CN111826053A - Environment-friendly anti-radiation coating and preparation method thereof - Google Patents
Environment-friendly anti-radiation coating and preparation method thereof Download PDFInfo
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- CN111826053A CN111826053A CN202010741620.6A CN202010741620A CN111826053A CN 111826053 A CN111826053 A CN 111826053A CN 202010741620 A CN202010741620 A CN 202010741620A CN 111826053 A CN111826053 A CN 111826053A
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- 238000000576 coating method Methods 0.000 title claims abstract description 38
- 239000011248 coating agent Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 230000003471 anti-radiation Effects 0.000 title claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229920005989 resin Polymers 0.000 claims abstract description 68
- 239000011347 resin Substances 0.000 claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 49
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 49
- 239000000945 filler Substances 0.000 claims abstract description 42
- 239000002904 solvent Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims abstract description 19
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 18
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 18
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 11
- 239000011733 molybdenum Substances 0.000 claims abstract description 11
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 11
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 59
- 238000003756 stirring Methods 0.000 claims description 45
- 238000002156 mixing Methods 0.000 claims description 34
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 33
- 239000011737 fluorine Substances 0.000 claims description 33
- 229910052731 fluorine Inorganic materials 0.000 claims description 33
- 150000002221 fluorine Chemical class 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 28
- 239000002270 dispersing agent Substances 0.000 claims description 22
- 239000005055 methyl trichlorosilane Substances 0.000 claims description 22
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 22
- 239000002562 thickening agent Substances 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 21
- 239000002518 antifoaming agent Substances 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- 238000003851 corona treatment Methods 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 239000002048 multi walled nanotube Substances 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 8
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical group CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 7
- 239000012295 chemical reaction liquid Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- 235000015393 sodium molybdate Nutrition 0.000 claims description 7
- 239000011684 sodium molybdate Substances 0.000 claims description 7
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- DKCWBFMZNUOFEM-UHFFFAOYSA-L oxovanadium(2+);sulfate;hydrate Chemical compound O.[V+2]=O.[O-]S([O-])(=O)=O DKCWBFMZNUOFEM-UHFFFAOYSA-L 0.000 claims description 2
- 229910052704 radon Inorganic materials 0.000 abstract description 49
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 abstract description 49
- 238000001179 sorption measurement Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 125000001153 fluoro group Chemical class F* 0.000 abstract 1
- -1 alcohol amine salt Chemical class 0.000 description 13
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 239000004814 polyurethane Substances 0.000 description 7
- 229920002635 polyurethane Polymers 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 6
- 229940041260 vanadyl sulfate Drugs 0.000 description 6
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- 206010058467 Lung neoplasm malignant Diseases 0.000 description 4
- 201000005202 lung cancer Diseases 0.000 description 4
- 208000020816 lung neoplasm Diseases 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 210000002345 respiratory system Anatomy 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 206010028980 Neoplasm Diseases 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 208000019155 Radiation injury Diseases 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000002375 environmental carcinogen Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 239000003915 liquefied petroleum gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000002285 radioactive effect Effects 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 210000000577 adipose tissue Anatomy 0.000 description 1
- 210000000601 blood cell Anatomy 0.000 description 1
- 201000011510 cancer Diseases 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
- 239000000919 ceramic Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010438 granite Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- 208000023504 respiratory system disease Diseases 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000000391 smoking effect Effects 0.000 description 1
- 229920005792 styrene-acrylic resin Polymers 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C09D161/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C09D161/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
The invention relates to an environment-friendly anti-radiation coating and a preparation method thereof, wherein melamine formaldehyde resin and modified fluorine-containing resin are used as film forming substances, a coating product is prepared by adding a filler, water is used as a solvent, the environment-friendly coating is green and has good film forming compactness, and radon in walls and stratums is effectively prevented from escaping into the air; the filler is prepared by taking a carbon nano tube as a raw material through vanadium and molybdenum doping, hexamethylene diisocyanate modification and polyacrylic acid urethanization reaction, has good compatibility and dispersibility in a system, is beneficial to the increase of the specific surface area of a coating film, has good adsorption effect on radon in the air, and reduces the radon content in indoor air.
Description
Technical Field
The invention belongs to the technical field of coating processing, and relates to an environment-friendly anti-radiation coating and a preparation method thereof.
Background
Radon is widely existed in the living environment of people, and particularly, radon released from indoor building materials and house foundation soil is extremely easy to accumulate indoors, so that the content of indoor radon is very high, and great potential safety hazards are brought to people. Radon gas is the only radioactive element in human contact, is a simple substance inert gas with inactive chemical properties, is colorless, odorless and tasteless, is difficult to chemically react with other elements, but can decay to generate alpha particles after being inhaled into a human body to cause radiation damage to a respiratory system to cause lung cancer, and is the second major factor causing lung cancer except smoking. According to the international cancer research center of the world health organization, radon is one of the main environmental carcinogens, the radiation injury to the human body accounts for more than 55% of the total radiation injury to the human body in a lifetime, and one fifth of lung cancer patients in the world are related to radon. After the radon and the derivatives thereof enter a human body through the respiratory tract, the radon and the derivatives thereof are usually retained in the whole respiratory tract of the human body for a long time, and are one of the important reasons for causing the respiratory system diseases of the human body. The harm of radon to human health is mainly shown as follows: under exposure to high radon concentrations, the body develops blood cell changes. Radon has a high affinity for human body fat, and is particularly harmful when combined with the nervous system. Another manifestation is the occurrence of tumors, which can induce lung cancer when inhaled by a person, due to the fact that radon is a radioactive gas. Radon is published by the WHO (world health organization) as one of the 19 major environmental carcinogens. Radon was listed as an important carcinogen in the room by the international agency for research on cancer in 1987.
