CN115725229B - Self-repairing flame-retardant, anti-dripping and anti-abrasion polyurethane coating material - Google Patents
Self-repairing flame-retardant, anti-dripping and anti-abrasion 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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- 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
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- 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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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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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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Abstract
The invention relates to a preparation and application method of self-repairing flame-retardant anti-drip abrasion-resistant polyurethane coating, which comprises the steps of loading isocyanate on vacuum glass beads, adding polypropylene glycol, polytetrahydrofuran ether glycol, isophorone diisocyanate and HGB-DI into a reaction vessel protected by nitrogen, heating the system to 80 ℃, adding dibutyl tin dilaurate, reducing the temperature to 50-70 ℃ by using a chain extender of 2, 2-dithio-diethyl alcohol and a nitrogen-phosphorus intumescent flame retardant, and adding a viscosity reducer of N, N-diethyl formamide; and then 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 polyurethane emulsion, wherein the obtained polyurethane emulsion is obviously superior to the prior art in flame retardant self-repairing, molten drop resistance and abrasion resistance.
Description
The invention is a division of 202111473297X.
Technical Field
The invention relates to a preparation method of polyurethane paint, in particular to a preparation method of self-repairing flame-retardant, melt-drip-resistant and wear-resistant polyurethane paint, and also relates to an application method of the prepared polyurethane paint.
Background
The aqueous polyurethane has the advantages of safety, innocuity and strong adhesive force, and is widely applied to the fields of furniture, fabric coating, automobile leather and the like. In the use process of the waterborne polyurethane as a coating material, the waterborne polyurethane is often subjected to the actions of friction, collision, bending and the like, and the surface of the waterborne polyurethane is subjected to physical damage such as scratches, microcracks and the like, 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 means of self-structure, and is characterized in that after the polymer material is lowered, the self-repairing polymer material is repaired by means of self-structure, so that the service life of polyurethane is prolonged, and the self-repairing polymer material is required to be self-repaired.
Feng Jianyan (Feng Jianyan, preparation of waterborne polyurethane/polyacrylate self-repairing material based on disulfide bond and performance [ J ]. Polymer science and engineering, 2021-09-29) the self-repairing waterborne polyurethane/polyacrylate (AWPUS) composite material containing disulfide bond is prepared by using polytetrahydrofuran glycol (PTMEG), isophorone diisocyanate (IPDI), 2-dimethylolpropionic acid (DMPA), 2-dithiodiethanol (HEDS), PA and the like as raw materials. The introduction of S-S bonds endows the material with damage-self-repairing performance, PA (polyamide) hot-sticking cold-embrittlement improves the fluidity of the chain at a certain temperature, promotes the self-healing of the polymer material, and improves the self-repairing efficiency from 73.4% of 6h repairing to 81.7% of 2h repairing at 60 ℃; meanwhile, the mechanical properties are still good at room temperature. The AWPUS exhibits excellent reworkability, and after molding at 100deg.C for 10min, the recovered sample returns to its original state, with less loss of mechanical properties, and with higher economic applicability, the technique does not involve the repair of flame retardant functionality, is suitable only for mechanical property repair, and the existing structure cannot find that it has flame retardant repair.
Polyurethane belongs to a class of organic polymer materials with carbon-carbon bonds as basic structural units. Since the raw materials used in polyurethane synthesis are often combustible organic compounds or polymer materials, polyurethane is a flammable substance, and is accompanied by a potential fire hazard during use. On the other hand, the burning of such polymers is accompanied by the release of smoke and toxic gases, and can produce droplets, damage the 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 polyurethane synthesis, polyester and polyether polyol with flame retardant effects such as phosphorus, nitrogen and silicon are selected, so that the synthesized polyurethane material has certain flame retardance. (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 carbon and nitrogen six-membered ring isocyanurate groups into a macromolecular structure, or to use flame retardant phosphorus compound polyol as a prepolymer monomer in synthesis, or to use flame retardant phosphorus material, nitrogen phosphorus compound and the like as a chain extender, or to use nitrogen, nitrogen phosphorus compound, organosilicon and boron compound for re-modification after chain extension. (C) In the polyurethane synthesis, the auxiliary agent with flame retardant effect is added, and the flame retardant can be divided into an organic flame retardant and an inorganic flame retardant, wherein the former is mainly composed of flame retardant element compounds containing phosphorus, bromine, antimony, boron and the like, and the latter is mainly composed of inorganic compounds containing organic ammonium phosphate, aluminum hydroxide and the like.
The preparation and application method of the flame-retardant abrasion-resistant low-VOC polyurethane coating of the Chinese issued patent with the publication number of CN112646475B comprises the steps of adding polyester diol, isocyanate and dibutyltin dilaurate into a reaction vessel, stirring and reacting at 75-90 ℃ to obtain a polyurethane prepolymer, adding a hydrophilic chain extender dimethylolpropionic acid, a nitrogen-phosphorus intumescent flame retardant and an acetone solvent into the polyurethane prepolymer, and stirring and reacting at 70-90 ℃ for 1-2 hours; adding triethylamine and water to emulsify for 20-60 min, adding a substance A and epoxy-terminated polyether silicone oil, regulating the pH value to 6.5, and stirring at 70-80 ℃ to react to obtain the flame-retardant abrasion-resistant low-VOC polyurethane coating, wherein the obtained polyurethane film has obvious flame retardance and abrasion resistance in the aspects of flame burning time, molten drop resistance and the like, but the patent does not relate to the self-repairing of polyurethane flame retardance.
At present, DMF (dimethylformamide) and acetone are used as common solvents in polyurethane synthesis, and the solvents have strong stimulation effects on eyes, skin and mucous membrane, and cause general cramps, painful constipation, nausea, vomiting and the like after inhalation. DMF and acetone are limited in the European Union exemption catalogue, simultaneously VOC is required to be lower than 1000ppm, N-diethyl formamide DEF solvent is a novel solvent, and substitution of DMF by the novel solvent is a trend of development in the polyurethane field.
