CN108107132A - The detection method of phenol total content in a kind of leather and its leather products - Google Patents
The detection method of phenol total content in a kind of leather and its leather products Download PDFInfo
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- CN108107132A CN108107132A CN201711443270.XA CN201711443270A CN108107132A CN 108107132 A CN108107132 A CN 108107132A CN 201711443270 A CN201711443270 A CN 201711443270A CN 108107132 A CN108107132 A CN 108107132A
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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
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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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Abstract
The present invention relates to technical field of analysis and detection, the detection method of phenol total content specifically in a kind of leather and its leather products.This comprises the following steps：1）Sample preparation：Leather sample is cut into 5mm × below 5mm samples, mixing is to be measured；2）Specimen eliminating；3）Acetylization reaction：Filtrate is transferred to separatory funnel, adds in 2mL acetic anhydrides, 3 mL n-hexanes extract 30min, centrifuge 5min using oscillator, stand, upper strata n-hexane extract is taken to be settled to 3mL, to be measured through 0.45 μm of organic filter membrane filtration；4）Analysis detection：By step 3）The prepare liquid of acquisition carries out analysis detection with gaschromatographic mass spectrometry technology；5）It is quantitative to calculate.The detection method is simple, quick, accurate, automation, and the quality of quality control, the field of circulation suitable for enterprise's production is checked on and the supervision of Related product safety controls.
Description
Technical field
The present invention relates to technical field of analysis and detection, the inspection of phenol total content specifically in a kind of leather and its leather products
Survey method.
Background technology
Phenol is important basic organic chemical industry raw material, and product is related to various fields downstream.It is industrially main to use
In manufacture phenolic resin, bisphenol-A and caprolactam.In addition, phenol derivatives such as halogenated phenols, nitrophenols, alkyl phenol can be used for curing
The production of medicine, pesticide, paint, dyestuff, explosive, petroleum additive, paint stripper, timber preservative, fragrance etc..In leather and leather
In product, phenol may from handled from leather processing disinfectant, antioxidant, surfactant, dyeing assistant, varnish,
Coating, adhesive, retanning agent and fire retardant etc..
Phenol has skin, mucous membrane strong corrosiveness, can inhibit nervous centralis or damage Liver and kidney function.Sucking is high
Concentration vapor can cause headache, dizzy, weak, blurred vision, pulmonary edema etc..It wrongly takes and alimentary canal is caused to be burnt, burning pain occur, exhale
Outlet band phenol taste, vomitus or the possibility that with blood, can have gastric-intestinal perforation greatly may occur in which shock, pulmonary edema, liver or kidney damage
, there is acute renal failure, can die of respiratory failure in evil.Eye contact can cause to burn, and phenol is absorbed through skin ambustion, certain
After incubation period, acute renal failure can be caused.Therefore the phenol content in detection leather has important practical significance.
The relevant report of the detection technique of total phenol content in leather and products thereof is had no at present.Measure the standard of phenol
Method has GB/T30696-2014《The measure of hard phenol formaldehyde foam products free-phenol》, this method is using acetone extract sample
In free-phenol, using gas chromatograph hydride ion detector measure, inner mark method ration.Measure phenol in leather
The standard method of class substance has ISO 17070:2015(E) Leather-Chemical tests-Determination of
Tetrachlorophenol-, trichlorophenol-, dichlorophenol-, monochlorophenol-isomers
and pentachlorophenol content（Leather chemistry experiment four, three, two, monochlorphenol-isomers and pentachlorophenol
The measure of content）, this method adds in sulfuric acid solution in the sample, then using vapor distillation method, n-hexane extraction, gas-chromatography
Instrument electron capture detector（ECD）It measures, quantified by external standard method measures the content of chlorobenzene aldehydes matter in leather sample.
The content of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide phenol total content in a kind of leather and leather and fur products
Detection method.The detection method is simple, quick, accurate, automation, quality control, the field of circulation suitable for enterprise's production
Quality check on and the supervision of Related product safety control, filled up the inspection of China's phenol content in leather and leather products
Technological gap in survey.
