CN116694211A - Preparation method and application of water-based two-component polyurethane flame-retardant material - Google Patents

Preparation method and application of water-based two-component polyurethane flame-retardant material Download PDF

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CN116694211A
CN116694211A CN202310634767.9A CN202310634767A CN116694211A CN 116694211 A CN116694211 A CN 116694211A CN 202310634767 A CN202310634767 A CN 202310634767A CN 116694211 A CN116694211 A CN 116694211A
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aqueous
retardant material
dispersion
preparation
flame
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谭卉文
余军
胡建新
张政
谢武挺
梁巧仪
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Guangzhou Yele New Material Technology Co ltd
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Guangzhou Yele New Material Technology Co ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • 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
    • 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
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6291—Polymers of phosphorus containing compounds having carbon-to-carbon double bonds
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The application discloses a preparation method and application of a water-based two-component polyurethane flame-retardant material, which comprises the following steps: s1: synthesizing an aqueous hydroxypropyl dispersion; s2, synthesizing an aqueous polyurethane curing agent; s3: the synthesized aqueous hydroxypropyl dispersion is made into varnish or color paint, and uniformly mixing the prepared varnish or colored paint with a waterborne polyurethane curing agent to obtain the polyurethane adhesive. The paint film obtained by spraying and film making has smooth and flawless surface, good fullness, high glossiness, high hardness and good water resistance, can be extinguished immediately after leaving fire, has excellent flame retardant property, and can be widely applied to the field of flame retardant coating to be coated.

Description

Preparation method and application of water-based two-component polyurethane flame-retardant material
Technical Field
The application relates to the technical field of flame retardant coatings, in particular to the field of IPC C08, and more particularly relates to a preparation method and application of a water-based two-component polyurethane flame retardant material.
Background
Solvent-based flame retardant coatings have good mechanical and chemical resistance properties and have been rapidly developed and applied over the past several decades. The water-based flame-retardant coating takes water as a solvent, is nontoxic and harmless to the environment after being dried, and forms a paint film with excellent mechanical property and chemical property, so that the water-based flame-retardant coating becomes one of main directions of development of the flame-retardant coating. The water-based paint has single-component and double-component water-based paint, the single-component paint has low paint film hardness, poor water resistance and flame retardance, and limited application, and the double-component water-based polyurethane flame-retardant paint has excellent physical and chemical properties and excellent flame retardance in the double-component paint.
CN 101768250 provides a high flame retardant polyurethane composition and a preparation method thereof. The high flame-retardant polyurethane composition consists of a component A and a component B, wherein the component A consists of polyether polyol, flame-retardant polyether polyol, a cross-linking agent, a foam stabilizer, water, a physical foaming agent and a catalyst; the component B consists of polyether polyol, flame retardant, polymeric MDI and toluene diisocyanate prepolymer. When in use, A, B component materials are uniformly mixed according to the mass ratio of A:B=100:50-60, then are injected into a mold with the mold temperature of 45-65 ℃, after 5-10 minutes, the mold is opened, and the mold is placed for 24 hours at normal temperature. The high-flame-retardance polyurethane composition prepared by the application has the advantages of high fluidity, high storage stability and the like, is convenient for a foaming manufacturer to use and store, and has insufficient flame retardance and hardness.
Disclosure of Invention
In order to solve the problems, the first aspect of the application provides a preparation method of an aqueous two-component polyurethane flame retardant material, which comprises the following steps:
s1: synthesizing an aqueous hydroxypropyl dispersion;
s2, synthesizing an aqueous polyurethane curing agent;
s3: the synthesized aqueous hydroxypropyl dispersion is made into varnish or color paint, and uniformly mixing the prepared varnish or colored paint with a waterborne polyurethane curing agent to obtain the polyurethane adhesive.
Preferably, the specific steps of S1 are as follows: uniformly mixing an organic acid, a hard monomer, a soft monomer, a difunctional monomer and acrylic acid phosphate to obtain a mixed monomer; heating the solvent to 130-150 ℃, and simultaneously dropwise adding the mixed monomer and the initiator into the solvent to finish the dropwise adding of the mixed monomer in 4-8 hours; and then the first neutralizer is used for neutralization, the temperature is reduced to 75-85 ℃, and water is added and stirred uniformly to obtain the water-based hydroxypropyl dispersion.
