CN114544304B - Preparation method of water-based paint sample to be measured and precipitation clarification-AHMT method for measuring free formaldehyde content in water-based paint - Google Patents
Preparation method of water-based paint sample to be measured and precipitation clarification-AHMT method for measuring free formaldehyde content in water-based paint Download PDFInfo
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- CN114544304B CN114544304B CN202210044944.3A CN202210044944A CN114544304B CN 114544304 B CN114544304 B CN 114544304B CN 202210044944 A CN202210044944 A CN 202210044944A CN 114544304 B CN114544304 B CN 114544304B
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 295
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000003973 paint Substances 0.000 title claims abstract description 76
- 229910001868 water Inorganic materials 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 53
- 238000001556 precipitation Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 8
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 4
- 230000001376 precipitating effect Effects 0.000 claims abstract description 3
- 239000006228 supernatant Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 68
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical group [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 24
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 24
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 24
- 239000000276 potassium ferrocyanide Substances 0.000 claims description 21
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical group [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 claims description 21
- MLIWQXBKMZNZNF-KUHOPJCQSA-N (2e)-2,6-bis[(4-azidophenyl)methylidene]-4-methylcyclohexan-1-one Chemical compound O=C1\C(=C\C=2C=CC(=CC=2)N=[N+]=[N-])CC(C)CC1=CC1=CC=C(N=[N+]=[N-])C=C1 MLIWQXBKMZNZNF-KUHOPJCQSA-N 0.000 claims description 19
- 238000000576 coating method Methods 0.000 claims description 17
- 238000002835 absorbance Methods 0.000 claims description 15
- 230000031700 light absorption Effects 0.000 claims description 15
- 239000004246 zinc acetate Substances 0.000 claims description 15
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 13
- 150000003751 zinc Chemical class 0.000 claims description 10
- 238000011161 development Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 238000006482 condensation reaction Methods 0.000 claims description 7
- 238000002137 ultrasound extraction Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims 2
- 238000001514 detection method Methods 0.000 abstract description 34
- 238000005352 clarification Methods 0.000 abstract description 15
- 229920000642 polymer Polymers 0.000 abstract description 7
- 239000012535 impurity Substances 0.000 abstract description 4
- 239000000523 sample Substances 0.000 description 38
- 238000012360 testing method Methods 0.000 description 28
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 22
- 235000012249 potassium ferrocyanide Nutrition 0.000 description 19
- 230000000694 effects Effects 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 12
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 11
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 11
- 235000011130 ammonium sulphate Nutrition 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 238000011084 recovery Methods 0.000 description 11
- 238000000605 extraction Methods 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000003153 chemical reaction reagent Substances 0.000 description 9
- 230000007246 mechanism Effects 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 239000011550 stock solution Substances 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- 239000011256 inorganic filler Substances 0.000 description 5
- 229910003475 inorganic filler Inorganic materials 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000002798 spectrophotometry method Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 238000004949 mass spectrometry Methods 0.000 description 4
- 238000003908 quality control method Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- UOULCEYHQNCFFH-UHFFFAOYSA-M sodium;hydroxymethanesulfonate Chemical compound [Na+].OCS([O-])(=O)=O UOULCEYHQNCFFH-UHFFFAOYSA-M 0.000 description 4
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 238000000703 high-speed centrifugation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000007344 nucleophilic reaction Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- HORQAOAYAYGIBM-UHFFFAOYSA-N 2,4-dinitrophenylhydrazine Chemical compound NNC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O HORQAOAYAYGIBM-UHFFFAOYSA-N 0.000 description 1
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 description 1
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 description 1
- 235000010703 Modiola caroliniana Nutrition 0.000 description 1
- 244000038561 Modiola caroliniana Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 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
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000003988 headspace gas chromatography Methods 0.000 description 1
- 238000001319 headspace solid-phase micro-extraction Methods 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 231100000405 induce cancer Toxicity 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000013062 quality control Sample Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/34—Purifying; Cleaning
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/4044—Concentrating samples by chemical techniques; Digestion; Chemical decomposition
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/4055—Concentrating samples by solubility techniques
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/4077—Concentrating samples by other techniques involving separation of suspended solids
-
- 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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/4055—Concentrating samples by solubility techniques
- G01N2001/4061—Solvent extraction
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/4077—Concentrating samples by other techniques involving separation of suspended solids
- G01N2001/4083—Concentrating samples by other techniques involving separation of suspended solids sedimentation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/4077—Concentrating samples by other techniques involving separation of suspended solids
- G01N2001/4088—Concentrating samples by other techniques involving separation of suspended solids filtration
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/4077—Concentrating samples by other techniques involving separation of suspended solids
- G01N2001/4094—Concentrating samples by other techniques involving separation of suspended solids using ultrasound
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
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- Spectroscopy & Molecular Physics (AREA)
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Abstract
The invention relates to a preparation method of a sample to be tested of a water-based paint and a precipitation clarification-AHMT method for measuring the content of free formaldehyde in the water-based paint. The preparation method of the water-based paint sample to be measured comprises the following steps: mixing the water-based paint containing free formaldehyde, the extracting agent, the precipitating agent and water to obtain a mixed solution, carrying out ultrasonic treatment, filtering, and taking supernatant to obtain the sample to be detected. According to the invention, through specific precipitation clarification treatment, free formaldehyde in the water-based paint can be efficiently enriched under normal temperature conditions, meanwhile, impurities such as polymers, color paste and the like which influence detection are removed, and the obtained sample to be detected has good clarity, can reduce interference of various factors, is convenient to detect, and has low treatment cost.