For achieving the above object, the present invention adopts the following technical scheme that：
The detection method of phenol content, comprises the following steps in a kind of leather and its leather products：
1）Sample preparation：Leather sample is cut into 5mm × below 5mm samples, mixing is to be measured；
2）Specimen eliminating：The accurate 2.000g samples that weigh add in 20mL1 mol/L potassium hydroxide solutions in a conical flask with cover,
After clearing up 60min in 70 DEG C of ultrasonic cleaning machines, then add 20 mL solution of potassium carbonate resolution 60min, filtering；(concentration of potassium hydroxide
1 mol/L is cannot be below, temperature cannot be below 70 DEG C, and otherwise resolution is incomplete, influences testing result)
3）Acetylization reaction：Filtrate is transferred to separatory funnel, adds in 2mL acetic anhydrides, 3 mL n-hexanes are extracted using oscillator
30min, centrifuge 5min stand, upper strata n-hexane extract are taken to be settled to 3mL, through 0.45 μm of organic filter film mistake
Filter, it is to be measured；
4）Analysis detection：By step 3）The prepare liquid of acquisition carries out analysis detection with gaschromatographic mass spectrometry technology；
5）It is quantitative to calculate：By step 4）It obtains each parameter value and substitutes into following formula（1）It is calculated, to obtain the reality of phenol in leather
Border measured value；
（1）
In formula：
XPhenol content in-sample, unit are milligrams per kilogram（mg/kg）；
cPhenol concentration in-sample extracting solution, unit are milligrams per liter（mg/L）；
c oPhenol concentration in-blank solution, unit are milligrams per liter（mg/L）；
The volume of V-n-hexane extract, unit are milliliter（mL）；
mThe quality of-sample, unit are gram（g）.
Step 2）Clear up condition during sample, it is ensured that fully dissolve leather sample, avoid extraction incomplete, extraction efficiency
It is low.Phenol is generated acetylization reaction by step 3) using acetic anhydride, and the structure of phenol is made more to stablize, avoids object to be measured object quilt
Oxidation or reduction, so as to ensure to detect the accuracy of phenol content result in sample.
Step 4）Specially：By step 3）The prepare liquid of acquisition carries out machine analysis, to obtain measured object benzene in prepare liquid
The response signal of phenol chooses the corresponding standard working solution of response according to the response signal of measured object in prepare liquid afterwards and carries out color
Spectrum analysis, standard working solution are equipped with comprising six concentration gradients including zero point, and phenol in standard working solution and prepare liquid
The response of substance should all be in instrument linear response range, and sets a blank control simultaneously.
Step 4）In the condition of gas chromatography mass spectrometer be：
a）Chromatographic column：5% pheiiyldimetliyl poly (arylene ether) siloxanes quartz capillary column, long 30 m, 0.25 mm of internal diameter, film thickness
0.25 μm or suitable person；
b）Carrier gas：Helium, purity >=99.999%；
c）Carrier gas flux：1 mL/min；
d）Injector temperature：200℃；
e）Sample size：1 µL；
F) mode is ionized：EI sources；
G) ionizing energy：70 eV；
H) detection mode：Select ion detection（SIM）；
I) chromatography-mass spectroscopy interface temperature：230℃；
j）Chromatographic column temperature program：After 50 DEG C of initial temperature keeps 2 min, 180 DEG C are risen to 20 DEG C/min, keeps 2 min, then
240 DEG C are risen to 40 DEG C/min, keeps 2 min.
The beneficial effects of the present invention are：
（1）The method of the present invention is simple and quick, and not only step is few, can improve the accuracy of experiment to avoid the loss of object,
And the solvent species toxicity that uses is smaller can reduce the environmental pollution brought by experiment.
（2）Accurately and reliably, phenol content has good detection method in the range of 1-100 mg/L in leather
Linearly, correlation coefficient r is more than 0.9996, and recovery of standard addition is between 85.0%-107.2%.
（3）The present invention is suitable for the quality control of enterprise's production, the quality of the field of circulation is checked on and Related product safety
Supervision control, filled up technological gap of the China in leather and leather and fur products in the detection of phenol content.
Specific embodiment
Further to disclose rather than limiting the present invention, below in conjunction with example, the present invention is described in further detail.
The detection method of phenol content in leather of the present invention, specifically includes following operating procedure：
Step 1: sample preparation：
Leather sample is cut into 5mm × below 5mm samples, mixing is to be measured.
Step 2: extraction
Accurately weigh 2.0 g（It is accurate to 1 mg）Sample is in conical flask with cover.20 mL 1mol/L potassium hydroxide solutions are added in,
After extracting 60min in 70 DEG C of ultrasonic cleaning machines, then add 20 mL0.1 mol/L solution of potassium carbonate extraction 60min；Filtrate is transferred to
Separatory funnel, adds in 2 mL acetic anhydrides, and 3 mL n-hexanes extract 30min, centrifuge 5min using oscillator, stand, take
Upper strata n-hexane extract is settled to 3mL, to be measured through 0.45 μm of organic filter membrane filtration.
