CN113418875B - Method for measuring phosphorus content of phosphate flame retardant - Google Patents
Method for measuring phosphorus content of phosphate flame retardant Download PDFInfo
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- CN113418875B CN113418875B CN202110570995.5A CN202110570995A CN113418875B CN 113418875 B CN113418875 B CN 113418875B CN 202110570995 A CN202110570995 A CN 202110570995A CN 113418875 B CN113418875 B CN 113418875B
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- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 60
- 239000011574 phosphorus Substances 0.000 title claims abstract description 60
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 42
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 42
- 239000010452 phosphate Substances 0.000 title claims abstract description 42
- 239000003063 flame retardant Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 40
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000000243 solution Substances 0.000 claims abstract description 70
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 36
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000002133 sample digestion Methods 0.000 claims abstract description 24
- 238000002474 experimental method Methods 0.000 claims abstract description 16
- 238000011161 development Methods 0.000 claims abstract description 11
- 239000012086 standard solution Substances 0.000 claims abstract description 9
- 238000005259 measurement Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000000523 sample Substances 0.000 claims description 27
- 238000002835 absorbance Methods 0.000 claims description 24
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 24
- 239000012224 working solution Substances 0.000 claims description 17
- 230000029087 digestion Effects 0.000 claims description 16
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 14
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000010790 dilution Methods 0.000 claims description 9
- 239000012895 dilution Substances 0.000 claims description 9
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000012360 testing method Methods 0.000 claims description 8
- ASLWPAWFJZFCKF-UHFFFAOYSA-N tris(1,3-dichloropropan-2-yl) phosphate Chemical compound ClCC(CCl)OP(=O)(OC(CCl)CCl)OC(CCl)CCl ASLWPAWFJZFCKF-UHFFFAOYSA-N 0.000 claims description 8
- KVMPUXDNESXNOH-UHFFFAOYSA-N tris(1-chloropropan-2-yl) phosphate Chemical compound ClCC(C)OP(=O)(OC(C)CCl)OC(C)CCl KVMPUXDNESXNOH-UHFFFAOYSA-N 0.000 claims description 8
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 claims description 8
- 235000010323 ascorbic acid Nutrition 0.000 claims description 7
- 229960005070 ascorbic acid Drugs 0.000 claims description 7
- 239000011668 ascorbic acid Substances 0.000 claims description 7
- 239000013642 negative control Substances 0.000 claims description 6
- 238000007865 diluting Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- 150000003017 phosphorus Chemical class 0.000 claims description 4
- 239000012490 blank solution Substances 0.000 claims description 3
- 238000011981 development test Methods 0.000 claims description 3
- 238000013215 result calculation Methods 0.000 claims description 3
- 239000012488 sample solution Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 4
- XEMZLVDIUVCKGL-UHFFFAOYSA-N hydrogen peroxide;sulfuric acid Chemical compound OO.OS(O)(=O)=O XEMZLVDIUVCKGL-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000209 wet digestion Methods 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 2
- 238000004458 analytical method Methods 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 238000010000 carbonizing Methods 0.000 abstract 1
- 238000002372 labelling Methods 0.000 description 6
- 238000003556 assay Methods 0.000 description 5
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 4
- 235000019796 monopotassium phosphate Nutrition 0.000 description 4
- 238000004737 colorimetric analysis Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000002798 spectrophotometry method Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WYWFMUBFNXLFJK-UHFFFAOYSA-N [Mo].[Sb] Chemical compound [Mo].[Sb] WYWFMUBFNXLFJK-UHFFFAOYSA-N 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- TVBSSDNEJWXWFP-UHFFFAOYSA-N nitric acid perchloric acid Chemical compound O[N+]([O-])=O.OCl(=O)(=O)=O TVBSSDNEJWXWFP-UHFFFAOYSA-N 0.000 description 2
