CN108034323B - Environment-friendly interior wall coating and preparation method thereof - Google Patents
Environment-friendly interior wall coating and preparation method thereof Download PDFInfo
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- CN108034323B CN108034323B CN201810098819.4A CN201810098819A CN108034323B CN 108034323 B CN108034323 B CN 108034323B CN 201810098819 A CN201810098819 A CN 201810098819A CN 108034323 B CN108034323 B CN 108034323B
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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
- 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
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
- C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
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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
- 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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- 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
- C09D5/18—Fireproof paints including high temperature resistant paints
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- C—CHEMISTRY; METALLURGY
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
Abstract
The invention discloses an environment-friendly interior wall coating which comprises the following components in parts by weight: 35-45 parts of fluorine-containing triazine film-forming polymer, 10-15 parts of phosphonic acid modified nano titanium dioxide, 20-30 parts of pigment and filler, 2-5 parts of defoaming agent, 3-7 parts of film-forming additive and 20-30 parts of water. The preparation method of the environment-friendly interior wall coating comprises the following steps: putting the fluorine-containing triazine film-forming polymer, phosphonic acid modified nano titanium dioxide, pigment filler, defoaming agent, dispersing agent and film-forming aid into a high-speed mixer in proportion, mixing for 20-30min, then putting into a ball milling tank, carrying out ball milling treatment for 5-8 h to obtain mixed powder, adding water into the mixed powder, dispersing for 10-15 min at the rotating speed of 1200-1500 rpm, post-curing for 2-5 days, sampling, inspecting, sieving and packaging after qualification. The environment-friendly interior wall coating disclosed by the invention is lower in price, more remarkable in formaldehyde absorption and decomposition effect, higher in efficiency, free of secondary pollution, high in visible light response speed, stronger in fireproof performance and bonding capability and better in weather resistance.
Description
Technical Field
The invention relates to the technical field of building decoration materials, in particular to an environment-friendly interior wall coating and a preparation method thereof.
Background
In recent years, with the increasing living standard of people, various decorative coatings come up endlessly, which bring about more and more serious environmental problems while bringing comfort to people, and bring fatal harm to people's life and body. The interior wall coating, one of the decorative coatings, is directly coated on the inner surface of a building or a structure, is closely related to the living and working relationships of people, and the green, non-toxic and odorless characteristics of the interior wall coating are more concerned with the health and environment attention of people.
The important substance that interior wall coating pollutes the air environment of the room is formaldehyde, which is mainly released by wood adhesive and plastic used in interior decoration, decorative materials and furniture, thereby causing great threat to human health and becoming the first killer of human health. How to remove formaldehyde and other volatile organic compounds in indoor air has become a focus of attention.
At present, the main methods for removing formaldehyde are physical adsorption and chemical decomposition. Physical adsorption has adsorption equilibrium, namely saturation exists, formaldehyde can not be absorbed after saturation, and when conditions are changed, such as temperature is increased, absorbed formaldehyde can be released into air again, and secondary pollution is caused. The chemical decomposition is to decompose formaldehyde by adding photocatalyst titanium dioxide, and has the characteristics of high efficiency, no secondary pollution and the like. However, titanium dioxide only absorbs ultraviolet light, has low response to visible light, and due to the recombination of photo-generated electrons and holes, the light quantum efficiency is very low, which severely restricts the wide application of the titanium dioxide.
Therefore, there is a need for an environmentally friendly interior wall coating with good weather resistance, strong adhesion to walls, antibacterial property and fire resistance.
Disclosure of Invention
The invention aims to provide an environment-friendly interior wall coating and a preparation method thereof, wherein the preparation method is simple and easy to implement, has low requirements on equipment, is easy to obtain components, is convenient to post-treat and low in price, and is suitable for large-scale production; the prepared environment-friendly interior wall coating overcomes the defects that the traditional interior wall coating is high in cost, poor in fireproof grade, high in construction difficulty, poor in binding capacity, easy to fall off, easy to release formaldehyde, and capable of causing environmental pollution threatening the health of people. Compared with the traditional interior wall coating in the prior art, the environment-friendly interior wall coating disclosed by the invention is lower in price, more remarkable in formaldehyde absorption and decomposition effect, higher in efficiency, free of secondary pollution, high in visible light response speed, stronger in fireproof performance and bonding capability and better in weather resistance.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows: an environment-friendly interior wall coating comprises the following components in parts by weight: 35-45 parts of fluorine-containing triazine film-forming polymer, 10-15 parts of phosphonic acid modified nano titanium dioxide, 20-30 parts of pigment and filler, 2-5 parts of defoaming agent, 3-7 parts of film-forming additive and 20-30 parts of water.
Preferably, the pigment and filler is one or more of rutile titanium dioxide, lithopone, heavy calcium carbonate, light calcium carbonate, talcum powder, calcined kaolin, mica powder, wollastonite powder, superfine aluminum silicate, barite powder, quartz powder, asbestos powder and white carbon black, and the proportion of any two or more of the above is arbitrary.
The antifoaming agent is preferably one or more of tributyl phosphate, antifoaming agent Droju 3100 and antifoaming agent BYK 088.
The film-forming auxiliary agent is one or more of propylene glycol, methyl ether, propylene glycol butyl ether, alcohol ester twelve, diethylene glycol butyl ether or benzyl alcohol.