Polyurethane is one of the main coatings of leather and synthetic leather products, and the existence of organic solvents in the system can increase the VOC content in the air, so that improvement is needed to solve the problem.
Polyurethane is often used as a coating in the use process, and the coating is often worn by a human body in the use process, so that the flame retardant performance is reduced, and no public literature is involved in the research at present.
In summary, the synthesis of self-healing flame retardant, melt drop resistant, abrasion resistant and low VOC polyurethanes is very critical.
Disclosure of Invention
The invention aims to solve the technical problems of providing a preparation and application method of self-repairing flame-retardant, melt-drip-resistant, abrasion-resistant and low-VOC polyurethane coating, which further improves the flame-retardant effect of the polyurethane coating and improves 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, melt-drip-resistant and wear-resistant polyurethane coating is characterized by comprising the following steps of:
the preparation method of the self-repairing flame-retardant, melt-drip-resistant and wear-resistant polyurethane coating is characterized by comprising the following steps of:
(1) Adding hollow glass beads and alkali solution into a reaction vessel protected by nitrogen, heating and stirring the system, filtering the obtained product, washing the product with water to be neutral, adding ethanol and water, and performing ultrasonic dispersion to obtain HGB-OH dispersion; adding an aminopropyl triethoxy silane coupling agent and 4-bromoaniline into the HGB-OH dispersion, heating, stirring for reaction, filtering, and vacuum drying the product to obtain HGB-NH 2 The method comprises the steps of carrying out a first treatment on the surface of the In HGB-NH 2 Adding a dispersing agent into the mixture, and performing ultrasonic dispersion to obtain HGB-NH 2 Adding isocyanate and 2-chloroacetoacetic acid methyl ester, stirring and reacting to obtain HGB-isocyanate dispersion, 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, adding dibutyl tin dilaurate and stirring for reaction; adding a chain extender 2, 2-dithiodiglycol and a nitrogen-phosphorus intumescent flame retardant into the system, and continuing the reaction time; adding a viscosity reducer N, N-diethyl formamide DEF after cooling; cooling again and adding triethylamine, and reacting to obtain transparent viscous liquid; adding deionized water, epoxy resin E51, trimethylolpropane trimethacrylate and 3,4' -diaminodiphenyl ether into the transparent viscous liquid, and stirring for reaction to obtain polyurethane emulsion, namely the prepared polyurethane coating.
The preparation method of the self-repairing flame-retardant, melt-drip-resistant and wear-resistant polyurethane coating is characterized by comprising the following specific steps of:
(1) Adding 15 into a reaction vessel with nitrogen protection10g of hollow glass microsphere (HGB is abbreviated) with the thickness of about 65 micrometers and 90mL of alkali solution with the mass fraction of 10 percent, the system temperature is raised to 70-85 ℃ and stirred for 2-3 hours, the obtained product is filtered and washed to be neutral, 90g of ethanol and 10g of deionized water are added into the obtained filtered product, and ultrasonic dispersion is carried out for 30-40 minutes, thus obtaining HGB-OH dispersion; adding 0.1-0.2 g of aminopropyl triethoxy silane coupling agent and 0.1g of 4-bromoaniline into HGB-OH dispersion, heating to 70-85 ℃ and stirring for reaction for 2-3 h, carrying out suction filtration, respectively washing with 15mL of ethanol in a Buchner funnel for three times in the suction filtration process, and carrying out vacuum drying on the product at 70 ℃ for 14h to obtain HGB-NH 2 The method comprises the steps of carrying out a first treatment on the surface of the In HGB-NH 2 Adding 30mL of dispersing agent, and performing ultrasonic dispersion to obtain HGB-NH 2 Adding 15g of isocyanate and 1-2 g of methyl 2-chloroacetoacetate, heating to 25 ℃, stirring and reacting for 3-4 hours to obtain HGB-isocyanate dispersion, standing for 12 hours, 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 vessel protected by nitrogen, heating the system to 80 ℃ by using 2g of HGB-DI in the step (1), adding 0.24g of dibutyltin dilaurate, stirring and reacting 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-diethyl formamide 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, and stirring to react 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 dispersing agent is any one of ethyl acetate and butyl acetate.
The molecular weight of the polypropylene glycol and the polytetrahydrofuran ether glycol is 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 for 30-60 min at room temperature, 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 ℃, preserving heat and stirring for 30-60 min, cooling to room temperature, dropwise adding 12.2g of ethanolamine within 30-60 min, and continuing to react 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 sodium hydroxide solution to adjust the pH to 6.0, adding 2.5-3.6 g of 3-aminopropyl triethoxysilane (KH 550) into a reaction container, and stirring at 70-110 ℃ for reaction for 1-7 h to obtain an intermediate B;
(3) Taking the intermediate A of the flame retardant in the step (1), the intermediate B of the step (2) and 4.2-8.6 g of sodium lignin sulfonate, stirring and reacting for 1-2 hours 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 hours at 70-80 ℃, and 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 2-3 hours at 70-80 ℃ to obtain the nitrogen-phosphorus intumescent flame retardant.
The application method of the self-repairing flame-retardant, melt-drip-resistant and wear-resistant polyurethane coating prepared by the preparation method comprises the following steps: adding 0.2-0.7 part of film forming accelerator and 0.1 part of trimethylolpropane into 10 parts of the polyurethane coating; the parts are mass parts.
The preparation method of the film forming promoter comprises the following steps: stirring 6 parts of polyethylenimine and 8.2-9.4 parts of 2-acetoxyl isobutyryl chloride at 50-60 ℃ for reaction for 1-2 hours, adding 1.1-1.4 parts of salicylic acid, adding 1.1-2.3 parts of semicarbazide, and reacting for 30-90 minutes at 50-70 ℃ to obtain a film forming accelerator; the parts are mass parts.
The invention has the main technical advantages that:
(1) The hollow glass microballoons of micron are reacted with polyol on the premise that NCO is grafted or adsorbed, the invention adopts alkali solution to process and form HGB-OH, and then adopts aminopropyl triethoxy silane coupling agent under the assistance of 4-bromoaniline to react to form HGB-NH 2 And then, the methyl 2-chloroacetoacetate is fully contacted with isocyanate, so that the adsorption or grafting of NCO on the micron-sized hollow glass microspheres is improved, and the subsequent reaction of the isocyanate and the polyol is facilitated.
