CN102269744B - Rapid detection method of residual amount of dimethylformamide in textiles - Google Patents
Rapid detection method of residual amount of dimethylformamide in textiles Download PDFInfo
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- CN102269744B CN102269744B CN 201110193568 CN201110193568A CN102269744B CN 102269744 B CN102269744 B CN 102269744B CN 201110193568 CN201110193568 CN 201110193568 CN 201110193568 A CN201110193568 A CN 201110193568A CN 102269744 B CN102269744 B CN 102269744B
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- dimethyl formamide
- chlorobenzene
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Abstract
The invention belongs to the field of product quality detection and in particular relates to a rapid detection method of residual amount of dimethylformamide in textiles. The method provided by the invention comprises the following steps of: preparing a guide sample and an internal standard solution; pre-treating the sample; extracting DMF (Dimethyl Formamide) in the sample; carrying out GC/MS (Gas Chromatograph/Metabolic Syndrome) analysis; and detecting the content of DMF through a standard addition method. The method provided by invention can be used for detecting the residual amount of DMF in products including leather, textiles, paper products and the like and various raw materials. Compared with the prior art, the method disclosed by the invention has the advantages of flexibility, accuracy, environment friendliness, simplicity, reliability and easiness of being popularized and is highly effective in detection of the residual amount of DMF in various products and raw materials.
Description
Technical field
The invention belongs to the product quality detection field, be specifically related to the method for quick of dimethyl formamide residual quantity in a kind of textile.
Background technology
Dimethyl formamide (Dimethyl Formamide, DMF) is a kind of anhydrous transparency liquid, molecular formula C
3H
7NO, molecular weight 73.Energy and water and majority of organic solvent dissolve each other, and are the common solvent of chemical reaction.Absolute dimethylformamide is not have odorously, but technical grade or rotten dimethyl formamide have a fish like smell because of the impurity that contains dimethyl amine.
Dimethyl formamide is mainly used in the industries such as polyurethane, acrylic fibers, medicine, agricultural chemicals, dyestuff, electronics as important industrial chemicals and the solvent of function admirable.In the polyurethane industry, as the washing hardening agent, be mainly used in wet-method synthetic leather production; In pharmaceuticals industry, as the synthetic drug intermediate, be widely used in the production of producing fortimicin, cortisone, sulfa; In acrylic fiber industry, as solvent, be mainly used in the dry spinning production of acrylic fibers; In pesticide industry for the synthesis of the higher effective and lower toxic pesticide pesticide; At dye industry as dye solvent; In electron trade as the quenching of zinc-plated parts and the cleaning of circuit board etc.; The carrier, crystallized medicine that other industry comprises hazardous gas is with solvent, bonding agent etc.DMF mainly exists in various leathers, textile, the fabric in residual mode.
The toxic effect mechanism of DMF is not yet fully clear, thinks at present relevant with its internal metabolism process.Acute poisoning generally occurs after sucking in respiratory tract after about 6～12 hours; Skin is invaded, and latent period can be longer, and the report that occurs again poisoning after skin burn heals is substantially also arranged.The DMF steam can cause eye, light, the moderate irritation of the upper respiratory tract.And skin, intestines and stomach, liver etc. there is in various degree infringement.Therefore, a lot of countries and the European Union hygienic standard of all having worked out DMF: workshop air hygienic standard: Chinese MAC 10.0 mg/m
3U.S. ACGIH TLV-TWA 30 mg/m
3(10ppm) (skin) danger rule: GB3.3 class 33627.UN?NO.2265。IMDG CODE 3132-2 page or leaf, 3.3 classes.
Prior art adopts the content of gas chromatography determination dimethyl formamide.Specifically take absolute ethyl alcohol as solvent, take biphenyl as internal standard compound, it is that the glass column of filling material separates the dimethyl formamide in the sample with hydrogen flame ionization detector and measures at GAS CHRAME Q carrier that practical QF-1 immobile liquid is coated with stain.This method exists the pre-treatment reagent consumption large, the length that expends time in, and method detects limit for height, qualitative inaccurate (the false positive phenomenon is arranged) and the shortcoming that easily is disturbed.The method that therefore, the mensuration dimethyl formamide of sensitiveer, quick, environmental protection need to be arranged.