Further, the preparation method of the fluorine-containing triazine film-forming polymer comprises the following steps:
1) adding glycidyl methacrylate and 4, 6-bis (2,2, 2-trifluoroethoxy) -1,3, 5-triazine-2-amine (CAS:301211-00-7) into an organic solvent, adding a polymerization inhibitor tetrachlorobenzoquinone into the organic solvent, stirring and reacting for 6 to 8 hours at the temperature of between 80 and 90 ℃, then performing rotary evaporation to remove the solvent, washing for 4 to 6 times by using diethyl ether, and performing rotary evaporation again to remove the diethyl ether;
2) adding glycidyl methacrylate and 2, 4-dioxohexahydro-1, 3, 5-triazine (CAS:27032-78-6) into tetrahydrofuran, adding polymerization inhibitor tetrachlorobenzoquinone, stirring and reacting at 80-90 ℃ for 6-8 hours, performing rotary evaporation to remove the solvent, washing with diethyl ether for 4-6 times, and performing rotary evaporation to remove the diethyl ether again;
3) dissolving the crude product prepared in the step 1), the crude product prepared in the step 2), methyl methacrylate and 1-isopropenyl-2-benzimidazolone in a high-boiling-point solvent, adding an initiator, stirring and reacting for 2-3 hours at 55-65 ℃ in a nitrogen atmosphere, precipitating in acetone, washing for 4-6 times by using ethyl acetate, and drying for 10-15 hours at 60-80 ℃ in a vacuum drying oven.
Preferably, the mass ratio of the glycidyl methacrylate, the 4, 6-bis (2,2, 2-trifluoroethoxy) -1,3, 5-triazine-2-amine, the organic solvent and the chloranil in the step 1) is 1: (2-3): (10-15): (0.01-0.03).
The organic solvent is selected from one or more of isopropanol, dichloromethane, acetone and acetonitrile.
In the step 2), the mass ratio of the glycidyl methacrylate to the 2, 4-dioxohexahydro-1, 3, 5-triazine to the tetrahydrofuran to the tetrachlorobenzoquinone is 1: (2-4): (10-15): (0.01-0.03).
In the step 3), the mass ratio of the crude product prepared in the step 1) to the crude product prepared in the step 2) to the methyl methacrylate, 1-isopropenyl-2-benzimidazolone, the high-boiling-point solvent and the initiator is 1: (2-3):1: (10-15): (0.03-0.06).
The high boiling point solvent is selected from one or more of dimethyl sulfoxide, N-methyl pyrrolidone and N, N-dimethylformamide; the initiator is selected from one or more of azobisisobutyronitrile and azobisisoheptonitrile.
The preparation method of the phosphonic acid modified nano titanium dioxide comprises the following steps:
s1) dissolving [ phosphorylmethyl imine ] bis [2, 1-ethylideneiminodimethylene ] tetraphosphonic acid (CAS:15827-60-8) in ether, adding chloropropyltrimethoxysilane, stirring and reacting at 30-40 ℃ for 4-8 hours, removing the solvent by rotary evaporation, washing with ethyl acetate for 3-5 times, and then removing the ethyl acetate by rotary evaporation again;
s2) dispersing the nano titanium dioxide into ethanol, adding the product prepared in the step S1), stirring and reacting for 2-3 hours at 30-40 ℃, and then removing the solvent by rotary evaporation to obtain the surface-modified nano titanium dioxide;
s3) soaking the surface-modified nano titanium dioxide prepared in the step S2) in a solution of 10-20% by mass of 2,2' - (1, 2-vinylidene) bis [5- [ (1, 4-dihydro-4-oxo-6-phenylamino) -1,3, 5-triazinyl-2-yl ] amino ] benzenesulfonic acid disodium salt (CAS:1264-32-0) at 60 ℃ for 30-40 hours, washing with water by centrifugation for 4-6 times, and drying in a vacuum drying oven at 60-80 ℃ for 12-16 hours.
Preferably, in step S1), the mass ratio of [ phosphorylmethyl imine ] bis [2, 1-ethylidenediaminodimethylene ] tetraphosphonic acid, diethyl ether and chloropropyltrimethoxysilane is 1: (5-10):1.2.
The mass ratio of the nano titanium dioxide, the ethanol and the product prepared in the step S1) in the step S2) is (3-5): (10-15):1.
The mass ratio of the solution of the surface-modified nano titanium dioxide and the solution of the 2,2' - (1, 2-vinylidene) bis [5- [ (1, 4-dihydro-4-oxo-6-phenylamino) -1,3, 5-triazinyl-2-yl ] amino ] benzenesulfonic acid disodium salt in the step S3) is 1: (50-100).
Preferably, the preparation method of the environment-friendly interior wall coating comprises the following steps: putting the fluorine-containing triazine film-forming polymer, phosphonic acid modified nano titanium dioxide, pigment filler, defoaming agent, dispersing agent and film-forming aid into a high-speed mixer in proportion, mixing for 20-30min, then putting into a ball milling tank, carrying out ball milling treatment for 5-8 h to obtain mixed powder, adding water into the mixed powder, dispersing for 10-15 min at the rotating speed of 1200-1500 rpm, post-curing for 2-5 days, sampling, inspecting, sieving and packaging after qualification.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
(1) the environment-friendly interior wall coating disclosed by the invention is easy to obtain components, low in price, simple and feasible in preparation method, low in requirement on equipment and suitable for large-scale production.
