CN106970164A - A kind of method of content of formaldehyde in LC-MS test leather - Google Patents
A kind of method of content of formaldehyde in LC-MS test leather Download PDFInfo
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- CN106970164A CN106970164A CN201710203073.4A CN201710203073A CN106970164A CN 106970164 A CN106970164 A CN 106970164A CN 201710203073 A CN201710203073 A CN 201710203073A CN 106970164 A CN106970164 A CN 106970164A
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
The invention belongs to the method for the content of formaldehyde in the detection method technical field of the consumer goods, more particularly to a kind of LC-MS test leather, comprise the following steps：Leather sample is shredded；Leather sample is weighed, is fitted into container, sodium dodecyl sulfate solution is then added into container, container is rocked, leather sample is moistened；Container is placed in water bath chader and vibrated, leather sample is then filtered out, filtrate is transferred in another container, and is cooled to room temperature, obtains sample extraction liquid；Sample extraction liquid is transferred in volumetric flask, acetonitrile is added and to hydrazino-benzoic acid solution, with being shaken up after deionized water constant volume, after placement, with membrane filtration, then filtrate is analyzed with UPLC MS/MS.The present invention has following advantage：Formaldehyde in leather can completely be extracted；Can be by the complete derivatization of formaldehyde in extract, and derivative products are easy to ionization, are tested with facilitating with UPLC MS/MS；The content of formaldehyde derivatives in sample liquid can rapidly and accurately be detected.
Description
Technical field
The invention belongs to the first in the detection method technical field of the consumer goods, more particularly to a kind of LC-MS test leather
The method of aldehyde.
Background technology
Formaldehyde is a kind of toxic gas that is colourless, having intense irritation stink, is highly soluble in water, and have for skin and mucosa
Very strong stimulation.It recent studies have shown that, formaldehyde has strong carcinogenesis, be defined as by the World Health Organization
One class is carcinogenic and teratogenesis material.Leather and leather products syntans used in conventional machining process, resin tanning agent, fixation
Formaldehyde or formaldehyde precursor material may all be contained in the chemicals such as agent, dyestuff, coating material.Because formaldehyde is highly soluble in the spy of water
Formaldehyde in property, leather and leather products through skin can enter human body by the dipping of sweat, and then cause allergic, or even meeting
Increase the risk of human carcinogen.So current, countries in the world are limited Determination of Formaldehyde in Leather one after another.
Due to formaldehyde molecular weight very little and without the UV absorption available for test, so during test, it usually needs to first
Aldehyde is first performed the derivatization, the derivative content of re-test formaldehyde, and the content of formaldehyde is calculated with this.Existing formaldehyde total amount test side
The analysis means commonly used in method have two kinds, and one is by being tested after being developed the color with acetylacetone,2,4-pentanedione with spectrophotometer (UV-VIS) two
It is by being tested after deriving with 2,4 dinitrophenyl hydrazine with high performance liquid chromatograph (HPLC).Tested with spectrophotometer
When, test result is generally very big by the interference of solution colour, particularly with colouring leather, and this method can not obtain accurate formaldehyde
Content.And in efficient liquid-phase chromatography method, the reaction of DNPH and formaldehyde is non-selective, major part has carbonyl
The aldehydes or ketone of base can be reacted with DNPH, and the absorption spectrum of derivative is also similar, so
Have in the presence of the materials such as acetaldehyde or acetone, the test result of formaldehyde suffers from interference.
In view of this, the present invention is intended to provide the method for the content of formaldehyde in a kind of LC-MS test leather, it is used
The derivative of ultra performance liquid chromatography tandem mass spectrum combined instrument (UPLC-MS/MS) PARA FORMALDEHYDE PRILLS(91,95) and p- hydrazino-benzoic acid is surveyed
Examination, it is qualitative to being carried out to target compound with companion ion with retention time, color in both the above method is solved well
The problem of interference and allied substances are disturbed, can obtain more accurate content of formaldehyde result.Meanwhile, in view of UPLC-MS/MS
Separating rate is fast, and the lower advantage of test limit, analysis efficiency of the invention is very high, and two kind sides of the detection limit well below more than
Method, can detect the content of formaldehyde of ppb ranks in leather.
