CN104730187B - Method for simultaneously determining content of two organic lead salts in plastic sample - Google Patents
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Abstract
The invention relates to a method for simultaneously determining the content of two organic lead salts in a plastic sample. The method is characterized by comprising the following steps: after crushing and grinding the plastic sample, determining methyl palmitate, methyl stearate and dimethyl phthalate before and after methyl esterification by using GC-MS, wherein C16-C18 fatty acid lead salt methyl esterification products comprise methyl palmitate and methyl stearate, and a dibasic lead phthalate methyl esterification product is dimethyl phthalate; subtracting the amount before the methyl esterification from a total value after the methyl esterification to obtain values of C16-C18 fatty acid lead salt and dibasic lead phthalate; detecting the content of total lead in the sample by using microwave acid digestion-ICP-OES; and calculating the content of C16-C18 fatty acid lead and dibasic lead phthalate according to the amount of lead substances, the determined content of methyl palmitate, methyl stearate and dimethyl phthalate, and the content of C16-C18 fatty acid lead, which is the sum of the content of methyl palmitate and methyl stearate.
Description
Technical field
The present invention relates to harmful substance detection field in plastic cement sample, in particular it relates in plastic cement sample
C16-18 lead stearate, the method for measuring simultaneously of Dythal content.
Background technology
C16-18 fatty acid lead salt, English name fatty acids, c16-18, lead salts, main inclusion Petiolus Trachycarpi lead plumbate
And lead stearate, white powder, water insoluble, be dissolved in hot ethanol, benzene and Oleum Terebinthinae, heating for dissolving in normal hexane and after cooling down
Become jelly, meet strong acid and resolve into stearic acid and corresponding salt, have hygroscopicity.It is mainly used as rubber smoothing preparation and transparent
Softening agent.
C16-18 lead stearate structural formula
Dythal, English name dibasic lead phthalate, cas 69011-06-9, molecule
Formula is c8h4o6pb3, molecular weight 818.08, white crystalline powder, insoluble in water and usual vehicle, it is dissolved in nitric acid and acetic acid.Structural formula
See below:
Dythal structural formula
Dythal is the heat stabilizer of polrvinyl chloride.Not only the ability of absorbing hydrogen chloride is strong, but also
Play the role of to absorb ultraviolet, therefore have excellent heat stability and light stability concurrently.Electrical insulating property and dispersibility are also excellent.It is suitable for
In high-temperature electric Insulation Material, foamed product and rolled products.C16-18 lead stearate, Dythal are because of tool within 2012
There are potential genotoxicity, carcinogenic toxicity or be put into European Union reach (chemicals registration, assessment, license and limit) regulation the
Eight batches of high concern substance list.According to reach rules and regulations, if containing in svhc candidate list in exporting to the article of European Union
Material, and this material meets following condition, then enterprise has a responsibility for circulating a notice of the relevant information of this material in product to echa, and
Inform down-stream enterprise: the amount of this material outlet to European Union is more than or equal to 1 ton/year；Content in article for this material is more than or equal to
0.1%.
There is no the assay method with regard to c16-18 lead stearate, Dythal at present.Therefore, it is necessary to build
C16-18 lead stearate, the adjacent benzene of dibasic in a kind of vertical easy, effective, accurate detection European Union reach regulation high concern material
The method of dioctyl phthalate lead content, the monitoring to this two kinds of materials, realize exported product and European Union's reach regulation svhc is met
Property, break through the tradeing mutual compensation of European Union's setting.
By substantial amounts of experiment test, c16-18 lead stearate, dibasic neighbour's benzene two in the plastic material of applicant's research and development
The detection method of lead formate, method is reliable, and accuracy is high, meets detection and requires.
Content of the invention
The technical problem to be solved is, extracts the object in sample from suitable solvent and method,
Extracting solution carries out quantitative analyses with combined gas chromatography mass spectrometry (gc-ms) after esterification.
