CN109486297B - White fluorocarbon finish paint and preparation process thereof - Google Patents

White fluorocarbon finish paint and preparation process thereof Download PDF

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CN109486297B
CN109486297B CN201811411093.1A CN201811411093A CN109486297B CN 109486297 B CN109486297 B CN 109486297B CN 201811411093 A CN201811411093 A CN 201811411093A CN 109486297 B CN109486297 B CN 109486297B
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CN109486297A (en
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张平
张人彦
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Shanghai Kaihong Special Materials Technology Co ltd
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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
    • C09D127/00—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 a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1675—Polyorganosiloxane-containing compositions
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    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1687—Use of special additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils

Abstract

The invention discloses a white fluorocarbon finish paint and a preparation process thereof, relates to the technical field of paints, and solves the problem that the finish paint is easy to crack in the using process due to poor toughness after curing and forming. The composition comprises a component A and a component B which are independently stored and mixed according to the weight part ratio of (7-9) to 1 when in use, wherein the component A comprises the following raw materials in parts by weight: 40-50 parts of fluorocarbon resin; 8-12 parts of methyl silicone resin; 15-20 parts of titanium dioxide; 3-5 parts of barium sulfate; 5-8 parts of butyl acetate; 13-15 parts of dimethylbenzene; 0.1-0.4 part of defoaming agent; 3-6 parts of nano cellulose whiskers; the component B comprises the following raw materials: 80-89 parts of a curing agent; 4-7 parts of a special auxiliary agent. The white fluorocarbon finish paint has good toughness after being used and cured, and is not easy to crack.

Description

White fluorocarbon finish paint and preparation process thereof
Technical Field
The invention relates to the technical field of coatings, in particular to a white fluorocarbon finish and a preparation process thereof.
Background
Paint is a chemical mixture coating that can be firmly covered on the surface of an object for protection, decoration, marking and other special purposes.
The invention discloses a volcanic formaldehyde-resistant wall paint in Chinese patent with publication number CN108559351A, which is prepared from the following components in parts by weight: 270-290 parts of water, 53-58 parts of alkaline porous volcanic rock, 22-25 parts of purple sandy soil, 2-5 parts of hydrous silicate, 12-16 parts of waterborne acrylic resin, 6-8 parts of waterborne fluorocarbon resin, 3-5 parts of imported cellulose, 18-21 parts of hexanediol, 95-105 parts of titanium dioxide, 98-105 parts of calcined kaolin, 170-185 parts of heavy calcium carbonate, 28-33 parts of talcum powder, 7-11 parts of barium sulfate, 140-160 parts of formaldehyde-removing emulsion and 23-30 parts of film-forming auxiliary agent.
In the above patent, the formaldehyde is absorbed and reacted and degraded by the alkaline porous volcanic, and then the SF-105 acrylic acid polymer emulsion is used to improve the indoor air quality, but the porous volcanic easily causes poor toughness of the volcanic formaldehyde-resistant wall paint after curing and forming, and the overall hardness is high, so that the volcanic formaldehyde-resistant wall paint is easy to crack in the using process, and therefore, a new scheme needs to be provided to solve the above problems.
Disclosure of Invention
Aiming at the problem that the finish paint is easy to crack in the using process due to poor toughness of the finish paint after curing and forming in the prior art, the invention aims to provide the white fluorocarbon finish paint which has good compounding effect in use by adding the methyl silicone resin and the nano cellulose whiskers so as to solve the problem, has good toughness after use and curing and is not easy to crack.
In order to achieve the first purpose, the invention provides the following technical scheme:
a white fluorocarbon finish paint comprises a component A and a component B which are separately stored and mixed according to the weight part ratio of (7-9) to 1 when in use, wherein the component A comprises the following raw materials in parts by weight:
40-50 parts of fluorocarbon resin;
8-12 parts of methyl silicone resin;
15-20 parts of titanium dioxide;
3-5 parts of barium sulfate;
5-8 parts of butyl acetate;
13-15 parts of dimethylbenzene;
0.1-0.4 part of defoaming agent;
3-6 parts of nano cellulose whiskers;
the component B comprises the following raw materials:
80-89 parts of a curing agent;
4-7 parts of a special auxiliary agent.
