CN110346465A - A kind of method that gas chromatography measures acrylonitrile content in adhesive - Google Patents
A kind of method that gas chromatography measures acrylonitrile content in adhesive 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 methods of acrylonitrile content in a kind of gas chromatography measurement adhesive, use the modified polyethylene glycol capillary column of nitroterephthalic acid；Use programmed temperature method: column temperature is 30 DEG C of holding 2min；10 DEG C/min is warming up to 70 DEG C, keeps 1min；1 DEG C/min rises to 75 DEG C, keeps 2min；1 DEG C/min rises to 80 DEG C, keeps 2min；20 DEG C/min rises to 250 DEG C, keeps 2min；Detector temperature: 280 DEG C.It is detected with flame ionization ditector, peak area inner mark method ration qualitative with standard appearance time.The present invention is measured for acrylonitrile content in adhesive, and protection health of human body safety, prevention is potentially hazardous using adhesive products, accurate and effective feasible.
Description
Technical field
The invention belongs to analysis detection fields, and in particular to acrylonitrile content in a kind of gas chromatography measurement adhesive
Method.
Background technique
Aqueous adhesive is mainly polyvinyl alcohol adhesive and vinyl acetate adhesive.The levelling main use of indoor wall
After polyvinyl alcohol adhesive, calcite in powder and water match by a certain percentage, blade coating and metope form smooth bright and clean horizontal plane,
Convenient for brushing inside and outside wall emulsion paint or other paints, finishing beautification function is played；On the other hand it is used with cement mixing as adhesive
It is viscous glutinous in the laying of metope and floor ceramic tile；Vinyl acetate adhesive is mainly used for the glue of the processing and making process of wood furniture
It is viscous.Two kinds of aqueous adhesives have been used as decorating and renovating material to be widely used in manufacturer in order to reduce production cost, using third
Acrylamide enhances the stream cloud of adhesive, it is too fast to avoid adhesive stemness as thickener after polyacrylamide is added
The phenomenon that overturning is easy with putty work progress.
Aqueous adhesive production technology is all molten to polyacrylamide using first addition polyacrylamide and water stirring heating
Xie Hou；Heat preservation 2h after polyvinyl alcohol is warming up to 95 DEG C is added to be completely dissolved to polyvinyl alcohol；65 DEG C of water heat preservations are added, are added third
Acrylamide, stirring is to being completely dissolved；Crosslinking agent, wetting agent, counter rise agent and water is added, stirs to being completely dissolved.In detection engineering
It crosses, the sample that acrylamide is added in polyvinyl alcohol adhesive has strong irritation, and after Mass Spectrometer Method, discovery is containing residual
Remaining acrylonitrile.
Acrylonitrile is a kind of colourless irritant odor liquids, and inflammable, steam can form explosive mix with air
Object.This product is extremely toxic, and the toxicity to warm-blooded animal is about the 1/30 of hydrogen cyanide.Not only steam is toxic for acrylonitrile, but also is attached to skin
Also The book of Changes dermal toxicity on skin.
The existing acrylonitrile method of inspection has:
" industrial the 12nd part of acrylonitrile: the measurement gas-chromatography of purity and impurity content GB/T 7717.12-2008
Method " method that uses of standard for liquid sample evaporation after by capillary chromatographic column, separate each component to be determined, use FID
Detection, records the chromatographic peak area of each impurity composition, using inner mark method ration.Acrylonitrile purity reduces this part by 100.00
Impurity and with other parts method measure other impurities (such as moisture) total amount acquire.
The method that HJ 806-2016 " the measurement purge and trap gas chromatography of water quality acrylonitrile and methacrylaldehyde " standard uses
It is adsorbed in trap tube after high pure nitrogen (or other inert gases) purging for the target compound in sample, heats rapidly
Trap tube and with high pure nitrogen (or other inert gases) blowback, after the group lease making gas chromatographic column separation come out by thermal desorption,
It is detected with flame ionization ditector.Qualitative with retention time, chromatographic peak area is quantitative.
