CN113429858A - Heat-insulating porcelain-coated material and preparation method and application thereof - Google Patents
Heat-insulating porcelain-coated material and preparation method and application thereof Download PDFInfo
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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
- C09D151/08—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 otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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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
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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
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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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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Abstract
The invention provides a heat insulation porcelain-coated material and a preparation method and application thereof, wherein the heat insulation porcelain-coated material comprises a combination of twice modified composite ceramic hollow particles, polyurethane modified acrylic emulsion, nano cellulose, a flatting agent and a thickening agent, and the heat insulation porcelain-coated material with good heat insulation effect, simple construction process and excellent machining performance is obtained by adding a combination of four ceramic particles with different particle size ranges; the heat insulation porcelain-coated material can be applied to a heat insulation plate of a passenger car, has the advantages of high heat insulation efficiency, difficulty in generating dust and germ pollution, long service life, superior machining performance and easiness in cleaning, and can greatly improve the environment quality and the heat insulation effect in the passenger car.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a heat-insulating ceramic-coated material as well as a preparation method and application thereof.
Background
At present, the heat insulation material of the passenger car mainly adopts inorganic asbestos material or organic low-density polyethylene foaming material. The inorganic asbestos material is high in brittleness, and is easy to break into a plurality of tiny dusts after being extruded or collided, the dusts have carcinogenicity, lung cancer is easy to cause after being inhaled by a human body, and the human body is not good for health; although the organic low-density polyethylene heat insulation cotton has no carcinogenic risk of inorganic heat insulation cotton, dust is easy to accumulate on the surface of the heat insulation cotton along with the increase of the service life of a passenger car, and dust is easy to accumulate at the gap position where the heat insulation cotton is contacted with an aluminum profile.
The heat insulation coating is a functional coating, can effectively prevent heat conduction, and can reduce the temperature of a surface coating and the internal environment, thereby achieving the purposes of improving the working environment and reducing the energy consumption, and therefore, the heat insulation coating is widely applied to the fields of building outer walls, ship decks, automobile shells, oil tank outer walls, military aerospace and the like. The heat-insulating layer is directly sprayed on the surface of the metal section in a spraying mode, the problems of carcinogenesis and bacterial breeding which are possibly caused are directly solved, the heat-insulating layer is different from the traditional inorganic heat-insulating material and organic polymer foaming material, the energy consumption is saved, the service life is long, the pulverization is avoided, the mechanical processing performance is superior, the cleaning is easy, disinfectant can be used for wiping and spraying, and the environment quality in the vehicle is greatly improved.
The heat insulation coating is divided into 4 types according to the mechanism, wherein the types are respectively a barrier type heat insulation coating, a reflection type heat insulation coating, a radiation type heat insulation coating and a composite type heat insulation coating, the heat insulation porcelain belongs to the composite heat insulation coating with the best performance, the composite type heat insulation coating integrates the advantages and the disadvantages of the three heat insulation coatings, the advantages and the disadvantages are taken out, and the heat insulation effect is better and excellent.
CN111793402A discloses an interior wall heat-insulating coating and a preparation method thereof, wherein the interior wall heat-insulating coating comprises the following raw materials in parts by weight: 30-40 parts of modified styrene-acrylic emulsion, 15-30 parts of silicone-acrylic emulsion, 5-10 parts of aluminum dihydrogen phosphate, 10-18 parts of hollow ceramic microspheres, 5-9 parts of aluminum silicate fibers, 3-6 parts of graphene, 4-8 parts of diatomite, 3-6 parts of zirconium silicate, 2-5 parts of tourmaline powder, 1-4 parts of medical stone, 0.8-2 parts of silane coupling agent, 1-3 parts of dispersing agent, 0.5-1.2 parts of thickening agent, 0.5-1 part of defoaming agent, 0.4-0.8 part of preservative and 18-32 parts of water. Solves the problems that the inner wall heat-insulating coating has single function, only has heat-insulating effect, insufficient adhesive force and the like, and simultaneously endows the coating with the health-care effect. CN104212285A discloses a mixed heat insulation coating for vehicle windows, which is prepared from the following raw materials in parts by weight: 10-40 parts of acrylic emulsion, 1-5 parts of defoaming agent, 1-5 parts of dispersing agent, 1-10 parts of thickening agent, 1-10 parts of flatting agent, 10-20 parts of titanium dioxide, 1-10 parts of hollow silica, 1-10 parts of alumina, 1-10 parts of ceramic microspheres, 10-20 parts of film-forming assistant and 20-0 part of water. The mixed heat-insulating coating for the vehicle window has better heat-insulating property and wide prospect in industrial application. CN102504664A discloses a solvent-based vehicle thermal insulation coating containing nano metal oxides, which comprises the following components in percentage by solid except solvent: 17-48 wt% of acrylic resin containing nano metal oxide, 7-21 wt% of amino resin, 0-20 wt% of coloring pigment, 0-4 wt% of filler, 1-6 wt% of assistant and the balance of solvent; the acrylic resin containing nano metal oxide is prepared by dripping mixed solution containing vinyl monomer and initiator into nano metal oxide sol formed by nano metal oxide, silane coupling agent and solvent to carry out free radical polymerization reaction. The solvent-based vehicle heat-insulating coating containing the nano metal oxide has good heat-insulating effect, and simultaneously, the mechanical properties and various medium-resistant properties of the coating can still reach the level of the vehicle coating using common acrylic resin, thereby achieving the aim of taking heat-insulating property, decoration and corrosion resistance into consideration.
