CN112876921B - Oily fireproof paint with water-absorbing powder and preparation process thereof - Google Patents

Oily fireproof paint with water-absorbing powder and preparation process thereof Download PDF

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CN112876921B
CN112876921B CN202110073750.1A CN202110073750A CN112876921B CN 112876921 B CN112876921 B CN 112876921B CN 202110073750 A CN202110073750 A CN 202110073750A CN 112876921 B CN112876921 B CN 112876921B
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powder
water
polyphenylene sulfide
fireproof coating
silicon dioxide
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CN112876921A (en
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王宏辉
马年
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Jiangsu Zhaohui Chemical 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and 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
    • C09D133/04—Homopolymers or copolymers of esters
    • 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
    • C09D181/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
    • C09D181/02—Polythioethers; Polythioether-ethers
    • 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
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • 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

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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)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention relates to an oily fire-retardant coating with water-absorbing powder and a preparation process thereof, which is prepared by mixing thermoplastic resin, polyphenylene sulfide porous water-absorbing powder, butyl acetate, ammonium polyphosphate, melamine, pentaerythritol, titanium dioxide, chopped fiber, a dispersing agent and the like. The invention adopts the high molecular material modified by a special microstructure as an important raw material, which does not belong to inorganic matters, can not inhibit the foaming of the fireproof coating when foaming, but can also increase the residual carbon content, so that the carbon layer of the fireproof coating has increased strength, the desorption temperature of moisture is matched with the decomposition temperature of an acid source in the fireproof coating, the moisture is vaporized into water vapor after desorption, the water vapor is used as an air source to promote the foaming of the fireproof coating, and a large amount of heat is absorbed, so that the temperature rise of the protected steel substrate is slow.