(2) The environment-friendly interior wall coating disclosed by the invention overcomes the defects that the traditional interior wall coating is high in cost, poor in fireproof grade, high in construction difficulty, poor in binding capacity, easy to fall off, easy to release formaldehyde, and capable of causing environmental pollution threatening the health of people. Compared with the traditional interior wall coating in the prior art, the environment-friendly interior wall coating disclosed by the invention is lower in price, more remarkable in formaldehyde absorption and decomposition effect, higher in efficiency, free of secondary pollution, high in visible light response speed, stronger in fireproof performance and bonding capability and better in weather resistance.
(3) The environment-friendly interior wall coating disclosed by the invention is added with phosphonic acid modified nano titanium dioxide, has better capability of absorbing and decomposing formaldehyde, effectively avoids the defect that the nano titanium dioxide which is singly used and is photocatalyst can be degraded only by depending on ultraviolet light, realizes the effect of long-acting degradation and pollution, is favorable for improving the dispersibility of nano materials by modifying the surface of the nano titanium dioxide, and avoids the influence of agglomeration on the coating performance.
(4) The phosphonic acid modified nano titanium dioxide is added into the environment-friendly interior wall coating disclosed by the invention, and the flame retardant and fireproof performance of the coating can be obviously improved due to the addition of the N/P element.
(5) The invention discloses an environment-friendly interior wall coating, which is prepared by adding phosphonic acid modified nano titanium dioxide, fixing 2,2' - (1, 2-ethenylidene) bis [5- [ (1, 4-dihydro-4-oxo-6-phenylamino) -1,3, 5-triazinyl-2-yl ] amino ] benzene sulfonate through ionic bonds, and due to the conjugated structure of the nano titanium dioxide, the nano titanium dioxide has certain visible light response capability, can further improve the capability of decomposing formaldehyde, and due to the introduction of a quaternary ammonium salt structure, the antibacterial and mildew resistance of the coating can be improved.
(6) The environment-friendly interior wall coating disclosed by the invention adopts the fluorine-containing triazine film-forming polymer, on one hand, the ultraviolet aging resistance and the weather resistance of the coating can be obviously improved, and the 2, 4-dioxohexahydro-1, 3, 5-triazine structure is introduced, so that the formaldehyde can be further absorbed.
(7) The environment-friendly interior wall coating disclosed by the invention does not need to use an organic solvent with higher volatility as a solvent, and is safe and environment-friendly to use.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
An environment-friendly interior wall coating comprises the following components in parts by weight: 35 parts of fluorine-containing triazine film-forming polymer, 10 parts of phosphonic acid modified nano titanium dioxide, 20 parts of rutile titanium dioxide, 2 parts of tributyl phosphate, 3 parts of propylene glycol and 20 parts of water.
The preparation method of the fluorine-containing triazine film-forming polymer comprises the following steps:
1) adding 10g of glycidyl methacrylate and 20g of 4, 6-bis (2,2, 2-trifluoroethoxy) -1,3, 5-triazine-2-amine (CAS:301211-00-7) into 100g of isopropanol, adding 0.1g of polymerization inhibitor tetrachlorobenzoquinone, stirring and reacting at 80 ℃ for 6 hours, then performing rotary evaporation to remove the solvent, washing with diethyl ether for 4 times, and performing rotary evaporation again to remove the diethyl ether;
2) adding 10g of glycidyl methacrylate and 20g of 2, 4-dioxohexahydro-1, 3, 5-triazine (CAS:27032-78-6) into 100g of tetrahydrofuran, adding 0.1g of polymerization inhibitor tetrachlorobenzoquinone, stirring and reacting at 80 ℃ for 6 hours, removing the solvent by rotary evaporation, washing with diethyl ether for 4 times, and removing the diethyl ether by rotary evaporation again;
3) dissolving 8g of the crude product prepared in the step 1), 8g of the crude product prepared in the step 2), 16g of methyl methacrylate and 8g of 1-isopropenyl-2-benzimidazolone in 80g of dimethyl sulfoxide, adding 0.24g of azobisisobutyronitrile into the mixture, stirring the mixture for reaction for 2 hours at 55 ℃ in a nitrogen atmosphere, precipitating the mixture in acetone, washing the mixture for 4 times by using ethyl acetate, and drying the mixture for 10 hours at 60 ℃ in a vacuum drying oven.
The preparation method of the phosphonic acid modified nano titanium dioxide comprises the following steps:
s1) dissolving 10g of [ phosphorylmethyl imine ] bis [2, 1-ethylideneiminodimethylene ] tetraphosphonic acid (CAS:15827-60-8) in 50g of diethyl ether, adding 12g of chloropropyltrimethoxysilane, stirring and reacting at 30 ℃ for 4 hours, removing the solvent by rotary evaporation, washing with ethyl acetate for 3 times, and then removing the ethyl acetate by rotary evaporation again;
s2) dispersing 30g of nano titanium dioxide into 100g of ethanol, adding 10g of the product prepared in the step S1), stirring and reacting at 30 ℃ for 2 hours, and then removing the solvent by rotary evaporation to obtain surface-modified nano titanium dioxide;
s3) soaking 10g of the surface-modified nano titanium dioxide prepared in the step S2) in 1000g of a solution of 2,2' - (1, 2-vinylidene) bis [5- [ (1, 4-dihydro-4-oxo-6-phenylamino) -1,3, 5-triazinyl-2-yl ] amino ] benzenesulfonic acid disodium salt with the mass fraction of 10% at 60 ℃ for 30 hours, then washing with water by centrifugation for 4 times, and then placing in a vacuum drying oven for drying at 60 ℃ for 12 hours.