Radon in indoor environments is mainly derived from several sources:
1. from the soil of the underground foundation. The diffusion of the foundation soil enters the room through cracks of the earth surface and the wall body;
2. from groundwater. Research proves that when the radon concentration in water reaches 104 Beck/cubic meter, the radon is an important indoor radon source;
3. from the outdoor atmosphere. Radon in outdoor atmosphere can enter the room along with outdoor air;
4. from the combustion of natural gas. When natural gas and liquefied petroleum gas are burnt, if the indoor ventilation is poor, all radon in the natural gas and liquefied petroleum gas is released into the room;
5. from building materials and interior materials; in particular to building materials such as slag bricks, slag bricks and the like (generally containing radium in different degrees) and indoor decoration materials with high uranium content, such as granite, ceramic tiles, sanitary wares and the like.
At present, related researches on prevention and treatment of indoor radon are still lacked, and products for reducing indoor radon content are rarely reported.
Patent CN107353720B discloses a radon-absorbing radiation-resistant paint, which is prepared by mixing graphene-polyacrylic acid, matrix resin and the like as raw materials, wherein the matrix resin is at least one of styrene-acrylic resin, vinyl acetate-acrylic resin, pure acrylic resin, cyclopropyl resin or silicone-acrylic resin, but the radon adsorption rate of the paint is not as high as 90%, which is far from meeting the control of environmental radon content, and the paint has no popularization significance.
Disclosure of Invention
In view of the above, the invention aims to provide an environment-friendly anti-radiation coating and a preparation method thereof, which can well resist radon radiation, are environment-friendly and have excellent popularization significance.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of an environment-friendly anti-radiation coating comprises the following specific steps in parts by weight:
(1) firstly, 0.5-0.7 part of thickening agent and 10-12 parts of deionized water are uniformly stirred and mixed, then 100 parts of melamine formaldehyde resin is added, and the components A are uniformly dispersed to obtain a component A;
(2) then uniformly mixing 2-3 parts of dispersing agent, 0.2-0.3 part of defoaming agent, 40-60 parts of modified fluorine-containing resin, 6-9 parts of propylene glycol methyl ether acetate and 11-15 parts of deionized water, then adding 3-5 parts of filler, and uniformly dispersing to obtain a component B;
(3) finally, stirring and uniformly mixing the component A obtained in the step (1) and the component B obtained in the step (2), and curing to obtain the environment-friendly anti-radiation coating;
wherein the modified fluorine-containing resin is obtained by modifying fluorine-containing resin with methyltrichlorosilane, and the filler is prepared by the following method: doping the carbon nano tube with vanadium and molybdenum to obtain a doped carbon nano tube, reacting the doped carbon nano tube with hexamethylene diisocyanate to obtain a modified carbon nano tube, and finally performing urethane reaction on the modified carbon nano tube and polyacrylic acid to obtain the modified carbon nano tube.
Preferably, the thickener is a polyurethane associative thickener, the dispersant is a polyammonium alcohol amine salt dispersant, and the defoamer is an organic silicon defoamer.
Preferably, in the step (3), the curing time is 10-15 minutes.
Preferably, the fluorine-containing resin is selected from polytetrafluoroethylene or polyvinylidene fluoride.
Preferably, the preparation method of the modified fluorine-containing resin comprises the following steps of: firstly, drying and corona-treating the fluorine-containing resin, then stirring and heating 100 parts of the pretreated fluorine-containing resin, 120-130 parts of solvent and 0.5-1 part of silane coupling agent to 60-80 ℃, dropwise adding 0.1-0.15 part of methyl trichlorosilane, carrying out heat preservation reaction for 4-6 hours after dropwise adding is finished, and carrying out post-treatment to obtain the modified fluorine-containing resin.
Further preferably, the drying process conditions are as follows: drying at 120-140 ℃ to constant weight; the specific process conditions of the corona treatment are as follows: and (3) carrying out corona treatment for 5-8 s by using a point corona treatment machine under the current condition of 3-5A, and repeating for 3-5 times.
Further preferably, the solvent is any one selected from tetrahydrofuran, N-dimethylformamide or N, N-dimethylacetamide, and the silane coupling agent is 3-aminopropyltrimethoxysilane.
More preferably, the dropping speed of the methyltrichlorosilane is 1-2 drops/s.
Further preferably, the post-treatment method comprises the following specific steps: and (3) performing rotary evaporation on the reaction liquid obtained after the heat preservation reaction to recover the solvent to obtain a solid, washing the solid with water for 2-3 times, and drying the solid at 80-100 ℃ to constant weight.
