CN114544304A - Preparation method of sample to be detected of water-based paint and precipitation clarification-AHMT method for determining content of free formaldehyde in water-based paint - Google Patents
Preparation method of sample to be detected of water-based paint and precipitation clarification-AHMT method for determining content of free formaldehyde in water-based paint Download PDFInfo
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- CN114544304A CN114544304A CN202210044944.3A CN202210044944A CN114544304A CN 114544304 A CN114544304 A CN 114544304A CN 202210044944 A CN202210044944 A CN 202210044944A CN 114544304 A CN114544304 A CN 114544304A
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- based paint
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 283
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910001868 water Inorganic materials 0.000 title claims abstract description 73
- 239000003973 paint Substances 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 58
- 238000001556 precipitation Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 9
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 8
- 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 6
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 4
- 239000006228 supernatant Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 71
- 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
- 230000031700 light absorption Effects 0.000 claims description 21
- 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
- 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
- 150000003751 zinc Chemical class 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 238000002835 absorbance Methods 0.000 claims description 7
- 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
- 238000011161 development Methods 0.000 claims description 5
- 239000012716 precipitator 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
- 230000035484 reaction time Effects 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
- 239000013049 sediment Substances 0.000 claims 1
- 238000004062 sedimentation Methods 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 32
- 238000005352 clarification Methods 0.000 abstract description 16
- 229920000642 polymer Polymers 0.000 abstract description 7
- 239000012535 impurity Substances 0.000 abstract description 4
- 230000001376 precipitating effect Effects 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 40
- 238000012360 testing method Methods 0.000 description 32
- 238000000576 coating method Methods 0.000 description 23
- 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 17
- 239000011248 coating agent Substances 0.000 description 16
- 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
- 238000006243 chemical reaction 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
- 238000000605 extraction Methods 0.000 description 9
- 230000007246 mechanism Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000011550 stock solution Substances 0.000 description 7
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000011256 inorganic filler Substances 0.000 description 5
- 229910003475 inorganic filler Inorganic materials 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
- 238000010521 absorption reaction Methods 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000002244 precipitate Substances 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
- 239000011701 zinc Substances 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 230000008859 change Effects 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
- 238000004949 mass spectrometry Methods 0.000 description 3
- 238000003908 quality control method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 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
- 239000004480 active ingredient Substances 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
- 238000007865 diluting Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000703 high-speed centrifugation Methods 0.000 description 2
- 230000002452 interceptive effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000001819 mass spectrum 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
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000006467 substitution reaction 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
- 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 238000011481 absorbance measurement Methods 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
- 230000015572 biosynthetic process 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
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000003988 headspace gas chromatography Methods 0.000 description 1
- 230000036541 health Effects 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
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000002514 liquid chromatography mass spectrum Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004853 microextraction Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 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
- 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
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 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
-
- 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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- Health & Medical Sciences (AREA)
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- General Health & Medical Sciences (AREA)
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- Spectroscopy & Molecular Physics (AREA)
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- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention relates to a preparation method of a sample to be measured 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 sample to be tested of the water-based paint comprises the following steps: mixing the water-based paint containing free formaldehyde, an extracting agent, a precipitating agent and water to obtain a mixed solution, performing 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 at normal temperature, and impurities such as polymers and color paste which affect detection are removed, so that the obtained sample to be detected has better clarity, the interference of various factors can be reduced, the detection is convenient, and the treatment cost is low.
Description
Technical Field
The invention belongs to the technical field of formaldehyde detection, and particularly relates to a preparation method of a sample to be detected of a water-based paint and a precipitation clarification-AHMT method for determining the content of free formaldehyde in the water-based paint.
Background
Formaldehyde (HCHO), a colorless, pungent odor-causing gas, can induce cancer, and is classified as a potentially dangerous carcinogen by the world health and the United states environmental protection agency. The formaldehyde pollution in daily life mainly comes from urea-formaldehyde resin in the artificial board, and residual unreacted free formaldehyde is released in the coating production process. The limit of free formaldehyde of the water-based paint for buildings is reduced from 100mg/kg to 50mg/kg in the new national standard GB18582-2020, which shows that the prevention and the treatment of formaldehyde pollution are increasingly emphasized by people, and simultaneously, new requirements are provided for the detection of formaldehyde.