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 2
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- IIQJBVZYLIIMND-UHFFFAOYSA-J potassium;antimony(3+);2,3-dihydroxybutanedioate Chemical compound [K+].[Sb+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O IIQJBVZYLIIMND-UHFFFAOYSA-J 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- 238000000184 acid digestion Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229940026189 antimony potassium tartrate Drugs 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- WBTCZEPSIIFINA-MSFWTACDSA-J dipotassium;antimony(3+);(2r,3r)-2,3-dioxidobutanedioate;trihydrate Chemical compound O.O.O.[K+].[K+].[Sb+3].[Sb+3].[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O.[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O WBTCZEPSIIFINA-MSFWTACDSA-J 0.000 description 1
- 201000006549 dyspepsia Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WUJISAYEUPRJOG-UHFFFAOYSA-N molybdenum vanadium Chemical compound [V].[Mo] WUJISAYEUPRJOG-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- IBIRZFNPWYRWOG-UHFFFAOYSA-N phosphane;phosphoric acid Chemical compound P.OP(O)(O)=O IBIRZFNPWYRWOG-UHFFFAOYSA-N 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/3103—Atomic absorption analysis
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Biochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Plasma & Fusion (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention discloses a method for measuring the phosphorus content of a phosphate flame retardant, which comprises the following steps: 1) Preparing and detecting a solution to be detected: firstly, dehydrating and carbonizing a phosphate flame retardant sample at a high temperature by using concentrated sulfuric acid, then removing carbon by using hydrogen peroxide and converting phosphate into phosphoric acid to obtain a sample digestion solution; then, carrying out a color development experiment on the sample digestion solution, and then, carrying out spectroscopical measurement; 2) Preparing a standard solution and drawing a standard curve: 3) And (5) content measurement. The method is characterized in that the total phosphorus content in the phosphate flame retardant is determined by a concentrated sulfuric acid-hydrogen peroxide wet digestion method, the recovery rate is within 100+/-5%, the result accuracy is high, the RSD is less than 1%, the result reproducibility is good, the analysis method is simple to operate, the pollution is small, and the time is short.
Description
Technical Field
The invention relates to a method for measuring the phosphorus content of a phosphate flame retardant.
Background
The flame retardant is a functional auxiliary agent for improving the flame resistance of the material, and the traditional flame retardant is mainly halogen flame retardant but generates carcinogenic substances such as dioxin when burning, so that the phosphate flame retardant has the advantages of low smoke, no toxicity, low halogen, no halogen and the like, and accords with the development direction of future flame retardants.
The flame retardant effect of the phosphate flame retardant is determined by the total phosphorus content, and the total phosphorus content is determined by a national standard method at present mainly through persulfate oxidation digestion, a molybdenum-antimony colorimetry or a vanadium-molybdenum colorimetry. However, the phosphate phosphorus content and the carbon content are higher, the digestion is difficult to complete by using a national standard method, and researches related to digestion by using a perchloric acid-nitric acid method are also available in the domestic literature, so that the sample still cannot be completely digested in a short time for the phenyl phosphate with higher stability, and the technical problem of lower recovery rate of a measurement result exists.
Disclosure of Invention
Aiming at the technical problems existing in the prior art, the invention aims to provide a method for measuring the phosphorus content of a phosphate flame retardant.