Step 3: analysis detection：
The survey liquid of acquisition is subjected to analysis detection with gaschromatographic mass spectrometry technology, specifically, prepare liquid is subjected to upper machine analysis
To obtain the response signal for being measured object phenol in prepare liquid, response is chosen according to the response signal of measured object in prepare liquid afterwards
It is worth corresponding standard working solution and carries out chromatography, standard working solution is equipped with comprising six concentration gradients including zero point, and is marked
The response of phenol type substances should all be in instrument linear response range in quasi- working solution and prepare liquid, and sets a sky simultaneously
White control；
Step 4: quantitative calculate：
Gaschromatographic mass spectrometry method is obtained into each parameter value and substitutes into following formula（1）It is calculated, to obtain the reality of phenol in leather
Border measured value；
(1)
In formula：
XPhenol content in-sample, unit are milligrams per kilogram（mg/kg）；
cPhenol concentration in-sample extracting solution, unit are milligrams per liter（mg/L）；
c oPhenol concentration in-blank solution, unit are milligrams per liter（mg/L）；
The volume of V-n-hexane extract, unit are milliliter（mL）；
mThe quality of-sample, unit are gram（g）.
The average value of measurement result twice is taken, is as a result retained to one decimal place.
Further, the condition of gas chromatography mass spectrometer is：
a）Chromatographic column：5% pheiiyldimetliyl poly (arylene ether) siloxanes quartz capillary column, long 30 m, 0.25 mm of internal diameter, film thickness
0.25 μm or suitable person；
b）Carrier gas：Helium, purity >=99.999%；
c）Carrier gas flux：1 mL/min；
d）Injector temperature：200℃；
e）Sample size：1 µL；
F) mode is ionized：EI sources；
G) ionizing energy：70 eV；
H) detection mode：Select ion detection（SIM）；
I) chromatography-mass spectroscopy interface temperature：230℃；
j）Chromatographic column temperature program：After 50 DEG C of initial temperature keeps 2 min, 180 DEG C are risen to 20 DEG C/min, keeps 2 min, then
240 DEG C are risen to 40 DEG C/min, keeps 2 min.
k）Then according to the characteristic ion fragment 94,136,66,43 and its abundance of phenol than 100：16：12：18, quota ion
Fragment 94.
L) this method, which detects, is limited to 0.04mg/kg, between the rate of recovery 85% ~ 107.2%, relative standard deviation（RSD）Exist
Within 8.0%, related coefficient is more than 0.9996.
In order to be preferably described to the present invention, the application is for following several embodiments, and in each example
The feasibility and accuracy of detection method are verified.
Embodiment 1
Sample to be tested --- negative leather sample（Negative sample）
Sample preparation：
1st, prepared by extracting solution：
Negative leather sample is cut into 5mm × below 5mm samples, mixing is to be measured.Accurately weigh 2.0 g（It is accurate to 1 mg）Leather
Six parts of sample is in conical flask with cover.Operation is extracted according to step 2, extracting solution is to be measured.
2nd, analysis detection：
The extracting solution prepared in above-mentioned 1 is operated respectively according to step 3 in the present invention and step 4 successively, and will
Each actual measured value for finally calculating gained is listed in Table 1 below, and calculates the average value and RSD of actual measured value（Relative standard is inclined
Difference) as shown in table 1, which is background values.0.5 mg/L, 1.0 mg/L and 1.5 mg/L benzene will be added in negative sample
Phenol, the rate of recovery and RSD are as shown in table 1.
The background values determination data of phenol content in the negative leather sample of table 1（n=6）
Embodiment 2
Sample to be tested --- positive leather sample（Positive）
Sample preparation：
1st, prepared by extracting solution：
Positive leather sample is cut into 5mm × below 5mm samples, mixing is to be measured.Accurately weigh 2.0 g（It is accurate to 1 mg）Leather
Six parts of sample is in conical flask with cover.Operation is extracted according to step 2, extracting solution is to be measured.
2nd, analysis detection：
The extracting solution prepared in above-mentioned 1 is operated respectively according to step 3 in the present invention and step 4 successively, and will
Each actual measured value for finally calculating gained is listed in Table 1 below, and calculates the average value and RSD of actual measured value（Relative standard is inclined
Difference) as shown in table 2, which is background values.
The determination data of phenol content in the positive leather sample of table 2（n=6）
The pre-treatment extracting method of the detection method of the current existing phenol of comparison or related phenol derivatives, GB/T30696-
2014 and ISO 17070:2015 (E) detect phenol content in leather sample, the results are shown in Table 3.
3 correlation technique of table compares
The leather positive containing phenol is selected, is measured using method in above-mentioned 3, ISO is found in detection process
17070:2015 (E) and the 1st measurement result of GB/T30696-2014 are relatively low, and the sample extracted is carried out again to carry for the 2nd time
It takes, measurement result such as table 4.