However, the components in the coating are poor in compatibility, and a single heat insulation filler is adopted; the heat insulation effect of the finally obtained heat insulation coating still needs to be improved.
Therefore, the development of a heat-insulating porcelain-coated material with excellent comprehensive performance is a technical problem to be solved urgently in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a heat-insulating porcelain-coated material and a preparation method and application thereof, wherein the heat-insulating porcelain-coated material comprises a combination of twice-modified composite ceramic hollow particles, polyurethane modified acrylic emulsion, nano-cellulose, a leveling agent and a thickening agent; by adding four twice-modified composite ceramic hollow particles with different particle size ranges and matching with polyurethane modified acrylic emulsion, the heat-insulating ceramic coating material with good heat-insulating effect, simple construction process and excellent machining performance is finally obtained.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a thermal insulation porcelain-coated material, which comprises the following components in parts by weight:
the twice modified composite ceramic hollow particle can be 35 parts by weight, 40 parts by weight, 45 parts by weight, 50 parts by weight, 55 parts by weight, 60 parts by weight or 65 parts by weight and the like.
The urethane-modified acrylic emulsion may be 91 parts by weight, 92 parts by weight, 93 parts by weight, 94 parts by weight, 95 parts by weight, 96 parts by weight, 97 parts by weight, 98 parts by weight, 99 parts by weight, or the like.
The nanocellulose may be 2 parts by weight, 4 parts by weight, 6 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight, 16 parts by weight, 18 parts by weight, or the like.
The leveling agent may be 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, or the like.
The thickener may be 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, or the like.
The twice-modified composite ceramic hollow particles include a combination of first ceramic particles having a particle size of 115 to 125 μm (e.g., 116 μm, 117 μm, 118 μm, 119 μm, 120 μm, 121 μm, 122 μm, 123 μm, 124 μm, etc.), second ceramic particles having a particle size of 75 to 85 μm (e.g., 76 μm, 77 μm, 78 μm, 79 μm, 80 μm, 81 μm, 82 μm, 83 μm, 84 μm, etc.), third ceramic particles having a particle size of 55 to 65 μm (e.g., 56 μm, 57 μm, 58 μm, 59 μm, 60 μm, 61 μm, 62 μm, 63 μm, 64 μm, etc.), and fourth ceramic particles having a particle size of 25 to 35 μm (e.g., 26 μm, 27 μm, 28 μm, 29 μm, 30 μm, 31 μm, 32 μm, 33 μm, 34 μm, etc.).
The invention provides a heat-insulating porcelain-coated material; the heat-insulating ceramic-coated material comprises a combination of twice-modified composite ceramic hollow particles, polyurethane modified acrylic emulsion, nano cellulose, a leveling agent and a thickening agent; in order to add more hollow ceramic particles into a unit coating, screening and grading the ceramic hollow particles, four twice-modified hollow ceramic particles with different particle size ranges are added into a porcelain-coated material for compounding, a certain mathematical particle size proportion arrangement is met, and how to pile small balls with different sizes is similar to how to pile small gaps, so that the heat insulation performance of the obtained heat insulation porcelain-coated material is greatly improved; the polyurethane modified acrylic emulsion is matched, various auxiliary agents are adjusted to the emulsion, the prepared ceramic-coated material is guaranteed to have good performance and be uniformly and firmly attached to a metal section, the suspension of the ceramic-coated material is kept by adding the nano-cellulose, and the polyurethane modified acrylic emulsion can be crosslinked and solidified with the nano-cellulose in the self-crosslinking process to form a unique IPN cross system, so that the finally obtained ceramic-coated material is stronger in binding force with a metal base, a coating is more compact, and the hardness is higher.
The heat-insulating porcelain-coated material provided by the invention can be sprayed on an aluminum plate of a passenger car to be used as a heat-insulating plate of the passenger car, so that the risk of carcinogens and bacteria can be avoided, and the overall comfort in the car is greatly improved.
The twice-modified composite ceramic hollow particles provided by the invention can be obtained by modifying, crushing, screening and grading the purchased ceramic hollow particles, and then selecting hollow ceramic particles with proper particle size for compounding.
Preferably, the twice-modified composite ceramic hollow particle is prepared by a method comprising the following steps:
(A1) mixing the composite ceramic hollow particles with a coupling agent solution, and drying to obtain primary modified composite ceramic hollow particles;
(A2) and (C) mixing the primary modified composite ceramic hollow particles obtained in the step (A1), modified carbonate and a chloroform solution, and drying to obtain the secondary modified composite ceramic hollow particles.
As a preferred technical scheme, the twice-modified composite ceramic hollow particles provided by the invention are subjected to twice chemical modification, so that the twice-modified composite ceramic hollow particles can be well compatible and infiltrated with polyurethane modified acrylic emulsion, and the heat insulation performance of the twice-modified composite ceramic hollow particles cannot be influenced.
