WO2021000653A1 - 一种水性环保防火涂料及其制备方法和应用 - Google Patents

一种水性环保防火涂料及其制备方法和应用 Download PDF

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Publication number
WO2021000653A1
WO2021000653A1 PCT/CN2020/090248 CN2020090248W WO2021000653A1 WO 2021000653 A1 WO2021000653 A1 WO 2021000653A1 CN 2020090248 W CN2020090248 W CN 2020090248W WO 2021000653 A1 WO2021000653 A1 WO 2021000653A1
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parts
water
emulsion
environmentally friendly
fireproof coating
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PCT/CN2020/090248
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English (en)
French (fr)
Inventor
谢海
胡明
钱金均
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江苏冠军科技集团股份有限公司
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Publication of WO2021000653A1 publication Critical patent/WO2021000653A1/zh

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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
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/04—Homopolymers or copolymers of ethene
    • C09D123/08—Copolymers of ethene
    • C09D123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09D123/0853—Vinylacetate
    • 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
    • C09D5/08—Anti-corrosive paints
    • 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
    • C09D5/185—Intumescent paints
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/322—Ammonium phosphate
    • C08K2003/323—Ammonium polyphosphate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the invention belongs to the technical field of coating materials, and in particular relates to a water-based environmentally friendly fireproof coating and a preparation method and application thereof.
  • Steel structure is widely used in modern construction industry due to its light weight, high strength, large span, large space, good seismic performance, convenient lifting construction and short construction time.
  • steel structure is a non-combustible building material, its mechanical properties such as yield strength, tensile strength and elastic modulus will drop significantly under the action of high temperature, especially at 450 ⁇ 650°C, it will drop sharply and lose its bearing capacity. Huge deformation occurs, and steel columns and beams bend, and even cause building collapse.
  • the fire resistance limit of conventional steel structures is only about 15 minutes. Therefore, taking fire protection measures for steel structures has become one of the important research topics.
  • Fire protection methods for steel structures such as outer coating, water filling, and shielding, have characteristics such as uneconomical and difficult to operate.
  • coating a layer of fire-retardant coating on steel structures is an economical, practical and easy-to-operate method.
  • all fireproof coatings used generally have the disadvantages of being environmentally unfriendly and poor fireproof performance. Therefore, it is urgent to develop an environmentally friendly, pollution-free, and good flame retardant fireproof coating.
  • the purpose of the present invention is to provide a water-based environmentally friendly fireproof coating.
  • the coating provided by the present invention has excellent fireproof performance and can be used to protect ultra-thin steel structures.
  • the present invention provides a water-based environmentally friendly fireproof coating, comprising the following components by mass: 20 to 35 parts of composite emulsion, 6 to 8 parts of dehydrating agent, 3 to 5 parts of char-forming agent, 5 to 8 parts of foaming agent, and filler 15-18 parts, 8-14 parts auxiliary and 20-25 parts water;
  • the composite emulsion includes EVA emulsion, tertiary vinegar emulsion and vinegar acrylic emulsion;
  • the additives include sodium pyrophosphate, amide imidazoline, sodium alkyl naphthalene sulfonate, ethylene glycol butyl ether, polyethylene glycol, hydroxyethyl cellulose and silicon dioxide.
  • the mass ratio of the EVA emulsion, the tertiary vinegar emulsion and the vinegar-acrylic emulsion is (0.4-0.6): (0.25-0.35): 0.2.
  • the mass ratio of sodium pyrophosphate to amide imidazoline is (1.3 to 1.8): (0.3 to 0.5);
  • the mass ratio of sodium pyrophosphate to sodium alkylnaphthalene sulfonate is (1.3 ⁇ 1.8): (0.3 ⁇ 0.5);
  • the mass ratio of sodium pyrophosphate to ethylene glycol butyl ether is (1.3 ⁇ 1.8): (5 ⁇ 10);
  • the mass ratio of sodium pyrophosphate to polyethylene glycol is (1.3 ⁇ 1.8): (0.6 ⁇ 1.2);
  • the mass ratio of sodium pyrophosphate to hydroxyethyl cellulose is (1.3 ⁇ 1.8): (0.5 ⁇ 1.0);
  • the mass ratio of sodium pyrophosphate to silica is (1.3 to 1.8): (0.2 to 0.5).
  • the dehydrating agent includes one or more of ammonium polyphosphate, magnesium ammonium phosphate and urea phosphate.
  • the char-forming agent includes one or more of sucrose, starch, pentaerythritol and dipentaerythritol.
  • the foaming agent includes one or more of urea-formaldehyde resin, polyamide and urea.
  • the filler includes one or more of kaolin, wollastonite powder, barium sulfate, talc powder, attapulgite, quartz powder and asbestos powder.
  • the present invention provides a preparation method of the water-based environmentally friendly fireproof coating described in the above technical scheme, which includes the following steps:
  • the second mixture is mixed with the composite emulsion, ethylene glycol butyl ether, polyethylene glycol, hydroxyethyl cellulose and silicon dioxide for the third time to obtain a water-based environmentally friendly fireproof coating.
  • the stirring speed of the first mixing is 80-100 r/min, and the time is 10-15 min;
  • the stirring speed of the second mixing is 80-100 r/min, and the time is 15-20 min;
  • the fineness of the second mixture is less than 60 ⁇ m
  • the stirring speed of the third mixing is 500-700 r/min, and the time is 20-30 min.