The content of the invention
It is an object of the invention to：In view of the shortcomings of the prior art, the first in a kind of LC-MS test leather is provided
The method of aldehyde, it uses ultra performance liquid chromatography tandem mass spectrum combined instrument (UPLC-MS/MS) PARA FORMALDEHYDE PRILLS(91,95) and p- diazanyl benzene
The derivative of formic acid is tested, qualitative to being carried out to target compound with companion ion with retention time, is solved well
The problem of color interference and allied substances are disturbed in two methods of the prior art, can obtain more accurate content of formaldehyde
As a result.Meanwhile, in view of UPLC-MS/MS separating rate is fast, the lower advantage of test limit, analysis efficiency of the invention is very high, and
Detection limit can detect the content of formaldehyde of ppb ranks in leather well below two methods of the prior art.
In order to achieve the above object, the present invention is adopted the following technical scheme that：
A kind of method of content of formaldehyde in LC-MS test leather, comprises the following steps：
The first step, leather sample is shredded；
Second step, weighs leather sample, is fitted into container, and sodium dodecyl sulfate solution is then added into container, shakes
Container is shaken, leather sample is moistened, wherein, the mass ratio of leather sample and dodecyl sodium sulfate is 1：(0.01-0.1)；
3rd step, container is placed in water bath chader and vibrated, leather sample is then filtered out, filtrate is transferred to another appearance
In device, and room temperature is cooled to, obtains sample extraction liquid, this is sample extraction process；
4th step, sample extraction liquid is transferred in volumetric flask, adds acetonitrile and p- hydrazino-benzoic acid solution, wherein, sample
The volume ratio of product extract, acetonitrile and p- hydrazino-benzoic acid solution is 5：(2-6)：(0.3-3), with being shaken after deionized water constant volume
It is even, place after 1min-2h, it is then right with ultra performance liquid chromatography tandem mass spectrum combined instrument (UPLC-MS/MS) with membrane filtration
Filtrate is analyzed, you can.The purpose for adding acetonitrile is to increase dissolving each other for sample extraction liquid and p- hydrazino-benzoic acid solution
Property, accelerate the progress of derivatization reaction.
Using above method carry out formaldehyde extraction and PARA FORMALDEHYDE PRILLS(91,95) perform the derivatization and with ultra performance liquid chromatography connect matter
Spectrum combined instrument (UPLC-MS/MS) carries out the interference that analysis eliminates color sample and formaldehyde allied substances to filtrate, so that
The applicability of the present invention is stronger, and faster, test data is more accurate for analyze speed.
The a kind of of the method for the content of formaldehyde tested as LC-MS of the present invention in leather improves, and is shredded described in the first step
Be with scissors by sample be cut into any side be not more than 5mm polygon, diameter be not more than 5mm circle or major axis fail to grow up in
5mm oval sample blocks.Sample is cut into the less sample blocks of size, is easy to the extraction in later stage.
The a kind of of the method for the content of formaldehyde tested as LC-MS of the present invention in leather improves, in second step, and 12
Alkyl sulfonic acid sodium solution is preheated to 75 DEG C -90 DEG C in advance, and the concentration of sodium dodecyl sulfate solution is 0.03%-0.5%.Ten
The temperature of dialkyl sulfonates solution is higher, can improve leather wetting effect and formaldehyde dissolution rate.
The a kind of of the method for the content of formaldehyde tested as LC-MS of the present invention in leather improves, dodecyl sodium sulfate
The preparation method of solution is：0.3g-5g dodecyl sodium sulfates are weighed, 800mL deionized water dissolvings is added, is then settled to
1000mL, obtains 0.03%-0.5% sodium dodecyl sulfate solution.
The a kind of of the method for the content of formaldehyde tested as LC-MS of the present invention in leather is improved, and water-bath is shaken in the 3rd step
Device is swung for thermostatic control oscillator vibration, and temperature is 75 DEG C -90 DEG C, hunting speed is 40 turns -80 turns per minute, duration of oscillation
For 2h-3h.By improving extraction temperature, increase extraction time, be obviously improved the effect of extracting of formaldehyde in leather.
