CN110514763A - A kind of high-efficiency liquid chromatography method for detecting directly measuring Analysis of Formic acid Residual in methyl formate - Google Patents
A kind of high-efficiency liquid chromatography method for detecting directly measuring Analysis of Formic acid Residual in methyl formate Download PDFInfo
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- CN110514763A CN110514763A CN201910827547.1A CN201910827547A CN110514763A CN 110514763 A CN110514763 A CN 110514763A CN 201910827547 A CN201910827547 A CN 201910827547A CN 110514763 A CN110514763 A CN 110514763A
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Abstract
A kind of high-efficiency liquid chromatography method for detecting directly measuring Analysis of Formic acid Residual in methyl formate, the preparation including methyl formate test solution, the preparation of formic acid reference substance solution, the drafting of formic acid standard curve and efficient liquid phase measurement.Condition when efficient liquid phase measures are as follows: C18 chromatographic column, 35 DEG C of column temperature, Detection wavelength 215nm, with 0.01M sodium dihydrogen phosphate (with phosphoric acid tune PH to 3.0) for mobile phase A, acetonitrile is Mobile phase B, flow velocity 1.0mL/min, 10 μ L of sample volume, is eluted.Operation of the present invention is simple, and measurement result is accurate, high sensitivity, favorable reproducibility.Linear test the result shows that, within the scope of a certain concentration, the standard curve of formic acid is in good linear relationship (R2=0.9999).
Description
Technical field
The invention belongs to high performance liquid chromatography chemical analysis detection technique fields, and in particular to a kind of directly to measure formic acid
The high-efficiency liquid chromatography method for detecting of Analysis of Formic acid Residual in methyl esters.
Background technique
High performance liquid chromatography is that developed recently is most fast, a kind of currently used analysis means, has high sensitivity, detection
Speed is fast, repeatability is high, chromatographic column can Reusability, can automatic operation, accuracy it is high and have a wide range of application etc. a variety of excellent
Point, therefore the analysis and detection of particularly suitable various samples.
Methyl formate is a kind of colourless dulcet volatile liquid, is mainly used for medicine and chemical field, can make organic
The raw material of synthesis can be used for the production of the products such as insecticide, war gas and solvent, can make formylating agent in organic synthesis,
It can also be used in fragrance and dry fruit, processing cereal etc..
Methyl formate is led because many reasons such as synthetic method cause wherein containing impurity such as formic acid and methanol with medical
Domain needs exploitation one to substance more stringent requirement related in starting material in order to preferably control the quality of the product
It is kind easy, accurately and fast, directly in Ethyl formate Analysis of Formic acid Residual detection method.
Comprehensive detection method relevant now, when research is found using gas phase spectrometry measurement formic acid, formic acid is in fid detector
Lower no response, can not directly detect.In this regard, there is the method using pre-column derivatization measurement formic acid, such as formic acid and ethyl alcohol are carried out
Esterification generates Ethyl formate, then obtains the content of formic acid by measuring the amount of Ethyl formate.The method is complicated for operation,
And esterification and ester-type hydrolysis reaction are reversible reaction, not only can not accurately illustrate the esterification yield of formic acid, also not can guarantee
A series of problems, such as Ethyl formate part reversible hydrolysis formic acid being derivatized to.Furthermore what is measured herein is in methyl formate
Analysis of Formic acid Residual, and methyl formate itself is the esterification products of formic acid, and formic acid such as will be further increased using derivatization method measurement
Methyl esters hydrolysis generates the uncontrollable factors such as formic acid.Therefore, derivatization method is not suitable for detecting the Analysis of Formic acid Residual in methyl formate.
With gas chromatography, when being detected using ECD detector, discovery formic acid need in higher concentrations detector just have sound
It answers, and peak shape is very poor, it is difficult to which accurate integration, poor repeatability are as a result inaccurate；And because formic acid is residual in methyl formate
Impurity, content are extremely low, it is difficult to reach the high concentration of ECD detector response.Therefore gas chromatography can not using ECD detector
Achieve the purpose that Analysis of Formic acid Residual in directly accurate measurement methyl formate.
To sum up, it needs to develop a kind of method that can directly measure Analysis of Formic acid Residual in methyl formate, and the method need to have
The advantage that separating degree is high, easy to operate, favorable reproducibility, result are accurate.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of efficient liquid for directly measuring Analysis of Formic acid Residual in methyl formate
Phase chromatographic detection method and its application.
