CN115725229A - Self-repairing flame-retardant, molten drop-resistant and abrasion-resistant polyurethane coating material - Google Patents
Self-repairing flame-retardant, molten drop-resistant and abrasion-resistant polyurethane coating material Download PDFInfo
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- 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
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- 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
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- 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
- C08G18/40—High-molecular-weight compounds
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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
- C09D5/185—Intumescent paints
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Abstract
The invention relates to a preparation and application method of a self-repairing flame-retardant molten-drop-resistant abrasion-resistant polyurethane coating, which comprises the steps of loading isocyanate on vacuum glass beads HGB-DI, adding polypropylene glycol, polytetrahydrofuran ether glycol, isophorone diisocyanate and HGB-DI into a reaction container protected by nitrogen, raising the temperature of the system to 80 ℃, adding dibutyltin dilaurate, a chain extender 2,2-dithioglycol and a nitrogen-phosphorus intumescent flame retardant, cooling to 50-70 ℃, and adding a thickening agent N, N-diethylformamide; and cooling to 40 ℃, adding triethylamine to obtain transparent viscous liquid, cooling to room temperature, adding deionized water, epoxy resin E51, trimethylolpropane trimethacrylate and 3,4' -diaminodiphenyl ether to finally obtain the polyurethane emulsion, wherein the obtained polyurethane emulsion is obviously superior to the prior art in the aspects of flame-retardant self-repairing, molten drop resistance and wear resistance.
Description
The invention is a division of 202111473297X.
Technical Field
The invention relates to a preparation method of a polyurethane coating, in particular to a preparation method of a self-repairing flame-retardant, molten drop-resistant and abrasion-resistant polyurethane coating, and also relates to an application method of the prepared polyurethane coating.
Background
The waterborne polyurethane has the advantages of safety, harmlessness and strong adhesive force, and can be widely applied to the fields of furniture, fabric coatings, automobile leather and the like. When the waterborne polyurethane is used as a coating material, the waterborne polyurethane is subjected to the actions of friction, collision, bending and the like, and the physical damages such as scratches, microcracks and the like appear on the surface, so that the coating is damaged, the function is lost, and the service life is shortened. The self-repairing polymer material has the capability of repairing external physical damage by depending on the self structure, which is shown in that the self structure is used for repairing after the polymer material is reduced, and the self-repairing polymer material needs to be self-repaired in order to prolong the service life of the polyurethane.
Feng Jianyan, etc. (Feng Jianyan, the preparation and performance of disulfide bond-based waterborne polyurethane/polyacrylate self-repairing material [ J ]. Polymer Material science and engineering, 2021-09-29) people adopt polytetrahydrofuran ether glycol (PTMEG), isophorone diisocyanate (IPDI), 2,2-dimethylolpropionic acid (DMPA), 2,2-dithiodiethanol (HEDS), PA, etc. as raw materials to prepare self-repairing waterborne polyurethane/polyacrylate (AWPUS) composite material containing disulfide bonds. The introduction of the S-S bond endows the material with damage-self-repairing performance, the PA is hot-bonded and cold-brittle, the fluidity of the chain at a certain temperature is improved, the self-repairing of the polymer material is promoted, and the self-repairing efficiency is improved from 73.4% in 6h to 81.7% in 2h at 60 ℃; meanwhile, the mechanical property is still kept at room temperature. AWPUS shows excellent reworkability, a recovered sample is recovered to the original state after being molded for 10min at 100 ℃, the loss of mechanical properties is small, and the AWPUS has high economic applicability.
Polyurethane belongs to a class of organic high molecular materials which take carbon-carbon bonds as basic structural units. The raw materials used in polyurethane synthesis are mostly flammable organic compounds or high molecular materials, so that the polyurethane is flammable substance and has potential fire hazard in the using process. On the other hand, such polymers burn with the release of smoke and toxic gases and can produce molten droplets that can damage human skin or initiate flames.
As the prior art, the flame retardant modification of polyurethane paint mainly comprises the following three methods: (A) use of flame retardant chemical components: in the polyurethane synthesis, polyester and polyether polyol containing phosphorus, nitrogen, silicon and the like with flame retardant effect are selected, so that the synthesized polyurethane material has certain flame retardant property. (B) By utilizing the modification reaction of the polyurethane material, certain heat-resistant structural groups are introduced into the generated macromolecular structure, so that the combustion point temperature of the material and the heat resistance and flame retardance of the material are improved. At present, the common method is to introduce isocyanurate groups of carbon and nitrogen six-membered rings into a macromolecular structure, or to use flame-retardant phosphorus compound polyol as a prepolymer monomer in the synthesis, or to use flame-retardant phosphorus materials, nitrogen and phosphorus compounds and the like as chain extenders, or to modify nitrogen, nitrogen and phosphorus compounds, organic silicon and boron compounds after chain extension. (C) In the polyurethane synthesis, an auxiliary agent with a flame retardant effect is added, and the flame retardant can be divided into an organic flame retardant and an inorganic flame retardant, wherein the flame retardant is mainly a compound containing flame retardant elements such as phosphorus, bromine, antimony, boron and the like, and the flame retardant is mainly an inorganic compound such as organic ammonium phosphate, aluminum hydroxide and the like.
The invention discloses a preparation and application method of a flame-retardant wear-resistant low-VOC (volatile organic compound) polyurethane coating with an authorization publication number of CN112646475B, which is a Chinese granted patent of invention, polyester diol, isocyanate and dibutyltin dilaurate are added into a reaction container, stirred and reacted at 75-90 ℃ to obtain a polyurethane prepolymer, hydrophilic chain extender dimethylolpropionic acid, a nitrogen-phosphorus intumescent flame retardant and an acetone solvent are added into the polyurethane prepolymer, and stirred and reacted for 1-2 hours at 70-90 ℃; adding triethylamine and water for emulsification for 20-60 min, adding a substance A and epoxy-terminated polyether silicone oil, adjusting the pH value to 6.5, stirring and reacting at 70-80 ℃ to obtain the flame-retardant wear-resistant low-VOC polyurethane coating, wherein the obtained polyurethane film shows obvious flame-retardant and wear-resistant performance in the aspects of flame combustion time, droplet resistance and the like, but the patent does not relate to flame-retardant self-repair of polyurethane.
At present, DMF (dimethylformamide) and acetone are used as common solvents in polyurethane synthesis, and the solvents have strong irritation on eyes, skin and mucous membranes and cause general spasm, painful constipation, nausea, vomiting and the like after inhalation. DMF and acetone are restricted in the exemption list of the European Union, VOC is required to be less than 1000ppm, and a DEF solvent of N, N-diethylformamide is a novel solvent and is a trend for the development of the field of polyurethane by replacing DMF.
Polyurethane is used as one of main coatings of leather and synthetic leather products, and the VOC content in the air is increased due to the presence of an organic solvent in the system, so that improvement on the problem is needed.
The polyurethane is often used as a coating layer in the using process, the coating layer is contacted with a human body in the using process and often abrades the coating layer to cause the reduction of the flame retardant property, and no published documents are related at present.
In conclusion, the synthesis research of self-repairing flame-retardant, anti-dripping, abrasion-resistant and low-VOC polyurethane is very critical.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation and application method of a self-repairing flame-retardant, droplet-resistant, wear-resistant and low-VOC polyurethane coating, further improving the flame-retardant effect of the polyurethane coating and improving the flame retardance of self-repairing property.