Preferably, the mass ratio of the organic acid to the hard monomer to the soft monomer to the difunctional monomer to the acrylic phosphate is (2-3): (12-18): (10-15): (6-13): (5-10).
Preferably, the initiator is at least one of di-tert-amyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate and tert-butyl peroxyisooctanoate.
Preferably, the initiator is di-t-amyl peroxide.
Preferably, the organic acid is at least one of acrylic acid, methacrylic acid and carboxyethyl acrylate.
Preferably, the organic acid is acrylic acid.
Preferably, the hard monomer is at least one of methyl methacrylate, styrene, vinyl acetate, acrylonitrile, isobornyl acrylate and cyclohexyl acrylate.
Preferably, the hard monomer is methyl methacrylate and isobornyl methacrylate.
Preferably, the soft monomer is at least one of butyl acrylate, ethyl acrylate, butyl methacrylate, isooctyl acrylate and tert-butyl acrylate.
Preferably, the soft monomer is butyl acrylate.
Preferably, the difunctional monomer is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, ethylene glycol diacrylate and ethylene glycol dimethacrylate.
Preferably, the difunctional monomer is hydroxypropyl acrylate.
Preferably, the acrylic acid phosphate is at least one of acrylic acid methyl diethyl phosphate, acrylic acid ethyl dimethyl phosphate, methacrylic acid methyl dimethyl phosphate, 2-hydroxyethyl methacrylic acid phosphate and ethylene glycol methacrylate phosphate.
Preferably, the acrylic acid phosphate is diethyl methyl phosphate and diethyl ethyl phosphate.
Preferably, the solvent is at least one of ethylene glycol butyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether, tripropylene glycol methyl ether and dipropylene glycol propyl ether.
Preferably, the solvent is ethylene glycol butyl ether.
Preferably, the first neutralizing agent is at least one of dimethylethanolamine, diethanolamine, triethanolamine and triethylamine.
Preferably, the first neutralizing agent is dimethylethanolamine.
Preferably, the specific steps of S1 are as follows: uniformly mixing 2-3 parts by weight of organic acid, 12-18 parts by weight of hard monomer, 10-15 parts by weight of soft monomer, 6-13 parts by weight of difunctional monomer and 5-10 parts by weight of acrylic phosphate to obtain mixed monomer; heating 4-8 parts by weight of solvent to 130-150 ℃, and simultaneously dropwise adding the mixed monomer and 0.5-1.5 parts by weight of initiator into the solvent to ensure that the mixed monomer is completely dripped in 4-8 hours; then 1-3 parts of first neutralizer is used for neutralization, then the temperature is reduced to 75-85 ℃, 44-55 parts of water by weight is added for uniform stirring, and the aqueous hydroxypropyl dispersion is obtained.
Preferably, the modified amount of the aqueous hydroxypropyl dispersion is 5-10%, the solid content is 40-50%, and the hydroxyl content is 2-4.5%.
The modified amount of the aqueous hydroxypropyl dispersion is the mass ratio of the acrylic phosphate in the raw materials for preparing the aqueous hydroxypropyl dispersion.
Preferably, the specific step of S2 is as follows: heating the isocyanate trimer to 80-120 ℃, adding solid acid, preserving heat for 1-5h, adding a second neutralizing agent for neutralization, cooling to 65-75 ℃, adding phosphorus-containing polyether, preserving heat for 1-3h, and cooling to obtain the waterborne polyurethane curing agent.
Preferably, the specific step of S2 is as follows: heating 70-85 parts by weight of isocyanate trimer to 80-120 ℃, adding 3-8 parts by weight of solid acid, preserving heat for 1-5 hours, adding 1-5 parts by weight of second neutralizer for neutralization, cooling to 65-75 ℃, adding 10-15 parts of phosphorus-containing polyether, preserving heat for 1-3 hours, and cooling to obtain the waterborne polyurethane curing agent.
Preferably, the isocyanate trimer is at least one of hexamethylene diisocyanate trimer, isophorone diisocyanate trimer, hexamethylene diisocyanate-toluene diisocyanate trimer, xylylene diisocyanate trimer, hexamethylene diisocyanate-trimethyl phosphate adduct, diphenylmethane diisocyanate trimer, toluene diisocyanate trimer.
