CN106290589A - The assay method of antioxidant in macromolecule food contact material - Google Patents
The assay method of antioxidant in macromolecule food contact material Download PDFInfo
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- CN106290589A CN106290589A CN201510241375.1A CN201510241375A CN106290589A CN 106290589 A CN106290589 A CN 106290589A CN 201510241375 A CN201510241375 A CN 201510241375A CN 106290589 A CN106290589 A CN 106290589A
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Abstract
The invention discloses the assay method of antioxidant in a kind of macromolecule food contact material, comprise the following steps: () sample pre-treatments；() is treated sample measuring liquid and is used gas Chromatographic Determination；() draws standard curve and quantitatively；The mensuration of () sample size.The present invention uses antioxidant in gas chromatogram/ECD detection macromolecule food contact material, pre-treating method is simple, process is easy, detection limit is low, accuracy is high, result is accurately, reliably, favorable reproducibility, can be used for the detection of phenolic antioxidant in macromolecule food contact material, fill up the detection technique method blank of phenolic antioxidant in macromolecule food contact material at present, provide important technical support for food contact material quality control, safety detection, there is good economic and social profit.
Description
Technical field
The invention belongs to utilize chromatography analysis Material Field, be specifically related to the assay method of antioxidant in a kind of macromolecule food contact material.
Background technology
nullAntioxidant dibenzylatiooluene (butylated hydrosytoluene，BHT)、Butylated hydroxyanisole (butylated hydroxyanisole，BHA)、Tert-butylhydroquinone (tertiary butylhydroquinone，TBHQ) it is important universal phenol antioxidant，Can be as plastics、Rubber、Oil product、The excellent age resistor of the multiple materials such as oils and fats uses，Fade delaying macromolecular material、Yellowing、Hardening loss of gloss or transparent while，Promote material impact strength、Anti-flexing intensity、The physical property such as tensile strength and percentage elongation，But it is as chemosynthesis antioxidant，While promoting material capability，Equally exist the high risks to human body，The BHT in medical rubber plug is may result in such as the use in syringe、BHA flows directly into human vein along with medicinal liquid，It is detrimental to health，The exposure in short-term of BHT can cause human allergy to react，Feel sick、Vomiting、Dyspnea、Disorientation，Exposing for a long time or repeatedly may infringement human liver、Lung、The organs such as thyroid，And a certain amount of TBHQ takes in and can cause human body regurgitation、Tinnitus、Feel sick，Even can feel to suffocate and collapse.In current cosmetics, food and packaging material (such as plastics, rubber) thereof, the content of BHT, BHA is by strict control.
For in the detection research report of oxidation preventive content, predominantly detect object and include animal blood slurry, edible oil, jet fuel etc., relate to method and include gas chromatography/mass spectrometry, gas chromatogram/FID (flame ionization detector, flame ionization detector), high performance liquid chromatography/ultraviolet, liquid chromatograph/fluorescence method etc..Based on gas chromatography, FID is limited by detection limit, it is impossible to meet the requirement of low detection limit, and mass detector is high to sample requirement, pretreatment process complicated, limits antioxidant detection technique method based on gas chromatography.
Summary of the invention
The present invention is to overcome FID present in prior art can not meet low detection limit, the shortcomings such as mass detector is high to sample requirement, pretreatment process is complicated and propose, its objective is to provide the assay method of antioxidant in a kind of macromolecule food contact material.
The technical scheme is that
The assay method of antioxidant in a kind of macromolecule food contact material, described detection method comprises the following steps:
(I) sample pre-treatments
Being pulverized by macromolecule food contact material, then with extractant, it is carried out ultrasonic extraction, obtained extract carries out purified treatment, obtains treating sample measuring liquid；
(II) treating sample measuring liquid and use gas Chromatographic Determination, chromatographic determination condition is as follows:
(a) chromatographic column: HP-50+ capillary column；
(b) column temperature: initial 150 DEG C keep 1 min, with 10 DEG C/min ramp to 250 DEG C, keep 10 min；
(c) injector temperature: 230 DEG C；
(d) sample size: 1 μ L；
(e) carrier gas: high pure nitrogen；
(f) flow rate of carrier gas: 1.5 mL/min；
(g) split ratio: 20:1；
(h) detector: ECD
(i) detector temperature: 300 DEG C；
(j) auxiliary gas: high pure nitrogen；
(k) secondary air speed: 30 mL/min.
