CN102033113B - Method for determining content of dimethylformamide - Google Patents
Method for determining content of dimethylformamide Download PDFInfo
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- CN102033113B CN102033113B CN 201010501424 CN201010501424A CN102033113B CN 102033113 B CN102033113 B CN 102033113B CN 201010501424 CN201010501424 CN 201010501424 CN 201010501424 A CN201010501424 A CN 201010501424A CN 102033113 B CN102033113 B CN 102033113B
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Abstract
The invention provides a method for determining the content of dimethylformamide, sequentially comprising the following steps of, firstly, pretreating a sample; secondly, preparing a sample extract and a standard working fluid; thirdly, carrying out gas phase chromatography-mass spectrometry (GC-MS) analysis; fourthly, drawing a standard curve; and fifthly, quantitatively determining the content of the dimethylformamide with an external standard method. The method is sensitive, accurate, exclusive, convenient, feasible and easy to popularize and is necessary to control residues of the dimethylformamide.
Description
Technical field
The present invention relates to the product quality detection range, relate in particular to a kind of method that dimethyl formamide content in leather and the textile is detected.
Background technology
Dimethyl formamide (Dimethylformamide; DMF) be a kind of liquid of colourless, light amine flavor.Molecular formula C
3H
7NO, molecular weight 73.10, relative density 0.9445 (25 ℃), fusing point-61 ℃, 152.8 ℃ of boiling points, 57.78 ℃ of flash-points, vapour density 2.51, vapor pressure 0.49kpa (3.7mmHg25 ℃), 445 ℃ of spontaneous ignition temperatures, steam and air mixture explosion limits 2.2～15.2%, it meets naked light, Gao Re can cause combustion explosion.
Dimethyl formamide (DMF) is as the solvent water-soluble and most of organic solvents of energy and the inorganic liquid of important chemical material and function admirable, and dissolving power is very strong, is called as omnipotent organic solvent.Dimethyl formamide is good solvent to multiple superpolymer such as tygon, Polyvinylchloride, polyacrylonitrile, polyamide etc., wet spinning silk, polyurethane synthetic that can be used for synthon such as polyacrylonitrile fibre, be used for plastics film processed, also can remove the paint stripper of paint.It can also dissolve the pigment of some low solubility, makes pigment have the characteristics of dyestuff.Mainly be present in various leathers, textile, the fabric, and be as residual and exist.
Dimethyl formamide can enter in the body through respiratory tract, skin and gastrointestinal absorption, and skin, mucous membrane are had pungency, enters and can damage the central nervous system important organs such as liver, kidney, stomach of unifying behind the human body.Acute poisoning mainly show as eye and the irritation of the upper respiratory tract, as shed tears, cough, to have a headache also can appear in the poisoner, dizzy, drowsiness, nauseating, nerve and gastrointestinal symptom such as upper abdomen has an intense pain, hemorrhage of digestive tract can appear in severe patient.Poison after a couple of days, hepatic lesion symptom and renal dysfunctions such as hepatomegaly, hepatic region tenderness, jaundice, dysfunction of liver can appear in the patient, the property a crossed heart injury also can occur.Skin fash, oedema, blister, ulceration, furfur etc. can occur after being polluted by dimethyl formamide, and numbness, itch and cusalgia symptom can occur.Dimethyl formamide comprises skin, MMi to the chronic influence of human body, neurasthenic syndrome, and blood pressure is on the low side.Nauseating, vomiting, uncomfortable in chest, poor appetite, stomachache, constipation and changes of liver function are still arranged.
Prior art adopts the content of gas chromatography determination dimethyl formamide.Specifically being to be solvent with the absolute ethyl alcohol, is internal standard compound with biphenyl, uses the QF-1 immobile liquid to be coated with stain and the dimethyl formamide in the sample is separated with hydrogen flame ionization detector as the glass column of filling material and measure at GAS CHRAME Q carrier.Vapor-phase chromatography flow operations complexity, the pre-treatment reagent consumption is big, and method detects limit for height, and recovery instability is quantitatively inaccurate.Therefore, need to adopt advanced analysis means, accurately quantitative measurement dimethyl formamide and set up corresponding method of testing.