Description

Oily fireproof paint with water-absorbing powder and preparation process thereof
The technical field is as follows:
the invention relates to the technical field of coatings, in particular to an oily fireproof coating with water-absorbing powder, a preparation process thereof and a preparation process of organic polymer porous water-absorbing powder for the oily fireproof coating with the water-absorbing powder.
Background art:
inorganic mineral fillers are generally added into the fireproof coating in the market at present to increase the strength of a carbon layer after combustion, the foaming ratio of the carbon layer is reduced due to excessive addition amount, and if inorganic materials are thermally decomposed by adding, the decomposition temperature is very high, and the heat absorption effect on the fireproof coating is not large.
The invention content is as follows:
the invention provides an oily fireproof paint with water-absorbing powder and a preparation process thereof, which can greatly enhance the strength of the oily paint and absorb a large amount of heat at the same time, so that the temperature of a protected steel substrate is slowly raised.
The invention is realized by the following technical scheme:
the invention provides an oily fireproof paint with water-absorbing powder, which comprises the following components in percentage by mass: 10-15% of thermoplastic resin, 5-15% of polyphenylene sulfide porous water-absorbing powder, 15-20% of butyl acetate, 20-30% of ammonium polyphosphate, 15-20% of melamine, 15-20% of pentaerythritol, 3-6% of titanium dioxide, 1-2% of chopped fibers and the balance of processing aid.
In order to obtain a melting temperature matched with the fireproof coating, resins with different melting temperatures can be selected, but care should be taken that the resin can resist corrosion of hydrofluoric acid, so that the thermoplastic resin is preferably one of acrylic resin, high chlorinated polyethylene and chlorinated rubber. In addition, in the case of solvent-based fire-retardant coatings, it must be ensured that the resins used in the above-mentioned powders are resistant to attack by solvents.
Because the oily paint contains a solvent, the polyphenylene sulfide porous water-absorbing powder which is insoluble in the solvent is selected, and the preparation process of the polyphenylene sulfide porous water-absorbing powder comprises the following steps:
(1) placing the nano silicon dioxide powder into a container, dropwise adding oleic acid with the concentration not more than 0.03%, and then placing the nano silicon dioxide powder into a ball mill or a high-speed closed stirrer for dispersion until powder particles do not agglomerate visually;
(2) mixing the treated nano silicon dioxide powder with polyphenylene sulfide in a matching ratio (the polyphenylene sulfide is 100: 5-15), uniformly mixing, granulating, extruding by a screw machine, and granulating;
(3) freezing and crushing the particles in a crusher, screening fine powder with the granularity of more than 400 meshes, and continuously crushing coarse particles until all the coarse particles pass through the 400 meshes;
(4) placing the powder into hydrofluoric acid, and washing away silicon dioxide to obtain pores with nanometer-scale surface;
(5) washing the polyphenylene sulfide fine powder after acid washing with alkali, washing with clear water until the pH value is neutral, and performing suction filtration and discharging;
(6) and (3) slowly drying the filter material at 60 ℃, and scattering the agglomerated powder again to uniformly disperse the powder for later use.
The invention also provides a preparation process of the oily fireproof coating with the water-absorbing powder, which comprises the following steps: dissolving the thermoplastic resin with the formula amount in 80% butyl acetate to obtain viscous resin liquid; putting other materials except the chopped fibers into the mixture, and dispersing the materials at a high speed until the materials are uniform; adjusting the viscosity of the system by using the residual butyl acetate; then, the chopped fibers were gradually added and kneaded in a kneader to obtain a fireproof coating in the form of a paste.
The invention has the beneficial effects that: the invention adopts a high molecular material modified by a special microstructure as an important raw material, nano open pores are densely distributed on the surface of the material, water is fully adsorbed in the pores, the principle of the material is similar to that of a molecular sieve, when combustion occurs, the water is desorbed and lost at about 300 ℃, residual organic polymer shells are melted, dehydrated and carbonized to form a part of a carbon layer, and the material does not belong to inorganic substances compared with the existing molecular sieve raw powder in the market, the foaming of the fireproof coating cannot be inhibited when the fireproof coating is foamed, on the contrary, the residual carbon content can be increased, the carbon layer of the fireproof coating is strengthened, the desorption temperature of the water is matched with the acid source decomposition temperature in the fireproof coating, the water is vaporized into water vapor after desorption, the water vapor is used as a gas source to promote the foaming of the fireproof coating, and a large amount of heat is absorbed, so that the temperature rise of a protected steel substrate is slow.
Description of the drawings:
FIG. 1 is a graph showing the results of the combustion test according to the present invention.
The specific implementation mode is as follows:
the following detailed description of the preferred embodiments of the present invention is provided to enable those skilled in the art to more readily understand the advantages and features of the present invention and to clearly define the scope of the invention.
Example 1:
preparing polyphenylene sulfide porous water-absorbing powder:
the nano silicon dioxide powder is put into a container, no more than 0.03 percent of oleic acid is dripped, and then the nano silicon dioxide powder is put into a ball mill or a high-speed closed stirrer for dispersion until the powder particles do not agglomerate visually.
Mixing the treated nano silicon dioxide powder with polyphenylene sulfide in a mixing ratio (the polyphenylene sulfide and the nano silicon dioxide are 100: 5-15), uniformly mixing, granulating, extruding by a screw machine, and granulating.
Pulverizing the granules in a pulverizer, sieving to obtain fine powder with a particle size of above 400 meshes, and pulverizing the coarse granules until all the coarse granules pass through the particle size of 400 meshes.
And putting the powder into hydrofluoric acid, and washing away silicon dioxide to obtain the nano-scale pores fully distributed on the surface.
And (3) washing the polyphenylene sulfide after acid washing with alkali, washing with clear water until the pH value is neutral, and performing suction filtration and discharging.
And (3) slowly drying the filter material at 60 ℃, and scattering the agglomerated powder again to uniformly disperse the powder for later use.
The following acrylic fire-retardant coating (oil-based coating) is taken as an example:
example 2:
the formula comprises the following components:
Figure GDA0002986143090000031
example 3:
the formula comprises the following components:
Figure GDA0002986143090000032
Figure GDA0002986143090000041
example 4:
the formula comprises the following components:
Figure GDA0002986143090000042
the preparation process of the oily fire retardant coating with water-absorbing powder in the above embodiments 2 to 4 is as follows:
dissolving the acrylic resin with the formula amount in about 80% of butyl acetate in the formula to obtain viscous resin liquid, putting other materials except the chopped carbon fibers into the viscous resin liquid, dispersing the materials at a high speed until the materials are uniform, adjusting the viscosity of the system by using the residual butyl acetate, then slowly adding the chopped carbon fibers, and kneading the materials in a kneader to obtain the fireproof coating similar to a paste.
The oily fire-retardant coating material having water-absorbent powder in example 4 was designated as sample 1, and a blank (not containing polyphenylene sulfide porous water-absorbent powder) was prepared in the same manner and designated as a blank.
Sample 1 was compared to the blank:
plate manufacturing: and (3) airless spraying the two fire-retardant coatings on a steel plate with the thickness of 3mm and an anti-rust primer, wherein each wet film is 1mm, the subsequent coating is sprayed after the previous coating is dried, the total thickness is three, and the thickness of the dry film is 2-3 mm.
1. Water resistance:
sample 1 was soaked for 48 hours with no abnormalities.
The blank was soaked for 48 hours without abnormality.
2. Adhesion (pull off method): mean value of
Sample 10.91 MPa.
Blank 1.19 MPa.
As can be seen, in the conventional performance comparison, the fireproof coating added with the polyphenylene sulfide porous water absorption powder has no change and adverse effect compared with the blank sample 1.
3. The results of the combustion test were:
as shown in the graph of FIG. 1, when the blank sample without the water-absorbent powder added reaches 580 ℃ in about 92min, the sample 1 with the water-absorbent powder added reaches 580 ℃ after 100 min.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.

