CN102359994B - Detection method for polychlorinated naphthalene content in electronic and electrical product rubber part - Google Patents
Detection method for polychlorinated naphthalene content in electronic and electrical product rubber part Download PDFInfo
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Abstract
The present invention discloses a detection method for a polychlorinated naphthalene content in an electronic and electrical product rubber part. The method comprises the following steps: (1) crushing an electronic and electrical rubber sample to obtain a homogeneous sample; (2) adding heavy metal powder to the crushed sample, adopting an accelerated solvent extraction method to completely extract the polychlorinated naphthalene in the sample, taking the extracting solution; (3) completely transferring the extracting solution to a solid phase extraction column, adopting a mixed solvent to carry out elution, and collecting and concentrating the eluent to obtain the purified extracting solution; (4) preparing a mixed standard solution, loading the purified extracting solution and the prepared mixed standard solution on a gas chromatograph to carry out detection, adopting an electron capture detector to collect the signal, adopting a chemistry station to carry out data processing and quantitative analysis to obtain the polychlorinated naphthalene content in the electronic and electrical product rubber part. With the method of the present invention, the impurities with interference in the rubber can be effectively removed, the polychlorinated naphthalene can be completely extracted, the purification degree is high, the detection sensitivity is high and the detection cost is low.
Description
Technical field
The present invention relates to a kind of detection method of many chloronaphthalenes content, be specifically related to the detection method of many chloronaphthalenes 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 to China has formed powerful Green Trade Barrier.Many chloronaphthalenes are exactly a kind of environment management and control material wherein, although it can be used as superior isolation body in electronic and electrical equipment and fire retardant etc., but because it has the toxic mechanism that is similar to bioxin, there is potential embryotoxicity, hepatotoxicity, immunotoxicity, teratogenesis toxicity and skin lesion, it is highly suspicious carcinogenic substance, and bioaccumulation effect and environmental transport and transfer effect with height, banned use of in electronic and electrical equipment by the country such as Japanese, German, Canadian.
At present, for the detection set of many chloronaphthalenes, 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 the many chloronaphthalenes of trace level, need to use expensive isotopic label; Fully there are no report, because rubber is difficult to use organic solvent dissolution, wherein many containing chaff interference for the assay method of many chloronaphthalenes in elastomeric material, be difficult to carry out qualitative and quantitative analysis accurately.
Summary of the invention
The object of the present invention is to provide the detection method of many chloronaphthalenes content in a kind of electronic and electrical equipment rubber components, the method can effectively be removed the interference impurity in rubber, and many chloronaphthalenes extract fully, and degree of purification is high, and detection sensitivity is high, and the test sample cost is low.
Detection method of the present invention be take quality of rubber materials as matrix, can effectively remove the interference impurity in rubber, in elastomeric material, many chloronaphthalenes extract fully, by adopting the solid phase pillar to be purified, degree of purification is high, adopt the just high-sensitive many chloronaphthalenes that determine trace level in rubber sample of energy of conventional gas chromatograph, cost is low.
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 usually, sulphur has played crosslinked action in the molecular structure of rubber, makes between rubber macromolecule to have formed fine and close spatial structure, and 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 be extracted by organic solvent, 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 contain the chlorine atom that electronegativity is very strong in many chloronaphthalenes molecular structure, on electron capture detector, can obtain very high sensitivity, very strong selectivity is also arranged.As long as sample pretreatment process can fully be removed the interference impurity in rubber totally, also can obtain splendid sensitivity so on conventional gas chromatograph.
Above-mentioned purpose of the present invention is achieved by the following technical solution: the detection method of many chloronaphthalenes content in a kind of electric rubber components comprises the following steps:
(1) sample preparation: electric rubber sample is pulverized, obtained the sample of homogeneous;
(2) extract the many chloronaphthalenes in sample: add heavy metal powder in the rubber sample of pulverizing, the employing accelerated solvent extraction is got extract after following the example of the many chloronaphthalenes in sample fully being extracted;
(3) purify extract: extract is transferred on solid phase extraction column fully, with mixed solvent, carries out wash-out, collect eluent and concentrated the extract after being purified;
(4) mensuration of many chloronaphthalenes: preparation mixed standard solution, extract after the purification obtained is gone up to gas chromatograph simultaneously with the mixed standard solution of preparing to be measured, use the electron capture detector collection signal, after carrying out data processing and quantitative test with chem workstation, the content of many chloronaphthalenes in the electric rubber components of electron gain.