Summary of the invention
The invention provides a kind of method of measuring dimethyl formamide content, may further comprise the steps:
(1) sample pretreatment;
(2) preparation sample extracting solution and standard operation liquid;
(3) carry out gas chromatography-mass spectrum (GC-MS) analysis;
(4) drawing standard curve;
(5) content of external standard method quantitative measurement dimethyl formamide.
The sample that detects is applicable to leather and textile.Sample should pass through pre-service earlier, and it is cut mixing to the fragment.
Ultrasonic extraction or extraction under normal temperature or 40～50 ℃ of water bath condition adopted in the preparation of sample extracting solution.Selecting for use low cost, hypotoxicity to reach in sample extraction or the extraction step extracts or extracts the little organic solvent of dimethyl formamide detection interference.Because dimethyl formamide is a kind of strong polar material, so have dissolubility preferably in ethyl acetate.In addition, ethyl acetate has characteristics such as boiling point is low, toxic and side effect is little, so selects for use ethyl acetate to remain in dimethyl formamide in the sample as solvent extraction among the present invention.
Standard operation liquid is formulated with the dimethyl formamide standard items.Take by weighing dimethyl formamide standard items preparing standard solution earlier, the dimethyl formamide standard solution is diluted to standard operation liquid from a plurality of variable concentrations between 0.1ug/mL～5ug/mL.When if the concentration of sample extracting solution is higher than the Cmax of standard operation liquid, it should be diluted to below the standard operation liquid Cmax during test.
Gas chromatography-mass spectrum (GC-MS) analytic process is under certain conditions, and the peak area of dimethyl formamide in sample extracting solution and the standard operation liquid is measured.
Be horizontal ordinate with sample size (ug/mL), peak area is ordinate drawing standard curve, and obtains the typical curve equation.
At last, calculate the content of dimethyl formamide in the sample by external standard method.
Concrete technical scheme is as follows:
(1) sample pretreatment:
Get representative sample, it is shredded fragment to 5mm * 5mm, mixing.
(2) preparation sample extracting solution and standard operation liquid:
Take by weighing sample (being accurate to 0.1mg) in test tube, add ethyl acetate solvent, extract or extract 1～3 time, extraction or extraction process can carry out under normal temperature or 40～50 ℃ of water bath condition, can or ultrasonicly extract or extract by jolting, concentrate after merging extraction or extract, use the ethyl acetate solvent constant volume, as sample extracting solution.
Measure an amount of dimethyl formamide standard items, preparing standard solution, and this standard solution is diluted to the standard operation liquid of 0.1ug/mL, 0.5ug/mL, 1ug/mL, 2ug/mL, 5ug/mL concentration respectively.
(3) chromatographic peak area of dimethyl formamide in gas chromatography-mass spectrum (GC-MS) working sample extract and the standard operation liquid.
The GC-MS analysis condition is as follows:
Dimethyl formamide is strong polar material, and boiling point is low, selects the middle polarity chromatographic column for use;
Initial column temperature is 60 ℃, keeps 1min; Rise to 120 ℃ with 10 ℃/min, keep 2min; Rise to 200 ℃ with 20 ℃/min, keep 5min;
Carrier gas is helium, and flow velocity is 1.0mL/min;
Input mode: split sampling not, drive valve behind the 1min; Sample size: 1 μ L; Injector temperature: 160～180 ℃; Chromatography-mass spectroscopy interface temperature: 270-290 ℃;
Ion gun: EI source; Ion source temperature: 230 ℃; Ionizing energy: 70eV; Quadrupole rod temperature: 200 ℃;
Scan mode: Scan+SIM; The solvent delay time: 3～4min.
