Environment-friendly water-based paint, and preparation method and application thereof
阅读说明：本技术 一种环保水性漆、其制备方法及应用 (Environment-friendly water-based paint, and preparation method and application thereof ) 是由 黄宏存 胡远南 朱清梅 陈招强 于 2021-08-23 设计创作，主要内容包括：本发明提供了一种环保水性漆,包括：环氧丙烯酸酯20～30重量份；丙烯酸酯类单体5～10重量份；聚氨酯5～10重量份；氧化石墨烯0.5～3重量份；丙烯酸类单体0.1～0.5重量份；烷基二醇二丙烯酸酯类单体1～5重量份；乳化剂0.1～0.5重量份；引发剂0.1～0.2重量份；电解质0.01～0.05重量份；水45～70重量份。与现有技术相比,本发明利用聚氨酯中的碳碳双键和环氧丙烯酸酯分子进行接枝共聚,形成互穿网络结构,结构表面富集极性键使氧化石墨烯具有很好的分散效果,并使涂层固化后具有很强的内聚力,可以达到防水效果,同时其粘结力大、涂层密实具有很好的防腐性能；再者氧化石墨烯石墨烯可起到阻燃的作用。(The invention provides an environment-friendly water-based paint, which comprises the following components: 20-30 parts by weight of epoxy acrylate; 5-10 parts by weight of an acrylate monomer; 5-10 parts by weight of polyurethane; 0.5-3 parts by weight of graphene oxide; 0.1 to 0.5 part by weight of an acrylic monomer; 1-5 parts by weight of an alkyl glycol diacrylate monomer; 0.1-0.5 part by weight of an emulsifier; 0.1-0.2 parts by weight of an initiator; 0.01-0.05 parts by weight of electrolyte; 45-70 parts of water. Compared with the prior art, the carbon-carbon double bond in polyurethane and epoxy acrylate molecules are used for graft copolymerization to form an interpenetrating network structure, and the enriched polar bonds on the surface of the structure enable graphene oxide to have a good dispersion effect and enable a coating to have strong cohesive force after being cured, so that a waterproof effect can be achieved, and meanwhile, the adhesive force is large, the coating is dense and has good corrosion resistance; moreover, the graphene oxide and graphene can play a flame-retardant role.)
1. An environment-friendly water-based paint, characterized by comprising:
2. the environment-friendly water-based paint according to claim 1, wherein the acrylate monomer is selected from one or more of methyl acrylate, methyl methacrylate, ethyl acrylate and ethyl methacrylate;
the acrylic monomer is selected from acrylic acid and/or methacrylic acid;
the alkyl glycol diacrylate monomer is selected from triethylene glycol dimethacrylate.
3. The environment-friendly aqueous paint according to claim 1, wherein the emulsifier is selected from sodium dodecyl sulfate and/or sodium dodecyl benzene sulfonate;
the initiator is selected from sodium persulfate and/or potassium persulfate;
the electrolyte is selected from sodium chloride and/or potassium chloride.
4. The environment-friendly water-based paint according to claim 1, further comprising 0.01-0.2 part by weight of a defoaming agent; the defoaming agent is selected from polyoxypropylene glycerol ether and/or organic silicon.
5. The environmentally friendly aqueous paint according to claim 1, comprising:
6. a method for preparing the environment-friendly water-based paint according to claim 1, which comprises:
mixing epoxy acrylate, an acrylate monomer, polyurethane, an emulsifier and water, heating, adding the acrylate monomer and an alkyl glycol diacrylate monomer, adding graphene oxide, and finally adding an initiator and an electrolyte to obtain the environment-friendly water-washing paint.
7. The preparation method according to claim 6, wherein the rotation speed of the mixing is 600-700 rpm; the heating temperature is 88-90 ℃;
the addition of the acrylic ester monomer and the alkyl glycol diacrylate monomer is controlled to be finished within 30-60 min;
and the initiator and the electrolyte are added within 1-1.5 h.
8. The preparation method of claim 6, wherein after the graphene oxide is added, the constant temperature is kept for 20-40 min, and then the initiator and the electrolyte are added;
and (3) adding an initiator and electrolyte, cooling to below 40 ℃, and adding a defoaming agent to obtain the environment-friendly water-based paint.