By adopting the technical scheme, the fluorocarbon resin takes a firm C-F bond as a framework, has good heat resistance, cold resistance and low-temperature toughness, the methyl silicone resin has the advantages of high heat resistance, strong oxidation resistance and strong weather resistance, and the fluorocarbon resin and the methyl silicone resin can form an interpenetrating network structure, thereby being beneficial to reducing the surface tension of the white fluorocarbon finish paint and reducing the water contact angle, and greatly improving the hydrophobicity and the anti-contamination property of the white fluorocarbon finish paint after curing and forming. Meanwhile, the toughness of the coating is increased due to the introduction of silicon atoms, and the surface of the coating is not easy to crack.
Titanium dioxide is a good toner, has good dispersibility and good hiding power in white fluorocarbon finish paint. Barium sulfate is a good antirust agent, so that the white fluorocarbon finish has good corrosion resistance after being cured. The defoaming agent has good defoaming effect, so that when the component A and the component B are mixed for use, large bubbles can be avoided in the curing process, and the white fluorocarbon finish paint has good and stable toughness after curing and forming. The dimethylbenzene and the butyl acetate are good solvents, have a certain dilution effect and are beneficial to fully mixing raw materials of all components.
The nanocellulose whisker is a good high-strength reinforcing agent, and under the nano effect of the nanocellulose whisker, the toughness of the white fluorocarbon finish paint after curing and forming is greatly improved, and meanwhile, the nanocellulose whisker and silicon atoms in the methyl silicone resin have good bonding performance, so that a good compounding effect can be achieved, the overall toughness of the white fluorocarbon finish paint after curing and forming can be greatly improved, and the white fluorocarbon finish paint is not easy to crack in the using process. The curing agent and the special auxiliary agent are favorable for quickly curing the white fluorocarbon finish after use, can improve the binding force among the raw materials of each component, and greatly improves the bonding strength between the white fluorocarbon finish and an adherend.
More preferably, the nanocellulose whisker is subjected to modification treatment, and the modification treatment comprises the following steps:
s1, putting the nano cellulose whiskers in corresponding weight parts into a four-neck flask, adding a sulfuric acid solution with the weight part ratio of (6-8): 1, and carrying out constant-temperature stirring reaction for 4-6 hours at the temperature of 40-50 ℃;
s2, adding 400-450 ml of deionized water into a four-neck flask, diluting to stop the reaction, cooling to room temperature, standing for a period of time, pouring out supernatant, and performing centrifugal filtration to obtain a base material;
s3, adding NH with the pH value of 10 into the base material slowly3-NH4Cl buffer solution under constant stirringStirring, neutralizing until the pH value is 7, washing with deionized water, washing with ethanol, and centrifuging to obtain a solid product;
and S4, carrying out vacuum drying on the solid product at high temperature to obtain the modified nano cellulose whisker.
By adopting the technical scheme, the nano-cellulose whiskers have good agglomeration property and are not easy to be re-dispersed in the white fluorocarbon finish paint, and although the agglomerated nano-cellulose whiskers can also improve the toughness of the white fluorocarbon finish paint after curing, the dispersed nano-cellulose whiskers can enable the toughness of the white fluorocarbon finish paint after curing to be higher, so that the nano-cellulose whiskers are difficult to agglomerate after being modified, have good dispersibility in the white fluorocarbon finish paint, are beneficial to enabling the cured white fluorocarbon finish paint to have higher toughness and are not easy to crack in the using process.
Further preferably, 3.5-5.5 parts by weight of polyaniline is added into the raw materials of the component A.
By adopting the technical scheme, the polyaniline has good electrochemical performance, can react with metal ions in metal products or air, and forms an oxide layer with a protective effect on the surface of the white fluorocarbon finish paint, and the oxide layer has good isolation and protection effects on the cured white fluorocarbon finish paint, so that the toughness and strength of the cured white fluorocarbon finish paint are greatly improved. Meanwhile, when the white fluorocarbon finish paint is applied to a metal product, an oxide layer formed between the white fluorocarbon finish paint and the metal product greatly improves the bonding force between the cured white fluorocarbon finish paint and the metal product, so that the white fluorocarbon finish paint is not easy to break in the using process.
Further preferably, 2-3 parts by weight of silica sol is added into the raw materials of the component A.
