spectrogram；According to azodicarbonamide standard solution spectrogram, azodicarbonamide
The appearance time of standard solution is 8.593min；By the standard reserving solution in step 1, being diluted to concentration with dimethyl sulfoxide (DMSO) is
1st, 10,50,100 and 1000mg/L, is measured according to high-efficient liquid phase chromatogram condition, using solution content as abscissa, with peak face
Product ordinate, draws standard curve；Azodicarbonamide linear relationship in the range of 1 ~ 1000 μ g/mL is good, linear regression side
Journey is Y=2.5351X-26.639, linearly dependent coefficient (R2)For 0.9995；
C, the test sample of step 1 is measured according to high-efficient liquid phase chromatogram condition, obtains the chromatogram of test sample；Root
According to the chromatogram of test sample, test sample in leather has a small peak appearance in 8.593min, and linear regression equation Y=
2.5351X-26.639 calculating has micro azodicarbonamide detection in the test sample in leather.
The chromatographic condition is：
Chromatographic column：The size of hydrophilic column HILIC is 250mm × 4.6mm, 5 μm；
Column temperature：25-35℃；
Mobile phase：The volume of acetonitrile：Volume=60-70 of water:40-30V/V；
Flow velocity 0.5-1.2mL/min；
Elution time：12-15min；
Detection wavelength：240-250nm.
The column temperature is 30 DEG C.The mobile phase is the volume of acetonitrile：Volume=70 of water:30V/V.The flow velocity
For 1mL/min, elute 12 minutes.The Detection wavelength is 245nm.
The invention has the advantages that：Azodicarbonamide contains in the high effective liquid chromatography for measuring leather of the present invention
The method pre-treatment of amount is simple, and matrix interference is small and accuracy is high, and azodicarbonamide essence in leather is realized under normal temperature condition
Certainly amount control, with good economic efficiency and social benefit.
Brief description of the drawings
Fig. 1 is the spectrogram of azodicarbonamide blank solution in high effective liquid chromatography for measuring leather of the present invention.
Fig. 2 is the spectrogram of azodicarbonamide standard solution in high effective liquid chromatography for measuring leather of the present invention.
Fig. 3 is the spectrogram of azodicarbonamide content in high effective liquid chromatography for measuring leather of the present invention.
Fig. 4 is even in the leather that high effective liquid chromatography for measuring addition concentration of the present invention is 500mg/kg azodicarbonamides
The content of nitrogen diformamide.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is further elaborated.
First, in high effective liquid chromatography for measuring leather azodicarbonamide blank solution content
1st, blank solution is prepared：Take the leather of two formyl of no azo appropriate, it is accurately weighed, add dimethyl sulfoxide (DMSO) 40mL, put
50mL volumetric flasks, ultrasonic extraction 30min, adds dimethyl sulfoxide (DMSO) constant volume after placing cooling, is blank with 0.45 μm of membrane filtration
Sample；
2nd, high performance liquid chromatography measures：
Above-mentioned blank sample is subjected to high performance liquid chromatography measure, chromatographic condition is：Chromatographic column：Hydrophilic column HILIC 250mm
×4.6mm, 5µm；Column temperature：30℃；Mobile phase：The volume of acetonitrile：Volume=60-70 of water:40-30V/V；Flow velocity 1mL/min；
Elution time：12min；Detection wavelength：245nm.
3rd, azodicarbonamide standard blank solution spectrogram is established
Accurate aspiration step（1）10 μ l of blank solution, according to high-efficient liquid phase chromatogram condition be measured, obtain two formyl of azo
Amine standard blank solution spectrogram；The azodicarbonamide standard blank solution spectrogram is as shown in Figure 1；There is Fig. 1 to understand, azo two
The dimethyl sulfoxide (DMSO) appearance time of formamide standard blank solution is 9.135min.
2nd, in high effective liquid chromatography for measuring leather azodicarbonamide standard solution content
1st, azodicarbonamide standard solution is prepared
Take azodicarbonamide standard items appropriate, it is accurately weighed, the azodicarbonamide Standard Stock solutions of 2g/L are prepared, are used
0.45 μm of membrane filtration, dilution, is standard solution；
2nd, high performance liquid chromatography measures
Standard solution sample in above-mentioned 1 is subjected to high performance liquid chromatography measure, chromatographic condition is：
Chromatographic column：Hydrophilic column HILIC 250mm × 4.6mm, 5 μm；Column temperature：30℃；Mobile phase：The volume of acetonitrile：The volume of water
=60-70:40-30V/V；Flow velocity 1mL/min；Elution time：12min；Detection wavelength：245nm.