In step of the present invention (1), sample freezing crushing to its maximum particle diameter is less than to 1mm.
Heavy metal powder described in step of the present invention (2) is copper powder, silver powder or lead powder, and the 0.1-1.0 that its consumption is rubber sample weight doubly.
First activated processing before heavy metal of the present invention 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, add acetone-concentrated hydrochloric acid mixed solution in heavy metal powder, wherein the volume ratio of acetone and concentrated hydrochloric acid is 1:1, starts magnetic stirring apparatus vigorous stirring 5-15min, then uses the sand core funnel suction filtration, so repeat 1 time, then be washed with water to neutrality, then wash successively with acetone and absolute ether respectively, drain and get final product; Wherein the reactivation process of silver powder or lead powder is: the mass volume ratio by copper powder or lead powder and acetone-nitric acid mixed solution is 1g:5-7mL, add acetone-nitric acid mixed solution in heavy metal powder, wherein the volume ratio of acetone and nitric acid is 1:1, start magnetic stirring apparatus vigorous stirring 5min, use again the sand core funnel suction filtration, so repeat 1 time, then be washed with water to neutrality, wash successively with acetone and absolute ether respectively again, drain and get final product.
In step of the present invention (2) in the rubber sample of pulverizing except adding heavy metal powder, also add drying agent arranged, described drying agent is anhydrous sodium sulfate, the 0.1-0.5 that its consumption is rubber sample weight is doubly.
The solvent that adopts accelerated solvent extraction to follow the example of when the many chloronaphthalenes in sample are fully extracted in step of the present invention (2) is toluene, and its consumption is 10-20mL solvent/every gram rubber sample.
The extraction temperature that adopts accelerated solvent extraction to follow the example of when the many chloronaphthalenes in sample are 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.
Solid phase extraction column described in step of the present invention (3) 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.
Mixed solvent described in step of the present invention (3) is toluene-n-propanol, toluene-isopropyl alcohol, toluene-methylene chloride or toluene-cyclohexanone, and wherein the volume ratio of the two is 1:0.2-4.
Mixed standard solution described in step of the present invention (4) contains a chloronaphthalene, dichloronaphtalene, trichloronaphthalene, Tetrachloronaphthalene, Pentachloronaphthalene, hexachloronaphthalene, heptachlor naphthalene and Octachloronaphthalene standard items.
The present invention has the following advantages:
(1) through simple sample pre-treatments, many chloronaphthalenes in rubber are extracted fully, and effectively removed the interfering material in the rubber matrix, and be convenient to the many chloronaphthalenes in rubber are carried out to Accurate Determining, also be conducive to protect the gas chromatography 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 many chloronaphthalenes in the electronic and electrical equipment rubber components.
The accompanying drawing explanation
The detection method process flow diagram that Fig. 1 is many chloronaphthalenes in electronic and electrical equipment rubber components of the present invention;
Fig. 2 is the standard solution gas chromatogram that the many chloronaphthalenes of the present invention detect, wherein 1, one chloronaphthalene; 2, dichloronaphtalene; 3, trichloronaphthalene; 4, Tetrachloronaphthalene; 5, Pentachloronaphthalene; 6, hexachloronaphthalene; 7, heptachlor naphthalene; 8, Octachloronaphthalene;
The gas chromatogram that Fig. 3 is nitrile rubber oil seal washer sample solution in embodiment 1, sequence number 8 represents the chromatographic peak of Octachloronaphthalene;
The gas chromatogram that Fig. 4 is styrene-butadiene rubber insulating trip sample solution in embodiment 2, sequence number 1,2,4,8 represents respectively the chromatographic peak of a chloronaphthalene, dichloronaphtalene, Tetrachloronaphthalene, Octachloronaphthalene;
The gas chromatogram that Fig. 5 is ethylbenzene RUBBER O RunddichtringO sample solution in embodiment 3, sequence number 3,5,6 represents respectively the chromatographic peak of trichloronaphthalene, Pentachloronaphthalene, hexachloronaphthalene.
