CN110187034A - A method of the free formaldehyde in oil paint and its raw material is measured using high performance liquid chromatography - Google Patents
A method of the free formaldehyde in oil paint and its raw material is measured using high performance liquid chromatography Download PDFInfo
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
The present invention relates to the formaldehyde examination technical fields of oil paint, more particularly to a kind of method using the free formaldehyde in high performance liquid chromatography measurement oil paint and its raw material, this method includes the steps that preparation, sample detection, sample pre-treatments and the HPLC measurement of formaldehyde standard working curve；Wherein sample pre-treatments are divided into: c1) without containing ketone compounds diluent class sample pre-treatment；C2 the pre-treatment of ketone, isocyanate ester compound and non-diluted dose of oiliness sample) is not contained；C3) the pre-treatment of the oiliness sample containing ketone compounds；C4) the pre-treatment of the oiliness sample containing isocyanate ester compound.Formaldehyde determination of the present invention suitable for the oil paints such as alcohol acids, acrylic compounds, Isocyanates curing agent and its raw material, detection is efficiently, accurately, and after loading, the mobile phase of sample and HPLC can be compatible well, will not damage completely to HPLC instrument.
Description
Technical field
The present invention relates to the formaldehyde examination technical fields of oil paint, and in particular to a kind of to be measured using high performance liquid chromatography
The method of free formaldehyde in oil paint and its raw material.
Background technique
Coating belongs to organic chemical industry's macromolecular material, be often referred to be coated on body surface under certain conditions can be formed it is thin
Film and rise protection, decoration or other specific functions (insulation, antirust, mould proof, heat-resisting etc.) a kind of liquid or solid material.Coating
Including water paint and oil paint, and solvent type oil paint contains a certain amount of organic volatile mostly, room air
Pollution has become the inducement of a variety of diseases, and wherein formaldehyde has become one of major pollutants of indoor environment, it is at normal temperature
One kind is colourless, has strong and stimulating smell product, and soluble easily in water, pure and mild ether, formaldehyde has a major impact the health of human body, to people
Body respiratory mucosa and skin have strong impulse effect, and Long Term Contact low dosage formaldehyde can cause chronic respiratory disease, note
Recall power decline, chromosome abnormality, immunologic dysfunction etc..Therefore, the content of formaldehyde in coating is whether evaluation coating is environmentally friendly
Important indicator.
For the examination criteria of formaldehyde in coating, the newest standards that China formulates are " GB/T23993-2009 water paints
The measurement of middle content of formaldehyde ", which is for the formaldehyde examination in water paint, wherein using the way of distillation by the trip in sample
It is steamed from formaldehyde, then in acid condition by the formaldehyde and acetylacetone,2,4-pentanedione reaction solution in fraction, then with ultraviolet spectrometry light
Degree method surveys absorbance at 412nm and calculates the content of free formaldehyde in coating according to standard working curve.But ultraviolet point
There is colour developing and interfere vulnerable to other factors in light photometry, therefore accuracy is not high.In addition, the color of some coating itself is in 412nm
Also there is absorption, this will cause false positive results, further reduced the accuracy of detection.
Analysis for complex sample, high performance liquid chromatography have that analysis speed is fast, be widely used, high sensitivity etc. is excellent
Point is widely used to the composition detection analysis of every field, such as the formaldehyde examination in field of food at present.Since formaldehyde does not have
There are inherent chromophore and fluorophor, therefore, is derived when analyzing the content of formaldehyde in sample, that is, pass through derivatization
Reaction introduces the group for having strong UV absorption, these derivatives can be measured by high performance liquid chromatography and be detected, most common derivating agent
It is 2,4-dinitrophenylhydrazine (DNPH), principle is that formaldehyde is derivatized to 2,4- dinitro with 2,4-dinitrophenylhydrazine in acid condition
Base phenylhydrazone carries out a series for the treatment of processes such as extracting through organic solvent, finally carries out high performance liquid chromatography measurement.Such as publication number
A kind of method of testing formaldehyde in food by means of derivation extraction is disclosed for the Chinese invention patent of CN101762660A, this method is adopted
It is directly derivative to extract formaldehyde in sample, after liquid-liquid extraction purification, progress with acetonitrile-acetate buffer solution of 2,4-dinitrophenylhydrazine
Liquid chromatogram measuring.
