CN112724789A - Outdoor ultraviolet-resistant wear-resistant epoxy floor coating and preparation method thereof - Google Patents
Outdoor ultraviolet-resistant wear-resistant epoxy floor coating and preparation method thereof Download PDFInfo
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- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/61—Additives non-macromolecular inorganic
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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Abstract
The invention discloses an outdoor ultraviolet-resistant wear-resistant epoxy floor coating and a preparation method thereof. The epoxy floor coating comprises the following raw material components: acrylic group/epoxy resin composite liquid, porous asbestos, a silane coupling agent, zinc chloride, a dispersing agent, an epoxy resin curing agent, a toughening agent, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, an activated carbon quantum dot solution, a calcium hydroxide solution, ethyl orthosilicate and a tertiary amine accelerator. The antibacterial performance of the epoxy floor coating is realized under the coordination of the zinc oxide/carbon quantum dot/calcium silicate ternary compound and an antibacterial network, and compared with the common epoxy floor coating, the epoxy floor coating has an obvious antibacterial effect; the epoxy floor coating disclosed by the invention is simple in preparation process, simple and easily available in materials, good in weather resistance, good in mechanical property, not easy to peel off, good in wear resistance, strong in antibacterial property, very suitable for industrial production and wide in market prospect.
Description
Technical Field
The invention relates to the technical field of epoxy terraces, in particular to an outdoor ultraviolet-resistant wear-resistant epoxy terrace coating and a preparation method thereof.
Background
The main components of the epoxy floor coating are epoxy resin and a curing agent, and the epoxy floor coating is usually used for coating floors, so as to improve the aesthetic property and the durability of the floors. The epoxy floor coatings on the market at present are mainly divided into solvent type epoxy floor coatings and water-based epoxy floor coatings. Solvent-based epoxy floor coating can produce a large amount of volatile substances such as toluene, xylene etc. in the preparation process, has certain harm to workman's healthy and natural environment, along with people's attention to air pollution, solvent-based epoxy floor coating can not satisfy people's needs yet, and compared with, the toxic gas that epoxy floor coating with water as the solvent discharged is little, and the adhesion is high, and comprehensive properties is good, and is safer environmental protection more, has become the development trend of future epoxy floor coating gradually.
However, the common water-based epoxy floor coating has too high hardness, cracks are easy to appear on the surface when the common water-based epoxy floor coating is stressed, and yellowing and aging phenomena are easy to occur under the action of ultraviolet rays particularly due to the existence of benzene rings in the epoxy resin, so that the common epoxy floor coating has insufficient weather resistance, and the application of the common epoxy floor coating in the environment such as outdoor or ultraviolet disinfection laboratories is limited. Ordinary epoxy is not good in wear resistance, lacks antibacterial property, and is particularly easy to peel off, drop, mildew and other problems in long-term use, so that the later maintenance cost of the terrace is increased, and the use feeling is influenced.
In order to solve the problems mentioned above, people need an anti-ultraviolet wear-resistant epoxy floor coating with good weather resistance, good antibacterial activity and difficult peeling and shedding, and a preparation method thereof.
Disclosure of Invention
The invention aims to provide an outdoor ultraviolet-resistant wear-resistant epoxy floor coating and a preparation method thereof, and aims to solve the problems in the background art.
The utility model provides an outdoor wear-resisting epoxy terrace coating of ultraviolet resistance, each raw materials component is as follows: by weight, 100-200 parts of acrylic group/epoxy resin composite liquid, 60-90 parts of porous asbestos, 20-30 parts of silane coupling agent, 25-35 parts of zinc chloride, 10-30 parts of dispersing agent, 18-24 parts of epoxy resin curing agent, 20-30 parts of toughening agent, 5-35 parts of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, 50-70 parts of activated carbon quantum dot solution, 10-20 parts of calcium hydroxide solution, 14-18 parts of ethyl orthosilicate and 10-16 parts of tertiary amine accelerator.
Further, the tertiary amine accelerator is one or more of DMP-30, triethanolamine and dimethylaniline. The invention particularly uses the tertiary amine accelerant, can promote the reaction of the epoxy floor coating, and is also beneficial to the formation of the quaternary ammonium salt bacteriostatic network.
Further, the acrylic/epoxy resin is obtained by stirring and mixing acrylic resin emulsion, epoxy resin and water, wherein the mass ratio of the acrylic resin emulsion to the epoxy resin to the water is (15-20): 17:10.
Further, the porous asbestos is obtained by soaking common asbestos in acid liquor, washing and drying; the acid solution mainly comprises 20-30 parts of acetic acid and 30-50 parts of hydrochloric acid.
Further, the silane coupling agent is one or more of an amino-hydrocarbon silane coupling agent, a hydroxyl silane coupling agent and a carboxyl silane coupling agent.
A preparation method of an outdoor ultraviolet-resistant wear-resistant epoxy floor coating comprises the following steps:
(1) preparing raw materials:
A. mixing acetic acid and hydrochloric acid, and stirring to obtain acid solution;
B. preparing a sodium hydroxide solution, adding the carbon quantum dots, and stirring to obtain an activated carbon quantum dot solution;
C. adding asbestos into acid liquor under the heating condition, oscillating, cooling to room temperature, taking out the asbestos, washing with deionized water, and drying to obtain porous asbestos;
(2) preparing acrylic group/epoxy resin complex liquid: adding acrylic group resin emulsion, stirring, adding epoxy resin and water, and continuously mixing and stirring until the mixture is uniform to obtain acrylic group/epoxy resin composite liquid;
(3) preparing an epoxy floor coating: porous asbestos, a silane coupling agent, a zinc chloride solution, an acrylic group/epoxy resin composite solution, a dispersing agent, an epoxy resin curing agent, a toughening agent, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, an activated carbon quantum dot solution, a calcium hydroxide solution, methanol, deionized water, ethyl orthosilicate and a tertiary amine accelerator are stirred and mixed to obtain the epoxy floor coating.