The method for measuring the phosphorus content of the phosphate flame retardant is characterized by comprising the following steps of:
1. preparing a solution to be tested:
s1, sample digestion:
weighing 0.02-0.04g of phosphate flame retardant sample, putting the phosphate flame retardant sample into a 100mL high beaker, putting the beaker into a magnetic stirrer, adding 2mL of concentrated sulfuric acid, covering a surface dish, magnetically stirring the mixture for 8-12min at 140-160 ℃, then adjusting the temperature to 180-220 ℃ and magnetically stirring the mixture for 4-6 min, and stopping heating and cooling to room temperature after the color is observed to be gradually blackened; then adding 0.5ml of hydrogen peroxide, heating to 180-220 ℃ and magnetically stirring for 8-12min, stopping heating and cooling to room temperature after the gradual lightening of the color is observed, dripping 3-5 drops of hydrogen peroxide, heating to 180-220 ℃ and magnetically stirring until the color becomes colorless and transparent, and continuously heating for 20-40min to remove residual hydrogen peroxide to obtain a sample digestion solution; then cooling the sample digestion solution, transferring the sample digestion solution into a 250mL volumetric flask, and diluting the sample digestion solution with pure water to a constant volume;
performing a digestion test according to the sample digestion method, preparing blank digestion liquid and performing constant volume dilution;
s2 color development experiment:
transferring 1mL of the sample digestion solution obtained in the step S1 after constant volume dilution into a 50mL volumetric flask, adding a proper amount of water, adding 1-2 drops of phenolphthalein reagent, dropwise adding sodium hydroxide solution until the solution is just reddish, dropwise adding sulfuric acid solution to enable reddish color to be just removed, fully and uniformly mixing, adding 2mL of ferrous ammonium sulfate solution, adding 1mL of ascorbic acid solution, uniformly mixing, adding 2mL of molybdate solution after 30S, fully and uniformly mixing, and then using pure water to constant volume to 50mL, thus preparing a sample solution to be measured;
1mL of the blank digestion solution obtained in the step S1 after constant volume dilution is removed, and a color development test is carried out according to the same method, so that a blank solution to be measured is prepared;
2. preparing a phosphorus working solution and drawing a standard curve:
1) Preparing a series of phosphorus working solutions with different concentrations;
2) Respectively carrying out color development experiment treatment on the phosphorus working solutions with different concentrations prepared in the step 1) according to the same operation steps as the color development experiment method in the step S2, respectively measuring absorbance by taking pure water as a negative control, respectively subtracting the absorbance value of the negative control water from the absorbance value of the phosphorus working solution with different concentrations as an ordinate, and drawing a standard curve by taking the content of P element in the phosphorus working solution as an abscissa;
3. and (3) content measurement:
m1: measuring the absorbance of the sample to-be-measured solution and the absorbance of the blank to-be-measured solution obtained in the first step, subtracting the absorbance of the blank to-be-measured solution from the absorbance value of the sample to-be-measured solution, and then detecting the corresponding phosphorus content from the standard curve;
m2: result calculation
The total phosphorus content in the sample is expressed in ω (%), calculated as:
in the formula, m 1 The total phosphorus mass of the sample is shown in mug, which is obtained by looking up a standard curve;
m 0 sample mass, g.
The method for measuring the phosphorus content of the phosphate flame retardant is characterized by comprising the following steps of, by mass, 25-35% of hydrogen peroxide; the mass fraction of the concentrated sulfuric acid is 98%.
The method for measuring the phosphorus content of the phosphate flame retardant is characterized in that in the first step, the mass concentration of the phenolphthalein reagent is 8-12g/L, the concentration of the sodium hydroxide solution is 0.8-1.2mol/L, the concentration of the sulfuric acid solution is 0.5-1 mol/L, and the concentration of the ascorbic acid solution is 80-120g/L.
The method for determining the phosphorus content of the phosphate flame retardant is characterized by comprising the following steps of: 10g of ferrous ammonium sulfate was weighed and dissolved in water, 5mL of 98% strength by mass concentrated sulfuric acid was added while stirring, and the volume was fixed to 500mL with pure water.
The method for measuring the phosphorus content of the phosphate flame retardant is characterized in that in the second or third step, the conditions for measuring the absorbance are as follows: absorbance was measured at a wavelength of 700nm using a cuvette with an optical path length of 10 mm.
The method for measuring the phosphorus content of the phosphate flame retardant is characterized in that in the first step, the phosphate flame retardant is at least one of bisphenol A bis (diphenyl phosphate), tri (1-chloro-2-propyl) phosphate, tri (1, 3-dichloro-2-propyl) phosphate, tributoxyethyl phosphate and diethylene glycol bis (di- (2-chloroisopropyl) phosphate).
The method for measuring the phosphorus content of the phosphate flame retardant is characterized by comprising the following steps of:
(1) Firstly, preparing a phosphorus standard solution with the concentration of the P element of 100.0 mug/ml: weighing 0.4394 +/-0.001 g of dried and cooled monopotassium phosphate, dissolving with water, transferring to a 1000mL volumetric flask, adding 700-800mL of water, adding 5mL of sulfuric acid with the mass fraction of 98%, diluting with water, and fixing the volume to a scale, thus obtaining a phosphorus standard solution;
(2) Preparing a series of phosphorus working solutions with different concentrations: taking 6 50mL volumetric flasks, adding 0.0, 1.00, 2.00, 5.00, 10.0 and 15.0mL of the phosphorus standard solution in the step (1) respectively, and fixing the volume to 50mL by water respectively, thus completing the preparation.
