CN107422045A - The detection method of para aminophenyl ethyl ether impurity content in a kind of ethoxyquin product - Google Patents
The detection method of para aminophenyl ethyl ether impurity content in a kind of ethoxyquin product Download PDFInfo
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- CN107422045A CN107422045A CN201610348851.4A CN201610348851A CN107422045A CN 107422045 A CN107422045 A CN 107422045A CN 201610348851 A CN201610348851 A CN 201610348851A CN 107422045 A CN107422045 A CN 107422045A
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- ethoxyquin
- ethyl ether
- aminophenyl ethyl
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/027—Liquid chromatography
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Abstract
The HPLC analytical method of para aminophenyl ethyl ether impurity in ethoxyquin product.The preparation of ethoxyquin product solution, weighs 1g sample solution in 50mL volumetric flasks, and constant volume is carried out with second eyeball organic solvent.Testing sample is configured to after filtering.Using nonpolar performance liquid chromatographic column, stationary phase is 10 μm of reverse-phase chromatographic column silica fillers, makees mobile phase with the mixed liquor of the pure second eyeball of liquid chromatogram and deionized water.30 DEG C of column temperature, μ L of sample size 100, wavelength 238nm liquid chromatographic detection under the conditions of, high performance liquid chromatography quantitative analysis is carried out to para aminophenyl ethyl ether impurity in ethoxyquin product and product using UV-detector, described UV-detector is the 400nm of wavelength 200；The analysis method can be such that ethoxyquin and para aminophenyl ethyl ether component separates completely, and analysis result is accurate, analysis efficiency is high, sample treatment is simple.
Description
Technical field
It is specifically a kind of the present invention relates to a kind of high-efficiency antioxidant agent purity and the wherein analysis method of impurity content
Ethoxyquinoline product purity and the wherein HPLC analytical method of para aminophenyl ethyl ether impurity content.
Background technology
Ethoxyquin (ethoxyquin), the entitled 6- ethyoxyls -2,2 of chemistry, 4- trimethyl -1,2 EEDQs, chemistry knot
Structure formula such as following formula (I)：
Vitamin A. D. E, K, carrotene and aliphatic acid, fish meal, digested tankage, bone meal, blood meal, feather meal in feed etc. are main
Want nutritional ingredient to be easily oxidized in the production, transport and storage process of feed and influence the food effect and security performance of feed,
Therefore antioxidant must be added.In various antioxidants, ethoxyquinoline is to generally acknowledge a kind of most effective, most economical practical feeding
Expect antioxidant.
Ethoxyquin can typically be carried out under catalyst action by para aminophenyl ethyl ether (p-phenetidine) with acetone
Condensation reaction produces to obtain, its reaction equation such as following formula (II)：
From reaction equation, the impurity that is mainly likely to occur in product is from unconverted reactant acetone, right
Phenetidine and water byproduct, wherein acetone and water boiling point are relatively low, can be removed by the method for distillation.Para aminophenyl ethyl ether and
Ethoxyquin boiling point is higher, is often taken out of in the lump in still-process, thus in ethoxyquin product often containing it is a small amount of (~
0.5wt.%) remained to the para aminophenyl ethyl ether component of micro (tens of mg/L).Therefore, Accurate Determining ethoxyquin product purity
And wherein para aminophenyl ethyl ether impurity content is significant to complete analysis ethoxyquin product property.
Document and examination criteria have been related generally to using high performance liquid chromatography in the products such as each agricultural products, feed at present
The analysis that micro ethoxyquin product residue concentration is carried out, such as State Administration for the Inspection of Import and Export commodities of the People's Republic of China (PRC) (SN
The ethoxyquin residual quantity method of inspection-liquid chromatography [S] Beijing in 0287-93 inlet and outlet fruit：China Standards Press,
, and the relevant fish meals of PingHe and Robert G Ackman (J.Sci.Food Agric, 80,1,10-16,2000) 1993)
In ethoxyquin Content Test method.On utilizing high performance liquid chromatography to para aminophenyl ethyl ether impurity in ethoxyquin product
There is presently no the patent or document report of correlation for content analysis method.
The content of the invention
It is a kind of for low concentration or ultralow dense in ethoxyquin product purity detection and product present invention aims at providing
Spend para aminophenyl ethyl ether impurity content high performance liquid chromatography detection analysis method, have analysis result is accurate, analysis efficiency is high,
The advantages of sample treatment is simple.