Preferably, the second neutralizing agent is at least one of dimethylethanolamine, diethanolamine, triethanolamine and triethylamine.
Preferably, the second neutralizing agent is dimethylethanolamine.
Preferably, the solid acid is at least one of hydroxycarboxylic acid, sulfamic acid, periodic acid, trichloroacetic acid.
Preferably, the solid acid is sulfamic acid.
Preferably, the modification amount of the aqueous polyurethane curing agent is 10-15%.
The modification amount of the waterborne polyurethane curing agent is the mass ratio of the phosphorus-containing polyether in the raw materials for preparing the waterborne polyurethane curing agent.
According to the application, the modified amount of the acrylic acid phosphate ester of the aqueous hydroxypropyl dispersion is 5-10%, so that the flame retardant property and the water resistance of the aqueous hydroxypropyl dispersion can be effectively improved, the carboxyl is introduced in the synthesis process of the aqueous hydroxypropyl dispersion, and the neutralizing agent is added to form salt so as to achieve the effect of making the aqueous hydroxypropyl dispersion waterborne, however, in a high-humidity environment, the water resistance of the aqueous hydroxypropyl dispersion in the high-humidity environment is obviously reduced due to the strong association of the carboxyl and water, the acrylic acid phosphate ester is modified, and the acrylic acid phosphate ester is crosslinked between groups to form a space network structure, so that the water resistance and the mechanical property of the aqueous hydroxypropyl dispersion are enhanced, in addition, as the phosphate ester can be dehydrated to form a compact carbon layer in the combustion process, the heat insulation and oxygen isolation effects are realized on the surface of the material, and meanwhile, a large amount of phosphorus remains in the carbon layer is further improved, and the formed highly compact and stable carbon layer can effectively organize oxygen into the interior of the material, and combustible volatile matters under the carbon layer can be prevented from entering air, so that the flame retardant property of the aqueous hydroxypropyl dispersion is improved.
Preferably, the specific step of S3 is as follows: 1) Preparing varnish: dispersing the synthesized aqueous hydroxypropyl dispersion in a container at 800-1000r/min, adding an antifoaming agent for dispersing for 4-6min, adding a wetting agent and a leveling agent for dispersing for 4-6min, adding a film forming auxiliary agent and water for dispersing for 5-15min, and adding a thickening agent for dispersing uniformly to obtain varnish; 2) And uniformly mixing the varnish with the aqueous polyurethane curing agent to obtain the flame-retardant material.
Preferably, in the step S3, the mass ratio of the aqueous hydroxypropyl dispersion to the aqueous polyurethane curing agent is (3-8): 1.
the application of the preparation method of the aqueous two-component polyurethane flame-retardant material is used for preparing flame-retardant paint.
The beneficial effects are that:
1. the application provides a water-based two-component polyurethane flame-retardant material, which has the advantages of smooth and flawless surface of a paint film obtained by spraying and film making, good fullness, high glossiness, high hardness, good water resistance, capability of extinguishing after leaving fire and excellent flame-retardant property, and can be widely applied to the field of flame-retardant coating to be coated.
2. The synthetic waterborne polyurethane curing agent adopts the modified amount of the phosphorus-containing polyether to be 10-15%, and the phosphorus content in the molecule of the synthetic waterborne polyurethane curing agent is controlled, so that the phosphorus can catalyze and promote the rapid formation of a carbon layer in the combustion process, the carbon residue of a coating film at high temperature is improved, and the flame retardant property of the prepared flame retardant material is further improved.
3. According to the application, the modification amount of the acrylic acid phosphate of the aqueous hydroxypropyl dispersion is 8%, so that the groups are crosslinked to form a space network structure, the water resistance and mechanical property of the aqueous hydroxypropyl dispersion are enhanced, meanwhile, the phosphate can be dehydrated to form a compact carbon layer in the combustion process, and the compact carbon layer is covered on the surface of the material to play a role in heat insulation and oxygen insulation, so that the flame retardant property of the aqueous hydroxypropyl dispersion is improved.