  • the present invention provides the application of the water-based environmentally friendly fireproof coating described in the above technical solution or the water-based environmentally friendly fireproof coating prepared by the preparation method described in the above technical solution in the surface protection of metal structures.
  • the water-based environmentally friendly fireproof coating includes the following components by mass: 20 to 35 parts of composite emulsion, 6 to 8 parts of dehydrating agent, 3 to 5 parts of charring agent, 5 to 8 parts of foaming agent, and 15 to 15 parts of filler 18 parts, 8-14 parts of auxiliary agent and 20-25 parts of water;
  • the composite emulsion includes EVA emulsion, tertiary vinegar emulsion and acrylic acid-acrylate emulsion;
  • the auxiliary agent includes sodium pyrophosphate, amide imidazoline, alkyl naphthalene sulfonic acid Sodium, ethylene glycol butyl ether, polyethylene glycol, hydroxyethyl cellulose and silicon dioxide.
  • the invention uses the composite emulsion as the basic material liquid.
  • the emulsion used can be miscible with water, providing a basis for preparing water-based environmentally friendly coatings and reducing VOC emissions; in addition, the combined effect of dehydrating agent, char-forming agent and foaming agent can achieve long-term
  • the continuous foaming is beneficial to obtain coatings with better mechanical properties and fire resistance; with the aid of additives, the filler can be uniformly and stably dispersed in the fire retardant coating to obtain better corrosion resistance, wear resistance and fire resistance.
  • Good paint; in addition, the additives formed by the above components can also improve the dispersion and film-forming properties of the paint, and can be applied by brushing, spraying or roller coating, which further improves the application performance of the paint.
  • the implementation results show that the initial thermal decomposition temperature of the fireproof coating provided by the present invention is above 350°C, the maximum thermal decomposition temperature reaches above 640°C, the maximum heat release rate is reduced to 200W/g, and the heat release is as low as 20kJ/g. Performance has been significantly improved.
  • the present invention provides a water-based environmentally friendly fireproof coating, comprising the following components by mass: 20 to 35 parts of composite emulsion, 6 to 8 parts of dehydrating agent, 3 to 5 parts of char-forming agent, 5 to 8 parts of foaming agent, and filler 15-18 parts, 8-14 parts auxiliary and 20-25 parts water;
  • the composite emulsion includes EVA emulsion, tertiary vinegar emulsion and vinegar acrylic emulsion;
  • the additives include sodium pyrophosphate, amide imidazoline, sodium alkyl naphthalene sulfonate, ethylene glycol butyl ether, polyethylene glycol, hydroxyethyl cellulose and silicon dioxide.
  • the water-based environmentally friendly fireproof coating provided by the present invention includes 20-35 parts of composite emulsion, preferably 21-32 parts, more preferably 23-30 parts; said composite emulsion includes EVA emulsion (ethylene-vinyl acetate) , Tertiary vinegar emulsion and acrylate-acrylate emulsion, the mass ratio of the EVA emulsion, tertiary vinegar emulsion and acrylate-acrylate emulsion is preferably (0.4 ⁇ 0.6):(0.25 ⁇ 0.35):0.2, more preferably (0.45 ⁇ 0.55):( 0.27 ⁇ 0.32): 0.2, more preferably 0.5: 0.3: 0.2.
  • EVA emulsion ethylene-vinyl acetate
  • Tertiary vinegar emulsion and acrylate-acrylate emulsion the mass ratio of the EVA emulsion, tertiary vinegar emulsion and acrylate-acrylate emulsion is preferably (0.4 ⁇ 0.6):(0.25 ⁇
  • EVA emulsion, acetic acid emulsion and vinegar-acrylic emulsion are compounded to form a composite emulsion, which is used to improve the film-forming performance of the coating, thereby obtaining a coating with better adhesion and tear resistance.
  • the water-based environmentally friendly fireproof coating of the present invention includes 6 to 8 parts of a dehydrating agent, preferably 6.3 to 7.5 parts, more preferably 6.5 to 7.0 parts; the dehydrating agent preferably includes polyphosphoric acid One or more of ammonium, magnesium ammonium phosphate and urea phosphate, more preferably ammonium polyphosphate or urea phosphate.
  • the dehydrating agent is a mixture of several components, the present invention has no special requirements on the mass ratio of each component in the mixture.
  • the water-based environmentally friendly fireproof coating of the present invention includes 3 to 5 parts of a char-forming agent, preferably 3.2 to 4.7 parts, more preferably 3.5 to 4.5 parts;
  • the char-forming agent preferably includes One or more of sucrose, starch, pentaerythritol and dipentaerythritol, more preferably a mixture of starch and pentaerythritol; when the char-forming agent is a mixture of starch and pentaerythritol, the mass ratio of the starch to pentaerythritol is preferably ( 0.6 to 0.8): 1, more preferably 0.5:1.
  • the water-based environmentally friendly fireproof coating of the present invention includes 5-8 parts of foaming agent, preferably 5.4-7.5 parts, more preferably 5.7-7.3; said foaming agent preferably includes urea-formaldehyde One or more of resin, polyamide and urea, more preferably urea resin or polyamide.
