CN113150662B - PAE polyurea foaming flame-retardant heat-preservation high-strength coating - Google Patents
PAE polyurea foaming flame-retardant heat-preservation high-strength coating Download PDFInfo
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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
- C09D175/02—Polyureas
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- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/335—Polymers modified by chemical after-treatment with organic compounds containing phosphorus
- C08G65/3353—Polymers modified by chemical after-treatment with organic compounds containing phosphorus containing oxygen in addition to phosphorus
- C08G65/3355—Polymers modified by chemical after-treatment with organic compounds containing phosphorus containing oxygen in addition to phosphorus having phosphorus bound to carbon and oxygen
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- 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
- C09D5/18—Fireproof paints including high temperature resistant paints
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
The invention discloses a PAE polyurea foaming flame-retardant heat-preservation high-strength coating which comprises the following components in parts by weight: 45-55 parts of hydrophilic flame-retardant modified polyaspartic acid ester, 1-3 parts of water, 0.1-0.2 part of dibutyltin dilaurate and 45-55 parts of water-based isocyanate curing agent. The preparation method of the hydrophilic flame-retardant modified polyaspartic acid ester comprises the following steps: (1) reacting maleic anhydride with hydroxyl-containing phosphate to obtain maleic acid diphosphate; (2) and reacting the obtained maleic acid diphosphate with polyether amine or diamino polyethylene glycol to obtain the hydrophilic flame-retardant modified polyaspartic acid ester. According to the invention, the hydrophilic flame-retardant modified polyaspartic acid ester and the water-based isocyanate curing agent are compounded, so that the obtained PAE polyurea coating has good performances of heat preservation, fire prevention, crack resistance, high strength, chemical medium resistance and the like, and can meet the use requirements of floors and wall surfaces when being used for heat preservation treatment of residential buildings.
Description
Technical Field
The invention relates to the technical field of polymers and high-molecular coatings, in particular to a PAE polyurea foaming flame-retardant heat-preservation high-strength coating.
Background
For the heat preservation of the unit residential building, the heat preservation design and construction of the ground and the wall surface are technical measures for effectively improving the heat preservation energy efficiency of the residential building. Due to the principle that air is heated to rise, the temperature of the roof surface is higher for a room with warm air and is an important heat dissipation position, and if ground heat preservation is not arranged, a large amount of heat of a lower-layer room is supplied to an upper-layer building, so that the use energy efficiency of the room is reduced.
In the prior art, generally, only an inorganic heat-insulating layer is arranged for heat insulation treatment of the ground and the wall surface of a residential building, for example, a floor heat-insulating structure disclosed in the Chinese patent literature, the publication No. CN110629975A of which comprises a facing layer and a heat-insulating layer, wherein the facing layer is arranged above the heat-insulating layer, the floor heat-insulating structure further comprises a leveling layer, the leveling layer is used for being connected to a floor base layer, the leveling layer is arranged below the heat-insulating layer, the leveling layer and the facing layer are both made of cement-based self-leveling mortar, and the heat-insulating layer is made of an A-grade fireproof heat-insulating material. However, the inorganic heat-insulating layer has poor heat-insulating effect, cannot meet the heat-insulating requirement of residential buildings, often cannot meet the decoration requirements of customers on strength, crack resistance, slotting and the like before the decoration of indoor and indoor walls in China, and the inorganic heat-insulating layer on the ground or the wall surface needs to be removed to a certain extent, and cannot play a good heat-insulating effect after the removal.
Therefore, the building heat insulation coating is more and more popular and favored by the users due to the advantages of economy, convenient use, good heat insulation effect and the like. The existing heat insulation coating mainly uses epoxy floor coating, such as 'a heat insulation coating' disclosed in patent document with publication number CN104403390A, and comprises the following components in percentage by weight: 3-12 parts of water-based acrylic acid; 10-14 parts of propylene glycol; 8-11 parts of epoxy resin; 0.8-1.8 parts of methyl methacrylate; 23-36 parts of heavy calcium carbonate; 2-8 parts of diatomite; 9-12 parts of plant cellulose; 3-7 parts of a curing agent. However, the epoxy heat-insulating coating has the defects of poor application property, short working life, poor fire resistance and chemical medium resistance of a coating film and the like.