(III) standard curve and quantitatively is drawn
With extractant by antioxidant standard reserving solution stepwise dilution, obtain the hybrid standard working solution that concentration is 0.05,0.1,0.3,0.5,0.7,1.0 mg/L, by step (II) described chromatographic determination condition, measure according to concentration sample introduction from low to high, with peak area/concentration mapping, obtaining standard curve regression equation, equation is as follows:
Wherein: the content of antioxidant in W macromolecule food contact material, unit is mg/kg；C standard curve finds antioxidant concentration in sample liquid, and unit is mg/L；The final constant volume of V sample liquid, unit is mL；M weighs testing sample quality, and unit is kg；
(IV) mensuration of sample size
By step (II) described chromatographic determination condition, the antioxidant treated in sample measuring liquid by external standard method is measured, and goes out to treat the content of antioxidant in sample measuring liquid by standard curve regression equation calculation obtained by step (III).
Described in step (I), extractant is hexamethylene.
The time of ultrasonic extraction described in step (I) is 20min.
Described in step (I), the step of purified treatment is: extract is through filtration, rotary evaporation to about 2mL, nitrogen is blown near dry, with the dissolving of 1mL extractant hexamethylene, after 0.45 μm microporous filter membrane filtration, being transferred to constant volume in volumetric flask, constant volume solution is as treating sample measuring liquid.
Described in step (IV), antioxidant is one or more in BHT, BHA or TBHQ.
The invention has the beneficial effects as follows:
The present invention uses gas chromatogram/ECD(electron
Capture detector, electron capture detector) detect antioxidant in macromolecule food contact material, pre-treating method is simple, process is easy, detection limit is low, accuracy is high, result is accurately, reliably, favorable reproducibility, can be used for the detection of phenolic antioxidant in macromolecule food contact material, fill up the detection technique method blank of phenolic antioxidant in macromolecule food contact material at present, provide important technical support for food contact material quality control, safety detection, there is good economic and social profit.
Accompanying drawing explanation
Fig. 1 is to use detection method of the present invention to carry out BHT, BHA and TBHQ detecting gained gas chromatogram spectrogram.
Detailed description of the invention
Below in conjunction with Figure of description and embodiment, the assay method of antioxidant in macromolecule food contact material of the present invention is described in detail:
Embodiment 1(is as a example by antioxidant BHT, BHA, TBHQ)
The assay method of antioxidant in a kind of macromolecule food contact material, including herein below:
(1) reagent and material
(1.1) except as otherwise noted, agents useful for same is analytical pure, and water is secondary deionized water or heavily steams distilled water.
(1.2) extractant: chromatographically pure hexamethylene.
(1.3) BHT standard substance: purity is not less than 99%.
(1.4) BHA standard substance: purity is not less than 99%.
(1.5) TBHQ standard substance: purity is not less than 99%.
(2) configuration of standard reserving solution: the most accurately measure each 2.5mL of BHT, BHA and TBHQ standard solution of 200mg/L, it is transferred in 50mL volumetric flask, it is settled to scale with extractant hexamethylene, is configured to concentration and is the standard reserving solution of 10mg/L, preserve under the conditions of-5 DEG C.
(3) instrument and equipment
(3.1) gas chromatogram/ECD detector；
(3.2) supersonic generator；
(3.3) Rotary Evaporators；
(3.4) pulverizer
(3.5) analytical balance, sensibility reciprocal 0.001g
(3.6) microporous filter membrane, 0.45 μm, organic facies
(4) sample determination
(4.1) pre-treatment
Take macromolecule food contact material sample, after size-reduced machine is pulverized, accurately weigh 0.5g sample, be placed in 50mL tool plug conical flask, add 30mL hexamethylene ultrasonic extraction 20min, stand, filter, on a small quantity, repeatedly rinse filtering residue, merging filtrate with hexamethylene.Filtrate is rotated is evaporated to 2mL, is blown to nitrogen near dry, adds 1mL hexamethylene dissolved residue, and through 0.45 μm filtering with microporous membrane, constant volume is that 5mL is as treating sample measuring liquid.
