CN102662020A - 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
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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 the textile.
Background technology
Phosphate plasticizer is one of main kind of plastifier; Phosphate plasticizer has concurrently fire-retardant and the plasticising dual-use function; Can make fire retardant and can make plastifier again, can be used for PVC, rubber, polyurethane and other synthetic material, be used in the PVC goods; Make goods under solar exposure, good anti-fragility arranged, anti-tarnishing ability and have excellent flame-retardant performance, cryogenic property is good.The goods of making plastifier with it can improve in wearing quality, water tolerance and electric property.Also has good function such as wear-resisting, antibiotic; Has good compatibility with polyolefin resines such as PVC, acetic acid and NC Nitroncellulose, polystyrene, tygon, synthetic rubber etc.; Has good plasticising, fire-retardant, wear-resisting, antibiotic etc. multi-functional; Be multi-functional plastifier, the primary plasticizer of doing commonly used.The aromatic phosphoric acid ester low temperature properties is poor, and fatty alcohol (ether) phosphate is then better, and other performances are similar basically.Containing halophosphate generally uses as fire retardant; Aromatic phosphoric ester, aliphatic phosphate ester or aromatic-aliphatic phosphate then use as flame-retardant plasticizer; Be one of primary categories in the 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, fire-retardant polyvinyl etc.Along with progress of science and technology; Various countries recently Development and Production multiple fire resistance fibre, like 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 very big purposes is arranged.Therefore in great demand to the phosphoric acid ester flame-retardant plasticizer, demand increases very fast.
At present, phosphoric acid ester flame-retardant plasticizer kind commonly used both at home and abroad has tributyl phosphate (TBP), trioctyl phosphate (TOP), triphenyl phosphate (TPP), tricresyl phosphate (TCP), diphenyl octyl phosphate (DPOP), phosphate toluene diphenyl ester a plurality of kinds such as (CDP).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.The requirement of the flame retardancy of being everlasting is used down, and trioctyl phosphate (TOP) output is also very big, and it is water insoluble; Be soluble in mineral oil and gasoline, have 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 bigger; Processing characteristics is poorer than tricresyl phosphate (TCP), and normal and phthalate is pieced together usefulness.TCP is water insoluble, and can be dissolved in organic solvent and vegetable oil, have fire-retardant, hydrolytic stability is high, oil resistant and characteristics such as fungus resistance is good, electrical property is good, but poisonous, low temperature resistance is relatively poor.Diphenyl octyl phosphate (DPOP) compatibility is good, as primary plasticizer, has that anti-flammability, volatility are low, cold-resistant, an against weather, fast light, characteristics that heat-resistant stability is good.Nontoxic again, can improve goods wearing quality, water tolerance and electric property, but cost an arm and a leg.Tributyl phosphate (TBP) mainly as the primary plasticizer of cellulose nitrate, cellulose acetate, chlorinated rubber and PVC, is also used always and is made solvent, the foam-breaking agent of coating, bonding agent and printing ink, the electrostatic agent that disappears, the extractant of REE, rat LD
50Be 3000mg/kg.
Follow the fast development of textile industry, synthetic fiber industry, plastifier has become one of most important processing aid, can process and improve the performance of goods in order to make textile, can add various plastifier during production.But add plastifier meeting stripping, migration and the volatilization loss in the process of processing, use in the textile to; Influence the usability of goods on the one hand; Be discharged on the other hand in the surrounding environment, particularly move to human body, possibly cause damage health and environment.After in tissue, detecting dioctyl phthalate (DOP) when the postmortem, big quantity research has confirmed that plastifier can absorb and number of ways such as environmental pollution gets in the human body and impairs one's health through the daily suction of people, skin.Therefore, the plastifier toxicity problem causes the extensive concern of international community, and the research of plastifier assay method also comes into one's own day by day in the textile.