Currently, the detection of free formaldehyde in the water-based paint mainly comprises the following three types: 1. a distillation method (ChenRong, Zhangjie, Chenxiangui, etc. research on the determination of formaldehyde content in indoor water-based paint and water-based adhesive [ J ]. analytical laboratory, 2008,27(z2):284 + 286.; Dulong, CaoJingyi, Li Liang, etc. acetylacetone spectrophotometry determines the formaldehyde content in the inner wall paint [ J ]. modern scientific instrument, 2016 (1): 99-102.). The principle of the method is that the coating is heated, formaldehyde is collected in a distillation mode and reacts with acetylacetone to generate a stable yellow complex, and the yellow complex is detected by a spectrophotometry method. In the method, the heating distillation process needs manual monitoring, the whole detection needs long time, and the detection efficiency is low. 2. derivatization-Mass Spectrometry (Oliva-Teles M T, Paiga P, Deleure-Matos C M, et al. determination of free for molecular in underlying resins as its 2, 4-dinophylylhydroxy by liquid chromatography [ J ]. Analytica Chimica Acta 2002,467 (S1-2): 97-103; Mcguire J M, Nahm S H.determination, by GC-MS using determined internal standards, of for molecular and molecular evolution during the course of coatings [ J ]. Journal of Science 2015,14(4): 241). The principle of the method is that after the coating is diluted by water and extracted, formaldehyde is derived by 2, 4-dinitrophenylhydrazine, and the derivative is determined by a liquid chromatography-mass spectrum method or a gas chromatography-mass spectrum method. The pretreatment is simple, but the method needs a strict derivatization process for 5 to 24 hours. 3. The Headspace method (Maring, Zhouyu, Martema. Headspace-Gas Chromatography Mass Spectrometry Rapid determination of free Formaldehyde [ J ] in aqueous coatings and adhesives, analytical laboratories 2015,34(5): 558. 561.; Lo KM, Yung Y L. integration of Headspace solvent Micro-Extraction with Gas Chromatography for Quantitative Analysis of Formaldehyde [ J ]. Bulletin of the Korea Chemical Society,2013,34(1): 139. 142.). The coating is heated in a headspace device, formaldehyde is separated out in a gas phase and reaches pressure balance in the gas phase and is injected into a chromatogram through a quantitative ring, and mass spectrum detection is carried out. The method relates to the combination of two sets of instruments, and the use cost is higher.
Therefore, the development of the method for rapidly and efficiently detecting the content of the formaldehyde in the water-based paint at normal temperature with low cost and high accuracy 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 for a sample to be detected of the water-based paint. According to the invention, through specific precipitation clarification treatment, free formaldehyde in the water-based paint can be efficiently enriched at normal temperature, and impurities such as polymers and color paste which affect detection are removed, so that the obtained sample to be detected has better clarity, the interference of various factors can be reduced, the detection is convenient, and the treatment cost is low.
Another object of the present invention is to provide a precipitation clarification-AHMT method for determining the content of free formaldehyde in a water-based paint. 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 purpose, the invention adopts the following technical scheme:
a preparation method of a sample to be tested of a water-based paint comprises the following steps: mixing and dissolving the water-based paint containing free formaldehyde, an extracting agent and a precipitator to obtain a mixed solution, performing ultrasonic treatment, filtering, and taking supernatant to obtain the sample to be detected;
the extractant is sodium metabisulfite or an aqueous solution thereof; the precipitator is potassium ferrocyanide and zinc salt or an aqueous solution thereof, and the molar ratio of zinc ions in the potassium ferrocyanide to 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 common method for detecting the content of formaldehyde in air, and has the advantages of no need of heating, less interference and low detection limit.