To realize the above-mentioned technical purpose and other related purposes, present invention provide the technical scheme that a kind of directly measurement
The high-efficiency liquid chromatography method for detecting of Analysis of Formic acid Residual in methyl formate, the method include the following steps:
Step 1, methyl formate test solution preparation: will methyl formate be added acetonitrile in dissolve, after constant volume to obtain the final product.
The preparation of step 2, formic acid reference substance solution: formic acid reference substance is added in acetonitrile and is dissolved, after constant volume to obtain the final product.
The drafting of step 3, formic acid standard curve: formic acid being added in acetonitrile solution and is dissolved, up to standard control after constant volume
Product stock solution, is diluted to different multiples, and with high-efficient liquid phase technique, its peak area is measured at wavelength 215nm, is cross with concentration
Coordinate, peak area are that ordinate draws standard curve；
Step 4, efficient liquid phase measurement: the chromatographic column of filler is made of octadecylsilane chemically bonded silica, 35 DEG C of column temperature, is examined
Wavelength 215nm is surveyed, with 0.01M sodium dihydrogen phosphate (with phosphoric acid tune PH to 3.0) for mobile phase A, acetonitrile is Mobile phase B, stream
Fast 1.0mL/min, is eluted；Each 10 μ of test solution and control solution is drawn respectively and injects liquid chromatograph, is measured,
Up to result.
Formic acid content (%)=AFor/AIt is right×CIt is right×VFor/WFor/1000×100
The content of formic acid in methyl formate is calculated by above-mentioned formula；
In formula, AForFor the peak area of formic acid in test solution；AIt is rightFor the peak area of formic acid in reference substance solution；CIt is rightFor
The concentration of formic acid reference substance solution, unit are μ g/mL；VForFor the volume of test solution, unit mL；WForFor test sample formic acid
The sampling amount of methyl esters, unit mg.
Preferred technical solution are as follows: the ratio of the mobile phase is A:B=96:4.
The present invention has the advantages that the method provided according to the present invention, can be used high performance liquid chromatography and directly measures first
Analysis of Formic acid Residual in sour methyl esters, it is inadequate not only to avoid gas chromatography FID and ECD detector sensitivity, can not effectively examine
The problem of formic acid remains out, and avoid pre-column derivatization and be not suitable in formate ester organic matter detection formic acid is remaining to ask
Topic.In addition, method provided by the invention, easy to operate, separating degree is high, reproducible, as a result accurately, and the minimum detection of formic acid
Concentration is up to 1 μ g/mL.
Detailed description of the invention
The high-efficient liquid phase chromatogram of Fig. 1 methyl formate test solution.
The high-efficient liquid phase chromatogram of Fig. 2 formic acid reference substance solution (5 μ g/mL).
The canonical plotting of Fig. 3 formic acid.
The high-efficient liquid phase chromatogram of Fig. 4 blank solvent (acetonitrile)
Specific embodiment
Above content of the invention is described in further details by the following examples, but does not therefore limit this hair
Bright content.
Embodiment 1:
Major experimental instrument and chromatographic condition:
Waters e2695 high performance liquid chromatograph matches autosampler and 2998PDA detector.Chromatographic column: C18 chromatography
Column, 4.6 × 250mm, 5 μm；Mobile phase: 0.01M sodium dihydrogen phosphate (phosphoric acid tune PH3.0): acetonitrile=(96:4)；Flow velocity:
1.0mL/min；Column temperature: 35 DEG C；Detection wavelength: 215nm；Sample volume: 10 μ L.
Reagent and drug:
Formic acid (chromatographically pure, purity > 99.0%), phosphoric acid (excellent pure grade), methyl formate (analysis is pure), sodium dihydrogen phosphate (point
Analyse pure), acetonitrile (chromatographically pure), ultrapure water
Implementation steps 1: the preparation of methyl formate test solution
It takes methyl formate appropriate, sets in volumetric flask, acetonitrile is added to dissolve and be configured to the solution that concentration is about 30mg/mL, i.e.,
.
Implementation steps 2: the preparation of formic acid contrast solution
It takes formic acid reference substance appropriate, sets in volumetric flask, acetonitrile is added to dissolve and be configured to the solution that concentration is about 5 μ g/mL, i.e.,
.
Implementation steps 3: efficient liquid phase measurement: chromatographic column C18 column, 4.6 × 250mm × 5 μm；Mobile phase: 0.01M di(2-ethylhexyl)phosphate
Hydrogen sodium solution (phosphoric acid tune PH3.0): acetonitrile=(96:4)；Flow velocity: 1.0mL/min；Column temperature: 35 DEG C；Detection wavelength: 215nm；Into
Sample amount: 10 μ L are eluted.
