CN102628843B - Gas chromatography for detection of phosphate fire-retardant plasticizer in textile - Google Patents
Gas chromatography for detection of phosphate fire-retardant plasticizer in textile Download PDFInfo
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Abstract
The invention discloses a gas chromatography for detection of a phosphate fire-retardant plasticizer in a textile. The gas chromatography comprises the following steps of 1, preparing a test sample solution which is supernatant, 2, preparing a gradient standard solution having the concentration of 1 to 10 micrograms per milliliter by dissolving at least one phosphate fire-retardant plasticizer in a solvent, 3, injecting the gradient standard solution into a gas chromatograph, carrying out detection by a flame photometric detector to determinate peak positions of the at least one phosphate fire-retardant plasticizer, recording corresponding peak areas, and making a standard curvilinear equation by concentrations as horizontal coordinates and the peak areas as vertical coordinates, and 4, replacing the gradient standard solution used in the step 3 with the supernatant obtained by the step 1, detecting the at least one phosphate fire-retardant plasticizer in the test sample solution and the peak areas of the at least one phosphate fire-retardant plasticizer according to the step 3, and carrying out calculation by the standard curvilinear equation obtained by the step 3 to obtain the content of the at least one phosphate fire-retardant plasticizer in the test sample solution.
Description
Technical field
The present invention relates to a kind of vapor-phase chromatography that in textile, 8 kind phosphate ester class flame-retardant plasticizers detect that is applicable to.
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 valency is 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.In tissue and during postmortem, detect after dioctyl phthalate (DOP), 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 migration of plasticizer 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 detection method that adopts vapor-phase chromatography to measure quickly and accurately 8 kind phosphate ester class flame-retardant plasticizers in textile.
In order to solve the problems of the technologies described above, the invention provides a kind of vapor-phase chromatography that in textile, phosphoric acid ester flame-retardant plasticizer detects that is applicable to, comprise the following steps:
1), prepare testing sample solution:
A), in testing sample, add extraction agent,, in the ultrasound wave of 30～45kHz, at bath temperature, be then 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/20～40mL;
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 in 1g testing sample (steps A)) amount ratio of the extraction agent of corresponding 1～20ml, concentrated residue is fully dissolved with extraction agent, and (the sample liquid of gained, with after 0.45 μ m membrane filtration, obtain testing sample solution, by filtering the clear liquid of gained, also claim supernatant liquor)
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 gradient standard operation solution (preferred concentration is 1～10 μ g/mL);
3), by described gradient standard operation solution inject gas chromatograph, flame photometric detector (FPD) (FPD) is measured, and determines the peak position that of phosphoric acid ester flame-retardant plasticizer, record corresponding peak area, take concentration as horizontal ordinate, and peak area is ordinate, production standard curvilinear equation;
4), get step 1) the testing sample solution alternative steps 3 of gained) in gradient standard operation solution, then by step 3) method measures phosphoric acid ester flame-retardant plasticizer and the peak area thereof in testing sample solution; Then using step 3) typical curve of gained calculates, and obtains the phosphoric acid ester flame-retardant plasticizer content in testing sample.
As the improvement that is applicable to the vapor-phase chromatography that phosphoric acid ester flame-retardant plasticizer in textile detects of the present invention:
Gas-chromatography detection method chromatographic condition used is:
Chromatographic column: HP-5,30m * 0.32mm * 0.25 μ m;
Chromatographic column heating schedule: initial temperature 70C, is warming up to 250 ℃ with the speed of 30C/min, insulation 1min; Speed with 5C/min is warming up to 300 ℃ again, insulation 3min;
Flow rate of carrier gas: 1～2mL/min;
Injector temperature: 200～250 ℃;
245 ℃ of flame photometric detector (FPD) (P-FPD) temperature; Hydrogen flow rate: 20～75mL/min; Air velocity: 50～100mL/min; Complemental air (N
2) flow velocity: 20～60mL/min; Sampling volume: 0.1～2 μ L.
