CN102662020B - GC-MS detection method for phosphate ester flame retardant plasticizers in textiles - Google Patents
GC-MS detection method for phosphate ester flame retardant plasticizers in textiles Download PDFInfo
- Publication number
- CN102662020B CN102662020B CN201210066134.4A CN201210066134A CN102662020B CN 102662020 B CN102662020 B CN 102662020B CN 201210066134 A CN201210066134 A CN 201210066134A CN 102662020 B CN102662020 B CN 102662020B
- Authority
- CN
- China
- Prior art keywords
- phosphoric acid
- phosphate
- flame
- solution
- ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a GC-MS detection method for phosphate ester flame retardant plasticizers in textiles, comprising the following steps: 1) preparing a sample solution to be tested; 2) preparing standard solutions: dissolving the phosphate ester flame retardant plasticizers with a solvent, thus preparing gradient standard working solutions; 3) injecting the gradient standard working solutions to GC-MS, selecting an ion monitoring mode to assay, determining peak positions of the phosphate ester flame retardant plasticizers, recording peak areas of quantitative ions, making a standard curvilinear equation with concentration for x-axis and peak area for y-axis; 4) replacing the gradient standard work-solutions in the step 3) with the sample solution obtained in the step 1), determining the phosphate ester flame retardant plasticizers in the sample solution and peak areas thereof with the method in step 3), calculating with the standard curvilinear equation obtained in the step 3) so as to obtain the contents of the phosphate ester flame retardant plasticizers in the sample solution.
Description
Technical field
The present invention relates to a kind of gas chromatography-mass spectrography detection method that is applicable to 8 kind phosphate ester class flame-retardant plasticizers in textile.
Background technology
Phosphate plasticizer is one of main species of plastifier, phosphate plasticizer has fire-retardant and plasticising dual-use function concurrently, fire retardant can be made and plastifier can be made again, can be used for Polyvinylchloride, rubber, polyurethane and other synthetic material, be used in PVC goods, make goods under solar exposure, have good anti-fragility, anti-tarnishing ability and there is good anti-flammability, cryogenic property is good.The goods of making plastifier with it can improve in wearing quality, water tolerance and electrical resistance.Also there is the good function such as wear-resisting, antibacterial, there is good compatibility with polyolefin resin, synthetic rubber etc. such as Polyvinylchloride, acetic acid and NC Nitroncellulose, polystyrene, tygon, there is good plasticising, fire-retardant, wear-resisting, antibacterial etc. multi-functional, be multi-functional plastifier, be commonly used for primary plasticizer.Aromatic phosphoric acid ester low temperature properties is poor, and fatty alcohol (ether) phosphate is better, and other performances are substantially similar.Containing halophosphate, generally as fire retardant, use, aromatic phosphoric ester, aliphatic phosphate ester or aromatic-aliphatic phosphate are used as flame-retardant plasticizer, be one of primary categories in synthetic material processing aid, be widely used in the fields such as synthon, plastics, synthetic rubber, timber, paper, coating.In recent years, because of developing rapidly of flame-retardant textile material, such as flame-resistant terylene, flame-retardant acrylic fibre, Flame Vinylon etc.Along with scientific and technical progress, various countries recently Development and Production multiple fire resistance fibre, as polyisophthaloyl metaphenylene diamide fibre, polyamide one imide fiber, polyimide 2080 fibers, heterocycle polymer PBI fibre (PIM2080), phenolic fibre, Basofil fiber.The flame retardant effect of these fibers is all relatively good, in industry and special dimension, has very large purposes.Therefore in great demand to phosphoric acid ester flame-retardant plasticizer, demand increases very fast.
At present, conventional phosphoric acid ester flame-retardant plasticizer kind has a plurality of kinds such as tributyl phosphate (TBP), trioctyl phosphate (TOP), triphenyl phosphate (TPP), tricresyl phosphate (TCP), diphenyl octyl phosphate (DPOP), phosphate toluene diphenyl ester (CDP) both at home and abroad.Maximum with tricresyl phosphate (TCP) output in aromatic phosphoric acid ester, phosphate toluene diphenyl ester (CDP) takes second place, and triphenyl phosphate (TPP) more takes second place.Under the requirement of the flame retardancy of being everlasting, use, trioctyl phosphate (TOP) output is also very large, it is water insoluble, is soluble in mineral oil and gasoline, has fire-retardant and mildew-proof function, lower temperature resistance is good, in wider temperature range, its pliability changes not obvious, and its animal migration, volatility are larger, processing characteristics is poorer than tricresyl phosphate (TCP), and normal and phthalate is spelled and used.TCP is water insoluble, and can be dissolved in organic solvent and vegetable oil, have fire-retardant, hydrolytic stability is high, oil resistant and the feature such as fungus resistance is good, electrical property is good, but poisonous, low temperature resistance is poor.Diphenyl octyl phosphate (DPOP) compatibility is good, as primary plasticizer, has that anti-flammability, volatility are low, cold-resistant, an against weather, the feature that fast light, heat-resistant stability is good.Nontoxic again, can improve goods wearing quality, water tolerance and electric property, but expensive.Tributyl phosphate (TBP) mainly, as the primary plasticizer of cellulose nitrate, cellulose acetate, chlorinated rubber and Polyvinylchloride, is also commonly used for solvent, the defoamer of coating, bonding agent and ink, the electrostatic agent that disappears, the extractant of rare earth element, rat LD
50for 3000mg/kg.
Follow the fast development of textile industry, synthetic fiber industry, plastifier has become one of most important processing aid, in order to make textile can process and improve the performance of goods, during production, can add various plastifier.But add plastifier meeting stripping, migration and the volatilization loss in the process of processing, use in textile to, affect on the one hand the usability of goods, be discharged on the other hand in surrounding environment, particularly move to human body, to health and environment, may cause damage.Since detecting after dioctyl phthalate (DOP) in tissue and during postmortem, large quantity research has confirmed that plastifier can absorb and the number of ways such as environmental pollution enter in human body and impair one's health by the daily suction of people, skin.Therefore, plastifier toxicity problem causes the extensive concern of international community, and in textile, the research of plastifier assay method also comes into one's own day by day.