(4.2) condition determination
A) chromatographic column: HP-50+ capillary column (30 × 0.53mm × 1 μm), or quite person；
B) column temperature: initial 150 DEG C keep 1 min, with 10 DEG C/min ramp to 250 DEG C, keep 10 min；
C) injector temperature: 230 DEG C；
D) sample size: 1 μ L；
(e) carrier gas: high pure nitrogen；
(f) flow rate of carrier gas: 1.5 mL/min；
(g) split ratio: 20:1；
(h) detector: ECD
(i) detector temperature: 300 DEG C；
(j) auxiliary gas: high pure nitrogen；
(k) secondary air speed: 30 mL/min.
(4.3) standard curve
With hexamethylene by antioxidant standard reserving solution stepwise dilution, obtain the hybrid standard working solution that concentration is 0.05,0.1,0.3,0.5,0.7,1.0 mg/L, by step (4.2) condition determination, measure according to concentration sample introduction from low to high, with peak area/concentration mapping, obtain standard curve regression equation；Under above-mentioned analysis condition, the chromatogram of each standard substance is as shown in Figure 1.
(4.4) measure
Treating sample measuring liquid according to the condition determination of (4.2) to be measured, retention time is qualitative, quantified by external standard method.Treat that the response value of antioxidant in sample measuring liquid in the standard curve range of linearity, should exceed sample introduction analysis again after the sample of the range of linearity then should dilute.
Measuring sample, standard working solution according to above-mentioned condition, in sample, chromatographic peak retention time is consistent with standard working solution, excursion ± 2.5%；Standard addition method chromatographic peak retention time keeps consistent, and excursion ± 2.5% then can determine whether to exist in sample antioxidant.
(4.5) blank assay
In addition to not weighing testing sample, all carry out by said determination condition and step.
(5) result calculates
In testing sample, antioxidant content calculates (result retains 2 position effective digitals, and should deduct blank value) by formula (1)
... ... ... ... ... ... ... ... ... ... ... (1)
In formula:
The content of antioxidant in W macromolecule food contact material, unit is milligrams per kilogram (mg/kg).
C standard curve finds antioxidant concentration in sample liquid, and unit is milligrams per liter (mg/L).
The final constant volume of V sample liquid, unit is milliliter (mL).
M weighs testing sample quality, and unit is kilogram (kg).
(6) detection limit
Assay method of the present invention is limited to 0.05mg/kg for the detection of dibenzylatiooluene (BHT), Butylated hydroxyanisole (BHA), and the detection of tert-butylhydroquinone (TBHQ) is limited to 0.08mg/kg
(7) response rate, precision
In the range of adding concentration 1.2 ~ 4.0mg/kg (each interpolation concentration parallel assay 6 times), 3 kinds of antioxidant BHTs, average recovery rate scopes of BHA, TBHQ are respectively 88% ~ 93%, 92% ~ 101%, 83% ~ 97%, relative standard deviation 2.01% ~ 2.89%, 2.11% ~ 3.19%, 2.99% ~ 4.02%, the results are shown in Table 1.
Table 1 response rate and Precision Experiment result
(8) method linear relationship
It is respectively configured series concentration standard working solution with BHT, BHA and TBHQ standard substance, it is measured under selected chromatographic condition, in standard concentration scope 0.05,0.1,0.3,0.5,0.7,1.0 mg/L, the linear equation of tri-kinds of antioxidant of BHT, BHA, TBHQ is respectively as follows: y=35120.3x+92.2, r=0.9994；Y=19214.5x-113.7, r=0.9997；Y=54539.9x-96.5, r=0.9992.
In sum, this detection method response rate, the every technology such as limit, precision that detect all meet the requirements, and are applied to macromolecule food contact material sample detection, and repeatability is good.The detection method that the present invention sets up is easy and simple to handle, result accurate, can be used for the detection of antioxidant in macromolecule food contact material.