Existing detection method sample component is relatively easy, detect to acrylonitrile using gas chromatographic column easy to be real
It is existing.Adhesive is made of host agent and auxiliary agent, and host agent is generally high polymer, auxiliary agent have curing agent, diluent, plasticizer, filler,
Coupling agent, initiator, thickener, anti-aging agent, polymerization inhibitor, stabilizer, complexing agent, emulsifier etc., according to requiring with purposes also
It may include the ingredients such as fire retardant, foaming agent, defoaming agent, colorant and mould inhibitor, be not suitable for existing detection method.
The prior art is directed to the detection method of acrylonitrile in adhesive not yet, for protection health of human body safety, promotes to produce
Quality is promoted, and prevention product is potentially hazardous, should establish a kind of detection method, copes with security risk and wind existing for product
Danger.
Summary of the invention
The present invention is in view of the shortcomings of the prior art, provide the side of acrylonitrile content in a kind of gas chromatography measurement adhesive
Method.Solve the problems, such as that the detection difficult of acrylonitrile in adhesive, the method for the present invention have feasibility, accuracy and actual effect.
The technical solution that the present invention solves its technical problem is as follows:
A kind of method that gas chromatography measures acrylonitrile content in adhesive, uses chromatographic column to change for nitroterephthalic acid
The polyethylene glycol capillary column of property；It is detected with flame ionization ditector.
Preferred chromatographic column is the modified capillary column of HP-FFAP polyethylene glycol nitrobenzene, column specification 60m × 0.52mm ×
1.00μm。
Preferably, the gas chromatography uses programmed temperature method.More preferable temperature program are as follows: column temperature is 30 DEG C of holdings
2min；10 DEG C/min is warming up to 70 DEG C, keeps 1min；1 DEG C/min rises to 75 DEG C, keeps 2min；1 DEG C/min rises to 80 DEG C,
Keep 2min；20 DEG C/min rises to 250 DEG C, keeps 2min；Detector temperature: 280 DEG C.
Preferably, internal standard compound is added in the method for the invention, and using peak area inner mark method ration, the internal standard compound is heptan
Alkane.
Preferably, the present invention uses ethyl acetate as solvent dilute sample.
Preferably, adhesive of the present invention is watersoluble polyvinyl alcohol adhesive or vinyl acetate adhesive.
The invention has the advantages that
The present invention is directed to the characteristics of adhesive, right in terms of three of chromatography column polarity, temperature program and sample solvent
Chromatogram analysis method is investigated, and the method that can be measured to acrylonitrile content in adhesive is established, and the method is accurate
It is effective and feasible.The method and standard that the present invention establishes are conducive to the quality control of adhesive products, to protection health of human body peace
Entirely, it takes precautions against potentially hazardous with very big application value.
Detailed description of the invention
Fig. 1 is the Elevated Temperature Conditions acrylonitrile appearance time and peak type of the embodiment of the present invention 1.
Fig. 2 is the detection spectrogram of the DB-1301 chromatographic column of the embodiment of the present invention 2.
Fig. 3 is the detection spectrogram of the DB-WAX chromatographic column of the embodiment of the present invention 2.
Fig. 4 is the detection spectrogram of the HP-FFAP chromatographic column of the embodiment of the present invention 2.
Fig. 5 is the spectrogram of the Selection of internal standard of the embodiment of the present invention 3.
Fig. 6 is the spectrogram of the measurement acrylonitrile using chromatographic column constant temperature method of the embodiment of the present invention 5.
Fig. 7 is the spectrogram of the measurement acrylonitrile using chromatographic column programmed temperature method of the embodiment of the present invention 5.
Fig. 8 is the canonical plotting of the acrylonitrile relative correction factor of the embodiment of the present invention 6.
Specific embodiment
Present invention is further described in detail with reference to the accompanying drawings and in conjunction with the embodiments.But the present invention is not limited to be given
Example out.Term as used in the present invention generally has those of ordinary skill in the art usual unless otherwise indicated
The meaning of understanding.The present invention is described in further detail below with reference to specific example and referring to data.