At present, European Union has issued relevant decree EN71-9:2005, the phosphate compounds such as the tributyl phosphate in requirement detection toy, triphenyl phosphate, tricresyl phosphate, but the domestic research report that there is no relevant phosphate plasticizer detection method in textile.It is inexorable trend that the ecology production of textile product, ecological consumption and ecology are processed, developing ecology textile is related to the foreign exchange earning level of China's textile product, be related to the industry strategy of sustainable development, Ye Dui China textile industry of running business big and strong will play considerable effect.In order to safeguard national basic security, ensure human health, to preserve the ecological environment; break through the TBT (Technical Barriers to Trade) of developed country; also in order to carry out cleaner production enterprise self-technique development level, the detection method of studying and defining phosphoric acid ester flame-retardant plasticizer in textile product has important practical significance.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of GC-MS(gas chromatography-mass spectrography) detection method of phosphoric acid ester flame-retardant plasticizer in qualitative, quantitative measurement textile rapidly and accurately that adopts.
In order to solve the problems of the technologies described above, the invention provides the gas chromatography-mass spectrum detection method of phosphoric acid ester flame-retardant plasticizer in a kind of textile, comprise the following steps:
1), prepare testing sample solution:
A), in testing sample, add extraction agent, in the ultrasound wave that is then 30～45kHz in frequency, at bath temperature, be ultrasonic extraction 0.5～30min at 20～70 ℃; Obtain respectively the rear sample residue of extract and extraction;
The solid-liquid ratio of testing sample and extraction agent is: 1g/5～50mL;
B), by steps A) sample residue washs with extraction agent after the extraction of gained, obtains cleansing solution;
Extraction agent and steps A) in the liquid ratio of testing sample be: 1～20mL/1g;
C), combining extraction liquid and cleansing solution, at bath temperature, be at 20～70 ℃, reduced pressure concentration after drying up, obtains concentrated residue again;
D), according to the amount ratio of the extraction agent of 1g testing sample correspondence 1～20ml, concentrated residue is fully dissolved with extraction agent, and the sample liquid of gained is with after 0.45 μ m membrane filtration, and the supernatant liquor of gained is testing sample solution, be placed in sample injection bottle and seal, for gas chromatograph-mass spectrometer (GCMS), measure;
2), preparation standard solution:
Using ethyl acetate, acetone, methylene chloride or normal hexane as solvent, phosphoric acid ester flame-retardant plasticizer is dissolved, be mixed with the gradient standard operation solution (being preferably concentration is the gradient standard operation solution of 1～10 μ g/mL) of phosphoric acid ester flame-retardant plasticizer;
3), by gradient standard operation solution injection gas chromatography-GC-MS, select ion monitoring (SIM) pattern to measure, determine the peak position that of phosphoric acid ester flame-retardant plasticizer, record the peak area of quota ion, take concentration as horizontal ordinate, peak area is ordinate, production standard curvilinear equation;
4), get step 1) the testing sample solution step of replacing 3 of gained) in gradient standard operation solution, by step 3) method measures phosphoric acid ester flame-retardant plasticizer and the peak area thereof in testing sample solution, use step 3) typical curve of gained calculates, thereby obtains the phosphoric acid ester flame-retardant plasticizer content in testing sample.
Improvement as the gas chromatography-mass spectrum detection method of phosphoric acid ester flame-retardant plasticizer in textile of the present invention: adopt electron impact ion source (EI source) to detect, select ion monitoring (SIM) pattern;
The chromatographic condition that gas chromatography-mass spectrum detects use is:
Chromatographic column: DB-5MS, 30m * 0.25mm * 0.25 μ m;
Chromatographic column heating schedule: 70 ℃ of initial temperatures, are warming up to 280 ℃ with the speed of 25 ℃/min, insulation 6min;
Carrier gas (helium) flow velocity: 1～2mL/min;
Injector temperature: 200～280 ℃ (preferably 250 ℃);
Ion gun: electron impact ion source (EI source);
Detection mode: select ion monitoring (SIM) pattern;
Ion source temperature: 120～180 ℃ (preferably 150 ℃);
Quadrupole rod temperature: 150～280 ℃ (preferably 230 ℃);
Interface temperature: 200～280 ℃ (preferably 280 ℃);
Sampling volume: 0.1～2 μ L (preferably 1 μ L).
Further improvement as the gas chromatography-mass spectrum detection method of phosphoric acid ester flame-retardant plasticizer in textile of the present invention: phosphoric acid ester flame-retardant plasticizer be between tributyl phosphate (TBP), triphenyl phosphate (TPP), diphenyl octyl phosphate (DPOP), trioctyl phosphate (TOP), phosphate toluene diphenyl ester (CDP), phosphoric acid hemimellitol ester (ToCP), phosphoric acid front three phenyl ester (TmCP) and phosphoric acid at least one in front three phenyl ester (TpCP).
Further improvement as the gas chromatography-mass spectrum detection method of phosphoric acid ester flame-retardant plasticizer in textile of the present invention: the extraction agent step 1) is ethyl acetate, acetone, methylene chloride or normal hexane.
Further improvement as the gas chromatography-mass spectrum detection method of phosphoric acid ester flame-retardant plasticizer in textile of the present invention: step 2): the concentration that is mixed with phosphoric acid ester flame-retardant plasticizer is the gradient standard operation solution of following 5 concentration: 1.0,3.0,5.0,7.0,10 μ g/mL.
Further improvement as the gas chromatography-mass spectrum detection method of phosphoric acid ester flame-retardant plasticizer in textile of the present invention: phosphate toluene diphenyl ester comprises isomeride I (CDP I) and the isomeride II (CDP II) of phosphate toluene diphenyl ester.