Preferably, the preparation method of the filler comprises the following steps in parts by weight:
(A) dispersing 10 parts of multi-walled carbon nano tube in a mixed solution of 20-30 parts of water and ethylene glycol by ultrasonic waves, adding 0.5-0.8 part of vanadyl sulfate hydrate and 0.2-0.3 part of sodium molybdate, stirring and uniformly mixing, and carrying out hydrothermal reaction at 220-250 ℃ for 7-9 hours in a nitrogen atmosphere to obtain a doped carbon nano tube;
(B) then dispersing the doped carbon nano tube in 30-40 parts of N, N-dimethylformamide by ultrasonic waves, adding 1-2 parts of hexamethylene diisocyanate, stirring at 80-100 ℃ and reacting for 3-4 hours to obtain a dispersion liquid containing the modified carbon nano tube;
(C) and finally, adding 1-2 parts of polyacrylic acid into the dispersion liquid, stirring and reacting for 3-4 hours at 50-60 ℃, and removing the solvent to obtain the filler.
Further preferably, the mixed solution of water and ethylene glycol is prepared by mixing water and ethylene glycol according to a mass ratio of 1: 1.2-1.5, and uniformly mixing.
The environment-friendly anti-radiation coating is prepared by the preparation method.
The invention has the beneficial effects that:
the coating product is prepared by taking melamine formaldehyde resin and modified fluorine-containing resin as film forming substances and adding a filler, and water as a solvent, so that the coating product is green and environment-friendly, has good film forming compactness, and effectively prevents radon in walls and stratums from escaping into the air; the filler is prepared by taking a carbon nano tube as a raw material through vanadium and molybdenum doping, hexamethylene diisocyanate modification and polyacrylic acid urethanization reaction, has good compatibility and dispersibility in a system, is beneficial to the increase of the specific surface area of a coating film, has good adsorption effect on radon in the air, and reduces the radon content in indoor air.
The modified fluorine-containing resin is obtained by modifying fluorine-containing resin by using methyltrichlorosilane, and is subjected to modification treatment to enrich branching; the chemical structure of the melamine formaldehyde resin contains a large amount of amino and imino, the modified fluorine-containing resin contains fluorine, amino brought by a silane coupling agent and the like, and the groups can form hydrogen bond action with the amino and imino and the like, so that the coating film is more densified through the hydrogen bond action, radon in walls and stratums is effectively prevented from escaping into the air, and the radon radiation resistance effect is achieved. The densification is carried out, meanwhile, small micro pores are ensured, and the radon gas is prevented from passing through and simultaneously the adsorption effect on the radon in the air is achieved.
The filler is prepared by using carbon nano tubes as main raw materials, the carbon nano tubes have microscopic pores and strong adsorption effect, and can adsorb radon in the air and reduce the radon content in the indoor air. Vanadium and molybdenum doping is carried out on the carbon nano tube, charge transfer is induced by metal doping, the charge distribution on the surface of the carbon nano tube is changed, and the electrostatic adsorption effect on radon is enhanced. The subsequent hexamethylene diisocyanate modification and polyacrylic acid urethanization reaction can mainly improve the compatibility of the filler in an organic system, so that the filler is uniformly dispersed in the filler, according to the principle of similar intermiscibility, organic groups are closer to film-forming substances, and carbon nano tubes are slightly floated on the surface of a coating film, so that the specific surface of the coating film is increased, the adsorption performance is further improved, and the radon content in indoor air is effectively reduced.
Detailed Description
The preferred embodiments of the present invention will be described in detail below.
Example 1:
a preparation method of an environment-friendly anti-radiation coating comprises the following specific steps:
(1) firstly, 0.5kg of thickening agent and 12kg of deionized water are uniformly stirred, then 100kg of melamine formaldehyde resin is added, and the components A are uniformly dispersed to obtain a component A;
(2) then, uniformly mixing 2kg of dispersing agent, 0.3kg of defoaming agent, 40kg of modified fluorine-containing resin, 9kg of propylene glycol methyl ether acetate and 11kg of deionized water, then adding 5kg of filler, and uniformly dispersing to obtain a component B;
(3) finally, stirring and uniformly mixing the component A obtained in the step (1) and the component B obtained in the step (2), and curing to obtain the environment-friendly anti-radiation coating;
wherein the modified fluorine-containing resin is obtained by modifying fluorine-containing resin with methyltrichlorosilane, and the filler is prepared by the following method: doping the carbon nano tube with vanadium and molybdenum to obtain a doped carbon nano tube, reacting the doped carbon nano tube with hexamethylene diisocyanate to obtain a modified carbon nano tube, and finally performing urethane reaction on the modified carbon nano tube and polyacrylic acid to obtain the modified carbon nano tube.
The thickening agent is a polyurethane associated thickening agent, the dispersing agent is a polyammonium amine salt dispersing agent, and the defoaming agent is an organic silicon defoaming agent.
In the step (3), the aging time is 10 minutes.
The fluorine-containing resin is polytetrafluoroethylene.
The preparation method of the modified fluorine-containing resin comprises the following steps: firstly, drying and corona-treating the fluorine-containing resin, then stirring and heating 100kg of pretreated fluorine-containing resin, 130kg of solvent and 0.5kg of silane coupling agent to 80 ℃, dropwise adding 0.1kg of methyl trichlorosilane, carrying out heat preservation reaction for 6 hours after dropwise adding is finished, and carrying out post-treatment to obtain the modified fluorine-containing resin.
