CN104502487A - Method for determining chloromethyl methyl ether in automotive materials - Google Patents
Method for determining chloromethyl methyl ether in automotive materials Download PDFInfo
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- CN104502487A CN104502487A CN201410856746.2A CN201410856746A CN104502487A CN 104502487 A CN104502487 A CN 104502487A CN 201410856746 A CN201410856746 A CN 201410856746A CN 104502487 A CN104502487 A CN 104502487A
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Abstract
The invention belongs to the technical field of analytic chemistry, and particularly relates to a method for determining the content of chloromethyl methyl ether in automotive materials. The method comprises the following determining steps: (1) cutting a to-be-determined sample into small cubes with sizes of about 2mm*2mm*2mm, and sealing for later use; (2) weighing a certain amount of sample and placing the sample in a headspace bottle, adding acetone, adding toluene-d8 as an internal standard, after fastening the bottle cover down, placing in a headspace sampler; and (3) determining the content of chloromethyl methyl ether in a sample by adopting a gas chromatography-mass spectroscopy meter. According to the method, the content of chloromethyl methyl ether in the automotive materials is determined by adopting the gas chromatography-mass spectroscopy meter, and is quantified by adopting an internal standard method; the method is little in sampling amount, simple in pretreatment operation, and rapid in testing; accurate determination of the content of chloromethyl methyl ether in the automotive materials can be realized, and the detection limit of the method is 100mg/kg.
Description
[technical field]
The invention belongs to technical field of analytical chemistry, specifically a kind of method measuring chloromethyl methyl ether in materials used in auto manufacturing.
[background technology]
Along with the progress of science and technology and the raising of living standards of the people, there is the development of blowout formula in auto industry, can say that automobile has now become the necessity of people's lives.But nearly tens kinds automotive interior material may pollute automotive interior air, the health and lives safety of passenger in serious threat, people have started the pollution problem paying close attention to automotive interior material, have multinationally also put into effect corresponding laws and regulations to control the pollution of automotive interior material.
Chloromethyl methyl ether is a kind of colourless transparent liquid, volatile, irritant stink, have tearing property, severe toxicity, Acute inhalation can cause serious stimulation to skin, eyes, mucous membrane, respiratory tract, and cause pulmonary edema and pneumonia, chronic (for a long time) sucks can be carcinogenic.Chloromethyl methyl ether is mainly used in the alkylating reagent in organic compound synthesis, produces anion exchange resins and synthetic mesophase substrate introducing methoxy protecting group, is also used as solvent.In many and numerous and disorderly automotive interior materials, some material may discharge chloromethyl methyl ether, works the mischief to the personal safety of passenger, so in the urgent need to a kind of method that can measure chloromethyl methyl ether content in materials used in auto manufacturing.
[summary of the invention]
For solving the problem, the invention provides a kind of employing headspace sampling, gas chromatograph-mass spectrometer measures the method for chloromethyl methyl ether in materials used in auto manufacturing, this assay method sampling amount is few, pre-treatment is simple to operate, test fast, and can realize the Accurate Determining of chloromethyl methyl ether in materials used in auto manufacturing.
Measure a method for chloromethyl methyl ether in materials used in auto manufacturing, comprise the following steps:
1) sample pretreatment: testing sample is cut into the cube being not more than 2 × 2 × 2mm;
2) sample extraction: take appropriate amount of sample in ml headspace bottle, adds acetone and deuterated toluene solution, covers tightly bottle cap and put into head-space sampler;
3) sample test: adopt static headspace-GC-MS combined instrument determination step 2) content of chloromethyl methyl ether in gained sample, adopt inner mark method ration.
Step 2) in, the concentration of deuterated toluene solution is 500ug/mL.
Step 3) in, the condition determination of gas chromatograph-mass spectrometer is:
1) gas chromatographic column adopts DB-624 capillary column, and specification is column length 30 meters, column internal diameter 0.25 millimeter, thickness 1.4 microns;
2) gas chromatographic sample introduction mouth temperature is set as 230 DEG C, and temperature programme is initial temperature 35 DEG C, keeps 5 minutes, is warmed up to 220 DEG C by 40 DEG C per minute, keeps 1 minute;
3) mass spectrum collection selects full scan and Selective ion mode scan mode to carry out simultaneously, and scan ion is m/z 15, m/z 29, m/z 45, m/z 70, m/z 98, m/z 100.
Step 3) in, the headspace analysis instrument condition of gas chromatograph-mass spectrometer is:
1) quantitative loop volume: 1mL;
2) furnace temperature: 80 DEG C;
3) quantitative loop temperature: 100 DEG C;
4) transmission line temperature: 120 DEG C;
5) gas phase cycling time: 20min;
6) Sample equilibration time: 10min;
7) pressing time: 1.0min;
8) time of quantitative loop is filled: 0.2min;
9) sample injection time: 1.0min.
Step 3) in, the retention time of sample peak with standard items peak is compared, and sample peak mass spectrogram is compared with standard substance mass spectrogram, if identical with standard substance, then contain chloromethyl methyl ether in confirmatory sample, adopt typical curve inner mark method ration, computing formula is as follows:
Content (the mg/kg)=C/M of chloromethyl methyl ether, wherein,
C: instrument readings (ug),
M: sample quality (g).
