CN115201346A - Preparation and detection method of to-be-detected sample of photoinitiator in packaging material - Google Patents
Preparation and detection method of to-be-detected sample of photoinitiator in packaging material Download PDFInfo
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- CN115201346A CN115201346A CN202110390487.9A CN202110390487A CN115201346A CN 115201346 A CN115201346 A CN 115201346A CN 202110390487 A CN202110390487 A CN 202110390487A CN 115201346 A CN115201346 A CN 115201346A
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- 239000005022 packaging material Substances 0.000 title claims abstract description 33
- 238000001514 detection method Methods 0.000 title abstract description 30
- 238000002360 preparation method Methods 0.000 title description 4
- 238000000034 method Methods 0.000 claims abstract description 60
- 238000000605 extraction Methods 0.000 claims abstract description 46
- 238000011282 treatment Methods 0.000 claims abstract description 45
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000000523 sample Substances 0.000 claims description 53
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims description 16
- 238000003672 processing method Methods 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- 238000004806 packaging method and process Methods 0.000 claims description 12
- 230000009089 cytolysis Effects 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
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- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 claims description 4
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- 238000005259 measurement Methods 0.000 claims description 4
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- 238000000926 separation method Methods 0.000 claims description 4
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 claims description 3
- 235000013305 food Nutrition 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- CKGKXGQVRVAKEA-UHFFFAOYSA-N (2-methylphenyl)-phenylmethanone Chemical compound CC1=CC=CC=C1C(=O)C1=CC=CC=C1 CKGKXGQVRVAKEA-UHFFFAOYSA-N 0.000 claims description 2
- URBLVRAVOIVZFJ-UHFFFAOYSA-N (3-methylphenyl)-phenylmethanone Chemical compound CC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1 URBLVRAVOIVZFJ-UHFFFAOYSA-N 0.000 claims description 2
- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 2
- IKVYHNPVKUNCJM-UHFFFAOYSA-N 4-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(C(C)C)=CC=C2 IKVYHNPVKUNCJM-UHFFFAOYSA-N 0.000 claims description 2
- ZYMCJDAUBJFVSM-UHFFFAOYSA-N 6-methylheptyl 4-(dimethylamino)benzoate Chemical compound CC(C)CCCCCOC(=O)C1=CC=C(N(C)C)C=C1 ZYMCJDAUBJFVSM-UHFFFAOYSA-N 0.000 claims description 2
- -1 C 6 Carboxylic acid esters Chemical class 0.000 claims description 2
- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 claims description 2
- RVWADWOERKNWRY-UHFFFAOYSA-N [2-(dimethylamino)phenyl]-phenylmethanone Chemical compound CN(C)C1=CC=CC=C1C(=O)C1=CC=CC=C1 RVWADWOERKNWRY-UHFFFAOYSA-N 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 2
- 150000001924 cycloalkanes Chemical class 0.000 claims description 2
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 claims description 2
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 claims description 2
- 239000012488 sample solution Substances 0.000 claims description 2
- RCUCEVZJUUYESD-UHFFFAOYSA-N phenyl-[2-(2-phenylphenyl)phenyl]methanone Chemical compound C=1C=CC=C(C=2C(=CC=CC=2)C=2C=CC=CC=2)C=1C(=O)C1=CC=CC=C1 RCUCEVZJUUYESD-UHFFFAOYSA-N 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 30
- 239000005003 food packaging material Substances 0.000 abstract description 12
- 238000000746 purification Methods 0.000 abstract description 10
- 238000011084 recovery Methods 0.000 abstract description 10
- 238000002203 pretreatment Methods 0.000 abstract description 6
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- 238000005336 cracking Methods 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 11
- 239000006228 supernatant Substances 0.000 description 11
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 10
- 238000010561 standard procedure Methods 0.000 description 9
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- 239000012634 fragment Substances 0.000 description 4
- 239000000976 ink Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000012224 working solution Substances 0.000 description 4
- UFLGIAIHIAPJJC-UHFFFAOYSA-N Tripelennamine Chemical compound C=1C=CC=NC=1N(CCN(C)C)CC1=CC=CC=C1 UFLGIAIHIAPJJC-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000011002 quantification Methods 0.000 description 3
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 2
- VZEZONWRBFJJMZ-UHFFFAOYSA-N 3-allyl-2-[2-(diethylamino)ethoxy]benzaldehyde Chemical compound CCN(CC)CCOC1=C(CC=C)C=CC=C1C=O VZEZONWRBFJJMZ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 235000015895 biscuits Nutrition 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- 239000011885 synergistic combination Substances 0.000 description 2