Sample thief extract and standard operation liquid are measured with GC-MS, in the operation, at first make total ion current figure (TIC) by full scan mode (Scan), then at specimen, select the fragmention that abundance is higher relatively, molecular mass is relatively large in the mass spectrogram to carry out SIM selection test.The present invention selects m/z=73amu to carry out quantitatively as the monitoring ion under the SIM pattern.
(4) typical curve of drawing standard working fluid: be horizontal ordinate with sample size (ug/mL), peak area is ordinate drawing standard curve, obtains the typical curve equation.
(5) mass ratio of dimethyl formamide in the external standard method quantitative measurement sample
Determine the concentration of sample liquid by standard operation liquid typical curve equation, calculate the mass ratio of dimethyl formamide in the sample then.
Computing formula is as follows:
Wherein, X
iMass ratio (μ g/g) for residual dimethyl formamide in the sample; C
iMass concentration (μ gmL for dimethyl formamide close with sample extracting solution concentration in the standard operation liquid
-1); V
iBe the final constant volume of sample extracting solution; M is sample quality.
The detection that the present invention measures the dimethyl formamide content method is limited to 5mg/kg.
Whether method of the present invention can be for detection of there being dimethyl formamide residual in leather and the textile.
Compare with prior art, the present invention provides a kind of dimethyl formamide in the sample has been carried out method for measuring according to the characteristics of detected sample, can accurately measure the content of dimethyl formamide.This method sensitivity, accurate, exclusive, and easy, feasible, easy popularization are residual very necessary to dimethyl formamide in control leather and the textile.
Description of drawings
Figure 1 shows that the total ion current figure of the embodiment of the invention 1 sample;
Figure 2 shows that the mass spectrogram of the embodiment of the invention 1 sample characteristic chromatographic peak;
Figure 3 shows that the typical curve of the embodiment of the invention 1 standard operation liquid.
Embodiment
Following examples will help those of ordinary skill in the art further to understand the present invention, but not limit the present invention in any form.
Employed instrument and equipment is as follows among the following embodiment: gas chromatograph-mass spectrometer (GCMS) (GC-MS7890A-5975C Agilent), rotary evaporator, ultrasonic cleaner, water bath with thermostatic control oscillator.
Get the black ox head layer sofa artificial leather sample that certain enterprise produces, shred the fragment to 5mm * 5mm, mixing.Precision takes by weighing sample 2.1856g (being accurate to 0.1mg) in test tube and adds 20mL ethyl acetate, ultrasonic extraction 2h in 40 ℃ of water-baths, add 20mL ethyl acetate ultrasonic extraction 2h again, merge twice extract and be concentrated into 3mL at Rotary Evaporators, be settled to 10mL with ethyl acetate at last, as sample extracting solution.
The GC-MS condition enactment is as follows:
Chromatographic column: DB-5MS post, 30m * 0.25mm (i.d.) * 0.25 μ m;
Column temperature: 60 ℃ of initial temperatures, keep 1min, rise to 120 ℃ with 10 ℃/min; Keep 2min, rise to 200 ℃ with 20 ℃/min, keep 5min;
Carrier gas: helium, purity 〉=99.999%; Control mode: constant current; Flow velocity: 1.0mL/min;
Input mode: split sampling not, drive valve behind the 1min; Sample size: 1 μ L; Injector temperature: 160 ℃; Chromatography-mass spectroscopy interface temperature: 280 ℃;
Ion gun: EI source; Ion source temperature: 230 ℃; Ionizing energy: 70eV; Quadrupole rod temperature: 200 ℃;
Scan mode: Scan+SIM; The solvent delay time: 3.6min.
Under these conditions, make total ion current figure (TIC) by full scan mode (Scan) earlier, as shown in Figure 1, record the characteristic chromatographic peak of dimethyl formamide, its retention time is the 4.01min (see figure 1).Analyze the mass spectrogram (see figure 2) of this chromatographic peak again, can see feature mass spectra peak m/z=73amu and m/z=44amu.Select m/z=73amu as the monitoring ion under the SIM pattern in the present embodiment.The spectrogram of the dimethyl formamide in the empirical tests, the mass spectrogram of this chromatographic peak shown in Figure 2 and standard picture library is consistent.