Embodiment
embodiment 1
The detection method of many chloronaphthalenes in the nitrile rubber oil seal washer that the present embodiment provides mainly comprises the following steps:
(1) preparation of sample
Nitrile rubber oil seal washer sample freezing crushing to maximum particle diameter is less than to 1mm, mixes, obtain the sample of homogeneous.
(2) extraction of many chloronaphthalenes
Put into the 0.5g anhydrous sodium sulfate in the abstraction pool bottom.Take the about 1g of the sample crushed (being accurate to 0.1mg), copper powder after adding 0.5g activated, stir and with filter paper, wrap and put into abstraction pool afterwards, and its complementary space of abstraction pool is filled and led up with zeyssatite, put on accelerated solvent extraction, with toluene, be that solvent carries out accelerated solvent extraction, setting solvent consumption 20mL, extraction temperature is 120 ℃, extracting pressure is 150bar, the static extracting pattern, cycle index 3 times extracts 10min at every turn.After having extracted, with Rotary Evaporators, extract is concentrated into to about 2-3mL.
The reactivation process of copper powder is: the 5g copper powder is placed in to the ground conical flask of 100ml drying, (be 1:1 by volume, wherein the massfraction of concentrated hydrochloric acid is approximately 37%, commercially available to add acetone-concentrated hydrochloric acid.) mixed solution 30mL, start magnetic stirring apparatus vigorous stirring 10 min, then use the sand core funnel suction filtration.Repeat so more once (this time vigorous stirring 5 min get final product), then water, acetone, absolute ether wash successively, drain.
(3) purification of extract
Use in advance 5mL toluene wash silica gel solid phase extraction column, discard cleansing solution, the extract then step (2) obtained is transferred on solid phase extraction column fully, with toluene+methylene chloride (3:2, v/v) mixed solvent carries out wash-out, collects eluent, and parallel evaporation and concentration is to 1mL.
(4) preparation of standard solution
Take respectively a chloronaphthalene, dichloronaphtalene, trichloronaphthalene, Tetrachloronaphthalene, Pentachloronaphthalene, hexachloronaphthalene, heptachlor naphthalene, the Octachloronaphthalene standard items of 20mg (being accurate to 0.1mg) in same 25mL volumetric flask, make dissolution with solvents with toluene, be mixed with the standard stock solution of concentration 800mg/L.By standard stock solution stepwise dilution, be mixed with that concentration is respectively 0.01,0.02,0.05,0.1,0.2,0.5,1,2, many chloronaphthalenes standard operation solution of 5mg/L with toluene.
(5) mensuration of many chloronaphthalenes
By the mixed standard solution of preparing in the scavenging solution that obtains in step (3) and step (4), respectively get gas chromatograph on 1 μ L and measured.With electron capture detector (ECD) collection signal, carry out the data processing with chem workstation, to standard operation solution drawing standard curve, by external standard method, sample is carried out to quantitative test.
The gas chromatographic detection condition is: Agilent 6890N gas chromatograph (band ECD detecting device).Chromatographic column: HP-5 capillary column.Column temperature: 100 ℃ of initial temperatures keep 2min; Rise to 300 ℃ with 10 ℃/min speed, 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.
The gas chromatogram of nitrile rubber oil seal washer sample solution is shown in Figure of description 3.Only detect Octachloronaphthalene in sample, one does not all detect to the heptachlor naphthalene.
(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 Octachloronaphthalene in table 1 pair nitrile rubber oil seal washer
As can be seen from Table 1, the relative standard deviation of 8 replicate determinations is 5.51%, shows that the precision of measurement result meets related request.
Recording Octachloronaphthalene content in this rubber oil seal sample is 0.508mg/kg.
(7) accuracy of test-mark-on recovery test
Sample is carried out to the mark-on recovery test of varying level, its result is as follows:
Table 2 pair nitrile rubber oil seal washer sample solution carries out Octachloronaphthalene mark-on recovery test result
As can be seen from Table 2, the recovery of standard addition of varying level, between 88.0%～96.8%, shows that the accuracy of measurement result meets the demands.
embodiment 2
The present embodiment provides the detection method of many chloronaphthalenes in the styrene-butadiene rubber insulating trip, mainly comprises the following steps:
(1) preparation of sample
Styrene-butadiene rubber insulating trip freezing crushing to maximum particle diameter is less than to 1mm, mixes, obtain the sample of homogeneous.