- CQNUMTMWJRSIRY-UHFFFAOYSA-N 1,1'-biphenyl;diphenylmethanone Chemical compound C1=CC=CC=C1C1=CC=CC=C1.C=1C=CC=CC=1C(=O)C1=CC=CC=C1 CQNUMTMWJRSIRY-UHFFFAOYSA-N 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
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- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
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- 235000008446 instant noodles Nutrition 0.000 description 1
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- 230000010355 oscillation Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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Images
Classifications
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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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- 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
- G01N30/86—Signal analysis
- G01N30/8675—Evaluation, i.e. decoding of the signal into analytical information
-
- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
Abstract
The invention provides a rapid pretreatment and detection method of one or more photoinitiators in a packaging material, which can simultaneously realize the crushing of the food packaging material and the extraction of up to 18 photoinitiators within one minute by utilizing the developed rapid pretreatment technology. The pretreatment method provided by the invention greatly shortens the pretreatment time due to the high extraction efficiency; low levels of photoinitiator, undetectable by conventional means, are detectable; the photoinitiator in the food packaging material can be completely extracted; the required solvent is obviously reduced compared with the traditional treatment method; the detected detection limit and the quantitative limit are smaller than the values detected by the traditional method, and the sensitivity is higher; the purification treatment is not needed, so that the cost and the manual operation can be greatly saved; the extraction efficiency is high, the test accuracy is good, the recovery rate is high, the repeatability is good, and the requirement of actual test can be met.
Description
Technical Field
The invention belongs to the field of sample treatment and detection, and particularly relates to a method for quickly pretreating and detecting a photoinitiator in a packaging material.
Background
The paper packaging material in the food packaging material is the most widely used packaging material at the present stage, the packaging material has low price and low processing cost, and the paper packaging material is beneficial to production and decoration and is very convenient to store and transport.
The food packaging material has an important influence on the safety of the product, and the harm of the packaging material to the product needs to be concerned, particularly whether the food packaging material has an influence on the health of people.
The photoinitiator is also called a light curing agent, is a compound capable of initiating polymerization, crosslinking and curing of monomers, and is a main component of printing ink. When photoinitiators harmful to human bodies are used in printing inks for food packaging materials, the photoinitiators can be harmful to human health through contact and the like. Therefore, accurate detection of the photoinitiator content in the packaging material is required.
In the traditional method, a test sample needs to undergo a complicated sample pretreatment process before entering chromatographic separation detection, and a large amount of manpower, solvent and time are consumed. With the increase of the number of samples in practical detection, how to rapidly and completely extract a target object in a short time is a problem which needs to be solved urgently by an analyst.
Disclosure of Invention
Aiming at the defects existing in the existing packaging material photoinitiator determination, the first purpose of the invention is to provide a sample processing method for determining the photoinitiator in the packaging material, and the invention aims to provide a sample processing method which can rapidly process a sample, improve the sample extraction rate and avoid the omission factor.
The invention also provides a method for measuring the photoinitiator in the packaging material.
The components of the photoinitiator in the packaging material are complex, the content of many photoinitiators is low, the detection rate is not high, and the condition of missed detection is easy to occur. Aiming at the technical situation, the industrial standard method is not only complicated in treatment, but also difficult to avoid false negative caused by missed detection of certain photoinitiator components, and aiming at the technical problem, the invention provides the following technical scheme:
a sample processing method for determining photoinitiator in a packaging material comprises the steps of extracting the packaging material to be detected in a medium collision extraction instrument, and then carrying out centrifugal treatment to obtain a sample solution to be detected;
the extractant is a single solvent or a miscible mixed solvent in alcohol, acetone, acetonitrile, ester and alkane.
