CN104237423B - In a kind of quick detection emulsifying essence phthalic ester sample-pretreating method and use its detection method - Google Patents
In a kind of quick detection emulsifying essence phthalic ester sample-pretreating method and use its detection method Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 53
- 230000001804 emulsifying effect Effects 0.000 title claims abstract description 51
- 150000002148 esters Chemical class 0.000 title claims abstract description 46
- 238000001514 detection method Methods 0.000 title abstract description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000002203 pretreatment Methods 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims description 4
- 230000005540 biological transmission Effects 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000012423 maintenance Methods 0.000 claims description 3
- 238000004949 mass spectrometry Methods 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 3
- 238000005227 gel permeation chromatography Methods 0.000 abstract description 5
- 239000003960 organic solvent Substances 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 30
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 30
- 238000012360 testing method Methods 0.000 description 28
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 20
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 17
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 17
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 17
- IPKKHRVROFYTEK-UHFFFAOYSA-N dipentyl phthalate Chemical compound CCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCC IPKKHRVROFYTEK-UHFFFAOYSA-N 0.000 description 17
- VOWAEIGWURALJQ-UHFFFAOYSA-N Dicyclohexyl phthalate Chemical compound C=1C=CC=C(C(=O)OC2CCCCC2)C=1C(=O)OC1CCCCC1 VOWAEIGWURALJQ-UHFFFAOYSA-N 0.000 description 15
- YVCVYCSAAZQOJI-JHQYFNNDSA-N 4'-demethylepipodophyllotoxin Chemical compound COC1=C(O)C(OC)=CC([C@@H]2C3=CC=4OCOC=4C=C3[C@@H](O)[C@@H]3[C@@H]2C(OC3)=O)=C1 YVCVYCSAAZQOJI-JHQYFNNDSA-N 0.000 description 13
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 13
- -1 Phthalate compound Chemical class 0.000 description 13
- CMCJNODIWQEOAI-UHFFFAOYSA-N bis(2-butoxyethyl)phthalate Chemical compound CCCCOCCOC(=O)C1=CC=CC=C1C(=O)OCCOCCCC CMCJNODIWQEOAI-UHFFFAOYSA-N 0.000 description 13
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 13
- FNVBALFTMLKFEC-UHFFFAOYSA-N bis(4-methyl-2-oxochromen-7-yl) phosphono phosphate Chemical compound CC1=CC(=O)OC2=CC(OP(=O)(OC3=CC=4OC(=O)C=C(C=4C=C3)C)OP(O)(O)=O)=CC=C21 FNVBALFTMLKFEC-UHFFFAOYSA-N 0.000 description 13
- 238000011084 recovery Methods 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 10
- 239000000523 sample Substances 0.000 description 10
- 239000011521 glass Substances 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 239000004615 ingredient Substances 0.000 description 6
- 239000012086 standard solution Substances 0.000 description 6
- 238000004445 quantitative analysis Methods 0.000 description 5
- KCXZNSGUUQJJTR-UHFFFAOYSA-N Di-n-hexyl phthalate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCC KCXZNSGUUQJJTR-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000004945 emulsification Methods 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 238000012417 linear regression Methods 0.000 description 3
- 239000012496 blank sample Substances 0.000 description 2
- DROMNWUQASBTFM-UHFFFAOYSA-N dinonyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCC DROMNWUQASBTFM-UHFFFAOYSA-N 0.000 description 2
- DWNAQMUDCDVSLT-UHFFFAOYSA-N diphenyl phthalate Chemical compound C=1C=CC=C(C(=O)OC=2C=CC=CC=2)C=1C(=O)OC1=CC=CC=C1 DWNAQMUDCDVSLT-UHFFFAOYSA-N 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 2
- JQCXWCOOWVGKMT-UHFFFAOYSA-N phthalic acid diheptyl ester Natural products CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 244000144730 Amygdalus persica Species 0.000 description 1
- 244000241257 Cucumis melo Species 0.000 description 1
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 1
- 235000016623 Fragaria vesca Nutrition 0.000 description 1
- 240000009088 Fragaria x ananassa Species 0.000 description 1
- 235000011363 Fragaria x ananassa Nutrition 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 231100000507 endocrine disrupting Toxicity 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- 231100000683 possible toxicity Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention provides the sample-pretreating method of phthalic ester in a kind of quick detection emulsifying essence, comprising: a, in emulsifying essence to be measured, add normal hexane and mix, obtain mixed liquor; B, by mixed liquor in a water bath nitrogen dry up; C, dry up to nitrogen after container in add normal hexane and vortex, get liquid to be measured.Its simple to operate, consuming time short, consumption of organic solvent is less and without the need to using gel permeation chromatography device to implement purification, reduce cost.Present invention also offers the method for phthalic ester in a kind of quick detection emulsifying essence, comprising: according to above-mentioned sample-pretreating method, pre-treatment is carried out to emulsifying essence; With combined gas chromatography mass spectrometry, the phthalic ester in the liquid obtained after pre-treatment is detected.Its sample pretreatment process is simple to operate, consuming time short, consumption of organic solvent is less and without the need to using gel permeation chromatography device to implement purification, reduce the cost of detection.