Preferably, the mixing time in the step (A1) is 1-3 h, such as 1.2h, 1.4h, 1.6h, 1.8h, 2h, 2.2h, 2.4h, 2.6h or 2.8 h.
Preferably, the temperature of the mixing in the step (A1) is 50 to 60 ℃, for example, 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃, 56 ℃, 57 ℃, 58 ℃ or 59 ℃.
Preferably, the drying temperature in the step (A1) is 100-110 ℃, such as 101 ℃, 102 ℃, 103 ℃, 104 ℃, 105 ℃, 106 ℃, 107 ℃, 108 ℃ or 109 ℃.
Preferably, the drying time in the step (A1) is 2-4 h, such as 2.2h, 2.4h, 2.6h, 2.8h, 3h, 3.2h, 3.4h, 3.6h or 3.8 h.
Preferably, the coupling agent of step (a1) includes a silane coupling agent 550 and/or a silane coupling agent 570.
Preferably, the mixing time in the step (A2) is 1-4 h, such as 1.5h, 2h, 2.5h, 3h or 3.5 h.
Preferably, the temperature of the mixing in the step (A2) is 40 to 60 ℃, for example 42 ℃, 44 ℃, 46 ℃, 48 ℃, 50 ℃, 52 ℃, 54 ℃, 56 ℃ or 58 ℃.
Preferably, the drying temperature in the step (A2) is 100 to 110 ℃, such as 101 ℃, 102 ℃, 103 ℃, 104 ℃, 105 ℃, 106 ℃, 107 ℃, 108 ℃ or 109 ℃.
Preferably, the drying time in the step (A2) is 3-4 h, such as 3.1h, 3.2h, 3.3h, 3.4h, 3.5h, 3.6h, 3.7h, 3.8h or 3.9 h.
Preferably, the modified polycarbonate of step (a2) comprises an epoxy-modified polycarbonate and/or a polyester-modified polycarbonate.
Preferably, the number ratio of the first ceramic particles to the second ceramic particles is 1 (1.5-2), such as 1:1.55, 1:1.6, 1:1.65, 1:1.7, 1:1.75, 1:1.8, 1:1.85, 1:1.9, or 1: 1.95.
Preferably, the number ratio of the first ceramic particles to the third ceramic particles is 1 (2-4), such as 1:2.2, 1:2.4, 1:2.6, 1:2.8, 1:3, 1:3.2, 1:3.4, 1:3.6, or 1: 3.8.
Preferably, the number ratio of the first ceramic particles to the fourth ceramic particles is 1 (0.25-0.75), such as 1:0.3, 1:0.35, 1:0.4, 1:0.45, 1:0.5, 1:0.55, 1:0.6, 1:0.65, or 1:0.7, etc.
As a preferred technical scheme, the composite ceramic hollow particle comprises a first particle, a second particle, a third particle and a fourth particle in a mass ratio of 1 (1.5-2): (2-4): (0.25-0.75); the mass ratio is controlled within the range of the proportion, so that the optimal heat insulation performance can be provided, and the finally obtained heat insulation porcelain-coated material has the most excellent heat insulation effect.
Preferably, the preparation raw materials of the polyurethane modified acrylic resin comprise the following components in parts by weight: 1-20 parts of diacetone acrylamide, 5-30 parts of acrylic acid, 2-10 parts of an emulsifier, 5-30 parts of butyl acrylate, 2-20 parts of methyl methacrylate or styrene, 2-20 parts of acrylamide or vinyl versatate, 1.1-4.5 parts of an initiator, 1-10 parts of adipic dihydrazide and 5-30 parts of a blocked polyurethane prepolymer.
The diacetone acrylamide may be 2 parts by weight, 4 parts by weight, 6 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight, 16 parts by weight, 18 parts by weight, or the like.
The acrylic acid may be 7 parts by weight, 9 parts by weight, 11 parts by weight, 13 parts by weight, 16 parts by weight, 19 parts by weight, 23 parts by weight, 26 parts by weight, 29 parts by weight, or the like.
The emulsifier can be 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, or 9 parts by weight, and the like.
The butyl acrylate may be 7 parts by weight, 9 parts by weight, 11 parts by weight, 13 parts by weight, 16 parts by weight, 19 parts by weight, 23 parts by weight, 26 parts by weight, 29 parts by weight, or the like.
The methyl methacrylate or styrene may be 2 parts by weight, 4 parts by weight, 6 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight, 16 parts by weight, 18 parts by weight, or the like.
The 2 to 20 parts by weight of the acrylamide or the vinyl versatate may be 2 parts by weight, 4 parts by weight, 6 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight, 16 parts by weight, 18 parts by weight, or the like.
The initiator may be 1.5, 2, 2.5, 3, 3.5, 4, 4.5, etc. parts by weight.
The adipic acid dihydrazide may be 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, or the like.
The blocked polyurethane prepolymer may be 7 parts by weight, 9 parts by weight, 11 parts by weight, 13 parts by weight, 16 parts by weight, 19 parts by weight, 23 parts by weight, 26 parts by weight, 29 parts by weight, or the like.