The drying process conditions are as follows: drying at 120 ℃ to constant weight; the specific process conditions of the corona treatment are as follows: corona treatment was repeated 5 times with a point corona treater under a current condition of 5A for 5 seconds.
The solvent is tetrahydrofuran, and the silane coupling agent is 3-aminopropyltrimethoxysilane.
The dropping rate of the methyltrichlorosilane was 1 drop/s.
The specific method of post-treatment is as follows: and (3) performing heat preservation reaction, performing rotary evaporation on the obtained reaction liquid to recover the solvent to obtain a solid, washing the solid with water for 3 times, and drying the solid at 80 ℃ to constant weight.
The preparation method of the filler comprises the following steps:
(A) firstly, dispersing 10kg of multi-walled carbon nano-tube in 30kg of mixed solution of water and ethylene glycol by ultrasonic waves, then adding 0.5kg of hydrated vanadyl sulfate and 0.3kg of sodium molybdate, stirring and uniformly mixing, and carrying out hydrothermal reaction at 220 ℃ for 9 hours in a nitrogen atmosphere to obtain a doped carbon nano-tube;
(B) then dispersing the doped carbon nano tube in 30kgN, N-dimethylformamide by ultrasonic wave, adding 2kg of hexamethylene diisocyanate, and stirring and reacting for 4 hours at 80 ℃ to obtain dispersion liquid containing the modified carbon nano tube;
(C) and finally, adding 1kg of polyacrylic acid into the dispersion liquid, stirring and reacting for 3 hours at the temperature of 60 ℃, and removing the solvent to obtain the filler.
The mixed solution of water and glycol is prepared from water and glycol according to a mass ratio of 1: 1.5 stirring and mixing evenly.
Example 2:
a preparation method of an environment-friendly anti-radiation coating comprises the following specific steps:
(1) firstly, 0.7kg of thickening agent and 10kg of deionized water are uniformly stirred, then 100kg of melamine formaldehyde resin is added, and the components A are uniformly dispersed to obtain a component A;
(2) then uniformly mixing 3kg of dispersing agent, 0.2kg of defoaming agent, 60kg of modified fluorine-containing resin, 6kg of propylene glycol methyl ether acetate and 15kg of deionized water, then adding 3kg of filler, and uniformly dispersing to obtain a component B;
(3) finally, stirring and uniformly mixing the component A obtained in the step (1) and the component B obtained in the step (2), and curing to obtain the environment-friendly anti-radiation coating;
wherein the modified fluorine-containing resin is obtained by modifying fluorine-containing resin with methyltrichlorosilane, and the filler is prepared by the following method: doping the carbon nano tube with vanadium and molybdenum to obtain a doped carbon nano tube, reacting the doped carbon nano tube with hexamethylene diisocyanate to obtain a modified carbon nano tube, and finally performing urethane reaction on the modified carbon nano tube and polyacrylic acid to obtain the modified carbon nano tube.
The thickening agent is a polyurethane associated thickening agent, the dispersing agent is a polyammonium amine salt dispersing agent, and the defoaming agent is an organic silicon defoaming agent.
In the step (3), the aging time is 15 minutes.
The fluorine-containing resin is polyvinylidene fluoride.
The preparation method of the modified fluorine-containing resin comprises the following steps: firstly, drying and corona-treating the fluorine-containing resin, then stirring and heating 100kg of pretreated fluorine-containing resin, 120kg of solvent and 1kg of silane coupling agent to 60 ℃, dropwise adding 0.15kg of methyl trichlorosilane, preserving heat and reacting for 4 hours after dropwise adding is finished, and carrying out post-treatment to obtain the modified fluorine-containing resin.
The drying process conditions are as follows: drying at 140 ℃ to constant weight; the specific process conditions of the corona treatment are as follows: corona treatment was repeated 3 times with a point corona treater under a current condition of 3A for 8 s.
The solvent is N, N-dimethylformamide, and the silane coupling agent is 3-aminopropyltrimethoxysilane.
The dropping rate of the methyltrichlorosilane was 2 drops/s.
The specific method of post-treatment is as follows: and (3) performing heat preservation reaction, performing rotary evaporation on the obtained reaction liquid to recover the solvent to obtain a solid, washing the solid with water for 2 times, and drying the solid at 100 ℃ to constant weight.
The preparation method of the filler comprises the following steps:
(A) firstly, dispersing 10kg of multi-walled carbon nano-tube in a mixed solution of 20kg of water and ethylene glycol by ultrasonic waves, then adding 0.8kg of hydrated vanadyl sulfate and 0.2kg of sodium molybdate, stirring and uniformly mixing, and carrying out hydrothermal reaction at 250 ℃ for 7 hours in a nitrogen atmosphere to obtain a doped carbon nano-tube;
(B) then dispersing the doped carbon nano tube in 40kgN, N-dimethylformamide by ultrasonic wave, adding 1kg of hexamethylene diisocyanate, stirring and reacting for 3 hours at 100 ℃ to obtain dispersion liquid containing the modified carbon nano tube;
(C) and finally, adding 2kg of polyacrylic acid into the dispersion liquid, stirring and reacting for 4 hours at 50 ℃, and removing the solvent to obtain the filler.