The method specifically comprises the following steps:
(1) preparing raw materials:
A. mixing 7-10% by mass of acetic acid and 10-12% by mass of hydrochloric acid, and stirring uniformly to prepare acid liquor;
B. preparing a sodium hydroxide solution with the mass fraction of 8-10%, adding carbon quantum dots, stirring and reacting at the rotating speed of 300-400r/min for 30-50min to obtain an activated carbon quantum dot solution; activating active functional groups such as hydroxyl, carbonyl, carboxyl and the like on the surface of the carbon quantum dot by using sodium hydroxide, so that the later stage of the carbon quantum dot is favorably complexed with zinc ions and calcium ions to form a zinc oxide/carbon quantum dot/calcium silicate ternary compound;
C. adding asbestos into the acid liquor under the heating condition of 30-50 ℃, carrying out oscillation reaction for 2-3h at the frequency of 24-30kHz, taking out the asbestos after the temperature is reduced to the room temperature, and washing and drying the asbestos with deionized water to obtain porous asbestos; in the process, the heating and reaction time needs to be strictly controlled to obtain the porous asbestos which has certain mechanical property and a proper pore structure. The heating temperature is too low, the reaction time is too long, asbestos fibers are brittle and easy to break, the asbestos fibers are difficult to serve as carriers of composite materials, the mechanical properties of epoxy floor are difficult to obviously improve, metal oxides are not sufficiently dissolved when the heating temperature is too low and the reaction time is too short, the surface roughness of asbestos is insufficient, the contact area between the asbestos and other functional materials in epoxy floor paint is small, the load rate of the composite materials is reduced, the contact sites between the asbestos and the epoxy floor paint are few, the compatibility is insufficient, stress is difficult to disperse in time under the action of stress, and cracks are easy to appear on the surface of the epoxy floor paint.
(2) Preparing acrylic group/epoxy resin complex liquid: setting the stirring speed at 1200-1400r/min, adding the acrylic-based resin emulsion, stirring and dispersing for 10-15min, adding the epoxy resin and water, and continuously mixing and stirring for 10-15min until the mixture is uniform to obtain acrylic-based/epoxy resin composite liquid;
(3) preparing an epoxy floor coating:
A. adding porous asbestos into a silane coupling agent mixed solution, stirring, adding a zinc chloride solution, and performing ultrasonic dispersion to obtain a solution A;
B. mixing the acrylic group/epoxy resin composite liquid and the solution A, sequentially adding a dispersing agent, an epoxy resin curing agent, a toughening agent and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, and after the materials are added, raising the rotating speed and stirring to obtain a solution B;
C. adding the activated carbon quantum dot solution and the calcium hydroxide solution into the solution B, stirring, supplementing sodium hydroxide to adjust the pH value, adding methanol and deionized water according to a proportion, simultaneously dropwise adding ethyl orthosilicate, stirring, adding a tertiary amine promoter, continuously stirring, and standing to obtain the epoxy floor coating.
Further, the specific operation process of step a in step (3) is as follows: adjusting the pressure to 1.0-1.2MPa and the temperature to 60-70 ℃, adding the porous asbestos into the silane coupling agent mixed solution, stirring and reacting for 20-30min, adding a zinc chloride solution, and performing ultrasonic dispersion for 1-2h to obtain a solution A.
Further, the specific operation process of step b in step (3) is as follows: mixing the acrylic group/epoxy resin composite liquid and the solution A, adjusting the rotating speed to be 400-year-old 700r/min, sequentially adding a dispersing agent, an epoxy resin curing agent, a toughening agent and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, raising the rotating speed to be 850-year-old 1150r/min after the addition is finished, and stirring for 25-45min to obtain a solution B.
Further, the specific operation process of step c in step (3) is as follows: adding activated carbon quantum dot solution and 15-25% calcium hydroxide solution into the solution B, stirring and reacting for 10-25min, setting the pressure at 1.0-1.5MPa and the temperature at 100-110 ℃, adding sodium hydroxide to adjust the pH value to 10.2-12.8, reacting free zinc ions in the reaction system with hydroxide ions to generate Zn (OH)4 in situ on porous asbestos2-，Zn(OH)42-Further hydrolyzing and compounding with calcium silicate and carbon quantum dots to form a zinc oxide/carbon quantum dot/calcium silicate ternary compound; the pH value range of the invention needs to be strictly controlled between 10.2 and 12.8, too small pH value can cause the particle size of the zinc oxide/carbon quantum dot/calcium silicate ternary complex to be too large and uneven, and the function of filling the porous asbestos pores is difficult to play, and too large pH value can cause the particle size of the zinc oxide/carbon quantum dot/calcium silicate ternary complex to be too small and the structure to be too compact, and the functions of adsorbing and degrading waste gas can be influenced. Methanol and deionized water according to the weight ratio of (4-6): 3, simultaneously dripping ethyl orthosilicate, stirring and reacting at the rotating speed of 100-Oxygen floor coating.
