CN112552753B

CN112552753B - Strippable decontamination coating and preparation method and application thereof

Info

Publication number: CN112552753B
Application number: CN202011448923.5A
Authority: CN
Inventors: 陈运法; 薛杨; 岳仁亮; 王好盛; 李晓飞
Original assignee: Institute of Process Engineering of CAS
Current assignee: Institute of Process Engineering of CAS
Priority date: 2020-12-09
Filing date: 2020-12-09
Publication date: 2021-12-17
Anticipated expiration: 2040-12-09
Also published as: CN112552753A

Abstract

The invention provides a strippable stain removal coating and a preparation method and application thereof, wherein the strippable stain removal coating comprises a combination of a water-based polymer solution and a modified adsorption nano material; the modified adsorption nano material comprises a combination of a porous nano material, a nonporous nano material and a complexing agent. The strippable decontamination coating has excellent decontamination efficiency and processability, is easy to strip after being coated, has very excellent tensile strength, can be coated on the surface of a base material in a large area by adopting various methods, is convenient to operate, safe and environment-friendly, can be applied to various base materials, has simple post-treatment, and can remove radionuclide pollution, heavy metal pollution, organic matter pollution and other industrial and civil surface pollution.

Description

Strippable decontamination coating and preparation method and application thereof

Technical Field

The invention belongs to the technical field of coatings, and particularly relates to a strippable dirt-removing coating as well as a preparation method and application thereof.

Background

Fossil energy emits greenhouse gases to cause global warming, and nuclear energy is a substitute of fossil energy; however, the main disadvantage of nuclear power is that in the event of an accident, malfunction or even retirement, a large amount of harmful radioactive materials can produce life-threatening substances that can harm the environment along with animals. The strippable coating is a functional coating for removing and protecting pollutants on the surface of a matrix, can form a closed film after being coated on the surface of a material workpiece and dried, has no adverse effect on the surface of a substrate material, can be used for cleaning the surfaces of metal, cement, plastic, glass, wood and many other solids, and has wide application prospect in the national defense industry and civil use.

The existing strippable coating in the domestic market is mainly a solvent type, the use of the strippable coating on a physical drying type coating is limited due to the dissolving effect of the solvent, and the strippable coating has high VOC content, is volatilized into the air to pollute the environment, is harmful to the health of human bodies and causes resource waste. Therefore, the environment-friendly pollution-free water-based strippable protective coating has great development potential and social significance.

The water-based strippable coating provides a unique method for removing various pollutants on the surface of a solid, and the high molecular compound with various functional groups, the high-adsorbability non-porous nano material and the complexing agent are coupled, so that the pollutants on the surface of the substrate material are adsorbed by the adsorption action of the non-porous nano material and the complexing agent in the film forming process and are transferred from the surface of the substrate material to the film to form a part of the film; and the macromolecular film-forming substance has certain viscosity and adheres to pollutants and harmful residual substances on the surface of the substrate material under the action of viscous force. The result of the action of the two acting forces is that pollutants are enriched on the film, the pollutants on the substrate material can be removed only by removing the film, the coating can adopt various coating modes when in use, large-area decontamination is convenient to carry out, and the post-treatment and recovery of the stripped film are simple and convenient. At present, there are many reports on the coating, and CN108034324A discloses a radioactive decontamination high-strength peelable film, a preparation method and an application thereof, which are prepared from the following raw materials in percentage by weight: 50-70% of polyisoprene, 0.3-3% of sulfur, 0.25-3% of nano white carbon black, 0.3-2% of accelerator ZDC, 0.5-2% of anti-aging agent D, and zinc oxide0.1 percent of casein, 0.05 to 1.0 percent of casein, 0.5 to 2 percent of EDTA, 0.02 to 0.5 percent of dispersant BX and 20 to 40 percent of water. The radiation decontamination high-strength strippable film is obtained by vulcanizing and modifying polyisoprene base stock and compounding the polyisoprene base stock with other components, and the obtained strippable decontaminant has high film forming strength and tensile strength of up to 110kg/cm through practical verification²And in practical application, the method has remarkable improvement significance for decontaminating the surface pollution to a level below the cleaning and control level. CN104403481A discloses a preparation and use method of modified starch and degradable polyester compounded strippable detergent, which comprises the following steps: firstly, preparing modified starch through atom transfer radical polymerization, then adding 5-15 parts by weight of the modified starch and 4-12 parts by weight of polyester into 100 parts by weight of mixed solvent, stirring and dissolving for 1-4 hours, then adding 0.1-2.0 parts by weight of emulsifier, 0.1-2.5 parts by weight of thickener, 0.5-3.5 parts by weight of flatting agent and 0.1-1 part by weight of defoaming agent, stirring and dissolving for 0.5-10 hours, finally performing ultrasonic defoaming treatment for 0.2-1 hours to obtain a decontaminating agent, spraying the decontaminating agent on the surface of a material with radioactive stains, simultaneously spraying a water-soluble complexing agent with the mass fraction of 5-30%, and stripping the material after coating solidification to complete the decontaminating process. The biodegradable efficient environment-friendly detergent is prepared by taking the modified starch and the polyester as raw materials, and after the detergent is formed into a film and decontaminated, the film body can be completely peeled without the phenomenon of fracture residue, so that the decontamination working efficiency is improved. CN103214903A discloses a strippable nano-decontamination coating, which comprises the following formula components: polyvinyl alcohol 1-30%, nano-grade TiO₂0.3-12% of detergent, 0.7-13% of at least one auxiliary agent capable of dehydrating polyvinyl alcohol to form a strippable polymeric film, and the strippable nano decontamination coating is subjected to nano TiO₂The addition of the surfactant is effectively combined with various auxiliary agents, the formed polymeric membrane is easy to peel, has high tensile strength, is not easy to break, has obvious decontamination effect, and solves the defects that the solid surface after the mesonuclear pollution and other pollutions can not be cleaned by a large amount of water and the decontamination quantity is small. However, the release efficiency of the peelable stain release coatings disclosed in the above prior art and the tensile strength after film formation are still in need of improvement.