4. According to the application, the water-based hydroxypropyl dispersion and the water-based polyurethane curing agent are synthesized, the synthesized water-based hydroxypropyl dispersion is prepared into varnish or colored paint, and the varnish or colored paint is matched with the water-based polyurethane curing agent synthesized by the application to obtain the flame-retardant coating, so that the excellent flame-retardant effect can be achieved, and the surface effect, the water resistance and the mechanical property of the coating are excellent. The aqueous hydroxypropyl dispersion synthesized by the application alone is matched with other common curing agents or the aqueous polyurethane curing agent synthesized by the application alone is matched with other common hydroxypropyl dispersions, so that the same excellent flame retardant effect as the application can not be obtained.
Detailed Description
Examples
Example 1:
example 1 provides a preparation method of an aqueous two-component polyurethane flame retardant material, which comprises the following steps:
s1: synthesis of aqueous hydroxypropyl dispersion: uniformly mixing 2.5 parts by weight of organic acid, 15 parts by weight of hard monomer, 12 parts by weight of soft monomer, 8 parts by weight of difunctional monomer and 8 parts by weight of acrylic phosphate to obtain a mixed monomer; heating 5 parts by weight of solvent to 140 ℃, and simultaneously dropwise adding the mixed monomer and 1 part by weight of initiator into the solvent to finish the dropwise adding of the mixed monomer at 6 hours; then, after neutralization with 2.5 parts of the first neutralizing agent, the temperature is reduced to 80 ℃, 46 parts by weight of water is added and stirred uniformly, and the aqueous hydroxypropyl dispersion is obtained.
S2, synthesizing an aqueous polyurethane curing agent: 81 parts by weight of isocyanate trimer is heated to 100 ℃, 5 parts by weight of solid acid is added, the temperature is kept for 3 hours, 2 parts by weight of second neutralizer is added for neutralization, then the temperature is reduced to 70 ℃, 12 parts of phosphorus-containing polyether is added, and the temperature is reduced to 25 ℃ after the temperature is kept for 2 hours, so that the aqueous polyurethane curing agent is obtained.
S3: dispersing 84 parts by weight of synthesized aqueous hydroxypropyl dispersoid in a container at 1000r/min, adding 0.3 part by weight of defoamer for 5min, adding 0.3 part by weight of wetting agent and 0.2 part by weight of flatting agent for 5min, adding 6 parts by weight of film forming additive, 8.9 parts by weight of water dispersing agent for 10min, and adding 0.3 part by weight of thickener for even dispersion to obtain varnish; 2) And uniformly mixing the varnish and the aqueous polyurethane curing agent, wherein the mass ratio of the varnish to the aqueous polyurethane curing agent is 5:1, and thus the flame retardant material is obtained.
The organic acid is acrylic acid;
the hard monomer is methyl methacrylate and isobornyl methacrylate, and the mass ratio of the methyl methacrylate to the isobornyl methacrylate is 1:2;
the soft monomer is butyl acrylate;
the difunctional monomer is hydroxypropyl acrylate;
the acrylic acid phosphate is acrylic acid methyl diethyl phosphate and acrylic acid ethyl diethyl phosphate, and the mass ratio of the acrylic acid methyl diethyl phosphate to the acrylic acid ethyl diethyl phosphate is 1:1;
the solvent is ethylene glycol butyl ether;
the first neutralizer is dimethylethanolamine;
the isocyanate trimer is hexamethylene diisocyanate trimer;
the second neutralizer is dimethylethanolamine;
the solid acid is sulfamic acid;
the matching weight ratio of the synthesized aqueous hydroxypropyl dispersion to the aqueous polyurethane curing agent is 5:1.
The modification amount of the synthesized aqueous hydroxypropyl dispersion was 8%, the solid content was 46.5%, and the hydroxyl content was 2.25%
The modification amount of the synthesized waterborne polyurethane curing agent is 12 percent, and the isocyanate group content is 15.1 percent.
The phosphorus-containing polyether is polypropylene glycol phosphate.
Dimethylethanolamine was purchased from basf.
Hexamethylene diisocyanate trimer was purchased from basf, model HI100.
The defoamer was a first-creation 561PL defoamer purchased from synthon chemicals, france.
The wetting agent was dihigh TEGO270, the leveling agent was dihigh TEGO450, purchased from dihigh TEGO, germany.
The film forming additive is dipropylene glycol methyl ether and dipropylene glycol butyl ether, the weight ratio of the dipropylene glycol methyl ether to the dipropylene glycol butyl ether is 1:1, and the film forming additive is purchased from the Dow chemical company.