The research of the invention finds that the synergistic combination of the extracting agent and the cracking extraction process can unexpectedly and effectively realize the synchronous, quick and efficient extraction of the photoinitiator in the packaging material, is beneficial to avoiding the missed detection of the components of the photoinitiator and is beneficial to avoiding the condition of false negative.
The research of the invention finds that the synergistic combination of the extracting agent and the cracking extraction process is the key for improving the extraction rate of the photoinitiator of the sample to be detected and reducing the false negative. Research also finds that the combined control of the cracking medium type, the extraction agent components and the extraction program is beneficial to further synergy, further improves the extraction effect of the photoinitiator of the sample to be detected, reduces the omission condition of certain photoinitiators difficult to identify, and is also beneficial to improving the determination effects such as the recovery rate and the sensitivity of determination.
In the invention, the alcohol is C 1 ～C 4 The monoalcohol of (1);
preferably, the ester is C 3 ～C 6 Carboxylic acid esters of (a);
preferably, the alkane is C 3 ～C 12 Alkane or cycloalkane.
Preferably, the extractant is a single solvent or a miscible mixed solvent of methanol, ethanol, acetonitrile, acetone, n-hexane and ethyl acetate.
More preferably, the extractant is methanol. Methanol is adopted as an extracting agent, and the methanol has better cooperativity with an extraction process, so that the extraction effect of the photoinitiator in a sample to be detected is further improved, the extraction leakage rate is reduced, the false negative condition is reduced, and in addition, the subsequent detection recovery rate, sensitivity and accuracy are further improved.
In the invention, the material-liquid ratio of the sample (area) to be measured to the extracting agent (volume) is 1-10 cm 2 Per mL; more preferably 4 to 6cm 2 /mL。
In the present invention, the medium impact extractor is, for example, fastPrep from MP Biomedicals @ -24 instruments.
In the process of uniform grinding, the cracking medium is at least one of medium S, medium M or medium D;
wherein the medium S is a 1/8 inch stainless steel ball;
media M is 1/4 inch cylindrical ceramic beads;
medium D is 1.4mm ceramic beads;
preferably, the lysis medium used is medium M.
Preferably, the linear velocity of the extractor is 4 m.s -1 ～6.5m·s -1 。
In the extraction treatment process, the time of single cracking extraction treatment is less than or equal to 60s; the total time of the extraction treatment process is 1-3 min.
In the invention, the photoinitiator is at least one of 2-hydroxy-2-methyl-1-phenyl acetone, methyl benzoylformate, benzophenone, 2-methylbenzophenone, 1-hydroxycyclohexyl phenyl ketone, ethyl p-N, N-dimethylaminobenzoate, 3-methylbenzophenone, 4-methylbenzophenone, 2-dimethoxy-2-phenyl acetophenone, methyl o-benzoylbenzoate, isooctyl p-dimethylaminobenzoate, 2-methyl-1- (4-methylthio) phenyl 2-morpholinyl-1-propanone, 4-isopropylthioxanthone, 2-isopropylthioxanthone, biphenyl benzophenone, 2, 4-diethylthioxanthone, 4-bis (dimethylamino) benzophenone, 4-bis (diethylamino) benzophenone;
preferably, the number of the photoinitiators is two or more, and more preferably 18. The technical scheme of the invention can realize the synchronous extraction of up to 18 photoinitiators, avoid the extraction omission rate and contribute to reducing the false negative condition.
In the invention, the wrapping paper is various food wrapping paper.
The sample preparation method provided by the invention has the advantages that the time for extracting the photoinitiator in the food packaging material is short, the extraction efficiency is high, the solvent consumption is low, and the traditional pretreatment mode and method mainly depending on extraction modes such as oscillation and ultrasound can be changed.
The invention also provides a method for measuring the photoinitiator in the packaging material, the solution to be measured is prepared by the method, and GC-MS measurement is carried out.