(2) The invention takes polypropylene glycol and polytetrahydrofuran ether glycol as polyalcohol, isocyanate and modified HGB-NCO as isocyanate, 2-dithio diethanol chain extender and intumescent flame retardant as monomer raw materials, and prepares the HGB-waterborne polyurethane prepolymer through prepolymerization reaction. And then adding a neutralizing agent to neutralize the prepolymer, and finally adding water with equal proportion to emulsify to finally obtain the HGB-WPU. The hollow glass bead is a novel hollow material and has the advantages of low heat conductivity, incombustibility and the like, and is mainly composed of soda lime borosilicate, is a non-combustible substance, and is added into WPU (waterborne polyurethane) to reduce the volume fraction of the hollow glass bead, thereby indirectly playing a role of a flame retardant. In addition, due to the advantages of light weight and heat insulation of the hollow glass beads, the hollow glass beads can migrate from the inside of the coating to the surface of the sample during the combustion of the HGB-WPU, so that the hollow glass beads isolate a fire source, and have the effects of good flame retardance, enhanced carbon layer stability and reduced molten drop phenomenon.
(3) Phosphoric acid is used as an acid source, pentaerythritol is used as a carbon source, and pentaerythritol phosphate is synthesized through esterification reaction. Wherein the carbon source is heated to generate carbide to form the basis of the carbon layer; the acid source is heated to decompose, and the resultant can promote the dehydration of organic matters into carbon. POCl is added on the basis 3 The acid source in the system is supplemented, and then ethanolamine is added as a gas source, so that the gas source is heated to generate nonflammable and flame-retardant gas which is distributed in the carbon layer, the carbon layer is promoted to foam, the distance between the heat source and the base material is lengthened, and the mass transfer and heat transfer effects during combustion are reduced, so that better flame retardant performance is achieved, and the synergistic effect of nitrogen and phosphorus is achieved; boric acid is used as an acid source, and the tetrakis (hydroxymethyl) phosphonium sulfate is used as an acid source and a carbon source, and is synthesized into a cage shape under the catalysis of concentrated sulfuric acid3-aminopropyl triethoxy silane is adopted to react with cage-shaped hydroxyl-containing compounds, silicon base is introduced into the compound, and the synthesized intermediate B has cage-shaped rigidity and ethoxy side chains, so that the strength of the intermediate is improved, and meanwhile, the coordination flame retardance of boron, phosphorus and silicon is also achieved; then 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 in heating, grafting the intermediate A with the intermediate B, dispersing the product obtained by the reaction on sodium lignin sulfonate (Jinan Shengshi chemical industry Co., ltd.) with the form of C-C bond, C-O-C bond as the main form and the like connected to form a polyphenol three-dimensional reticular space structure, uniformly dispersing the obtained product, then adopting the open chain of the butyric anhydride by adopting the unreacted hydroxyl in the butyric anhydride and the obtained product, reacting the 2, 4-dihydroxybenzaldehyde with the hydroxyl obtained by the open chain, introducing carboxyl and aldehyde groups into the system, reacting the ethylenediamine tetraacetic acid with the hydroxyl of the system, introducing the carboxyl, the rigidity of the system is also increased, 4-carboxyphenylboronic acid and 2-acetoxyl isobutyryl chloride are reacted with hydroxyl groups and amino groups (imines) of the system, so that the obtained flame retardant has a large number of hydroxyl groups, carboxyl groups, aldehyde groups and imino groups, the subsequent flame retardant self-repairing is facilitated, meanwhile, the flame retardant system is dispersed in a three-dimensional network structure with sodium lignin sulfonate as a structural system, a compact carbon layer is formed by the flame retardant structure, gas released in the combustion process is coated in the compact carbon layer and is difficult to release in a short time, the heat insulation effect is achieved, and meanwhile, the synergistic effect of nitrogen, phosphorus, silicon and boron is utilized by the flame retardant, so that the advantages of high expansion rate and high residual carbon rate which are difficult to achieve by the existing expansion type nitrogen-phosphorus flame retardant are exerted.
(4) The invention uses the interpenetrating polymer network polymer of polyurethane and epoxy resin polymer, wherein the epoxy resin participates in dispersing between polyurethane macromolecules, cross penetration and intertwining, thus playing the roles of interpenetrating and mutually synergistic. The epoxy resin and the polyurethane are mutually entangled to enable different structures to be micronized, the entanglement among networks can obviously improve the dispersibility of the polyurethane, and improve the property of the polyurethane, especially under the action of the epoxy resin E51 (Jinan Baihui biotechnology Co., ltd.), the molecular chains of the polyurethane and the molecular chains of the epoxy resin E51 are mutually staggered, and simultaneously, the chain distribution of the polyurethane and the epoxy resin is uniform and not entangled too tightly due to high steric hindrance, so that the polyurethane can be repaired in time after partial damage is facilitated, and meanwhile, the dispersibility of the N, N-diethyl formamide DEF to the polyurethane is poorer than that of the acetone and DMF, and the dispersibility of the trimethylolpropane trimethacrylate and the 3,4' -diaminodiphenyl ether is improved.
(5) In the film forming process, DEF, toluene and water molecules are required to be quickly volatilized or slowly released later in order to accelerate the film forming of polyurethane. Although polyethyleneimine is a curing agent in the field, the effect is not particularly ideal in the aspect of polyurethane preparation, the invention adopts the imine of polyethyleneimine to react with acyl chloride of 2-acetoxy isobutyryl chloride, then 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 to accelerate the release of VOC. At the same time, amino can also react with carbonyl of acetone, especially in the environment of film forming and heating (such as drying in a drying tunnel is needed in leather coating finishing), the VOC release of polyurethane can be improved.
Detailed Description
The present invention will be further described with reference to examples, comparative examples and technical effects thereof.