In view of the problems of the conventional methods (distillation method, derivatization-mass spectrometry, headspace method) for detecting free formaldehyde in the aqueous coating, such as the need for heating, the long treatment time, and the low detection efficiency, the inventors of the present invention tried to pretreat the aqueous coating and then detect the free formaldehyde in the aqueous coating by using an AHMT method (AHMT spectrophotometry).
The formaldehyde in the air is easy to collect, the interference of impurities is less, 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 in the components. The current pretreatment technology of a sample to be detected by an ultraviolet spectrophotometry method can only obtain the sample to be detected by heating and distilling a water-based paint. In the pretreatment technologies such as high-speed centrifugation and filter paper filtration which do not involve heating and distillation, it is difficult to effectively separate and extract free formaldehyde to obtain a sample to be detected, and in this case, detection by the AHMT method cannot be performed. How to efficiently extract free formaldehyde from complex components in the water-based paint without heating and distilling, simultaneously avoid the interference of each component to the detection process, and detect the content of the free formaldehyde by using an AHMT method under proper reaction conditions is a key point and a difficulty point.
(1) For the enrichment of free formaldehyde: at present, various substances, such as pure water, ammonium sulfate and the like, can realize extraction and enrichment of formaldehyde. The research finds that the content of the active ingredients in the active ingredients is high,
when pure water is used as an extracting solution, the extracting mechanism of a sample to be detected is as follows:
when the ammonium sulfate solution is used as the extracting solution to obtain the sample to be detected, the extracting mechanism is as follows:
researches find that when pure water and an ammonium sulfate solution are used as extracting solutions to enrich free methanol in the water-based paint, the enrichment efficiency is not high, the obtained formaldehyde cannot be effectively released under the detection condition of an AHMT method, and the detection effect is poor.
Further research shows that the sample to be detected obtained by taking the sodium metabisulfite as the extracting solution has the advantages of good enrichment effect and capability of being directly detected by an AHMT method. Specifically, 1) sodium metabisulfite can be subjected to nucleophilic reaction with formaldehyde to obtain HO-CH2-SO3Na (sodium hydroxymethyl sulfonate) realizes the high-efficiency enrichment of free formaldehyde. This may be because: in order to maintain the storage stability of the coating, the water-based coating is generally weakly alkaline, and in the mixed solution, the sodium hydroxymethyl sulfonate which is the product of formaldehyde in sodium metabisulfite solution is in a more stable state than the product of formaldehyde in ammonium sulfate solution and the product of formaldehyde in water, so that the extraction efficiency of formaldehyde is higher. 2) When the AHMT method is used for developing the color of three samples to be detected, after the potassium hydroxide solution is added, the formaldehyde and sodium hydroxymethyl sulfonate which is a product of sodium metabisulfite in the samples to be detected release formaldehyde, so that the subsequent detection of the formaldehyde can be effectively carried out, and the samples to be detected which are obtained by taking the sodium metabisulfite as an extracting solution have better enrichment and detection results.
(2) Clarification of aqueous coating solutions: due to the complex components in the water-based paint, besides high molecular polymers such as water-soluble resin and the like, the water-based paint can also comprise interfering components such as acetaldehyde with a structure close to that of 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 the like. If the clarification treatment is not carried out, the components can absorb or shield light at the detection wavelength, so that the absorbance value is subjected to error, and the accurate detection cannot be carried out.
However, due to the characteristics of the coating preparation process, all components are uniformly mixed, and the particle size of particles in the coating is very small, namely dozens of microns, so that water-soluble resin, inorganic filler, organic color paste and the like are difficult to remove by high-speed centrifugation or filter paper filtration when a sample to be detected is prepared. Therefore, a new clarification process needs to be developed, so that the effective precipitates of the high-molecular polymer, the organic color paste, the inorganic filler and the like can achieve the clarification effect during clarification, and free formaldehyde is prevented from being carried and precipitated during clarification; the effect of interfering components on the precipitation effect is also taken into account.