In the invention, the extraction can be carried out by adopting the process, and then the extract is obtained by centrifugal separation and membrane filtration. And then the GC-MS measurement is carried out on the extracting solution:
in the invention, the GC-MS determination conditions are as follows: using a capillary chromatography column, stationary phase: 5% phenyl/95% methylpolysiloxane, specification: [30m (length) × 0.25mm (inner diameter) × 0.25 μm (film thickness) ]; the temperature of a sample inlet is set to 300 ℃; the carrier gas is helium (the purity is more than or equal to 99.999%), the constant flow rate is as follows: 1.0mL/min; the sample feeding amount is 1 mu L, and the split sample feeding is carried out, wherein the split ratio is 40; temperature rising procedure: the initial temperature is 70 ℃, the temperature is increased to 300 ℃ at the speed of 10 ℃/min and is kept for 5min, and the later operation mode is kept for 5min at the temperature of 300 ℃. The temperature of the mass spectrum transmission line is set to 300 ℃; adopting an electron impact source (EI) ionization mode, wherein the ionization energy is 70eV; the ion source temperature was set at 280 ℃; the temperature of the quadrupole rods is set to be 150 ℃; the solvent delay was 6min.
The invention can simultaneously carry out batch pretreatment operation on a plurality of samples according to the characteristics of the adapter. The adapter used was mainly 48X 2mL, 24X 4.5mL, 12X 15mL and 2X 50mL in terms of its standard. The adapter specifications are selected based on the amount of sample that needs to be processed.
Advantageous effects
1. Aiming at the particularity and identification difficulty of the photoinitiator in the packaging material, the invention innovatively provides a medium collision extraction treatment process, and on the basis, the extraction effect of the photoinitiator can be effectively improved and the extraction omission rate can be reduced based on the combined control of a cracking medium, an extracting agent, an extraction program and the like. The method can quickly realize the high-efficiency extraction of up to 18 photoinitiators in the food packaging material, greatly shortens the pretreatment time, for example, the treatment time can be reduced to 1min, the dosage of the extracting agent is reduced, the sample does not need to be purified, the process is simple and high-efficiency, and not only can a better detection effect be obtained, but also the false negative condition can be effectively reduced.
2. Thanks to the innovative sample processing method, the technical scheme of the invention can measure up to 18 photoinitiators in the packaging material, reduce false negative conditions, and is also beneficial to improving the recovery rate, sensitivity and accuracy of the measurement.
Drawings
FIG. 1 is a chromatogram of the separation of 18 photoinitiators and an internal standard (deuterated anthracene);
fig. 2 shows the difference in photoinitiator test results when different extractants were used (S5: n-hexane: ethyl acetate =3, s8: acetonitrile: n-hexane: ethyl acetate = 20;
FIG. 3 is a comparison of test results of the conventional processing method and the new processing method;
FIG. 4 is a chromatogram map for detecting photoinitiator in biscuit wrapping paper;
FIG. 5 change of paper samples before and after treatment with the new method.
The specific implementation mode is as follows:
1) Optimizing pretreatment conditions: selecting a part of cracking medium with larger impact force for screening according to the hardness and thickness of the food packaging material; screening different extracting agents according to the polarity and the solubility of the photoinitiator; in order to realize the extraction of the photoinitiator to the maximum extent, a pretreatment program is optimized, and the treatment time is reduced as much as possible; and (5) inspecting the influence of the purification operation on the test result, and judging whether a purification treatment step needs to be added or not.
2) Recovery experiments were performed for 18 photoinitiators.
3) And detecting the actual sample by using a GC-MS method, comparing the difference of the test results of the traditional treatment method and the new treatment method, performing a precision experiment, and further investigating whether the new treatment method meets the actual test requirement.
In this case, the media impact extractor apparatus is, except where specifically stated, manufactured by MP Biomedicals, inc., model number FastPrep @ -24。
In the invention, the time of single extraction is 1min unless otherwise stated, and when the extraction time is multiple of 1min, the extraction is repeated for a plurality of times, and when the extraction is repeated for a plurality of times, the time interval between the extraction times is, for example, 1-2 min.
The pretreatment method of the traditional method refers to the gas chromatography-mass spectrometry combination method for determining the photoinitiator in YQ/T31-2013 cigarette sticks and box packing paper in the industry standard.
