CN113418875A - 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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- CN113418875A CN113418875A CN202110570995.5A CN202110570995A CN113418875A CN 113418875 A CN113418875 A CN 113418875A CN 202110570995 A CN202110570995 A CN 202110570995A CN 113418875 A CN113418875 A CN 113418875A
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- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 61
- 239000011574 phosphorus Substances 0.000 title claims abstract description 61
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 41
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 41
- 239000010452 phosphate Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000003063 flame retardant Substances 0.000 title claims abstract description 36
- 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 32
- 239000000243 solution Substances 0.000 claims abstract description 62
- 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 25
- 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
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 25
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 24
- 238000002835 absorbance Methods 0.000 claims description 23
- 239000012224 working solution Substances 0.000 claims description 18
- 239000000523 sample Substances 0.000 claims description 17
- 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 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
- 230000029087 digestion Effects 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000012360 testing method Methods 0.000 claims description 12
- 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
- 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 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000012490 blank solution Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 9
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 9
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 9
- 239000012488 sample solution Substances 0.000 claims description 9
- 229940010514 ammonium ferrous sulfate Drugs 0.000 claims description 8
- 235000010323 ascorbic acid Nutrition 0.000 claims description 8
- 229960005070 ascorbic acid Drugs 0.000 claims description 8
- 239000011668 ascorbic acid Substances 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
- 238000007865 diluting Methods 0.000 claims description 6
- 239000013642 negative control Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 5
- 238000010790 dilution Methods 0.000 claims description 4
- 239000012895 dilution Substances 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- 150000003017 phosphorus Chemical class 0.000 claims description 4
- 239000012470 diluted sample Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 2
- 238000011084 recovery Methods 0.000 abstract description 11
- 238000002798 spectrophotometry method Methods 0.000 abstract description 5
- 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 2
- 238000004458 analytical method Methods 0.000 abstract description 2
- 238000010000 carbonizing Methods 0.000 abstract 1
- 238000003556 assay Methods 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 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
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 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
- 238000004737 colorimetric analysis Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005259 measurement Methods 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
- 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
- 238000012421 spiking Methods 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 238000010998 test method 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005262 decarbonization Methods 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
- 239000007788 liquid Substances 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
- 239000003973 paint Substances 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
- 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
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- 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
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- 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
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- 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
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- 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
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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 by using concentrated sulfuric acid at high temperature, then decarbonizing by using hydrogen peroxide and converting phosphate into phosphoric acid to obtain a sample digestion solution; then, performing a color development experiment on the sample digestion solution, and then performing spectrophotometry; 2) preparing a standard solution and drawing a standard curve: 3) and (4) measuring the content. The method disclosed by the invention is used for determining the total phosphorus content in the phosphate flame retardant by concentrated sulfuric acid-hydrogen peroxide wet digestion and molybdate spectrophotometry, the recovery rate is within 100 +/-5%, the accuracy of the result 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 consumption is short.
Description
Technical Field
The invention relates to a method for measuring 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 a halogen flame retardant but generates carcinogenic substances such as dioxin and the like during combustion, 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 the current national standard method mainly through persulfate oxidation digestion and a molybdenum-antimony colorimetric resistance method or a vanadium-molybdenum colorimetric method. However, the phosphorus content and the carbon content of the phosphate are high, the phosphate is difficult to digest completely by using a national standard method, the research related to the digestion by using a perchloric acid-nitric acid method also exists in domestic literature, and the phenyl phosphate with higher stability still cannot digest a sample completely in a short time, so that the technical problem of low recovery rate of a measurement result exists.