The preparation method of the polyurethane modified acrylic resin provided by the invention comprises the following steps: adding distilled water, an emulsifier, diacetone acrylamide, acrylic acid, butyl acrylate, methyl methacrylate or styrene, acrylamide or vinyl versatate into a reaction kettle provided with a reflux condenser as required for mixing, adding 30 mass percent of the mixed monomer into the reaction kettle, heating the reaction kettle to 80 ℃, adding an initiator, dropwise adding the rest 70 mass percent of the monomer into the reaction kettle within 2 hours, adding 0.1-1.5 parts of the initiator every half hour, heating to 90 ℃, keeping the temperature for 1 hour, cooling, and adding adipic dihydrazide and a blocked polyurethane prepolymer at 50 ℃.
Preferably, the emulsifier comprises polyoxyethylene octyl phenol ether-10 and/or sodium dodecylbenzene sulfonate.
In the invention, the emulsifier is a compound emulsifier, and the preparation method comprises the following steps: mixing polyoxyethylene octyl phenol ether-10, sodium dodecyl benzene sulfonate and silane coupling agent according to the mass ratio of 4:3:1 at 50-80 ℃ for 30 minutes to prepare the composite emulsifier.
Preferably, the initiator comprises ammonium persulfate.
Preferably, the ratio of length to diameter of the nanocellulose is (50-100): 1, such as 55:1, 60:1, 65:1, 70:1, 75:1, 80:1, 85:1, 90:1 or 95: 1.
Preferably, the thickener comprises polyacrylamide and/or neutral polyacrylic acid.
Preferably, the thermal insulation porcelain-coated material further comprises any one or a combination of at least two of a stabilizer, an orange peel prevention agent or a thixotropic agent.
Preferably, the stabilizer is contained in the thermal-insulation porcelain-coated material in an amount of 0.5 to 5 parts by weight, for example, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, or 4.5 parts by weight.
Preferably, the heat-insulating porcelain-coated material contains 0.5 to 5 parts by weight of an orange peel inhibitor, for example, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, or 4.5 parts by weight.
Preferably, the thixotropic agent is contained in the thermal insulation porcelain-coated material in an amount of 0.5 to 5 parts by weight, for example, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, or 4.5 parts by weight. Preferably, the thixotropic agent is fumed silica.
In a second aspect, the present invention provides a method for preparing the thermal insulating porcelain-coated material according to the first aspect, the method comprising the steps of:
(1) mixing the polyurethane modified acrylic emulsion, the leveling agent, the thickening agent, the optional stabilizer, the optional orange peel preventing agent and the optional thixotropic agent to obtain a mixed emulsion;
(2) and (2) mixing the mixed emulsion obtained in the step (1), nano-cellulose and twice modified composite ceramic hollow particles to obtain the heat-insulating ceramic-coated material.
Preferably, the mixing time in step (1) is 1-3 h, such as 1.2h, 1.4h, 1.6h, 1.8h, 2h, 2.2h, 2.4h, 2.6h or 2.8 h.
Preferably, the mixing in step (1) is performed under stirring conditions, and further, under stirring conditions at a rotation speed of 2000 to 4000rpm (for example, 2200rpm, 2400rpm, 2600rpm, 2800rpm, 3000rpm, 3200rpm, 3400rpm, 3600rpm, 3800rpm, or the like).
Preferably, the mixing in step (2) is performed under stirring conditions, and further performed under stirring conditions at a rotation speed of 500 to 1500rpm (e.g., 600rpm, 700rpm, 800rpm, 900rpm, 1000rpm, 1100rpm, 1200rpm, 1300rpm, 1400rpm, etc.).
Preferably, the mixing in step (2) specifically comprises: and (3) mixing the twice modified composite ceramic hollow particles with the mixed emulsion and the nano-cellulose obtained in the step (1) in batches according to the particle size.
In the invention, as a preferred technical scheme, in the step (2), after the mixed emulsion and the nanocellulose are mixed, stirring is carried out for 10min, then the first ceramic particle, the second ceramic particle, the third ceramic particle and the fourth ceramic particle are added slowly, after one particle size is added, stirring is carried out for 30-40 min, then the next particle size is added, the stirring revolution is controlled to be 500-1500 rpm, and after the stirring is finished, the heat-insulating ceramic-coated material can be obtained; the composite ceramic hollow particles are added according to the mode, so that the compatibility of the composite ceramic hollow particles and emulsion is better, the mixing is more uniform, and the heat insulation performance of the porcelain-coated material is further improved.
In a third aspect, the present invention provides the use of a thermal insulating porcelain according to the first aspect in automotive or building construction.
Compared with the prior art, the invention has the following beneficial effects:
(1) the heat-insulating ceramic-coated material provided by the invention comprises a combination of twice-modified composite ceramic hollow particles, polyurethane modified acrylic emulsion, nano-cellulose, a leveling agent and a thickening agent; through adding the ceramic particle of four kinds of different particle diameter scope, collocation polyurethane modification acrylic acid emulsion and nanocellulose, make the thermal-insulated porcelain-coated material that finally obtains have the effectual advantage that keeps warm, can spray and use as passenger train heat insulating board to passenger train aluminum plate, compare in traditional thermal-insulated cotton material have the environmental protection, do not have carcinogenic risk, thermal-insulated efficient, be difficult for producing dust and germ pollution, long service life, machining performance is superior and priorities such as easy cleaning, can improve the car internal environment quality and the heat preservation effect of passenger train greatly, important research significance is had.
