CN102944637A - Method for determining hexabromocyclododecane in plastic - Google Patents
Method for determining hexabromocyclododecane in plastic Download PDFInfo
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- CN102944637A CN102944637A CN2012104602203A CN201210460220A CN102944637A CN 102944637 A CN102944637 A CN 102944637A CN 2012104602203 A CN2012104602203 A CN 2012104602203A CN 201210460220 A CN201210460220 A CN 201210460220A CN 102944637 A CN102944637 A CN 102944637A
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Abstract
The invention provides a method for determining hexabromocyclododecane in plastic, which comprises the following steps of: A) preparing hexabromocyclododecane standard stock solution with mass concentration being 1000mg/L; B) preparing hexabromocyclododecane solutions with mass concentration being 10mg/L, 20mg/L, 50mg/L and 100mg/L respectively by diluting the standard stock solution; C) respectively determining chromatograms of the hexabromocyclododecane solutions prepared in the step B by using a gas chromatograph-mass spectrometer; D) drawing standard curves according to the chromatograms to obtain a standard function relationship; E) preparing to-be-determined solution of a to-be-determined plastic sample; F) determining the chromatogram of the to-be-determined solution; and G) calculating the concentration of the hexabromocyclododecane in the to-be-determined solution according to the chromatogram, so as to calculate the content of the hexabromocyclododecane in the plastic sample. By determining the content of the hexabromocyclododecane in plastic through gas chromatography-mass spectrometry, the method provided by the invention has the advantages of low determination limit, high sensitivity and rapid determining speed.
Description
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Technical field
The present invention relates to the detection field of poisonous and harmful substance, particularly relate to the detection method of hexabromo-Cyclododecane content in a kind of plastics.
Background technology
Hexabromo-Cyclododecane is called for short HBCD or HBCDD, molecular weight 642, white crystals.Good to heat and ultraviolet light stability.Bromine content 74.7% is dissolved in methyl alcohol, ethanol, acetone, amyl acetate.Beginning dehydrobromination more than 170 ℃, becoming violent at 190 ℃ of dehydrobrominations.Hexabromo-Cyclododecane is mainly used in the fire-retardant of acrylic plastering and fiber, polystyrene foam, also can be used for the fire-retardant of dacron flame-retardant after-finishing and the two-sided leather of polyvinyl plastic-coated.As additive flame retardant, be applicable to polystyrene, unsaturated polyester (UP), polycarbonate, polypropylene, synthetic rubber etc.For the production of macromolecular materials such as polycarbonate (PC), epoxy resin, polysulfone resin, polyphenylene oxide resins.Although hexabromo-Cyclododecane (HBCD) has good flame retardant effect, it can consist of potential long-term harm to human and environment, causes easily harm substantive and that be difficult to reverse.Become violent at hexabromo-Cyclododecane dehydrobromination more than 190 ℃ in addition.The harm meeting of hydrogen bromide steam is more remarkable.Can produce poisonous and hazardous smog during as fire retardant.Hexabromo-Cyclododecane (HBCD) belongs to the material of Norway PoHS management and control, belongs to the REACH of European Union management and control material, is put into simultaneously ROHS2.0 restrictive substance candidate list.Therefore, detect the content that contains hexabromo-Cyclododecane in the hexabromo-Cyclododecane goods and become the effective means that its standard of control is used.
At present, there is no unified efficient method the hexabromo-Cyclododecane content in the plastics is detected, therefore, how fast, efficiently, at low cost the detection of carrying out hexabromo-Cyclododecane content in the plastics becomes poisonous and harmful substance and detects the industry problem demanding prompt solution.