Disclosure of Invention
Aiming at the technical problems 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:
firstly, preparing a solution to be detected:
s1 sample digestion:
weighing 0.02-0.04g of phosphate flame retardant sample in a 100mL tall beaker, placing a magnetic stirrer, adding 2mL of concentrated sulfuric acid, covering a watch glass, magnetically stirring at 160 ℃ for 8-12min, regulating to 180 ℃ and 220 ℃ for 4-6 min, and stopping heating and cooling to room temperature after the color gradually turns black; then adding 0.5ml of hydrogen peroxide, heating to the temperature of 180-220 ℃, magnetically stirring for 8-12min, stopping heating and cooling to room temperature after the color is observed to gradually become light, dropwise adding 3-5 drops of hydrogen peroxide, heating to the temperature of 180-220 ℃, magnetically stirring until the color becomes colorless and transparent, and continuing heating for 20-40min to remove the 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;
carrying out digestion test according to the sample digestion method, preparing blank digestion solution and carrying out constant volume dilution;
s2 color development experiment:
transferring 1mL of the diluted sample digestion solution with constant volume obtained in the step S1 into a 50mL volumetric flask, adding a proper amount of water, adding 1-2 drops of a phenolphthalein reagent, dropwise adding a sodium hydroxide solution until the solution is just reddish, dropwise adding a sulfuric acid solution to ensure that the reddish color just drops off, fully and uniformly mixing, adding 2mL of an ammonium ferrous sulfate solution, adding 1mL of an ascorbic acid solution, uniformly mixing, adding 2mL of a molybdate solution after 30S, fully and uniformly mixing, then using pure water to fix the volume to 50mL, and preparing to obtain a sample solution to be detected;
transferring 1mL of the blank digestion solution obtained in the step S1 and diluted with constant volume to perform a color test according to the same method, and preparing to obtain a blank solution to be tested;
secondly, preparing a phosphorus working solution and drawing a standard curve:
1) preparing a series of phosphorus working solutions with different concentrations;
2) according to the same operation steps as the color development experiment method of the step S2 of the step I, color development experiment treatment is respectively carried out on the phosphorus working solutions with different concentrations prepared in the step 1), pure water is used as negative control, then the absorbance is respectively measured, the absorbance value of the negative control water is subtracted from the absorbance value of the phosphorus working solutions with different concentrations to be used as a vertical coordinate, the content of a P element in the phosphorus working solution is used as a horizontal coordinate, and a standard curve is drawn;
thirdly, content determination:
m1: measuring the absorbance of the sample solution to be measured and the blank solution to be measured obtained in the step one, subtracting the absorbance of the blank solution to be measured from the absorbance value of the sample solution to be measured, and then finding out the corresponding phosphorus content from the standard curve;
m2: calculation of results
The total phosphorus content in the sample is represented by ω (%) and is calculated as follows:
in the formula, m1The total phosphorus mass of the sample is shown to be checked from a standard curve, and the weight is mug;
m0denotes the sample mass, g.
The method for measuring the phosphorus content of the phosphate flame retardant is characterized in that in the first step, the mass fraction of hydrogen peroxide is 25-35%; the mass fraction of 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 a sodium hydroxide solution is 0.8-1.2mol/L, the concentration of a sulfuric acid solution is 0.5-1 mol/L, and the concentration of an ascorbic acid solution is 80-120 g/L.
The method for measuring the phosphorus content of the phosphate flame retardant is characterized in that in the first step, the preparation method of the ammonium ferrous sulfate solution comprises the following steps: 10g of ammonium ferrous sulfate is weighed and dissolved in water, 5mL of concentrated sulfuric acid with the mass fraction of 98% is added while stirring, and the volume is increased to 500mL by pure water.
The method for measuring the phosphorus content of the phosphate flame retardant is characterized in that in the second step or the third step, the conditions for measuring the absorbance are as follows: the absorbance was measured at a wavelength of 700nm using a colorimetric tube having an optical path of 10 mm.
The method for measuring the phosphorus content of the phosphate flame retardant is characterized in that in the step one, the phosphate flame retardant is at least one of bisphenol A bis (diphenyl phosphate), tris (1-chloro-2-propyl) phosphate, tris (1, 3-dichloro-2-propyl) phosphate, tributoxyethyl phosphate and diethylene glycol bis (bis- (2-chloroisopropyl) phosphate).