Description
Technical Field
The invention belongs to the technical field of formaldehyde detection, and particularly relates to a preparation method of a water-based paint sample to be detected and a precipitation clarification-AHMT method for measuring the free formaldehyde content in the water-based paint.
Background
Formaldehyde (HCHO), colorless with a pungent odor gas that can induce cancer, is classified as a potentially dangerous carcinogen by the world and environmental protection agency. In daily life, formaldehyde pollution mainly comes from urea formaldehyde resin in artificial boards, and unreacted free formaldehyde remained in the production process of the coating is released. In the new implementation national standard GB18582-2020, the limit of free formaldehyde in the water paint for building is reduced from 100mg/kg to 50mg/kg, which proves that the prevention and treatment of formaldehyde pollution are increasingly paid attention to, and simultaneously, new requirements for formaldehyde detection are also put forward.
At present, the detection of free formaldehyde in the water-based paint mainly comprises the following three types: 1. distillation (Chen Rong, zhang Yu, chen Weilian, et al. Study of determination of formaldehyde content in aqueous paints and adhesives for indoor use [ J ]. Analytical laboratory, 2008,27 (z 2): 284-286.; du Long, cao Jingyi, liguang, et al. Acetylacetonate spectrophotometry. Determination of formaldehyde content in interior wall paints [ J ]. Modern scientific instrument, 2016, (1): 99-102.). The principle of the method is that formaldehyde is collected by a distillation mode through heating the paint and reacts with acetylacetone to generate a stable yellow complex, and spectrophotometry is used for detection. In the method, the heating distillation process needs to be monitored manually, the whole detection time is long, and the detection efficiency is low. 2. Derivatization-mass spectrometry (Oliva-Teles M T,Paiga P,Delerue-Matos C M,et al.Determination of free formaldehyde in foundry resins as its 2,4-dinitrophenylhydrazone by liquid chromatography[J].Analytica Chimica Acta,2002,467(s 1–2):97-103;Mcguire J M,Nahm S H.Determination,by GC-MS using deuterated internal standards,of formaldehyde and methanol evolved during curing of coatings[J].Journal of Separation Science,2015,14(4):241-244.). the principle of the method is that after the paint is diluted and extracted by water, formaldehyde is derivatized by 2, 4-dinitrophenylhydrazine, and the derivative is measured by liquid chromatography-mass spectrometry or gas chromatography-mass spectrometry. The pretreatment is simple and convenient, but the derivatization process with strict conditions needs to be carried out for 5-24 hours. 3. Headspace method (Ma Ming, zhou Yuyan, ma Tengzhou. Headspace-gas chromatography mass spectrometry method for rapidly measuring free formaldehyde content [ J ] in aqueous paint and adhesive. Analytical laboratory ,2015,34(5):558-561.;Lo KM,Yung Y L.Integration of Headspace Solid Phase Micro-Extraction with Gas Chromatography for Quantitative Analysis of Formaldehyde[J].Bulletin of the Korean Chemical Society,2013,34(1):139-142.).. The method involves heating paint in a headspace device, and injecting formaldehyde into a chromatograph through a quantitative ring when the formaldehyde is precipitated in a gas phase and reaches pressure equilibrium in a gas-liquid phase, so as to perform mass spectrometry detection.
Therefore, developing a method for rapidly, efficiently, low-cost and high-accuracy detecting formaldehyde content in water paint at normal temperature has important research significance and application value.
Disclosure of Invention
The invention aims to overcome the defects or shortcomings of the existing detection method for detecting the water-based paint and provides a preparation method of a water-based paint sample to be detected. According to the invention, through specific precipitation clarification treatment, free formaldehyde in the water-based paint can be efficiently enriched under normal temperature conditions, meanwhile, impurities such as polymers, color paste and the like which influence detection are removed, and the obtained sample to be detected has good clarity, can reduce interference of various factors, is convenient to detect, and has low treatment cost.
