CN105403650A - Determination method for chlorophosphate flame retardant in wood product - Google Patents
Determination method for chlorophosphate flame retardant in wood product Download PDFInfo
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Abstract
Belonging to the field of flame retardant detection, the invention in particular relates to a determination method for a chlorophosphate flame retardant in a wood product. The method includes: firstly conducting pretreatment on a sample, then performing centrifugation, subjecting the sample to passing through a PSA column, carrying out evaporation to a constant volume, and then conducting determination by gas chromatographic mass spectrometry or liquid chromatography mass spectrometry. The determination method for chlorophosphate flame retardant in the wood product provided by the invention can effectively reduce the matrix interference in detection of three flame retardants in the wood product, has the advantages of simple operation, rapidity, accuracy, high sensitivity and good repeatability, and is an innovation of the detection method for toxic and harmful substances in the wood product.
Description
Technical field
The invention belongs to fire retardant detection field, be specifically related to the assay method of chlorinated phosphate ester based flame retardant in woodwork.
Background technology
Along with the reinforcement day by day of global safety environmental consciousness, the requirement of people to fire safety and fire block articles is more and more higher, and the environment friendly flame retardant of Halogen, low cigarette, low toxicity has become the target of people's pursuit.Specify that the definition of public place fire-retardant product and assembly thereof and classification in the up-to-date GB20826 of China " public place fire-retardant product and assembly burning performance require and mark ", burning performance requires and the content such as mark proposes grade of burning accordingly.The burning grade of also clear stipulaties Related product in the standard such as " flame-retardant plywood ", " flame retardant fibre board ", " flame-proof composite floor board ", " Code for design of timber structures " subsequently.
Organophosphate (Organophosphateesters, OPs) is the widely used fire retardant of large class and a plastifier, and OPs can be divided into two groups: one group according to the difference of its side-chain radical is that chloro OPs, Chang Zuowei fire retardant uses; Another group group is that non-chloro OPs, Chang Zuowei plastifier uses.Organophosphate based flame retardant (Organophosphorusflameretardants, OPFRs), with its outstanding fire retardation, is widely used in the industries such as weaving, electronics, building materials of house fitting-up.Common OPFRs mainly comprises tricresyl phosphate (2-chlorine) ethyl ester (TCEP), tricresyl phosphate (2-chlorine) propyl ester (TCPP), tricresyl phosphate (1,3-dichloro) propyl ester (TDCP).Along with 2004, the brominated flame-retardants such as pentabromo-Biphenyl Ether, octa-BDE were successively forbidden in Europe, and OPFRs improves rapidly in global output and consumption.And China's output of 2007 has exceeded 70,000 tons.Due to OPFRs for physically and the mode of non-bonding is added in the product, therefore these products in production, to use and in recycling process, the OPs monomer in OPFRs is very easily escaped and volatilized in the environment of surrounding.At present, be reported in air, topsoil, sewage and biological sample and human body and detect OPs monomer, it is remarkable that the toxicology of researchist to OPs conducts in-depth research its toxicological effect of rear discovery, carcinogenesis is had as TCEP has, TCPP and TDCP can disturb hormonal readiness, have potential carcinogenicity, human body new home syndrome also has significant correlativity with OPs.Along with the increase of output and the continuous expansion of usable range, current OPFRs has caused showing great attention to of national governments.The use of OPFRs is all strictly limited in European Union 79/663/EEC, 83/264/EEC instruction, Germany's " food and daily necessities method ", Britain's " objectionable impurities security legislation ", Japan's " household products hazard substance control method ", European toy EN71 standard.China's national standard " ecological textile technical requirement " is to organophosphorus compounds material forbidding in TDCP etc. 5.
China's timber and goods thereof, when carrying out flame treatment, should consider the impact of these factors and generation thereof, actively take suitable counter-measure.Explore effective detection method, set up operating specification and the supervisory system of unified phosphate ester flame retardants.This is conducive to protection of the environment safety, the healthy and safe and social sustainable development of protection human and animal.
The method of the organophosphorus ester compound utilized in solid phase extraction techniques fast enriching superficial water is disclosed in the people such as He Lixiong disclose in " analytical test journal " " in a Solid-Phase Extraction/Gas chromatographyMass spectrometry Fast Measurement water organophosphate ester flame retardant and plastifier " literary composition, and in conjunction with gas chromatography-mass spectrography analytical technology, establish the method for common phosphate compounds in Fast Measurement water.The feature of the method utilizes solid phase extraction column to purify, target substance is adsorbed onto on purification pillar, then adopt organic solvent to elute to measure, but above-mentioned method belongs to low pole material for chlorinated phosphate ester based flame retardant especially tricresyl phosphate (2 chlorine) ethyl ester, tricresyl phosphate (2 chlorine) propyl diester, these three kinds of chlorinated phosphate ester fire retardants of tricresyl phosphate (1.3-2 chlorine) isopropyl esters, and Solid-Phase Extraction is easily adsorbed not exclusively affects the recovery; Simultaneously because woodwork is different from water sample, composition is various, and form complicated, matrix interference is serious, and the polar material outside target detection thing is easily adsorbed onto on solid phase extraction column by Solid-Phase Extraction, thus affects testing result.