Description
Technical field
The present invention relates to and a kind ofly detect the sample-pretreating method of phthalic ester and use its detection method, be particularly useful for detecting the phthalic ester in emulsifying essence.
Background technology
Phthalate compound (Phthalates, PAEs) also known as phthalate compound, being the chemicals that a class can play emollescence, is the general name of about 30 kinds of compounds, and its general chemical constitution is made up of 1 rigid plane aromatic hydrocarbons and 2 plastic non-linear aliphatic side chainses.Phthalate compound Chang Zuowei plastifier is used for plastics-production.Phthalate compound has potential toxicity to animal, and shows endocrine disrupting.
Emulsifying essence is the flavoring essence that a class is commonly used, the risk that phthalate compound pollutes is there is in the processing and transportation of emulsifying essence, common phthalic ester component comprises repefral, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, phthalic acid two (2-methoxyl) ethyl ester, phthalic acid two (4-methyl-2-amyl group) ester, phthalic acid two (2-ethoxy) ethyl ester, diamyl phthalate, dihexylphthalate, butyl benzyl phthalate, phthalic acid two (2-butoxy) ethyl ester, dicyclohexyl phthalate, phthalic acid two (2-ethyl) own ester, diphenyl phthalate, di-n-octyl phthalate, dinonyl phthalate.
At present, the method provided in conventional national standard " mensuration of GB/T21911-2008 Phthalic Acid Esters in Food ", to detect Phthalic Acid Esters in Food, need carry out different pre-treatments to not containing grease sample and containing grease sample in method.Emulsifying essence is detected according to said method, if according to not carrying out pre-treatment containing grease style, due in emulsifying essence containing emulsifying agent, cause extraction not realize, cannot examinations; If carry out pre-treatment according to grease-contained sample, need the pre-treatment time of about 2.5 ~ 3.0 hours, need to consume a large amount of organic solvent simultaneously, also need the special gel permeation chromatography device of preparation to implement purification, its complicated operation and cost is higher.
Summary of the invention
The object of this invention is to provide the sample-pretreating method of phthalic ester in a kind of quick detection emulsifying essence, it is simple to operate and cost is lower.
Another object of the present invention is to provide the method for phthalic ester in a kind of quick detection emulsifying essence, and it is simple to operate and cost is lower.
The invention provides the sample-pretreating method of phthalic ester in a kind of quick detection emulsifying essence, comprising: a, in emulsifying essence to be measured, add normal hexane and mix, obtain mixed liquor; B, by mixed liquor in a water bath nitrogen dry up; C, dry up to nitrogen after container in add normal hexane and vortex, get liquid to be measured.
Detecting fast in a kind of exemplary embodiment of sample-pretreating method of phthalic ester in emulsifying essence, in step a, the amount adding normal hexane in every 1 gram of emulsifying essence to be measured is 4 to 6 milliliters.
Detecting in a kind of exemplary embodiment of sample-pretreating method of phthalic ester in emulsifying essence fast, in step b, the temperature of water-bath is 40 DEG C to 50 DEG C.
Detecting in a kind of exemplary embodiment of sample-pretreating method of phthalic ester in emulsifying essence fast, in step c, the speed of vortex is not higher than 3000 revs/min, and duration is 20 to 30 seconds.
Present invention also offers the method for phthalic ester in a kind of quick detection emulsifying essence, comprising: according to above-mentioned sample-pretreating method, pre-treatment is carried out to emulsifying essence to be measured; With combined gas chromatography mass spectrometry, the phthalic ester in the liquid obtained after pre-treatment is detected.
Detecting in a kind of exemplary embodiment of method of phthalic ester in emulsifying essence fast, the chromatographic condition of combined gas chromatography mass spectrometry is: chromatographic column: capillary chromatographic column, specification is 30m × 0.25mm × 0.25 μm, and Stationary liquid is 5% phenyl and 95% dimethyl polysiloxane; Injector temperature: 250 DEG C; Shunting mode: do not shunt; Carrier gas: helium; Flow velocity: 1.0mL/min; Heating schedule: initial temperature is 60 DEG C and maintains 1min, is then raised to 210 DEG C with 15 DEG C/min, then be raised to 280 DEG C of maintenance 2.5min with 4 DEG C/min; Sample size: 1 μ L.
Detecting in a kind of exemplary embodiment of method of phthalic ester in emulsifying essence fast, the Mass Spectrometry Conditions of combined gas chromatography mass spectrometry is: ionization mode: electron bombardment ionization source; Ionizing energy: 70eV; Ion source temperature: 200 DEG C; Transmission line temperature: 250 DEG C; The solvent delay time: 8.5min; Scan pattern: Selective ion mode scan pattern.