The a kind of of the method for the content of formaldehyde tested as LC-MS of the present invention in leather improves, p- hydrazine in the 4th step
The concentration of yl benzoic acid solution is 0.3%-0.8%.
The a kind of of the method for the content of formaldehyde tested as LC-MS of the present invention in leather improves, p- hydrazino-benzoic acid
The preparation method of solution is：The p- hydrazino-benzoic acids of 0.3g-0.8g are weighed, 10mL methanol and 10mL deionized waters is successively added, used
Glass bar is stirred to uniformly turbid liquid, then be slowly added into 50mL phosphoric acid is formed, stirring while adding, treats that solid is completely dissolved simultaneously in solution
It is cooled to after room temperature, 100mL is settled to phosphoric acid, obtains the p- hydrazino-benzoic acid solution of 0.3%-0.8%.Using water-methanol-
Phosphoric acid mixed system solves the problem of p- hydrazino-benzoic acid is not readily dissolved well as solvent.
The a kind of of the method for the content of formaldehyde tested as LC-MS of the present invention in leather improves, second step and the 3rd step
In container be band plug triangular flask, with play a part of preventing interference.
The a kind of of the method for the content of formaldehyde tested as LC-MS of the present invention in leather improves, and is filtered described in the 4th step
It is to be filled into supernatant liquor in sample bottle by a diameter of 0.22 μm~0.45 μm of organic system filtering head, impurity is removed
Totally wherein, the material of the organic system filtering head is at least one in Kynoar, nylon, polytetrafluoroethylene (PTFE) and polyethers phenol
Kind, this several material is durable in use, and anticorrosive property is strong, and is not easily dissolved into liquid component.
The a kind of of the method for the content of formaldehyde tested as LC-MS of the present invention in leather improves, in the 4th step, superelevation
The specification of chromatographic column used is 50mm × 2.1mm × 1.7 μm in effect liquid phase chromatogram tandem mass spectrum combined instrument (UPLC-MS/MS)
Water generation ACQUITY UPLC BEH C18 chromatographic columns；
Leacheate used is in rinse procedures in ultra performance liquid chromatography tandem mass spectrum combined instrument (UPLC-MS/MS)
The mixture of water and acetonitrile, wherein, the volume ratio of water and acetonitrile is 3:7, the elution liquid energy rapidly flushes out formaldehyde derivatives,
Formaldehyde derivatives can be separated with impurity well again.
During elution, the flow of leacheate is 0.1mL/min-0.3mL/min, and column temperature is 30 DEG C -50 DEG C；
Capillary voltage in ultra performance liquid chromatography tandem mass spectrum combined instrument (UPLC-MS/MS) is 0.3kV-0.8kV,
It is 500L/h-1100L/h to go solvent stream amount, and taper hole throughput is 10L/h-30L/h, and formaldehyde derivatives are in series connection under the conditions of this
Response highest in mass spectrum.
Relative to prior art, the present invention extracts the formaldehyde in leather sample with sodium dodecyl sulfate solution, can
Formaldehyde is extracted completely, p- hydrazino-benzoic acid solution again can be by the complete derivatization of the formaldehyde extracted, and spreading out of obtaining
Production thing is easy to ionization, is tested with facilitating with UPLC-MS/MS, and the present invention is using ultra performance liquid chromatography series connection matter
Spectrum combined instrument (UPLC-MS/MS) PARA FORMALDEHYDE PRILLS(91,95) and p- hydrazino-benzoic acid derivative tested, with retention time with match from
Son is to (165>136、165>108 and 165>92) it is qualitative to target compound progress, of the prior art two are solved well
The problem of color interference and allied substances are disturbed in the method for kind, can obtain more accurate content of formaldehyde result.Meanwhile, in view of
UPLC-MS/MS separating rate is fast, and the lower advantage of test limit, analysis efficiency of the invention is very high, and detection limit well below
Two methods of the prior art, can detect the content of formaldehyde of ppb ranks in leather.
In a word, the present invention has following advantage：
One is that the present invention uses suitable extracting process, can extract the formaldehyde in leather completely.