The technical scheme of the invention is as follows: the preparation method of the self-repairing flame-retardant, droplet-resistant and abrasion-resistant polyurethane coating is characterized by comprising the following steps of:
the preparation method of the self-repairing flame-retardant, droplet-resistant and abrasion-resistant polyurethane coating is characterized by comprising the following steps of:
(1) Adding hollow glass beads and an alkali solution into a reaction container protected by nitrogen, heating and stirring the system, carrying out suction filtration and washing on the obtained product to be neutral, then adding ethanol and water, and carrying out ultrasonic dispersion to obtain an HGB-OH dispersion liquid; adding aminopropyltriethoxysilane coupling agent and 4-bromoaniline into HGB-OH dispersion liquid, heating, stirring for reaction, filtering, and vacuum drying the product to obtain HGB-NH 2 (ii) a At HGB-NH 2 Adding a dispersant, and performing ultrasonic dispersion to obtain HGB-NH 2 Adding isocyanate and 2-chloroacetoacetic acid methyl ester into the dispersion liquid, stirring and reacting to obtain HGB-isocyanate dispersion liquid, standing, filtering and drying to obtain HGB-DI;
(2) Adding polypropylene glycol, polytetrahydrofuran ether glycol and isophorone diisocyanate into a reaction vessel protected by nitrogen, heating the system and adding dibutyl tin dilaurate into the HGB-DI prepared in the step (1), and stirring for reaction; adding chain extender 2,2-dithioglycol and nitrogen phosphorus intumescent flame retardant into the system, and continuing the reaction for a while; cooling and adding a thickening agent N, N-diethylformamide DEF; cooling again and adding triethylamine to react to obtain transparent viscous liquid; and adding deionized water, epoxy resin E51, trimethylolpropane trimethacrylate and 3,4' -diaminodiphenyl ether into the transparent viscous liquid, and stirring for reaction to obtain a polyurethane emulsion, namely the prepared polyurethane coating.
The preparation method of the self-repairing flame-retardant, droplet-resistant and abrasion-resistant polyurethane coating is characterized by comprising the following specific steps of:
(1) Adding 10g (HGB abbreviated) of 15-65 micron hollow glass microsphere and 90mL of aqueous alkali with the mass fraction of 10% into a reaction container protected by nitrogen, raising the temperature of the system to 70-85 ℃, stirring for 2-3h, carrying out suction filtration and washing on the obtained product until the obtained product is neutral, adding 90g of ethanol and 10g of deionized water into the obtained suction filtration product, and carrying out ultrasonic dispersion for 30-40 min to obtain HGB-OH dispersion liquid; adding 0.1-0.2 g of aminopropyltriethoxysilane coupling agent and 0.1g of 4-bromoaniline into HGB-OH dispersion liquid, heating to 70-85 ℃, stirring for reaction for 2-3h, performing suction filtration, washing with 15mL of ethanol in a Buchner funnel for three times during the suction filtration process, and performing vacuum drying on the product at 70 ℃ for 14h to obtain HGB-NH 2 (ii) a At HGB-NH 2 Adding 30mL of dispersant, and performing ultrasonic dispersion to obtain HGB-NH 2 Adding 15g of isocyanate and 1-2 g of 2-chloroacetoacetic acid methyl ester into the dispersion, heating to 25 ℃, stirring and reacting for 3-4 h to obtain HGB-isocyanate dispersion, standing for 12h, filtering and drying to obtain HGB-DI;
(2) Adding 9.6g of polypropylene glycol, 9.6g of polytetrahydrofuran ether glycol and 11.5g of isophorone diisocyanate into a reaction container protected by nitrogen, adding 2g of HGB-DI in the step (1), raising the temperature of the system to 80 ℃, adding 0.24g of dibutyltin dilaurate, stirring for reaction for 2 hours, adding 0.7-3.6 g of chain extender 2,2-dithiodiethanol and 3.7-6.3 g of nitrogen-phosphorus intumescent flame retardant into the system, and reacting for 2-3 hours; cooling to 50-70 ℃, and adding 15-30 mL of a viscosity reducer N, N-diethylformamide DEF; cooling to 40 ℃, adding 1.7-2.5 g of triethylamine, and reacting for 0.5h to obtain transparent viscous liquid; cooling to room temperature, adding 75-85 mL of deionized water, 14-16 g of epoxy resin E51, 0.8g of trimethylolpropane trimethacrylate and 1.2g of 3,4' -diaminodiphenyl ether, stirring and reacting for 30-60 min to finally obtain polyurethane emulsion, namely the prepared polyurethane coating.
The method is characterized in that the alkali is any one of sodium hydroxide and potassium hydroxide.
The dispersant is any one of ethyl acetate and butyl acetate.
The molecular weights of the polypropylene glycol and the polytetrahydrofuran ether glycol are both 1000g/mol.
The isocyanate is any one of 4,4' -diphenylmethane diisocyanate, isophorone diisocyanate and toluene diisocyanate.
The preparation method of the nitrogen-phosphorus intumescent flame retardant comprises the following steps:
(1) Adding 27.2g of pentaerythritol and 138.4g of phosphoric acid into a three-neck flask, stirring at room temperature for 30-60 min, raising the temperature of the system to 90-130 ℃, and reacting for 1-5 h to obtain pentaerythritol phosphate; cooling pentaerythritol phosphate to room temperature, adding 20.8g of phosphorus oxychloride, heating the system to 45-50 ℃, keeping the temperature, stirring for 30-60 min, cooling to room temperature, dropwise adding 12.2g of ethanolamine within 30-60 min, and continuously reacting for 1-2 h to obtain a flame retardant intermediate A;
(2) Stirring 6.2-8.4 g of boric acid, 81.2g of tetrakis (hydroxymethyl) phosphonium sulfate and 0.98g of concentrated sulfuric acid at 70-90 ℃ for reaction for 1-3 h, adding a sodium hydroxide solution to adjust the pH value to 6.0, adding 2.5-3.6 g (KH 550) of 3-aminopropyltriethoxysilane into a reaction vessel, stirring at 70-110 ℃ for reaction for 1-7 h to obtain an intermediate B;
(3) Taking the flame retardant intermediate A in the step (1), the intermediate B in the step (2) and 4.2-8.6 g of sodium lignosulfonate, stirring and reacting for 1-2 h at 60-70 ℃, adding 1.2-1.7 g of butyric anhydride and 0.6-1.2 g of 2,4-dihydroxybenzaldehyde, reacting for 1-3 h at 70-80 ℃, adding 0.5-1.2 g of ethylenediamine tetraacetic acid, 0.2-0.4 g of 4-carboxyphenylboronic acid and 0.1-0.4 g of 2-acetoxyisobutyryl chloride, and reacting for 2-3h at 70-80 ℃ to obtain the nitrogen-phosphorus intumescent flame retardant.
The application method of the polyurethane coating prepared by the preparation method of the self-repairing flame-retardant, droplet-resistant and abrasion-resistant polyurethane coating comprises the following steps: adding 0.2-0.7 part of film forming accelerator and 0.1 part of trimethylolpropane into 10 parts of polyurethane coating; the parts are parts by mass.
The preparation method of the film forming accelerant comprises the following steps: mixing 6 parts of polyethyleneimine and 8.2-9.4 parts of 2-acetoxyisobutyryl chloride at 50-60 ℃ for stirring and reacting for 1-2 h, adding 1.1-1.4 parts of salicylic acid, adding 1.1-2.3 parts of aminourea, and reacting at 50-70 ℃ for 30-90 min to obtain a film forming promoter; the parts are parts by mass.