The preparation method of the self-repairing flame-retardant, melt-drip-resistant and wear-resistant polyurethane coating is characterized by comprising the following steps of:
(1) 15 mu m hollow glass beads (10 g; HGB is abbreviated) and 90mL of 10% sodium hydroxide solution by mass fraction are added into a three-necked flask protected by nitrogen, the temperature of the system is raised to 70 ℃ and the mixture is stirred for reaction 2h, filtering and washing the obtained product to be neutral, adding 90g of ethanol and 10g of deionized water into the obtained filtered product, and performing ultrasonic dispersion for 30min to obtain HGB-OH dispersion; adding 0.1g of aminopropyl triethoxy silane coupling agent and 0.1g of 4-bromoaniline into HGB-OH dispersion, heating to 70 ℃ and stirring for reaction for 2 hours, carrying out suction filtration, respectively washing with 15mL of ethanol in a Buchner funnel three times in the suction filtration process (namely, washing with 15mL of ethanol each time, and carrying out the same applies below), and carrying out vacuum drying on the product at 70 ℃ for 14 hours to obtain HGB-NH 2 The method comprises the steps of carrying out a first treatment on the surface of the In 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 methyl 2-chloroacetoacetate, heating to 25 ℃, stirring and reacting for 3 hours to obtain HGB-isocyanate dispersion, standing for 12 hours, filtering and drying to obtain HGB-DI;
(2) In a three-neck flask reaction under the protection of nitrogen, adding 9.6g of polypropylene glycol (with the molecular weight of 1000 g/mol), 9.6g of polytetrahydrofuran ether glycol (with the molecular weight of 1000 g/mol) and 11.5g of isophorone diisocyanate (HGB-DI 2g in the step (1), heating the system to 80 ℃, adding 0.24g of dibutyltin dilaurate, stirring and reacting 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 viscosity reducing agent N, N-diethyl formamide DEF; cooling to 40 ℃ and adding 1.7g of triethylamine to react for 0.5h to obtain transparent viscous liquid; and 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, and stirring to react 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) 27.2g of pentaerythritol and 138.4g of phosphoric acid are added into a three-neck flask, the mixture is stirred at room temperature for 30min, the temperature of the system is increased to 90 ℃, and the reaction is carried out for 1h, thus obtaining pentaerythritol phosphate; cooling pentaerythritol phosphate to room temperature, adding 20.8g of phosphorus oxychloride, heating the system to 45 ℃, preserving heat and 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 reaction for 1h, adding sodium hydroxide solution to adjust the pH to 6.0, adding 2.5g of 3-aminopropyl triethoxysilane into a three-neck flask, and stirring at 70 ℃ for reaction for 1h to obtain an intermediate B;
(3) Taking (all) the flame retardant intermediate A (in the step (1), the intermediate B (in the step (2)) and 4.2g of sodium lignin sulfonate, stirring and reacting for 1h at 60 ℃, adding 1.2g of butyric anhydride and 0.6g of 2, 4-dihydroxybenzaldehyde, reacting for 1h at 70 ℃, adding 0.5g of ethylenediamine tetraacetic acid, 0.2g of 4-carboxyphenylboronic acid and 0.1g of 2-acetoxyisobutyryl chloride, and reacting for 2h at 70 ℃ to obtain the nitrogen-phosphorus intumescent flame retardant.
Application example 1
The application method of polyurethane comprises the steps of adding 0.2 part of film forming accelerator and 0.1 part of trimethylolpropane into 10 parts of polyurethane paint; the components are evenly mixed, the materials are placed on a glass plate to be naturally volatilized, and the film can be naturally peeled off and then tested.
The preparation method of the film forming promoter comprises the following steps: stirring 6 parts of polyethylenimine and 8.2 parts of 2-acetoxyisobutyryl chloride at 50 ℃ for reaction for 1h, adding 1.1 parts of salicylic acid, adding 1.1 parts of semicarbazide, and reacting for 30min at 50 ℃ to obtain a film forming accelerator; the parts are mass parts. (Polyethylenimine purchased a commercially available 50% aqueous solution, the same applies below)
The preparation method of the self-repairing flame-retardant, melt-drip-resistant and wear-resistant polyurethane coating is characterized by comprising the following steps of:
(1) Adding 10g of 65-micrometer hollow glass beads (HGB is abbreviated) and 90mL of potassium hydroxide solution with the mass fraction of 10% into a three-neck flask protected by nitrogen, heating the system to 85 ℃ and stirring for 3 hours, filtering the obtained product, washing the obtained product with water to be neutral, adding 90g of ethanol and 10g of deionized water into the obtained filtered product, and performing ultrasonic dispersion for 40 minutes to obtain HGB-OH dispersion; adding 0.2g of aminopropyl triethoxy silane coupling agent and 0.1g of 4-bromoaniline into HGB-OH dispersion, heating to 85 ℃, stirring and reacting for 3h, suction filtering, and respectively using 15mL of ethanol in a Buchner funnel in the suction filtering processWashing for three times, and vacuum drying the product at 70 ℃ for 14h to obtain HGB-NH 2 The method comprises the steps of carrying out a first treatment on the surface of the In HGB-NH 2 Adding 30mL butyl acetate, and performing ultrasonic dispersion to obtain HGB-NH 2 Adding 15g isophorone diisocyanate and 2g methyl 2-chloroacetoacetate, heating to 25 ℃, stirring and reacting for 4 hours to obtain HGB-isophorone diisocyanate dispersion, 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 weight of the polypropylene glycol and the polytetrahydrofuran ether glycol is 1000 g/mol) and 11.5g of isophorone diisocyanate into a three-neck flask protected by nitrogen, heating 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 viscosity reducing agent N, N-diethyl formamide DEF; cooling to 40 ℃, and adding 2.5g of triethylamine to react 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, and stirring to react 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) 27.2g of pentaerythritol and 138.4g of phosphoric acid are added into a three-neck flask, the mixture is stirred at room temperature for 60min, the temperature of the system is increased to 130 ℃, and the reaction is carried out for 5h, thus obtaining pentaerythritol phosphate; cooling pentaerythritol phosphate to room temperature, adding 20.8g of phosphorus oxychloride, heating the system to 50 ℃, preserving heat, stirring and 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) 8.4g of boric acid, 81.2g of tetrakis (hydroxymethyl) phosphonium sulfate and 0.98g of concentrated sulfuric acid are stirred and reacted for 3 hours at 90 ℃, then sodium hydroxide solution is added to adjust the pH value to 6.0, and then 3.6g of 3-aminopropyl triethoxysilane is added into a reaction vessel to be stirred and reacted for 7 hours at 110 ℃ to obtain an intermediate B;
(3) Taking (all) the flame retardant intermediate A (in the step (1), the intermediate B (in the step (2)) and 8.6g of sodium lignin sulfonate, stirring and reacting for 2 hours at 70 ℃, adding 1.7g of butyric anhydride and 1.2g of 2, 4-dihydroxybenzaldehyde, reacting for 3 hours at 80 ℃, adding 1.2g of ethylenediamine tetraacetic acid, 0.4g of 4-carboxyphenylboronic acid and 0.4g of 2-acetoxyisobutyryl chloride, and reacting for 3 hours at 80 ℃ 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 accelerator and 0.1 part of trimethylolpropane into 10 parts of polyurethane paint prepared in the second embodiment; the components are evenly mixed, the materials are placed on a glass plate to be naturally volatilized, and the film can be naturally peeled off and then tested.
