CN117363116A - Water-based intumescent fireproof coating and preparation method thereof - Google Patents

Water-based intumescent fireproof coating and preparation method thereof Download PDF

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Publication number
CN117363116A
CN117363116A CN202311325118.7A CN202311325118A CN117363116A CN 117363116 A CN117363116 A CN 117363116A CN 202311325118 A CN202311325118 A CN 202311325118A CN 117363116 A CN117363116 A CN 117363116A
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China
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parts
water
retardant coating
intumescent fire
fire retardant
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CN202311325118.7A
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Chinese (zh)
Inventor
江拥
杨柳
杨汝良
杨飞
郭鹏飞
尹迪
岳渊
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Chengdu Hongrun Paint Co ltd
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Chengdu Hongrun Paint Co ltd
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Priority to CN202311325118.7A priority Critical patent/CN117363116A/en
Publication of CN117363116A publication Critical patent/CN117363116A/en
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D133/00Coating 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 at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42Block-or graft-polymers containing polysiloxane sequences
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18Fireproof paints including high temperature resistant paints
    • C09D5/185Intumescent paints
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/32Phosphorus-containing compounds
    • C08K2003/321Phosphates
    • C08K2003/322Ammonium phosphate
    • C08K2003/323Ammonium polyphosphate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant

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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)
  • Paints Or Removers (AREA)

Abstract

The invention relates to the technical field of fireproof paint, in particular to a water-based expansion type fireproof paint and a preparation method thereof, wherein modified emulsion is added in a formula, so that the performance of the fireproof paint is greatly improved; the thermal degradation product of the dihydroxy-terminated polyphosphonate at high temperature can rapidly dehydrate and carbonize the surface of the material, and can form a compact carbonization layer on the surface of the material, thereby blocking heat transfer and improving the flame retardant effect of the water-based intumescent fire retardant coating; meanwhile, during polycondensation reaction of polysiloxane and dihydroxy end-capped polyphosphonate, a cross-linking network can be formed between hydroxyl groups and active groups, so that the strength and toughness of the material are improved.

