CN102288715B - Method for detecting mirex content of rubber part of electronic/electric product - Google Patents
Method for detecting mirex content of rubber part of electronic/electric product Download PDFInfo
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Abstract
The invention discloses a method for detecting the mirex content of a rubber part of an electronic/electric product. The method comprises the following steps of: (1) preparing a sample; (2) extracting mirex: adding a smashed rubber sample into heavy metal powder, mixing uniformly, and putting into an accelerated agent extraction pond for performing accelerated solvent extraction to obtain an extracting solution; (3) purifying the extracting solution : adding an internal standard into the extracting solution, performing solid phase extraction colonnette adsorption and purification, eluting with a mixed solvent, collecting eluent and concentrating to obtain a purified extraction solution; and (4) measuring the mirex: measuring the purified extraction solution and a mirex mixed standard solution containing the internal standard with a gas phase chromatograph, acquiring a signal with an electronic capture detector, and performing data processing and quantitative analysis to obtain the content of the mirex. The method has the advantages of capability of effectively removing interference impurities from rubber, full extraction of the mirex, high purifying degree, high detection sensitivity and low sample measuring cost.
Description
Technical field
The present invention relates to a kind of detection method of mirex content, be specifically related to the detection method of mirex content in a kind of electronic and electrical equipment rubber components.
Background technology
Along with various countries more and more pay attention to various safe, health and environmental issue that in industry and the consumer goods, poisonous and harmful substance causes, the various measures of control that western developed country proposes are more and more, also more and more severeer, this export trade for China has formed powerful Green Trade Barrier.(formal name used at school ten dichloro-octahydro-methylene-ring fourths are [cd] pentalene also, has another name called mirex for mirex.Molecular formula is C
10cl
12molecular weight 545.6, CAS is encoded to 2385-85-5) be exactly a kind of environment management and control material wherein, it is a kind of very stable and persistent efficient pesticides, half life period reaches 10 years, and water insoluble, is not subject to current and rinses and run off, the specific drug of Zeng Zuowei control termites is widely used, in electronic and electrical equipment for buried end cable and the parts of electric product; In addition, it is also used to the fire proofing material of electric product as a kind of efficient flame-retarding agent.But more and more research shows, mirex can affect the immune system of human body, is a kind of suspicious carcinogenic substance, and can in environment, has considerable time, by biologic chain enrichment, affects health, is a kind of persistence organic pollutant.Most of developed country starts to forbid successively mirex in the later stage eighties in last century, the former economic and commercial committee of China has also signed the Convention of Stockholm > > of < < about persistence organic pollutant (POPs) May 23 calendar year 2001, has wherein just stipulated comprehensively eliminating mirex.But owing to affected by traditional concept, and the low cost of mirex, still have part unit that mirex is used as to the fire retardant of electric product and the anti-termite agent of buried electric product and parts.On April 16th, 2009, Chinese Ministry of Environmental Protection, National Development and Reform Committee, Ministry of Industry and Information, the Zhu Jianbu, Ministry of Agriculture, Department of Commerce, the Ministry of Public Health, General Customs Administration, State Administration of Quality Supervision, Inspection and Quarantine, Deng10 department of Administration of Work Safety Supervision issue jointly about forbidding producing, circulate, use and importing and exporting No. 23 bulletin of D.D.T. (dichloro-diphenyl-trichloroethane), Niran, mirex and hexachloro-benzene, requirement, from 17 days Mays in 2009, is completely forbidden and in China, is produced, circulates, uses and import and export mirex within the border.Although mirex has expressly been forbidden producing and used, the plastics of electronic and electrical equipment and rubber components have quite a few to take waste or used plastics and rubber as Raw material processing forms at present, therefore wherein still can detect mirex composition.
At present, for the detection set of mirex, to materials such as soil and water environment, biosome, plastics, and these detection meanss mostly are gas chromatography-mass spectrography, if will obtain the testing result of trace level mirex, need to use expensive isotopic label; Completely there are no report, because rubber is difficult to organic solvent dissolution, wherein many containing chaff interference for the assay method of mirex in elastomeric material, be difficult to carry out qualitative and quantitative analysis accurately.