The mixed solution of water and glycol is prepared from water and glycol according to a mass ratio of 1: 1.2 stirring and mixing evenly.
Example 3:
a preparation method of an environment-friendly anti-radiation coating comprises the following specific steps:
(1) firstly, uniformly stirring 0.6kg of thickening agent and 11kg of deionized water, adding 100kg of melamine-formaldehyde resin, and uniformly dispersing to obtain a component A;
(2) then, uniformly mixing 2.5kg of dispersing agent, 0.25kg of defoaming agent, 50kg of modified fluorine-containing resin, 8kg of propylene glycol methyl ether acetate and 13kg of deionized water, then adding 4kg of filler, and uniformly dispersing to obtain a component B;
(3) finally, stirring and uniformly mixing the component A obtained in the step (1) and the component B obtained in the step (2), and curing to obtain the environment-friendly anti-radiation coating;
wherein the modified fluorine-containing resin is obtained by modifying fluorine-containing resin with methyltrichlorosilane, and the filler is prepared by the following method: doping the carbon nano tube with vanadium and molybdenum to obtain a doped carbon nano tube, reacting the doped carbon nano tube with hexamethylene diisocyanate to obtain a modified carbon nano tube, and finally performing urethane reaction on the modified carbon nano tube and polyacrylic acid to obtain the modified carbon nano tube.
The thickening agent is a polyurethane associated thickening agent, the dispersing agent is a polyammonium amine salt dispersing agent, and the defoaming agent is an organic silicon defoaming agent.
In the step (3), the aging time is 12 minutes.
The fluorine-containing resin is polytetrafluoroethylene.
The preparation method of the modified fluorine-containing resin comprises the following steps: firstly, drying and corona-treating the fluorine-containing resin, then stirring and heating 100kg of pretreated fluorine-containing resin, 125kg of solvent and 0.8kg of silane coupling agent to 70 ℃, dropwise adding 0.12kg of methyl trichlorosilane, carrying out heat preservation reaction for 5 hours after dropwise adding is finished, and carrying out post-treatment to obtain the modified fluorine-containing resin.
The drying process conditions are as follows: drying at 130 ℃ to constant weight; the specific process conditions of the corona treatment are as follows: corona treatment was repeated 4 times for 6s with a point corona treater under a current condition of 4A.
The solvent is N, N-dimethylacetamide, and the silane coupling agent is 3-aminopropyltrimethoxysilane.
The dropping rate of the methyltrichlorosilane was 1 drop/s.
The specific method of post-treatment is as follows: and (3) performing rotary evaporation on the reaction liquid obtained after the heat preservation reaction to recover the solvent to obtain a solid, washing the solid for 3 times by using water, and drying the solid at 90 ℃ to constant weight.
The preparation method of the filler comprises the following steps:
(A) firstly, dispersing 10kg of multi-walled carbon nano-tubes in 25kg of mixed solution of water and ethylene glycol by ultrasonic waves, then adding 0.7kg of hydrated vanadyl sulfate and 0.25kg of sodium molybdate, stirring and uniformly mixing, and carrying out hydrothermal reaction at 240 ℃ for 8 hours in a nitrogen atmosphere to obtain doped carbon nano-tubes;
(B) then dispersing the doped carbon nano tube in 35kgN, N-dimethylformamide by ultrasonic waves, adding 1.5kg of hexamethylene diisocyanate, and stirring and reacting at 90 ℃ for 3.5 hours to obtain a dispersion liquid containing the modified carbon nano tube;
(C) and finally, adding 1.5kg of polyacrylic acid into the dispersion liquid, stirring and reacting for 3.5 hours at 55 ℃, and removing the solvent to obtain the filler.
The mixed solution of water and glycol is prepared from water and glycol according to a mass ratio of 1: 1.4 stirring and mixing evenly.
Comparative example 1
A preparation method of an environment-friendly anti-radiation coating comprises the following specific steps:
(1) firstly, 0.5kg of thickening agent and 12kg of deionized water are uniformly stirred, then 100kg of melamine formaldehyde resin is added, and the components A are uniformly dispersed to obtain a component A;
(2) then, uniformly mixing 2kg of dispersing agent, 0.3kg of defoaming agent, 40kg of fluorine-containing resin, 9kg of propylene glycol methyl ether acetate and 11kg of deionized water, then adding 5kg of filler, and uniformly dispersing to obtain a component B;
(3) finally, stirring and uniformly mixing the component A obtained in the step (1) and the component B obtained in the step (2), and curing to obtain the environment-friendly anti-radiation coating;
wherein the filler is prepared by the following method: doping the carbon nano tube with vanadium and molybdenum to obtain a doped carbon nano tube, reacting the doped carbon nano tube with hexamethylene diisocyanate to obtain a modified carbon nano tube, and finally performing urethane reaction on the modified carbon nano tube and polyacrylic acid to obtain the modified carbon nano tube.