For achieving the above object, the invention provides low concentration in a kind of ethoxyquin product purity detection and product
Or the HPLC analytical method of super low concentration para aminophenyl ethyl ether impurity content, realized by following steps：
Pure ethoxyquin and para aminophenyl ethyl ether are weighed respectively, are placed in 50mL volumetric flasks, it is fixed after being dissolved with organic solvent
Hold, the standard sample solution being configured to after ultrasound filtration respectively containing 0.1~1000mg/L of ethoxyquin and para aminophenyl ethyl ether is treated
Survey；
Standard sample solution is passed through in chromatographic column, it is described using reverse phase liquid chromatography external standard percentage method quantitative analysis
Liquid phase chromatogram condition is：
Column temperature is arranged on 20~50 DEG C, flow velocity：1~2mL/min, flowed with the mixed liquor of organic solvent acetonitrile and water
Phase, mobile phase volume ratio are CH3CN:H2O is 50%:50% to 90%:10%, the μ L of sample size 2~100, with UV-detector pair
Ethoxyquin and its impurity para aminophenyl ethyl ether carry out efficient liquid phase chromatographic analysis, and Detection wavelength is in 210~270nm.
Described organic solvent is liquid chromatographic grade acetonitrile and high purity deionized water.
Described performance liquid chromatographic column is 10 μm of half preparation scale C18 post of 10mm × 150mm.
Described UV-detector is DAD UV-detectors.
On the basis of above-mentioned technical proposal, Detection wavelength is to be adjusted in 210~270nm, passes through both ultraviolet suctions of analysis
Signal value is received, it can be found that both have preferable response in 238nm (para aminophenyl ethyl ether) and 229nm (ethoxyquin) respectively,
Because para aminophenyl ethyl ether is trace impurity component, preferably 238nm is as Detection wavelength.
On the basis of above-mentioned technical proposal, flow rate of mobile phase and the ratio of acetonitrile and water are adjusted, it is considered that, separation factor
Preferable separation can be realized during more than 2, is analyzed by comprehensive disengaging time, separating effect and acetonitrile consumption, flowing can be selected
Phase flow velocity 1mL/min, ethane nitrile content can realize preferable separating effect for 80%, more save time and required acetonitrile solvent amount
Also it is less.Thus carry out the separation situation test under the various different sampling conditions of next step, be specifically shown in Table 1.
The ethoxyquin of table 1 and para aminophenyl ethyl ether chromatographic isolation parametric results
The retention time of described para aminophenyl ethyl ether on a column is 9.45min, and the retention time of ethoxyquin is
18.48min。
On the basis of above-mentioned technical proposal, adjustment sample size is in 2~100 μ L, in below 5mg/L low concentration sample
Para aminophenyl ethyl ether composition detection, preferably 100 μ L, for para aminophenyl ethyl ether concentration more than 10mg/L sample, from 20 μ
L, for more than 500mg/L high concentration para aminophenyl ethyl ether composition detections, from 5 μ L.Repeated detection data standard deviation is less than
5%.
Compared with existing conventional gas chromatographic analysis technique, the beneficial effects of the invention are as follows：Second provided by the present invention
In oxygen quinoline product the high efficient liquid phase analysis method of low concentration para aminophenyl ethyl ether impurity content have practical reliable, stability compared with
Well, the advantages of data reappearance is strong, and can be by changing sample size, realization is directed to various concentrations para aminophenyl ethyl ether component
The accurate detection of residual.Because liquid chromatogram can greatly increase single sample size, can accurately be determined with gas-chromatography ratio
The content of a wide range of various concentrations (0.25mg/L~1000mg/L) para aminophenyl ethyl ether in sample, it is a kind of preferably detection side
Method.In addition, if any the needs of bigger concentration range detection, also specific aim can be realized by further increasing or reducing sample size
Detection.
Brief description of the drawings
Fig. 1 is the UV absorption peak figure of para aminophenyl ethyl ether and ethoxyquin；
Fig. 2 is para aminophenyl ethyl ether and ethoxyquin chromatogram under the conditions of different acetonitriles and water ratio；
Fig. 3 is that para aminophenyl ethyl ether concentration corresponds to chromatographic peak area standard curve；
Fig. 4 is the chromatogram that different para aminophenyl ethyl ether concentration obtain in ethoxyquin.