(2) extraction of many chloronaphthalenes
Put into the 0.3g anhydrous sodium sulfate in the abstraction pool bottom.Take the about 1g of the sample crushed (being accurate to 0.1mg), silver powder after adding 0.3g activated, stir and with filter paper, wrap and put into abstraction pool afterwards, and its complementary space of abstraction pool is filled and led up with zeyssatite, put on accelerated solvent extraction, with toluene, be that solvent carries out accelerated solvent extraction, setting solvent consumption 15mL, extraction temperature is 150 ℃, extracting pressure is 100bar, the static extracting pattern, cycle index 4 times extracts 30min at every turn.After having extracted, with Rotary Evaporators, extract is concentrated into to about 2-3mL.
The activation of silver powder: 5g silver powder is placed in to the ground conical flask of 100ml drying, 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 the sand core funnel suction filtration.Repeat so more once, then be washed with water to cleansing solution and be neutral, then wash successively with acetone, absolute ether 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 toluene wash aluminium oxide solid phase extraction column, discard cleansing solution, then extract step (2) obtained is transferred to the aluminium oxide solid phase extraction column fully, with toluene-isopropyl alcohol (1:2, v/v) mixed solvent carries out wash-out, collect eluent, parallel evaporation and concentration is to 1mL.
(4) preparation of standard solution
Take respectively a chloronaphthalene, dichloronaphtalene, trichloronaphthalene, Tetrachloronaphthalene, Pentachloronaphthalene, hexachloronaphthalene, heptachlor naphthalene, the Octachloronaphthalene standard items of 20mg (being accurate to 0.1mg) in same 25mL volumetric flask, make dissolution with solvents with toluene, be mixed with the standard stock solution of concentration 800mg/L.By standard stock solution stepwise dilution, be mixed with that concentration is respectively 0.01,0.02,0.05,0.1,0.2,0.5,1,2, many chloronaphthalenes standard operation solution of 5mg/L with toluene.
(5) mensuration of many chloronaphthalenes
By the mixed standard solution of preparing in the scavenging solution that obtains in step (3) and step (4), respectively get gas chromatograph on 1 μ L and measured.With electron capture detector (ECD) collection signal, carry out the data processing with chem workstation, to standard operation solution drawing standard curve, by external standard method, sample is carried out to quantitative test.
The gas chromatographic detection condition is: Agilent 6890N gas chromatograph (band ECD detecting device).Chromatographic column: HP-5 capillary column.Column temperature: 100 ℃ of initial temperatures keep 2min; Rise to 300 ℃ with 10 ℃/min speed, 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.
The gas chromatogram of sample solution is shown in Figure of description 4.Detect a chloronaphthalene in sample, dichloronaphtalene, Tetrachloronaphthalene, Octachloronaphthalene, trichloronaphthalene, Pentachloronaphthalene, hexachloronaphthalene, heptachlor naphthalene all do not detect.
(6) precision---the 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 Octachloronaphthalene in table 3 pair styrene-butadiene rubber insulating trip
As can be seen from Table 1, the relative standard deviation of 8 replicate determinations is 2.22%～6.67%, shows that the precision of measurement result meets related request.
Recording a chloronaphthalene content in this rubber-covered sheet sample is 2.23mg/kg, and dichloronaphtalene content is 3.19mg/kg, and Tetrachloronaphthalene content is 0.712mg/kg, and Octachloronaphthalene content is 1.80mg/kg.
(7) accuracy of test-mark-on recovery test carries out the mark-on recovery test of varying level to sample, and result is as follows:
Table 4 pair electrostatic prevention styrene-butadiene rubber insulating trip sample solution carries out many chloronaphthalenes mark-on recovery test result
As can be seen from Table 4, the recovery of standard addition of varying level, between 82.0%～107%, shows that the accuracy of measurement result meets the demands.
The detection method of many chloronaphthalenes in the ethylbenzene RUBBER O RunddichtringO that the present embodiment provides mainly comprises the following steps:
(1) preparation of sample
Ethylbenzene RUBBER O RunddichtringO freezing crushing to maximum particle diameter is less than to 1mm, mixes, obtain the sample of homogeneous.
