CN114456671B - Coating and preparation method and application thereof - Google Patents
Coating and preparation method and application thereof Download PDFInfo
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- CN114456671B CN114456671B CN202210143676.0A CN202210143676A CN114456671B CN 114456671 B CN114456671 B CN 114456671B CN 202210143676 A CN202210143676 A CN 202210143676A CN 114456671 B CN114456671 B CN 114456671B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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Abstract
The invention provides a coating and a preparation method and application thereof, belonging to the technical field of chemical decontamination. The coating obtained by the preparation method provided by the invention is composed of acrylic resin emulsion, is coated on the polluted surface when in use, and forms a strippable sheet-shaped object after being solidified, thereby achieving the purpose of decontamination while stripping the sheet-shaped object. The results of the examples show that the coating obtained by the preparation method provided by the invention has the maximum decontamination efficiency of more than 90% for alpha nuclide pollution and decaying nuclide pollution.
Description
The application is a divisional application with an application date of 2020, 08 and 31 months, and an application number of 202010892889.4, namely, a preparation method of the coating and the coating.
Technical Field
The invention relates to the technical field of chemical decontamination, and particularly relates to a coating as well as a preparation method and application thereof.
Background
In the related places of nuclear power stations, facilities, equipment and workshops are easily polluted by radioactive nuclides, and the radioactive nuclide pollution needs to be removed no matter in the operation process of the facilities and the equipment or in the nuclear decommissioning activity, so that the radiation hazard of the radioactive nuclide pollution to workers is reduced, and the safety of the operation environment is improved.
At present, methods for removing radionuclide contamination include physical methods and chemical methods, and the physical methods include laser lift-off, mechanical polishing, spraying, ultrasonic waves, and the like; the chemical method comprises soaking and scrubbing with chemical detergent, which is divided into acidic, alkaline and neutral detergents, and comprises acid, alkali, salt, surfactant, complexing agent, redox agent, etc.
The chemical method for removing radionuclide contamination has certain defects: the chemical detergent contains a large amount of organic solvents, so that the use safety is poor; secondary waste can be generated in the using process, and secondary pollution is easily caused; and has adverse potential hazards (such as corrosion of surfaces) to facilities and equipment. It is necessary to provide a detergent which is highly safe to use and has a good detergency effect.
Disclosure of Invention
The invention provides a coating, a preparation method and application thereof, wherein the coating can be used for radionuclide decontamination. The coating is an acrylic resin emulsion, is coated on the polluted surface when in use, and forms a strippable sheet-like object after being solidified, thereby achieving the purpose of decontamination while stripping the sheet-like object. The embodiment result shows that the coating obtained by the preparation method has decontamination efficiency of more than 90 percent at most for alpha nuclide pollution and decay nuclide pollution.
According to one aspect of the present invention, there is provided a method of preparing a coating material, comprising the steps of:
acrylic resin treatment: dissolving acrylic resin in deionized water, adding ammonia water to obtain an acrylic resin solution, adding an emulsifier into the acrylic resin solution, and performing an emulsification reaction to obtain an acrylic resin emulsion;
the dosage of the deionized water is 2-4 times of that of the acrylic resin, and the dosage of the ammonia water is 0.5-0.6 time of that of the acrylic resin;
preparing the coating: carrying out polymerization reaction on the acrylic resin emulsion, the initiator and the monomer for acrylic resin polymerization, and preparing the coating after the reaction is finished;
the monomers for polymerization are methyl methacrylate, styrene and butyl acrylate;
the molecular weight of the acrylic resin is 2000-5000;
the coating comprises the following raw material components in percentage by mass: 25-35% of acrylic resin, 50-65% of styrene, 5-10% of butyl acrylate, 1-5% of methyl methacrylate, 1-1.5% of initiator and 0.5-1.5% of emulsifier.
In some embodiments, the step of preparing the coating comprises: mixing the acrylic resin emulsion, deionized water and a first preset amount of initiator to obtain an acrylic resin solution; dissolving a second predetermined amount of initiator in deionized water to obtain an initiator solution; heating the acrylic resin solution until the heating temperature is the polymerization reaction temperature; and simultaneously adding the initiator solution and the acrylic resin polymerization monomer into the acrylic resin solution at the polymerization reaction temperature to carry out polymerization reaction.
