CN105548394B - A kind of method of Supercritical fluid chromatography quick separating phthalic acid ester - Google Patents
A kind of method of Supercritical fluid chromatography quick separating phthalic acid ester Download PDFInfo
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- CN105548394B CN105548394B CN201510940193.3A CN201510940193A CN105548394B CN 105548394 B CN105548394 B CN 105548394B CN 201510940193 A CN201510940193 A CN 201510940193A CN 105548394 B CN105548394 B CN 105548394B
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- Prior art keywords
- phthalate
- ester
- phthalic
- phthalic acid
- supercritical fluid
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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
-
- 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
Abstract
The invention discloses a kind of methods of Supercritical fluid chromatography quick separating phthalic ester plasticizer, belong to separate analytical technique field.The present invention is insufficient existing for consumptive material etc. for be taken with liquid phase or gas-chromatography separation phthalic ester plasticizer at present, provides a kind of separation method of quick economical environment-protective, the method for this method Supercritical fluid chromatography detaches target substance, using CO2+ adjuvant is mobile phase, can detach ten several above phthalic ester plasticizers in a few minutes, and the method is quick, green, and environmental protection is nontoxic to experimenter, and favorable reproducibility.And the detecting instruments such as technical scheme of the present invention and ultraviolet, FID, MS are used in conjunction, and the quick separating detection of phthalic ester plasticizer may be implemented.
Description
One, technical field
The present invention relates to a kind of methods of Supercritical fluid chromatography quick separating phthalic acid ester, belong to separate analytical technique neck
Domain
Two, background technology
Phthalic acid ester, which is a kind of is added to, makes its flexible and flexibility additive in material, can also be adjacent benzene
Diformic ester plasticizer or plasticiser, in food, the national industrial extensive use such as chemical industry.Such as：Plastics,
Cosmetic package, stationery etc..The type of country's external plasticizer is relatively more at present, there is phthalate, aliphatic
Binary acid esters, phosphoric acid ester, epoxy compound species etc., what wherein usage amount maximum was most wide is exactly phthalate plasticising
Agent (PAEs).To after " mist generating agent " event and white wine event in 2012 in May, 2011 Taiwan, plasticizer draws in country
Strong concern is played.
Phthalic ester plasticizer is a kind of and the much like effect of estrogen environmental hormone.So-called environmental hormone,
It is exactly incretion interferent and Environmental Hormone, refers to a kind of exogen chemical substance for influencing human normal hormone function, generally
Influence includes immune system, reproductive function and the nervous system of the mankind or various biologies；Phthalate plasticizers are also led
It causes people's teratogenesis and generates embryotoxicity；Influence human endocrine；Cause human cancer cell to be proliferated, disturbs in human body strongly
The secretion of hormone, long-term accumulated may lead to canceration, deformity and cause gene mutation in human body.Phthalic acid lipid plasticizer
Many is all the colourless transparent liquid of oily class, is soluble in organic solvent, is not readily dissolved in water.Can be by oral cavity, breathing and skin
Skin contact is one to the murder by poisoning of health into phthalic ester plasticizers in animal and human body and grows chronic mistake slowly
Journey has certain incubation period, longer time is needed just to will appear.Once there are some major accidents, and led to some small early childhood
The harmful effects such as preceding precocity.
There are stringent regulation, China in European Union at present, multiple countries such as U.S. to the content and type of plasticizer in material
There is GB/T21928-2008《The measurement of phthalic acid ester in plastic package material》Mainly phthalate is plasticized
Agent proposes legal provisions, includes repefral (DMP), diethyl phthalate (DEP), O-phthalic to 16 kinds
Sour diisobutyl ester (DIBP), dibutyl phthalate (DBP), phthalic acid two (2- methoxyl groups) ethyl ester (DMEP), adjacent benzene
Dioctyl phthalate two (- 2 amyl of 4- methyl) ester (BMPP), phthalic acid two (2- ethyoxyls) ethyl ester (DEEP), phthalic acid two
Pentyl ester (DPP), dihexyl phthalate (DHXP), butyl benzyl phthalate (BBP), (the 2- fourths of phthalic acid two
Oxygroup) ethyl ester (DBEP), dicyclohexyl phthalate (DCHP), the own ester (DEHP) of phthalic acid two (2- ethyls), adjacent benzene
Diformazan diphenyl phthalate (DPhP), di-n-octyl phthalate (DNOP), dinonyl phthalate (DNP).The U.S. is also to it
In 6 kinds be included in blacklist, European Union, Japan is multinational to be all made that policy of the law.