Summary of the invention
For solve there is no in the prior art unified efficient method to the hexabromo-Cyclododecane content in the plastics carry out fast, the problem of efficient, low-cost detection, the invention provides following technical scheme:
Hexabromo-Cyclododecane assay method in a kind of plastics may further comprise the steps:
A, take by weighing the hexabromo-Cyclododecane standard items, with acetone+normal hexane (1:1) dissolving and constant volume, making mass concentration is the hexabromo-Cyclododecane standard reserving solution of 1000mg/L;
B, get the hexabromo-Cyclododecane standard reserving solution, using respectively acetone+normal hexane (1:1) dilution is the hexabromo-Cyclododecane solution of 10mg/L, 20mg/L, 50mg/L, 100mg/L;
C, use Gc/ms Analyser to measure respectively concentration to be the chromatogram of the hexabromo-Cyclododecane solution of 10mg/L, 20mg/L, 50mg/L, 100mg/L;
D, respectively take hexabromo-Cyclododecane concentration as horizontal ordinate, the 3rd peak area on the chromatogram is drawn and is obtained typical curve as ordinate, draws the canonical function relation;
E, take by weighing plastic sample to be measured and make certain density liquid to be measured;
F, use Gc/ms Analyser are measured the chromatogram of liquid to be measured;
The area at chromatogram the 3rd peak that G, basis are measured calculates the concentration of plastic sample solution hexabromo-Cyclododecane to be measured, thereby calculates the content of hexabromo-Cyclododecane in the plastic sample.
As a preferred embodiment of the present invention, the parameter of Gc/ms Analyser is set in described step C and the step F:
Capillary chromatographic column: DB-5MS 0.25mm * 30m * 0.15m;
Injector temperature: 290 ℃;
Carrier gas: helium, helium purity 〉=99.999%;
Post flow: 1.8ml/min;
Column temperature: 100 ℃ keep 2min, are increased to 320 ℃ with the speed of 25 ℃/min, and keep 3.5min;
Mass spectrometer interface temperature: 250 ℃;
Scanning of the mass spectrum mode: selectivity ionic means;
The monitoring ion is: m/z157,401,561;
Input mode: Splitless injecting samples;
Sample size: 1ul;
Ionization mode: EI, 70eV.
The present invention has the following advantages: the inventive method detects the hexabromo-Cyclododecane content in the plastics by combined gas chromatography mass spectrometry, its detectability is low, and is highly sensitive, and detection speed is fast, can carry out qualitative, quantitative detection to hexabromo-Cyclododecane in the sample exactly, be suitable for standardization.
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Description of drawings
The chromatogram of Fig. 1 the inventive method Gc/ms Analyser;
The standard model curve map that Fig. 2 the inventive method obtains;
Embodiment
The below elaborates this process implementing example, thereby so that advantages and features of the invention can be easier to be it will be appreciated by those skilled in the art that protection scope of the present invention is made more explicit defining.
Present embodiment is measured the hexabromo-Cyclododecane content in certain plastic product, and concrete operation step is as follows:
A, take by weighing hexabromo-Cyclododecane standard items 100mg, dissolve and be settled to 100mL with acetone+normal hexane (1:1), making mass concentration is the hexabromo-Cyclododecane standard reserving solution of 1000mg/L;
B, get the hexabromo-Cyclododecane standard reserving solution, using respectively acetone+normal hexane (1:1) dilution is the hexabromo-Cyclododecane solution of 10mg/L, 20mg/L, 50mg/L, 100mg/L;
C, use Gc/ms Analyser to measure respectively concentration to be the chromatogram of the hexabromo-Cyclododecane solution of 10mg/L, 20mg/L, 50mg/L, 100mg/L, chromatogram as shown in Figure 1, the parameter of Gc/ms Analyser is set to:
Capillary chromatographic column: DB-5MS 0.25mm * 30m * 0.15m;
Injector temperature: 290 ℃;
Carrier gas: helium, helium purity 〉=99.999%;
Post flow: 1.8ml/min;
Column temperature: 100 ℃ keep 2min, are increased to 320 ℃ with the speed of 25 ℃/min, and keep 3.5min;
Mass spectrometer interface temperature: 250 ℃;
Scanning of the mass spectrum mode: selectivity ionic means;
The monitoring ion is: m/z157,401,561;
Input mode: Splitless injecting samples;
Sample size: 1ul;
Ionization mode: EI, 70eV;
D, respectively take hexabromo-Cyclododecane concentration as horizontal ordinate, the 3rd peak area on the chromatogram is drawn and is obtained typical curve as ordinate, as shown in Figure 2, draws the canonical function relation: y=915998x-6.80939 * 10
6
, related coefficient is R
2
=0.9990;
E, take by weighing the plastic sample to be measured of three parts of 0.5000mg, be respectively Duplicate Samples 1, Duplicate Samples 2 and Duplicate Samples 3, ultrasonic oscillation 1h under 40 ℃ of water bath condition adopts the filter membrane of 0.45um to filter, and obtains plastic sample liquid to be measured after the filtration;
F, use Gc/ms Analyser are measured respectively the chromatogram of plastic sample liquid to be measured, and the Gc/ms Analyser parameter arranges with step B;
G, calculate the concentration of plastic sample solution hexabromo-Cyclododecane to be measured according to the area at chromatogram the 3rd peak measured, result of calculation such as table 1, thus calculate the content of hexabromo-Cyclododecane in the plastic sample,
The content of hexabromo-Cyclododecane in table 1 plastics
U is to Duplicate Samples 1 replication 6 times, and measurement result sees Table 2, and the relative standard deviation of replication is 2.92%, shows that the inventive method testing result has very high precision.