(2) Specifically, the heat-insulating porcelain-coated material provided by the invention is qualified in a copper-accelerated acetate spray test, has pencil hardness of HB-2H, is qualified in a high-low temperature alternation test, is qualified in an acid resistance test and is qualified in an alkali resistance test, is qualified in an oil resistance 0# diesel oil test or only slightly discolors, is qualified in paint film hardness determined by an anti-corrosion (neutral salt spray test) method, is qualified in a water resistance test or slightly whitens, and has a heat conductivity coefficient of 0.0692-0.0723W/(m.K).
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Preparation example 1
The preparation method of the twice modified composite ceramic hollow particles comprises the following steps:
(1) mixing the composite ceramic hollow particles (the particle diameters are respectively 120 mu m, 80 mu m, 60 mu m and 30 mu m, and the mass ratio is 2:4:7:1) and a silane coupling agent 570 in an ethanol solution for 3 hours at the temperature of 50 ℃, and drying for 4 hours at the temperature of 100 ℃ to obtain primary modified composite ceramic hollow particles;
(2) mixing the primary modified composite ceramic hollow particles obtained in the step (1), epoxy modified polycarbonate (Corsai Polymer Co., Ltd., model 1803) and chloroform solution at 40 ℃ for 1h, and drying at 100 ℃ for 3h to obtain the secondary modified composite ceramic hollow particles.
Preparation example 2
The preparation method of the twice modified composite ceramic hollow particles comprises the following steps:
(1) mixing the composite ceramic hollow particles (the particle diameters are respectively 115 mu m, 75 mu m, 55 mu m and 25 mu m, and the mass ratio is 2:4:7:1) and a silane coupling agent 550 in an ethanol solution for 1h under vacuum at 50 ℃, and drying for 2h at 100 ℃ to obtain primary modified composite ceramic hollow particles;
(2) and (2) mixing the primary modified composite ceramic hollow particles obtained in the step (1), epoxy modified polycarbonate (Sauter basic industries, Inc., 945A-116) and a chloroform solution at 40 ℃ for 4 hours, and drying at 100 ℃ for 4 hours to obtain the secondary modified composite ceramic hollow particles.
Preparation example 3
The preparation method of the twice modified composite ceramic hollow particles comprises the following steps:
(1) mixing the composite ceramic hollow particles (the particle diameters are respectively 125 microns, 85 microns, 65 microns and 35 microns, and the mass ratio is 2:4:7:1) and a silane coupling agent 550 in an ethanol solution for 3 hours at the temperature of 60 ℃ in vacuum, and drying for 4 hours at the temperature of 100 ℃ to obtain primary modified composite ceramic hollow particles;
(2) and (2) mixing the primary modified composite ceramic hollow particles obtained in the step (1), epoxy modified polycarbonate (Sauter basic industries, Inc., 945A-116) and a chloroform solution at 40 ℃ for 4 hours, and drying at 100 ℃ for 3 hours to obtain the secondary modified composite ceramic hollow particles.
Preparation example 4
The preparation method of the twice modified composite ceramic hollow particles comprises the following steps:
(1) mixing the composite ceramic hollow particles (the particle diameters are respectively 120 mu m, 80 mu m, 60 mu m and 30 mu m, and the mass ratio is 2:4:7:1) and a silane coupling agent 550 in an ethanol solution for 2 hours at the temperature of 60 ℃ under vacuum, and drying for 3 hours at the temperature of 100 ℃ to obtain primary modified composite ceramic hollow particles;
(2) mixing the primary modified composite ceramic hollow particles obtained in the step (1), epoxy modified polycarbonate (Korean Samsung, SC-1220R) and a chloroform solution at 50 ℃ for 3h, and drying at 100 ℃ for 3h to obtain the secondary modified composite ceramic hollow particles.
Preparation example 5
The preparation method of the twice modified composite ceramic hollow particles comprises the following steps:
(1) mixing the composite ceramic hollow particles (the particle diameters are respectively 120 mu m, 80 mu m, 60 mu m and 30 mu m, and the mass ratio is 2:4:7:1) and a silane coupling agent 550 in an ethanol solution for 1h under vacuum at 50 ℃, and drying for 3h at 100 ℃ to obtain primary modified composite ceramic hollow particles;
(2) and (2) mixing the primary modified composite ceramic hollow particles obtained in the step (1), epoxy modified polycarbonate (Korean Samsung, SC-1220R) and a chloroform solution at 40 ℃ for 4 hours, and drying at 100 ℃ for 3 hours to obtain the secondary modified composite ceramic hollow particles.