Beneficial effect of the present invention: this assay method sampling amount is few, pre-treatment is simple to operate, test fast, and the Accurate Determining of chloromethyl methyl ether in materials used in auto manufacturing can be realized, detecting of the method is limited to 100mg/kg, avoid in automotive interior material because polluting automotive interior air containing chloromethyl methyl ether, and then the health and lives safety of serious threat passenger, for motor vehicle operators and passengers provide safe, comfortable, healthy environment, ensure that the personal safety of motor vehicle operators and passengers.
[accompanying drawing explanation]
Fig. 1 is the gas chromatogram of chloromethyl methyl ether and deuterated toluene in embodiment;
Fig. 2 is the mass spectrogram of chloromethyl methyl ether in embodiment;
Fig. 3 is the mass spectrogram of deuterated toluene in embodiment.
[specific embodiment]
The invention provides a kind of method measuring chloromethyl methyl ether in materials used in auto manufacturing, comprise the following steps:
1) sample pretreatment: testing sample is cut into the cube being not more than 2 × 2 × 2mm, this testing sample is materials used in auto manufacturing, and test substance is chloromethyl methyl ether;
2) sample extraction: take appropriate amount of sample in ml headspace bottle, adds acetone and deuterated toluene inner mark solution, covers tightly bottle cap and put into head-space sampler, the concentration of deuterated toluene solution is 500ug/mL, and wherein, acetone is solvent, internal standard compound is deuterated toluene, and its molecular formula is C
7d
8;
3) sample test: adopt static headspace-GC-MS combined instrument determination step 2) content of chloromethyl methyl ether in gained sample, adopt inner mark method ration; Be specially, the retention time of sample peak with standard items peak is compared, and sample peak mass spectrogram is compared with standard substance mass spectrogram, if identical with standard substance, then contain chloromethyl methyl ether in confirmatory sample, adopt typical curve inner mark method ration, computing formula is as follows:
Content (the mg/kg)=C/M of chloromethyl methyl ether, wherein,
C: instrument readings (ug),
M: sample quality (g).
Step 3) in, the condition determination of gas chromatograph-mass spectrometer is:
1) gas chromatographic column adopts DB-624 capillary column, and specification is column length 30 meters, column internal diameter 0.25 millimeter, thickness 1.4 microns;
2) gas chromatographic sample introduction mouth temperature is set as 230 DEG C, and temperature programme is initial temperature 35 DEG C, keeps 5 minutes, is warmed up to 220 DEG C by 40 DEG C per minute, keeps 1 minute;
3) mass spectrum collection selects full scan and Selective ion mode scan mode to carry out simultaneously, and scan ion is m/z 15, m/z 29, m/z 45, m/z 70, m/z 98, m/z 100.
Step 3) in, the headspace analysis instrument condition of gas chromatograph-mass spectrometer is:
1) quantitative loop volume: 1mL;
2) furnace temperature: 80 DEG C;
3) quantitative loop temperature: 100 DEG C;
4) transmission line temperature: 120 DEG C;
5) gas phase cycling time: 20min;
6) Sample equilibration time: 10min;
7) pressing time: 1.0min;
8) time of quantitative loop is filled: 0.2min;
9) sample injection time: 1.0min.
Below in conjunction with specific embodiment, following further illustrating is done to the present invention:
The mensuration of chloromethyl methyl ether content in plastics
1. the preparation of sample:
Testing sample is cut into the small cubes of size about 2 millimeters × 2 millimeters × 2 millimeters, accurately take the sample of 100mg in the ml headspace bottle of 20mL, add the deuterated toluene inner mark solution of 100uL acetone and 100uL 500ug/mL, covering tightly bottle cap is immediately placed in head-space sampler to be analyzed, adopt head-space sampler sample introduction, inner mark method ration.
2. set instrument parameter:
1) condition of headspace analysis instrument
Head-space sampler: Agilent 7694
Quantitative loop volume: 1mL
Furnace temperature: 80 DEG C
Quantitative loop temperature: 100 DEG C
Transmission line temperature: 120 DEG C
Gas phase cycling time: 20min
Sample equilibration time: 10min
Pressing time: 1.0min
Fill the time of quantitative loop: 0.2min
Sample injection time: 1.0min
2) gas chromatograph condition
Gas chromatograph: Agilent 6890
Chromatographic column: DB-624 capillary column 30m × 0.25mm × 1.4um
Injector temperature: 230 DEG C
Flow rate of carrier gas: 1.0mL/min, constant current
Sample introduction pattern: split sampling
Split ratio: 10:1
Temperature programme: initial temperature 35 DEG C, is warmed up to 220 DEG C by 40 DEG C per minute, keeps 1 minute.