Researches show that the compound of potassium ferrocyanide and zinc salt is used as a precipitator, so that the effective precipitation of high molecular polymers, organic color paste, inorganic fillers and the like can be realized, a sample to be detected after the precipitation is filtered is clear and transparent, the detection requirement of a spectrophotometer is met, and the extraction and enrichment of free formaldehyde are not influenced. In particular, potassium ferrocyanide and zinc salts can react to form Zn2[Fe(CN)6]，Zn2[Fe(CN)6]High molecular polymer organic color paste and inorganic filler can be selectively precipitated).
[Fe(CN)6]4-+2Zn2+→Zn2[Fe(CN)6]↓
According to the invention, through the addition of the specific extracting agent and the precipitating agent, the precipitation clarification of the aqueous solution of the water-based paint and the high-efficiency enrichment of free formaldehyde can be realized, and the obtained sample to be detected of the water-based paint is easy to carry out formaldehyde content determination.
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 the sodium metabisulfite in the mixed solution is 0.01-1.0 g/L.
Preferably, the molar concentration of the 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 claims a precipitation clarification-AHMT method for determining the content of free formaldehyde in the water-based paint.
A precipitation clarification-AHMT method for measuring the content of free formaldehyde in a water-based paint comprises the following steps: 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 prepared by the method has high clarity of a sample to be detected, effectively enriches free formaldehyde, and can determine the content of the formaldehyde by using an AHMT method so as to obtain the content of the free formaldehyde in the water-based paint. Specifically, under the alkaline condition, the enriched formaldehyde returns to the free state again, then is oxidized into 6-mercapto-5-triazocene [4,3-b ] -S-tetraazabenzene (III) with purple by an AHMT reagent, and the light absorption value is measured by a spectrophotometer to obtain the formaldehyde content. The color rendering principle is as follows
The linear range of the detection of the free formaldehyde is 0.5 to 64 mu g, r is detected by the method2The limit of quantitation was 2.5mg/kg, which is 0.9990. The test was carried out with a quality control standard with a relative deviation of 1.5%. The repeatability and recovery rate test is carried out by using 4 water-based coatings, 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 an alkaline substance and an AHMT solution into a sample to be detected, carrying out condensation reaction, then adding a potassium periodate solution, carrying out oxidation reaction, measuring a 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 detected to the alkaline substance is 1: 0.00005-0.00025 mL/moL.
Preferably, the alkaline substance is one or both of potassium hydroxide and sodium hydroxide.
More preferably, the volume-to-mass ratio of the sample to be detected to AHMT is 1: 0.1-0.4 mL/mg.
More preferably, the mass ratio of AHMT to 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 light absorption value 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 at normal temperature, and impurities such as polymers and color paste which affect detection are removed, so that the obtained sample to be detected has better clarity, can eliminate interference of various factors, is convenient to detect and has low treatment cost;
(2) the AHMT method is utilized to detect the sample to be detected, the accurate determination of the free formaldehyde in the water-based paint can be realized, the linear range of the detection is 0.5-64 mu g, r20.9990, quantitative limit 2.5 mg/kg. The repeatability and recovery rate test is carried out by using 4 water-based coatings, 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 by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
(1) The main instrument and reagent information used in each example is as follows:
shimadzu UV-1800 UV-visible spectrophotometer (with 10mm cuvette).
GTSONIC-P ultrasonic cleaning instrument (power 50W, frequency 40 KHz).
0.25mol/L potassium ferrocyanide solution: 10.6g of potassium hexacyanoferrate (II) trihydrate are weighed out and dissolved in water and diluted to 100 mL.
1.0mol/L zinc acetate solution: 22g of zinc acetate dihydrate was weighed out and dissolved in water and diluted to 100 mL.
280g/L potassium hydroxide solution: 28g of potassium hydroxide were weighed out, dissolved in water and diluted to 100 mL.
5g/L AHMT solution: 0.5g of AHMT was weighed out and dissolved in 0.5moL/L hydrochloric acid solution and diluted to 100 mL.
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 100 mL.