At present; European Union has issued relevant decree EN71-9:2005; Phosphate compounds such as the tributyl phosphate in the requirement detection toy, triphenyl phosphate, tricresyl phosphate, but the domestic research report that does not still have relevant phosphate plasticizer detection method in textile.It is inexorable trend that the ecology production of textile product, ecological consumption and ecology are handled; The 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, also will play considerable effect China's textile industry of running business big and strong.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 and to promote enterprise's self-technique development level, the detection method of studying and defining phosphoric acid ester flame-retardant plasticizer in the textile product has important practical significance.
Summary of the invention
The technical matters that the present invention will solve provides and a kind ofly adopts that GC-MS is qualitative rapidly and accurately, the detection method of phosphoric acid ester flame-retardant plasticizer in the quantitative measurement textile.
In order to solve the problems of the technologies described above, the present invention provides the gas chromatography-mass spectrum detection method of phosphoric acid ester flame-retardant plasticizer in a kind of textile, may further comprise the steps:
1), preparation testing sample solution:
A), in testing sample, add extraction agent, be in the ultrasound wave of 30～45kHz in frequency then, be 20～70 ℃ of following ultrasonic extraction 0.5～30min at bath temperature; Get extract and extraction back sample residue respectively;
The solid-liquid ratio of testing sample and extraction agent is: 1g/5～50mL;
B), with steps A) the sample residue washs with extraction agent after the extraction of gained, cleansing solution;
Extraction agent and steps A) in the liquid material ratio of testing sample be: 1～20mL/1g;
C), combining extraction liquid and cleansing solution, be under 20～70 ℃ at bath temperature, concentrating under reduced pressure again after drying up, concentrated residue;
D), according to the amount ratio of the extraction agent of the corresponding 1～20ml of 1g testing sample; Concentrated residue is fully dissolved with extraction agent, gained the appearance liquid with 0.45 μ m membrane filtration after, the supernatant liquor of gained is a testing sample solution; Place the sample introduction bottle to seal, supply gas chromatograph-mass spectrometer (GCMS) to measure;
2), preparation standard solution:
As solvent,, 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 with ethyl acetate, acetone, methylene chloride or normal hexane with the dissolving of phosphoric acid ester flame-retardant plasticizer;
3), with gradient standard operation solution injection gas chromatography-GC-MS, select ion monitoring (SIM) pattern to measure, confirm the peak position that of phosphoric acid ester flame-retardant plasticizer; The peak area of record quota ion; With concentration is horizontal ordinate, and peak area is an ordinate, the production standard curvilinear equation;
4), get the testing sample solution step of replacing 3 of step 1) gained) in gradient standard operation solution; Set by step 3) method is measured phosphoric acid ester flame-retardant plasticizer and the peak area thereof in the testing sample solution; Use the typical curve of step 3) gained to calculate, thereby obtain the phosphoric acid ester flame-retardant plasticizer content in the testing sample.
Improvement as the gas chromatography-mass spectrum detection method of phosphoric acid ester flame-retardant plasticizer in the textile of the present invention: adopt electron impact ion source (EI source) to detect, select ion monitoring (SIM) pattern;
Gas chromatography-mass spectrum detects the chromatographic condition that uses:
Chromatographic column: DB-5MS, 30m * 0.25mm * 0.25 μ m;
The 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 ℃ (preferred 250 ℃);
Ion gun: electron impact ion source (EI source);
Detection mode: select ion monitoring (SIM) pattern;
Ion source temperature: 120～180 ℃ (preferred 150 ℃);
Quadrupole rod temperature: 150～280 ℃ (preferred 230 ℃);
Interface temperature: 200～280 ℃ (preferred 280 ℃);
Sampling volume: 0.1～2 μ L (preferred 1 μ L).
Further improvement as the gas chromatography-mass spectrum detection method of phosphoric acid ester flame-retardant plasticizer in the textile of the present invention: the phosphoric acid ester flame-retardant plasticizer is at least a in the front three phenyl ester (TpCP) of front three phenyl ester (TmCP) and phosphoric acid 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.