The sample-pretreating method of phthalic ester in a kind of quick detection emulsifying essence provided by the invention, its simple to operate, consuming time short, consumption of organic solvent is less and without the need to using gel permeation chromatography device to implement purification, reduce cost.
The method of phthalic ester in a kind of quick detection emulsifying essence provided by the invention, its sample pretreatment process is simple to operate, consuming time short, consumption of organic solvent is less and without the need to using gel permeation chromatography device to implement purification, reduce the cost of detection.
Embodiment
In order to the technical characteristic to invention, object and effect have understanding clearly, now with the following Examples the specific embodiment of the present invention is described.
The normal hexane used in the specific embodiment of the invention is chromatographically pure.
first embodiment: sample-pretreating method.
Emulsifying essence to be measured selects emulsification strawberry essence.
Method step:
A, get 1 gram of emulsifying essence to be measured in glass test tube, add 5 ml n-hexanes and mix, obtaining mixed liquor;
B, the glass test tube filling mixed liquor is placed in 40 DEG C of water-baths, mixed liquor nitrogen is dried up simultaneously;
C, dry up to nitrogen after glass test tube in add 1 ml n-hexane, and under the rotating speed of 3000 revs/min vortex 20 seconds, get liquid to be measured.
second embodiment: sample-pretreating method.
Emulsifying essence to be measured selects emulsification Hami melon essence.
Method step:
A, get 1 gram of emulsifying essence to be measured in glass test tube, add 4 ml n-hexanes and mix, obtaining mixed liquor;
B, the glass test tube filling mixed liquor is placed in 45 DEG C of water-baths, mixed liquor nitrogen is dried up simultaneously;
C, dry up to nitrogen after glass test tube in add 1 ml n-hexane, and under the rotating speed of 2500 revs/min vortex 25 seconds, get liquid to be measured.
3rd embodiment: sample-pretreating method.
Emulsifying essence to be measured selects emulsification peach flavor.
Method step:
A, get 1 gram of emulsifying essence to be measured in glass test tube, add 6 ml n-hexanes and mix, obtaining mixed liquor;
B, the glass test tube filling mixed liquor is placed in 50 DEG C of water-baths, mixed liquor nitrogen is dried up simultaneously;
C, dry up to nitrogen after glass test tube in add 1 ml n-hexane, and under the rotating speed of 2000 revs/min vortex 30 seconds, get liquid to be measured.
4th embodiment: detection method.
1, experiment condition and qualitative-and-quantitative method.
The chromatographic condition of 1.1 combined gas chromatography mass spectrometries:
Chromatographic column: capillary chromatographic column, specification is 30m × 0.25mm × 0.25 μm, and Stationary liquid is 5% phenyl and 95% dimethyl polysiloxane; Injector temperature: 250 DEG C; Shunting mode: do not shunt; Carrier gas: helium; Flow velocity: 1.0mL/min; Heating schedule: initial temperature is 60 DEG C and maintains 1min, is then raised to 210 DEG C with 15 DEG C/min, then be raised to 280 DEG C of maintenance 2.5min with 4 DEG C/min; Sample size: 1 μ L.
The Mass Spectrometry Conditions of 1.2 combined gas chromatography mass spectrometries:
Ionization mode: electron bombardment ionization source; Ionizing energy: 70eV; Ion source temperature: 200 DEG C; Transmission line temperature: 250 DEG C; The solvent delay time: 8.5min; Scan pattern: Selective ion mode scan pattern, monitoring ion is as shown in the table.
| Peak sequence | Retention time (min) | Chinese | Abbreviation | Qualitative ion | Quota ion |
| 1 | 9.23 | Repefral | DMP | 77、135、163、194 | 163 |
| 2 | 10.35 | Diethyl phthalate | DEP | 121、149、177、222 | 149 |
| 3 | 12.60 | Diisobutyl phthalate | DIBP | 149、167、223、205 | 149 |
| 4 | 13.61 | Dibutyl phthalate | DBP | 121、149、205、223 | 149 |
| 5 | 14.05 | Phthalic acid two (2-methoxyl) ethyl ester | DMEP | 59、149、193、251 | 59 |
| 6 | 14.81 | Phthalic acid two (4-methyl-2-amyl group) ester | BMPP | 121、149、167、251 | 149 |
| 7 | 15.42 | Phthalic acid two (2-ethoxy) ethyl ester | DEEP | 45、72、149、221 | 45 |
| 8 | 15.90 | Diamyl phthalate | DPP | 149、167、219、237 | 149 |
| 9 | 18.72 | Dihexylphthalate | DHXP | 76、104、149、251 | 104 |
| 10 | 18.95 | Butyl benzyl phthalate | BBP | 91、149、206、238 | 149 |
| 11 | 20.72 | Phthalic acid two (2-butoxy) ethyl ester | DBEP | 149、205、223、278 | 149 |
| 12 | 21.60 | Dicyclohexyl phthalate | DCHP | 83、149、167、249 | 149 |
