CN113956777A - 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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CN113956777A
CN113956777A CN202111473297.XA CN202111473297A CN113956777A CN 113956777 A CN113956777 A CN 113956777A CN 202111473297 A CN202111473297 A CN 202111473297A CN 113956777 A CN113956777 A CN 113956777A
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hgb
stirring
resistant
retardant
reaction
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CN113956777B (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
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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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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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • 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
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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  • 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, reducing the temperature to 50-70 ℃, and adding a thickening agent N, N-diethylformamide; and cooling to 40 ℃, adding triethylamine to obtain transparent viscous liquid, cooling to room temperature, adding deionized water, epoxy resin E51, trimethylolpropane trimethacrylate and 3,4' -diaminodiphenyl ether to finally obtain 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 often subjected to the actions of friction, collision, bending and the like, and the surface of the waterborne polyurethane is physically damaged by scratches, microcracks and the like, so that the coating is damaged, the function of the coating is lost, and the service life of the coating is shortened. The self-repairing polymer material has the capability of repairing external physical damage by depending on the self structure, which is shown in that the self structure is used for repairing after the polymer material is reduced, and the self-repairing polymer material needs to be self-repaired in order to prolong the service life of the polyurethane.
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 and the like 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 are mostly flammable organic compounds or high molecular materials, so that the polyurethane is flammable and has 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) the 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 polyol as a prepolymer monomer in the synthesis, or to use flame-retardant phosphorus materials, nitrogen and phosphorus compounds and the like as chain extenders, or to modify nitrogen, nitrogen and phosphorus compounds, organic silicon and boron compounds after chain extension. (C) In the polyurethane synthesis, an auxiliary agent with a flame retardant effect is added, and the flame retardant can be divided into an organic flame retardant and an inorganic flame retardant, wherein the flame retardant is mainly a compound containing flame retardant elements such as phosphorus, bromine, antimony, boron and the like, and the flame retardant is mainly an inorganic compound such as organic ammonium phosphate, aluminum hydroxide and the like.
The invention discloses a preparation and application method of a flame-retardant wear-resistant low-VOC (volatile organic compound) polyurethane coating, which is granted in China with the publication number of CN112646475B, and comprises the steps of adding polyester diol, isocyanate and dibutyltin dilaurate into a reaction container, stirring and reacting at 75-90 ℃ 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 and reacting at 70-90 ℃ 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 at 70-80 ℃ for reaction to obtain the flame-retardant wear-resistant low-VOC (volatile organic compound) 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 irritation on eyes, skin and mucous membranes and cause general spasm, painful constipation, nausea, vomiting and the like after inhalation. DMF and acetone are limited in exemption catalogues of the European Union, VOC is required to be lower than 1000ppm, and N, N-diethylformamide DEF solvent is a novel solvent and is a trend for the development of the field of polyurethane by replacing DMF with the solvent.
Polyurethane is used as one of main coatings of leather and synthetic leather products, and the VOC content in the air is increased due to the presence of an organic solvent in the system, so that improvement on the problem is needed.
The polyurethane is often used as a coating layer in the using process, the coating layer is contacted with a human body in the using process and often abrades the coating layer to cause the reduction of the flame retardant property, and no published documents are related at present.
In conclusion, the synthesis research of self-repairing flame-retardant, anti-dripping, abrasion-resistant and low-VOC polyurethane is very critical.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation and application method of a self-repairing flame-retardant, droplet-resistant, wear-resistant and low-VOC polyurethane coating, further improving the flame-retardant effect of the polyurethane coating and improving the flame retardance of self-repairing property.