In some embodiments, the step of preparing the coating comprises: dissolving a third predetermined amount of initiator in deionized water to obtain an initiator solution; heating the acrylic resin emulsion until the heating temperature is the polymerization reaction temperature; and at the polymerization reaction temperature, simultaneously adding the initiator solution and the monomer for acrylic resin polymerization into the acrylic resin emulsion to carry out polymerization reaction.
In some embodiments, the initiator comprises: ammonium persulfate, sodium persulfate, and potassium persulfate;
the emulsifier comprises: octyl phenol polyoxyethylene ether (OP), octyl phenol polyoxyethylene ether-10 (OP-10), sodium dodecyl benzene sulfonate and sodium carboxymethyl cellulose.
In some embodiments, the method of preparing the coating further comprises: after the coating is prepared, the pH value of the coating is adjusted to 7.0-8.0.
In some embodiments, the method of preparing the coating further comprises: after the coating is prepared, adding a chelating agent into the coating; the chelating agent is selected from one or more of amino chelating agent, organic phosphoric acid chelating agent, trisodium zinc diethylenetriamine pentaacetate, disodium ethylenediamine tetraacetate, diethylenetriamine pentaacetic acid and sodium tripolyphosphate.
In some embodiments, the method of preparing the coating further comprises: after the coating is prepared, adding an auxiliary agent into the coating to adjust the viscosity of the coating; the auxiliary agent comprises: sodium silicate, silicon dioxide, calcium carbonate, diatomite, bentonite, polypropylene fiber and sodium stearate.
According to another aspect of the invention, the invention also provides a coating obtained by the technical scheme.
According to another aspect of the invention, the invention also provides the application of the coating obtained by the technical scheme in removing radionuclide contamination. The use in the present invention preferably comprises the following steps: the coating is applied to a contaminated surface and cured to form a peelable sheet.
Drawings
Other objects and advantages of the present invention will become apparent from the following description of the invention which refers to the accompanying drawings, and may assist in a comprehensive understanding of the invention.
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows a schematic diagram of a method of preparing a coating according to an embodiment of the invention;
FIG. 2 shows a schematic diagram of the coating preparation steps according to an embodiment of the invention;
FIG. 3 shows a schematic diagram of the coating preparation steps according to other embodiments of the present invention;
fig. 4 shows a schematic view of a method of preparing a coating material according to other embodiments of the present invention.
It is to be noted that the drawings are not necessarily drawn to scale but are merely shown in a schematic manner which does not detract from the understanding of the reader.
Detailed Description
In order to make those skilled in the art better understand the technical solutions of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless defined otherwise, technical or scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The coating preparation method of the embodiment of the invention prepares an acrylic resin emulsion coating through emulsion polymerization, and unlike the method of directly polymerizing monomers, the invention carries out polymerization on the basis of acrylic resin with relatively small molecular weight so as to obtain the acrylic resin coating with optimized molecular weight, solid content and viscosity. Namely, acrylic resin with relatively small molecular weight is used as a part of reaction raw material, and is treated to have polymerization reaction with monomer. The preparation method of the invention is easy to control the molecular weight, solid content and viscosity of the coating.
For example, the present invention can reduce the final residual amount of the monomer by improving the timing of adding the initiator to influence the polymerization effect of the monomer. The total amount of initiator may be matched to the amount of reactants to be polymerized, on the basis of which the initiator may be added in one portion or in portions, for example by adding a portion of the initiator at one stage of the reaction and the remainder at other stages of the reaction. The invention influences the effect of the acrylic resin raw material and the monomer for acrylic resin polymerization (hereinafter referred to as monomer) to carry out polymerization reaction and influences the reaction efficiency by controlling the adding time, adding amount, adding speed and the like of the initiator.
The invention can control the emulsion state, the strippable degree and the size of the stripped sheet-shaped object of the synthesized acrylic resin by adjusting the types and the adding amounts of the hard monomer, the soft monomer and the auxiliary agent.