The measuring method of free acrylonitrile content in 1. aqueous adhesive of embodiment
1, range: this standard defines acrylic acid content measurement-gas chromatography of dissociating in aqueous adhesive；Suitable for adopting
The measurement of the free acrylonitrile content of the aqueous adhesive for using acrylamide as thickener.
2, principle
It weighs sample to be placed in quantitative solvent bottle, internal standard compound is added, is diluted to regulation scale with heptane or other solvents
Afterwards, after concussion mixes, filtering by gas-chromatography post separation, is detected with flame ionization ditector, when with standard appearance
Between qualitative, peak area inner mark method ration.
Unless otherwise indicated, it is used only in analysis and is confirmed as analyzing pure or above reagent and meets the rule of GB/T 6682
Fixed tertiary effluent.Portion of reagent used in this test method is toxic, and testing crew should have laboratory safety knowledge.
3, reagent
Acrylonitrile: 99.5% or more content；
Heptane: 99.5% or more；
Ethyl acetate: chromatographically pure.
4, instrument and equipment
Color-comparison tube or volumetric flask: 50mL；
Pipette and liquid-transfering gun: 1mL liquid-transfering gun, 1mL, 2mL, 5mL pipette；
Reciprocating constant temperature water bath oscillator: 40 DEG C, 50HZ；
Balance: precision 0.1mg
Gas chromatograph matches fid detector and temperature programming, and has the functional software for automatically generating calibration and calculating.
5, test procedure
The drafting of 5.1 standard working curves
5.1.1 standard solution 10mg/mL: weighing the acrylonitrile of 0.5g or so 4.1, is placed in advance equipped with about 10mL
In the 50mL volumetric flask or tool plug clogged tube of 4.3 ethyl acetate, it is diluted to scale with 4.3 ethyl acetate, is mixed spare.
5.1.2 6mg/mL heptane uses the configuration of liquid: weighing the heptane of 0.3g or so 4.1, is placed in advance equipped with about 10mL
4.3 ethyl acetate 50mL volumetric flask or tool plug clogged tube in, be diluted to scale with 4.3 ethyl acetate, mix standby
With.
5.1.3 the configuration of standard working solution: taking 6 50mL color-comparison tubes or volumetric flask, respectively move into 0.00mL,
The acrylonitrile standard solution and immigration 2.00mL of 1.00mL, 2.00mL, 3.00mL, 4.00mL, 5.00mL, 10.00mL6.1.1
6.1.2 normal heptane use liquid, mixed after being diluted to scale with 4.3 ethyl acetate, standard working solution be transferred to
It is to be measured after number in 2mL chromatography column feed materials bottle.
5.2 gas chromatograph conditions
5.2.1 chromatographic column: HP-FFAP polyethylene glycol nitrobenzene modified capillary column (60m × 0.52mm × 1.00 μm) or
Suitable model
5.2.2 carrier gas: nitrogen, column press 3.67psi, total flow 19.789mL/min, split ratio: 5:1；
5.2.2.3 injector temperature: 260 DEG C.Column temperature: 30 DEG C of holding 2min；10 DEG C/min is warming up to 70 DEG C, keeps
1min；1 DEG C/min rises to 75 DEG C, keeps 2min；1 DEG C/min rises to 80 DEG C, keeps 2min；20 DEG C/min rises to 250 DEG C, protects
Hold 2min.Detector temperature: 280 DEG C.
5.2.2.4 sample volume: 1 μ L.
5.2.2.5 best instrument condition can also be selected according to test specimens actual conditions.
The test and calibration of the 5.3 acrylonitrile relative calibration factors
5.3.1 the test of the acrylonitrile relative calibration factor
Optimize instrument parameter by 5.2 regulation under chromatographic condition identical with test sample.The standard of 5.1.3 is worked
Solution is recorded chromatogram, is calculated separately every kind of concentration third by formula 1 as in the injection gas chromatograph of sample volume as defined in 5.2.2.4
The relative calibration factor of alkene nitrile standard working solution:
In formula:
Ri--- the relative calibration factor of acrylonitrile；
mi--- the quality of acrylonitrile, μ g；
ms--- the quality of internal standard compound heptane, μ g；
Ai--- the peak area of acrylonitrile；
As--- the peak area of internal standard compound heptane.