It is above illustrating of the possible embodiments for the present invention, but this embodiment be not used to limit the scope of the claims of the present invention, all equivalences without departing from the present invention are implemented or change, are intended to be limited solely by the scope of the claims of the present invention.
Claims (5)
1. the assay method of antioxidant in a macromolecule food contact material, it is characterised in that: described detection method comprises the following steps:
(I) sample pre-treatments
Being pulverized by macromolecule food contact material, then with extractant, it is carried out ultrasonic extraction, obtained extract carries out purified treatment, obtains treating sample measuring liquid；
(II) treating sample measuring liquid and use gas Chromatographic Determination, chromatographic determination condition is as follows:
(a) chromatographic column: HP-50+ capillary column；
(b) column temperature: initial 150 DEG C keep 1 min, with 10 DEG C/min ramp to 250 DEG C, keep 10 min；
(c) injector temperature: 230 DEG C；
(d) sample size: 1 μ L；
(e) carrier gas: high pure nitrogen；
(f) flow rate of carrier gas: 1.5 mL/min；
(g) split ratio: 20:1；
(h) detector: ECD
(i) detector temperature: 300 DEG C；
(j) auxiliary gas: high pure nitrogen；
(k) secondary air speed: 30 mL/min；
(III) standard curve and quantitatively is drawn
With extractant by antioxidant standard reserving solution stepwise dilution, obtain the hybrid standard working solution that concentration is 0.05,0.1,0.3,0.5,0.7,1.0 mg/L, by step (II) described chromatographic determination condition, measure according to concentration sample introduction from low to high, with peak area/concentration mapping, obtaining standard curve regression equation, equation is as follows:
Wherein: the content of antioxidant in W macromolecule food contact material, unit is mg/kg；C standard curve finds antioxidant concentration in sample liquid, and unit is mg/L；The final constant volume of V sample liquid, unit is mL；M weighs testing sample quality, and unit is kg；
(IV) mensuration of sample size
By step (II) described chromatographic determination condition, the antioxidant treated in sample measuring liquid by external standard method is measured, and goes out to treat the content of antioxidant in sample measuring liquid by standard curve regression equation calculation obtained by step (III).
The assay method of antioxidant in a kind of macromolecule food contact material the most according to claim 1, it is characterised in that: described in step (I), extractant is hexamethylene.
The assay method of antioxidant in a kind of macromolecule food contact material the most according to claim 1, it is characterised in that: the time of ultrasonic extraction described in step (I) is 20min.
The assay method of antioxidant in a kind of macromolecule food contact material the most according to claim 1, it is characterized in that: described in step (I), the step of purified treatment is: extract is through filtration, rotary evaporation to about 2mL, nitrogen is blown near dry, dissolve with 1mL extractant hexamethylene, after 0.45 μm microporous filter membrane filtration, being transferred to constant volume in volumetric flask, constant volume solution is as treating sample measuring liquid.
The assay method of antioxidant in a kind of macromolecule food contact material the most according to claim 1, it is characterised in that: described in step (IV), antioxidant is one or more in BHT, BHA or TBHQ.
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| CN109061014A (en) * | 2018-10-29 | 2018-12-21 | 上海金发科技发展有限公司 | Irgasfos 168 and its oxide content survey method and application in a kind of resin combination |
| CN115015421A (en) * | 2022-06-02 | 2022-09-06 | 深圳海关工业品检测技术中心 | Method for rapidly determining additive in food contact material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106770801A (en) * | 2017-02-21 | 2017-05-31 | 福建出入境检验检疫局检验检疫技术中心 | Gas chromatography determines 5 kinds of methods of antioxidant migration amount in packaging material |
| CN109061014A (en) * | 2018-10-29 | 2018-12-21 | 上海金发科技发展有限公司 | Irgasfos 168 and its oxide content survey method and application in a kind of resin combination |
| CN115015421A (en) * | 2022-06-02 | 2022-09-06 | 深圳海关工业品检测技术中心 | Method for rapidly determining additive in food contact material |
| CN115015421B (en) * | 2022-06-02 | 2024-04-26 | 深圳海关工业品检测技术中心 | Method for rapidly determining additive in food contact material |
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