Disclosure of Invention
The invention aims to overcome the defects of poor construction performance, short working life, poor fireproof performance and chemical medium resistance of a coating film and the like of a heat insulation and heat preservation coating in the prior art, and provides a PAE polyurea foaming flame-retardant heat preservation high-strength coating.
In order to achieve the purpose, the invention adopts the following technical scheme:
the PAE polyurea foaming flame-retardant heat-preservation high-strength coating comprises the following components in parts by weight:
according to the invention, the hydrophilic flame-retardant modified polyaspartic ester, the aqueous isocyanate curing agent and water are compounded to prepare the aqueous polyaspartic ester polyurea (PAE polyurea) coating, and the PAE polyurea coating has high compressive strength and very high adhesive force on the surface of a base material; in addition, the PAE polyurea coating has a proper working life, is quick in drying time, has excellent acid resistance, alkali resistance and salt spray resistance, and has excellent performance when being used as a surface protective topcoat material. Because the polyaspartic ester is subjected to flame retardant modification, the coating also has good fireproof performance; simultaneously, a catalyst dibutyltin dilaurate is added into the coating, when the coating is used, firstly, the hydrophilic flame-retardant modified polyaspartic acid ester reacts with the water-based isocyanate curing agent to gradually become viscous, and then the water-based isocyanate curing agent and water generate carbon dioxide gas under the catalysis of the dibutyltin dilaurate to seal a viscous surface layer to form a carbon dioxide foaming coating; the foaming rate can be controlled by controlling the adding amount of dibutyltin dilaurate, the foaming degree can be controlled by controlling the proportion of the water-based isocyanate curing agent and water, and a uniform microporous structure foaming layer is formed in the finally obtained coating, so that the coating has good heat preservation and noise resistance.
Preferably, the preparation method of the hydrophilic flame-retardant modified polyaspartic acid ester comprises the following steps:
(1) reacting maleic anhydride with hydroxyl-containing phosphate to obtain maleic acid diphosphate;
(2) and reacting the obtained maleic acid diphosphate with polyether amine or diamino polyethylene glycol to obtain the hydrophilic flame-retardant modified polyaspartic acid ester.
The invention uses phosphate ester containing hydroxyl to modify maleic anhydride, and then uses Michael addition reaction of maleic acid diphosphate and polyether amine or diamino polyethylene glycol obtained after modification to obtain hydrophilic flame-retardant modified polyaspartic acid ester, wherein the reaction mechanism is as follows:
wherein, X is a polyether group or a polyethylene glycol group.
The existing polyaspartic ester polyurea coating has low fire-retardant grade, is easy to burn and generate dense smoke, and limits the use of materials, so that the invention modifies polyaspartic ester by using hydroxy phosphate, introduces phosphate groups into the molecular structure of the polyaspartic ester to serve as phosphorus flame-retardant side groups, can play a role in wrapping and protecting the whole molecule, and thus the obtained modified polyaspartic ester has good flame-retardant property; in addition, the larger phosphate side group can provide a better telescopic group for the whole system, so that the coating film has better elasticity, and the elongation at break is obviously improved; the introduced side group cavity can also provide better heat insulation performance for the system, and effectively improves the heat insulation performance of the coating. Meanwhile, polyether groups or polyethylene glycol groups and other hydrophilic groups are introduced into the molecular chain of the polyaspartic acid ester, so that the polyaspartic acid ester obtains good hydrophilicity, can be compounded with a water-based isocyanate curing agent to form a water-based PAE polyurea coating, reduces the use of organic solvents harmful to the environment and human bodies, and improves the environmental protection and safety performance of the coating.
Preferably, the molar ratio of the maleic anhydride to the hydroxyl-containing phosphate ester in the step (1) is 1: 2-2.4. At this ratio, it is ensured that the carboxyl groups in the maleic anhydride are sufficiently esterified.
Preferably, the hydroxyl-containing phosphate ester in step (1) is one or more selected from dimethyl hydroxymethyl phosphate, dimethyl hydroxyethyl phosphate, diethyl hydroxymethyl phosphate, diethyl hydroxyethyl phosphate, dimethyl hydroxypropyl phosphate and diethyl hydroxypropyl phosphate.
Preferably, the reaction conditions of step (1) are: adding maleic anhydride and hydroxyl-containing phosphate into a xylene solvent, adding a catalyst, reacting for 3-10 h at 140-160 ℃, and then removing the solvent under reduced pressure to obtain maleic acid diphosphate.
Preferably, the catalyst is selected from one or more of p-toluenesulfonic acid, sodium methoxide and triethylamine, and the amount of the catalyst is 0.01-0.1% of the mass of the reactant.
Preferably, the molar ratio of the maleic acid diphosphate to the amino group in the polyether amine or the diamino polyethylene glycol in the step (2) is 1-1.2: 1. At this ratio, sufficient conversion of primary amine to secondary amine in the system can be ensured.
Preferably, the polyetheramine is selected from one or more of D230, D400, T403, D800, D1000, D2000.
Preferably, the molecular weight of the bisaminopolyethylene glycol is 800 to 2000.
The molecular weight of the polyether amine and the diamino polyethylene glycol is in the range, so that the obtained polyaspartic acid ester has good hydrophilicity and can be prepared into waterborne coatings.
Preferably, the reaction conditions of step (2) are: mixing polyether amine or diamino polyethylene glycol with a catalyst sodium methoxide, wherein the addition amount of the sodium methoxide is 0.03-0.1% of the mass of a reactant; dropwise adding maleic acid diphosphate into the mixture at 40-45 ℃ under the protection of nitrogen, wherein the dropwise adding time is controlled to be 40-80 min; and then heating to 60-80 ℃, introducing nitrogen, and reacting for 16-30 hours to obtain the hydrophilic flame-retardant modified polyaspartic acid ester.
Therefore, the invention has the following beneficial effects:
(1) the hydrophilic flame-retardant modified polyaspartic acid ester, a water-based isocyanate curing agent and a dibutyltin dilaurate catalyst are compounded to obtain a water-based PAE polyurea coating, and when the PAE polyurea coating is used, the PAE polyurea coating can react to obtain a closed carbon dioxide terrace foaming coating with uniform foaming, so that good heat preservation, flame retardance, water resistance, noise resistance, impact resistance and other effects are realized;
(2) modifying polyaspartic acid ester with hydroxy phosphate to obtain phosphorus flame retardant group modified polyaspartic acid ester, which significantly improves the flame retardant property and can also improve the heat preservation property and the elongation at break of a coating film;
(3) the polyether group or polyethylene glycol group and other hydrophilic groups are introduced into the molecular chain of the polyaspartic acid ester, so that the polyaspartic acid ester obtains good hydrophilicity, and can be compounded with the water-based isocyanate curing agent to form the water-based PAE polyurea coating, thereby reducing the use of organic solvents harmful to the environment and human bodies, and improving the environmental protection and safety performance of the coating.
Detailed Description
The invention is further described with reference to specific embodiments.
In the present invention, all the raw materials are commercially available or commonly used in the industry, and the methods in the following examples are conventional in the art unless otherwise specified.
Example 1:
the PAE polyurea foaming flame-retardant heat-preservation high-strength coating comprises the following components in parts by weight:
the preparation method of the hydrophilic flame-retardant modified polyaspartic acid ester comprises the following steps:
(1) adding maleic anhydride, dimethyl hydroxymethyl phosphate, a polymerization inhibitor p-hydroxyanisole (MEHQ), p-toluenesulfonic acid and a solvent xylene into a flask with a water separator, wherein the molar ratio of the maleic anhydride to the dimethyl hydroxymethyl phosphate is 1:2.1, the addition amount of the MEHQ is 0.02 percent of the total mass of the maleic anhydride and the dimethyl hydroxymethyl phosphate, and the addition amount of the p-toluenesulfonic acid is 0.05 percent of the total mass of the maleic anhydride and the dimethyl hydroxymethyl phosphate; heating to 150 ℃, carrying out reflux dehydration esterification reaction for 5 hours, and then removing a xylene solvent under reduced pressure to obtain yellowish dimethyl maleate liquid;
(2) adding diamino polyethylene glycol (molecular weight is 1000, an Aladdin reagent) into a flask, adding sodium methoxide, wherein the addition amount of the sodium methoxide is 0.03 percent of the total mass of reactants, heating to 40 ℃, introducing nitrogen, then dropwise adding dimethyl maleate into a constant-pressure dropping funnel for 1h, wherein the molar ratio of the added dimethyl maleate to amino in the diamino polyethylene glycol is 2.1: 1; then heating to 70 ℃, introducing nitrogen for reaction for 12h, and obtaining the hydrophilic flame-retardant modified polyaspartic acid ester.
Example 2:
the PAE polyurea foaming flame-retardant heat-preservation high-strength coating comprises the following components in parts by weight:
the preparation method of the hydrophilic flame-retardant modified polyaspartic acid ester comprises the following steps:
(1) adding maleic anhydride, dimethyl hydroxymethyl phosphate, a polymerization inhibitor p-hydroxyanisole (MEHQ), p-toluenesulfonic acid and a solvent xylene into a flask with a water separator, wherein the molar ratio of the maleic anhydride to the dimethyl hydroxymethyl phosphate is 1:2.1, the addition amount of the MEHQ is 0.02 percent of the total mass of the maleic anhydride and the dimethyl hydroxymethyl phosphate, and the addition amount of the p-toluenesulfonic acid is 0.05 percent of the total mass of the maleic anhydride and the dimethyl hydroxymethyl phosphate; heating to 150 ℃, carrying out reflux dehydration esterification reaction for 5 hours, and then removing a xylene solvent under reduced pressure to obtain yellowish dimethyl maleate liquid;
(2) adding polyetheramine D800 (Hensmei) into a flask, adding sodium methoxide, wherein the addition amount of the sodium methoxide is 0.1 percent of the total mass of reactants, heating to 45 ℃, introducing nitrogen, then dropwise adding dimethyl maleate into a constant-pressure dropping funnel for 80min, wherein the molar ratio of the added dimethyl maleate to amino in the polyetheramine is 1.1: 1; then heating to 70 ℃, introducing nitrogen for reaction for 12h, and obtaining the hydrophilic flame-retardant modified polyaspartic acid ester.
Example 3:
the PAE polyurea foaming flame-retardant heat-preservation high-strength coating comprises the following components in parts by weight:
the preparation method of the hydrophilic flame-retardant modified polyaspartic acid ester comprises the following steps:
(1) adding maleic anhydride, dimethyl hydroxymethyl phosphate, a polymerization inhibitor p-hydroxyanisole (MEHQ), p-toluenesulfonic acid and a solvent xylene into a flask with a water separator, wherein the molar ratio of the maleic anhydride to the dimethyl hydroxymethyl phosphate is 1:2.4, the addition amount of the MEHQ is 0.1% of the total mass of the maleic anhydride and the dimethyl hydroxymethyl phosphate, and the addition amount of the p-toluenesulfonic acid is 0.1% of the total mass of the maleic anhydride and the dimethyl hydroxymethyl phosphate; heating to 160 ℃, refluxing, dehydrating and esterifying for 3 hours, and then removing the xylene solvent under reduced pressure to obtain yellowish dimethyl maleate liquid;
(2) mixing polyether amine D800 (Hensmei) and diamino polyethylene glycol (molecular weight 1000, and Aladdin reagent) according to a mass ratio of 3: 7, mixing, adding sodium methoxide into a flask, adding sodium methoxide, wherein the adding amount of the sodium methoxide is 0.1 percent of the total mass of reactants, heating to 45 ℃, introducing nitrogen, then dropwise adding dimethyl maleate into a constant-pressure dropping funnel for 80min, wherein the molar ratio of the added dimethyl maleate to amino in the mixture of the diamino polyethylene glycol and the polyether amine is 1.1: 1; then heating to 70 ℃, introducing nitrogen for reaction for 16h, and obtaining the hydrophilic flame-retardant modified polyaspartic acid ester.
