CN113637379A - Fireproof anticorrosive paint and preparation method thereof - Google Patents

Fireproof anticorrosive paint and preparation method thereof Download PDF

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Publication number
CN113637379A
CN113637379A CN202111123204.0A CN202111123204A CN113637379A CN 113637379 A CN113637379 A CN 113637379A CN 202111123204 A CN202111123204 A CN 202111123204A CN 113637379 A CN113637379 A CN 113637379A
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China
Prior art keywords
parts
mass
fireproof
coating
stabilizer
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CN202111123204.0A
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Inventor
王荣国
刘文博
徐忠海
蔡朝灿
赫晓东
杨帆
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Zhaoqing Haite Composite Technology Research Institute
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Zhaoqing Haite Composite Technology Research Institute
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Priority to CN202111123204.0A priority Critical patent/CN113637379A/en
Publication of CN113637379A publication Critical patent/CN113637379A/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
    • C09D161/00Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/02Condensation polymers of aldehydes or ketones only
    • 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
    • C09D5/08Anti-corrosive paints
    • 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
    • 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
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2217Oxides; Hydroxides of metals of magnesium
    • C08K2003/222Magnesia, i.e. magnesium oxide
    • 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
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2227Oxides; Hydroxides of metals of aluminium
    • 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)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

A fireproof anticorrosive paint and a preparation method thereof belong to the technical field of paint preparation. The coating aims to solve the problems that the existing coating with the fireproof and anticorrosive double-layer protection function is unstable in properties and has bubbling, cracking and stripping after coating. The coating is prepared from organic silicon modified acrylic resin, aldehyde ketone resin, propylene glycol, organic silicon advection agent, magnesium oxide, aluminum hydroxide, ammonium polyphosphate, pentaerythritol or erythritol, benzoic acid functionalized graphene, stabilizer, anti-settling agent and deionized water. The method comprises the following steps: firstly, weighing raw materials; secondly, preparing a mixed solution; thirdly, adding resin and auxiliary agent and stirring. The fireproof anticorrosive paint disclosed by the invention integrates fireproof and anticorrosive functions, is simple in preparation process and low in cost, can be coated on the inner surface of steel by one-time brush coating and adopting airless spray coating, blade coating or roller coating, has low thermal conductivity of the coating, and meets the requirements of GB14907-2002 steel structure fireproof paint. The fireproof anticorrosive paint is suitable for fireproof and anticorrosive of steel structure materials.