However, the above method is only applicable to the detection of formaldehyde in aqueous sample, it is not used to formaldehyde in oil paint
Detection.This is because oil paint is mainly by resin, pigments and fillers, curing agent, diluent (such as acetone, dimethylbenzene, ethyl acetate
Deng), the raw material composition such as various auxiliary agents, ingredient is increasingly complex compared to water paint, such as: it is big in the raw material of oil paint
Contain ketone compounds more, contain isocyanate ester compound in curing agent, these react at branch and derivating agent, therefore nothing
Method directly performs the derivatization the formaldehyde extracted in sample；On the other hand, the resin body in water paint sample is water-based emulsion,
Can be demulsified after addition acetonitrile solvent precipitating in its detection method, and the upper layer by centrifugation is clear liquid, and lower layer is the lotion of demulsification, that
, deposited phenomenon will not be occurred in instrument by sampling after entering high performance liquid chromatography, not injured to instrument；But oiliness sample
The resin body of product is then macromolecule resin, together with macromolecule resin and second nitrile solvents can be good at mixing, by from
It is not in layering in addition to pigments and fillers after the heart, if the method using water paint is analyzed, sample enters efficient liquid
After phase chromatography, the macromolecule resin meeting Precipitation of the inside causes very big injury to instrument, it will be apparent that can see in instrument
It presses and increases to column, there is a phenomenon where block up column.
Oil paint has the excellent characteristics such as hardness is high, adhesive force is strong, still there is no small occupation rate on the market, aqueous
Coating can not also replace at present, therefore, need to study and develop to be specially adapted for oiliness painting using high performance liquid chromatography measurement
The detection method of formaldehyde in material and its raw material.
Summary of the invention
It is an object of the invention to aiming at the shortcomings in the prior art, and provides and a kind of measure oil using high performance liquid chromatography
The method of property coating and its free formaldehyde in raw material, this method can efficiently and accurately determine alcohol acids, acrylic acid
Content of formaldehyde in the oil paints such as class, Isocyanates curing agent and UV coating and its raw material, and will not be to HPLC
Instrument damages.
The purpose of the present invention is achieved through the following technical solutions:
A kind of method measuring the free formaldehyde in oil paint and its raw material with high performance liquid chromatography, this method are provided
The ingredient contained according to sample is different, comprising the following steps:
Step a, the preparation of formaldehyde standard working curve
A1) the preparation of derivatization reagent: weighing a certain amount of 2,4-dinitrophenylhydrazine, obtains derivatization examination with solvent constant volume
Agent；
A2) the preparation of formaldehyde standard working solution: weighing a certain amount of formaldehyde standard substance, and formaldehyde standard is prepared after dilution
Then dilution pipettes a certain amount of formaldehyde standard dilution, the formaldehyde standard work for being configured to a series of various concentration is molten
Liquid；
A3) formaldehyde standard working curve makes: pipetting a certain amount of derivatization reagent and is added to formaldehyde standard working solution
In perform the derivatization, then carry out HPLC test, test result is using formaldehyde standard working solution concentration as abscissa, the peak of test
Area is ordinate, draws formaldehyde standard working curve；
Step b, sample detection
A certain amount of sample is taken, is diluted according to sample viscosity with acetone, then carries out FTIR and GC-MS test, really
In random sample product whether the ingredient containing ketone, isocyanate ester compound, then carry out next step pre-treatment；
Step c, sample pre-treatments
According in sample detection ingredient whether containing ketone compounds, isocyanates and different preceding places is carried out to sample
Reason, including following pre-treatment step:
C1) for the pre-treatment of the diluent class sample without containing ketone compounds
Weigh a certain amount of sample, solvent be added and carries out ultrasonic wave extraction, then takes out a certain amount of sample solution, first plus
Enter a certain amount of acetonitrile, adds after a certain amount of derivatization reagent performs the derivatization, filtering obtains sample to be tested；
C2) for the pre-treatment without containing ketone, isocyanate ester compound and non-diluted dose of oiliness sample
A certain amount of sample is weighed, solvent is added and carries out ultrasonic wave extraction, centrifugal treating is carried out after the completion of extracting, then takes
A certain amount of upper layer sample out, is first added a certain amount of acetonitrile, and level-one water is then added, adds a certain amount of derivatization reagent
After performing the derivatization, filtering obtains sample to be tested；
C3) for the pre-treatment of the oiliness sample containing ketone compounds
A certain amount of sample is weighed, solvent is added and carries out ultrasonic wave extraction, centrifugal treating is carried out after the completion of extracting, then takes
A certain amount of upper layer sample out, is first added a certain amount of acetonitrile and level-one water, further according to ketone in sample detected by step b
The content of compound and excessive derivatization reagent is added, it is ensured that after complete derivatization, filtering obtains sample to be tested；
C4) for the pre-treatment of the oiliness sample containing isocyanate ester compound
A certain amount of sample is weighed, the resin reaction containing hydroxyl group is added for a period of time, solvent is then added and carries out
Ultrasonic wave extraction carries out centrifugal treating after the completion of extracting, then takes out a certain amount of upper layer sample, a certain amount of acetonitrile is first added
With level-one water, add after a certain amount of derivatization reagent performs the derivatization, filtering obtains sample to be tested；
Step d, HPLC is measured
By step c pre-treatment obtain sample to be tested be placed on be protected from light under the conditions of a period of time, then filter, upper machine sample introduction into
Row measurement, the content of formaldehyde of measurement calculate as follows: X=C × V/m
In formula: X --- the content of formaldehyde in sample to be tested, unit mg/kg
C --- the volumetric concentration content value being calculated from standard curve, unit mg/l；
The constant volume of V --- sample to be tested, unit ml；
M --- the quality of weighed sample to be tested, unit g.