Further improvement as the gas chromatography-mass spectrum detection method of phosphoric acid ester flame-retardant plasticizer in textile of the present invention: the phosphoric acid ester flame-retardant plasticizer step 2) is comprised of following 8 kind phosphate ester class flame-retardant plasticizers: between tributyl phosphate, triphenyl phosphate, diphenyl octyl phosphate, trioctyl phosphate, phosphate toluene diphenyl ester, phosphoric acid hemimellitol ester, phosphoric acid, front three phenyl ester and phosphoric acid are to front three phenyl ester; Phosphate toluene diphenyl ester comprises the isomeride I of phosphate toluene diphenyl ester and the isomeride II of phosphate toluene diphenyl ester;
Using ethyl acetate, acetone, methylene chloride or normal hexane as solvent, respectively 8 kind phosphate ester class flame-retardant plasticizers are dissolved, thereby be mixed with respectively the 8 class standard solution that independent concentration is 1000 μ g/mL;
Respectively getting after above-mentioned 8 class standard solution mix and dilute with solvent, is the standard mixed solution of 100 μ g/mL thereby be mixed with the concentration that contains above-mentioned 8 kind phosphate ester class flame-retardant plasticizers respectively; Utilize this standard mixed solution to be mixed with containing described 8 kind phosphate ester class flame-retardant plasticizers is the gradient standard operation solution of following 5 concentration respectively again: 1.0,3.0,5.0,7.0,10 μ g/mL.
The gas chromatography-mass spectrum detection method of phosphoric acid ester flame-retardant plasticizer in textile of the present invention, adopts electron impact ion source (EI source) to detect, and selects ion monitoring (SIM) pattern; Except above-mentioned condition, other mass spectrum parameters are in Table 1.
Table 1,8 kind phosphate ester class flame-retardant plasticizer mass spectrum parameters
Note 1, Q1 represent quota ion, and Q2～Q4 is qualitative ion.
Note 2, phosphate toluene diphenyl ester (CDP I) are isomers with phosphate toluene diphenyl ester (CDP II).
The present invention compared with prior art has following remarkable result:
(1) have not yet to see the detection method report of above-mentioned 8 kind phosphate ester class flame-retardant plasticizers (phosphate toluene diphenyl ester comprises CDP I and CDP II) in relevant textile.
(2) feature that employing gas chromatography-mass spectrography selection ion measurement pattern can be accurately qualitative, quantitative, directly measures, and highly sensitive, impurity disturbs little.
(3) assay method disclosed by the invention is in 1～10 μ g/mL concentration range, and 8 kind phosphate ester class flame-retardant plasticizer linear equations and linearly dependent coefficient be in Table 2, and result shows, the linear relationship of 8 kind phosphate ester class flame-retardant plasticizers is all better.
Table 2, gas chromatography/mass spectrometry 8 kind phosphate ester class flame-retardant plasticizers (phosphate toluene diphenyl ester is containing 2 kinds of isomeride) linear equation and linearly dependent coefficient
(4) adopt ethyl acetate etc. as the extraction solvent of phosphoric acid ester flame-retardant plasticizer, 8 kind phosphate ester class flame-retardant plasticizers in textile samples can be accessed comparatively thoroughly and extract.
(5) ultrasound wave that proportion is 30～45kHz, is ultrasonic extraction 0.5～30min at 20～70 ℃ at bath temperature, simple and convenient extraction, easy operating.
(6) gas chromatography-mass spectrography analytical approach can be effectively separated by 8 kind phosphate ester class flame-retardant plasticizers (containing isomeride) in 15min, carries out qualitative, quantitative mensuration.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Fig. 1 is the gas chromatography-mass spectrum figure of phosphoric acid ester flame-retardant plasticizer of the present invention;
Fig. 2 is the Linear equations of gas chromatography/mass spectrometry tributyl phosphate (TBP) in 1.0～10.0 μ g/mL concentration ranges;
Fig. 3 is the Linear equations of gas chromatography/mass spectrometry triphenyl phosphate (TPP) in 1.0～10.0 μ g/mL concentration ranges;
Fig. 4 is the Linear equations of gas chromatography/mass spectrometry diphenyl octyl phosphate (DPOP) in 1.0～10.0 μ g/mL concentration ranges;
Fig. 5 is the Linear equations of gas chromatography/mass spectrometry trioctyl phosphate (TOP) in 1.0～10.0 μ g/mL concentration ranges;
Fig. 6 is isomer C DP I in the gas chromatography/mass spectrometry phosphate toluene diphenyl ester Linear equations in 1.0～10.0 μ g/mL concentration ranges;
Fig. 7 is isomer C DP II in the gas chromatography/mass spectrometry phosphate toluene diphenyl ester Linear equations in 1.0～10.0 μ g/mL concentration ranges;
Fig. 8 is the Linear equations of gas chromatography/mass spectrometry phosphoric acid hemimellitol ester (ToCP) in 1.0～10.0 μ g/mL concentration ranges;
Fig. 9 is the Linear equations of front three phenyl ester (TmCP) in 1.0～10.0 μ g/mL concentration ranges between gas chromatography/mass spectrometry phosphoric acid;
Figure 10 be gas chromatography/mass spectrometry phosphoric acid to front three phenyl ester (TpCP) Linear equations in 1.0～10.0 μ g/mL concentration ranges.
Embodiment
Below in conjunction with embodiment and comparative example, the present invention is set forth, yet protection scope of the present invention is not only confined to following examples.Person of an ordinary skill in the technical field, according to content disclosed by the invention, all can realize result of the present invention.
1 reagent and material
Unless otherwise specified, it is pure that agents useful for same is analysis.
1.1 ethyl acetate: AR level.
1.2 triphenyl phosphates (TPP) standard items: purity >=99.7%.
1.3 phosphoric acid hemimellitol ester (ToCP) standard items: purity >=96%.
Front three phenyl ester (TmCP) standard items between 1.4 phosphoric acid: purity >=95%.
1.5 phosphoric acid are to front three phenyl ester (TpCP) standard items: purity >=98%.
1.6 tributyl phosphates (TBP) standard items: purity >=98.5%.
1.7 trioctyl phosphates (TOP) standard items: purity >=98%.
1.8 diphenyl octyl phosphates (DPOP) standard items: purity >=90%.
1.9 phosphate toluene diphenyl esters (CDP) standard items: purity >=93%.