| 13 | 21.75 | Phthalic acid two (2-ethyl) own ester | DEHP | 113、149、167、279 | 149 |
| 14 | 21.99 | Diphenyl phthalate | DPHP | 77、153、197、225 | 225 |
| 15 | 24.97 | Di-n-octyl phthalate | DNOP | 149、167、261、279 | 149 |
| 16 | 25.62 | Dinonyl phthalate | DNP | 57、71、149、167 | 57 |
1.3 quantivative approachs:
External standard method.Wherein the concentration of standard solution is 0.10 μ g/mL, 0.20 μ g/mL, 0.40 μ g/mL, 0.80 μ g/mL and 1.6 μ g/mL, and the solvent of standard solution is normal hexane.And get normal hexane and detect as blank sample.With the concentration of standard solution of each phthalic ester component for horizontal ordinate, the peak area of corresponding quota ion is ordinate, makes typical curve equation of linear regression; And by formula: X=(Ci-Co) × V/m calculates the content of various phthalic ester component in emulsifying essence, in formula: X is the content of phthalic ester component x in emulsifying essence, and unit is mg/Kg; Ci is the concentration that in emulsifying essence, phthalic ester component x peak area is corresponding in equation of linear regression; Unit is μ g/mL; Co is the concentration that in blank sample, phthalic ester component x peak area is corresponding in equation of linear regression; Unit is μ g/mL; V is the constant volume after sample pre-treatments, and unit is mL; M is the consumption of emulsifying essence, and unit is g.
1.4 qualitative criteria:
Testing liquid occurs identical retention time place (± 0.5%) with the Selective ion mode chromatographic peak of standard solution, and the mass-to-charge ratio of corresponding mass spectrometric fragment ion is consistent with standard solution, its abundance ratio should meet compared with standard solution: relative abundance >50%, allows ± 10% deviation; Relative abundance 20%-50%, allows ± 15% deviation; Relative abundance 10%-20%, allows ± 20% deviation; Relative abundance <10%, allows ± 50% deviation, now qualitatively can determine target analytes.
2, method step.
A, according to the sample-pretreating method of the first embodiment, pre-treatment is carried out to emulsifying essence;
B, with combined gas chromatography mass spectrometry, kind of the phthalic ester component of 16 in the liquid obtained after pre-treatment to be detected, and calculate the content of various phthalic ester component in emulsifying essence.
3, method recovery test: preparing various phthalic ester component concentration is respectively that the emulsifying essence of 0.1mg/Kg, 0.2mg/Kg and 0.5mg/Kg carries out recovery experiment.Recovery test result is as shown in the table, and illustration method accuracy can meet the needs of detection.
| Ingredient names | Add concentration (mg/Kg) | Testing result (mg/Kg) | The recovery (%) |
| DMP | 0.1 | 0.0998 | 99.8 |
| DMP | 0.2 | 0.1832 | 91.6 |
| DMP | 0.5 | 0.4623 | 92.5 |
| DEP | 0.1 | 0.0978 | 97.8 |
| DEP | 0.2 | 1.0862 | 543.1 |
| DEP | 0.5 | 0.4687 | 93.7 |
| DIBP | 0.1 | 0.1021 | 102.1 |
| DIBP | 0.2 | 1.8952 | 947.6 |
| DIBP | 0.5 | 0.4824 | 96.5 |
| DBP | 0.1 | 0.1044 | 104.4 |
| DBP | 0.2 | 0.1926 | 96.3 |
| DBP | 0.5 | 0.4714 | 94.3 |
| DMEP | 0.1 | 0.0992 | 99.2 |
| DMEP | 0.2 | 0.1894 | 94.7 |
| DMEP | 0.5 | 0.4523 | 90.5 |
| BMPP | 0.1 | 0.0967 | 96.7 |
| BMPP | 0.2 | 0.2021 | 101.1 |
| BMPP | 0.5 | 0.5031 | 100.6 |
| DEEP | 0.1 | 0.0987 | 98.7 |
| DEEP | 0.2 | 1.9845 | 992.3 |
| DEEP | 0.5 | 0.4857 | 97.1 |
| DPP | 0.1 | 0.105 | 105 |
| DPP | 0.2 | 0.2103 | 105.2 |
| DPP | 0.5 | 0.4982 | 99.6 |
| DHXP | 0.1 | 0.0998 | 99.8 |
| DHXP | 0.2 | 0.1842 | 92.1 |
| DHXP | 0.5 | 0.4672 | 93.4 |
| BBP | 0.1 | 0.0972 | 97.2 |
| BBP | 0.2 | 0.1769 | 88.5 |
| BBP | 0.5 | 0.5042 | 100.8 |
| DBEP | 0.1 | 0.0968 | 96.8 |
| DBEP | 0.2 | 0.1985 | 99.3 |
| DBEP | 0.5 | 0.4987 | 99.7 |
| DCHP | 0.1 | 0.102 | 102 |
| DCHP | 0.2 | 0.1872 | 93.6 |
| DCHP | 0.5 | 0.4826 | 96.5 |
| DEHP | 0.1 | 0.1031 | 103.1 |
| DEHP | 0.2 | 0.1852 | 92.6 |
| DEHP | 0.5 | 0.4972 | 99.4 |
| DPHP | 0.1 | 0.0998 | 99.8 |
| DPHP | 0.2 | 0.1877 | 93.9 |
| DPHP | 0.5 | 0.4899 | 98 |
| DNOP | 0.1 | 0.0898 | 89.8 |
| DNOP | 0.2 | 0.1879 | 94 |
| DNOP | 0.5 | 0.4672 | 93.4 |
| DNP | 0.1 | 0.0983 | 98.3 |
| DNP | 0.2 | 0.1856 | 92.8 |
| DNP | 0.5 | 0.4856 | 97.1 |
4, method precision test: prepare the blank mark-on sample that various phthalic ester concentration of component is 0.2mg/Kg respectively, Parallel testing 6 times, and calculate the relative standard deviation RSD% of testing result.Result is as shown in the table, and the precision of illustration method can meet the requirement of detection.