  • foaming agent when the foaming agent is a mixture of several components, the present invention does not specifically limit the amount ratio of each component in the mixture.
  • the water-based environmentally friendly fireproof coating of the present invention includes 5 to 8 parts of filler, preferably 5.2 to 7.8, more preferably 5.5 to 7.5 parts; the particle size of the filler is preferably used in the art The particle size well known to the skilled person is sufficient.
  • the filler preferably includes one or more of kaolin, wollastonite powder, barium sulfate, talc, attapulgite, quartz powder and asbestos powder, more preferably a mixture of kaolin and asbestos powder, kaolin A mixture of quartz powder, kaolin and barium sulfate; when the filler is a mixture of two components, the two components in the mixture are preferably in equal mass ratio.
  • the water-based environmentally friendly fireproof coating of the present invention includes 8-14 parts of auxiliary agents, preferably 9-13 parts, and more preferably 10-12 parts.
  • the additives include sodium pyrophosphate, amide imidazoline, sodium alkyl naphthalene sulfonate, ethylene glycol butyl ether, polyethylene glycol, hydroxyethyl cellulose and silicon dioxide; among them:
  • the mass ratio of the sodium pyrophosphate to the amide imidazoline is preferably (1.3 to 1.8): (0.3 to 0.5), more preferably (1.4 to 1.6): 0.4;
  • the mass ratio of the sodium pyrophosphate to sodium alkylnaphthalene sulfonate is preferably (1.3 to 1.8): (0.3 to 0.5), more preferably (1.4 to 1.6): 0.4;
  • the mass ratio of the sodium pyrophosphate to ethylene glycol butyl ether is preferably (1.3 to 1.8): (5 to 10), more preferably (1.4 to 1.6): (6 to 9), and even more preferably (1.4 to 1.6) ): (7 ⁇ 8);
  • the mass ratio of the sodium pyrophosphate to polyethylene glycol is preferably (1.3 to 1.8): (0.6 to 1.2), more preferably (1.4 to 1.6): (0.7 to 1.0), and even more preferably (1.4 to 1.6) : (0.8 ⁇ 1.0);
  • the mass ratio of the sodium pyrophosphate to hydroxyethyl cellulose is preferably (1.3 to 1.8): (0.5 to 1.0), more preferably (1.4 to 1.6): (0.6 to 0.9), and even more preferably (1.4 to 1.6) ): (0.7 ⁇ 0.8);
  • the mass ratio of the sodium pyrophosphate to silica is preferably (1.3 to 1.8): (0.2 to 0.5), more preferably (1.4 to 1.6): (0.3 to 0.4).
  • the invention uses the composite emulsion as the basic material liquid.
  • the emulsion used can be miscible with water, providing a basis for preparing water-based environmentally friendly coatings and reducing VOC emissions; in addition, the combined effect of dehydrating agent, char-forming agent and foaming agent can achieve long-term
  • the continuous foaming is beneficial to obtain coatings with better mechanical properties and fire resistance; with the aid of additives, the filler can be uniformly and stably dispersed in the fire retardant coating to obtain better corrosion resistance, wear resistance and fire resistance.
  • Good paint; in addition, the additives formed by the above components can also improve the dispersion and film-forming properties of the paint, and can be applied by brushing, spraying or roller coating, which further improves the application performance of the paint.
  • the present invention provides a preparation method of the water-based environmentally friendly fireproof coating described in the above technical scheme, which includes the following steps:
  • the second mixture is mixed with the composite emulsion, ethylene glycol butyl ether, polyethylene glycol, hydroxyethyl cellulose and silicon dioxide for the third time to obtain a water-based environmentally friendly fireproof coating.
  • water, sodium pyrophosphate, amide imidazoline and sodium alkylnaphthalene sulfonate are first mixed to obtain a first mixture.
  • the stirring speed of the first mixing is preferably 80-100 r/min, more preferably 100 r/min; the time is preferably 10-15 min, more preferably 12-15 min.
  • the first mixture and the dehydrating agent, the char-forming agent, the foaming agent and the filler are sequentially subjected to second mixing and grinding to obtain the second mixture.
  • the stirring speed of the second mixing is preferably 80-100r/min, more preferably 100r/min; the time is preferably 15-20min, more preferably 16-18min; after the second mixing, the present invention
  • the second mixed material is ground to obtain a second mixed material.
  • the fineness of the second mixture is less than 60 ⁇ m, more preferably 20-50 ⁇ m.
  • the grinding is preferably performed in a sander. The present invention does not have special requirements for the specific parameter setting of the sander, as long as the mixture of the above fineness can be obtained.
  • the second mixture is mixed with the composite emulsion, ethylene glycol butyl ether, polyethylene glycol, hydroxyethyl cellulose and silicon dioxide for a third mixing to obtain a water-based environmentally friendly fireproof coating .
  • the composite emulsion is preferably obtained after mixing emulsions of the components.
  • the stirring speed of the third mixing is preferably 500 to 700 r/min, more preferably 550 to 650 r/min, and even more preferably 600 r/min; the stirring time is preferably 20 to 30 min, more preferably 22 ⁇ 28min, more preferably 24-25min.
  • the above-mentioned components are mixed in batches, which can improve the mixing effect of each component, uniformly disperse different functional components, and obtain uniform and stable coatings.