The method for measuring the phosphorus content of the phosphate flame retardant is characterized in that 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 P element being 100.0 mu g/ml: weighing 0.4394 +/-0.001 g of dried and cooled potassium dihydrogen phosphate, dissolving the potassium dihydrogen phosphate with water, transferring the potassium dihydrogen phosphate into a 1000mL volumetric flask, adding 700-800mL of water, adding 5mL of sulfuric acid with the mass fraction of 98%, diluting with water to a constant volume to a scale, and preparing a phosphorus standard solution;
(2) preparing a series of phosphorus working solutions with different concentrations: and (3) taking 6 50mL volumetric flasks, adding 0.0 mL, 1.00 mL, 2.00 mL, 5.00 mL, 10.0 mL and 15.0mL of the phosphorus standard solution obtained in the step (1), and respectively adding water to a constant volume of 50mL to complete the preparation.
The beneficial effects obtained by the invention are as follows:
1) the method disclosed by the invention is used for determining the total phosphorus content in the phosphate flame retardant by concentrated sulfuric acid-hydrogen peroxide wet digestion and molybdate spectrophotometry, the recovery rate is within 100 +/-5%, the accuracy of the result 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 consumption is short.
2) The embodiment of the invention mainly describes the determination of total phosphorus content of bisphenol A bis (diphenyl phosphate), tris (1-chloro-2-propyl) phosphate, TDCP tris (1, 3-dichloro-2-propyl) phosphate, tributoxyethyl phosphate and diethylene glycol bis (di- (2-chloroisopropyl) phosphate, wherein a sample is dehydrated and carbonized at high temperature by using concentrated sulfuric acid, then hydrogen peroxide is used for decarbonization and is converted into phosphoric acid, a molybdenum-antimony spectroresistance broad-spectrum colorimetric method is used for determination, and the sample testing time is within 4 hours.
Drawings
FIG. 1 is a standard graph plotted in example 1 of the present application.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1:
1. reagent
Reagent: concentrated sulfuric acid; sodium hydroxide; ascorbic acid; ammonium molybdate; antimony potassium tartrate; potassium dihydrogen phosphate, ammonium ferrous sulfate; phenolphthalein; the above reagents are all analytically pure.
1.1 sulfuric acid solution (1+1), which is prepared by mixing 98% mass fraction concentrated sulfuric acid and water according to the volume ratio of 1:1, according to GB 603.
1.2 ferrous ammonium sulfate solution (20 g/L): 10g of ammonium ferrous sulfate is weighed and dissolved in water, 5mL of concentrated sulfuric acid with the mass fraction of 98% is added while stirring, and the volume is adjusted to 500 mL.
1.3 sodium hydroxide c (naoh) 1mol/L solution: 40g of sodium hydroxide are dissolved in water and diluted to 1000mL with water.
1.4 sulfuric acid solution (0.5 mol/L): 27mL of sulfuric acid with the mass fraction of 98% is added into 973mL of water to prepare the water-based paint.
1.5 ascorbic acid solution (100 g/L): 10g ascorbic acid was dissolved in water and diluted to 100mL, and the solution was stored in a brown reagent bottle and allowed to stabilize in the cold for several weeks. If the color is not changed, the product can be used for a long time.
1.6 molybdate solution: 13g of ammonium molybdate were first dissolved in 100mL of water and then added with constant stirring to 300mL of sulfuric acid solution (1+1), and then the potassium antimony tartrate solution (0.35g of potassium antimony tartrate in 100mL of water) was added and mixed well.
1.7 phosphorus Standard solution (100.0. mu.g/ml in terms of P): 0.4394 + -0.001 g of potassium dihydrogen phosphate dried at 110 ℃ for 2h, cooled in a desiccator, dissolved in water, are transferred to a 1000mL volumetric flask, approximately 800mL of water are added, 5mL of sulfuric acid with a mass fraction of 98% are added, diluted to the marked line with water and mixed well.