A preparation method of the environment-friendly interior wall coating comprises the following steps: putting the fluorine-containing triazine film-forming polymer, phosphonic acid modified nano titanium dioxide, pigment filler, defoaming agent, dispersing agent and film-forming aid into a high-speed mixer in proportion, mixing for 20min, then putting into a ball milling tank, carrying out ball milling treatment for 5 hours to obtain mixed powder, adding water into the mixed powder, dispersing for 10 min at the rotating speed of 1200 rpm, carrying out post-curing for 2 days, sampling, inspecting, sieving and packaging after being qualified.
Example 2
An environment-friendly interior wall coating comprises the following components in parts by weight: 38 parts of fluorine-containing triazine film-forming polymer, 12 parts of phosphonic acid modified nano titanium dioxide, 23 parts of lithopone, a defoaming agent, a humble 31003 part, 4 parts of methyl ether and 23 parts of water.
The preparation method of the fluorine-containing triazine film-forming polymer comprises the following steps:
1) adding 10g of glycidyl methacrylate and 25g of 4, 6-bis (2,2, 2-trifluoroethoxy) -1,3, 5-triazine-2-amine (CAS:301211-00-7) into 120g of dichloromethane, adding 0.15g of polymerization inhibitor tetrachlorobenzoquinone, stirring and reacting at 83 ℃ for 6.5 hours, removing the solvent by rotary evaporation, washing with diethyl ether for 5 times, and removing the diethyl ether by rotary evaporation again;
2) adding 10g of glycidyl methacrylate and 25g of 2, 4-dioxohexahydro-1, 3, 5-triazine (CAS:27032-78-6) into 125g of tetrahydrofuran, adding 0.16g of polymerization inhibitor tetrachlorobenzoquinone, stirring and reacting at 84 ℃ for 7 hours, removing the solvent by rotary evaporation, washing with diethyl ether for 5 times, and removing the diethyl ether by rotary evaporation again;
3) dissolving 8g of the crude product prepared in the step 1), 8g of the crude product prepared in the step 2), 18g of methyl methacrylate and 8g of 1-isopropenyl-2-benzimidazolone in 100g of N-methylpyrrolidone, adding 0.3g of azobisisoheptonitrile into the mixture, stirring and reacting for 2.5 hours at 58 ℃ in a nitrogen atmosphere, precipitating in acetone, washing for 5 times by using ethyl acetate, and drying for 12 hours at 66 ℃ in a vacuum drying oven.
The preparation method of the phosphonic acid modified nano titanium dioxide comprises the following steps:
s1) dissolving 10g of [ phosphorylmethyl imine ] bis [2, 1-ethylideneiminodimethylene ] tetraphosphonic acid (CAS:15827-60-8) in 65g of diethyl ether, adding 12g of chloropropyltrimethoxysilane, stirring and reacting at 35 ℃ for 6 hours, removing the solvent by rotary evaporation, washing with ethyl acetate for 4 times, and then removing the ethyl acetate by rotary evaporation again;
s2) dispersing 35g of nano titanium dioxide into 120g of ethanol, adding 10g of the product prepared in the step S1), stirring and reacting at 34 ℃ for 2.3 hours, and then removing the solvent by rotary evaporation to obtain surface-modified nano titanium dioxide;
s3) soaking 10g of the surface-modified nano titanium dioxide prepared in the step S2) in 900g of a solution of 2,2' - (1, 2-vinylidene) bis [5- [ (1, 4-dihydro-4-oxo-6-phenylamino) -1,3, 5-triazinyl-2-yl ] amino ] benzenesulfonic acid disodium salt with the mass fraction of 13% at 60 ℃ for 33 hours, then washing the solution 5 times by water centrifugation, and then placing the solution in a vacuum drying oven for drying at 69 ℃ for 14 hours.
A preparation method of the environment-friendly interior wall coating comprises the following steps: putting the fluorine-containing triazine film-forming polymer, phosphonic acid modified nano titanium dioxide, pigment filler, defoaming agent, dispersing agent and film-forming aid in a high-speed mixer in proportion, mixing for 23min, then putting into a ball mill tank, carrying out ball milling treatment for 6.5 hours to obtain mixed powder, adding water into the mixed powder, dispersing for 13 min at the rotating speed of 1300 r/min, carrying out post-curing for 3 days, sampling, inspecting, sieving and packaging after the product is qualified.
Example 3
An environment-friendly interior wall coating comprises the following components in parts by weight: 40 parts of fluorine-containing triazine film-forming polymer, 14 parts of phosphonic acid modified nano titanium dioxide, 27 parts of ground calcium carbonate, a defoaming agent BYK0884 parts, 5 parts of propylene glycol butyl ether and 26 parts of water.