  • the present invention also provides the application of the water-based environmentally friendly fireproof coating described in the above technical solution or the water-based environmentally friendly fireproof coating prepared by the preparation method described in the above technical solution.
  • the application method preferably includes the following steps:
  • the water-based environmentally friendly fireproof coating is coated on the substrate, and an environmentally friendly fireproof coating is formed after drying.
  • the coating method preferably includes brushing, spraying or roller coating;
  • the substrate preferably includes a metal structure, a steel structure, and the surface to be coated of the substrate is preferably a clean plane or curved surface; dry
  • the method is preferably oxidative drying;
  • the thickness of the environmentally friendly fireproof coating is preferably 1.5 mm, more preferably 2 mm.
  • the present invention has no special requirements on coating amount and coating times, as long as the coating with the above thickness can be obtained.
  • the preparation process is as follows:
  • additives-sodium pyrophosphate polyethylene glycol: sodium alkylnaphthalene sulfonate: amide imidazoline: ethylene glycol butyl ether: hydroxyethyl cellulose: fumed silica, the mass ratio is 1.7:1.0:0.5 : 0.4: 5:1: 0.4;
  • the water-based environmental protection coating and the fireproof coating were prepared according to the method of Example 1, except that the base emulsion was an EVA emulsion.
  • Example 1 Example 2
  • Example 3 Comparison Compressive strength (MPa) 350 330 330 230 Strain at break (%) 40 42
  • Initial thermal decomposition temperature (°C) 350 360 355 250
  • Paint film adhesion (kN/cm 3 ) 0.55 0.5 0.5 0.4
  • Flame resistance time (h) 0.2 0.3 0.2 0.1 Flame spread ratio 15 16 15 25 Carbonization volume (cm 3 ) twenty one 19 19
  • J Paint film adhesion
  • h 0.2 0.3 0.2 0.1 Flame spread ratio 15 16 15 25 Carbonization volume (cm 3 ) twenty one 19 19
  • the water-based environmentally friendly fireproof coating provided by the present invention can form an ultra-thin coating with a thickness of 2 mm, and still maintains excellent fireproof and mechanical properties.