RiThe average value tested twice is taken, relative deviation should be less than 5%, and test result retains after decimal point 3.
5.3.2 the calibration and calculating of the acrylonitrile relative calibration factor
If instrument has calibration method, calibrated, and this method is saved, is made by calibration method using different concentration
For the calibration and calculation method of sample, the error of single concentration is avoided.
The measurement of 5.4 samples
5.4.1 the preparation of adhesive samples: representative sample about 2g is replaced (to be accurate to from taken whole samples
It 0.0001g) being placed in 50mL colorimetric cylinder or volumetric flask, adds ethyl acetate about 30mL, the heptane for moving into 5.1.2 uses liquid 2mL,
It erects to be placed in after closed and has been set to 40 DEG C, reciprocating frequence is shaking in the reciprocating water-bath constant temperature oscillator of 50Hz
30min takes out sample and is cooled to room temperature, be diluted to scale with ethyl acetate, be transferred in 2mL chromatography column feed materials bottle after shaking up, compiles
It is to be measured after number.
5.4.2 sample measures: according to the measurement of method as defined in 5.3.1, recording chromatogram.
5.4.3 the calculation formula of acrylonitrile content is formula 2 in sample:
In eliminant:
W --- the content of acrylonitrile, mg/kg in sample；
mi--- the quality of sample, μ g；
ms--- the quality of internal standard compound heptane, μ g；
Ai--- the peak area of acrylonitrile in sample；
As--- the peak area of internal standard compound heptane in sample.
The detection of this method is limited to 0.05mg/kg.
Fig. 1 is seen according to the appearance time of above-mentioned Elevated Temperature Conditions acrylonitrile and peak type.
The selection of 2. chromatographic column of embodiment
Acrylonitrile belongs to polar compound, according to the principle of similar compatibility, should select polarity chromatographic column, the present embodiment selection
Polarity chromatographic column: DB-1301 [(6%- cyanogen propvl-phenvl)-methyl polysiloxane], DB-WAX (polyethylene glycol) and HP-FFAP
(the modified polyethylene glycol of nitroterephthalic acid) capillary chromatographic column, uses ethyl acetate conduct using acrylonitrile standard substance
Solvent, heptane are detected, chromatogram is as in Figure 2-4 as internal standard compound using the condition of embodiment 1.Wherein use DB-
The detection spectrogram of 1301 chromatographic columns is shown in Fig. 2, sees Fig. 3 using the detection spectrogram of DB-WAX chromatographic column；Use HP-FFAP chromatographic column
Detection spectrogram see Fig. 4.
It is compared: being detected using DB-1301 chromatographic column, acrylonitrile is without response, DB- by three spectrograms above
WAX column is bad to internal standard compound heptane separating effect, and HP-FFAP column is fine to the separating effect of heptane and acrylonitrile, it is therefore highly preferred that
Chromatographic column is HP-FFAP chromatographic column.
The selection of 3. internal standard compound of embodiment
The selection of internal standard compound should follow following principle: similar to the boiling point of analyte, polarity, chemical structure；Sample
In be not present；It must be completely dissolved in tested solvent and the not color with sample chemically reactive and with each component in sample
Spectral peak is kept completely separate；The amount that internal standard compound can be added should be close to tested component；It the position of chromatographic peak should be with the chromatography of tested component
The position divided is close or among several tested components；Both internal standard compound and measured matter peak area ratio should be greater than 75%.According to
The internal standard compound that the above principle combination water paint and adhesive characteristic are usually selected is isopropanol, isobutanol, benzene, heptane, positive ten
Four alkane.The present embodiment selects isopropanol, isobutanol, heptane as internal standard compound respectively, using ethyl acetate as solvent, with HP-
FFAP column is detected using the chromatographic condition of embodiment 1.As the result is shown using isopropanol, isobutanol as internal standard compound, response
Very low, the chromatogram using heptane as internal standard compound is as shown in Figure 5.It can be seen that heptan by the appearance time and peak area of spectrogram
Alkane has response peak shape well as internal standard compound.