Further improvement as the gas chromatography-mass spectrum detection method of phosphoric acid ester flame-retardant plasticizer in the textile of the present invention: the extraction agent in the 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 the textile of the present invention: step 2): the concentration that is mixed with the 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 the textile of the present invention: phosphate toluene diphenyl ester comprises the 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 the textile of the present invention: the phosphoric acid ester flame-retardant plasticizer step 2) is made up of following 8 kind phosphate ester class flame-retardant plasticizers: front three phenyl ester and phosphoric acid are to the front three phenyl ester between tributyl phosphate, triphenyl phosphate, diphenyl octyl phosphate, trioctyl phosphate, phosphate toluene diphenyl ester, phosphoric acid hemimellitol ester, phosphoric acid; Phosphate toluene diphenyl ester comprises the isomeride I of phosphate toluene diphenyl ester and the isomeride II of phosphate toluene diphenyl ester;
As solvent,, thereby be mixed with the 8 class standard solution that independent concentration is 1000 μ g/mL respectively with ethyl acetate, acetone, methylene chloride or normal hexane respectively with the dissolving of 8 kind phosphate ester class flame-retardant plasticizers;
Respectively getting and dilute with solvent after above-mentioned 8 class standard solution mix, 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 again to contain said 8 kind phosphate ester class flame-retardant plasticizers and be the gradient standard operation solution of following 5 concentration respectively: 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 the 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 seen table 1.
Table 1,8 kind phosphate ester class flame-retardant plasticizer mass spectrum parameters
Notes 1, Q1 represent quota ion, and Q2～Q4 is qualitative ion.
Notes 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:
The detection method of (1) not seeing above-mentioned 8 kind phosphate ester class flame-retardant plasticizers (phosphate toluene diphenyl ester comprises CDP I and CDP II) in the relevant textile is at present as yet reported.
(2) adopt gas chromatography-mass spectrography to select the ion measurement pattern can accurately qualitative, quantitative characteristics, directly measure, 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 are seen table 2, and the result shows that the linear relationship of 8 kind phosphate ester class flame-retardant plasticizers is all better.
Table 2, GC-MS are measured 8 kind phosphate ester class flame-retardant plasticizers (phosphate toluene diphenyl ester contains 2 kinds of isomeride) linear equation and linearly dependent coefficient
(4) adopt the extraction solvent as the phosphoric acid ester flame-retardant plasticizer such as ethyl acetate, make 8 kind phosphate ester class flame-retardant plasticizers in the textile samples can access comparatively completely and extract.
(5) adopting frequency is the ultrasound wave of 30～45kHz, is 20～70 ℃ of following ultrasonic extraction 0.5～30min at bath temperature, simple and convenient extraction, easy operating.
(6) the gas chromatography-mass spectrography analytical approach can be separated 8 kind phosphate ester class flame-retardant plasticizers (containing isomeride) in 15min effectively, carries out qualitative, quantitative and measures.
Description of drawings
Do further explain below in conjunction with the accompanying drawing specific embodiments of the invention.
Fig. 1 is the gas chromatography-mass spectrum figure of phosphoric acid ester flame-retardant plasticizer of the present invention;
Fig. 2 is that GC-MS is measured the linear equation figure of tributyl phosphate (TBP) in 1.0～10.0 μ g/mL concentration ranges;
Fig. 3 is that GC-MS is measured the linear equation figure of triphenyl phosphate (TPP) in 1.0～10.0 μ g/mL concentration ranges;
Fig. 4 is that GC-MS is measured the linear equation figure of diphenyl octyl phosphate (DPOP) in 1.0～10.0 μ g/mL concentration ranges;
Fig. 5 is that GC-MS is measured the linear equation figure of trioctyl phosphate (TOP) in 1.0～10.0 μ g/mL concentration ranges;
Fig. 6 is that GC-MS is measured the linear equation figure of isomer C DP I in 1.0～10.0 μ g/mL concentration ranges in the phosphate toluene diphenyl ester;
Fig. 7 is that GC-MS is measured the linear equation figure of isomer C DP II in 1.0～10.0 μ g/mL concentration ranges in the phosphate toluene diphenyl ester;
Fig. 8 is that GC-MS is measured the linear equation figure of phosphoric acid hemimellitol ester (ToCP) in 1.0～10.0 μ g/mL concentration ranges;
Fig. 9 is that GC-MS is measured the linear equation figure of front three phenyl ester (TmCP) in 1.0～10.0 μ g/mL concentration ranges between phosphoric acid;
Figure 10 is that GC-MS is measured phosphoric acid to the linear equation figure of front three phenyl ester (TpCP) in 1.0～10.0 μ g/mL concentration ranges.
