CN112063282A - Flame-retardant conductive polypyrrole-polyurethane water-based composite coating and preparation method thereof - Google Patents

Flame-retardant conductive polypyrrole-polyurethane water-based composite coating and preparation method thereof Download PDF

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CN112063282A
CN112063282A CN202010779611.6A CN202010779611A CN112063282A CN 112063282 A CN112063282 A CN 112063282A CN 202010779611 A CN202010779611 A CN 202010779611A CN 112063282 A CN112063282 A CN 112063282A
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polyurethane
flame
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许东
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Xinchang Pinhong Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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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
    • C09D5/24—Electrically-conducting paints
    • C—CHEMISTRY; METALLURGY
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

The invention relates to the technical field of polyurethane materials, and discloses a flame-retardant conductive polypyrrole-polyurethane water-based composite coating, which comprises the following formula raw materials: waterborne polyurethane, nitrogen-phosphorus-based flame retardant, pyrrole and FeCl3And hydroxylated carbon nanotubes. According to the flame-retardant conductive polypyrrole-polyurethane water-based composite coating, pyrrole is polymerized in situ on a hydroxylated carbon nanotube and then is crosslinked with polyurethane to form a copolymer, the carbon nanotube and the polypyrrole have good conductivity, the polypyrrole-polyurethane copolymer is endowed with good conductivity, and the nitrogen-phosphorus flame-retardant polypyrrole-polyurethane copolymer has good nitrogen-phosphorus flame-retardant performanceThermal decomposition of the agent at high temperature to produce NH3、N2When the flame retardant gas is used, the phosphoric acid and phosphorous acid generated by thermal decomposition have dehydration performance, so that the coating curing film loses moisture to form a compact carbon foam layer, the high-temperature conduction is hindered, and the materials and O are reduced2The contact area of the composite coating inhibits the further combustion of the material, so that the composite coating has excellent flame retardant property after being cured into a film.

Description

Flame-retardant conductive polypyrrole-polyurethane water-based composite coating and preparation method thereof
Technical Field
The invention relates to the technical field of polyurethane materials, in particular to a flame-retardant conductive polypyrrole-polyurethane water-based composite coating and a preparation method thereof.
Background
Polyurethane is a new organic polymer material, is known as 'fifth plastic', is divided into polyester type and polyether type, has the advantages of low temperature resistance, aging resistance, high hardness, good elasticity and the like, mainly comprises foamed plastic, elastomers, fibers, coatings, adhesives and the like, and has wide application in the aspects of chemical industry, electronics, building and building materials, aerospace and the like, wherein the polyurethane coating is divided into aqueous polyurethane coating, modified polyurethane coating and environment-friendly polyurethane coating.
The waterborne polyurethane coating does not need to be additionally added with a dispersing agent or an emulsifying agent, has good appearance and short drying time, and has great advantages in the related fields of wood coatings, plastics, vehicles, industry, corrosion prevention and the like, but the existing polyurethane has lower ignition point, poorer flame retardant property after the coating is formed into a film, larger resistivity and lower conductivity, limits the application of the polyurethane material in the aspects of metal anticorrosive coatings, electromagnetic shielding and electronic and electrical elements, and greatly reduces the practicability of the polyurethane material.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a flame-retardant conductive polypyrrole-polyurethane water-based composite coating and a preparation method thereof, which solve the problems of low ignition point and poor flame retardant property of a polyurethane material and solve the problem of low conductivity of polyurethane.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: the flame-retardant conductive polypyrrole-polyurethane water-based composite coating comprises the following formula raw materials in parts by weight: 44-62 parts of waterborne polyurethane, 5-12 parts of nitrogen-phosphorus flame retardant, 6-8 parts of pyrrole and 25-32 parts of FeCl3And 2-4 parts of hydroxylated carbon nanotubes.
Preferably, the preparation method of the polyurethane prepolymer comprises the following steps:
(1) adding a mixed solvent of ethanol and ethyl acetate into a reaction bottle, wherein the volume ratio of the mixed solvent to the ethanol to the ethyl acetate is 1:1-1.5, adding p-phenylene diisocyanate and ethylene glycol, placing the reaction bottle in an oil bath pot, heating to 75-85 ℃, stirring at a constant speed, reacting for 3-5h, heating to 90-100 ℃, and adding sodium 3, 5-diaminobenzoate to perform chain extension reaction for 4-6 h.
(2) And cooling the solution to room temperature, concentrating under reduced pressure to remove the solvent, adding an n-hexane solvent into the concentrated product, uniformly stirring, separating and purifying the solution by a high-speed centrifuge, and removing the upper-layer liquid to remove impurities to prepare the waterborne polyurethane.
Preferably, the weight molar ratio of the p-phenylene diisocyanate, the ethylene glycol and the 3, 5-diaminosodium benzoate is 1.5-2:1: 0.4-0.7.
Preferably, the oil bath pot includes the base, and the controller is installed in the front of base, and the top of base is provided with the oil bath pot, and temperature probe has been placed to the inside of oil bath pot, and it has the quartz capsule to peg graft in the side of oil bath pot, the right side fixedly connected with vacuum pump interface of quartz capsule, the left side fixed connection intake pipe of quartz capsule, and the pneumatic valve is installed in the outside of vacuum pump interface and intake pipe.
Preferably, the preparation method of the nitrogen-phosphorus-based combustion agent comprises the following steps:
(1) introducing N2 into a dry reaction bottle to discharge air, adding a mixed solvent of anhydrous 1, 2-dichloromethane solvent and anhydrous 1, 2-dichloropropane with the volume ratio of 1:1.5-2, adding pentaerythritol and phosphorus oxychloride, stirring at a constant speed at 80-100 ℃ for reaction for 10-15h, cooling the solution to room temperature, concentrating under reduced pressure to remove the solvent, washing the solid product with distilled water and diethyl ether, and fully drying to prepare the pentaerythritol phosphate.
(2) Adding a mixed solvent of 1, 4-dioxane and ethanol into a reaction bottle, wherein the volume ratio of the two is 2-3:1, dropwise adding hydrochloric acid to adjust the pH value of the solution to 3-4, then adding pentaerythritol phosphate, oteracil potassium and a catalyst p-toluenesulfonic acid, placing the reaction bottle into an oil bath pot, heating to 120-130 ℃, uniformly stirring to react for 20-30h, concentrating the solution under reduced pressure to remove the solvent, washing the solid product with distilled water and diethyl ether until the solid product is neutral, and fully drying to prepare the nitrogen-phosphorus-based flame retardant.
Preferably, the molar ratio of the pentaerythritol to the phosphorus oxychloride is 1: 1.2-1.5.
Preferably, the pentaerythritol phosphate, the oteracil potassium and the p-toluenesulfonic acid are in a mass molar ratio of 1:1.5-2: 0.08-0.12.
Preferably, the preparation method of the flame-retardant conductive polypyrrole-polyurethane water-based composite coating comprises the following steps:
(1) adding hydrochloric acid solution with pH of 1-2 into a reaction bottle, adding 2-4 parts of hydroxylated carbon nanotube and 6-8 parts of pyrrole, placing the reaction bottle in an ultrasonic treatment instrument with ultrasonic frequency of 20-28KHz, performing ultrasonic treatment for 1-2h, placing the reaction bottle in a low-temperature reaction instrument, adding 25-32 parts of FeCl at-5-0 deg.C3Stirring at constant speed for 5-7h, adding 44-62 parts of waterborne polyurethane and 5-12 parts of nitrogen-phosphorus based flame retardant, placing the reaction bottle in an ultrasonic treatment instrument, and carrying out ultrasonic treatment for 2-4h at the ultrasonic frequency of 25-35 KHz.
(2) Adding distilled water into the solution, separating and purifying by a high-speed centrifuge until the upper layer liquid is colorless and neutral, placing the lower layer oily matter into a mixed solvent of distilled water and ethanol with the volume ratio of 3-5:1, controlling the solid-liquid ratio to be 25-40%, and uniformly stirring to obtain the flame-retardant conductive polypyrrole-polyurethane waterborne composite coating.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the flame-retardant conductive polypyrrole-polyurethane water-based composite coating uses p-phenylene diisocyanate and ethylene glycol as monomers, and 3, 5-diaminosodium benzoate as a chain extender, the prepared polyurethane has good hydrophilic performance, the pyrrole is polymerized on a hydroxylated carbon nano tube in situ, imino groups in the polypyrrole and hydroxyl groups of the carbon nano tube form hydrogen bonds, so that the generated polypyrrole is uniformly dispersed, irregular particles are avoided, the uniformly dispersed polypyrrole and polyurethane are well crosslinked to form a copolymer, the polypyrrole has good conductivity, the conductivity of the polyurethane is greatly increased, the good conductivity of the polypyrrole-polyurethane copolymer is endowed, the carbon nano tube also has high conductivity, the conductivity of a cured film of the composite coating is enhanced, and the conductivity of the polyurethane coating on a metal anti-corrosion coating, a metal anti-corrosion coating and the like are expanded, Electromagnetic shielding, electronic and electric elements, etc.
The flame-retardant conductive polypyrrole-polyurethane waterborne composite coating uses a nitrogen-phosphorus-based flame retardant as an additive, the structure of the flame-retardant conductive polypyrrole-polyurethane waterborne composite coating contains a plurality of amino groups and ether bonds, the flame-retardant conductive polypyrrole-polyurethane waterborne composite coating has good hydrophilicity and good dispersibility and compatibility with a waterborne polyurethane coating, and the nitrogen-phosphorus-based flame retardant is thermally decomposed at high temperature to generate NH3、N2Reducing surrounding O by flame-retardant gas2The concentration of the nitrogen-phosphorus based flame retardant is high, the thermal decomposition of the nitrogen-phosphorus based flame retardant is an absorption process, the heat on the surface of the material is absorbed, the combustion process is slowed down, and meanwhile, the nitrogen-phosphorus based flame retardant is thermally decomposed to generate a phosphoric acid and phosphorous acid structure with dehydration performance, so that a coating curing film loses moisture to form a compact carbon foam layer, the carbon layer hinders the high-temperature conduction, and the material and O are reduced2The contact area of the composite coating inhibits the further combustion of the material, so that the composite coating has excellent flame retardant property after being cured into a film.
Drawings
FIG. 1 is a front view of the connection structure of the present invention;
fig. 2 is a top view of the connection structure of the present invention.
In the figure: 1-base, 2-controller, 3-oil bath pan, 4-temperature measuring probe, 5-quartz tube, 6-sealing flange, 7-vacuum pump interface, 8-air inlet pipe, 9-air valve.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: the flame-retardant conductive polypyrrole-polyurethane water-based composite coating comprises the following formula raw materials in parts by weight: 44-62 parts of waterborne polyurethane, 5-12 parts of nitrogen-phosphorus flame retardant, 6-8 parts of pyrrole and 25-32 parts of FeCl3And 2-4 parts of hydroxylated carbon nanotubes.
The preparation method of the polyurethane prepolymer comprises the following steps:
(1) adding a mixed solvent of ethanol and ethyl acetate into a reaction bottle, wherein the volume ratio of the mixed solvent to the ethanol and the ethyl acetate is 1:1-1.5, adding p-phenylene diisocyanate and ethylene glycol, placing the reaction bottle in an oil bath pot, heating to 75-85 ℃, wherein the oil bath pot comprises a base, a controller is arranged on the front surface of the base, the top of the base is provided with the oil bath pot, a temperature measuring probe is arranged in the oil bath pot, a quartz tube is inserted into the side surface of the oil bath pot, the right side of the quartz tube is fixedly connected with a vacuum pump connector, the left side of the quartz tube is fixedly connected with an air inlet tube, an air valve is arranged on the outer side of the vacuum pump connector and the air inlet tube, stirring at a constant speed for reaction for 3-5h, raising the temperature to 90-100 ℃, adding 3, 5-diaminosodium benzoate, carrying, the mass molar ratio of the three substances is 1.5-2:1:0.4-0.7, the solution is cooled to room temperature, the solvent is removed by decompression concentration, the normal hexane solvent is added into the concentrated product, the solution is separated and purified by a high-speed centrifuge after being stirred uniformly, and the upper layer liquid is removed to remove impurities, so that the waterborne polyurethane is prepared.
The preparation method of the nitrogen-phosphorus-based combustion agent comprises the following steps:
(1) introducing N2 into a dry reaction bottle to discharge air, adding a mixed solvent of anhydrous 1, 2-dichloromethane solvent and anhydrous 1, 2-dichloropropane with the volume ratio of 1:1.5-2, adding pentaerythritol and phosphorus oxychloride with the mass molar ratio of 1:1.2-1.5, uniformly stirring the solution at 80-100 ℃ for reaction for 10-15h, cooling the solution to room temperature, concentrating under reduced pressure to remove the solvent, washing the solid product with distilled water and diethyl ether, and fully drying to obtain the pentaerythritol phosphate.
(2) Adding a mixed solvent of 1, 4-dioxane and ethanol into a reaction bottle, wherein the volume ratio of the two is 2-3:1, dropwise adding hydrochloric acid to adjust the pH value of the solution to 3-4, then adding pentaerythritol phosphate, oteracil potassium and a catalyst p-toluenesulfonic acid, wherein the molar ratio of the three substances is 1:1.5-2:0.08-0.12, placing the reaction bottle into an oil bath, heating to 120-130 ℃, stirring at a constant speed for reaction for 20-30h, concentrating the solution under reduced pressure to remove the solvent, washing the solid product with distilled water and diethyl ether until the product is neutral, and fully drying to prepare the nitrogen-phosphorus based flame retardant.
The preparation method of the flame-retardant conductive polypyrrole-polyurethane water-based composite coating comprises the following steps:
(1) adding hydrochloric acid solution with pH of 1-2 into a reaction bottle, and addingAdding 2-4 parts of hydroxylated carbon nanotube and 6-8 parts of pyrrole, placing the reaction flask in an ultrasonic treatment instrument with the ultrasonic frequency of 20-28KHz, performing ultrasonic treatment for 1-2h, placing the reaction flask in a low-temperature reaction instrument, adding 25-32 parts of FeCl at-5-0 deg.C3Stirring at constant speed for 5-7h, adding 44-62 parts of waterborne polyurethane and 5-12 parts of nitrogen-phosphorus based flame retardant, placing the reaction bottle in an ultrasonic treatment instrument, and carrying out ultrasonic treatment for 2-4h at the ultrasonic frequency of 25-35 KHz.
(2) Adding distilled water into the solution, separating and purifying by a high-speed centrifuge until the upper layer liquid is colorless and neutral, placing the lower layer oily matter into a mixed solvent of distilled water and ethanol with the volume ratio of 3-5:1, controlling the solid-liquid ratio to be 25-40%, and uniformly stirring to obtain the flame-retardant conductive polypyrrole-polyurethane waterborne composite coating.
Example 1
(1) Preparing a waterborne polyurethane component 1: adding a mixed solvent of ethanol and ethyl acetate into a reaction bottle, wherein the volume ratio of the mixed solvent to the ethanol and the ethyl acetate is 1:1, adding p-phenylene diisocyanate and ethylene glycol, placing the reaction bottle in an oil bath pot, heating to 75 ℃, wherein the oil bath pot comprises a base, a controller is arranged on the front surface of the base, an oil bath pot is arranged on the top of the base, a temperature measuring probe is arranged in the oil bath pot, a quartz tube is inserted into the side surface of the oil bath pot, a vacuum pump connector is fixedly connected to the right side of the quartz tube, an air inlet tube is fixedly connected to the left side of the quartz tube, an air valve is arranged on the outer side of the vacuum pump connector and the air inlet tube, stirring at a constant speed for reaction for 3 hours, heating to 90 ℃, adding 3, 5-diaminosodium benzoate, carrying out chain extension reaction for 4 hours, wherein the molar ratio of the p-phenylene diisocyanate, the ethylene glycol and the, and (3) decompressing and concentrating to remove the solvent, adding a normal hexane solvent into the concentrated product, stirring uniformly, separating and purifying the solution through a high-speed centrifuge, and removing the upper-layer liquid to remove impurities to prepare the waterborne polyurethane component 1.
(2) Preparation of pentaerythritol phosphate component 1: introducing N2 into a dry reaction bottle to discharge air, adding a mixed solvent of anhydrous 1, 2-dichloromethane solvent and anhydrous 1, 2-dichloropropane with the volume ratio of 1:1.5, adding pentaerythritol and phosphorus oxychloride with the mass molar ratio of 1:1.2, uniformly stirring the solution at 80 ℃ for 10 hours, cooling the solution to room temperature, concentrating under reduced pressure to remove the solvent, washing a solid product with distilled water and diethyl ether, and fully drying to prepare the pentaerythritol phosphate ester component 1.
(3) Preparation of nitrogen-phosphorus-based flame retardant component 1: adding a mixed solvent of 1, 4-dioxane and ethanol into a reaction bottle, wherein the volume ratio of the two is 2:1, dropwise adding hydrochloric acid to adjust the pH value of the solution to 4, then adding pentaerythritol phosphate component 1, oteracil potassium and catalyst p-toluenesulfonic acid, wherein the molar ratio of the three substances is 1:1.5:0.08, placing the reaction bottle into an oil bath pot, heating to 120 ℃, uniformly stirring and reacting for 20 hours, decompressing and concentrating the solution to remove the solvent, washing the solid product with used distilled water and ether until the solid product is neutral, and fully drying to prepare the nitrogen-phosphorus-based flame retardant component 1.
(4) Preparing a flame-retardant conductive polypyrrole-polyurethane water-based composite coating 1: adding hydrochloric acid solution with pH of 2 into a reaction bottle, adding 2 parts of hydroxylated carbon nanotube and 6 parts of pyrrole, placing the reaction bottle in an ultrasonic treatment instrument with ultrasonic frequency of 20KHz for ultrasonic treatment for 1h, placing the reaction bottle in a low-temperature reaction instrument, adding 25 parts of FeCl at 0 DEG C3Stirring at a constant speed for 5 hours, adding 62 parts of waterborne polyurethane component 1 and 5 parts of nitrogen-phosphorus based flame retardant component 1, placing a reaction bottle in an ultrasonic treatment instrument, carrying out ultrasonic treatment for 2 hours at an ultrasonic frequency of 25KHz, adding distilled water into the solution, separating and purifying by a high-speed centrifuge until the upper-layer liquid is colorless and neutral, placing the lower-layer oily matter in a mixed solvent of distilled water and ethanol with a volume ratio of 3:1, controlling the solid-liquid ratio to be 25%, and stirring uniformly to obtain the flame-retardant conductive polypyrrole-polyurethane waterborne composite coating 1.
Example 2
(1) Preparing a waterborne polyurethane component 2: adding a mixed solvent of ethanol and ethyl acetate into a reaction bottle, wherein the volume ratio of the mixed solvent to the ethanol and the ethyl acetate is 1:1, adding p-phenylene diisocyanate and ethylene glycol, placing the reaction bottle in an oil bath pot, heating to 75 ℃, wherein the oil bath pot comprises a base, a controller is arranged on the front surface of the base, an oil bath pot is arranged on the top of the base, a temperature measuring probe is arranged in the oil bath pot, a quartz tube is inserted into the side surface of the oil bath pot, a vacuum pump connector is fixedly connected to the right side of the quartz tube, an air inlet tube is fixedly connected to the left side of the quartz tube, an air valve is arranged on the outer side of the vacuum pump connector and the air inlet tube, stirring at a constant speed for reaction for 3 hours, heating to 90 ℃, adding 3, 5-diaminosodium benzoate, carrying out chain extension reaction for 6 hours, wherein the molar ratio of the p-phenylene diisocyanate, the ethylene glycol and the, and (3) decompressing and concentrating to remove the solvent, adding a normal hexane solvent into the concentrated product, stirring uniformly, separating and purifying the solution through a high-speed centrifuge, and removing the upper-layer liquid to remove impurities to prepare the waterborne polyurethane component 2.
(2) Preparation of pentaerythritol phosphate component 2: introducing N2 into a dry reaction bottle to discharge air, adding a mixed solvent of anhydrous 1, 2-dichloromethane solvent and anhydrous 1, 2-dichloropropane with the volume ratio of 1:2, adding pentaerythritol and phosphorus oxychloride with the mass molar ratio of 1:1.2, uniformly stirring the solution at 80 ℃ for reaction for 15 hours, cooling the solution to room temperature, concentrating under reduced pressure to remove the solvent, washing a solid product by using distilled water and diethyl ether, and fully drying to prepare the pentaerythritol phosphate component 2.
(3) Preparation of nitrogen-phosphorus based flame retardant component 2: adding a mixed solvent of 1, 4-dioxane and ethanol into a reaction bottle, wherein the volume ratio of the two is 3:1, dropwise adding hydrochloric acid to adjust the pH value of the solution to 3, then adding pentaerythritol phosphate component 2, oteracil potassium and catalyst p-toluenesulfonic acid, wherein the molar ratio of the three substances is 1:2:0.08, placing the reaction bottle into an oil bath pot, heating to 120 ℃, uniformly stirring to react for 20 hours, decompressing and concentrating the solution to remove the solvent, washing the solid product with distilled water and diethyl ether until the solid product is neutral, and fully drying to prepare the nitrogen-phosphorus-based flame retardant component 2.
(4) Preparing a flame-retardant conductive polypyrrole-polyurethane water-based composite coating 2: adding hydrochloric acid solution with pH of 2 into a reaction bottle, adding 2.5 parts of hydroxylated carbon nanotube and 6.5 parts of pyrrole, placing the reaction bottle in an ultrasonic treatment instrument with ultrasonic frequency of 20KHz for ultrasonic treatment for 1h, placing the reaction bottle in a low-temperature reaction instrumentIn (b), 27 parts of FeCl are added at-5 DEG C3Stirring at a constant speed for 5 hours, adding 57 parts of waterborne polyurethane component 2 and 7 parts of nitrogen-phosphorus based flame retardant component 2, placing a reaction bottle in an ultrasonic treatment instrument with the ultrasonic frequency of 25KHz for ultrasonic treatment for 2 hours, adding distilled water into the solution, separating and purifying by a high-speed centrifuge until the upper-layer liquid is colorless and neutral, placing the lower-layer oily matter in a mixed solvent of distilled water and ethanol with the volume ratio of 3:1, controlling the solid-liquid ratio to be 28%, and stirring uniformly to prepare the flame-retardant conductive polypyrrole-polyurethane waterborne composite coating 2.
Example 3
(1) Preparing a waterborne polyurethane component 3: adding a mixed solvent of ethanol and ethyl acetate into a reaction bottle, wherein the volume ratio of the mixed solvent to the ethanol to the ethyl acetate is 1:1.2, adding p-phenylene diisocyanate and ethylene glycol, placing the reaction bottle in an oil bath pot, heating to 80 ℃, wherein the oil bath pot comprises a base, a controller is arranged on the front surface of the base, the top of the base is provided with the oil bath pot, a temperature measuring probe is arranged in the oil bath pot, a quartz tube is inserted into the side surface of the oil bath pot, the right side of the quartz tube is fixedly connected with a vacuum pump connector, the left side of the quartz tube is fixedly connected with an air inlet tube, an air valve is arranged on the outer side of the vacuum pump connector and the air inlet tube, stirring at a constant speed for reaction for 4 hours, raising the temperature to 95 ℃, adding 3, 5-diaminosodium benzoate for chain extension reaction for 5 hours, wherein the p-phenylene diisocyanate, the ethylene glycol and the 3,5-, and (3) decompressing and concentrating to remove the solvent, adding a normal hexane solvent into the concentrated product, stirring uniformly, separating and purifying the solution through a high-speed centrifuge, and removing the upper-layer liquid to remove impurities to prepare the waterborne polyurethane component 3.
(2) Preparation of pentaerythritol phosphate component 3: introducing N2 into a dried reaction bottle to discharge air, adding a mixed solvent of anhydrous 1, 2-dichloromethane solvent and anhydrous 1, 2-dichloropropane with the volume ratio of 1:1.7, adding pentaerythritol and phosphorus oxychloride with the mass molar ratio of 1:1.4, uniformly stirring the solution at 90 ℃ for reaction for 12 hours, cooling the solution to room temperature, concentrating under reduced pressure to remove the solvent, washing a solid product by using distilled water and diethyl ether, and fully drying to prepare the pentaerythritol phosphate component 3.
(3) Preparation of nitrogen-phosphorus based flame retardant component 3: adding a mixed solvent of 1, 4-dioxane and ethanol into a reaction bottle, wherein the volume ratio of the two is 2.5:1, dropwise adding hydrochloric acid to adjust the pH value of the solution to 4, then adding pentaerythritol phosphate component 3, oteracil potassium and catalyst p-toluenesulfonic acid, wherein the molar ratio of the three substances is 1:1.8:0.1, placing the reaction bottle into an oil bath pot, heating to 125 ℃, stirring at a constant speed for reaction for 25 hours, concentrating the solution under reduced pressure to remove the solvent, washing the solid product with distilled water and diethyl ether until the solid product is neutral, and fully drying to obtain the nitrogen-phosphorus based flame retardant component 3.
(4) Preparing a flame-retardant conductive polypyrrole-polyurethane water-based composite coating 3: adding hydrochloric acid solution with pH of 2 into a reaction bottle, adding 3 parts of hydroxylated carbon nanotube and 7 parts of pyrrole, placing the reaction bottle in an ultrasonic treatment instrument with ultrasonic frequency of 25KHz for ultrasonic treatment for 1.5h, placing the reaction bottle in a low-temperature reaction instrument, adding 29 parts of FeCl at-2 DEG C3Stirring at a constant speed for 6 hours, adding 52 parts of waterborne polyurethane component 3 and 9 parts of nitrogen-phosphorus based flame retardant component 3, placing a reaction bottle in an ultrasonic treatment instrument, carrying out ultrasonic treatment for 3 hours at the ultrasonic frequency of 30KHz, adding distilled water into the solution, carrying out separation and purification by a high-speed centrifuge until the upper-layer liquid is colorless and neutral, placing the lower-layer oily matter in a mixed solvent of distilled water and ethanol with the volume ratio of 4:1, controlling the solid-liquid ratio to be 32%, and uniformly stirring to obtain the flame-retardant conductive polypyrrole-polyurethane waterborne composite coating 3.
Example 4
(1) Preparing a waterborne polyurethane component 4: adding a mixed solvent of ethanol and ethyl acetate into a reaction bottle, wherein the volume ratio of the mixed solvent to the ethanol and the ethyl acetate is 1:1, adding p-phenylene diisocyanate and ethylene glycol, placing the reaction bottle in an oil bath pot, heating to 85 ℃, wherein the oil bath pot comprises a base, a controller is arranged on the front surface of the base, an oil bath pot is arranged on the top of the base, a temperature measuring probe is arranged in the oil bath pot, a quartz tube is inserted into the side surface of the oil bath pot, a vacuum pump connector is fixedly connected to the right side of the quartz tube, an air inlet tube is fixedly connected to the left side of the quartz tube, an air valve is arranged on the outer side of the vacuum pump connector and the air inlet tube, stirring at a constant speed for reaction for 3 hours, heating to 100 ℃, adding 3, 5-diaminosodium benzoate, carrying out chain extension reaction for 6 hours, wherein the molar ratio of the p-phenylene diisocyanate, the ethylene, and (3) decompressing and concentrating to remove the solvent, adding a normal hexane solvent into the concentrated product, stirring uniformly, separating and purifying the solution through a high-speed centrifuge, and removing the upper-layer liquid to remove impurities to prepare the waterborne polyurethane component 4.
(2) Preparation of pentaerythritol phosphate component 4: introducing N2 into a dried reaction bottle to discharge air, adding a mixed solvent of anhydrous 1, 2-dichloromethane solvent and anhydrous 1, 2-dichloropropane with the volume ratio of 1:2, adding pentaerythritol and phosphorus oxychloride with the mass molar ratio of 1:1.5, uniformly stirring the solution at 80 ℃ for reaction for 15 hours, cooling the solution to room temperature, concentrating under reduced pressure to remove the solvent, washing a solid product by using distilled water and diethyl ether, and fully drying to prepare the pentaerythritol phosphate component 4.
(3) Preparation of nitrogen-phosphorus based flame retardant component 4: adding a mixed solvent of 1, 4-dioxane and ethanol into a reaction bottle, wherein the volume ratio of the two is 2:1, dropwise adding hydrochloric acid to adjust the pH value of the solution to 3, then adding pentaerythritol phosphate component 4, oteracil potassium and catalyst p-toluenesulfonic acid, wherein the molar ratio of the three substances is 1:2:0.08, placing the reaction bottle into an oil bath pot, heating to 130 ℃, uniformly stirring and reacting for 20 hours, decompressing and concentrating the solution to remove the solvent, washing the solid product with distilled water and diethyl ether until the solid product is neutral, and fully drying to prepare the nitrogen-phosphorus-based flame retardant component 4.
(4) Preparing a flame-retardant conductive polypyrrole-polyurethane water-based composite coating 4: adding hydrochloric acid solution with pH of 1 into a reaction bottle, adding 3.5 parts of hydroxylated carbon nanotube and 7.5 parts of pyrrole, placing the reaction bottle into an ultrasonic treatment instrument with ultrasonic frequency of 20KHz for ultrasonic treatment for 1h, placing the reaction bottle into a low-temperature reaction instrument, adding 30.5 parts of FeCl at-5 DEG C3Stirring at constant speed for reaction for 7h, adding 48 parts of waterborne polyurethane component 4 and 10.5 parts of nitrogen-phosphorus based flame retardant component 4, placing the reaction bottle in an ultrasonic treatment instrument, wherein the ultrasonic frequency is 35KHz,and (2) carrying out ultrasonic treatment for 2h, adding distilled water into the solution, separating and purifying by using a high-speed centrifuge until the upper-layer liquid is colorless and neutral, placing the lower-layer oily matter into a mixed solvent of distilled water and ethanol with the volume ratio of 5:1, controlling the solid-liquid ratio to be 36%, and uniformly stirring to obtain the flame-retardant conductive polypyrrole-polyurethane waterborne composite coating 4.
Example 5
(1) Preparing a waterborne polyurethane component 5: adding a mixed solvent of ethanol and ethyl acetate into a reaction bottle, wherein the volume ratio of the mixed solvent to the ethanol to the ethyl acetate is 1:1.5, adding p-phenylene diisocyanate and ethylene glycol, placing the reaction bottle in an oil bath pot, heating to 85 ℃, wherein the oil bath pot comprises a base, a controller is arranged on the front surface of the base, the top of the base is provided with the oil bath pot, a temperature measuring probe is arranged in the oil bath pot, a quartz tube is inserted into the side surface of the oil bath pot, the right side of the quartz tube is fixedly connected with a vacuum pump connector, the left side of the quartz tube is fixedly connected with an air inlet tube, an air valve is arranged on the outer side of the vacuum pump connector and the air inlet tube, stirring at a constant speed for reaction for 5 hours, raising the temperature to 100 ℃, adding 3, 5-diaminosodium benzoate for chain extension reaction for 6 hours, wherein the molar ratio of the p-phenylene diisocyanate, the ethylene, and (3) decompressing and concentrating to remove the solvent, adding a normal hexane solvent into the concentrated product, stirring uniformly, separating and purifying the solution through a high-speed centrifuge, and removing the upper-layer liquid to remove impurities to prepare the waterborne polyurethane component 5.
(2) Preparation of pentaerythritol phosphate component 5: introducing N2 into a dried reaction bottle to discharge air, adding a mixed solvent of anhydrous 1, 2-dichloromethane solvent and anhydrous 1, 2-dichloropropane with the volume ratio of 1:2, adding pentaerythritol and phosphorus oxychloride with the mass molar ratio of 1:1.5, uniformly stirring the solution at 100 ℃ for reaction for 15 hours, cooling the solution to room temperature, concentrating under reduced pressure to remove the solvent, washing a solid product by using distilled water and diethyl ether, and fully drying to prepare the pentaerythritol phosphate component 5.
(3) Preparation of nitrogen-phosphorus based flame retardant component 5: adding a mixed solvent of 1, 4-dioxane and ethanol into a reaction bottle, wherein the volume ratio of the two is 3:1, dropwise adding hydrochloric acid to adjust the pH value of the solution to 3, then adding pentaerythritol phosphate component 5, oteracil potassium and catalyst p-toluenesulfonic acid, wherein the molar ratio of the three substances is 1:2:0.12, placing the reaction bottle into an oil bath pot, heating to 130 ℃, uniformly stirring for reaction for 30 hours, carrying out reduced pressure concentration on the solution to remove the solvent, washing the solid product with distilled water and diethyl ether until the solid product is neutral, and fully drying to prepare the nitrogen-phosphorus-based flame retardant component 5.
(4) Preparing a flame-retardant conductive polypyrrole-polyurethane water-based composite coating 5: adding hydrochloric acid solution with pH of 1 into a reaction bottle, adding 4 parts of hydroxylated carbon nanotube and 8 parts of pyrrole, placing the reaction bottle into an ultrasonic treatment instrument with ultrasonic frequency of 28KHz, performing ultrasonic treatment for 2h, placing the reaction bottle into a low-temperature reaction instrument, adding 32 parts of FeCl at-5 DEG C3Stirring at a constant speed for 7 hours, adding 44 parts of waterborne polyurethane component 5 and 12 parts of nitrogen-phosphorus based flame retardant component 5, placing a reaction bottle in an ultrasonic treatment instrument, carrying out ultrasonic treatment at an ultrasonic frequency of 35KHz for 4 hours, adding distilled water into the solution, separating and purifying by a high-speed centrifuge until the upper-layer liquid is colorless and neutral, placing the lower-layer oily matter in a mixed solvent of distilled water and ethanol with a volume ratio of 5:1, controlling the solid-liquid ratio to be 40%, and uniformly stirring to obtain the flame-retardant conductive polypyrrole-polyurethane waterborne composite coating 5.
The flame-retardant conductive polypyrrole-polyurethane waterborne composite coating in the examples 1 to 5 is cured into a film, and a YZS-8A type full-automatic oxygen index tester is used for testing the limiting oxygen index and the flame retardant property of the film material, wherein the testing standards are GB/T2408-2008 and GB/T8332-2008.
Figure BDA0002619718270000121
To sum up, the flame-retardant conductive polypyrrole-polyurethane water-based composite coating uses p-phenylene diisocyanate and ethylene glycol as monomers, and 3, 5-diaminosodium benzoate as a chain extender, so that the prepared polyurethane has good hydrophilic performance, the imino groups in the polypyrrole and the hydroxyl groups of the carbon nano tubes form hydrogen bonds through in-situ polymerization of pyrrole on the hydroxylated carbon nano tubes, so that the generated polypyrrole is uniformly dispersed, irregular particles are avoided, the uniformly dispersed polypyrrole and polyurethane are well crosslinked to form a copolymer, the polypyrrole has good conductivity, the conductivity of the polyurethane is greatly increased, the good conductivity of the polypyrrole-polyurethane copolymer is endowed, the carbon nano tubes also have high conductivity, the conductivity of a composite coating curing film is enhanced, and the application range of the polyurethane coating on a metal anti-corrosion coating is expanded, Electromagnetic shielding, electronic and electric elements, etc.
The nitrogen-phosphorus based flame retardant is used as an additive, the structure of the additive contains a plurality of amino groups and ether bonds, the additive shows good hydrophilicity, and has good dispersibility and compatibility with the aqueous polyurethane coating, and the nitrogen-phosphorus based flame retardant is thermally decomposed at high temperature to generate NH3、N2Reducing surrounding O by flame-retardant gas2The concentration of the nitrogen-phosphorus based flame retardant is high, the thermal decomposition of the nitrogen-phosphorus based flame retardant is an absorption process, the heat on the surface of the material is absorbed, the combustion process is slowed down, and meanwhile, the nitrogen-phosphorus based flame retardant is thermally decomposed to generate a phosphoric acid and phosphorous acid structure with dehydration performance, so that a coating curing film loses moisture to form a compact carbon foam layer, the carbon layer hinders the high-temperature conduction, and the material and O are reduced2The contact area of the composite coating inhibits the further combustion of the material, so that the composite coating has excellent flame retardant property after being cured into a film.

