CN115340628A - Preparation method and application of water-based fireproof wood paint - Google Patents

Preparation method and application of water-based fireproof wood paint Download PDF

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CN115340628A
CN115340628A CN202211165803.3A CN202211165803A CN115340628A CN 115340628 A CN115340628 A CN 115340628A CN 202211165803 A CN202211165803 A CN 202211165803A CN 115340628 A CN115340628 A CN 115340628A
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triazine
acrylate
water
thiourea
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CN115340628B (en
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陈勇
容七英
容月新
罗春平
彭向阳
章鸿
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Jiangxi Longzheng Technology Development Co Ltd
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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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
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/02—Homopolymers or copolymers of monomers containing phosphorus
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints

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Abstract

The invention relates to the technical field of fireproof wood lacquer, and discloses a preparation method and application of a water-based fireproof wood lacquer coating, wherein 2-ethanolamine-s-triazine and 4-aldehydic phenylimine thiourea are subjected to Schiff base reaction, and then are sequentially subjected to Schiff base reaction with acryloyl chloride and 5,5-dimethyl-1,3,2-dioxy heterocyclic already-available acyl chloride to synthesize a novel 2-acrylate ethylamine-4,6 (phenylimine phosphorylthiourea) -s-triazine reactive flame retardant, and the flame retardant is polymerized with monomers such as n-butyl acrylate and the like to obtain the water-based fireproof wood lacquer coating, so that a nitrogen-phosphorus synergistic flame-retardant structure containing phosphoramide and triazine and a flame-retardant thiourea structure are chemically bonded into an acrylic resin molecular chain, the flame-retardant and fireproof performance of the acrylic resin wood lacquer are endowed, and the development and application of the acrylic resin wood lacquer in the aspects of wood household articles, building materials, ancient building wood structure protection and the like are expanded.

Description

Preparation method and application of water-based fireproof wood paint
Technical Field
The invention relates to the technical field of fireproof wood lacquer, in particular to a water-based fireproof wood lacquer coating and a preparation method thereof.
Background
The water-based acrylic resin has the advantages of excellent mechanical property, good color and gloss retention, high solvent resistance and the like, can be used as wood lacquer, adhesive and anticorrosive coating, and has important application in the aspects of building materials, historic building wood structure protection and the like, the traditional acrylic resin has low fire resistance and flame retardant property, and the development and application of the acrylic resin in the aspects of wood lacquer and the like are hindered, so that the water-based acrylic resin wood lacquer needs to be subjected to flame retardant modification, and the addition of the flame retardant is the most effective method.
The reactive flame retardant is used as a polymerization monomer, participates in the polymerization reaction process, can enhance the long-acting flame retardance of a high polymer material, and has smaller influence on the service performance of the material, for example, chinese patent CN109810216A, a flame-retardant waterborne acrylic resin and a preparation method thereof, discloses a flame-retardant waterborne acrylic resin prepared by a phosphorus-containing vinyl flame-retardant monomer and an acrylate monomer through an emulsion polymerization method, has good flame retardance, solves the problems of dispersibility and compatibility of an additive flame retardant in the acrylic resin, and aims to synthesize a novel acrylate-based phosphoryl thiourea-based triazine flame retardant which is polymerized with the acrylate monomer to obtain the waterborne fireproof wood lacquer coating.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a water-based acrylic resin fireproof wood paint, which solves the problems of poor fire resistance and flame retardance of the water-based acrylic resin wood paint.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: the preparation method of the water-based fireproof wood paint comprises the following steps:
s1, adding 2-ethanolamine-S-triazine and 4-aldehydic thiosemicarbazide into an ethanol solvent, dropwise adding glacial acetic acid, reacting after stirring, neutralizing, distilling under reduced pressure, extracting, washing and recrystallizing to obtain 2-ethanolamine-4,6 (thiosemicarbazide) -S-triazine;
s2, adding 2-ethanolamine-4,6 (phenylimine thiourea) -S-triazine, acryloyl chloride and triethylamine into a dichloromethane solvent according to the mass molar ratio of 1.4-1, stirring for reaction, concentrating under reduced pressure, washing, and recrystallizing to obtain 2-acrylate ethylamine-4,6 (phenylimine thiourea) -S-triazine;
s3, adding 2-acrylate ethylamine-4,6 (phenylimidothiourea) -S-triazine and 5,5-dimethyl-1,3,2-dioxaphosphorinane internal acyl chloride into an N, N-dimethylformamide solvent under ice bath, then reacting at 15-35 ℃ for 12-24 h, and extracting, washing and recrystallizing after reaction to obtain 2-acrylate ethylamine-4,6 (phenylimido phosphorylthiourea) -S-triazine;
s4, adding an acrylate monomer, 2-acrylate ethylamine-4,6 (phenylimido phosphorylthiourea) -S-triazine, sodium dodecyl sulfate and OP-10 into deionized water, wherein the acrylate monomer comprises methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, acrylic acid, methacrylic acid and hydroxyethyl acrylate, and uniformly stirring to prepare a pre-polymerization monomer solution;
s5: dropping initiator potassium persulfate or ammonium persulfate into 30-40% volume of pre-polymerization monomer solution, reacting for 20-60 min at 60-75 ℃ in nitrogen atmosphere, then adding the rest pre-polymerization monomer solution, and supplementing initiator, wherein the total dosage of the initiator is 0.5-1% of the total mass of the acrylate monomer, continuing reacting for 2-5 h, cooling after reaction, adding defoamer accounting for 0.2-0.8% of the total mass of the acrylate monomer, wetting dispersant accounting for 0.2-1%, and flatting agent accounting for 0.1-0.6%, and shearing and emulsifying at high speed to obtain the water-based fireproof wood lacquer coating.
Preferably, the molar ratio of the 2-ethanolamine-S-triazine and the 4-aldehyde phenylimine thiourea in the S1 is 1:1-1.4.
Preferably, the amount of the glacial acetic acid in the S1 is 2-4% of the total mass of the reactants.
Preferably, the reaction in S2 is carried out at 15-30 ℃ for 3-8 h.
Preferably, the molar ratio of the 2-acrylate ethylamine-4,6 (phenylimine thiourea) -S-triazine, 5,5-dimethyl-1,3,2-dioxaphosphorinane chloride in S3 is 1:2-2.8.
Preferably, the dosage of the 2-acrylate ethylamine-4,6 (phenylimido phosphorylthiourea) -S-triazine in the S4 is 1-8% of the total mass of the acrylate monomer.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
2-ethanolamine-s-triazine and 4-aldehydic benzene imine thiourea are subjected to Schiff base reaction to synthesize 2-ethanolamine-4,6 (benzene imine thiourea) -s-triazine, and then are subjected to esterification reaction with acryloyl chloride in sequence and are subjected to phosphonamidation reaction with 5,5-dimethyl-1,3,2-dioxy heterocyclic chloride, so that a novel 2-acrylate ethylamine-4,6 (benzene imine phosphorylthiourea) -s-triazine reactive flame retardant is synthesized, and is polymerized with monomers such as n-butyl acrylate to obtain the water-based fireproof wood lacquer coating, so that a nitrogen-phosphorus synergistic flame-retardant structure containing phosphoramide and triazine and a flame-retardant thiourea structure are chemically bonded into an acrylic resin molecular chain, the problems of poor dispersibility and compatibility of the flame retardant and an acrylic resin matrix are avoided, the flame-retardant and fireproof performances of the acrylic resin lacquer are endowed, the limit oxygen index is improved, the peak value of the flame release rate during combustion is reduced, and the heat release PHRR of the acrylic resin lacquer is expanded in the aspects of wood lacquer, building materials and household wood structures and ancient wood materials are developed.
Drawings
FIG. 1 is a reaction scheme for the preparation of 2-propenoic acid ester ethylamine-4,6 (benzimidophosphorylthiourea) -s-triazine.