Embodiment
Below in conjunction with embodiment and Comparative Examples the present invention is set forth, yet protection scope of the present invention is not only to be confined to following examples.The those of ordinary skill of affiliated technical field all can be realized result of the present invention according to content disclosed by the invention.
1 reagent and material
Except as otherwise herein provided, it is pure that agents useful for same is analysis.
1.1 ethyl acetate: AR level.
1.2 triphenyl phosphate (TPP) standard items: purity >=99.7%.
1.3 phosphoric acid hemimellitol ester (ToCP) standard items: purity >=96%.
1.4 front three phenyl ester (TmCP) standard items between phosphoric acid: purity >=95%.
1.5 phosphoric acid is to front three phenyl ester (TpCP) standard items: purity >=98%.
1.6 tributyl phosphate (TBP) standard items: purity >=98.5%.
1.7 trioctyl phosphate (TOP) standard items: purity >=98%.
1.8 diphenyl octyl phosphate (DPOP) standard items: purity >=90%.
1.9 phosphate toluene diphenyl ester (CDP) standard items: purity >=93%.
Table 3,8 kinds of phosphoric acid ester flame-retardant plasticizer chemical information tables
Annotate: phosphate toluene diphenyl ester comprises isomer C DP I and isomer C DP II.
1.10 standard reserving solution: accurately take by weighing an amount of above 8 class standard article respectively; Using ethyl acetate to be mixed with concentration respectively is the standard reserving solution (standard solution) about 1000 μ g/mL, and the concentration of using ethyl acetate to be mixed with above-mentioned 8 kind phosphate ester class flame-retardant plasticizers again is the standard mixed solution of 100 μ g/mL respectively.
1.11 standard operation liquid: pipette an amount of volume of standard mixed solution respectively; With the 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): be furnished with the EI ion gun.
2.2 gas chromatographic column: DB-5MS, 30m * 250 μ m * 0.25 μ m or suitable person.
2.3 ultrasonic generator: frequency of operation is 30～45kHz.
2.5 rotary vacuum evaporator.
2.6 vortex appearance.
2.7 organic phase filtering membrane: 0.45 μ m.
2.8 glasswares such as flat bottom flask 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 may further comprise the steps:
1), preparation testing sample solution:
1. get the 5.0g testing sample, it is shredded to 0.5cm * 0.5cm mixing.
2. testing sample 1.0 grams of getting after above-mentioned the shredding (being accurate to 0.01 gram) place conical flask, add the abundant submergence sample of 20mL extraction agent-ethyl acetate, are in the ultrasound wave of 40kHz in frequency then, are 50 ℃ of following ultrasonic extraction 30min at bath temperature; Get extract and extraction back sample residue respectively; Extract is changed in the flat bottom flask.
3. sample residue adding 10mL extraction agent washs after extraction, gets cleansing solution;
4. with the 2. extract and the 3. cleansing solution merging of gained of step of gained of step, decompression (0.008MPa) concentrates near doing in 40 ℃ of water-baths, uses N then
2Dry up, get concentrated residue.Accurately add ethyl acetate, thereby vortex dissolves concentrated residue after being settled to 5.0mL, get an appearance liquid.
Get 1mL appearance liquid with 0.45 μ m membrane filtration, the clear liquid of gained (being supernatant liquor) is a testing sample solution, places the sample introduction bottle to seal, and supplies gas chromatograph-mass spectrometer (GCMS) to measure.