The technical scheme of the invention is as follows: the preparation method of the self-repairing flame-retardant, droplet-resistant and abrasion-resistant polyurethane coating is characterized by comprising the following steps of:
the preparation method of the self-repairing flame-retardant, droplet-resistant and abrasion-resistant polyurethane coating is characterized by comprising the following steps of:
(1) adding hollow glass beads and an alkali solution into a reaction container protected by nitrogen, heating and stirring the system, carrying out suction filtration and washing on the obtained product to be neutral, then adding ethanol and water, and carrying out ultrasonic dispersion to obtain an HGB-OH dispersion liquid; adding aminopropyltriethoxysilane coupling agent and 4-bromoaniline into HGB-OH dispersion liquid, heating, stirring for reaction, filtering, and vacuum drying the product to obtain HGB-NH2(ii) a At HGB-NH2Adding a dispersant, and performing ultrasonic dispersion to obtain HGB-NH2Adding 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 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 the polyurethane emulsion.
The preparation method of the self-repairing flame-retardant, droplet-resistant and abrasion-resistant polyurethane coating is characterized by comprising the following specific steps of:
(1) adding 10g (HGB abbreviated) of 15-65 micron hollow glass beads and 90mL of aqueous alkali with the mass fraction of 10% into a reaction container protected by nitrogen, raising the temperature of the system to 70-85 ℃, stirring for 2-3h, carrying out suction filtration and washing on the obtained product until the obtained product is neutral, adding 90g of ethanol and 10g of deionized water into the obtained suction filtration product, and carrying out ultrasonic dispersion for 30-40 min to obtain 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 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-NH2(ii) a At HGB-NH2Adding 30mL of dispersant, and performing ultrasonic dispersion to obtain HGB-NH2Adding 15g of isocyanate and 1-2 g of methyl 2-chloroacetoacetate, 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 thickening agent N, N-diethylformamide DEF; cooling to 40 ℃, adding 1.7-2.5 g of triethylamine, and reacting for 0.5h to obtain transparent viscous liquid; cooling to room temperature, adding 75-85 mL of deionized water, 14-16 g of epoxy resin E51, 0.8g of trimethylolpropane trimethacrylate and 1.2g of 3,4' -diaminodiphenyl ether, and stirring to react for 30-60 min to finally obtain the polyurethane emulsion.
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 1000 g/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 (KH550) of 3-aminopropyltriethoxysilane 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 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 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 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 ℃, then adding 1.1-1.4 parts of salicylic acid, then adding 1.1-2.3 parts of semicarbazide, and reacting for 30-90 min 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-NH2And then the 2-chloroacetoacetic acid methyl ester is fully contacted with the isocyanate, so that the absorption or grafting of NCO on the micron-sized hollow glass beads 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 beads, the hollow glass beads can migrate to the surface of a sample from the inside of the coating when HGB-WPU is burnt, so that a fire source is isolated, and the effects of good flame retardance, carbon layer stability enhancement and molten drop phenomenon reduction are achieved.
(3) Phosphoric acid is used as an acid source, pentaerythritol is used as a carbon source, and pentaerythritol phosphate is synthesized through an esterification reaction. Wherein the carbon source is heated to generate carbide to form the basis of a carbon layer; the acid source is heated to decompose, and the resultant can promote the dehydration of organic matters to form carbon. Adding POCl on the basis3An 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 the heat source and the base material is increased, and the mass transfer and heat transfer effects during combustion are reduced, so that the better flame retardant property is achieved, and the synergistic effect of nitrogen and phosphorus is achieved; then adopting boric acid as acidThe source, tetrakis (hydroxymethyl) phosphonium sulfate has both acid source and carbon source, under the catalysis of concentrated sulfuric acid, a cage-shaped compound containing hydroxyl is synthesized, 3-aminopropyltriethoxysilane is adopted to react with the cage-shaped compound containing hydroxyl, silicon base is introduced, the synthesized intermediate B has both cage-shaped rigidity and an ethoxy side chain, 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 reacts with the hydroxyl on boron in heating, the intermediate A and the intermediate B react and are grafted, the product obtained by the reaction is dispersed