Table 3,8 kinds of phosphoric acid ester flame-retardant plasticizer chemical information tables
Note: phosphate toluene diphenyl ester comprises isomer C DP I and isomer C DP II.
1.10 standard reserving solutions: accurately take respectively appropriate above 8 class standard product, with ethyl acetate, be mixed with the standard reserving solution (standard solution) that concentration is 1000 about μ g/mL respectively, then be the standard mixed solution of 100 μ g/mL respectively by the concentration that ethyl acetate is mixed with above-mentioned 8 kind phosphate ester class flame-retardant plasticizers.
1.11 standard operation liquid: pipette respectively the appropriate volume of standard mixed solution, with ethyl acetate dilution, the concentration that is mixed with above-mentioned 8 kind phosphate ester class flame-retardant plasticizers (phosphate toluene diphenyl ester comprises isomer C DP I and isomer C DP II) is 5 gradient standard operation solution of 1 μ g/mL, 3 μ g/mL, 5 μ g/mL, 7 μ g/mL, 10 μ g/mL respectively.
2 equipment and instrument
2.1 gas chromatograph-mass spectrometer (GCMS)s: be furnished with EI ion gun.
2.2 gas chromatographic columns: DB-5MS, μ m * 0.25,30m * 250 μ m or quite person.
2.3 ultrasonic generators: frequency of operation is 30～45kHz.
2.5 rotary vacuum evaporator.
2.6 vortex instrument.
2.7 organic phase filtering membranes: 0.45 μ m.
The glasswares such as 2.8 flat bottom flasks and graduated cylinder, conical flask.
The gas chromatography-mass spectrum detection method of phosphoric acid ester flame-retardant plasticizer in embodiment 1, a kind of textile, comprises the following steps:
1), prepare testing sample solution:
1. get 5.0g testing sample, shredded to 0.5cm * 0.5cm, mix.
2. the testing sample 1.0 grams (being accurate to 0.01 gram) of getting after above-mentioned shredding is placed in conical flask, adds the abundant submergence sample of 20mL extraction agent-ethyl acetate, in the ultrasound wave that is then 40kHz in frequency, at bath temperature, is ultrasonic extraction 30min at 50 ℃; Obtain respectively the rear sample residue of extract and extraction; Extract is proceeded in flat bottom flask.
3. after extraction, sample residue adds 10mL extraction agent to wash, and obtains cleansing solution;
4. by 2. extract and the 3. cleansing solution merging of gained of step of gained of step, in 40 ℃ of water-baths, concentrated near the doing of decompression (0.008MPa), then uses N
2dry up, obtain concentrated residue.Accurately add ethyl acetate, thereby after being settled to 5.0mL, vortex dissolves concentrated residue, obtains sample liquid.
Get 0.45 μ m membrane filtration for 1mL sample liquid, the clear liquid of gained (being supernatant liquor) is testing sample solution, is placed in sample injection bottle to seal, and for gas chromatograph-mass spectrometer (GCMS), measures.
2), preparation standard solution:
Using ethyl acetate as solvent;
Triphenyl phosphate (TPP) standard items: purity >=99.7%;
Phosphoric acid hemimellitol ester (ToCP) standard items: purity >=96%;
Front three phenyl ester (TmCP) standard items between phosphoric acid: purity >=95%;
Phosphoric acid is to front three phenyl ester (TpCP) standard items: purity >=98%;
Tributyl phosphate (TBP) standard items: purity >=98.5%;
Trioctyl phosphate (TOP) standard items: purity >=98%;
Diphenyl octyl phosphate (DPOP) standard items: purity >=90%;
Phosphate toluene diphenyl ester (containing CDP I and CDP II) standard items: purity >=93%.
Taking molecular formula is C
12h
27o
4the about 0.0100g of tributyl phosphate (being accurate to 0.0001g) of P, in the volumetric flask of 10mL, is settled to scale with above solvent (being ethyl acetate), and liquid is mixed with the tributyl phosphate stock solution that concentration is 1000 μ g/mL;
Taking molecular formula is C
18h
15o
4the triphenyl phosphate 0.0100g (being accurate to 0.0001g) of P, in the volumetric flask of 10mL, is settled to scale with above solvent, and liquid is mixed with the triphenyl phosphate stock solution that concentration is 1000 μ g/mL;
Taking molecular formula is C
21h
21o
4the phosphoric acid hemimellitol ester 0.0100g (being accurate to 0.0001g) of P, in the volumetric flask of 10mL, is settled to scale with above solvent, and liquid is mixed with the phosphoric acid hemimellitol ester stock solution that concentration is 1000 μ g/mL;
Taking molecular formula is C
21h
21o
4between the phosphoric acid of P, front three phenyl ester 0.0100g (being accurate to 0.0001g), in the volumetric flask of 10mL, is settled to scale with above solvent, and liquid is mixed with front three phenyl ester stock solution between the phosphoric acid that concentration is 1000 μ g/mL;
Taking molecular formula is C
21h
21o
4the phosphoric acid of P in the volumetric flask of 10mL, is settled to scale with above solvent to front three phenyl ester 0.0100g (being accurate to 0.0001g), and it is that the phosphoric acid of 1000 μ g/mL is to front three phenyl ester stock solution that liquid is mixed with concentration;
Taking molecular formula is C
24h
51o
4the trioctyl phosphate 0.0100g (being accurate to 0.0001g) of P, in the volumetric flask of 10mL, is settled to scale with above solvent, and liquid is mixed with the trioctyl phosphate stock solution that concentration is 1000 μ g/mL;
Taking molecular formula is C
20h
27o
4the diphenyl octyl phosphate 0.0100g (being accurate to 0.0001g) of P, in the volumetric flask of 10mL, is settled to scale with above solvent, and liquid is mixed with the diphenyl octyl phosphate stock solution that concentration is 1000 μ g/mL;
Taking molecular formula is C
19h
17o
4the phosphate toluene diphenyl ester of P (containing CDP I and CDP II) 0.0100g (being accurate to 0.0001g) is in the volumetric flask of 10mL, with above solvent, be settled to scale, liquid is mixed with the phosphate toluene diphenyl ester stock solution that melting concn is 1000 μ g/mL;
Respectively get respectively successively stock solution 1mL that more above-mentioned 8 kinds of concentration are 1000 μ g/mL in the volumetric flask of 10mL, with ethyl acetate constant volume, to scale, be mixed with and contain the mixing stock solution (being standard mixed solution) that above-mentioned 8 kind phosphate ester class flame-retardant plasticizer concentration are 100 μ g/mL;
In the volumetric flask of last mixing stock solution 50 μ L, 150 μ L, 250 μ L, 350 μ L and L to 5 50mL of 500 μ that gets respectively successively 100 μ g/mL, with ethyl acetate, be settled to scale, thereby the concentration that is mixed with 8 kind phosphate ester class flame-retardant plasticizers is the gradient standard operation solution of 1,3,5,7,10 these 5 concentration of μ g/mL respectively.