2), preparation standard solution:
With 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 by weighing molecular formula is C
12H
27O
4The about 0.0100g of the tributyl phosphate of P (being accurate to 0.0001g) is settled to scale with above solvent (being ethyl acetate) in the volumetric flask of 10mL, liquid is mixed with the tributyl phosphate stock solution that concentration is 1000 μ g/mL;
Taking by weighing molecular formula is C
18H
15O
4The triphenyl phosphate 0.0100g (being accurate to 0.0001g) of P is settled to scale with above solvent in the volumetric flask of 10mL, liquid is mixed with the triphenyl phosphate stock solution that concentration is 1000 μ g/mL;
Taking by weighing molecular formula is C
21H
21O
4The phosphoric acid hemimellitol ester 0.0100g (being accurate to 0.0001g) of P is settled to scale with above solvent in the volumetric flask of 10mL, liquid is mixed with the phosphoric acid hemimellitol ester stock solution that concentration is 1000 μ g/mL;
Taking by weighing molecular formula is C
21H
21O
4Front three phenyl ester 0.0100g (being accurate to 0.0001g) is settled to scale with above solvent between the phosphoric acid of P in the volumetric flask of 10mL, and liquid is mixed with front three phenyl ester stock solution between the phosphoric acid that concentration is 1000 μ g/mL;
Taking by weighing 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 by weighing molecular formula is C
24H
51O
4The trioctyl phosphate 0.0100g (being accurate to 0.0001g) of P is settled to scale with above solvent in the volumetric flask of 10mL, liquid is mixed with the trioctyl phosphate stock solution that concentration is 1000 μ g/mL;
Taking by weighing molecular formula is C
20H
27O
4The diphenyl octyl phosphate 0.0100g (being accurate to 0.0001g) of P is settled to scale with above solvent in the volumetric flask of 10mL, liquid is mixed with the diphenyl octyl phosphate stock solution that concentration is 1000 μ g/mL;
Taking by weighing 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 settled to scale with above solvent in the volumetric flask of 10mL, liquid is mixed with the phosphate toluene diphenyl ester stock solution that melting concn is 1000 μ g/mL;
Respectively get stock solution 1mL that above-mentioned 8 kinds of concentration are 1000 μ g/mL more successively respectively in the volumetric flask of 10mL;, be mixed with and contain the mixing stock solution (being the standard mixed solution) that above-mentioned 8 kind phosphate ester class flame-retardant plasticizer concentration are 100 μ g/mL to scale with the ethyl acetate constant volume;
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 100 μ g/mL successively respectively; Be settled to scale with ethyl acetate, 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), with above-mentioned gradient standard operation solution injection gas chromatography-GC-MS; Select ion monitoring (SIM) pattern to measure, confirm the peak position that of each phosphoric acid ester flame-retardant plasticizer, the peak area that record is corresponding; With concentration is horizontal ordinate; Peak area is an ordinate, and the production standard curvilinear equation is seen 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) the 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 the testing sample solution step of replacing 3 of step 1) gained) in gradient standard operation solution; Set by step 3) phosphoric acid ester flame-retardant plasticizer and the peak area thereof measured in the testing sample solution of method (promptly substitutes the gradient standard operation solution of 1 μ L with the testing sample solution of 1 μ L; All the other are equal to); The typical curve (linear equation) that utilizes step 3) to set up, the content of phosphoric acid ester flame-retardant plasticizer in the testing sample solution; Extension rate (being the conversion relation between testing sample 1g and the constant volume 5.0mL) per sample again; Obtain the content of phosphoric acid ester flame-retardant plasticizer in the testing sample.
5), qualitative analysis
Corresponding step 4); Under same test conditions; Determinand has identical retention time with the standard substance that detects simultaneously in the sample; And the relative abundance of corresponding qualitative ion compares in the relative abundance of the qualitative ion of sample and the approaching standard solution spectrogram of concentration, if deviation is no more than the scope of table 5 regulation, then decidable is to have corresponding determinand in the sample.