Summary of the invention
The detection method that the object of the present invention is to provide a kind of electronic and electrical equipment rubber components mirex content, the method can effectively be removed the interference impurity in rubber, and mirex extracts fully, and degree of purification is high, and detection sensitivity is high, and test sample cost is low.
This detection method be take quality of rubber materials as matrix, by accelerated solvent extraction, mirex is extracted fully, can effectively remove the interference impurity in rubber sample again simultaneously, and adopt solid phase pillar to purify to the extract that accelerated solvent extraction is followed the example of acquisition, further remove the impurity in rubber sample, thereby obtain the method for trace mirex content in low-cost, highly sensitive gas chromatography-electron capture monitor test electronic and electrical equipment rubber components.
In the prior art, accelerated solvent extraction is a kind of effective extractive technique, object effectively can be extracted from matrix.But because rubber has passed through sulfidation in process of production conventionally, sulphur has played crosslinked action in the molecular structure of rubber, make to have formed fine and close spatial structure between rubber macromolecule, general organic solvent molecule is difficult to penetrate in rubber matrix.Therefore, utilizing inorganic heavy metal to spin off from rubber by sulphur becomes very crucial factor, can make like this object fully by organic solvent, be extracted, and also can when sample detection, avoid being subject to the interference of sulfocompound.
Because common Sample Pretreatment Technique is not enough to various interference Impurity removals in rubber clean, therefore must use expensive gas chromatograph-mass spectrometer (GCMS) analyzes mensuration, and need to use the interior mark of expensive isotopic label work can accurate quantitative analysis simultaneously.But in mirex molecular structure, contain the chlorine atom that electronegativity is very strong, on electron capture detector, can obtain very high sensitivity, also have very strong selectivity.As long as sample pretreatment process can fully be removed the interference impurity in rubber totally, on conventional gas chromatograph, also can obtain splendid sensitivity so.
Above-mentioned purpose of the present invention is achieved by the following technical solution: the detection method of mirex content in a kind of electric rubber components, comprises the following steps:
(1) sample preparation: will mix after electric rubber sample fragmentation, obtain the sample of homogeneous;
(2) mirex extracts: in the sample obtaining in step (1), add heavy metal powder, put into accelerated solvent extraction pond and utilize organic solvent to carry out accelerated solvent extraction to the mirex of sample after mixing, after fully extracting, obtain extract;
(3) extract purifies: in the extract obtaining in step (2), add interior mark, after mixing, extract is transferred on solid phase extraction column completely, then with mixed solvent, carry out wash-out, collect eluent and concentrate the extract after being purified;
(4) mensuration of mirex: the mirex mixed standard solution that first preparation contains interior mark Octachloronaphthalene, then gas chromatograph on extract after the purification obtaining in step (3) and the mirex mixed standard solution that contains interior mark Octachloronaphthalene solution is measured, use electron capture detector collection signal, with chem workstation, carry out after data processing and quantitative test the content of mirex in the electric rubber components of electron gain.
Wherein: in above-mentioned steps:
In step of the present invention (1), electric rubber sample is carried out to freezing crushing to its maximum particle diameter and be less than 0.5mm.
In step of the present invention (2), heavy metal powder is copper powder, silver powder or lead powder, and its consumption is 0.1-1.0 times of rubber sample weight.
First activated processing before described heavy metal is used, wherein the reactivation process of copper powder is: the mass volume ratio by copper powder and acetone-concentrated hydrochloric acid mixed solution is 1g:5-7mL, in heavy metal powder, add acetone-concentrated hydrochloric acid mixed solution, wherein the volume ratio of acetone and concentrated hydrochloric acid is 1:1, starts magnetic stirring apparatus vigorous stirring 5-15min, then uses sand core funnel suction filtration, so repeat 1 time, then be washed with water to neutrality, then with acetone and absolute ether, wash successively respectively, drain; Wherein the reactivation process of silver powder or lead powder is: the mass volume ratio by silver powder or lead powder and acetone-nitric acid mixed solution is 1g:5-7mL, in heavy metal powder, add acetone-nitric acid mixed solution, wherein the volume ratio of acetone and nitric acid is 1:1, start magnetic stirring apparatus vigorous stirring 5min, use again sand core funnel suction filtration, so repeat 1 time, be then washed with water to neutrality, with acetone and absolute ether, wash successively respectively again, drain.