The beneficial effects obtained by the invention are as follows:
1) The method is characterized in that the total phosphorus content in the phosphate flame retardant is determined by a concentrated sulfuric acid-hydrogen peroxide wet digestion method, the recovery rate is within 100+/-5%, the result accuracy is high, the RSD is less than 1%, the result reproducibility is good, the analysis method is simple to operate, the pollution is small, and the time is short.
2) The embodiment of the invention mainly describes bisphenol A bis (diphenyl phosphate), tri (1-chloro-2-propyl) phosphate, TDCP tri (1, 3-dichloro-2-propyl) phosphate, tributoxyethyl phosphate, diethylene glycol bis (di- (2-chloroisopropyl) phosphate, and the determination of the total phosphorus content of five flame retardants, wherein a sample is dehydrated and carbonized at high temperature by concentrated sulfuric acid, then is decarbonized by hydrogen peroxide and converted into phosphoric acid, and is determined by a molybdenum-antimony anti-spectral breadth colorimetric method, and the test time of the sample is within 4 hours.
Drawings
Fig. 1 is a standard graph drawn in example 1 of the present application.
Detailed Description
The invention will be further illustrated with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1:
1. reagent(s)
Reagent: concentrated sulfuric acid; sodium hydroxide; anti-cyclohaemarrhena; ammonium molybdate; antimony potassium tartrate; potassium dihydrogen phosphate, ferrous ammonium sulfate; phenolphthalein; the above reagents were all analytically pure.
1.1 sulfuric acid solution (1+1), namely, 98% by mass of concentrated sulfuric acid and water are prepared according to a volume ratio of 1:1, and the preparation is carried out according to GB 603.
1.2 ferrous ammonium sulphate solution (20 g/L): 10g of ferrous ammonium sulfate is weighed and dissolved in water, 5mL of 98% concentrated sulfuric acid is added while stirring, and the volume is fixed to 500mL.
1.3 sodium hydroxide c (NaOH) =1 mol/L solution: 40g of sodium hydroxide was dissolved in water and diluted to 1000mL with water.
1.4 sulfuric acid solution (0.5 mol/L): 27mL of 98% sulfuric acid by mass fraction was added to 973mL of water to prepare the product.
1.5 ascorbic acid solution (100 g/L): 10g of ascorbic acid was dissolved in water and diluted to 100mL, and this solution was stored in a brown reagent bottle and allowed to stabilize at cold for several weeks. Can be used for a long time if the color is not changed.
1.6 molybdate solution: 13g of ammonium molybdate was added to 100mL of water, followed by continuous stirring, and then 300mL of sulfuric acid solution (1+1), followed by addition of a solution of potassium antimony tartrate (0.35 g of potassium antimony tartrate in 100mL of water), and mixed well.
1.7 phosphorus standard solution (100.0. Mu.g/ml in P): 0.4394 + -0.001 g of monopotassium phosphate which is dried at 110 ℃ for 2 hours and cooled in a dryer is weighed, dissolved by water and transferred into a 1000mL volumetric flask, approximately 800mL of water is added, 5mL of sulfuric acid with the mass fraction of 98% is added, and the mixture is diluted to a marked line by water and uniformly mixed.
1.8 phosphorus working solution: 6 50mL volumetric flasks were taken, and 0.0, 1.00, 2.00, 5.00, 10.0, 15.0mL of phosphorus standard solution was added, respectively, and the volumes were fixed with water to 50mL, respectively, at P concentrations of 0 μg/mL, 2 μg/mL, 4 μg/mL, 10 μg/mL, 20 μg/mL, 30 μg/mL, respectively.
1.9 phenolphthalein reagent (10 g/L): 0.5g phenolphthalein was dissolved in 50mL95% ethanol.
In the present invention, a visible light spectrophotometer is used to perform measurement spectrophotometry.