  • the coating provided by the present invention is a water-soluble coating, which reduces the release of VOCs and is more environmentally friendly compared to solvent-based coatings.
  • the coating provided by the present invention has excellent mechanical properties and fire resistance, and can be used for metal structural parts. Play an effective protective effect; the preparation method of the water-soluble coating of the present invention is simple and easy to scale production.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

一种水性环保防火涂料及其制备方法和应用，所述水性环保防火涂料包括以下质量份的组分：复合乳液20～35份，脱水剂6～8份，成炭剂3～5份，发泡剂5～8份，填料15～18份，助剂8～14份和水20～25份；所述复合乳液包括EVA乳液、醋叔乳液和醋丙乳液；所述助剂包括焦磷酸钠、酰胺咪唑啉、烷基萘磺酸钠、乙二醇丁醚、聚乙二醇、羟乙基纤维素和二氧化硅。实施结果表明，所述防火涂料的起始热分解温度在350℃以上，最高热分解温度达到640℃以上，最大热释放速率降低至200W/g，热释放量低至20kJ/g，防火性能有了明显提升。

Description

一种水性环保防火涂料及其制备方法和应用 技术领域
本发明属于涂料材料技术领域，具体涉及一种水性环保防火涂料及其制备方法和应用。
背景技术
钢结构由于自重轻、强度高、跨度大、空间大、抗震性能好、吊装施工方便和建设时间短，在现代建筑业得到广泛应用。钢结构虽然是一种不燃建筑材料，但在高温作用下，其力学性能如屈服强度、抗拉强度及弹性模量会大幅度下降，尤其在450～650℃更会急剧下降，失去承载能力，产生巨大的形变，进而出现钢柱、钢梁弯曲，甚至引起建筑坍塌。据研究，常规的钢结构的耐火极限仅为15min左右，因此，对钢结构采取防火保护措施成为重要的研究课题之一。
钢结构防火保护的方法，如外包层、充水以及屏蔽等，都存在如不经济、不易操作等特点。相比较而言，在钢结构上涂覆一层防火涂料是一种既经济实用又便于操作的方法。目前所用防火涂料都普遍存在环境不友好、防火性能差的不足，因此，开发一种环保无污染、阻燃效果好的防火涂料迫在眉睫。
发明内容
本发明的目的在于在于提供一种水性环保防火涂料，本发明提供的涂料防火性能优异，可用于保护超薄型钢结构。
为了实现上述目的，本发明提供如下技术方案：
本发明提供了一种水性环保防火涂料，包括以下质量份的组分：复合乳液20～35份，脱水剂6～8份，成炭剂3～5份，发泡剂5～8份，填料15～18份，助剂8～14份和水20～25份；
所述复合乳液包括EVA乳液、醋叔乳液和醋丙乳液；
所述助剂包括焦磷酸钠、酰胺咪唑啉、烷基萘磺酸钠、乙二醇丁醚、聚乙二醇、羟乙基纤维素和二氧化硅。
优选的，所述复合乳液中，EVA乳液、醋叔乳液和醋丙乳液的质量比为(0.4～0.6)：(0.25～0.35)：0.2。
优选的，所述助剂中，焦磷酸钠与酰胺咪唑啉的质量比为(1.3～1.8)： (0.3～0.5)；
焦磷酸钠与烷基萘磺酸钠的质量比为(1.3～1.8)：(0.3～0.5)；
焦磷酸钠与乙二醇丁醚的质量比为(1.3～1.8)：(5～10)；
焦磷酸钠与聚乙二醇的质量比为(1.3～1.8)：(0.6～1.2)；
焦磷酸钠与羟乙基纤维素的质量比为(1.3～1.8)：(0.5～1.0)；
焦磷酸钠与二氧化硅的质量比为(1.3～1.8)：(0.2～0.5)。
优选的，所述脱水剂包括聚磷酸铵、磷酸铵镁和磷酸尿素中的一种或几种。
优选的，所述成炭剂包括蔗糖、淀粉、季戊四醇和二季戊四醇中的一种或几种。
优选的，所述发泡剂包括脲醛树脂、聚酰胺和尿素中的一种或几种。
优选的，所述填料包括高岭土、硅灰石粉、硫酸钡、滑石粉、凹凸棒土、石英粉和石棉粉中的一种或几种。
本发明提供了上述技术方案所述的水性环保防火涂料的制备方法，包括以下步骤：
将水、焦磷酸钠、酰胺咪唑啉和烷基萘磺酸钠进行第一混合，得到第一混合料；
将所述第一混合料与脱水剂、成炭剂、发泡剂和填料依次进行第二混合和研磨，得到第二混合料；
将所述第二混合料与复合乳液、乙二醇丁醚、聚乙二醇、羟乙基纤维素和二氧化硅进行第三混合，得到水性环保防火涂料。
优选的，所述第一混合的搅拌速度为80～100r/min，时间为10～15min；
所述第二混合的搅拌速度为80～100r/min，时间为15～20min；
所述第二混合料的细度低于60μm；
所述第三混合的搅拌速度为500～700r/min，时间为20～30min。
本发明提供了上述技术方案所述的水性环保防火涂料或上述技术方案所述的制备方法制备得到的水性环保防火涂料在金属结构件表面保护中的应用。