Therefore, need to improve for above-mentioned method, invent the method for a kind of energy accurate quantitative and qualitative analysis chlorine detection substituted phosphate based flame retardant.
Summary of the invention
In order to solve above-mentioned technical matters, the invention provides the accurate quantitative and qualitative analysis of a kind of energy and carry out method for measuring to chlorinated phosphate ester based flame retardant.
Sample pre-treatments of the present invention is the improvement to classical wood millwork mechanical shaking extraction method, due to woodwork especially particieboard and density board raw material complexity, it is larger that conventional surge extracts matrix interference, the present invention selects Microwave Extraction, and extract is limpid, and target substance loss is little, ensure that the extraction efficiency of three kinds of fire retardants, purifying step chooses PSA post, simple to operate, and clean-up effect is better.
Therefore, detection of the present invention, its pre-treatment is by tricresyl phosphate (2 chlorine) ethyl ester, tricresyl phosphate (2 chlorine) propyl diester, tricresyl phosphate (1.3-2 chlorine) isopropyl esters in acetone Microwave Extraction woodwork sample, PSA post is selected to purify extract again, finally in conjunction with the fragments characteristic ion of gaschromatographic mass spectrometry (GC-MS) by compound, liquid chromatography mass (LC-MS/MS) realizes qualitative and quantitative analysis accurately, to fill up the blank of organophosphate ester flame retardant detection method in woodwork respectively by detecting ion pair.
Assay method of the present invention comprises the steps:
In woodwork, the assay method of three kinds of chlorinated phosphate ester fire retardants, comprises the steps:
(1) extract
Take the sample homogenized and add acetone vortex oscillation, Microwave Extraction twice; Preferably, the vortex oscillation time in this step is 1min;
(2) purify
Pipette supernatant that above-mentioned steps (1) obtains in plastic centrifuge tube, centrifugal, cross PSA decontaminating column, rotary evaporation, near dry, adopts organic solvent constant volume, carries out gaschromatographic mass spectrometry GC-MS mensuration or liquid chromatography tandem mass spectrometry LC-MS/MS measures.
Preferably, the centrifugal 5000r/min in step (2), centrifugation time 5min.
Measure according to gaschromatographic mass spectrometry GC-MS, concrete determination step is as follows:
In above-mentioned step (2), adopt acetone to be settled to 2mL, carry out gaschromatographic mass spectrometry GC-MS mensuration, concrete steps are as follows:
Preparation standard working solution: with acetone at 50 ~ 1000 μ g/L latitude of formulation various chlorinated phosphate ester based flame retardant series concentration standard working solution;
Gaschromatographic mass spectrometry measures: a) quantitative measurement: each concentration standard working fluid in above-mentioned preparation standard working solution step is carried out GC-MS mensuration, with the chromatographic peak area of each concentration standard working fluid, regretional analysis is carried out to its respective concentration, obtain standard working curve; Sample liquid step (2) obtained under the same conditions is injected GC-MS and is measured, record the chromatographic peak area of each chlorinated phosphate ester based flame retardant in sample liquid, substitute into typical curve, obtain the content of each chlorinated phosphate ester based flame retardant in sample liquid, then the Mass Calculation of sample representated by liquid obtains the residual quantity of each chlorinated phosphate ester based flame retardant in sample per sample;
B) qualitative determination: target compound in the sample liquid that detecting step (2) obtains, if its quasi-molecular ion chromatographic peak retention time is consistent with standard working solution; And when the relative standard deviation of the exact mass number of target compound is no more than 5ppm in its exact mass number standard solution suitable with concentration, then judge to there is target compound in this sample; If above-mentioned two conditions can not meet simultaneously, then judge not containing target compound;
Measure according to liquid chromatography tandem mass spectrometry LC-MS/MS, concrete determination step is as follows:
In above-mentioned step (2), adopt methanol constant volume to 5mL, carry out liquid chromatography tandem mass spectrometry LC-MS/MS and measure;
Preparation standard working solution: with methyl alcohol at 2 ~ 1000 μ g/L latitude of formulation each chlorinated phosphate ester based flame retardant series concentration standard working solution.