9. The use of the environmentally friendly water-based paint according to any one of claims 1 to 5 or the environmentally friendly water-based paint prepared by the preparation method according to any one of claims 6 to 8 as a wood coating.
10. The application of claim 9, wherein the coating amount of the environment-friendly water-based paint on the wood surface is 1-3 g/m2。
Technical Field
The invention belongs to the technical field of water-based paint, and particularly relates to environment-friendly water-based paint, and a preparation method and application thereof.
Background
With the development of economy and the continuous improvement of living standard, people pay more and more attention to living environment, and the wood structure house is not limited in rural areas at present and is gradually accepted by cities. Meanwhile, the energy consumption and energy conservation of ecological buildings are more and more emphasized by the nation, and particularly, the functional buildings in natural conservation areas and forest parks of the nation are generally in wooden structures so as to take the natural place and finally return to the natural place.
The wood structure house has the advantages of low construction cost, short construction period, environment-friendly development and the like, but the surface of the wood structure has some defects to be perfect, such as water resistance, corrosion resistance, safety, fire resistance and the like. At present, common wood paint on the market is solvent-based wood paint, a layer of wood paint is coated on the surface of a wood board to achieve the waterproof and anticorrosive effects, but the solvent-based wood paint easily generates volatile toxic gas, is harmful to human bodies and is not environment-friendly. Therefore, it is necessary to develop a water-based paint with good usability and environmental friendliness to replace the solvent-based wood paint currently used in the market.
Chinese patent publication No. CN107964308A discloses an environment-friendly wood coating, which is composed of polymethacrylic acid emulsion, deionized water, titanium dioxide, silicone glycol, sodium alginate, polyurethane, hydroxyethyl cellulose and hydroxy fluorocarbon resin, and the formed coating has the characteristics of fire resistance, moisture resistance and the like, but the fluorocarbon resin, which is the main raw material of the coating, often has the problem of poor adhesion in the application of the coating, thereby affecting the protection of the coating on wood.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an environment-friendly water-based paint having good waterproof, anticorrosive and fireproof effects on wood, and a preparation method and an application thereof.
The invention provides an environment-friendly water-based paint, which comprises the following components:
preferably, the acrylate monomer is selected from one or more of methyl acrylate, methyl methacrylate, ethyl acrylate and ethyl methacrylate;
the acrylic monomer is selected from acrylic acid and/or methacrylic acid;
the alkyl glycol diacrylate monomer is selected from triethylene glycol dimethacrylate.
Preferably, the emulsifier is selected from sodium dodecyl sulfate and/or sodium dodecyl benzene sulfonate;
the initiator is selected from sodium persulfate and/or potassium persulfate;
the electrolyte is selected from sodium chloride and/or potassium chloride.
Preferably, the coating also comprises 0.01 to 0.2 weight part of defoaming agent; the defoaming agent is selected from polyoxypropylene glycerol ether and/or organic silicon.
Preferably, the method comprises the following steps:
the invention also provides a preparation method of the environment-friendly water-based paint, which comprises the following steps:
mixing epoxy acrylate, an acrylate monomer, polyurethane, an emulsifier and water, heating, adding the acrylate monomer and an alkyl glycol diacrylate monomer, adding graphene oxide, and finally adding an initiator and an electrolyte to obtain the environment-friendly water-washing paint.
Preferably, the rotation speed of the mixing is 600-700 rpm; the heating temperature is 88-90 ℃;
the addition of the acrylic ester monomer and the alkyl glycol diacrylate monomer is controlled to be finished within 30-60 min;
and the initiator and the electrolyte are added within 1-1.5 h.
Preferably, after adding the graphene oxide, keeping the constant temperature for 20-40 min, and then adding the initiator and the electrolyte;
and (3) adding an initiator and electrolyte, cooling to below 40 ℃, and adding a defoaming agent to obtain the environment-friendly water-based paint.
The invention also provides application of the environment-friendly water-based paint as a wood coating.