Therefore, the development of the strippable stain-removal coating with high stain-removal efficiency and high tensile strength after film formation is of great significance.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a strippable stain-removal coating, a preparation method and application thereof, wherein the strippable stain-removal coating comprises a combination of a water-based polymer solution and a modified adsorption nano material; the modified adsorption nano material comprises a combination of a porous nano material, a non-porous nano material and a complexing agent, and through the combination of the three materials, the strippable decontamination coating has excellent decontamination efficiency and processability, is easy to strip after film forming, has very excellent tensile strength, can be applied to the surfaces of various base materials, is simple in post-treatment, and can remove radionuclide pollution, heavy metal pollution, organic matter pollution and other industrial and civil surface decontamination.

In order to achieve the purpose, the invention adopts the following technical scheme:

in a first aspect, the present invention provides a peelable stain release coating comprising a combination of an aqueous polymer solution and a modified adsorbent nanomaterial;

the modified adsorption nano material comprises a combination of a porous nano material, a nonporous nano material and a complexing agent.

Firstly, the strippable dirt-removing paint provided by the invention comprises a combination of a water-based polymer solution and a modified adsorption nano material, the modified adsorption nano material can fully exert the nano effect of nano particles, and by utilizing the special functional group, surface and pore channel structures of the modified adsorption nano material, through various adsorption mechanisms such as surface adsorption complexation and the like, the strippable dirt-removing paint is beneficial to improving the dirt-removing efficiency of the strippable dirt-removing paint on various pollution components, improving the processing performance of the paint, enhancing the interface combination, improving the tensile strength after film formation and being beneficial to stripping after film formation, thereby improving the comprehensive performance of the water-based dirt-removing paint.

Secondly, the modified adsorption nano material provided by the invention comprises a combination of a porous nano material, a nonporous nano material and a complexing agent, the porous nano material is selected to match with the nonporous nano material, so that the nano effect of the modified adsorption nano material can be further improved, and the modified adsorption nano material is mixed with the complexing agent, so that the decontamination efficiency and the processing performance of the strippable decontamination coating are further improved.

Preferably, the mass percentage of the aqueous polymer solution in the strippable stain-removal paint is 55-99.3%, such as 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95%, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.

Preferably, the content of the aqueous polymer in the aqueous polymer solution is 5 to 79% by mass, for example, 10%, 15%, 20%, 25%, 30%, 40%, 50%, 60% or 70%, and the specific values therebetween are limited by space and for brevity, the present invention does not exhaustive list the specific values included in the range, and further preferably 15 to 65%.

Preferably, the aqueous polymer comprises any one of polyvinyl alcohol, polyurethane, chitosan, gelatin, sodium alginate or modified starch or a combination of at least two thereof.

Preferably, the aqueous polymer comprises a combination of any two of polyvinyl alcohol, polyurethane, chitosan, gelatin, sodium alginate or modified starch.

As the preferable technical scheme of the invention, the strippable dirt-removing coating prepared by adopting two water-based polymers has more excellent film-forming and dirt-removing effects, because different water-based polymers have different performance advantages which have synergistic effect, the film-forming property of the coating can be improved, the tensile strength of the film is increased, the adhesive force of the film is optimized so that the film is easy to strip, and the viscosity of the polymer solution is improved so as to enhance the dirt-removing effect.

Preferably, the content of the modified adsorption nanomaterial in the strippable dirt-removing paint is 0.5-40% by mass, such as 10%, 15%, 19%, 22%, 25%, 28%, 31%, 35% or 38%, and specific values therebetween, limited to space and for brevity, the invention is not exhaustive of the specific values included in the range, and preferably 4-25%.

Preferably, the mass ratio of the porous nanomaterial to the nonporous nanomaterial is 1 (0.3-9), such as 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, or 1: 8.

According to the preferred technical scheme, when the mass ratio of the porous nano material to the nonporous nano material is 1 (0.3-9), the strippable decontamination coating with high decontamination efficiency can be obtained; on one hand, if the dosage of the porous nano material is too much, the film forming effect of the strippable stain-removal coating is reduced, and on the other hand, if the dosage of the porous nano material is too low, the adsorption and film forming effect of the strippable stain-removal coating is not obvious.

Preferably, the mass ratio of the porous nano material to the complexing agent is 1 (0.016-3), such as 1:0.3, 1:0.6, 1:0.9, 1:1.1, 1:1.4, 1:1.7, 1:2, 1:2.3, 1:2.6 or 1: 2.9.