Summary of the invention
The object of the invention is to provide the method for quick of dimethyl formamide residual quantity in a kind of textile, and the method has method sensitivity, accurate, environmentally friendly, and simple, reliable, the advantage that is easy to promote.
The method for quick of dimethyl formamide residual quantity in a kind of textile that the present invention proposes, concrete steps are as follows:
(1) preparation standard specimen and inner mark solution: take by weighing the methyl alcohol standard specimen solution that DMF is mixed with 0.5-5.0 mg/mL; Take by weighing the chlorobenzene methanol inner mark solution of chlorobenzene preparation 0.5-5.0 mg/mL;
(2) sample pretreatment: sample is shredded, mix, the sample 1.0-5.0 g that takes by weighing two parts of identical weight places respectively the in advance dry head space bottle of crossing, the chlorobenzene methanol inner mark solution that all adds the configuration of 2.0 μ L steps (1), mix after the sealing, also add the methyl alcohol standard specimen solution of 2.0 μ L steps (1) configuration in a copy of it sample;
(3) DMF in the sample is extracted: two parts of samples of step (2) configuration are carried out respectively solid-phase microextraction 10-30min behind the balance 3-10 min in 40-80 ℃ of oil bath, wherein solid phase micro-extracting head before inserting at aging 5 min of GC injection port;
(4) carrying out GC/MS analyzes: the solid phase micro-extracting head in the step (3) is carried out respectively GC/MS analyze, wherein, the GC/MS condition is for selecting the middle polarity capillary chromatographic column; 60 ℃ of initial temperatures keep 3min, and 20 ℃/min is raised to 250 ℃, keep 5min, carrier gas is helium, and purity is 99.999%, and flow velocity is 1mL/min, injector temperature: 230 ℃, sample injection time is 3 min, and split ratio is 10:1,230 ℃ of chromatogram mass spectrum connector temperature, and ion gun adopts the EI source; Ion source temperature is 200 ℃; Ionizing energy is 70eV; Level Four bar temperature is 200 ℃, and sweep limit is 41 ~ 350 a.m.u.;
(5) content of Standard Addition Method for Determination DMF: the ratio of the characteristic ion 112 of the characteristic ion 44 of detected DMF and 73 peak area sum and chlorobenzene and 114 peak area sum is as Quantitative Factors, by the DMF residual quantity of each sample of standard deviation subtraction in the step (4).
Among the present invention, the solid phase micro-extracting head that uses in the step (3) adopts 75 μ m Carboxen
TM-PDMS.
According to the difference of sampling amount in the step (5), the detectability that the present invention measures DMF content can reach 0.10 mg/kg.
Beneficial effect of the present invention is: can be residual for detection of the DMF of the products such as leather, textile, papery product and various raw materials.Compare with existing method, this method has method sensitivity, accurate, environmentally friendly, and simple, reliable, is easy to promote, and is very effective to the residual mensuration of the DMF of various products and raw material.
Description of drawings
Fig. 1 is the chromatogram of embodiment 3 sample detection; Wherein: curve 1 is the chromatographic peak of chlorobenzene, and curve 2 is the chromatographic peak of DMF.
Fig. 2 is the mass spectrogram of DMF.
Fig. 3 is the mass spectrogram of chlorobenzene.
Embodiment
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
The GC/MS condition is: dimethyl formamide is strong polar material, and boiling point is low, selects the middle polarity capillary chromatographic column; 60 ℃ of initial temperatures keep 3min, and 20 ℃/min is raised to 250 ℃, keep 5min.
Carrier gas is helium, and purity is 99.999%, and flow velocity is 1mL/min.
Injector temperature: 230 ℃.
Solid-phase microextraction handle, extracting head adopt 75 μ m Carboxen
TM-PDMS.
Sample injection time: 3 min.