The invention uses acetic acid and hydrochloric acid to etch asbestos, and the acid liquor dissolves the metal oxide in the asbestos to obtain porous asbestos; the specific surface area of the porous asbestos is increased, the surface roughness is increased, the contact area of the porous asbestos and the epoxy floor coating is increased, a physical lock catch can be formed between the porous asbestos and the epoxy floor coating, the compatibility of the porous asbestos and the epoxy floor coating is increased, and the problems of peeling and peeling of the epoxy floor coating are solved; and simultaneously, the method is beneficial to the load of the ternary compound of zinc oxide/carbon quantum dots/calcium silicate in the later period. The invention further puts the porous asbestos in a silane coupling agent for reaction, and hydroxyl in silane coupling reacts with silicon hydroxyl on the surface of the porous asbestos and in pores of the porous asbestos, so that a large number of active groups are modified on the porous asbestos. The active group has stronger complexing action on zinc ions, activated carbon quantum dot solution and calcium ions, and intermolecular force also exists among the zinc ions, the activated carbon quantum dot solution and the calcium ions, so that the zinc oxide/carbon quantum dot/calcium silicate ternary compound is generated in situ in the porous asbestos.
The zinc oxide/carbon quantum dot/calcium silicate ternary compound has rich pores and a higher specific surface area, has certain adsorption capacity on toxic gases such as ammonia gas, formaldehyde and the like, can effectively reduce the unpleasant smell of the epoxy floor paint in the generation process, absorbs the gases such as formaldehyde, ethyl acetate, toluene, xylene and the like in an ultraviolet laboratory or outdoor environment, and purifies the working environment; the zinc oxide/carbon quantum dot/calcium silicate ternary compound can absorb ultraviolet light, effectively reduce the damage of the ultraviolet light to the epoxy terrace, prevent the epoxy terrace from aging and yellowing, prolong the service life of the epoxy terrace and reduce the later maintenance cost. The zinc oxide/carbon quantum dot/calcium silicate ternary compound also has certain photocatalytic capacity, zinc oxide can generate electron transition under the action of sunlight so as to effectively degrade harmful gas adsorbed by the zinc oxide, the carbon quantum dot can assist the zinc oxide, the photo-generated electron hole pair is prevented from being compounded, and the photocatalytic degradation efficiency is improved. The zinc oxide/carbon quantum dot/calcium silicate ternary complex also has certain sterilization and bacteriostasis effects, and can be used for inhibiting the generation of mildew stains under the synergistic effect with a quaternary ammonium salt network generated in a reaction system.
The surface of the zinc oxide/carbon quantum dot/calcium silicate ternary compound can contain rich hydrophilic groups, and the load of the zinc oxide/carbon quantum dot/calcium silicate ternary compound on the porous asbestos obviously improves the dispersibility of the porous asbestos in the epoxy floor coating; meanwhile, the combination of the porous asbestos and the hydrophilic chain segment in the epoxy floor paint is facilitated, so that the porous asbestos is used as a connecting node to form physical crosslinking with the hydrophilic chain segment, a compact network structure is formed in the epoxy floor paint, and the compatibility of the porous asbestos in the epoxy floor paint is improved; the load of the zinc oxide/carbon quantum dot/calcium silicate ternary compound on the porous fiber not only improves the contact area and reaction sites of the porous asbestos and functional materials in the epoxy floor paint, improves the interface binding force, avoids the peeling and falling problem of the epoxy floor paint, but also strengthens the mechanical property of the porous asbestos, strengthens the stress dispersion capability of the porous asbestos, and improves the wear resistance and the pressure resistance of the epoxy floor.
The porous asbestos loaded with the zinc oxide/carbon quantum dot/calcium silicate ternary compound also contains a silane coupling agent, and the silane coupling agent is an amphiphilic molecule, so that a hydrophilic molecule can react with the porous asbestos and a hydrophilic chain segment to form a firm chemical bond, and a hydrophobic molecule can be further entangled with a polymer molecule chain segment in the epoxy floor coating to strengthen the original physical network structure; the network structure in the epoxy floor coating can improve the mechanical property of the epoxy floor coating, improve the toughness of the epoxy floor coating, avoid the brittle fracture problem of the epoxy floor coating under the action of stress, and effectively prolong the service life of the epoxy floor.
The 3-chloro-2-hydroxypropyl trimethyl ammonium chloride can react with active functional groups on the surface of a zinc oxide/carbon quantum dot/calcium silicate ternary compound to be further modified on the porous asbestos, and the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride can react with a tertiary amine promoter to generate a quaternary ammonium salt antibacterial network in the epoxy floor paint, so that the compatibility of the porous asbestos and the epoxy floor paint is further improved, the crosslinking network in the epoxy floor paint is more compact and stable, and the mechanical property of the epoxy floor paint is enhanced; on the other hand, the full coverage of the antibacterial performance of the epoxy floor paint is realized, the antibacterial dead angle is avoided, and the antibacterial performance of the epoxy floor paint is optimized.
Compared with the prior art, the invention has the following beneficial effects:
1. the epoxy floor paint is obtained by compounding acrylic-based resin emulsion and epoxy resin; the addition of the acrylic-based resin emulsion can obviously improve the ultraviolet resistance of the epoxy resin, and alleviate the yellowing and aging problems of the epoxy resin, so that the service life of the prepared epoxy floor paint can be prolonged outdoors or under an ultraviolet condition.