20mg/L Formaldehyde stock solution: 20.0mL of formaldehyde standard solution (100mg/L) was pipetted into a 100mL brown flask and made to volume with distilled water.
(2) The information on the test samples used in each example is as follows:
1 pot of each of an aqueous acrylic resin coating for construction (designated as sample a), an aqueous latex paint for construction (designated as sample B), an aqueous epoxy resin floor paint for construction (designated as sample C), and an aqueous inorganic coating for construction (designated as sample D). Free formaldehyde standard in the paint (RM-19015, formaldehyde content nominally 132mg/kg, labeled quality control).
Example 1 AHMT method Condition optimization
In this example, a formaldehyde stock solution was used as a solution to be tested, and each condition in the AHMT method was optimized.
1. Absorbance measurement section
(1) Determination of the wavelength of maximum absorption
Adding 1mL of formaldehyde stock solution, 2mL of potassium hydroxide solution and 2mL of AHMT solution into a 50mL colorimetric tube in sequence, mixing for 30min, adding 2mL of potassium periodate solution, fixing the volume with distilled water, carrying out color development for 20min, loading the device on the device, and carrying out spectrum scanning at the position of 400-600 nm. According to the scanning result, the following steps are carried out: the 6-mercapto-5-triazacyclo [4,3-b ] -S-tetraazabenzene (III) generated by the reaction has the maximum absorption value at the wavelength of 549.9-550.2nm, and the 550nm is selected as the measurement wavelength in the subsequent experiments.
(2) Influence of the amount of potassium hydroxide solution on the absorbance
550 mL cuvettes were taken, and changes in absorbance were observed according to the procedure and conditions for determining the maximum absorption wavelength in (1), except that the amounts of potassium hydroxide solution added were 0, 0.5, 1.0, 1.5, 2.0, and 2.5mL (the amounts of potassium hydroxide were 0, 0.14, 0.28, 0.42, 0.56, and 0.7g, respectively). The experimental result shows that when the addition amount of the potassium hydroxide solution is gradually increased, the light absorption value is increased, and when the addition amount is 2.0mL, the light absorption value is the largest, so that the dosage of the potassium hydroxide solution is selected to be 2.0 mL.
(3) Influence of AHMT and potassium periodate dosage on absorbance
Taking 16 50mL colorimetric tubes, using 4 tubes as a group, and carrying out the rest steps according to the optimal conditions obtained before, wherein the adding amount of the AHMT solution is respectively changed into 1.0, 2.0, 3.0 and 4.0mL (the mass of the AHMT is respectively 0.005, 0.010, 0.015 and 0.020g), then 0.5, 1.0, 2.0 and 3.0mL of potassium periodate solution is added into each concentration (the mass of the potassium periodate is respectively 0.0075, 0.015, 0.030 and 0.045g), and the change of the light absorption value is observed. The results are shown in Table 1.
TABLE 1 Effect of reagent amounts on absorbance values
From the above table, it can be seen that: when the volume combination ratio of the AHMT solution to 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 reactions reach the optimal reaction concentration, the formaldehyde conversion rate is the highest, and the light absorption value is the largest, so that the adding amount of the AHMT solution is selected to be 3mL, and the adding amount of the potassium periodate solution is selected to be 1.5 mL.
(4) Influence of condensation reaction time on light absorption value
Taking 5 colorimetric tubes of 50mL, carrying out the rest steps according to the optimal conditions obtained before, respectively adding a potassium periodate solution after mixing the potassium hydroxide solution and the AHMT solution for 5min, 10min, 15min, 20min, 25min and 30min, and observing the change of the light absorption value. The experimental results show that: the light absorption value tends to be stable at 20-25min after the AHMT and the potassium hydroxide solution are mixed, so that 20min is determined as the optimal condensation reaction time.
(5) Influence of Oxidation reaction time on light absorption value
Taking 8 colorimetric tubes with the volume of 50mL, carrying out the rest steps according to the optimal conditions obtained before, adding potassium periodate solution for 1, 2, 3, 4, 5, 10, 20 and 60min, then loading the machine, and observing the change of the light absorption value.
