CN112625526A - Gradient heat-insulating fireproof coating and preparation method thereof - Google Patents
Gradient heat-insulating fireproof coating and preparation method thereof Download PDFInfo
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- C09D123/32—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing phosphorus or sulfur
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Abstract
The invention discloses a gradient heat-insulating fireproof coating and a preparation method thereof. According to the invention, the coating prepared by blending the modified acrylic emulsion, the first resin and the second resin has a porous structure and a low heat conductivity coefficient according to the properties and preparation process of materials, so that the heat insulation and fire prevention effects are achieved; when the fire is on fire and the temperature is raised, water vapor is evaporated, chemical bonds begin to break, ammonia and nitrogen oxides are released, materials begin to expand, more pores and a more stable carbon layer structure are finally formed, silicon dioxide, aluminum oxide and magnesium oxide generated by organic silicon, aluminum hydroxide and magnesium hydroxide are attached to inner cavities of the pores to form a spherical sheet structure, and the pores are cooperated to block the circulation of volatile substances, gas and heat in the coating, so that smoke and flame are suppressed, the fire resistance is prolonged, and the fire resistance is realized.
Description
Technical Field
The invention relates to the technical field of fireproof coatings, in particular to a gradient type heat-insulating fireproof coating and a preparation method thereof.
Background
In various disasters, one of the most common main disasters during fire disasters is serious in fire behavior, so that the combustion is out of control in time and space, the public safety and social development are seriously threatened, and along with the development of modern technology, in order to prevent the loss caused by the fire disasters, a fireproof process is added in a product preparation process to eliminate the hidden danger of the fire disasters and prevent the fire disasters. The fireproof coating is one of fireproof technologies, and is coated on the surface of an object to prevent the spread and propagation of fire, or isolate the object from a fire source, prolong the ignition time of the object, or improve the heat insulation performance of the object and the outside, delay the structural damage of the object, give people sufficient reaction time, and achieve the purposes of slowing down the fire and reducing loss. The heat insulation performance of the coating can delay the speed of heat introduction into a protected object at the initial stage of a fire, prevent combustion from moving towards the protected object and realize the fireproof performance. Therefore, we propose a gradient thermal insulation fireproof coating and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a gradient type heat-insulating fireproof coating and a preparation method thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: the gradient heat-insulating fireproof coating is prepared from modified acrylic emulsion, chlorosulfonated polyethylene, first resin, second resin and chlorinated paraffin, wherein the first resin is modified polyimide, and the second resin is modified furfural resin.
Further, the first resin comprises the following components in parts by weight: 20-33 parts of inorganic particles, 0.4-0.6 part of gamma-aminopropyltriethoxysilane, 0.18-0.30 part of polyvinylpyrrolidone, 0.5-0.8 part of sodium dodecyl sulfate, 13.7-22.6 parts of triethylamine, 0.21-0.24 part of gamma-glycidoxypropyltrimethoxysilane, 6.4-10.5 parts of 4,4' -diaminodiphenyl ether and 6.3-10.3 parts of pyromellitic dianhydride.
Further, the second resin comprises the following components in parts by weight: 67.2-96.1 parts of furfural, 25.2-63.0 parts of melamine, 12.6-18.0 parts of fructose, 54.3-62.0 parts of tetrabromobisphenol A, 40.8-68.0 parts of pentaerythritol and 68.6-98 parts of phosphoric acid.
Further, the inorganic particles are one or a mixture of two of nano aluminum hydroxide and nano magnesium hydroxide.
Further, the modified acrylic emulsion is prepared from polyoxyethylene octyl phenol ether-10, acrylic acid and chlorinated paraffin
A preparation method of a gradient heat-insulating fireproof coating comprises the following steps:
(1) preparation of the first resin:
mixing nano aluminum hydroxide, nano magnesium hydroxide and gamma-aminopropyltriethoxysilane to obtain modified inorganic particles A; taking modified inorganic particles A, polyvinylpyrrolidone and sodium dodecyl sulfate, adding deionized water, triethylamine and gamma-glycidyl ether oxypropyltrimethoxysilane to prepare modified particles B; adding 4,4' -diaminodiphenyl ether into the modified particles B and pyromellitic dianhydride, and reacting to prepare first resin;
(2) preparation of the second resin:
taking raw materials for mixing and reacting to prepare second resin:
(3) preparing a coating:
mixing acrylic acid and chlorinated paraffin to prepare modified acrylic emulsion; adding chlorosulfonated polyethylene, the first resin and the second resin to form a coating, and coating to obtain the coating.
Further, the step (1) comprises the steps of:
mixing nano aluminum hydroxide and nano magnesium hydroxide, adding absolute ethyl alcohol and gamma-aminopropyl triethoxysilane, and stirring for 1-2 hours to obtain modified inorganic particles A;
taking modified inorganic particles A, polyvinylpyrrolidone and sodium dodecyl sulfate, adding deionized water, fully mixing, adding triethylamine, stirring for reaction for 7.5-8.8 h, adding gamma-glycidyl ether oxypropyltrimethoxysilane, and continuing stirring for 100-140 min to obtain modified particles B;
adding 4,4' -diaminodiphenyl ether into N, N-dimethylformamide, and fully mixing to obtain a diamine solution; adding the modified particles B, reacting at 75-105 ℃ for 2-4 h, cooling to room temperature, slowly adding pyromellitic dianhydride, reacting at 280-320 ℃ for 100-140 min, washing and drying the product to obtain the first resin.
Further, the step (2) comprises the following steps:
taking tetrabromobisphenol A, and adding absolute ethyl alcohol to prepare a tetrabromobisphenol A solution;
mixing fructose and furfural, dissolving the mixture in deionized water, and adding a tetrabromobisphenol A solution to prepare a mixed solution;
mixing pentaerythritol with phosphoric acid, and reacting at 120-150 ℃ for 30-50 min to obtain pentaerythritol diphosphate;
and (3) keeping the temperature of the system, adding melamine, stirring and reacting for 7-15 min, adding the mixed solution, stirring and mixing, adding phosphoric acid, and reacting for 5-8 h at 75-105 ℃ to obtain second resin.
Further, the step (3) comprises the following steps:
emulsifying chlorinated paraffin to obtain chlorinated paraffin emulsion;
dissolving polyoxyethylene octylphenol ether-10 in deionized water, adding acrylic acid, performing ultrasonic emulsification for 20-30 min, adding the mixture into chlorinated paraffin emulsion, heating to 80-85 ℃, stirring for 45-55 min at a stirring speed of 1000r/min, adding potassium persulfate, stirring for 3-5 h at a temperature of 70-80 ℃ at a stirring speed of 1000r/min, and then adding acrylic acid emulsion to prepare modified acrylic acid emulsion;
and (3) blending the second resin and chlorosulfonated polyethylene, adding the modified acrylic emulsion and the first resin, fully mixing to form a coating, and coating to obtain the coating.
Furthermore, the addition amounts of the polyoxyethylene octyl phenol ether-10, the acrylic acid, the chlorinated paraffin and the potassium persulfate in the modified acrylic emulsion are respectively 6-8%, 10-20%, 18-24% and 0.5-1.5% of the weight of the system.
In the technical scheme, when the first resin is prepared, the hydroxyl on the surface of nano aluminum hydroxide and nano magnesium hydroxide and the ethoxy in the gamma-aminopropyltriethoxysilane are utilized to graft inorganic particles and the gamma-aminopropyltriethoxysilane, the product is hydrolyzed and condensed in an aqueous solution system of polyvinylpyrrolidone and sodium dodecyl sulfate, and is spheroidized under the action of the gamma-glycidyl ether oxypropyltrimethoxysilane to form a core layer of the first resin; 4,4' -diaminodiphenyl ether and pyromellitic dianhydride are subjected to cross-linking polymerization on the surface of the core layer to form a shell of the first resin, so that a core-shell structure of the first resin is formed; the first resin is prepared from nano aluminum hydroxide, nano magnesium hydroxide, epoxy siloxane and polyimide from inside to outside, so that the impact resistance of the prepared coating is improved, and the heat resistance and the heat stability of the coating are improved;
when the second resin is prepared, fructose, furfural and melamine react to prepare a copolymer, a complex space structure is formed, active functional groups are reduced, the stability of the prepared second resin is improved, the adhesion of the prepared coating to a coated object is improved, and the corrosion resistance and the wear resistance of the prepared coating are improved; the melamine is crosslinked with pentaerythritol diphosphate prepared from pentaerythritol and phosphoric acid, so that the thermal stability of a system can be improved, and the residual rate at high temperature is high; tetrabromobisphenol A is added into a reaction system, so that the flame retardant property of the system is improved;
when the coating is prepared, acrylic acid is emulsified and then reacts with carbon chains in chlorinated paraffin to form modified polyacrylic acid, and then the modified polyacrylic acid is mixed with acrylic acid emulsion to improve the waterproof performance and the heat resistance of a system; the amino on the surface of the first resin is crosslinked with the second resin, so that the mechanical strength of the coating is improved, the amino is blended with the modified acrylic emulsion and the chlorosulfonated polyethylene to form a coating, the curing of the coating is promoted, the coating is prepared after coating, the toughness and the heat resistance of the prepared coating are improved, pores are formed in the prepared coating due to the emulsification of acrylic acid and chlorinated paraffin, the heat transfer performance of the thermal coating is reduced, and the heat insulation effect is achieved;
at the initial stage of use, moisture in the prepared coating absorbs heat and evaporates, the temperature of the coating system is prevented from being increased, and the effect of initial heat insulation and fire prevention is achieved due to the low heat conductivity coefficient of the coating material and the heat transfer blocked by the pores in the coating; along with the continuous transmission of fire heat, in the service period, chemical bonds in the first resin are stable, the structure can be kept unchanged for a long time, the temperature is continuously raised, epoxy siloxane and polyimide are cracked to generate ammonia gas and nitric oxide, the formation of a porous carbon layer is promoted, in the process, inorganic particles absorb a large amount of heat and release water vapor, the flammable gas in the environment is diluted, the temperature raising speed of the coating is reduced, the degradation is delayed, the coating is not fully combusted, along with the rise of the temperature, aluminum hydroxide and magnesium hydroxide are melted, the specific surface area is increased, the specific surface area is adhered to pores of the carbon layer, magnesium oxide and aluminum oxide are formed, a porous carbon layer structure is formed, the structural stability is high, the collapse of the carbon layer is not easy to generate, the improvement of the residual quality of the coating is facilitated, the heat transmission is inhibited, the circulation of the gas in the coating can be blocked, the flame retardant effect; chemical bonds in the second resin are broken to release ammonia gas, fructose is decomposed and expanded, molecules are interconnected to form a stable carbon-nitrogen structure, the ammonia gas is continuously released to finally form more stable carbide, and the coating has better durability and thermal stability, so that the prepared coating has higher residue;
in the later stage of use, a carbon layer structure with silicon dioxide, magnesium oxide and aluminum oxide is formed, the thermal conductivity coefficient of the carbon layer structure is low, the heat transferred to the coating can be reflected, the purpose of protecting the coated object is achieved, the porous structure of the carbon layer can block volatile gas, overflow of organic matters is reduced, the heat on the surface of the coating is reduced, the physical structure of the carbon layer structure is more beneficial to blocking the heat, the fire-resistant time of the coated object is delayed, and the flame retardant property is achieved.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the gradient heat-insulating fireproof coating and the preparation method thereof, the coating formed by blending the modified acrylic emulsion, the first resin and the second resin is formed by setting the components and the preparation process, and the prepared coating has a porous structure and a lower heat conductivity coefficient at the initial stage of use according to the properties of materials and the preparation process, so that the heat-insulating fireproof effect is achieved; when the coating is ignited and heated, water vapor is evaporated, chemical bonds begin to break, ammonia and nitric oxide are released, materials in the coating begin to expand, more pores and a more stable carbon layer structure are finally formed, silicon dioxide, aluminum oxide and magnesium oxide generated by organic silicon, aluminum hydroxide and magnesium hydroxide in the materials are attached to inner cavities of the pores to form a spherical sheet structure, and the pores are cooperated to block the circulation of volatile substances, gas and heat in the coating, so that smoke suppression and flame retardance are realized, the fire resistance is prolonged, and the fireproof performance is realized.
2. The gradient heat-insulating fireproof coating and the preparation method thereof form a coating blended by modified acrylic emulsion, first resin and second resin by setting components and a preparation process, wherein the first resin is a core-shell spherical structure consisting of modified organic silicon and polyimide, the impact resistance of the prepared coating is improved, and a higher flame-retardant time and a more stable carbon layer structure can be achieved in fireproof application, the second resin is a copolymer of fructose, furfural, melamine and tetrabromobisphenol A, the adhesion of the prepared coating is improved, the coating expands in the fireproof application, the fireproof performance is realized, compared with the first resin, the expansion coefficient of the second resin is larger, the expansion time of the first resin is earlier, the pores in the second resin are compressed when the first resin expands, so that the pores are converted into a layered structure, and the directions of partial layered pores are the same as the direction of heat flow, the heat conductivity coefficient of the prepared coating can be reduced, and due to the difference of angles between the layered pore and the heat flow direction, the heat transfer in the coating is more tortuous, the heat transfer efficiency is reduced, and the fireproof performance of the prepared coating is improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Preparation of the first resin:
taking materials in parts by weight for later use: 20 parts of inorganic particles (a mixture of nano aluminum hydroxide and nano magnesium hydroxide), 0.4 part of gamma-aminopropyltriethoxysilane, 0.18 part of polyvinylpyrrolidone, 0.5 part of sodium dodecyl sulfate, 13.7 parts of triethylamine, 0.21 part of gamma-glycidoxypropyltrimethoxysilane, 6.4 parts of 4,4' -diaminodiphenyl ether and 6.3 parts of pyromellitic dianhydride;
mixing nano aluminum hydroxide and nano magnesium hydroxide, adding absolute ethyl alcohol and gamma-aminopropyl triethoxysilane, and stirring for 1h to obtain modified inorganic particles A;
taking modified inorganic particles A, polyvinylpyrrolidone and sodium dodecyl sulfate, adding deionized water, fully mixing, adding triethylamine, stirring for reaction for 7.5h, adding gamma-glycidyl ether oxypropyltrimethoxysilane, and continuing stirring for 100min to obtain modified particles B;
adding 4,4' -diaminodiphenyl ether into N, N-dimethylformamide, and fully mixing to obtain a diamine solution; adding the modified particles B, reacting at 75 ℃ for 2h, cooling to room temperature, slowly adding pyromellitic dianhydride, reacting at 280 ℃ for 100min, washing and drying the product to obtain first resin;
(2) preparation of the second resin:
taking materials in parts by weight for later use: 67.2 parts of furfural, 25.2 parts of melamine, 12.6 parts of fructose, 54.3 parts of tetrabromobisphenol A, 40.8 parts of pentaerythritol and 68.6 parts of phosphoric acid;
taking tetrabromobisphenol A, and adding absolute ethyl alcohol to prepare a tetrabromobisphenol A solution;
mixing fructose and furfural, dissolving the mixture in deionized water, and adding a tetrabromobisphenol A solution to prepare a mixed solution;
mixing pentaerythritol with phosphoric acid, and reacting at 120 ℃ for 30min to obtain pentaerythritol diphosphate;
keeping the temperature of the system, adding melamine, stirring and reacting for 7min, adding the mixed solution, stirring and mixing, adding phosphoric acid, and reacting for 5h at 75 ℃ to obtain a second resin:
(3) preparing a coating:
emulsifying chlorinated paraffin to obtain chlorinated paraffin emulsion;
dissolving polyoxyethylene octyl phenol ether-10 in deionized water, adding acrylic acid, performing ultrasonic emulsification for 20min, adding the mixture into chlorinated paraffin emulsion, heating to 80 ℃, stirring for 45min at a stirring speed of 1000r/min, adding potassium persulfate, stirring for 3h at a temperature of 70 ℃ at a stirring speed of 1000r/min, and then adding acrylic acid emulsion to prepare modified acrylic acid emulsion; the addition amounts of polyoxyethylene octyl phenol ether-10, acrylic acid, chlorinated paraffin and potassium persulfate in the modified acrylic emulsion are respectively 6%, 10%, 18% and 0.5% of the weight of the system;
and (3) blending the second resin and chlorosulfonated polyethylene, adding the modified acrylic emulsion and the first resin, fully mixing to form a coating, and coating to obtain the coating.
Example 2
(1) Preparation of the first resin:
taking materials in parts by weight for later use: 26 parts of inorganic particles (a mixture of nano aluminum hydroxide and nano magnesium hydroxide), 0.5 part of gamma-aminopropyltriethoxysilane, 0.24 part of polyvinylpyrrolidone, 0.6 part of sodium dodecyl sulfate, 18.2 parts of triethylamine, 0.213 part of gamma-glycidoxypropyltrimethoxysilane, 8.4 parts of 4,4' -diaminodiphenyl ether and 8.3 parts of pyromellitic dianhydride;
mixing nano aluminum hydroxide and nano magnesium hydroxide, adding absolute ethyl alcohol and gamma-aminopropyl triethoxysilane, and stirring for 1.5h to obtain modified inorganic particles A;
taking modified inorganic particles A, polyvinylpyrrolidone and sodium dodecyl sulfate, adding deionized water, fully mixing, adding triethylamine, stirring for reacting for 8 hours, adding gamma-glycidyl ether oxypropyltrimethoxysilane, and continuing stirring for 120min to obtain modified particles B;
adding 4,4' -diaminodiphenyl ether into N, N-dimethylformamide, and fully mixing to obtain a diamine solution; adding the modified particles B, reacting at 90 ℃ for 3h, cooling to room temperature, slowly adding pyromellitic dianhydride, reacting at 300 ℃ for 120min, washing and drying the product to obtain first resin;
(2) preparation of the second resin:
taking materials in parts by weight for later use: 81.7 parts of furfural, 44.1 parts of melamine, 15.3 parts of fructose, 58.1 parts of tetrabromobisphenol A, 54.4 parts of pentaerythritol and 83.3 parts of phosphoric acid;
taking tetrabromobisphenol A, and adding absolute ethyl alcohol to prepare a tetrabromobisphenol A solution;
mixing fructose and furfural, dissolving the mixture in deionized water, and adding a tetrabromobisphenol A solution to prepare a mixed solution;
mixing pentaerythritol with phosphoric acid, and reacting at 135 deg.C for 40min to obtain pentaerythritol diphosphate;
keeping the temperature of the system, adding melamine, stirring and reacting for 12min, adding the mixed solution, stirring and mixing, adding phosphoric acid, and reacting for 6.5h at 90 ℃ to obtain a second resin:
(3) preparing a coating:
emulsifying chlorinated paraffin to obtain chlorinated paraffin emulsion;
dissolving polyoxyethylene octyl phenol ether-10 in deionized water, adding acrylic acid, performing ultrasonic emulsification for 25min, adding the mixture into chlorinated paraffin emulsion, heating to 82 ℃, stirring for 50min at a stirring speed of 1000r/min, adding potassium persulfate, stirring for 4h at a stirring speed of 1000r/min at a temperature of 75 ℃, and then adding acrylic acid emulsion to prepare modified acrylic acid emulsion; the addition amounts of polyoxyethylene octyl phenol ether-10, acrylic acid, chlorinated paraffin and potassium persulfate in the modified acrylic emulsion are respectively 7%, 15%, 21% and 1% of the weight of the system;
and (3) blending the second resin and chlorosulfonated polyethylene, adding the modified acrylic emulsion and the first resin, fully mixing to form a coating, and coating to obtain the coating.
Example 3
(1) Preparation of the first resin:
taking materials in parts by weight for later use: 33 parts of inorganic particles (a mixture of nano aluminum hydroxide and nano magnesium hydroxide), 0.6 part of gamma-aminopropyltriethoxysilane, 0.30 part of polyvinylpyrrolidone, 0.8 part of sodium dodecyl sulfate, 22.6 parts of triethylamine, 0.24 part of gamma-glycidoxypropyltrimethoxysilane, 10.5 parts of 4,4' -diaminodiphenyl ether and 10.3 parts of pyromellitic dianhydride;
mixing nano aluminum hydroxide and nano magnesium hydroxide, adding absolute ethyl alcohol and gamma-aminopropyl triethoxysilane, and stirring for 2h to obtain modified inorganic particles A;
taking modified inorganic particles A, polyvinylpyrrolidone and sodium dodecyl sulfate, adding deionized water, fully mixing, adding triethylamine, stirring for reacting for 8.8h, adding gamma-glycidyl ether oxypropyltrimethoxysilane, and continuing stirring for 140min to obtain modified particles B;
adding 4,4' -diaminodiphenyl ether into N, N-dimethylformamide, and fully mixing to obtain a diamine solution; adding the modified particles B, reacting at 105 ℃ for 4h, cooling to room temperature, slowly adding pyromellitic dianhydride, reacting at 320 ℃ for 140min, washing and drying the product to obtain first resin;
(2) preparation of the second resin:
taking materials in parts by weight for later use: 96.1 parts of furfural, 63.0 parts of melamine, 18.0 parts of fructose, 62.0 parts of tetrabromobisphenol A, 68.0 parts of pentaerythritol and 98 parts of phosphoric acid;
taking tetrabromobisphenol A, and adding absolute ethyl alcohol to prepare a tetrabromobisphenol A solution;
mixing fructose and furfural, dissolving the mixture in deionized water, and adding a tetrabromobisphenol A solution to prepare a mixed solution;
mixing pentaerythritol with phosphoric acid, and reacting at 150 ℃ for 50min to obtain pentaerythritol diphosphate;
keeping the temperature of the system, adding melamine, stirring and reacting for 15min, adding the mixed solution, stirring and mixing, adding phosphoric acid, and reacting for 8h at 105 ℃ to obtain a second resin:
(3) preparing a coating:
emulsifying chlorinated paraffin to obtain chlorinated paraffin emulsion;
dissolving polyoxyethylene octyl phenol ether-10 in deionized water, adding acrylic acid, performing ultrasonic emulsification for 30min, adding the mixture into chlorinated paraffin emulsion, heating to 85 ℃, stirring for 55min at a stirring speed of 1000r/min, adding potassium persulfate, stirring for 5h at a stirring speed of 1000r/min at a temperature of 80 ℃, and then adding acrylic acid emulsion to prepare modified acrylic acid emulsion; the addition amounts of polyoxyethylene octyl phenol ether-10, acrylic acid, chlorinated paraffin and potassium persulfate in the modified acrylic emulsion are respectively 8%, 20%, 24% and 1.5% of the weight of the system;
and (3) blending the second resin and chlorosulfonated polyethylene, adding the modified acrylic emulsion and the first resin, fully mixing to form a coating, and coating to obtain the coating.
Comparative example 1
(1) Preparation of modified resin:
taking materials in parts by weight for later use: 81.7 parts of furfural, 44.1 parts of melamine, 15.3 parts of fructose, 58.1 parts of tetrabromobisphenol A, 54.4 parts of pentaerythritol and 83.3 parts of phosphoric acid;
taking tetrabromobisphenol A, and adding absolute ethyl alcohol to prepare a tetrabromobisphenol A solution;
mixing fructose and furfural, dissolving the mixture in deionized water, and adding a tetrabromobisphenol A solution to prepare a mixed solution;
mixing pentaerythritol with phosphoric acid, and reacting at 135 deg.C for 40min to obtain pentaerythritol diphosphate;
keeping the temperature of the system, adding melamine, stirring and reacting for 12min, adding the mixed solution, stirring and mixing, adding phosphoric acid, and reacting for 6.5h at 90 ℃ to obtain modified resin:
(3) preparing a coating:
emulsifying chlorinated paraffin to obtain chlorinated paraffin emulsion;
dissolving polyoxyethylene octyl phenol ether-10 in deionized water, adding acrylic acid, performing ultrasonic emulsification for 25min, adding the mixture into chlorinated paraffin emulsion, heating to 82 ℃, stirring for 50min at a stirring speed of 1000r/min, adding potassium persulfate, stirring for 4h at a stirring speed of 1000r/min at a temperature of 75 ℃, and then adding acrylic acid emulsion to prepare modified acrylic acid emulsion; the addition amounts of polyoxyethylene octyl phenol ether-10, acrylic acid, chlorinated paraffin and potassium persulfate in the modified acrylic emulsion are respectively 7%, 15%, 21% and 1% of the weight of the system;
and (3) blending the modified resin and chlorosulfonated polyethylene, adding the modified acrylic emulsion, fully mixing to form a coating, and coating to obtain the coating.
Comparative example 2
(1) Preparation of modified resin:
taking materials in parts by weight for later use: 26 parts of inorganic particles (a mixture of nano aluminum hydroxide and nano magnesium hydroxide), 0.5 part of gamma-aminopropyltriethoxysilane, 0.24 part of polyvinylpyrrolidone, 0.6 part of sodium dodecyl sulfate, 18.2 parts of triethylamine, 0.213 part of gamma-glycidoxypropyltrimethoxysilane, 8.4 parts of 4,4' -diaminodiphenyl ether and 8.3 parts of pyromellitic dianhydride;
mixing nano aluminum hydroxide and nano magnesium hydroxide, adding absolute ethyl alcohol and gamma-aminopropyl triethoxysilane, and stirring for 1.5h to obtain modified inorganic particles A;
taking modified inorganic particles A, polyvinylpyrrolidone and sodium dodecyl sulfate, adding deionized water, fully mixing, adding triethylamine, stirring for reacting for 8 hours, adding gamma-glycidyl ether oxypropyltrimethoxysilane, and continuing stirring for 120min to obtain modified particles B;
adding 4,4' -diaminodiphenyl ether into N, N-dimethylformamide, and fully mixing to obtain a diamine solution; adding the modified particles B, reacting at 90 ℃ for 3h, cooling to room temperature, slowly adding pyromellitic dianhydride, reacting at 300 ℃ for 120min, washing and drying the product to obtain modified resin;
(2) preparing a coating:
emulsifying chlorinated paraffin to obtain chlorinated paraffin emulsion;
dissolving polyoxyethylene octyl phenol ether-10 in deionized water, adding acrylic acid, performing ultrasonic emulsification for 25min, adding the mixture into chlorinated paraffin emulsion, heating to 82 ℃, stirring for 50min at a stirring speed of 1000r/min, adding potassium persulfate, stirring for 4h at a stirring speed of 1000r/min at a temperature of 75 ℃, and then adding acrylic acid emulsion to prepare modified acrylic acid emulsion; the addition amounts of polyoxyethylene octyl phenol ether-10, acrylic acid, chlorinated paraffin and potassium persulfate in the modified acrylic emulsion are respectively 7%, 15%, 21% and 1% of the weight of the system;
adding chlorosulfonated polyethylene into the modified acrylic emulsion and the modified resin, fully mixing to form a coating, and coating to obtain the coating.
Comparative example 3
(1) Preparation of the first resin:
taking materials in parts by weight for later use: 26 parts of inorganic particles (a mixture of nano aluminum hydroxide and nano magnesium hydroxide), 0.5 part of gamma-aminopropyltriethoxysilane, 0.24 part of polyvinylpyrrolidone, 0.6 part of sodium dodecyl sulfate, 18.2 parts of triethylamine, 0.213 part of gamma-glycidoxypropyltrimethoxysilane, 8.4 parts of 4,4' -diaminodiphenyl ether and 8.3 parts of pyromellitic dianhydride;
mixing nano aluminum hydroxide and nano magnesium hydroxide, adding absolute ethyl alcohol and gamma-aminopropyl triethoxysilane, and stirring for 1.5h to obtain modified inorganic particles A;
taking modified inorganic particles A, polyvinylpyrrolidone and sodium dodecyl sulfate, adding deionized water, fully mixing, adding triethylamine, stirring for reacting for 8 hours, adding gamma-glycidyl ether oxypropyltrimethoxysilane, and continuing stirring for 120min to obtain modified particles B;
adding 4,4' -diaminodiphenyl ether into N, N-dimethylformamide, and fully mixing to obtain a diamine solution; adding the modified particles B, reacting at 90 ℃ for 3h, cooling to room temperature, slowly adding pyromellitic dianhydride, reacting at 300 ℃ for 120min, washing and drying the product to obtain first resin;
(2) preparation of the second resin:
taking materials in parts by weight for later use: 81.7 parts of furfural, 44.1 parts of melamine, 15.3 parts of fructose, 58.1 parts of tetrabromobisphenol A, 54.4 parts of pentaerythritol and 83.3 parts of phosphoric acid;
taking tetrabromobisphenol A, and adding absolute ethyl alcohol to prepare a tetrabromobisphenol A solution;
mixing fructose and furfural, dissolving the mixture in deionized water, and adding a tetrabromobisphenol A solution to prepare a mixed solution;
mixing pentaerythritol with phosphoric acid, and reacting at 135 deg.C for 40min to obtain pentaerythritol diphosphate;
keeping the temperature of the system, adding melamine, stirring and reacting for 12min, adding the mixed solution, stirring and mixing, adding phosphoric acid, and reacting for 6.5h at 90 ℃ to obtain a second resin:
(3) preparing a coating:
and adding polyacrylic acid and the first resin into the second resin, fully mixing to form a coating, and coating to obtain the coating.
Comparative example 4
(1) Preparation of the first resin:
taking materials in parts by weight for later use: 26 parts of inorganic particles (a mixture of nano aluminum hydroxide and nano magnesium hydroxide), 8.4 parts of 4,4' -diaminodiphenyl ether and 8.3 parts of pyromellitic dianhydride;
adding 4,4' -diaminodiphenyl ether into N, N-dimethylformamide, and fully mixing to obtain a diamine solution; adding the modified particles B, reacting at 90 ℃ for 3h, cooling to room temperature, slowly adding pyromellitic dianhydride, reacting at 300 ℃ for 120min at constant temperature, washing and drying the product, adding inorganic particles, and blending to obtain first resin;
(2) preparation of the second resin:
taking materials in parts by weight for later use: 81.7 parts of furfural, 44.1 parts of melamine, 15.3 parts of fructose, 58.1 parts of tetrabromobisphenol A, 54.4 parts of pentaerythritol and 83.3 parts of phosphoric acid;
taking tetrabromobisphenol A, and adding absolute ethyl alcohol to prepare a tetrabromobisphenol A solution;
mixing fructose and furfural, dissolving the mixture in deionized water, and adding a tetrabromobisphenol A solution to prepare a mixed solution;
mixing pentaerythritol with phosphoric acid, and reacting at 135 deg.C for 40min to obtain pentaerythritol diphosphate;
keeping the temperature of the system, adding melamine, stirring and reacting for 12min, adding the mixed solution, stirring and mixing, adding phosphoric acid, and reacting for 6.5h at 90 ℃ to obtain a second resin:
(3) preparing a coating:
emulsifying chlorinated paraffin to obtain chlorinated paraffin emulsion;
dissolving polyoxyethylene octyl phenol ether-10 in deionized water, adding acrylic acid, performing ultrasonic emulsification for 25min, adding the mixture into chlorinated paraffin emulsion, heating to 82 ℃, stirring for 50min at a stirring speed of 1000r/min, adding potassium persulfate, stirring for 4h at a stirring speed of 1000r/min at a temperature of 75 ℃, and then adding acrylic acid emulsion to prepare modified acrylic acid emulsion; the addition amounts of polyoxyethylene octyl phenol ether-10, acrylic acid, chlorinated paraffin and potassium persulfate in the modified acrylic emulsion are respectively 7%, 15%, 21% and 1% of the weight of the system;
and (3) blending the second resin and chlorosulfonated polyethylene, adding the modified acrylic emulsion and the first resin, fully mixing to form a coating, and coating to obtain the coating.
Comparative example 5
(1) Preparation of the first resin:
taking materials in parts by weight for later use: 26 parts of inorganic particles (a mixture of nano aluminum hydroxide and nano magnesium hydroxide), 0.5 part of gamma-aminopropyltriethoxysilane, 0.24 part of polyvinylpyrrolidone, 0.6 part of sodium dodecyl sulfate, 18.2 parts of triethylamine, 0.213 part of gamma-glycidoxypropyltrimethoxysilane, 8.4 parts of 4,4' -diaminodiphenyl ether and 8.3 parts of pyromellitic dianhydride;
mixing nano aluminum hydroxide and nano magnesium hydroxide, adding absolute ethyl alcohol and gamma-aminopropyl triethoxysilane, and stirring for 1.5h to obtain modified inorganic particles A;
taking modified inorganic particles A, polyvinylpyrrolidone and sodium dodecyl sulfate, adding deionized water, fully mixing, adding triethylamine, stirring for reacting for 8 hours, adding gamma-glycidyl ether oxypropyltrimethoxysilane, and continuing stirring for 120min to obtain modified particles B;
adding 4,4' -diaminodiphenyl ether into N, N-dimethylformamide, and fully mixing to obtain a diamine solution; adding the modified particles B, reacting at 90 ℃ for 3h, cooling to room temperature, slowly adding pyromellitic dianhydride, reacting at 300 ℃ for 120min, washing and drying the product to obtain first resin;
(2) preparation of the second resin:
taking materials in parts by weight for later use: 81.7 parts of furfural, 44.1 parts of melamine and 15.3 parts of fructose;
mixing fructose and furfural, and dissolving in deionized water to obtain a mixed solution;
adding melamine into the mixed solution, stirring and mixing, adding phosphoric acid, and reacting at 90 ℃ for 6.5 hours to obtain a second resin:
(3) preparing a coating:
emulsifying chlorinated paraffin to obtain chlorinated paraffin emulsion;
dissolving polyoxyethylene octyl phenol ether-10 in deionized water, adding acrylic acid, performing ultrasonic emulsification for 25min, adding the mixture into chlorinated paraffin emulsion, heating to 82 ℃, stirring for 50min at a stirring speed of 1000r/min, adding potassium persulfate, stirring for 4h at a stirring speed of 1000r/min at a temperature of 75 ℃, and then adding acrylic acid emulsion to prepare modified acrylic acid emulsion; the addition amounts of polyoxyethylene octyl phenol ether-10, acrylic acid, chlorinated paraffin and potassium persulfate in the modified acrylic emulsion are respectively 7%, 15%, 21% and 1% of the weight of the system;
and (3) blending the second resin and chlorosulfonated polyethylene, adding the modified acrylic emulsion and the first resin, fully mixing to form a coating, and coating to obtain the coating.
Comparative example 6
(1) Preparation of the first resin:
taking materials in parts by weight for later use: 26 parts of inorganic particles (a mixture of nano aluminum hydroxide and nano magnesium hydroxide), 0.5 part of gamma-aminopropyltriethoxysilane, 0.24 part of polyvinylpyrrolidone, 0.6 part of sodium dodecyl sulfate, 18.2 parts of triethylamine, 0.213 part of gamma-glycidoxypropyltrimethoxysilane, 8.4 parts of 4,4' -diaminodiphenyl ether and 8.3 parts of pyromellitic dianhydride;
mixing nano aluminum hydroxide and nano magnesium hydroxide, adding absolute ethyl alcohol and gamma-aminopropyl triethoxysilane, and stirring for 1.5h to obtain modified inorganic particles A;
taking modified inorganic particles A, polyvinylpyrrolidone and sodium dodecyl sulfate, adding deionized water, fully mixing, adding triethylamine, stirring for reacting for 8 hours, adding gamma-glycidyl ether oxypropyltrimethoxysilane, and continuing stirring for 120min to obtain modified particles B;
adding 4,4' -diaminodiphenyl ether into N, N-dimethylformamide, and fully mixing to obtain a diamine solution; adding the modified particles B, reacting at 90 ℃ for 3h, cooling to room temperature, slowly adding pyromellitic dianhydride, reacting at 300 ℃ for 120min, washing and drying the product to obtain first resin;
(2) preparation of the second resin:
taking materials in parts by weight for later use: 81.7 parts of furfural, 44.1 parts of melamine, 15.3 parts of fructose, 58.1 parts of tetrabromobisphenol A, 54.4 parts of pentaerythritol and 83.3 parts of phosphoric acid;
taking tetrabromobisphenol A, and adding absolute ethyl alcohol to prepare a tetrabromobisphenol A solution;
mixing fructose and furfural, dissolving the mixture in deionized water, and adding a tetrabromobisphenol A solution to prepare a mixed solution;
mixing pentaerythritol with phosphoric acid, and reacting at 135 deg.C for 40min to obtain pentaerythritol diphosphate;
keeping the temperature of the system, adding melamine, stirring and reacting for 12min, adding the mixed solution, stirring and mixing, adding phosphoric acid, and reacting for 6.5h at 90 ℃ to obtain a second resin:
(3) preparing a coating:
and (3) blending the second resin and chlorosulfonated polyethylene, adding chlorinated paraffin, acrylic acid, potassium persulfate and the first resin, fully mixing to form a coating, and coating to obtain the coating.
Comparative example 7
43 parts of water-based acrylic emulsion, 3.68 parts of diammonium hydrogen phosphate, 2.00 parts of pentaerythritol, 3.06 parts of melamine, 4.23 parts of magnesium oxide and 4.23 parts of aluminum oxide are fully mixed to form a coating, and the coating is prepared after coating.
Experiment of
Taking the coatings obtained in examples 1-3 and comparative examples 1-7, preparing samples, respectively testing the performances of the samples, and recording the detection results, wherein the following performances are tested:
(1) impact strength: the drop hammer test is adopted, and the technical indexes are as follows: GB 1732-93;
(2) adhesion force: adopting a cross-cut method to test the adhesive force, wherein the grades are respectively as follows: level 0-the cut edge is completely smooth with no one lattice falling off; level 1-there is little coating to drop off at the intersection of the cuts, but the cross cut area is affected and cannot be significantly more than 5%; level 2-there is coating that drops off at the intersection of the incision and or along the edge of the incision, the cross-cut area affected is obviously greater than 5%, but can not be obviously greater than 15%; grade 3-the affected cross-cut area where the coating partially or totally falls off as large fragments along the cut edge and or partially or totally falls off at different parts of the grid is significantly greater than 15%, but not significantly greater than 35%; level 4-the coating is peeled off along the large fragments of the cutting edge and/or some grids are partially or completely peeled off, and the affected cross cutting area is obviously more than 35 percent but not more than 65 percent; grade 5-degree of exfoliation exceeds grade 4;
(3) and (3) testing the fireproof performance: testing by adopting a simulated large-plate combustion method, and evaluating the fireproof performance by using combustion time;
the experimental steps are as follows: horizontally placing a sample downwards, adjusting the height to ensure that the outer flame of the alcohol lamp just directly contacts the coating, terminating the experiment until the back fire surface of the sample is subjected to fire penetration, recording the time from the flame contact with the sample to the back fire penetration, recording the time as the flame-resistant time, observing the fuming condition, and measuring the expansion height of the carbon layer; the technical indexes are as follows: GB/T12441-2005;
(4) and (3) testing thermal stability: scraping 7mg of the dried coating, heating the coating from room temperature to 800 ℃ at a heating rate of 10 ℃/min in a nitrogen environment, and measuring the carbon residue rate of the coating;
from the data in the table above, it is clear that the following conclusions can be drawn:
the coatings obtained in examples 1 to 3 were compared with the coatings obtained in comparative examples 1 to 7, and the results of the tests showed that:
1. compared with the coating obtained in the comparative example 7, the coating obtained in the examples 1 to 3 is a conventional expansion fireproof coating, and the experimental data of the impact strength, the adhesion level, the flame-retardant time, the carbon layer expansion height, the smoke generation condition and the carbon residue rate of the samples in the examples 1 to 3 are improved, which fully shows that the fireproof performance and the thermal stability of the prepared coating can be improved, and meanwhile, the service performances such as the impact resistance, the bonding performance and the like of the coating are improved;
2. compared with the example 2, the first resin is not added in the comparative example 1, the second resin is not added in the comparative example 2, the polyacrylic acid is not modified in the comparative example 3, the first resin is prepared differently in the comparative example 4, the second resin is prepared differently in the comparative example 5, the acrylic acid is treated differently in the comparative example 6, the experimental data of the adhesion grade, the flame-resistant time, the carbon layer expansion height, the fuming condition and the carbon residue rate are improved, and the change trend is deterioration compared with the example 2, and it is known that the treatment process, the component configuration and the like of the first resin, the second resin and the acrylic acid in the invention can promote the improvement of the impact resistance, the bonding performance, the fireproof performance and the thermal stability of the prepared coating.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Furthermore, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process method article or apparatus.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A gradient type heat-insulating fireproof coating is characterized in that: the coating is prepared from modified acrylic emulsion, chlorosulfonated polyethylene, first resin, second resin and chlorinated paraffin, wherein the first resin is modified polyimide, and the second resin is modified furfural resin.
2. A gradient insulating and fire-retardant coating according to claim 1, characterized in that: the first resin comprises the following components in parts by weight: 20-33 parts of inorganic particles, 0.4-0.6 part of gamma-aminopropyltriethoxysilane, 0.18-0.30 part of polyvinylpyrrolidone, 0.5-0.8 part of sodium dodecyl sulfate, 13.7-22.6 parts of triethylamine, 0.21-0.24 part of gamma-glycidoxypropyltrimethoxysilane, 6.4-10.5 parts of 4,4' -diaminodiphenyl ether and 6.3-10.3 parts of pyromellitic dianhydride.
3. A gradient insulating and fire-retardant coating according to claim 1, characterized in that: the second resin comprises the following components in parts by weight: 67.2-96.1 parts of furfural, 25.2-63.0 parts of melamine, 12.6-18.0 parts of fructose, 54.3-62.0 parts of tetrabromobisphenol A, 40.8-68.0 parts of pentaerythritol and 68.6-98 parts of phosphoric acid.
4. A gradient insulating and fire-retardant coating according to claim 2, characterized in that: the inorganic particles are one or a mixture of two of nano aluminum hydroxide and nano magnesium hydroxide.
5. A gradient insulating and fire-retardant coating according to claim 1, characterized in that: the modified acrylic emulsion is prepared from polyoxyethylene octyl phenol ether-10, acrylic acid and chlorinated paraffin.
6. A preparation method of a gradient heat-insulating fireproof coating is characterized by comprising the following steps:
(1) preparation of the first resin:
mixing nano aluminum hydroxide, nano magnesium hydroxide and gamma-aminopropyltriethoxysilane to obtain modified inorganic particles A; taking modified inorganic particles A, polyvinylpyrrolidone and sodium dodecyl sulfate, adding deionized water, triethylamine and gamma-glycidyl ether oxypropyltrimethoxysilane to prepare modified particles B; adding 4,4' -diaminodiphenyl ether into the modified particles B and pyromellitic dianhydride, and reacting to prepare first resin;
(2) preparation of the second resin:
taking raw materials for mixing and reacting to prepare second resin:
(3) preparing a coating:
mixing acrylic acid and chlorinated paraffin to prepare modified acrylic emulsion; adding chlorosulfonated polyethylene, the first resin and the second resin to form a coating, and coating to obtain the coating.
7. The method for preparing a gradient thermal insulation fireproof coating according to claim 6, wherein the step (1) comprises the following steps:
mixing nano aluminum hydroxide and nano magnesium hydroxide, adding absolute ethyl alcohol and gamma-aminopropyl triethoxysilane, and stirring for 1-2 hours to obtain modified inorganic particles A;
taking modified inorganic particles A, polyvinylpyrrolidone and sodium dodecyl sulfate, adding deionized water, fully mixing, adding triethylamine, stirring for reaction for 7.5-8.8 h, adding gamma-glycidyl ether oxypropyltrimethoxysilane, and continuing stirring for 100-140 min to obtain modified particles B;
adding 4,4' -diaminodiphenyl ether into N, N-dimethylformamide, and fully mixing to obtain a diamine solution; adding the modified particles B, reacting at 75-105 ℃ for 2-4 h, cooling to room temperature, slowly adding pyromellitic dianhydride, reacting at 280-320 ℃ for 100-140 min, washing and drying the product to obtain the first resin.
8. The method for preparing a gradient thermal-insulating fireproof coating according to claim 6, wherein: the step (2) comprises the following steps:
taking tetrabromobisphenol A, and adding absolute ethyl alcohol to prepare a tetrabromobisphenol A solution;
mixing fructose and furfural, dissolving the mixture in deionized water, and adding a tetrabromobisphenol A solution to prepare a mixed solution;
mixing pentaerythritol with phosphoric acid, and reacting at 120-150 ℃ for 30-50 min to obtain pentaerythritol diphosphate;
and (3) keeping the temperature of the system, adding melamine, stirring and reacting for 7-15 min, adding the mixed solution, stirring and mixing, adding phosphoric acid, and reacting for 5-8 h at 75-105 ℃ to obtain second resin.
9. The method for preparing a gradient thermal-insulating fireproof coating according to claim 6, wherein: the step (3) comprises the following steps:
emulsifying chlorinated paraffin to obtain chlorinated paraffin emulsion;
dissolving polyoxyethylene octylphenol ether-10 in deionized water, adding acrylic acid, performing ultrasonic emulsification for 20-30 min, adding the mixture into chlorinated paraffin emulsion, heating to 80-85 ℃, stirring for 45-55 min at a stirring speed of 1000r/min, adding potassium persulfate, stirring for 3-5 h at a temperature of 70-80 ℃ at a stirring speed of 1000r/min, and then adding acrylic acid emulsion to prepare modified acrylic acid emulsion;
and (3) blending the second resin and chlorosulfonated polyethylene, adding the modified acrylic emulsion and the first resin, fully mixing to form a coating, and coating to obtain the coating.
10. The method for preparing a gradient thermal insulation fireproof coating according to claim 9, wherein: the addition amounts of the polyoxyethylene octyl phenol ether-10, the acrylic acid, the chlorinated paraffin and the potassium persulfate in the modified acrylic emulsion are respectively 6-8%, 10-20%, 18-24% and 0.5-1.5% of the weight of the system.
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| CN113462272A (en) * | 2021-06-15 | 2021-10-01 | 厦门双瑞船舶涂料有限公司 | Heat-insulating radiation-proof coating and preparation method thereof |
| CN113462272B (en) * | 2021-06-15 | 2022-04-19 | 厦门双瑞船舶涂料有限公司 | Heat-insulating radiation-proof coating and preparation method thereof |
| CN113650940A (en) * | 2021-08-13 | 2021-11-16 | 珠海市华鹰药用包装材料有限公司 | Medicinal aluminum-plastic combined cover and preparation process thereof |
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