Comparative example 1 (without dibutyltin dilaurate addition):
the PAE polyurea coating comprises the following components in parts by weight:
50 parts of hydrophilic flame-retardant modified polyaspartic acid ester
2 portions of water
50 parts of a water-based isocyanate curing agent.
The preparation method of the hydrophilic flame-retardant modified polyaspartic acid ester is the same as that in the example 3.
Comparative example 2 (too much dibutyltin dilaurate added):
the PAE polyurea coating comprises the following components in parts by weight:
the preparation method of the hydrophilic flame-retardant modified polyaspartic acid ester is the same as that in the example 3.
Comparative example 3 (changing the ratio of water to aqueous isocyanate curing agent):
the PAE polyurea coating comprises the following components in parts by weight:
the preparation method of the hydrophilic flame-retardant modified polyaspartic acid ester is the same as that in the example 3.
Comparative example 4 (without maleic anhydride modification):
the PAE polyurea coating comprises the following components in parts by weight:
the preparation method of the hydrophilic polyaspartic acid ester comprises the following steps: mixing polyether amine D800 (Hensmei) and diamino polyethylene glycol (molecular weight 1000, and Aladdin reagent) according to a mass ratio of 3: 7, mixing, adding sodium methoxide into a flask, adding sodium methoxide, wherein the adding amount of the sodium methoxide is 0.1 percent of the total mass of reactants, heating to 45 ℃, introducing nitrogen, then dropwise adding dimethyl maleate into a constant-pressure dropping funnel for 80min, wherein the molar ratio of the added dimethyl maleate to amino in the mixture of the diamino polyethylene glycol and the polyether amine is 1.1: 1; then heating to 70 ℃, introducing nitrogen for reaction for 16h, and obtaining the hydrophilic flame-retardant modified polyaspartic acid ester.
Comparative example 5 (without hydrophilic modification):
the PAE polyurea foaming flame-retardant heat-preservation high-strength coating comprises the following components in parts by weight:
the preparation method of the flame-retardant modified polyaspartic acid ester comprises the following steps:
(1) adding maleic anhydride, dimethyl hydroxymethyl phosphate, a polymerization inhibitor p-hydroxyanisole (MEHQ), p-toluenesulfonic acid and a solvent xylene into a flask with a water separator, wherein the molar ratio of the maleic anhydride to the dimethyl hydroxymethyl phosphate is 1:2.1, the addition amount of the MEHQ is 0.02 percent of the total mass of the maleic anhydride and the dimethyl hydroxymethyl phosphate, and the addition amount of the p-toluenesulfonic acid is 0.05 percent of the total mass of the maleic anhydride and the dimethyl hydroxymethyl phosphate; heating to 150 ℃, carrying out reflux dehydration esterification reaction for 5 hours, and then removing a xylene solvent under reduced pressure to obtain yellowish dimethyl maleate liquid;
(2) adding hexamethylene diamine into a flask, adding sodium methoxide, wherein the adding amount of the sodium methoxide is 0.03 percent of the total mass of reactants, heating to 40 ℃, introducing nitrogen, dropwise adding dimethyl maleate into a constant-pressure dropping funnel for 1 hour, wherein the molar ratio of the added dimethyl maleate to the ethylene diamine is 2.2: 1; then heating to 70 ℃, introducing nitrogen for reaction for 12 hours to obtain the flame-retardant modified polyaspartic acid ester.