2. Experimental method
2.1 sample digestion:
weighing 0.03g (accurate to 0.00001 g) of a flame retardant sample, putting the flame retardant sample into a 100mL high beaker, putting the beaker into a magnetic stirrer, adding 2mL of 98% by mass concentrated sulfuric acid, covering a surface dish, magnetically stirring at 150 ℃ for 10min, adjusting to 200 ℃ for magnetically stirring for 5min, observing that the color is gradually blackened, stopping heating and cooling to room temperature, adding 0.5mL of 30% by mass hydrogen peroxide, heating to 200 ℃ for magnetically stirring for about 10min, observing that the color is gradually shallowed, stopping heating and cooling to room temperature, dripping 3-5 drops of 30% by mass hydrogen peroxide, heating to 200 ℃ for magnetically stirring until the color is colorless and transparent, and continuing heating for 30min to remove residual hydrogen peroxide to obtain a sample digestion solution; then cooling the sample digestion solution, transferring the sample digestion solution into a 250mL volumetric flask, and diluting the sample digestion solution with pure water to a constant volume;
performing a digestion test according to the sample digestion method, preparing blank digestion liquid and performing constant volume dilution;
2.2 color development experiments:
transferring 1mL of the sample digestion solution obtained in the step 2.1, after constant volume dilution, into a 50mL volumetric flask, adding about 20mL of water, adding one drop of phenolphthalein reagent (10 g/L), dropwise adding sodium hydroxide solution (1 mol/L) until the solution is just reddish, dropwise adding sulfuric acid solution (0.5 mol/L) to enable reddish color to be just removed, fully and uniformly mixing, adding 2mL of ferrous ammonium sulfate solution (20 g/L), adding 1mL of ascorbic acid solution (100 g/L), uniformly mixing, adding 2mL of molybdate solution after 30s, fully and uniformly mixing, and preparing a sample to be measured by water to 50 mL;
1mL of the blank digestion solution obtained in the step 2.1 after constant volume dilution is removed, and a color development test is carried out according to the same method, so that a blank solution to be measured is prepared;
2.3 drawing working curves:
according to the same operation steps as the color development experiment method in the step 2.2 of the step one, 1ml of phosphorus working solution with P concentration of 0 mug/ml, 2 mug/ml, 4 mug/ml, 10 mug/ml, 20 mug/ml and 30 mug/ml is respectively subjected to color development experiment treatment, pure water is used as a negative control, absorbance is measured respectively (a color tube with an optical path of 10mm is used, a visible light spectrophotometer is used for spectrophotometry at a wavelength of 700 nm), absorbance values of negative control water are subtracted by absorbance values of phosphorus working solutions with different concentrations to obtain an ordinate, P element content in the phosphorus working solution is used as an abscissa, and a standard curve is drawn, wherein the result is shown in figure 1.
2.4 content determination:
m1: measuring the absorbance of the sample to-be-measured solution and the blank to-be-measured solution (using a colorimetric tube with an optical path length of 10mm and using a visible light spectrophotometer to measure spectrophotometry at a wavelength of 700 nm), subtracting the absorbance of the blank to-be-measured solution from the absorbance value of the obtained sample to-be-measured solution, and then detecting the corresponding phosphorus content from a standard curve;
m2: result calculation
The total phosphorus content in the sample is expressed in ω (%), calculated as:
in the formula, m 1 The total phosphorus mass of the sample is shown in mug, which is obtained by looking up a standard curve;
m 0 sample mass, g.
Example 2:
according to the sample pretreatment and test method of example 1, total phosphorus content measurement and standard recovery experiments were performed on 5 phosphate flame retardants of Zhejiang Wansheng Co., ltd, and the test results are shown in tables 1 to 10. Among the 5 phosphate flame retardants tested were bisphenol A bis (diphenyl phosphate), tris (1-chloro-2-propyl) phosphate, tris (1, 3-dichloro-2-propyl) phosphate, tributoxyethyl phosphate, diethylene glycol bis (di- (2-chloroisopropyl) phosphate), respectively.
TABLE 1 bisphenol A bis (diphenyl phosphate) assay results
TABLE 2 bisphenol A bis (diphenyl phosphate) labeled recovery assay results
Comparative table 1 the procedure of the experimental procedure of example 1 was repeated for bisphenol a bis (diphenyl phosphate). The test results in Table 1 correspond to the formulas used for the calculation of the results of step M2 in step 2.4 of example 1.