The main technical advantages of the invention are as follows:
(1) The micron hollow glass bead and polyol react on the premise that NCO is grafted or adsorbed, the method adopts alkali solution to treat the reaction product to form HGB-OH, and then adopts aminopropyltriethoxysilane coupling agent assisted by 4-bromoaniline to react to form HGB-NH 2 And then 2-chloroacetoacetic acid methyl ester is adopted to be in full contact with isocyanate, so that NCO is adsorbed or grafted on the micron-sized hollow glass beads, and the subsequent reaction of the isocyanate and the polyol is facilitated.
(2) The method takes polypropylene glycol and polytetrahydrofuran ether glycol as polyhydric alcohol, isocyanate and modified HGB-NCO as isocyanate, 2,2-dithiodiethanol chain extender and intumescent flame retardant as monomer raw materials, and synthesizes the HGB-waterborne polyurethane prepolymer through prepolymerization. And adding a neutralizing agent to neutralize the prepolymer, and finally adding water in equal proportion to emulsify to finally obtain the HGB-WPU. The hollow glass microspheres are a novel hollow material, have the advantages of low heat conductivity coefficient, non-inflammability and the like, are mainly composed of soda lime borosilicate, are non-combustible materials, are added into WPU (waterborne polyurethane) to reduce the volume fraction of the WPU, and indirectly play a role of a flame retardant. In addition, due to the advantages of light weight and heat insulation of the hollow glass microspheres, the hollow glass microspheres can migrate to the surface of a sample from the inside of the coating when HGB-WPU is burnt, so that a fire source is isolated, and the effects of good flame retardance, carbon layer stability enhancement and molten drop phenomenon reduction are achieved.
(3) Phosphoric acid is used as an acid source, pentaerythritol is used as a carbon source, and pentaerythritol is synthesized through esterification reactionA phosphoric acid ester. Wherein the carbon source is heated to generate carbide to form the basis of a carbon layer; the acid source is heated to decompose, and the resultant can promote the dehydration of organic matters to form carbon. Adding POCl on the basis 3 An acid source in a supplementary system is added, ethanolamine is added as a gas source, the gas source is heated to generate non-combustible and flame-retardant gas which is distributed in the carbon layer to promote the foaming of the carbon layer, the distance between the heat source and the base material is increased, and the mass transfer and heat transfer effects during combustion are reduced, so that the better flame retardant property is achieved, and the synergistic effect of nitrogen and phosphorus is achieved; then boric acid is used as an acid source, tetrakis (hydroxymethyl) phosphonium sulfate has both an acid source and a carbon source, a cage-shaped compound containing hydroxyl is synthesized under the catalysis of concentrated sulfuric acid, 3-aminopropyltriethoxysilane is used for reacting with the cage-shaped compound containing hydroxyl, a silicon base is introduced, and the synthesized intermediate B has both cage-shaped rigidity and an ethoxy side chain, so that the strength of the intermediate is improved, and the coordinated flame retardance of boron, phosphorus and silicon is achieved; reacting the flame-retardant intermediate A with the intermediate B, wherein the hydroxyl of the flame-retardant intermediate A reacts with the hydroxyl on boron when being heated, reacting and grafting the intermediate A and the intermediate B, dispersing the reaction product on sodium lignosulfonate with a polyphenol three-dimensional net-shaped space structure (chemical industry limited company created by Shannan Sheng) formed by connecting in forms of C-C bond, C-O-C bond and the like, uniformly dispersing the obtained product, opening the chain of butyric anhydride by adopting butyric anhydride and unreacted hydroxyl in the obtained product, reacting 2,4-dihydroxybenzaldehyde with the hydroxyl obtained by opening the chain, introducing carboxyl and aldehyde groups into the system, reacting ethylene diamine tetraacetic acid with the hydroxyl of the system, introducing carboxyl and increasing the rigidity of the system, reacting with 4-carboxyphenylboronic acid, 2-acetoxyisobutyryl chloride and the hydroxyl and amino (compact) of the system, releasing a large amount of hydroxyl, carboxyl, aldehyde and imine groups of the flame retardant, facilitating subsequent flame-retardant sodium sulfonate, dispersing the flame-retardant system in the three-dimensional net-dimensional structure for constructing the flame-retardant system, facilitating the release of the carbon, and forming a compact heat-insulating layer in the short-insulating carbon layer, and being difficult to be coated in the heat-insulating layerThe synergistic effect of nitrogen, phosphorus, silicon and boron exerts the advantages of high expansion rate and high residual carbon rate which are difficult to achieve by the existing intumescent nitrogen-phosphorus flame retardant.
(4) The invention utilizes the interpenetrating of polyurethane and epoxy resin polymer to form the interlaced network polymer, wherein the epoxy resin participates in and disperses among polyurethane macromolecules, and the epoxy resin is crossed, permeated and intertwined to play the roles of interpenetrating and cooperating with each other. Epoxy resin and polyurethane are mutually intertwined to enable different structures to be refined, the intertwining among networks can obviously improve the dispersibility of the polyurethane and improve the property of the polyurethane, particularly under the action of the epoxy resin E51 (Jinan Yun Baihui Biotech Co., ltd.), polyurethane molecular chains and epoxy resin E51 molecular chains are mutually staggered, and trimethylolpropane trimethyl acrylate and 3,4 '-diaminodiphenyl ether are used for realizing the large steric hindrance force, so that the chain-shaped distribution of the polyurethane and the epoxy resin is uniform and not intertwined tightly, the polyurethane and the epoxy resin can be repaired in time after the polyurethane and the epoxy resin are partially damaged, and meanwhile, the dispersibility of N, N-diethylformamide DEF on the polyurethane is poor compared with acetone and DMF, and the dispersibility of the trimethylolpropane trimethyl acrylate and 3,4' -diaminodiphenyl ether is adopted for improving.
(5) In the film forming process, in order to accelerate the film forming of polyurethane, DEF, toluene and water molecules are required to be quickly volatilized or subsequently and slowly released, and the polyethyleneimine reacts with 2-acetoxyisobutyryl chloride. Although polyethyleneimine is a curing agent in the field, the effect is not particularly ideal in the aspect of polyurethane preparation, the imine of the polyethyleneimine is adopted to react with the acyl chloride of 2-acetoxy isobutyryl chloride, semicarbazide is added to react with the residual acyl chloride, and the obtained compound reacts with hydroxyl and carboxyl of polyurethane in the polyurethane film forming process, so that the release of VOC is accelerated. Meanwhile, the amino group can also react with the carbonyl group of acetone, and particularly, the VOC release of polyurethane can be improved in the film-forming heating environment (such as drying in a drying tunnel in leather coating and finishing).
Detailed Description
The present invention will be further described with reference to examples, comparative examples and technical effects thereof.