Preparation example 6
The polyurethane modified acrylic resin comprises the following raw materials in parts by weight: 1 part by weight of diacetone acrylamide, 5 parts by weight of acrylic acid, 2 parts by weight of emulsifier, 5 parts by weight of butyl acrylate, 20 parts by weight of methyl methacrylate, 5 parts by weight of vinyl versatate, ammonium persulfate, 5 parts by weight of adipic dihydrazide, 5 parts by weight of blocked polyurethane prepolymer and 50 parts by weight of distilled water;
the preparation method of the polyurethane modified acrylic resin provided by the preparation example comprises the following steps:
(1) mixing diacetone acrylamide, distilled water, acrylic acid, an emulsifier, butyl acrylate, methyl methacrylate and vinyl versatate to obtain a mixed monomer;
(2) mixing the mixed monomer obtained in the step (1) with the mass percentage of 30% and 3 parts by weight of ammonium persulfate in a reaction kettle, heating the reaction kettle to 80 ℃, dropwise adding the remaining mixed monomer obtained in the step (1) with the mass percentage of 70% into the reaction kettle within 2h, dropwise adding 1.5 parts by weight of ammonium persulfate four times within 2h, heating to 90 ℃, keeping the temperature for 1h, cooling to 50 ℃, and adding adipic dihydrazide and end-capped polyurethane prepolymer (Dow, MDI prepolymer isocyanate NE466) to obtain the polyurethane modified acrylic resin.
Comparative preparation example 1
A modified composite ceramic hollow particle, the preparation method comprises: and (2) mixing the composite ceramic hollow particles (the particle diameters are respectively 120 mu m, 80 mu m, 60 mu m and 30 mu m, and the mass ratio is 2:4:7:1) and a silane coupling agent 570 in an ethanol solution for 3 hours at the temperature of 50 ℃, and drying for 4 hours at the temperature of 100 ℃ to obtain the modified composite ceramic hollow particles.
Comparative preparation example 2
A modified composite ceramic hollow particle, the preparation method comprises: the modified composite ceramic hollow particles are obtained by mixing composite ceramic hollow particles (the particle diameters are respectively 120 mu m, 80 mu m, 60 mu m and 30 mu m, and the mass ratio is 2:4:7:1) with epoxy modified polycarbonate (Corcission Polymer Co., Ltd., model 1803) and a chloroform solution at 40 ℃ for 1h under vacuum and 50 ℃, and drying at 100 ℃ for 3 h.
Comparative preparation example 3
Composite ceramic hollow particles with the particle diameters of 120 microns, 80 microns, 60 microns and 30 microns respectively and the mass ratio of 2:4:7: 1.
Comparative preparation example 4
A modified ceramic hollow particle differing from production example 1 only in that, in step (1), a ceramic particle having a particle diameter of 120 μm was used in place of four of the composite ceramic hollow particles.
Comparative preparation example 5
A modified ceramic hollow particle differing from production example 1 only in that, in step (1), a ceramic particle having a particle diameter of 80 μm was used in place of four of the composite ceramic hollow particles.
Comparative preparation example 6
A modified ceramic hollow particle differing from production example 1 only in that, in step (1), a ceramic particle having a particle diameter of 60 μm was used in place of four of the composite ceramic hollow particles.
Comparative preparation example 7
A modified ceramic hollow particle differing from production example 1 only in that, in step (1), four of the composite ceramic hollow particles having a particle size were replaced with ceramic particles having a particle size of 30 μm.
Example 1
A heat-insulating porcelain-coated material comprises the following components in parts by weight:
the preparation method comprises the following steps:
(1) mixing polyurethane modified acrylic emulsion (preparation example 6), a leveling agent (German Bick chemical BYK346), polyacrylamide, a stabilizer (German bear thermal stabilizer, BAEROSTABNT 340RF), an orange peel preventing agent (Guangzhou Yitong polymer materials Co., Ltd. EFKA6700) and fumed silica for 3 hours at the rotating speed of 2000rpm to obtain mixed emulsion;
(2) and (2) mixing the mixed emulsion obtained in the step (1) with the nano-cellulose for 10min, adding the twice modified composite ceramic hollow particles (preparation example 1) and mixing for 2h under the condition that the rotating speed is 500rpm to obtain the heat insulation porcelain-coated material.
Example 2
A heat-insulating porcelain-coated material comprises the following components in parts by weight:
the preparation method comprises the following steps:
(1) mixing polyurethane modified acrylic emulsion (preparation example 6), a leveling agent (German Bick chemical BYK346), polyacrylamide, a stabilizer (German bear thermal stabilizer BAEROSTABNT 340RF), an orange peel preventing agent (Guangzhou Kogyoto polymer materials Co., Ltd., EFKA6700) and fumed silica for 3 hours at the rotating speed of 2000rpm to obtain mixed emulsion;
(2) and (2) mixing the mixed emulsion obtained in the step (1) with nano-cellulose for 10min, adding the twice modified composite ceramic hollow particles (preparation example 2), and mixing for 2h under the condition that the rotating speed is 500rpm to obtain the heat insulation porcelain-coated material.