FIG. 2 is a FT-IR spectrum of the aqueous flameproof acrylic resin prepared in example 1.
FIG. 3 is a PHRR curve for an aqueous fire-retardant wood paint coating.
FIG. 4 is an oxygen index test of an aqueous fire-retardant wood paint coat.
Detailed Description
2-Ethanolamine-s-triazine, journal of the American Chemical society, rearrangement Reactions of 1-azidinyl-s-triazines, dihydramidozo [1,2-a ] -s-triazines, 1955, vol.77, P.5922-5928:
adding 0.28 g of 2-chloro-s-triazine and 0.14 g of ethanolamine into tetrahydrofuran, dropwise adding a 15% sodium hydroxide aqueous solution, reacting at 70 ℃ for 6 h, dropwise adding dilute hydrochloric acid for neutralization after reaction, distilling under reduced pressure to remove tetrahydrofuran, then adding dichloromethane and deionized water for extraction, adding anhydrous sodium sulfate into a dichloromethane organic layer for drying and dewatering, filtering and collecting filtrate, distilling under reduced pressure, and washing a petroleum ether washing product to obtain the 2-ethanolamine-s-triazine.
Preparation of 4-aldehyde-based phthalimide thiourea reference journal, bioorganic Chemistry, synthesis of 4-thiozolidinone Analogs as force in Vitro Anti-urea Agents 2015, vol.63, p.123-131: 0.13 g of terephthalaldehyde and 0.09 g of thiosemicarbazide are added into an ethanol solvent, 3 mL of hydrochloric acid solution is dropwise added, and heating reflux reaction is carried out on 4 h to obtain 4-aldehyde phenylimine thiourea.
To achieve the above object, the present invention provides the following embodiments:
example 1
S1, adding 0.5 g of 2-ethanolamine-S-triazine and 0.68 g of 4-aldehyde-benzene imine thiourea into 15mL of ethanol solvent, dropwise adding 0.025 g of glacial acetic acid, stirring for reaction, dropwise adding sodium hydroxide for neutralization after reaction, distilling under reduced pressure to remove ethanol, adding dichloromethane and deionized water for extraction, and carrying out dichloromethane extraction on dichloromethane and deionized waterAdding anhydrous sodium sulfate into the alkane organic layer, drying for removing water, filtering, collecting filtrate, distilling under reduced pressure, washing the product with acetone, adding the product into dichloromethane for recrystallization to obtain 2-ethanolamine-4,6 (phenylimidothiourea) -s-triazine,
Figure DEST_PATH_IMAGE001
；1H NMR (CDCl 3 , 300 MHz) δ: 8.78-8.52(m, 2H)，8.47-8.12 (m, 6H)，8.03-7.47 (m, 8H)，4.13-4.02 (m, 1H)，3.65-3.52 (m, 4H)，3.43 (s, 1H)，1.92-1.86(m, 2H)。
s2, adding 2-ethanolamine-4,6 (phenylimine thiourea) -S-triazine of 2 g, acryloyl chloride of 0.32 g and triethylamine of 0.3 g into a dichloromethane solvent of 20 mL, reacting 8 h at 15 ℃, stirring, concentrating under reduced pressure after reaction, washing a product with acetone, adding the product into ethyl acetate for recrystallization to obtain 2-acrylic ester ethylamine-4,6 (phenylimine thiourea) -S-triazine,
Figure 143841DEST_PATH_IMAGE002
，1H NMR (CDCl 3 , 300 MHz) δ: 8.92-8.61(m, 2H)，8.53-8.11 (m, 6H)，8.02-7.37 (m, 8H)，6.33-6.28 (m, 1H)，6.17-6.08 (m, 1H)，5.53-5.48 (m, 1H)，4.63-4.50 (m, 2H)，4.17-4.10 (m, 1H)，3.47-3.40 (m, 2H)，1.98-1.87(m, 2H)。