Step d, HPLC is measured
By step c pre-treatment obtain sample to be tested be placed on be protected from light under the conditions of a period of time, then filter, upper machine sample introduction into
Row measurement, the content of formaldehyde of measurement calculate as follows: X=C × V/m
In formula: X --- the content of formaldehyde in sample to be tested, unit mg/kg
C --- the volumetric concentration content value being calculated from standard curve, unit mg/l；
The constant volume of V --- sample to be tested, unit ml；
M --- the quality of weighed sample to be tested, unit g.
In above-mentioned steps c2, c3 and c4, acetonitrile is first added in upper layer sample after ultrasonic wave extraction, centrifugation, then plus
Enter level-one water, wherein the purpose that acetonitrile is added is to ensure that formaldehyde can be sufficiently dissolved in acetonitrile and be diluted upper layer by supernatant liquor
Clear liquid, and ensure that the mobile phase of itself and subsequent high performance liquid chromatography can be compatible, the effect that level-one water is then added are to allow dissolution
Macromolecule resin in acetonitrile is precipitated, and is finally added derivatization reagent and is performed the derivatization, obtains sample to be tested；
In above-mentioned technical proposal, in step c, the solvent is appointing in methanol, chloroform, isopropanol, acetonitrile and normal heptane
It anticipates one kind.
In above-mentioned technical proposal, in step c1, the volume ratio of acetonitrile and derivatization reagent is 1:(0.1-0.2).
In above-mentioned technical proposal, in step c2, the volume ratio of acetonitrile, level-one water and derivatization reagent is 1:(0.5-1):
(0.1-0.2)。
In above-mentioned technical proposal, in step c3, the volume ratio of acetonitrile, level-one water and derivatization reagent is 1:1:(0.2-
0.6)。
In above-mentioned technical proposal, in step c4, the volume ratio of acetonitrile, level-one water and derivatization reagent is 1:1 (0.2-
0.6)。
In above-mentioned technical proposal, in step c, the filter core of filtering is 0.20-0.24 μm.
Beneficial effects of the present invention:
A kind of method that the free formaldehyde in oil paint and its raw material is measured using high performance liquid chromatography of the present invention, root
Mainly contain according to (mainly including resin, pigments and fillers, curing agent, diluent, auxiliary agent etc.) in the ingredient of oil paint and its raw material
The presence of the complicated particularity of some ketone compounds and isocyanate ester compound, these compounds can interfere formaldehyde and derivative
The derivatization of agent, thus can not be using progress high performance liquid chromatography measurement after the direct derivatization of prior art water paint sample
Method, the present invention created a kind of new detection method suitable for oil paint, and principle is to be directed to the spy of oiliness sample
Different ingredient and be classified as four seed types and carry out different pre-treatments respectively, which includes: c1) for not containing ketone chemical combination
The pre-treatment of the diluent class sample of object, diluent class sample composition is most simple, and a certain amount of acetonitrile, which is first added, enables formaldehyde to fill
After dividing dissolution, extraction and centrifugation step are not needed, derivatization reagent can be directly added into and performed the derivatization, it is laggard to obtain sample to be tested
The measurement of row high performance liquid chromatography；C2) for without containing ketone, isocyanate ester compound and non-diluted dose of oiliness sample
Pre-treatment after the oiliness sample first passes through extraction, a certain amount of upper layer sample is taken out in centrifugation, is first added acetonitrile and adds level-one
Water is eventually adding performing the derivatization of derivatization reagent, carries out high performance liquid chromatography measurement after obtaining sample to be tested；C3) for
The pre-treatment of oiliness sample containing ketone compounds, the key of the step need to remove ketone, thus the oiliness sample first extract,
After a certain amount of upper layer sample is taken out in centrifugation, acetonitrile is added, level-one water is then added, it is last according to ketone in the sample detected
The content of compound and after excessive derivatization reagent is added to ensure complete derivatization, obtain sample to be tested and carry out efficient liquid again
Phase chromatographic determination；C4) for the pre-treatment of the oiliness sample containing isocyanate ester compound, the key of the step needs to remove
Fall isocyanate ester compound, i.e., the resin reaction containing hydroxyl group is first added for a period of time, this has the tree of hydroxyl group
Rouge molecular weight is big, can be crosslinked with the isocyanate ester compound in oil paint and polyaddition reaction occurs and is formed extremely difficult molten
The film of solution then after extracting, being centrifuged, sequentially adds acetonitrile, level-one water so that isocyanate ester compound be got rid of
And derivatization reagent, high performance liquid chromatography measurement is carried out after obtaining sample to be tested.Method of the invention is suitable for alkyd as a result,
The measurement of the oil paints such as class, acrylic compounds, Isocyanates curing agent and UV coating and its content of formaldehyde in raw material,
Applied widely, efficiently, accurately, and after loading, the mobile phase of test sample and HPLC can be compatible well, completely for detection
HPLC instrument will not be damaged.Therefore, detection method of the invention is in the market for oil paint and its raw material
Environmental protection tests demand provides new detection means, fast and easy, accurate, practical, has extraordinary application prospect.