Two be that the present invention uses suitable derivative reagent and reaction condition, can derive the formaldehyde in extract completely
Change, and derivative products are easy to ionization, are tested with facilitating with UPLC-MS/MS.Specifically, the present invention is to diazanyl benzene
Formic acid solution is as derivating agent, and PARA FORMALDEHYDE PRILLS(91,95) carries out derivative advantage and is：Formaldehyde can not be ionized in itself, formaldehyde with to diazanyl benzene first
Acid reaction, the product of generation is easy to ionization, can be detected well by UPLC-MS/MS.
Three be that the present invention uses suitable instrument condition, can rapidly and accurately detect containing for formaldehyde derivatives in sample liquid
Amount.Specifically, the present invention can be not only avoided in existing method (such as with ultraviolet from UPLC-MS/MS as test equipment
AAS (UV) is tested) sample solution color to qualitatively disturbing caused by it is qualitative wrong and quantitative inaccurate；And
And (as with high performance liquid chromatography (HPLC) tested) other aldehyde materials or ketone thing can be avoided in existing method
Verify qualitative wrong caused by qualitatively disturbing and quantitative inaccurate；Moreover, being had from UPLC-MS/MS as test equipment
Faster detection speed, reduces at least half of testing time, while having lower sensitivity, detection limit can than HPLC method
Up to ppb ranks.
Brief description of the drawings
With reference to the accompanying drawings and detailed description, the present invention and its advantageous effects are described in detail.
Fig. 1 is chromatogram of the formaldehyde derivatives on UPLC-MS/MS in embodiment 1 in the present invention, wherein, upper figure is TIC
Figure, figure below is 165>136 ion pairs extract figure.
Embodiment
Embodiment 1
The method for present embodiments providing the content of formaldehyde in a kind of LC-MS test leather, comprises the following steps：
Leather sample, 4mm × 4mm fritter is cut into scissors by the first step；
Second step, weighs 2.0g samples, is fitted into 100mL band plug triangular flasks, and adding 50mL into bottle is preheated to 80 DEG C
0.1% sodium dodecyl sulfate solution, rocking moistens leather sample, stoppers plug；Wherein, sodium dodecyl sulfate solution
Preparation method is：1g dodecyl sodium sulfates are weighed, 800mL deionized water dissolvings is added, is then settled to 1000mL, obtains
0.1% sodium dodecyl sulfate solution.
3rd step, sample is placed in 80 DEG C of thermostatic control oscillator vibration with 60 rpms of velocity fluctuation 2h, taken out
Triangular flask, sample filtering while hot stoppered plug, solution is cooled to room temperature, obtain sample into another 100mL triangular flask
Extract, this is sample extraction process；
4th step, takes 5mL sample extractions liquid into 10mL volumetric flasks, adds 4mL acetonitriles and the p- diazanyl benzene of 1mL 0.5%
Formic acid solution, with deionized water constant volume and shakes up.Solution is placed into 60min, with 0.22 μm of membrane filtration, ultra high efficiency liquid is then used
Phase chromatographic tandem GC-MS (UPLC-MS/MS) is analyzed filtrate, you can.Wherein, p- hydrazino-benzoic acid solution
Preparation method is：The p- hydrazino-benzoic acids of 0.5g are weighed, 10mL methanol and 10mL deionized waters is successively added, is stirred with glass bar
To uniform turbid liquid, then 50mL phosphoric acid is slowly added into, stirring while adding, solid is completely dissolved and is cooled to after room temperature in band solution,
100mL is settled to phosphoric acid, 0.5% p- hydrazino-benzoic acid solution is obtained.
Wherein, UPLC-MS/MS condition setting is as shown in table 1：
Table 1：UPLC-MS/MS condition setting.
Chromatogram of the formaldehyde derivatives on UPLC-MS/MS is as shown in figure 1, wherein, upper figure is TIC figures, and figure below is 165>
136 ion pairs extract figure.As seen from Figure 1：The derivative that the present invention can be good at PARA FORMALDEHYDE PRILLS(91,95) and p- hydrazino-benzoic acid enters
Row detection.
