CN108084835B - Ultrathin fireproof coating and preparation method thereof - Google Patents
Ultrathin fireproof coating and preparation method thereof Download PDFInfo
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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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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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
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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
- 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
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- 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
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- 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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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Paints Or Removers (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention provides an ultrathin fireproof coating and a preparation method thereof, wherein the ultrathin fireproof coating comprises the following components in parts by weight: 400 parts of water 200-containing material, 2-5 parts of wetting agent, 4-7 parts of dispersing agent, 2-6 parts of pH regulator (95), 2-8 parts of defoaming powder, 50-60 parts of titanium dioxide, 300 parts of ammonium polyphosphate powder 200-containing material, 75-85 parts of melamine, 25-40 parts of pentaerythritol, 120 parts of film-forming assistant 100-containing material, 3-8 parts of cellulose, 200 parts of halogen emulsion 150-containing material and 3-6 parts of thickening agent. The fireproof coating prepared by the invention not only has good adhesive force, can be better attached to metal and walls to prevent the coating from being weathered and falling off, but also has good durability and waterproofness, and an effective fireproof insulating layer can be formed when the coating thickness is less than 1mm to achieve the purposes of fire prevention and flame retardance; meanwhile, the fireproof coating prepared by the invention also has the characteristics of environmental protection, convenient construction, good decoration and the like.
Description
Technical Field
The invention relates to the field of fireproof coatings, in particular to an ultrathin fireproof coating and a preparation method thereof.
Background
The fireproof coating is used on the surface of a combustible substrate and used for changing the surface combustion characteristic of the material and retarding the rapid spread of fire; or a special type of coating applied to building components to increase the fire endurance of the component. From the old theory of the thickness of the coating layer, the fireproof coating is mainly divided into three main categories: the thickness of the thick fireproof coating on a thick steel structure or a wall body is generally 8-50 mm, so that the fireproof time of the fireproof coating can be kept for 0.5-3 h, the fireproof and heat insulation principle of the thick fireproof coating is that the coating can resist flame and the heat conduction coefficient of the coating is low, and the self heat absorption function can delay the expansion of the coating layer and protect the safety of the steel structure and the wall body, but the coating is thick and the dead weight of a building is increased due to the large consumption of the coating.
In addition, the thick fireproof coating has the advantage of water solubility and fire resistance compared with other fireproof coatings, but after the thick fireproof coating is coated on a steel structure and a wall body, when the fire resistance reaches a certain period, the coating becomes thinner gradually, the fireproof function is reduced, and the appearance is poor.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide an ultrathin fireproof coating and a preparation method thereof, the fireproof coating prepared by the invention has good adhesive force, can be better attached to metal and walls, prevents the coating from being weathered and falling off, has good durability and waterproofness, and can form an effective fireproof insulating layer when the coating thickness is less than 1mm, thereby achieving the purposes of fire prevention and flame retardation; meanwhile, the fireproof coating prepared by the invention also has the characteristics of environmental protection, convenient construction, good decoration and the like.
The invention aims to provide an ultrathin fireproof coating.
The second purpose of the invention is to provide a preparation method of the ultrathin fireproof coating.
The invention also aims to provide the ultra-thin fireproof coating and the application of the preparation method thereof.
In order to realize the purpose, the invention discloses the following technical scheme:
the invention discloses an ultrathin fireproof coating, which is prepared from water, ammonium polyphosphate powder, titanium dioxide, melamine, halogen emulsion and a film-forming agent as basic raw materials, and cellulose, pentaerythritol and a thickening agent as auxiliary materials.
Specifically, the ultrathin fireproof coating comprises the following components in parts by weight: 400 parts of water 200-containing material, 2-5 parts of wetting agent, 4-7 parts of dispersing agent, 2-6 parts of pH regulator (95), 2-8 parts of defoaming powder, 50-60 parts of titanium dioxide, 300 parts of ammonium polyphosphate powder 200-containing material, 75-85 parts of melamine, 25-40 parts of pentaerythritol, 120 parts of film-forming assistant 100-containing material, 3-8 parts of cellulose, 200 parts of halogen emulsion 150-containing material and 3-6 parts of thickening agent.
Preferably, the ultrathin fireproof coating consists of the following components in parts by weight: 300 parts of water 200-containing material, 2-3.5 parts of wetting agent, 4-5 parts of dispersing agent, 2-4 parts of pH regulator (95), 2-5 parts of defoaming powder, 50-55 parts of titanium dioxide, 250 parts of ammonium polyphosphate powder, 75-80 parts of melamine, 25-30 parts of pentaerythritol, 110 parts of film-forming assistant 100-containing material, 3-5 parts of cellulose, 180 parts of halogen emulsion 150-containing material and 3-4.5 parts of thickening agent.
Preferably, the ultrathin fireproof coating consists of the following components in parts by weight: 400 parts of water, 3.5-5 parts of wetting agent, 5-7 parts of dispersing agent, 4-6 parts of pH regulator (95), 5-8 parts of defoaming powder, 55-60 parts of titanium dioxide, 300 parts of polyammonium phosphate powder, 80-85 parts of melamine, 30-40 parts of pentaerythritol, 120 parts of film-forming additive, 5-8 parts of cellulose, 200 parts of halogen emulsion and 4.5-6 parts of thickening agent.