Detailed description of the invention
Fig. 1 is the detection of embodiment 1 without containing the high-efficient liquid phase chromatogram of the diluent class sample of ketone compounds.
Fig. 2 is the detection of embodiment 2 without containing ketone, isocyanate ester compound and non-diluted dose of oiliness sample
High-efficient liquid phase chromatogram.
Fig. 3 is the high-efficient liquid phase chromatogram of oiliness sample of the detection of embodiment 3 containing ketone compounds.
Fig. 4 is the high-efficient liquid phase chromatogram of oiliness sample of the detection of embodiment 4 containing isocyanate ester compound.
Specific embodiment
The invention will be further described with the following Examples.
Embodiment 1:
The test sample of the present embodiment is the dilution of the model SA-0001 of Dongguan Dabao Chemical Products Co., Ltd.'s production
Agent class sample.
A kind of method measuring the free formaldehyde in oil paint and its raw material with high performance liquid chromatography of the present embodiment,
The following steps are included:
Step a, the preparation of formaldehyde standard working curve
A1) the preparation of derivatization reagent: weighing the 2,4-dinitrophenylhydrazine of 0.5g, is derived with phosphoric acid constant volume to 50ml
Change reagent；
A2) the preparation of formaldehyde standard working solution: weighing the formaldehyde standard substance of 100ul, and standard substance concentration is
9.6mg/ml is settled to 100ml with acetonitrile, is configured to formaldehyde standard dilution, then pipettes 0.0ml, 0.1ml respectively,
0.2ml, 0.5ml, 1.0ml, 3.0ml, 5.0ml, 8.0ml, 10.0ml formaldehyde standard dilution, are settled to 10ml with acetonitrile, match
A series of formaldehyde standard working solution of various concentrations is made；
A3) formaldehyde standard working curve makes: above-mentioned formaldehyde standard working solution 4ml is pipetted respectively, and acetonitrile 4ml is added,
Derivatization reagent 0.4ml is added, 20min is reacted under the conditions of room temperature is protected from light, then carries out HPLC test, test result is with first
Aldehyde standard working solution concentration is abscissa, and the peak area of test is ordinate, draws formaldehyde standard working curve.
Step b, sample detection
1g sample is taken, is first diluted according to sample viscosity with acetone, carries out FTIR and GC-MS test, then with determination
In the sample whether the ingredient containing ketone, isocyanate ester compound, test result determine the sample be diluent class sample,
And ketone compounds are not contained in the sample composition.
Step c, the pre-treatment of the diluent class sample without containing ketone compounds
2.5g (being accurate to 1mg) sample is weighed, acetonitrile solvent is added and is settled to 25ml, carries out ultrasonic wave extraction 10min, so
The sample solution of 4ml is taken out afterwards, and the acetonitrile that 4ml is first added enables formaldehyde to be substantially dissolved in acetonitrile, according still further to acetonitrile: derivatization
Volume ratio=1:(0.1-0.2 of reagent) derivatization reagent is added, the present embodiment is preferably added to the derivatization reagent of 0.4ml,
Room temperature performs the derivatization 20min under conditions of being protected from light, then the sample after 3ml derivatization is drawn with injector for medical purpose, with 0.22 μm
Filter core be filtered, obtain sample to be tested；
Above all of test is both needed to do skip test.
Step d, HPLC is measured
Machine sample introduction on the sample to be tested obtained by pre-treatment is measured, the determination condition of high performance liquid chromatography is such as
Under:
It is that eluent composed by Mobile phase B is washed according to following elution program by mobile phase A and level-one water of acetonitrile
It is de-:
Time is respectively as follows: 20min；
The mass percent of mobile phase A is respectively as follows: 55%；
The mass percent of Mobile phase B is respectively as follows: 45%；
Wherein, column temperature is 25 DEG C, flow velocity 1.0ml/min, and sample volume is 20 μ l, Detection wavelength 355nm；
Chromatographic column is C18 reversed-phase column, and 5.0 μm, 4.6mm × 150mm, mobile phase A contains 0.1% phosphoric acid, and Mobile phase B contains
0.1% phosphoric acid.