The technical problem to be solved can be addressed by the following technical programs:
(1) sample pretreatment: first carry out coarse powder with high efficiency cutting pulverizer after taking plastic cement sample to shred, then with efficiently cutting
Cut pulverizer low temperature (liquid nitrogen) fine powder, the sample powder after pulverizing passes through standard screen 35 mesh；
(2) sample normal hexane extraction: after weighing process sample 1.0g (being accurate to 0.0001g) in conical flask with stopper, plus
Enter 10ml normal hexane, supersound extraction 30min, filter paper filtering, then repeat said extracted three times, each 10ml with normal hexane, merge
Extracting solution normal hexane is settled to 50ml, does corresponding dilution, gas chromatogram-matter in preparation according to the content of object in sample
Spectrometer detects；
(3) sample esterification: sample 1.0g (being accurate to 0.0001g) after weighing process, add 7ml 15% boron trifluoride
Methanol solution, 80 DEG C of derivatization reaction 10min, add 10ml n-hexane extraction after cooling, after supernatant crosses anhydrous sodium sulfate water suction,
Cross 0.22 μm of organic filter membrane, the derivative products methyl hexadecanoate of c16-18 fatty acid lead salt, methyl stearate adopt gas chromatogram-
Spectrometer analysis, the derivative products dimethyl phthalate of Dythal is divided using gas chromatograph-mass spectrometer
Analysis；
(4) gas chromatograph-mass spectrometer instrument condition: chromatographic column: hp-5ms, 30m × 0.25mm × 0.25 μm, injection port
280 DEG C, split sampling, split ratio 10: 1, sampling volume 1 μ l, 60 DEG C of holding 1min of column temperature, it is warming up to 260 DEG C with 10 DEG C/min,
300 DEG C of holding 5min, carrier gas helium, flow velocity 1.0ml/min constant current are warming up to 30 DEG C/min, gas chromatograph-mass spectrometer is analyzed
280 DEG C of transmission line temperature, solvent delay 8min, voltage 1.5kv, ion source temperature, 230 DEG C, Salbutamol Selected Ion Monitoring pattern, Petiolus Trachycarpi
The qualitative ion of sour methyl ester is that m/z87, m/z43, m/z74, quota ion m/z74, and the qualitative ion of methyl stearate are respectively m/
Z87, m/z43, m/z74, quota ion m/z74, the qualitative ion of dimethyl phthalate is respectively m/z77, m/z194, m/
Z163, quota ion m/z163；
(5) mensure of lead
Sample pre-treatments: sample is shredded (low-temperature grinding if necessary), all sizes of sample are not in the state of pressurized
It is necessarily less than 6mm.The sample weighing about 0.2g-0.5g (being accurate to 0.0001g), to micro-wave diminishing pot, adds the dense nitre of 5-6ml
Acid and 1-2ml h2o2, react 15min in advance, be placed in heating 1h in water-bath, after being cooled to room temperature after taking-up, counteracting tank put
Enter in microwave dissolver, do reagent blank simultaneously, clear up program and be shown in Table 1.
Table 1 micro-wave digestion program
After microwave oven clear up EP (end of program) after, unnecessary nitric acid of rushing, sample liquid is concentrated into 1～2ml.Diluted with high purity water
And transfer in the volumetric flask of 50ml, add appropriate nitric acid, make overall acidity 5%, be diluted to graduation mark with high purity water fixed
Hold, shake up, filter if necessary, standby.If failing thoroughly to clear up clarification through said process, 2-3ml concentrated nitric acid can be added,
1ml hydrogen peroxide or other reagent such as hf, hcl is cleared up one time again.But always add reagent volume not exceed 5ml.
(6) inductive coupling plasma emission spectrum elemental analyser instrument working condition
Instrument working condition, is shown in Table 2.
The icp-oes instrument parameter of the several frequently seen element of table 2
The choice of spectrum of metal is typically chosen kαLine.
(7) computing formula:
External standard method calculates, and calculates methyl hexadecanoate, methyl stearate, dimethyl phthalate in sample as follows
Content
In formula:
The content of methyl hexadecanoate, methyl stearate, dimethyl phthalate in w- sample, unit be milligrams per kilogram
(mg/kg)；
cSampleThe concentration of methyl hexadecanoate, methyl stearate, dimethyl phthalate in-sample liquid, unit is the every milli of microgram
Rise (μ g/ml)；
V- test solution constant volume, unit is milliliter (ml)；
M- sample quality, unit is gram (g).