3), by above-mentioned gradient standard operation solution injection gas chromatography-GC-MS, select ion monitoring (SIM) pattern to measure, determine the peak position that of each phosphoric acid ester flame-retardant plasticizer, record corresponding peak area, take concentration as horizontal ordinate, peak area is ordinate, and production standard curvilinear equation, in Table 4.Specific as follows:
Chromatogram mass spectrum condition is:
A) ion gun: electron impact ion source (EI source);
B) detection mode: select ion monitoring (SIM) pattern;
C) ion source temperature is 150 ℃;
D) quadrupole rod temperature is 230 ℃;
E) chromatographic column: DB-5MS, 30m * 0.25mm * 0.25 μ m;
F) chromatographic column heating schedule: 70 ℃, 0min, is warming up to 280 ℃ with the speed of 25 ℃/min, insulation 6min;
G) injector temperature: 250 ℃;
H) interface temperature is 280 ℃;
I) sample size: 1 μ L;
J) carrier gas (helium) flow velocity: 1mL/min;
K) other mass spectrum conditions are referring to table 1.
Table 4, peak area and linear equation that phosphoric acid ester flame-retardant plasticizer gas chromatography-mass spectrometry analysis is corresponding
4), get step 1) the testing sample solution step of replacing 3 of gained) in gradient standard operation solution, by step 3) method phosphoric acid ester flame-retardant plasticizer and the peak area thereof measured in testing sample solution (substitute the gradient standard operation solution of 1 μ L with the testing sample solution of 1 μ L, all the other are equal to), utilize step 3) typical curve (linear equation) set up, obtain the content of phosphoric acid ester flame-retardant plasticizer in testing sample solution; Extension rate (being the conversion relation between testing sample 1g and constant volume 5.0mL) per sample again; Obtain the content of phosphoric acid ester flame-retardant plasticizer in testing sample.
5), qualitative analysis
Corresponding step 4), under same test conditions, in sample, determinand has identical retention time with the standard substance detecting simultaneously, and in the relative abundance of the qualitative ion of the sample standard solution spectrogram approaching with concentration, the relative abundance of corresponding qualitative ion compares, if deviation is no more than the scope of table 5 regulation, can be judged to be and in sample, has corresponding determinand.
The maximum allowable offset of relative abundance of ions when table 5, qualitative confirmation
| Relative abundance of ions, % | ＞50 | ＞20～50 | ＞10～20 | ≤10 |
| The maximum deviation allowing, % | ±20 | ±25 | ±30 | ±50 |
6), quantitative test
Corresponding step 4), this method adopts external standard method quantitative, according to measured matter content situation in sample liquid (testing sample solution), the selected close standard operation solution of concentration, standard operation solution and sample liquid equal-volume ginseng is injected to sample and measure, standard operation solution and treat that the response of determinand in sample measuring liquid all should be in the range of linearity of instrument.If the detection response of sample liquid exceeds the range of linearity that instrument detects, after can suitably diluting, in the range of linearity that sample detection response is detected at instrument, carry out quantitative measurement.Note: above-mentioned how dilution is the routine techniques of the industry.
Be described as follows: the gradient standard operation solution of selecting 8 kind phosphate ester class flame-retardant plasticizers to be mixed with (phosphate toluene diphenyl ester comprises isomer C DP I and isomer C DP II) 1～10 μ g/mL; In order to consider sample solution (testing sample solution) to the ionogenic protection of gas chromatograph-mass spectrometer (GCMS), if the maximum concentration of gradient standard operation solution improves, with regard to the higher testing sample of energy detectable concentration.Generally, in textile, the detection of the concentration of phosphoric acid ester flame-retardant plasticizer can directly be carried out completely with " the gradient standard operation solution of 1～10 μ g/mL ", that is, and and without sample liquid is carried out to dilution process.When in particular cases, when the concentration of phosphoric acid ester flame-retardant plasticizer is considerably beyond normal concentration in textile, can rely on the range of linearity of typical curve, thus the multiple that judgement need to be diluted sample liquid, and then detect accordingly.
For the present invention, in textile during the concentration≤40mg/kg of phosphoric acid ester flame-retardant plasticizer, can directly use the gradient standard operation solution of 1～10 μ g/mL that the present invention sets, without diluting.