Testing result is as shown in Figure 1, content of formaldehyde in available prepare liquid:
The content of formaldehyde of measurement calculates as follows: X=C × V/m
In formula: X --- the content of formaldehyde in sample to be tested, unit mg/kg
C --- the volumetric concentration content value being calculated from standard curve, unit mg/l；
The constant volume of V --- sample to be tested, unit ml；
M --- the quality of weighed sample to be tested, unit g.
Embodiment 2:
The test sample of the present embodiment is the oiliness of the model AA-4029 of Dongguan Dabao Chemical Products Co., Ltd.'s production
Sample.
A kind of method measuring the free formaldehyde in oil paint and its raw material with high performance liquid chromatography of the present embodiment,
The following steps are included:
Step a, the preparation of formaldehyde standard working curve
A1) the preparation of derivatization reagent: weighing the 2,4-dinitrophenylhydrazine of 0.5g, is derived with phosphoric acid constant volume to 50ml
Change reagent；
A2) the preparation of formaldehyde standard working solution: weighing the formaldehyde standard substance of 100ul, and standard substance concentration is
9.6mg/ml is settled to 100ml with acetonitrile, is configured to formaldehyde standard dilution, then pipettes 0.0ml, 0.1ml respectively,
0.2ml, 0.5ml, 1.0ml, 3.0ml, 5.0ml, 8.0ml, 10.0ml formaldehyde standard dilution, are settled to 10ml with acetonitrile, match
A series of formaldehyde standard working solution of various concentrations is made；
A3) formaldehyde standard working curve makes: above-mentioned formaldehyde standard working solution 4ml is pipetted respectively, and acetonitrile 4ml is added,
Derivatization reagent 0.4ml is added, 20min is reacted under the conditions of room temperature is protected from light, then carries out HPLC test, test result is with first
Aldehyde standard working solution concentration is abscissa, and the peak area of test is ordinate, draws formaldehyde standard working curve.
Step b, sample detection
1g sample is taken, is first diluted according to sample viscosity with acetone, carries out FTIR and GC-MS test, then with determination
In the sample whether the ingredient containing ketone, isocyanate ester compound, test result determine the sample be non-diluted dose of class oil
Property sample, and in the sample composition do not contain ketone, isocyanate ester compound.
Step c, the pre-treatment without containing ketone, isocyanate ester compound and non-diluted dose of oiliness sample
The sample of 2.5g (being accurate to 1mg) is weighed, acetonitrile solvent is added and is settled to 25ml, carries out ultrasonic wave extraction 10min,
10ml extracting solution is taken out after the completion of extracting and carries out centrifugal treating under 18000rpm revolving speed, then takes out the upper layer sample of 2ml, so
Afterwards according to volume ratio acetonitrile: level-one water: derivatization reagent=1:(0.5-1): (0.1-0.2) sequentially add acetonitrile, level-one water and
In the present embodiment, the acetonitrile of 4ml is added as preferred embodiment in derivatization reagent, and (second is added in the level-one water for reentering 2ml
The purpose of nitrile is to ensure that formaldehyde sufficiently can be dissolved in acetonitrile and dilute supernatant liquor by supernatant liquor, and ensure its with it is subsequent
The mobile phase of high performance liquid chromatography can be compatible, and the effect that level-one water is added is that the macromolecule resin being dissolved in acetonitrile is allowed to be analysed
Out), the derivatization reagent for adding 0.4ml performs the derivatization 20min under conditions of room temperature is protected from light, then uses medical injection
Device draws the sample after 3ml derivatization, is filtered with 0.20 μm of filter core, obtains sample to be tested；
Above all of test is both needed to do skip test.
Step d, HPLC is measured
Machine sample introduction on the sample to be tested of step c pre-treatment acquisition is measured, the determination condition of high performance liquid chromatography is such as
Under:
It is that eluent composed by Mobile phase B is washed according to following elution program by mobile phase A and level-one water of acetonitrile
It is de-:
Time is respectively as follows: 20min；
The mass percent of mobile phase A is respectively as follows: 55%
The mass percent of Mobile phase B is respectively as follows: 45%
Wherein, column temperature is 25 DEG C, flow velocity 1.0ml/min, and sample volume is 20 μ l, Detection wavelength 355nm；
Chromatographic column is C18 reversed-phase column, and 5.0 μm, 4.6mm × 150mm, mobile phase A contains 0.1% phosphoric acid, and Mobile phase B contains
0.1% phosphoric acid.
Testing result is as shown in Fig. 2, content of formaldehyde in available prepare liquid:
The content of formaldehyde of measurement calculates as follows: X=C × V/m
In formula: X --- the content of formaldehyde in sample to be tested, unit mg/kg
C --- the volumetric concentration content value being calculated from standard curve, unit mg/l；
The constant volume of V --- sample to be tested, unit ml；
M --- the quality of weighed sample to be tested, unit g.