The selection of 4. solvent of embodiment
The chemical property of acrylonitrile is dissolved in water, be dissolved in methanol, ethyl alcohol, benzene, carbon tetrachloride, ethyl acetate, ethyl acetate,
Ether etc., the compounds such as acrylamide, polyacrylamide, polyvinyl alcohol, polyvinyl acetate are all water-soluble.For verifying we
The correctness of method selects formaldehyde, ethyl alcohol as water-soluble solvent, selects acetone, ethyl acetate water-insoluble solvent as we
The solvent of method, the foundation by acrylonitrile recovery of standard addition as determination method validity (poison because acetone belongs to easily system
Product put aside the product as diluent).Test data and recovery of standard addition are shown in Table 1.
It can be seen that the method for inspection is feasible, effective by the above verification result；It can be seen that from recovery of standard addition
Ethyl acetate is best as the recovery of standard addition of retarder thinner, because ethyl acetate dissolubility is strong, and sample is not easy hair and rises,
It is easy filtering, there are sample dilution rear thicks to spend greatly for ethyl alcohol, it is not easy to which the situation of filtering, methanol is small as solvent solubility, rings
It should be worth low.
The selection of 5. column temperature of embodiment
So-called programmed temperature chromatography refers to program that the temperature of chromatographic column is arranged according to component boiling range continuously at any time
It linearly or nonlinearly gradually rises, corresponds to each other column temperature with the boiling point of component, so that low boiling component and high boiling component exist
Have that suitable reservation, chromatographic peak are evenly distributed and peak shape is symmetrical in chromatographic column.The retention of each component can be with chromatographic peak highest
The relevant temperature at place, that is, retening temperature indicates.The detection object of this method is mainly acrylonitrile and heptane, passes through its molecular weight
Compare with boiling point, programmed temperature method and constant temperature method can be selected.
Constant temperature method: according to the boiling point of object, the present embodiment selects direct column temperature is constant to measure at 90 DEG C, time 30min,
Appearance spectrogram, cannot effective discrimination objective compound as shown in fig. 6, its appearance time and separating effect are bad as the result is shown.
Programmed temperature method: according to the boiling point of target compound, and the method for setting program heating usually, column temperature setting
Are as follows: 30 DEG C of holding 2min；10 DEG C/min is warming up to 70 DEG C, keeps 1min；1 DEG C/min rises to 75 DEG C, keeps 2min；1℃/min
80 DEG C are risen to, 2min is kept；20 DEG C/min rises to 250 DEG C, keeps 2min.Spectrogram appearance spectrogram is as shown in Figure 7.As the result is shown
Under the conditions of this temperature program, target compound and other substances are efficiently separated, and interval time is very long, conducive to object
Identification and calculating.
The measurement of 6. relative correction factor of embodiment
The acrylonitrile standard substance of 6 kinds of various concentrations and the peak face of internal standard compound are measured using the method for inspection of the present invention
Long-pending and appearance time, the results are shown in Table 2.
The acrylonitrile standard substance of 26 kinds of various concentrations of table and the peak area and appearance time of internal standard compound
| Heptane concentration μ g/mL | Appearance time min | Peak area | Acrylonitrile concentration μ g/mL | Appearance time min | Peak area |
| 134.80 | 12.892 | 425.56200 | 219.88 | 13.667 | 465.07360 |
| 269.60 | 12.991 | 839.09125 | 439.76 | 13.675 | 913.85486 |
| 404.40 | 12.904 | 1256.80835 | 659.64 | 13.684 | 1371.77795 |
| 539.20 | 12.915 | 1666.38580 | 879.52 | 13.693 | 1816.94769 |
| 674.00 | 12.921 | 2163.15698 | 1099.40 | 13.699 | 2346.97498 |
| 1348.00 | 12.945 | 4271.21534 | 2198.80 | 13.703 | 4633.55030 |
The standard curve of relative correction factor is as shown in Figure 8.Acrylonitrile calibration factor is 1.5041, from curve R2=1 can
To find out that detection method of the invention is correct.