1.8 phosphorus working solution: taking 6 50mL volumetric flasks, adding 0.0, 1.00, 2.00, 5.00, 10.0 and 15.0mL phosphorus standard solution respectively, and fixing the volume to 50mL with water respectively, wherein the concentration measured by P is 0 mu g/mL, 2 mu g/mL, 4 mu g/mL, 10 mu g/mL, 20 mu g/mL and 30 mu g/mL respectively.
1.9 phenolphthalein reagent (10 g/L): 0.5g phenolphthalein was dissolved in 50mL 95% ethanol.
In the present invention, a visible spectrophotometer is used to measure the spectrophotometry.
2. Experimental methods
2.1 sample digestion:
weighing 0.03g (accurate to 0.00001g) of flame retardant sample into a 100mL high-type beaker, placing a magnetic stirrer, adding 2mL of concentrated sulfuric acid with the mass fraction of 98%, covering a watch glass, magnetically stirring for 10min at 150 ℃, adjusting to 200 ℃, magnetically stirring for 5min, observing that the color gradually becomes black, stopping heating and cooling to room temperature, adding 0.5mL of hydrogen peroxide with the mass fraction of 30%, heating to 200 ℃, magnetically stirring for about 10min, observing that the color gradually becomes light, stopping heating and cooling to room temperature, dripping 3-5 drops of hydrogen peroxide with the mass fraction of 30%, heating to 200 ℃ until the color becomes colorless and transparent, magnetically stirring for further 30min, removing the residual hydrogen peroxide, and obtaining 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;
carrying out digestion test according to the sample digestion method, preparing blank digestion solution and carrying out constant volume dilution;
2.2 color development experiment:
transferring 1mL of the diluted sample digestion solution with constant volume obtained in the step 2.1 into a 50mL volumetric flask, adding about 20mL of water, adding one drop of phenolphthalein reagent (10g/L), dropwise adding a sodium hydroxide solution (1mol/L) until the sample digestion solution is just reddish, dropwise adding a sulfuric acid solution (0.5mol/L) to ensure that the reddish color is just removed, fully and uniformly mixing, adding 2mL of an ammonium ferrous sulfate solution (20g/L), adding 1mL of an ascorbic acid solution (100g/L), uniformly mixing, adding 2mL of a molybdate solution after 30s, fully and uniformly mixing, and diluting to 50mL with water to obtain a sample solution to be detected;
transferring 1mL of the blank digestion solution obtained in the step 2.1 after constant volume dilution to perform a color test according to the same method, and preparing a blank solution to be tested;
2.3 drawing of working curve:
according to the same operation steps as the color development experiment method of the step 2.2 in the first step, 1ml of phosphorus working solution with the concentration of 0 mug/ml, 2 mug/ml, 4 mug/ml, 10 mug/ml, 20 mug/ml and 30 mug/ml respectively calculated by P is taken to be respectively subjected to color development experiment treatment, pure water is used as a negative control, then the absorbance is respectively measured (the absorbance is measured by using a colorimetric tube with the optical path of 10mm and using a visible light spectrophotometer under the wavelength of 700 nm), the absorbance of the negative control water is subtracted from the absorbance of the phosphorus working solution with different concentrations to be used as a vertical coordinate, the content of P element in the phosphorus working solution is used as a horizontal coordinate, and a standard curve is drawn, and the result is shown in figure 1.
2.4 content determination:
m1: measuring the absorbance of the sample solution to be measured and the blank solution to be measured obtained in the first step (measuring the spectrophotometry by using a colorimetric tube with an optical path of 10mm and using a visible light spectrophotometer under the wavelength of 700 nm), subtracting the absorbance of the blank solution to be measured from the absorbance of the sample solution to be measured, and then finding out the corresponding phosphorus content from the standard curve;
m2: calculation of results
The total phosphorus content in the sample is represented by ω (%) and is calculated as follows:
in the formula, m1The total phosphorus mass of the sample is shown to be checked from a standard curve, and the weight is mug;
m0denotes the sample mass, g.
