CN113956777B - Preparation and application methods of self-repairing flame-retardant, droplet-resistant and abrasion-resistant polyurethane coating - Google Patents

Preparation and application methods of self-repairing flame-retardant, droplet-resistant and abrasion-resistant polyurethane coating Download PDF

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CN113956777B
CN113956777B CN202111473297.XA CN202111473297A CN113956777B CN 113956777 B CN113956777 B CN 113956777B CN 202111473297 A CN202111473297 A CN 202111473297A CN 113956777 B CN113956777 B CN 113956777B
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stirring
resistant
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reacting
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CN113956777A (en
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段宝荣
李国荣
唐志海
翁永根
冯练享
于涵
王全杰
王琦研
扈乐成
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Yantai University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4808—Mixtures of two or more polyetherdiols
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—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
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    • C09D5/185—Intumescent paints
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D7/40—Additives
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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  • Polyurethanes Or Polyureas (AREA)

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 to 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 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

Preparation and application methods of self-repairing flame-retardant, droplet-resistant and abrasion-resistant polyurethane coating
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 of the waterborne polyurethane, so that the coating is damaged, the function of the waterborne polyurethane is lost, and the service life of the waterborne polyurethane 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 the self structure 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 polyurethane.
Von et al (von et al, availability and performance of disulfide bond-based waterborne polyurethane/polyacrylate self-repairing material [ J ] polymer material science and engineering, 2021-09-29) prepared self-repairing waterborne polyurethane/polyacrylate (AWPUS) composite materials containing disulfide bonds by using polytetrahydrofuran ether glycol (PTMEG), isophorone diisocyanate (IPDI), 2-dimethylolpropionic acid (DMPA), 2-dithiodiethanol (HEDS), PA, etc. as raw materials. 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 good mechanical property is still kept at room temperature. AWPUS shows excellent reworkability, a recovered sample is recovered to the original state after being molded at 100 ℃ for 10min, the mechanical property loss 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 mostly belong to combustible organic compounds or high molecular materials, so that polyurethane belongs to combustible substances and is accompanied with potential fire hazard in the using process. On the other hand, the burning of such polymers is accompanied by the release of smoke and toxic gases, and can produce droplets that can damage human skin or cause 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 six-membered rings of carbon and nitrogen into a macromolecular structure, or to use flame-retardant phosphorus compound polyalcohol 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 compounds, 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 provided by the invention of China, and comprises the following steps of adding polyester diol, isocyanate and dibutyltin dilaurate into a reaction container, stirring at 75-90 ℃ for reaction to obtain a polyurethane prepolymer, adding hydrophilic chain extender dimethylolpropionic acid, a nitrogen-phosphorus intumescent flame retardant and an acetone solvent into the polyurethane prepolymer, and stirring at 70-90 ℃ for reaction for 1-2 hours; and adding triethylamine and water for emulsification for 20-60 min, adding the 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 retardance and wear resistance in the aspects of flame combustion time, droplet resistance and the like, but the patent does not relate to flame retardance and self-repair of polyurethane.
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 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, abrasion-resistant and low-VOC polyurethane coating, further improving the flame-retardant effect of the polyurethane coating and simultaneously 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, reacting, suction filtering, and vacuum-filteringDrying 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 dibutyltin dilaurate into the HGB-DI prepared in the step (1), and stirring for reaction; adding a chain extender 2, 2-dithiodiethanol and a nitrogen and 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 as 15-65 micron) of hollow glass microsphere and 90mL of aqueous alkali with the mass fraction of 10% into a reaction container protected by nitrogen, heating 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; then cooling to 40 ℃, and adding 1.7-2.5 g of triethylamine 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-aminopropyl triethoxysilane into a reaction vessel, and 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 the temperature of 60-70 ℃, then 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 the temperature of 70-80 ℃, 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 for 2-3h at the temperature of 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: stirring 6 parts of polyethyleneimine and 8.2-9.4 parts of 2-acetoxyisobutyryl chloride for reaction for 1-2 hours at 50-60 ℃, 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 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 the 2-chloroacetoacetic acid methyl ester is fully contacted with the 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 method takes polypropylene glycol and polytetrahydrofuran ether glycol as polyhydric alcohol, isocyanate, modified HGB-NCO as isocyanate, 2-dithiodiethanol chain extender and intumescent flame retardant as monomer raw materials, and the HGB-waterborne polyurethane prepolymer is synthesized through prepolymerization. And adding a neutralizer to neutralize the prepolymer, and finally adding water in equal proportion to emulsify to finally obtain the HGB-WPU. The hollow glass beads 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 combusted, so that a fire source is isolated, and the effects of good flame retardance, carbon layer stability enhancement and molten drop reduction are achieved.