In step of the present invention (2) in the rubber sample of pulverizing except adding heavy metal powder, also add and have drying agent, described drying agent is anhydrous sodium sulfate, its consumption for the 0.1-0.5 for rubber sample weight doubly.
Organic solvent described in step of the present invention (2) is normal hexane-isopropyl alcohol, and the volume ratio of the two is 1:0.5-2, and its consumption is 10-20mL solvent/every gram of rubber sample.
The extraction temperature that adopts accelerated solvent extraction to follow the example of when the mirex in sample is fully extracted in step of the present invention (2) is 80-150 ℃, and extracting pressure is 100-150bar, quiet cycle extraction 3-5 time, and extraction time is 10-60min
In step of the present invention (3), solid phase extraction column is C
18solid phase extraction column, aluminium oxide solid phase extraction column, silica gel solid phase extraction column or sulfonic group solid phase extraction column.
Solid phase extraction column of the present invention first washs activation with extraction solvent before using.
Mixed solvent described in step of the present invention (3) is normal hexane-isopropyl alcohol, and its volume ratio is 1:0.5-3.
In adopting in step of the present invention (3)-step (4), be designated as Octachloronaphthalene solution.
The present invention has the following advantages:
(1) through simple sample pre-treatments, mirex in rubber is extracted fully, and effectively removed the interfering material in rubber matrix, be convenient to the mirex in rubber to carry out Accurate Determining, be also conducive to protect the injection port-chromatographic column-detecting device of gas chromatograph instrument few contaminated;
(2) method is sensitive, and detectability is low, without using expensive gas chromatograph-mass spectrometer (GCMS) and isotope labeling standard items, can carry out trace analysis to the mirex in electronic and electrical equipment rubber components.
Accompanying drawing explanation
Fig. 1 is the overhaul flow chart of mirex in electronic and electrical equipment rubber components of the present invention;
Fig. 2 is the gas chromatogram of standard operation solution, 1 chromatographic peak that represents mirex in figure, the chromatographic peak of mark (Octachloronaphthalene) in 2 representatives;
Fig. 3 is the gas chromatogram of buried cable nitrile rubber protective sleeve sample solution in embodiment 1,1 chromatographic peak that represents mirex in figure, the chromatographic peak of mark (Octachloronaphthalene) in 2 representatives;
Fig. 4 is the gas chromatogram of neoprene insulating trip sample solution in embodiment 2,1 chromatographic peak that represents mirex in figure, the chromatographic peak of mark (Octachloronaphthalene) in 2 representatives.
Fig. 5 is the gas chromatogram of embodiment 3 EP rubbers water proof ring sample solutions, 1 chromatographic peak that represents mirex in figure, the chromatographic peak of mark (Octachloronaphthalene) in 2 representatives.
Embodiment
embodiment 1
The detection method of mirex in the buried cable nitrile rubber protective sleeve that the present embodiment provides, as shown in Figure 1, mainly comprises the following steps:
(1) preparation of sample
Buried cable nitrile rubber protective sleeve sample freezing crushing to maximum particle diameter is less than to 0.5mm, mixes, obtain the sample of homogeneous;
(2) extraction of mirex
In abstraction pool bottom, put into 0.5g anhydrous sodium sulfate, take the about 1g of the sample crushing (being accurate to 0.1mg), copper powder after adding 0.5g activated, after stirring, with filter paper, wrap and put into abstraction pool, its complementary space of abstraction pool is filled and led up with zeyssatite, put on accelerated solvent extraction, with normal hexane-isopropyl alcohol (1:1, v/v) for solvent carries out accelerated solvent extraction, setting solvent consumption 20mL, extraction temperature is 110 ℃, extracting pressure is 150bar, static extracting pattern, cycle index 3 times, each extraction 10min, after having extracted, with Rotary Evaporators, extract is concentrated into about 2-3mL.