s3, adding 1 g 2-acrylate ethylamine-4,6 (phenylimidothiourea) -S-triazine and 0.62 5,5-dimethyl-1,3,2-dioxaphosphorinane internal acyl chloride into 15mL N, N-dimethylformamide solvent under ice bath, then reacting at 25 ℃ for 24 h, adding ethyl acetate and deionized water for extraction after the reaction, adding anhydrous sodium sulfate into an ethyl acetate organic layer for drying and removing water, filtering and collecting filtrate, carrying out reduced pressure distillation and acetone washing products, then adding the products into ethyl acetate for recrystallization to obtain 2-acrylate ethylamine-4,6 (phenylimidothioureido) -S-triazine,
Figure DEST_PATH_IMAGE003
，1H NMR (CDCl 3 , 300 MHz) δ: 8.90-8.64(m, 2H)，8.60-8.40 (m, 2H)，8.12-7.43 (m, 8H)，6.30-6.26 (m, 1H)，6.15-6.07 (m, 1H)，5.54-5.46 (m, 1H)，4.67-4.51 (m, 2H)，4.39-4.17 (m, 8H)，4.16-4.11 (m, 1H)，3.49-3.40 (m, 2H)，3.49-3.40 (m, 2H)，2.08-1.99(m, 2H)，1.08(s, 12H)。
s4, adding 2.5 g methyl acrylate, 10 g n-butyl methacrylate, 0.8 g methacrylic acid, 1.2 g hydroxyethyl acrylate, 0.5 g 2-acrylate ethylamine-4,6 (phenylimido phosphorylthiourea) -S-triazine, 0.2 g sodium dodecyl sulfate, 0.2 g OP-10 into deionized water, wherein the acrylate monomers comprise, are uniformly stirred to prepare a prepolymer monomer solution;
s5: dropwise adding ammonium persulfate of an initiator 0.03 g into a 35% volume prepolymerization monomer solution, heating to 75 ℃ in a nitrogen atmosphere for reaction for 30 min, then adding the rest prepolymerization monomer solution, supplementing ammonium persulfate of 0.06 g, continuing to react for 4 h, cooling after reaction to obtain aqueous fireproof acrylic resin, then adding an antifoaming agent STA-6300 of 0.04 g, a wetting dispersant BYK-190 of 0.04 g and a leveling agent BYK-333 of 0.05 g in the total mass of acrylate monomers, and carrying out high-speed shearing emulsification to obtain the aqueous fireproof wood lacquer coating.
Example 2
S1, adding 0.5-g 2-ethanolamine-S-triazine and 0.85 g 4-aldehydine thiourea into 20 mL ethanol solvent, dropwise adding 0.03 g glacial acetic acid, stirring for reaction, dropwise adding sodium hydroxide for neutralization, distilling under reduced pressure to remove ethanol, adding dichloromethane and deionized water for extraction, adding anhydrous sodium sulfate into a dichloromethane organic layer, drying for water removal, filtering, collecting filtrate, distilling under reduced pressure, washing products with acetone, and then adding the products into dichloromethane for recrystallization to obtain 2-ethanolamine-4,6 (phenylimine thiourea) -S-triazine.
S2, adding 2-ethanolamine-4,6 (phenylimine thiourea) -S-triazine of 2 g, acryloyl chloride of 0.32 g and triethylamine of 0.18 g into a dichloromethane solvent of 20 mL, reacting at 30 ℃ for 3 h, concentrating under reduced pressure after stirring reaction, washing a product with acetone, adding the product into ethyl acetate, and recrystallizing to obtain 2-acrylic ester ethylamine-4,6 (phenylimine thiourea) -S-triazine.
S3, adding 2-acrylate ethylamine-4,6 (phenylimidothiourea) -S-triazine of 1 g and 5,5-dimethyl-1,3,2-dioxaphosphorinane of 0.85 g into N, N-dimethylformamide solvent of 10 mL under ice bath, then reacting at 35 ℃ for 18 h, adding ethyl acetate and deionized water for extraction after reaction, adding anhydrous sodium sulfate into an ethyl acetate organic layer, drying and removing water, filtering and collecting filtrate, carrying out reduced pressure distillation and acetone washing on a product, then adding the product into ethyl acetate for recrystallization, and obtaining 2-acrylate ethylamine-4,6 (phenylimidothiophosphoryl thiourea) -S-triazine.