The method is characterized in that a labeling recovery experiment is carried out on bisphenol A bis (diphenyl phosphate) to verify the accuracy of the method, the labeling recovery is carried out to verify the accuracy of the method, a labeling sample adopted in the labeling experiment is potassium dihydrogen phosphate, the experimental results are shown in Table 2, and the accuracy of the experimental method is higher.
The following test methods for tris (1-chloro-2-propyl) phosphate, tris (1, 3-dichloro-2-propyl) phosphate, tributoxyethyl phosphate, diethylene glycol bis (di- (2-chloroisopropyl) phosphate), all repeated the bisphenol A bis (diphenyl phosphate) test procedure.
TABLE 3 determination of tris (1-chloro-2-propyl) phosphate
TABLE 4 labeled recovery of tris (1-chloro-2-propyl) phosphate assay results
TABLE 5 tributoxyethyl phosphate assay results
TABLE 6 tributoxyethyl phosphate labeling recovery determination results
TABLE 7 determination of diethylene glycol bis (di- (2-chloroisopropyl) phosphate)
TABLE 8 determination of the labeled recovery of diethylene glycol bis (di- (2-chloroisopropyl) phosphate
TABLE 9 determination of tris (1, 3-dichloro-2-propyl) phosphate
TABLE 10 labeling recovery of tris (1, 3-dichloro-2-propyl) phosphate assay results
The problems of difficult digestion, long digestion time and the like exist in the detection of phenyl phosphate with higher stability, and the problems of incomplete digestion are described in the bisphenol A bis (diphenyl phosphate), tri (1-chloro-2-propyl) phosphate, tri (1, 3-dichloro-2-propyl) phosphate, tributoxyethyl phosphate, diethylene glycol bis (di- (2-chloroisopropyl) phosphate) and other 5 phosphate flame retardants, and after the existing conventional perchloric acid-nitric acid digestion method is adopted for treatment, oily matters can be obviously seen to float on the surface of liquid, so that the problem of incomplete digestion exists, and the test result of the final phosphorus content can be greatly adversely affected. After the concentrated sulfuric acid-hydrogen peroxide wet digestion treatment is carried out by the method provided by the invention, the sample digestion solution basically presents a colorless transparent form, the digestion treatment process is complete, and the test accuracy is relatively high.
What has been described in this specification is merely an enumeration of possible forms of implementation for the inventive concept and may not be considered limiting of the scope of the present invention to the specific forms set forth in the examples.
Claims (7)
1. The method for measuring the phosphorus content of the phosphate flame retardant is characterized by comprising the following steps of:
1. preparing a solution to be tested:
s1, sample digestion:
weighing 0.02-0.04g of phosphate flame retardant sample, putting the phosphate flame retardant sample into a 100mL high beaker, putting the beaker into a magnetic stirrer, adding 2mL of concentrated sulfuric acid, covering a surface dish, magnetically stirring the mixture for 8-12min at 140-160 ℃, then adjusting the temperature to 180-220 ℃ and magnetically stirring the mixture for 4-6 min, and stopping heating and cooling to room temperature after the color is observed to be gradually blackened; then adding 0.5ml of hydrogen peroxide, heating to 180-220 ℃ and magnetically stirring for 8-12min, stopping heating and cooling to room temperature after the gradual lightening of the color is observed, dripping 3-5 drops of hydrogen peroxide, heating to 180-220 ℃ and magnetically stirring until the color becomes colorless and transparent, and continuously heating for 20-40min to remove residual hydrogen peroxide to obtain a sample digestion solution; then cooling the sample digestion solution, transferring the sample digestion solution into a 250mL volumetric flask, and diluting the sample digestion solution with pure water to a constant volume;
performing a digestion test according to the sample digestion method, preparing blank digestion liquid and performing constant volume dilution;
s2 color development experiment:
transferring 1mL of the sample digestion solution obtained in the step S1 after constant volume dilution into a 50mL volumetric flask, adding a proper amount of water, adding 1-2 drops of phenolphthalein reagent, dropwise adding sodium hydroxide solution until the solution is just reddish, dropwise adding sulfuric acid solution to enable reddish color to be just removed, fully and uniformly mixing, adding 2mL of ferrous ammonium sulfate solution, adding 1mL of ascorbic acid solution, uniformly mixing, adding 2mL of molybdate solution after 30S, fully and uniformly mixing, and then using pure water to constant volume to 50mL, thus preparing a sample solution to be measured;