7), detect lower bound
When sample introduction concentration is 0.1 μ g/mL, the S/N of tributyl phosphate (TBP) is 5440.8, with 3 times of signal to noise ratio (S/N ratio)s (S/N=3), determine concentration limit (LOD), therefore, this method is 0.055 μ g/kg to the LOD of TBP in textile, with 10 times of signal to noise ratio (S/N ratio)s (S/N=10), determine minimum quantitative concentrations (LOQ), therefore, this method is 0.18 μ g/kg to the LOQ of TBP in textile; In like manner, the LOD of triphenyl phosphate (TPP) is 0.082 μ g/kg, and LOQ is 0.27 μ g/kg; The LOD of diphenyl octyl phosphate (DPOP) is 0.12 μ g/kg, and LOQ is 0.40 μ g/kg; The LOD of trioctyl phosphate (TOP) is 0.088 μ g/kg, and LOQ is 0.29 μ g/kg; The LOD of phosphate toluene diphenyl ester (CDP I) is 0.48 μ g/kg, and LOQ is 1.57 μ g/kg; The LOD of phosphate toluene diphenyl ester (CDP II) is 0.93 μ g/kg, and LOQ is 3.07 μ g/kg; The LOD of phosphoric acid hemimellitol ester (ToCP) is 0.25 μ g/kg, and LOQ is 0.81 μ g/kg; Between phosphoric acid, the LOD of front three phenyl ester (TmCP) is 0.23 μ g/kg, and LOQ is 0.75 μ g/kg; Phosphoric acid is 0.29 μ g/kg to the LOD of front three phenyl ester (TpCP), and LOQ is 0.95 μ g/kg;
Experiment 1, recovery experiment and Precision Experiment (cotton cloth):
With the in advance known basic cotton cloth that does not contain this 8 kind phosphate ester class flame-retardant plasticizer (phosphate toluene diphenyl ester comprises isomer C DP I and isomer C DP II), add and contain above-mentioned 8 kind phosphate ester class flame-retardant plasticizer standard solution, carried out interpolation recovery test, making the concentration of above-mentioned 8 kind phosphate ester class flame-retardant plasticizers in sample is 1mg/kg respectively, 5mg/kg and 10mg/kg, according to embodiment 1, operate, , sample constant volume is 5mL, corresponding to the concentration in sample solution (testing sample solution), should be respectively 0.2 μ g/mL, 1 μ g/mL and 2 μ g/mL, every group is repeated 6 times, the sample obtaining adds recovery sample peak area in Table 6, corresponding sample concentration is in Table 7.
In table 6, cotton, add the sample peak area result (n=6) that recovery test is corresponding
In table 7, cotton, add the sample concentration result (n=6) that recovery test is corresponding
Note: RSD (%) represents relative standard deviation.
Experiment 2, recovery experiment and Precision Experiment (terylene cloth)
With the in advance known basic terylene cloth that does not contain this 8 kind phosphate ester class flame-retardant plasticizer (phosphate toluene diphenyl ester comprises isomer C DP I and isomer C DP II), add and contain above-mentioned 8 kind phosphate ester class flame-retardant plasticizer standard solution, carried out interpolation recovery test, making the concentration of above-mentioned 8 kind phosphate ester class flame-retardant plasticizers in sample is 1mg/kg respectively, 5mg/kg and 10mg/kg, according to embodiment 1, operate, , sample constant volume is 5mL, corresponding to the concentration in sample solution (testing sample solution), should be respectively 0.2 μ g/mL, 1 μ g/mL and 2 μ g/mL, every group is repeated 6 times, the sample obtaining adds recovery sample peak area in Table 8, corresponding sample concentration is in Table 9.
In table 8, terylene cloth, add the sample peak area result (n=6) that recovery test is corresponding
In table 9, woven dacron, add the sample concentration result (n=6) that recovery test is corresponding
Comparative example 1, by the step 1 of embodiment 1) in extraction solvent (being extraction agent) and step 2 used) in solvent used by ethyl acetate corresponding changing into respectively: acetone, methylene chloride, ethyl acetate, normal hexane and methyl alcohol; And in step 1) in, the amount ratio according to the extraction agent of the corresponding 10ml of 1g testing sample, fully dissolves concentrated residue with extraction agent; All the other are equal to embodiment 1.Then the content that is equal to experiment 2 is tested.
With the in advance known basic terylene cloth that does not contain this 8 kind phosphate ester class flame-retardant plasticizer (phosphate toluene diphenyl ester comprises isomer C DP I and isomer C DP II), add and contain above-mentioned 8 kind phosphate ester class flame-retardant plasticizer standard solution, carried out interpolation recovery test, make the concentration equal 20mg/kg of above-mentioned 8 kind phosphate ester class flame-retardant plasticizers in sample, according to comparative example 1, operate, , sample constant volume is 10mL, corresponding to the concentration in analytical solution, should be 2 μ g/mL, every group is repeated 3 times, the sample obtaining adds recovery sample peak area in Table 10, corresponding sample concentration is in Table 11.
In table 10, woven dacron, add the sample peak area result (n=2) that recovery test is corresponding
In table 11, woven dacron, add the sample concentration result (n=3) that recovery test is corresponding
From the data of table 10 and table 11, can find out, acetone, methylene chloride, ethyl acetate, normal hexane are more approaching to the extraction efficiency of 8 kinds of phosphoric acid ester flame-retardant plasticizers in textile, extraction comparison is complete, all higher than the extraction efficiency of methyl alcohol, therefore, acetone, methylene chloride, ethyl acetate, normal hexane all can be used as extraction solvent.
Finally, it is also to be noted that, what more than enumerate is only several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, can also have many distortion.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.