Embodiment 3:
The test sample of the present embodiment is the oiliness of the model HU-0072 of Dongguan Dabao Chemical Products Co., Ltd.'s production
Sample.
A kind of method measuring the free formaldehyde in oil paint and its raw material with high performance liquid chromatography of the present embodiment,
The following steps are included:
Step a, the preparation of formaldehyde standard working curve
A1) the preparation of derivatization reagent: weighing the 2,4-dinitrophenylhydrazine of 0.5g, is derived with phosphoric acid constant volume to 50ml
Change reagent；
A2) the preparation of formaldehyde standard working solution: weighing the formaldehyde standard substance of 100ul, and standard substance concentration is
9.6mg/ml is settled to 100ml with acetonitrile, is configured to formaldehyde standard dilution, then pipettes 0.0ml, 0.1ml respectively,
0.2ml, 0.5ml, 1.0ml, 3.0ml, 5.0ml, 8.0ml, 10.0ml formaldehyde standard dilution, are settled to 10ml with acetonitrile, match
A series of formaldehyde standard working solution of various concentrations is made；
A3) formaldehyde standard working curve makes: above-mentioned formaldehyde standard working solution 4ml is pipetted respectively, and acetonitrile 4ml is added,
Derivatization reagent 0.4ml is added, 20min is reacted under the conditions of room temperature is protected from light, then carries out HPLC test, test result is with first
Aldehyde standard working solution concentration is abscissa, and the peak area of test is ordinate, draws formaldehyde standard working curve.
Step b, sample detection
1g sample is taken, is first diluted according to sample viscosity with acetone, FTIR and GC-MS test is then carried out, determining should
In sample whether the ingredient containing ketone, isocyanate ester compound, testing result determine the sample be contain ketone compounds
Oiliness sample.
Step c, for the pre-treatment of the oiliness sample containing ketone compounds
The sample of 2.5g (being accurate to 1mg) is weighed, acetonitrile solvent is added and is settled to 25ml, carries out ultrasonic wave extraction 10min,
10ml extracting solution is taken out after the completion of extracting, and centrifugal treating is carried out under 18000rpm revolving speed, then takes out the upper layer sample of 2ml,
According to volume ratio acetonitrile: level-one water: derivatization reagent=1:1:(0.2-0.6) acetonitrile, level-one water and derivatization reagent is added, make
For preferred embodiment, in the present embodiment, the level-one water of 4ml is first added, (purpose of acetonitrile is added in the acetonitrile that 4ml is added
It is to ensure that formaldehyde sufficiently can be dissolved in acetonitrile and dilute supernatant liquor by supernatant liquor, and ensures itself and subsequent efficient liquid phase
The mobile phase of chromatography can be compatible, and the effect that level-one water is added is that the macromolecule resin being dissolved in acetonitrile is allowed to be precipitated), then plus
The derivatization reagent for entering 0.8ml performs the derivatization 20min under conditions of room temperature is protected from light, and then draws 3ml with injector for medical purpose
Sample after derivatization is filtered with 0.24 μm of filter core, obtains sample to be tested；
Above all of test is both needed to do skip test.
Step d, HPLC is measured
Machine sample introduction on the sample to be tested of step c pre-treatment acquisition is measured, the determination condition of high performance liquid chromatography is such as
Under:
It is that eluent composed by Mobile phase B is washed according to following elution program by mobile phase A and level-one water of acetonitrile
It is de-:
Time is respectively as follows: 20min；
The mass percent of mobile phase A is respectively as follows: 55%
The mass percent of Mobile phase B is respectively as follows: 45%
Wherein, column temperature is 25 DEG C, flow velocity 1.0ml/min, and sample volume is 20 μ l, Detection wavelength 355nm；
Chromatographic column is C18 reversed-phase column, and 5.0 μm, 4.6mm × 150mm, mobile phase A contains 0.1% phosphoric acid, and Mobile phase B contains
0.1% phosphoric acid.
Testing result is as shown in figure 3, content of formaldehyde in available prepare liquid:
The content of formaldehyde of measurement calculates as follows: X=C × V/m
In formula: X --- the content of formaldehyde in sample to be tested, unit mg/kg
C --- the volumetric concentration content value being calculated from standard curve, unit mg/l；
The constant volume of V --- sample to be tested, unit ml；
M --- the quality of weighed sample to be tested, unit g.
Embodiment 4:
The test sample of the present embodiment is the oiliness of the model CR-62NB of Dongguan Dabao Chemical Products Co., Ltd.'s production
Sample.