It is another object of the present invention to provide a precipitation clarification-AHMT method for determining the content of free formaldehyde in aqueous paints. The AHMT method is used for detecting the sample to be detected, so that the detection of free formaldehyde in the water-based paint can be realized, and the accuracy is high.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
A preparation method of a water-based paint sample to be measured comprises the following steps: mixing and dissolving the water-based paint containing free formaldehyde, an extracting agent and a precipitating agent to obtain a mixed solution, carrying out ultrasonic treatment, filtering, and taking a supernatant to obtain the sample to be detected;
the extractant is sodium metabisulfite or aqueous solution thereof; the precipitant is potassium ferrocyanide and zinc salt or aqueous solution thereof, and the molar ratio of zinc ions in the potassium ferrocyanide and the zinc salt is 1:0.1-10;
The mass ratio of the water-based paint to the potassium ferrocyanide is 1:0.00739-0.0924; the mass ratio of the water-based paint to the sodium metabisulfite is 1:0.0005-0.05.
The AHMT method (AHMT spectrophotometry) is the most commonly used method for detecting formaldehyde content in air, and has the advantages of no need of heating, less interference and low detection limit.
In view of the problems of heating, long treatment time, low detection efficiency and the like of the existing methods for detecting free formaldehyde in the water-based paint (distillation method, derivatization-mass spectrometry and headspace method), the inventor tries to pretreat the water-based paint and then uses an AHMT method (AHMT spectrophotometry) to detect the free formaldehyde in the water-based paint.
The formaldehyde in the air is easy to collect, less impurity interference is caused, and a sample to be detected is easy to prepare; the water paint consists of water soluble resin, inorganic stuffing, color paste, etc. and the free formaldehyde in the paint is dispersed into the components. The current pretreatment technology of the sample to be detected by ultraviolet spectrophotometry can only obtain the sample to be detected by heating and distilling the water-based paint. However, in the pretreatment technique such as high-speed centrifugation or non-heating distillation such as filtration with filter paper, it is difficult to obtain a sample to be measured by efficiently separating and extracting free formaldehyde, and in this case, detection by the AHMT method is impossible. How to extract free formaldehyde from complex components in a water-based paint with high efficiency without heating and distilling, and simultaneously avoid the interference of each component on the detection process, and detect the free formaldehyde content by using an AHMT method under proper reaction conditions is important and difficult.
(1) Enrichment for free formaldehyde: at present, various substances such as pure water, ammonium sulfate and the like can be used for extracting and enriching formaldehyde. It was found that,
When pure water is used as the extracting solution, the extracting mechanism of the sample to be detected is as follows:
When a sample to be tested is obtained using an ammonium sulfate solution as an extraction solution, the extraction mechanism is as follows:
The research shows that when pure water and ammonium sulfate solution are used as extracting solution to enrich free methanol in the water-based paint, the enrichment efficiency is low, and the obtained formaldehyde cannot be effectively released under the detection condition of an AHMT method, so that the detection effect is poor.
Further researches show that the sample to be detected obtained by taking sodium metabisulfite as the extracting solution has the advantages of good enrichment effect and capability of being directly detected by using an AHMT method. Specifically, 1) sodium metabisulfite can carry out nucleophilic reaction with formaldehyde to obtain HO-CH 2-SO3 Na (sodium hydroxymethanesulfonate), so as to realize the efficient enrichment of free formaldehyde. This may be because: in order to maintain the storage stability of the coating, the water-based coating is generally in weak alkalinity, so that the product sodium hydroxymethanesulfonate of formaldehyde in sodium metabisulfite solution is in a more stable state in the mixed solution than the product of formaldehyde in ammonium sulfate solution and the product of formaldehyde in water, and the extraction efficiency of formaldehyde is higher. 2) When the AHMT method is used for developing the three samples to be detected, formaldehyde is released from formaldehyde in the samples to be detected and sodium hydroxymethanesulfonate which is a product of sodium metabisulfite after potassium hydroxide solution is added, so that the subsequent detection of formaldehyde can be effectively performed, and the samples to be detected obtained by taking the sodium metabisulfite as an extracting solution have better enrichment and detection results.
(2) Clarification of aqueous coating solutions: because of the complex components in the water-based paint, besides high molecular polymers such as water-soluble resin, the water-based paint may also contain acetaldehyde which has a very similar structure to formaldehyde, organic solvents (such as ethylene glycol, tripropylene glycol monobutyl ether and the like), organic color paste, inorganic fillers (such as kaolin, silicon dioxide and titanium dioxide) and other interference components. If clarification treatment is not performed, the components may absorb or block light rays at the detection wavelength, so that errors occur in absorbance values, and accurate detection cannot be performed in time.