The preparation method of the film forming promoter comprises the following steps: stirring 6 parts of polyethylenimine and 9.4 parts of 2-acetoxyl isobutyryl chloride at 60 ℃ for 2 hours, adding 1.4 parts of salicylic acid, adding 2.3 parts of semicarbazide, and reacting at 70 ℃ for 90 minutes to obtain a film forming accelerator; the parts are mass parts.
The preparation method of the self-repairing flame-retardant, melt-drip-resistant and wear-resistant polyurethane coating is characterized by comprising the following steps of:
(1) Adding 10g of 40-micrometer hollow glass beads (HGB is abbreviated) and 90mL of sodium hydroxide solution with the mass fraction of 10% into a reaction vessel protected by nitrogen, heating the system to 75 ℃ and stirring for 2.5h, filtering the obtained product, washing the obtained product with water to be neutral, adding 90g of ethanol and 10g of deionized water into the obtained filtered product, and performing ultrasonic dispersion for 35min to obtain HGB-OH dispersion; adding 0.15g of aminopropyl triethoxy silane coupling agent and 0.1g of 4-bromoaniline into HGB-OH dispersion, heating to 75 ℃, stirring for reaction for 2.5h, suction filtering, respectively washing with 15mL of ethanol in a Buchner funnel for three times in the suction filtering process, and vacuum drying the product at 70 ℃ for 14h to obtain HGB-NH 2 The method comprises the steps of carrying out a first treatment on the surface of the In 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 3.5 hours to obtain HGB-isocyanate dispersion, 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 weight of the polypropylene glycol and the polytetrahydrofuran ether glycol is 1000 g/mol) and 11.5g of isophorone diisocyanate into a three-neck flask protected by nitrogen, heating the system to 80 ℃, adding 0.24g of dibutyltin dilaurate, stirring for 2 hours, adding 2.15g of chain extender 2, 2-dithio-diethanol 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 viscosity reducing agent N, N-diethyl formamide DEF; cooling to 40 ℃, and adding 2.1g of triethylamine to react for 0.5h to obtain transparent viscous liquid; and 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, and stirring to react 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) 27.2g of pentaerythritol and 138.4g of phosphoric acid are added into a three-neck flask, the mixture is stirred at room temperature for 45min, the temperature of the system is increased to 110 ℃, and the reaction is carried out for 3h, thus obtaining pentaerythritol phosphate; cooling pentaerythritol phosphate to room temperature, adding 20.8g of phosphorus oxychloride, heating the system to 45 ℃, preserving heat and 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) 7.3g of boric acid, 81.2g of tetrakis (hydroxymethyl) phosphonium sulfate and 0.98g of concentrated sulfuric acid are stirred and reacted for 2 hours at 80 ℃, then sodium hydroxide solution is added to adjust the pH value to 6.0, 3.0g of 3-aminopropyl triethoxysilane is added into a three-neck flask, and stirred and reacted for 4 hours at 90 ℃ to obtain an intermediate B;
(3) Taking (all) the flame retardant intermediate A (in the step (1), the intermediate B (in the step (2)) and 7.4g of sodium lignin sulfonate, stirring and reacting for 1.5h at 65 ℃, adding 1.4g of butyric anhydride and 0.9g of 2, 4-dihydroxybenzaldehyde, reacting for 2h at 75 ℃, 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 III
Adding 0.35 part of film forming accelerator and 0.1 part of trimethylolpropane into 10 parts of the polyurethane coating prepared in the third embodiment; the components are evenly mixed, the materials are placed on a glass plate to be naturally volatilized, and the film can be naturally peeled off and then tested.
The preparation method of the film forming accelerator of the polyurethane emulsion in film forming comprises the following steps: 6 parts of polyethylenimine and 8.7 parts of 2-acetoxyl isobutyryl chloride are stirred and reacted for 1.5 hours at 55 ℃, 1.25 parts of salicylic acid is added, 1.7 parts of semicarbazide is added, and the reaction is carried out for 60 minutes at 60 ℃ to obtain the film forming accelerant.