Example 2:
according to the sample pretreatment and test method of example 1, 5 phosphate flame retardants from Wansheng GmbH in Zhejiang were subjected to total phosphorus content determination and standard recovery experiments, and the test results are shown in tables 1-10. 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 (bis- (2-chloroisopropyl) phosphate), respectively.
TABLE 1 bisphenol A bis (diphenylphosphate) assay results
TABLE 2 bisphenol A bis (diphenylphosphate) spiking recovery assay results
In comparison to Table 1, the procedure for testing bisphenol A bis (diphenyl phosphate) was repeated for the experimental procedure of example 1. The results are shown in Table 1, corresponding to the formula used in the calculation of the results of step M2 in step 2.4 of example 1.
The standard addition recovery experiment of bisphenol A bis (diphenyl phosphate) is carried out to verify the accuracy of the method, the standard addition recovery is carried out to verify the accuracy of the method, a standard addition sample adopted in the standard addition experiment is potassium dihydrogen phosphate, the experimental result is shown in table 2, and the accuracy of the experimental method is high.
The procedure for testing bisphenol A bis (diphenyl phosphate) was repeated, as follows for the test methods for tris (1-chloro-2-propyl) phosphate, tris (1, 3-dichloro-2-propyl) phosphate, tributoxyethyl phosphate, diethylene glycol bis (bis- (2-chloroisopropyl) phosphate).
TABLE 3 determination of tris (1-chloro-2-propyl) phosphate
TABLE 4 Tri (1-chloro-2-propyl) phosphate spiked recovery assay results
TABLE 5 tributoxyethyl phosphate measurement results
TABLE 6 Tributoxyethyl phosphate spiked recovery assay results
TABLE 7 diethylene glycol bis (bis- (2-chloroisopropyl) phosphate assay results
TABLE 8 diethylene glycol bis (bis- (2-chloroisopropyl) phosphate spiking recovery assay results
TABLE 9 determination of tris (1, 3-dichloro-2-propyl) phosphate
TABLE 10 Tri (1, 3-dichloro-2-propyl) phosphate spiked recovery assay results
The phenyl phosphate detection with higher stability has the problems of difficult digestion, long digestion time and the like, and 5 phosphate flame retardants such as 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) and the like are treated by the conventional perchloric acid-nitric acid digestion method, so that oily matters can be obviously seen to float on the liquid surface, which indicates that the problem of incomplete digestion exists, and the problem can generate great adverse effect on the test result of the final phosphorus content. After the concentrated sulfuric acid-hydrogen peroxide wet digestion treatment is carried out by the method, the sample digestion solution basically presents a colorless transparent state, the digestion treatment process is complete, and the test accuracy is relatively high.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular 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:
firstly, preparing a solution to be detected:
s1 sample digestion:
weighing 0.02-0.04g of phosphate flame retardant sample in a 100mL tall beaker, placing a magnetic stirrer, adding 2mL of concentrated sulfuric acid, covering a watch glass, magnetically stirring at 160 ℃ for 8-12min, regulating to 180 ℃ and 220 ℃ for 4-6 min, and stopping heating and cooling to room temperature after the color gradually turns black; then adding 0.5ml of hydrogen peroxide, heating to the temperature of 180-220 ℃, magnetically stirring for 8-12min, stopping heating and cooling to room temperature after the color is observed to gradually become light, dropwise adding 3-5 drops of hydrogen peroxide, heating to the temperature of 180-220 ℃, magnetically stirring until the color becomes colorless and transparent, and continuing heating for 20-40min to remove the 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;
carrying out digestion test according to the sample digestion method, preparing blank digestion solution and carrying out constant volume dilution;
s2 color development experiment:
transferring 1mL of the diluted sample digestion solution with constant volume obtained in the step S1 into a 50mL volumetric flask, adding a proper amount of water, adding 1-2 drops of a phenolphthalein reagent, dropwise adding a sodium hydroxide solution until the solution is just reddish, dropwise adding a sulfuric acid solution to ensure that the reddish color just drops off, fully and uniformly mixing, adding 2mL of an ammonium ferrous sulfate solution, adding 1mL of an ascorbic acid solution, uniformly mixing, adding 2mL of a molybdate solution after 30S, fully and uniformly mixing, then using pure water to fix the volume to 50mL, and preparing to obtain a sample solution to be detected;