3) Mass Spectrometry Conditions
Solvent delay: 3min
Acquisition mode: SCAN pattern and SIM pattern are carried out simultaneously
Ion source temperature: 230 DEG C
Quadrupole rod temperature: 150 DEG C
SCAN scan ion (m/z): 15 ~ 200
SIM scan ion (m/z): 3.00 ~ 6.99min, 15,29,45
7.00～10.63min，70、98、100
3. quantitative and qualitative analysis
1) qualitative
Retention time through sample peak with standard items peak is compared, and sample peak mass spectrogram is compared with standard substance mass spectrogram, determines whether detect determinand in sample.
2) quantitative
Adopt typical curve inner mark method ration
4. calculate
Computing formula is as follows:
Content (the mg/kg)=C/M of compound
Wherein C: instrument readings (ug)
M: sample quality (g).
The present invention, by the restriction of above-mentioned embodiment, change, the modification done, substitutes, combines, simplifies under other any does not deviate from Spirit Essence of the present invention and principle, all should be equivalent substitute mode, is included within protection scope of the present invention.
Claims (5)
1. measure a method for chloromethyl methyl ether in materials used in auto manufacturing, it is characterized in that, comprise the following steps:
1) sample pretreatment: testing sample is cut into the cube being not more than 2 × 2 × 2mm;
2) sample extraction: take appropriate amount of sample in ml headspace bottle, adds acetone and deuterated toluene solution, covers tightly bottle cap and put into head-space sampler;
3) sample test: adopt static headspace-GC-MS combined instrument determination step 2) content of chloromethyl methyl ether in gained sample, adopt inner mark method ration.
2. the method for claim 1, is characterized in that, step 2) in, the concentration of deuterated toluene solution is 500ug/mL.
3. the method for claim 1, is characterized in that, step 3) in, the condition determination of gas chromatograph-mass spectrometer is:
1) gas chromatographic column adopts DB-624 capillary column, and specification is column length 30 meters, column internal diameter 0.25 millimeter, thickness 1.4 microns;
2) gas chromatographic sample introduction mouth temperature is set as 230 DEG C, and temperature programme is initial temperature 35 DEG C, keeps 5 minutes, is warmed up to 220 DEG C by 40 DEG C per minute, keeps 1 minute;
3) mass spectrum collection selects full scan and Selective ion mode scan mode to carry out simultaneously, and scan ion is m/z 15, m/z 29, m/z 45, m/z 70, m/z 98, m/z 100.
4. the method for claim 1, is characterized in that, step 3) in, the headspace analysis instrument condition of gas chromatograph-mass spectrometer is:
1) quantitative loop volume: 1mL;
2) furnace temperature: 80 DEG C;
3) quantitative loop temperature: 100 DEG C;
4) transmission line temperature: 120 DEG C;
5) gas phase cycling time: 20min;
6) Sample equilibration time: 10min;
7) pressing time: 1.0min;
8) time of quantitative loop is filled: 0.2min;
9) sample injection time: 1.0min.
5. the method for claim 1, it is characterized in that: step 3) in, the retention time of sample peak with standard items peak is compared, and sample peak mass spectrogram is compared with standard substance mass spectrogram, if identical with standard substance, then contain chloromethyl methyl ether in confirmatory sample, adopt typical curve inner mark method ration, computing formula is as follows:
Content (the mg/kg)=C/M of chloromethyl methyl ether, wherein,
C: instrument readings (ug),
M: sample quality (g).
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106338568A (en) * | 2016-09-12 | 2017-01-18 | 上海微谱化工技术服务有限公司 | Method for detecting odor substances of automobile and automobile interior decoration |
| CN106706745A (en) * | 2017-02-17 | 2017-05-24 | 神华集团有限责任公司 | Measuring device and measuring method of water content in coal liquefaction oil product |
| CN107688065A (en) * | 2017-09-11 | 2018-02-13 | 上海药明康德新药开发有限公司 | The gas chromatography combined with mass spectrometry detection method that chloromethyl methyl ether remains in bulk drug |
-
2014
- 2014-12-29 CN CN201410856746.2A patent/CN104502487B/en active Active
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| 中华人民共和国化学工业部: "《HG/T 2543-93 工业氯甲基甲醚》", 25 September 1993, article "氯甲基甲醚总氯量的测定", pages: 1-4 * |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106338568A (en) * | 2016-09-12 | 2017-01-18 | 上海微谱化工技术服务有限公司 | Method for detecting odor substances of automobile and automobile interior decoration |
| CN106338568B (en) * | 2016-09-12 | 2017-10-27 | 上海微谱化工技术服务有限公司 | A kind of method for detecting automobile and automotive trim odoring substance |
| CN106706745A (en) * | 2017-02-17 | 2017-05-24 | 神华集团有限责任公司 | Measuring device and measuring method of water content in coal liquefaction oil product |
| CN107688065A (en) * | 2017-09-11 | 2018-02-13 | 上海药明康德新药开发有限公司 | The gas chromatography combined with mass spectrometry detection method that chloromethyl methyl ether remains in bulk drug |
| CN107688065B (en) * | 2017-09-11 | 2020-08-14 | 上海药明康德新药开发有限公司 | Gas chromatography-mass spectrometry combined detection method for chloromethyl methyl ether residue in bulk drug |
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