A kind of method measuring the free formaldehyde in oil paint and its raw material with high performance liquid chromatography of the present embodiment,
The following steps are included:
Step a, the preparation of formaldehyde standard working curve
A1) the preparation of derivatization reagent: weighing the 2,4-dinitrophenylhydrazine of 0.5g, is derived with phosphoric acid constant volume to 50ml
Change reagent；
A2) the preparation of formaldehyde standard working solution: weighing the formaldehyde standard substance of 100ul, and standard substance concentration is
9.6mg/ml is settled to 100ml with acetonitrile, is configured to formaldehyde standard dilution, then pipettes 0.0ml, 0.1ml respectively,
0.2ml, 0.5ml, 1.0ml, 3.0ml, 5.0ml, 8.0ml, 10.0ml formaldehyde standard dilution, are settled to 10ml with acetonitrile, match
A series of formaldehyde standard working solution of various concentrations is made；
A3) formaldehyde standard working curve makes: above-mentioned formaldehyde standard working solution 4ml is pipetted respectively, and acetonitrile 4ml is added,
Add derivatization reagent 0.4ml, 20min reacted under the conditions of room temperature is protected from light, then carry out HPLC test, test result with
Formaldehyde standard working solution concentration is abscissa, and the peak area of test is ordinate, draws formaldehyde standard working curve.
Step b, sample detection
1g sample is taken, is first diluted according to sample viscosity with acetone, FTIR and GC-MS test is then carried out, determining should
In sample whether the ingredient containing ketone, isocyanate ester compound, testing result determine the sample be contain isocyanates
The oiliness sample of compound.
Step c, the pre-treatment of the oiliness sample containing isocyanate ester compound
The sample of 2.5g (being accurate to 1mg) is weighed, the resin 5g containing hydroxyl group is added, and (resin is Dongguan Dabao
Work Products Co., Ltd production model CR-62NA5 commodity, be accurate to 1mg) reaction 10min obviously increase to sample viscosity
Add, acetonitrile solvent is added and is settled to 25ml, then carries out ultrasonic wave extraction 10min, takes out 10ml extracting solution after the completion of extracting,
Centrifugal treating is carried out under 18000rpm revolving speed, then takes out the upper layer sample of 2ml, according to volume ratio acetonitrile: level-one water: derivatization
Reagent=1:1:(0.2-0.6) acetonitrile, level-one water and derivatization reagent is added, as preferred embodiment, in the present embodiment,
The acetonitrile of 4ml is added, then (purpose that acetonitrile is added is to ensure that supernatant liquor can be sufficiently molten by formaldehyde to the level-one water of addition 4ml
Solution is in acetonitrile and dilutes supernatant liquor, and ensures that the mobile phase of itself and subsequent high performance liquid chromatography can be compatible, is added one
The effect of grade water is that the macromolecule resin being dissolved in acetonitrile is allowed to be precipitated), the derivatization reagent for adding 2.4ml is kept away in room temperature
20min is performed the derivatization under conditions of light, the sample after drawing 3ml derivatization with injector for medical purpose, with 0.22 μm of filter core
It is filtered, obtains sample to be tested；
Above all of test is both needed to do skip test.
Step d, HPLC is measured
Machine sample introduction on the sample to be tested of step c pre-treatment acquisition is measured, the determination condition of high performance liquid chromatography is such as
Under:
It is that eluent composed by Mobile phase B is washed according to following elution program by mobile phase A and level-one water of acetonitrile
It is de-:
Time is respectively as follows: 20min；
The mass percent of mobile phase A is respectively as follows: 55%
The mass percent of Mobile phase B is respectively as follows: 45%
Wherein, column temperature is 25 DEG C, flow velocity 1.0ml/min, and sample volume is 20 μ l, Detection wavelength 355nm；
Chromatographic column is C18 reversed-phase column, and 5.0 μm, 4.6mm × 150mm, mobile phase A contains 0.1% phosphoric acid, and Mobile phase B contains
0.1% phosphoric acid.
Testing result is as shown in figure 4, content of formaldehyde in available prepare liquid:
The content of formaldehyde of measurement calculates as follows: X=C × V/m
In formula: X --- the content of formaldehyde in sample to be tested, unit mg/kg
C --- the volumetric concentration content value being calculated from standard curve, unit mg/l；
The constant volume of V --- sample to be tested, unit ml；
M --- the quality of weighed sample to be tested, unit g.
The present embodiment is merely illustrative of the technical solution of the present invention, rather than limiting the scope of the invention, although ginseng
The present invention is explained in detail according to preferred embodiment, those skilled in the art should understand that, it can be to the present invention
Technical solution be modified or replaced equivalently, without departing from the spirit and scope of technical solution of the present invention.