As the improvement that is applicable to the vapor-phase chromatography that phosphoric acid ester flame-retardant plasticizer in textile detects of the present invention:
Phosphoric acid ester flame-retardant plasticizer is: 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 are at least one in front three phenyl ester (TpCP).
As the further improvement that is applicable to the vapor-phase chromatography that phosphoric acid ester flame-retardant plasticizer in textile detects of the present invention: the extraction agent step 1) is ethyl acetate, acetone, methylene chloride or normal hexane.
As the further improvement that is applicable to the vapor-phase chromatography that phosphoric acid ester flame-retardant plasticizer in textile detects 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/nL.
As the further improvement that is applicable to the vapor-phase chromatography that phosphoric acid ester flame-retardant plasticizer in textile detects of the present invention: phosphate toluene diphenyl ester comprises the isomeride I of phosphate toluene diphenyl ester and the isomeride II of phosphate toluene diphenyl ester.
As the further improvement that is applicable to the vapor-phase chromatography that phosphoric acid ester flame-retardant plasticizer in textile detects 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 above-mentioned 8 kind phosphate ester class flame-retardant plasticizers are dissolved, thereby be mixed with respectively independent concentration and be the 8 class standard solution of 1000 μ g/mL (, in every class standard solution, the concentration of such phosphoric acid ester flame-retardant plasticizer is 1000 μ g/mL accordingly);
Respectively get after above-mentioned 8 class standard solution mix and dilute with solvent, thereby be mixed with the concentration that contains above-mentioned 8 kind phosphate ester class flame-retardant plasticizers and be respectively the standard mixed solution of 100 μ g/mL (, in this standard mixed solution, the concentration of every kind phosphate ester class flame-retardant plasticizer is 100 μ g/mL); The concentration of utilizing this standard mixed solution to be mixed with again to contain described 8 kind phosphate ester class flame-retardant plasticizers is the gradient standard operation solution of following 5 concentration respectively: 1.0,3.0,5.0,7.0,10 μ g/mL (, in each gradient standard operation solution, the concentration of every kind phosphate ester class flame-retardant plasticizer is all identical; The gradient concentration of every kind phosphate ester class flame-retardant plasticizer is 1.0,3.0,5.0,7.0,10 μ g/mL).
The present invention compared with prior art has following remarkable result:
(1) adopt gas chromatography (flame photometric detector (FPD)) optionally to measure phosphoric acid ester flame-retardant plasticizer, highly sensitive, impurity disturbs little.
(2) assay method disclosed by the invention is in 1～10 μ g/mL concentration range, and linear equation and linearly dependent coefficient be respectively in Table 1, and result shows, 8 kind phosphate ester class flame-retardant plasticizer linear relationships are all better.
Table 1, gas chromatography determination 8 kind phosphate ester class flame-retardant plasticizer linear equation and linearly dependent coefficients
(3) adopt ethyl acetate, methylene chloride, acetone or normal hexane as the extraction agent of phosphoric acid ester flame-retardant plasticizer, make 8 kind phosphate ester class flame-retardant plasticizers in textile samples can access extraction comparatively thoroughly.
(4) ultrasound wave that proportion is 30～45kHz, is ultrasonic extraction 0～30min at 20～70 ℃ at bath temperature, simple and convenient extraction, easy operating.
(5) gas chromatography analysis method can be effectively separated by 8 kind phosphate ester class flame-retardant plasticizers in 15min, carries out qualitative, quantitative and measure.
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 standard substance gas chromatography chromatogram of phosphoric acid ester flame-retardant plasticizer;
Fig. 2 is the Linear equations of gas chromatography determination tributyl phosphate (TBP) in 1.0～10.0 μ g/mL concentration ranges;
Fig. 3 is the Linear equations of gas chromatography determination triphenyl phosphate (TPP) in 1.0～10.0 μ g/mL concentration ranges;
Fig. 4 is the Linear equations of gas chromatography determination diphenyl octyl phosphate (DPOP) in 1.0～10.0 μ g/mL concentration ranges;
Fig. 5 is the Linear equations of gas chromatography determination trioctyl phosphate (TOP) in 1.0～10.0 μ g/mL concentration ranges;
Fig. 6 is isomer C DP I in the gas chromatography determination 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 determination 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 determination 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 determination phosphoric acid;
Figure 10 be gas chromatography determination 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
1.1 ethyl acetate: chromatographically pure.