on sodium lignosulfonate with a polyphenol three-dimensional net-shaped space structure (chemical industry limited company of Shanghai province) which is formed by connecting in forms of C-C bond, C-O-C bond and the like, the obtained product is uniformly dispersed, the butyric anhydride and the unreacted hydroxyl in the obtained product are adopted for ring opening of the butyric anhydride, 2, 4-dihydroxybenzaldehyde is reacted with the hydroxyl obtained by ring opening, carboxyl and aldehyde are introduced into the system, the ethylene diamine tetraacetic acid is adopted for reacting with the hydroxyl of the system, the carboxyl is introduced, the rigidity of the system is also increased, and the 4-carboxyphenylboronic acid, 2-acetoxyisobutyryl chloride and the hydroxyl, the boron and the boron are reacted with the product obtained by the butyric anhydride, the reaction of the 4-carboxylphenylboronic acid and the 2-acetoxy isobutyryl chloride, The amino (imine) reacts to enable the obtained flame retardant to have a large number of hydroxyl groups, carboxyl groups, aldehyde groups and imino groups, so that subsequent flame retardance and self repair are facilitated, meanwhile, the flame retardant system is dispersed in a three-dimensional network structure taking sodium lignosulfonate as a construction system, a compact carbon layer is formed in a flame-retardant construction mode, gas released in the combustion process is coated in the compact carbon layer and is difficult to release in a short time, and a heat insulation effect is achieved.
(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. The epoxy resin and the polyurethane are mutually intertwined to micronize 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 in epoxy resin E51 (Jinan Yun Baihui Biotech Co., Ltd.), the molecular chain of the polyurethane and the molecular chain of the epoxy resin E51 are mutually interlaced, meanwhile, the chain distribution of the polyurethane and the epoxy resin is uniform without being too tight due to the multiple branched chains and 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 part of the polyurethane and the epoxy resin is damaged, meanwhile, the dispersibility of N, N-diethylformamide DEF on polyurethane is poor compared with that of acetone and DMF, and the dispersibility of trimethylolpropane trimethacrylate and 3,4' -diaminodiphenyl ether is improved.
(5) In the film forming process, in order to accelerate the film forming of polyurethane, DEF, toluene and water molecules are required to be capable of volatilizing rapidly or releasing slowly subsequently, and polyethyleneimine is adopted to react with 2-acetoxyisobutyryl chloride. Although polyethyleneimine is a curing agent in the field, the effect is not particularly ideal in the aspect of polyurethane preparation, the imine of polyethyleneimine is adopted to react with the acyl chloride of 2-acetoxy isobutyryl chloride, semicarbazide is added to react with the residual acyl chloride, and the obtained compound reacts with the hydroxyl and carboxyl of polyurethane in the polyurethane film forming process, so that the release of VOC is accelerated. 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.
Preparation example 1
The preparation method of the self-repairing flame-retardant, droplet-resistant and abrasion-resistant polyurethane coating is characterized by comprising the following steps of:
(1) adding into a three-mouth bottle protected by nitrogen10g of 15-micron hollow glass beads (HGB is abbreviated), 90mL of sodium hydroxide solution with the mass fraction of 10%, heating the system to 70 ℃, stirring and reacting for 2h, carrying out suction filtration and water washing on the obtained product to neutrality, adding 90g of ethanol and 10g of deionized water into the obtained suction filtration product, and carrying out ultrasonic dispersion for 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-NH2(ii) a At HGB-NH2Adding 30mL of ethyl acetate, and performing ultrasonic dispersion to obtain HGB-NH2Adding 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 1000g/mol), 9.6g of polytetrahydrofuran ether glycol (molecular weight is 1000g/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 a thickening agent N, N-diethylformamide DEF15 mL; then cooling to 40 ℃, adding 1.7g of triethylamine for reaction for 0.5h to obtain transparent viscous liquid; the temperature is reduced to room temperature, 75mL of deionized water, 14g of epoxy resin E51, 0.8g of trimethylolpropane trimethacrylate and 1.2g of 3,4' -diaminodiphenyl ether are added, and the mixture is stirred and reacted for 30min to finally obtain the polyurethane emulsion.
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 for adjusting 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 comprises the steps of adding 0.2 part of film forming accelerant and 0.1 part of trimethylolpropane into 10 parts of polyurethane emulsion; the materials are uniformly mixed in parts by mass, a solvent is placed on a glass plate to naturally volatilize, a film can be naturally peeled off, and then the test is carried out.