Description

Water-based intumescent fireproof coating and preparation method thereof
Technical Field
The invention relates to the technical field of fireproof coatings, in particular to a water-based intumescent fireproof coating and a preparation method thereof.
Background
The expansion type fireproof paint is a special paint with fireproof performance, and is widely used in various steel structure buildings due to the advantages of low application film thickness, small coating self weight, good decoration, convenient construction and the like, the main components of the expansion type fireproof paint comprise an expanding agent, an adhesive and a filler, the expanding agent is usually inorganic salts or organic compounds, and when the expansion type fireproof paint encounters high temperature, chemical reaction or physical change can occur, and a large amount of gas is generated so as to expand the paint; adhesives are used to provide adhesion and weatherability of the coating, and common adhesives are polymers, adhesives, and the like; the filler is used to increase the thickness and fire resistance of the coating.
The expansion type fireproof paint has the action mechanism that an expansion layer is formed under the high temperature condition mainly through the action of an expansion agent, so that the effects of heat insulation and fire spreading prevention are achieved, when the paint encounters a fire disaster, the expansion agent can be rapidly decomposed or expanded to generate a large amount of gas to form a heat insulation layer, the spread of the fire disaster is blocked, and meanwhile, the adhesive and the filler in the paint can play a certain role of heat insulation and flame retardance, so that the fireproof effect is improved. According to dispersion media, the intumescent fire-retardant coating can be classified into aqueous and solvent type, the traditional solvent type fire-retardant coating has high VOC emission (300-500 g/L), combustibility and explosiveness, and the aqueous conversion is an important conversion direction of the intumescent fire-retardant coating, but the aqueous intumescent fire-retardant coating prepared by the prior art has the problems of unstable performance, poor weather resistance and low coating strength, and the development of a novel preparation method of the aqueous intumescent fire-retardant coating is needed.
Disclosure of Invention
The invention aims to solve the technical problems that: the water-based intumescent fire-retardant coating prepared by the prior art has unstable performance, poor weather resistance and low coating strength, and the problems in the background art are solved by providing the water-based intumescent fire-retardant coating and the preparation method thereof.
In order to achieve the above purpose, the present invention provides the following technical solutions: an aqueous expansion type fireproof paint is composed of the following components:
30-60 parts of acrylic emulsion, 15-30 parts of modified emulsion, 20-30 parts of intumescent flame retardant, 1-2 parts of wetting dispersant, 0.5-1 part of antifreeze agent, 0.8-1.5 parts of film forming auxiliary agent, 0.1-0.5 part of defoaming agent, 0.1-0.6 part of flash rust inhibitor, 0.2-1 part of thickener and 1-2 parts of polycarbodiimide.
Preferably, the intumescent flame retardant consists of 10-20 parts of ammonium polyphosphate, 8-16 parts of dipentaerythritol and 10-17 parts of melamine.
Preferably, the polymerization degree of the ammonium polyphosphate is more than 1000, and the content of small molecules is less than 0.5wt%.
Preferably, the preparation method of the modified emulsion comprises the following steps:
s1: weighing 40-60g of diphenyl dimethoxy silane, 10-20ml of water and 90-110ml of DMF, and mixing and reacting to obtain a mixed solution;
s2: weighing 20-30g of the dihydroxy terminated polyphosphonate, dissolving in 40-60ml of DMF, and slowly dripping into the mixed solution for continuous reaction;
s3: and adding an emulsifier for high-speed dispersion after the reaction is finished, so as to obtain the modified emulsion.
Preferably, in the preparation method of the modified emulsion, diphenyl dimethoxy silane is heated to remove a part of methanol to obtain polysiloxane, and the reaction formula involved in the polycondensation reaction with the dihydroxy-terminated polyphosphonate is as follows:
preferably, the pH value of the mixture in the step S1 is adjusted to be 1-3 before the mixture is mixed and reacted.
Preferably, the temperature of the mixing reaction in the step S1 is 50-80 ℃ and the time is 3-6h.
Preferably, the temperature of the continuous reaction in the step S2 is 100-140 ℃ and the time is 20-30h.
Preferably, the preparation method of the fireproof paint comprises the following steps:
s1: adding an intumescent flame retardant, a wetting dispersant and a defoaming agent, uniformly dispersing at a high speed, and grinding;
s2: then adding the acrylic emulsion, the modified emulsion, the antifreeze agent, the film forming auxiliary agent and the flash rust inhibitor, uniformly stirring, and adding the thickener to adjust the viscosity of the system;
s3: finally adding polycarbodiimide, stirring and curing for 20-30h to obtain the water-based intumescent fire-retardant coating.
Preferably, the viscosity of the system after the adjustment in the step S2 is 100 KU to 130KU.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the modified emulsion prepared by polycondensation reaction of polysiloxane and dihydroxy end-capped polyphosphonate is dehydrated and carbonized at high temperature, and a compact carbonized layer can be formed on the surface of the material, so that heat transfer is blocked, and the flame retardant effect of the water-based intumescent fire retardant coating is greatly improved; meanwhile, during the polycondensation reaction of polysiloxane and dihydroxy end-capped polyphosphonate, a cross-linked network can be formed between hydroxyl groups and active groups, so that the strength of the coating is increased, and the stability is stronger.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preparing modified emulsion: 50g of diphenyl dimethoxy silane, 16ml of water and 98ml of DMF are added into a beaker, the pH value of the mixed solution is adjusted to 2.0 by HCL solution, and the beaker is placed into a magnetic stirring water bath kettle at 60 ℃ for reaction for 5 hours and then taken out; 25g of the dihydroxy-terminated polyphosphonate is weighed and dissolved in 45ml of DMF, and the mixture is slowly dripped into the mixture for continuous reaction, the reaction temperature is set to be 110 ℃, and after 26 hours of reaction, a small amount of emulsifier is added for high-speed dispersion, so that the modified emulsion is obtained.
Wherein, diphenyl dimethoxy silane is heated to remove a part of methanol to obtain polysiloxane, and the reaction formula involved in the polycondensation reaction with dihydroxy end-capped polyphosphonate is as follows:
adding 12 parts of ammonium polyphosphate, 10 parts of dipentaerythritol, 14 parts of melamine, 2 parts of wetting dispersant and 0.3 part of defoamer into a paint mixing kettle, transferring into grinding equipment after high-speed dispersion, grinding to the fineness of less than 45 mu M, adding 40 parts of acrylic emulsion, 23 parts of modified emulsion, 0.5 part of antifreeze agent, 1.2 parts of film forming auxiliary agent and 0.3 part of anti-flash rust agent, and uniformly stirring; and adding a thickener to regulate the viscosity of the system to 125KU, finally adding polycarbodiimide, stirring and curing for 26 hours to obtain the water-based intumescent fire retardant coating.
Example 2
Preparing modified emulsion: adding 40g of diphenyl dimethoxy silane, 12ml of water and 90ml of DMF into a beaker, adjusting the pH of the mixed solution to 2.0 by using HCL solution, placing the beaker into a magnetic stirring water bath kettle at 70 ℃ for reaction for 4 hours, and taking out; 28g of the dihydroxy-terminated polyphosphonate is weighed and dissolved in 50ml of DMF, the mixture is slowly dripped into the mixture for continuous reaction, the reaction temperature is set to 120 ℃, and after 24 hours of reaction, a small amount of emulsifier is added for high-speed dispersion, so that the modified emulsion is obtained.
15 parts of ammonium polyphosphate, 12 parts of dipentaerythritol, 12 parts of melamine, 2 parts of wetting dispersant and 0.3 part of defoamer are added into a paint mixing kettle, the paint mixing kettle is transferred into grinding equipment after high-speed dispersion, the grinding equipment is used for grinding until the fineness is less than 45 mu M, and then 50 parts of acrylic emulsion, 18 parts of modified emulsion, 0.5 part of antifreeze agent, 1.2 parts of film forming auxiliary agent and 0.3 part of flash rust inhibitor are added and stirred uniformly; and adding a thickener to regulate the viscosity of the system to 125KU, finally adding polycarbodiimide, stirring and curing for 26 hours to obtain the water-based intumescent fire retardant coating.
Example 3
Preparing modified emulsion: 60g of diphenyl dimethoxy silane, 18ml of water and 105ml of DMF are added into a beaker, the pH value of the mixed solution is adjusted to 2.0 by HCL solution, and the beaker is placed into a magnetic stirring water bath kettle at 80 ℃ for reaction for 6 hours and then taken out; 22g of dihydroxy end-capped polyphosphonate is weighed and dissolved in 40ml of DMF, the mixture is slowly dripped into the mixture for continuous reaction, the reaction temperature is set to be 130 ℃, and after 26 hours of reaction, a small amount of emulsifier is added for high-speed dispersion, so that modified emulsion is obtained.
Adding 18 parts of ammonium polyphosphate, 10 parts of dipentaerythritol, 16 parts of melamine, 2 parts of wetting dispersant and 0.3 part of defoamer into a paint mixing kettle, transferring into grinding equipment after high-speed dispersion, grinding to the fineness of less than 45 mu M, adding 45 parts of acrylic emulsion, 20 parts of modified emulsion, 0.5 part of antifreeze agent, 1.2 parts of film forming auxiliary agent and 0.3 part of anti-flash rust agent, and uniformly stirring; and adding a thickener to regulate the viscosity of the system to 125KU, finally adding polycarbodiimide, stirring and curing for 26 hours to obtain the water-based intumescent fire retardant coating.
Comparative example 1
The difference from example 1 is that no modified emulsion was added;
adding 12 parts of ammonium polyphosphate, 10 parts of dipentaerythritol, 14 parts of melamine, 2 parts of wetting dispersant and 0.3 part of defoamer into a paint mixing kettle, dispersing at high speed, transferring into grinding equipment, grinding to a fineness of less than 45 mu M, adding 40 parts of acrylic emulsion, 0.5 part of antifreeze agent, 1.2 parts of film forming auxiliary agent and 0.3 part of anti-flash rust agent, and uniformly stirring; and adding a thickener to regulate the viscosity of the system to 125KU, finally adding polycarbodiimide, stirring and curing for 26 hours to obtain the water-based intumescent fire retardant coating.
Comparative example 2
The difference from example 1 is that the modified emulsion is prepared without adding dihydroxy-terminated polyphosphonate, and after a part of methanol is removed by heating diphenyl dimethoxy silane to obtain polysiloxane, the polysiloxane is directly emulsified to obtain emulsion;
the preparation method of the emulsion comprises the following steps: 50g of diphenyl dimethoxy silane, 16ml of water and 98ml of DMF are added into a beaker, the pH value of the mixed solution is adjusted to 2.0 by HCL solution, and the beaker is placed into a magnetic stirring water bath kettle at 60 ℃ for reaction for 5 hours and then taken out; adding a small amount of emulsifying agent to disperse at high speed to obtain emulsion.
Adding 12 parts of ammonium polyphosphate, 10 parts of dipentaerythritol, 14 parts of melamine, 2 parts of wetting dispersant and 0.3 part of defoamer into a paint mixing kettle, transferring into grinding equipment after high-speed dispersion, grinding to the fineness of less than 45 mu M, adding 40 parts of acrylic emulsion, 23 parts of emulsion, 0.5 part of antifreeze agent, 1.2 parts of film forming auxiliary agent and 0.3 part of flash rust inhibitor, and uniformly stirring; and adding a thickener to regulate the viscosity of the system to 125KU, finally adding polycarbodiimide, stirring and curing for 26 hours to obtain the water-based intumescent fire retardant coating.
The performance of the aqueous intumescent fire-retardant coatings prepared in examples 1-3 and comparative example 1 was tested with reference to the coating test-related standard (GB 14007-2002), and the performance indexes of the tests are shown in Table 1;
table 1 performance index measured
From the analysis of the results in table 1, it can be seen that: the water-based intumescent fire-retardant coating prepared by the embodiment has good flame retardant and fire-resistant properties, high coating strength, good toughness, good impact resistance, sagging resistance and wet heat resistance, and the heat degradation product of the dihydroxy end-capped polyphosphonate at high temperature is beneficial to rapidly dehydrating and carbonizing the surface of the material, and a compact carbonized layer can be formed on the surface of the material, so that heat transfer is blocked, and the flame retardant effect of the water-based intumescent fire-retardant coating is greatly improved; meanwhile, during polycondensation reaction of polysiloxane and dihydroxy end-capped polyphosphonate, a cross-linking network can be formed between hydroxyl groups and active groups, so that the strength and toughness of the material are improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims (9)