The uncertainty of Water By Gas Chromatography adhesive acrylonitrile content shown in 7. present invention of embodiment
1. measuring uncertain source
When assessing overall uncertainty, each source of uncertainty is analyzed, to determine its contribution to overall uncertainty.
The main source of the uncertainty of measurement of this method of inspection includes:
(1) uncertainty u (R caused by relative correction factori)；
(2) uncertainty u (P caused by standard substance purityis)；
(3) the uncertainty u (m that internal standard compound heptane and sample weighis)、u(mi)
(4) in formula 1 and 2, Ai、AisAs a partial uncertainty u (Ai/Ais)
Acrylonitrile is formula 2 by partial uncertainty u (Ri), u (Pis), u (mis), u (mi), u (Ai/Ais):
2. uncertainty caused by 2.1 correction factor of evaluation of uncertainty of measurement
2.1.1 the uncertain source of correction factor and mathematical model
In actually detected, relative correction factor of the acrylonitrile to heptane, method are as follows: weigh internal standard compound heptan are detected first
Alkane 0.03 and acrylonitrile 0.05g, are tested after being settled to 50ml with ethyl acetate.Correction factor has formula 4 to ask:
2.1.2 correction factor relative standard uncertainty
(1) the uncertainty u (m) that acrylonitrile standard items weigh
Weigh uncertainty mainly from two aspect, first, weigh mobility generate uncertainty.Within 50g,
Mobility standard deviation is 0.07mg；Second, the uncertainty that balance correction generates.It is given as ± 1.0mg by calibration certificate,
It is 95% (k=1.96) by fiducial probability, then standard deviation is 1.0/1.96=0.510mg, this two synthesis weigh not true
Fixed degree are as follows:
Each component relative standard uncertainty are as follows:
(2) u (P is not known caused by standard substance purityi)
The purity of acrylonitrile standard items is 99.5% ± 0.05%, is converted by being uniformly distributed are as follows:
(3) internal standard/acrylic object peak area ratio Ais/AiCaused uncertainty u (Ais/Ai)
u(Ais/Ai) it is mainly as caused by instrument replication, by calibration solution average measurement 6 times, by Bessel Formula
Calculate standard deviation s (Ais/ A), then standard uncertainty Relative standard uncertainty urel(Ais/ A)=u (Ais/ A)/average value, internal standard test process
In (Ais/Ai) uncertainty calculation for example the following table 3 indicate.
3 (A of tableis/Ai) 6 parallel determinations
4.1.3 correction factor Composite Seismogram
It is obtained by formula 4, urel(wAcrylonitrile)=0.022715
Uncertainty u (P caused by 4.2 internal standard purityInternal standard)
The same 4.1.2 of method (2), the purity of heptane standard items are 99.9% ± 0.1%, by being uniformly distributed standard deviation
Relative standard uncertainty are as follows:
The uncertainty u (m) of 4.3 internal standards and sample sample weighting amount
The same 4.1.2 of method (1), weigh uncertainty mainly from two aspect, first, weigh mobility generate not really
Fixed degree.Within 50g, mobility standard deviation is 0.07mg；Second, the uncertainty that balance correction generates.By calibration certificate
It is given as ± 1.0mg, is 95% (k=1.96) by fiducial probability, then standard deviation is 1.0/1.96=0.510mg, internal standard matter
Measure 0.0331g, sample mass 1.9874g, the uncertainty that this two synthesis weigh are as follows:
Relative standard uncertainty are as follows:
4.4 acrylonitrile/heptane peak area ratio Ai/AisCaused uncertainty
The same 4.1.2 of method (3), u (Ai/Ais) it is mainly as caused by instrument replication, by calibration solution average measurement
6 times, by Bessel Formula
Calculate standard deviation s (Ais/ A), then standard uncertainty Relative standard uncertainty urel(Ai/Ais)=u (Ai/Ais)/average value, interior mapping
(A during examinationis/Ai) uncertainty calculation for example the following table 4 indicate.
