CN111423771A - High-flame-retardancy polymer cement composite water-based waterproof coating and preparation method thereof - Google Patents
High-flame-retardancy polymer cement composite water-based waterproof coating and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of waterproof coatings, and provides a high-flame-retardancy polymer cement composite water-based waterproof coating and a preparation method thereof. The preparation method comprises the steps of firstly preparing 1-vinyl-3-aminopropylimidazole tetrafluoroborate ionic liquid, then utilizing the amino group of the ionic liquid to react with the carboxyl group of carboxylated graphene, modifying vinyl imidazole on the surface of a graphene sheet layer, then utilizing the reaction of the vinyl group and the P-H bond of DOPO to graft the DOPO on the surface of the graphene sheet layer, and preparing the graphene/nitrogen/phosphorus composite flame retardant. The composite flame retardant is added into the polymer cement waterproof coating, so that the interface combination between graphene and a polymer can be enhanced, the graphene is prevented from agglomerating, a synergistic flame retardant effect can be generated by the graphene, nitrogen and phosphorus, and the flame retardant property of the coating is remarkably improved.
Description
Technical Field
The invention belongs to the technical field of waterproof coatings, and provides a high-flame-retardancy polymer cement composite water-based waterproof coating and a preparation method thereof.
Background
In the building engineering, the water infiltration to some parts of the building influences the use function and safety of the building. Therefore, people start from building materials or structures and adopt corresponding waterproof measures to achieve the aim of waterproofing or improve the impermeability and avoid the harm of water to buildings. The waterproof material is used for covering and sealing members and gaps by utilizing the impermeability of the material, and blocking the water passage, such as coiled material waterproof, waterproof coating, concrete and cement mortar rigid waterproof, clay and lime soil waterproof and the like, and is commonly used for waterproofing of roofs, outer walls, basements and the like. The structural waterproof is realized by utilizing the shape of the member and mutual lap joint, such as a water stop belt, a cavity structure and the like, and is mainly used for the joint of the member self-waterproof roof, an assembled building external wall panel and the like.
The polymer cement waterproof paint is used for building waterproofing, and belongs to one kind of waterproof material. The polymer cement waterproof coating is a water-based coating taking water as a solvent, belongs to an environment-friendly coating, and has the advantages of good bonding property with a wet base layer, adjustable rigidity and flexibility, high cost performance and the like, so that the polymer cement waterproof coating is widely applied to waterproof in kitchens, toilets, outer walls and balconies. The polymer cement waterproof coating comprises polymer emulsion (or redispersible latex powder and water), various auxiliaries, cement, inorganic filler and the like, wherein the polymer is a main film-forming substance, and the polymer material is flammable, so that the material needs to be subjected to flame retardant modification in order to improve the safety of the polymer cement waterproof coating.
The appearance of the graphene provides a new way for flame retardant modification of polymer materials. Due to the unique two-dimensional lamellar structure of the graphene, the graphene has a good physical barrier effect in a polymer material to play a flame retardant role, and the heat release rate of material combustion can be reduced. On one hand, however, the flame retardant effect of graphene is not ideal enough, and a large amount of addition is required, which results in high cost; on the other hand, graphene sheets have strong interaction, and the interface bonding between graphene and a polymer is weak, so that the graphene sheets are agglomerated, and particularly, the agglomeration phenomenon is serious when the addition amount is large.
Disclosure of Invention
In view of the above, the invention provides a high-flame-retardancy polymer cement composite water-based waterproof coating and a preparation method thereof, which can enhance the interface bonding between graphene and a polymer, prevent graphene from agglomerating, and remarkably improve the flame-retardant performance of the coating by generating a synergistic flame-retardant effect through the graphene, nitrogen and phosphorus.