3rd, azodicarbonamide standard solution spectrogram is established
Precision draws 10 μ l of standard solution, is measured according to high-efficient liquid phase chromatogram condition, it is molten to obtain azodicarbonamide standard
Liquid spectrogram；The azodicarbonamide standard solution spectrogram is as shown in Figure 2；There is Fig. 2 to understand, azodicarbonamide standard solution
Appearance time is 8.593min.
3rd, in high effective liquid chromatography for measuring leather azodicarbonamide content spectrogram
1st, test sample solution is prepared
1.0g samples accurately are weighed, sample is accurate to 0.0001g, adds dimethyl sulfoxide (DMSO) 40mL, puts 50mL volumetric flasks, ultrasonic extraction
30min, adds dimethyl sulfoxide (DMSO) constant volume after placing cooling, is test sample solution with 0.45 μm of membrane filtration；
2nd, high performance liquid chromatography measures
Test sample in above-mentioned 1 is subjected to high performance liquid chromatography measure, chromatographic condition is：
Chromatographic column：Hydrophilic column HILIC 250mm × 4.6mm, 5 μm；Column temperature：30℃；Mobile phase：The volume of acetonitrile：The volume of water
=60-70:40-30V/V；Flow velocity 1mL/min；Elution time：12min；Detection wavelength：245nm.
3rd, the chromatographic condition measured according to high performance liquid chromatography is measured test sample solution, obtains test sample
Chromatogram；The chromatogram of the test sample is as shown in figure 3, the test sample in leather has small peak appearance in 8.593min, warp
Equation of linear regression Y=2.5351X-26.639, which is calculated, micro azodicarbonamide detection in the test sample in leather.
4th, high effective liquid chromatography for measuring addition concentration is two formyl of azo in the leather of 500mg/kg azodicarbonamides
The content of amine
1st, test sample solution is prepared
1.0g samples accurately are weighed, sample is accurate to 0.0001g, adds dimethyl sulfoxide (DMSO) 40mL, adds a certain amount of standard solution,
50mL volumetric flasks are put, ultrasonic extraction 30min, adds dimethyl sulfoxide (DMSO) constant volume after placing cooling, with 0.45 μm of membrane filtration, as supply
Test agent solution II；
2nd, high performance liquid chromatography measures：
Above-mentioned blank sample is subjected to high performance liquid chromatography measure, chromatographic condition is：Chromatographic column：Hydrophilic column HILIC 250mm
×4.6mm, 5µm；Column temperature：30℃；Mobile phase：The volume of acetonitrile：Volume=60-70 of water:40-30V/V；Flow velocity 1mL/min；
Elution time：12min；Detection wavelength：245nm.
3rd, the chromatographic condition measured according to high performance liquid chromatography is measured test sample solution II, in test sample
Chromatogram is as shown in figure 4, as shown in Figure 4, test sample leather has peak appearance in 8.045min, measure test sample solution II
Go out peak area, the content that linear regression equation Y=2.5351X-26.639 calculates azodicarbonamide in test sample leather is
440mg/kg, the rate of recovery 88%.