The present invention can provide a coating material prepared based on the above preparation method. The coating is water-based and has certain viscosity, when in use, the coating can be sprayed on the polluted surface by a machine or manually, after being dried, the coating forms solidified sheet-like objects on the polluted surface, and the sheet-like objects can be peeled off under the action of self gravity or manual action, so that pollutants can be removed together. Therefore, the coating is convenient to use, does not need to be cleaned or washed after being used, the stripped flaky objects can be cleaned by the sweeping robot so as to reduce the radiation dose level of workers, secondary waste and pollution are not generated in the use process of the coating, and the use safety and the environmental protection are higher. In some embodiments, the coating contains chelating agent, complexing agent, etc. to enhance the chemical force with the pollutant so as to exchange and adsorb the pollutant. In some embodiments, the coating has a suitable solid content and a viscosity that ensures that when the coating is applied to a contaminated surface, particularly a vertical surface (i.e., a direction toward the ground), the coating does not drip due to its high fluidity, thereby increasing coverage of the contaminated surface and increasing soil removal.
In one embodiment, there is provided a method of preparing a coating, comprising: acrylic resin treatment: dissolving acrylic resin to obtain acrylic resin dissolved solution, adding an emulsifier into the acrylic resin dissolved solution, and performing an emulsification reaction to obtain acrylic resin emulsion; preparing the coating: and carrying out polymerization reaction on the acrylic resin emulsion, the initiator and the monomer for acrylic resin polymerization, and preparing the coating after the reaction is finished.
Referring to fig. 1, the preparation method of the coating of the embodiment of the invention is simple to operate, and the reaction raw materials include acrylic resin and monomers, and the coating of the invention is prepared by emulsion polymerization under the action of the initiator. Among them, usable acrylic resins have relatively small molecular weights, for example, 2000 to 5000, and on this basis, the molecular weight of the coating (acrylic resin emulsion) formed by polymerization is increased, for example, 10000 to 20000. The kind of the raw material acrylic resin used in the present invention is not limited herein.
The coating prepared by the method is water-based, so that deionized water is used as a solvent in the preparation process. For example, in the acrylic resin treatment step, an appropriate amount of ammonia water may be added to deionized water to dissolve the acrylic resin, and an emulsifier may be added to emulsify the resin.
In some embodiments, the timing and amount of the initiator can be controlled to optimize monomer conversion and improve polymerization. Referring to fig. 2, a schematic diagram of the coating preparation steps according to an embodiment of the present invention is shown. The preparation method of the coating comprises the following steps: mixing acrylic resin emulsion, deionized water and a first preset amount of initiator to obtain acrylic resin solution; dissolving a second predetermined amount of initiator in deionized water to obtain an initiator solution; heating the acrylic resin solution until the heating temperature is the polymerization reaction temperature; at the polymerization temperature, an initiator solution and an acrylic resin polymerization monomer are added to an acrylic resin solution at the same time to carry out polymerization.
For example, a portion of the initiator is added to the acrylic resin emulsion, the acrylic resin solution is added to the reactor first, and when the temperature of the reactor rises to the polymerization temperature, the initiator solution (i.e., another portion of the initiator) and the monomer are added to the reactor at the same time, and the monomer undergoes polymerization reaction, and the coating is formed after the reaction. Wherein the total amount of initiator may be the sum of the amounts of the first and second predetermined amounts of initiator. The amount of the first predetermined amount of initiator may be less than the amount of the second predetermined amount of initiator. The amount of initiator solution formed by the second predetermined amount of initiator may be adapted to the amount of monomer feed so that both are added simultaneously at a suitable rate. The rate of addition of the initiator solution may be less than the rate of addition of the monomer. The rate of addition of the initiator solution may be proportional to the rate of addition of the monomer to ensure adequate reaction of the monomer.
In some embodiments, the initiator has other timing and amounts of addition. Referring to fig. 3, a schematic diagram of the steps of preparing a coating according to other embodiments of the present invention is shown. The preparation method of the coating comprises the following steps: dissolving a third predetermined amount of initiator in deionized water to obtain an initiator solution; heating the acrylic resin emulsion until the heating temperature is the polymerization reaction temperature; at the polymerization reaction temperature, an initiator solution and an acrylic resin polymerization monomer are added into the acrylic resin emulsion at the same time to carry out polymerization reaction.