| Ingredient names | Parallel 1 | Parallel 2 | Parallel 3 | Parallel 4 | Parallel 5 | Parallel 6 | Mean value | RSD% |
| DMP | 0.198 | 0.188 | 0.184 | 0.192 | 0.193 | 0.182 | 0.190 | 3.16 |
| DEP | 0.184 | 0.183 | 0.179 | 0.182 | 0.188 | 0.192 | 0.185 | 2.51 |
| DIBP | 0.186 | 0.193 | 0.194 | 0.193 | 0.194 | 0.188 | 0.191 | 1.80 |
| DBP | 0.194 | 0.199 | 0.204 | 0.192 | 0.201 | 0.203 | 0.199 | 2.45 |
| DMEP | 0.199 | 0.203 | 0.204 | 0.203 | 0.193 | 0.199 | 0.332 | 2.06 |
| BMPP | 0.186 | 0.189 | 0.188 | 0.198 | 0.190 | 0.192 | 0.191 | 2.20 |
| DEEP | 0.206 | 0.209 | 0.203 | 0.186 | 0.199 | 0.198 | 0.200 | 4.04 |
| DPP | 0.195 | 0.205 | 0.203 | 0.189 | 0.204 | 0.204 | 0.200 | 3.26 |
| DHXP | 0.184 | 0.183 | 0.204 | 0.183 | 0.201 | 0.206 | 0.194 | 5.82 |
| BBP | 0.183 | 0.179 | 0.192 | 0.198 | 0.204 | 0.203 | 0.193 | 5.39 |
| DBEP | 0.179 | 0.182 | 0.201 | 0.199 | 0.208 | 0.201 | 0.195 | 5.99 |
| DCHP | 0.182 | 0.183 | 0.204 | 0.191 | 0.198 | 0.188 | 0.191 | 4.52 |
| DEHP | 0.188 | 0.179 | 0.192 | 0.192 | 0.186 | 0.175 | 0.185 | 3.76 |
| DPHP | 0.192 | 0.182 | 0.201 | 0.198 | 0.201 | 0.213 | 0.198 | 5.23 |
| DNOP | 0.182 | 0.183 | 0.206 | 0.206 | 0.186 | 0.206 | 0.195 | 6.31 |
| DNP | 0.199 | 0.195 | 0.201 | 0.182 | 0.191 | 0.192 | 0.193 | 3.50 |
(in upper table, in 2-8 row, the unit of numerical value is mg/Kg).
5th embodiment: detection method.
1, experiment condition and qualitative-and-quantitative method.
Identical with the experiment condition described in the 4th embodiment and qualitative-and-quantitative method.
2, method step.
A, according to the sample-pretreating method of the second embodiment, pre-treatment is carried out to emulsifying essence;
B, with combined gas chromatography mass spectrometry, kind of the phthalic ester component of 16 in the liquid obtained after pre-treatment to be detected, and calculate the content of various phthalic ester component in emulsifying essence.
3, method recovery test: preparing various phthalic ester component concentration is respectively that the emulsifying essence of 0.1mg/Kg, 0.2mg/Kg and 0.5mg/Kg carries out recovery experiment.Recovery test result is as shown in the table, and illustration method accuracy can meet the needs of detection.