本发明提供的水性环保防火涂料，包括以下质量份的组分：复合乳液20～35份，脱水剂6～8份，成炭剂3～5份，发泡剂5～8份，填料15～18份，助剂8～14份和水20～25份；所述复合乳液包括EVA乳液、醋叔乳液和醋丙乳液；所述助剂包括焦磷酸钠、酰胺咪唑啉、烷基萘磺酸钠、乙二醇丁醚、聚乙二醇、羟乙基纤维素和二氧化硅。本发明以复合乳液为基础料液，所用乳液能够与水互溶，为制备水性环保涂料，降低VOC的排放量提供基础；另外，脱水剂、成炭剂和发泡剂配合作用，能够实现长时间的持续发泡，对获得力学性能和防火性能较好的涂料有利；填料在助剂的辅助下，能够均匀、稳定的分散在防火涂料中，进而得到耐腐蚀性能、耐磨性能和防火性能较好的涂料；此外，上述组分形成的助剂还能改善涂料的分散和成膜性能，可采用刷涂、喷涂或辊涂的方式施工，进一步提高了涂料的施工性能。实施结果表明，本发明提供的防火涂料的起始热分解温度在350℃以上，最高热分解温度达到640℃以上，最大热释放速率降低至200W/g，热释放量低至20kJ/g，防火性能有了明显提升。
具体实施方式
本发明提供了一种水性环保防火涂料，包括以下质量份的组分：复合乳液20～35份，脱水剂6～8份，成炭剂3～5份，发泡剂5～8份，填料15～18份，助剂8～14份和水20～25份；
所述复合乳液包括EVA乳液、醋叔乳液和醋丙乳液；
所述助剂包括焦磷酸钠、酰胺咪唑啉、烷基萘磺酸钠、乙二醇丁醚、聚乙二醇、羟乙基纤维素和二氧化硅。
以质量份计，本发明提供的水性环保防火涂料包括复合乳液20～35份，优选为21～32份，更优选为23～30份；所述复合乳液包括EVA乳液(乙烯-醋酸乙烯酯)、醋叔乳液和醋丙乳液，所述EVA乳液、醋叔乳液和醋丙乳液的质量比优选为(0.4～0.6)：(0.25～0.35)：0.2，更优选为(0.45～0.55)：(0.27～0.32)：0.2，再优选为0.5：0.3：0.2。本发明将EVA乳液、醋酸乳液和醋丙乳液复配形成复合乳液，用于改善涂料的成膜性能，进而得到粘附性和耐撕裂性能较好的涂层。
以所述质量份的复合乳液为基准，本发明所述水性环保防火涂料包括脱水剂6～8份，优选为6.3～7.5份，更优选为6.5～7.0份；所述脱水剂优选包括聚磷酸铵、磷酸铵镁和磷酸尿素中的一种或几种，更优选为聚磷酸铵或磷酸尿素。当脱水剂为几种组分的混合物时，本发明对所述混合物中各组分的质量比没有特殊要求。
以所述质量份的复合乳液为基准，本发明所述水性环保防火涂料包括成炭剂3～5份，优选为3.2～4.7份，更优选为3.5～4.5份；所述成炭剂优选包括蔗糖、淀粉、季戊四醇和二季戊四醇中的一种或几种，更优选为淀粉和季戊四醇的混合物；当所述成炭剂为淀粉和季戊四醇的混合物时，所述淀粉与季戊四醇的质量比优选为(0.6～0.8)：1，更优选为0.5：1。
以所述质量份的复合乳液为基准，本发明所述水性环保防火涂料包括发泡剂5～8份，优选为5.4～7.5份，更优选为5.7～7.3；所述发泡剂优选包括脲醛树脂、聚酰胺和尿素中的一种或几种，更优选为脲醛树脂或聚酰胺。在本发明中，当发泡剂为几种组分的混合物时，本发明对所述混合物中的各组分的用量比没有特殊限定。
以所述质量份的复合乳液为基准，本发明所述水性环保防火涂料包括填料5～8份，优选为5.2～7.8，更优选为5.5～7.5份；所述填料的粒径优选采用本领域技术人员熟知的粒径即可。在本发明中，所述填料优选包括高岭土、硅灰石粉、硫酸钡、滑石粉、凹凸棒土、石英粉和石棉粉中的一种或几种，更优选为高岭土和石棉粉的混合物、高岭土和石英粉的混合物、高岭土和硫酸钡的混合物；当填料为两种组分的混合物时，混合物中两种组分优选为等质量比。
以所述质量份的复合乳液为基准，本发明所述水性环保防火涂料包括助剂8～14份，优选为9～13份，再优选为10～12份。在本发明中，所述助剂包括焦磷酸钠、酰胺咪唑啉、烷基萘磺酸钠、乙二醇丁醚、聚乙二醇、羟乙基纤维素和二氧化硅；其中：
所述焦磷酸钠与酰胺咪唑啉的质量比优选为(1.3～1.8)：(0.3～0.5)，更优选为(1.4～1.6)：0.4；
所述焦磷酸钠与烷基萘磺酸钠的质量比优选为(1.3～1.8)：(0.3～0.5)， 更优选为(1.4～1.6)：0.4；
所述焦磷酸钠与乙二醇丁醚的质量比优选为(1.3～1.8)：(5～10)，更优选为(1.4～1.6)：(6～9)，再优选为(1.4～1.6)：(7～8)；
所述焦磷酸钠与聚乙二醇的质量比优选为(1.3～1.8)：(0.6～1.2)，更优选为(1.4～1.6)：(0.7～1.0)，再优选为(1.4～1.6)：(0.8～1.0)；
所述焦磷酸钠与羟乙基纤维素的质量比优选为(1.3～1.8)：(0.5～1.0)，更优选为(1.4～1.6)：(0.6～0.9)，再优选为(1.4～1.6)：(0.7～0.8)；
所述焦磷酸钠与二氧化硅的质量比优选为(1.3～1.8)：(0.2～0.5)，更优选为(1.4～1.6)：(0.3～0.4)。
本发明以复合乳液为基础料液，所用乳液能够与水互溶，为制备水性环保涂料，降低VOC的排放量提供基础；另外，脱水剂、成炭剂和发泡剂配合作用，能够实现长时间的持续发泡，对获得力学性能和防火性能较好的涂料有利；填料在助剂的辅助下，能够均匀、稳定的分散在防火涂料中，进而得到耐腐蚀性能、耐磨性能和防火性能较好的涂料；此外，上述组分形成的助剂还能改善涂料的分散和成膜性能，可采用刷涂、喷涂或辊涂的方式施工，进一步提高了涂料的施工性能。
本发明提供了上述技术方案所述的水性环保防火涂料的制备方法，包括以下步骤：