(3) Phosphoric acid is used as an acid source, pentaerythritol is used as a carbon source, and pentaerythritol phosphate is synthesized through an esterification reaction. Wherein the carbon source is a base for generating a carbide by heating to form 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 carbon layer to foam, the distance between a 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, tetramethylolthiophosphate 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, 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; then the flame-retardant intermediate A and the intermediate B are reacted, wherein the hydroxyl of the flame-retardant intermediate A can react with the hydroxyl on boron in heating, the intermediate A and the intermediate B are reacted and grafted, the product obtained by the reaction is dispersed on sodium lignosulfonate (a chemical company Limited in Shanghai province of Jinan) with a polyphenol three-dimensional net-shaped space structure which is formed by connecting in forms of C-C bonds and C-O-C bonds mainly, the obtained product is uniformly dispersed, then the butyric anhydride and the unreacted hydroxyl in the obtained product are adopted for chain opening of the butyric anhydride, the 2, 4-dihydroxybenzaldehyde is reacted with the hydroxyl obtained by chain opening, carboxyl and aldehyde are introduced into the system, and the ethylenediamine tetraacetic acid and the body are adopted for reactionThe hydroxyl of the system is reacted, so that not only is carboxyl introduced, but also the rigidity of the system is increased, 4-carboxyphenylboronic acid and 2-acetoxyisobutyryl chloride are adopted to react with the hydroxyl and amino (imine) of the 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 construction 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 the heat insulation effect is achieved.
(4) The invention utilizes the interpenetrating of polyurethane and epoxy resin polymers to form an interwoven network polymer, wherein the epoxy resin participates in and is dispersed among polyurethane macromolecules, and the epoxy resin is subjected to cross permeation and mutual entanglement to play the roles of interpenetrating and mutual synergy. Epoxy resin and polyurethane are mutually intertwined to refine different structures, 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 polyurethane on epoxy resin E51 (Jinan Yunbaihui Biotech Co., ltd.), polyurethane molecular chains and epoxy resin E51 molecular chains are mutually interlaced, and trimethylolpropane trimethacrylate and 3,4' -diaminodiphenyl ether are used for realizing the uniform chain distribution of the polyurethane and the epoxy resin without being intertwined too tightly due to the multi-branched chains and the large steric hindrance of the trimethylolpropane trimethacrylate and the 3,4' -diaminodiphenyl ether, so that the polyurethane and the epoxy resin can be repaired in time after being partially damaged, and simultaneously, the dispersibility of the trimethylolpropane trimethacrylate and the 3,4' -diaminodiphenyl ether is improved due to the poor dispersibility of the N, N-diethylformamide DEF compared with acetone and DMF on the polyurethane.
(5) In the film forming process, in order to accelerate the film forming of polyurethane, DEF, methylbenzene and water molecules are required to be quickly volatilized or subsequently and slowly released, and the invention adopts polyethyleneimine to react with 2-acetoxy isobutyryl 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 polyethyleneimine is reacted with the acyl chloride of 2-acetoxyisobutyryl chloride, semicarbazide is added to react with the residual acyl chloride, and the obtained compound is reacted with the hydroxyl and carboxyl of polyurethane in the polyurethane film forming process to accelerate the release of VOC. Meanwhile, the amino can also react with the carbonyl 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.