The activation of copper powder: 5g copper powder is placed in to the ground conical flask that 100mL is dry, adds acetone-concentrated hydrochloric acid (1:1, v/v, wherein concentrated hydrochloric acid is commercially available, massfraction is approximately 37%) mixed solution 30mL, starts magnetic stirring apparatus vigorous stirring 10 min, then uses sand core funnel suction filtration.Repeat so more once (this time vigorous stirring 5 min), be then washed with water to cleansing solution and be neutral, then with acetone, absolute ether, wash successively respectively, drain.
(3) purification of extract
Use in advance 5mL normal hexane-isopropyl alcohol (1:1, v/v) washing C
18solid phase extraction column, discards cleansing solution, then in the extract that step (2) obtains, add concentration be the Octachloronaphthalene solution 1mL of 1 μ g/mL as interior mark, after mixing, will contain target extract in Octachloronaphthalene and be transferred to C completely
18on solid phase extraction column, then use normal hexane-isopropyl alcohol (1:2, v/v) mixed solvent to carry out wash-out, collect eluent, parallel evaporation and concentration is to 1mL.
(4) preparation of standard operation solution
In 25mL volumetric flask, take 25mg mirex standard items, with n-hexane dissolution constant volume, being mixed with concentration is the standard stock solution of 1000mg/L.
In 50mL volumetric flask, take 10mg Octachloronaphthalene standard items, with n-hexane dissolution constant volume, being mixed with concentration is the interior mark stock solution of 200mg/L.
Get appropriate standard stock solution and interior mark stock solution is used respectively normal hexane stepwise dilution, be mixed with and include mark in Octachloronaphthalene and be that 0.1 μ g/mL and mirex concentration are respectively 0.01,0.05,0.1,0.5, the standard operation solution series of 1mg/L.
(5) mensuration of mirex
By the standard operation solution of extract after the purification obtaining in step (3) and step (4) preparation, respectively getting gas chromatograph on 1 μ L measures, use electron capture detector collection signal, with chem workstation, carry out data processing, drawing standard curve, by internal standard method, carry out quantitative test, the content of mirex in the electric rubber components of electron gain.
Gas chromatographic detection condition is: Agilent 6890N gas chromatograph.Chromatographic column: HP-5 capillary column; Column temperature: 100 ℃ of initial temperatures, keep 2min; With 10 ℃/min speed, rise to 300 ℃, keep 10min; Injector temperature: 280 ℃, Splitless injecting samples 1 μ L.Carrier gas: nitrogen, flow: 1mL/min.Detector temperature: 300 ℃, make-up gas nitrogen flow: 60mL/min.
The gas chromatogram of standard solution is shown in Figure of description 2, and the gas chromatogram of sample solution is shown in Figure of description 3.
(6) precision-replica test of test
Sample is carried out to 8 parallel sample tests, and testing result is in Table 1.
8 replicate determination experimental results of mirex in table 1 pair buried cable nitrile rubber protective sleeve
As can be seen from Table 1, the relative standard deviation of 8 replicate determinations is 2.26%, shows that the precision of measurement result meets related request.
Recording mirex content in this nitrile rubber protective sleeve sample is 66.3mg/kg.
(7) accuracy-mark-on recovery test of test
The mark-on recovery test that sample is carried out to varying level, its result is as follows:
Table 2 pair buried cable nitrile rubber protective sleeve sample solution carries out mark-on recovery test result
As can be seen from Table 2, the recovery of standard addition of varying level, between 88.0-106%, shows that the accuracy of measurement result meets the demands.
embodiment 2
The detection method of mirex in the neoprene insulating trip that the present embodiment provides, as shown in Figure 1, mainly comprises the following steps:
(1) preparation of sample
Neoprene insulating trip sample freezing crushing to maximum particle diameter is less than to 0.5mm, mixes, obtain the sample of homogeneous;
(2) extraction of mirex
In abstraction pool bottom, put into 0.3g anhydrous sodium sulfate, take the about 1g of the sample crushing (being accurate to 0.1mg), lead powder after adding 0.3g activated, after stirring, with filter paper, wrap and put into abstraction pool, its complementary space of abstraction pool is filled and led up with zeyssatite, put on accelerated solvent extraction, with normal hexane-isopropyl alcohol (2:3, v/v) for solvent carries out accelerated solvent extraction, setting solvent consumption 10mL, extraction temperature is 80 ℃, extracting pressure is 100bar, static extracting pattern, cycle index 5 times, each extraction 60min, after having extracted, with Rotary Evaporators, extract is concentrated into about 2-3mL.