Comparative example 6 (diamino polyethylene glycol too large molecular weight):
the preparation method of the hydrophilic flame-retardant modified polyaspartic acid ester in the comparative example 6 comprises the following steps:
(1) adding maleic anhydride, dimethyl hydroxymethyl phosphate, a polymerization inhibitor p-hydroxyanisole (MEHQ), p-toluenesulfonic acid and a solvent xylene into a flask with a water separator, wherein the molar ratio of the maleic anhydride to the dimethyl hydroxymethyl phosphate is 1:2.1, the addition amount of the MEHQ is 0.02 percent of the total mass of the maleic anhydride and the dimethyl hydroxymethyl phosphate, and the addition amount of the p-toluenesulfonic acid is 0.05 percent of the total mass of the maleic anhydride and the dimethyl hydroxymethyl phosphate; heating to 150 ℃, carrying out reflux dehydration esterification reaction for 5 hours, and then removing a xylene solvent under reduced pressure to obtain yellowish dimethyl maleate liquid;
(2) adding diamino polyethylene glycol (with the molecular weight of 5000) into a flask, adding sodium methoxide, wherein the addition amount of the sodium methoxide is 0.03 percent of the total mass of reactants, heating to 40 ℃, introducing nitrogen, dropwise adding dimethyl maleate into a constant-pressure dropping funnel for 1h, wherein the molar ratio of the added dimethyl maleate to amino in the diamino polyethylene glycol is 1.1: 1; then heating to 70 ℃, introducing nitrogen for reaction for 12h, and obtaining the hydrophilic flame-retardant modified polyaspartic acid ester.
The rest is the same as in example 1.
The service performance of the coating is tested according to the GB/T22374-2018 terrace coating standard and the heat preservation performance of the coating is tested according to the test method of GB/T10294-2008 ' determination of steady-state thermal resistance of heat-insulating material and related characteristics ' method for testing heat-protection plate ', and the results are shown in Table 1.
Table 1: and testing results of the service performance and the heat preservation performance of the coating.
The fire resistance tests were carried out on the coatings prepared in accordance with the national standard GB/T14402-2007 "determination of combustion performance and heat value of combustion of building materials and products", the test objects were all paint films with a thickness of 100 μm obtained by the roll coating method, and the test results were shown in Table 2 after 72 hours.
Table 2: and (5) testing the combustion performance.
As can be seen from tables 1 and 2, the PAE polyurea coatings prepared by using the raw materials and the formula of the invention in examples 1-3 have good heat preservation and fire resistance and compressive strength. However, the polyether amine has better strength, and the polyethylene glycol has better foaming performance. Therefore, the comprehensive effect is better by comprehensively considering the mixing of the polyether amine and the polyethylene glycol. In the comparative example 1, a dibutyltin dilaurate catalyst is not added, so that the foaming rate is too low, and sufficient bubbles are not generated in the reaction of isocyanate and water in a system after polyurea reaction curing molding, so that insufficient foaming is caused; in the comparative example 2, too much dibutyltin dilaurate is added, so that the foaming rate is too high, the surface of the coating is poor, and the strength of the coating is poor due to too much foaming; in the comparative example 3, the effect of foaming more bubbles generated by changing the proportion of water and the water-based isocyanate curing agent is good, but the integral crosslinking density is larger, the material rigidity is larger and the performance is poor; in comparative example 4, maleic anhydride is not modified by hydroxyl phosphate, and the whole molecule cannot be protected from burning by wrapping of the flame-retardant side group, so that the flame-retardant property of the coating is reduced; in comparative example 5, the resin and water were separated from each other without hydrophilic modification of polyaspartic acid ester with polyethylene glycol group, and polyaspartic acid ester reacted with isocyanate rapidly, only with water at the interface, and no bubbles were generated inside the surface was poor; in comparative example 6, the molecular weight of the bisaminopolyethylene glycol used for hydrophilic modification of polyaspartic acid ester is beyond the range of the invention, the hydrophilicity is too strong, the system strength is poor, and the foaming is violent and difficult to control.