However, due to the characteristics of the coating manufacturing process, the components are uniformly mixed, and the particle size of particles in the coating is very small and is as low as tens of micrometers, so that water-soluble resin, inorganic filler, organic color paste and the like are difficult to remove in a high-speed centrifugation or filter paper filtering mode when preparing a sample to be tested. Therefore, a new clarification process needs to be developed, and during clarification, the high-molecular polymer, the organic color paste, the inorganic filler and the like are effectively precipitated to achieve a clarification effect, so that free formaldehyde is prevented from being carried and precipitated during clarification; the influence of interfering components on the precipitation effect is also taken into account.
The research shows that the compound of potassium ferrocyanide and zinc salt is used as the precipitant, which can realize the effective precipitation of high molecular polymer, organic color paste, inorganic filler and the like, and the sample to be measured after the precipitation is filtered is clear and transparent, meets the detection requirement of a spectrophotometer, and does not influence the extraction and enrichment of free formaldehyde. Specifically, potassium ferrocyanide and zinc salt can react to generate Zn 2[Fe(CN)6],Zn2[Fe(CN)6 which can selectively precipitate high molecular polymer organic color paste and inorganic filler).
[Fe(CN)6]4-+2Zn2+→Zn2[Fe(CN)6]↓
According to the invention, through the addition of the specific extractant and the precipitant, the precipitation clarification and the high-efficiency enrichment of free formaldehyde of the aqueous coating aqueous solution can be realized, and the obtained aqueous coating sample to be measured is easy to measure the formaldehyde content.
Preferably, the power of ultrasonic extraction is 20-60 kHZ, and the time is 10-15 min.
Preferably, the zinc salt is one or more of zinc acetate, zinc chloride, zinc sulfate or zinc nitrate.
Preferably, the concentration of sodium metabisulfite in the mixed solution is 0.01-1.0 g/L.
Preferably, the molar concentration of potassium ferrocyanide in the mixed solution is 0.004-0.005 moL/L; the molar concentration of zinc ions in the zinc salt is 0.008-0.01 moL/L.
The invention also discloses a precipitation clarification-AHMT method for determining the content of free formaldehyde in the water-based paint.
A precipitation clarification-AHMT method for determining the content of free formaldehyde in an aqueous coating, comprising the steps of: and detecting the sample to be detected obtained by the preparation method by using an AHMT method to obtain the content of free formaldehyde in the water-based paint.
The water-based paint to be measured prepared by the method has high clarity, free formaldehyde is effectively enriched, and the formaldehyde content can be measured by using an AHMT method, so that the free formaldehyde content in the water-based paint is obtained. Specifically, under alkaline conditions, the enriched formaldehyde returns to a free state again, is oxidized into mauve 6-solo-5-triazacene [4,3-b ] -S-tetraazabenzene (III) by an AHMT reagent, and the formaldehyde content is obtained by measuring the absorbance value by a spectrophotometer. The color development principle is as follows
By using the method for detection, the linear range of free formaldehyde detection is 0.5-64 mug, r 2 =0.9990, and the quantitative limit is 2.5mg/kg. The test was performed with a quality control standard, with a relative deviation of 1.5%. The repeatability and recovery rate tests are carried out by 4 water-based paints, the relative standard deviation is 1.8-8.8%, and the recovery rate of three concentration levels is 88% -105%.
Preferably, the specific process of the AHMT method is as follows: adding alkaline substances and AHMT solution into a sample to be detected for condensation reaction, then adding potassium periodate solution for oxidation reaction, measuring the light absorption value by using a spectrophotometer after color development, and comparing with a standard curve to obtain the content of free formaldehyde in the water-based paint.
More preferably, the volume molar ratio of the sample to be tested and the alkaline substance is 1:0.00005-0.00025 mL/moL.
Preferably, the alkaline substance is one or two of potassium hydroxide or sodium hydroxide.
More preferably, the volume-to-mass ratio of the sample to be tested to AHMT is 1:0.1-0.4 mL/mg.
More preferably, the mass ratio of the AHMT to the potassium periodate is 1:0.125-2.
Preferably, the time of the condensation reaction is 20-25 min; the time of the oxidation reaction is 2-60 min.
The wavelength used for measuring the absorbance is 549.9-550.2 nm.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, through specific precipitation clarification treatment, free formaldehyde in the water-based paint can be efficiently enriched under normal temperature conditions, meanwhile, impurities such as polymers, color paste and the like which influence detection are removed, and the obtained sample to be detected has good clarity, can eliminate the interference of various factors, is convenient to detect, and has low treatment cost;
(2) The AHMT method is used for detecting the sample to be detected, so that the accurate determination of free formaldehyde in the water-based paint can be realized, the linear range of detection is 0.5-64 mug, and the quantitative limit is 2.5mg/kg with r 2 =0.9990. The repeatability and recovery rate tests are carried out by 4 water-based paints, the relative standard deviation is 1.8-8.8%, and the recovery rate of three concentration levels is 88% -105%.