1mL of the blank digestion solution obtained in the step S1 after constant volume dilution is removed, and a color development test is carried out according to the same method, so that a blank solution to be measured is prepared;
2. preparing a phosphorus working solution and drawing a standard curve:
1) Preparing a series of phosphorus working solutions with different concentrations;
2) Respectively carrying out color development experiment treatment on the phosphorus working solutions with different concentrations prepared in the step 1) according to the same operation steps as the color development experiment method in the step S2, respectively measuring absorbance by taking pure water as a negative control, respectively subtracting the absorbance value of the negative control water from the absorbance value of the phosphorus working solution with different concentrations as an ordinate, and drawing a standard curve by taking the content of P element in the phosphorus working solution as an abscissa;
3. and (3) content measurement:
m1: measuring the absorbance of the sample to-be-measured solution and the absorbance of the blank to-be-measured solution obtained in the first step, subtracting the absorbance of the blank to-be-measured solution from the absorbance value of the sample to-be-measured solution, and then detecting the corresponding phosphorus content from the standard curve;
m2: result calculation
Total phosphorus content in the sample(%) represents, calculated as:
in the formula, m 1 The total phosphorus mass of the sample is shown in mug, which is obtained by looking up a standard curve;
m 0 sample mass, g.
2. The method for determining the phosphorus content of a phosphate flame retardant according to claim 1, wherein in the first step, the mass fraction of hydrogen peroxide is 25-35%; the mass fraction of the concentrated sulfuric acid is 98%.
3. The method for measuring the phosphorus content of the phosphate flame retardant according to claim 1, wherein in the first step, the mass concentration of the phenolphthalein reagent is 8-12g/L, the concentration of the sodium hydroxide solution is 0.8-1.2mol/L, the concentration of the sulfuric acid solution is 0.5-1 mol/L, and the concentration of the ascorbic acid solution is 80-120g/L.
4. The method for determining phosphorus content of phosphate flame retardant according to claim 1, wherein in the first step, the preparation method of the ferrous ammonium sulfate solution is as follows: 10g of ferrous ammonium sulfate was weighed and dissolved in water, 5mL of 98% strength by mass concentrated sulfuric acid was added while stirring, and the volume was fixed to 500mL with pure water.
5. The method for measuring phosphorus content of phosphate flame retardant according to claim 1, wherein in the second or third step, the conditions for measuring absorbance are as follows: absorbance was measured at a wavelength of 700nm using a cuvette with an optical path length of 10 mm.
6. The method for measuring phosphorus content of phosphate flame retardant according to claim 1, wherein in the first step, the phosphate flame retardant is at least one of bisphenol A bis (diphenyl phosphate), tri (1-chloro-2-propyl) phosphate, tri (1, 3-dichloro-2-propyl) phosphate, tributoxyethyl phosphate, diethylene glycol bis (di- (2-chloroisopropyl) phosphate).
7. The method for determining phosphorus content of phosphate flame retardant according to claim 1, wherein in the second step, the specific preparation process of the phosphorus working solution is as follows:
(1) Firstly, preparing a phosphorus standard solution with the concentration of the P element of 100.0 mug/ml: weighing 0.4394 +/-0.001 g, drying, cooling, dissolving with water, transferring to a 1000mL volumetric flask, adding 700-800mL of water, adding 5mL mass percent 98% sulfuric acid, diluting with water, and fixing volume to scale to obtain phosphorus standard solution;
(2) Preparing a series of phosphorus working solutions with different concentrations: taking 6 50mL volumetric flasks, adding 0.0, 1.00, 2.00, 5.00, 10.0 and 15.0mL of the phosphorus standard solution in the step (1) respectively, and fixing the volume to 50mL by water respectively, thus completing the preparation.
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