| Ingredient names | Add concentration (mg/Kg) | Testing result (mg/Kg) | The recovery (%) |
| DMP | 0.1 | 0.0989 | 98.9 |
| DMP | 0.2 | 0.1932 | 96.6 |
| DMP | 0.5 | 0.4703 | 94.1 |
| DEP | 0.1 | 0.0911 | 91.1 |
| DEP | 0.2 | 0.1862 | 93.1 |
| DEP | 0.5 | 0.4723 | 94.5 |
| DIBP | 0.1 | 0.0879 | 87.9 |
| DIBP | 0.2 | 0.1021 | 51.1 |
| DIBP | 0.5 | 0.4502 | 90.0 |
| DBP | 0.1 | 0.0892 | 89.2 |
| DBP | 0.2 | 0.1909 | 95.5 |
| DBP | 0.5 | 0.4567 | 91.3 |
| DMEP | 0.1 | 0.0959 | 95.9 |
| DMEP | 0.2 | 0.2016 | 100.8 |
| DMEP | 0.5 | 0.4682 | 93.6 |
| BMPP | 0.1 | 0.0859 | 85.9 |
| BMPP | 0.2 | 0.1682 | 84.1 |
| BMPP | 0.5 | 0.4861 | 97.2 |
| DEEP | 0.1 | 0.0894 | 89.4 |
| DEEP | 0.2 | 0.1904 | 95.2 |
| DEEP | 0.5 | 0.4752 | 95.0 |
| DPP | 0.1 | 0.0962 | 96.2 |
| DPP | 0.2 | 0.1687 | 84.4 |
| DPP | 0.5 | 0.4698 | 94.0 |
| DHXP | 0.1 | 0.0942 | 94.2 |
| DHXP | 0.2 | 0.1826 | 91.3 |
| DHXP | 0.5 | 0.4872 | 97.4 |
| BBP | 0.1 | 0.0892 | 89.2 |
| BBP | 0.2 | 0.1692 | 84.6 |
| BBP | 0.5 | 0.4853 | 97.1 |
| DBEP | 0.1 | 0.0957 | 95.7 |
| DBEP | 0.2 | 0.1753 | 87.7 |
| DBEP | 0.5 | 0.4651 | 93.0 |
| DCHP | 0.1 | 0.0902 | 90.2 |
| DCHP | 0.2 | 0.1906 | 95.3 |
| DCHP | 0.5 | 0.4592 | 91.8 |
| DEHP | 0.1 | 0.0842 | 84.2 |
| DEHP | 0.2 | 0.2013 | 100.7 |
| DEHP | 0.5 | 0.4691 | 93.8 |
| DPHP | 0.1 | 0.0943 | 94.3 |
| DPHP | 0.2 | 0.1852 | 92.6 |
| DPHP | 0.5 | 0.4952 | 99.0 |
| DNOP | 0.1 | 0.0853 | 85.3 |
| DNOP | 0.2 | 0.1643 | 82.2 |
| DNOP | 0.5 | 0.4536 | 90.7 |
| DNP | 0.1 | 0.0869 | 86.9 |
| DNP | 0.2 | 0.1842 | 92.1 |
| DNP | 0.5 | 0.4659 | 93.2 |
4, method precision test: prepare the blank mark-on sample that various phthalic ester concentration of component is 0.2mg/Kg respectively, Parallel testing 6 times, and calculate the relative standard deviation RSD% of testing result.Result is as shown in the table, and the precision of illustration method can meet the requirement of detection.
| Ingredient names | Parallel 1 | Parallel 2 | Parallel 3 | Parallel 4 | Parallel 5 | Parallel 6 | Mean value | RSD% |
| 0.191 | 0.198 | 0.174 | 0.121 | 0.182 | 0.179 | 0.183 | 5.62 | |
| DEP | 0.193 | 0.179 | 0.182 | 0.195 | 0.176 | 0.183 | 0.183 | 4.18 |
| DIBP | 0.189 | 0.183 | 0.174 | 0.183 | 0.184 | 0.178 | 0.183 | 2.84 |
| DBP | 0.194 | 0.189 | 0.194 | 0.182 | 0.202 | 0.199 | 0.183 | 3.90 |
| DMEP | 0.183 | 0.182 | 0.201 | 0.196 | 0.183 | 0.192 | 0.182 | 4.40 |
| BMPP | 0.187 | 0.181 | 0.192 | 0.193 | 0.182 | 0.173 | 0.182 | 4.16 |
| DEEP | 0.193 | 0.183 | 0.183 | 0.176 | 0.179 | 0.178 | 0.181 | 3.34 |
| DPP | 0.185 | 0.195 | 0.183 | 0.173 | 0.183 | 0.171 | 0.181 | 4.82 |
| DHXP | 0.162 | 0.172 | 0.183 | 0.184 | 0.191 | 0.182 | 0.181 | 5.69 |
| BBP | 0.176 | 0.170 | 0.180 | 0.182 | 0.194 | 0.183 | 0.182 | 4.41 |
| DBEP | 0.172 | 0.192 | 0.201 | 0.191 | 0.201 | 0.182 | 0.182 | 6.20 |
| DCHP | 0.162 | 0.183 | 0.172 | 0.182 | 0.188 | 0.178 | 0.180 | 5.16 |
| DEHP | 0.178 | 0.181 | 0.192 | 0.180 | 0.192 | 0.169 | 0.181 | 4.89 |
| DPHP | 0.162 | 0.192 | 0.183 | 0.177 | 0.169 | 0.184 | 0.180 | 6.05 |
| DNOP | 0.172 | 0.193 | 0.173 | 0.182 | 0.189 | 0.194 | 0.182 | 5.36 |
| DNP | 0.169 | 0.183 | 0.188 | 0.176 | 0.177 | 0.184 | 0.180 | 3.81 |
(in upper table, in 2-8 row, the unit of numerical value is mg/Kg).