S4, adding 2.8 g methyl methacrylate, 10 g n-butyl methacrylate, 1 g acrylic acid, 1.6 g hydroxyethyl acrylate, 0.7 g 2-acrylate ethylamine-4,6 (phenylimido phosphorylthiourea) -S-triazine, 0.15 g sodium dodecyl sulfate, and 0.25 g OP-10 into deionized water, wherein the acrylate monomers comprise a prepolymer monomer solution which is uniformly stirred;
s5: dropwise adding potassium persulfate of an initiator 0.04 g into a 30% volume of prepolymer monomer solution, heating to 70 ℃ in a nitrogen atmosphere for reaction for 20 min, then adding the rest prepolymer monomer solution, supplementing potassium persulfate of 0.06 g, continuing to react for 4 h, cooling after reaction, adding an antifoaming agent STA-6300 of 0.08 g, a wetting dispersant BYK-190 of 0.06 g, a leveling agent BYK-333 of 0.02 g based on the total mass of acrylate monomers, and carrying out high-speed shearing emulsification to obtain the water-based fireproof wood lacquer coating.
Example 3
S1, adding 0.5-g 2-ethanolamine-S-triazine and 0.6 g 4-aldehydine thiourea into 20 mL ethanol solvent, dropwise adding 0.03 g glacial acetic acid, stirring for reaction, dropwise adding sodium hydroxide for neutralization, distilling under reduced pressure to remove ethanol, adding dichloromethane and deionized water for extraction, adding anhydrous sodium sulfate into a dichloromethane organic layer, drying for water removal, filtering, collecting filtrate, distilling under reduced pressure, washing products with acetone, and then adding the products into dichloromethane for recrystallization to obtain 2-ethanolamine-4,6 (phenylimine thiourea) -S-triazine.
S2, adding 2-ethanolamine-4,6 (phenylimine thiourea) -S-triazine of 2 g, acryloyl chloride of 0.32 g and triethylamine of 0.28 g into a dichloromethane solvent of 20 mL, reacting at 15 ℃ for 6 h, concentrating under reduced pressure after stirring reaction, washing a product with acetone, adding the product into ethyl acetate, and recrystallizing to obtain 2-acrylic ester ethylamine-4,6 (phenylimine thiourea) -S-triazine.
S3, adding 2-acrylate ethylamine-4,6 (phenylimidothiourea) -S-triazine of 1 g and 5,5-dimethyl-1,3,2-dioxaphosphorinane lactam of 0.68 g into an N, N-dimethylformamide solvent of 15mL under an ice bath, then reacting at 15 ℃ for 24 h, adding ethyl acetate and deionized water for extraction after the reaction, adding anhydrous sodium sulfate into an ethyl acetate organic layer for drying and removing water, filtering and collecting filtrate, carrying out reduced pressure distillation and acetone washing on a product, then adding the product into ethyl acetate for recrystallization, and obtaining 2-acrylate ethylamine-4,6 (phenylimidothiophosphoryl thiourea) -S-triazine.
S4, adding 2 g methyl acrylate, 10 g n-butyl methacrylate, 1.5 g methacrylic acid, 1.2 g hydroxyethyl acrylate, 0.8 g 2-acrylate ethylamine-4,6 (phenylimido phosphorylthiourea) -S-triazine, 0.15 g sodium dodecyl sulfate, and 0.3 g OP-10 into deionized water, wherein the acrylate monomers comprise a prepolymer monomer solution which is uniformly stirred;
s5: dropwise adding ammonium persulfate of an initiator 0.04 g into a 40% volume prepolymerization monomer solution, heating to 60 ℃ in a nitrogen atmosphere for reaction for 60 min, then adding the rest prepolymerization monomer solution, supplementing ammonium persulfate of 0.09 g, continuing to react for 2 h, cooling after reaction, adding a defoaming agent STA-6300 of 0.04 g, a wetting dispersant BYK-190 of 0.05 g and a leveling agent BYK-333 of 0.02 g in the total mass of the acrylate monomers, and performing high-speed shearing and emulsification to obtain the water-based fireproof wood lacquer coating.