The preparation method of the film forming accelerant comprises the following steps: stirring 6 parts of polyethyleneimine and 8.2 parts of 2-acetoxyisobutyryl chloride for reaction for 1 hour at 50 ℃, adding 1.1 parts of salicylic acid and 1.1 parts of semicarbazide, and reacting for 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 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 ℃, stirring for 3 hours, 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 40min to obtain an HGB-OH dispersion liquid; adding aminopropyl triethoxy into HGB-OH dispersion liquidHeating silane coupling agent 0.2g and 4-bromoaniline 0.1g to 85 ℃, stirring and reacting for 3h, carrying out suction filtration, washing with 15mL 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-NH2(ii) a At HGB-NH2Adding 30mL of butyl acetate, and performing ultrasonic dispersion to obtain HGB-NH2Adding 15g of isophorone diisocyanate and 2g of methyl 2-chloroacetoacetate, heating to 25 ℃, stirring and reacting for 4h to obtain HGB-isophorone diisocyanate dispersion, standing for 12h, filtering and drying to obtain HGB-DI;
(2) adding 9.6g of polypropylene glycol, 9.6g of polytetrahydrofuran ether glycol (the molecular weights of the polypropylene glycol and the polytetrahydrofuran ether glycol are both 1000g/mol) and 11.5g of isophorone diisocyanate into a nitrogen-protected three-neck flask, adding 2g of HGB-DI in the step (1), raising the temperature of the system to 80 ℃, adding 0.24g of dibutyltin dilaurate, stirring for reaction 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 a thickening agent N, N-diethylformamide DEF30 mL; then cooling to 40 ℃, and adding 2.5g of triethylamine for reaction for 0.5h to obtain transparent viscous liquid; cooling to room temperature, adding 85mL of deionized water, adding 16g of epoxy resin E51, 0.8g of trimethylolpropane trimethacrylate and 1.2g of 3,4' -diaminodiphenyl ether, stirring and reacting for 60min to finally obtain the polyurethane emulsion.
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, and stirring at 110 ℃ for reaction for 7 hours to obtain an intermediate B;
(3) taking the flame retardant intermediate A (all) in the step (1), the intermediate B (all) in the step (2) and 8.6g of sodium lignosulfonate, stirring at 70 ℃ for reaction for 2 hours, adding 1.7g of butyric anhydride and 1.2g of 2, 4-dihydroxybenzaldehyde, reacting at 80 ℃ for 3 hours, adding 1.2g of ethylenediamine tetraacetic acid, 0.4g of 4-carboxyphenylboronic acid and 0.4g of 2-acetoxyisobutyryl chloride, and reacting at 80 ℃ for 3 hours to obtain the nitrogen-phosphorus intumescent flame retardant.
Application example two
The application method comprises the steps of adding 0.7 part of film forming accelerant and 0.1 part of trimethylolpropane into 10 parts of polyurethane emulsion prepared in the second embodiment; the materials are uniformly mixed in parts by mass, a solvent is placed on a glass plate to naturally volatilize, a film can be naturally peeled off, and then the test is carried out.
The preparation method of the film forming accelerant comprises the following steps: stirring 6 parts of polyethyleneimine and 9.4 parts of 2-acetoxyisobutyryl chloride 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.
Preparation example three
The preparation method of the self-repairing flame-retardant, droplet-resistant and abrasion-resistant polyurethane coating is characterized by comprising the following steps of:
(1) adding 10g of 40-micron hollow glass beads (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 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-NH2(ii) a At HGB-NH2Adding 30mL of ethyl acetate, and performing ultrasonic dispersion to obtain HGB-NH215g of toluene diisocyanate and 1.5g of methyl 2-chloroacetoacetate were added to the dispersion, and the reaction was stirred at 25 ℃ for reaction 3.Standing for 12h to obtain HGB-isocyanate dispersion liquid, 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 1000g/mol) and 11.5g of isophorone diisocyanate into a nitrogen-protected three-neck flask, adding 2g of HGB-DI in the step (1), raising the temperature of a system to 80 ℃, adding 0.24g of dibutyltin dilaurate, stirring for 2 hours, adding 2.15g of a chain extender 2, 2-dithiodiethanol and 3.7g of a nitrogen-phosphorus intumescent flame retardant into the system, and reacting for 2.5 hours; cooling to 60 ℃, and adding a thickening agent N, N-diethylformamide DEF22 mL; 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, and stirring to react for 45min to finally obtain the polyurethane emulsion.
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 emulsion prepared in the third example, adding 0.35 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 polyurethane emulsion forms a film forming accelerant in film forming, and the preparation method of the film forming accelerant comprises the following steps: 6 parts of polyethyleneimine and 8.7 parts of 2-acetoxyisobutyryl chloride are stirred and reacted for 1.5 hours at the temperature of 55 ℃, 1.25 parts of salicylic acid and 1.7 parts of semicarbazide are added, and the reaction is carried out for 60 minutes at the temperature of 60 ℃ to obtain the film forming promoter.