Implementation steps 4: the drafting of standard curve
The formic acid reference substance for drawing 1 μ g/mL, 2 μ g/mL, 5 μ g/mL, 10 μ g/mL, 25 μ g/mL and 50 μ g/mL respectively is molten
Liquid measures its peak area with HPLC method, and using concentration as abscissa, peak area is ordinate, and calculating linear equation is Y=
290.2289X-86.9915, R2=0.9999.Experiments have shown that formic acid is within the scope of 0.92 μ of μ g/mL~46.2 g/mL in good
Linear relationship.
Implementation steps 5: the measurement of sample
The methyl formate test solution of 10 μ L is drawn, high performance liquid chromatograph, the height of comparative sample and reference substance are injected
Effect liquid phase chromatogram figure carries out qualitative analysis according to component retention time and contains formic acid in the sample of detection as depicted in figs. 1 and 2.
Peak area ratio with same time in the high-efficient liquid phase chromatogram of reference substance is compared with progress quantitative analysis.First is calculated according to the following formula
The content of formic acid in sour methyl esters.
Formic acid content (%)=AFor/AIt is right×CIt is right×VFor/WFor/1000×100
In formula, AForFor the peak area of formic acid in test solution；AIt is rightFor the peak area of formic acid in reference substance solution；CIt is rightFor
The concentration of formic acid reference substance solution, unit are μ g/mL；VForFor the volume of test solution, unit mL；WForFor test sample formic acid
The sampling amount of methyl esters, unit mg.
The content of formic acid is 0.01% in the methyl formate measured, and the concentration limit of formic acid is 1 μ g/mL, is equivalent to
0.003% in relation to substance sample introduction concentration (30mg/mL).
Please refer to FIG. 1 to FIG. 4.It should be clear that structure, ratio, size etc. that this specification institute accompanying drawings are painted, only to match
The revealed content of specification is closed, so that those skilled in the art understands and reads, is not intended to limit the invention implementable
Qualifications, therefore do not have technical essential meaning, the modification of any structure, the change of proportionate relationship or the adjustment of size,
In the case where not influencing the effect of present invention can be generated and the purpose that can reach, should all still fall in disclosed technology
In the range of Rong Suoneng is covered.Meanwhile cited such as "upper" in this specification, "lower", "left", "right" term, also only
To be illustrated convenient for describing, rather than to limit the scope of the invention, relativeness is altered or modified, in no essence
It changes under technology contents, when being also considered as the enforceable scope of the present invention.
As described above is only to be not intended to have this and do any shape to the present invention terminating the preferred embodiments of the invention
Limitation in formula should all wrap therefore all have any modification or change for making the related present invention under identical spirit
It includes in the scope that the invention is intended to protect.
Claims (2)
1. a kind of high-efficiency liquid chromatography method for detecting for directly measuring Analysis of Formic acid Residual in methyl formate, it is characterised in that can adopt
The residual quantity of formic acid in methyl formate is directly measured with high performance liquid chromatography, method operation is as follows:
Step 1, methyl formate test solution preparation: will methyl formate be added acetonitrile in dissolve, after constant volume to obtain the final product；
The preparation of step 2, formic acid reference substance solution: formic acid reference substance is added in acetonitrile and is dissolved, after constant volume to obtain the final product；
The drafting of step 3, formic acid standard curve: formic acid being added in acetonitrile solution and is dissolved, and is stored up after constant volume up to standard reference material
Standby liquid, is diluted to different multiples, with high-efficient liquid phase technique, its absorption peak is measured at wavelength 215nm, with concentration for horizontal seat
Mark, peak area are that ordinate draws standard curve；
Step 4, efficient liquid phase measurement: the chromatographic column of filler is made of octadecylsilane chemically bonded silica, 35 DEG C of column temperature, detects wave
Long 215nm, with 0.01M sodium dihydrogen phosphate (with phosphoric acid tune PH to 3.0) for mobile phase A, acetonitrile is Mobile phase B, flow velocity
1.0mL/min is eluted；Each 10 μ L of test solution and control solution is drawn respectively and injects liquid chromatograph, is measured, i.e.,
Obtain result.
2. detection method according to claim 1, which is characterized in that the volume ratio of the mobile phase is A:B=96:4.
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