The experimental results show that: after the potassium periodate solution is added, the oxidation reaction is rapid, the light absorption value tends to be balanced after 2min, and the light absorption value is in a stable state within 2-60 min. Therefore, the color development time is determined to be 2-60min
Absorbance was measured internally.
(6) Standard curve and quantitative limit
Taking 8 50mL colorimetric tubes, adding 0, 0.025, 0.050, 0.10, 0.20, 0.40, 0.80, 1.6 and 3.2mL formaldehyde stock solutions (the mass of formaldehyde is 0.0, 0.5, 1.0, 2.0, 4.0, 8.0, 16.0, 32.0 and 64.0 μ g respectively), measuring the light absorption value according to the optimal test condition, and making a standard working curve. The results show that: under the best test condition, the mass of the free formaldehyde and the corresponding light absorption value show good linear relation in the range of 0.5-32 mu g, the linear regression equation is that y is 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 mass of formaldehyde is calculated by the lowest concentration gradient of 0.5 mu g of a standard curve, and the lowest detection limit is 2.5 mg/kg.
EXAMPLE 2 optimization of treatment conditions for samples to be tested
(1) Influence of potassium ferrocyanide and zinc acetate addition on clarification effect of extract
1g of 4 paints (sample A, B, C, D) were weighed into 50ml colorimetric tubes, 5 times each, and a total of 5 sets and 20 samples were obtained. About 40mL of 1.0g/L sodium metabisulfite solution was added to each of the paint to predisperse and dilute the paint, and shaken up. Adding 0.2, 0.4, 06, 0.8 and 1.0mL of potassium ferrocyanide solution (the mass of the added potassium hexacyanoferrate (II) trihydrate is 0.0212, 0.0424, 0.0636, 0.0848 and 0.106g respectively) into each group respectively, uniformly mixing, adding 0.1, 0.2, 0.3, 0.4 and 0.5mL of zinc acetate solution (the mass of the added zinc acetate dihydrate is 0.022, 0.044, 0.066, 0.088 and 0.11 respectively), fixing the volume of the extracting solution to 50mL, respectively marking as 1-5 groups, carrying out ultrasonic treatment for 10 minutes, filtering, and observing the condition of the filtrate. At the same time, reagent blank was made, and the iron and zinc contents of 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 dosage on clarification
Note: "●" indicated the filtrate was cloudy and "O" indicated the filtrate was clear.
Analysis by the ICP method revealed that both the iron and zinc concentrations in the reagent blank filtrate were less than 0.01mg/L, and it was considered that when the volume ratio of the potassium ferrocyanide solution to the zinc acetate solution was 2:1, the precipitation reaction tended to be complete, conforming to the precipitation equation, and therefore the volume ratio of the potassium ferrocyanide solution to the zinc acetate solution was determined to be 2:1 (molar ratio of 2: 1).
When the zinc acetate solution is added, precipitate is rapidly generated in the sample solution, and after 2-3 minutes, the precipitate and the clear solution are separated, and the precipitation reaction is finished. As shown in Table 2, potassium ferrocyanide reacts with zinc acetate to form flocculent precipitate Zn2[Fe(CN)6]The product can wrap and adsorb polymer resin, organic pigment, silicon dioxide and the like in the paint, and has better clarification effect. When 0.8-1.0 mL of potassium ferrocyanide solution and 0.4-0.5 mL of zinc acetate solution are added, the clarification effect can be achieved on the 4 coating samples. In order to avoid the filtration difficulty caused by excessive precipitation and ensure representative sampling, the sample weighing of about 1g is more suitable.
Through analysis of the nonvolatile matter content in the 4 coatings, the nonvolatile matter content of the 4 coatings ranges from 20% to 60%, and when the nonvolatile matter content of the coatings is higher, the amount of potassium ferrocyanide and zinc acetate required is higher. In actual detection, the nonvolatile content can be estimated through sample component declaration or sample fluidity, and the dosage of the potassium ferrocyanide and the zinc acetate solution is determined according to the situation.