The activation of lead powder: 5g lead powder is placed in to the ground conical flask that 100mL is dry, adds acetone and (1+1) mixed solution of nitric acid (the two volume ratio is 1:1) 30mL, start magnetic stirring apparatus vigorous stirring 5min, then use sand core funnel suction filtration.Repeat so more once, be then washed with water to cleansing solution and be neutral, then with acetone, absolute ether, wash successively respectively, drain.
Wherein (1+1) nitric acid is approximately 68% red fuming nitric acid (RFNA) by 1 volume water and 1 volume mass mark and mixes.
(3) purification of extract
Use in advance 5mL normal hexane-isopropyl alcohol (2:3, v/v) washing aluminium oxide solid phase extraction column, discard cleansing solution, then in the extract that step (2) obtains, adding concentration is that the Octachloronaphthalene solution 1mL of 1 μ g/mL is as interior mark, after mixing, will contain target extract in Octachloronaphthalene and be transferred to completely on aluminium oxide solid phase extraction column, and then use normal hexane-isopropyl alcohol (1:2, v/v) mixed solvent to carry out wash-out, collect eluent, parallel evaporation and concentration is to 1mL.
(4) preparation of standard operation solution
In 25mL volumetric flask, take 25mg mirex standard items, with n-hexane dissolution constant volume, being mixed with concentration is the standard stock solution of 1000mg/L.
In 50mL volumetric flask, take 10mg Octachloronaphthalene standard items, with n-hexane dissolution constant volume, being mixed with concentration is the interior mark stock solution of 200mg/L.
Get appropriate standard stock solution and interior mark stock solution is used respectively normal hexane stepwise dilution, be mixed with and include mark in Octachloronaphthalene and be that 0.1 μ g/mL and mirex concentration are respectively 0.01,0.05,0.1,0.5, the standard operation solution series of 1mg/L.
(5) mensuration of mirex
By the standard operation solution of extract after the purification obtaining in step (3) and step (4) preparation, respectively getting gas chromatograph on 1 μ L measures, use electron capture detector collection signal, with chem workstation, carry out data processing, drawing standard curve, by internal standard method, carry out quantitative test, the content of mirex in the electric rubber components of electron gain.
Gas chromatographic detection condition is: Agilent 6890N gas chromatograph.Chromatographic column: HP-5 capillary column; Column temperature: 100 ℃ of initial temperatures, keep 2min; With 10 ℃/min speed, rise to 300 ℃, keep 10min; Injector temperature: 280 ℃, Splitless injecting samples 1 μ L.Carrier gas: nitrogen, flow: 1mL/min.Detector temperature: 300 ℃, make-up gas nitrogen flow: 60mL/min.
The gas chromatogram of standard solution is shown in Figure of description 2, and the gas chromatogram of sample solution is shown in Figure of description 4.
(6) precision-replica test of test
Sample is carried out to 8 parallel sample tests, and testing result is in Table 3.
8 replicate determination experimental results of mirex in table 3 pair neoprene insulating trip
As can be seen from Table 3, the relative standard deviation of 8 replicate determinations is 2.15%, shows that the precision of measurement result meets related request.
Recording mirex content in this sample is 0.555mg/kg.