Preparation example four
The preparation method of the self-repairing flame-retardant, droplet-resistant and abrasion-resistant polyurethane coating is characterized by comprising the following steps of:
(1) adding 10g of 15-micrometer hollow glass beads (HGB abbreviated as follows) and 90mL of potassium hydroxide solution with the mass fraction of 10% into a three-necked flask under the protection of nitrogen, heating the system to 85 ℃, stirring for 3 hours, carrying out suction filtration and washing on the obtained product until the product is neutral, adding 90g of ethanol and 10g of deionized water into the obtained suction filtration product, and carrying out ultrasonic dispersion for 40min to obtain HGB-OH dispersion liquid; adding 0.1g of 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-NH2(ii) a At HGB-NH2Adding 30mL of butyl acetate, and performing ultrasonic dispersion to obtain HGB-NH2Adding 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 into a reaction vessel protected by nitrogen, adding 2g of HGB-DI in the step (1), raising the temperature of a system to 80 ℃, adding 0.24g of dibutyltin dilaurate, stirring for 2 hours, adding 1.0g of chain extender 2, 2-dithiodiethanol and 4.0g of nitrogen-phosphorus intumescent flame retardant into the system, and reacting for 2.5 hours; cooling to 60 ℃, and adding 20mL of a thickening agent N, N-diethylformamide DEF; cooling to 40 ℃, adding 2g of triethylamine, and reacting for 0.5h to obtain transparent viscous liquid; the temperature is reduced to room temperature, 75mL of deionized water, 14g of epoxy resin E51, 0.8g of trimethylolpropane trimethacrylate and 1.2g of 3,4' -diaminodiphenyl ether are added, and the mixture is stirred and reacted for 40min to finally obtain the polyurethane emulsion.
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, 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 5.3g 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 emulsion prepared in example four, and 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 emulsion comprises the following steps: 6 parts of polyethyleneimine and 8.5 parts of 2-acetoxyisobutyryl chloride are stirred and reacted for 1 hour at 50 ℃, 1.3 parts of salicylic acid and 1.6 parts of semicarbazide are added, and the reaction is carried out for 60 minutes at 50 ℃ to obtain the film forming promoter.
Preparation example five
The preparation method of the self-repairing flame-retardant, droplet-resistant and abrasion-resistant polyurethane coating is characterized by comprising the following steps of:
(1) adding 10g of 65-micrometer hollow glass microspheres (HGB is abbreviated as follows) and 90mL of sodium hydroxide solution with the mass fraction of 10% into a three-neck flask under the protection of nitrogen, heating the system to 80 ℃, stirring for 3 hours, carrying out suction filtration and washing on the obtained product until the product is neutral, adding 90g of ethanol and 10g of deionized water into the obtained suction filtration product, and carrying out ultrasonic dispersion for 35min to obtain HGB-OH dispersion liquid; adding 0.1g of 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-NH2(ii) a At HGB-NH2Adding 30mL of ethyl acetate, and performing ultrasonic dispersion to obtain HGB-NH2Adding 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 into a nitrogen-protected three-neck flask, adding 2g of HGB-DI in the step (1), raising the temperature of a system to 80 ℃, adding 0.24g of dibutyltin dilaurate, stirring for 2h, 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 h; cooling to 70 ℃, and adding a thickening agent N, N-diethylformamide DEF30 mL; then cooling to 40 ℃, adding 2.5g of triethylamine, and reacting for 0.5h to obtain transparent viscous liquid; the temperature is reduced to room temperature, 75mL of deionized water, 14g of epoxy resin E51, 0.8g of trimethylolpropane trimethacrylate and 1.2g of 3,4' -diaminodiphenyl ether are added, and the mixture is stirred and reacted for 60min to finally obtain the polyurethane emulsion.
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) and (2) taking the flame retardant intermediate A (all) in the step (1), the intermediate B (all) in the step (2) and 5.7g of sodium lignosulfonate, stirring at 70 ℃ for reaction for 2 hours, adding 1.7g of butyric anhydride and 0.7g of 2, 4-dihydroxybenzaldehyde, reacting at 75 ℃ for 2 hours, adding 0.9g of ethylenediamine tetraacetic acid, 0.25g of 4-carboxyphenylboronic acid and 0.15g of 2-acetoxyisobutyryl chloride, and reacting at 70 ℃ for 2.5 hours to obtain the nitrogen-phosphorus intumescent flame retardant.
Application example five
Taking 10 parts of polyurethane emulsion prepared in the fifth embodiment, 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 rate and the expansion height are referred to 2019106431795 test standards.
GB/T5455-1997 textile burning performance test the flame burning time (afterflame time) of a film formed by the polyurethane coating is measured by a vertical method, the length of the sample is 20cm multiplied by 10cm, and the thickness is 1 mm.