By adopting the technical scheme, when the silicon solution in the white fluorocarbon finish paint loses moisture, the monomer silicic acid is gradually polymerized into high polymer silica gel, and the colloidal molecules are increased along with the evaporation of the moisture, and the white fluorocarbon finish paint has good film-forming property due to the silica sol, so that the structural strength and the toughness of the white fluorocarbon finish paint after curing and forming are greatly improved. Meanwhile, the silica sol has stronger permeability to the base layer, so that the white fluorocarbon finish paint can be firmly adhered to the base layer after being cured and formed, and the silica sol is not easy to absorb ash, so that the white fluorocarbon finish paint keeps good cleanliness in the using process, and has good using effect.
Further preferably, the special auxiliary agent mainly comprises polyamide wax and vinyl trimethoxy silane, and the weight part ratio of the polyamide wax to the vinyl trimethoxy silane is 1: (0.8 to 1.2).
By adopting the technical scheme, the polyamide wax is a good anti-settling agent, can improve the integral viscosity of the white fluorocarbon finish paint, can prevent the titanium dioxide, the barium sulfate and the nanocellulose whisker from settling in the component A, is favorable for storing the component A and the component B of the white fluorocarbon finish paint, and can fully mix raw materials of the components. The vinyltrimethoxysilane is a good silane coupling agent, can generate chemical adsorption with methyl silicone resin, can reduce the surface energy of the methyl silicone resin, enables the methyl silicone resin and the nanocellulose whisker to have good bonding performance, and further improves the bonding strength and the overall toughness of the white fluorocarbon finish paint.
More preferably, the defoaming agent is one or more of silicone emulsion, polyoxypropylene glycerol ether and polydimethylsiloxane.
Through adopting above-mentioned technical scheme, in the mixing process of A component and B component, because the stirring, make the air get into the inside formation micro bubble of white fluorocarbon finish paint easily, when white fluorocarbon finish paint is in the curing process, its inside micro bubble takes place to migrate easily and gathers together and form great bubble, and the defoaming agent has the effect of good bubble of getting rid of, make the inside of white fluorocarbon finish paint after curing forming be difficult for appearing great bubble, and keep good stable toughness in the use, and difficult production is cracked in the use.
More preferably, the curing agent is one or more of vinyl triamine, m-xylylenediamine and diaminodiphenylmethane.
By adopting the technical scheme, the curing agent, namely a hardening agent, a curing agent or a setting agent, is a substance or a mixture for enhancing or controlling a curing reaction, and the vinyl triamine, the m-xylylenediamine and the diaminodiphenylmethane are good curing agents, have high overall reaction activity, can be quickly cured at room temperature or low temperature, still have good curing property under a humid condition, and can improve the toughness and the overall structural strength of the white fluorocarbon finish after curing and forming.
The second purpose of the invention is to provide a preparation method of the white fluorocarbon finish paint, and the white fluorocarbon finish paint prepared by the method has good toughness and is not easy to crack after being used and cured.
In order to achieve the second purpose, the invention provides the following technical scheme, which comprises the following steps:
step one, mixing materials, namely uniformly mixing fluorocarbon resin, methyl silicone resin, xylene and butyl acetate in parts by weight to obtain a mixed material;
step two, proportioning the base materials, adding titanium dioxide, barium sulfate, nano cellulose whiskers and a defoaming agent in corresponding parts by weight into the mixed materials, and fully stirring and mixing to obtain the base materials;
grinding the base material, namely grinding the base material to ensure that the fineness of the base material is 15-30 mu to obtain a component A, and storing for later use;
and step four, curing and matching, namely fully mixing the curing agent and the special auxiliary agent in corresponding parts by weight to obtain the component B, and storing for later use.
By adopting the technical scheme, the base material is ground, so that the integral fineness of the white fluorocarbon finish paint is improved, the integral quality of the white fluorocarbon finish paint is improved, uniform coating is facilitated in the use process, the white fluorocarbon finish paint has good and stable toughness after curing and forming, and the white fluorocarbon finish paint is not easy to crack in the use process. Meanwhile, the white fluorocarbon finish paint prepared by the process can be tightly adhered to the surface of a base layer after being cured and formed, and has good curing performance.