Liquid chromatography tandem mass spectrometry measures: a) quantitative measurement: each concentration standard working fluid in above-mentioned preparation standard working solution step is carried out LC-MS/MS mensuration, with the chromatographic peak area of each concentration standard working fluid, regretional analysis is carried out to its respective concentration, obtain standard working curve; Sample liquid step (2) obtained under the same conditions is injected LC-MS/MS and is measured, record the chromatographic peak area of each chlorinated phosphate ester based flame retardant in sample liquid, substitute into typical curve, obtain the content of each chlorinated phosphate ester based flame retardant in sample liquid, then the Mass Calculation of sample representated by liquid obtains the residual quantity of each chlorinated phosphate ester based flame retardant in sample per sample;
B) qualitative determination: target compound in the sample liquid that detecting step (2) obtains, if its quasi-molecular ion chromatographic peak retention time is consistent with standard working solution; And when the relative standard deviation of the exact mass number of target compound is no more than 5ppm in its exact mass number standard solution suitable with concentration, then judge to there is target compound in this sample; If above-mentioned two conditions can not meet simultaneously, then judge not containing target compound.
The chromatographic column adopted in gas Chromatographic Determination is HP-5MS chromatographic column;
During gaschromatographic mass spectrometry measures, chromatographic condition is: chromatographic column: HP-5MS30m × 250 μm × 0.25 μm; Post case program: 100 DEG C keep 2min, keeps 1min with 20 DEG C/min to 160 DEG C, keeps 5min with 8 DEG C/min to 300 DEG C; Injector temperature: 270 DEG C; Chromatography-mass spectroscopy interface temperature: 280 DEG C; Carrier gas: nitrogen, purity >=99.999%, flow velocity: 1mL/min; Ionization mode: EI; Mensuration mode: Selected ion monitoring mode; Input mode: pulse is not shunted, sample size 1 μ L;
Above-mentioned Mass Spectrometer Method uses full scan pattern, the fragments characteristic ion of tricresyl phosphate (2 chlorine) ethyl ester is 63,143,204.9,249, the fragments characteristic ion of tricresyl phosphate (2 chlorine) propyl diester is 41.1,99,125.0,157.0,201.0, and the fragments characteristic ion of tricresyl phosphate (1.3-2 chlorine) isopropyl esters is 75,99,191,208.9.
The chromatographic column of liquid chromatography is ZORBAXSB-C18 chromatographic column.
In liquid chromatogram measuring, chromatographic condition is: chromatographic column: AgilentZORBAXSB-C18, and the specification of described chromatographic column is 2.1mm × 150mm × 5 μm; Mobile phase: A is acetonitrile solution, and B is 0.1% aqueous formic acid, chromatographic column temperature: 35 DEG C; Sampling volume: 5 μ L, gradient elution program is as follows:
Triple level Four bar Mass Spectrometry Conditions: ion gun: ESI, positive ion scans; Nebulizer pressure: 45psi; Dryer temperature: 350 DEG C; Exsiccator flow velocity: 11L/min; Capillary voltage: 4000V; Detection mode: many reaction detection; Scan mode: MRM.
Above-mentioned Mass Spectrometer Method uses many reaction detection MRM pattern, tricresyl phosphate (2 chlorine) ethyl ester parent ion is 286, daughter ion is 98.9,161, tricresyl phosphate (2 chlorine) propyl diester parent ion is 327, daughter ion is 98.9,174.9, tricresyl phosphate (1.3-2 chlorine) isopropyl esters parent ion is 431, and daughter ion is 99.0,209.2.
Above-mentioned chlorinated phosphate ester fire retardant is any one in tricresyl phosphate (2 chlorine) ethyl ester, tricresyl phosphate (2 chlorine) propyl diester, tricresyl phosphate (1.3-2 chlorine) isopropyl esters.
Beneficial effect of the present invention is:
Adopt method of the present invention, effectively can carry out quantitative and qualitative analysis detection to chlorinated phosphate ester based flame retardant in various woodwork, be particularly useful for tricresyl phosphate in woodwork (2 chlorine) ethyl ester, tricresyl phosphate (2 chlorine) propyl diester, the detection of these three kinds of fire retardants of tricresyl phosphate (1.3-2 chlorine) isopropyl esters, this pre-treating method is applied to the qualitative confirmation of three kinds of chlorinated phosphate ester fire retardants in woodwork in conjunction with GC-MS and quantitatively detects, the average recovery rate of tricresyl phosphate (2 chlorine) ethyl ester is 87.0-98.1%, relative standard deviation (RSD) is 3.8-16.3%, the average recovery rate of tricresyl phosphate (2 chlorine) propyl diester is 93.4-111.2%, relative standard deviation (RSD) is 4.2-6.0%, the average recovery rate of tricresyl phosphate (1.3-2 chlorine) isopropyl esters is 89.0-101.2%, relative standard deviation (RSD) is 3.6-11.2%, this pre-treating method is applied to the qualitative confirmation of three kinds of chlorinated phosphate ester fire retardants in woodwork in conjunction with LC-MS/MS and quantitatively detects, the average recovery rate of tricresyl phosphate (2 chlorine) ethyl ester is 83.6-85.3%, relative standard deviation (RSD) is 4.3-10.8%, the average recovery rate of tricresyl phosphate (2 chlorine) propyl diester is 82.7-87.1%, relative standard deviation (RSD) is 4.8-9.7%, the average recovery rate of tricresyl phosphate (1.3-2 chlorine) isopropyl esters is 85.0-98.3%, and relative standard deviation (RSD) is 1.8-3.7%.The present invention has easy and simple to handle, quick, accurate, highly sensitive and reproducible advantage, it is the innovation to poisonous and harmful substance detection method in woodwork, meet the technical requirement that China's toy safety detects, provide strong technical support by for China's woodwork safety and foreign trade develop in a healthy way.