In order to achieve the purpose, the invention relates to the following specific technical scheme:
a preparation method of a high-flame-retardancy polymer cement composite water-based waterproof coating comprises the following steps:
(1) adding 1-vinylimidazole and 3-bromopropylamine hydrobromide into acetonitrile, heating to 80 ℃ under the protection of nitrogen, carrying out reflux reaction for 24 hours, then adding deionized water for dilution, adjusting the pH value to 7, then adding sodium tetrafluoroborate, stirring for reaction for 24 hours, then extracting for 2-3 times by using dichloromethane, and evaporating the upper layer solution to dryness to obtain 1-vinyl-3-aminopropylimidazole tetrafluoroborate ionic liquid;
(2) adding carboxylated graphene into 1-vinyl-3-aminopropylimidazole tetrafluoroborate ionic liquid, dropwise adding concentrated sulfuric acid, heating to 40-45 ℃ under the protection of nitrogen, enabling amino groups of the ionic liquid and carboxyl groups of the graphene to generate a dehydration condensation reaction, stopping heating after 6-8 hours, naturally cooling to room temperature, performing suction filtration, washing and drying to obtain vinylimidazole modified graphene;
(3) adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) into toluene, heating to 85 ℃, stirring and dissolving under the protection of nitrogen, then adding vinylimidazole modified graphene and azobisisobutyronitrile, reacting P-H bond of DOPO with vinyl under stirring, stopping heating after 10-12H, naturally cooling to room temperature, filtering, washing and drying to obtain the graphene/nitrogen/phosphorus composite flame retardant;
(4) uniformly mixing the graphene/nitrogen/phosphorus composite flame retardant with EVA rubber powder, water, a dispersing agent, a water reducing agent, a defoaming agent, a film forming auxiliary agent, portland cement, calcium carbonate, quartz sand and wollastonite to obtain the high-flame-retardancy polymer cement composite water-based waterproof coating.
Preferably, in the step (1), the mass ratio of the 1-vinylimidazole to the 3-bromopropylamine hydrobromide to the sodium tetrafluoroborate to the acetonitrile to the deionized water is 4: 8-10: 4-5: 38-42: 100.
preferably, in the step (2), the mass ratio of the carboxylated graphene to the 1-vinyl-3-aminopropylimidazole tetrafluoroborate ionic liquid to the concentrated sulfuric acid is 15-20: 100: 1 to 3.
Preferably, in the step (3), the mass ratio of the DOPO, the vinyl imidazole modified graphene, the azobisisobutyronitrile and the toluene is 10-20: 10-20: 0.02-0.04: 100.
preferably, in the step (4), the mass ratio of the graphene/nitrogen/phosphorus composite flame retardant to the EVA rubber powder to the water to the dispersant to the water reducer to the defoamer to the film-forming assistant to the silicate cement to the calcium carbonate to the quartz sand to the wollastonite is 3-5: 30-40: 100: 0.5-1: 1-2: 0.01-0.02: 1-2: 25-30: 7-9: 2-4: 3 to 5.
Preferably, the dispersant is one of sodium polyacrylate or polyethylene glycol.
Preferably, the water reducing agent is a polycarboxylic acid high-efficiency water reducing agent.
Preferably, the defoaming agent is one of a silicone defoaming agent or a polyether modified silicone defoaming agent.
Preferably, the coalescing agent is a dodecanol ester.
In addition, the invention also provides a high-flame-retardance polymer cement composite water-based waterproof coating, which comprises the components of a graphene/nitrogen/phosphorus composite flame retardant, EVA rubber powder, water, a dispersing agent, a water reducing agent, a defoaming agent, a film-forming assistant, Portland cement, calcium carbonate, quartz sand and wollastonite.