In summary, compared with the prior art, the invention has the following beneficial effects:
(1) the addition of the nanocellulose whiskers can greatly improve the toughness of the white fluorocarbon finish after curing and forming, and the addition of the methyl silicone resin can ensure that the nanocellulose whiskers and silicon atoms in the methyl silicone resin have good bonding property and can play a good compounding effect, so that the overall toughness of the white fluorocarbon finish after curing and forming can be greatly improved, and the white fluorocarbon finish is not easy to crack in the use process;
(2) the nanocellulose whiskers are easy to form a ball on the white fluorocarbon finish, so that the toughening effect of the nanocellulose whiskers on the white fluorocarbon finish is greatly reduced, the nanocellulose whiskers are not easy to agglomerate after being modified, the nanocellulose whiskers have good dispersibility in the white fluorocarbon finish, the cured white fluorocarbon finish has high toughness, and the nanocellulose whiskers are not easy to break in the using process;
(3) the silica sol is added, so that the white fluorocarbon finish has stronger penetrability to the base layer, can be firmly adhered to the base layer after being cured and formed, and has good film forming property, so that the structural strength and the toughness of the white fluorocarbon finish after being cured and formed are greatly improved.
Drawings
FIG. 1 is a flow chart of a preparation process of a white fluorocarbon finish paint of the present invention.
Detailed Description
The invention is described in detail below with reference to the figures and examples.
Example 1: a white fluorocarbon finish paint comprises a component A and a component B which are separately stored and mixed according to the weight part ratio of 8:1 when in use, wherein the raw materials of the components and the corresponding weight parts are shown in table 1, and the white fluorocarbon finish paint is prepared by the following steps:
step one, mixing materials, namely stirring fluorocarbon resin, methyl silicone resin, xylene and butyl acetate in corresponding parts by weight in a stirring barrel by using a dispersion machine, wherein the rotating speed of the dispersion machine is 300rpm, and stirring for 25min to obtain a mixed material;
step two, proportioning the base materials, adding titanium dioxide, barium sulfate, nano cellulose whiskers and emulsified silicone oil in corresponding parts by weight into the mixed materials, stirring and mixing by using a dispersion machine, wherein the rotating speed of the dispersion machine is 600rpm, and stirring for 20min to obtain the base materials;
grinding the base material, namely grinding the base material in a horizontal grinder to ensure that the temperature of circulating water is kept at 55 ℃ and the working pressure is 1Mpa/m3The fineness of the base material is 25 mu, so that the component A can be obtained and stored for later use;
and step four, curing and matching, namely stirring the corresponding parts by weight of the vinyl triamine and the special auxiliary agent in a stirring barrel by using a dispersion machine, wherein the rotating speed of the dispersion machine is 480rpm, stirring for 15min, and obtaining the component B, and storing for later use.
Note: the special assistant in the steps mainly comprises polyamide wax and vinyl trimethoxy silane, and the weight part ratio of the polyamide wax to the vinyl trimethoxy silane is 1: 0.8.
examples 2 to 8: a white fluorocarbon finish paint is different from the white fluorocarbon finish paint in example 1 in that raw materials of the components and corresponding parts by weight are shown in Table 1.
TABLE 1 raw materials and their parts by weight in examples 1-8
Figure BDA0001878515650000051
Figure BDA0001878515650000061
Example 9: a white fluorocarbon finish paint is different from that in embodiment 1 in that a special auxiliary agent mainly comprises polyamide wax and vinyl trimethoxy silane, and the weight part ratio of the polyamide wax to the vinyl trimethoxy silane is 1:1.
Example 10: a white fluorocarbon finish paint is different from that in embodiment 1 in that a special auxiliary agent mainly comprises polyamide wax and vinyl trimethoxy silane, and the weight part ratio of the polyamide wax to the vinyl trimethoxy silane is 1: 1.2.
Example 11: the white fluorocarbon finish paint is different from the white fluorocarbon finish paint in the embodiment 1 in that the nano cellulose whiskers are subjected to modification treatment, and the modification treatment comprises the following steps:
s1, putting corresponding parts by weight of nano-cellulose whiskers into a four-neck flask, adding a sulfuric acid solution with the weight part ratio of 6:1 and the mass part ratio of 47%, putting the four-neck flask into a constant-temperature magnetic stirrer, and carrying out constant-temperature stirring reaction for 4 hours at the temperature of 40 ℃;
s2, adding 400ml of deionized water into the four-neck flask, diluting to stop the reaction, cooling to room temperature, standing for 30min, pouring out the supernatant, pouring the lower layer solution into a centrifugal filter for centrifugal filtration at the centrifugal speed of 4000rpm for 20min to obtain a base material;
s3, placing the data into a beaker, and slowly adding NH with pH value of 103-NH4The solution is Cl buffer solution, and is continuously stirred in the process, when the solution is neutralized to the pH value of 7, the solution is washed by deionized water for 3 times, then washed by ethanol for 3 times, and then centrifugally filtered in a centrifugal filter, wherein the centrifugal rotating speed is 4000rpm, and the time is 25min, so that a solid product is obtained;
and S4, drying the solid product in a vacuum drying oven for 24 hours, and maintaining the temperature at 80 ℃ to obtain the modified nano cellulose whisker.