2. Asbestos belongs to natural mineral fiber, has good heat insulation, wear resistance and chemical corrosion resistance, is rich in reserves in nature and is low in price; etching asbestos by using acid liquor to prepare porous asbestos, and loading a zinc oxide/carbon quantum dot/calcium silicate ternary compound on the porous asbestos; the compatibility of the porous asbestos and the epoxy floor coating is obviously enhanced, the mechanical property is obviously improved, the finally prepared epoxy floor coating also has certain functions of adsorbing, photocatalytic degrading waste gas, and has the advantages of good wear resistance, strong toughness, difficult peeling, yellowing and fracture, and the heat insulation capability of the porous asbestos can effectively reduce the problem of epoxy floor coating aging caused by heat brought by outdoor sunlight.
3. The 3-chloro-2-hydroxypropyl trimethyl ammonium chloride can react with active functional groups on the surface of a zinc oxide/carbon quantum dot/calcium silicate ternary compound to be further modified on the porous asbestos, and the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride can react with a tertiary amine promoter to generate a quaternary ammonium salt antibacterial network in the epoxy floor paint, so that the compatibility of the porous asbestos and the epoxy floor paint is further improved, the crosslinking network in the epoxy floor paint is more compact and stable, and the mechanical property of the epoxy floor paint is enhanced; on the other hand, the full coverage of the antibacterial performance of the epoxy floor paint is realized, the antibacterial dead angle is avoided, and the antibacterial performance of the epoxy floor paint is optimized.
4. The antibacterial performance of the epoxy floor coating is realized under the coordination of the zinc oxide/carbon quantum dot/calcium silicate ternary compound and the antibacterial network, and compared with the common epoxy floor coating, the epoxy floor coating has an obvious antibacterial effect.
5. The epoxy floor coating disclosed by the invention is simple in preparation process, simple and easily available in materials, good in weather resistance, good in mechanical property, not easy to peel off, good in wear resistance, strong in antibacterial property, very suitable for industrial production and wide in market prospect.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.
And (3) testing: the epoxy floor coatings prepared in examples 1-6 were subjected to the following performance tests;
(1) and (3) wear resistance test: with reference to GB/T1768-; arm weight of the wear-resistant instrument: 750g, abrasion resistance: 500r, the coating film quality before and after the test is poor (g), and the smaller the quality difference, the better the wear resistance. The difference between the coating quality before and after the national standard is not more than 0.02 g.
(2) And (3) testing the impact resistance: according to the GB/T22374-2008 standard, 500g of steel balls are used, and the steel balls fall at the height of 100cm to test the impact resistance grade; the I-grade coating has no cracks and no falling; the V-level coating film has a large amount of cracks and falls off.
(3) And (3) aging resistance testing: testing is carried out according to GB/T1865-2009 xenon arc radiation of artificial weathering aging and artificial radiation exposure filtering and GB/T-1766-; evaluation method: best on level 0, worst on level 5.
(4) And (3) antibacterial property test: the bacteriostatic rate of the example paint sample on staphylococcus aureus is tested by referring to GB/T21866-2008 standard.
Example 1
(1) Preparing raw materials:
A. mixing 7% by mass of acetic acid and 10% by mass of hydrochloric acid, and stirring uniformly to prepare acid liquor;
B. preparing a sodium hydroxide solution with the mass fraction of 8%, adding carbon quantum dots, stirring at the rotating speed of 300r/min for reaction for 30min to obtain an activated carbon quantum dot solution;
C. adding asbestos into the acid liquor under the heating condition of 30 ℃, oscillating and reacting for 2 hours at the frequency of 24kHz, taking out the asbestos after the temperature is reduced to the room temperature, and washing and drying the asbestos with deionized water to obtain porous asbestos;
(2) preparing acrylic group/epoxy resin complex liquid: setting the stirring speed at 1200r/min, adding the acrylic group resin emulsion, stirring and dispersing for 10min, adding the epoxy resin and the water, and continuously mixing and stirring for 10min until the mixture is uniform to obtain acrylic group/epoxy resin composite liquid;
(3) preparing an epoxy floor coating:
A. adjusting the pressure to 1.0MPa and the temperature to 60 ℃, adding the porous asbestos into the silane coupling agent mixed solution, stirring and reacting for 20min, adding a zinc chloride solution, and performing ultrasonic dispersion for 1h to obtain a solution A;
B. mixing the acrylic group/epoxy resin composite liquid and the solution A, adjusting the rotating speed to 400r/min, sequentially adding a dispersing agent, an epoxy resin curing agent, a toughening agent and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, raising the rotating speed to 850r/min after the materials are added, and stirring for 25min to obtain a solution B;
C. adding an activated carbon quantum dot solution and a 15% calcium hydroxide solution into the solution B, stirring and reacting for 10min, setting the pressure to be 1.0MPa and the temperature to be 100 ℃, supplementing sodium hydroxide to adjust the pH value to be 10.2, and mixing methanol and deionized water according to the weight ratio of 4: 3, simultaneously dropwise adding ethyl orthosilicate, stirring and reacting at the rotating speed of 100r/min for 1h, adding a tertiary amine accelerator, continuously stirring and reacting for 4h, and standing for 20min to obtain the epoxy floor coating.