Description

Fireproof anticorrosive paint and preparation method thereof
Technical Field
The invention belongs to the technical field of paint preparation; in particular to a fireproof anticorrosive paint and a preparation method thereof.
Background
Steel is a common building material, but because of the problems of easy corrosion and low fire resistance, the steel structure is protected by fireproof and anticorrosive paint, and the service life of the steel structure is prolonged; in construction, the anticorrosive paint and the fireproof paint are respectively coated, the anticorrosive paint is coated firstly, and then the fireproof paint is coated, so that the process is complex, the construction period is prolonged, and the cost is higher.
At present, the coating with the fireproof and anticorrosive double-layer protection function is a hot point of use and research, wherein high-temperature-resistant materials are usually expanded perlite, expanded vermiculite and other materials, but the coating prepared from the materials has the problem of larger thickness, so that the application range of the coating is narrow; in addition, the organic components in some coatings are more, so that the fire resistance, the corrosion resistance and the durability of the coatings are all limited to a certain extent, and the cost of the coatings is higher, so that the application and popularization range of the coatings is limited. The coating with the fireproof and anticorrosive double-layer protection function generally has the problems of unstable coating properties, bubbling, cracking, peeling and the like after coating, and the protection effect on a steel structure is seriously influenced.
Disclosure of Invention
The invention aims to solve the problems of unstable properties and bubbling, cracking and peeling after coating of the existing coating with the fireproof and anticorrosive double-layer protection function, and provides a fireproof and anticorrosive coating and a preparation method thereof.
The fireproof anticorrosive coating is prepared from, by mass, 10-18 parts of organic silicon modified acrylic resin, 20-35 parts of aldehyde ketone resin, 2-6 parts of propylene glycol, 1-3 parts of organic silicon advection agent, 10-15 parts of magnesium oxide, 4-6 parts of aluminum hydroxide, 2-4 parts of ammonium polyphosphate, 2-4 parts of pentaerythritol or erythritol, 8-15 parts of benzoic acid functionalized graphene, 1-3 parts of stabilizer, 1-3 parts of anti-settling agent and 10-20 parts of deionized water.
The preparation method of the fireproof anticorrosive paint comprises the following steps:
weighing 10-18 parts of organic silicon modified acrylic resin, 20-35 parts of aldehyde ketone resin, 2-6 parts of propylene glycol, 1-3 parts of organic silicon advection agent, 10-15 parts of magnesium oxide, 4-6 parts of aluminum hydroxide, 2-4 parts of ammonium polyphosphate, 2-4 parts of pentaerythritol or erythritol, 8-15 parts of benzoic acid functionalized graphene, 1-3 parts of stabilizer, 1-3 parts of anti-settling agent and 10-20 parts of deionized water according to parts by weight;
secondly, sequentially adding weighed ammonium polyphosphate, pentaerythritol or erythritol, benzoic acid functionalized graphene and deionized water into a container under a stirring state, and then continuously stirring and dispersing at a rotating speed of 400-500 r/min for 20-25 min to obtain a mixed solution;
and thirdly, adding the weighed propylene glycol, magnesium oxide and aluminum hydroxide into the mixed solution, stirring and dispersing for 15-20 min at the rotating speed of 700-800 r/min, adding the organic silicon modified acrylic resin, the aldehyde ketone resin, the organic silicon advection agent, the stabilizer and the anti-settling agent in a stirring state, and stirring and dispersing for 10-20 min at the rotating speed of 600-650 r/min to complete the preparation of the fireproof anticorrosive paint.
The fireproof and anticorrosive paint disclosed by the invention has the advantages that the fireproof and anticorrosive components are reasonably matched, the defects of a coating film are avoided by mixing the resin base material, the benzoic acid functionalized graphene with high compatibility with the base material is added to serve as a fireproof and anticorrosive filler, and the stabilizer and the anti-settling agent are added, so that the paint is stable in property, the construction performance is improved, the mechanical strength is improved, and bubbling, cracking and peeling are not easy to occur after the paint is coated; high-temperature-resistant magnesium oxide and aluminum hydroxide with good flame-retardant effect are added to enhance the fireproof effect of the coating, and the organosilicon advection agent is added to increase the surface smoothness of the coating, so that the binding force is high, and the influence of insufficient binding force between the coatings on the fireproof and anticorrosive effects is avoided. The long-acting protection effect on the steel structure can be achieved, and the loss caused by steel structure corrosion is reduced.