The molar concentration of object
X=1000 × w/ × m------------------------------- (2)
W- unit is milligrams per kilogram (mg/kg)；
X- unit is mol per kilogram (mol/kg)；
M- unit is gram every mole (g/mol)；
If (i) xLead≥2xMethyl hexadecanoate, then with the molar concentration meter of methyl hexadecanoate, that is,
wPetiolus Trachycarpi lead plumbate=xMethyl hexadecanoate×mPetiolus Trachycarpi lead plumbate×10-3---------------(3)
If xLead＜ 2xMethyl hexadecanoate, then with the molar concentration meter of lead, that is,
wPetiolus Trachycarpi lead plumbate=xLead×mPetiolus Trachycarpi lead plumbate×10-3---------------(4)
(ii) if xLead≥2xMethyl stearate, then with the molar concentration meter of methyl stearate, that is,
wLead stearate=xMethyl stearate×mLead stearate×10-3---------------(5)
If xLead＜ 2xMethyl stearate, then with the molar concentration meter of lead, that is,
wLead stearate=xLead×mLead stearate×10-3---------------(6)
(iii) if xLead≥1/3xDimethyl phthalate, then with the molar concentration meter of dimethyl phthalate, that is,
wDythal=xDimethyl phthalate×mDythal×10-3------------(7)
If xLead＜ 1/3xDimethyl phthalate, then with the molar concentration meter of lead, that is,
wDythal=xLead×mDythal×10-3---------------(8)
The content of c16-18 lead stearate is Petiolus Trachycarpi lead plumbate and lead stearate sum.
Beneficial effect: the method have technical effect that, with ultrasonic extraction, the object in sample is extracted separation, mesh
Mark thing, after 15% boron trifluoride methanol solution esterification, is converted to the methyl ester of object being easily vaporized, using gas phase
Chromatography-mass spectroscopy instrument quantitative analyses.Measure the total lead content in product, using the pass between object lead and methyl ester derivation simultaneously
System, can detect the content of c16-18 lead stearate, Dythal respectively simultaneously.The method is easy, novel,
Effectively.
Figure of description
Fig. 1 dimethyl phthalate, methyl hexadecanoate, methyl stearate total ion current figure, wherein (1) phthalic acid
Dimethyl ester (rt=8.266min)；(2) methyl hexadecanoate (11.152min)；(3) methyl stearate (12.104min).
Fig. 2 dimethyl phthalate, methyl hexadecanoate, methyl stearate standard curve
Specific embodiment
With reference to specific embodiment, the present invention will be described, but the scope of the invention is not limited to this.
Embodiment 1:
(1) drafting of standard curve: take the dimethyl phthalate of 1000 μ g/ml, methyl hexadecanoate, methyl stearate
Standard solution normal hexane is configured to series standard solution, dimethyl phthalate concentration of standard solution be 2.0,5.0,
10.0th, 20.0,25.0 μ g/ml, upper gas chromatograph-mass spectrometer is analyzed.With concentration of standard solution as abscissa, peak area is
Vertical coordinate.
Dimethyl phthalate standard curve linear equation y=34705x, correlation coefficient r2=0.9990；
Methyl hexadecanoate standard curve linear equation y=216144x, correlation coefficient r2=0.9999；
Methyl stearate directrix curve linear equation y=24995x, correlation coefficient r2=0.9997；
(2) analytical procedure: take certain plastic toy sample to be placed in freezing crusher and pulverize, mix.Weigh sample after process
1.0g (being accurate to 0.0001g), in conical flask with stopper, adds 10ml normal hexane, supersound extraction 30min, filter paper filtering, then uses
Normal hexane repeats said extracted three times, each 10ml, and united extraction liquid normal hexane is settled to 50ml, according to object in sample
Content do corresponding dilution, in preparations, gas chromatograph-mass spectrometer detects；Sample esterification step: weigh sample after process
1.0g (is accurate to 0.0001g), adds 7ml 15% boron trifluoride methanol solution, 80 DEG C of derivatization reaction 10min, adds after cooling
10ml n-hexane extraction, after supernatant crosses anhydrous sodium sulfate water suction, crosses 0.22 μm of organic filter membrane, c16-18 fatty acid lead salt, spreads out
Produce thing methyl hexadecanoate, methyl stearate adopts gas chromatograph-mass spectrometer to analyze.
(3) gas chromatograph-mass spectrometer analysis condition
Chromatographic column: hp-5ms, 30m × 0.25mm, 0.25 μm；
Injection port: 280 DEG C；
Input mode: shunting, split ratio: 10: 1；
Sampling volume: 1 μ l；
Column temperature: 60 DEG C (keeping 1min), be warming up to 260 DEG C with 10 DEG C/min, be warming up to 300 DEG C with 30 DEG C/min and (keep
5min)；
Carrier gas: helium；
Flow velocity: 1.0ml/min (constant current)；
Gas chromatograph-mass spectrometer analysis transmission line temperature: 280 DEG C；
Solvent delay: 8min；
Voltage: 1.5kv
Ion source temperature: 230 DEG C；
Salbutamol Selected Ion Monitoring pattern is shown in Table 3, and quota ion monitoring is shown in Table 3.