Example 12: a white fluorocarbon finish paint, which is different from the embodiment 11 in that the second step specifically comprises the following steps of adding 15 parts by weight of titanium dioxide, 5 parts by weight of barium sulfate, 3 parts by weight of nanocellulose whisker and 0.1 part by weight of polyoxypropylene glycerol ether into a mixed material, stirring and mixing by using a dispersion machine, wherein the rotating speed of the dispersion machine is 600rpm, and stirring for 20min to obtain a base material.
Example 13: a white fluorocarbon finish paint, which is different from the embodiment 11 in that the second step specifically comprises the following steps of adding 15 parts by weight of titanium dioxide, 5 parts by weight of barium sulfate, 3 parts by weight of nanocellulose whisker and 0.1 part by weight of polydimethylsiloxane into a mixed material, stirring and mixing by using a dispersion machine, wherein the rotating speed of the dispersion machine is 600rpm, and stirring for 20min to obtain a base material.
Example 14: a white fluorocarbon finish paint, which is different from that in the embodiment 11, the second step specifically comprises the following steps of adding 15 parts by weight of titanium dioxide, 5 parts by weight of barium sulfate, 3 parts by weight of nanocellulose whiskers, 0.5 part by weight of polydimethylsiloxane, 0.3 part by weight of silicone emulsion and 0.2 part by weight of polyoxypropylene glycerol ether into a mixed material, stirring and mixing by using a dispersion machine, wherein the rotating speed of the dispersion machine is 600rpm, and stirring for 20min to obtain a base material.
Example 15: a white fluorocarbon finish paint, which is different from that in example 14 in that the fourth step specifically comprises the following steps of stirring 80 parts by weight of m-xylylenediamine and 7 parts by weight of a special auxiliary agent in a stirring barrel by using a dispersion machine, wherein the rotation speed of the dispersion machine is 480rpm, and stirring is carried out for 15min, so as to obtain a component B.
Example 16: a white fluorocarbon finish paint, which is different from that in the embodiment 14, the fourth step specifically comprises the following steps of stirring 80 parts by weight of diaminodiphenylmethane and 7 parts by weight of a special auxiliary agent in a stirring barrel by using a dispersion machine, wherein the rotation speed of the dispersion machine is 480rpm, and stirring for 15min to obtain a component B.
Example 17: a white fluorocarbon finish paint, which is different from that in embodiment 14 in that the fourth step specifically comprises the following steps of stirring, in a stirring barrel, 40 parts by weight of diaminodiphenylmethane, 20 parts by weight of m-xylylenediamine, 20 parts by weight of vinyl triamine and 7 parts by weight of a special auxiliary agent by using a dispersion machine at the rotating speed of 480rpm for 15min to obtain a component B.
Example 18: a white fluorocarbon finish paint, which is different from that in the embodiment 11, the second step specifically comprises the following steps of adding 15 parts by weight of titanium dioxide, 5 parts by weight of barium sulfate, 3 parts by weight of nanocellulose whiskers, 0.1 part by weight of silicone emulsion and 3.5 parts by weight of polyaniline into a mixed material, and stirring and mixing by using a dispersion machine, wherein the rotating speed of the dispersion machine is 600rpm, and stirring for 20min to obtain a base material.
Example 19: a white fluorocarbon finish paint, which is different from that in the embodiment 11, the second step specifically comprises the following steps of adding 15 parts by weight of titanium dioxide, 5 parts by weight of barium sulfate, 3 parts by weight of nanocellulose whiskers, 0.1 part by weight of silicone emulsion and 4.5 parts by weight of polyaniline into a mixed material, and stirring and mixing by using a dispersion machine, wherein the rotating speed of the dispersion machine is 600rpm, and stirring for 20min to obtain a base material.