The fireproof anticorrosive coating integrates the fireproof and anticorrosive functions, only needs one-time brushing, can be sprayed on the inner surface of steel by airless spraying, blade coating or roller coating, forms a coating, has low thermal conductivity, and meets the requirements of GB14907-2002 Steel structure fireproof coating.
The invention has simple preparation process and low cost, and the product can be widely used for fire prevention and corrosion prevention of steel structures of buildings, chemical engineering, petroleum, electric power, metallurgy, ships, traffic, aerospace and the like.
The fireproof anticorrosive paint is suitable for fireproof and anticorrosive of steel structures.
Detailed Description
The technical solution of the present invention is not limited to the following specific embodiments, but includes any combination of the specific embodiments.
The first embodiment is as follows: the fireproof anticorrosive coating is prepared from, by mass, 10-18 parts of an organic silicon modified acrylic resin, 20-35 parts of an aldehyde ketone resin, 2-6 parts of propylene glycol, 1-3 parts of an organic silicon advection agent, 10-15 parts of magnesium oxide, 4-6 parts of aluminum hydroxide, 2-4 parts of ammonium polyphosphate, 2-4 parts of pentaerythritol or erythritol, 8-15 parts of benzoic acid functionalized graphene, 1-3 parts of a stabilizer, 1-3 parts of an anti-settling agent and 10-20 parts of deionized water.
The second embodiment is as follows: this embodiment differs from the first embodiment in that the stabilizer is triphenyl phosphite. The rest is the same as the first embodiment.
The third concrete implementation mode: the difference between this embodiment and the first or second embodiment is that the anti-settling agent is BYK 410. The other is the same as in the first or second embodiment.
The fourth concrete implementation mode: the present embodiment is different from the first to third embodiments in that the magnesium oxide has a particle size of 40 to 70 μm and a thermal expansion coefficient of 1.38 × 10-6and/K. The others are the same as in one of the first to third embodiments.
The fifth concrete implementation mode: the difference between the embodiment and one of the first to third embodiments is that the modified acrylic resin is prepared from 15 parts by mass of organic silicon modified acrylic resin, 25 parts by mass of aldehyde ketone resin, 4 parts by mass of propylene glycol, 2 parts by mass of organic silicon advection agent, 12 parts by mass of magnesium oxide, 5 parts by mass of aluminum hydroxide, 3 parts by mass of ammonium polyphosphate, 3 parts by mass of pentaerythritol or erythritol, 10 parts by mass of benzoic acid functionalized graphene, 2 parts by mass of stabilizer, 2 parts by mass of anti-settling agent and 15 parts by mass of deionized water. The others are the same as in one of the first to third embodiments.
The sixth specific implementation mode: the preparation method of the fireproof anticorrosive paint comprises the following steps:
weighing 10-18 parts of organic silicon modified acrylic resin, 20-35 parts of aldehyde ketone resin, 2-6 parts of propylene glycol, 1-3 parts of organic silicon advection agent, 10-15 parts of magnesium oxide, 4-6 parts of aluminum hydroxide, 2-4 parts of ammonium polyphosphate, 2-4 parts of pentaerythritol or erythritol, 8-15 parts of benzoic acid functionalized graphene, 1-3 parts of stabilizer, 1-3 parts of anti-settling agent and 10-20 parts of deionized water according to parts by weight;
secondly, sequentially adding weighed ammonium polyphosphate, pentaerythritol or erythritol, benzoic acid functionalized graphene and deionized water into a container under a stirring state, and then continuously stirring and dispersing at a rotating speed of 400-500 r/min for 20-25 min to obtain a mixed solution;
and thirdly, adding the weighed propylene glycol, magnesium oxide and aluminum hydroxide into the mixed solution, stirring and dispersing for 15-20 min at the rotating speed of 700-800 r/min, adding the organic silicon modified acrylic resin, the aldehyde ketone resin, the organic silicon advection agent, the stabilizer and the anti-settling agent in a stirring state, and stirring and dispersing for 10-20 min at the rotating speed of 600-650 r/min to complete the preparation of the fireproof anticorrosive paint.