Claims (8)

1. The flame-retardant conductive polypyrrole-polyurethane water-based composite coating comprises the following formula raw materials in parts by weight, and is characterized in that: 44-62 parts of waterborne polyurethane, 5-12 parts of nitrogen-phosphorus flame retardant, 6-8 parts of pyrrole and 25-32 parts of FeCl3And 2-4 parts of hydroxylated carbon nanotubes.
2. The flame-retardant conductive polypyrrole-polyurethane aqueous composite coating according to claim 1, wherein: the preparation method of the polyurethane prepolymer comprises the following steps:
(1) adding p-phenylene diisocyanate and ethylene glycol into a mixed solvent of ethanol and ethyl acetate with the volume ratio of 1:1-1.5, placing the solution in an oil bath pot, heating to 75-85 ℃, reacting for 3-5h, heating to 90-100 ℃, and adding 3, 5-diaminosodium benzoate to carry out chain extension reaction for 4-6 h.
(2) And removing the solvent from the solution, adding a normal hexane solvent into the concentrated product, uniformly stirring, separating and purifying the solution by a high-speed centrifuge, and removing the upper-layer liquid and impurities to prepare the waterborne polyurethane.
3. The flame-retardant conductive polypyrrole-polyurethane aqueous composite coating according to claim 2, wherein: the mass molar ratio of the p-phenylene diisocyanate, the ethylene glycol and the 3, 5-diaminosodium benzoate is 1.5-2:1: 0.4-0.7.
4. The flame-retardant conductive polypyrrole-polyurethane aqueous composite coating according to claim 2, wherein: the oil bath pot comprises a base (1), a controller (2) is installed on the front face of the base (1), an oil bath pot (3) is arranged at the top of the base (1), a temperature measuring probe (4) is placed inside the oil bath pot (3), a quartz tube (5) is inserted into the side face of the oil bath pot (3), a vacuum pump interface (7) is fixedly connected to the right side of the quartz tube (5), a left side fixedly connected with air inlet tube (8) of the quartz tube (5), and an air valve (9) is installed outside the vacuum pump interface (7) and the air inlet tube (8).
5. The flame-retardant conductive polypyrrole-polyurethane aqueous composite coating according to claim 1, wherein: the preparation method of the nitrogen-phosphorus-based combustion agent comprises the following steps:
(1) introducing N2 into a dry reaction bottle to discharge air, adding a mixed solvent of anhydrous 1, 2-dichloromethane solvent and anhydrous 1, 2-dichloropropane with the volume ratio of the two solvents being 1:1.5-2, adding pentaerythritol and phosphorus oxychloride, stirring at a constant speed at 80-100 ℃ for reaction for 10-15h, removing the solvent from the solution, washing a solid product, and drying to prepare the pentaerythritol phosphate.
(2) Adding hydrochloric acid dropwise into a mixed solvent of 1, 4-dioxane and ethanol with the volume ratio of 2-3:1 to adjust the pH value of the solution to 3-4, adding pentaerythritol phosphate, oteracil potassium and a catalyst p-toluenesulfonic acid, heating the solution to 120-130 ℃, reacting for 20-30h, removing the solvent from the solution, washing a solid product, and drying to prepare the nitrogen-phosphorus-based flame retardant.
6. The flame-retardant conductive polypyrrole-polyurethane aqueous composite coating according to claim 5, wherein: the mass molar ratio of the pentaerythritol to the phosphorus oxychloride is 1: 1.2-1.5.
7. The flame-retardant conductive polypyrrole-polyurethane aqueous composite coating according to claim 5, wherein: the mass molar ratio of the pentaerythritol phosphate, the oteracil potassium and the p-methylbenzenesulfonic acid is 1:1.5-2: 0.08-0.12.
8. The flame-retardant conductive polypyrrole-polyurethane aqueous composite coating according to claim 1, wherein: the preparation method of the flame-retardant conductive polypyrrole-polyurethane water-based composite coating comprises the following steps:
(1) adding 2-4 parts of hydroxylated carbon nanotube and 6-8 parts of pyrrole into hydrochloric acid solution with pH of 1-2, performing ultrasonic treatment on the solution for 1-2h at the ultrasonic frequency of 20-28KHz, and adding 25-32 parts of FeCl into the solution at-5-0 deg.C3Reacting for 5-7h, then adding 44-62 parts of waterborne polyurethane and 5-12 parts of nitrogen-phosphorus based flame retardant, and carrying out ultrasonic treatment on the solution for 2-4h, wherein the ultrasonic frequency is 25-35 KHz.
(2) Adding distilled water into the solution, separating and purifying by a high-speed centrifuge, placing the lower layer oily matter into a mixed solvent of distilled water and ethanol with the volume ratio of 3-5:1, controlling the solid-liquid ratio to be 25-40%, and preparing the flame-retardant conductive polypyrrole-polyurethane waterborne composite coating.
CN202010779611.6A 2020-08-05 2020-08-05 Flame-retardant conductive polypyrrole-polyurethane water-based composite coating and preparation method thereof Withdrawn CN112063282A (en)

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