将水、焦磷酸钠、酰胺咪唑啉和烷基萘磺酸钠进行第一混合，得到第一混合料；
将所述第一混合料与脱水剂、成炭剂、发泡剂和填料依次进行第二混合和研磨，得到第二混合料；
将所述第二混合料与复合乳液、乙二醇丁醚、聚乙二醇、羟乙基纤维素和二氧化硅进行第三混合，得到水性环保防火涂料。
本发明将水、焦磷酸钠、酰胺咪唑啉和烷基萘磺酸钠进行第一混合，得到第一混合料。在本发明中，所述第一混合的搅拌速度优选为80～100r/min，更优选为100r/min；时间优选为10～15min，更优选为12～15min。
得到第一混合料后，本发明将所述第一混合料与脱水剂、成炭剂、发泡 剂和填料依次进行第二混合和研磨，得到第二混合料。在本发明中，所述第二混合的搅拌速度优选为80～100r/min，更优选为100r/min；时间优选为15～20min，更优选为16～18min；第二混合后，本发明对所述第二混合后的物料进行研磨，得到第二混合料。在本发明中，所述第二混合料的细度低于60μm，更优选为20～50μm。在本发明中，所述研磨优选在磨砂机中进行。本发明对所述磨砂机的具体参数设置没有特殊要求，能得到上述细度的混合料即可。
得到第二混合料后，本发明将所述第二混合料与复合乳液、乙二醇丁醚、聚乙二醇、羟乙基纤维素和二氧化硅进行第三混合，得到水性环保防火涂料。在本发明中，所述复合乳液优选将所述组分的乳液混合后得到。在本发明中，所述第三混合的搅拌速度优选为500～700r/min，更优选为550～650r/min，再优选为600r/min；搅拌的时间优选为20～30min，更优选为22～28min，再优选为24～25min。
本发明将上述组分分批混合，可提高各组分混合效果，使不同功能组分均匀分散，得到分散均匀和稳定的涂料。
本发明还提供了上述技术方案所述的水性环保防火涂料或上述技术方案所述的制备方法制备得到的水性环保防火涂料的应用。在本发明中，所述应用的方式优选包括如下步骤：
将所述水性环保防火涂料涂覆至基底上，干燥后形成环保防火涂层。
在本发明中，所述涂覆的方式优选包括刷涂、喷涂或辊涂；所述基底优选包括金属结构件、钢结构，所述基底的待涂覆面优选为洁净的平面或曲面；干燥的方式优选为氧化干燥；所述环保防火涂层的厚度优选为1.5mm，更优选为2mm。本发明对涂覆量、涂覆次数没有特殊要求，能得到上述厚度的涂层即可。
为了进一步说明本发明，下面结合实施例对本发明提供的水性环保防火涂料及其制备方法和应用进行详细地描述，但不能将它们理解为对本发明保护范围的限定。
实施例1
配料以质量份计：
25份复合乳液-EVA乳液、醋酸乳液和醋丙乳液按照0.5：0.3：0.2的质量比混合而成；
8份脱水剂-聚磷酸铵；
5份成炭剂-二季戊四醇；
8份发泡剂-脲醛树脂；
18份填料-高岭土；
13份助剂-焦磷酸钠：聚乙二醇：烷基萘磺酸钠：酰胺咪唑啉：乙二醇丁醚：羟乙基纤维素：气相二氧化硅的质量比为1.5：1.0：0.3：0.2：9.0：0.5：0.5；
23份去离子水。
制备工艺如下：
1)将去离子水、焦磷酸钠、聚乙二醇、酰胺咪唑啉及烷基萘磺酸钠依次加入分散缸中混合，以约50r/min的速度搅拌10min，得到第一混合料；
2)向上述第一混合料中依次加入聚磷酸铵、二季戊四醇、脲醛树脂和高岭土，分散搅拌约15min左右；然后将混合物转入磨砂机中以1200r/min的速度进行研磨，研磨时间约70min，研磨细度要求＜60μm，得到第二混合料；
3)将上述第二混合料转入分散罐中，加入复合乳液、乙二醇丁醚和羟乙基纤维素进行充分混合，最后加入气相二氧化硅调节黏度，以800r/min的转速分散15min后即得水性环保防火涂料；
4)将所得水性环保防火涂料采用喷涂的方式涂覆在钢结构上，在氧化干燥条件下干燥，形成厚度为2mm的防火涂层。
实施例2
配料以质量份计：
28份复合乳液-EVA乳液、醋酸乳液和醋丙乳液按照0.7：0.4：0.2的质量比混合而成；
4份脱水剂-磷酸铵镁；
10份成炭剂-季戊四醇；
6份发泡剂-聚酰胺；
25份填料-硅灰石粉；
14份助剂-焦磷酸钠：聚乙二醇：烷基萘磺酸钠：酰胺咪唑啉：乙二醇丁醚：羟乙基纤维素：气相二氧化硅的质量比为1.8：0.5：0.4：0.3：10：0.8：0.2；
25份去离子水。
制备工艺：
1)将去离子水、焦磷酸钠、酰胺咪唑啉、聚乙二醇及烷基萘磺酸钠依次加入分散缸中，以约80r/min的速度搅拌10min，得到第一混合料；
2)向第一混合料中加入磷酸铵镁、季戊四醇、聚酰胺以及硅灰石粉，分散搅拌20min；然后将所得混合物转入磨砂机中以1000r/min的速度进行研磨，研磨时间约60min，研磨细度要求＜60μm，得到第二混合料；
3)将第二混合料转入分散罐中，加入复合乳液、乙二醇丁醚和羟乙基纤维素进行充分混合，最后加入气相二氧化硅调节黏度，以700r/min的转速分散10min后即得水性环保防火涂料；
4)将所得水性环保防火涂料采用喷涂的方式涂覆在钢结构上，在氧化干燥条件下干燥，形成厚度为2mm的防火涂层。
实施例3
配料以质量份计：
30份复合乳液-EVA乳液、醋酸乳液和醋丙乳液按照0.8：0.3：0.2的质量比混合而成；
6份脱水剂-磷酸尿素；
3份成炭剂-淀粉；
6份发泡剂-尿素；
17份填料-石棉粉；
10份助剂-焦磷酸钠：聚乙二醇：烷基萘磺酸钠：酰胺咪唑啉：乙二醇丁醚：羟乙基纤维素：气相二氧化硅的质量比为1.7：1.0：0.5：0.4：5：1：0.4；