Accompanying drawing explanation
Fig. 1 is tricresyl phosphate (2 chlorine) ethyl ester characteristic ion;
Fig. 2 tricresyl phosphate (2 chlorine) propyl diester characteristic ion;
Fig. 3 tricresyl phosphate (1.3-2 chlorine) isopropyl esters characteristic ion;
Three kinds of fire retardant standard substance figure during Fig. 4 gas chromatography mass spectrometer detects;
Fig. 5 is that tricresyl phosphate (2 chlorine) ethyl ester detects ion pair;
Fig. 6 tricresyl phosphate (2 chlorine) propyl diester detects ion pair;
Fig. 7 tricresyl phosphate (1.3-2 chlorine) isopropyl esters detects ion pair;
Fig. 8 is three kinds of fire retardant standard substance figure during liquid chromatography tandem mass spectrometry detects.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is further described, so that those skilled in the art more understands the present invention, but does not limit the present invention with this.
The instrument used in the embodiment of the present invention and reagent:
Gas chromatograph-mass spectrometer (GCMS): Agilent7890A-5975C, is furnished with mass selective detector (MSD); Microwave dissolver: MARS6-classic; Vacuum drying chamber: memmert; Homogenizer: ULTRA-TURRAXT25; Hydro-extractor: EppendorfCR22G III; Rotary Evaporators: chillerF100; Primary secondary amine adsorption column: SAXPSA; Eddy current vortex mixer: IKAMS3 basic model; Superpure water machine: Milli-Q; Electronic balance: sensibility reciprocal 0.001; Plastic centrifuge tube: 50mL; Bench drill: Z516-1.
Reagent: acetone: chromatographically pure; Normal hexane: chromatographically pure.
Standard substance: tricresyl phosphate (2 chlorine) ethyl ester TCEP: purity >=99.0%; Tricresyl phosphate (2 chlorine) propyl diester TCPP: purity >=95.5%; Tricresyl phosphate (1.3-2 chlorine) isopropyl esters TDCP: purity >=96.0%.
Liquid Chromatography-Tandem Mass Spectrometry instrument: Agilent1200 fast liquid chromatography instrument, 6410TripleQuad mass spectrometer; Microwave dissolver: MARS6-classic; Vacuum drying chamber: memmert; Homogenizer: ULTRA-TURRAXT25; Hydro-extractor: EppendorfCR22G III; Rotary Evaporators: chillerF100; Primary secondary amine adsorption column: SAXPSA; Eddy current vortex mixer: IKAMS3 basic model; Superpure water machine: Milli-Q; Electronic balance: sensibility reciprocal 0.001; Plastic centrifuge tube: 50mL; Bench drill: Z516-1.
Reagent: acetonitrile: chromatographically pure; Methyl alcohol: chromatographically pure; Acetone: chromatographically pure; Formic acid: analyze pure
Standard substance: tricresyl phosphate (2 chlorine) ethyl ester TCEP: purity >=99.0%; Tricresyl phosphate (2 chlorine) propyl diester TCPP: purity >=95.5%; Tricresyl phosphate (1.3-2 chlorine) isopropyl esters TDCP: purity >=96.0%.
Embodiment 1
Be detected as example with three kinds of chlorinated phosphate ester fire retardants in particieboard, detection method is specific as follows:
(1) sample pre-treatments
Accurately take 1.0g sample (being accurate to 0.01g) and be placed in microwave abstracting tank, add 20mL acetone, vortex concussion 2min, extracts 30min at 70 DEG C, collects supernatant in centrifuge tube, adds 20mL acetone reextraction, merge supernatant.With the centrifugal 5min of 5000r/min, be transferred to rotary evaporation in heart bottle and, to 3-4mL, cross PSA and purify pillar, clean heart bottle 3 times with acetone.Scavenging solution rotary evaporation, to nearly dry (N2 dries up if desired), is settled to 2mL with acetone, carries out GC-MS mensuration.