Claims (7)
1. The PAE polyurea foaming flame-retardant heat-preservation high-strength coating is characterized by comprising the following components in parts by weight:
45-55 parts of hydrophilic flame-retardant modified polyaspartic acid ester
1-3 parts of water
0.1-0.2 part of dibutyltin dilaurate
45-55 parts of a water-based isocyanate curing agent;
the preparation method of the hydrophilic flame-retardant modified polyaspartic acid ester comprises the following steps:
(1) reacting maleic anhydride with hydroxyl-containing phosphate to obtain maleic acid diphosphate; the mol ratio of the maleic anhydride to the hydroxyl-containing phosphate ester is 1: 2-2.4;
(2) reacting the obtained maleic acid diphosphate with polyether amine or diamino polyethylene glycol to obtain the hydrophilic flame-retardant modified polyaspartic acid ester; the molar ratio of the maleic acid diphosphate to the amino group in the polyether amine or the diamino polyethylene glycol is 1-1.2: 1.
2. The PAE polyurea foaming flame-retardant heat-preservation high-strength coating as claimed in claim 1, wherein the hydroxyl-containing phosphate ester in step (1) is selected from one or more of dimethyl hydroxymethyl phosphate, dimethyl hydroxyethyl phosphate, diethyl hydroxymethyl phosphate, diethyl hydroxyethyl phosphate, dimethyl hydroxypropyl phosphate and diethyl hydroxypropyl phosphate.
3. The PAE polyurea foaming flame-retardant heat-preservation high-strength coating as claimed in claim 1, wherein the reaction conditions of the step (1) are as follows: adding maleic anhydride and hydroxyl-containing phosphate into a xylene solvent, adding a catalyst, reacting for 3-10 h at 140-160 ℃, and then removing the solvent under reduced pressure to obtain maleic acid diphosphate.
4. The PAE polyurea foaming flame-retardant heat-preservation high-strength coating as claimed in claim 3, wherein the catalyst is one or more selected from p-toluenesulfonic acid, sodium methoxide and triethylamine, and the amount of the catalyst is 0.01-0.1% of the mass of the reactant.
5. The PAE polyurea foaming flame-retardant heat-preservation high-strength coating as claimed in claim 1, wherein the polyetheramine is selected from one or more of D230, D400, T403, D800, D1000 and D2000.
6. The PAE polyurea foaming flame-retardant heat-preservation high-strength coating as claimed in claim 1, wherein the molecular weight of the diamino polyethylene glycol is 800-2000.
7. The PAE polyurea foaming flame-retardant heat-preservation high-strength coating as claimed in claim 1, wherein the reaction conditions of the step (2) are as follows: mixing polyether amine or diamino polyethylene glycol with a catalyst sodium methoxide, wherein the addition amount of the sodium methoxide is 0.03-0.1% of the mass of a reactant; dropwise adding maleic acid diphosphate into the mixture at 40-45 ℃ under the protection of nitrogen, wherein the dropwise adding time is controlled to be 40-80 min; and then heating to 60-80 ℃, introducing nitrogen, and reacting for 16-30 hours to obtain the hydrophilic flame-retardant modified polyaspartic acid ester.
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| US5736604A (en) * | 1996-12-17 | 1998-04-07 | Bayer Corporation | Aqueous, two-component polyurea coating compositions |
| WO2004044026A1 (en) * | 2002-11-08 | 2004-05-27 | Bayer Materialscience Llc | Polyurea coatings having improved pot life |
| CN109761834B (en) * | 2019-03-05 | 2021-10-22 | 郁维铭 | Preparation method and application of water-dispersible polyaspartic ester resin and water-based polyurea coating |
| US20200354504A1 (en) * | 2019-05-06 | 2020-11-12 | Covestro Llc | Polyaspartic compositions |
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