Claims (7)
1. a kind of method for being measured the free formaldehyde in oil paint and its raw material using high performance liquid chromatography, feature are existed
In: this method is different according to the ingredient that sample contains, comprising the following steps:
Step a, the preparation of formaldehyde standard working curve
A1) the preparation of derivatization reagent: weighing a certain amount of 2,4-dinitrophenylhydrazine, obtains derivatization reagent with solvent constant volume；
A2) the preparation of formaldehyde standard working solution: weighing a certain amount of formaldehyde standard substance, and formaldehyde standard dilution is prepared after dilution
Then liquid pipettes a certain amount of formaldehyde standard dilution, be configured to the formaldehyde standard working solution of a series of various concentration；
A3) formaldehyde standard working curve make: pipette a certain amount of derivatization reagent be added into formaldehyde standard working solution into
Then row derivatization carries out HPLC test, test result is using formaldehyde standard working solution concentration as abscissa, the peak area of test
For ordinate, formaldehyde standard working curve is drawn；
Step b, sample detection
A certain amount of sample is taken, is diluted according to sample viscosity with acetone, FTIR and GC-MS test is then carried out, determines sample
In product whether the ingredient containing ketone, isocyanate ester compound, then carry out next step pre-treatment；
Step c, sample pre-treatments
According in sample detection ingredient whether containing ketone compounds, isocyanates and different pre-treatments is carried out to sample, wrap
Include following pre-treatment step:
C1) for the pre-treatment of the diluent class sample without containing ketone compounds
A certain amount of sample is weighed, solvent is added and carries out ultrasonic wave extraction, then takes out a certain amount of sample solution, is first added one
Quantitative acetonitrile adds after a certain amount of derivatization reagent performs the derivatization, and filtering obtains sample to be tested；
C2) for the pre-treatment without containing ketone, isocyanate ester compound and non-diluted dose of oiliness sample
A certain amount of sample is weighed, solvent is added and carries out ultrasonic wave extraction, centrifugal treating is carried out after the completion of extracting, then takes out one
Quantitative upper layer sample, is first added a certain amount of acetonitrile, and level-one water is then added, and adds a certain amount of derivatization reagent and carries out
After derivatization, filtering obtains sample to be tested；
C3) for the pre-treatment of the oiliness sample containing ketone compounds
A certain amount of sample is weighed, solvent is added and carries out ultrasonic wave extraction, centrifugal treating is carried out after the completion of extracting, then takes out one
Quantitative upper layer sample, is first added a certain amount of acetonitrile and level-one water, further according to ketone chemical combination in sample detected by step b
The content of object and excessive derivatization reagent is added, it is ensured that after complete derivatization, filtering obtains sample to be tested；
C4) for the pre-treatment of the oiliness sample containing isocyanate ester compound
A certain amount of sample is weighed, the resin reaction containing hydroxyl group is added for a period of time, solvent is then added and carries out ultrasound
Wave extracts, and carries out centrifugal treating after the completion of extracting, then takes out a certain amount of upper layer sample, a certain amount of acetonitrile and one is first added
Grade water adds after a certain amount of derivatization reagent performs the derivatization, and filtering obtains sample to be tested；
Step d, HPLC is measured
The sample to be tested that step c pre-treatment obtains is placed on to a period of time under the conditions of being protected from light, is then filtered, upper machine sample introduction is surveyed
Fixed, the content of formaldehyde of measurement calculates as follows: X=C × V/m
In formula: X --- the content of formaldehyde in sample to be tested, unit mg/kg
C --- the volumetric concentration content value being calculated from standard curve, unit mg/l；
The constant volume of V --- sample to be tested, unit ml；
M --- the quality of weighed sample to be tested, unit g.
2. a kind of free first measured in oil paint and its raw material using high performance liquid chromatography according to claim 1
The method of aldehyde, it is characterised in that: in step c, the solvent is any one in methanol, chloroform, isopropanol, acetonitrile and normal heptane
Kind.
3. a kind of free first measured in oil paint and its raw material using high performance liquid chromatography according to claim 1
The method of aldehyde, it is characterised in that: in step c1, the volume ratio of acetonitrile and derivatization reagent is 1:(0.1-0.2).
4. a kind of free first measured in oil paint and its raw material using high performance liquid chromatography according to claim 1
The method of aldehyde, it is characterised in that: in step c2, the volume ratio of acetonitrile, level-one water and derivatization reagent is 1:(0.5-1): (0.1-
0.2)。
5. a kind of free first measured in oil paint and its raw material using high performance liquid chromatography according to claim 1
The method of aldehyde, it is characterised in that: in step c3, the volume ratio of acetonitrile, level-one water and derivatization reagent is 1:1:(0.2-0.6).
6. a kind of free first measured in oil paint and its raw material using high performance liquid chromatography according to claim 1
The method of aldehyde, it is characterised in that: in step c4, the volume ratio of acetonitrile, level-one water and derivatization reagent is 1:1:(0.2-0.6).
7. a kind of free first measured in oil paint and its raw material using high performance liquid chromatography according to claim 1
The method of aldehyde, it is characterised in that: in step c, the filter core of filtering is 0.20-0.24 μm.
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