The preparation example is a preparation method of self-repairing flame-retardant, droplet-resistant and abrasion-resistant polyurethane coating, and is characterized by comprising the following steps:
(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 aminopropyltriethoxysilane 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 methyl 2-chloroacetoacetate, heating to 25 ℃, stirring and reacting for 3h to obtain HGB-isocyanate dispersion, standing for 12h, 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), 11.5g of isophorone diisocyanate and 2g of HGB-DI in the step (1) into a three-neck flask reaction under the protection of nitrogen, 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-diethylformamide DEF; then cooling to 40 ℃, adding 1.7g of triethylamine for reaction 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 reaction for 1 hour, adding a sodium hydroxide solution to adjust the pH value to 6.0, adding 2.5g of 3-aminopropyltriethoxysilane into a three-neck flask, and stirring at 70 ℃ for reaction for 1 hour 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 at 60 ℃ for reaction for 1h, adding 1.2g of butyric anhydride and 0.6g of 2, 4-dihydroxybenzaldehyde, reacting at 70 ℃ for 1h, adding 0.5g of ethylenediamine tetraacetic acid, 0.2g of 4-carboxyphenylboronic acid and 0.1g of 2-acetoxyisobutyryl chloride, and reacting at 70 ℃ for 2h 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 by mass, the solvent is placed on a glass plate to naturally volatilize, and the film can be naturally peeled off and then tested.
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 30 minutes 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 aminopropyltriethoxysilane coupling agent and 0.1g of 4-bromoaniline into HGB-OH dispersion liquid, heating to 85 ℃, stirring for reaction for 3 hours, performing suction filtration, washing the product three times in a Buchner funnel by using 15mL of ethanol respectively in the process of suction filtration, and performing 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 weight of both polypropylene glycol and polytetrahydrofuran ether glycol is 1000 g/mol), 11.5g of isophorone diisocyanate and 2g of HGB-DI (Lightungin) in the step (1) into a three-neck flask under the protection of nitrogen, raising the temperature of the system to 80 ℃, adding 0.24g of dibutyltin dilaurate, stirring for 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 reducer 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 the mixture 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 reacting 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 by mass, the solvent is placed on a glass plate to naturally volatilize, and the film can be naturally peeled off and then tested.
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 for reaction for 2 hours at the temperature of 60 ℃, adding 1.4 parts of salicylic acid and 2.3 parts of semicarbazide, and reacting for 90 minutes at the temperature of 70 ℃ to obtain a film-forming promoter; the parts are parts by mass.
The preparation method of the self-repairing flame-retardant, droplet-resistant and abrasion-resistant polyurethane coating in the preparation example III is characterized by comprising the following steps of:
(1) Adding 10g of 40-micrometer hollow glass microspheres (HGB is abbreviated as follows) and 90mL of sodium hydroxide solution with the mass fraction of 10% into a reaction container protected by nitrogen, heating the system to 75 ℃, stirring for 2.5h, 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 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-diisocyanate) in the step (1) into a three-neck flask under the protection of nitrogen, raising the temperature of the 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, 0.35 part of film forming accelerator and 0.1 part of trimethylolpropane are added into the 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 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.