(7) accuracy---the mark-on recovery test of test
The mark-on recovery test that sample is carried out to varying level, its result is as follows:
Table 4 pair neoprene insulating trip sample solution carries out mark-on recovery test result
As can be seen from Table 4, the recovery of standard addition of varying level, between 87.5%-91.8%, shows that the accuracy of measurement result meets the demands.
embodiment 3
The detection method of mirex in the EP rubbers water proof ring that the present embodiment provides, as shown in Figure 1, mainly comprises the following steps:
(1) preparation of sample
EP rubbers water proof ring sample freezing crushing to maximum particle diameter is less than to 0.5mm, mixes, obtain the sample of homogeneous;
(2) extraction of mirex
In abstraction pool bottom, put into 0.1g anhydrous sodium sulfate, take the about 1g of the sample crushing (being accurate to 0.1mg), silver powder after adding 0.8 g activated, after stirring, with filter paper, wrap and put into abstraction pool, its complementary space of abstraction pool is filled and led up with zeyssatite, put on accelerated solvent extraction, with normal hexane-isopropyl alcohol (3:2, v/v) for solvent carries out accelerated solvent extraction, setting solvent consumption 15mL, extraction temperature is 150 ℃, extracting pressure is 100bar, static extracting pattern, cycle index 5 times, each extraction 30min, after having extracted, with Rotary Evaporators, extract is concentrated into about 2-3mL.
The activation of silver powder: 5g silver powder is placed in to the ground conical flask that 100mL is dry, adds acetone and (1+1) mixed solution of nitric acid (the two volume ratio is 1:1) 30mL, start magnetic stirring apparatus vigorous stirring 5min, then use sand core funnel suction filtration.Repeat so more once, be then washed with water to cleansing solution and be neutral, then with acetone, absolute ether, wash successively respectively, drain.
Wherein (1+1) nitric acid is approximately 68% red fuming nitric acid (RFNA) by 1 volume water and 1 volume mass mark and mixes.
(3) purification of extract
Use in advance 5mL normal hexane-isopropyl alcohol (3:2, v/v) washing sulfonic group solid phase extraction column, discard cleansing solution, then in the extract that step (2) obtains, adding concentration is that the Octachloronaphthalene solution 1mL of 1 μ g/mL is as interior mark, after mixing, will contain target extract in Octachloronaphthalene and be transferred to completely on sulfonic group solid phase extraction column, and then use normal hexane-isopropyl alcohol (1:2, v/v) mixed solvent to carry out wash-out, collect eluent, parallel evaporation and concentration is to 1mL.
(4) preparation of standard operation solution
In 25mL volumetric flask, take 25mg mirex standard items, with n-hexane dissolution constant volume, being mixed with concentration is the standard stock solution of 1000mg/L.
In 50mL volumetric flask, take 10mg Octachloronaphthalene standard items, with n-hexane dissolution constant volume, being mixed with concentration is the interior mark stock solution of 200mg/L.
Get appropriate standard stock solution and interior mark stock solution is used respectively normal hexane stepwise dilution, be mixed with and include mark in Octachloronaphthalene and be that 0.1 μ g/mL and mirex concentration are respectively 0.01,0.05,0.1,0.5, the standard operation solution series of 1mg/L.
(5) mensuration of mirex
By the standard operation solution of extract after the purification obtaining in step (3) and step (4) preparation, respectively getting gas chromatograph on 1 μ L measures, use electron capture detector collection signal, with chem workstation, carry out data processing, drawing standard curve, by internal standard method, carry out quantitative test, the content of mirex in the electric rubber components of electron gain.
Gas chromatographic detection condition is: Agilent 6890A gas chromatograph.Chromatographic column: HP-5 capillary column; Column temperature: 100 ℃ of initial temperatures, keep 2min; With 10 ℃/min speed, rise to 300 ℃, keep 10min; Injector temperature: 280 ℃, Splitless injecting samples 1 μ L.Carrier gas: nitrogen, flow: 1mL/min.Detector temperature: 300 ℃, make-up gas nitrogen flow: 60mL/min.
The gas chromatogram of standard solution is shown in Figure of description 2, and the gas chromatogram of sample solution is shown in Figure of description 5.
(6) precision-replica test of test
Sample is carried out to 8 parallel sample tests, and testing result is in Table 1.