1.2 methylene chloride: chromatographically pure.
1.3 acetone: chromatographically pure.
1.4 normal hexanes: chromatographically pure.
1.5 triphenyl phosphates (TPP) standard items: purity >=99.7%.
1.6 phosphoric acid hemimellitol ester (ToCP) standard items: purity >=96%.
Front three phenyl ester (TmCP) standard items between 1.7 phosphoric acid: purity >=95%.
1.8 phosphoric acid are to front three phenyl ester (TpCP) standard items: purity >=98%.
1.9 tributyl phosphates (TBP) standard items: purity >=98.5%.
1.10 trioctyl phosphates (TOP) standard items: purity >=98%.
1.11 diphenyl octyl phosphates (DPOP) standard items: purity >=90%.
1.12 phosphate toluene diphenyl esters (CDP) standard items: purity >=93%.
Table 2,8 kind phosphate ester class flame-retardant plasticizer chemical information tables
| Chinese | English name | English abbreviation | Chemical abstracts numbering | Chemical molecular formula |
| Tributyl phosphate | Tributyl phosphate | TBP | 126-73-8 | C 12H 27O 4P |
| Triphenyl phosphate | Triphenyl phosphate | TPP | 115-86-6 | C 18H 15O 4P |
| Phosphoric acid hemimellitol ester | Tri-o-tolyl phosphate | ToCP | 78-30-8 | C 21H 21O 4P |
| Front three phenyl ester between phosphoric acid | Tri-m-tolyl phosphate | TmCP | 563-04-2 | C 21H 21O 4P |
| Phosphoric acid is to front three phenyl ester | Tri-p-tolyl phosphate | TpCP | 78-32-0 | C 21H 21O 4P |
| Trioctyl phosphate | Trioctyl phosphate | top | 78-42-2 | C 24H 51O 4P |
| Diphenyl octyl phosphate | Diphenyl 2-ethylhexyl | DPOP | 1241-94-7 | C 20H 27O 4P |
| phosphate | ||||
| Phosphate toluene diphenyl ester | Cresyl Diphenyl Phosphate | CDP | 26444-49-5 | C 19H 17O 4P |
1.13 standard reserving solutions: the standard items that accurately take respectively appropriate above 8 kind phosphate ester class flame-retardant plasticizers, with ethyl acetate, be mixed with the standard reserving solution that concentration is 1000 μ g/mL left and right respectively, then be mixed with ethyl acetate the hybrid standard storing solution that above-mentioned 8 constituents concentration are 100 μ g/mL respectively.
1.14 standard operation liquid: pipette respectively the appropriate volume of hybrid standard storing solution, with ethyl acetate dilution, being mixed with the above-mentioned 8 kind phosphate ester class flame-retardant plasticizer concentration that contain is 5 hybrid standard working fluids 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 chromatographs: be furnished with flame photometric detector (FPD) (FPD).
2.2 gas chromatographic columns: HP-5, μ m * 0.25,30m * 320 μ m or quite person.
2.3 ultrasonic generators: frequency of operation is 40kHz.
2.4 rotary vacuum evaporator.
2.5 vortex instrument.
2.6 organic phase filtering membranes: 0.45 μ m.
The glasswares such as 2.7 flat bottom flasks and graduated cylinder, conical flask.
Embodiment 1, a kind of vapor-phase chromatography that is applicable to 8 kind phosphate ester class flame-retardant plasticizers detections in textile, comprise 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, add 20mL to extract solvent (extraction agent)-ethyl acetate, abundant submergence sample, in frequency of operation, be 40kHz, bath temperature is to extract 30min in the ultrasonic generator of 30 ℃, respectively sample residue after extract and extraction; Extract is proceeded in flat bottom flask.