Wherein: 100 parts of acrylic group/epoxy resin composite liquid, 60 parts of porous asbestos, 20 parts of silane coupling agent, 25 parts of zinc chloride, 10 parts of dispersing agent, 18 parts of epoxy resin curing agent, 20 parts of toughening agent, 5 parts of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, 50 parts of activated carbon quantum dot solution, 10 parts of calcium hydroxide solution, 14 parts of ethyl orthosilicate and 10 parts of tertiary amine accelerator.
The acrylic/epoxy resin is prepared by stirring and mixing acrylic resin emulsion, epoxy resin and water, wherein the mass ratio of the acrylic resin emulsion to the epoxy resin to the water is 15: 17:10.
The acid solution mainly comprises 20 parts of acetic acid and 30 parts of hydrochloric acid.
The epoxy terrace coating that this embodiment made:
the difference between the front and rear coating qualities of the epoxy floor coating is 0.013g, the epoxy floor coating conforms to the national standard, and the wear resistance is good; the impact resistance is I grade, and the coating film has no crack and no falling off. The shock resistance is excellent; the weather resistance is 0 grade, the aging and yellowing phenomena are avoided, the weather resistance is good, and the coating can be completely used outdoors; the bacteriostatic rate of the antibacterial agent on staphylococcus aureus reaches 98.7%, and the antibacterial agent has excellent bacteriostatic property.
Example 2
(1) Preparing raw materials:
A. mixing 8% by mass of acetic acid and 11% by mass of hydrochloric acid, and stirring uniformly to prepare acid liquor;
B. preparing a sodium hydroxide solution with the mass fraction of 9%, adding carbon quantum dots, stirring at the rotating speed of 350r/min for reaction for 40min, and obtaining an activated carbon quantum dot solution;
C. adding asbestos into the acid liquor under the heating condition of 40 ℃, oscillating and reacting for 2.5 hours at the frequency of 28kHz, taking out the asbestos after the temperature is reduced to the room temperature, and washing and drying by deionized water to obtain porous asbestos;
(2) preparing acrylic group/epoxy resin complex liquid: setting the stirring speed at 1300r/min, adding the acrylic group resin emulsion, stirring and dispersing for 13min, adding the epoxy resin and the water, and continuously mixing and stirring for 13min until the mixture is uniform to obtain acrylic group/epoxy resin composite liquid;
(3) preparing an epoxy floor coating:
A. adjusting the pressure to 1.1MPa and the temperature to 65 ℃, adding the porous asbestos into the silane coupling agent mixed solution, stirring for reaction for 25min, adding a zinc chloride solution, and performing ultrasonic dispersion for 1.5h to obtain a solution A;
B. mixing the acrylic group/epoxy resin composite liquid and the solution A, adjusting the rotating speed to 500r/min, sequentially adding a dispersing agent, an epoxy resin curing agent, a toughening agent and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, raising the rotating speed to 1000r/min after the materials are added, and stirring for 35min to obtain a solution B;
C. adding an activated carbon quantum dot solution and a 20% calcium hydroxide solution in mass percentage into the solution B, stirring and reacting for 20min, setting the pressure to be 1.3MPa and the temperature to be 105 ℃, supplementing sodium hydroxide to adjust the pH value to be 11.8, and mixing methanol and deionized water according to the weight ratio of 5: 3, simultaneously dropwise adding ethyl orthosilicate, stirring and reacting at the rotating speed of 150r/min for 1.5h, adding a tertiary amine accelerator, continuously stirring and reacting for 5h, and standing for 25min to obtain the epoxy floor coating.
Wherein: 150 parts of acrylic group/epoxy resin composite liquid, 70 parts of porous asbestos, 25 parts of silane coupling agent, 30 parts of zinc chloride, 20 parts of dispersing agent, 20 parts of epoxy resin curing agent, 25 parts of toughening agent, 20 parts of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, 60 parts of activated carbon quantum dot solution, 15 parts of calcium hydroxide solution, 16 parts of ethyl orthosilicate and 13 parts of tertiary amine accelerator.
The acrylic group/epoxy resin is obtained by stirring and mixing acrylic group resin emulsion, epoxy resin and water, wherein the mass ratio of the acrylic group resin emulsion to the epoxy resin to the water is 18: 17:10.
The acid solution mainly comprises 25 parts of acetic acid and 40 parts of hydrochloric acid.
The quality difference of front and back coating films of the epoxy floor coating is 0.012g, the epoxy floor coating meets the national standard, and the epoxy floor coating has good wear resistance; the impact resistance is I grade, and the coating film has no crack and no falling off. The shock resistance is excellent; the weather resistance is 0 grade, the aging and yellowing phenomena are avoided, the weather resistance is good, and the coating can be completely used outdoors; the bacteriostatic rate of the antibacterial agent on staphylococcus aureus reaches 98.9%, and the antibacterial agent has excellent bacteriostatic property.