The pretreatment method of the industrial standard YQ/T31-2013 comprises the following steps: a10.0 cm by 5.0cm sample was accurately cut. The cut specimens were cut into pieces of about 0.5cm by 0.5 cm. Placing the cut sample into a 50mL triangular flask with a plug, adding 20mL water, standing for 30min, then adding 20mL acetonitrile and 200 mu L internal standard solution (deuterated anthracene, 1 mg/mL), carrying out ultrasonic extraction for 40min, standing for 5min, taking 4mL supernatant into a 15mL centrifuge tube, adding 3mL n-hexane-ethyl acetate solution, oscillating on a vortex oscillator at a linear velocity of 500r/min for 5min, standing, taking the supernatant, and purifying. A (1.5. + -. 0.2) mL portion of the supernatant was transferred to a 2mL centrifuge tube containing 150mg of anhydrous magnesium sulfate, 50mg of PSA and 50mg of C18 adsorbent, shaken on a vortex shaker at a linear velocity of 500r/min for 5min, centrifuged at a linear velocity of 5000r/min for 10min, and the supernatant was subjected to GC-MS analysis.
Example 1:
preparation of an internal standard solution deuterated anthracene: 100mg of deuterated anthracene is accurately weighed in a 100mL volumetric flask, and the volume is determined by acetonitrile to prepare an internal standard solution with the concentration of 1 mg/mL. The solution can be stored in a refrigerator (4 ℃) protected from light for two months.
Preparation of 18 photoinitiator mixed standard curve working solutions: 0.01mL,0.04mL,0.1mL,0.2mL,0.4mL,1mL,2.0mL of the mixed standard solutions of 18 photoinitiators (100. Mu.g/mL) were accurately transferred into 7 10mL volumetric flasks, and 40. Mu.L of the above internal standard solution was accurately transferred into each flask, and finally the volume was fixed with acetonitrile. The concentrations of the prepared 18 photoinitiator mixed standard solutions are 0.1,0.4,1.0,2.0,4.0,10 and 20 mu g/mL respectively. The chromatogram separation of 18 photoinitiators and an internal standard (deuterated anthracene) is shown in the attached figure 1.
GC-MS analysis was performed on a series of standard working solutions. Taking the ratio of the quantitative ion peak area of the photoinitiator to the internal standard substance in each standard working solution as the ordinate, taking the content of the photoinitiator in each standard working solution as the abscissa, obtaining the standard working curves and regression coefficients (R) of 18 photoinitiators, wherein the 18 photoinitiators have good linear relationship in the range of 0.1-20 mu g/mL, and the correlation coefficient R 2 Are all greater than 0.99. The detection limit of the test method is 0.06-0.18 mg/m 2 The limit of quantification is 0.20-0.60 mg/m 2 The result is far smaller than that of the utilization industryThe value measured by the standard method (the detection limit in the industry standard method YQ/T31-2013 is 0.30-0.90 mg/m) 2 The limit of quantification is 1.00-3.00 mg/m 2 ) The results are shown in table 1, which indicates that the method is more sensitive.
TABLE 1 Linear equation, correlation coefficient, detection limit and quantitation limit for 18 photoinitiators
Example 2: investigation of lysis media:
the initial part of the lysis medium with high impact force was selected: medium S, medium M, and medium D. Wherein the medium S is a 1/8 inch stainless steel ball; the medium M is 1/4 inch cylindrical ceramic beads; medium D was 1.4mm ceramic beads. A10.0 cm × 5.0cm sample is accurately cut, the cut sample is cut into fragments of about 0.5cm × 0.5cm, the fragments are placed in 15mL centrifuge tubes containing different types of lysis media respectively, 10mL of an extracting agent (a mixed solution of n-hexane and ethyl acetate: volume ratio of 3 -1 (line speed), 1min; centrifuging (4,000rpm) for 2min, filtering the supernatant with a filter membrane, and performing GC-MS analysis. In order to compare different test results after different cracking media are treated, a real sample cigarette box packaging paper a is detected, and the detection results are shown in table 2.