Preferably, the coating weight of the environment-friendly water-based paint on the surface of the wood is 1-3 g/m2。
The invention provides an environment-friendly water-based paint, which comprises the following components: 20-30 parts by weight of epoxy acrylate; 5-10 parts by weight of an acrylate monomer; 5-10 parts by weight of polyurethane; 0.5-3 parts by weight of graphene oxide; 0.1 to 0.5 part by weight of an acrylic monomer; 1-5 parts by weight of an alkyl glycol diacrylate monomer; 0.1-0.5 part by weight of an emulsifier; 0.1-0.2 parts by weight of an initiator; 0.01-0.05 parts by weight of electrolyte; 45-70 parts of water. Compared with the prior art, the carbon-carbon double bond in polyurethane and epoxy acrylate molecules are used for graft copolymerization, the molecular chains of the carbon-carbon double bond and the epoxy acrylate molecules penetrate and are entangled with each other to form an interpenetrating network structure, polar bonds such as carbamate and the like are enriched on the surface of the structure, and the polar bonds can interact with oxygen-containing functional groups on the surface of graphene oxide, so that the graphene oxide has a good dispersion effect, the emulsion has good service performance, the coating has good mechanical performance, the coating has strong cohesion after being cured, the molecular structure is compact, water molecules cannot penetrate through the coating, the waterproof effect can be achieved, meanwhile, the adhesive force is large, the mechanical strength is high, the coating is compact, the anti-corrosion performance is good, and the service life of a house is greatly prolonged; moreover, because the thermal isolation of self lamellar structure, the graphene oxide is isolated or the heat exchange is carried out on the surface of polymer and the outside under the condition that the base body is heated, thereby reducing the combustion heat release rate of combustible materials and playing a role in flame retardance.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to 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.
The invention provides an environment-friendly water-based paint, which comprises the following components:
in the present invention, the sources of all raw materials are not particularly limited, and they may be commercially available.
The content of the epoxy acrylate in the environment-friendly water-based paint provided by the invention is preferably 20-28 parts by weight; in the embodiment provided by the invention, the content of the epoxy acrylate is specifically 20 parts by weight, 25 parts by weight or 28 parts by weight; the epoxy acrylate is obtained by the esterification reaction of epoxy resin and acrylic acid or methacrylic acid, and the molecular weight is preferably about 158-187; in the embodiment provided by the invention, the epoxy acrylate is specifically epoxy acrylate produced by Xiamen Kema chemical Co., Ltd, and the grade is PE 110.
The content of the acrylate monomer is preferably 5-9 parts by weight; in the embodiment provided by the invention, the content of the acrylate monomer is specifically 5 parts by weight, 7 parts by weight or 9 parts by weight; the acrylic ester monomer is preferably one or more of methyl acrylate, methyl methacrylate, ethyl acrylate and ethyl methacrylate; in the embodiment provided by the invention, the acrylate monomer is ethyl methacrylate.
The content of the polyurethane is preferably 5-9 parts by weight; in the examples provided by the present invention, the content of the polyurethane is specifically 5 parts by weight, 7 parts by weight, or 9 parts by weight; according to the invention, the dispersion effect of graphene oxide is improved mainly by crosslinking epoxy acrylate molecules and polyurethane molecules, so that the emulsion has excellent performance; therefore, the mass of the polyurethane is preferably 20 to 35 percent, more preferably 25 to 35 percent, and even more preferably 25 to 32 percent of the mass of the epoxy acrylate; in the embodiment provided by the invention, the mass of the polyurethane is preferably 25%, 28% or 32% of the mass of the epoxy acrylate; the elongation at break of the polyurethane is preferably 300-800%; in the present invention, the kind of the polyurethane is preferably polyurethane produced by Shanghai Tuodede industries, Ltd., and the brand is M5355A-M5374D.
The content of the graphene oxide is preferably 0.5-2.5 parts by weight; in the embodiment provided by the invention, the content of the graphene oxide is specifically 0.5 part by weight, 1.5 parts by weight or 2.5 parts by weight; the graphene oxide is of a multilayer sheet structure, and the surface of the graphene oxide contains a large number of oxygen functional groups, so that the graphene oxide can achieve a good dispersion effect only by interacting with a large number of molecules containing polar bonds. Therefore, in the invention, the carbon-carbon double bond in polyurethane and the epoxy acrylate molecule are used for graft copolymerization, the molecular chains of the polyurethane and the epoxy acrylate molecule are mutually penetrated and intertwined to form an interpenetrating network structure, the surface of the structure is enriched with polar bonds such as carbamate and the like, and the polar bonds can interact with oxygen-containing functional groups on the surface of graphene oxide, so that the graphene oxide has a good dispersion effect, the emulsion has good service performance, and the coating has good mechanical performance.