For example, the initiator is added only during the stage in which polymerization occurs. The third predetermined amount of initiator is used as the total amount of initiator. The third predetermined amount of initiator is the sum of the first predetermined amount of initiator and the second predetermined amount of initiator.
Initiators according to embodiments of the invention include: ammonium persulfate, sodium persulfate, and potassium persulfate.
It is understood that, in addition to the above-mentioned timing and amount of addition of the initiator affecting the quality of the coating material to be produced, the kind and amount of addition of the monomer raw material are also one of factors affecting the quality of the coating material. The monomer of the embodiment of the present invention includes a first monomer, also referred to as a hard monomer, which is used to improve the cohesion of the coating material, the hardness of a sheet formed after the coating material is dried, and the like; the second monomer, also known as a soft monomer, is used to improve the tack, extensibility, and durability of the coating. The first monomer and the second monomer are used in a matching way, so that the coating prepared by polymerization reaction has proper performance, before use, the coating is uniform emulsion and can be sprayed to a polluted surface, a sheet-shaped object is formed after solidification, and the sheet-shaped object is easy to peel under the self-weight or manual action.
The first monomer includes, for example, methyl methacrylate, styrene, methyl acrylate, hydroxypropyl acrylate. The second monomer includes, for example, butyl acrylate, ethyl acrylate, isooctyl acrylate. The monomer used for the reaction may include only the first monomer. The monomer used for the reaction may include only the second monomer. Alternatively, the monomers used for the reaction may include both the first monomer and the second monomer. When a plurality of monomers are selected, the proportion among the monomers can be adjusted.
When the monomer reacts with the acrylic resin having a relatively small molecular weight, the amount of the monomer may be greater than that of the acrylic resin. By controlling the dosage ratio of the two, the initial molecular weight of the acrylic resin, the types of the monomers, the composition of the monomers and the like, the coating with proper molecular weight and solid content (the coating is in an emulsion state) is prepared, and the coating is not easy to drip before drying and easy to peel after drying in the using process.
According to the preparation method of the coating, the prepared coating can be used as a detergent. For example, in removing radionuclide contamination, decontamination mechanisms include: surface adsorption, in which the coating sprayed on facilities and equipment coats pollutants due to the action of surface adsorption force before curing, so that the pollutants become a part of a film formed by the sprayed coating; the viscosity of the coating is such that the coating can take away pollutants when peeled off after being cured; the chemical acting force, the components such as complexing agent, chelating agent and the like in the coating and the ionic pollutants have the functions of ion exchange, complexation, chemical bonding and the like, and the pollutants are taken away when the coating is stripped after being cured.
In some cases, contaminants that have penetrated into the substrate or into the crystal lattice can be readily reacted with the contaminants by enhancing the adsorption or chemical action of the coating.
It can be appreciated that the performance of the coating can be adaptively optimized in different application scenarios. Referring to fig. 4, a schematic diagram of a coating preparation method according to other embodiments of the present invention is shown. In contrast to the method of preparing the dope in FIG. 1, after the dope is prepared after the polymerization reaction, the pH of the dope may be adjusted to be weakly alkaline, for example, 7.0 to 8.0. Useful pH adjusters include ammonia, sodium bicarbonate, ammonium bicarbonate, sodium hydroxide, potassium hydroxide.
In some embodiments, a chelating agent may be added to the coating to further ion exchange and complex with the contaminants, corresponding to the type of contaminants to be removed, e.g., where the contaminants are in a mostly ionic form. The chelating agent may include amino chelating agent, organic phosphoric acid chelating agent, trisodium zinc salt of diethylenetriaminepentaacetic acid, sodium tripolyphosphate, and disodium ethylenediaminetetraacetate. Of course, other functional additives, such as film forming additives, can be added to the paint in order to more easily adsorb or coat the contaminants and thus improve the decontamination rate.
In some embodiments, to adjust the solids/viscosity of the coating, additives are added to the coating, and the types of additives include sodium silicate, silica, calcium carbonate, diatomaceous earth, bentonite, polypropylene fiber, and sodium stearate. The auxiliary agent can also be other curing agents.