Table 3 quota ion and qualitative ion table
| Tested component | Retention time | Quota ion | Qualitative ion 1 | Qualitative ion 2 | Qualitative ion 3 |
| Dimethyl phthalate | 8.266 | 163 | 77 | 164 | 135 |
| Methyl hexadecanoate | 11.152 | 74 | 87 | 74 | 43 |
| Methyl stearate | 12.104 | 74 | 87 | 74 | 43 |
(4) mensure of lead: sample pre-treatments: sample is shredded (low-temperature grinding if necessary), all sizes of sample are not
It is necessarily less than 6mm in the state of pressurized.Weigh about 0.2g-0.5g (being accurate to 0.0001g) sample to micro-wave diminishing pot, plus
Enter 5-6ml concentrated nitric acid and 1-2ml h2o2, react 15min in advance, be placed in heating 1h in water-bath, after being cooled to room temperature after taking-up,
Counteracting tank is put in microwave dissolver, does reagent blank simultaneously.The program of clearing up of microwave oven is shown in Table 1.Treat clearing up of microwave oven
After EP (end of program), unnecessary nitric acid of rushing, sample liquid is concentrated into 1～2ml.Dilute and transfer to the volumetric flask of 50ml with high purity water
In, add appropriate nitric acid, make overall acidity 5%, be diluted to graduation mark constant volume with high purity water, shake up, filter if necessary, standby
With.
(5) varian 710-es Inductively coupled plasma optical emission spectrometer measures the content of total pb, and instrument working condition is shown in
Table 2
(6) testing result: contain total pb 0.23mg/kg in this plastic cement sample, but dimethyl phthalate, Palmic acid first
Ester, methyl stearate all do not detect, and detection limit is respectively 1.0mg/kg, 0.15mg/kg, 1.0mg/kg.Conclusion, this sample does not contain
C16-18 lead stearate, Dythal.
Above-described embodiment is used for illustrative purposes only, and is not limitation of the present invention, general about technical field
Logical technical staff, without departing from the present invention, acceptable various changes can be made and modification, therefore all equivalent
Technical scheme also should belong to scope of the invention, and the scope of patent protection of the present invention should be limited by each claim.
Claims (1)
1. two kinds of organic lead-salt content methods for measuring simultaneously in a kind of plastic cement sample, its feature comprises the steps:
(1) sample pretreatment: first carry out coarse powder with high efficiency cutting pulverizer after taking plastic cement sample to shred, then use high efficiency cutting powder
Broken machine utilizes liquid nitrogen cryogenics fine powder, and the sample powder after pulverizing passes through standard screen 35 mesh；
(2) sample normal hexane extraction: weigh sample 1.0g after process, be accurate to 0.0001g, in conical flask with stopper, add
10ml normal hexane, supersound extraction 30min, filter paper filtering, then repeat said extracted three times, each 10ml with normal hexane, merging carries
Take liquid normal hexane to be settled to 50ml, corresponding dilution, gas chromatography-mass spectrum in preparation are done according to the content of object in sample
Instrument detects；
(3) sample esterification: weigh sample 1.0g after process, be accurate to 0.0001g, add 7ml 15% boron trifluoride methanol molten
Liquid, 80 DEG C of derivatization reaction 10min, add 10ml n-hexane extraction after cooling, after supernatant crosses anhydrous sodium sulfate water suction, cross 0.22
μm organic filter membrane, the derivative products methyl hexadecanoate of c16-18 fatty acid lead salt, methyl stearate adopt gas chromatograph-mass spectrometer
Analysis, the derivative products dimethyl phthalate of Dythal adopts gas chromatograph-mass spectrometer to analyze；
(4) gas chromatograph-mass spectrometer instrument condition: chromatographic column: hp-5ms, 30m × 0.25mm × 0.25 μm, 280 DEG C of injection port,
Split sampling, split ratio 10: 1, sampling volume 1 μ l, 60 DEG C of holding 1min of column temperature, it is warming up to 260 DEG C with 10 DEG C/min, with 30