The content of the acrylic monomer is preferably 0.1-0.45 part by weight; in the examples provided by the present disclosure, the acrylic monomer is specifically included in an amount of 0.1 parts by weight, 0.25 parts by weight, or 0.45 parts by weight; the kind of the acrylic monomer is preferably acrylic acid and/or methacrylic acid; in the embodiment provided by the invention, the acrylic monomer is methacrylic acid.
The content of the alkyl glycol diacrylate monomer is preferably 2-4 parts by weight; in the embodiment provided by the invention, the content of the alkyl diol diacrylate monomer is specifically 2 parts by weight, 3 parts by weight or 4 parts by weight; the kind of the alkyl diol diacrylate monomer is preferably triethylene glycol dimethacrylate.
The content of the emulsifier is preferably 0.1-0.4 part by weight; in the examples provided by the present invention, the content of the emulsifier is specifically 0.1 part by weight, 0.25 part by weight, or 0.4 part by weight; the emulsifier is not particularly limited as long as it is well known to those skilled in the art, and in the present invention, alkyl sulfate and/or alkylbenzene sulfonate are preferable, and sodium dodecylsulfate and/or sodium dodecylbenzenesulfonate are more preferable.
In the examples provided by the present disclosure, the initiator is specifically included in an amount of 0.1 parts by weight, 0.15 parts by weight, or 0.2 parts by weight; the initiator is not particularly limited as long as it is known to those skilled in the art, and in the present invention, a peroxide initiator is preferable, an inorganic peroxide initiator is more preferable, and sodium persulfate and/or potassium persulfate is still more preferable.
The content of the electrolyte is preferably 0.01-0.04 parts by weight; in the examples provided by the present invention, the content of the electrolyte is specifically 0.01 parts by weight, 0.03 parts by weight, or 0.04 parts by weight; the electrolyte is not particularly limited as long as it is well known to those skilled in the art, and sodium chloride and/or potassium chloride are preferable in the present invention.
According to the invention, the coating also preferably comprises 0.01-0.2 weight part of defoaming agent, and more preferably also comprises 0.01-0.1 weight part of defoaming agent; in the examples provided by the present invention, the content of the defoaming agent is specifically 0.01 parts by weight, 0.05 parts by weight, or 0.1 parts by weight; the antifoaming agent is preferably polyoxypropylene glyceryl ether and/or silicone.
The water is preferably deionized water; the content thereof is preferably 100 parts by weight in total of the supplementary environment-friendly water-based paint.
Further preferably, the environment-friendly water-based paint provided by the invention comprises:
according to the invention, carbon-carbon double bonds in polyurethane and epoxy acrylate molecules are utilized to carry out graft copolymerization, the molecular chains of the polyurethane and the epoxy acrylate molecules penetrate and are entangled with each other to form an interpenetrating network structure, polar bonds such as carbamate and the like are enriched on the surface of the structure, and the structure can interact with oxygen-containing functional groups on the surface of graphene oxide, so that the graphene oxide has a good dispersion effect, the emulsion has good service performance, the coating has good mechanical performance, the coating has strong cohesion after being cured, the molecular structure is compact, water molecules cannot permeate through the coating, the waterproof effect can be achieved, meanwhile, the adhesion force is large, the mechanical strength is high, the coating is dense, the anti-corrosion performance is good, and the service life of a house is greatly prolonged; moreover, because the thermal isolation of self lamellar structure, the graphene oxide is isolated or the heat exchange is carried out on the surface of polymer and the outside under the condition that the base body is heated, thereby reducing the combustion heat release rate of combustible materials and playing a role in flame retardance.
The invention also provides a preparation method of the environment-friendly water-based paint, which comprises the following steps: mixing epoxy acrylate, an acrylate monomer, polyurethane, an emulsifier and water, heating, adding the acrylate monomer and an alkyl glycol diacrylate monomer, adding graphene oxide, and finally adding an initiator and an electrolyte to obtain the environment-friendly water-washing paint.