(2) preparation of standard working solution
Accurately take appropriate tricresyl phosphate (2 chlorine) ethyl ester, tricresyl phosphate (2 chlorine) propyl diester, tricresyl phosphate (1.3-2 chlorine) isopropyl esters standard items respectively, 100ppm standard reserving solution is mixed with acetone, get 2.5mL100ppm standard reserving solution in 50mL volumetric flask, acetone is settled to scale, be configured to storing solution in the middle of 5ppm standard, stepwise dilution to 2.0,1.0,0.5,0.2,0.1,0.05,0.02, the mixed standard solution of 0.01ppm.
(3) gas chromatography-mass spectrum (GC-MS) measures
Quantitative measurement:
Each concentration standard working fluid is carried out GC-MS mensuration, with the chromatographic peak area of each concentration standard working fluid, regretional analysis is carried out to its respective concentration, obtain standard working curve, sample liquid step (2) obtained under the same conditions is injected GC-MS and is measured, record tricresyl phosphate in sample liquid (2 chlorine) ethyl ester, tricresyl phosphate (2 chlorine) propyl diester, the chromatographic peak area of tricresyl phosphate (1.3-2 chlorine) isopropyl esters, substitute into typical curve, obtain tricresyl phosphate in sample liquid (2 chlorine) ethyl ester, tricresyl phosphate (2 chlorine) propyl diester, the content of tricresyl phosphate (1.3-2 chlorine) isopropyl esters, then the Mass Calculation of sample representated by liquid obtains tricresyl phosphate in sample (2 chlorine) ethyl ester per sample, tricresyl phosphate (2 chlorine) propyl diester, the residual quantity of tricresyl phosphate (1.3-2 chlorine) isopropyl esters.
Wherein chromatographic mass spectrometry condition is: chromatographic column: HP-5MS30m × 250 μm × 0.25 μm, or quite; Post case program: 100 DEG C keep 2min, keeps 1min with 20 DEG C/min to 160 DEG C, keeps 5min with 8 DEG C/min to 300 DEG C; Injector temperature: 270 DEG C; Chromatography-mass spectroscopy interface temperature: 280 DEG C; Carrier gas: nitrogen, purity >=99.999%, flow velocity: 1mL/min; Ionization mode: EI; Mensuration mode: Selected ion monitoring mode; Input mode: pulse is not shunted, sample size 1 μ L.
Qualitative determination: target compound in the sample liquid obtained by detecting step, if its quasi-molecular ion chromatographic peak retention time is consistent with standard working solution; And when the relative standard deviation of the exact mass number of target compound is no more than 5ppm in its exact mass number standard solution suitable with concentration, then judge to there is target compound in this sample; If above-mentioned two conditions can not meet simultaneously, then judge not containing target compound.
Standard working curve and detection limit:
With the chromatographic peak area of standard working solution, regretional analysis is carried out to its respective concentration, obtain standard working curve.In the sample that 3 times of signal to noise ratio (S/N ratio)s (S/N) are corresponding, target compound concentration is as detection limit (LOD), in the sample of 10 times of signal to noise ratio (S/N ratio) (S/N) correspondences, target compound concentration is as quantitative limit (LOQ), obtains detection limit and the quantitative limit of each target compound.The results are shown in Table 1.
The retention time of table 1 three kinds of fire retardants, regression equation, related coefficient, quantitative limit and detection limit
Recovery of standard addition and repeatability:
Blank sample is done with the wood particle not containing fire retardant, add tricresyl phosphate (2 chlorine) ethyl ester of low middle high variable concentrations level, tricresyl phosphate (2 chlorine) propyl diester, tricresyl phosphate (1.3-2 chlorine) isopropyl esters mixed standard solution, measure by above-mentioned treatment step after vacuum drying, mensuration concentration is added concentration with theory compare, obtain the TIANZHU XINGNAO Capsul of three kinds of fire retardants, each Pitch-based sphere replicate determination 6 times, obtain its relative standard deviation, measurement result is in table 2.From table 2, in 3 mark-on levels, the average recovery rate of tricresyl phosphate (2 chlorine) ethyl ester is 87.0-98.1%, relative standard deviation (RSD) is 3.8-16.3%, the average recovery rate of tricresyl phosphate (2 chlorine) propyl diester is 93.4-111.2%, relative standard deviation (RSD) is 4.2-6.0%, the average recovery rate of tricresyl phosphate (1.3-2 chlorine) isopropyl esters is 89.0-101.2%, and relative standard deviation (RSD) is 3.6-11.2%.Illustrate that the recovery of the inventive method is higher, reproducible.