The thickening agent is a polyurethane associated thickening agent, the dispersing agent is a polyammonium amine salt dispersing agent, and the defoaming agent is an organic silicon defoaming agent.
In the step (3), the aging time is 10 minutes.
The fluorine-containing resin is polytetrafluoroethylene.
The preparation method of the filler comprises the following steps:
(A) firstly, dispersing 10kg of multi-walled carbon nano-tube in 30kg of mixed solution of water and ethylene glycol by ultrasonic waves, then adding 0.5kg of hydrated vanadyl sulfate and 0.3kg of sodium molybdate, stirring and uniformly mixing, and carrying out hydrothermal reaction at 220 ℃ for 9 hours in a nitrogen atmosphere to obtain a doped carbon nano-tube;
(B) then dispersing the doped carbon nano tube in 30kgN, N-dimethylformamide by ultrasonic wave, adding 2kg of hexamethylene diisocyanate, and stirring and reacting for 4 hours at 80 ℃ to obtain dispersion liquid containing the modified carbon nano tube;
(C) and finally, adding 1kg of polyacrylic acid into the dispersion liquid, stirring and reacting for 3 hours at the temperature of 60 ℃, and removing the solvent to obtain the filler.
The mixed solution of water and glycol is prepared from water and glycol according to a mass ratio of 1: 1.5 stirring and mixing evenly.
Comparative example 2
A preparation method of an environment-friendly anti-radiation coating comprises the following specific steps:
(1) firstly, 0.5kg of thickening agent and 12kg of deionized water are uniformly stirred, then 100kg of melamine formaldehyde resin is added, and the components A are uniformly dispersed to obtain a component A;
(2) then, uniformly mixing 2kg of dispersing agent, 0.3kg of defoaming agent, 40kg of modified fluorine-containing resin, 9kg of propylene glycol methyl ether acetate and 11kg of deionized water, then adding 5kg of filler, and uniformly dispersing to obtain a component B;
(3) finally, stirring and uniformly mixing the component A obtained in the step (1) and the component B obtained in the step (2), and curing to obtain the environment-friendly anti-radiation coating;
wherein the modified fluorine-containing resin is obtained by modifying fluorine-containing resin with methyltrichlorosilane, and the filler is prepared by the following method: firstly, vanadium doping is carried out on a carbon nano tube to obtain a doped carbon nano tube, then the doped carbon nano tube is reacted with hexamethylene diisocyanate to obtain a modified carbon nano tube, and finally the modified carbon nano tube is subjected to urethane reaction with polyacrylic acid to obtain the modified carbon nano tube.
The thickening agent is a polyurethane associated thickening agent, the dispersing agent is a polyammonium amine salt dispersing agent, and the defoaming agent is an organic silicon defoaming agent.
In the step (3), the aging time is 10 minutes.
The fluorine-containing resin is polytetrafluoroethylene.
The preparation method of the modified fluorine-containing resin comprises the following steps: firstly, drying and corona-treating the fluorine-containing resin, then stirring and heating 100kg of pretreated fluorine-containing resin, 130kg of solvent and 0.5kg of silane coupling agent to 80 ℃, dropwise adding 0.1kg of methyl trichlorosilane, carrying out heat preservation reaction for 6 hours after dropwise adding is finished, and carrying out post-treatment to obtain the modified fluorine-containing resin.
The drying process conditions are as follows: drying at 120 ℃ to constant weight; the specific process conditions of the corona treatment are as follows: corona treatment was repeated 5 times with a point corona treater under a current condition of 5A for 5 seconds.
The solvent is tetrahydrofuran, and the silane coupling agent is 3-aminopropyltrimethoxysilane.
The dropping rate of the methyltrichlorosilane was 1 drop/s.
The specific method of post-treatment is as follows: and (3) performing heat preservation reaction, performing rotary evaporation on the obtained reaction liquid to recover the solvent to obtain a solid, washing the solid with water for 3 times, and drying the solid at 80 ℃ to constant weight.
The preparation method of the filler comprises the following steps:
(A) firstly, dispersing 10kg of multi-walled carbon nano-tube in 30kg of mixed solution of water and glycol by ultrasonic waves, then adding 0.5kg of hydrated vanadyl sulfate, stirring and uniformly mixing, and carrying out hydrothermal reaction for 9 hours at 220 ℃ in a nitrogen atmosphere to obtain a doped carbon nano-tube;
(B) then dispersing the doped carbon nano tube in 30kgN, N-dimethylformamide by ultrasonic wave, adding 2kg of hexamethylene diisocyanate, and stirring and reacting for 4 hours at 80 ℃ to obtain dispersion liquid containing the modified carbon nano tube;
(C) and finally, adding 1kg of polyacrylic acid into the dispersion liquid, stirring and reacting for 3 hours at the temperature of 60 ℃, and removing the solvent to obtain the filler.
The mixed solution of water and glycol is prepared from water and glycol according to a mass ratio of 1: 1.5 stirring and mixing evenly.