Example 2
Example 2 provides a preparation method of an aqueous two-component polyurethane flame retardant material, and the specific implementation manner is the same as that of example 1, and the difference is that in step S1: synthesis of aqueous hydroxypropyl dispersion: uniformly mixing 3 parts by weight of organic acid, 13 parts by weight of hard monomer, 10 parts by weight of soft monomer, 12 parts by weight of difunctional monomer and 9 parts by weight of acrylic phosphate to obtain a mixed monomer; heating 5 parts by weight of solvent to 140 ℃, and simultaneously dropwise adding the mixed monomer and 1 part by weight of initiator into the solvent to finish the dropwise adding of the mixed monomer at 6 hours; then, the temperature is reduced to 80 ℃ after neutralization by using 2.5 parts of first neutralizer, and 44.5 parts of water by weight is added and stirred uniformly to obtain the aqueous hydroxypropyl dispersion.
In the step S3, 2) the varnish and the aqueous polyurethane curing agent are uniformly mixed, and the mass ratio of the varnish to the aqueous polyurethane curing agent is 3.5:1.
The modified amount of the synthesized aqueous hydroxypropyl dispersion was 9%, the solid content was 48%, and the hydroxyl content was 3.27%.
Comparative example 1
Comparative example 1 provides a preparation method of a water-based two-component polyurethane flame-retardant material, and the specific implementation mode of the preparation method is the same as example 1, except that water-based resin XJ-303H purchased from Guangzhou municipal Biheng chemical industry Co., ltd and a synthesized water-based polyurethane curing agent are mixed uniformly in a weight ratio of 5:1, so that the flame-retardant material is obtained.
Comparative example 2
Comparative example 2 provides a preparation method of a water-based two-component polyurethane flame-retardant material, and the specific implementation mode is the same as example 1, except that a synthesized water-based hydroxypropyl dispersion and a water-based polyurethane curing agent 2655 purchased from Cordson Germany are adopted, diluted to the content of isocyanate consistent with the example, and uniformly mixed in a weight ratio of 5:1, so that the flame-retardant material is obtained.
Comparative example 3:
comparative example 3 provides a preparation method of a water-based two-component polyurethane flame-retardant material, and the specific implementation mode is the same as example 1, and is characterized in that water-based resin XJ-303H purchased from Biheng chemical industry Co., ltd., guangzhou and water-based polyurethane curing agent 2655 purchased from Kochia, which are diluted to the content of isocyanate consistent with the example, are uniformly mixed in a weight ratio of 5:1, so that the flame-retardant material is obtained.
Comparative example 4
Comparative example 4 provides a method for preparing an aqueous two-component polyurethane flame retardant material, the specific embodiment of which is the same as example 1, except that step S1: synthesis of aqueous hydroxypropyl dispersion: uniformly mixing 2.5 parts by weight of organic acid, 11 parts by weight of hard monomer, 11 parts by weight of soft monomer, 8 parts by weight of difunctional monomer and 15 parts by weight of acrylic phosphate to obtain a mixed monomer; heating 5 parts by weight of solvent to 140 ℃, and simultaneously dropwise adding the mixed monomer and 1 part by weight of initiator into the solvent to finish the dropwise adding of the mixed monomer at 6 hours; then, after neutralization with 2.5 parts of the first neutralizing agent, the temperature is reduced to 80 ℃, 39 parts by weight of water is added and stirred uniformly, and the aqueous hydroxypropyl dispersion is obtained.
The modified amount of the synthesized aqueous hydroxypropyl dispersion was 15%, the solid content was 48.5%, and the hydroxyl content was 2.5%.
Comparative example 5
Comparative example 5 provides a method for preparing an aqueous two-component polyurethane flame retardant material, the specific embodiment of which is the same as example 1, except that step S1: synthesis of aqueous hydroxypropyl dispersion: uniformly mixing 3 parts by weight of organic acid, 18 parts by weight of hard monomer, 15 parts by weight of soft monomer, 8.5 parts by weight of difunctional monomer and 3 parts by weight of acrylic phosphate to obtain a mixed monomer; heating 5 parts by weight of solvent to 140 ℃, and simultaneously dropwise adding the mixed monomer and 1 part by weight of initiator into the solvent to finish the dropwise adding of the mixed monomer at 6 hours; then using 2.5 parts of first neutralizer to neutralize, then cooling to 80 ℃, adding 51 parts by weight of water, stirring uniformly to obtain aqueous hydroxypropyl dispersoid,
the modified amount of the synthesized aqueous hydroxypropyl dispersion was 3%, the solid content was 48.5%, and the hydroxyl content was 2.28%.