Preferably, the specific surface area of the porous nano material is 50-2200 m²In g, e.g. 100m²/g、200m²/g、400m²/g、600m²/g、800m²/g、1000m²/g、1200m²/g、1400m²/g、1600m²(g or 1800 m)²The present invention is not intended to be exhaustive of the specific point values included in the ranges, limited to space and for the sake of brevity, as well as the specific point values between the point values recited above.

Preferably, the pore diameter of the porous nanomaterial is 0.5-40 nm, such as 10nm, 13nm, 16nm, 19nm, 22nm, 25nm, 28nm, 31nm, 35nm, or 39nm, and the specific values therebetween are limited by space and for brevity, the invention is not exhaustive of the specific values included in the ranges.

Preferably, the porous nanomaterial comprises any one of or a combination of at least two of a porous nanocarbon material, a porous nanoceramic material or a nanometal organic framework material.

Preferably, the porous nanocarbon material comprises any one of activated carbon, biochar, activated carbon fibers or porous carbon spheres or a combination of at least two of the foregoing.

Preferably, the porous nanoceramic material comprises any one of or a combination of at least two of porous silica, porous alumina, porous silicon carbide or diatomaceous earth.

Preferably, the nanometal-organic framework material comprises any one of, or a combination of at least two of, MOF-n, ZIF-n, MLI-n, PCN-n, or UIO-n.

Wherein n represents different numbers.

Preferably, the non-porous nanomaterial comprises any one of or a combination of at least two of a nano-oxide, a nano-carbonate, or a two-dimensional nanoplate.

Preferably, the particle size of the nano-oxide and the nano-carbonate is 5 to 350nm, such as 10nm, 20nm, 40nm, 60nm, 80nm, 120nm, 140nm, 180nm, 200nm, 230nm, 260nm, 290nm or 320nm, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the ranges.

Preferably, the two-dimensional nanoplatelets have a platelet diameter of 0.05 to 10 μm, such as 1 μm, 2 μm, 3 μm, 4 μm, 6 μm or 8 μm, and the specific values therebetween, are limited in space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the ranges.

Preferably, the nano oxide comprises any one or a combination of at least two of nano titanium oxide, nano silicon oxide, nano aluminum oxide, nano zinc oxide, nano iron oxide, nano zirconium oxide or nano cerium oxide.

Preferably, the nano-carbonate comprises nano-calcium carbonate and/or nano-magnesium carbonate.

Preferably, the two-dimensional nanoplatelets comprise any one of or a combination of at least two of a bimetallic hydroxide, graphene, boron nitride or a layered silicate.

Preferably, the phyllosilicate comprises any one of montmorillonite, clay, bentonite or mica flakes or a combination of at least two thereof.

Preferably, the complexing agent comprises any one of ethylenediaminetetraacetic acid, citric acid, aminotriacetic acid, diethylenetriaminepentaacetic acid, tartaric acid, hydroxyethylethylenediaminetriacetic acid, sodium tripolyphosphate, aminotrimethylenephosphonic acid, polyacrylic acid, or polymethacrylic acid, or a combination of at least two thereof.

Preferably, the modified adsorption nanomaterial is prepared by a method comprising the following steps: and carrying out ball milling on the porous nano material, the nonporous nano material and the complexing agent to obtain the modified nano adsorption material.

Preferably, the ball milling time is 5-50 min, such as 10min, 15min, 20min, 25min, 30min, 35min, 40min or 45min, and the specific values therebetween are limited by space and for brevity, the invention is not exhaustive, and further preferably 9-30 min.

Preferably, the ball milling is performed at a rotation speed of 50 to 300r/min (e.g., 90r/min, 120r/min, 150r/min, 180r/min, 210r/min, 240r/min, 270r/min, etc.), and more preferably at a rotation speed of 70 to 230 r/min.

Preferably, the strippable stain release coating further comprises an auxiliary agent.

Preferably, the content of the auxiliary agent in the strippable dirt-removing paint is 0.2-5% by mass, such as 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4% or 4.5%, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive list of the specific values included in the range.

Preferably, the auxiliary agent comprises any one or a combination of at least two of an antifoaming agent, a dispersing agent, a wetting agent, a leveling agent or a pigment.

Preferably, the amount of the defoaming agent in the auxiliary agent is 0.02 to 2% by mass, for example, 0.2%, 0.4%, 0.6%, 0.8%, 1%, 1.2%, 1.4%, 1.6% or 1.8%, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.

Preferably, the dispersing agent in the auxiliary agent is present in an amount of 0.03 to 0.5% by mass, such as 0.06%, 0.09%, 0.12%, 0.16%, 0.19%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4% or 0.45%, and the specific values therebetween are not exhaustive for reasons of brevity and conciseness.

Preferably, the content of the wetting agent in the auxiliary agent is 0.03-1% by mass, such as 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8% or 0.9%, and the specific values therebetween are limited by the space and for the sake of brevity, and the invention is not exhaustive.

Preferably, the leveling agent is contained in the auxiliary agent in an amount of 0.02 to 0.5% by mass, for example, 0.06%, 0.09%, 0.12%, 0.16%, 0.19%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, or 0.45%, and specific values therebetween are not intended to be exhaustive, and for the sake of brevity and conciseness, and the invention is not intended to include the specific values within the scope.

Preferably, the mass percentage content of the pigment in the auxiliary agent is 0.02-1%, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8% or 0.9%, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.

In a second aspect, the present invention provides a method of preparing a peelable stain release coating according to the first aspect, the method comprising: and reacting the aqueous polymer solution with the modified nano adsorption particles to obtain the strippable dirt-removing paint.