Claims (5)
1. the gas chromatography-mass spectrum detection method of phosphoric acid ester flame-retardant plasticizer in textile, is characterized in that comprising the following steps:
1), prepare testing sample solution:
A), in testing sample, add extraction agent, in the ultrasound wave that is then 30～45kHz in frequency, at bath temperature, be ultrasonic extraction 0.5～30min at 20～70 ℃; Obtain respectively the rear sample residue of extract and extraction;
The solid-liquid ratio of described testing sample and extraction agent is: 1g/5～50mL;
B), by steps A) sample residue washs with extraction agent after the extraction of gained, obtains cleansing solution;
Described extraction agent and steps A) in the liquid ratio of testing sample be: 1～20mL/1g;
C), combining extraction liquid and cleansing solution, at bath temperature, be at 20～70 ℃, reduced pressure concentration after drying up, obtains concentrated residue again;
D), according to the amount ratio of the extraction agent of 1g testing sample correspondence 1～20ml, concentrated residue is fully dissolved with extraction agent, the sample liquid of gained is with after 0.45 μ m membrane filtration, the clear liquid of gained is testing sample solution;
2), preparation standard solution:
Using ethyl acetate, acetone, methylene chloride or normal hexane as solvent, phosphoric acid ester flame-retardant plasticizer is dissolved, thereby be mixed with the gradient standard operation solution of phosphoric acid ester flame-retardant plasticizer;
Described phosphoric acid ester flame-retardant plasticizer is comprised of following 8 kind phosphate ester class flame-retardant plasticizers: between tributyl phosphate, triphenyl phosphate, diphenyl octyl phosphate, trioctyl phosphate, phosphate toluene diphenyl ester, phosphoric acid hemimellitol ester, phosphoric acid, front three phenyl ester and phosphoric acid are to front three phenyl ester; Phosphate toluene diphenyl ester comprises the isomeride I of phosphate toluene diphenyl ester and the isomeride II of phosphate toluene diphenyl ester;
3), by gradient standard operation solution injection gas chromatography-GC-MS, employing electron impact ion source detects, select ion monitoring pattern to measure, determine the peak position that of phosphoric acid ester flame-retardant plasticizer, record the peak area of quota ion, take concentration as horizontal ordinate, and peak area is ordinate, production standard curvilinear equation;
The chromatographic condition that gas chromatography-mass spectrum detects use is:
Chromatographic column: DB-5MS, 30m * 0.25mm * 0.25 μ m;
Chromatographic column heating schedule: 70 ℃ of initial temperatures, are warming up to 280 ℃ with the speed of 25 ℃/min, insulation 6min;
Flow rate of carrier gas: 1～2mL/min; Carrier gas is helium;
Injector temperature: 200～280 ℃;
Ion gun: electron impact ion source;
Detection mode: select ion monitoring pattern;
Ion source temperature: 120～180 ℃;
Quadrupole rod temperature: 150～280 ℃;
Interface temperature: 200～280 ℃;
Sampling volume: 0.1～2 μ L;
4), get step 1) the testing sample solution step of replacing 3 of gained) in gradient standard operation solution, by step 3) method measures phosphoric acid ester flame-retardant plasticizer and the peak area thereof in testing sample solution, use step 3) typical curve of gained calculates, thereby obtains the phosphoric acid ester flame-retardant plasticizer content in testing sample;
Described phosphoric acid ester flame-retardant plasticizer be between tributyl phosphate, triphenyl phosphate, diphenyl octyl phosphate, trioctyl phosphate, phosphate toluene diphenyl ester, phosphoric acid hemimellitol ester, phosphoric acid front three phenyl ester and phosphoric acid to front three phenyl ester.
2. the gas chromatography-mass spectrum detection method of phosphoric acid ester flame-retardant plasticizer in textile according to claim 1, is characterized in that: the concentration that is mixed with phosphoric acid ester flame-retardant plasticizer described step 2) is the gradient standard operation solution of 1～10 μ g/mL.
3. the gas chromatography-mass spectrum detection method of phosphoric acid ester flame-retardant plasticizer in textile according to claim 2, is characterized in that: the extraction agent described step 1) is ethyl acetate, acetone, methylene chloride or normal hexane.
4. the gas chromatography-mass spectrum detection method of phosphoric acid ester flame-retardant plasticizer in textile according to claim 3, is characterized in that: described step 2): the concentration that is mixed with phosphoric acid ester flame-retardant plasticizer is the gradient standard operation solution of following 5 concentration: 1.0,3.0,5.0,7.0,10 μ g/mL.
5. according to the gas chromatography-mass spectrum detection method of phosphoric acid ester flame-retardant plasticizer in the arbitrary described textile of claim 1～4, it is characterized in that:
Using ethyl acetate, acetone, methylene chloride or normal hexane as solvent, respectively 8 kind phosphate ester class flame-retardant plasticizers are dissolved, thereby be mixed with respectively the 8 class standard solution that independent concentration is 1000 μ g/mL;
Respectively getting after above-mentioned 8 class standard solution mix and dilute with solvent, is the standard mixed solution of 100 μ g/mL thereby be mixed with the concentration that contains above-mentioned 8 kind phosphate ester class flame-retardant plasticizers respectively; Utilize this standard mixed solution to be mixed with containing described 8 kind phosphate ester class flame-retardant plasticizers is the gradient standard operation solution of following 5 concentration respectively again: 1.0,3.0,5.0,7.0,10 μ g/mL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210066134.4A CN102662020B (en) | 2012-03-14 | 2012-03-14 | GC-MS detection method for phosphate ester flame retardant plasticizers in textiles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210066134.4A CN102662020B (en) | 2012-03-14 | 2012-03-14 | GC-MS detection method for phosphate ester flame retardant plasticizers in textiles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102662020A CN102662020A (en) | 2012-09-12 |
| CN102662020B true CN102662020B (en) | 2014-11-12 |
Family