(2) Test of influence and quality control of extractive solution on extraction effect
27 groups are weighedControlling quality, adding distilled water, 4 concentrations of ammonium sulfate solution and 4 concentrations of sodium metabisulfite solution into each group, respectively, extracting (specific conditions are shown in Table 3), performing the rest steps according to optimal determination conditions, performing parallel determination for each concentration of extractive solution for 3 times, and taking average value CaCalculating and controlling the nominal indicating value C of the sampletRelative deviation of (d).
TABLE 3 Effect of the extract on the test results
Because the target substance of the test is free formaldehyde, the test is extracted by an ultrasonic method. Through tests, the ultrasonic extraction time is 10-15 min, and the extraction effect is good, so that the ultrasonic extraction time is determined to be 10 min. From table 3, it can be seen that: the result of using distilled water or ammonium sulfate as the extraction liquid is not preferable, the relative deviation is 45 to 84%, and the relative deviation becomes larger as the concentration of ammonium sulfate increases in 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%, and the result values are relatively balanced, so that the method has a relatively good extraction effect. The dissolution mechanism of formaldehyde in water, ammonium sulfate and sodium metabisulfite is as follows:
the mechanism of dissolving formaldehyde in water is as follows:
the mechanism of dissolving formaldehyde by ammonium sulfate is as follows:
the mechanism of dissolving formaldehyde by sodium metabisulfite is as follows:
formaldehyde acts as a dissolution mechanism in the form of a hydration reaction in water and a nucleophilic reaction in the form of an ammonium sulfate solution and a sodium metabisulfite solution. In addition, after the potassium hydroxide solution is added, the product sodium hydroxymethyl sulfonate in the reaction (3) releases formaldehyde, so that the subsequent detection of formaldehyde can be effectively carried out, and a better test result is obtained in the reaction system. However, the reaction between (1) and (2) has no such reaction mechanism, and the test effect is poor.
In addition, when the sodium metabisulfite solution is exposed to air, a small part of sodium metabisulfite can be oxidized, and for convenient storage, the sodium metabisulfite solution with the concentration of 1g/L is determined as an extracting solution and is prepared for use.
In summary, the best test conditions are: weighing 1g of water-based paint, adding 0.8-1.0 mL of potassium ferrocyanide solution, 0.4-0.5 mL of zinc acetate solution and about 40mL of 1g/L of sodium metabisulfite solution, shaking uniformly, diluting to 50mL with the sodium metabisulfite solution, carrying out ultrasonic extraction for 10min, filtering, sucking 10mL of clear liquid, adding 2mL of potassium hydroxide solution and 3mL of HMT solution, adding 1.5mL of potassium periodate solution for developing after 20min, diluting to 50mL with distilled water, and developing for 5-15 min (the oxidation product is in a stable state 2-60min after the potassium periodate is added, so as to reserve the control of the on-machine operation time and ensure the repeatability and reproducibility of the on-machine test result, wherein the light absorption value is determined in a spectrophotometer at 550nm in the on-machine test (all the subsequent tests are performed) with the control of the developing time of 5-15 min.
Example 3 sample repeatability and recovery test.
4 paint samples (sample A, B, C, D) were weighed and tested under optimal test conditions, eight replicates of each paint were tested, and the mean and relative standard deviation RSD were calculated.
To 4 paint samples, 3 concentration levels of formaldehyde stock solutions were added, and formaldehyde masses were 1, 4, and 10 μ g (equivalent added mass concentrations were 5, 20, and 50mg/kg), and each concentration level was measured in parallel 2 times, and the average value was taken to calculate the recovery rate.
From the results in table 4, it can be seen that: the content of formaldehyde in 4 samples is measured, the RSD is 1.8-8.8%, the recovery rate is 88.0-105%, and the method has good repeatability and reproducibility and small interference on the measurement of free formaldehyde in water-based acrylic resin paint, water-based emulsion paint for buildings, water-based epoxy resin floor paint for buildings and water-based inorganic paint for buildings in daily sample detection.