3. add again 10mL to extract the rear sample residue of solvent-ethyl acetate washing extraction, obtain cleansing solution;
4., by step 2. the extract of gained and step 3. the cleansing solution of gained merge, obtain sample extraction solution.
Sample extraction solution reduced pressure concentration in 40 ℃ of water-baths is closely dry, then use N
2dry up, thus concentrated residue.Thereby accurately add ethyl acetate to be settled to after 5.0mL, vortex dissolves concentrated residue, obtains sample liquid.
Get 0.45 μ m membrane filtration for 1mL sample liquid, gained clear liquid (also referred to as supernatant liquor) is testing sample solution, is placed in sample injection bottle and seals, and for gas chromatograph, 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 (being formed by two kinds of isomer C DP I and CDP II) standard items: purity >=93%;
Taking molecular formula is C
12h
27o
4the tributyl phosphate 0.0100g (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
170
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 class 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 that 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 above-mentioned 100 μ g/mL, with ethyl acetate, be settled to scale, thereby be mixed with the gradient standard operation solution that 8 kind phosphate ester class flame-retardant plasticizer melting concns are respectively 1,3,5,7,10 these 5 concentration of μ g/mL.
3), by above-mentioned gradient standard operation solution inject gas chromatograph, flame photometric detector (FPD) is measured, and determines the peak position that of each phosphoric acid ester flame-retardant plasticizer, record corresponding peak area, take concentration as horizontal ordinate, and peak area is ordinate, production standard curvilinear equation.Specific as follows:
GC conditions:
A) chromatographic column: HP-5,30m * 0.32mm * 0.25 μ m;
B) chromatogram column temperature: 70 ℃ of initial temperatures, are warming up to 250 ℃ with the speed of 30 ℃/min, insulation 1min; Speed with 5 ℃/min is warming up to 300 ℃ again, insulation 3min;
C) injector temperature: 250 ℃;
D) P-FPD detector temperature: 245 ℃; Hydrogen flow rate: 75mL/min; Air velocity: 100mL/min; Complemental air (N2) flow velocity: 60mL/min;
E) carrier gas: nitrogen, purity >=99.999%, 2mL/min;
F) input mode: without split sampling, drive valve after 2min;
G) sample size: 1 μ L.
Utilize instrument workstation automatic integration, obtain front three phenyl ester (TmCP), the peak area of phosphoric acid to front three phenyl ester (TpCP) between tributyl phosphate (TBP), triphenyl phosphate (TPP), diphenyl octyl phosphate (DPOP), trioctyl phosphate (TOP), phosphate toluene diphenyl ester (CDP I), phosphate toluene diphenyl ester (CDP II), phosphoric acid hemimellitol ester (ToCP), phosphoric acid, result is specifically in Table 3:
Table 3, peak area corresponding to phosphoric acid ester flame-retardant plasticizer gas chromatographic analysis
4), get step 1) testing sample solution of gained is by step 3) the phosphoric acid ester flame-retardant plasticizer measured in testing sample solution of method (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), utilize the typical curve (linear equation) of setting up, obtain the content of phosphoric acid ester flame-retardant plasticizer in testing sample solution; Extension rate (being the conversion relation between sample 1g and constant volume) 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 of detection simultaneously, can be judged to be and in sample, have corresponding determinand.
6), quantitative test
Corresponding step 4), this method adopts external standard method quantitative, can be according to measured matter content situation in testing sample solution, the selected close gradient standard operation solution (being standard solution) of concentration, gradient standard operation solution and testing sample solution equal-volume ginseng is injected to sample and measure, thereby make its response all should be in the range of linearity of instrument.The typical curve range of linearity that the detection response of testing sample solution detects from instrument can be read, if detect response in the range of linearity of instrument detection, can directly carry out quantitative measurement.If the detection response of testing sample solution exceeds the range of linearity that instrument detects, can suitably dilute after testing sample solution, in the range of linearity that sample detection response is detected at instrument, carry out quantitative measurement.The mode of operation how this kind dilutes is the general knowledge of the industry.