Detailed Description
The invention is further illustrated below with reference to examples. These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. The experimental procedures in the examples below, without specific details, are generally performed under conditions conventional in the art or recommended by the manufacturer; the raw materials, reagents and the like used, unless otherwise specified, are those commercially available from conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art in light of the above teachings are intended to be within the scope of the invention as claimed.
(1) The main instrument, reagent information used in each example is as follows:
shimadzu UV-1800 UV-visible spectrophotometer (with 10mm cuvette).
GTSONIC-P ultrasonic cleaner (power 50W, frequency 40 KHz).
0.25Mol/L potassium ferrocyanide solution: 10.6g of potassium hexacyanoferrate (II) trihydrate are weighed out in water and diluted to 100mL.
1.0Mol/L zinc acetate solution: 22g of zinc acetate dihydrate was weighed out and dissolved in water and diluted to 100mL.
280G/L potassium hydroxide solution: 28g of potassium hydroxide was weighed out in water and diluted to 100mL.
5G/L AHMT solution: 0.5g AHMT was weighed into 0.5moL/L hydrochloric acid solution and diluted to 100mL.
15G/L potassium periodate solution: 1.5g of potassium periodate was weighed out and dissolved in 0.2moL/L potassium hydroxide solution and diluted to 100mL.
20Mg/L formaldehyde stock: 20.0mL of formaldehyde standard solution (100 mg/L) was pipetted into a 100mL brown volumetric flask and the volume was fixed with distilled water.
(2) The information for the test samples used in each example is as follows:
1 tank each of a water-based acrylic resin paint for construction (marked as a sample), a water-based emulsion paint for construction (marked as a sample B), a water-based epoxy resin floor paint for construction (marked as a sample C) and a water-based inorganic paint for construction (marked as a sample D). Free formaldehyde standard substance (RM-19015, formaldehyde content of 132mg/kg, labeled quality control sample) was used in the coating.
Example 1 AHMT method Condition optimization
In this example, formaldehyde stock solution was used as the test solution, and conditions in the AHMT method were optimized.
1. Absorbance measuring section
(1) Determination of the absorption maximum wavelength
1ML of formaldehyde stock solution, 2mL of potassium hydroxide solution and 2mL of AHMT solution are added into a 50mL colorimetric tube in sequence, mixed for 30min, then 2mL of potassium periodate solution is added, distilled water is used for constant volume, the color development is carried out for 20min, and then the machine is started, and spectrum scanning is carried out at 400-600 nm. The scanning result shows that: the absorption value of the 6-solo-5-triazacyclopentadienyl [4,3-b ] -S-tetraazabenzene (III) generated by the reaction is maximum at the wavelength 549.9-550.2nm, and the subsequent experiments all select 550nm as the measurement wavelength.
(2) Influence of the amount of Potassium hydroxide solution on the absorbance
Taking 5 colorimetric tubes of 50mL, according to the steps and conditions in the determination of the maximum absorption wavelength of (1), except that the addition amount of potassium hydroxide solution is 0, 0.5, 1.0, 1.5, 2.0 and 2.5mL (the mass of potassium hydroxide is 0, 0.14, 0.28, 0.42, 0.56 and 0.7g respectively), the rest steps are unchanged, and the change of the light absorption value is observed. The experimental result shows that when the adding amount of the potassium hydroxide solution is gradually increased, the light absorption value is increased, and when the adding amount is 2.0mL, the light absorption value is maximum, so that the using amount of the potassium hydroxide solution is selected to be 2.0mL.
(3) Influence of AHMT and Potassium periodate usage on absorbance
Taking 16 50mL colorimetric tubes, taking 4 tubes as a group, carrying out the rest steps according to the optimal conditions obtained before, changing the adding amount of AHMT solution into 1.0, 2.0, 3.0 and 4.0mL (the mass of AHMT is 0.005, 0.010, 0.015 and 0.020g respectively), then adding 0.5, 1.0, 2.0 and 3.0mL (the mass of potassium periodate is 0.0075, 0.015, 0.030 and 0.045g respectively) of potassium periodate solution into each concentration, and observing the change of the absorbance value. The results are shown in Table 1.
TABLE 1 influence of the amount of reagent on the absorbance
From the above table, it can be seen that: when the volume combination ratio of the AHMT solution and the potassium periodate solution is 2:1, the light absorption value is larger than that of other combinations, and when the volume of the AHMT solution is 3mL and the volume of the potassium periodate solution is 1.5mL, the condensation and oxidation reaction reaches the optimal reaction concentration, the formaldehyde conversion rate is highest, and the light absorption value is largest, so that the addition amount of the AHMT solution is 3mL, and the addition amount of the potassium periodate solution is 1.5mL.