Comparative example 3
A preparation method of an environment-friendly anti-radiation coating comprises the following specific steps:
(1) firstly, 0.5kg of thickening agent and 12kg of deionized water are uniformly stirred, then 100kg of melamine formaldehyde resin is added, and the components A are uniformly dispersed to obtain a component A;
(2) then, uniformly mixing 2kg of dispersing agent, 0.3kg of defoaming agent, 40kg of modified fluorine-containing resin, 9kg of propylene glycol methyl ether acetate and 11kg of deionized water, then adding 5kg of filler, and uniformly dispersing to obtain a component B;
(3) finally, stirring and uniformly mixing the component A obtained in the step (1) and the component B obtained in the step (2), and curing to obtain the environment-friendly anti-radiation coating;
wherein the modified fluorine-containing resin is obtained by modifying fluorine-containing resin with methyltrichlorosilane, and the filler is prepared by the following method: doping the carbon nano tube with vanadium and molybdenum to obtain a doped carbon nano tube, and then reacting the doped carbon nano tube with hexamethylene diisocyanate to obtain the carbon nano tube.
The thickening agent is a polyurethane associated thickening agent, the dispersing agent is a polyammonium amine salt dispersing agent, and the defoaming agent is an organic silicon defoaming agent.
In the step (3), the aging time is 10 minutes.
The fluorine-containing resin is polytetrafluoroethylene.
The preparation method of the modified fluorine-containing resin comprises the following steps: firstly, drying and corona-treating the fluorine-containing resin, then stirring and heating 100kg of pretreated fluorine-containing resin, 130kg of solvent and 0.5kg of silane coupling agent to 80 ℃, dropwise adding 0.1kg of methyl trichlorosilane, carrying out heat preservation reaction for 6 hours after dropwise adding is finished, and carrying out post-treatment to obtain the modified fluorine-containing resin.
The drying process conditions are as follows: drying at 120 ℃ to constant weight; the specific process conditions of the corona treatment are as follows: corona treatment was repeated 5 times with a point corona treater under a current condition of 5A for 5 seconds.
The solvent is tetrahydrofuran, and the silane coupling agent is 3-aminopropyltrimethoxysilane.
The dropping rate of the methyltrichlorosilane was 1 drop/s.
The specific method of post-treatment is as follows: and (3) performing heat preservation reaction, performing rotary evaporation on the obtained reaction liquid to recover the solvent to obtain a solid, washing the solid with water for 3 times, and drying the solid at 80 ℃ to constant weight.
The preparation method of the filler comprises the following steps:
(A) firstly, dispersing 10kg of multi-walled carbon nano-tube in 30kg of mixed solution of water and ethylene glycol by ultrasonic waves, then adding 0.5kg of hydrated vanadyl sulfate and 0.3kg of sodium molybdate, stirring and uniformly mixing, and carrying out hydrothermal reaction at 220 ℃ for 9 hours in a nitrogen atmosphere to obtain a doped carbon nano-tube;
(B) and then dispersing the doped carbon nano tube in 30kgN, N-dimethylformamide by ultrasonic waves, adding 2kg of hexamethylene diisocyanate, stirring at 80 ℃ for reaction for 4 hours, and removing the solvent to obtain the filler.
The mixed solution of water and glycol is prepared from water and glycol according to a mass ratio of 1: 1.5 stirring and mixing evenly.
Test examples
The coatings obtained in examples 1 to 3 and comparative examples 1 to 3 were examined for their performance, and the results are shown in Table 1.
Wherein the adhesive force refers to GB/T1720;
the detection method of the radon adsorption rate comprises the following steps: 6 rooms with completely consistent sizes, the coatings obtained in examples 1-3 and comparative examples 1-3 are respectively and uniformly brushed on the inner walls of the rooms to form coating films with the thickness of 1mm, and the radon content in each room is 150Bq/m by using a radon source3The radon content in the room is detected 2 hours after the radon is filled, the detection is repeated 30 days and 1 year after the brushing, and the adsorption rate is calculated as (initial content value-final content value)/initial content value multiplied by 100 percent.
TABLE 1 Performance test of the coatings
As shown in Table 1, the paint obtained in examples 1 to 3 has good adhesion, high adsorption rate to radon gas, and high radon adsorption rate after 1 year of painting.
The comparative example 1 replaces the modified fluorine-containing resin with the fluorine-containing resin, the comparative example 2 omits molybdenum doping when preparing the filler, and the comparative example 3 omits a urethanization reaction step when preparing the carbon nano tube, so that the adsorption rate of radon gas is obviously reduced, and the radon radiation resistant effect is influenced; the indexes of the film adhesion and radon adsorption rate after brushing for a period of time of the comparative examples 1 and 3 are also obviously poor, which shows that the modification treatment of the fluorine-containing resin and the urethane reaction of the filler are beneficial to the uniform dispersion of the system, thereby improving the film performance and the stability of the coating.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (10)
1. The preparation method of the environment-friendly anti-radiation coating is characterized by comprising the following specific steps in parts by weight:
(1) firstly, 0.5-0.7 part of thickening agent and 10-12 parts of deionized water are uniformly stirred and mixed, then 100 parts of melamine formaldehyde resin is added, and the components A are uniformly dispersed to obtain a component A;
(2) then uniformly mixing 2-3 parts of dispersing agent, 0.2-0.3 part of defoaming agent, 40-60 parts of modified fluorine-containing resin, 6-9 parts of propylene glycol methyl ether acetate and 11-15 parts of deionized water, then adding 3-5 parts of filler, and uniformly dispersing to obtain a component B;
(3) finally, stirring and uniformly mixing the component A obtained in the step (1) and the component B obtained in the step (2), and curing to obtain the environment-friendly anti-radiation coating;
wherein the modified fluorine-containing resin is obtained by modifying fluorine-containing resin with methyltrichlorosilane, and the filler is prepared by the following method: doping the carbon nano tube with vanadium and molybdenum to obtain a doped carbon nano tube, reacting the doped carbon nano tube with hexamethylene diisocyanate to obtain a modified carbon nano tube, and finally performing urethane reaction on the modified carbon nano tube and polyacrylic acid to obtain the modified carbon nano tube.