In the present invention, the concentration≤40mg/kg of phosphoric acid ester flame-retardant plasticizer in sample, the gradient concentration that all can set according to method of the present invention directly detects, without dilution.
7), detect lower bound
When sample introduction concentration is 0.1 μ g/mL, the S/N of tributyl phosphate (TBP) is 1661.4, with 3 times of signal to noise ratio (S/N ratio)s (S/N=3), determine concentration limit (LOD), therefore, this method is 0.90 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 2.97 μ g/kg to the LOQ of TBP in textile.
In like manner, the LOD of triphenyl phosphate (TPP) is 2.85 μ g/kg, and LOQ is 9.40 μ g/kg;
The LOD of diphenyl octyl phosphate (DPOP) is 4.47 μ g/kg, and LOQ is 14.75 μ g/kg;
The LOD of trioctyl phosphate (TOP) is 5.82 μ g/kg, and LOQ is 19.21 μ g/kg;
The LOD of phosphate toluene diphenyl ester (CDP I) is 17.20 μ g/kg, and LOQ is 56.76 μ g/kg;
The LOD of phosphate toluene diphenyl ester (CDP II) is 32.40 μ g/kg, and LOQ is 106.92 μ g/kg;
The LOD of phosphoric acid hemimellitol ester (ToCP) is 5.25 μ g/kg, and LOQ is 17.32 μ g/kg;
Between phosphoric acid, the LOD of front three phenyl ester (TmCP) is 2.58 μ g/kg, and LOQ is 8.51 μ g/kg;
Phosphoric acid is 2.93 μ g/kg to the LOD of front three phenyl ester (TpCP), and LOQ is 9.67 μ g/kg.
Experiment 1, recovery experiment and Precision Experiment (basic cotton cloth):
With the in advance known basic cotton cloth that does not contain this 8 kind phosphate ester class flame-retardant plasticizer, add the standard solution that contains 8 kind phosphate ester class flame-retardant plasticizers (note: phosphate toluene diphenyl ester comprises isomer C DP I and isomer C DP II), carried out interpolation recovery test, make the concentration of 8 kind phosphate ester class flame-retardant plasticizers in sample be respectively 1mg/kg, 5mg/kg and 10mg/kg, then according to embodiment 1, detect, even if cloth sample constant volume is 5mL, corresponding to the concentration in sample solution (being 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 4, corresponding sample concentration is in Table 5.
In table 4, cotton, add the sample peak area result (n=6) that recovery test is corresponding
In table 5, cotton, add sample concentration result that recovery test is corresponding and relative standard deviation RSD (%) (n=6)
Note: RSD (%) represents relative standard deviation.
Experiment 2, recovery experiment and Precision Experiment (basic terylene cloth)
With the in advance known basic terylene cloth that does not contain this 8 kind phosphate ester class flame-retardant plasticizer, add the standard solution that contains 8 kind phosphate ester class flame-retardant plasticizers (note: phosphate toluene diphenyl ester comprises isomer C DP I and isomer C DP II), carried out interpolation recovery test, make the concentration of 8 kind phosphate ester class flame-retardant plasticizers in sample be respectively 1mg/kg, 5mg/kg and 10mg/kg, then according to embodiment 1, detect, even if cloth sample constant volume is 5mL, corresponding to the concentration in sample solution (being 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, woven dacron, add the sample peak area result (n=6) that recovery test is corresponding
In table 7, woven dacron, add sample concentration result that recovery test is corresponding and relative standard deviation RSD (%) (n=6)
Comparative example 1, by the step 1 of embodiment 1) in extraction solvent (being extraction agent) used by ethyl acetate, changed into respectively: acetone, methylene chloride, ethyl acetate, normal hexane and methyl alcohol; Step 2) solvent in is also done correspondence change; 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 with embodiment 1.Then according to the content of experiment 2, test,
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 8, corresponding sample concentration is in Table 9.