(4) Influence of the condensation reaction time on the absorbance
Taking 550 mL colorimetric tubes, carrying out the rest steps according to the optimal conditions obtained before, respectively adding potassium periodate solution after mixing potassium hydroxide solution and AHMT solution for 5, 10, 15, 20, 25 and 30min, and observing the change of absorbance value. The experimental results show that: the absorbance values tended to stabilize at 20-25min after mixing AHMT with potassium hydroxide solution, so 20min was determined to be the optimal condensation reaction time.
(5) Influence of the oxidation reaction time on the absorbance
Taking 8 colorimetric tubes of 50mL, performing the rest steps according to the optimal conditions obtained before, adding potassium periodate solutions 1,2, 3, 4,5, 10, 20 and 60min, and then loading the colorimetric tubes on a machine to observe the change of the light absorption value.
The experimental results show that: the oxidation reaction is rapid after the potassium periodate solution is added, the light absorption value tends to be balanced after 2min, and the light absorption value is in a stable state within 2-60 min. Thus, the color development time is 2-60 min
The absorbance was measured internally.
(6) Standard curve and quantitative limit
850 ML color comparison tubes were taken, and 0, 0.025, 0.050, 0.10, 0.20, 0.40, 0.80, 1.6, 3.2mL formaldehyde stock solutions (formaldehyde mass was 0.0, 0.5, 1.0, 2.0, 4.0, 8.0, 16.0, 32.0, 64.0. Mu.g) were added, respectively, and absorbance values were measured under the optimal test conditions to prepare a standard working curve. The results show that: under the optimal test condition, the mass of the free formaldehyde and the corresponding light absorption value thereof show good linear relation within the range of 0.5-32 mug, the linear regression equation is y=0.0339x+0.0173, and the correlation coefficient is 0.9990. According to a formaldehyde content calculation formula, 1.00g of sample is weighed, the formaldehyde mass is calculated according to a standard curve minimum concentration gradient of 0.5 mug, and the minimum detection limit is 2.5mg/kg.
Example 2 optimization of sample processing conditions to be tested
(1) Influence of added amount of potassium ferrocyanide and zinc acetate on clarification effect of extract
1G of 4 kinds of paint (samples A, B, C, D) are weighed into a 50ml colorimetric tube, 5 times each, and 5 groups of 20 samples are taken. About 40mL of 1.0g/L sodium metabisulfite solution was added to the coating to pre-disperse and dilute the coating, and shaking was performed. 0.2, 0.4, 06, 0.8 and 1.0mL of potassium ferrocyanide solution (the mass of added potassium hexacyanoferrate (II) trihydrate is respectively 0.0212, 0.0424, 0.0636, 0.0848 and 0.106 g) are added into each group, 0.1, 0.2, 0.3, 0.4 and 0.5mL of zinc acetate solution (the mass of added zinc acetate dihydrate is respectively 0.022, 0.044, 0.066, 0.088 and 0.11) are added into each group, the volume of the extract is fixed to 50mL, the obtained mixture is respectively recorded as 1-5 groups, and after ultrasonic treatment is carried out for 10 minutes, the filtrate is filtered and the condition of the filtrate is observed. Meanwhile, a reagent blank was prepared, and the iron and zinc contents in the filtrate of the reagent blank were measured (ICP method), and the results are shown in table 2.
TABLE 2 Effect of Potassium ferrocyanide-Zinc acetate usage on clarification Effect
Note that: "≡" indicates cloudiness of the filtrate and "ζ" indicates clarification of the filtrate.
When the concentration of iron and zinc in the reagent blank filtrate is less than 0.01mg/L through ICP method analysis, it is considered that the precipitation reaction tends to be complete when the volume ratio of the potassium ferrocyanide solution to the zinc acetate solution is 2:1, and the precipitation reaction formula is consistent, so that the volume ratio of the potassium ferrocyanide solution to the zinc acetate solution is determined to be 2:1 (the molar ratio is 2:1).
When zinc acetate solution is added, precipitation is generated in the sample solution rapidly, and after 2-3 minutes, the precipitation and the clarified liquid are layered, and the precipitation reaction is completed. As is clear from Table 2, the reaction of potassium ferrocyanide with zinc acetate produced flocculent precipitate Zn 2[Fe(CN)6, which was wrapped and adsorbed in the paint to form polymer resin, organic pigment, silica, etc. to give a good clarifying effect. When 0.8-1.0 mL of potassium ferrocyanide solution and 0.4-0.5 mL of zinc acetate solution are added, the clarifying effect can be achieved on the 4 paint samples. In order to avoid filtration difficulties caused by excessive precipitation, and ensure that the sample is representative, the sample weighing amount is about 1 g.
Through analysis of the nonvolatile content of the 4 kinds of coatings, the nonvolatile content of the 4 kinds of coatings ranges from 20% to 60%, and when the nonvolatile content of the coatings is larger, the required amounts of potassium ferrocyanide and zinc acetate are larger. In the actual detection, the nonvolatile content can be estimated through the declaration of the sample components or the flowability of the sample, and the dosage of the potassium ferrocyanide and zinc acetate solution can be determined according to the situation.