The contents and types of the epoxy acrylate, the acrylate monomer, the polyurethane, the emulsifier, the water, the acrylate monomer, the alkyl glycol diacrylate monomer, the graphene oxide, the initiator and the electrolyte are the same as those described above, and are not described herein again.
Mixing epoxy acrylate, acrylate monomer, polyurethane, emulsifier and water, and heating; the rotation speed of the mixing is preferably 600-700 rpm. In the invention, the preparation process is carried out under stirring condition unless otherwise specified; the heating temperature is preferably 88 to 90 ℃.
Then adding an acrylate monomer and an alkyl glycol diacrylate monomer; in the invention, the acrylic ester monomer and the alkyl glycol diacrylate monomer are preferably added in a dropwise manner, and more preferably, the dropwise addition is completed within 30-60 min.
Then adding graphene oxide; after adding the graphene oxide, preferably keeping the constant temperature for 20-40 min, and then adding an initiator and an electrolyte; the initiator and the electrolyte are preferably added in a dropwise manner, and more preferably, the addition is controlled within 1-1.5 h.
After the initiator and the electrolyte are added, the temperature is preferably reduced to below 40 ℃, and the defoaming agent is added to obtain the environment-friendly water-based paint.
The invention also provides application of the environment-friendly water-based paint as a wood coating, and more preferably as a special wood coating for houses.
The coating weight of the environment-friendly water-based paint on the wood surface is preferably 1-3 g/m2. The environment-friendly water-based paint can be cured at normal temperature, and the formed coating has good waterproof, anticorrosive and flame-retardant effects.
In order to further illustrate the present invention, the following examples are provided to describe the present invention in detail with reference to the environment-friendly water-based paint, its preparation method and application.
The reagents used in the following examples are all commercially available. The raw materials used in the examples were: the epoxy acrylate is the epoxy acrylate produced by Xiamen Kema chemical Co Ltd, and the brand is PE 110; the polyurethane is polyurethane produced by Shanghai Tuodede industry Co., Ltd, and the mark is M5355A; sodium dodecyl sulfate (emulsifier), sodium persulfate (initiator), sodium chloride (electrolyte), and silicone (defoamer).
Examples and comparative examples
Putting epoxy acrylate, ethyl methacrylate, polyurethane, an emulsifier and deionized water into a reaction kettle according to the weight ratio shown in table 1, starting a stirring paddle in the whole production process, controlling the rotating speed to be 600-700 revolutions per minute, starting heating, keeping the temperature to be 88-90 ℃, dropwise adding methacrylic acid and ethylene glycol dimethacrylate while keeping the temperature, controlling dropwise adding to be completed within 1 hour, adding graphene oxide, keeping the constant temperature for 30 minutes, dropwise adding an initiator and an electrolyte while keeping the temperature to be 88-90 ℃, controlling dropwise adding to be completed within 1.5 hours, and finally cooling to below 40 ℃ and adding a defoaming agent to obtain the environment-friendly water-based paint.
The performance of the environment-friendly water-based paint obtained in the examples and the comparative examples was measured, and the results are shown in table 2.
TABLE 1 Components and proportions of examples and comparative examples
TABLE 2 detection results of the properties of the environmental protection water-based paint
Note 1) comparative example 4 the final product prepared using the example of Chinese patent CN 107964308A;
2) emulsion stability test method: the emulsion is prepared according to the formula and then placed in a laboratory environment at 25 ℃ for 30 days, and after 30 days, the emulsion is taken out to observe the external form of the emulsion;
3) the water-blocking effect test method comprises drying and solidifying the emulsion to obtain a film with a thickness of 3 μm, and testing according to standard method ASTMF-1249;
4) a decay grading and ant-eating grading test method comprises the following steps: testing according to a standard method GBT 29900-;
5) the oxygen index was measured according to standard method ISO4589-3:1996, prepared as follows: the test was carried out on a sample having a length of 130mm, a width of 6.5mm and a thickness of 3 mm;
6) the smoke density was measured according to standard method GB8323-1987, prepared as follows: a sample 75mm long, 75mm wide and 10mm thick was tested.