(2) extraction of many chloronaphthalenes
Put into the 0.1g anhydrous sodium sulfate in the abstraction pool bottom.Take the about 1g of the sample crushed (being accurate to 0.1mg), lead powder after adding 0.8g activated, stir and with filter paper, wrap and put into abstraction pool afterwards, and its complementary space of abstraction pool is filled and led up with zeyssatite, put on accelerated solvent extraction, with toluene, be that solvent carries out accelerated solvent extraction, setting solvent consumption 10mL, extraction temperature is 80 ℃, extracting pressure is 120bar, the static extracting pattern, cycle index 5 times extracts 60min at every turn.After having extracted, with Rotary Evaporators, extract is concentrated into to about 2-3mL.
The activation of lead powder: the 5g lead powder is placed in to the ground conical flask of 100mL drying, 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 the sand core funnel suction filtration.Repeat so more once, then be washed with water to cleansing solution and be neutral, then wash successively with acetone, absolute ether respectively, drain.
Wherein (1+1) nitric acid is that 68% red fuming nitric acid (RFNA) mixes by 1 volume water and 1 volume mass percentage composition.
(3) purification of extract
Use in advance 5mL toluene wash C
18solid phase extraction column, discard cleansing solution, and the extract then step (2) obtained is transferred to C fully
18solid phase extraction column, carry out wash-out with toluene-n-propanol (1:4, v/v) mixed solvent, collects eluent, and parallel evaporation and concentration is to 1mL.
(4) preparation of standard solution
Take respectively a chloronaphthalene, dichloronaphtalene, trichloronaphthalene, Tetrachloronaphthalene, Pentachloronaphthalene, hexachloronaphthalene, heptachlor naphthalene, the Octachloronaphthalene standard items of 20mg (being accurate to 0.1mg) in same 25mL volumetric flask, make dissolution with solvents with toluene, be mixed with the standard stock solution of concentration 800mg/L.By standard stock solution stepwise dilution, be mixed with that concentration is respectively 0.01,0.02,0.05,0.1,0.2,0.5,1,2, many chloronaphthalenes standard operation solution of 5mg/L with toluene.
(5) mensuration of many chloronaphthalenes
By the mixed standard solution of preparing in the scavenging solution that obtains in step (3) and step (4), respectively get gas chromatograph on 1 μ L and measured.With electron capture detector (ECD) collection signal, carry out the data processing with chem workstation, to standard operation solution drawing standard curve, by external standard method, sample is carried out to quantitative test.
The gas chromatographic detection condition is: Agilent 6890A gas chromatograph (band ECD detecting device).Chromatographic column: HP-5 capillary column.Column temperature: 100 ℃ of initial temperatures keep 2min; Rise to 300 ℃ with 10 ℃/min speed, 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.
The gas chromatogram of sample solution is shown in Figure of description 5, detects trichloronaphthalene in sample, Pentachloronaphthalene and hexachloronaphthalene.
(6) precision-replica test of test carries out 8 parallel sample tests to sample, and testing result is in Table 5.
8 replicate determination experimental results of many chloronaphthalenes in table 5 pair ethylbenzene RUBBER O RunddichtringO
As can be seen from Table 5, the relative standard deviation of 8 replicate determinations is 2.10%～5.65%, shows that the precision of measurement result meets related request.
Recording trichloronaphthalene content in this rubber blanket is 1.93mg/kg, and Pentachloronaphthalene content is 0.764mg/kg, and hexachloronaphthalene content is 0.443mg/kg.
(7) accuracy-mark-on recovery test of test, carry out the mark-on recovery test of varying level to sample, its result is as follows:
Table 6 pair ethylbenzene RUBBER O RunddichtringO sample solution carries out many chloronaphthalenes mark-on recovery test result
As can be seen from Table 6, the recovery of standard addition of varying level, between 89.5%～105%, shows that the accuracy of measurement result meets the demands.