(2) Influence of extracting solution on extracting effect and quality control test
And weighing 27 groups of quality control samples, respectively adding distilled water, 4 ammonium sulfate solutions with the concentration and 4 sodium metabisulfite solutions with the concentration into each group for extraction (specific conditions are shown in table 3), carrying out the rest steps according to the optimal measurement conditions, measuring the extracting solution with each concentration for 3 times in parallel, taking an average value C a, and calculating the relative deviation with the nominal indication value C t of the quality control samples.
TABLE 3 influence of the extract on the detection results
Because the test target is free formaldehyde, the test is carried out by an ultrasonic method. Through experiments, the ultrasonic extraction time is 10-15 min, and the extraction effect is good, so that the ultrasonic extraction time is determined to be 10min. As can be seen from table 3: the distilled water or ammonium sulfate is not ideal as the extraction solution, the relative deviation is between 45 and 84 percent, and the relative deviation is larger as the concentration of the ammonium sulfate is increased for the ammonium sulfate extraction effect. When the concentration of the sodium metabisulfite solution is in the range of 0.01-1.0 g/L, the relative deviation is 2.3-1.5%, the result value is balanced, and the extraction effect is good. The dissolution mechanism of formaldehyde in water, ammonium sulfate and sodium metabisulfite is as follows:
Water-soluble formaldehyde mechanism:
Ammonium sulfate dissolves formaldehyde mechanism:
Sodium metabisulfite dissolves formaldehyde mechanism:
Formaldehyde takes a hydration reaction form as a dissolution mechanism in water, and takes a nucleophilic reaction form as a dissolution mechanism in an ammonium sulfate solution and a sodium metabisulfite solution. In addition, after the potassium hydroxide solution is added, the sodium hydroxymethanesulfonate product in the reaction (3) releases formaldehyde, so that the subsequent formaldehyde detection can be effectively performed, and the reaction system has better test results. The reaction of (1) and (2) does not have the reaction mechanism, so that the test effect is poor.
In addition, because the sodium metabisulfite solution is exposed in the air, a small part of sodium metabisulfite can be oxidized, and the sodium metabisulfite solution with the concentration of 1g/L is determined as an extracting solution for convenient storage and is prepared for use.
In summary, the optimal test conditions were: 1g of water-based paint is weighed, 0.8-1.0 mL of potassium ferrocyanide solution, 0.4-0.5 mL of zinc acetate solution and about 40mL of 1g/L sodium metabisulfite solution are added, shaking is carried out uniformly, 50mL of constant volume is carried out by the sodium metabisulfite solution, ultrasonic extraction is carried out for 10min, filtration is carried out, 10mL of clear liquid is absorbed, 2mL of potassium hydroxide solution and 3mLAHMT solution are added, 1.5mL of potassium periodate solution is added for 20min for color development, 50mL of distilled water constant volume is carried out, color development is carried out for 5-15 min (an oxidation product is in a stable state for 2-60min after the potassium periodate is added, the control of the operation time of the machine is reserved, the repeatability and the reproducibility of the test result of the machine are ensured, and the light absorption value is measured at 550nm of a spectrophotometer in the machine test (all subsequent tests) within 5-15 min of color development time is controlled.
Example 3 sample repeatability and recovery test.
4 Paint samples (sample A, B, C, D) were weighed and tested under the best test conditions, each paint was measured in eight replicates and the mean and relative standard deviation RSD was calculated.
To 4 kinds of paint samples, 3 concentration levels of formaldehyde stock solution was added, and the mass of formaldehyde was 1, 4, and 10 μg (converted to addition mass concentration of 5, 20, and 50 mg/kg), and each concentration level was measured 2 times in parallel, and the average value was taken, to calculate the recovery rate.
From the results in table 4, it can be seen that: the measurement value RSD of the formaldehyde content of the 4 samples is 1.8-8.8%, and the recovery rate is 88.0-105%, and the method has good repeatability and reproducibility for measuring free formaldehyde in water-based acrylic resin paint, water-based emulsion paint for building, water-based epoxy resin floor paint for building and water-based inorganic paint for building in daily sample detection, and has less interference.
TABLE 4 repeatability and recovery test
Example 4 influence of interference factors on detection results
Because the Zn 2[Fe(CN)6 formed in the test has adsorption clarification effect, the components in the water paint are complex, and the interference of reagents and components on the measurement result needs to be considered.