The invention provides a high flame-retardant polymer cement composite water-based waterproof coating and a preparation method thereof, compared with the prior art, the high flame-retardant polymer cement composite water-based waterproof coating has the outstanding characteristics and excellent effects that: the preparation method comprises the steps of firstly preparing 1-vinyl-3-aminopropylimidazole tetrafluoroborate ionic liquid, then utilizing the amino group of the ionic liquid to react with the carboxyl group of carboxylated graphene, modifying vinyl imidazole on the surface of a graphene sheet layer, then utilizing the reaction of the vinyl group and the P-H bond of DOPO to graft the DOPO on the surface of the graphene sheet layer, and preparing the graphene/nitrogen/phosphorus composite flame retardant. The composite flame retardant is added into the polymer cement waterproof coating, on one hand, as the surface of the graphene sheet layer is modified with an organic group, the interface combination between graphene and a polymer can be enhanced, and the graphene is prevented from agglomerating; on the other hand, in the composite flame retardant, the imidazolyl group provides nitrogen element, the DOPO provides phosphorus element, and the graphene, nitrogen and phosphorus generate a synergistic flame retardant effect, so that the flame retardant property of the coating can be remarkably improved.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
(1) Adding 1-vinylimidazole and 3-bromopropylamine hydrobromide into acetonitrile, heating to 80 ℃ under the protection of nitrogen, carrying out reflux reaction for 24 hours, then adding deionized water for dilution, adjusting the pH value to 7, then adding sodium tetrafluoroborate, stirring for reaction for 24 hours, then extracting for 2 times by using dichloromethane, and evaporating the upper layer solution to dryness to obtain 1-vinyl-3-aminopropylimidazole tetrafluoroborate ionic liquid; the mass ratio of 1-vinylimidazole to 3-bromopropylamine hydrobromide to sodium tetrafluoroborate to acetonitrile to deionized water is 4: 8: 5: 38: 100, respectively;
(2) adding carboxylated graphene into 1-vinyl-3-aminopropylimidazole tetrafluoroborate ionic liquid, dropwise adding concentrated sulfuric acid, heating to 45 ℃ under the protection of nitrogen, enabling amino groups of the ionic liquid and carboxyl groups of the graphene to generate a dehydration condensation reaction, stopping heating after 8 hours, naturally cooling to room temperature, performing suction filtration, washing and drying to obtain vinylimidazole modified graphene; the mass ratio of the carboxylated graphene to the 1-vinyl-3-aminopropylimidazole tetrafluoroborate ionic liquid to the concentrated sulfuric acid is 15: 100: 3;
(3) adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) into toluene, heating to 85 ℃, stirring and dissolving under the protection of nitrogen, then adding vinylimidazole modified graphene and azobisisobutyronitrile, reacting P-H bond of DOPO with vinyl under stirring, stopping heating after 10H, naturally cooling to room temperature, filtering, washing and drying to obtain the graphene/nitrogen/phosphorus composite flame retardant; the mass ratio of DOPO, vinyl imidazole modified graphene, azodiisobutyronitrile and toluene is 10: 20: 0.03: 100, respectively;
(4) uniformly mixing the graphene/nitrogen/phosphorus composite flame retardant with EVA rubber powder, water, a dispersing agent, a water reducing agent, a defoaming agent, a film-forming auxiliary agent, portland cement, calcium carbonate, quartz sand and wollastonite to obtain the high-flame-retardancy polymer cement composite water-based waterproof coating; the mass ratio of the graphene/nitrogen/phosphorus composite flame retardant to the EVA rubber powder to the water to the dispersant to the water reducer to the defoaming agent to the film forming auxiliary agent to the silicate cement to the calcium carbonate to the quartz sand to the wollastonite is 4: 38: 100: 0.7: 1.5: 0.02: 1: 25: 9: 3: 3; the dispersant is sodium polyacrylate; the water reducing agent is a polycarboxylic acid high-efficiency water reducing agent; the defoaming agent is an organic silicon defoaming agent; the film-forming assistant is dodecyl alcohol ester.