Example 20: a white fluorocarbon finish paint, which is different from that in the embodiment 11, the second step specifically comprises the following steps of adding 15 parts by weight of titanium dioxide, 5 parts by weight of barium sulfate, 3 parts by weight of nanocellulose whiskers, 0.1 part by weight of silicone emulsion and 5.5 parts by weight of polyaniline into a mixed material, and stirring and mixing by using a dispersion machine, wherein the rotating speed of the dispersion machine is 600rpm, and stirring for 20min to obtain a base material.
Example 21: a white fluorocarbon finish paint, which is different from the embodiment 11 in that the second step specifically comprises the following steps of adding 15 parts by weight of titanium dioxide, 5 parts by weight of barium sulfate, 3 parts by weight of nanocellulose whiskers, 0.1 part by weight of emulsified silicone oil and 2 parts by weight of silica sol into a mixed material, stirring and mixing by using a dispersion machine, wherein the rotating speed of the dispersion machine is 600rpm, and stirring for 20min to obtain a base material.
Example 22: a white fluorocarbon finish paint, which is different from the embodiment 11 in that the second step specifically comprises the following steps of adding 15 parts by weight of titanium dioxide, 5 parts by weight of barium sulfate, 3 parts by weight of nanocellulose whiskers, 0.1 part by weight of emulsified silicone oil and 2.5 parts by weight of silica sol into a mixed material, stirring and mixing by using a dispersion machine, wherein the rotating speed of the dispersion machine is 600rpm, and stirring for 20min to obtain a base material.
Example 23: a white fluorocarbon finish paint, which is different from the embodiment 11 in that the second step specifically comprises the following steps of adding 15 parts by weight of titanium dioxide, 5 parts by weight of barium sulfate, 3 parts by weight of nanocellulose whiskers, 0.1 part by weight of emulsified silicone oil and 3 parts by weight of silica sol into a mixed material, stirring and mixing by using a dispersion machine, wherein the rotating speed of the dispersion machine is 600rpm, and stirring for 20min to obtain a base material.
Example 24: a white fluorocarbon finish paint, which is different from that in the embodiment 11, the second step specifically comprises the following steps of adding 15 parts by weight of titanium dioxide, 5 parts by weight of barium sulfate, 3 parts by weight of nanocellulose whiskers, 0.1 part by weight of emulsified silicone oil, 3.5 parts by weight of polyaniline and 2 parts by weight of silica sol into a mixed material, and stirring and mixing the mixture by using a dispersion machine, wherein the rotating speed of the dispersion machine is 600rpm, and stirring the mixture for 20min to obtain a base material.
Comparative example 1: the difference between the white fluorocarbon finish paint and the embodiment 1 is that the first step specifically comprises the following steps of stirring 40 parts by weight of fluorocarbon resin, 15 parts by weight of xylene and 5 parts by weight of butyl acetate in a stirring barrel by using a dispersion machine, wherein the rotation speed of the dispersion machine is 300rpm, and stirring for 25min to obtain a mixed material.
Comparative example 2: the difference between the white fluorocarbon finish paint and the embodiment 1 is that the second step specifically comprises the following steps of adding 15 parts by weight of titanium dioxide, 5 parts by weight of barium sulfate and 0.1 part by weight of emulsified silicone oil into a mixed material, and stirring and mixing the materials by using a dispersion machine, wherein the rotating speed of the dispersion machine is 600rpm, and stirring the materials for 20min to obtain a base material.
Comparative example 3: a white fluorocarbon finish paint is different from that of the comparative example 1 in that the second step specifically comprises the following steps of adding 15 parts by weight of titanium dioxide, 5 parts by weight of barium sulfate and 0.1 part by weight of emulsified silicone oil into a mixed material, and stirring and mixing the mixture by using a dispersion machine, wherein the rotating speed of the dispersion machine is 600rpm, and stirring the mixture for 20min to obtain a base material.
Test paint film toughness test
Test samples: the white fluorocarbon finishes obtained in examples 1-24 were used as test samples 1-24, and the white fluorocarbon finishes obtained in comparative examples 1-3 were used as control samples 1-3.
The test method comprises the following steps: the test samples 1-24 and the control samples 1-3 are respectively made into 10 standard samples according to the relevant standards in GB/T1731-1993 paint film flexibility test method, the test is carried out according to the method in the standard, the phenomena of damage such as reticulation, crack and peeling of the paint film on the 10 standard samples are observed visually or by a 4-time magnifier, and the flexibility of the paint film is expressed by the minimum diameter of the shaft rod of which the sample plate is bent on shaft rods with different diameters without causing the damage of the paint film.