In table 8, woven dacron, add the sample peak area result (n=3) that recovery test is corresponding
In table 9, woven dacron, add the sample concentration result (n=3) that recovery test is corresponding
From the data of table 8 and table 9, can find out, acetone, methylene chloride, ethyl acetate, normal hexane are more approaching to the extraction efficiency of 8 kind phosphate ester class 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. can detect the vapor-phase chromatography of 8 kinds of phosphoric acid ester flame-retardant plasticizers in textile simultaneously, it is characterized in that:
Described 8 kinds of phosphoric acid ester flame-retardant plasticizers are: 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;
Comprise the following steps:
1), prepare testing sample solution:
A), in testing sample, add extraction agent,, in the ultrasound wave of 30～45kHz, at bath temperature, be then ultrasonic extraction 30min at 30 ℃; Obtain respectively the rear sample residue of extract and extraction;
The solid-liquid ratio of described testing sample and extraction agent is: 1g/20mL;
Described extraction agent is ethyl acetate, acetone, methylene chloride or normal hexane;
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: 10mL/1g;
C), combining extraction liquid and cleansing solution, at bath temperature, be at 40 ℃, reduced pressure concentration after drying up, obtains concentrated residue again;
D), according to the concentrated residue of 1g testing sample, with extraction agent, be settled to the amount ratio of 5.0mL, concentrated residue is fully dissolved with extraction agent, the sample liquid of gained, with after 0.45 μ m membrane filtration, obtains 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 gradient standard operation solution;
3), by described gradient standard operation solution inject gas chromatograph, flame photometric detector (FPD) is measured, and determines the peak position that of phosphoric acid ester flame-retardant plasticizer, record corresponding peak area, take concentration as horizontal ordinate, and peak area is ordinate, production standard curvilinear equation;
Described gas-chromatography detection method chromatographic condition used is:
Chromatographic column: HP-5,30m * 0.32mm * 0.25 μ m;
Chromatographic column heating schedule: 70 ℃ of initial temperatures, are warming up to 250 ℃ with the speed of 30 ℃/min, insulation 1min; Speed with 5 ℃/min is warming up to 300 ℃ again, insulation 3min;
Flow rate of carrier gas: 1～2mL/min;
Injector temperature: 200～250 ℃;
245 ℃ of flame photometric detector (FPD) temperature; Hydrogen flow rate: 20～75mL/min; Air velocity: 50～100mL/min; Complemental air (N
2) flow velocity: 20～60mL/min; Sampling volume: 0.1～2 μ L;
4), get step 1) the testing sample solution alternative steps 3 of gained) in gradient standard operation solution, then by step 3) method measures phosphoric acid ester flame-retardant plasticizer and the peak area thereof in testing sample solution; Then using step 3) typical curve of gained calculates, and obtains the phosphoric acid ester flame-retardant plasticizer content in testing sample.
2. the vapor-phase chromatography that can simultaneously detect 8 kinds of phosphoric acid ester flame-retardant plasticizers in textile according to claim 1, is characterized in that: described step 2) for being mixed with the gradient standard operation solution that concentration is 1～10 μ g/mL.
3. the vapor-phase chromatography that can simultaneously detect 8 kinds of phosphoric acid ester flame-retardant plasticizers in textile according to claim 2, 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.
4. the vapor-phase chromatography that can simultaneously detect 8 kinds of phosphoric acid ester flame-retardant plasticizers in textile according to claim 3, is characterized in that: described phosphate toluene diphenyl ester comprises the isomeride I of phosphate toluene diphenyl ester and the isomeride II of phosphate toluene diphenyl ester.