The typical curve of standard operation liquid as shown in Figure 3, its linear equations is y=740591x+4408.4, R
2Be that 0.999, y represents peak area, x represents sample size (ug/mL), and the concentration that can try to achieve sample liquid according to the typical curve equation is 4.72ug/mL.
According to formula
Calculate, the mass ratio of residual dimethyl formamide is 21.6mg/kg in the black ox head layer sofa artificial leather sample.
Claims (1)
1. method of measuring dimethyl formamide content in leather and/or the textile, formed by following steps successively:
(1) sample pretreatment: sample is cut to fragment mixing;
(2) preparation sample extracting solution and standard operation liquid: with ethyl acetate sample is extracted or extracts, extract or extraction process in heating and/or ultrasonicly carry out down, merge extract or extract after concentrated, the ethyl acetate constant volume is as sample extracting solution; Take by weighing the dimethyl formamide standard items, preparing standard solution, and described standard solution is diluted to the standard operation liquid of variable concentrations;
(3) carry out gas chromatography-mass spectrum (GC-MS) analysis: described sample extracting solution and standard operation liquid are carried out the GC-MS analysis, select the middle polarity chromatographic column for use, injector temperature is at 160～180 ℃, the chromatography-mass spectroscopy interface temperature is at 270～290 ℃, be carrier gas with the helium, the mass ion source temperature is 230 ℃, and electron impact ionization source EI is 70eV, adopt not split sampling, and select m/z=73amu as the monitoring ion under the SIM pattern;
(4) drawing standard curve: be horizontal ordinate with the sample size, peak area is ordinate drawing standard curve;
(5) content of external standard method quantitative measurement dimethyl formamide: the mass ratio of dimethyl formamide in the external standard method quantitative measurement sample.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102854265A (en) * | 2012-09-11 | 2013-01-02 | 广州广电计量检测股份有限公司 | Analyzing method of N,N-dimethylformamide in leather and textile products |
| CN103472176B (en) * | 2013-09-17 | 2015-12-09 | 嘉兴学院 | Detect the method for DMF residual quantity in PU leather |
| CN103512996B (en) * | 2013-10-22 | 2014-10-22 | 广州广电计量检测股份有限公司 | Analysis method for amide compounds |
| CN103969389A (en) * | 2014-05-14 | 2014-08-06 | 合肥工业大学 | Gas chromatography detection method for trace N,N-dimethyl formamide in synthesized leather |
| CN104792887A (en) * | 2014-12-30 | 2015-07-22 | 东莞市正明检测技术有限公司 | A method of measuring the content of dimethylformamide in soil |
| CN109490456A (en) * | 2018-11-21 | 2019-03-19 | 山东省产品质量检验研究院 | The detection method of formamide content in a kind of foamed plastic pad |
| CN111239305B (en) * | 2020-03-20 | 2020-11-13 | 山东省产品质量检验研究院 | Method for rapidly detecting formamide in child ground mat and yoga mat |
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Non-Patent Citations (5)
| Title |
|---|
| 吴邦华等.GC/MS法同时检测尿中N N-二甲基甲酰胺及其代谢产物N-甲基甲酰胺.《中国卫生检验杂志》.2002 |
| 吴邦华等.GC/MS法同时检测尿中N,N-二甲基甲酰胺及其代谢产物N-甲基甲酰胺.《中国卫生检验杂志》.2002,第12卷(第1期),文章摘要、第1-2节. * |
| 沙云菲等.马来酸替加色罗中有机溶剂残留量的气相色谱法测定.《复旦学报(医学版)》.2004,第31卷(第1期),93-95,98. * |
| 王卫.气相色谱法测定格列本脲胶囊中二甲基甲酰胺的含量.《中国药学杂志》.2001,第36卷(第2期),120-122. * |
| 郁沁明等.工作场所空气中二甲基甲酰胺、十一烷等混合物的测定方法研究.《环境与职业医学》.2008,第25卷(第1期),105-107. * |
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