8 replicate determination experimental results of mirex in table 5 pair EP rubbers water proof ring
As can be seen from Table 5, the relative standard deviation of 8 replicate determinations is 3.27%, shows that the precision of measurement result meets related request.
Recording mirex content in this nitrile rubber protective sleeve sample is 55.6mg/kg.
(7) accuracy-mark-on recovery test of test
The mark-on recovery test that sample is carried out to varying level, its result is as follows:
Table 6 pair EP rubbers water proof ring sample solution carries out mark-on recovery test result
As can be seen from Table 6, the recovery of standard addition of varying level, between 94.8%～107%, shows that the accuracy of measurement result meets the demands.
The above embodiment of the present invention is according to the feature of quality of rubber materials, proposed a kind ofly can to mirex, fully be extracted, effectively remove again the interference impurity in rubber simultaneously and carry out the method for high-sensitivity detection by quick solvent extraction.By the element sulphur in effective removal rubber, in conjunction with quick solvent-extracted strong extractability, mirex can fully extract from rubber; By the purification of solid phase extraction column, further removed again interference impurity wherein, thereby made to carry out accurate quantitative and qualitative analysis with the trace mirex that the relatively low gas chromatography-electron capture monitor of price is sent out containing in quality of rubber materials.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under Spirit Essence of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, be included in protection scope of the present invention.
Claims (2)
1. a detection method for mirex content in electric rubber components, is characterized in that comprising the following steps:
(1) sample preparation: will mix after electric rubber sample fragmentation, obtain the sample of homogeneous;
(2) mirex extracts: in the sample obtaining in step (1), add heavy metal powder, put into accelerated solvent extraction pond and utilize organic solvent to carry out accelerated solvent extraction to the mirex of sample after mixing, after fully extracting, obtain extract;
In step (2), heavy metal powder is copper powder, silver powder or lead powder, and its consumption is 0.1-1.0 times of rubber sample weight;
Extraction temperature while utilizing organic solvent to carry out accelerated solvent extraction to the mirex in sample in step (2) is 80-150 ℃, and extracting pressure is 100-150bar, quiet cycle extraction 3-5 time, and extraction time is 10-60min;
Organic solvent described in step (2) is normal hexane-isopropyl alcohol, and the volume ratio of the two is 1:0.5-2, and its consumption is 10-20mL solvent/every gram of rubber sample;
(3) extract purifies: in the extract obtaining in step (2), add interior mark, after mixing, will contain interior target extract is transferred on solid phase extraction column completely, then with mixed solvent, carry out wash-out, collect eluent and concentrate the extract after being purified;
Mixed solvent described in step (3) is normal hexane-isopropyl alcohol, and the volume ratio of the two is 1:0.5-3;
(4) mensuration of mirex: first preparation contains interior target mirex mixed standard solution, then by extract after the purification obtaining in step (3) with contain gas chromatograph on interior target mirex mixed standard solution and measure, use electron capture detector collection signal, with chem workstation, carry out after data processing and quantitative test the content of mirex in the electric rubber components of electron gain;
Gas chromatographic detection condition: Agilent 6890N gas chromatograph, chromatographic column: HP-5 capillary column, column temperature: 100 ℃ of initial temperatures, keep 2min; With 10 ℃/min speed, rise to 300 ℃, keep 10min, injector temperature: 280 ℃, Splitless injecting samples 1 μ L, carrier gas: nitrogen, flow: 1mL/min, detector temperature: 300 ℃, tail nitrogen blowing flow: 60mL/min;
In adopting in step (3)-step (4), be designated as Octachloronaphthalene solution.
2. the detection method of mirex content in electric rubber components according to claim 1, is characterized in that: in step (1), electric rubber sample is carried out to freezing crushing to its maximum particle diameter and be less than 0.5mm.