4 distinct methods testing result of table
As can be drawn from Table 4, this method directly clears up leather sample, simple and quick can determine the phenol in leather sample
Total content.Using the total content of phenol as 100%, then the rate of recovery that ISO17070 methods extract 2 times is 76.3%, method GB/
The rate of recovery that T30696 extracts 2 times is 61.9%.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification should all belong to the covering scope of the present invention.
Claims (3)
1. a kind of detection method of phenol total content in leather and its leather products, it is characterised in that：Comprise the following steps：
1）Sample preparation：Leather sample is cut into 5mm × below 5mm samples, mixing is to be measured；
2）Specimen eliminating：The accurate 2.000g samples that weigh add in 20mL1 mol/L potassium hydroxide solutions in conical flask with cover,
After clearing up 60min in 70 DEG C of ultrasonic cleaning machines, then add 20 mL solution of potassium carbonate resolution 60min, filtering；
3）Acetylization reaction：Filtrate is transferred to separatory funnel, adds in 2mL acetic anhydrides, 3 mL n-hexanes are extracted using oscillator
30min, centrifuge 5min stand, upper strata n-hexane extract are taken to be settled to 3mL, through 0.45 μm of organic filter film mistake
Filter, it is to be measured；
4）Analysis detection：By step 3）The prepare liquid of acquisition carries out analysis detection with gaschromatographic mass spectrometry technology；
5）It is quantitative to calculate：By step 4）It obtains each parameter value and substitutes into following formula（1）It is calculated, to obtain the reality of phenol in leather
Border measured value；
（1）
In formula：
XPhenol content in-sample, unit are milligrams per kilogram（mg/kg）；
cPhenol concentration in-sample extracting solution, unit are milligrams per liter（mg/L）；
c oPhenol concentration in-blank solution, unit are milligrams per liter（mg/L）；
The volume of V-n-hexane extract, unit are milliliter（mL）；
mThe quality of-sample, unit are gram（g）.
2. the detection method of phenol total content in leather according to claim 1 and its leather products, it is characterised in that：Step
Rapid 4）Specially：By step 3）The prepare liquid of acquisition carries out machine analysis, to obtain the response of measured object phenol in prepare liquid letter
Number, the corresponding standard working solution of response is chosen according to the response signal of measured object in prepare liquid afterwards and carries out chromatography, mark
Quasi- working solution be equipped with comprising six concentration gradients including zero point, and in standard working solution and prepare liquid phenol type substances response
Value should all be in instrument linear response range, and sets a blank control simultaneously.
3. the detection method of phenol content in leather according to claim 1 and its leather products, it is characterised in that：Step
4）In the condition of gas chromatography mass spectrometer be：
a）Chromatographic column：5% pheiiyldimetliyl poly (arylene ether) siloxanes quartz capillary column, long 30 m, 0.25 mm of internal diameter, film thickness
0.25 μm or suitable person；
b）Carrier gas：Helium, purity >=99.999%；
c）Carrier gas flux：1 mL/min；
d）Injector temperature：200℃；
e）Sample size：1 µL；
F) mode is ionized：EI sources；
G) ionizing energy：70 eV；
H) detection mode：Select ion detection（SIM）；
I) chromatography-mass spectroscopy interface temperature：230℃；
j）Chromatographic column temperature program：After 50 DEG C of initial temperature keeps 2 min, 180 DEG C are risen to 20 DEG C/min, keeps 2 min, then
240 DEG C are risen to 40 DEG C/min, keeps 2 min.
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| CN201711443270.XA CN108107132B (en) | 2017-12-27 | 2017-12-27 | Method for detecting total content of phenol in leather and leather products thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711443270.XA CN108107132B (en) | 2017-12-27 | 2017-12-27 | Method for detecting total content of phenol in leather and leather products thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109541076A (en) * | 2019-01-11 | 2019-03-29 | 深圳天祥质量技术服务有限公司 | The detection method of triclosan in a kind of textile |
| CN110568104A (en) * | 2019-09-24 | 2019-12-13 | 杭州市质量技术监督检测院 | Method for simultaneously measuring migration volumes of various chlorinated phenols in wooden tableware |
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| CN106645448A (en) * | 2016-09-28 | 2017-05-10 | 广州纤维产品检测研究院 | Separation detection method of phenol compounds in textiles |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109541076A (en) * | 2019-01-11 | 2019-03-29 | 深圳天祥质量技术服务有限公司 | The detection method of triclosan in a kind of textile |
| CN110568104A (en) * | 2019-09-24 | 2019-12-13 | 杭州市质量技术监督检测院 | Method for simultaneously measuring migration volumes of various chlorinated phenols in wooden tableware |
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