TABLE 2 results of experiments using different lysis media for detection
By comparing the above experimental results with the damage degrees of the packing paper treated by different cracking media, the damage degree of the paper pattern is the most thorough when the medium M is used for treatment, and the test result is the highest, so the medium M is selected as the optimal cracking medium for the experiment.
Example 3: research of the extractant:
the cigarette box packaging paper b is accurately cut into 10.0cm in volume5.0cm samples, cut the sample into pieces of about 0.5cm by 0.5cm, place in a 15mL centrifuge tube containing lysis medium M, add 10mL of the extractant and internal standard deuterated anthracene shown in the table below, and perform medium collision extraction to treat 4 m.s -1 1min; centrifuging (4,000rpm) for 2min, filtering the supernatant with a filter membrane, and performing GC-MS analysis. The results of the tests using different extractants are shown in table 3. The traditional treatment method is carried out according to the industry standard gas chromatography-mass spectrometry combination method for determining the photoinitiator in the YQ/T31-2013 cigarette strip and the box packaging paper, and is compared with the test result of the method. The effect of using different extractants on the test results can be seen more intuitively in FIG. 2.
TABLE 3 results of tests with different extractants
Remarking: 1) ND: when the content is lower than the detection limit, the content cannot be determined;
2) S5: n-hexane: ethyl acetate = 3;
3) S8: acetonitrile: n-hexane: ethyl acetate = 20.
From the experimental results in the above table, it can be seen that when different extracting agents are used to extract various photoinitiators in the carton packaging paper, the test results are different after the different extracting agents are used for treatment due to the different polarities and solubility of the photoinitiators. In summary, methanol is the optimal extractant for photoinitiators in test box packaging paper. Then, the test results of the photoinitiator 4-MBP 907 are similar to those of the photoinitiator in the industry standard method, the test results of the new DETX and EHDBA treatment methods are far greater than those of the traditional test results, and it is suspected that part of the photoinitiator exists on the surface of the packaging box, also exists in the ink layer or in the polymer, and cannot be completely extracted by the traditional ultrasonic pretreatment. For 2-ITX, DEAB, PBZ and EDB, the traditional method has the conditions of omission and false negative, and the content of the 2-ITX, DEAB, PBZ and EDB can be detected by the method, which embodies the advantages of the new method.
Example 4: extraction processes such as line speed and time studies:
for the optimization experiment of the processing procedure, the box packaging paper b is used for carrying out the experiment, the processing method is to accurately cut a sample with the thickness of 10.0cm multiplied by 5.0cm, cut the sample into fragments with the thickness of about 0.5cm multiplied by 0.5cm, place the fragments into a 15mL centrifugal tube containing a cracking medium M, add 10mL extracting agent methanol and internal standard deuterated anthracene, and carry out the processing procedures of medium collision extraction according to the following table; centrifuging (4,000rpm) for 2min, filtering the supernatant with a filter membrane, and performing GC-MS analysis. From Table 4, it can be seen that the processing speed (linear velocity, from 4 m.s.) -1 →6.5m·s -1 ) The measured content of the photoinitiator is slightly reduced after the increase of the processing speed, and the analysis is that the photoinitiator is degraded due to the increase of heat generated after the increase of the processing speed; at a proper line speed and time, the detection effect is further improved.
TABLE 4 results of experiments with extraction treatments at different treatment rates and times
Example 5: research on purification experiments
For whether the new treatment method needs purification treatment to reduce the interference of the matrix, the following comparative experiment is carried out, a certain packaging paper pattern c is tested for 2 times in parallel by respectively utilizing an industry standard method and a newly developed method (carrying out purification treatment and not carrying out purification treatment), and the specific operation is as follows: accurately cutting 10.0cm × 5.0cm sample, cutting the sample into pieces of about 0.5cm × 0.5cm, placing into 15mL centrifuge tube containing lysis medium M, adding 10mL extractant methanol and internal standard deuterated anthracene, performing medium collision extraction to treat 4 m.s -1 ,1min; (with purification treatment, the operation is added: moving (1.5 +/-0.2) mL of supernatant into a 2mL centrifuge tube containing 150mg of anhydrous magnesium sulfate, 50mg of PSA and 50mg of C18 adsorbent, oscillating for 5min at a linear speed of 500r/min on a vortex oscillator, centrifuging (4, 000rpm) for 2min, filtering the supernatant with a filter membrane, and performing GC-MS analysis. The results of the industry standard method and the new method (with or without purification treatment) are shown in Table 5. Fig. 3 shows the difference between the results of the industry standard method and the new method (without purification) more intuitively.