Preferably, the reaction temperature is 70-95 ℃, such as 72 ℃, 74 ℃, 76 ℃, 78 ℃, 80 ℃, 82 ℃, 84 ℃, 86 ℃, 88 ℃, 90 ℃, 92 ℃ or 94 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the ranges.

Preferably, the reaction time is 10-240 min, such as 20min, 40min, 60min, 80min, 100min, 120min, 140min, 160min, 180min, 200min or 220min, and the specific values therebetween are limited by space and for the sake of brevity, the invention is not exhaustive of the specific values included in the ranges.

Preferably, the method also comprises the step of adding an auxiliary agent after the reaction is finished.

As a preferred technical scheme, the preparation method comprises the following steps: and (3) reacting the aqueous polymer solution with the modified nano adsorption particles at 70-95 ℃ for 10-240 min, and adding an auxiliary agent to obtain the strippable dirt-removing coating.

In a third aspect, the present invention provides the use of a strippable stain release coating according to the first aspect for cleaning a material surface.

Compared with the prior art, the invention has the following beneficial effects:

(1) the strippable stain-removal coating provided by the invention is successfully prepared by compounding the aqueous polymer solution and the modified adsorption nano material and combining the porous nano material, the nonporous nano material and the complexing agent; compared with the prior art, the strippable decontamination coating provided by the invention has excellent decontamination efficiency and processability, is easy to strip after being coated, has very excellent tensile strength, can be coated on the surface of a base material in a large area by adopting various methods, is convenient to operate, is safe and environment-friendly, can be applied to various base materials, has simple post-treatment, and can remove radionuclide pollution, heavy metal pollution, organic matter pollution and other industrial and civil surface decontamination.

(2) Specifically, the strippable decontamination coating provided by the invention has the decontamination rate of 95.5-99.5%, the tensile strength of 30.3-37.4 MPa, the elongation at break of 195-240%, good film forming physical properties, easy stripping, excellent comprehensive properties and simple post-treatment, and can be used for removing radionuclide pollution, heavy metal pollution, organic matter pollution and the like.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

Preparation example 1

A modified adsorption nano material comprises 0.5g of specific surface area 50m²Active carbon with a pore diameter of 40nm (Aladdin, C299186); 0.5g of nano calcium carbonate (Meclin, C886288) with a particle size of 50nm and 0.25g of citric acid;

the preparation method comprises the following steps: and uniformly mixing the activated carbon, the nano calcium carbonate and the citric acid, putting the mixture into a ball mill, and carrying out ball milling for 5min at the rotating speed of 50r/min to obtain the modified adsorption nano material.

Preparation example 2

The modified adsorption nano material comprises 3g of specific surface area of 800m²(iii) bio-porous carbon with pore size of 15nm (trimeric zekun); 2g specific surface area 1900m²(xi) porous silica with a pore size of 1.5nm (Sienna Rexi); 0.5g of graphene (Xifeng technology, XF 182-1; 1g of nano titanium oxide (Aladdin, T298674) with the particle size of 80nm and 0.25g of ethylenediamine tetraacetic acid) with the thickness of 2nm and the sheet diameter of 2-3 μm;

the preparation method comprises the following steps: uniformly mixing biological porous carbon, porous silicon oxide, graphene, nano titanium oxide and ethylenediamine tetraacetic acid, putting the mixture into a ball mill, and carrying out ball milling for 12min at the rotating speed of 150r/min to obtain the modified adsorption nano material.

Preparation example 3

A modified nanometer adsorption material comprises 4.5g of specific surface area 50m²(xi) g, porous silica with pore size of 25nm (Sienna Rexi); 2g of a specific surface area of 2200m²ZIF-8 (Xian Feng technology, 103042) with a pore size of 0.5 nm; 1.7g of nano-silica (nonapo, CY-SP20) with a particle size of 50nm and 1.5g of nitrilotriacetic acid;

the preparation method comprises the following steps: uniformly mixing porous silicon oxide, ZIF-8, nano silicon oxide and nitrilotriacetic acid, putting the mixture into a ball mill, and carrying out ball milling for 25min at the rotating speed of 220r/min to obtain the modified adsorption nano material.

Preparation example 4

A modified nano-adsorbent material comprises 7.5g of nano-adsorbent material with specific surface area of 50m²A porous carbon sphere (Xian Qie Yue) with a pore diameter of 90 nm; 3g of a specific surface area of 1000m²(ii) porous alumina (crystalline) with a pore size of 3.8 nm; 2.5g of magnesium iron cerium hydrotalcite (Mg-Fe-CeLDH) with the particle size of 100nm and 1.3g of sodium tripolyphosphate;

the preparation method comprises the following steps: uniformly mixing the porous carbon spheres, the porous alumina, the Mg-Fe-Ce LDH and the sodium tripolyphosphate, putting the mixture into a ball mill, and carrying out ball milling for 30min at the rotating speed of 230r/min to obtain the modified adsorption nano material.