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-micron hollow glass micro-beads (HGB abbreviated as 'HGB') 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 ℃, and stirringStirring for 3h, 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 aminopropyltriethoxysilane 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 At HGB-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 3.5h 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 weights of the polypropylene glycol and the polytetrahydrofuran ether glycol are both 1000) and 11.5g of isophorone diisocyanate and 2g of HGB-DI in the step (1) into a reaction vessel protected by nitrogen, raising the temperature of the system to 80 ℃, adding 0.24g of dibutyltin dilaurate, stirring for 2h, adding 1.0g of chain extender 2, 2-dithiodiethanol and 4.0g of nitrogen-phosphorus intumescent flame retardant into the system, and reacting for 2.5h; 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; 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 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 polyurethane coating prepared in example four, adding 0.4 part of film forming accelerator and 0.1 part of trimethylolpropane; 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 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 preparation methods of self-repairing flame-retardant, droplet-resistant and abrasion-resistant polyurethane coating, which is characterized by comprising the following steps:
(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 aminopropyltriethoxysilane 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 the mixturePerforming ultrasonic dispersion on the ethyl acetate 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 weights of polypropylene glycol and polytetrahydrofuran ether glycol are both 1000) and 11.5g of isophorone diisocyanate and 2g of HGB-DI in the step (1) into a nitrogen-protected three-neck flask, raising the temperature of a 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 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 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 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 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 5.7g of sodium lignosulfonate, stirring at 70 ℃ for reacting 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 is the performance test and the comparison of the technical effects of the products of the embodiment and the application examples of the invention and the products of the comparison group.
The abrasion resistance is as per GB/T22374-2018;
the carbon residue rate and the expansion height refer to 2019106431795 test standards.
GB/T5455-1997 textile burning performance test measures the flame burning time (afterflame time) of the film formed by the polyurethane coating 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 deg.C 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 reaction masses) and mass m after heating 2 (see 201710902448.6);
the phenomenon of dripping is observed by the naked eye.
Self-repairing flame-retardant test: the self-repairing of the 1-cut sample is that the thickness of a test sample is 0.1cm, the depth of the test sample is cut by a blade at the position of every 1cm in length, the cut is dyed, and the test is carried out after the repair effect is achieved after the cut is dried for 5 hours at 80 ℃ (an oven).
2, wear self-repair: taking a test sample with the thickness of 0.1cm, carrying out abrasion resistance for 50 times according to GB/T22374-2018, 100g/100r and the like, and drying for 5 hours at 80 ℃ (an oven) to achieve the repairing effect, and then testing.
TABLE 1 film Forming Performance index for polyurethane coatings
Figure GDA0003903937620000141
Figure GDA0003903937620000151
Comparative example (202011624359.8, example 1 of the comparison), from the above data, it can be found that, although the invention is equivalent to the index of the comparative example in terms of the dropping of molten droplets, the invention is superior to the comparative example 1 in terms of the flaming combustion time, VOC and abrasion resistance, because compared to the comparative example, the invention adopts micron hollow glass beads and polyhydric alcohol to react 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 the structural system, so as to form a compact carbon layer for flame retardant, and the gas released in the combustion process is coated in the compact carbon layer, thus being difficult to release in a short time, playing a role of heat insulation, reducing the flaming combustion, and simultaneously having abrasion resistance and effective sealing of VOC, and having better performance than the comparative example.
TABLE 2 Performance index of the nitrogen-phosphorus intumescent flame retardant
Figure GDA0003903937620000152
The nitrogen and phosphorus intumescent flame retardant is obtained 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, and meanwhile, the flame retardant system is dispersed in a three-dimensional network structure taking sodium lignosulfonate as a construction system, so that a compact carbon layer is formed in a flame-retardant manner, and gases released in the combustion process are coated in the compact carbon layer and are difficult to release in a short time, so that a heat insulation effect is achieved.
TABLE 3 flame retardant Properties of the materials without addition of part (example five)
Figure GDA0003903937620000153
Figure GDA0003903937620000161
It can be seen from table 3 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, ethylenediaminetetraacetic acid, 4-carboxyphenylboronic acid and 2-acetoxyisobutyryl chloride are both reduced, showing 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 in the three-dimensional network flame retardant system of the construction system, a compact carbon layer is formed in a flame retardant construction, and the gas released in the combustion process is coated in the compact carbon layer, so that the gas is difficult to release in a short time, plays a role in heat insulation, and improves the carbon residue and the expansion height. (Note that no chemical material is added, other materials are added)
TABLE 4 Properties of polyurethane films obtained without addition of part of the chemical materials (example two)
Figure GDA0003903937620000162
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)
Figure GDA0003903937620000171
Comparative example (202011624359.8, the flame burning time and the droplet of example four are compared), and from the flame burning time and the droplet condition, it can be found that the repair is carried out, the flame burning time and the droplet drop are less, and the drop amplitude of the unrepaired is large.