Comparative example 6
Comparative example 6 provides a method for preparing an aqueous two-component polyurethane flame retardant material, the specific embodiment of which is the same as example 1, except that step S2: synthesis of an aqueous polyurethane curing agent: and (3) heating 78 parts by weight of isocyanate trimer to 100 ℃, adding 6 parts by weight of solid acid, preserving heat for 3 hours, adding 4 parts by weight of second neutralizer to neutralize, cooling to 70 ℃, adding 20 parts of phosphorus-containing polyether, preserving heat for 2 hours, and cooling to 25 ℃ to obtain the waterborne polyurethane curing agent.
In the step S3, 2) the varnish and the aqueous polyurethane curing agent are uniformly mixed, and the mass ratio of the varnish to the aqueous polyurethane curing agent is 5:1.1.
The modification amount of the synthesized waterborne polyurethane curing agent is 20 percent, and the isocyanate group content is 13.5 percent.
Comparative example 7
Comparative example 7 provides a method for preparing an aqueous two-component polyurethane flame retardant material, the specific embodiment of which is the same as example 1, except that step S2: synthesis of an aqueous polyurethane curing agent: and (3) heating 85 parts by weight of isocyanate trimer to 100 ℃, adding 6 parts by weight of solid acid, preserving heat for 3 hours, adding 4 parts by weight of second neutralizer to neutralize, cooling to 70 ℃, adding 5 parts of phosphorus-containing polyether, preserving heat for 2 hours, and cooling to 25 ℃ to obtain the waterborne polyurethane curing agent.
In the step S3, 2) the varnish and the aqueous polyurethane curing agent are uniformly mixed, and the mass ratio of the varnish to the aqueous polyurethane curing agent is 5:0.91.
The modification amount of the synthesized waterborne polyurethane curing agent is 5 percent, and the isocyanate group content is 16.5 percent.
Performance test:
the uniformly mixed flame retardant materials obtained in examples 1 to 2 and comparative examples 1 to 7 were sprayed onto
1. Coating hardness: the films of 30 μm in thickness, which were uniformly sprayed with the flame retardant materials obtained in examples 1 to 2 and comparative examples 1 to 7, were subjected to hardness test by GB/T6739-2006 film hardness pencil test, and the average values of the measured results are shown in Table 1.
2. Film gloss: the flame retardant materials obtained in examples 1-2 and comparative examples 1-7 were uniformly sprayed to give coating films having a thickness of 30. Mu.m, and the results of the gloss test were measured by the GB/T1743-1979 film gloss measurement method, and the average values of the measured results are shown in Table 1.
3. Flame retardant properties: the flame retardant property test was conducted on the coating films of 30 μm thickness uniformly sprayed with the flame retardant materials obtained in examples 1 to 2 and comparative examples 1 to 7 by using GB/T2408-2008 "determination of the flame retardant property of plastics horizontal method and vertical method", and the average values of the measured results are shown in Table 1.
4. Water resistance: the flame retardant materials obtained in examples 1-2 and comparative examples 1-7 were uniformly sprayed with a coating film having a thickness of 30 μm and subjected to a water resistance test by using a GB/T1733-93 coating film water resistance test, and the average value of the results obtained by immersing at 25℃for 10 days is shown in Table 1.
TABLE 1

Claims (10)

1. The preparation method of the water-based two-component polyurethane flame-retardant material is characterized by comprising the following steps of:
s1: synthesizing an aqueous hydroxypropyl dispersion;
s2, synthesizing an aqueous polyurethane curing agent;
s3: the synthesized aqueous hydroxypropyl dispersion is made into varnish or color paint, and uniformly mixing the prepared varnish or colored paint with a waterborne polyurethane curing agent to obtain the polyurethane adhesive.