The preparation method of the self-repairing flame-retardant, melt-drip-resistant and wear-resistant polyurethane coating is characterized by comprising the following steps of:
(1) Adding 10g of 15-micrometer hollow glass beads (HGB is abbreviated) and 90mL of potassium hydroxide solution with the mass fraction of 10% into a three-port bottle protected by nitrogen, heating the system to 85 ℃ and stirring for 3 hours, filtering the obtained product, washing the obtained product with water to be neutral, adding 90g of ethanol and 10g of deionized water into the obtained filtered product, and performing ultrasonic dispersion for 40 minutes to obtain HGB-OH dispersion; adding 0.1g of aminopropyl triethoxy silane coupling agent and 0.1g of 4-bromoaniline into HGB-OH dispersion, heating to 85 ℃ and stirring for reaction for 2 hours, carrying out suction filtration, respectively washing with 15mL of ethanol in a Buchner funnel for three times in the suction filtration process, and carrying out vacuum drying on the product at 70 ℃ for 14 hours to obtain HGB-NH 2 The method comprises the steps of carrying out a first treatment on the surface of the In HGB-NH 2 Adding 30mL butyl acetate, and performing ultrasonic dispersion to obtain HGB-NH 2 15g of 4, 4-diphenylmethane diisocyanate and 1.5g of methyl 2-chloroacetoacetate are added, the temperature is raised to 25 ℃ and stirred for 3.5 hours to obtain HGB-isocyanate dispersion, and the HGB-DI is obtained after standing for 12 hours, filtering and drying;
(2) Adding 9.6g of polypropylene glycol, 9.6g of polytetrahydrofuran ether glycol (the molecular weight of the polypropylene glycol and the polytetrahydrofuran ether glycol is 1000), 11.5g of isophorone diisocyanate (HGB-DI) in the step (1), heating the 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 viscosity reducing agent N, N-diethyl formamide DEF; cooling to 40 ℃ and adding 2g of triethylamine to react 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, and stirring to react 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) 27.2g of pentaerythritol and 138.4g of phosphoric acid are added into a three-neck flask, the mixture is stirred at room temperature for 40min, the temperature of the system is increased to 110 ℃, and the reaction is carried out for 2h, thus obtaining pentaerythritol phosphate; cooling pentaerythritol phosphate to room temperature, adding 20.8g of phosphorus oxychloride, heating the system to 50 ℃, preserving heat and stirring for 60min, cooling to room temperature, dropwise adding 12.2g of ethanolamine within 60min, and continuing to react for 1.5h to obtain a flame retardant intermediate A;
(2) 7.6g of boric acid, 81.2g of tetrakis (hydroxymethyl) phosphonium sulfate and 0.98g of concentrated sulfuric acid are stirred and reacted for 1h at 80 ℃, then sodium hydroxide solution is added to adjust the pH to 6.0, and then 2.7g of 3-aminopropyl triethoxysilane is added into a reaction vessel to be stirred and reacted for 3h at 80 ℃ to obtain an intermediate B;
(3) Taking (all) the flame retardant intermediate A (in the step (1), the intermediate B (in the step (2)) and 5.3g of sodium lignin sulfonate, stirring and reacting for 1.5h at 65 ℃, adding 1.4g of butyric anhydride and 0.7g of 2, 4-dihydroxybenzaldehyde, reacting for 2h at 75 ℃, 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 IV
Taking 10 parts of polyurethane coating prepared in the fourth embodiment, and adding 0.4 part of film forming accelerator and 0.1 part of trimethylolpropane; the components are evenly mixed, the materials are placed on a glass plate to be naturally volatilized, and the film can be naturally peeled off and then tested.
The preparation method of the film forming promoter used in the film forming process of the polyurethane coating comprises the following steps: 6 parts of polyethylenimine and 8.5 parts of 2-acetoxyl isobutyryl chloride are stirred and reacted for 1h at 50 ℃, 1.3 parts of salicylic acid is added, 1.6 parts of semicarbazide is added, and the reaction is carried out for 60min at 50 ℃ to obtain the film forming accelerant.
Preparation example five the preparation method of self-repairing flame-retardant, melt-drip-resistant and wear-resistant polyurethane coating is characterized by comprising the following steps:
(1) Adding 10g (HGB is abbreviated) of 65-micrometer hollow glass beads and 90mL of sodium hydroxide solution with the mass fraction of 10% into a three-neck flask protected by nitrogen, heating the system to 80 ℃ and stirring for 3 hours, filtering the obtained product, washing the obtained product with water to be neutral, adding 90g of ethanol and 10g of deionized water into the obtained filtered product, and performing ultrasonic dispersion for 35 minutes to obtain HGB-OH dispersion; adding 0.1g of aminopropyl triethoxy silane coupling agent and 0.1g of 4-bromoaniline into HGB-OH dispersion, heating to 85 ℃ and stirring for reaction for 3 hours, carrying out suction filtration, respectively washing with 15mL of ethanol in a Buchner funnel for three times in the suction filtration process, and carrying out vacuum drying on the product at 70 ℃ for 14 hours to obtain HGB-NH 2 The method comprises the steps of carrying out a first treatment on the surface of the In 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 2-chloroacetoacetic acid methyl ester, heating to 25 ℃, stirring and reacting for 4 hours to obtain HGB-isocyanate dispersion, 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 weight of the polypropylene glycol and the polytetrahydrofuran ether glycol is 1000), 11.5g of isophorone diisocyanate (HGB-DI) in the step (1), heating the system to 80 ℃, adding 0.24g of dibutyltin dilaurate, stirring for 2 hours, adding 1.2g 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 70 ℃, and adding 30mL of a viscosity reducing agent N, N-diethyl formamide DEF; cooling to 40 ℃ and adding 2.5g of triethylamine to react for 0.5h to obtain transparent viscous liquid; and 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, and stirring to react 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) 27.2g of pentaerythritol and 138.4g of phosphoric acid are added into a three-neck flask, the mixture is stirred at room temperature for 40min, the temperature of the system is increased to 110 ℃, and the reaction time is 3h, so that pentaerythritol phosphate is obtained; cooling pentaerythritol phosphate to room temperature, adding 20.8g of phosphorus oxychloride, heating the system to 50 ℃, preserving heat and 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) 7.3g of boric acid, 81.2g of tetrakis (hydroxymethyl) phosphonium sulfate and 0.98g of concentrated sulfuric acid are stirred and reacted for 2 hours at 80 ℃, then sodium hydroxide solution is added to adjust the pH value to 6.0, 3.0g of 3-aminopropyl triethoxysilane is added into a three-neck flask, and stirred and reacted for 3 hours at 80 ℃ to obtain an intermediate B;
(3) Taking (all) the flame retardant intermediate A (in the step (1), the intermediate B (in the step (2)) and 5.7g of sodium lignin sulfonate, stirring and reacting for 2 hours at 70 ℃, adding 1.7g of butyric anhydride and 0.7g of 2, 4-dihydroxybenzaldehyde, reacting for 2 hours at 75 ℃, adding 0.9g of ethylenediamine tetraacetic acid, 0.25g of 4-carboxyphenylboronic acid and 0.15g of 2-acetoxyisobutyryl chloride, and reacting for 2.5 hours at 70 ℃ to obtain the nitrogen-phosphorus intumescent flame retardant.
Application example five
Taking 10 parts of polyurethane coating prepared in the fifth embodiment, adding 0.5 part of film forming accelerator and 0.1 part of trimethylolpropane; the parts are mass parts. The materials are uniformly mixed, the mixture is placed on a glass plate, a solvent is naturally volatilized, a film can be naturally peeled off, and then the test is carried out.
The preparation method of the film forming promoter comprises the following steps: stirring 6 parts of polyethylenimine and 8.2 parts of 2-acetoxyisobutyryl chloride at 60 ℃ for 2 hours, adding 1.4 parts of salicylic acid, adding 1.7 parts of semicarbazide, and reacting for 50 minutes at 60 ℃ to obtain a film forming accelerator; the parts are mass parts.
The following is a comparison of performance test and technical effects of the example and application products of the present invention and the control product.
Abrasion resistance is according to GB/T22374-2018;
the char yield and swell height are referenced to 2019106431795 test standards.
GB/T5455-1997 flame burning time (after-burning time) of a film formed by polyurethane coating is measured by a textile burning performance test vertical method, and the length of a sample is 20cm multiplied by 10cm, and the thickness is 1mm.
The VOC measuring method comprises the following steps: the metal pan was baked in an oven at 105±2 ℃ for 30min and then placed in a desiccator until use. After mixing polyurethane, spreading the polyurethane on a metal flat-bottom dish, standing for 24 hours at the temperature of 23+/-2 ℃ and the humidity of 50+/-5%, and then baking the polyurethane in an oven at the temperature of 105+/-2 ℃ for 60 minutes, and carrying out two tests in parallel. Weighing m before heating 1 (Metal container m) 0 And the sum of the reactant masses) and the mass after heating m 2 (see 201710902448.6);
the phenomenon of the molten drop is observed by naked eyes.
Self-repairing flame retardant test: 1-cut self-repairing test samples with the thickness of 0.1cm and the cutting depth of 0.05cm by a blade at each 1cm, dyeing the cut, and drying for 5 hours at 80 ℃ (oven) to achieve the repairing effect.
2 self-repairing abrasion: the thickness of the test sample is 0.1cm, the abrasion resistance is 50 times according to GB/T22374-2018 and 100g/100r, the other test samples are not changed, and the test samples are baked for 5 hours at 80 ℃ (oven) to achieve the repairing effect.
TABLE 1 film Forming Performance index of polyurethane coating
Comparative example (202011624359.8, comparison of flame burning time of example 1) it can be seen from the above data that although the present invention is comparable to comparative example in terms of droplet drop, the present invention is superior to comparative example 1 in flame burning time, VOC and abrasion resistance, since the present invention is superior to comparative example in terms of flame burning time, VOC and abrasion resistance, because the present invention is superior to comparative example in that the present invention is based on the premise of reacting micro hollow glass beads with polyol, which is to graft or adsorb NCO, while the flame retardant system is dispersed in a three-dimensional network structure with sodium lignin sulfonate as a structural system, a dense carbon layer is formed by the flame retardant structure, and the gas released during the combustion is coated in the dense carbon layer, which is difficult to release in a short time, thereby achieving heat insulation, reducing flame burning, and at the same time, abrasion resistance and VOC are effectively blocked, and performance is superior to the comparative example.
TABLE 2 Performance index of Nitrogen-phosphorus intumescent flame retardant
As shown in Table 2, 4-carboxyphenylboronic acid and 2-acetoxyisobutyryl chloride are adopted to react with hydroxyl groups and amino groups (imines) of a system, so that the obtained flame retardant has a large number of hydroxyl groups, carboxyl groups, aldehyde groups and imino groups, the subsequent flame retardant self-repairing is facilitated, meanwhile, the flame retardant system is dispersed in a three-dimensional network structure with sodium lignin sulfonate as a structural system, a compact carbon layer is conveniently formed by the flame retardant structure, gas released in the combustion process is coated in the compact carbon layer and is difficult to release in a short time, the heat insulation effect is achieved, and meanwhile, the flame retardant adopts the synergistic effect of nitrogen, phosphorus, silicon and boron, so that the advantages of high expansion rate and residual carbon rate which are difficult to achieve by the intumescent nitrogen-phosphorus flame retardant are exerted, and the flame retardant has obvious advantages compared with a comparative sample.
Table 3 flame retardant Properties of the non-added Material (example five)
As can be seen from Table 3, taking example five as an example, the residual carbon ratio and the expansion height of the flame retardant obtained without adding 3-aminopropyl triethoxysilane, without adding sodium lignin sulfonate, without adding butyric anhydride, without adding 2, 4-dihydroxybenzaldehyde, without adding ethylenediamine tetraacetic acid, without adding 4-carboxyphenylboric acid, and without adding 2-acetoxyisobutyryl chloride are reduced, which shows that the substances exert the effects on an expansion system, wherein the sodium lignin sulfonate has the greatest influence on the properties of the expansion flame retardant, because the sodium lignin sulfonate is a three-dimensional network structure flame retardant system with a structural system, a compact carbon layer is formed by the structure which facilitates flame retardance, the gas released in the combustion process is coated in the compact carbon layer and is difficult to release in a short time, the effects of heat insulation are achieved, and the residual carbon ratio and the expansion height are improved. (note that chemical materials of the type not added are added, other materials are added)
Table 4 Properties of polyurethane film obtained without adding part of chemical Material (example two)
Specifically, since HGB-DI is based on the dispersion of the vacuum glass beads, the present invention does not add the micron vacuum glass beads, and therefore step (1) is omitted, but the amount thereof is replaced with the corresponding isocyanate, and from the aspect of the polyurethane film obtained by adding no part of chemical raw materials in table 4, both 4-bromoaniline and 2-chloroacetoacetic acid methyl ester are used for adding the vacuum glass beads in the system, so that the amount of the vacuum glass beads is small, the influence on the melt drop resistance property is relatively large, and the property is not affected.