And (3) test results: the test results of the test samples 1 to 24 and the control samples 1 to 3 are shown in Table 2. As can be seen from table 2, the test results of the test samples 1 to 8 and the control samples 1 to 3 are compared, and both the nanocellulose whisker and the methyl silicone resin are added, so that the toughness of the white fluorocarbon finish after curing and molding can be greatly improved, and the methyl silicone resin and the nanocellulose whisker can play a good compounding effect, so that the overall toughness of the white fluorocarbon finish after curing and molding can be greatly improved. From the comparison of the test results of test samples 1 to 8 with test samples 9 to 10, the weight ratio of polyamide wax to vinyltrimethoxysilane was 1: (0.8-1.2), the toughening effect is good. The comparison of the test results of the test samples 1-8 and the test sample 11 can be used, and the modification treatment of the nanocellulose whiskers is beneficial to enabling the cured white fluorocarbon finish paint to have higher toughness. The comparison of the test results of the test sample 11 and the test samples 18-24 can obtain that the polyaniline and the silica sol can improve the overall toughness of the white fluorocarbon finish after curing and forming.
TABLE 2 test results of test samples 1-24 and control samples 1-3
Figure BDA0001878515650000091
Figure BDA0001878515650000101
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.

Claims (4)

1. The white fluorocarbon finish paint is characterized by comprising a component A and a component B which are stored independently and mixed according to the weight part ratio of (7-9) to 1 when in use, wherein the component A comprises the following raw materials in parts by weight:
40-50 parts of fluorocarbon resin;
8-12 parts of methyl silicone resin;
15-20 parts of titanium dioxide;
3-5 parts of barium sulfate;
5-8 parts of butyl acetate;
13-15 parts of dimethylbenzene;
0.1-0.4 part of defoaming agent;
3-6 parts of nano cellulose whiskers;
3.5-5.5 parts of polyaniline;
2-3 parts of silica sol;
the component B comprises the following raw materials:
80-89 parts of a curing agent;
4-7 parts of a special auxiliary agent;
the special auxiliary agent mainly comprises polyamide wax and vinyl trimethoxy silane, and the weight part ratio of the polyamide wax to the vinyl trimethoxy silane is 1: (0.8 to 1.2);
the nano cellulose whisker is modified, and the modification treatment comprises the following steps:
s1, putting the nano cellulose whiskers in corresponding weight parts into a four-neck flask, adding a sulfuric acid solution with the weight part ratio of (6-8): 1, and carrying out constant-temperature stirring reaction for 4-6 hours at the temperature of 40-50 ℃;
s2, adding 400-450 mL of deionized water into a four-neck flask, diluting to stop the reaction, cooling to room temperature, standing for a period of time, pouring out supernatant, and performing centrifugal filtration to obtain a base material;
s3, adding NH with the pH value of 10 into the base material slowly3-NH4Continuously stirring the Cl buffer solution, neutralizing until the pH value is 7, washing with deionized water, washing with ethanol, and performing centrifugal filtration to obtain a solid product;
and S4, carrying out vacuum drying on the solid product at high temperature to obtain the modified nano cellulose whisker.
2. The white fluorocarbon topcoat as claimed in claim 1, wherein the defoamer is selected from one or more of silicone emulsion, polyoxypropylene glyceryl ether and polydimethylsiloxane.
3. The white fluorocarbon topcoat of claim 1, wherein the curing agent is selected from one or more of vinyl triamine, m-xylylenediamine, and diaminodiphenylmethane.
4. A method of preparing a white fluorocarbon topcoat as claimed in any one of claims 1 to 3, characterized by comprising the steps of:
step one, mixing materials, namely uniformly mixing fluorocarbon resin, methyl silicone resin, xylene and butyl acetate in parts by weight to obtain a mixed material;
step two, proportioning base materials, adding titanium dioxide, barium sulfate, nano cellulose whiskers, a defoaming agent, polyaniline and silica sol in corresponding parts by weight into the mixed materials, and fully stirring and mixing to obtain the base materials;
grinding the base material, namely grinding the base material to ensure that the fineness of the base material is 15-30 mu m to obtain a component A, and storing for later use;
and step four, curing and matching, namely fully mixing the curing agent and the special auxiliary agent in corresponding parts by weight to obtain the component B, and storing for later use.
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