Preparation example 5

A modified nano-adsorbent material comprises 5g of nano-adsorbent material with specific surface area of 900m²Activated carbon fibers having a pore diameter of 8nm (Shenyang constant); 0.5g of specific surface area 1800m²(ii) MOF-5 with a pore size of 1nm (Xiancheng technology, 103042); 4.5g of clay (Nanocor, I.44P) having a flake diameter of 200nm and 0.85g of hydroxyethylethylenediaminetriacetic acid;

the preparation method comprises the following steps: uniformly mixing activated carbon fibers, MOF-5, clay and hydroxyethyl ethylenediamine triacetic acid, putting the mixture into a ball mill, and carrying out ball milling for 15min at the rotating speed of 90r/min to obtain the modified adsorption nano material.

Preparation example 6

A modified nano-adsorbent material comprises 5.5g of specific surface area 700m²(xi) g, porous silica with pore size of 24nm (Sienna Rexi); 3.5g of nano calcium carbonate (Jiufen, CY-SP20) with a particle size of 50nm and 1.45g of citric acid;

the preparation method comprises the following steps: uniformly mixing the porous silicon oxide, the nano calcium carbonate and the citric acid, putting the mixture into a ball mill, and carrying out ball milling for 9min at the rotating speed of 70r/min to obtain the modified adsorption nano material.

Preparation example 7

A modified nanometer adsorption material comprises 2.5g of specific surface area 50m²Active carbon with a pore diameter of 40nm (Aladdin, C299186); 0.5g of nano zinc oxide (alatin, Z112849) with the particle size of 50nm and 0.25g of ethylenediamine tetraacetic acid;

the preparation method comprises the following steps: and uniformly mixing the activated carbon, the nano zinc oxide and the ethylene diamine tetraacetic acid, putting the mixture into a ball mill, and carrying out ball milling for 30min at the rotating speed of 70r/min to obtain the modified adsorption nano material.

Preparation example 8

A modified nano-adsorbent material comprises 25g of specific surface area 160m²Porous silicon carbide with a pore size of 35nm (the preparation method is referred to Master's paper sintering preparation process and characteristic research of nano porous silicon carbide; 3.5g nano alumina with a particle size of 10nm (Aladdin, A140296) and 0.5g citric acid;

the preparation method comprises the following steps: and uniformly mixing the porous silicon carbide, the nano-alumina and the citric acid, putting the mixture into a ball mill, and carrying out ball milling for 11min at the rotating speed of 200r/min to obtain the modified adsorption nano-material.

Preparation example 9

A modified adsorption nano material is different from the modified adsorption nano material in example 1 only in that the addition amount of nano calcium carbonate is 0.015g, and other components, the using amount and the preparation method are the same as those of the modified adsorption nano material in the preparation example 1.

Preparation example 10

A modified adsorption nano material is different from the modified adsorption nano material in example 1 only in that the addition amount of nano calcium carbonate is 4.5g, and other components, the using amount and the preparation method are the same as those of the modified adsorption nano material in the preparation example 1.

Preparation example 11

A modified adsorption nanomaterial is different from example 1 only in that the addition amount of nano calcium carbonate is 5g, and other components, the use amount and the preparation method are the same as those of preparation example 1.

Preparation example 12

A modified adsorption nano material is different from the modified adsorption nano material in example 1 only in that the addition amount of nano calcium carbonate is 0.01g, and other components, the using amount and the preparation method are the same as those of the modified adsorption nano material in the preparation example 1.

Comparative preparation example 1

A modified adsorption nano material comprises 1g of specific surface area 50m²Active carbon with a pore size of 40nm (Aladdin, C299186) and 0.25g citric acid;

the preparation method comprises the following steps: and uniformly mixing the activated carbon and the citric acid, putting the mixture into a ball mill, and carrying out ball milling for 5min at the rotating speed of 50r/min to obtain the modified adsorption nano material.

Comparative preparation example 2

A modified adsorption nano material comprises 1g of nano calcium carbonate with the particle size of 50nm and 0.25g of citric acid;

the preparation method comprises the following steps: and uniformly mixing the nano calcium carbonate and the citric acid, putting the mixture into a ball mill, and carrying out ball milling for 5min at the rotating speed of 50r/min to obtain the modified adsorption nano material.

Example 1

A strippable decontamination coating comprises 100g of water, 6g of polyvinyl alcohol (Alatin, 1799), 1.25g of the modified adsorption nano material obtained in preparation example 1 and 0.21g of an auxiliary agent (comprising antifoaming agents (bike, BYK-022), dispersing agents (bike, BYK-190), wetting agents (bike, BYK-348), leveling agents (bike, BYK-307) and pigments (Kunshan color Limited, Annao, with a mass ratio of 1:0.5:1:0.5: 1);

the preparation method comprises the following steps: adding water, polyvinyl alcohol and the modified adsorption nano material obtained in the preparation example 1 into a three-necked bottle, reacting at 95 ℃ for 60min, adding a defoaming agent, a dispersing agent, a wetting agent, a flatting agent and a pigment before the reaction is finished, and stirring to obtain the strippable dirt-removing coating.

Example 2

A strippable decontamination coating comprises 100g of water, 2.5g of waterborne polyurethane (Hunyuan, 3645), 10g of polyvinyl alcohol (Alatin, 1799), 6.75g of modified adsorption nano material obtained in preparation example 2 and 0.5g of auxiliary agent (comprising defoamer (Pic, BYK-022) with the mass ratio of 2:0.5:1:0.5: 1), dispersing agent (Pic, BYK-190), wetting agent (Pic, BYK-348), leveling agent (Pic, BYK-307) and pigment (Kunshan color Limited company, Annaugh);

the preparation method comprises the following steps: adding water, polyvinyl alcohol, waterborne polyurethane and the modified adsorption nano material obtained in the preparation example 2 into a three-necked bottle, reacting at 95 ℃ for 120min, adding a defoaming agent, a dispersing agent, a wetting agent, a flatting agent and a pigment before the reaction is finished, and stirring to obtain the strippable dirt-removing coating.