Table 5 characterization of flame retardant self healing ability of polyurethane coatings (cut)
Comparative example (comparison of flame burning time and droplet in example four of 202011624359.8), repair was performed with less flame burning time and droplet drop, and the drop width without repair was large.
Table 6 characterization of flame retardant self healing ability of polyurethane coatings (after abrasion resistance)
It can be seen from Table 6 that no wear repair was performed and a significant increase in flame burn time resulted in a large amount of droplets. Comparative example (example four of 202011624359.8)
Table 7 characterization of flame retardant self healing ability of polyurethane coatings (chemical materials, abrasion not added below)
From Table 7, it can be found that the flame burn time (abrasion) of the film without trimethylpropane trimethacrylate, 3,4' -diaminodiphenyl ether and epoxy resin E51 was significantly prolonged, showing that the above-mentioned substances exert a remarkable effect therein.
All materials are applied to the self-repairing flame-retardant, anti-dripping and abrasion-resistant polyurethane coating.
Claims (1)
1. The self-repairing flame-retardant melt-drip-resistant abrasion-resistant polyurethane coating is characterized by comprising the following steps of:
(1) Adding 15-65 micrometers of hollow glass beads 10g and 90mL of alkali solution with the mass fraction of 10% into a reaction vessel protected by nitrogen, heating the system to 70-85 ℃ and stirring for 2-3 hours, filtering the obtained product, washing the obtained product with water to be neutral, adding 90g of ethanol and 10g of deionized water into the obtained filtered product, and performing ultrasonic dispersion for 30-40min to obtain HGB-OH dispersion; adding 0.1-0.2g of aminopropyl triethoxy silane coupling agent and 0.1g of 4-bromoaniline into HGB-OH dispersion, heating to 70-85 ℃ and stirring for reaction for 2-3h, suction filtering, respectively washing with 15mL of ethanol in a Buchner funnel for three times in the suction filtering process, and vacuum drying the product at 70 ℃ for 14h to obtain HGB-NH 2 The method comprises the steps of carrying out a first treatment on the surface of the In HGB-NH 2 Adding 30mL of dispersing agent, 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 3-4 hours to obtain HGB-isocyanate dispersion, standing for 12 hours, 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 vessel protected by nitrogen, heating the system to 80 ℃ by using 2g of HGB-DI in the step (1), adding 0.24g of dibutyltin dilaurate, stirring and reacting for 2 hours, adding 0.7-3.6g of chain extender 2, 2-dithiodiethanol and 3.7-6.3g of nitrogen-phosphorus intumescent flame retardant into the system, and reacting for 2-3 hours; cooling to 50-70 ℃, and adding 15-30mL of a viscosity reducer N, N-diethyl formamide; cooling to 40 ℃, adding 1.7-2.5g of triethylamine, and reacting for 0.5-h to obtain transparent viscous liquid; cooling to room temperature, adding 75-85mL of deionized water, 14-16g of epoxy resin E51, 0.8g of trimethylolpropane trimethacrylate and 1.2g of 3,4' -diaminodiphenyl ether, and stirring to react for 30-60min to obtain polyurethane emulsion, namely the prepared polyurethane coating;
the dispersing agent is any one of ethyl acetate and butyl acetate;
the molecular weight of the polypropylene glycol and the polytetrahydrofuran ether glycol is 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:
(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 and stirring for 30-60min, cooling to room temperature, dropwise adding 12.2-g of ethanolamine within 30-60min, and continuing to react for 1-2h to obtain a flame retardant intermediate A;
(b) Stirring 6.2-8.4g of boric acid, 81.2g of tetrakis (hydroxymethyl) phosphonium sulfate and 0.98g of concentrated sulfuric acid at 70-90 ℃ for reaction for 1-3h, adding sodium hydroxide solution to adjust the pH to 6.0, adding 2.5-3.6g of 3-aminopropyl triethoxysilane into a reaction container, and stirring at 70-110 ℃ for reaction for 1-7h to obtain an intermediate B;
(c) Taking the intermediate A of the flame retardant in the step (a), the intermediate B of the step (B) and 4.2-8.6g of sodium lignin sulfonate, stirring and reacting for 1-2 hours at the temperature of 60-70 ℃, adding 1.2-1.7g of butyric anhydride and 0.6-1.2g of 2, 4-dihydroxybenzaldehyde, reacting for 1-3 hours at the temperature of 70-80 ℃, and adding 0.5-1.2g of ethylenediamine tetraacetic acid, 0.2-0.4g of 4-carboxyphenylboronic acid and 0.1-0.4g of 2-acetoxyisobutyryl chloride, and reacting for 2-3 hours at the temperature of 70-80 ℃ to obtain the nitrogen-phosphorus intumescent flame retardant.
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| CN116200111B (en) * | 2023-02-24 | 2024-04-19 | 华南理工大学 | Flame-retardant heat-insulating polyurea coating for new energy automobile battery box body, and preparation method and application thereof |
| CN116330793B (en) * | 2023-03-14 | 2023-09-26 | 南通北风橡塑制品有限公司 | High-temperature-resistant flame-retardant polyurethane composite board and processing technology thereof |
| CN116751360B (en) * | 2023-08-21 | 2024-04-05 | 辽宁拜斯特复合材料有限公司 | Polyester resin and preparation method thereof |
| CN117736637B (en) * | 2023-10-18 | 2024-06-11 | 山东卓高新材料有限公司 | Self-repairing waterproof paint and preparation method thereof |
| CN117363193B (en) * | 2023-11-01 | 2024-03-01 | 北京景泰消防科技有限公司 | Water-based polyurethane fireproof paint and preparation process thereof |
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