Claims (6)
1. a kind of method of azodicarbonamide content in high effective liquid chromatography for measuring leather, it is characterized in that it includes following step
Suddenly：
Step 1, prepares three kinds of samples
A, prepares blank solution：The leather of two formyl of no azo is taken, it is accurately weighed, add dimethyl sulfoxide (DMSO) 40mL, put 50mL appearances
Measuring bottle, ultrasonic extraction 30min, adds dimethyl sulfoxide (DMSO) constant volume after placing cooling, is blank sample with 0.45 μm of membrane filtration；
B, azodicarbonamide standard solution is prepared：Azodicarbonamide standard items are taken, it is accurately weighed, prepare the azo two of 2g/L
Formamide Standard Stock solutions, are standard solution with 0.45 μm of membrane filtration, dilution；
C, test sample solution 1 is prepared：1.0g samples accurately are weighed, adds dimethyl sulfoxide (DMSO) 40mL, puts 50mL volumetric flasks, ultrasound carries
30min is taken, adds dimethyl sulfoxide (DMSO) constant volume after placing cooling, is test sample solution with 0.45 μm of membrane filtration；
Step 2, three kinds of solution prepared by step 1 carry out high performance liquid chromatography measure under high-efficient liquid phase chromatogram condition：
A, the 10 μ l of blank solution in accurate aspiration step one, are measured according to high-efficient liquid phase chromatogram condition, establish azo two
Formamide standard blank solution spectrogram；According to standard blank solution spectrogram, the two of azodicarbonamide standard blank solution
Methyl sulfoxide appearance time is 9.135min；
B, the 10 μ l of azodicarbonamide standard solution in accurate aspiration step one, are surveyed according to high-efficient liquid phase chromatogram condition
It is fixed, obtain azodicarbonamide standard solution spectrogram；According to azodicarbonamide standard solution spectrogram, azodicarbonamide
The appearance time of standard solution is 8.593min；By the standard reserving solution in step 1, being diluted to concentration with dimethyl sulfoxide (DMSO) is
1st, 10,50,100 and 1000mg/L, is measured according to high-efficient liquid phase chromatogram condition, using solution content as abscissa, with peak face
Product ordinate, draws standard curve；Azodicarbonamide linear relationship in the range of 1 ~ 1000 μ g/mL is good, linear regression side
Journey is Y=2.5351X-26.639, linearly dependent coefficient (R2)For 0.9995,
C, the test sample of step 1 is measured according to high-efficient liquid phase chromatogram condition, obtains the chromatogram of test sample；Root
According to the chromatogram of test sample, test sample in leather has a small peak appearance in 8.593min, and linear regression equation Y=
2.5351X-26.639 calculating has micro azodicarbonamide detection in the test sample in leather.
2. the method for azodicarbonamide content in high effective liquid chromatography for measuring leather according to claim 1, it is special
Sign is that chromatographic condition is：
Chromatographic column：The size of hydrophilic column HILIC is 250mm × 4.6mm, 5 μm；
Column temperature：25-35℃；
Mobile phase：The volume of acetonitrile：Volume=60-70 of water:40-30V/V；
Flow velocity 0.5-1.2mL/min；
Elution time：12-15min；
Detection wavelength：240-250nm.
3. the method for azodicarbonamide content in high effective liquid chromatography for measuring leather according to claim 2, it is special
Sign is that the column temperature is 30 DEG C.
4. the method for azodicarbonamide content in high effective liquid chromatography for measuring leather according to claim 2, it is special
Sign is the volume that the mobile phase is acetonitrile：Volume=70 of water:30V/V.
5. the method for azodicarbonamide content in high effective liquid chromatography for measuring leather according to claim 1, it is special
Sign is that the flow velocity is 1mL/min, is eluted 12 minutes.
6. the method for azodicarbonamide content in high effective liquid chromatography for measuring leather according to claim 1, it is special
Sign is that the Detection wavelength is 245nm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108459107A (en) * | 2018-04-26 | 2018-08-28 | 南京明捷生物医药检测有限公司 | Utilize the remaining method of hydrazine hydrate in liquid chromatography and mass spectrometry drug |
| CN115267023A (en) * | 2022-07-28 | 2022-11-01 | 格力电器（武汉）有限公司 | Detection method and detection device for azodicarbonamide and readable storage medium |
| CN115266979A (en) * | 2022-07-27 | 2022-11-01 | 上海市质量监督检验技术研究院 | Method for determining azodicarbonamide in textiles and artificial leather |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108459107A (en) * | 2018-04-26 | 2018-08-28 | 南京明捷生物医药检测有限公司 | Utilize the remaining method of hydrazine hydrate in liquid chromatography and mass spectrometry drug |
| CN115266979A (en) * | 2022-07-27 | 2022-11-01 | 上海市质量监督检验技术研究院 | Method for determining azodicarbonamide in textiles and artificial leather |
| CN115266979B (en) * | 2022-07-27 | 2024-02-23 | 上海市质量监督检验技术研究院 | Method for measuring azodicarbonamide in textile and artificial leather |
| CN115267023A (en) * | 2022-07-28 | 2022-11-01 | 格力电器（武汉）有限公司 | Detection method and detection device for azodicarbonamide and readable storage medium |
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