TABLE 6 flame retardant self-healing capability characterization of polyurethane coatings (after abrasion resistance)
Figure GDA0003903937620000172
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)
Figure GDA0003903937620000181
From Table 7, it can be found that the flame burn time (abrasion) of the film without addition of trimethylolpropane trimethacrylate, 3,4' -diaminodiphenyl ether and epoxy resin E51 is remarkably prolonged, showing that the above substances exert a significant effect therein.

Claims (8)

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 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 dibutyltin dilaurate into the HGB-DI prepared in the step (1), and stirring for reaction; adding a chain extender 2, 2-dithiodiethanol and a nitrogen-phosphorus intumescent flame retardant into the system, and continuing to react; cooling and adding a thickening agent N, N-diethylformamide; cooling again and adding triethylamine to react 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 a polyurethane emulsion, namely the prepared polyurethane coating;
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, stirring for 30-60 min, cooling to room temperature, dropwise adding 12.2g of ethanolamine 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. The preparation method of the self-repairing flame-retardant, droplet-resistant and abrasion-resistant polyurethane coating of claim 1, characterized by comprising the following specific steps:
(1) Adding 10g of hollow glass microspheres with the diameter of 15-65 micrometers and 90mL of aqueous alkali with the mass fraction of 10% 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 an 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 30-40min 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;
(2) Adding 9.6g of polypropylene glycol, 9.6g of polytetrahydrofuran ether glycol and 11.5g of isophorone diisocyanate into a reaction vessel under nitrogen protection, 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 to 3.6g of chain extender 2, 2-dithiodiethanol and 3.7 to 6.3g of nitrogen-phosphorus intumescent flame retardant into the system, and reacting for 2 to 3 hours; cooling to 50 to 70 ℃, and adding 15 to 30mL of a thickening agent N, N-diethylformamide; cooling to 40 ℃, adding 1.7-2.5 g of triethylamine, and reacting for 0.5h to obtain a transparent viscous liquid; cooling to room temperature, adding 75-85mL of deionized water, 14-1691 g 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 finally obtain polyurethane emulsion, namely the prepared polyurethane coating.
3. The method for preparing the self-repairing flame-retardant, droplet-resistant, abrasion-resistant polyurethane coating according to claim 1 or 2, wherein the alkali is any one of sodium hydroxide and potassium hydroxide.
4. The preparation method of the self-repairing flame-retardant, droplet-resistant and abrasion-resistant polyurethane coating according to claim 1 or 2, characterized in that the dispersant is any one of ethyl acetate and butyl acetate.
5. The method for preparing the self-repairing flame-retardant, droplet-resistant, abrasion-resistant polyurethane coating of claim 1 or 2, wherein the molecular weights of the polypropylene glycol and the polytetrahydrofuran ether glycol are both 1000g/mol.
6. The method for preparing the self-repairing flame-retardant, droplet-resistant, abrasion-resistant polyurethane coating of claim 1 or 2, wherein the isocyanate is any one of 4,4' -diphenylmethane diisocyanate, isophorone diisocyanate, and toluene diisocyanate.
7. 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 of any one of claims 1 to 6 is characterized in that: 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.
8. The method according to claim 7, wherein the film forming promoter is prepared by: 6 parts of polyethyleneimine and 8.2 to 9.4 parts of 2-acetoxyisobutyryl chloride are stirred to react for 1 to 2h at 50 to 60 ℃, 1.1 to 1.4 parts of salicylic acid is added, 1.1 to 2.3 parts of semicarbazide is added, and the mixture reacts for 30 to 90min at 50 to 70 ℃ to obtain a film forming promoter; the parts are parts by mass.
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