Table 2 sample 1 replication result
| Numbering | 1 | 2 | 3 | 4 | 5 | 6 | Mean value | RSD（%） |
| Hexabromo-Cyclododecane (mg/kg) | 6.21 | 6.01 | 6.43 | 6.35 | 6.18 | 6.51 | 6.28 | 2.92% |
Can find out that from the testing result of present embodiment the detectability that the inventive method detects hexabromo-Cyclododecane in the plastics is low, highly sensitive, and the integrated operation step is simple, easy to implement.
The above; it only is one of the specific embodiment of the present invention; but protection scope of the present invention is not limited to this; any those of ordinary skill in the art are in the disclosed technical scope of the present invention; variation or the replacement that can expect without creative work all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain that claims were limited.
Claims (2)
1. hexabromo-Cyclododecane assay method in the plastics, it is characterized in that: the method may further comprise the steps:
A, take by weighing the hexabromo-Cyclododecane standard items, with acetone+normal hexane (1:1) dissolving and constant volume, making mass concentration is the hexabromo-Cyclododecane standard reserving solution of 1000mg/L;
B, get four parts of hexabromo-Cyclododecane standard reserving solutions, using respectively acetone+normal hexane (1:1) dilution is the hexabromo-Cyclododecane solution of 10mg/L, 20mg/L, 50mg/L, 100mg/L;
C, use Gc/ms Analyser to measure respectively concentration to be the chromatogram of the hexabromo-Cyclododecane solution of 10mg/L, 20mg/L, 50mg/L, 100mg/L;
D, respectively take hexabromo-Cyclododecane concentration as horizontal ordinate, the 3rd peak area on the chromatogram is drawn and is obtained typical curve as ordinate, draws the canonical function relation;
E, take by weighing plastic sample to be measured and make certain density liquid to be measured;
F, use Gc/ms Analyser are measured the chromatogram of liquid to be measured;
The area at chromatogram the 3rd peak that G, basis are measured calculates the concentration of plastic sample solution hexabromo-Cyclododecane to be measured, thereby calculates the content of hexabromo-Cyclododecane in the plastic sample.
2. hexabromo-Cyclododecane assay method in the plastics according to claim 1, it is characterized in that: the parameter of Gc/ms Analyser is set in described step C and the step F:
Capillary chromatographic column: DB-5MS 0.25mm * 30m * 0.15m;
Injector temperature: 290 ℃;
Carrier gas: helium, helium purity 〉=99.999%;
Post flow: 1.8ml/min;
Column temperature: 100 ℃ keep 2min, are increased to 320 ℃ with the speed of 25 ℃/min, and keep 3.5min;
Mass spectrometer interface temperature: 250 ℃;
Scanning of the mass spectrum mode: selectivity ionic means;
The monitoring ion is: m/z157,401,561;
Input mode: Splitless injecting samples;
Sample size: 1ul;
Ionization mode: EI, 70eV.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115015230A (en) * | 2022-02-22 | 2022-09-06 | 中国科学院生态环境研究中心 | Rapid detection method and device for hexabromocyclododecane content in EPS/XPS |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115015230A (en) * | 2022-02-22 | 2022-09-06 | 中国科学院生态环境研究中心 | Rapid detection method and device for hexabromocyclododecane content in EPS/XPS |
| CN115015230B (en) * | 2022-02-22 | 2024-03-01 | 中国科学院生态环境研究中心 | Rapid detection method and device for hexabromocyclododecane content in EPS/XPS |
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