For the detection of PAEs, according to the literature and national standard, separation detection phthalic ester plasticizer
Method has：
1. the phthalic ester plasticizer assay method that national standard is recorded
According to gas chromatography-mass spectrography (GB/T21928-2008《The measurement of phthalic acid ester in plastic package material》)
Chromatographic condition parameter see the table below：
Mass Spectrometry Conditions parameter see the table below：
Sample treatment：Select n-hexane as extractant, ultrasonic extraction, machine testing on constant volume.
Detach 16 kinds of phthalic ester plasticizers in this method, gas-chromatography tandem mass spectrum separation detection, finally
The appearance time of DNP is 23 minutes or so, and the program setting time is 26 minutes, i.e. total time-consuming 26 minutes.
2. document report measures phthalic ester plasticizer method for separating and detecting
2.1 according to high performance liquid chromatography mass spectrography (Food Science 212-215 pages of 18 phase of volume 33 of version in 2012)
Chromatographic condition：With the liquid chromatogram of the 1290-6410B models of Agilent company of the U.S.；C18 (2.1mm × 150mm,
3.5 μm) chromatographic column；Mobile phase uses+0.1% formic acid solution of methanol solution of 0.1% formic acid；Column temperature temperature is 30 DEG C；Into
Sample amount is 5 μ L.
Mass Spectrometry Conditions：Operation mode：ESI positive ion modes；Dry gas stream amount：10L/min；Dry temperature degree：350℃；
Capillary voltage：4000V；Atomisation pressure：30psi
Sample treatment：Use methanol for extractant, ultrasonic extraction, sample introduction is analyzed for constant volume.
16 kinds of phthalic ester plasticizers have been detached in this method, the appearance time of last DNP is 28 minutes or so,
The program setting time is 31 minutes, i.e. total time-consuming 31 minutes.
2.2 according to thin-layered chromatography separation plasticizer (applicating technology 22-23 pages of 6 phase of volume 27 of version in 2000)
Using thin-layered chromatography to the separation method of plastic plasticizer, by plastic plasticizer obtained by extraction on silica gel plate
With V (ethyl acetate): V (ether): V (isooctane)=1: 4: 15 is detached as mobile phase, is developed the color with iodine vapor, separation is qualitative
6 kinds of (DOS, DOP, DBS, DIBP, DBP, DMP) plasticizer.
Three, invention content
The present invention be directed to current phthalic ester plasticizer disengaging time is long and toxic solvent not environmentally, no
The deficiencies of saving, proposes the new method of separation phthalic ester plasticizer in the Supercritical fluid chromatography technology short time, this method
Have quickly, favorable reproducibility is easy to operate, but use quantity of solvent it is few, green, it is environmentally friendly the advantages that.Technical solution of the present invention with it is ultraviolet,
The detecting instruments such as FID, MS are used in conjunction, and the quick separating detection of phthalic ester plasticizer may be implemented.
Inventive principle：
Supercritical fluid chromatography uses supercritical CO2As main mobile phase, with methanol, acetonitrile, isopropanol, ethyl acetate etc. is
Adjuvant has very high separative efficiency, shortens disengaging time, and reduces the use of organic reagent, environmentally protective, principle
Similar liquid chromatogram.
Phthalic ester plasticizer is all similar benzene homologues, is more also isomer, so with meteorology
Chromatography, short time consumption is long when the methods of liquid chromatogram detaches, most of at 30 minutes or so.The present invention combines super at present
The advantages of critical chromatography, it is long to overcome the separation phthalic ester plasticizer time, the shortcomings that expending a large amount of solvents, invention
The method that quick separating goes out 17 kinds or more plasticizer.
Technical solution proposed by the present invention is with supercritical CO2As main mobile phase, with methanol, acetonitrile, isopropanol, second
Acetoacetic ester etc. is adjuvant, is detached by chromatographic column under certain eluent gradient, special due to supercritical fluid
Property can improve separative efficiency, shorten disengaging time, reduce the use of organic reagent, environmentally protective.
The technical solution of the above method of the present invention is：
1) phthalate substance is dissolved in non-polar organic solvent；
2) with CO2For main mobile phase, adds a certain proportion of adjuvant and mobile phase is modified.Adjuvant can be
The ratio of methanol, acetonitrile, isopropanol, ethyl acetate or combinations thereof, mobile phase and adjuvant can be in 100: 0 to 80: 20 variations；
Further, the non-polar organic solvent of the dissolving phthalate substance described in us is ethyl acetate,
N-hexane, a kind of or a few person mixing in acetone.
Further, we illustrate that adjuvant can be methanol, isopropanol, a kind of or a few person of the acetonitrile in them press than
Example mixing.
Further, we illustrate mobile phase CO2By further optimizing, optimal volume ratio is in 80%-100%
Centre, adjuvant is within 20%.