6th embodiment: detection method.
1, experiment condition and qualitative-and-quantitative method.
Identical with the experiment condition described in the 4th embodiment and qualitative-and-quantitative method.
2, method step.
A, according to the sample-pretreating method of the 3rd embodiment, pre-treatment is carried out to emulsifying essence;
B, with combined gas chromatography mass spectrometry, kind of the phthalic ester component of 16 in the liquid obtained after pre-treatment to be detected, and calculate the content of various phthalic ester component in emulsifying essence.
3, method recovery test: preparing various phthalic ester component concentration is respectively that the emulsifying essence of 0.1mg/Kg, 0.2mg/Kg and 0.5mg/Kg carries out recovery experiment.Recovery test result is as shown in the table, and illustration method accuracy can meet the needs of detection.
| Ingredient names | Add concentration (mg/Kg) | Testing result (mg/Kg) | The recovery (%) |
| DMP | 0.1 | 0.0862 | 86.2 |
| DMP | 0.2 | 0.1826 | 91.3 |
| DMP | 0.5 | 0.4659 | 93.2 |
| DEP | 0.1 | 0.0849 | 84.9 |
| DEP | 0.2 | 0.1692 | 84.6 |
| DEP | 0.5 | 0.4423 | 88.5 |
| DIBP | 0.1 | 0.0923 | 92.3 |
| DIBP | 0.2 | 0.1762 | 88.1 |
| DIBP | 0.5 | 0.4462 | 89.2 |
| DBP | 0.1 | 0.0792 | 79.2 |
| DBP | 0.2 | 0.1653 | 82.7 |
| DBP | 0.5 | 0.4628 | 92.6 |
| DMEP | 0.1 | 0.0916 | 91.6 |
| DMEP | 0.2 | 0.1672 | 83.6 |
| DMEP | 0.5 | 0.4653 | 93.1 |
| BMPP | 0.1 | 0.0954 | 95.4 |
| BMPP | 0.2 | 0.1672 | 83.6 |
| BMPP | 0.5 | 0.4752 | 95.0 |
| DEEP | 0.1 | 0.0653 | 65.3 |
| DEEP | 0.2 | 0.1725 | 86.3 |
| DEEP | 0.5 | 0.4682 | 93.6 |
| DPP | 0.1 | 0.0849 | 84.9 |
| DPP | 0.2 | 0.1657 | 82.9 |
| DPP | 0.5 | 0.4538 | 90.8 |
| DHXP | 0.1 | 0.0782 | 78.2 |
| DHXP | 0.2 | 0.1688 | 84.4 |
| DHXP | 0.5 | 0.4962 | 99.2 |
| BBP | 0.1 | 0.0801 | 80.1 |
| BBP | 0.2 | 0.1689 | 84.5 |
| BBP | 0.5 | 0.4673 | 93.5 |
| DBEP | 0.1 | 0.0953 | 95.3 |
| DBEP | 0.2 | 0.1642 | 82.1 |
| DBEP | 0.5 | 0.4592 | 91.8 |
| DCHP | 0.1 | 0.0752 | 75.2 |
| DCHP | 0.2 | 0.1675 | 83.8 |
| DCHP | 0.5 | 0.4836 | 96.7 |
| DEHP | 0.1 | 0.1043 | 104.3 |
| DEHP | 0.2 | 0.1523 | 76.2 |
| DEHP | 0.5 | 0.4459 | 89.2 |
| DPHP | 0.1 | 0.0789 | 78.9 |
| DPHP | 0.2 | 0.1643 | 82.2 |
| DPHP | 0.5 | 0.4629 | 92.6 |
| DNOP | 0.1 | 0.0852 | 85.2 |
| DNOP | 0.2 | 0.1647 | 82.4 |
| DNOP | 0.5 | 0.4528 | 90.6 |
| DNP | 0.1 | 0.1012 | 101.2 |
| DNP | 0.2 | 0.1789 | 89.5 |
| DNP | 0.5 | 0.4836 | 96.7 |
4, method precision test: prepare the blank mark-on sample that various phthalic ester concentration of component is 0.2mg/Kg respectively, Parallel testing 6 times, and calculate the relative standard deviation RSD% of testing result.Result is as shown in the table, and the precision of illustration method can meet the requirement of detection.