The preparation method of the fluorine-containing triazine film-forming polymer comprises the following steps:
1) adding 10g of glycidyl methacrylate and 26g of 4, 6-bis (2,2, 2-trifluoroethoxy) -1,3, 5-triazine-2-amine (CAS:301211-00-7) into 135g of acetone, adding 0.22g of polymerization inhibitor tetrachlorobenzoquinone, stirring and reacting at 86 ℃ for 7 hours, then performing rotary evaporation to remove the solvent, washing with diethyl ether for 6 times, and performing rotary evaporation again to remove the diethyl ether;
2) adding 10g of glycidyl methacrylate and 25g of 2, 4-dioxohexahydro-1, 3, 5-triazine (CAS:27032-78-6) into 140g of tetrahydrofuran, adding 0.23g of polymerization inhibitor tetrachlorobenzoquinone, stirring and reacting at 85 ℃ for 7 hours, removing the solvent by rotary evaporation, washing with diethyl ether for 5 times, and removing the diethyl ether by rotary evaporation again;
3) dissolving 10g of the crude product prepared in the step 1), 10g of the crude product prepared in the step 2), 26g of methyl methacrylate and 10g of 1-isopropenyl-2-benzimidazolone in 140g of N, N-dimethylformamide, adding 0.43g of azobisisobutyronitrile into the mixture, stirring the mixture to react for 2.6 hours at 61 ℃ in a nitrogen atmosphere, precipitating the mixture in acetone, washing the mixture for 6 times by using ethyl acetate, and drying the mixture for 14.2 hours at 72 ℃ in a vacuum drying oven.
The preparation method of the phosphonic acid modified nano titanium dioxide comprises the following steps:
s1) dissolving 10g of [ phosphorylmethyl imine ] bis [2, 1-ethylideneiminodimethylene ] tetraphosphonic acid (CAS:15827-60-8) in 75g of diethyl ether, adding 12g of chloropropyltrimethoxysilane, stirring and reacting at 37 ℃ for 7 hours, removing the solvent by rotary evaporation, washing with ethyl acetate for 5 times, and then removing the ethyl acetate by rotary evaporation again;
s2) dispersing 42g of nano titanium dioxide into 140g of ethanol, adding 10g of the product prepared in the step S1), stirring and reacting at 37 ℃ for 2.7 hours, and then removing the solvent by rotary evaporation to obtain surface-modified nano titanium dioxide;
s3) soaking 10g of the surface-modified nano titanium dioxide prepared in the step S2) in 800g of a solution of 2,2' - (1, 2-vinylidene) bis [5- [ (1, 4-dihydro-4-oxo-6-phenylamino) -1,3, 5-triazinyl-2-yl ] amino ] benzenesulfonic acid disodium salt with the mass fraction of 15% at 60 ℃ for 36 hours, then washing the solution by water centrifugation for 6 times, and then placing the solution in a vacuum drying oven for drying at 73 ℃ for 15 hours.
A preparation method of the environment-friendly interior wall coating comprises the following steps: putting the fluorine-containing triazine film-forming polymer, phosphonic acid modified nano titanium dioxide, pigment filler, defoaming agent, dispersing agent and film-forming aid into a high-speed mixer in proportion, mixing for 27min, then putting into a ball milling tank, carrying out ball milling treatment for 7 hours to obtain mixed powder, adding water into the mixed powder, dispersing for 14 min at the rotating speed of 1200-1500 rpm, post-curing for 4 days, sampling, inspecting, sieving and packaging after being qualified.
Example 4
An environment-friendly interior wall coating comprises the following components in parts by weight: 42 parts of a fluorine-containing triazine film-forming polymer, 15 parts of phosphonic acid modified nano titanium dioxide, 28 parts of a pigment and filler, 4 parts of a defoaming agent, 6 parts of benzyl alcohol and 30 parts of water; the pigment and filler is prepared by mixing heavy calcium carbonate, light calcium carbonate and talcum powder according to the mass ratio of 1:2: 3; the defoaming agent is preferably tributyl phosphate, a defoaming agent Demodex 3100 and a defoaming agent BYK088 which are mixed according to the mass ratio of 2:3: 1.
The preparation method of the fluorine-containing triazine film-forming polymer comprises the following steps:
1) adding 10g of glycidyl methacrylate and 28g of 4, 6-bis (2,2, 2-trifluoroethoxy) -1,3, 5-triazine-2-amine (CAS:301211-00-7) into 145g of acetonitrile, adding 0.25g of polymerization inhibitor tetrachlorobenzoquinone, stirring and reacting at 88 ℃ for 8 hours, removing the solvent by rotary evaporation, washing with diethyl ether for 5 times, and removing the diethyl ether by rotary evaporation again;
2) adding 10g of glycidyl methacrylate and 35g of 2, 4-dioxohexahydro-1, 3, 5-triazine (CAS:27032-78-6) into 140g of tetrahydrofuran, adding 0.28g of polymerization inhibitor tetrachlorobenzoquinone, stirring and reacting at 88 ℃ for 8 hours, removing the solvent by rotary evaporation, washing with diethyl ether for 6 times, and removing the diethyl ether by rotary evaporation again;
3) dissolving 10g of the crude product prepared in the step 1), 10g of the crude product prepared in the step 2), 28g of methyl methacrylate and 10g of 1-isopropenyl-2-benzimidazolone in 145g of a high-boiling-point solvent, adding 0.5g of an initiator into the mixture, stirring the mixture to react for 3 hours at 62 ℃ in a nitrogen atmosphere, precipitating the mixture in acetone, washing the mixture for 6 times by using ethyl acetate, and drying the mixture for 14 hours at 75 ℃ in a vacuum drying oven; the high-boiling-point solvent is prepared by mixing dimethyl sulfoxide and N, N-dimethylformamide according to the mass ratio of 3: 5; the initiator is prepared by mixing azodiisobutyronitrile and azodiisoheptonitrile according to the mass ratio of 2: 5.