Example 3
(1) Preparing raw materials:
A. mixing 10% by mass of acetic acid and 12% by mass of hydrochloric acid, and stirring uniformly to prepare acid liquor;
B. preparing a sodium hydroxide solution with the mass fraction of 10%, adding carbon quantum dots, stirring at the rotating speed of 400r/min for reaction for 50min, and obtaining an activated carbon quantum dot solution;
C. adding asbestos into the acid liquor under the heating condition of 50 ℃, oscillating and reacting for 3 hours at the frequency of 30kHz, taking out the asbestos after the temperature is reduced to the room temperature, and washing and drying the asbestos with deionized water to obtain porous asbestos;
(2) preparing acrylic group/epoxy resin complex liquid: setting the stirring speed at 1400r/min, adding the acrylic-based resin emulsion, stirring and dispersing for 15min, adding the epoxy resin and water, and continuously mixing and stirring for 15min until the mixture is uniformly mixed to obtain acrylic-based/epoxy resin composite liquid;
(3) preparing an epoxy floor coating:
A. adjusting the pressure to 1.2MPa and the temperature to 70 ℃, adding the porous asbestos into the silane coupling agent mixed solution, stirring and reacting for 30min, adding a zinc chloride solution, and performing ultrasonic dispersion for 2h to obtain a solution A;
B. mixing the acrylic group/epoxy resin composite liquid and the solution A, adjusting the rotating speed to 700r/min, sequentially adding a dispersing agent, an epoxy resin curing agent, a toughening agent and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, raising the rotating speed to 1150r/min and stirring for 45min after the materials are added to obtain a solution B;
C. adding an activated carbon quantum dot solution and a 25% calcium hydroxide solution in mass percentage into the solution B, stirring and reacting for 25min, setting the pressure to be 1.5MPa and the temperature to be 110 ℃, supplementing sodium hydroxide to adjust the pH value to be 12.8, and mixing methanol and deionized water according to the weight ratio of 6: 3, simultaneously dropwise adding ethyl orthosilicate, stirring and reacting at the rotating speed of 200r/min for 2 hours, adding a tertiary amine accelerator, continuously stirring and reacting for 6 hours, and standing for 30 minutes to obtain the epoxy floor coating.
Wherein: 200 parts of acrylic group/epoxy resin composite liquid, 90 parts of porous asbestos, 30 parts of silane coupling agent, 35 parts of zinc chloride, 30 parts of dispersing agent, 24 parts of epoxy resin curing agent, 30 parts of toughening agent, 35 parts of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, 70 parts of activated carbon quantum dot solution, 20 parts of calcium hydroxide solution, 18 parts of ethyl orthosilicate and 16 parts of tertiary amine accelerator.
The acrylic group/epoxy resin is obtained by stirring and mixing acrylic group resin emulsion, epoxy resin and water, wherein the mass ratio of the acrylic group resin emulsion to the epoxy resin to the water is 20: 17:10.
The acid solution mainly comprises 30 parts of acetic acid and 50 parts of hydrochloric acid.
The quality difference of the front and back coating films of the epoxy floor coating is 0.010g, the epoxy floor coating meets the national standard, and the epoxy floor coating has good wear resistance; the impact resistance is I grade, the coating film has no crack and no drop, and the impact resistance is excellent; the weather resistance is 0 grade, the aging and yellowing phenomena are avoided, the weather resistance is good, and the coating can be completely used outdoors; the bacteriostatic rate of the antibacterial agent on staphylococcus aureus reaches 99.3 percent, and the antibacterial agent has excellent bacteriostatic property.
Example 4
The parameters and the operation steps of the embodiment refer to embodiment 1, and the difference is that the asbestos is not etched by using acid liquor, and is not subjected to dipping treatment by using a silane coupling agent; this example directly treats asbestos using plasma treatment techniques. The difference between the front and rear coating film qualities of the epoxy floor coating is 0.014g, which meets the national standard; the impact resistance is grade III, the coating has fine lines and slight shedding, and the impact resistance is general; the weather resistance is grade 1, the aging and yellowing phenomena are avoided, the weather resistance is good, and the coating can be used outdoors; the bacteriostatic rate of the antibacterial agent on staphylococcus aureus reaches 97.5 percent, and the antibacterial agent has excellent bacteriostatic property. Although the rough surface of the asbestos can be constructed through plasma treatment, a large number of oxygen-containing functional groups are introduced to the surface of the asbestos, the etching capacity of the plasma treatment is limited, the surface etching of the asbestos can be only carried out, the surface roughness of the asbestos is insufficient, and the oxygen-containing functional groups are not stable enough, so that the bonding force between the zinc oxide/carbon quantum dot/calcium silicate ternary compound and the asbestos is insufficient, the asbestos is easy to fall off, the asbestos dispersion effect is not obvious, the bonding force between the asbestos and the epoxy floor coating interface is poor, the asbestos is easy to break under the action of stress, and the prepared epoxy floor coating has insufficient mechanical properties.
Example 5
In this embodiment, each parameter and operation step are referred to embodiment 1, and the difference is that in this embodiment, zinc chloride, calcium hydroxide, and a carbon quantum dot solution are not used, and at the same time, the carbon quantum dot solution is not activated, but instead, nano zinc oxide, nano calcium silicate, and carbon quantum dots are directly used; the quality difference of the front and the back coating films is 0.020g, the national standard is met, and the wear resistance is general; the impact resistance of the epoxy floor coating is grade III, a coating film has fine lines and is free from falling, and the impact resistance is general; the weather resistance is grade 2, the phenomenon of slight aging and yellowing occurs, and the weather resistance is general; the bacteriostatic rate of the antibacterial agent on staphylococcus aureus reaches 96.5%, and the antibacterial agent has excellent bacteriostatic performance. The zinc oxide/carbon quantum dot/calcium silicate ternary compound cannot be formed among the nano zinc oxide, the nano calcium silicate and the carbon quantum dot, the zinc oxide/carbon quantum dot/calcium silicate ternary compound is insufficient in surface functional group activity and insufficient for mutual complexation and compound formation, the photocatalytic property of the zinc oxide is deficient, the photo-generated electron pair is easy to complex, the carbon quantum dot is not helpful, and the photocatalytic efficiency of the nano zinc oxide is obviously reduced; the epoxy terrace of this embodiment ultraviolet resistance is not enough to some extent, and nanometer zinc oxide, nanometer calcium silicate, carbon quantum dot are less on porous asbestos's filling rate, are lacked to some extent to the reinforcing effect of asbestos, and comprehensive properties is less than some with embodiment 1.