Example 3
A heat-insulating porcelain-coated material comprises the following components in parts by weight:
the preparation method comprises the following steps:
(1) mixing polyurethane modified acrylic emulsion (preparation example 6), a leveling agent (German Bick chemical BYK346), polyacrylamide, a stabilizer (German bear thermal stabilizer BAEROSTABNT 340RF), an orange peel preventing agent (Guangzhou Kogyoto polymer materials Co., Ltd., EFKA6700) and fumed silica for 3 hours at the rotating speed of 2000rpm to obtain mixed emulsion;
(2) and (2) mixing the mixed emulsion obtained in the step (1) with the nano-cellulose for 10min, adding the twice modified composite ceramic hollow particles (preparation example 3) and mixing for 2h under the condition that the rotating speed is 500rpm to obtain the heat insulation porcelain-coated material.
Example 4
A thermal insulating porcelain-coated material which differs from example 1 only in that the twice-modified composite ceramic hollow particles obtained in production example 1 were replaced with the twice-modified composite ceramic hollow particles obtained in production example 4, and the other components, amounts and production methods were the same as in example 1.
Example 5
A thermal insulating porcelain-coated material which differs from example 1 only in that the twice-modified composite ceramic hollow particles obtained in production example 1 were replaced with the twice-modified composite ceramic hollow particles obtained in production example 5, and the other components, amounts and production methods were the same as in example 1.
Comparative example 1
A thermal insulating porcelain-coated material which differs from example 1 only in that the modified composite ceramic hollow particles obtained in comparative preparation example 1 were used in place of the twice-modified composite ceramic hollow particles obtained in preparation example 1, and the other components, amounts and preparation methods were the same as in example 1.
Comparative example 2
A thermal insulating porcelain-coated material which differs from example 1 only in that the twice-modified composite ceramic hollow particles obtained in production example 1 were replaced with the modified composite ceramic hollow particles obtained in comparative production example 2, and the other components, amounts and production methods were the same as in example 1.
Comparative example 3
A thermal insulating porcelain-coated material which differs from example 1 only in that the double-modified composite ceramic hollow particles obtained in production example 1 were replaced with the composite ceramic hollow particles obtained in comparative production example 3, and the other components, amounts and production methods were the same as in example 1.
Comparative example 4
A thermal insulating porcelain-coated material which differs from example 1 only in that the modified ceramic hollow particles obtained in comparative preparation example 4 were used in place of the twice-modified composite ceramic hollow particles obtained in preparation example 1, and the other components, amounts and preparation methods were the same as in example 1.
Comparative example 5
A thermal insulating porcelain-coated material which differs from example 1 only in that the modified ceramic hollow particles obtained in comparative preparation example 5 were used in place of the twice-modified composite ceramic hollow particles obtained in preparation example 1, and the other components, amounts and preparation methods were the same as in example 1.
Comparative example 6
A thermal insulating porcelain-coated material which differs from example 1 only in that the modified ceramic hollow particles obtained in comparative preparation example 6 were used in place of the twice-modified composite ceramic hollow particles obtained in preparation example 1, and the other components, amounts and preparation methods were the same as in example 1.
Comparative example 7
A thermal insulating porcelain-coated material which differs from example 1 only in that the modified ceramic hollow particles obtained in comparative preparation example 7 were used in place of the twice-modified composite ceramic hollow particles obtained in preparation example 1, and the other components, amounts and preparation methods were the same as in example 1.
Comparative example 8
A thermal insulating porcelain-coated material which differs from example 1 only in that the urethane-modified acrylic emulsion obtained in production example 6 was replaced with an unmodified acrylic emulsion, and the other components, amounts and production methods were the same as in example 1.
And (3) performance testing: the test items, test standards, methods and criteria are shown in table 1;
TABLE 1
The porcelain-coated materials provided in examples 1 to 5 and comparative examples 1 to 8 were tested according to the above-mentioned test method, and the test results are shown in tables 2 and 3:
table 2:
TABLE 3
As can be seen from the data in tables 2 and 3: the heat-insulating porcelain-coated material provided by the invention has excellent comprehensive performance, and specifically, the heat-insulating porcelain-coated materials obtained in the embodiments 1 to 5 are qualified through a copper-accelerated acetate fog test, pencil hardness is HB-2H, high and low temperature alternation tests, acid resistance tests, alkali resistance tests, oil resistance 0# diesel oil test or only slightly discolored, paint film hardness determined by a corrosion resistance (neutral salt fog test) method is qualified, water resistance tests are qualified or slightly whitened, and the thermal conductivity is 0.0692-0.0723W/(m.K).
Comparing example 1 with comparative examples 1 to 3, it can be found that the heat-insulating ceramic-coated material obtained by adding the once-modified or unmodified composite ceramic hollow particles is not qualified in the copper-accelerated acetate spray test, the pencil hardness is only B, the high-low temperature alternation test, the acid resistance and the alkali resistance are not qualified, the oil resistance 0# diesel oil test is discolored, and the corrosion resistance (neutral salt spray test) method is used for determining that the paint film hardness is not qualified and the water resistance test is whitened obviously.
Comparing example 1 with comparative examples 4 to 7, it was found that the modified ceramic hollow particles having only one particle size had a large thermal conductivity, indicating a decrease in heat insulating properties. Comparing example 1 with comparative example 8, it can be seen that the thermal insulation porcelain-coated material prepared by the unmodified acrylic emulsion has reduced or even unqualified performances.