Example 2
(1) Adding 1-vinylimidazole and 3-bromopropylamine hydrobromide into acetonitrile, heating to 80 ℃ under the protection of nitrogen, carrying out reflux reaction for 24 hours, then adding deionized water for dilution, adjusting the pH value to 7, then adding sodium tetrafluoroborate, stirring for reaction for 24 hours, then extracting for 3 times by using dichloromethane, and evaporating the upper layer solution to dryness to obtain 1-vinyl-3-aminopropylimidazole tetrafluoroborate ionic liquid; the mass ratio of 1-vinylimidazole to 3-bromopropylamine hydrobromide to sodium tetrafluoroborate to acetonitrile to deionized water is 4: 8: 4.5: 40: 100, respectively;
(2) adding carboxylated graphene into 1-vinyl-3-aminopropylimidazole tetrafluoroborate ionic liquid, dropwise adding concentrated sulfuric acid, heating to 42 ℃ under the protection of nitrogen, enabling amino groups of the ionic liquid and carboxyl groups of the graphene to generate a dehydration condensation reaction, stopping heating after 7h, naturally cooling to room temperature, performing suction filtration, washing and drying to obtain vinylimidazole modified graphene; the mass ratio of the carboxylated graphene to the 1-vinyl-3-aminopropylimidazole tetrafluoroborate ionic liquid to the concentrated sulfuric acid is 17: 100: 2;
(3) adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) into toluene, heating to 85 ℃, stirring and dissolving under the protection of nitrogen, then adding vinylimidazole modified graphene and azobisisobutyronitrile, reacting P-H bond of DOPO with vinyl under stirring, stopping heating after 10H, naturally cooling to room temperature, filtering, washing and drying to obtain the graphene/nitrogen/phosphorus composite flame retardant; the mass ratio of DOPO, vinyl imidazole modified graphene, azodiisobutyronitrile and toluene is 12: 15: 0.02: 100, respectively;
(4) uniformly mixing the graphene/nitrogen/phosphorus composite flame retardant with EVA rubber powder, water, a dispersing agent, a water reducing agent, a defoaming agent, a film-forming auxiliary agent, portland cement, calcium carbonate, quartz sand and wollastonite to obtain the high-flame-retardancy polymer cement composite water-based waterproof coating; the graphene/nitrogen/phosphorus composite flame retardant comprises 5 parts of graphene/nitrogen/phosphorus composite flame retardant, EVA rubber powder, water, a dispersing agent, a water reducing agent, a defoaming agent, a film forming auxiliary agent, portland cement, calcium carbonate, quartz sand and wollastonite in mass ratio: 30: 100: 1: 1: 0.02: 1: 25: 8: 4: 3; the dispersant is sodium polyacrylate; the water reducing agent is a polycarboxylic acid high-efficiency water reducing agent; the defoaming agent is polyether modified organic silicon defoaming agent; the film-forming assistant is dodecyl alcohol ester.
Example 3
(1) Adding 1-vinylimidazole and 3-bromopropylamine hydrobromide into acetonitrile, heating to 80 ℃ under the protection of nitrogen, carrying out reflux reaction for 24 hours, then adding deionized water for dilution, adjusting the pH value to 7, then adding sodium tetrafluoroborate, stirring for reaction for 24 hours, then extracting for 2 times by using dichloromethane, and evaporating the upper layer solution to dryness to obtain 1-vinyl-3-aminopropylimidazole tetrafluoroborate ionic liquid; the mass ratio of 1-vinylimidazole to 3-bromopropylamine hydrobromide to sodium tetrafluoroborate to acetonitrile to deionized water is 4: 8: 4.5: 38: 100, respectively;
(2) adding carboxylated graphene into 1-vinyl-3-aminopropylimidazole tetrafluoroborate ionic liquid, dropwise adding concentrated sulfuric acid, heating to 40 ℃ under the protection of nitrogen, enabling amino groups of the ionic liquid and carboxyl groups of the graphene to generate a dehydration condensation reaction, stopping heating after 6 hours, naturally cooling to room temperature, performing suction filtration, washing and drying to obtain vinylimidazole modified graphene; the mass ratio of the carboxylated graphene to the 1-vinyl-3-aminopropylimidazole tetrafluoroborate ionic liquid to the concentrated sulfuric acid is 18: 100: 2;
(3) adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) into toluene, heating to 85 ℃, stirring and dissolving under the protection of nitrogen, then adding vinylimidazole modified graphene and azobisisobutyronitrile, reacting P-H bond of DOPO with vinyl under stirring, stopping heating after 11H, naturally cooling to room temperature, filtering, washing and drying to obtain the graphene/nitrogen/phosphorus composite flame retardant; the mass ratio of DOPO, vinyl imidazole modified graphene, azodiisobutyronitrile and toluene is 15: 15: 0.03: 100, respectively;
(4) uniformly mixing the graphene/nitrogen/phosphorus composite flame retardant with EVA rubber powder, water, a dispersing agent, a water reducing agent, a defoaming agent, a film-forming auxiliary agent, portland cement, calcium carbonate, quartz sand and wollastonite to obtain the high-flame-retardancy polymer cement composite water-based waterproof coating; the mass ratio of the graphene/nitrogen/phosphorus composite flame retardant to the EVA rubber powder to the water to the dispersant to the water reducer to the defoaming agent to the film forming auxiliary agent to the silicate cement to the calcium carbonate to the quartz sand to the wollastonite is 4: 32: 100: 0.7: 2: 0.015: 1.8: 29: 7: 4: 4; the dispersant is polyethylene glycol; the water reducing agent is a polycarboxylic acid high-efficiency water reducing agent; the defoaming agent is an organic silicon defoaming agent; the film-forming assistant is dodecyl alcohol ester.