The maximum allowable offset of relative abundance of ions when table 5, qualitative conclusive evidence
| Relative abundance of ions, % | ＞50 | ＞20～50 | ＞10～20 | ≤10 |
| The maximum deviation that allows, % | ±20 | ±25 | ±30 | ±50 |
6), quantitative test
Corresponding step 4); This method adopts external standard method quantitative; According to measured matter content situation in the appearance liquid (testing sample solution); The selected close standard operation solution of concentration injects appearance to standard operation solution with appearance liquid equal-volume ginseng and measures, standard operation solution with treat that the response of determinand in the sample measuring liquid all should be in the range of linearity of instrument.If the detection response of appearance liquid exceeds the range of linearity of instrument detecting, after can suitably diluting, make the sample detection response in the range of linearity of instrument detecting, carry out quantitative measurement.Annotate: above-mentioned how the dilution is the routine techniques of the industry.
Specify as follows: the gradient standard operation solution of selecting 8 kind phosphate ester class flame-retardant plasticizers are mixed with (phosphate toluene diphenyl ester comprises isomer C DP I and isomer C DP II) 1～10 μ g/mL; Be in order to take all factors into consideration 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 ability detectable concentration.Generally speaking, the detection of the concentration of phosphoric acid ester flame-retardant plasticizer can directly be carried out with " the gradient standard operation solution of 1～10 μ g/mL " fully in the textile, that is, need not appearance liquid is carried out dilution process.When in particular cases, when the concentration of phosphoric acid ester flame-retardant plasticizer is considerably beyond conventional concentration in the textile, can rely on the range of linearity of typical curve, thus the multiple that judgements need be diluted appearance liquid, and then carry out relevant detection.
With regard to the present invention, during the concentration of phosphoric acid ester flame-retardant plasticizer in the textile≤40mg/kg, can directly use the gradient standard operation solution of 1～10 μ g/mL that the present invention sets, promptly need not to dilute.
7), detect lower bound
When sample introduction concentration is 0.1 μ g/mL; The S/N of tributyl phosphate (TBP) is 5440.8, confirms concentration limit (LOD) with 3 times of signal to noise ratio (S/N ratio)s (S/N=3), therefore; This method is 0.055 μ g/kg to the LOD of TBP in the textile; Confirm minimum quantitative concentrations (LOQ) with 10 times of signal to noise ratio (S/N ratio)s (S/N=10), therefore, this method is 0.18 μ g/kg to the LOQ of TBP in the 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; The LOD of front three phenyl ester (TmCP) is 0.23 μ g/kg between phosphoric acid, 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 prior known this 8 kind phosphate ester class flame-retardant plasticizer basic cotton cloth of (phosphate toluene diphenyl ester comprises isomer C DP I and isomer C DP II) that do not contain; Add and contain above-mentioned 8 kind phosphate ester class flame-retardant plasticizer standard solution; Carried out the interpolation recovery test, made the concentration of above-mentioned 8 kind phosphate ester class flame-retardant plasticizers in sample be 1mg/kg, 5mg/kg and 10mg/kg respectively, operated according to embodiment 1; Promptly; The sample constant volume is 5mL, should be respectively 0.2 μ g/mL, 1 μ g/mL and 2 μ g/mL corresponding to the concentration in the sample solution (testing sample solution), and every group is repeated 6 times; The sample that obtains adds recovery sample peak area and sees table 6, and corresponding sample concentration is seen table 7.
Add the corresponding sample peak area result (n=6) of recovery test in table 6, the cotton
Add the corresponding sample concentration result (n=6) of recovery test in table 7, the cotton
Annotate: RSD (%) represents relative standard deviation.