Example 3

A strippable decontamination coating comprises 100g of water, 1g of chitosan, 10g of polyvinyl alcohol (Alatin, 1799), 9.7g of the modified adsorption nano material obtained in preparation example 3 and 1.5g of an auxiliary agent (comprising defoaming agent (bike, BYK-022), dispersing agent (bike, BYK-190), wetting agent (bike, BYK-348), leveling agent (bike, BYK-307) and pigment (Kunshan color Limited, Annao, with the mass ratio of 1:0.3:1:0.2: 1);

the preparation method comprises the following steps: adding water, polyvinyl alcohol, waterborne polyurethane and the modified adsorption nano material obtained in the preparation example 3 into a three-necked bottle, reacting for 180min at 95 ℃, adding a defoaming agent, a dispersing agent, a wetting agent, a leveling agent and a pigment before the reaction is finished, and stirring to obtain the strippable dirt-removing coating.

Example 4

A strippable decontamination coating comprises 30G of water, 2G of gelatin (alatin, G108398), 5G of polyvinyl alcohol (alatin, 1799), 13.8G of the modified adsorption nano material obtained in preparation example 4 and 2.69G of an auxiliary agent (comprising defoamer (bike, BYK-022) with the mass ratio of 1:0.5:0.5:0.5: 0.5), a dispersing agent (bike, BYK-190), a wetting agent (bike, BYK-348), a leveling agent (bike, BYK-307) and a pigment (Kunshan color Limited company, Annaugh);

the preparation method comprises the following steps: adding water, polyvinyl alcohol, waterborne polyurethane and the modified adsorption nano material obtained in the preparation example 4 into a three-necked bottle, reacting at 95 ℃ for 150min, adding a defoaming agent, a dispersing agent, a wetting agent, a leveling agent and a pigment before the reaction is finished, and stirring to obtain the strippable dirt-removing coating.

Example 5

A strippable decontamination coating comprises 80g of water, 9g of sodium alginate (alatin, S100126), 10g of polyvinyl alcohol (alatin, 1799), 10.85g of the modified adsorption nano material obtained in preparation example 5 and 1.3g of an auxiliary agent (comprising defoamer (BYK, BYK-022) with the mass ratio of 2:0.5:0.5:0.5: 1), a dispersing agent (BYK, BYK-190), a wetting agent (BYK, BYK-348), a leveling agent (BYK, BYK-307) and a pigment (Kunshan color Limited, Ancai);

the preparation method comprises the following steps: adding water, polyvinyl alcohol, waterborne polyurethane and the modified adsorption nano material obtained in the preparation example 5 into a three-necked bottle, reacting at 87 ℃ for 200min, adding a defoaming agent, a dispersing agent, a wetting agent, a leveling agent and a pigment before the reaction is finished, and stirring to obtain the strippable dirt-removing coating.

Example 6

A strippable decontamination coating comprises 4g of water, 15g of modified starch (Innochem, I05375), 20g of polyvinyl alcohol (avastin, 1799), 1.25g of the modified adsorption nano material obtained in preparation example 6 and 1.2g of an auxiliary agent (comprising a defoaming agent (bike, BYK-022) with the mass ratio of 1:0.5:0.4:0.5:0.8, a dispersing agent (bike, BYK-190), a wetting agent (bike, BYK-348), a leveling agent (bike, BYK-307) and a pigment (Kunshan color Limited company, Ancai);

the preparation method comprises the following steps: adding water, polyvinyl alcohol, waterborne polyurethane and the modified adsorption nano material obtained in the preparation example 6 into a three-necked bottle, reacting at 70 ℃ for 240min, adding a defoaming agent, a dispersing agent, a wetting agent, a leveling agent and a pigment before the reaction is finished, and stirring to obtain the strippable dirt-removing coating.

Example 7

A strippable decontamination coating comprises 55g of water, 6g of waterborne polyurethane (Hunyuan, 3645), 18g of chitosan (Aladdin, C105801-), 4.25g of modified adsorption nano-material obtained in preparation example 7 and 0.89g of auxiliary agent (comprising defoamer (birk, BYK-022) with the mass ratio of 2:0.5:0.4:0.2: 0.9), dispersant (birk, BYK-190), wetting agent (birk, BYK-348), leveling agent (birk, BYK-307) and pigment (Kunshan color Limited company, Ancai);

the preparation method comprises the following steps: adding water, chitosan, waterborne polyurethane and the modified adsorption nano material obtained in the preparation example 7 into a three-necked bottle, reacting for 10min at 75 ℃, adding a defoaming agent, a dispersing agent, a wetting agent, a leveling agent and a pigment before the reaction is finished, and stirring to obtain the strippable dirt-removing coating.

