CN111826053B - 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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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 source3Are respectively atDetecting the radon content in the room 2 hours after the radon is filled, repeatedly detecting 30 days and 1 year after brushing respectively, and calculating the adsorption rate (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 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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| US20090208403A1 (en) * | 2008-02-17 | 2009-08-20 | Quaid-E-Azam University | Novel catalyst to manufacture carbon nanotubes and hydrogen gas |
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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 |
| CN108485401A (en) * | 2018-04-18 | 2018-09-04 | 济南大学 | Diamond Search fluoro coatings and preparation method and the application in heat dissipation element production |
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| KR100920138B1 (en) * | 2007-11-09 | 2009-10-08 | 건설화학공업주식회사 | Paint to prevent radon emissions |
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| 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 |
| CN107868521A (en) * | 2017-11-13 | 2018-04-03 | 济南大学 | Modified fluoride-containing cold coating and its preparation and application |
| CN108485401A (en) * | 2018-04-18 | 2018-09-04 | 济南大学 | Diamond Search fluoro coatings and preparation method and the application in heat dissipation element production |
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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 |