Preparation example 1
The preparation method of the self-repairing flame-retardant, droplet-resistant and abrasion-resistant polyurethane coating is characterized by comprising the following steps of:
(1) Adding 10g of 15-micrometer hollow glass beads (HGB is abbreviated as follows) and 90mL of sodium hydroxide solution with the mass fraction of 10% into a three-necked flask under the protection of nitrogen, heating the system to 70 ℃, stirring for reaction for 2 hours, carrying out suction filtration and washing on the obtained product until the product is neutral, adding 90g of ethanol and 10g of deionized water into the obtained suction filtration product, and carrying out ultrasonic dispersion for 30min to obtain HGB-OH dispersion liquid; adding 0.1g of aminopropyltriethoxy silane coupling agent and 0.1g of 4-bromoaniline into HGB-OH dispersion liquid, heating to 70 ℃, stirring for reaction for 2 hours, carrying out suction filtration, washing with 15mL of ethanol in a Buchner funnel for three times in the suction filtration process (namely washing with 15mL of ethanol in each suction filtration, the same below), and carrying out vacuum drying on the product at 70 ℃ for 14 hours to obtain HGB-NH 2 (ii) a At HGB-NH 2 Adding 30mL of ethyl acetate, and performing ultrasonic dispersion to obtain HGB-NH 2 Adding 15g of 4,4-diphenylmethane diisocyanate and 1g of 2-chloroacetoacetic acid methyl ester into the dispersion liquid, heating to 25 ℃, stirring and reacting for 3 hours to obtain HGB-isocyanate dispersion liquid, standing for 12 hours, filtering and drying to obtain HGB-DI;
(2) Adding 9.6g of polypropylene glycol (molecular weight is 1000 g/mol), 9.6g of polytetrahydrofuran ether glycol (molecular weight is 1000 g/mol) and 11.5g of isophorone diisocyanate into a three-neck flask reaction under nitrogen protection, adding 2g of HGB-DI in the step (1), raising the temperature of a system to 80 ℃, adding 0.24g of dibutyltin dilaurate, stirring for reaction for 2 hours, adding 0.7g of chain extender 2,2-dithiodiethanol and 3.7g of nitrogen-phosphorus intumescent flame retardant into the system, and reacting for 2 hours; cooling to 50 ℃, and adding 15mL of a thickening agent N, N-diethyl formamide DEF; then cooling to 40 ℃, adding 1.7g of triethylamine, and reacting for 0.5h to obtain transparent viscous liquid; cooling to room temperature, adding 75mL of deionized water, 14g of epoxy resin E51, 0.8g of trimethylolpropane trimethacrylate and 1.2g of 3,4' -diaminodiphenyl ether, stirring and reacting for 30min to finally obtain polyurethane emulsion, namely the prepared polyurethane coating.
The preparation method of the nitrogen-phosphorus intumescent flame retardant comprises the following steps:
(1) Adding 27.2g of pentaerythritol and 138.4g of phosphoric acid into a three-neck flask, stirring at room temperature for 30min, raising the temperature of the system to 90 ℃, and reacting for 1h to obtain pentaerythritol phosphate; cooling pentaerythritol phosphate to room temperature, adding 20.8g of phosphorus oxychloride, heating the system to 45 ℃, keeping the temperature, stirring for 30min, cooling to room temperature, dropwise adding 12.2g of ethanolamine within 30min, and continuing to react for 1h to obtain a flame retardant intermediate A;
(2) Stirring 6.2g of boric acid, 81.2g of tetrakis (hydroxymethyl) phosphonium sulfate and 0.98g of concentrated sulfuric acid at 70 ℃ for reacting for 1h, adding a sodium hydroxide solution to adjust the pH value to 6.0, adding 2.5g of 3-aminopropyltriethoxysilane into a three-neck flask, stirring at 70 ℃ for reacting for 1h to obtain an intermediate B;
(3) Taking the flame retardant intermediate A (all) in the step (1), the intermediate B (all) in the step (2) and 4.2g of sodium lignosulfonate, stirring and reacting for 1 hour at 60 ℃, then adding 1.2g of butyric anhydride and 0.6g of 2,4-dihydroxybenzaldehyde, reacting for 1 hour at 70 ℃, then adding 0.5g of ethylenediamine tetraacetic acid, 0.2g of 4-carboxyphenylboronic acid and 0.1g of 2-acetoxyisobutyryl chloride, and reacting for 2 hours at 70 ℃ to obtain the nitrogen-phosphorus intumescent flame retardant.
Application example one
The application method of the polyurethane is that 0.2 part of film forming accelerant and 0.1 part of trimethylolpropane are added into 10 parts of polyurethane coating; the materials are uniformly mixed in parts by mass, a solvent is placed on a glass plate to naturally volatilize, a film can be naturally peeled off, and then the test is carried out.
The preparation method of the film forming accelerant comprises the following steps: stirring 6 parts of polyethyleneimine and 8.2 parts of 2-acetoxyisobutyryl chloride for reaction for 1 hour at 50 ℃, adding 1.1 parts of salicylic acid and 1.1 parts of semicarbazide, and reacting for 30min at 50 ℃ to obtain a film-forming promoter; the parts are parts by mass. (polyethyleneimine is purchased as a commercially available 50% aqueous solution, the same applies hereinafter)
Preparation example two
The preparation method of the self-repairing flame-retardant, droplet-resistant and abrasion-resistant polyurethane coating is characterized by comprising the following steps of:
(1) Adding 10g of 65-micrometer hollow glass microspheres (HGB is abbreviated as follows) and 90mL of potassium hydroxide solution with the mass fraction of 10% into a three-neck flask under the protection of nitrogen, heating the system to 85 ℃, stirring for 3 hours, carrying out suction filtration and washing on the obtained product until the product is neutral, adding 90g of ethanol and 10g of deionized water into the obtained suction filtration product, and carrying out ultrasonic dispersion for 40min to obtain HGB-OH dispersion liquid; adding 0.2g of aminopropyltriethoxy silane coupling agent and 0.1g of 4-bromoaniline into HGB-OH dispersion liquid, heating to 85 ℃, stirring for reaction for 3 hours, carrying out suction filtration, washing with 15mL of ethanol for three times in a Buchner funnel during the suction filtration process, and carrying out vacuum drying on the product for 14 hours at 70 ℃ to obtain HGB-NH 2 (ii) a At HGB-NH 2 Adding 30mL of butyl acetate, and performing ultrasonic dispersion to obtain HGB-NH 2 Adding 15g of isophorone diisocyanate and 2g of methyl 2-chloroacetoacetate, heating to 25 ℃, stirring and reacting for 4h to obtain HGB-isophorone diisocyanate dispersion, standing for 12h, filtering and drying to obtain HGB-DI;
(2) Adding 9.6g of polypropylene glycol, 9.6g of polytetrahydrofuran ether glycol (the molecular weights of polypropylene glycol and polytetrahydrofuran ether glycol are both 1000 g/mol) and 11.5g of isophorone diisocyanate into a nitrogen-protected three-neck flask, adding 2g of HGB-DI in the step (1), raising the temperature of the system to 80 ℃, adding 0.24g of dibutyltin dilaurate, stirring and reacting for 2 hours, adding 3.6g of chain extender 2,2-dithiodiethanol and 6.3g of nitrogen phosphorus intumescent flame retardant into the three-neck flask, and reacting for 3 hours; cooling to 70 ℃, and adding 30mL of a thickening agent N, N-diethylformamide DEF; then cooling to 40 ℃, and adding 2.5g of triethylamine for reaction for 0.5h to obtain transparent viscous liquid; cooling to room temperature, adding 85mL of deionized water, adding 16g of epoxy resin E51, 0.8g of trimethylolpropane trimethacrylate and 1.2g of 3,4' -diaminodiphenyl ether, stirring and reacting for 60min to finally obtain polyurethane emulsion, namely the prepared polyurethane coating.
The preparation method of the nitrogen-phosphorus intumescent flame retardant comprises the following steps:
(1) Adding 27.2g of pentaerythritol and 138.4g of phosphoric acid into a three-neck flask, stirring at room temperature for 60min, raising the temperature of the system to 130 ℃, and reacting for 5h to obtain pentaerythritol phosphate; cooling pentaerythritol phosphate to room temperature, adding 20.8g of phosphorus oxychloride, heating the system to 50 ℃, keeping the temperature, stirring, reacting for 60min, cooling to room temperature, dropwise adding 12.2g of ethanolamine within 60min, and continuing to react for 2h to obtain a flame retardant intermediate A;
(2) Stirring 8.4g of boric acid, 81.2g of tetrakis (hydroxymethyl) phosphonium sulfate and 0.98g of concentrated sulfuric acid at 90 ℃ for reaction for 3 hours, adding a sodium hydroxide solution to adjust the pH value to 6.0, adding 3.6g of 3-aminopropyltriethoxysilane into a reaction vessel, stirring at 110 ℃ for reaction for 7 hours to obtain an intermediate B;
(3) Taking the flame retardant intermediate A (all) in the step (1), the intermediate B (all) in the step (2) and 8.6g of sodium lignosulfonate, stirring at 70 ℃ for reaction for 2 hours, adding 1.7g of butyric anhydride and 1.2g of 2,4-dihydroxybenzaldehyde, reacting at 80 ℃ for 3 hours, adding 1.2g of ethylenediamine tetraacetic acid, 0.4g of 4-carboxyphenylboronic acid and 0.4g of 2-acetoxyisobutyryl chloride, and reacting at 80 ℃ for 3 hours to obtain the nitrogen-phosphorus intumescent flame retardant.
Application example two
The application method comprises the steps of adding 0.7 part of film forming accelerant and 0.1 part of trimethylolpropane into 10 parts of polyurethane coating prepared in the second embodiment; the materials are uniformly mixed in parts by mass, a solvent is placed on a glass plate to naturally volatilize, a film can be naturally peeled off, and then the test is carried out.
The preparation method of the film forming accelerant comprises the following steps: stirring 6 parts of polyethyleneimine and 9.4 parts of 2-acetoxyisobutyryl chloride at 60 ℃ for 2 hours to react, adding 1.4 parts of salicylic acid and 2.3 parts of semicarbazide, and reacting at 70 ℃ for 90 minutes to obtain a film forming promoter; the parts are parts by mass.
Preparation example three
The preparation method of the self-repairing flame-retardant, droplet-resistant and abrasion-resistant polyurethane coating is characterized by comprising the following steps of:
(1) Adding 10g of 40-micron hollow glass micro-beads (HGB is abbreviated as follows) and 90mL of sodium hydroxide solution with the mass fraction of 10 percent into a reaction vessel protected by nitrogen, raising the temperature of the system to 75 ℃, and stirring the system for 2.5h, carrying out suction filtration and water washing on the obtained product to neutrality, adding 90g of ethanol and 10g of deionized water into the obtained suction filtration product, and carrying out ultrasonic dispersion for 35min to obtain HGB-OH dispersion liquid; adding 0.15g of aminopropyltriethoxysilane coupling agent and 0.1g of 4-bromoaniline into HGB-OH dispersion liquid, heating to 75 ℃, stirring for reaction for 2.5h, performing suction filtration, washing with 15mL of ethanol for three times in a Buchner funnel during the suction filtration process, and performing vacuum drying on the product at 70 ℃ for 14h to obtain HGB-NH 2 (ii) a At HGB-NH 2 Adding 30mL of ethyl acetate, and performing ultrasonic dispersion to obtain HGB-NH 2 Adding 15g of toluene diisocyanate and 1.5g of methyl 2-chloroacetoacetate, heating to 25 ℃, stirring and reacting for 3.5h to obtain HGB-isocyanate dispersion, standing for 12h, filtering and drying to obtain HGB-DI;
(2) Adding 9.6g of polypropylene glycol, 9.6g of polytetrahydrofuran ether glycol (the molecular weight of both polypropylene glycol and polytetrahydrofuran ether glycol is 1000 g/mol), 11.5g of isophorone diisocyanate and 2g of HGB-DI (high viscosity polyethylene glycol-Diisocynate) in the step (1) into a three-neck flask under the protection of nitrogen, raising the temperature of a system to 80 ℃, adding 0.24g of dibutyltin dilaurate, stirring for 2 hours, adding 2.15g of chain extender 2,2-dithiodiethanol and 3.7g of nitrogen phosphorus intumescent flame retardant into the system, and reacting for 2.5 hours; cooling to 60 ℃, and adding 22mL of a thickening agent N, N-diethylformamide DEF; then cooling to 40 ℃, and adding 2.1g of triethylamine for reaction for 0.5h to obtain transparent viscous liquid; cooling to room temperature, adding 80mL of deionized water, 15g of epoxy resin E51, 0.8g of trimethylolpropane trimethacrylate and 1.2g of 3,4' -diaminodiphenyl ether, stirring and reacting for 45min to finally obtain polyurethane emulsion, namely the prepared polyurethane coating.
The preparation method of the nitrogen-phosphorus intumescent flame retardant comprises the following steps:
(1) Adding 27.2g of pentaerythritol and 138.4g of phosphoric acid into a three-neck flask, stirring at room temperature for 45min, raising the temperature of the system to 110 ℃, and reacting for 3h to obtain pentaerythritol phosphate; cooling pentaerythritol phosphate to room temperature, adding 20.8g of phosphorus oxychloride, heating the system to 45 ℃, keeping the temperature, stirring for 45min, cooling to room temperature, dropwise adding 12.2g of ethanolamine within 45min, and continuing to react for 1.5h to obtain a flame retardant intermediate A;
(2) Stirring 7.3g of boric acid, 81.2g of tetrakis (hydroxymethyl) phosphonium sulfate and 0.98g of concentrated sulfuric acid at 80 ℃ for reaction for 2 hours, adding a sodium hydroxide solution to adjust the pH value to 6.0, adding 3.0g of 3-aminopropyltriethoxysilane into a three-neck flask, and stirring at 90 ℃ for reaction for 4 hours to obtain an intermediate B;
(3) Taking the flame retardant intermediate A (all) in the step (1), the intermediate B (all) in the step (2) and 7.4g of sodium lignosulfonate, stirring and reacting for 1.5h at 65 ℃, then adding 1.4g of butyric anhydride and 0.9g of 2,4-dihydroxybenzaldehyde, reacting for 2h at 75 ℃, then adding 0.9g of ethylenediamine tetraacetic acid, 0.3g of 4-carboxyphenylboronic acid and 0.2g of 2-acetoxyisobutyryl chloride, and reacting for 2.5h at 75 ℃ to obtain the nitrogen-phosphorus intumescent flame retardant.
Application example three
Taking 10 parts of polyurethane coating prepared in the third embodiment, adding 0.35 part of film forming accelerant and 0.1 part of trimethylolpropane; the materials are uniformly mixed in parts by mass, the glass plate is placed until the solvent is naturally volatilized and dried, and the film can be naturally stripped and tested.
The polyurethane emulsion forms a film forming accelerant in film forming, and the preparation method of the film forming accelerant comprises the following steps: 6 parts of polyethyleneimine and 8.7 parts of 2-acetoxyisobutyryl chloride are stirred and reacted for 1.5 hours at the temperature of 55 ℃, 1.25 parts of salicylic acid and 1.7 parts of semicarbazide are added, and the reaction is carried out for 60 minutes at the temperature of 60 ℃ to obtain the film forming promoter.
Preparation example four
The preparation method of the self-repairing flame-retardant, droplet-resistant and abrasion-resistant polyurethane coating is characterized by comprising the following steps of:
(1) Adding 10g of 15-micrometer hollow glass beads (HGB is abbreviated as follows) and 90mL of potassium hydroxide solution with the mass fraction of 10% into a three-necked flask under the protection of nitrogen, heating the system to 85 ℃, stirring for 3 hours, carrying out suction filtration and washing on the obtained product until the product is neutral, adding 90g of ethanol and 10g of deionized water into the obtained suction filtration product, and carrying out ultrasonic dispersion for 40min to obtain HGB-OH dispersion liquid; adding 0.1g of aminopropyltriethoxy silane coupling agent and 0.1g of 4-bromoaniline into HGB-OH dispersion liquid, heating to 85 ℃, stirring for reaction for 2 hours, carrying out suction filtration, washing with 15mL of ethanol for three times in a Buchner funnel during the suction filtration process, and carrying out vacuum drying on the product for 14 hours at 70 ℃ to obtain HGB-NH 2 (ii) a In thatHGB-NH 2 Adding 30mL of butyl acetate, and performing ultrasonic dispersion to obtain HGB-NH 2 Adding 15g of 4,4-diphenylmethane diisocyanate and 1.5g of methyl 2-chloroacetoacetate, heating to 25 ℃, stirring and reacting for 3.5 hours to obtain HGB-isocyanate dispersion liquid, standing for 12 hours, filtering and drying to obtain HGB-DI;
(2) Adding 9.6g of polypropylene glycol, 9.6g of polytetrahydrofuran ether glycol (the molecular weights of the polypropylene glycol and the polytetrahydrofuran ether glycol are both 1000) and 11.5g of isophorone diisocyanate into a reaction vessel protected by nitrogen, adding 2g of HGB-DI in the step (1), raising the temperature of a system to 80 ℃, adding 0.24g of dibutyltin dilaurate, stirring for 2 hours, adding 1.0g of chain extender 2,2-dithiodiethanol and 4.0g of nitrogen-phosphorus intumescent flame retardant into the system, and reacting for 2.5 hours; cooling to 60 ℃, and adding 20mL of a thickening agent N, N-diethylformamide DEF; cooling to 40 ℃, adding 2g of triethylamine, and reacting for 0.5h to obtain transparent viscous liquid; and cooling the mixture to room temperature, adding 75mL of deionized water, 14g of epoxy resin E51, 0.8g of trimethylolpropane trimethylacrylate and 1.2g of 3,4' -diaminodiphenyl ether, and stirring for reaction for 40min to finally obtain polyurethane emulsion, namely the prepared polyurethane coating.
The preparation method of the nitrogen-phosphorus intumescent flame retardant comprises the following steps:
(1) Adding 27.2g of pentaerythritol and 138.4g of phosphoric acid into a three-neck flask, stirring at room temperature for 40min, raising the temperature of the system to 110 ℃, and reacting for 2h to obtain pentaerythritol phosphate; cooling pentaerythritol phosphate to room temperature, adding 20.8g of phosphorus oxychloride, heating the system to 50 ℃, keeping the temperature, stirring for 60min, cooling to room temperature, dropwise adding 12.2g of ethanolamine within 60min, and continuously reacting for 1.5h to obtain a flame retardant intermediate A;
(2) Stirring 7.6g of boric acid, 81.2g of tetrakis (hydroxymethyl) phosphonium sulfate and 0.98g of concentrated sulfuric acid at 80 ℃ for reaction for 1 hour, adding a sodium hydroxide solution to adjust the pH value to 6.0, adding 2.7g of 3-aminopropyltriethoxysilane into a reaction vessel, stirring at 80 ℃ for reaction for 3 hours to obtain an intermediate B;
(3) Taking the flame retardant intermediate A (all) in the step (1), the intermediate B (all) in the step (2) and 5.3g of sodium lignosulfonate, stirring and reacting for 1.5h at 65 ℃, then adding 1.4g of butyric anhydride and 0.7g of 2,4-dihydroxybenzaldehyde, reacting for 2h at 75 ℃, then adding 0.7g of ethylenediamine tetraacetic acid, 0.3g of 4-carboxyphenylboronic acid and 0.2g of 2-acetoxyisobutyryl chloride, and reacting for 2.5h at 75 ℃ to obtain the nitrogen-phosphorus intumescent flame retardant.
Application example four
Taking 10 parts of the polyurethane coating prepared in the fourth example, adding 0.4 part of film forming accelerator and 0.1 part of trimethylolpropane; the materials are uniformly mixed in parts by mass, the glass plate is placed until the solvent is naturally volatilized and dried, and the film can be naturally stripped and tested.
The preparation method of the film forming accelerant used in the film forming process of the polyurethane coating comprises the following steps: 6 parts of polyethyleneimine and 8.5 parts of 2-acetoxyisobutyryl chloride are stirred and reacted for 1 hour at 50 ℃, 1.3 parts of salicylic acid and 1.6 parts of semicarbazide are added, and the reaction is carried out for 60 minutes at 50 ℃ to obtain the film forming promoter.
Preparation example five
The preparation method of the self-repairing flame-retardant, droplet-resistant and abrasion-resistant polyurethane coating is characterized by comprising the following steps of:
(1) Adding 10g of 65-micrometer hollow glass microspheres (HGB is abbreviated as follows) and 90mL of sodium hydroxide solution with the mass fraction of 10% into a three-neck flask under the protection of nitrogen, heating the system to 80 ℃, stirring for 3 hours, carrying out suction filtration and washing on the obtained product until the product is neutral, adding 90g of ethanol and 10g of deionized water into the obtained suction filtration product, and carrying out ultrasonic dispersion for 35min to obtain HGB-OH dispersion liquid; adding 0.1g of aminopropyltriethoxy silane coupling agent and 0.1g of 4-bromoaniline into HGB-OH dispersion liquid, heating to 85 ℃, stirring for reaction for 3 hours, carrying out suction filtration, washing with 15mL of ethanol for three times in a Buchner funnel during the suction filtration process, and carrying out vacuum drying on the product for 14 hours at 70 ℃ to obtain HGB-NH 2 (ii) a At HGB-NH 2 Adding 30mL of ethyl acetate, and performing ultrasonic dispersion to obtain HGB-NH 2 Adding 15g of isophorone diisocyanate and 2g of methyl 2-chloroacetoacetate, heating to 25 ℃, stirring and reacting for 4h to obtain HGB-isocyanate dispersion, standing for 12h, filtering and drying to obtain HGB-DI;
(2) Adding 9.6g of polypropylene glycol, 9.6g of polytetrahydrofuran ether glycol (the molecular weight of both the polypropylene glycol and the polytetrahydrofuran ether glycol is 1000), 11.5g of isophorone diisocyanate and 2g of HGB-DI in the step (1) into a three-neck flask protected by nitrogen, raising the temperature of a system to 80 ℃, adding 0.24g of dibutyltin dilaurate, stirring for 2 hours, adding a chain extender 2,2-dithiodiethanol 1.2g and 3.7g of nitrogen-phosphorus intumescent flame retardant into the system, and reacting for 2 hours; cooling to 70 ℃, and adding 30mL of a thickening agent N, N-diethylformamide DEF; then cooling to 40 ℃, adding 2.5g of triethylamine, and reacting for 0.5h to obtain transparent viscous liquid; cooling to room temperature, adding 75mL of deionized water, 14g of epoxy resin E51, 0.8g of trimethylolpropane trimethacrylate and 1.2g of 3,4' -diaminodiphenyl ether, stirring and reacting for 60min to finally obtain polyurethane emulsion, namely the prepared polyurethane coating.