Embodiment
Embodiment 1
Detecting instrument and chromatographic condition：
High performance liquid chromatograph：The DAD detectors of Thermo Scientific, Dionex Ultimate 3000
Chromatographic column：Reversed-phase column silicon C18 packed columns (150mm × 10mm, 10 μm), mobile phase：Volume ratio is 80：20
Acetonitrile solution, mobile phase：1mL/min, DAD detector Detection wavelength：200~400nm, column temperature：30℃.Experiment
Step：
(1) sample preparation：
Para aminophenyl ethyl ether sterling and each 2.5g of ethoxyquin sterling are taken, is placed in 50mL volumetric flasks, added with solvent second
Constant volume after nitrile dissolving, after ultrasound filtration dilution be configured to try containing para aminophenyl ethyl ether sterling and ethoxyquin sterling 250mg/L
Sample solution is to be measured；
(2) detect：
Said sample solution is taken, the μ L of sample introduction 20, it is ultraviolet in 200~400nm scannings to record appearance moment DAD detectors respectively
Absworption peak chromatogram.Obtained ultraviolet absorption peak typical case chromatogram is shown in accompanying drawing 1.
Embodiment 2：
Detecting instrument and chromatographic condition：
High performance liquid chromatograph：The DAD detectors of Thermo Scientific, Dionex Ultimate 3000
Chromatographic column：Reversed-phase column silicon C18 packed columns (150mm × 10mm, 10 μm), mobile phase：1mL/min, mobile phase：
Acetonitrile and water volume ratio are respectively 90：10、80：20、70：30、60：40、50：50 acetonitrile solution, DAD
Detector Detection wavelength：238nm, column temperature：30℃.
Experimental procedure：
(1) sample preparation：
Para aminophenyl ethyl ether sterling and each 2.5g of ethoxyquin sterling are taken, is placed in 50mL volumetric flasks, added with solvent second
Constant volume after nitrile dissolving, after ultrasound filtration dilution be configured to try containing para aminophenyl ethyl ether sterling and ethoxyquin sterling 250mg/L
Sample solution is to be measured；
(2) detect：
Take said sample solution, the μ L of sample introduction 20, liquid chromatogram peak when record DAD detectors Detection wavelength is 238nm.It is different
Typical chromatogram is obtained under the conditions of the mobile phase of acetonitrile and water volume ratio and sees accompanying drawing 2.
Embodiment 3
Detecting instrument and chromatographic condition：
High performance liquid chromatograph：Thermo Scientific, Dionex Ultimate 3000DAD detectors
Chromatographic column：Reversed-phase column silicon C18 packed columns (150mm × 10mm, 10 μm), mobile phase：1mLmin, mobile phase：
Acetonitrile is 80 with water volume ratio：20 acetonitrile solution, DAD detector Detection wavelengths：238nm, column temperature：30℃.
Experimental procedure：
(1) sample preparation：
Para aminophenyl ethyl ether sterling 2.5g is taken, is placed in 50mL volumetric flasks, adds constant volume after organic solvent acetonitrile dissolving, ultrasound
After filtering dilution be configured to containing para aminophenyl ethyl ether be 1000,800,600,500,250,200,100,50,20,10,5,
2.5th, 1.0,0.5,0.25mg/L sample solution is to be measured；
(2) detect：
Take said sample solution, the μ L of sample introduction 20, liquid chromatogram peak when record DAD detectors Detection wavelength is 238nm.It is different
The standard curve that para aminophenyl ethyl ether corresponds to chromatographic peak peak area is shown in accompanying drawing 3.
Embodiment 4
Detecting instrument and chromatographic condition：
High performance liquid chromatograph：The DAD detectors of Thermo Scientific, Dionex Ultimate 3000
Chromatographic column：Reversed-phase column silicon C18 packed columns (150mm × 10mm, 10 μm), mobile phase：1mL/min, mobile phase：
Acetonitrile is 80 with water volume ratio：20 acetonitrile solution, DAD detector Detection wavelengths：238nm, column temperature：30℃.
Experimental procedure：
(1) sample preparation：
Appropriate para aminophenyl ethyl ether sterling and ethoxyquin sterling are taken, is placed in 50mL volumetric flasks, adds organic solvent acetonitrile
Constant volume after dissolving, after ultrasound filtration dilution be configured to respectively containing the ethoxy that para aminophenyl ethyl ether is 2.5mg/L and 0.25mg/L
Quinoline sample solution is to be measured；
(2) detect：
Take said sample solution, the μ L of sample introduction 100, liquid chromatogram peak when record DAD detectors Detection wavelength is 238nm.Inspection
Survey result to show, para aminophenyl ethyl ether content corresponding to gained chromatographic peak area is respectively 2.534mg/L and 0.238mg/L, is demonstrate,proved
Understand that the detection method accuracy is excellent.Para aminophenyl ethyl ether various concentrations correspond to chromatographic peak and see accompanying drawing 4 in different samples.