Split ratio: 10:1..
230 ℃ of chromatogram mass spectrum connector temperature.
Ion gun: EI source; Ion source temperature: 200 ℃; Ionizing energy: 70eV; Level Four bar temperature: 200 ℃.
Sweep limit: 41 ~ 350 a.m.u.
Embodiment 1:
DMF standard solution: in the 100mL volumetric flask, add in advance about 50mL methyl alcohol, and then add 50.0 mgDMF, be mixed with the methanol solution of 0.5 mg/mL.
Interior mark (chlorobenzene) standard solution: in the 100mL volumetric flask, add in advance about 50mL methyl alcohol, and then add 50.0 mg chlorobenzenes, then add methyl alcohol to scale mark, be mixed with the methanol solution of 0.5 mg/mL.
Sample passes through first pre-service, and it is shredded rear mixing.Accurately take by weighing sample to be tested 1.0 g and place the in advance dry head space bottle of crossing, add mark (chlorobenzene) standard solution in the 2.0 μ L, mix after the sealing.
Add the sample pretreatment of standard specimen: accurately take by weighing sample to be tested 1.0 g and place the head space bottle, add mark (chlorobenzene) standard solution in the 2.0 μ L, add in addition 2.0 μ L DMF standard solution, mix after the sealing.
Two duplicate samples are inserted respectively solid phase micro-extracting head behind balance 10 min in 40 ℃ of oil baths, carry out GC/MS behind the extraction 30min and analyze.
Take the peak area ratio of the characteristic ion 112 of the peak area sum of the characteristic ion 44 of detected DMF and 73 and chlorobenzene and 114 sums as Quantitative Factors, by the DMF residual quantity of each sample of standard deviation subtraction.
Embodiment 2:
DMF standard solution: accurately take by weighing 200.0 mg DMF in 100 mL volumetric flasks, be mixed with the methanol solution of 2.0 mg/mL.
Interior mark (chlorobenzene) standard solution: accurately take by weighing 200.0 mg chlorobenzenes in 100 mL volumetric flasks, be mixed with the chlorobenzene methanol inner mark solution of 2.0 mg/mL.
Sample passes through first pre-service, and it is shredded rear mixing.Accurately take by weighing sample to be tested 2.5 g and place the in advance dry head space bottle of crossing, add mark (chlorobenzene) standard solution in the 2.0 μ L, mix after the sealing.
Add the sample pretreatment of standard specimen: accurately take by weighing sample to be tested 2.5 g and place the head space bottle, add mark (chlorobenzene) standard solution in the 2.0 μ L, add in addition 2.0 μ L DMF standard solution, mix after the sealing.
Two duplicate samples are inserted respectively solid phase micro-extracting head behind balance 5 min in 60 ℃ of oil baths, carry out GC/MS behind the extraction 20min and analyze.
Take the peak area ratio of the characteristic ion 112 of the peak area sum of the characteristic ion 44 of detected DMF and 73 and chlorobenzene and 114 sums as Quantitative Factors, by the DMF residual quantity of each sample of standard deviation subtraction.
Embodiment 3:
DMF standard solution: accurately take by weighing 500.0 mgDMF in 100 mL volumetric flasks, be mixed with the methanol solution of 5.0 mg/mL.
Interior mark (chlorobenzene) standard solution: accurately take by weighing 500.0 mg chlorobenzenes in 100 mL volumetric flasks, be mixed with the chlorobenzene methanol inner mark solution of 5.0 mg/mL.
Sample passes through first pre-service, and it is shredded rear mixing.Accurately take by weighing sample to be tested 5.0 g and place the in advance dry head space bottle of crossing, add mark (chlorobenzene) standard solution in the 2.0 μ L, mix after the sealing.
Add the sample pretreatment of standard specimen: accurately take by weighing sample to be tested 5.0 g and place the head space bottle, add mark (chlorobenzene) standard solution in the 2.0 μ L, add in addition 2.0 μ L DMF standard solution, mix after the sealing.