Claims (2)

1. The oily fireproof coating with the water-absorbing powder is characterized by comprising the following components in percentage by mass: 10-15% of thermoplastic resin, 5-15% of polyphenylene sulfide porous water-absorbing powder, 15-20% of butyl acetate, 20-30% of ammonium polyphosphate, 15-20% of melamine, 15-20% of pentaerythritol, 3-6% of titanium dioxide, 1-2% of chopped fibers and the balance of processing aid;
the thermoplastic resin is one of acrylic resin, high chlorinated polyethylene and chlorinated rubber;
the preparation process of the polyphenylene sulfide porous water-absorbing powder comprises the following steps:
(1) placing the nano silicon dioxide powder into a container, dropwise adding oleic acid with the concentration not more than 0.03%, and then placing the nano silicon dioxide powder into a ball mill or a high-speed closed stirrer for dispersion until powder particles do not agglomerate to obtain the treated nano silicon dioxide powder;
(2) mixing the treated nano silicon dioxide powder with polyphenylene sulfide, uniformly mixing, granulating, extruding by a screw machine, and granulating;
(3) freezing and crushing the granulated particles in a crusher to obtain fine powder, screening out fine powder with the granularity of more than 400 meshes, and continuously crushing coarse particles until all the fine particles pass through the 400 meshes;
(4) placing the fine powder into hydrofluoric acid, and washing away silicon dioxide to obtain polyphenylene sulfide fine powder with the surface fully distributed with nano-scale pores;
(5) washing the polyphenylene sulfide fine powder washed by the hydrofluoric acid with alkali, washing the polyphenylene sulfide fine powder with clear water until the pH value is neutral, and performing suction filtration and discharging;
(6) and (3) slowly drying the filter material at 60 ℃, and scattering the agglomerated powder again to uniformly disperse the powder for later use.
2. A process for preparing the oily fire retardant coating with water-absorbing powder according to claim 1, which comprises the following steps: dissolving the thermoplastic resin with the formula amount in 80% butyl acetate to obtain viscous resin liquid; putting other materials except the chopped fibers into the mixture, and dispersing the materials at a high speed until the materials are uniform; adjusting the viscosity of the system by using the residual butyl acetate; then, the chopped fibers were gradually added and kneaded in a kneader to obtain a fireproof coating in the form of a paste.
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CN114702898B (en) * 2022-04-20 2023-02-24 浙江新和成特种材料有限公司 Wear-resistant and corrosion-resistant polyphenylene sulfide coating on metal surface and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1408800A (en) * 2002-09-18 2003-04-09 同济大学 Super thin expansion type fire-proof corrosion resistant paint for steel structure and its preparing method
CN1709996A (en) * 2005-07-07 2005-12-21 复旦大学 Low-smoke superthin expansion steel structure fireproof coating and its preparing method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1408800A (en) * 2002-09-18 2003-04-09 同济大学 Super thin expansion type fire-proof corrosion resistant paint for steel structure and its preparing method
CN1709996A (en) * 2005-07-07 2005-12-21 复旦大学 Low-smoke superthin expansion steel structure fireproof coating and its preparing method

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