Example 6
The parameters and operating procedures of this example were as described in example 1, except that the accelerator used in this example was 2-methylimidazole; the difference between the front and rear coating qualities of the epoxy floor coating is 0.013g, the epoxy floor coating meets the national standard, and the wear resistance is general; the impact resistance is II grade, the coating has fine lines and no shedding, and the impact resistance is general; the weather resistance is grade 1, the slight aging and yellowing phenomena are avoided, and the weather resistance is good; the bacteriostatic rate to staphylococcus aureus is 65.5%, and the bacteriostatic performance is poor. 2-methylimidazole belongs to imidazole accelerators, but the accelerating effect of the accelerators on the whole reaction system is obviously lower than that of tertiary amine accelerators, and meanwhile, the imidazole catalysts cannot react with 3-chloro-2-hydroxypropyl trimethyl ammonium chloride specially added in the system to form a quaternary ammonium salt bacteriostatic network; the epoxy terrace coating provided by the embodiment has insufficient comprehensive performance.
From the above data and experiments, we can conclude that:
1. the epoxy floor paint is obtained by compounding acrylic-based resin emulsion and epoxy resin; the addition of the acrylic-based resin emulsion can obviously improve the ultraviolet resistance of the epoxy resin, and alleviate the yellowing and aging problems of the epoxy resin, so that the service life of the prepared epoxy floor paint can be prolonged outdoors or under an ultraviolet condition.
2. Asbestos belongs to natural mineral fiber, has good heat insulation, wear resistance and chemical corrosion resistance, is rich in reserves in nature and is low in price; etching asbestos by using acid liquor to prepare porous asbestos, and loading a zinc oxide/carbon quantum dot/calcium silicate ternary compound on the porous asbestos; the compatibility of the porous asbestos and the epoxy floor coating is obviously enhanced, the mechanical property is obviously improved, the finally prepared epoxy floor coating also has certain functions of adsorbing, photocatalytic degrading waste gas, and has the advantages of good wear resistance, strong toughness, difficult peeling, yellowing and fracture, and the heat insulation capability of the porous asbestos can effectively reduce the problem of epoxy floor coating aging caused by heat brought by outdoor sunlight.
3. The 3-chloro-2-hydroxypropyl trimethyl ammonium chloride can react with active functional groups on the surface of a zinc oxide/carbon quantum dot/calcium silicate ternary compound to be further modified on the porous asbestos, and the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride can react with a tertiary amine promoter to generate a quaternary ammonium salt antibacterial network in the epoxy floor paint, so that the compatibility of the porous asbestos and the epoxy floor paint is further improved, the crosslinking network in the epoxy floor paint is more compact and stable, and the mechanical property of the epoxy floor paint is enhanced; on the other hand, the full coverage of the antibacterial performance of the epoxy floor paint is realized, the antibacterial dead angle is avoided, and the antibacterial performance of the epoxy floor paint is optimized.
4. The antibacterial performance of the epoxy floor coating is realized under the coordination of the zinc oxide/carbon quantum dot/calcium silicate ternary compound and the antibacterial network, and compared with the common epoxy floor coating, the epoxy floor coating has an obvious antibacterial effect.
5. The epoxy floor coating disclosed by the invention is simple in preparation process, simple and easily available in materials, good in weather resistance, good in mechanical property, not easy to peel off, good in wear resistance, strong in antibacterial property, very suitable for industrial production and wide in market prospect.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The utility model provides an outdoor wear-resisting epoxy terrace coating of ultraviolet resistance which characterized in that: the raw material components are as follows: by weight, 100-200 parts of acrylic group/epoxy resin composite liquid, 60-90 parts of porous asbestos, 20-30 parts of silane coupling agent, 25-35 parts of zinc chloride, 10-30 parts of dispersing agent, 18-24 parts of epoxy resin curing agent, 20-30 parts of toughening agent, 5-35 parts of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, 50-70 parts of activated carbon quantum dot solution, 10-20 parts of calcium hydroxide solution, 14-18 parts of ethyl orthosilicate and 10-16 parts of tertiary amine accelerator.
2. The outdoor ultraviolet-resistant wear-resistant epoxy floor coating as claimed in claim 1, which is characterized in that: the tertiary amine accelerator is one or more of DMP-30, triethanolamine and dimethylaniline.
3. The outdoor ultraviolet-resistant wear-resistant epoxy floor coating as claimed in claim 1, which is characterized in that: the acrylic group/epoxy resin is obtained by stirring and mixing acrylic group resin emulsion, epoxy resin and water, wherein the mass ratio of the acrylic group resin emulsion to the epoxy resin to the water is (15-20): 17:10.
4. The outdoor ultraviolet-resistant wear-resistant epoxy floor coating as claimed in claim 1, which is characterized in that: the porous asbestos is obtained by soaking common asbestos in acid liquor, washing and drying; the acid solution mainly comprises 20-30 parts of acetic acid and 30-50 parts of hydrochloric acid.