It can be understood that the viscosity of the coating is a key factor influencing the use effect, and when the viscosity is lower, the fluidity is higher, and when the coating is applied to a vertical surface, the coating is easy to fall off (before curing); when the viscosity is high, the coating may not be easily peeled off (at least not easily peeled off by itself) after curing, which increases the workload and reduces the working efficiency. Therefore, it is important to ensure that the viscosity of the coating is moderate.
The type and the adding amount of the auxiliary agent can be adjusted according to actual conditions so as to adjust the state of the coating and the size of a sheet-shaped body (namely a shedding sheet) formed after the coating is cured, the state of the coating can be in an emulsion state or a paste state, for example, in some cases, the coating can be in a paste state so as to be convenient for decontamination of vertical surfaces, and the coating can not flow due to high fluidity after being coated on the surface, so that the pollution coverage of the coating is ensured. In some cases, the aid may be, for example, polypropylene filaments to adjust the size of the sheet to be shed.
According to the preparation of the coating, the state of the synthesized coating can be improved by adjusting the types and the using amounts of the hard monomer and the soft monomer for polymerization, so that the coating is in an emulsion state or a paste state and is suitable for different decontamination surfaces. Furthermore, an auxiliary agent can be added into the coating to improve the state of the coating and the size of a piece to be peeled after the coating is cured. The coating prepared by the invention can form flakes to be peeled off after being cured, so that in most cases, after the coating is coated on a polluted surface, a plurality of split flakes are formed by curing under natural conditions, and the flakes can be easily peeled off. The coating is different from the film-shaped detergent in the prior art, most of the detergent is organic components, and secondary pollution is easily caused.
The following description is given with reference to specific examples in order to better understand the technical solutions of the present invention for those skilled in the art.
Example 1:
the raw materials for preparing the coating comprise:
acrylic resins, for example having a molecular weight of 2000 to 5000;
monomers including a first monomer and/or a second monomer;
an initiator;
additive: comprises an emulsifier, a pH regulator, a chelating agent, an auxiliary agent and the like.
The preparation method of the coating comprises the following steps:
(1) Acrylic resin treatment: dissolving acrylic resin in deionized water, and adding a proper amount of ammonia water; after the acrylic resin is fully dissolved, adding an emulsifier, stirring and emulsifying for 20-30min to form acrylic resin emulsion;
wherein the dosage of the deionized water is 2-4 times of the dosage of the acrylic resin, and the dosage of the ammonia water is 0.5-0.6 time of the dosage of the acrylic resin;
(2) Monomer pretreatment: when the monomer contains styrene, washing the styrene by using an aqueous solution of 20% sodium chloride and 5% sodium hydroxide to remove impurities;
(3) Polymerization reaction: uniformly mixing the acrylic resin emulsion obtained in the step (1), deionized water and a part of initiator to obtain an acrylic resin solution;
dissolving the rest amount of initiator in deionized water and ammonia water to form an initiator solution;
adding an acrylic resin solution into the reactor under the stirring condition, and heating the reactor;
when the temperature of the reactor is raised to 80-90 ℃, simultaneously adding an initiator solution and a monomer into the reactor, wherein the addition speeds of the monomer and the initiator solution are ensured to be adapted and tend to be stable, so that the monomer and the initiator solution are simultaneously and completely added into the reactor in the reaction time;
controlling the reaction time, after the reaction is finished, keeping the temperature of the reactor at 80-90 ℃ for 2h, naturally cooling to room temperature, and filtering to prepare coating emulsion;
wherein the dosage of the monomer is 2-4 times of that of the acrylic resin;
(4) Optimizing the performance of the coating: adjusting the pH of the coating emulsion obtained in the step (3) by using a pH regulator to make the pH value to be 7.0-8;
adding a chelating agent at normal temperature and normal pressure, ultrasonically stirring for 15-20min, and standing for 2-5h to obtain the acrylic resin coating.
The mass percentages of the raw material components can be as follows: 25-35% of acrylic resin, 50-65% of styrene, 5-10% of butyl acrylate, 1-5% of methyl methacrylate, 1-1.5% of initiator and 0.5-1.5% of emulsifier.