1. The water-based intumescent fire-retardant coating is characterized by comprising the following components:
30-60 parts of acrylic emulsion, 15-30 parts of modified emulsion, 20-30 parts of intumescent flame retardant, 1-2 parts of wetting dispersant, 0.5-1 part of antifreeze agent, 0.8-1.5 parts of film forming auxiliary agent, 0.1-0.5 part of defoaming agent, 0.1-0.6 part of flash rust inhibitor, 0.2-1 part of thickener and 1-2 parts of polycarbodiimide.
2. An aqueous intumescent fire retardant coating as claimed in claim 1, characterized in that the intumescent flame retardant consists of 10-20 parts ammonium polyphosphate, 8-16 parts dipentaerythritol and 10-17 parts melamine.
3. An aqueous intumescent fire retardant coating as claimed in claim 2, characterized in that the degree of polymerization of the ammonium polyphosphate is greater than 1000 and the small molecule content is less than 0.5% by weight.
4. The water-based intumescent fire retardant coating of claim 1, wherein the preparation method of the modified emulsion comprises the following steps:
s1: weighing 40-60g of diphenyl dimethoxy silane, 10-20ml of water and 90-110ml of DMF, and mixing and reacting to obtain a mixed solution;
s2: weighing 20-30g of the dihydroxy terminated polyphosphonate, dissolving in 40-60ml of DMF, and slowly dripping into the mixed solution for continuous reaction;
s3: and adding an emulsifier for high-speed dispersion after the reaction is finished, so as to obtain the modified emulsion.
5. The water-based intumescent fire retardant coating as claimed in claim 4, wherein the pH of the coating is adjusted to 1-3 before the mixing reaction in S1.
6. The water-based intumescent fire retardant coating as claimed in claim 4, wherein the temperature of the mixing reaction in S1 is 50-80 ℃ for 3-6 hours.
7. An aqueous intumescent fire retardant coating as claimed in claim 4, characterized in that the temperature of the continuous reaction in S2 is 100-140 ℃ for 20-30 hours.
8. The water-based intumescent fire retardant coating as claimed in claim 1, wherein the preparation method of the fire retardant coating comprises the following steps:
s1: adding an intumescent flame retardant, a wetting dispersant and a defoaming agent, uniformly dispersing at a high speed, and grinding;
s2: then adding the acrylic emulsion, the modified emulsion, the antifreeze agent, the film forming auxiliary agent and the flash rust inhibitor, uniformly stirring, and adding the thickener to adjust the viscosity of the system;
s3: finally adding polycarbodiimide, stirring and curing for 20-30h to obtain the water-based intumescent fire-retardant coating.
9. The water-based intumescent fire retardant coating of claim 8, wherein the viscosity of the system after adjustment in S2 is 100-130KU.
CN202311325118.7A 2023-10-12 2023-10-12 Water-based intumescent fireproof coating and preparation method thereof Pending CN117363116A (en)

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CN202311325118.7A CN117363116A (en) 2023-10-12 2023-10-12 Water-based intumescent fireproof coating and preparation method thereof

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Application Number Priority Date Filing Date Title
CN202311325118.7A CN117363116A (en) 2023-10-12 2023-10-12 Water-based intumescent fireproof coating and preparation method thereof

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