ID=46771552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210066134.4A Expired - Fee Related CN102662020B (en) | 2012-03-14 | 2012-03-14 | GC-MS detection method for phosphate ester flame retardant plasticizers in textiles |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102662020B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103792307B (en) * | 2012-10-26 | 2015-09-16 | 中国石油化工股份有限公司 | Measure phthalic acid ester content extract and application thereof in polrvinyl chloride product |
| CN103913518A (en) * | 2012-12-31 | 2014-07-09 | 天士力制药集团股份有限公司 | Method for detecting content of plasticizer in white spirit and application thereof in detection of migration rate of plasticizer |
| CN103235053B (en) * | 2013-04-17 | 2015-01-21 | 江苏中烟工业有限责任公司 | Method for determining tributyl phosphate in dry food packaging paper |
| CN103926361B (en) * | 2014-04-14 | 2016-09-14 | 深圳市盛波光电科技有限公司 | A kind of method measuring triphenyl phosphate amount of precipitation |
| CN104076104A (en) * | 2014-07-15 | 2014-10-01 | 浙江出入境检验检疫局检验检疫技术中心 | Method for detecting transfer volume of phosphate ester plasticisers in acid sweat in textile |
| CN104391069B (en) * | 2014-11-27 | 2016-08-17 | 广州广电计量检测股份有限公司 | A kind of method of multiple phosphorus flame retardant in plastics of detection simultaneously |
| CN105806982B (en) * | 2016-05-12 | 2018-08-17 | 江苏亿科检测技术服务有限公司 | The assay method of tetrabromophthalic anhydride dioctyl ester in a kind of textile |
| CN106556653A (en) * | 2016-08-30 | 2017-04-05 | 北京碧水源膜科技有限公司 | Tributyl phosphate content assaying method in a kind of IsoparG |
| CN108562660B (en) * | 2018-02-08 | 2021-08-20 | 河南中烟工业有限责任公司 | Method for detecting content of phosphate plasticizer in paper packaging material for cigarettes |
| KR102241870B1 (en) * | 2018-02-23 | 2021-04-16 | 주식회사 엘지화학 | High-speed Processing Gas Chromatography System for Analyzing Additives and Analysis Method Using the Same |
| CN108872429A (en) * | 2018-06-29 | 2018-11-23 | 江苏亿科检测技术服务有限公司 | The detection method of 2- ethylhexyl diphenyl phosphate in a kind of leather |
| CN117203521A (en) * | 2021-03-31 | 2023-12-08 | 荣昌生物制药(烟台)股份有限公司 | Method for detecting TCEP content in ADC by LC-MS/MS method |
| CN114716823B (en) * | 2022-04-26 | 2023-01-06 | 金旸（厦门）新材料科技有限公司 | Flame-retardant reinforced bio-based long carbon chain nylon material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101776663A (en) * | 2010-02-05 | 2010-07-14 | 谱尼测试科技（北京）有限公司 | Method for determining content of tris (2-chloroethyl) phosphate |
| CN102279239A (en) * | 2011-07-21 | 2011-12-14 | 广东出入境检验检疫局检验检疫技术中心 | Method for detecting content of triocresyl phosphate fire retardant in rubber part of electrical or electronic product |
-
2012
- 2012-03-14 CN CN201210066134.4A patent/CN102662020B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101776663A (en) * | 2010-02-05 | 2010-07-14 | 谱尼测试科技（北京）有限公司 | Method for determining content of tris (2-chloroethyl) phosphate |
| CN102279239A (en) * | 2011-07-21 | 2011-12-14 | 广东出入境检验检疫局检验检疫技术中心 | Method for detecting content of triocresyl phosphate fire retardant in rubber part of electrical or electronic product |
Non-Patent Citations (4)
| Title |
|---|
| 气相色谱2质谱法测定玩具中的4种阻燃剂;马强 等;《分析实验室》;20110401;第29卷(第4期);第37－40页 * |
| 王成云 等.超声萃取/气相色谱－串联质谱法同时测定纺织品中6种禁用有机磷阻燃剂.《分析测试学报》.2011,第30卷(第8期),第917－921页. * |
| 郭春海 等.气相色谱－质谱法测定聚氯乙烯包装材料和食品模拟物中的46种增塑剂.《色谱》.2011,第29卷(第1期),第42－48页. * |
| 马强 等.气相色谱2质谱法测定玩具中的4种阻燃剂.《分析实验室》.2011,第29卷(第4期),第37－40页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102662020A (en) | 2012-09-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102662020B (en) | GC-MS detection method for phosphate ester flame retardant plasticizers in textiles | |
| CN102628843B (en) | Gas chromatography for detection of phosphate fire-retardant plasticizer in textile | |
| Farajzadeh et al. | Deep eutectic solvent-based dispersive liquid–liquid microextraction | |
| CN106841471B (en) | It is a kind of to measure 12 kinds of remaining methods of OPEs in water sample and deposit simultaneously | |
| CN106908549B (en) | It is a kind of to measure 12 kinds of remaining methods of OPEs in pedotheque simultaneously | |
| CN103713062B (en) | The method for quick of Determination of Residual Organic Solvents is limited the use of in a kind of textile | |
| CN101865886B (en) | Method for measuring residual quantity of chloramphenicol in propolis by using high performance liquid chromatography tandem mass spectrum | |
| CN103808847A (en) | Method for simultaneously detecting DMF (Dimethyl Formamide), DMAC (Dimethylacetamide) and NMP (N-Methylpyrrolidone) through gas chromatography-mass spectrometry | |
| CN101776663A (en) | Method for determining content of tris (2-chloroethyl) phosphate | |
| CN105498694A (en) | Temperature-sensitive polymer-coated metal organic framework magnetic material and application thereof | |
| CN102288691A (en) | Method for assaying short-chain chlorinated paraffin wax in plastics, rubbers and textile materials | |
| CN109374769A (en) | A kind of method of a variety of organophosphorus esters in ultra performance liquid chromatography-mass spectroscopy surface water | |
| CN104849373A (en) | Method for testing residual amount of perfluoro caprylic acid in leather based on precolumn derivatization-high performance liquid chromatography-fluorescence detector | |
| CN102279229A (en) | Method for measuring content of tetrabromobisphenol A, salts and ester compounds thereof | |
| CN106770820A (en) | Three kinds of detection methods of phosphorus flame retardant in a kind of polyurethane foam product | |
| CN101865890A (en) | Method for measuring content of decabromodiphenyl oxide in plastics by liquid phase chromatography | |
| CN101598716B (en) | Test strip for fast testing gossypol and preparation method and application thereof | |
| CN102062766B (en) | Method for measuring nonyl phenol in cosmetic | |
| CN102323342B (en) | Detecting method of aromatic amine compound in water sample | |
| CN101865887B (en) | Method for detecting nitromidazole residue in royal jelly by using high performance liquid chromatography tandem mass spectrum | |
| Raber et al. | Quantitative analysis of arsenic containing hydrocarbons in marine samples by GC-MS | |
| CN105738511A (en) | Method for detecting 1,2-benzenedicarboxylic acid-dialkyl ester plasticizer in plastic through gas chromatography-mass spectrometry | |
| CN103472176B (en) | Detect the method for DMF residual quantity in PU leather | |
| CN110824036B (en) | Method for measuring octabromos ether in daily consumer products | |
| CN102288690A (en) | Method for determining content of tri (2-chloroethyl) phosphate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141112 Termination date: 20190314 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |