CN111995922A - Environment-friendly fireproof coating and preparation method thereof - Google Patents
Environment-friendly fireproof coating and preparation method thereof Download PDFInfo
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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
- 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
- C09D5/18—Fireproof paints including high temperature resistant paints
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Abstract
The invention discloses an environment-friendly fireproof coating which is characterized by being prepared from the following components in parts by weight: 10-20 parts of vinyl modified hyperbranched polyphosphate, 5-10 parts of acrylate modified p-aminophenyl calixazole, 50-70 parts of 1, 3-bis (ethylene oxide methyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione/3, 3 '-diamino-4, 4' -difluoro diphenyl sulfone polycondensate, 0.5-1.5 parts of initiator, 15-25 parts of inorganic filler, 1-3 parts of defoaming agent and 1-3 parts of dispersing agent. The invention also provides a preparation method of the environment-friendly fireproof coating. The environment-friendly fireproof coating disclosed by the invention is good in comprehensive performance, remarkable in fireproof and flame-retardant effects, good in water resistance, decoration and storage stability, environment-friendly and pollution-free.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to an environment-friendly fireproof coating and a preparation method thereof.
Background
With the development of economy and the progress of science and technology, the living standard of people is improved year by year, the mental civilized building is also widely concerned by people, and the desires of people on improving the home environment and improving the comfort and the aesthetic feeling are more and more urgent. In view of this, the development of building decorative materials represented by paints has been accelerated, and particularly, with the recent widening of the range of use thereof, the market demand has been increased, and the demand for performance thereof has been increasing.
The coating can be coated on the surface of an object by different construction processes to form a continuous solid film with firm adhesion and certain strength. The ideal coating not only needs to be corrosion-resistant, wear-resistant, water-resistant, good in appearance decoration and strong in adhesion, but also needs to be heat-insulating, fireproof and free of environmental pollution. The fire-retardant coating is a common coating which can improve the fire resistance of materials, slow down the propagation speed of flame spread or stop burning for a certain time by brushing the coating on the surface of flammable materials. The fire-retardant coating is a special coating which is used on the surface of flammable base material, can reduce the flammability of the surface of the material to be coated, can retard the rapid spread of fire, and can be used for raising the fire endurance of the material to be coated, or can be used for building components to raise the fire endurance of the components.
Although the existing fireproof coating can play a role in fire prevention and flame retardance, the stability of the coating in a high-temperature environment can be poor, harmful gas can volatilize when the coating is heated, and if the existing fireproof coating is used for manufacturing fire-fighting clothing, the produced harmful gas can damage the health of firemen. In addition, the fire-retardant coatings on the market have the disadvantages of more or less poor water resistance and storage stability, short fire-resistant time, long drying time, poor decorativeness, etc., and generally achieve or enhance fire-retardant performance by adding halogen-containing materials which, in case of fire, generate a large amount of smoke and toxic corrosive gases due to thermal decomposition and combustion, thus preventing fire fighting and evacuation of people, and corroding instruments and equipment.
The Chinese patent with the application number of 201310603180.8 discloses an environment-friendly fireproof coating for tunnels, which is mainly prepared by stirring the following raw materials in parts by weight: 30-35 parts of refractory cement, 30-35 parts of sulphoaluminate cement, 30-35 parts of AEC expanded cement, 30-35 parts of urea-formaldehyde resin, 10-16 parts of soybean oil fatty acid alkyd resin, 5-9 parts of magnesium hydroxide, 5-9 parts of aluminum hydroxide, 10-15 parts of sepiolite, 5-9 parts of perlite, 10-15 parts of ethyl cellulose, 6-10 parts of glass fiber, 8-11 parts of aluminum silicate fiber, 5-7 parts of glass hollow floating beads, 4-8 parts of kaolin, 7-9 parts of vermiculite and 4-8 parts of ammonium dichromate. The coating disclosed by the invention is excellent in fire resistance, corrosion resistance and stability, high in bonding strength, safe, non-toxic, short in curing time, convenient to construct and high in efficiency. However, the raw materials of the coating are complex, the compatibility of the raw materials needs to be further improved, and the urea resin contained in the coating releases formaldehyde in the long-term use process, so that the environmental pollution is caused.
Therefore, the development of the environment-friendly fireproof coating which has good comprehensive performance, obvious fireproof and flame-retardant effects, good water resistance, decoration and storage stability, environmental protection and no pollution meets the market demand, has wide market value and application prospect, and has very important significance for promoting the development of the fireproof coating industry.
Disclosure of Invention
In view of the above, the invention aims to provide an environment-friendly fireproof coating and a preparation method thereof, wherein the preparation method has the advantages of short process flow, convenience in operation, low preparation cost, high preparation efficiency and high yield, and is suitable for continuous large-scale production; the prepared environment-friendly waterproof coating has the advantages of good comprehensive performance, obvious fireproof and flame-retardant effects, good water resistance, decoration and storage stability, environmental protection and no pollution.
In order to achieve the purpose, the invention adopts the technical scheme that:
the environment-friendly fireproof coating is characterized by comprising the following components in parts by weight: 10-20 parts of vinyl modified hyperbranched polyphosphate, 5-10 parts of acrylate modified p-aminophenyl calixazole, 50-70 parts of 1, 3-bis (ethylene oxide methyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione/3, 3 '-diamino-4, 4' -difluoro diphenyl sulfone polycondensate, 0.5-1.5 parts of initiator, 15-25 parts of inorganic filler, 1-3 parts of defoaming agent and 1-3 parts of dispersing agent.
Preferably, the dispersant is sodium hexametaphosphate and/or sodium polycarboxylate; the defoaming agent is one or more of tributyl phosphate, a defoaming agent Demodex 3100 and a defoaming agent BYK 088; the inorganic filler is at least one of attapulgite, volcanic ash, talcum powder or titanium dioxide.
Preferably, the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile.
Preferably, the method for preparing the polycondensate of 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione/3, 3 '-diamino-4, 4' -difluorodiphenyl sulfone comprises the following steps: adding 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, a 3,3' -diamino-4, 4' -difluorodiphenyl sulfone polycondensate, an alkaline catalyst and a polymerization inhibitor into a high boiling point solvent, stirring and reacting for 6-8 hours at 80-90 ℃, then reducing the temperature to room temperature, precipitating in water, washing the precipitated polymer with diethyl ether for 3-6 times, and then removing the diethyl ether by rotary evaporation to obtain 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione/3, 3' -diamino-4, 4' -difluorodiphenyl sulfone polycondensate.
Preferably, the molar ratio of the 1, 3-bis (ethylene oxide methyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione to the 3,3 '-diamino-4, 4' -difluoro diphenyl sulfone polycondensate to the alkaline catalyst to the polymerization inhibitor to the high boiling point solvent is 1:1 (0.8-1.2) to (0.1-0.3) to (10-16).
Preferably, the alkaline catalyst is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide; the polymerization inhibitor is at least one of 1, 4-naphthoquinone and chloranil.
Preferably, the preparation method of the acrylate modified p-aminophenyl calixazole comprises the following steps: adding Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole, 3, 4-epoxy cyclohexyl methyl methacrylate, sodium hydroxide and cuprous chloride into tetrahydrofuran, stirring and reacting at 70-80 ℃ for 4-6 hours, filtering to remove insoluble substances, carrying out rotary evaporation to remove tetrahydrofuran, washing the product with water for 3-7 times, and carrying out rotary evaporation to remove water to obtain the acrylate modified p-aminophenyl calix.
Preferably, the molar ratio of the Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole to the 3, 4-epoxycyclohexyl methyl methacrylate to the sodium hydroxide to the cuprous chloride to the tetrahydrofuran is 1:4 (2-3) to 0.5 (15-25).
Preferably, the preparation method of the vinyl modified hyperbranched polyphosphate ester comprises the following steps: adding epoxy-terminated hyperbranched polyphosphate, 2-amino-1-propenyl-1, 1, 3-trimethylnitrile, sodium hydroxide and cuprous chloride into tetrahydrofuran, stirring and reacting for 4-6 hours at 70-80 ℃, filtering to remove insoluble substances, performing rotary evaporation to remove tetrahydrofuran, washing a product with water for 3-7 times, and performing rotary evaporation to remove water to obtain the vinyl modified hyperbranched polyphosphate.
Preferably, the mass ratio of the epoxy-terminated hyperbranched polyphosphate to the 2-amino-1-propenyl-1, 1, 3-trimethylnitrile to the sodium hydroxide to the cuprous chloride to the tetrahydrofuran is (3-5):1, (2-3):0.6, (20-30).
Preferably, the Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole is prepared by the method described in: synthesis and characterization of Guo Yong, Shaosjun, He Li Jun, et al, meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole [ J ] chemical reagents, 2002(6) 344-; the preparation method of the epoxy-terminated hyperbranched polyphosphate is disclosed in example 8 of application No. 201810153507.9.
The invention also aims to provide a preparation method of the environment-friendly fireproof coating, which is characterized by comprising the following steps of: firstly, uniformly mixing the raw materials except the initiator according to the parts by weight to obtain a mixture, then adding the mixture into a double-screw extruder, extruding at the temperature of 120-130 ℃, uniformly mixing the mixture with the initiator after cooling, crushing and cyclone separation, and curing for 5-8 days.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
(1) the preparation method of the environment-friendly fireproof coating provided by the invention is short in process flow, convenient to operate, low in preparation cost, high in preparation efficiency and yield and suitable for continuous large-scale production.
(2) The environment-friendly fireproof coating provided by the invention overcomes the defects that the stability of the existing fireproof coating is poor in a high-temperature environment, harmful gas is volatilized at a high temperature, the water resistance and storage stability are poor, the fire-resistant time is short, the drying time is long, the decoration performance is poor and the like, and has the advantages of good comprehensive performance, obvious fireproof and flame-retardant effect, good water resistance, decoration performance and storage stability, environmental protection and no pollution.
(3) The environment-friendly fireproof coating provided by the invention takes air as a dispersion medium, does not use an organic solvent, does not release toxic gases such as formaldehyde and the like, does not have the problems of overlong drying time and the like, is safer and more environment-friendly to use, and has better bonding performance with a wall body because more active hydroxyl groups, amino groups and epoxy groups are introduced into molecular chains of each component.
(4) The invention provides an environment-friendly fireproof coating, which is prepared from added vinyl modified hyperbranched polyphosphate, acrylate modified p-aminophenyl calizole and a polycondensate of 1, 3-bis (ethylene oxide methyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione/3, 3 '-diamino-4, 4' -difluoro diphenyl sulfone, wherein molecular chains all contain vinyl, and the vinyl can generate free radical polymerization reaction under the action of an initiator in a curing structure, so that a three-dimensional network structure is formed, the comprehensive performance of the coating is effectively improved, the service life of the coating is prolonged, and the weather resistance and the performance stability of the coating are improved.
(5) According to the environment-friendly fireproof coating provided by the invention, the added vinyl modified hyperbranched polyphosphate ester provides active sites for subsequent curing, and active hydroxyl groups are introduced through modification, so that the bonding performance of the coating and a wall body can be effectively improved; the acrylate modified p-aminophenyl calixazole is introduced, and due to the introduction of the structure of the supermolecule calixazole, the fireproof and flame-retardant effects can be effectively achieved, and the adsorption effect on toxic gases is also achieved, so that the air purification effect is achieved; by modification, an acrylate structure is introduced, so that the polyacrylate film-forming polymer has excellent performance; the sulfuryl, fluorophenyl and triazinyl on the molecular chain of the 1, 3-bis (ethylene oxide methyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione/3, 3 '-diamino-4, 4' -difluoro diphenyl sulfone polycondensate can effectively resist corrosion, weather, fire and flame under the multiple actions of electronic effect, steric effect and conjugation effect, and is waterproof, so that the coating performance is better.
Detailed Description
In order to make the technical solutions of the present invention better understood and make the above features, objects, and advantages of the present invention more comprehensible, the present invention is further described with reference to the following examples. The examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
In the embodiment of the invention, the raw materials are all purchased commercially; preferably, the Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole is prepared by the method described in: synthesis and characterization of Guo Yong, Shaosjun, He Li Jun, et al, meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole [ J ] chemical reagents, 2002(6) 344-; the preparation method of the epoxy-terminated hyperbranched polyphosphate is disclosed in example 8 of application No. 201810153507.9.
Example 1
The environment-friendly fireproof coating is characterized by comprising the following components in parts by weight: 10 parts of vinyl modified hyperbranched polyphosphate, 5 parts of acrylate modified p-aminophenyl calixazole, 50 parts of a polycondensate of 1, 3-bis (ethylene oxide methyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione/3, 3 '-diamino-4, 4' -difluorodiphenyl sulfone, 0.5 part of azodiisobutyronitrile, 15 parts of attapulgite, 1 part of tributyl phosphate and 1 part of sodium hexametaphosphate.
The preparation method of the polycondensate of the 1, 3-bis (ethylene oxide methyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione/3, 3 '-diamino-4, 4' -difluoro diphenyl sulfone comprises the following steps: adding 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, a 3,3' -diamino-4, 4' -difluorodiphenyl sulfone polycondensate, sodium hydroxide and 1, 4-naphthoquinone into dimethyl sulfoxide, stirring and reacting at 80 ℃ for 6 hours, then reducing the temperature to room temperature, precipitating in water, washing the precipitated polymer with diethyl ether for 3 times, and then performing rotary evaporation to remove the diethyl ether to obtain 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione/3, 3' -diamino-4, 4' -difluorodiphenyl sulfone polycondensate; the molar ratio of the 1, 3-bis (ethylene oxide methyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, the 3,3 '-diamino-4, 4' -difluoro diphenyl sulfone polycondensate, the sodium hydroxide, the 1, 4-naphthoquinone and the dimethyl sulfoxide is 1:1:0.8:0.1: 10.
The preparation method of the acrylate modified p-aminophenyl calixazole comprises the following steps: adding Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole, 3, 4-epoxy cyclohexyl methyl methacrylate, sodium hydroxide and cuprous chloride into tetrahydrofuran, stirring and reacting at 70 ℃ for 4 hours, filtering to remove insoluble substances, performing rotary evaporation to remove tetrahydrofuran, washing a product with water for 3 times, and performing rotary evaporation to remove water to obtain the acrylate modified p-aminophenyl calix; the molar ratio of the Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole to the 3, 4-epoxy cyclohexyl methyl methacrylate to the sodium hydroxide to the cuprous chloride to the tetrahydrofuran is 1:4:2:0.5: 15.
The preparation method of the vinyl modified hyperbranched polyphosphate comprises the following steps: adding epoxy-terminated hyperbranched polyphosphate, 2-amino-1-propenyl-1, 1, 3-trimethylnitrile, sodium hydroxide and cuprous chloride into tetrahydrofuran, stirring and reacting for 4 hours at 70 ℃, filtering to remove insoluble substances, performing rotary evaporation to remove tetrahydrofuran, washing a product for 3 times with water, and performing rotary evaporation to remove water to obtain vinyl modified hyperbranched polyphosphate; the mass ratio of the epoxy-terminated hyperbranched polyphosphate to the 2-amino-1-propenyl-1, 1, 3-trimethylnitrile to the sodium hydroxide to the cuprous chloride to the tetrahydrofuran is 3:1:2:0.6: 20.
The preparation method of the environment-friendly fireproof coating is characterized by comprising the following steps: the preparation method comprises the steps of uniformly mixing the raw materials except the azobisisobutyronitrile according to the parts by weight to obtain a mixture, adding the mixture into a double-screw extruder, extruding at 120 ℃, cooling, crushing, performing cyclone separation, uniformly mixing the mixture with the azobisisobutyronitrile, and curing for 5 days.
Example 2
The environment-friendly fireproof coating is characterized by comprising the following components in parts by weight: 13 parts of vinyl modified hyperbranched polyphosphate, 6 parts of acrylate modified p-aminophenyl calixazole, 55 parts of 1, 3-bis (ethylene oxide methyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione/3, 3 '-diamino-4, 4' -difluorodiphenyl sulfone polycondensate, 0.7 part of azodiisoheptanonitrile, 17 parts of volcanic ash, 31001.5 parts of defoaming agent Delhi and 1.5 parts of sodium polycarboxylate.
The preparation method of the polycondensate of the 1, 3-bis (ethylene oxide methyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione/3, 3 '-diamino-4, 4' -difluoro diphenyl sulfone comprises the following steps: adding 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, a polycondensate of 3,3' -diamino-4, 4' -difluorodiphenyl sulfone, potassium hydroxide and tetrachlorobenzoquinone into N, N-dimethylformamide, stirring and reacting at 82 ℃ for 6.5 hours, then reducing the temperature to room temperature, precipitating in water, washing the precipitated polymer with diethyl ether for 4 times, and removing the diethyl ether by rotary evaporation to obtain 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione/3, 3' -diamino-4, 4' -difluorodiphenyl sulfone polycondensate; the molar ratio of the 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione to the 3,3 '-diamino-4, 4' -difluorodiphenyl sulfone polycondensate to the potassium hydroxide to the tetrachlorobenzoquinone to the N, N-dimethylformamide is 1:1:0.9:0.15: 12.
The preparation method of the acrylate modified p-aminophenyl calixazole comprises the following steps: adding Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole, 3, 4-epoxy cyclohexyl methyl methacrylate, sodium hydroxide and cuprous chloride into tetrahydrofuran, stirring and reacting at 73 ℃ for 4.5 hours, filtering to remove insoluble substances, performing rotary evaporation to remove tetrahydrofuran, washing a product with water for 3-7 times, and performing rotary evaporation to remove water to obtain the acrylate modified p-aminophenyl calix; the molar ratio of the Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole to the 3, 4-epoxycyclohexyl methyl methacrylate to the sodium hydroxide to the cuprous chloride to the tetrahydrofuran is 1:4:2.3:0.5: 17.
The preparation method of the vinyl modified hyperbranched polyphosphate comprises the following steps: adding epoxy-terminated hyperbranched polyphosphate, 2-amino-1-propenyl-1, 1, 3-trimethylnitrile, sodium hydroxide and cuprous chloride into tetrahydrofuran, stirring and reacting for 4.5 hours at 73 ℃, filtering to remove insoluble substances, performing rotary evaporation to remove tetrahydrofuran, washing a product with water for 4 times, and performing rotary evaporation to remove water to obtain vinyl-modified hyperbranched polyphosphate; the mass ratio of the epoxy-terminated hyperbranched polyphosphate to the 2-amino-1-propenyl-1, 1, 3-trimethylnitrile to the sodium hydroxide to the cuprous chloride to the tetrahydrofuran is 3.5:1:2.3:0.6: 23.
The preparation method of the environment-friendly fireproof coating is characterized by comprising the following steps: the preparation method comprises the steps of uniformly mixing the raw materials except the azobisisoheptonitrile according to the parts by weight to obtain a mixture, adding the mixture into a double-screw extruder, extruding at 123 ℃, cooling, crushing, performing cyclone separation, uniformly mixing the mixture with the azobisisoheptonitrile, and curing for 6 days.
Example 3
The environment-friendly fireproof coating is characterized by comprising the following components in parts by weight: 15 parts of vinyl modified hyperbranched polyphosphate, 7.5 parts of acrylate modified p-aminophenyl calixazole, 60 parts of 1, 3-bis (ethylene oxide methyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione/3, 3 '-diamino-4, 4' -difluoro diphenyl sulfone polycondensate, 1 part of azodiisoheptonitrile, 20 parts of talcum powder, 20 parts of defoaming agent BYK0882 and 2 parts of sodium hexametaphosphate.
The preparation method of the polycondensate of the 1, 3-bis (ethylene oxide methyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione/3, 3 '-diamino-4, 4' -difluoro diphenyl sulfone comprises the following steps: adding 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, a 3,3' -diamino-4, 4' -difluorodiphenyl sulfone polycondensate, sodium carbonate and 1, 4-naphthoquinone into N, N-dimethylacetamide, stirring and reacting at 85 ℃ for 7 hours, then reducing the temperature to room temperature, precipitating in water, washing the precipitated polymer with diethyl ether for 5 times, and removing the diethyl ether by rotary evaporation to obtain 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione/3, 3' -diamino-4, 4' -difluorodiphenyl sulfone polycondensate; the molar ratio of the 1, 3-bis (ethylene oxide methyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, the 3,3 '-diamino-4, 4' -difluoro diphenyl sulfone polycondensate, sodium carbonate, 1, 4-naphthoquinone and N, N-dimethylacetamide is 1:1:1:0.2: 13.
The preparation method of the acrylate modified p-aminophenyl calixazole comprises the following steps: adding Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole, 3, 4-epoxy cyclohexyl methyl methacrylate, sodium hydroxide and cuprous chloride into tetrahydrofuran, stirring and reacting at 75 ℃ for 5 hours, filtering to remove insoluble substances, performing rotary evaporation to remove tetrahydrofuran, washing a product with water for 5 times, and performing rotary evaporation to remove water to obtain the acrylate modified p-aminophenyl calix; the molar ratio of the Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole to the 3, 4-epoxycyclohexyl methyl methacrylate to the sodium hydroxide to the cuprous chloride to the tetrahydrofuran is 1:4:2.5:0.5: 20.
The preparation method of the vinyl modified hyperbranched polyphosphate comprises the following steps: adding epoxy-terminated hyperbranched polyphosphate, 2-amino-1-propenyl-1, 1, 3-trimethylnitrile, sodium hydroxide and cuprous chloride into tetrahydrofuran, stirring and reacting for 5 hours at 75 ℃, filtering to remove insoluble substances, performing rotary evaporation to remove tetrahydrofuran, washing a product with water for 5 times, and performing rotary evaporation to remove water to obtain vinyl modified hyperbranched polyphosphate; the mass ratio of the epoxy-terminated hyperbranched polyphosphate to the 2-amino-1-propenyl-1, 1, 3-trimethylnitrile to the sodium hydroxide to the cuprous chloride to the tetrahydrofuran is 4:1:2.5:0.6: 25.
The preparation method of the environment-friendly fireproof coating is characterized by comprising the following steps: the preparation method comprises the steps of uniformly mixing the raw materials except the azobisisoheptonitrile according to the parts by weight to obtain a mixture, adding the mixture into a double-screw extruder, extruding at 125 ℃, cooling, crushing, performing cyclone separation, uniformly mixing the mixture with the azobisisoheptonitrile, and curing for 6.5 days.
Example 4
The environment-friendly fireproof coating is characterized by comprising the following components in parts by weight: 18 parts of vinyl modified hyperbranched polyphosphate, 5-10 parts of acrylate modified p-aminophenyl calixazole, 65 parts of 1, 3-bis (ethylene oxide methyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione/3, 3 '-diamino-4, 4' -difluoro diphenyl sulfone polycondensate, 1.4 parts of initiator, 23 parts of inorganic filler, 2.5 parts of defoaming agent and 2.5 parts of dispersing agent.
The dispersing agent is formed by mixing sodium hexametaphosphate and sodium polycarboxylate according to the mass ratio of 3: 5; the defoaming agent is formed by mixing tributyl phosphate, a defoaming agent Demodex 3100 and a defoaming agent BYK088 according to the mass ratio of 1:2: 4; the inorganic filler is formed by mixing attapulgite, volcanic ash, talcum powder and titanium dioxide according to the mass ratio of 1:2:2: 4; the initiator is formed by mixing azodiisobutyronitrile and azodiisoheptonitrile according to the mass ratio of 3: 5.
The preparation method of the polycondensate of the 1, 3-bis (ethylene oxide methyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione/3, 3 '-diamino-4, 4' -difluoro diphenyl sulfone comprises the following steps: adding 1, 3-bis (ethylene oxide methyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, 3 '-diamino-4, 4' -difluoro diphenylsulfone polycondensate, alkaline catalyst and polymerization inhibitor into high boiling point solvent, stirring the reaction mixture at 88 deg.C for 7.5 hr, cooling to room temperature, precipitating in water, washing the precipitated polymer with diethyl ether 5 times, and rotary evaporating to remove diethyl ether to obtain 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione/3, 3 '-diamino-4, 4' -difluorodiphenyl sulfone polycondensate; the molar ratio of the 1, 3-bis (ethylene oxide methyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione to the 3,3 '-diamino-4, 4' -difluoro diphenyl sulfone polycondensate to the alkaline catalyst to the polymerization inhibitor to the high-boiling-point solvent is 1:1:1.1:0.25: 15; the alkaline catalyst is prepared by mixing sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate according to the mass ratio of 1:2:2: 3; the high boiling point solvent is formed by mixing dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide according to a mass ratio of 2:1: 4; the polymerization inhibitor is formed by mixing 1, 4-naphthoquinone and chloranil in a mass ratio of 3: 5.
The preparation method of the acrylate modified p-aminophenyl calixazole comprises the following steps: adding Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole, 3, 4-epoxy cyclohexyl methyl methacrylate, sodium hydroxide and cuprous chloride into tetrahydrofuran, stirring and reacting at 78 ℃ for 5.5 hours, filtering to remove insoluble substances, performing rotary evaporation to remove tetrahydrofuran, washing a product with water for 6 times, and performing rotary evaporation to remove water to obtain the acrylate modified p-aminophenyl calix; the molar ratio of the Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole to the 3, 4-epoxycyclohexyl methyl methacrylate to the sodium hydroxide to the cuprous chloride to the tetrahydrofuran is 1:4:2.8:0.5: 24.
The preparation method of the vinyl modified hyperbranched polyphosphate comprises the following steps: adding epoxy-terminated hyperbranched polyphosphate, 2-amino-1-propenyl-1, 1, 3-trimethylnitrile, sodium hydroxide and cuprous chloride into tetrahydrofuran, stirring and reacting at 78 ℃ for 5.8 hours, filtering to remove insoluble substances, performing rotary evaporation to remove tetrahydrofuran, washing a product with water for 6 times, and performing rotary evaporation to remove water to obtain vinyl-modified hyperbranched polyphosphate; the mass ratio of the epoxy-terminated hyperbranched polyphosphate to the 2-amino-1-propenyl-1, 1, 3-trimethylnitrile to the sodium hydroxide to the cuprous chloride to the tetrahydrofuran is 4.5:1:2.8:0.6: 28.
The preparation method of the environment-friendly fireproof coating is characterized by comprising the following steps: the preparation method comprises the steps of uniformly mixing the raw materials except the initiator according to the parts by weight to obtain a mixture, adding the mixture into a double-screw extruder, extruding at 128 ℃, uniformly mixing the mixture with the initiator after cooling, crushing and cyclone separation, and curing for 7.5 days.
Example 5
The environment-friendly fireproof coating is characterized by comprising the following components in parts by weight: 20 parts of vinyl modified hyperbranched polyphosphate, 10 parts of acrylate modified p-aminophenyl calixazole, 70 parts of 1, 3-bis (ethylene oxide methyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione/3, 3 '-diamino-4, 4' -difluoro diphenyl sulfone polycondensate, 1.5 parts of azodiisobutyronitrile, 25 parts of titanium dioxide, 3 parts of tributyl phosphate and 3 parts of sodium hexametaphosphate.
The preparation method of the polycondensate of the 1, 3-bis (ethylene oxide methyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione/3, 3 '-diamino-4, 4' -difluoro diphenyl sulfone comprises the following steps: adding 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, a 3,3' -diamino-4, 4' -difluorodiphenyl sulfone polycondensate, potassium carbonate and tetrachlorobenzoquinone into N, N-dimethylformamide, stirring and reacting at 90 ℃ for 8 hours, then reducing the temperature to room temperature, precipitating in water, washing the precipitated polymer with diethyl ether for 6 times, and then removing the diethyl ether by rotary evaporation to obtain 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione/3, 3' -diamino-4, 4' -difluorodiphenyl sulfone polycondensate; the molar ratio of the 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione to the 3,3 '-diamino-4, 4' -difluorodiphenyl sulfone polycondensate to the potassium carbonate to the chloranil and the N, N-dimethylformamide is 1:1:1.2:0.3: 16.
The preparation method of the acrylate modified p-aminophenyl calixazole comprises the following steps: adding Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole, 3, 4-epoxy cyclohexyl methyl methacrylate, sodium hydroxide and cuprous chloride into tetrahydrofuran, stirring and reacting at 80 ℃ for 6 hours, filtering to remove insoluble substances, performing rotary evaporation to remove tetrahydrofuran, washing a product with water for 7 times, and performing rotary evaporation to remove water to obtain the acrylate modified p-aminophenyl calix; the molar ratio of the Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole to the 3, 4-epoxycyclohexyl methyl methacrylate to the sodium hydroxide to the cuprous chloride to the tetrahydrofuran is 1:4:3:0.5: 25.
The preparation method of the vinyl modified hyperbranched polyphosphate comprises the following steps: adding epoxy-terminated hyperbranched polyphosphate, 2-amino-1-propenyl-1, 1, 3-trimethylnitrile, sodium hydroxide and cuprous chloride into tetrahydrofuran, stirring and reacting for 6 hours at 80 ℃, filtering to remove insoluble substances, performing rotary evaporation to remove tetrahydrofuran, washing a product with water for 7 times, and performing rotary evaporation to remove water to obtain vinyl modified hyperbranched polyphosphate; the mass ratio of the epoxy-terminated hyperbranched polyphosphate to the 2-amino-1-propenyl-1, 1, 3-trimethylnitrile to the sodium hydroxide to the cuprous chloride to the tetrahydrofuran is 5:1:3:0.6: 30.
The preparation method of the environment-friendly fireproof coating is characterized by comprising the following steps: the preparation method comprises the steps of uniformly mixing the raw materials except the azobisisobutyronitrile according to the parts by weight to obtain a mixture, adding the mixture into a double-screw extruder, extruding at 130 ℃, cooling, crushing, performing cyclone separation, uniformly mixing the mixture with the azobisisobutyronitrile, and curing for 8 days.
Comparative example 1
The present example provides an environment-friendly fire-retardant coating, the formulation and the preparation method are the same as those of example 1, except that no vinyl modified hyperbranched polyphosphate is added.
Comparative example 2
This example provides an environmentally friendly fire retardant coating having the same formulation and preparation method as example 1, except that no acrylate-modified p-aminophenyl calixazole was added.
Comparative example 3
This example provides an environmentally friendly fire retardant coating having the same formulation and preparation method as example 1 of application No. 201810070184.7.
The environmental protection fire-retardant coatings obtained in the above examples 1 to 5 and comparative examples 1 to 3 were tested, and the test results and test methods are shown in Table 1.
TABLE 1
As can be seen from Table 1, the environment-friendly fireproof coating disclosed by the embodiment of the invention has better flame retardance and fire resistance, higher adhesive force, and good water resistance and scrubbing resistance, which are the results of the synergistic effect of the components.
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 (10)
1. The environment-friendly fireproof coating is characterized by comprising the following components in parts by weight: 10-20 parts of vinyl modified hyperbranched polyphosphate, 5-10 parts of acrylate modified p-aminophenyl calixazole, 50-70 parts of 1, 3-bis (ethylene oxide methyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione/3, 3 '-diamino-4, 4' -difluoro diphenyl sulfone polycondensate, 0.5-1.5 parts of initiator, 15-25 parts of inorganic filler, 1-3 parts of defoaming agent and 1-3 parts of dispersing agent.
2. The environment-friendly fireproof paint of claim 1, wherein the dispersant is sodium hexametaphosphate and/or sodium polycarboxylate; the defoaming agent is one or more of tributyl phosphate, a defoaming agent Demodex 3100 and a defoaming agent BYK 088; the inorganic filler is at least one of attapulgite, volcanic ash, talcum powder or titanium dioxide; the initiator is at least one of azobisisobutyronitrile and azobisisoheptonitrile.
3. The environment-friendly fireproof paint according to claim 1, wherein the preparation method of the 1, 3-bis (ethylene oxide methyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione/3, 3 '-diamino-4, 4' -difluoro diphenyl sulfone polycondensate comprises the following steps: adding 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, a 3,3' -diamino-4, 4' -difluorodiphenyl sulfone polycondensate, an alkaline catalyst and a polymerization inhibitor into a high boiling point solvent, stirring and reacting for 6-8 hours at 80-90 ℃, then reducing the temperature to room temperature, precipitating in water, washing the precipitated polymer with diethyl ether for 3-6 times, and then removing the diethyl ether by rotary evaporation to obtain 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione/3, 3' -diamino-4, 4' -difluorodiphenyl sulfone polycondensate.
4. The environment-friendly fireproof paint according to claim 3, wherein the molar ratio of the 1, 3-bis (ethylene oxide methyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione to the 3,3 '-diamino-4, 4' -difluorodiphenyl sulfone polycondensate to the alkaline catalyst to the polymerization inhibitor to the high-boiling-point solvent is 1:1 (0.8-1.2) to (0.1-0.3) to (10-16).
5. The environment-friendly fireproof paint of claim 3, wherein the alkaline catalyst is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate; the high boiling point solvent is at least one of dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide; the polymerization inhibitor is at least one of 1, 4-naphthoquinone and chloranil.
6. The environment-friendly fireproof coating as claimed in claim 1, wherein the preparation method of the acrylate-modified p-aminophenyl calixazole comprises the following steps: adding Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole, 3, 4-epoxy cyclohexyl methyl methacrylate, sodium hydroxide and cuprous chloride into tetrahydrofuran, stirring and reacting at 70-80 ℃ for 4-6 hours, filtering to remove insoluble substances, carrying out rotary evaporation to remove tetrahydrofuran, washing the product with water for 3-7 times, and carrying out rotary evaporation to remove water to obtain the acrylate modified p-aminophenyl calix.
7. The environment-friendly fireproof paint of claim 6, wherein the molar ratio of Meso-tetramethyl-Meso-tetra-p-aminophenyl calix [4] pyrrole to 3, 4-epoxycyclohexyl methyl methacrylate to sodium hydroxide to cuprous chloride to tetrahydrofuran is 1:4 (2-3) to 0.5 (15-25).
8. The environment-friendly fireproof coating of claim 1, wherein the preparation method of the vinyl modified hyperbranched polyphosphate comprises the following steps: adding epoxy-terminated hyperbranched polyphosphate, 2-amino-1-propenyl-1, 1, 3-trimethylnitrile, sodium hydroxide and cuprous chloride into tetrahydrofuran, stirring and reacting for 4-6 hours at 70-80 ℃, filtering to remove insoluble substances, performing rotary evaporation to remove tetrahydrofuran, washing a product with water for 3-7 times, and performing rotary evaporation to remove water to obtain the vinyl modified hyperbranched polyphosphate.
9. The environment-friendly fireproof coating of claim 8, wherein the mass ratio of the epoxy-terminated hyperbranched polyphosphate, the 2-amino-1-propenyl-1, 1, 3-trimethylnitrile, the sodium hydroxide, the cuprous chloride and the tetrahydrofuran is (3-5):1, (2-3):0.6, (20-30).
10. The environment-friendly fireproof coating of any one of claims 1 to 9, wherein the preparation method of the environment-friendly fireproof coating comprises the following steps: firstly, uniformly mixing the raw materials except the initiator according to the parts by weight to obtain a mixture, then adding the mixture into a double-screw extruder, extruding at the temperature of 120-130 ℃, uniformly mixing the mixture with the initiator after cooling, crushing and cyclone separation, and curing for 5-8 days.
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| CN113773759A (en) * | 2021-09-08 | 2021-12-10 | 宁波捷傲创益新材料有限公司 | Strong sound absorption fixing adhesive tape for automobile and preparation method thereof |
| CN114093550A (en) * | 2021-10-11 | 2022-02-25 | 铜陵精达新技术开发有限公司 | Conductor wire for generator |
| CN115216217A (en) * | 2022-08-09 | 2022-10-21 | 宁波爱甬新材料科技有限公司 | Environment-friendly antibacterial coating and preparation method thereof |
| CN117024079A (en) * | 2023-08-15 | 2023-11-10 | 仪征河海工程建设有限公司 | Waterproof material for building engineering |
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| CN110885525A (en) * | 2019-12-20 | 2020-03-17 | 石旭艳 | Anti-aging high-molecular flame-retardant waterproof material and preparation method thereof |
| CN111304931A (en) * | 2020-02-13 | 2020-06-19 | 朱冬梅 | Wear-resistant flame-retardant floor leather for vehicles and preparation method thereof |
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| CN102304222A (en) * | 2011-06-16 | 2012-01-04 | 上海工程技术大学 | Hyperbranched polyphosphate flame retardant and preparation method thereof |
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| CN113773759A (en) * | 2021-09-08 | 2021-12-10 | 宁波捷傲创益新材料有限公司 | Strong sound absorption fixing adhesive tape for automobile and preparation method thereof |
| CN113773759B (en) * | 2021-09-08 | 2022-11-22 | 宁波捷傲创益新材料有限公司 | Strong sound absorption fixing adhesive tape for automobile and preparation method thereof |
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| CN115216217B (en) * | 2022-08-09 | 2023-03-31 | 宁波爱甬新材料科技有限公司 | Environment-friendly antibacterial coating and preparation method thereof |
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