The properties of the coating prepared by the preparation method are as follows:
appearance, state: milky white, uniform and stable emulsion;
-acid-base: alkalescence;
-solid content: 40-65%;
-storing: the package can be kept for 6-24 months under the condition of intact package;
-stain removal characteristics: after curing, a sheet is formed and can be stripped.
When the coating is used and pollutants in different scenes are treated, the solid content and the state of the coating can be adjusted by adding an auxiliary agent such as a curing agent, and the viscosity of the coating can be adjusted by adding the auxiliary agent or diluting the auxiliary agent with water, so that the emulsion state (such as emulsion state and paste state), the spraying effect, the curing time, the strippability and the like of the coating can be improved.
Example 2:
on the basis of the example 1, after the coating emulsion is prepared through the step (4), the auxiliary agent such as silica, calcium carbonate, diatomite and the like is added into the emulsion under neutral or alkaline conditions, the state of the emulsion is adjusted, for example, when the coating is used for decontaminating vertical surfaces (such as wall surfaces), the solid content of the coating emulsion is improved through adding the auxiliary agent, the fluidity of the coating emulsion is reduced, or the coating is formed into a paste state, so that the coating is favorably dispersed on the contaminated surfaces, the covering effect of the contaminated surfaces is improved, and the decontamination rate is improved.
Example 3:
the difference from example 2 is that: in step (3), all the initiator is in the polymerization stage and the monomer is added to the reactor at the same time.
Example 4:
the using method of the coating prepared by the method comprises the following steps:
1) When the pollutant adsorption effect of the pollutant adsorbed on the facilities, equipment or workplaces is weak (such as the condition of short pollution time), the coating is applied to Co by adopting a spraying (electric, pneumatic and the like) or manual brushing method 60 、Cs 137 Etc. the polluted substrate surface, the properties of the substrate comprise metal, ground, acrylic, etc.;
the coating is solidified to form a sheet-shaped object, and the sheet-shaped object is recovered and treated after being automatically dropped or manually stripped.
2) When the adsorption of the pollutants is strong (for example, the polluted time is long), a layer of common acidic, neutral or alkaline detergent can be sprayed on the polluted surface in advance in a spraying mode, and after the polluted surface is kept still for 15-20min, the polluted surface is treated and decontaminated by using the coating of the invention when the adsorption of the pollutants is weakened and becomes loose.
For example, for alpha nuclide pollution and decay nuclide pollution, the maximum decontamination efficiency can reach more than 90 percent by using the coating of the invention.
Example 5:
the coatings prepared using the raw materials of different compositions differed in their properties and the results were as follows.
The method of preparing the coating was the same as that of example 2.
TABLE 1 Properties of coatings prepared using different compositions of raw materials
Description of the addition of the initiator:
comparative example 1: 1.0g of initiator is added into the acrylic resin emulsion; the amount of the initiator in the initiator solution was 1.0g.
Comparative example 2: the amount of the initiator added to the acrylic resin emulsion was 0.75g; the initiator in the initiator solution was 1.0g.
Comparative example 3: the amount of the initiator added to the acrylic resin emulsion was 0.75g; the amount of the initiator in the initiator solution was 1.0g.
As can be seen from table 1, the coating of the present invention can be used to remove various types of radionuclide contamination, such as: alpha nuclide pollution, beta nuclide pollution, gamma nuclide pollution, co 60 、Cs 137 Nuclide contamination, and the like.
For example, in comparative example 2, the state and performance of the coating can be comprehensively improved and the decontamination rate can be improved by matching appropriate amounts of the hard monomer and the soft monomer and using an auxiliary agent in combination.
It is understood that other raw material amounts, types, etc. may also affect the quality of the coating.
Example 6:
as mentioned above, the timing of the initiator addition affects the polymerization effect, and the monomer conversion was measured under different reaction conditions, as shown in Table 2.
TABLE 2 monomer conversion under different reaction conditions
| Item | Reaction raw material | Preparation method | Monomer conversion/% | Decontamination efficiency/%) |
| Comparative example 4 | The formulation of comparative example 2 was used | Preparation method of example 2 was used | 94-98 | The one-time decontamination efficiency is more than 95 percent |
| Comparative example 5 | The formulation of comparative example 2 was used | Preparation method of example 3 was used | 85-95 | The one-time decontamination efficiency is more than 90 percent |
As can be seen from Table 2, in comparative example 4, the monomer conversion was high and the stain-removing effect of the coating material was good. Namely, in the process of preparing the coating, the initiator with the same amount is added at different time, and the prepared coating has different decontamination effects. The effect of polymerization reaction of monomers is promoted by controlling the proportion of the total dosage and the adding dosage of the initiator, so that the molecular weight and the solid content of the prepared coating are influenced, and the quality of the coating is improved.