5. according to the arbitrary described vapor-phase chromatography that can detect 8 kinds of phosphoric acid ester flame-retardant plasticizers in textile of claim 1～4 simultaneously, it is characterized in that: the phosphoric acid ester flame-retardant plasticizer described 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.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103616469A (en) * | 2013-12-13 | 2014-03-05 | 中华人民共和国北京出入境检验检疫局 | Method for detecting organophosphate flame retardant |
| 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 |
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| 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 |
| CN110702823A (en) * | 2019-11-12 | 2020-01-17 | 东莞市中鼎检测技术有限公司 | Method for efficiently extracting organic matters in textiles and similar materials |
| CN111948301B (en) * | 2019-11-29 | 2022-11-29 | 贵州省烟草科学研究院 | Qualitative and quantitative analysis method for organic additives in full-biodegradable mulching film |
| 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 |
| CN117969721A (en) * | 2024-04-01 | 2024-05-03 | 西安建筑科技大学 | Method for synchronously measuring organic phosphate in water |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5523481A (en) * | 1978-08-08 | 1980-02-19 | Sumitomo Chem Co Ltd | Gas chromatographing method for mixture of mirror image isomer of organophosphorus compound with nh radical combined with asymmetric phosphorus atom |
| US5177019A (en) * | 1991-05-20 | 1993-01-05 | Eastman Kodak Company | Method of quantitative analysis of organophosphorus compounds |
| RU2006103295A (en) * | 2006-02-07 | 2007-08-20 | Сергей Васильевич Новиков (RU) | METHOD FOR DETERMINING PHOSPHORORHANIC SUBSTANCES |
| 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 |
-
2012
- 2012-03-14 CN CN201210065808.9A patent/CN102628843B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5523481A (en) * | 1978-08-08 | 1980-02-19 | Sumitomo Chem Co Ltd | Gas chromatographing method for mixture of mirror image isomer of organophosphorus compound with nh radical combined with asymmetric phosphorus atom |
| US5177019A (en) * | 1991-05-20 | 1993-01-05 | Eastman Kodak Company | Method of quantitative analysis of organophosphorus compounds |
| RU2006103295A (en) * | 2006-02-07 | 2007-08-20 | Сергей Васильевич Новиков (RU) | METHOD FOR DETERMINING PHOSPHORORHANIC SUBSTANCES |
| 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 |
Non-Patent Citations (12)
| Title |
|---|
| Determination of ortho-cresyl phosphate isomers of tricresyl phosphate used in aircraft turbine engine oils by gas chromatography and mass spectrometry;G. De Nola et al;《Journal of Chromatography A》;20081231;第1200卷;摘要和标题 * |
| Determination of trialkyl and triaryl phosphates in environmental samples;S. Ishikawa et al;《 Water Resources》;19850131;第19卷(第1期);119页右栏倒数第1段 * |
| Development of a microporous membrane liquid–liquid extractor for organophosphate esters in human blood plasma;Ove B. Jonsson et al;《Journal of Chromatography B》;20011231;第755卷;704页表6、705页第3段至706页第2段 * |
| G. De Nola et al.Determination of ortho-cresyl phosphate isomers of tricresyl phosphate used in aircraft turbine engine oils by gas chromatography and mass spectrometry.《Journal of Chromatography A》.2008,第1200卷211-216. |
| Measuring emissions of organophosphate flame retardants using a passive flux sampler;Y. Ni et al;《Atmospheric Environment》;20071231;第41卷;3236页2.2节 * |
| Ove B. Jonsson et al.Development of a microporous membrane liquid–liquid extractor for organophosphate esters in human blood plasma.《Journal of Chromatography B》.2001,第755卷157–164. |
| S. Ishikawa et al.Determination of trialkyl and triaryl phosphates in environmental samples.《 Water Resources》.1985,第19卷(第1期),119-125. |
| Separation and recovery of materials from scrap printed circuit boards;William J. Hall et al;《Resources, Conservation and Recycling》;20071231;第51卷;摘要 * |
| William J. Hall et al.Separation and recovery of materials from scrap printed circuit boards.《Resources, Conservation and Recycling》.2007,第51卷691-709. |
| Y. Ni et al.Measuring emissions of organophosphate flame retardants using a passive flux sampler.《Atmospheric Environment》.2007,第41卷3235-3240. |
| 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),917-921. |
| 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;王成云 等;《分析测试学报》;20110831;第30卷(第8期);918页1.2-1.4节、919页2.3节、920页2.4节，以及表2和表3 * |
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