4 (A of tablei/Ais) 6 parallel determinations
| Ai/Ais | 1 | 2 | 3 | 4 | 5 | 6 | Average value | s(Ais/Ai) | u(Ais/Ai) | urel(Ais/Ai) |
| Internal standard/acrylonitrile | 0.00089 | 0.00084 | 0.00089 | 0.00086 | 0.00086 | 0.00084 | 0.00086 | 0.000023 | 0.000009 | 0.01066 |
5. combined standard uncertainty u (wAlways)
The Composite Seismogram of acrylonitrile is calculated by following formula in 5.1 samples:
Calculate to obtain urel(wAcrylonitrile)=0.0301
5.3 uncertainty sources and assay value are shown in Table 5.
5 analysis on Uncertainty table of table
| Serial number | Standard uncertainty component u (X) | Uncertainty source | Distribution | Relative standard uncertainty value |
| 1 | u(Ri) | Correction factor | Normal distribution | 0.022715 |
| 2 | u(Pi) | Internal standard purity | It is uniformly distributed | 0.00058 |
| 3 | u(mi) | Sample weighs | It is uniformly distributed | 0.0002591 |
| 4 | u(mis) | Interior nominal amount | It is uniformly distributed | 0.01556 |
| 5 | u(Ai/Ais) | Peak area ratio | Normal distribution | 0.01066 |
6 extension relative uncertainty degrees
Extend relative uncertainty degree Urel(X)=k × urel(X).Spreading factor removes k=2, U under normal circumstancesrel(XAcrylonitrile)
=0.05 × 2=0.1%.The measurement result of acrylonitrile is 0.052 ± 0.1%, and numerical value is examined to be shown in Table 6.
66 inspection parallel determinations % of table
| 1 | 2 | 3 | 4 | 5 | 6 | Average value | |
| Acrylonitrile | 0.05172 | 0.05242 | 0.05168 | 0.05147 | 0.05217 | 0.05214 | 0.05193 |
It should be understood that these embodiments model of the invention solely for the purpose of illustration, rather than limiting the invention in any way
It encloses.
In addition to the implementation, the present invention can also have other embodiments.It is all to use equivalent substitution or equivalent transformation shape
At technical solution, fall within the scope of protection required by the present invention.
Claims (6)
1. a kind of method of acrylonitrile content in gas chromatography measurement adhesive, it is characterised in that chromatographic column is nitro to benzene two
The modified polyethylene glycol capillary column of acid；It is detected with flame ionization ditector.
2. the method as described in claim 1, it is characterised in that described to use ethyl acetate as sample retarder thinner.
3. the method as described in claim 1, it is characterised in that the gas chromatography uses programmed temperature method, and column temperature is 30 DEG C
Keep 2min；10 DEG C/min is warming up to 70 DEG C, keeps 1min；1 DEG C/min rises to 75 DEG C, keeps 2min；1 DEG C/min rises to 80
DEG C, keep 2min；20 DEG C/min rises to 250 DEG C, keeps 2min；Detector temperature: 280 DEG C.
4. the method as described in claim 1, it is characterised in that internal standard compound is added in the method, legal using peak area internal standard
Amount, the internal standard compound are heptane.
5. method according to any of claims 1-4, it is characterised in that the gas chromatography testing conditions are as follows: chromatography
Column: modified capillary column 60m × 0.52mm × 1.00 μm of HP-FFAP polyethylene glycol nitrobenzene；Carrier gas: nitrogen；Column pressure
3.67psi；Total flow: 19.789mL/min；Split ratio: 5:1；Injector temperature: 260 DEG C.
6. method according to any of claims 1-4, it is characterised in that the adhesive is watersoluble polyvinyl alcohol adhesive
And vinyl acetate adhesive.
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| CN201910507773.1A CN110346465A (en) | 2019-06-12 | 2019-06-12 | A kind of method that gas chromatography measures acrylonitrile content in adhesive |
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| CN115452988A (en) * | 2022-09-15 | 2022-12-09 | 宣城研一新能源科技有限公司 | Method for detecting acrylonitrile content in wastewater through gas chromatography |
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