Experiment 2, recovery experiment and precision experiment (terylene cloth)
With prior known this 8 kind phosphate ester class flame-retardant plasticizer basic terylene cloth of (phosphate toluene diphenyl ester comprises isomer C DP I and isomer C DP II) that do not contain; Add and contain above-mentioned 8 kind phosphate ester class flame-retardant plasticizer standard solution; Carried out the interpolation recovery test, made the concentration of above-mentioned 8 kind phosphate ester class flame-retardant plasticizers in sample be 1mg/kg, 5mg/kg and 10mg/kg respectively, operated according to embodiment 1; Promptly; The sample constant volume is 5mL, should be respectively 0.2 μ g/mL, 1 μ g/mL and 2 μ g/mL corresponding to the concentration in the sample solution (testing sample solution), and every group is repeated 6 times; The sample that obtains adds recovery sample peak area and sees table 8, and corresponding sample concentration is seen table 9.
Add the corresponding sample peak area result (n=6) of recovery test in table 8, the terylene cloth
Add the corresponding sample concentration result (n=6) of recovery test in table 9, the woven dacron
Used extraction solvent (being extraction agent) and step 2 in Comparative Examples 1, the step 1) with embodiment 1) used solvent is by corresponding respectively the changing into of ethyl acetate in: acetone, methylene chloride, ethyl acetate, normal hexane and methyl alcohol; And in step 1), 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.The content that is equal to experiment 2 then experimentizes.
With prior known this 8 kind phosphate ester class flame-retardant plasticizer basic terylene cloth of (phosphate toluene diphenyl ester comprises isomer C DP I and isomer C DP II) that do not contain, add and contain above-mentioned 8 kind phosphate ester class flame-retardant plasticizer standard solution, carried out the interpolation recovery test; Make the equal 20mg/kg of above-mentioned 8 concentration of kind phosphate ester class flame-retardant plasticizer in sample; Operate according to Comparative Examples 1, that is, the sample constant volume is 10mL; Should be 2 μ g/mL corresponding to the concentration in the analytical solution; Every group is repeated 3 times, and the sample that obtains adds recovery sample peak area and sees table 10, and corresponding sample concentration is seen table 11.
Add the corresponding sample peak area result (n=2) of recovery test in table 10, the woven dacron
Add the corresponding sample concentration result (n=3) of recovery test in table 11, the woven dacron
Can find out from the data of table 10 and table 11; 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 the textile; Extract more complete; The extraction efficiency that all is higher than methyl alcohol, therefore, acetone, methylene chloride, ethyl acetate, normal hexane all can be used as the extraction solvent.
At last, it is also to be noted that what more than enumerate only is several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (8)
1. the gas chromatography-mass spectrum detection method of phosphoric acid ester flame-retardant plasticizer in the textile is characterized in that may further comprise the steps:
1), preparation testing sample solution:
A), in testing sample, add extraction agent, be in the ultrasound wave of 30～45kHz in frequency then, be 20～70 ℃ of following ultrasonic extraction 0.5～30min at bath temperature; Get extract and extraction back sample residue respectively;
The solid-liquid ratio of said testing sample and extraction agent is: 1g/5～50mL;
B), with steps A) the sample residue washs with extraction agent after the extraction of gained, cleansing solution;
Said extraction agent and steps A) in the liquid material ratio of testing sample be: 1～20mL/1g;
C), combining extraction liquid and cleansing solution, be under 20～70 ℃ at bath temperature, concentrating under reduced pressure again after drying up, concentrated residue;
D), according to the amount ratio of the extraction agent of the corresponding 1～20ml of 1g testing sample, concentrated residue is fully dissolved with extraction agent, the appearance liquid of gained with 0.45 μ m membrane filtration after, the clear liquid of gained is a testing sample solution;
2), preparation standard solution:
As solvent,, thereby be mixed with the gradient standard operation solution of phosphoric acid ester flame-retardant plasticizer with ethyl acetate, acetone, methylene chloride or normal hexane with phosphoric acid ester flame-retardant plasticizer dissolving;
3), with gradient standard operation solution injection gas chromatography-GC-MS, select the ion monitoring pattern to measure, confirm the peak position that of phosphoric acid ester flame-retardant plasticizer; The peak area of record quota ion; With concentration is horizontal ordinate, and peak area is an ordinate, the production standard curvilinear equation;
4), get the testing sample solution step of replacing 3 of step 1) gained) in gradient standard operation solution; Set by step 3) method is measured phosphoric acid ester flame-retardant plasticizer and the peak area thereof in the testing sample solution; Use the typical curve of step 3) gained to calculate, thereby obtain the phosphoric acid ester flame-retardant plasticizer content in the testing sample.