The applicant states that the present invention is illustrated by the above examples of a thermal insulating porcelain-coated material, and a method for preparing the same and an application thereof, but the present invention is not limited to the above examples, that is, it does not mean that the present invention must be implemented by the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The heat-insulation porcelain-coated material is characterized by comprising the following components in parts by weight:
the twice-modified composite ceramic hollow particles comprise a combination of first ceramic particles with the particle size of 115-125 microns, second ceramic particles with the particle size of 75-85 microns, third ceramic particles with the particle size of 55-65 microns and fourth ceramic particles with the particle size of 25-35 microns.
2. The insulated porcelain-coated material of claim 1, wherein the twice-modified composite ceramic hollow particles are prepared by a method comprising the steps of:
(A1) mixing the composite ceramic hollow particles with a coupling agent solution, and drying to obtain primary modified composite ceramic hollow particles;
(A2) mixing the primary modified composite ceramic hollow particles obtained in the step (A1), modified carbonate and a chloroform solution, and drying to obtain the secondary modified composite ceramic hollow particles;
preferably, the mixing time of the step (A1) is 1-3 h;
preferably, the temperature of the mixing in the step (A1) is 50-60 ℃;
preferably, the drying temperature of the step (A1) is 100-110 ℃;
preferably, the drying time of the step (A1) is 2-4 h;
preferably, the coupling agent of step (a1) comprises silane coupling agent 550 and/or silane coupling agent 570;
preferably, the mixing time of the step (A2) is 1-4 h;
preferably, the temperature of the mixing in the step (A2) is 40-60 ℃;
preferably, the drying temperature of the step (A2) is 100-110 ℃;
preferably, the drying time in the step (A2) is 3-4 h;
preferably, the modified polycarbonate of step (a2) comprises an epoxy-modified polycarbonate and/or a polyester-modified polycarbonate.
3. The heat-insulating porcelain-coated material according to claim 1 or 2, wherein the number ratio of the first ceramic particles to the second ceramic particles is 1 (1.5-2);
preferably, the number ratio of the first ceramic particles to the third ceramic particles is 1 (2-4);
preferably, the number ratio of the first ceramic particles to the fourth ceramic particles is 1 (0.25-0.75).
4. The heat-insulating porcelain-coated material according to any one of claims 1 to 3, wherein the polyurethane modified acrylic resin is prepared from the following raw materials in parts by weight: 1-20 parts of diacetone acrylamide, 5-30 parts of acrylic acid, 2-10 parts of an emulsifier, 5-30 parts of butyl acrylate, 2-20 parts of methyl methacrylate or styrene, 2-20 parts of acrylamide or vinyl versatate, 1.1-4.5 parts of a hair agent, 1-10 parts of adipic dihydrazide and 5-30 parts of a blocked polyurethane prepolymer.
5. The insulated porcelain coating material of claim 4, wherein the emulsifier comprises polyoxyethylene octylphenol ether-10 and/or sodium dodecylbenzene sulfonate;
preferably, the initiator comprises ammonium persulfate;
preferably, the length-diameter ratio of the nano cellulose is (50-100): 1.
6. The insulated porcelain coating material of any one of claims 1 to 5, wherein the thickener comprises polyacrylamide and/or neutral polyacrylic acid;
preferably, the thermal insulation porcelain-coated material further comprises any one or a combination of at least two of a stabilizer, an orange peel prevention agent or a thixotropic agent;
preferably, the content of the stabilizer in the heat insulation porcelain-coated material is 0.5-5 parts by weight;
preferably, the content of the orange peel preventing agent in the heat-insulating porcelain-coated material is 0.5-5 parts by weight;
preferably, the content of the thixotropic agent in the heat-insulating porcelain-coated material is 0.5-5 parts by weight;
preferably, the thixotropic agent is fumed silica.
7. A method for preparing the heat-insulating porcelain-coated material as claimed in any one of claims 1 to 6, which comprises the steps of:
(1) mixing the polyurethane modified acrylic emulsion, the leveling agent, the thickening agent, the optional stabilizer, the optional orange peel preventing agent and the optional thixotropic agent to obtain a mixed emulsion;
(2) and (2) mixing the mixed emulsion obtained in the step (1), nano-cellulose and twice modified composite ceramic hollow particles to obtain the heat-insulating ceramic-coated material.
8. The preparation method according to claim 7, wherein the mixing time in the step (1) is 1-3 h;
preferably, the mixing in the step (1) is carried out under the condition of stirring, and further under the stirring condition of the rotating speed of 2000-4000 rpm.
9. The production method according to claim 7 or 8, wherein the mixing in the step (2) is performed under stirring, and further under stirring at a rotation speed of 500 to 1500 rpm;
preferably, the mixing in step (2) specifically comprises: and (3) mixing the twice modified composite ceramic hollow particles with the mixed emulsion and the nano-cellulose obtained in the step (1) in batches according to the particle size.
10. Use of a thermal barrier porcelain according to any one of claims 1 to 6 in automobiles;
preferably, the automobile is a passenger car.
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