Comparative example 1
S1, adding 0.5 g of 2-ethanolamine-S-triazine and 0.8 g of 4-aldehyde-benzene imine thiourea into 20 mL of ethanol solvent, dropwise adding 0.025 g of glacial acetic acid, stirring for reaction, dropwise adding sodium hydroxide for neutralization after reaction, distilling under reduced pressure to remove ethanol, then adding dichloromethane and deionized water for extraction, adding anhydrous sodium sulfate into a dichloromethane organic layer, drying for water removal, filtering, collecting filtrate, distilling under reduced pressure, washing products with acetone, and then adding the products into dichloromethane for recrystallization to obtain 2-ethanolamine-4,6 (benzene imine thiourea) -S-triazine.
S2, adding 2-ethanolamine-4,6 (phenylimine thiourea) -S-triazine of 2 g, acryloyl chloride of 0.32 g and triethylamine of 0.3 g into a dichloromethane solvent of 40 mL, reacting 8 h at 15 ℃, stirring, concentrating under reduced pressure after reaction, washing a product with acetone, adding the product into ethyl acetate, and recrystallizing to obtain 2-acrylic ester ethylamine-4,6 (phenylimine thiourea) -S-triazine.
S3, adding 3 g methyl acrylate, 10 g n-butyl acrylate, 0.6 g methacrylic acid, 1 g hydroxyethyl acrylate, 0.2 g 2-acrylate ethylamine-4,6 (phenyliminothiourea) -S-triazine, 0.2 g sodium dodecyl sulfate, and 0.2 g OP-10 into deionized water, wherein the acrylate monomers comprise, and are uniformly stirred to prepare a prepolymer monomer solution;
s4: dropwise adding potassium persulfate of an initiator 0.03 g into a prepolymerization monomer solution with the volume of 40%, heating to 60 ℃ in a nitrogen atmosphere for reaction for 60 min, then adding the rest prepolymerization monomer solution, supplementing potassium persulfate of 0.08 g, continuing to react for 2 h, cooling after reaction, adding an antifoaming agent STA-6300 of 0.05 g, a wetting dispersant BYK-190 of 0.04 g and a leveling agent STA-3534-333 of 0.06 g in the total mass of the acrylic ester monomers, and carrying out high-speed shearing and emulsification to obtain the water-based wood paint coating.
The water-based fireproof wood paint is cured to form a glue film, a sample of 3 cm X3 cm X0.2 cm is prepared, and the combustion performance is tested in a cone calorimeter.
The water-based fireproof woodenware paint curing adhesive film is prepared into a sample of 5 cm X2 cm X0.2 cm, and the limited oxygen index is tested in an oxygen index tester.