It should also be noted that, in the case of the embodiments of the present invention, the features of the embodiments and examples may be combined with each other to obtain new embodiments, and the coatings with different properties may be combined according to a certain ratio to obtain new embodiments.
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and the scope of the present invention is subject to the scope of the claims.
Claims (9)
1. The preparation method of the coating is characterized by comprising the following steps:
acrylic resin treatment: dissolving acrylic resin in deionized water, adding ammonia water to obtain an acrylic resin solution, adding an emulsifier into the acrylic resin solution, and performing an emulsification reaction to obtain an acrylic resin emulsion;
the using amount of the deionized water is 2 to 4 times of that of the acrylic resin, and the using amount of the ammonia water is 0.5 to 0.6 time of that of the acrylic resin;
preparing the coating: carrying out polymerization reaction on the acrylic resin emulsion, an initiator and a monomer for acrylic resin polymerization, and adding a chelating agent after the reaction is finished to prepare the coating;
the chelating agent is selected from one or more of an amino chelating agent, an organic phosphate chelating agent, trisodium zinc diethylenetriaminepentaacetate, sodium tripolyphosphate and disodium ethylenediamine tetraacetate;
the monomers for polymerization are methyl methacrylate, styrene and butyl acrylate;
the molecular weight of the acrylic resin is 2000 to 5000;
the coating comprises the following raw material components in percentage by mass: 25 to 35 percent of acrylic resin, 50 to 65 percent of styrene, 5 to 10 percent of butyl acrylate, 1 to 5 percent of methyl methacrylate, 1 to 1.5 percent of initiator and 0.5 to 1.5 percent of emulsifier.
2. The method of preparing a coating according to claim 1, wherein the step of preparing the coating comprises:
mixing the acrylic resin emulsion, deionized water and a first preset amount of initiator to obtain an acrylic resin solution;
dissolving a second predetermined amount of initiator in deionized water to obtain an initiator solution;
heating the acrylic resin solution until the heating temperature is the polymerization reaction temperature;
and simultaneously adding the initiator solution and the acrylic resin polymerization monomer into the acrylic resin solution at the polymerization reaction temperature to carry out polymerization reaction.
3. The method of claim 1, wherein the step of preparing the coating comprises:
dissolving a third predetermined amount of initiator in deionized water to obtain an initiator solution;
heating the acrylic resin emulsion until the heating temperature is the polymerization reaction temperature;
and simultaneously adding the initiator solution and the acrylic resin polymerization monomer into the acrylic resin emulsion at the polymerization reaction temperature to carry out polymerization reaction.
4. The method for producing a paint according to any one of claims 1 to 3, wherein,
the initiator comprises the following components: ammonium persulfate, sodium persulfate, and potassium persulfate;
the emulsifier comprises: octyl phenol polyoxyethylene ether, octyl phenol polyoxyethylene ether-10, sodium dodecyl benzene sulfonate and sodium carboxymethyl cellulose.
5. The method of preparing a coating according to claim 1, wherein the step of preparing the coating further comprises:
after the coating is prepared, the pH value of the coating is adjusted to be 7.0-8.0.
6. The method for preparing a dope according to claim 2 or 3, further comprising:
after the coating is prepared, adding an auxiliary agent into the coating, and adjusting the viscosity of the coating;
the auxiliary agent comprises: sodium silicate, silicon dioxide, calcium carbonate, diatomite, bentonite, polypropylene fiber and sodium stearate.
7. A paint prepared by the method for preparing the paint according to any one of claims 1 to 6.
8. Use of the coating of claim 7 for removing radionuclide contamination.
9. Use according to claim 8, characterized in that it comprises the following steps: and (3) applying the coating to a polluted surface, curing to form a strippable sheet, and stripping the sheet.
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