3. the detection method of mirex content in electric rubber components according to claim 1, it is characterized in that: the first activated processing of described heavy metal powder, wherein the reactivation process of copper powder is: the mass volume ratio by copper powder and acetone-concentrated hydrochloric acid mixed solution is 1g:5-7mL, in heavy metal powder, add acetone-concentrated hydrochloric acid mixed solution, wherein the volume ratio of acetone and concentrated hydrochloric acid is 1:1, start magnetic stirring apparatus vigorous stirring 5-15min, use again sand core funnel suction filtration, so repeat 1 time, then be washed with water to neutrality, with acetone and absolute ether, wash successively respectively again, drain, wherein the reactivation process of silver powder or lead powder is: the mass volume ratio by silver powder or lead powder and acetone-nitric acid mixed solution is 1g:5-7mL, in heavy metal powder, add acetone-nitric acid mixed solution, wherein the volume ratio of acetone and nitric acid is 1:1, start magnetic stirring apparatus vigorous stirring 5min, use again sand core funnel suction filtration, so repeat 1 time, be then washed with water to neutrality, with acetone and absolute ether, wash successively respectively again, drain.
4. the detection method of mirex content in electric rubber components according to claim 1, it is characterized in that: in step (2) in the rubber sample of pulverizing except adding heavy metal powder, also add and have drying agent, described drying agent is anhydrous sodium sulfate, the 0.1-0.5 times of weight that its consumption is rubber sample.
5. the detection method of mirex content in electric rubber components according to claim 1, is characterized in that: in step (3), solid phase extraction column is C18 solid phase extraction column, aluminium oxide solid phase extraction column, silica gel solid phase extraction column or sulfonic group solid phase extraction column.
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| CN106324168A (en) * | 2015-07-01 | 2017-01-11 | 谱尼测试集团上海有限公司 | Detection method of chlorine-containing durable organic compounds in electronic information products |
| JP6665629B2 (en) * | 2016-03-30 | 2020-03-13 | 住友ゴム工業株式会社 | Method for quantifying components in rubber composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101393183A (en) * | 2008-10-30 | 2009-03-25 | 中国烟草总公司郑州烟草研究院 | Method for measuring pesticide residue of six kinds of dinitroaniline in tobacco and tobacco products |
| CN101793879A (en) * | 2010-02-05 | 2010-08-04 | 云南省烟草农业科学研究院 | Method for simultaneously measuring multiple residues of organic chloride and pyrethroid pesticides |
-
2011
- 2011-07-21 CN CN201110204830.2A patent/CN102288715B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101393183A (en) * | 2008-10-30 | 2009-03-25 | 中国烟草总公司郑州烟草研究院 | Method for measuring pesticide residue of six kinds of dinitroaniline in tobacco and tobacco products |
| CN101793879A (en) * | 2010-02-05 | 2010-08-04 | 云南省烟草农业科学研究院 | Method for simultaneously measuring multiple residues of organic chloride and pyrethroid pesticides |
Non-Patent Citations (10)
| Title |
|---|
| Adrián de la Torre et al ,.Concentrations and sources of Dechlorane Plus in sewage sludge.《Chemosphere》.2010,第82卷(第5期),692-697. |
| Adrián de la Torre et al,.Concentrations and sources of Dechlorane Plus in sewage sludge.《Chemosphere》.2010,第82卷(第5期),692-697. * |
| ASE-GC-MS测定电子电气产品塑料部件中的灭蚁灵;叶曦雯 等,;《塑料工业》;20090831;第37卷(第8期);56-60 * |
| Technology》.2011,第45卷(第12期),5156-5163. * |
| Yang Ruiqiang et al，.Historically and Currently Used Dechloranes in the Sediments of the Great Lake.《Environmental Science & Technology》.2011,第45卷(第12期),5156-5163. |
| Yang Ruiqiang et al,.Historically and Currently Used Dechloranes in the Sediments of the Great Lake.《Environmental Science & * |
| 中国环境监测总站等译,.方法3660 硫的净化.《固定废弃物试验分析评价手册》.中国环境科学出版社,1992,208-211. * |
| 叶曦雯 等,.ASE-GC-MS测定电子电气产品塑料部件中的灭蚁灵.《塑料工业》.2009,第37卷(第8期),56-60. |
| 李丹 等，.微波萃取-GC/MS法测定电子电气产品中的灭蚁灵.《质谱学报》.2009,第30卷230-232. * |
| 美国环境保护局编 * |
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