Table 2 precision and recovery test result (n=6)
Embodiment 2
The detection of three kinds of chlorinated phosphate ester fire retardants in particieboard
(1) sample pre-treatments
Accurately take 1.0g sample (being accurate to 0.01g) and be placed in microwave abstracting tank, add 20mL acetone, vortex concussion 2min, extracts 30min at 70 DEG C, collects supernatant in centrifuge tube, adds 20mL acetone reextraction, merge supernatant.With the centrifugal 5min of 5000r/min, be transferred to rotary evaporation in heart bottle and, to 3-4mL, cross PSA and purify pillar, clean heart bottle 3 times with acetone.Scavenging solution rotary evaporation, to nearly dry (N2 dries up if desired), by methanol constant volume to 5mL, carries out LC-MS/MS mensuration.
(2) preparation of standard working solution
Accurately take appropriate tricresyl phosphate (2 chlorine) ethyl ester respectively, tricresyl phosphate (2 chlorine) propyl diester, tricresyl phosphate (1.3-2 chlorine) isopropyl esters standard items, tricresyl phosphate (2 chlorine) ethyl ester is mixed with methyl alcohol, tricresyl phosphate (1.3-2 chlorine) isopropyl esters concentration 100ppm, tricresyl phosphate (2 chlorine) propyl diester concentration 10ppm standard reserving solution, get 2.5mL standard reserving solution in 50mL volumetric flask, methanol constant volume is to scale, be configured to tricresyl phosphate (2 chlorine) ethyl ester, tricresyl phosphate (1.3-2 chlorine) isopropyl esters concentration 5ppm, storing solution in the middle of tricresyl phosphate (2 chlorine) propyl diester concentration 0.5ppm standard, stepwise dilution is to tricresyl phosphate (2 chlorine) ethyl ester, tricresyl phosphate (1.3-2 chlorine) isopropyl esters concentration 1.0, 0.5, 0.2, 0.1, 0.05, the mixed standard solution of 0.02ppm, tricresyl phosphate (2 chlorine) propyl diester concentration 0.2, 0.1, 0.05, 0.02, 0.01, 0.005, the mixed standard solution of 0.002ppm.
(3) liquid chromatography tandem mass spectrometry (LC-MS/MS) measures
Quantitative measurement:
Each concentration standard working fluid is carried out LC-MS/MS mensuration, with the chromatographic peak area of each concentration standard working fluid, regretional analysis is carried out to its respective concentration, obtain standard working curve, sample liquid step (2) obtained under the same conditions is injected LC-MS/MS and is measured, record tricresyl phosphate in sample liquid (2 chlorine) ethyl ester, tricresyl phosphate (2 chlorine) propyl diester, the chromatographic peak area of tricresyl phosphate (1.3-2 chlorine) isopropyl esters, substitute into typical curve, obtain tricresyl phosphate in sample liquid (2 chlorine) ethyl ester, tricresyl phosphate (2 chlorine) propyl diester, the content of tricresyl phosphate (1.3-2 chlorine) isopropyl esters, then the Mass Calculation of sample representated by liquid obtains tricresyl phosphate in sample (2 chlorine) ethyl ester per sample, tricresyl phosphate (2 chlorine) propyl diester, the residual quantity of tricresyl phosphate (1.3-2 chlorine) isopropyl esters.
Wherein chromatographic mass spectrometry condition is:
Liquid phase chromatogram condition: chromatographic column: AgilentZORBAXSB-C18 (2.1mm × 150mm × 5 μm); Mobile phase: A is acetonitrile solution, and B is 0.1% aqueous formic acid, and gradient elution program is in table 3; Chromatographic column temperature: 35 DEG C; Sampling volume: 5 μ L.
Table 3 gradient elution program
Triple level Four bar Mass Spectrometry Conditions: ion gun: ESI, positive ion scans; Nebulizer pressure: 45psi; Dryer temperature: 350 DEG C; Exsiccator flow velocity: 11L/min; Capillary voltage: 4000V; Detection mode: many reaction detection; Scan mode: MRM.
Qualitative determination: target compound in the sample liquid obtained by detecting step, if its quasi-molecular ion chromatographic peak retention time is consistent with standard working solution; And when the relative standard deviation of the exact mass number of target compound is no more than 5ppm in its exact mass number standard solution suitable with concentration, then judge to there is target compound in this sample; If above-mentioned two conditions can not meet simultaneously, then judge not containing target compound.
Standard working curve and detection limit:
With the chromatographic peak area of standard working solution, regretional analysis is carried out to its respective concentration, obtain standard working curve.In the sample that 3 times of signal to noise ratio (S/N ratio)s (S/N) are corresponding, target compound concentration is as detection limit (LOD), in the sample of 10 times of signal to noise ratio (S/N ratio) (S/N) correspondences, target compound concentration is as quantitative limit (LOQ), obtains detection limit and the quantitative limit of each target compound.The results are shown in Table 4.