Example 4
(1) Adding 1-vinylimidazole and 3-bromopropylamine hydrobromide into acetonitrile, heating to 80 ℃ under the protection of nitrogen, carrying out reflux reaction for 24 hours, then adding deionized water for dilution, adjusting the pH value to 7, then adding sodium tetrafluoroborate, stirring for reaction for 24 hours, then extracting for 3 times by using dichloromethane, and evaporating the upper layer solution to dryness to obtain 1-vinyl-3-aminopropylimidazole tetrafluoroborate ionic liquid; the mass ratio of 1-vinylimidazole to 3-bromopropylamine hydrobromide to sodium tetrafluoroborate to acetonitrile to deionized water is 4: 8: 4: 40: 100, respectively;
(2) adding carboxylated graphene into 1-vinyl-3-aminopropylimidazole tetrafluoroborate ionic liquid, dropwise adding concentrated sulfuric acid, heating to 40 ℃ under the protection of nitrogen, enabling amino groups of the ionic liquid and carboxyl groups of the graphene to generate a dehydration condensation reaction, stopping heating after 8 hours, naturally cooling to room temperature, performing suction filtration, washing and drying to obtain vinylimidazole modified graphene; the mass ratio of the carboxylated graphene to the 1-vinyl-3-aminopropylimidazole tetrafluoroborate ionic liquid to the concentrated sulfuric acid is 20: 100: 1;
(3) adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) into toluene, heating to 85 ℃, stirring and dissolving under the protection of nitrogen, then adding vinylimidazole modified graphene and azobisisobutyronitrile, reacting P-H bond of DOPO with vinyl under stirring, stopping heating after 12H, naturally cooling to room temperature, filtering, washing and drying to obtain the graphene/nitrogen/phosphorus composite flame retardant; the mass ratio of DOPO, vinyl imidazole modified graphene, azodiisobutyronitrile and toluene is 18: 12: 0.03: 100, respectively;
(4) uniformly mixing the graphene/nitrogen/phosphorus composite flame retardant with EVA rubber powder, water, a dispersing agent, a water reducing agent, a defoaming agent, a film-forming auxiliary agent, portland cement, calcium carbonate, quartz sand and wollastonite to obtain the high-flame-retardancy polymer cement composite water-based waterproof coating; the graphene/nitrogen/phosphorus composite flame retardant comprises 3 mass ratios of graphene/nitrogen/phosphorus composite flame retardant, EVA rubber powder, water, dispersing agent, water reducing agent, defoaming agent, film forming additive, portland cement, calcium carbonate, quartz sand and wollastonite: 35: 100: 0.7: 2: 0.01: 1.2: 27: 8: 3: 4; the dispersant is sodium polyacrylate; the water reducing agent is a polycarboxylic acid high-efficiency water reducing agent; the defoaming agent is an organic silicon defoaming agent; the film-forming assistant is dodecyl alcohol ester.