2. the gas chromatography-mass spectrum detection method of phosphoric acid ester flame-retardant plasticizer in the textile according to claim 1 is characterized in that: adopt electron impact ion source to detect, select the ion monitoring pattern;
Said gas chromatography-mass spectrum detects the chromatographic condition that uses:
Chromatographic column: DB-5MS, 30m * 0.25mm * 0.25 μ m;
The 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 ℃;
Ion gun: electron impact ion source;
Detection mode: select the ion monitoring pattern;
Ion source temperature: 120～180 ℃;
Quadrupole rod temperature: 150～280 ℃;
Interface temperature: 200～280 ℃;
Sampling volume: 0.1～2 μ L.
3. the gas chromatography-mass spectrum detection method of phosphoric acid ester flame-retardant plasticizer in the textile according to claim 2 is characterized in that: the concentration that is mixed with the phosphoric acid ester flame-retardant plasticizer said step 2) is the gradient standard operation solution of 1～10 μ g/mL.
4. the gas chromatography-mass spectrum detection method of phosphoric acid ester flame-retardant plasticizer in the textile according to claim 3 is characterized in that: said phosphoric acid ester flame-retardant plasticizer is at least a in the front three phenyl ester of front three phenyl ester and phosphoric acid between tributyl phosphate, triphenyl phosphate, diphenyl octyl phosphate, trioctyl phosphate, phosphate toluene diphenyl ester, phosphoric acid hemimellitol ester, phosphoric acid.
5. the gas chromatography-mass spectrum detection method of phosphoric acid ester flame-retardant plasticizer in the textile according to claim 4 is characterized in that: the extraction agent in the said step 1) is ethyl acetate, acetone, methylene chloride or normal hexane.
6. the gas chromatography-mass spectrum detection method of phosphoric acid ester flame-retardant plasticizer in the textile according to claim 5 is characterized in that: said step 2): the concentration that is mixed with the 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.
7. the gas chromatography-mass spectrum detection method of phosphoric acid ester flame-retardant plasticizer in the textile according to claim 6 is characterized in that: phosphate toluene diphenyl ester comprises the isomeride I and the isomeride II of phosphate toluene diphenyl ester.
8. according to the gas chromatography-mass spectrum detection method of phosphoric acid ester flame-retardant plasticizer in the described textile of claim 1～7, it is characterized in that:
Said step 2) the phosphoric acid ester flame-retardant plasticizer in is made up of following 8 kind phosphate ester class flame-retardant plasticizers: front three phenyl ester and phosphoric acid are to the front three phenyl ester between tributyl phosphate, triphenyl phosphate, diphenyl octyl phosphate, trioctyl phosphate, phosphate toluene diphenyl ester, phosphoric acid hemimellitol ester, phosphoric acid; Phosphate toluene diphenyl ester comprises the isomeride I of phosphate toluene diphenyl ester and the isomeride II of phosphate toluene diphenyl ester;
As solvent,, thereby be mixed with the 8 class standard solution that independent concentration is 1000 μ g/mL respectively with ethyl acetate, acetone, methylene chloride or normal hexane respectively with the dissolving of 8 kind phosphate ester class flame-retardant plasticizers;
Respectively getting and dilute with solvent after above-mentioned 8 class standard solution mix, 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 again to contain said 8 kind phosphate ester class flame-retardant plasticizers and be the gradient standard operation solution of following 5 concentration respectively: 1.0,3.0,5.0,7.0,10 μ g/mL.
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