The above embodiment of the present invention is according to the characteristics of quality of rubber materials, proposed a kind ofly can fully extract, effectively remove again the interference impurity in rubber simultaneously and carry out the method for high-sensitivity detection many chloronaphthalenes by quick solvent extraction.By the element sulphur in effective removal rubber, in conjunction with quick solvent-extracted strong extractability, many chloronaphthalenes can fully extract from rubber; By the purification of solid phase extraction column, further removed again interference impurity wherein, thereby make can be relatively low by price gas chromatography-electron capture monitor the many chloronaphthalenes of trace that contain in quality of rubber materials are carried out to accurate quantitative and qualitative analysis.
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. the detection method of many chloronaphthalenes content in an electric rubber components is characterized in that comprising the following steps:
(1) sample preparation: electric rubber sample is pulverized, obtained the sample of homogeneous;
(2) extract the many chloronaphthalenes in sample: add heavy metal powder in the rubber sample of pulverizing, the employing accelerated solvent extraction is got extract after following the example of the many chloronaphthalenes in sample fully being extracted;
(3) purify extract: extract is transferred on solid phase extraction column fully, with mixed solvent, carries out wash-out, collect eluent and concentrated the extract after being purified;
(4) mensuration of many chloronaphthalenes: preparation mixed standard solution; extract after the purification that step (3) is obtained and the mixed standard solution of preparing are gone up gas chromatograph simultaneously and are measured; use the electron capture detector collection signal; after carrying out data processing and quantitative test with chem workstation, the content of many chloronaphthalenes in the electric rubber components of electron gain;
Heavy metal powder described in step (2) is copper powder, silver powder or lead powder, and the 0.1-1.0 that its consumption is rubber sample weight doubly;
The extraction temperature that adopts accelerated solvent extraction to follow the example of when the many chloronaphthalenes in sample are fully extracted in step (2) is 80 ℃-150 ℃, and extracting pressure is 100-150bar, quiet cycle extraction 3-5 time, and extraction time is 10-60min;
Mixed solvent described in step (3) is toluene-n-propanol, toluene-isopropyl alcohol, toluene-methylene chloride or toluene-cyclohexanone, and wherein the volume ratio of the two is 1:0.2-4;
Wherein the gas chromatographic detection condition is: Agilent 6890N gas chromatograph, and band ECD detecting device, chromatographic column: the HP-5 capillary column, column temperature: 100 ℃ of initial temperatures keep 2min; Rise to 300 ℃ with 10 ℃/min speed, 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.
2. the detection method of many chloronaphthalenes content in electric rubber components according to claim 1, is characterized in that: in step (1), sample freezing crushing to its maximum particle diameter is less than to 1mm.
3. the detection method of many chloronaphthalenes content in electric rubber components according to claim 1, it is characterized in that: 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, add acetone-concentrated hydrochloric acid mixed solution in heavy metal powder, wherein the volume ratio of acetone and concentrated hydrochloric acid is 1:1, start magnetic stirring apparatus vigorous stirring 5-15min, use again the 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 and get final product, 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, add acetone-nitric acid mixed solution in heavy metal powder, wherein the volume ratio of acetone and nitric acid is 1:1, start magnetic stirring apparatus vigorous stirring 5min, use again the sand core funnel suction filtration, so repeat 1 time, then be washed with water to neutrality, wash successively with acetone and absolute ether respectively again, drain and get final product.
4. the detection method of many chloronaphthalenes 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 drying agent is arranged, described drying agent is anhydrous sodium sulfate, and the 0.1-0.5 that its consumption is rubber sample weight doubly.
5. the detection method of many chloronaphthalenes content in electric rubber components according to claim 1, it is characterized in that: the solvent that adopts accelerated solvent extraction to follow the example of when the many chloronaphthalenes in sample are fully extracted in step (2) is toluene, and its consumption is 10-20mL solvent/every gram rubber sample.
6. the detection method of many chloronaphthalenes content in electric rubber components according to claim 1, it is characterized in that: the solid phase extraction column described in step (3) 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.
7. the detection method of many chloronaphthalenes content in electric rubber components according to claim 1, it is characterized in that: the mixed standard solution described in step (4) contains a chloronaphthalene, dichloronaphtalene, trichloronaphthalene, Tetrachloronaphthalene, Pentachloronaphthalene, hexachloronaphthalene, heptachlor naphthalene and Octachloronaphthalene standard items.
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