5. The outdoor ultraviolet-resistant wear-resistant epoxy floor coating as claimed in claim 1, which is characterized in that: the silane coupling agent is one or more of an amino alkyl silane coupling agent, a hydroxyl silane coupling agent and a carboxyl silane coupling agent.
6. A preparation method of an outdoor ultraviolet-resistant wear-resistant epoxy floor coating is characterized by comprising the following steps:
(1) preparing raw materials:
A. mixing acetic acid and hydrochloric acid, and stirring to obtain acid solution;
B. preparing a sodium hydroxide solution, adding the carbon quantum dots, and stirring to obtain an activated carbon quantum dot solution;
C. adding asbestos into acid liquor under the heating condition, oscillating, cooling to room temperature, taking out the asbestos, washing with deionized water, and drying to obtain porous asbestos;
(2) preparing acrylic group/epoxy resin complex liquid: adding acrylic group resin emulsion, stirring, adding epoxy resin and water, and continuously mixing and stirring until the mixture is uniform to obtain acrylic group/epoxy resin composite liquid;
(3) preparing an epoxy floor coating: porous asbestos, a silane coupling agent, a zinc chloride solution, an acrylic group/epoxy resin composite solution, a dispersing agent, an epoxy resin curing agent, a toughening agent, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, an activated carbon quantum dot solution, a calcium hydroxide solution, methanol, deionized water, ethyl orthosilicate and a tertiary amine accelerator are stirred and mixed to obtain the epoxy floor coating.
7. The preparation method of the outdoor ultraviolet-resistant wear-resistant epoxy floor coating according to claim 6, characterized in that: the method specifically comprises the following steps:
(1) preparing raw materials:
A. mixing 7-10% by mass of acetic acid and 10-12% by mass of hydrochloric acid, and stirring uniformly to prepare acid liquor;
B. preparing a sodium hydroxide solution with the mass fraction of 8-10%, adding carbon quantum dots, stirring and reacting at the rotating speed of 300-400r/min for 30-50min to obtain an activated carbon quantum dot solution;
C. adding asbestos into the acid liquor under the heating condition of 30-50 ℃, carrying out oscillation reaction for 2-3h at the frequency of 24-30kHz, taking out the asbestos after the temperature is reduced to the room temperature, and washing and drying the asbestos with deionized water to obtain porous asbestos;
(2) preparing acrylic group/epoxy resin complex liquid: setting the stirring speed at 1200-1400r/min, adding the acrylic-based resin emulsion, stirring and dispersing for 10-15min, adding the epoxy resin and water, and continuously mixing and stirring for 10-15min until the mixture is uniform to obtain acrylic-based/epoxy resin composite liquid;
(3) preparing an epoxy floor coating:
A. adding porous asbestos into a silane coupling agent mixed solution, stirring, adding a zinc chloride solution, and performing ultrasonic dispersion to obtain a solution A;
B. mixing the acrylic group/epoxy resin composite liquid and the solution A, sequentially adding a dispersing agent, an epoxy resin curing agent, a toughening agent and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, and after the materials are added, raising the rotating speed and stirring to obtain a solution B;
C. adding the activated carbon quantum dot solution and the calcium hydroxide solution into the solution B, stirring, supplementing sodium hydroxide to adjust the pH value, adding methanol and deionized water according to a proportion, simultaneously dropwise adding ethyl orthosilicate, stirring, adding a tertiary amine promoter, continuously stirring, and standing to obtain the epoxy floor coating.
8. The preparation method of the outdoor ultraviolet-resistant wear-resistant epoxy floor coating according to claim 7, characterized in that: the specific operation process of the step A in the step (3) is as follows: adjusting the pressure to 1.0-1.2MPa and the temperature to 60-70 ℃, adding the porous asbestos into the silane coupling agent mixed solution, stirring and reacting for 20-30min, adding a zinc chloride solution, and performing ultrasonic dispersion for 1-2h to obtain a solution A.
9. The preparation method of the outdoor ultraviolet-resistant wear-resistant epoxy floor coating according to claim 7, characterized in that: the specific operation process of step B in the step (3) is as follows: mixing the acrylic group/epoxy resin composite liquid and the solution A, adjusting the rotating speed to be 400-year-old 700r/min, sequentially adding a dispersing agent, an epoxy resin curing agent, a toughening agent and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, raising the rotating speed to be 850-year-old 1150r/min after the addition is finished, and stirring for 25-45min to obtain a solution B.
10. The preparation method of the outdoor ultraviolet-resistant wear-resistant epoxy floor coating according to claim 7, characterized in that: the specific operation process of step C in step (3) is as follows: adding an activated carbon quantum dot solution and a calcium hydroxide solution with the mass fraction of 15-25% into the solution B, stirring and reacting for 10-25min, setting the pressure to be 1.0-1.5MPa, the temperature to be 100-: 3, simultaneously dripping ethyl orthosilicate, stirring and reacting at the rotating speed of 100-200r/min for 1-2h, adding a tertiary amine promoter, continuously stirring and reacting for 4-6h, and standing for 20-30min to obtain the epoxy floor coating.
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| CN114806302A (en) * | 2022-05-28 | 2022-07-29 | 河南蓝翎环科防水材料有限公司 | Antioxidant waterproof protective coating for terrace and production process thereof |
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