TABLE 4 repeatability and recovery tests
Example 4 influence of interference factors on the test results
Due to Zn formation formed in the test2[Fe(CN)6]Has the function of adsorption clarification, and the components in the water-based paint are complex, so the interference of reagents and components on the measurement result needs to be considered.
Reagent interference test: weighing a paint sample, keeping the rest steps unchanged (adding 0.8-1.0 mL of potassium ferrocyanide solution, 0.4-0.5 mL of zinc acetate solution and about 40mL of 1g/L of sodium metabisulfite solution, shaking uniformly, fixing the volume of 50mL by using the sodium metabisulfite solution, carrying out ultrasonic extraction for 10min, filtering, absorbing 10mL of clear liquid, adding 2mL of potassium hydroxide solution and 3mL of HMT solution, adding 1.5mL of potassium periodate solution for developing after 20min, fixing the volume of 50mL by using distilled water, measuring a spectrophotometer at 550nm of a spectrophotometer within 5-15 min of developing), adding 1mL of formaldehyde stock solution (the mass of added formaldehyde is 20 mu g), carrying out the test under the optimal test conditions, measuring the light absorption value, and calculating the recovery rate of the formaldehyde content.
Component interference test: the coating sample is not weighed, 40% acetaldehyde solution, ethylene glycol, tripropylene glycol monobutyl ether, aqueous color paste (10% ferric oxide) and 1.0g of kaolin are respectively weighed, the rest steps are unchanged, formaldehyde stock solution (the mass of added formaldehyde is 20 mu g) is 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.
According to the interference test result, the recovery rate of formaldehyde is 101.0-97.5%, and Zn is obtained2[Fe(CN)6]The absorption clarification effect of the method has little influence on the measurement of formaldehyde; acetaldehyde with similar structure property with formaldehyde and common components of water paint such as ethylene glycol, tripropylene glycol monobutyl ether, water-based color paste and kaolin do not influence the test.
TABLE 5 interference test conditions and results
According to the invention, by optimizing the detection conditions, a set of scheme for rapidly determining 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 poor formaldehyde content on site by passing through a customs port or a laboratory. Meanwhile, a new paint sample pretreatment scheme is developed in the test, and reference can be provided for extraction and detection of other free substances in the paint.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The preparation method of the sample to be tested of the water-based paint is characterized by comprising the following steps of: mixing and dissolving the water-based paint containing free formaldehyde, an extracting agent and a precipitator to obtain a mixed solution, performing ultrasonic treatment, filtering, and taking supernatant to obtain the sample to be detected;
the extractant is sodium metabisulfite or an aqueous solution thereof; the precipitator is potassium ferrocyanide and zinc salt or an aqueous solution thereof, and the molar ratio of zinc ions in the potassium ferrocyanide to 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, and the time is 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 or zinc nitrate.
4. The method according to 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 measuring the content of free formaldehyde in a water-based paint is characterized by comprising the following steps: detecting the sample to be detected obtained by the preparation method of any one of claims 1 to 4 by using an AHMT method to obtain the content of free formaldehyde in the water-based paint.
6. The method of claim 5, wherein the specific process of the AHMT method is: adding an alkaline substance and an AHMT solution into a sample to be detected, carrying out condensation reaction, then adding a potassium periodate solution, carrying out oxidation reaction, measuring a 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 sediment clarification-AHMT method according to claim 6, wherein the volume molar ratio of the sample to be detected to the alkaline substance is 1:0.00005 to 0.00025 mL/moL; the volume-mass ratio of the sample to be detected to AHMT is 1: 0.1-0.4 mL/mg.
8. The sedimentation clarification-AHMT method according to claim 5, wherein the mass ratio of AHMT to potassium periodate is 1:0.125 to 2.
9. The method according to claim 5, wherein the condensation reaction time is 20-25 min; the time of the oxidation reaction is 2-60 min.
10. The method of claim 5, wherein the absorbance is measured at a wavelength of 549.9-550.2 nm.
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