The seventh embodiment: the sixth embodiment is different from the sixth embodiment in that the stabilizer in the first step is triphenyl phosphite; the anti-settling agent is BYK 410; the particle size of the magnesium oxide is 40-70 mu m, and the thermal expansion coefficient is 1.38 multiplied by 10-6and/K. Other steps and parameters are the same as those in the sixth embodiment.
The specific implementation mode is eight: the difference between the sixth embodiment and the seventh embodiment is that in the first step, 12 parts by mass of an organic silicon modified acrylic resin, 30 parts by mass of an aldehyde ketone resin, 5 parts by mass of propylene glycol, 2 parts by mass of an organic silicon advection agent, 14 parts by mass of magnesium oxide, 5 parts by mass of aluminum hydroxide, 3 parts by mass of ammonium polyphosphate, 3 parts by mass of pentaerythritol or erythritol, 12 parts by mass of benzoic acid functionalized graphene, 2 parts by mass of a stabilizer, 2 parts by mass of an anti-settling agent, and 18 parts by mass of deionized water are weighed. Other steps and parameters are the same as those of the sixth or seventh embodiment.
The specific implementation method nine: the difference between this embodiment and one of the sixth to eighth embodiments is that the stirring and dispersing are continued for 22min at a rotation speed of 450r/min in the second step. Other steps and parameters are the same as those in one of the sixth to eighth embodiments.
The detailed implementation mode is ten: the difference between the sixth embodiment and the ninth embodiment is that in the third step, the acrylic resin modified by organic silicon, the aldehyde ketone resin, the organic silicon advection agent, the stabilizing agent and the anti-settling agent are stirred and dispersed for 18min at the rotating speed of 750r/min, then the acrylic resin modified by organic silicon, the aldehyde ketone resin, the organic silicon advection agent, the stabilizing agent and the anti-settling agent are added under the stirring state, and then the acrylic resin modified by organic silicon is stirred and dispersed for 15min at the rotating speed of 620 r/min. Other steps and parameters are the same as those in one of the sixth to ninth embodiments.
The beneficial effects of the present invention are demonstrated by the following examples:
example (b):
a preparation method of a fireproof anticorrosive paint comprises the following steps:
weighing 12 parts of organic silicon modified acrylic resin, 30 parts of aldehyde ketone resin, 5 parts of propylene glycol, 2 parts of organic silicon advection agent, 14 parts of magnesium oxide, 5 parts of aluminum hydroxide, 3 parts of ammonium polyphosphate, 3 parts of pentaerythritol or erythritol, 12 parts of benzoic acid functionalized graphene, 2 parts of stabilizer, 2 parts of anti-settling agent and 18 parts of deionized water in parts by weight;
secondly, sequentially adding weighed ammonium polyphosphate, pentaerythritol or erythritol, benzoic acid functionalized graphene and deionized water into a container under a stirring state, and then continuously stirring and dispersing at a rotating speed of 450r/min for 25min to obtain a mixed solution;
thirdly, adding the weighed propylene glycol, magnesium oxide and aluminum hydroxide into the mixed solution, stirring and dispersing for 15min at the rotating speed of 750r/min, adding the organic silicon modified acrylic resin, the aldehyde ketone resin, the organic silicon advection agent, the stabilizer and the anti-settling agent under the stirring state, and stirring and dispersing for 10min at the rotating speed of 650r/min to finish the preparation of the fireproof anticorrosive paint.
In the first step of this embodiment, the stabilizer is triphenyl phosphite; the anti-settling agent is BYK 410; the particle size of the magnesium oxide is 40-70 mu m, and the thermal expansion coefficient is 1.38 multiplied by 10-6/K。
The fireproof anticorrosive paint prepared in the embodiment can be sprayed by airless spraying, blade coating or roller coating, is coated on the inner surface of steel by one-time brush coating to form a coating, and is stable in properties and not easy to bubble, crack and peel after coating, and the thermal conductivity of the coating is less than 0.050 w/m.k through testing; meets the requirements of GB14907-2002 steel structure fireproof paint.