The retention time of table 4 three kinds of fire retardants, regression equation, related coefficient, quantitative limit and detection limit
Recovery of standard addition and repeatability:
Blank sample is done with the wood particle not containing fire retardant, add tricresyl phosphate (2 chlorine) ethyl ester of low middle high variable concentrations level, tricresyl phosphate (2 chlorine) propyl diester, tricresyl phosphate (1.3-2 chlorine) isopropyl esters mixed standard solution, measure by above-mentioned treatment step after vacuum drying, mensuration concentration is added concentration with theory compare, obtain the TIANZHU XINGNAO Capsul of three kinds of fire retardants, each Pitch-based sphere replicate determination 6 times, obtain its relative standard deviation, measurement result is in table 5.From table 5, in 3 mark-on levels, the average recovery rate of tricresyl phosphate (2 chlorine) ethyl ester is 83.6-85.3%, relative standard deviation (RSD) is 4.3-10.8%, the average recovery rate of tricresyl phosphate (2 chlorine) propyl diester is 82.7-87.1%, relative standard deviation (RSD) is 4.8-9.7%, the average recovery rate of tricresyl phosphate (1.3-2 chlorine) isopropyl esters is 85.0-98.3%, and relative standard deviation (RSD) is 1.8-3.7%.Illustrate that the recovery of the inventive method is higher, reproducible.
Table 5 precision and recovery test result (n=6)
Above embodiment is only the description to the preferred embodiment of the present invention; not scope of the present invention is limited; under not departing from the present invention and designing the prerequisite of spirit; the various distortion that those of ordinary skill in the art make technical scheme of the present invention and conversion, all should fall into claims of the present invention.
Claims (9)
1. the assay method of chlorinated phosphate ester based flame retardant in woodwork, comprises the steps:
(1) extract
Take the sample homogenized and add acetone vortex oscillation, and Microwave Extraction twice;
(2) purify
Sample in removing step (1) after Microwave Extraction, centrifugal, cross PSA decontaminating column, rotary evaporation is closely dry to sample, adopt organic solvent constant volume, obtain analyte sample fluid, gaschromatographic mass spectrometry GC-MS mensuration is carried out to analyte sample fluid or liquid chromatography tandem mass spectrometry LC-MS/MS measures.
2. the assay method of chlorinated phosphate ester based flame retardant in woodwork as claimed in claim 1, is characterized in that,
Carry out gaschromatographic mass spectrometry GC-MS mensuration to analyte sample fluid, concrete steps are as follows:
In described step (2), after rotary evaporation is closely dry to sample, adopts acetone to be settled to 2mL, carry out gaschromatographic mass spectrometry GC-MS mensuration:
Preparation standard working solution: with acetone at 50 ~ 1000 μ g/L latitude of formulation various chlorophosphate ester type compound series concentration standard working solution;
Gaschromatographic mass spectrometry measures: a) quantitative measurement: each concentration standard working fluid in above-mentioned preparation standard working solution step is carried out GC-MS mensuration, with the chromatographic peak area of each concentration standard working fluid, regretional analysis is carried out to its respective concentration, obtain standard working curve; Sample liquid step (2) obtained under the same conditions is injected GC-MS and is measured, record the chromatographic peak area of each chlorophosphate ester type compound in sample liquid, substitute into typical curve, obtain the content of various chlorophosphate ester type compound in sample liquid, then the Mass Calculation of sample representated by liquid obtains the residual quantity of each chlorophosphate ester type compound in sample per sample;
B) qualitative determination: target compound in the sample liquid that detecting step (2) obtains, if its quasi-molecular ion chromatographic peak retention time is consistent with standard working solution; And when the relative standard deviation of the exact mass number of target compound is no more than 5ppm in its exact mass number standard solution suitable with concentration, then judge to there is target compound in this sample; If above-mentioned two conditions can not meet simultaneously, then judge not containing target compound;
Carry out liquid chromatography tandem mass spectrometry LC-MS/MS to analyte sample fluid to measure, concrete steps are as follows:
In described step (2), adopt methanol constant volume to 5mL, carry out liquid chromatography tandem mass spectrometry LC-MS/MS and measure;
Preparation standard working solution: with methyl alcohol at 2 ~ 1000 μ g/L latitude of formulation various chlorophosphate ester type compound series concentration standard working solution;
Liquid chromatography tandem mass spectrometry measures: a) quantitative measurement: each concentration standard working fluid in above-mentioned preparation standard working solution step is carried out LC-MS/MS mensuration, with the chromatographic peak area of each concentration standard working fluid, regretional analysis is carried out to its respective concentration, obtain standard working curve; Sample liquid step (2) obtained under the same conditions is injected LC-MS/MS and is measured, record the chromatographic peak area of various chlorophosphate ester type compound in sample liquid, substitute into typical curve, obtain the content of various chlorophosphate ester type compound in sample liquid, then the Mass Calculation of sample representated by liquid obtains the residual quantity of various chlorophosphate ester type compound in sample per sample;
B) qualitative determination: target compound in the sample liquid that detecting step (2) obtains, if its quasi-molecular ion chromatographic peak retention time is consistent with standard working solution; And when the relative standard deviation of the exact mass number of target compound is no more than 5ppm in its exact mass number standard solution suitable with concentration, then judge to there is target compound in this sample; If above-mentioned two conditions can not meet simultaneously, then judge not containing target compound.