20份去离子水。
制备工艺：
1)将去离子水、焦磷酸钠、聚乙二醇、酰胺咪唑啉及烷基萘磺酸钠依次加入分散缸中，以约75r/min的速度搅拌15min，得到第一混合料；
2)向上述第一混合料中加入磷酸尿素、淀粉、尿素以及石棉粉，分散搅拌10min，然后将所得混合物转入磨砂机中以1200r/min的速度进行研磨，研磨时间约50min，研磨细度要求＜60μm，得到第二混合料；
3)将第二混合料转入分散罐中，加入复合乳液、乙二醇丁醚和羟乙基纤维素等进行充分混合，最后加入气相二氧化硅调节黏度，以800r/min的转速分散20min后即得水性环保防火涂料。
4)将所得水性环保防火涂料采用喷涂的方式涂覆在钢结构上，在氧化干燥条件下干燥，形成厚度为2mm的防火涂层。
对比例1
按照实施例1的方式制备水性环保涂料和防火涂层，不同之处在于：基料乳液为EVA乳液。
性能表征与结果
按照GB 14907-2018标准测试实施例1～3所得涂层压缩强度、断裂应变、热稳定性能、防火性能等系列基础性能，具体测试内容和测试结果如表1所示。
表1实施例1～3制备的防火涂层的性能测试结果
测试项目 实施例1 实施例2 实施例3 对比例
压缩强度(MPa) 350 330 330 230
断裂应变(％) 40 42 35 28
起始热分解温度(℃) 350 360 355 250
最高热分解温度(℃) 640 660 640 440
最大热释放速率(W/g) 200 200 200 360
特定热释放(kJ/g) 20 20 20 35
漆膜附着力(kN/cm 3) 0.55 0.5 0.5 0.4
耐燃时间(h) 0.2 0.3 0.2 0.1
火焰传播比值 15 16 15 25
碳化体积(cm 3) 21 19 19 32
由表1可知，利用本发明提供的水性环保防火涂料能够形成2mm厚的超薄涂层，并且仍保持了优异的防火性能和机械性能。
由以上实施例可知，本发明提供的涂料为水溶性涂料，相对于溶剂型涂料，减少了VOC的释放，更为环保；本发明提供的涂料具有优异力学性能和防火性能，能对金属结构件起到有效的防护作用；本发明所述的水溶性涂料的制备方法简单，易于规模化生产。
尽管上述实施例对本发明做出了详尽的描述，但它仅仅是本发明一部分实施例，而不是全部实施例，人们还可以根据本实施例在不经创造性前提下获得其他实施例，这些实施例都属于本发明保护范围。

Claims (10)

  1. 一种水性环保防火涂料，包括以下质量份的组分：复合乳液20～35份，脱水剂6～8份，成炭剂3～5份，发泡剂5～8份，填料15～18份，助剂8～14份和水20～25份；
    所述复合乳液包括EVA乳液、醋叔乳液和醋丙乳液；
    所述助剂包括焦磷酸钠、酰胺咪唑啉、烷基萘磺酸钠、乙二醇丁醚、聚乙二醇、羟乙基纤维素和二氧化硅。
  2. 如权利要求1所述的水性环保防火涂料，其特征在于，所述复合乳液中，EVA乳液、醋叔乳液和醋丙乳液的质量比为(0.4～0.6)：(0.25～0.35)：0.2。
  3. 如权利要求1或2所述的水性环保防火涂料，其特征在于，所述助剂中，焦磷酸钠与酰胺咪唑啉的质量比为(1.3～1.8)：(0.3～0.5)；
    焦磷酸钠与烷基萘磺酸钠的质量比为(1.3～1.8)：(0.3～0.5)；
    焦磷酸钠与乙二醇丁醚的质量比为(1.3～1.8)：(5～10)；
    焦磷酸钠与聚乙二醇的质量比为(1.3～1.8)：(0.6～1.2)；
    焦磷酸钠与羟乙基纤维素的质量比为(1.3～1.8)：(0.5～1.0)；
    焦磷酸钠与二氧化硅的质量比为(1.3～1.8)：(0.2～0.5)。
  4. 如权利要求1所述的水性环保防火涂料，其特征在于，所述脱水剂包括聚磷酸铵、磷酸铵镁和磷酸尿素中的一种或几种。
  5. 如权利要求1、2或4所述的水性环保防火涂料，其特征在于，所述成炭剂包括蔗糖、淀粉、季戊四醇和二季戊四醇中的一种或几种。
  6. 如权利要求5所述的水性环保防火涂料，其特征在于，所述发泡剂包括脲醛树脂、聚酰胺和尿素中的一种或几种。
  7. 如权利要求1、2、4或6所述的水性环保防火涂料，其特征在于，所述填料包括高岭土、硅灰石粉、硫酸钡、滑石粉、凹凸棒土、石英粉和石棉粉中的一种或几种。
  8. 权利要求1～7任一项所述的水性环保防火涂料的制备方法，包括以下步骤：
    将水、焦磷酸钠、酰胺咪唑啉和烷基萘磺酸钠进行第一混合，得到第一 混合料；
    将所述第一混合料与脱水剂、成炭剂、发泡剂和填料依次进行第二混合和研磨，得到第二混合料；
    将所述第二混合料与复合乳液、乙二醇丁醚、聚乙二醇、羟乙基纤维素和二氧化硅进行第三混合，得到水性环保防火涂料。
  9. 如权利要求8所述的制备方法，其特征在于，所述第一混合的搅拌速度为80～100r/min，时间为10～15min；
    所述第二混合的搅拌速度为80～100r/min，时间为15～20min；
    所述第二混合料的细度低于60μm；
    所述第三混合的搅拌速度为500～700r/min，时间为20～30min。
  10. 权利要求1～7任一项所述的水性环保防火涂料或权利要求8或9所述的制备方法制备得到的水性环保防火涂料在金属结构件表面保护中的应用。
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