TABLE 5 comparison of the cleaning experiments
Remarking: ND: below the detection limit, the content cannot be determined.
From the experimental results in the above table, it can be seen that most of the photoinitiators showed almost no change in the test results when the decontamination treatment was performed, while the test results of EHDBA were slightly reduced, and the analysis was due to the selective adsorption of the decontaminant. Therefore, the new treatment method does not need purification treatment, and saves more cost and time.
Example 6: experimental study of recovery
Then, a recovery rate experiment is carried out by using an optimized method through a currently-manufactured simulation sample (prepared by coating the ink mixed with the photoinitiator and the standard on the blank cardboard), namely: accurately cutting 10.0cm × 5.0cm sample, cutting the sample into pieces of about 0.5cm × 0.5cm, placing into a 15mL centrifuge tube containing lysis medium M, adding 10mL extractant methanol and internal standard deuterated anthracene, and performing medium collision extraction treatment to obtain 4 m.s -1 1min; centrifuging (4,000rpm) for 2min, filtering the supernatant with a membrane, and performing GC-MS analysis. The results are shown in Table 6.
TABLE 6 recovery Experimental test results
As shown in the table above, when the photoinitiator mixed standard solution with low and high horizontal contents is added respectively, the standard recovery rate of the 18 photoinitiators is between 85.7% and 120.3%, which indicates that the developed method has high test accuracy.
Example 7: experimental study on sample precision
Testing the actual sample by using an industry standard processing method and an optimized new processing method for a certain packaging paper pattern d, and testing for 3 times in parallel; the new method comprises the following treatment operations: accurately cutting 10.0cm × 5.0cm sample, cutting the sample into pieces of about 0.5cm × 0.5cm, placing into a 15mL centrifuge tube containing lysis medium M, adding 10mL extractant methanol and internal standard deuterated anthracene, and performing medium collision extraction treatment to obtain 4 m.s -1 1min; centrifuging (4,000rpm) for 2min, filtering the supernatant with a membrane, and performing GC-MS analysis. The results of the in-day precision and in-day precision tests conducted on the new treatment methods are shown in Table 7. The precision RSD in the day is 0.36-3.94%, the precision RSD in the day is 1.55-5.23%, the test stability is high, and the low-content photoinitiator which cannot be detected by an industry standard method can be detected.
TABLE 7.1 comparison of the test of the conventional method and the new method and the precision experiment of the new method in the day
TABLE 7.2 results of day-to-day precision experimental testing of the new method
Remarking: ND: below the detection limit, the content cannot be determined.
Example 8: detection of actual samples
The optimized medium collision extraction pretreatment method and the GC-MS method are combined to analyze the photoinitiators contained in various packaging materials in life. 20 paper packaging samples of food (including milk, cookies, instant noodles, yogurt, disposable paper cups) were tested, each sample tested in parallel 3 times. 11 positive samples were detected, and the test results are shown in Table 7. Among them, 1173 in 5 samples, 2 in 2 samples, 4-MBP in 2 samples, 184 in 2 samples, BDK in 1 sample, 907 in 1 sample, PBZ in 2 samples, BP in 3 samples, MBF in 2 samples, and EHDBA in 1 sample were detected. FIG. 4 shows the detection of 4-MBP (0.973 mg/m) in the biscuit wrapping paper 2 ) And EHDBA (2.452 mg/m) 2 ) The chromatogram of (2). The quantitative result shows that the method can rapidly and effectively detect and quantify various photoinitiators. Figure 5 shows the change of paper samples before and after treatment with the method developed by the present invention.