DEG C/min be warming up to 300 DEG C holding 5min, carrier gas helium, flow velocity 1.0ml/min constant current, gas chromatograph-mass spectrometer analysis transmission
280 DEG C of line temperature, solvent delay 8min, voltage 1.5kv, ion source temperature, 230 DEG C, Salbutamol Selected Ion Monitoring pattern, Palmic acid first
The qualitative ion of ester is that m/z87, m/z43, m/z74, quota ion m/z74, and the qualitative ion of methyl stearate are respectively m/z87,
M/z43, m/z74, quota ion m/z74, the qualitative ion of dimethyl phthalate is respectively m/z77, m/z194, m/z163,
Quota ion m/z163；
(5) sample, after micro-wave digestion acid is cleared up, measures the content of total lead through Inductively coupled plasma optical emission spectrometer；
(6) computing formula
External standard method calculates, and calculates methyl hexadecanoate, methyl stearate, the containing of dimethyl phthalate in sample as follows
Amount
In formula:
The content of methyl hexadecanoate, methyl stearate, dimethyl phthalate in w- sample, unit is milligrams per kilogram (mg/
kg)；
cSampleThe concentration of methyl hexadecanoate, methyl stearate, dimethyl phthalate in-sample liquid, unit is micrograms per millilitre (μ
g/ml)；
V- test solution constant volume, unit is milliliter (ml)；
M- sample quality, unit is gram (g)；
The molar concentration of object
X=1000 × w/m---------------------------------- (2)
W- unit is milligrams per kilogram (mg/kg)；
X- unit is mol per kilogram (mol/kg)；
M- unit is gram every mole (g/mol)；
If (i) xLead≥2xMethyl hexadecanoate, then with the molar concentration meter of methyl hexadecanoate, that is,
wPetiolus Trachycarpi lead plumbate=xMethyl hexadecanoate×mPetiolus Trachycarpi lead plumbate×10-3---------------(3)
If xLead＜ 2xMethyl hexadecanoate, then with the molar concentration meter of lead, that is,
wPetiolus Trachycarpi lead plumbate=xLead×mPetiolus Trachycarpi lead plumbate×10-3---------------(4)
(ii) if xLead≥2xMethyl stearate, then with the molar concentration meter of methyl stearate, that is,
wLead stearate=xMethyl stearate×mLead stearate×10-3---------------(5)
If xLead＜ 2xMethyl stearate, then with the molar concentration meter of lead, that is,
wLead stearate=xLead×mLead stearate×10-3---------------(6)
(iii) if xLead≥1/3xPhthalic acid dioctyl phthalate, then with the molar concentration meter of dimethyl phthalate, that is,
wDythal=xDimethyl phthalate×mDythal×10-3------------(7)
If xLead＜ 1/3xDimethyl phthalate, then with the molar concentration meter of lead, that is,
wDythal=xLead×mDythal×10-3---------------(8)
The content of c16-18 lead stearate is Petiolus Trachycarpi lead plumbate and lead stearate sum.
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| CN107957454A (en) * | 2017-10-23 | 2018-04-24 | 广西壮族自治区食品药品检验所 | The detection method of fatty acid component and application in a kind of alctasin strain |
| CN110108807A (en) * | 2018-02-01 | 2019-08-09 | 佛山市华祥检测技术服务有限公司 | A kind of REACH pays high attention to the measuring method of substance Dythal content |
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| US3870469A (en) * | 1973-04-30 | 1975-03-11 | Nalco Chemical Co | Apparatus and method for monitoring the presence of volatile organic lead compounds |
| DE3644608A1 (en) * | 1986-12-29 | 1988-07-07 | Bosch Gmbh Robert | Method of determining a lead content in fuels and device for carrying out the method |
| SU1658085A1 (en) * | 1989-04-18 | 1991-06-23 | Уфимский Нефтяной Институт | Method of determination of metalloorganic compounds of lead |
| CN102023192A (en) * | 2010-06-21 | 2011-04-20 | 云南出入境检验检疫局检验检疫技术中心 | Method for measuring harmful elements of lead, arsenic, cadmium, copper and chromium in eucalyptus oil food additive |
| CN103115972A (en) * | 2013-01-14 | 2013-05-22 | 宁波谱尼测试技术有限公司 | Method for determining content of REACH substance of very high concern C16-18-fatty acid lead |
| CN103499479B (en) * | 2013-10-17 | 2016-04-27 | 方玉枝 | A kind of method detecting content of beary metal in polymeric material |
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