Comparative example 1
As different from Example 1：
Second step, weighs 2.0g samples, is fitted into 100mL band plug triangular flasks, and adding 50mL into bottle is preheated to 40 DEG C
0.1% sodium dodecyl sulfate solution, rocking moistens leather sample, stoppers plug；Wherein, sodium dodecyl sulfate solution
Preparation method is：1g dodecyl sodium sulfates are weighed, 800mL deionized water dissolvings is added, is then settled to 1000mL, obtains
0.1% sodium dodecyl sulfate solution.
3rd step, sample is placed in 40 DEG C of thermostatic control oscillator vibration with 60 rpms of velocity fluctuation 2h, taken out
Triangular flask, sample filtering while hot stoppered plug, solution is cooled to room temperature, obtain sample into another 100mL triangular flask
Extract, this is sample extraction process；
Remaining be the same as Example 1, is repeated no more here.
Comparative example 2
As different from Example 1：
Second step, weighs 2.0g samples, is fitted into 100mL band plug triangular flasks, and adding 50mL into bottle is preheated to 60 DEG C
0.1% sodium dodecyl sulfate solution, rocking moistens leather sample, stoppers plug；Wherein, sodium dodecyl sulfate solution
Preparation method is：1g dodecyl sodium sulfates are weighed, 800mL deionized water dissolvings is added, is then settled to 1000mL, obtains
0.1% sodium dodecyl sulfate solution.
3rd step, sample is placed in 60 DEG C of thermostatic control oscillator vibration with 60 rpms of velocity fluctuation 2h, taken out
Triangular flask, sample filtering while hot stoppered plug, solution is cooled to room temperature, obtain sample into another 100mL triangular flask
Extract, this is sample extraction process；
Remaining be the same as Example 1, is repeated no more here.
In order to further study the influence of extraction temperature and time to test effect, by embodiment 1, comparative example 1 and contrast
Time in example 2 is adjusted to 30min, 60min and 150min respectively, and acquired results are shown in Table 2：
Table 2：Under different extraction conditions in (temperature and time), same leather sample content of formaldehyde test result.
As can be seen from Table 2：By improving extraction temperature, increase extraction time, formaldehyde in leather can be obviously improved
Effect of extracting.Slective extraction temperature of the present invention is 75 DEG C -90 DEG C, and extraction time is 2h-3h, can be more thoroughly by leather
Formaldehyde extract.
Embodiment 2
The method for present embodiments providing the content of formaldehyde in a kind of LC-MS test leather, comprises the following steps：
Leather sample, a diameter of 4mm rounded nubs are cut into scissors by the first step；
Second step, weighs 2.0g samples, is fitted into 100mL band plug triangular flasks, and adding 50mL into bottle is preheated to 85 DEG C
0.3% sodium dodecyl sulfate solution, rocking moistens leather sample, stoppers plug；Wherein, sodium dodecyl sulfate solution
Preparation method is：3g dodecyl sodium sulfates are weighed, 800mL deionized water dissolvings is added, is then settled to 1000mL, obtains
0.3% sodium dodecyl sulfate solution.
3rd step, sample is placed in 85 DEG C of thermostatic control oscillator vibration with 70 rpms of velocity fluctuation 2.5h, taken
Go out triangular flask, sample filtering is stoppered plug, solution is cooled to room temperature, obtain sample into another 100mL triangular flask while hot
Product extract, this is sample extraction process；
4th step, takes 5mL sample extractions liquid into 10mL volumetric flasks, adds 4mL acetonitriles and the p- diazanyl benzene of 1mL 0.7%
Formic acid solution, with deionized water constant volume and shakes up.Solution is placed into 30min, with 0.22 μm of membrane filtration, ultra high efficiency liquid is then used
Phase chromatographic tandem GC-MS (UPLC-MS/MS) is analyzed filtrate, you can.Wherein, p- hydrazino-benzoic acid solution
Preparation method is：The p- hydrazino-benzoic acids of 0.7g are weighed, 10mL methanol and 10mL deionized waters is successively added, is stirred with glass bar
To uniform turbid liquid, then 50mL phosphoric acid is slowly added into, stirring while adding, solid is completely dissolved and is cooled to after room temperature in band solution,
100mL is settled to phosphoric acid, 0.7% p- hydrazino-benzoic acid solution is obtained.