The VOC determination method comprises the following steps: the metal plate was baked in an oven at 105. + -. 2 ℃ for 30min and then placed in a desiccator until use. After mixing, the polyurethane was spread on a metal flat-bottomed dish, placed at a temperature of 23 + -2 deg.C and a humidity of 50 + -5% for 24 hours, and then baked in an oven at 105 + -2 deg.C for 60 minutes, and two tests were performed in parallel. Weighing m before heating1(Metal Container m)0And sum of mass of reactants) and mass m after heating2(see 201710902448.6);
the phenomenon of dripping was observed by the naked eye.
Self-repairing flame-retardant test: the self-repairing of the 1-cut sample is 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 to be 0.05cm, a 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 50 times of abrasion resistance according to GB/T22374-2018 and 100g/100r without changing the others, and testing after baking for 5 hours at 80 ℃ (oven) to achieve the repairing effect.
TABLE 1 film Forming Performance index for polyurethane coatings
Figure BDA0003392758010000181
Figure BDA0003392758010000191
Comparative example (202011624359.8 comparison of flame combustion time of preparation 1), from the above data, it can be found that, although the invention is equivalent to the index of the comparative example in terms of droplet dropping, the invention is superior to the comparative example in terms of flame combustion time, VOC and abrasion resistance, because compared with 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, so that the gas is difficult to release in a short time, plays a role of heat insulation, reduces the flame combustion, and simultaneously, the abrasion resistance and the VOC are effectively sealed, and the performance is superior to the comparative example.
TABLE 2 Performance index of the nitrogen phosphorus intumescent flame retardant
Figure BDA0003392758010000192
The nitrogen-phosphorus intumescent flame retardant is prepared by comparing the data of 202011624359.8 in the fourth preparation example, 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 amount of hydroxyl, carboxyl, aldehyde and imino, 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 conveniently constructed in a flame-retardant manner, gas released in the combustion process is coated in the compact carbon layer and is difficult to release in a short time, and a heat insulation effect is achieved, meanwhile, the fire retardant adopts the synergistic effect of nitrogen, phosphorus, silicon and boron, exerts the advantages of high expansion rate and high residual carbon rate which are difficult to achieve by the existing intumescent nitrogen-phosphorus fire retardant, and has obvious advantages compared with a comparison sample.
TABLE 3 flame retardant Properties of the materials not added (preparation example five)
Figure BDA0003392758010000201
It can be found from table 3 that, taking preparation example five 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, which shows that the above substances all play a role in an expansion system, wherein the sodium lignosulfonate has the greatest influence on the properties of the intumescent flame retardant, because the sodium lignosulfonate is used as a main skeleton for constructing a three-dimensional network flame retardant system, a compact carbon layer is formed in a flame retardant structure, and 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 materials are added, other materials are added)
TABLE 4 Properties of polyurethane film obtained without addition of part of chemical materials (preparation example II)
Figure BDA0003392758010000202
Figure BDA0003392758010000211
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 BDA0003392758010000212
In the comparative example (202011624359.8 comparison between the flaming combustion time and the molten droplets in preparation example four), it was found that, when repairing was performed, the flaming combustion time and the molten droplets were decreased relatively little, and the extent of decrease was large when no repairing was performed.
TABLE 6 flame retardant self-healing capability characterization of polyurethane coatings (after abrasion resistance)
Figure BDA0003392758010000221
From Table 6, it can be seen that the flame burning time is remarkably prolonged without performing the abrasion repair, and a large amount of molten droplets are generated. COMPARATIVE EXAMPLE (preparation example four of 202011624359.8)
TABLE 7 characterization of the flame retardant self-healing capability of the polyurethane coatings (without chemical materials, abrasion)
Figure BDA0003392758010000222
Figure BDA0003392758010000231
From Table 7, it can be found that the flame burn time (abrasion) of the film without the addition of trimethylolpropane trimethacrylate, 3,4' -diaminodiphenyl ether and epoxy resin E51 is remarkably prolonged, showing that the above substances exert a remarkable effect therein and the flame burn time for abrasion repair can be shortened.