Claims (6)

1. A preparation method of a water-based fireproof wood paint is characterized by comprising the following steps: the preparation method comprises the following steps:
s1, adding 2-ethanolamine-S-triazine and 4-aldehydic thiosemicarbazide into an ethanol solvent, dropwise adding glacial acetic acid, reacting after stirring, neutralizing, distilling under reduced pressure, extracting, washing and recrystallizing to obtain 2-ethanolamine-4,6 (thiosemicarbazide) -S-triazine;
s2, adding 2-ethanolamine-4,6 (phenylimine thiourea) -S-triazine, acryloyl chloride and triethylamine into a dichloromethane solvent according to the mass molar ratio of 1.4-1, stirring for reaction, concentrating under reduced pressure, washing, and recrystallizing to obtain 2-acrylate ethylamine-4,6 (phenylimine thiourea) -S-triazine;
s3, adding 2-acrylate ethylamine-4,6 (phenylimidothiourea) -S-triazine and 5,5-dimethyl-1,3,2-dioxaphosphacycle lactoyl chloride into an N, N-dimethylformamide solvent under ice bath, then reacting at 15-35 ℃ for 12-24 h, and extracting, washing and recrystallizing after reaction to obtain 2-acrylate ethylamine-4,6 (phenylimidothiophosphoryl) -S-triazine;
s4, adding an acrylate monomer, 2-acrylate ethylamine-4,6 (phenylimidophosphorylthiourea) -S-triazine, sodium dodecyl sulfate and OP-10 into deionized water, wherein the acrylate monomer comprises methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, acrylic acid, methacrylic acid and hydroxyethyl acrylate, and uniformly stirring to prepare a pre-polymerization monomer solution;
s5: dropping initiator potassium persulfate or ammonium persulfate into 30-40% volume of pre-polymerization monomer solution, reacting for 20-60 min at 60-75 ℃ in nitrogen atmosphere, then adding the rest pre-polymerization monomer solution, and supplementing initiator, wherein the total dosage of the initiator is 0.5-1% of the total mass of the acrylate monomer, continuing reacting for 2-5 h, cooling after reaction, adding defoamer accounting for 0.2-0.8% of the total mass of the acrylate monomer, wetting dispersant accounting for 0.2-1%, and flatting agent accounting for 0.1-0.6%, and shearing and emulsifying at high speed to obtain the water-based fireproof wood lacquer coating.
2. The preparation method of the water-based fireproof wood paint coating according to claim 1, characterized in that: the mass molar ratio of the 2-ethanolamine-S-triazine and the 4-aldehyde phenylimine thiourea in the S1 is 1:1-1.4.
3. The preparation method of the water-based fireproof wood paint coating according to claim 1, characterized in that: the dosage of the glacial acetic acid in the S1 is 2-4% of the total mass of the reactants.
4. The preparation method of the water-based fireproof wood paint coating according to claim 1, characterized in that: the reaction in S2 is carried out at 15-30 ℃ for 3-8 h.
5. The preparation method of the water-based fireproof wood paint coating according to claim 1, characterized in that: the molar ratio of the 2-acrylate ethylamine-4,6 (phenylimidothiourea) -S-triazine in S3 to the material of 5,5-dimethyl-1,3,2-dioxaphosphorinane caprolactam is 1:2-2.8.
6. The preparation method of the water-based fireproof wood paint coating according to claim 1, characterized in that: in the S4, the dosage of 2-acrylate ethylamine-4,6 (phenylimido phosphoryl thiourea) -S-triazine is 1-8% of the total mass of the acrylate monomer.
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CN111349189A (en) * 2020-04-26 2020-06-30 杨光云 Flame-retardant nitrogen-phosphorus synergistic carbon nanotube modified acrylic resin material and preparation method thereof
CN114262554A (en) * 2021-12-31 2022-04-01 李天龙 Nitrogen-phosphorus-containing epoxy resin fireproof coating and preparation method thereof
CN114478961A (en) * 2021-12-16 2022-05-13 徐州盛安化工科技有限公司 Fireproof functionalized TiO2Grafted acrylic resin, preparation method and application

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US2664425A (en) * 1952-02-06 1953-12-29 Schenley Ind Inc Substituted monothiosemicarbazones of diformylbenzenes
CN101343387A (en) * 2007-07-12 2009-01-14 上海化工研究院 Halogen-free water resistant expansion type phosphor nitrogen combustion inhibitor for polyolefin and preparation thereof
WO2009121603A1 (en) * 2008-03-31 2009-10-08 Borealis Agrolinz Melamine Gmbh Method for producing a compound with at least one at least monosubstituted amino group
CN111349189A (en) * 2020-04-26 2020-06-30 杨光云 Flame-retardant nitrogen-phosphorus synergistic carbon nanotube modified acrylic resin material and preparation method thereof
CN114478961A (en) * 2021-12-16 2022-05-13 徐州盛安化工科技有限公司 Fireproof functionalized TiO2Grafted acrylic resin, preparation method and application
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