Wherein, UPLC-MS/MS condition setting is as shown in table 1：
Table 1：UPLC-MS/MS condition setting.
Embodiment 3
The method for present embodiments providing the content of formaldehyde in a kind of LC-MS test leather, comprises the following steps：
Leather sample, a length of 3mm of major axis oval fritter is cut into scissors by the first step；
Second step, weighs 2.0g samples, is fitted into 100mL band plug triangular flasks, and adding 50mL into bottle is preheated to 75 DEG C
0.25% sodium dodecyl sulfate solution, rocking moistens leather sample, stoppers plug；Wherein, sodium dodecyl sulfate solution
Preparation method be：2.5g dodecyl sodium sulfates are weighed, 800mL deionized water dissolvings is added, is then settled to 1000mL, obtains
To 0.25% sodium dodecyl sulfate solution.
3rd step, sample is placed in 75 DEG C of thermostatic control oscillator vibration with 80 rpms of velocity fluctuation 2.8h, taken
Go out triangular flask, sample filtering is stoppered plug, solution is cooled to room temperature, obtain sample into another 100mL triangular flask while hot
Product extract, this is sample extraction process；
4th step, takes 5mL sample extractions liquid into 10mL volumetric flasks, adds 4mL acetonitriles and the p- diazanyl benzene of 1mL 0.7%
Formic acid solution, with deionized water constant volume and shakes up.Solution is placed into 90min, with 0.45 μm of membrane filtration, ultra high efficiency liquid is then used
Phase chromatographic tandem GC-MS (UPLC-MS/MS) is analyzed filtrate, you can.Wherein, p- hydrazino-benzoic acid solution
Preparation method is：The p- hydrazino-benzoic acids of 0.4g are weighed, 10mL methanol and 10mL deionized waters is successively added, is stirred with glass bar
To uniform turbid liquid, then 50mL phosphoric acid is slowly added into, stirring while adding, solid is completely dissolved and is cooled to after room temperature in band solution,
100mL is settled to phosphoric acid, 0.4% p- hydrazino-benzoic acid solution is obtained.
Wherein, UPLC-MS/MS condition setting is as shown in table 1：
Table 1：UPLC-MS/MS condition setting.
The announcement and teaching of book according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and changed.Therefore, the invention is not limited in embodiment disclosed and described above, to the present invention's
Some modifications and changes should also be as falling into the scope of the claims of the present invention.Although in addition, being used in this specification
Some specific terms, but these terms are merely for convenience of description, do not constitute any limitation to the present invention.
Claims (10)
1. the method for the content of formaldehyde in a kind of LC-MS test leather, it is characterised in that comprise the following steps：
The first step, leather sample is shredded；
Second step, weighs leather sample, is fitted into container, and sodium dodecyl sulfate solution is then added into container, rocks appearance
Device, moistens leather sample, wherein, the mass ratio of leather sample and dodecyl sodium sulfate is 1：(0.01-0.1)；
3rd step, container is placed in water bath chader and vibrated, leather sample is then filtered out, filtrate is transferred to another container
In, and room temperature is cooled to, obtain sample extraction liquid；
4th step, sample extraction liquid is transferred in volumetric flask, adds acetonitrile and p- hydrazino-benzoic acid solution, wherein, sample extraction
The volume ratio for taking liquid, acetonitrile and p- hydrazino-benzoic acid solution is 5：(2-6)：(0.3-3), with being shaken up after deionized water constant volume, puts
Put after 1min-2h, with membrane filtration, then filtrate is entered with ultra performance liquid chromatography tandem mass spectrum combined instrument (UPLC-MS/MS)
Row analysis, you can.
2. the method for the content of formaldehyde in LC-MS test leather according to claim 1, it is characterised in that：The first step
Described shred is that sample is cut into any side with scissors to be not more than the circular or long axial length that 5mm polygon, diameter are not more than 5mm
No more than 5mm oval sample blocks.
3. the method for the content of formaldehyde in LC-MS test leather according to claim 1, it is characterised in that：Second step
In, sodium dodecyl sulfate solution is preheated to 75 DEG C -90 DEG C in advance, and the concentration of sodium dodecyl sulfate solution is 0.03%-
0.5%.