A series of detailed description listed above only for the present invention feasibility embodiment specifically
Bright, they simultaneously are not used to limit the scope of the invention, all equivalent implementations made without departing from skill spirit of the present invention
Or change should be included in the scope of the protection.
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment, Er Qie
In the case of without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, embodiment all should be regarded as exemplary, and be nonrestrictive, the scope of the present invention is by appended power
Profit requires rather than described above limits, it is intended that all in the implication and scope of the equivalency of claim by falling
Change is included in the present invention.Any reference in claim should not be considered as to the involved claim of limitation.
Moreover, it will be appreciated that although the present specification is described in terms of embodiments, not each embodiment is only wrapped
Containing an independent technical scheme, this narrating mode of specification is only that those skilled in the art should for clarity
Using specification as an entirety, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
It is appreciated that other embodiment.
Claims (2)
- A kind of 1. determination method of para aminophenyl ethyl ether impurity content in ethoxyquin product, it is characterised in that the inspection Analysis method is surveyed to comprise the following steps：(1) high-efficient liquid phase chromatogram condition is set：Using reversed-phase column silicon packed column, chromatogram column condition is 10mm × 150mm × 10 μm, Column temperature is arranged on 30 DEG C, and Detection wavelength is arranged to 238nm, using chromatographic grade second eyeball as mobile phase A, using deionized water as Mobile phase B, Flow rate of mobile phase is set as 1mL/min, and using equal proportion elution program, mobile phase A ratio is 80%, and Mobile phase B ratio is 20%；(2) preparation of standard liquidPure ethoxyquin and para aminophenyl ethyl ether are weighed respectively, is placed in 50mL volumetric flasks, constant volume after being dissolved with organic solvent, are surpassed The solution being configured to after sound filtering respectively containing ethoxyquin and para aminophenyl ethyl ether 0.25mg/L~1000mg/L is to be measured；(3) preparation of sample solution1g ethoxyquin products are weighed, are placed in 50mL volumetric flasks, constant volume after being dissolved with organic solvent, are configured to after ultrasound filtration Sample solution is to be measured；(4) solution detectsTake the standard liquid of step (2), the μ L of μ L of sample size 2~100, be recorded as chromatogram, obtain ethoxyquin after analysis respectively With the standard curve of para aminophenyl ethyl ether；Take the sample solution of step (3), the μ L of μ L of sample size 2~100, be recorded as chromatogram, it is right The impurity content of para aminophenyl ethyl ether in ethoxyquin product is obtained after the analysis of sighting target directrix curve.
- 2. determination method according to claim 1, it is characterised in that：Wherein described para aminophenyl ethyl ether is in chromatogram Retention time on post is 9.45min, and the retention time of ethoxyquin is 18.48min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115494176A (en) * | 2022-09-28 | 2022-12-20 | 中国水产科学研究院黄海水产研究所 | Method for detecting residual quantity of ethoxyquin and dipolyoxyquin in krill meal |
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| US6221414B1 (en) * | 1998-09-02 | 2001-04-24 | Xeda International | Process for treating fruits and vegetables after harvesting, with purification of plant-protection products contaminated with aromatic primary amines |
| CN103207243A (en) * | 2012-10-12 | 2013-07-17 | 湖北航天化学技术研究所 | Determination method for migration components in nitrate ester plasticized polyether (NEPE) propellant bonding system |
| CN105001157A (en) * | 2015-07-23 | 2015-10-28 | 泰兴瑞泰化工有限公司 | Method for preparing ethoxy quinoline |
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2016
- 2016-05-24 CN CN201610348851.4A patent/CN107422045A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US6221414B1 (en) * | 1998-09-02 | 2001-04-24 | Xeda International | Process for treating fruits and vegetables after harvesting, with purification of plant-protection products contaminated with aromatic primary amines |
| CN103207243A (en) * | 2012-10-12 | 2013-07-17 | 湖北航天化学技术研究所 | Determination method for migration components in nitrate ester plasticized polyether (NEPE) propellant bonding system |
| CN105001157A (en) * | 2015-07-23 | 2015-10-28 | 泰兴瑞泰化工有限公司 | Method for preparing ethoxy quinoline |
Non-Patent Citations (2)
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| L.TAIMR 等: "Chromatographic behaviour of the antidegradant ethoxyquin and its transformation products", 《JOURNAL OF CHROMATOGRAPHY》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115494176A (en) * | 2022-09-28 | 2022-12-20 | 中国水产科学研究院黄海水产研究所 | Method for detecting residual quantity of ethoxyquin and dipolyoxyquin in krill meal |
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