Example 8

A strippable decontamination coating comprises 90G of water, 6G of gelatin (alatin, G108398), 20G of sodium alginate (alatin, S100126), 29G of the modified adsorption nano material obtained in preparation example 7 and 7.6G of an auxiliary agent (comprising antifoaming agent (bike, BYK-022), dispersing agent (bike, BYK-190), wetting agent (bike, BYK-348), leveling agent (bike, BYK-307) and pigment (Kunshan color Ltd, Ancai) in a mass ratio of 1.5:0.2:1:0.4: 1);

the preparation method comprises the following steps: adding water, gelatin, sodium alginate and the modified adsorption nano material obtained in the preparation example 8 into a three-necked bottle, reacting for 90min at 95 ℃, adding a defoaming agent, a dispersing agent, a wetting agent, a flatting agent and a pigment before the reaction is finished, and stirring to obtain the strippable decontamination coating.

Examples 9 to 12

The strippable decontamination coating is different from the coating in the embodiment 1 only in that the modified adsorption nano-materials prepared in the preparation examples 9-12 are respectively adopted to replace the modified adsorption nano-materials obtained in the preparation example 1, and other components, the using amounts and the preparation method are the same as those in the embodiment 1.

Example 13

A strippable stain-removing paint is different from the paint in example 2 only in that no waterborne polyurethane is added, the addition amount of polyvinyl alcohol is 12.5g, and other components, the use amount and the preparation method are the same as those in example 1.

Comparative examples 1 and 2

A strippable stain-removal coating is different from example 1 only in that the modified adsorption nano-materials obtained in the preparation example 1 are respectively replaced by the modified adsorption nano-materials obtained in the comparative preparation examples 1 and 2, and other components, the using amounts and the preparation method are the same as those of the example 1.

And (3) performance testing:

10ml of uranium solution with the concentration of 1g/L is coated on a stainless steel sample plate, a cement concrete sample plate, a glass plate, a plastic plate, a tin plate and a wood plate, after the mixture is naturally dried, the strippable decontamination coating obtained in the examples 1-13 and the comparative examples 1-2 is coated on the mixture, the coating thickness is 0.25 mu m, and the coating is formed and stripped after 12 hours to obtain a coating film.

(1) Decontamination rate: and (4) testing the surface pollution level of the sample plate before and after film uncovering by adopting a pollution monitor, and calculating the decontamination rate.

(2) Tensile strength and elongation at break: the coating films were tested according to GBT 13022-1991 method for testing tensile Properties of plastics and films.

The adhesive films formed by the strippable stain-removal coatings obtained in examples 1 to 13, comparative example 1 and comparative example 2 were tested according to the test method, and the test results are shown in table 1:

TABLE 1

As can be seen from the data in table 1: the strippable stain-removal coating provided by the invention has higher stain removal rate, and excellent tensile strength and elongation at break.

Specifically, the stain removal rate of the strippable stain removal coating obtained in the examples 1 to 13 is 95.5 to 99.5%, the tensile strength is 30.3 to 37.4MPa, and the elongation at break is 195 to 240%, which is higher than that of the strippable stain removal coating obtained in the comparative examples 1 and 2 by 4 to 13%, 4 to 39% and 0.5 to 24%, and thus, the strippable stain removal coating with high stain removal rate, high film forming tensile strength and high elongation at break is prepared by selecting and using the combination of three materials, namely the porous nanomaterial, the nonporous nanomaterial and the complexing agent.

Further, comparing examples 1 and 9 to 12, it can be seen that the strippable stain-removal coating obtained by the mass ratio of the porous nanomaterial to the nonporous nanomaterial exceeding 1:9 (example 11) or being less than 1:0.3 (example 12) has a reduced stain removal rate, which means that a coating having an excellent stain removal effect can be obtained only by adding the modified adsorptive nanomaterial consisting of the porous nanomaterial and the nonporous nanomaterial in a specific ratio.

Finally, by observing the film forming effect of the strippable stain-removing coatings obtained in examples 1 and 13, the coating film obtained in example 13 has wrinkles on the surface, is difficult to be flattened, is difficult to be stripped and affects the use effect. The applicant states that the present invention is illustrated by the above examples to provide a soil release coating and a method of making and using the same, but the present invention is not limited to the above examples, i.e. it is not meant to imply that the present invention must be practiced by relying on the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims

1. A strippable stain release coating which is characterized by comprising a combination of an aqueous polymer solution and a modified adsorbent nanomaterial;

the modified adsorption nano material comprises a combination of a porous nano material, a nonporous nano material and a complexing agent;

the porous nano material comprises any one or the combination of at least two of a porous nano carbon material, a porous nano ceramic material or a nano metal organic framework material;

the pore diameter of the porous nano material is 0.5-40 nm.

2. The strippable stain-removal paint as claimed in claim 1, wherein the mass percentage of the aqueous polymer solution in the strippable stain-removal paint is 55-99.3%.

3. The strippable stain-removal coating material of claim 1, wherein the mass percentage of the water-based polymer in the water-based polymer solution is 5-79%.

4. The strippable stain-removal coating material of claim 3, wherein the mass percentage of the water-based polymer in the water-based polymer solution is 15-65%.

5. The peelable stain release coating according to claim 1 wherein the aqueous polymer comprises any one or a combination of at least two of polyvinyl alcohol, polyurethane, chitosan, gelatin, sodium alginate or modified starch.

6. The peelable stain release coating of claim 5 wherein the aqueous polymer is a combination of any two of polyvinyl alcohol, polyurethane, chitosan, gelatin, sodium alginate or modified starch.