Example 5
(1) Adding 1-vinylimidazole and 3-bromopropylamine hydrobromide into acetonitrile, heating to 80 ℃ under the protection of nitrogen, carrying out reflux reaction for 24 hours, then adding deionized water for dilution, adjusting the pH value to 7, then adding sodium tetrafluoroborate, stirring for reaction for 24 hours, then extracting for 3 times by using dichloromethane, and evaporating the upper layer solution to dryness to obtain 1-vinyl-3-aminopropylimidazole tetrafluoroborate ionic liquid; the mass ratio of 1-vinylimidazole to 3-bromopropylamine hydrobromide to sodium tetrafluoroborate to acetonitrile to deionized water is 4: 8: 4: 38: 100, respectively;
(2) adding carboxylated graphene into 1-vinyl-3-aminopropylimidazole tetrafluoroborate ionic liquid, dropwise adding concentrated sulfuric acid, heating to 45 ℃ under the protection of nitrogen, enabling amino groups of the ionic liquid and carboxyl groups of the graphene to generate a dehydration condensation reaction, stopping heating after 7h, naturally cooling to room temperature, performing suction filtration, washing and drying to obtain vinylimidazole modified graphene; the mass ratio of the carboxylated graphene to the 1-vinyl-3-aminopropylimidazole tetrafluoroborate ionic liquid to the concentrated sulfuric acid is 18: 100: 2;
(3) adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) into toluene, heating to 85 ℃, stirring and dissolving under the protection of nitrogen, then adding vinylimidazole modified graphene and azobisisobutyronitrile, reacting P-H bond of DOPO with vinyl under stirring, stopping heating after 12H, naturally cooling to room temperature, filtering, washing and drying to obtain the graphene/nitrogen/phosphorus composite flame retardant; the mass ratio of DOPO, vinyl imidazole modified graphene, azodiisobutyronitrile and toluene is 15: 18: 0.03: 100, respectively;
(4) uniformly mixing the graphene/nitrogen/phosphorus composite flame retardant with EVA rubber powder, water, a dispersing agent, a water reducing agent, a defoaming agent, a film-forming auxiliary agent, portland cement, calcium carbonate, quartz sand and wollastonite to obtain the high-flame-retardancy polymer cement composite water-based waterproof coating; the mass ratio of the graphene/nitrogen/phosphorus composite flame retardant to the EVA rubber powder to the water to the dispersant to the water reducer to the defoaming agent to the film forming auxiliary agent to the silicate cement to the calcium carbonate to the quartz sand to the wollastonite is 4: 33: 100: 0.7: 1.6: 0.01: 2: 27: 8: 2: 5; the dispersant is polyethylene glycol; the water reducing agent is a polycarboxylic acid high-efficiency water reducing agent; the defoaming agent is polyether modified organic silicon defoaming agent; the film-forming assistant is dodecyl alcohol ester.
Comparative example 1
Directly and uniformly mixing the carboxylated graphene with EVA rubber powder, water, a dispersing agent, a water reducing agent, a defoaming agent, a film forming aid, portland cement, calcium carbonate, quartz sand and wollastonite to obtain the flame-retardant polymer cement composite water-based waterproof coating; the mass ratio of the carboxylated graphene to the EVA rubber powder to the water to the dispersant to the water reducer to the defoamer to the film-forming auxiliary agent is 4: 33: 100: 0.7: 1.6: 0.01: 2: 27: 8: 2: 5; the dispersant is polyethylene glycol; the water reducing agent is a polycarboxylic acid high-efficiency water reducing agent; the defoaming agent is polyether modified organic silicon defoaming agent; the film-forming assistant is dodecyl alcohol ester.
The performance test is that a 20cm × 20cm three-splint sample is taken, the flame retardant coating prepared in the examples and the comparative examples is coated on one side of the sample respectively, the coating thickness is 5mm, the sample is dried for 12h at 80 ℃, then the sample is placed on a fuel cup containing absolute ethyl alcohol, the coating surface faces downwards, the distance from the upper edge of the fuel cup to the coating surface is 2.5cm, the ethyl alcohol is ignited, the time required for carbonization of the three-splint surface, namely the flame retardant time, is observed and recorded for measuring the flame retardant performance of the coating, and the obtained data are shown in table 1.