The preparation method of the phosphonic acid modified nano titanium dioxide comprises the following steps:
s1) dissolving 10g of [ phosphorylmethyl imine ] bis [2, 1-ethylideneiminodimethylene ] tetraphosphonic acid (CAS:15827-60-8) in 90g of diethyl ether, adding 12g of chloropropyltrimethoxysilane, stirring and reacting at 38 ℃ for 7.5 hours, removing the solvent by rotary evaporation, washing with ethyl acetate for 5 times, and then removing the ethyl acetate by rotary evaporation again;
s2) dispersing 47g of nano titanium dioxide into 145g of ethanol, adding 10g of the product prepared in the step S1), stirring and reacting at 38 ℃ for 3 hours, and then removing the solvent by rotary evaporation to obtain surface-modified nano titanium dioxide;
s3) soaking the surface-modified nano titanium dioxide prepared in the step S2) in 700g of a solution of 18% by mass of 2,2' - (1, 2-vinylidene) bis [5- [ (1, 4-dihydro-4-oxo-6-phenylamino) -1,3, 5-triazinyl-2-yl ] amino ] benzenesulfonic acid disodium salt at 60 ℃ for 37 hours, then washing the solution by water centrifugation for 6 times, and then placing the solution in a vacuum drying oven for drying at 77 ℃ for 15 hours.
A preparation method of the environment-friendly interior wall coating comprises the following steps: putting the fluorine-containing triazine film-forming polymer, phosphonic acid modified nano titanium dioxide, pigment filler, defoaming agent, dispersing agent and film-forming aid in a high-speed mixer according to a proportion, mixing for 29min, then putting into a ball mill tank, carrying out ball milling treatment for 7.5 hours to obtain mixed powder, adding water into the mixed powder, dispersing for 14 min at the rotating speed of 1400 rpm, post-curing for 4.5 days, sampling, inspecting, sieving and packaging after being qualified.
Example 5
An environment-friendly interior wall coating comprises the following components in parts by weight: 45 parts of fluorine-containing triazine film-forming polymer, 15 parts of phosphonic acid modified nano titanium dioxide, 30 parts of talcum powder, 5 parts of tributyl phosphate, 7 parts of diethylene glycol monobutyl ether and 30 parts of water.
The preparation method of the fluorine-containing triazine film-forming polymer comprises the following steps:
1) adding 10g of glycidyl methacrylate and 30g of 4, 6-bis (2,2, 2-trifluoroethoxy) -1,3, 5-triazine-2-amine (CAS:301211-00-7) into 150g of isopropanol, adding 0.3g of polymerization inhibitor tetrachlorobenzoquinone, stirring and reacting at 90 ℃ for 8 hours, then performing rotary evaporation to remove the solvent, washing with diethyl ether for 6 times, and performing rotary evaporation again to remove the diethyl ether;
2) adding 10g of glycidyl methacrylate and 40g of 2, 4-dioxohexahydro-1, 3, 5-triazine (CAS:27032-78-6) into 150g of tetrahydrofuran, adding 0.3g of polymerization inhibitor tetrachlorobenzoquinone, stirring and reacting at 90 ℃ for 8 hours, removing the solvent by rotary evaporation, washing with diethyl ether for 6 times, and removing the diethyl ether by rotary evaporation again;
3) dissolving 10g of the crude product prepared in the step 1), 10g of the crude product prepared in the step 2), 30g of methyl methacrylate and 10g of 1-isopropenyl-2-benzimidazolone in 150g of N-methylpyrrolidone, adding 0.6g of azobisisoheptonitrile into the mixture, stirring and reacting for 3 hours at 65 ℃ in a nitrogen atmosphere, precipitating in acetone, washing for 6 times by using ethyl acetate, and drying for 15 hours at 80 ℃ in a vacuum drying oven.
The preparation method of the phosphonic acid modified nano titanium dioxide comprises the following steps:
s1) dissolving 10g of [ phosphorylmethyl imine ] bis [2, 1-ethylideneiminodimethylene ] tetraphosphonic acid (CAS:15827-60-8) in 100g of diethyl ether, adding 12g of chloropropyltrimethoxysilane, stirring at 40 ℃ for reacting for 8 hours, removing the solvent by rotary evaporation, washing with ethyl acetate for 5 times, and then removing the ethyl acetate by rotary evaporation again;
s2) dispersing 50g of nano titanium dioxide into 150g of ethanol, adding 10g of the product prepared in the step S1), stirring and reacting at 40 ℃ for 3 hours, and then removing the solvent by rotary evaporation to obtain surface-modified nano titanium dioxide;
s3) soaking 10g of the surface-modified nano titanium dioxide prepared in the step S2) in 560g of a solution of 2,2' - (1, 2-vinylidene) bis [5- [ (1, 4-dihydro-4-oxo-6-phenylamino) -1,3, 5-triazinyl-2-yl ] amino ] benzenesulfonic acid disodium salt with the mass fraction of 20% at 60 ℃ for 40 hours, then washing the solution 6 times by water centrifugation, and then placing the solution in a vacuum drying oven for drying at 80 ℃ for 16 hours.