Reagent interference test: the paint sample is not weighed, the other steps are unchanged (0.8-1.0 mL of potassium ferrocyanide solution, 0.4-0.5 mL of zinc acetate solution and about 40mL of 1g/L sodium metabisulfite solution are added, shaking is carried out uniformly, 50mL of constant volume is carried out by the sodium metabisulfite solution, ultrasonic extraction is carried out for 10min, filtration is carried out, 10mL of clear liquid is absorbed, 2mL of potassium hydroxide solution and 3mLAHMT solution are added, 1.5mL of potassium periodate solution is added for 20min for color development, the constant volume is carried out by distilled water for 50mL, the light absorption value is measured at 550nm of a spectrophotometer within 5-15 min, 1mL of formaldehyde stock solution (the mass of added formaldehyde is 20 mug) is added, the test is carried out under the optimal test condition, the light absorption value is measured, and the recovery rate of formaldehyde content is calculated.
Component interference test: the paint sample is not weighed, 40% of acetaldehyde solution, ethylene glycol, tripropylene glycol monobutyl ether, water-based color paste (10% of ferric oxide) and 1.0g of kaolin are respectively weighed, the rest steps are unchanged, formaldehyde stock solutions (the mass of added formaldehyde is 20 mu g) are respectively added, the test is carried out under the optimal test condition, the light absorption value is measured, and the formaldehyde content and the recovery rate are calculated.
From the interference test results, the formaldehyde recovery rate is between 101.0 and 97.5 percent, and the adsorption clarification effect of Zn 2[Fe(CN)6 has little influence on the measurement of formaldehyde; the acetaldehyde with similar structural properties to formaldehyde and common components of ethylene glycol, tripropylene glycol monobutyl ether, water-based color paste and kaolin of the water-based paint do not influence the test.
TABLE 5 interference test conditions and results
According to the invention, by optimizing the detection conditions, the scheme for rapidly measuring the free formaldehyde in the water-based paint for the building at normal temperature is established, and the method has the characteristics of high efficiency, low cost and high accuracy, and can be used for rapidly screening products with bad formaldehyde content on site in a customs clearance port or laboratory. Meanwhile, the test develops a new scheme for pretreatment of paint samples, and can provide references for extraction and detection of other free substances in the paint.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. The preparation method of the water-based paint sample to be measured is characterized by comprising the following steps of: mixing and dissolving the water-based paint containing free formaldehyde, an extracting agent and a precipitating agent to obtain a mixed solution, carrying out ultrasonic treatment, filtering, and taking a supernatant to obtain the sample to be detected;
The extractant is sodium metabisulfite or aqueous solution thereof; the precipitant is potassium ferrocyanide and zinc salt or aqueous solution thereof, and the molar ratio of zinc ions in the potassium ferrocyanide and the zinc salt is 1:0.1-10;
the mass ratio of the water-based paint to the potassium ferrocyanide is 1:0.00739-0.0924; the mass ratio of the water-based paint to the sodium metabisulfite is 1:0.0005-0.05.
2. The preparation method according to claim 1, wherein the power of ultrasonic extraction is 20-60 kHZ for 10-15 min.
3. The preparation method according to claim 1, wherein the zinc salt is one or more of zinc acetate, zinc chloride, zinc sulfate and zinc nitrate.
4. The preparation method of claim 1, wherein the concentration of sodium metabisulfite in the mixed solution is 0.01-1.0 g/L; the molar concentration of the potassium ferrocyanide is 0.004-0.005 mol/L; the molar concentration of zinc ions in the zinc salt is 0.008-0.01 moL/L.
5. A precipitation clarification-AHMT method for determining the content of free formaldehyde in an aqueous coating, comprising the steps of: detecting the sample to be detected obtained by the preparation method according to any one of claims 1-4 by using an AHMT method to obtain the content of free formaldehyde in the water-based paint.
6. The precipitation clarification-AHMT method according to claim 5, wherein the specific process of said AHMT method is: adding alkaline substances and AHMT solution into a sample to be detected for condensation reaction, then adding potassium periodate solution for oxidation reaction, measuring the light absorption value by using a spectrophotometer after color development, and comparing with a standard curve to obtain the content of free formaldehyde in the water-based paint.
7. The sedimentation clarification-AHMT method according to claim 6, wherein the volume molar ratio of said sample to be tested and alkaline substance is 1:0.00005~0.00025 mL/moL; the volume-mass ratio of the sample to be tested and the AHMT is 1:0.1-0.4 mL/mg.
8. The precipitation clarification-AHMT method according to claim 6, wherein the mass ratio of the AHMT to the potassium periodate is 1:0.125-2.
9. The precipitation clarification-AHMT method according to claim 6, wherein the time of the condensation reaction is 20 to 25min; the time of the oxidation reaction is 2-60 min.
10. The sedimentation clarification-AHMT method according to claim 6, wherein the wavelength selected for measuring the absorbance is 549.9 to 550.2 nm.
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| 室内用水性涂料及水性胶粘剂中甲醛含量的检测研究;陈荣;张玉婕;陈玮廉;朱小红;;中国胶粘剂;20090130(第01期);全文 * |
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