Two duplicate samples are inserted respectively solid phase micro-extracting head behind balance 3 min in 80 ℃ of oil baths, carry out GC/MS behind the extraction 10min and analyze.
Take the peak area ratio of the characteristic ion 112 of the peak area sum of the characteristic ion 44 of detected DMF and 73 and chlorobenzene and 114 sums as Quantitative Factors, by the DMF residual quantity of each sample of standard deviation subtraction.
The Specimen Determination of interpolation DMF standard specimen three times, twice of the Specimen Determination that does not add.
The recovery that embodiment 1-3 records, reappearance and quantitative scope are as follows:
Recovery data see Table 1:
Three kinds of sample determination results that add level of table 1
Six parallel results' relative standard deviation is 7.1%.
Show that through blank mark-on test the detection of the method is limited to 0.10 mg/kg.
Claims (1)
1. the method for quick of dimethyl formamide residual quantity in the textile is characterized in that concrete steps are as follows:
(1) preparation standard specimen and inner mark solution: taking by weighing the dimethyl formamide compound concentration is the methyl alcohol standard specimen solution of 0.5-5.0 mg/mL; Taking by weighing the chlorobenzene compound concentration is the chlorobenzene methanol inner mark solution of 0.5-5.0 mg/mL;
(2) sample pretreatment: sample is shredded, mix, the sample 1.0-5.0 g that takes by weighing two parts of identical weight places respectively the in advance dry head space bottle of crossing, the chlorobenzene methanol inner mark solution that all adds the configuration of 2.0 μ L steps (1), mix after the sealing, also add the methyl alcohol standard specimen solution of 2.0 μ L steps (1) configuration in a copy of it sample;
(3) dimethyl formamide in the sample is extracted: two parts of samples of step (2) configuration are carried out respectively solid-phase microextraction 10-30min behind the balance 3-10 min in 40-80 ℃ of oil bath, wherein solid phase micro-extracting head before inserting at aging 5 min of GC injection port; The solid phase micro-extracting head that uses adopts 75 μ m Carboxen
TM-PDMS;
(4) carrying out GC/MS analyzes: the solid phase micro-extracting head in the step (3) is carried out respectively GC/MS analyze, wherein, the GC/MS condition is for selecting the middle polarity capillary chromatographic column; 60 ℃ of initial temperatures keep 3min, and 20 ℃/min is raised to 250 ℃, keep 5min, carrier gas is helium, and purity is 99.999%, and flow velocity is 1mL/min, injector temperature: 230 ℃, sample injection time is 3 min, and split ratio is 10:1,230 ℃ of chromatogram mass spectrum connector temperature, and ion gun adopts the EI source; Ion source temperature is 200 ℃; Ionizing energy is 70eV; Level Four bar temperature is 200 ℃, and sweep limit is 41 ~ 350 a.m.u.;
(5) content of Standard Addition Method for Determination dimethyl formamide: in the step (4) characteristic ion of detected dimethyl formamide at the peak area ratio of characteristic ion on 112 and 114 of the peak area on 44 and 73 and chlorobenzene as Quantitative Factors, by the dimethyl formamide residual quantity of each sample of standard deviation subtraction.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN103713062B (en) * | 2013-12-31 | 2015-07-29 | 深圳出入境检验检疫局工业品检测技术中心 | The method for quick of Determination of Residual Organic Solvents is limited the use of in a kind of textile |
| CN103808847A (en) * | 2014-02-26 | 2014-05-21 | 惠州出入境检验检疫局检验检疫综合技术中心 | Method for simultaneously detecting DMF (Dimethyl Formamide), DMAC (Dimethylacetamide) and NMP (N-Methylpyrrolidone) through gas chromatography-mass spectrometry |
| 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 |
| CN104698119B (en) * | 2015-03-31 | 2017-01-25 | 中国科学院长春应用化学研究所 | Method for detecting amide compounds in environment water sample |
| CN105203681A (en) * | 2015-09-02 | 2015-12-30 | 兰州科天新材料股份有限公司 | Method for determining N,N-dimethyl formamide |
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