Claims (9)

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-NH2(ii) a At HGB-NH2Adding a dispersant, and performing ultrasonic dispersion to obtain HGB-NH2Adding 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 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 the polyurethane emulsion.
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 (HGB abbreviated) of 15-65 micron hollow glass beads and 90mL of aqueous alkali with the mass fraction of 10% into a reaction container protected by nitrogen, raising the temperature of the system to 70-85 ℃, stirring for 2-3h, carrying out suction filtration and washing on the obtained product until the obtained product is neutral, adding 90g of ethanol and 10g of deionized water into the obtained suction filtration product, and carrying out ultrasonic dispersion for 30-40 min to obtain 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 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-NH2(ii) a At HGB-NH2Adding 30mL of dispersant, and performing ultrasonic dispersion to obtain HGB-NH2Adding 15g of isocyanate and 1-2 g of methyl 2-chloroacetoacetate, 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 thickening agent N, N-diethylformamide DEF; cooling to 40 ℃, adding 1.7-2.5 g of triethylamine, and reacting for 0.5h to obtain transparent viscous liquid; cooling to room temperature, adding 75-85 mL of deionized water, 14-16 g of epoxy resin E51, 0.8g of trimethylolpropane trimethacrylate and 1.2g of 3,4' -diaminodiphenyl ether, and stirring to react for 30-60 min to finally obtain the polyurethane emulsion.
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, wherein the dispersing agent is any one of ethyl acetate and butyl acetate.
5. The method for preparing the self-repairing flame-retardant, droplet-resistant and abrasion-resistant polyurethane coating according to claim 1 or 2, wherein the molecular weights of the polypropylene glycol and the polytetrahydrofuran ether glycol are both 1000 g/mol.
6. The method for preparing the self-repairing flame-retardant, droplet-resistant, abrasion-resistant polyurethane coating according to claim 1 or 2, characterized in that the isocyanate is any one of 4, 4' -diphenylmethane diisocyanate, isophorone diisocyanate, and toluene diisocyanate.
7. 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 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 (KH550) of 3-aminopropyltriethoxysilane 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 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 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 70-80 ℃ to obtain the nitrogen-phosphorus intumescent flame retardant.
8. 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 7 is as follows: 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.
9. The method of use according to claim 8, wherein the film forming promoter is prepared by: stirring 6 parts of polyethyleneimine and 8.2-9.4 parts of 2-acetoxyisobutyryl chloride for reaction for 1-2 hours at 50-60 ℃, then adding 1.1-1.4 parts of salicylic acid, then adding 1.1-2.3 parts of semicarbazide, and reacting for 30-90 min at 50-70 ℃ to obtain a film forming promoter; the parts are parts by mass.
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Denomination of invention: Preparation and application methods of self-healing flame retardant, droplet resistant, and wear-resistant polyurethane coatings

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Denomination of invention: Preparation and application methods of self-healing flame retardant, droplet resistant, and wear-resistant polyurethane coatings

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Assignee: Jiangmen hongchuangxin Material Co.,Ltd.

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Denomination of invention: Preparation and application methods of self-healing flame retardant, droplet resistant, and wear-resistant polyurethane coatings

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Denomination of invention: Preparation and application methods of self-healing flame retardant, droplet resistant, and wear-resistant polyurethane coatings

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Inventor after: Duan Baorong

Inventor after: Weng Yonggen

Inventor after: Feng Lianxiang

Inventor after: Li Guorong

Inventor after: Wang Qiyan

Inventor after: Yu Han

Inventor after: Hu Lecheng

Inventor after: Wang Quanjie

Inventor after: Tang Zhihai

Inventor before: Duan Baorong

Inventor before: Li Guorong

Inventor before: Tang Zhihai

Inventor before: Weng Yonggen

Inventor before: Feng Lianxiang

Inventor before: Yu Han

Inventor before: Wang Quanjie

Inventor before: Wang Qiyan

Inventor before: Hu Lecheng