TABLE 8 detection results of photoinitiators in food packaging materials
The invention establishes a rapid pretreatment and detection method for detecting 18 Photoinitiators (PIs) in food packaging materials, has high recovery rate, and the detection limit and the quantification limit of the detection are far smaller than the numerical values of the industrial standard method. The analysis result of the actual sample shows that the method is rapid, simple, convenient, high in extraction efficiency and good in accuracy, and can be used for high-throughput treatment and detection of 18 photoinitiators in food packaging materials. And due to the advantages of the treatment method, the sensitivity of the photoinitiator is higher, and the photoinitiator with low content which cannot be detected by the traditional method can be detected.
Claims (12)
1. A sample processing method for determining photoinitiator in a packaging material is characterized in that the packaging material to be determined is extracted in a medium collision extractor, and then a sample solution to be determined is obtained through solid-liquid separation;
the extractant is a single solvent or a mixed solvent which is mutually soluble in alcohol, acetone, acetonitrile, ester and alkane.
2. The sample treatment method for the determination of photoinitiator in packaging material according to claim 1 wherein the alcohol is C 1 ～C 4 The monoalcohol of (1);
preferably, the ester is C 3 ～C 6 Carboxylic acid esters of (a);
preferably, the alkane is C 3 ～C 12 Alkane or cycloalkane.
3. The sample processing method for detecting the photoinitiator in the packaging material as claimed in claim 2, wherein the extracting agent is a single solvent or a miscible mixed solvent of methanol, ethanol, acetonitrile, acetone, n-hexane and ethyl acetate.
4. The sample processing method for the determination of photoinitiator in packaging material of claim 1 wherein the extractant is methanol.
5. The sample treatment method for measuring photoinitiator in packaging material according to any one of claims 1 to 4, wherein the feed-to-liquid ratio of the sample to be measured (area of the paper pattern) to the extractant (volume) is 1 to 10cm 2 /mL。
6. The package for detecting photoinitiator samples as set forth in claim 1The method is characterized in that the linear velocity of the medium collision extraction instrument is 4 m.s -1 ～6.5m·s -1 。
7. The sample treatment method for measuring photoinitiator in packaging material according to claim 1, characterized in that the lysis medium used in the extraction treatment is at least one of medium S, medium M or medium D;
wherein the medium S is a 1/8 inch stainless steel ball;
media M is 1/4 inch cylindrical ceramic beads;
medium D is 1.4mm ceramic beads;
preferably, the lysis medium used is medium M.
8. The sample processing method for the determination of photoinitiator in packaging material according to claim 1 wherein the medium impact extractor is FastPrep from MP Biomedicals @ -24 instruments.
9. The sample processing method for the determination of photoinitiators in packaging materials of claim 1, wherein during the extraction treatment, the time of a single extraction treatment is less than or equal to 60s; the total time of the extraction treatment process is 1-3 min.
10. The sample processing method for measuring a photoinitiator in a packaging material according to claim 1, wherein the photoinitiator is at least one of 2-hydroxy-2-methyl-1-phenylacetone, methyl benzoylformate, benzophenone, 2-methylbenzophenone, 1-hydroxycyclohexyl phenyl ketone, ethyl p-N, N-dimethylaminobenzoate, 3-methylbenzophenone, 4-methylbenzophenone, 2-dimethoxy-2-phenylacetophenone, methyl benzoylbenzoate, isooctyl p-dimethylaminobenzoate, 2-methyl-1- (4-methylthio) phenyl 2-morpholinyl-1-propanone, 4-isopropylthioxanthone, 2-isopropylthioxanthone, biphenylbenzophenone, 2, 4-diethylthioxanthone, 4-bis (dimethylamino) benzophenone, 4-bis (diethylamino) benzophenone;
preferably, the number of the photoinitiators is two or more, and more preferably 18.
11. The sample processing method for measuring photoinitiator in packaging material as recited in claim 1 wherein the packaging paper is a food packaging paper.
12. A method for measuring photoinitiator in packaging materials is characterized in that a solution to be measured is prepared by the method of any one of claims 1 to 11, the solution is centrifugally treated for 2min, and GC-MS measurement is carried out after a filter membrane is filtered.
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