7. The strippable stain-removal paint as claimed in claim 1, wherein the mass percentage of the modified adsorption nano material in the strippable stain-removal paint is 0.5-40%.

8. The strippable stain-removal paint as claimed in claim 7, wherein the mass percentage of the modified adsorption nano material in the strippable stain-removal paint is 4-25%.

9. The strippable decontamination coating material of claim 1, wherein the mass ratio of the porous nanomaterial to the nonporous nanomaterial is 1 (0.03-9).

10. The strippable stain-removal coating material of claim 1, wherein the mass ratio of the porous nano material to the complexing agent is 1 (0.016-3).

11. The strippable stain-removal coating material of claim 1, wherein the specific surface area of the porous nanomaterial is 50-2200 m²/g。

12. The strippable stain release coating of claim 1, wherein the porous nanocarbon material comprises any one of activated carbon, biochar, activated carbon fibers or porous carbon spheres, or a combination of at least two of the foregoing.

13. The peelable stain release coating according to claim 1 wherein the porous nanoceramic material comprises any one of or a combination of at least two of porous silica, porous alumina, porous silicon carbide or diatomaceous earth.

14. The peelable stain release coating of claim 1 wherein the nano-metalorganic framework material comprises any one or a combination of at least two of MOF-n, ZIF-n, MLI-n, PCN-n or UIO-n.

15. The peelable stain release coating according to claim 1 wherein the non-porous nanomaterial comprises any one of or a combination of at least two of nano oxides, nano carbonates or two dimensional nanoplatelets.

16. The strippable stain release coating of claim 15 wherein the nano-oxides and nano-carbonates each independently have a particle size of 5 to 350 nm.

17. The peelable stain release coating according to claim 15 wherein the two dimensional nanoplatelets have a platelet size of from 0.005 to 10 μm.

18. The peelable stain release coating according to claim 15 wherein the nano-oxide comprises any one or a combination of at least two of nano-titania, nano-silica, nano-alumina, nano-zinc oxide, nano-iron oxide, nano-zirconia or nano-ceria.

19. The strippable stain release coating of claim 15, wherein the nano-carbonates comprise nano-calcium carbonate and/or nano-magnesium carbonate.

20. The strippable stain release coating of claim 15 wherein the two-dimensional nanoplatelets comprise any one of or a combination of at least two of a double metal hydroxide, graphene, boron nitride or a layered silicate.

21. The strippable stain release coating of claim 20, wherein the layered silicate comprises any one of montmorillonite, clay, bentonite or mica platelets or a combination of at least two thereof.

22. The strippable stain release coating of claim 1 wherein the complexing agent comprises any one or a combination of at least two of ethylenediaminetetraacetic acid, citric acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, tartaric acid, hydroxyethylethylenediaminetriacetic acid, sodium tripolyphosphate, aminotrimethylenephosphonic acid, polyacrylic acid, or polymethacrylic acid.

23. The peelable stain release coating according to claim 1 wherein the modified adsorbent nanomaterial is prepared by a process comprising: and carrying out ball milling on the porous nano material, the nonporous nano material and the complexing agent to obtain the modified nano adsorption material.

24. The strippable stain release coating of claim 23, wherein the ball milling time is 5-50 min.

25. The strippable stain release coating of claim 24, wherein the ball milling time is 9 to 30 min.

26. The strippable dirt-removing paint of claim 23, wherein the ball milling is carried out at a speed of 50-300 r/min.

27. The strippable dirt-removing paint of claim 26, wherein the ball milling is carried out at a rotation speed of 70-230 r/min.

28. The peelable stain release coating according to claim 1 further comprising an adjuvant.

29. The strippable stain-removal paint of claim 28, wherein the mass percentage of the auxiliary agent in the strippable stain-removal paint is 0.2-5%.

30. The strippable stain release coating of claim 28, wherein the adjuvant comprises any one or a combination of at least two of an anti-foaming agent, a dispersing agent, a wetting agent, a leveling agent or a pigment.

31. The strippable stain-removal coating of claim 30, wherein the defoaming agent in the auxiliary is 0.02-2% by mass.

32. The strippable stain-removal coating material of claim 30, wherein the dispersant is 0.03-0.5% by mass of the auxiliary.

33. The strippable stain-removal coating material of claim 30, wherein the wetting agent is contained in the auxiliary agent in an amount of 0.03-1% by mass.

34. The strippable stain-removal coating material of claim 30, wherein the leveling agent is contained in the auxiliary agent in an amount of 0.02-0.5% by mass.

35. The strippable stain-removal paint as claimed in claim 30, wherein the mass percentage of the pigment in the auxiliary is 0.02-1%.

36. A method of preparing the strippable stain-release coating of any one of claims 1 to 35, which comprises: and reacting the aqueous polymer solution with the modified nano adsorption particles to obtain the strippable dirt-removing paint.

37. The method according to claim 36, wherein the reaction temperature is 70 to 95 ℃.

38. The method according to claim 36, wherein the reaction time is 10 to 240 min.

39. The method of claim 36, further comprising the step of adding an auxiliary agent after the reaction is completed.

40. The method of manufacturing of claim 36, comprising: and (3) reacting the aqueous polymer solution with the modified nano adsorption particles at 70-95 ℃ for 10-240 min, and adding an auxiliary agent to obtain the strippable dirt-removing coating.

41. Use of a strippable stain release coating material according to any one of claims 1 to 35 in the cleaning of a material surface.