A preparation method of the environment-friendly interior wall coating comprises the following steps: placing the fluorine-containing triazine film-forming polymer, phosphonic acid modified nano titanium dioxide, pigment filler, defoaming agent, dispersing agent and film-forming aid in a high-speed mixer according to a certain proportion, mixing for 30min, then placing the mixture into a ball mill tank, carrying out ball milling treatment for 8 hours to obtain mixed powder, adding water into the mixed powder, dispersing for 15 min at the rotating speed of 1500 rpm, carrying out post-curing for 5 days, sampling, inspecting, sieving and packaging after the materials are qualified.
Comparative example
Common interior wall coatings are commercially available.
The interior wall coatings obtained in examples 1 to 5 and comparative example were tested, and the test results and test methods are shown in Table 1.
TABLE 1 examples and comparative examples interior wall coating Properties
From the above table, it can be seen that the environment-friendly interior wall coating disclosed by the embodiment of the invention has the formaldehyde purification rate of 98.9-100%, the adhesive force of 9.2-11.5MPa, the scrubbing resistance of 1200 times without leaking the substrate, and the fire resistance of 45.6-49.7min, while the commercially available common interior wall coating has the formaldehyde purification rate of 80%, the adhesive force of 4.3MPa, the scrubbing resistance of 1200 times without leaking the substrate, and the fire resistance of 19min, and thus, the environment-friendly interior wall coating disclosed by the embodiment of the invention has better fire resistance, formaldehyde purification performance and scrubbing resistance, and has larger adhesive force.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (8)
1. The environment-friendly interior wall coating is characterized by comprising the following components in parts by weight: 35-45 parts of fluorine-containing triazine film-forming polymer, 10-15 parts of phosphonic acid modified nano titanium dioxide, 20-30 parts of pigment and filler, 2-5 parts of defoaming agent, 3-7 parts of film-forming additive and 20-30 parts of water;
the preparation method of the fluorine-containing triazine film-forming polymer comprises the following steps:
1) adding glycidyl methacrylate and 4, 6-bis (2,2, 2-trifluoroethoxy) -1,3, 5-triazine-2-amine (CAS:301211-00-7) into an organic solvent, adding a polymerization inhibitor tetrachlorobenzoquinone into the organic solvent, stirring and reacting for 6 to 8 hours at the temperature of between 80 and 90 ℃, then performing rotary evaporation to remove the solvent, washing for 4 to 6 times by using diethyl ether, and performing rotary evaporation again to remove the diethyl ether;
2) adding glycidyl methacrylate and 2, 4-dioxohexahydro-1, 3, 5-triazine (CAS:27032-78-6) into tetrahydrofuran, adding polymerization inhibitor tetrachlorobenzoquinone, stirring and reacting at 80-90 ℃ for 6-8 hours, performing rotary evaporation to remove the solvent, washing with diethyl ether for 4-6 times, and performing rotary evaporation to remove the diethyl ether again;
3) dissolving the crude product prepared in the step 1), the crude product prepared in the step 2), methyl methacrylate and 1-isopropenyl-2-benzimidazolone in a high-boiling-point solvent, adding an initiator, stirring and reacting for 2-3 hours at 55-65 ℃ in a nitrogen atmosphere, precipitating in acetone, washing for 4-6 times by using ethyl acetate, and drying for 10-15 hours at 60-80 ℃ in a vacuum drying oven;
the preparation method of the phosphonic acid modified nano titanium dioxide comprises the following steps:
s1) dissolving [ phosphorylmethyl imine ] bis [2, 1-ethylideneiminodimethylene ] tetraphosphonic acid (CAS:15827-60-8) in ether, adding chloropropyltrimethoxysilane, stirring and reacting at 30-40 ℃ for 4-8 hours, removing the solvent by rotary evaporation, washing with ethyl acetate for 3-5 times, and then removing the ethyl acetate by rotary evaporation again;
s2) dispersing the nano titanium dioxide into ethanol, adding the product prepared in the step S1), stirring and reacting for 2-3 hours at 30-40 ℃, and then removing the solvent by rotary evaporation to obtain the surface-modified nano titanium dioxide;
s3) soaking the surface-modified nano titanium dioxide prepared in the step S2) in a solution of 10-20% by mass of 2,2' - (1, 2-vinylidene) bis [5- [ (1, 4-dihydro-4-oxo-6-phenylamino) -1,3, 5-triazinyl-2-yl ] amino ] benzenesulfonic acid disodium salt (CAS:1264-32-0) at 60 ℃ for 30-40 hours, washing with water by centrifugation for 4-6 times, and drying in a vacuum drying oven at 60-80 ℃ for 12-16 hours.
2. The environment-friendly interior wall coating according to claim 1, wherein the pigment and filler is any one or more than two of rutile type titanium dioxide, lithopone, heavy calcium carbonate, light calcium carbonate, talcum powder, calcined kaolin, mica powder, wollastonite powder, superfine aluminum silicate, barite powder, quartz powder, asbestos powder and white carbon black, and the proportion of any two or more than two of the above components is arbitrary; the defoaming agent is one or more of tributyl phosphate, a defoaming agent Demodex 3100 and a defoaming agent BYK 088; the film-forming auxiliary agent is one or more of propylene glycol, methyl ether, propylene glycol butyl ether, alcohol ester twelve, diethylene glycol butyl ether or benzyl alcohol.