3) solution of the substance containing phthalate is detached with certain condition by chromatographic column, and chromatographic column can be with
For HSS C18 SB；BEH；BEH 2-EP；CSH Fluoro-Pheny chromatographic columns, chromatogram column temperature are 25-75 DEG C, mobile phase stream
Speed is 0.5-2.0ml/min, and back pressure is in 1800-2200psi, sampling volume 1-5ul.
We further illustrate that preferred flow rate of mobile phase is 1.5ml/min, and chromatogram column temperature is 65 DEG C, and back pressure is
1800psi
Meanwhile finally we illustrate that the chromatographic column of optimal selection is HSS C18 SB chromatographic columns.
Beneficial effects of the present invention：
Phthalate substance is detached using technical solution proposed by the present invention, it can be within 10 minutes
The substance of 17 kinds of separation or more, this method have quickly, and favorable reproducibility is easy to operate, and use quantity of solvent few, green, environmental protection etc.
Advantage.
Four, specific implementation mode
Embodiment 1：
Since plasticizer contains in the plastic, so whole experiment process is not readily accessible to contain plastic products, all glass
Instrument need to impregnate 1 hour in acetone, and baking oven takes out spare after 2 hours.
Use CO2As mobile phase, acetonitrile is as adjuvant；Gradient is the CO for being initially 100%2, become in one minute
80% is changed in by 98%, 6 minute, is kept for 2 minutes, 98% is returned in half a minute, in the CO with half a minute to 100%2；Chromatography
Column temperature is 65 DEG C；Flow velocity is 1.5ml/min；Back pressure is 1800psi；The solution of the substance containing phthalate is pressed above-mentioned
Condition detaches, and can be detached in a few minutes ten several target substances.
Embodiment 2：
Since plasticizer contains in the plastic, so whole experiment process is not readily accessible to contain plastic products, all glass
Instrument need to impregnate 1 hour in acetone, and baking oven takes out spare after 2 hours.
Use CO2As mobile phase, isopropanol is adjuvant, the CO for being initial 96% according to wash-out concentration2, kept for 5 minutes
Constant volume ratio, reaches 80% CO in 8 minutes2, return to 100%CO within 9 minutes2；Chromatogram column temperature be 65 DEG C；Flow velocity is
1.5ml/min；Back pressure is 1800psi, can be detached in a few minutes class target substance, compared with example 1, retention time has not
Together.
Claims (2)
1. a kind of Supercritical fluid chromatography is to the fast separating process of phthalic ester plasticizer, which is characterized in that including：
Phthalate substance is dissolved in non-polar organic solvent, wherein non-polar organic solvent is acetone,
The solution of the substance containing phthalate is detached by chromatographic column, with CO2For main mobile phase, acetonitrile is added
Mobile phase is modified as adjuvant, by a variety of phthalic ester plasticizers of packing chromatography post separation,
Wherein gradient is：It is initially 100% CO2, 98% is changed in one minute, 80% is changed in 6 minutes, is kept for 2 points
Clock, returns to 98% in half a minute, then with the CO of half a minute to 100%2；Chromatogram column temperature is 65 DEG C；Flow velocity is 1.5ml/min；
Back pressure is 1800psi,
Wherein chromatographic column is HSS C18 SB, BEH, BEH 2-EP or CSH FP chromatographic columns.
2. Supercritical fluid chromatography according to claim 1 is to the fast separating process of phthalic ester plasticizer, special
Sign is：Phthalic ester plasticizer includes repefral (DMP), diethyl phthalate (DEP), neighbour
Phthalic acid diisobutyl ester (DIBP), dibutyl phthalate (DBP), phthalic acid two (2- methoxyl groups) ethyl ester
(DMEP), phthalic acid two (- 2 amyl of 4- methyl) ester (BMPP), phthalic acid two (2- ethyoxyls) ethyl ester (DEEP), neighbour
Phthalic acid diamyl ester (DPP), dihexyl phthalate (DHXP), butyl benzyl phthalate (BBP), O-phthalic
Sour two (2- butoxy) ethyl esters (DBEP), dicyclohexyl phthalate (DCHP), phthalic acid two (2- ethyls) own ester
(DEHP), diphenyl phthalate (DPhP), di-n-octyl phthalate (DNOP), dinonyl phthalate (DNP)
One or more of.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510940193.3A CN105548394B (en) | 2015-12-15 | 2015-12-15 | A kind of method of Supercritical fluid chromatography quick separating phthalic acid ester |
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| CN106404934A (en) * | 2016-08-25 | 2017-02-15 | 宁波检验检疫科学技术研究院 | Method for detecting phthalic acid di-n-propyl ester in washing product |
| CN108956813B (en) * | 2018-07-02 | 2021-05-14 | 中国检验检疫科学研究院 | Offline supercritical extraction-supercritical chromatography-mass spectrometry combined detection method for polyphenols |
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Granted publication date: 20180814 Termination date: 20211215 |