transferring 1mL of the blank digestion solution obtained in the step S1 and diluted with constant volume to perform a color test according to the same method, and preparing to obtain a blank solution to be tested;
secondly, preparing a phosphorus working solution and drawing a standard curve:
1) preparing a series of phosphorus working solutions with different concentrations;
2) according to the same operation steps as the color development experiment method of the step S2 of the step I, color development experiment treatment is respectively carried out on the phosphorus working solutions with different concentrations prepared in the step 1), pure water is used as negative control, then the absorbance is respectively measured, the absorbance value of the negative control water is subtracted from the absorbance value of the phosphorus working solutions with different concentrations to be used as a vertical coordinate, the content of a P element in the phosphorus working solution is used as a horizontal coordinate, and a standard curve is drawn;
thirdly, content determination:
m1: measuring the absorbance of the sample solution to be measured and the blank solution to be measured obtained in the step one, subtracting the absorbance of the blank solution to be measured from the absorbance value of the sample solution to be measured, and then finding out the corresponding phosphorus content from the standard curve;
m2: calculation of results
The total phosphorus content in the sample is as follows
(%) represents, calculated as:
in the formula, m1The total phosphorus mass of the sample is shown to be checked from a standard curve, and the weight is mug;
m0denotes the sample mass, g.
2. The method for measuring the phosphorus content of the phosphate flame retardant according to claim 1, wherein in the first step, the mass fraction of the hydrogen peroxide is 25-35%; the mass fraction of concentrated sulfuric acid is 98%.
3. The method for determining 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 80-120 g/L.
4. The method for measuring the phosphorus content of the phosphate flame retardant according to claim 1, wherein in the first step, the preparation method of the ferrous ammonium sulfate solution comprises the following steps: 10g of ammonium ferrous sulfate is weighed and dissolved in water, 5mL of concentrated sulfuric acid with the mass fraction of 98% is added while stirring, and the volume is increased to 500mL by pure water.
5. The method for measuring the phosphorus content of the phosphate ester flame retardant according to claim 1, wherein in the second step or the third step, the conditions for measuring the absorbance are as follows: the absorbance was measured at a wavelength of 700nm using a colorimetric tube having an optical path of 10 mm.
6. The method according to claim 1, wherein in the first step, the phosphate flame retardant is at least one of bisphenol A bis (diphenyl phosphate), tris (1-chloro-2-propyl) phosphate, tris (1, 3-dichloro-2-propyl) phosphate, tributoxyethyl phosphate, and diethylene glycol bis (bis- (2-chloroisopropyl) phosphate).
7. The method for determining the phosphorus content of the phosphate ester flame retardant as claimed in 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 P element being 100.0 mu g/ml: weighing 0.4394 +/-0.001 g of dried and cooled potassium dihydrogen phosphate, dissolving the potassium dihydrogen phosphate with water, transferring the potassium dihydrogen phosphate into a 1000mL volumetric flask, adding 700-800mL of water, adding 5mL of sulfuric acid with the mass fraction of 98%, diluting with water to a constant volume to a scale, and preparing a phosphorus standard solution;
(2) preparing a series of phosphorus working solutions with different concentrations: and (3) taking 6 50mL volumetric flasks, adding 0.0 mL, 1.00 mL, 2.00 mL, 5.00 mL, 10.0 mL and 15.0mL of the phosphorus standard solution obtained in the step (1), and respectively adding water to a constant volume of 50mL to complete the preparation.
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