4. the method for the content of formaldehyde in LC-MS test leather according to claim 3, it is characterised in that dodecane
The preparation method of base sodium sulfonate solution is：0.3g-5g dodecyl sodium sulfates are weighed, 800mL deionized water dissolvings are added, then
1000mL is settled to, 0.03%-0.5% sodium dodecyl sulfate solution is obtained.
5. the method for the content of formaldehyde in LC-MS test leather according to claim 1, it is characterised in that：3rd step
Middle water bath chader is thermostatic control oscillator vibration, and temperature is 75 DEG C -90 DEG C, and hunting speed is 40 turns -80 turns per minute, vibration
Duration is 2h-3h.
6. the method for the content of formaldehyde in LC-MS test leather according to claim 1, it is characterised in that：4th step
In p- hydrazino-benzoic acid solution concentration be 0.3%-0.8%.
7. the method for the content of formaldehyde in LC-MS test leather according to claim 6, it is characterised in that p- hydrazine
The preparation method of yl benzoic acid solution is：The p- hydrazino-benzoic acids of 0.3g-0.8g are weighed, 10mL methanol is successively added and is gone with 10mL
Ionized water, is stirred with glass bar to uniformly turbid liquid, then be slowly added into 50mL phosphoric acid is formed, stirring while adding, treats solid in solution
It is completely dissolved and is cooled to after room temperature, 100mL is settled to phosphoric acid, obtains the p- hydrazino-benzoic acid solution of 0.3%-0.8%.
8. the method for the content of formaldehyde in LC-MS test leather according to claim 1, it is characterised in that：Second step
It is band plug triangular flask with the container in the 3rd step.
9. the method for the content of formaldehyde in LC-MS test leather according to claim 1, it is characterised in that：4th step
The filtering is to be filled into supernatant liquor in sample bottle by a diameter of 0.22 μm~0.45 μm of organic system filtering head, its
In, the material of the organic system filtering head is at least one of Kynoar, nylon, polytetrafluoroethylene (PTFE) and polyethers phenol.
10. the method for the content of formaldehyde in LC-MS test leather according to claim 1, it is characterised in that：4th
In step, the specification of chromatographic column used is 50mm × 2.1mm in ultra performance liquid chromatography tandem mass spectrum combined instrument (UPLC-MS/MS)
× 1.7 μm of water generation ACQUITY UPLC BEH C18 chromatographic columns；
In rinse procedures in ultra performance liquid chromatography tandem mass spectrum combined instrument (UPLC-MS/MS) leacheate used for water and
The mixture of acetonitrile, wherein, the volume ratio of water and acetonitrile is 3:7；
During elution, the flow of leacheate is 0.1mL/min-0.3mL/min, and column temperature is 30 DEG C -50 DEG C；
Capillary voltage in ultra performance liquid chromatography tandem mass spectrum combined instrument (UPLC-MS/MS) is 0.3kV-0.8kV, is gone molten
Agent throughput is 500L/h-1100L/h, and taper hole throughput is 10L/h-30L/h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107702974A (en) * | 2017-11-28 | 2018-02-16 | 福建省国鼎检测技术有限公司 | PH detection method in a kind of artificial leather |
| CN108469472A (en) * | 2017-12-19 | 2018-08-31 | 江苏康达检测技术股份有限公司 | The assay method of concentration of formaldehyde in solid waste |
| CN115219627A (en) * | 2022-07-18 | 2022-10-21 | 宁波市产品食品质量检验研究院(宁波市纤维检验所) | Method for detecting acetaldehyde content in leather |
-
2017
- 2017-03-30 CN CN201710203073.4A patent/CN106970164B/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107702974A (en) * | 2017-11-28 | 2018-02-16 | 福建省国鼎检测技术有限公司 | PH detection method in a kind of artificial leather |
| CN108469472A (en) * | 2017-12-19 | 2018-08-31 | 江苏康达检测技术股份有限公司 | The assay method of concentration of formaldehyde in solid waste |
| CN115219627A (en) * | 2022-07-18 | 2022-10-21 | 宁波市产品食品质量检验研究院(宁波市纤维检验所) | Method for detecting acetaldehyde content in leather |
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