2. The method according to claim 1, wherein in the step (3), the aging time is 10 to 15 minutes.
3. The method according to claim 1, wherein the modified fluorine-containing resin is prepared by the following method in parts by weight: firstly, drying and corona-treating the fluorine-containing resin, then stirring and heating 100 parts of the pretreated fluorine-containing resin, 120-130 parts of solvent and 0.5-1 part of silane coupling agent to 60-80 ℃, dropwise adding 0.1-0.15 part of methyl trichlorosilane, carrying out heat preservation reaction for 4-6 hours after dropwise adding is finished, and carrying out post-treatment to obtain the modified fluorine-containing resin.
4. The preparation method according to claim 3, wherein the drying process conditions are as follows: drying at 120-140 ℃ to constant weight; the specific process conditions of the corona treatment are as follows: and (3) carrying out corona treatment for 5-8 s by using a point corona treatment machine under the current condition of 3-5A, and repeating for 3-5 times.
5. The method according to claim 3, wherein the solvent is any one selected from tetrahydrofuran, N-dimethylformamide and N, N-dimethylacetamide, and the silane coupling agent is 3-aminopropyltrimethoxysilane.
6. The method according to claim 3, wherein the dropping rate of methyltrichlorosilane is 1 to 2 drops/s.
7. The preparation method according to claim 3, characterized in that the post-treatment comprises the following specific steps: and (3) performing rotary evaporation on the reaction liquid obtained after the heat preservation reaction to recover the solvent to obtain a solid, washing the solid with water for 2-3 times, and drying the solid at 80-100 ℃ to constant weight.
8. The method of claim 1, wherein the filler is prepared by the following method in parts by weight:
(A) dispersing 10 parts of multi-walled carbon nano tube in a mixed solution of 20-30 parts of water and ethylene glycol by ultrasonic waves, adding 0.5-0.8 part of vanadyl sulfate hydrate and 0.2-0.3 part of sodium molybdate, stirring and uniformly mixing, and carrying out hydrothermal reaction at 220-250 ℃ for 7-9 hours in a nitrogen atmosphere to obtain a doped carbon nano tube;
(B) then dispersing the doped carbon nano tube in 30-40 parts of N, N-dimethylformamide by ultrasonic waves, adding 1-2 parts of hexamethylene diisocyanate, stirring at 80-100 ℃ and reacting for 3-4 hours to obtain a dispersion liquid containing the modified carbon nano tube;
(C) and finally, adding 1-2 parts of polyacrylic acid into the dispersion liquid, stirring and reacting for 3-4 hours at 50-60 ℃, and removing the solvent to obtain the filler.
9. The preparation method according to claim 8, wherein the mixed solution of water and ethylene glycol is prepared from water and ethylene glycol in a mass ratio of 1: 1.2-1.5, and uniformly mixing.
10. An environment-friendly anti-radiation coating obtained by the preparation method of any one of claims 1 to 9.
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| CN107868521A (en) * | 2017-11-13 | 2018-04-03 | 济南大学 | Modified fluoride-containing cold coating and its preparation and application |
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| KR20090047983A (en) * | 2007-11-09 | 2009-05-13 | 건설화학공업주식회사 | Paint to prevent radon emissions |
| US20090208403A1 (en) * | 2008-02-17 | 2009-08-20 | Quaid-E-Azam University | Novel catalyst to manufacture carbon nanotubes and hydrogen gas |
| CN105802402A (en) * | 2016-04-12 | 2016-07-27 | 湖州新奥克化工有限公司 | Environment-friendly and efficient anti-static coating and preparation method thereof |
| CN107353720A (en) * | 2017-08-08 | 2017-11-17 | 苏州大学 | Inhale radon radioresistance coating and its preparation method and application |
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Effective date of registration: 20211029 Address after: 272000 Huaxin Road, quanpu Industrial Park, Jining City, Shandong Province Applicant after: Shandong Beige paint Co.,Ltd. Address before: 330000 room 506, building 58, Branch Road 107, Lushan North Avenue, Nanchang Economic and Technological Development Zone, Jiangxi Province Applicant before: Xu Jie |
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| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: The invention relates to an environmental protection anti radiation coating and a preparation method thereof Effective date of registration: 20220426 Granted publication date: 20211116 Pledgee: Shandong Liangshan Rural Commercial Bank Co.,Ltd. Chengnan sub branch Pledgor: Shandong Beige paint Co.,Ltd. Registration number: Y2022980004836 |