3. the assay method of chlorinated phosphate ester based flame retardant in woodwork as claimed in claim 2, is characterized in that,
The chromatographic column adopted in described gas Chromatographic Determination is HP-5MS chromatographic column;
The chromatographic column adopted in described liquid chromatogram measuring is ZORBAXSB-C18 chromatographic column.
4. the assay method of chlorinated phosphate ester based flame retardant in woodwork as claimed in claim 2, is characterized in that,
During gaschromatographic mass spectrometry measures, chromatographic condition is: chromatographic column: HP-5MS30m × 250 μm × 0.25 μm; Post case program: 100 DEG C keep 2min, keeps 1min with 20 DEG C/min to 160 DEG C, keeps 5min with 8 DEG C/min to 300 DEG C; Injector temperature: 270 DEG C; Chromatography-mass spectroscopy interface temperature: 280 DEG C; Carrier gas: nitrogen, purity >=99.999%, flow velocity: 1mL/min; Ionization mode: EI; Mensuration mode: Selected ion monitoring mode; Input mode: pulse is not shunted, sample size 1 μ L;
In liquid chromatogram measuring, chromatographic condition is: chromatographic column: AgilentZORBAXSB-C18, and the specification of described chromatographic column is 2.1mm × 150mm × 5 μm; Mobile phase: A is acetonitrile solution, and B is 0.1% aqueous formic acid, chromatographic column temperature: 35 DEG C; Sampling volume: 5 μ L, gradient elution program is as follows:
Time 0, flow velocity 0.3mL/min, A acetonitrile 50%, B0.1% formic acid 50%;
Time 1min, flow velocity 0.3mL/min, A acetonitrile 50%, B0.1% formic acid 50%;
Time 7min, flow velocity 0.3mL/min, A acetonitrile 75%, B0.1% formic acid 25%;
Time 11min, flow velocity 0.3mL/min, A acetonitrile 100%, B0.1% formic acid 0;
Time 12min, flow velocity 0.3mL/min, A acetonitrile 50%, B0.1% formic acid 50%;
Triple level Four bar Mass Spectrometry Conditions: ion gun: ESI, positive ion scans; Nebulizer pressure: 45psi; Dryer temperature: 350 DEG C; Exsiccator flow velocity: 11L/min; Capillary voltage: 4000V; Detection mode: many reaction detection; Scan mode: MRM.
5. the assay method of chlorinated phosphate ester based flame retardant in woodwork as claimed in claim 2, it is characterized in that, the vortex oscillation time of described step (1) is 1min.
6. the assay method of chlorinated phosphate ester based flame retardant in woodwork as claimed in claim 2, is characterized in that, the centrifugal 5000r/min in described step (2), centrifugation time 5min.
7. the assay method of chlorinated phosphate ester based flame retardant in woodwork as claimed in claim 1, it is characterized in that, described chlorinated phosphate ester based flame retardant is any one in tricresyl phosphate (2 chlorine) ethyl ester, tricresyl phosphate (2 chlorine) propyl diester, tricresyl phosphate (1.3-2 chlorine) isopropyl esters.
8. the assay method of chlorinated phosphate ester based flame retardant in woodwork as claimed in claim 7, is characterized in that,
Described gaschromatographic mass spectrometry detects and uses full scan pattern, the fragments characteristic ion of tricresyl phosphate (2 chlorine) ethyl ester is 63,143,204.9,249, the fragments characteristic ion of tricresyl phosphate (2 chlorine) propyl diester is 41.1,99,125.0,157.0,201.0, and the fragments characteristic ion of tricresyl phosphate (1.3-2 chlorine) isopropyl esters is 75,99,191,208.9.
9. the assay method of chlorinated phosphate ester based flame retardant in woodwork as claimed in claim 7, is characterized in that,
Described liquid chromatography tandem mass spectrometry detects and uses many reaction detection MRM pattern, tricresyl phosphate (2 chlorine) ethyl ester parent ion is 286, daughter ion is 98.9,161, tricresyl phosphate (2 chlorine) propyl diester parent ion is 327, daughter ion is 98.9,174.9, tricresyl phosphate (1.3-2 chlorine) isopropyl esters parent ion is 431, and daughter ion is 99.0,209.2.
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