The preparation method of the nitrogen-phosphorus intumescent flame retardant comprises the following steps:
(1) Adding 27.2g of pentaerythritol and 138.4g of phosphoric acid into a three-neck flask, stirring at room temperature for 40min, raising the temperature of the system to 110 ℃, and reacting for 3h to obtain pentaerythritol phosphate; cooling pentaerythritol phosphate to room temperature, adding 20.8g of phosphorus oxychloride, heating the system to 50 ℃, keeping the temperature, stirring for 40min, cooling to room temperature, dropwise adding 12.2g of ethanolamine within 40min, and continuing to react for 1.5h to obtain a flame retardant intermediate A;
(2) Stirring 7.3g of boric acid, 81.2g of tetrakis (hydroxymethyl) phosphonium sulfate and 0.98g of concentrated sulfuric acid at 80 ℃ for reacting for 2 hours, adding a sodium hydroxide solution to adjust the pH value to 6.0, adding 3.0g of 3-aminopropyltriethoxysilane into a three-neck flask, stirring at 80 ℃ for reacting for 3 hours to obtain an intermediate B;
(3) Taking the flame retardant intermediate A (all) in the step (1), the intermediate B (all) in the step (2) and 5.7g of sodium lignosulfonate, stirring at 70 ℃ for reaction for 2 hours, adding 1.7g of butyric anhydride and 0.7g of 2,4-dihydroxybenzaldehyde, reacting at 75 ℃ for 2 hours, adding 0.9g of ethylenediamine tetraacetic acid, 0.25g of 4-carboxyphenylboronic acid and 0.15g of 2-acetoxyisobutyryl chloride, and reacting at 70 ℃ for 2.5 hours to obtain the nitrogen-phosphorus intumescent flame retardant.
Application example five
Taking 10 parts of the polyurethane coating prepared in the fifth example, adding 0.5 part of film forming accelerator and 0.1 part of trimethylolpropane; the parts are parts by mass. The materials are mixed evenly, the solvent is placed on a glass plate to be naturally volatilized, the film can be naturally stripped, and then the test is carried out.
The preparation method of the film forming accelerant comprises the following steps: stirring 6 parts of polyethyleneimine and 8.2 parts of 2-acetoxyisobutyryl chloride for reaction for 2 hours at 60 ℃, adding 1.4 parts of salicylic acid and 1.7 parts of semicarbazide, and reacting for 50 minutes at 60 ℃ to obtain a film-forming promoter; the parts are parts by mass.
The following are the performance tests and the comparison of the products of the embodiment and the application example of the invention with the products of the comparison group.
The abrasion resistance is as per GB/T22374-2018;
the carbon residue rate and the expansion height are referred to 2019106431795 test standard.
GB/T5455-1997 textile burning performance test the flame burning time (afterflame time) of the film formed by the polyurethane coating is measured by a vertical method, the length of the sample is 20cm multiplied by 10cm, and the thickness is 1mm.
The VOC determination method comprises the following steps: the metal plate was baked in an oven at 105. + -. 2 ℃ for 30min and then placed in a desiccator until use. After mixing, the polyurethane is spread on a metal flat-bottom dish, placed for 24 hours under the conditions that the temperature is 23 +/-2 ℃ and the humidity is 50 +/-5 percent, and then dried in an oven at the temperature of 105 +/-2 ℃ for 60 minutes, and two tests are carried out in parallel. Weighing m before heating 1 (Metal Container m) 0 And sum of mass of reactants) and mass m after heating 2 (see 201710902448.6);
the phenomenon of dripping was observed by the naked eye.
Self-repairing flame-retardant test: the self-repairing of the 1-cut sample is to take a test sample with the thickness of 0.1cm, cut the depth of 0.05cm at the position of every 1cm in length by a blade, dye the cut, and test after the repair effect is achieved by drying for 5 hours at 80 ℃ (an oven).
2, wear self-repairing: taking a test sample with the thickness of 0.1cm, carrying out the wear resistance for 50 times according to GB/T22374-2018, 100g/100r and the like, and testing after baking for 5 hours at 80 ℃ (oven) to achieve the repairing effect.
TABLE 1 film Forming Performance index for polyurethane coatings
| Example one | Example two | EXAMPLE III | Example four | Example five | Comparative example | |
| Flame combustion time/s | 1.2 | 0.1 | 0.3 | 0.4 | 1.1 | 1.4 |
| Phenomenon of burning molten drops | Does not melt and drip | Does not melt and drip | Does not melt and drip | Does not melt and drip | Does not melt and drip | Does not melt or drip |
| VOC/% | 1.2 | 0.8 | 1.4 | 1.8 | 0.6 | 2.3 |
| Abrasion resistance (750 g/500 r) | 0.0008 | 0.0012 | 0.0013 | 0.0012 | 0.0011 | 0.0014 |
Comparative example (comparison of flame burning time of example 1 of 202011624359.8), from the above data, it can be seen that, although the invention is equivalent to the index of the comparative example in terms of droplet dropping, the invention is superior to the comparative example 1 in terms of flame burning time, VOC and abrasion resistance, because compared to the comparative example, the invention adopts micron hollow glass beads to react with polyol on the premise that NCO is grafted or adsorbed on the hollow glass beads, and the flame retardant system is dispersed in the three-dimensional network structure taking sodium lignosulfonate as a structural system, so that a compact carbon layer is formed in a flame retardant manner, and gas released in the burning process is coated in the compact carbon layer, is difficult to release in a short time, plays a role in heat insulation, reduces flame burning, and has abrasion resistance and effective sealing of VOC, and the performance is superior to the comparative example.
TABLE 2 Performance index of the nitrogen phosphorus intumescent flame retardant
| Example one | Example two | Example three | Example four | Example five | Comparative example | |
| Carbon content/%) | 74.6 | 73.7 | 75.5 | 74.8 | 75.2 | 72.6 |
| Height of expansion/cm | 5.74 | 5.81 | 5.81 | 5.83 | 5.96 | 5.69 |
The nitrogen-phosphorus intumescent flame retardant is prepared by comparing data of example four of 202011624359.8, and table 2 shows that 4-carboxyphenylboronic acid and 2-acetoxyisobutyryl chloride are adopted to react with hydroxyl and amino (imine) of a system, so that the obtained flame retardant has a large number of hydroxyl, carboxyl, aldehyde and imino groups, and is convenient for subsequent flame retardance and self-repair, meanwhile, the flame retardant system is dispersed in a three-dimensional network structure taking sodium lignosulfonate as a structural system, so that a compact carbon layer is formed in a flame-retardant manner, gas released in the combustion process is coated in the compact carbon layer and is difficult to release in a short time, and a heat insulation effect is achieved.
TABLE 3 flame retardant Properties of the materials not part of (EXAMPLE five)
From table 3, it can be found that, taking the fifth example as an example, the carbon residue and the expansion height of the flame retardant obtained without adding 3-aminopropyltriethoxysilane, sodium lignosulfonate, butyric anhydride, 2,4-dihydroxybenzaldehyde, ethylenediamine tetraacetic acid, 4-carboxyphenylboronic acid and 2-acetoxyisobutyryl chloride are both reduced, which shows that the above substances all play a role in the expansion system, wherein the sodium lignosulfonate has the greatest influence on the properties of the intumescent flame retardant, because the sodium lignosulfonate is a three-dimensional network structure flame retardant system of the construction system, a compact carbon layer is formed in a flame retardant construction manner, and gas released in the combustion process is coated in the compact carbon layer and is difficult to release in a short time, so that the heat insulation effect is achieved, and the carbon residue and the expansion height are improved. (Note that no chemical materials are added, other materials are added)
TABLE 4 Properties of polyurethane films obtained without addition of part of the chemical materials (example two)
| Item | Drop property of polyurethane | Without addition of part of material |
| Phenomenon of burning molten drops | Melt in large quantities and drip in large quantities | Without addition of 4-bromoaniline |
| Phenomenon of burning molten drops | Melt in large quantities and drip in large quantities | Without addition of 2-chloroacetoacetic acid methyl ester |
| Phenomenon of burning molten drops | Melt in large quantities and drip in large quantities | Micron-size vacuum glass bead is not added |
| Abrasion resistance (750 g/500 r) | 0.0078 | Without trimethylolpropane |
In particular, since HGB-DI is based on the establishment of the dispersion of vacuum glass beads, the present invention does not add the micron vacuum glass beads, so step (1) is omitted, but the amount thereof is replaced by the corresponding isocyanate, and from the property of the polyurethane film obtained without adding part of chemical raw materials in table 4, 4-bromoaniline and methyl 2-chloroacetoacetate are both capable of adding vacuum glass beads in the system, so the amount of the vacuum glass beads is small, the effect on the droplet resistance property is large, and the property is not affected.
TABLE 5 flame retardant self-healing capability characterization of polyurethane coatings (cut)
In the comparative example (comparison of the flaming combustion time and the molten droplets in example four of 202011624359.8), it can be seen from the flaming combustion time and the molten droplets that the flaming combustion time and the molten droplets are reduced less and the reduction range without repairing is large.
TABLE 6 flame retardant self-healing capability characterization of polyurethane coatings (after abrasion resistance)
From Table 6, it can be seen that the flame burning time is significantly prolonged without performing the abrasion repair, and a large amount of droplet phenomenon is generated. COMPARATIVE EXAMPLE (example four of 202011624359.8)
TABLE 7 characterization of the flame retardant self-healing capability of the polyurethane coatings (without chemical materials, abrasion)
| Example two | Without addition of chemical materials | |
| Flaming combustion time/s (abraded, unrepaired) | 16.3 | Trimethacrylate without trimethylpropane |
| Flaming combustion time/s (wear, repair) | 14.2 | Trimethacrylate without trimethylpropane |
| Flaming combustion time/s (abraded, unrepaired) | 17.5 | Without 3,4' -bisAmino diphenyl ethers |
| Flaming combustion time/s (wear, repair) | 14.9 | 3,4' -diaminodiphenyl ether was not added |
| Flaming combustion time/s (abraded, unrepaired) | 15.8 | Without addition of epoxy resin E51 |
| Flaming combustion time/s (wear, repair) | 14.3 | Without addition of epoxy resin E51 |
From Table 7, it can be found that the flame burn time (abrasion) of the film without the addition of trimethylpropane trimethacrylate, 3,4' -diaminodiphenyl ether and epoxy resin E51 is significantly prolonged, showing that the above substances exert a significant effect therein.
Claims (3)
1. A preparation method of a nitrogen-phosphorus intumescent flame retardant required by a self-repairing flame-retardant, droplet-resistant and abrasion-resistant polyurethane coating is characterized by comprising the following steps:
(a) Adding 27.2g of pentaerythritol and 138.4g of phosphoric acid into a three-neck flask, stirring at room temperature for 30-60min, raising the temperature of the system to 90-130 ℃, and reacting for 1-5h to obtain pentaerythritol phosphate; cooling pentaerythritol phosphate to room temperature, adding 20.8g of phosphorus oxychloride, heating the system to 45-50 ℃, keeping the temperature, stirring for 30-60 min, cooling to room temperature, dropwise adding ethanolamine 12.2g within 30-60min, and continuously reacting for 1-2 h to obtain a flame retardant intermediate A;
(b) Stirring 6.2 to 8.4g of boric acid, 81.2g of tetrakis (hydroxymethyl) phosphonium sulfate and 0.98g of concentrated sulfuric acid at 70 to 90 ℃ for reaction for 1 to 3 hours, adding a sodium hydroxide solution to adjust the pH value to 6.0, adding 2.5 to 3.6g of 3-aminopropyltriethoxysilane into a reaction vessel, stirring at 70 to 110 ℃ for reaction for 1 to 7 hours to obtain an intermediate B;
(c) Taking 4.2-8.6 g of the flame retardant intermediate A in the step (a), the intermediate B in the step (B) and sodium lignosulfonate, reacting at 60-70 ℃ for 1-2h under stirring, then adding 1.2-1.7 g of butyric anhydride and 0.6-1.2 g of 2,4-dihydroxybenzaldehyde, reacting at 70-80 ℃ for 1-3h, then adding 0.5-1.2 g of ethylenediamine tetraacetic acid, 0.2-0.4 g of 4-carboxyphenylboronic acid and 0.1-0.4 g of 2-acetoxyisobutyryl chloride, and reacting at 70-80 ℃ for 2-3h to obtain the nitrogen phosphorus intumescent flame retardant.
2. A preparation method of HGB-DI required by a flame-retardant, droplet-resistant and abrasion-resistant polyurethane coating applied to self-repairing is characterized by comprising the following specific steps:
(1) Adding 10g of hollow glass microspheres of 15-65 micrometers and 90mL of aqueous alkali of 10 mass percent into a reaction container under the protection of nitrogen, heating the system to 70-85 ℃, stirring for 2-3h, carrying out suction filtration and water washing on the obtained product to neutrality, adding 90g of ethanol and 10g of deionized water into the obtained suction filtration product, and carrying out ultrasonic dispersion for 30-40min to obtain an HGB-OH dispersion liquid; adding 0.1-0.2 g of aminopropyltriethoxysilane coupling agent and 0.1g of 4-bromoaniline into HGB-OH dispersion, heating to 70-85 ℃, stirring for reaction for 2-3h, performing suction filtration, washing with 15mL of ethanol in a Buchner funnel for three times during the suction filtration process, and performing vacuum drying on the product at 70 ℃ for 14h to obtain HGB-NH 2 (ii) a At HGB-NH 2 Adding 30mL of dispersant, and performing ultrasonic dispersion to obtain HGB-NH 2 Adding 15g of isocyanate and 1-2g of methyl 2-chloroacetoacetate, heating to 25 ℃, stirring and reacting for 3-4h to obtain HGB-isocyanate dispersion, standing for 12h, filtering and drying to obtain HGB-DI.
3. The method of claim 2, wherein: adding 15-65 micron hollow glass microspheres 10g and 90mL of aqueous alkali with the mass fraction of 10% into a nitrogen-protected reaction container, heating the system to 70-85 ℃, stirring for 2-3h, carrying out suction filtration and washing on an obtained product until the product is neutral, adding 90g of ethanol and 10g of deionized water into the obtained suction filtration product, and carrying out ultrasonic separationDispersing for 30 to 40min to obtain HGB-OH dispersion liquid; adding 0.1 to 0.2g of aminopropyltriethoxysilane coupling agent and 0.1g of 4-bromoaniline into HGB-OH dispersion liquid, heating to 70 to 85 ℃, stirring for reaction for 2 to 3h, performing suction filtration, washing the mixture three times in a Buchner funnel by using 15mL of ethanol in the suction filtration process, and performing vacuum drying on the product at 70 ℃ for 14h to obtain HGB-NH 2 (ii) a At HGB-NH 2 Adding 30mL of dispersant, and performing ultrasonic dispersion to obtain HGB-NH 2 Adding 15g of isocyanate and 1 to 2g of 2-chloroacetoacetic acid methyl ester into the dispersion, heating to 25 ℃, stirring for reaction for 3 to 4 hours to obtain HGB-isocyanate dispersion, standing for 12 hours, filtering and drying to obtain HGB-DI.
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