| Ingredient names | Parallel 1 | Parallel 2 | Parallel 3 | Parallel 4 | Parallel 5 | Parallel 6 | Mean value | RSD% |
| DMP | 0.178 | 0.184 | 0.186 | 0.194 | 0.199 | 0.186 | 0.190 | 4.03 |
| DEP | 0.188 | 0.183 | 0.193 | 0.199 | 0.203 | 0.189 | 0.194 | 3.51 |
| DIBP | 0.184 | 0.179 | 0.194 | 0.204 | 0.204 | 0.188 | 0.193 | 4.76 |
| DBP | 0.192 | 0.182 | 0.193 | 0.192 | 0.203 | 0.198 | 0.194 | 3.29 |
| DMEP | 0.193 | 0.188 | 0.194 | 0.201 | 0.193 | 0.19 | 0.194 | 2.29 |
| BMPP | 0.182 | 0.192 | 0.188 | 0.203 | 0.199 | 0.192 | 0.194 | 3.54 |
| DEEP | 0.193 | 0.195 | 0.184 | 0.183 | 0.179 | 0.182 | 0.188 | 3.90 |
| DPP | 0.186 | 0.205 | 0.183 | 0.179 | 0.182 | 0.183 | 0.188 | 4.93 |
| DHXP | 0.191 | 0.203 | 0.204 | 0.192 | 0.201 | 0.204 | 0.199 | 2.57 |
| BBP | 0.186 | 0.189 | 0.183 | 0.198 | 0.199 | 0.191 | 0.192 | 3.26 |
| DBEP | 0.199 | 0.169 | 0.201 | 0.186 | 0.193 | 0.198 | 0.192 | 5.54 |
| DCHP | 0.198 | 0.186 | 0.178 | 0.193 | 0.188 | 0.188 | 0.190 | 3.67 |
| DEHP | 0.188 | 0.192 | 0.182 | 0.199 | 0.188 | 0.175 | 0.189 | 4.36 |
| DPHP | 0.179 | 0.182 | 0.183 | 0.195 | 0.186 | 0.169 | 0.185 | 5.14 |
| DNOP | 0.192 | 0.201 | 0.206 | 0.201 | 0.186 | 0.169 | 0.194 | 6.08 |
| DNP | 0.192 | 0.198 | 0.206 | 0.182 | 0.176 | 0.192 | 0.192 | 5.02 |
(in upper table, in 2-8 row, the unit of numerical value is mg/Kg).
In this article, the restriction in the mathematical meaning of " equal ", " identical " etc. non-critical, it also can comprise it will be appreciated by those skilled in the art that and preparation or use the error allowed when this product and method.
Be to be understood that, although this instructions describes according to each embodiment, but not each embodiment only comprises an independently technical scheme, this narrating mode of instructions is only for clarity sake, those skilled in the art should by instructions integrally, technical scheme in each embodiment also through appropriately combined, can form other embodiments that it will be appreciated by those skilled in the art that.
A series of detailed description listed is above only illustrating for possible embodiments of the present invention; they are also not used to limit the scope of the invention, all do not depart from the skill of the present invention Equivalent embodiments done of spirit or change all should be included within protection scope of the present invention.
Claims (4)
1. detect a sample-pretreating method for phthalic ester in emulsifying essence fast, it is characterized in that comprising:
A, add normal hexane and mix in emulsifying essence to be measured, the amount adding described normal hexane in every 1 gram of described emulsifying essence to be measured is 4 to 6 milliliters, obtains mixed liquor;
B, described mixed liquor nitrogen in the water-bath of 40 DEG C to 50 DEG C to be dried up;
C, dry up to described nitrogen after container in add normal hexane and vortex, the speed of described vortex is not higher than 3000 revs/min, and duration is 20 to 30 seconds, gets liquid to be measured.
2. detect a method for phthalic ester in emulsifying essence fast, it is characterized in that comprising: sample-pretreating method according to claim 1 carries out pre-treatment to emulsifying essence to be measured; With combined gas chromatography mass spectrometry, the phthalic ester in the liquid obtained after described pre-treatment is detected.
3. the method detecting phthalic ester in emulsifying essence fast as claimed in claim 2, the chromatographic condition of wherein said combined gas chromatography mass spectrometry is:
Chromatographic column: capillary chromatographic column, specification is 30m × 0.25mm × 0.25 μm, and Stationary liquid is 5% phenyl and 95% dimethyl polysiloxane;
Injector temperature: 250 DEG C;
Shunting mode: do not shunt;
Carrier gas: helium;
Flow velocity: 1.0mL/min;
Heating schedule: initial temperature is 60 DEG C and maintains 1min, is then raised to 210 DEG C with 15 DEG C/min, then be raised to 280 DEG C of maintenance 2.5min with 4 DEG C/min;
Sample size: 1 μ L.
4. the method detecting phthalic ester in emulsifying essence fast as claimed in claim 2, the Mass Spectrometry Conditions of wherein said combined gas chromatography mass spectrometry is:
Ionization mode: electron bombardment ionization source;
Ionizing energy: 70eV;
Ion source temperature: 200 DEG C;
Transmission line temperature: 250 DEG C;
The solvent delay time: 8.5min;
Scan pattern: Selective ion mode scan pattern.
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