Claims (10)

1. The fireproof anticorrosive coating is characterized by being prepared from 10-18 parts by mass of organic silicon modified acrylic resin, 20-35 parts by mass of aldehyde ketone resin, 2-6 parts by mass of propylene glycol, 1-3 parts by mass of organic silicon advection agent, 10-15 parts by mass of magnesium oxide, 4-6 parts by mass of aluminum hydroxide, 2-4 parts by mass of ammonium polyphosphate, 2-4 parts by mass of pentaerythritol or erythritol, 8-15 parts by mass of benzoic acid functionalized graphene, 1-3 parts by mass of stabilizer, 1-3 parts by mass of anti-settling agent and 10-20 parts by mass of deionized water.
2. The fire-proof anticorrosive paint according to claim 1, wherein the stabilizer is triphenyl phosphite.
3. The fire-proof anticorrosive paint according to claim 1, characterized in that the anti-settling agent is BYK 410.
4. The fireproof anticorrosive paint of claim 1, wherein the magnesium oxide has a particle size of 40-70 μm and a thermal expansion coefficient of 1.38 x 10-6/K。
5. A fire-proof anticorrosive coating according to claim 1, characterized by being prepared from 15 parts by mass of organosilicon modified acrylic resin, 25 parts by mass of aldehyde ketone resin, 4 parts by mass of propylene glycol, 2 parts by mass of organosilicon advection agent, 12 parts by mass of magnesium oxide, 5 parts by mass of aluminum hydroxide, 3 parts by mass of ammonium polyphosphate, 3 parts by mass of pentaerythritol or erythritol, 10 parts by mass of benzoic acid functionalized graphene, 2 parts by mass of stabilizer, 2 parts by mass of anti-settling agent and 15 parts by mass of deionized water.
6. The preparation method of the fireproof anticorrosive paint is characterized by comprising the following steps of:
weighing 10-18 parts of organic silicon modified acrylic resin, 20-35 parts of aldehyde ketone resin, 2-6 parts of propylene glycol, 1-3 parts of organic silicon advection agent, 10-15 parts of magnesium oxide, 4-6 parts of aluminum hydroxide, 2-4 parts of ammonium polyphosphate, 2-4 parts of pentaerythritol or erythritol, 8-15 parts of benzoic acid functionalized graphene, 1-3 parts of stabilizer, 1-3 parts of anti-settling agent and 10-20 parts of deionized water according to parts by weight;
secondly, sequentially adding weighed ammonium polyphosphate, pentaerythritol or erythritol, benzoic acid functionalized graphene and deionized water into a container under a stirring state, and then continuously stirring and dispersing at a rotating speed of 400-500 r/min for 20-25 min to obtain a mixed solution;
and thirdly, adding the weighed propylene glycol, magnesium oxide and aluminum hydroxide into the mixed solution, stirring and dispersing for 15-20 min at the rotating speed of 700-800 r/min, adding the organic silicon modified acrylic resin, the aldehyde ketone resin, the organic silicon advection agent, the stabilizer and the anti-settling agent in a stirring state, and stirring and dispersing for 10-20 min at the rotating speed of 600-650 r/min to complete the preparation of the fireproof anticorrosive paint.
7. The method for preparing fire-retardant anticorrosive paint according to claim 6, characterized in that in step one, the stabilizer is triphenyl phosphite; the anti-settling agent is BYK 410; the particle size of the magnesium oxide is 40-70 mu m, and the thermal expansion coefficient is 1.38 multiplied by 10-6/K。
8. The preparation method of the fireproof anticorrosive coating according to claim 6, characterized in that in step one, 12 parts of organosilicon modified acrylic resin, 30 parts of aldehyde ketone resin, 5 parts of propylene glycol, 2 parts of organosilicon advection agent, 14 parts of magnesium oxide, 5 parts of aluminum hydroxide, 3 parts of ammonium polyphosphate, 3 parts of pentaerythritol or erythritol, 12 parts of benzoic acid functionalized graphene, 2 parts of stabilizer, 2 parts of anti-settling agent and 18 parts of deionized water are weighed according to parts by mass.
9. The preparation method of the fireproof anticorrosive paint according to claim 6, wherein in the second step, the stirring and dispersing are continued for 22min at a rotating speed of 450 r/min.
10. The preparation method of the fireproof anticorrosive paint according to claim 6, characterized in that in the third step, stirring and dispersing are carried out at a rotation speed of 750r/min for 18min, then the organosilicon modified acrylic resin, the aldehyde ketone resin, the organosilicon advection agent, the stabilizer and the anti-settling agent are added under the stirring state, and then stirring and dispersing are carried out at a rotation speed of 620r/min for 15 min.
CN202111123204.0A 2021-09-24 2021-09-24 Fireproof anticorrosive paint and preparation method thereof Pending CN113637379A (en)

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Citations (6)

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Publication number Priority date Publication date Assignee Title
CN1709996A (en) * 2005-07-07 2005-12-21 复旦大学 Low-smoke superthin expansion steel structure fireproof coating and its preparing method
CN101857760A (en) * 2010-07-01 2010-10-13 华东理工大学 Aqueous ultra-thin expansion type steel structure fire-proof anti-corrosive paint and preparation method thereof
CN103805033A (en) * 2014-02-25 2014-05-21 绵阳惠利环氧工程有限公司 Ultrathin expansion steel structure fireproof coating and preparation method thereof
CN104130638A (en) * 2014-07-18 2014-11-05 安徽千和新材料科技发展有限公司 Aqueous fire-proof corrosion-proof paint for steel structure and preparation method thereof
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Publication number Priority date Publication date Assignee Title
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CN101857760A (en) * 2010-07-01 2010-10-13 华东理工大学 Aqueous ultra-thin expansion type steel structure fire-proof anti-corrosive paint and preparation method thereof
CN103805033A (en) * 2014-02-25 2014-05-21 绵阳惠利环氧工程有限公司 Ultrathin expansion steel structure fireproof coating and preparation method thereof
CN104130638A (en) * 2014-07-18 2014-11-05 安徽千和新材料科技发展有限公司 Aqueous fire-proof corrosion-proof paint for steel structure and preparation method thereof
CN105385310A (en) * 2016-01-04 2016-03-09 沈阳顺风实业集团有限公司 Steel structure fireproof anticorrosion function integrated coating and preparing method thereof
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Title
汪多仁: "《精细化学品实用生产技术手册:增塑剂化学品生产配方和合成工艺》", 31 August 1999, 科学技术文献出版社 *

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