Table 1:
Claims (7)
1. a preparation method of a high-flame-retardancy polymer cement composite water-based waterproof coating is characterized by comprising the following preparation steps:
(1) adding 1-vinylimidazole and 3-bromopropylamine hydrobromide into acetonitrile, heating to 80 ℃ under the protection of nitrogen, carrying out reflux reaction for 24 hours, then adding deionized water for dilution, adjusting the pH value to 7, then adding sodium tetrafluoroborate, stirring for reaction for 24 hours, then extracting for 2-3 times by using dichloromethane, and evaporating the upper layer solution to dryness to obtain 1-vinyl-3-aminopropylimidazole tetrafluoroborate ionic liquid;
(2) adding carboxylated graphene into 1-vinyl-3-aminopropylimidazole tetrafluoroborate ionic liquid, dropwise adding concentrated sulfuric acid, heating to 40-45 ℃ under the protection of nitrogen, enabling amino groups of the ionic liquid and carboxyl groups of the graphene to generate a dehydration condensation reaction, stopping heating after 6-8 hours, naturally cooling to room temperature, performing suction filtration, washing and drying to obtain vinylimidazole modified graphene;
(3) adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) into toluene, heating to 85 ℃, stirring and dissolving under the protection of nitrogen, then adding vinylimidazole modified graphene and azobisisobutyronitrile, reacting P-H bond of DOPO with vinyl under stirring, stopping heating after 10-12H, naturally cooling to room temperature, filtering, washing and drying to obtain the graphene/nitrogen/phosphorus composite flame retardant;
(4) uniformly mixing the graphene/nitrogen/phosphorus composite flame retardant with EVA rubber powder, water, a dispersing agent, a water reducing agent, a defoaming agent, a film forming auxiliary agent, portland cement, calcium carbonate, quartz sand and wollastonite to obtain the high-flame-retardancy polymer cement composite water-based waterproof coating.
2. The preparation method of the high flame retardant polymer cement composite water-based waterproof coating material according to claim 1, characterized in that: in the step (1), the mass ratio of the 1-vinylimidazole to the 3-bromopropylamine hydrobromide to the sodium tetrafluoroborate to the acetonitrile to the deionized water is 4: 8-10: 4-5: 38-42: 100.
3. the preparation method of the high flame retardant polymer cement composite water-based waterproof coating material according to claim 1, characterized in that: in the step (2), the mass ratio of the carboxylated graphene to the 1-vinyl-3-aminopropylimidazole tetrafluoroborate ionic liquid to the concentrated sulfuric acid is 15-20: 100: 1 to 3.
4. The preparation method of the high flame retardant polymer cement composite water-based waterproof coating material according to claim 1, characterized in that: in the step (3), the mass ratio of DOPO, the vinyl imidazole modified graphene, the azodiisobutyronitrile and the toluene is 10-20: 10-20: 0.02-0.04: 100.
5. the preparation method of the high flame retardant polymer cement composite water-based waterproof coating material according to claim 1, characterized in that: in the step (4), the mass ratio of the graphene/nitrogen/phosphorus composite flame retardant to the EVA rubber powder to the dispersant to the water reducer to the defoamer to the film forming auxiliary agent to the silicate cement to the wollastonite is 3-5: 30-40: 100: 0.5-1: 1-2: 0.01-0.02: 1-2: 25-30: 7-9: 2-4: 3 to 5.
6. The preparation method of the high flame retardant polymer cement composite water-based waterproof coating material according to claim 1, characterized in that: in the step (4), the dispersing agent is one of sodium polyacrylate or polyethylene glycol, the water reducing agent is a polycarboxylic acid high-efficiency water reducing agent, the defoaming agent is one of an organic silicon defoaming agent or a polyether modified organic silicon defoaming agent, and the film-forming assistant is dodecyl alcohol ester.
7. The high-flame-retardancy polymer cement composite water-based waterproof coating prepared by the preparation method of any one of claims 1 to 6 is characterized in that: the waterproof coating comprises the components of graphene/nitrogen/phosphorus composite flame retardant, EVA rubber powder, water, dispersant, water reducer, defoamer, film forming aid, portland cement, calcium carbonate, quartz sand and wollastonite.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114989090A (en) * | 2022-05-24 | 2022-09-02 | 沈阳化工大学 | Preparation method of amino functionalized ionic liquid |
| CN115385602A (en) * | 2022-08-12 | 2022-11-25 | 金陵科技学院 | Anti-seepage material for building and preparation method thereof |
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2020
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114989090A (en) * | 2022-05-24 | 2022-09-02 | 沈阳化工大学 | Preparation method of amino functionalized ionic liquid |
| CN115385602A (en) * | 2022-08-12 | 2022-11-25 | 金陵科技学院 | Anti-seepage material for building and preparation method thereof |
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Application publication date: 20200717 |