3. The environment-friendly interior wall coating according to claim 1, wherein the mass ratio of the glycidyl methacrylate, the 4, 6-bis (2,2, 2-trifluoroethoxy) -1,3, 5-triazin-2-amine, the organic solvent and the chloranil in the step 1) is 1: (2-3): (10-15): (0.01-0.03).
4. The environment-friendly interior wall coating according to claim 1, wherein the mass ratio of the glycidyl methacrylate to the 2, 4-dioxohexahydro-1, 3, 5-triazine to the tetrahydrofuran to the tetrachlorobenzoquinone in step 2) is 1: (2-4): (10-15): (0.01-0.03).
5. The environment-friendly interior wall coating material according to claim 1, wherein the mass ratio of the crude product prepared in step 3) through step 1) to the crude product prepared in step 2) to methyl methacrylate, 1-isopropenyl-2-benzimidazolone, the high-boiling solvent and the initiator is 1: (2-3):1: (10-15): (0.03-0.06).
6. The environment-friendly interior wall coating material according to claim 1, wherein the organic solvent is one or more selected from isopropanol, dichloromethane, acetone and acetonitrile; the high boiling point solvent is selected from one or more of dimethyl sulfoxide, N-methyl pyrrolidone and N, N-dimethylformamide; the initiator is selected from one or more of azobisisobutyronitrile and azobisisoheptonitrile.
7. The environment-friendly interior wall paint according to claim 1, wherein in the step S1), the mass ratio of the [ phosphorylmethyl imine ] bis [2, 1-ethylideneiminodimethylene ] tetraphosphonic acid to the diethyl ether to the chloropropyltrimethoxysilane is 1: (5-10) 1.2; the mass ratio of the nano titanium dioxide, the ethanol and the product prepared in the step S1) in the step S2) is (3-5): (10-15): 1; the mass ratio of the solution of the surface-modified nano titanium dioxide and the solution of the 2,2' - (1, 2-vinylidene) bis [5- [ (1, 4-dihydro-4-oxo-6-phenylamino) -1,3, 5-triazinyl-2-yl ] amino ] benzenesulfonic acid disodium salt in the step S3) is 1: (50-100).
8. A method for preparing the environment-friendly interior wall coating according to any one of claims 1 to 7, which comprises the following steps: putting the fluorine-containing triazine film-forming polymer, phosphonic acid modified nano titanium dioxide, pigment filler, defoaming agent, dispersing agent and film-forming aid into a high-speed mixer in proportion, mixing for 20-30min, then putting into a ball milling tank, carrying out ball milling treatment for 5-8 h to obtain mixed powder, adding water into the mixed powder, dispersing for 10-15 min at the rotating speed of 1200-1500 rpm, post-curing for 2-5 days, sampling, inspecting, sieving and packaging after qualification.
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| CN111499985A (en) * | 2019-01-30 | 2020-08-07 | 扬州力泰管业有限公司 | PVC-based power cable sleeve and preparation method thereof |
| CN113105820A (en) * | 2020-01-13 | 2021-07-13 | 宁波朗茵新材料有限公司 | Formula and preparation process of anti-condensation spray |
| CN111808322A (en) * | 2020-07-03 | 2020-10-23 | 浙江红励卓纺织有限公司 | Modified ammonium polyphosphate material for antibacterial flame-retardant carpet and preparation method thereof |
| CN112080194B (en) * | 2020-08-14 | 2022-02-11 | 江苏固迈新材料技术有限公司 | Self-luminous pavement |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1123808A (en) * | 1994-10-14 | 1996-06-05 | 泰奥塞集团服务有限公司 | Treated titanium dioxide |
| CN1265691A (en) * | 1997-11-22 | 2000-09-06 | 克罗内斯蒂垣两合公司 | Inorganic particles treated with phosphonatosiloxane |
| CN101356230A (en) * | 2006-01-05 | 2009-01-28 | 旭硝子株式会社 | Fluorine-containing polymer and fluorine-containing polymer composition containing same |
| CN104087107A (en) * | 2014-07-22 | 2014-10-08 | 淄博职业学院 | Scrubbing-resistant antibacterial fireproof environment-friendly children paint and preparation method thereof |
| CN106752531A (en) * | 2016-12-28 | 2017-05-31 | 毛葵燕 | A kind of Environment-friendlyexterior exterior wall paint and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005042649A1 (en) * | 2003-10-23 | 2005-05-12 | The Sherwin-Williams Company | Self-polishing anti-fouling compositions |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1123808A (en) * | 1994-10-14 | 1996-06-05 | 泰奥塞集团服务有限公司 | Treated titanium dioxide |
| CN1265691A (en) * | 1997-11-22 | 2000-09-06 | 克罗内斯蒂垣两合公司 | Inorganic particles treated with phosphonatosiloxane |
| CN101356230A (en) * | 2006-01-05 | 2009-01-28 | 旭硝子株式会社 | Fluorine-containing polymer and fluorine-containing polymer composition containing same |
| CN104087107A (en) * | 2014-07-22 | 2014-10-08 | 淄博职业学院 | Scrubbing-resistant antibacterial fireproof environment-friendly children paint and preparation method thereof |
| CN106752531A (en) * | 2016-12-28 | 2017-05-31 | 毛葵燕 | A kind of Environment-friendlyexterior exterior wall paint and preparation method thereof |
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