2. The preparation method of the aqueous two-component polyurethane flame retardant material according to claim 1, wherein the specific steps of S1 are as follows: uniformly mixing an organic acid, a hard monomer, a soft monomer, a difunctional monomer and acrylic acid phosphate to obtain a mixed monomer; heating the solvent to 130-150 ℃, and simultaneously dropwise adding the mixed monomer and the initiator into the solvent to finish the dropwise adding of the mixed monomer in 4-8 hours; and then the first neutralizer is used for neutralization, the temperature is reduced to 75-85 ℃, and water is added and stirred uniformly to obtain the water-based hydroxypropyl dispersion.
3. The preparation method of the aqueous two-component polyurethane flame retardant material according to claim 1, wherein the specific steps of S2 are as follows: heating the isocyanate trimer to 80-120 ℃, adding solid acid, preserving heat for 1-5h, adding a second neutralizing agent for neutralization, cooling to 65-75 ℃, adding phosphorus-containing polyether, preserving heat for 1-3h, and cooling to obtain the waterborne polyurethane curing agent.
4. The preparation method of the aqueous two-component polyurethane flame-retardant material according to claim 2, wherein the mass ratio of the organic acid to the hard monomer to the soft monomer to the difunctional monomer to the acrylic phosphate is (2-3): (12-18): (10-15): (6-13): (5-10).
5. The method for preparing the aqueous two-component polyurethane flame-retardant material according to claim 2, wherein the initiator is at least one of di-tert-amyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate and tert-butyl peroxyisooctanoate.
6. The preparation method of the aqueous two-component polyurethane flame-retardant material according to claim 1, wherein the modification amount of the aqueous hydroxypropyl dispersion is 5-10%, the solid content is 40-50%, and the hydroxyl content is 2-4.5%.
7. The method for preparing a water-based two-component polyurethane flame-retardant material according to claim 3, wherein the isocyanate trimer is at least one of hexamethylene diisocyanate trimer, isophorone diisocyanate trimer, hexamethylene diisocyanate-toluene diisocyanate trimer, xylylene diisocyanate trimer, hexamethylene diisocyanate-trimethyl phosphate adduct, diphenylmethane diisocyanate trimer, toluene diisocyanate trimer.
8. The preparation method of the aqueous two-component polyurethane flame retardant material according to claim 1, wherein the specific steps of S3 are as follows: 1) Preparing varnish: dispersing the synthesized aqueous hydroxypropyl dispersion in a container at 800-1000r/min, adding an antifoaming agent for dispersing for 4-6min, adding a wetting agent and a leveling agent for dispersing for 4-6min, adding a film forming auxiliary agent and water for dispersing for 5-15min, and adding a thickening agent for dispersing uniformly to obtain varnish; 2) And uniformly mixing the varnish with the aqueous polyurethane curing agent to obtain the flame-retardant material.
9. The preparation method of the aqueous two-component polyurethane flame-retardant material according to claim 8, wherein the mass ratio of the aqueous hydroxypropyl dispersion to the aqueous polyurethane curing agent is (3-8): 1.
10. use of a method for the preparation of an aqueous two-component polyurethane flame retardant material according to any one of claims 1 to 9, for the preparation of a flame retardant coating.
CN202310634767.9A 2023-05-31 2023-05-31 Preparation method and application of water-based two-component polyurethane flame-retardant material Pending CN116694211A (en)

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CN108250877A (en) * 2017-12-19 2018-07-06 吉力水性新材料科技（珠海）有限公司 A kind of phosphate modified acrylic acid aqueous industrial coating
CN109810216A (en) * 2018-12-25 2019-05-28 昆明理工大学 A kind of flame-retardant aqueous acrylic resin and preparation method thereof
CN109942792A (en) * 2019-03-21 2019-06-28 华南理工大学 A kind of phosphorous water-based polyurethane curing agent and its preparation method and application
CN114349896A (en) * 2021-12-13 2022-04-15 嘉宝莉化工集团股份有限公司 Hydroxyl polyacrylate dispersoid and preparation method thereof, high-performance water-based bi-component polyurethane coating and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103360606A (en) * 2013-07-23 2013-10-23 四川国和新材料有限公司 Halogen-free organophosphate fire retardant and its preparation method
CN104263182A (en) * 2014-10-29 2015-01-07 芜湖县双宝建材有限公司 Highly-flame-retardant modified acrylate coating
CN108250877A (en) * 2017-12-19 2018-07-06 吉力水性新材料科技（珠海）有限公司 A kind of phosphate modified acrylic acid aqueous industrial coating
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