Further preferably, the ultra-thin fireproof coating comprises the following components in parts by weight: 400 parts of water, 2 parts of wetting agent, 4 parts of dispersing agent, 2 parts of pH regulator (95), 3 parts of defoaming powder, 50 parts of titanium dioxide, 200 parts of ammonium polyphosphate powder, 75 parts of melamine, 25 parts of pentaerythritol, 100 parts of film-forming assistant, 3 parts of cellulose, 150 parts of halogen emulsion and 3 parts of thickening agent.
The halogen emulsion is characterized in that: polyacrylic acid emulsion grafted with halogen monomer.
The film-forming auxiliary agent is: a dodecacarbonate ester.
The pH regulator (95) is: diamino dimethyl isopropanol.
The thickening agent is: acrylic acid.
Preferably, the cellulose molecular weight of the ultra-thin fireproof coating component is 30000.
Secondly, the invention discloses a preparation method of an ultrathin fireproof coating, which specifically comprises the following steps:
(1) crushing and mixing water, cellulose, a wetting agent, a dispersing agent, a pH regulator (95), defoaming powder, titanium dioxide, ammonium polyphosphate powder, melamine and pentaerythritol to obtain a first mixed solution;
(2) and adding water, a film-forming assistant, defoaming powder, halogen emulsion, a pH regulator (95) and a thickening agent into the first mixed solution, stirring and standing to obtain the ultrathin fireproof coating.
Preferably, in the step (1) and the step (2), the adding amount ratio of the secondary water is 3: 1.
preferably, in the step (1) and the step (2), the addition amount ratio of the two pH regulators (95) is 1: 3.
preferably, in the step (1) and the step (2), the adding amount ratio of the two times of defoaming powder is 5: 1.
finally, the invention also discloses the application of the ultrathin fireproof coating and the preparation method thereof, wherein the application comprises the application of the ultrathin fireproof coating in the fire prevention of metal members, building members and building walls.
It should be noted that the cellulose with the molecular weight of 30000 is adopted in the invention, and the main reason is that the cellulose with the molecular weight of 30000 is more suitable for the technical scheme of the invention, and can play a role in thickening, water retention and viscosity regulation at the same time. In addition, because the cellulose has certain viscosity and thickening effect, the cellulose can form a flame-retardant expansion system with the ammonium polyphosphate powder, the pentaerythritol and the halogen emulsion, and when the cellulose meets open fire, the cellulose foams and expands to form a flame-retardant isolation layer; and the phosphorus-nitrogen-halogen element is contained to prevent flame from burning, so that the flame retardant effect is achieved.
Compared with the prior art, the invention has the following beneficial effects:
(1) the fireproof coating provided by the invention can form an effective fireproof insulating layer when the coating thickness is less than 1mm, so that the aims of fire prevention and flame retardation are fulfilled; meanwhile, the fireproof coating has the characteristics of high viscosity, difficult falling, good durability and water resistance, convenient construction, good decoration and the like.
(2) The fireproof coating provided by the invention takes water as a solvent, does not contain harmful volatile substances such as formaldehyde and the like, is beneficial to protecting the safety of a home environment, avoids the harm of harmful substances to human bodies, and ensures the health of people.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As described in the background of the invention, there are still many problems in the prior art fire retardant coating in use, and in order to solve the above problems, the present invention provides an ultra-thin fire retardant coating and a method for preparing the same, and the present invention will be further described with reference to the following specific examples.
Example 1:
a preparation method of an ultrathin fireproof coating specifically comprises the following steps:
(1) crushing and mixing 300 parts of water, 3 parts of cellulose, 2 parts of wetting agent, 4 parts of dispersing agent, 0.5 part of diamino dimethyl isopropanol, 2.5 parts of defoaming powder, 50 parts of titanium dioxide, 200 parts of ammonium polyphosphate powder, 75 parts of melamine and 25 parts of pentaerythritol to obtain a first mixed solution;
(2) adding 100 parts of water, 100 parts of dodecyl carbonate, 0.5 part of defoaming powder, 150 parts of polyacrylic acid emulsion grafted with halogen monomers, 1.5 parts of diamino dimethyl isopropanol and 3 parts of acrylic acid into the first mixed solution, stirring and standing to obtain the ultrathin fireproof coating.
Example 2:
a preparation method of an ultrathin fireproof coating specifically comprises the following steps:
(1) 200 parts of water, 8 parts of cellulose, 5 parts of wetting agent, 7 parts of dispersing agent, 4 parts of diamino dimethyl isopropanol, 5 parts of defoaming powder, 60 parts of titanium dioxide, 300 parts of ammonium polyphosphate powder, 85 parts of melamine and 40 parts of pentaerythritol are crushed and mixed to obtain a first mixed solution;
(2) adding 100 parts of water, 120 parts of dodecyl carbonate, 3 parts of defoaming powder, 200 parts of polyacrylic acid emulsion grafted with halogen monomers, 2 parts of diamino dimethyl isopropanol and 6 parts of acrylic acid into the first mixed solution, stirring and standing to obtain the ultrathin fireproof coating.
Example 3:
a preparation method of an ultrathin fireproof coating specifically comprises the following steps:
(1) 100 parts of water, 5 parts of cellulose, 3.5 parts of wetting agent, 5 parts of dispersing agent, 3 parts of diamino dimethyl isopropanol, 3 parts of defoaming powder, 55 parts of titanium dioxide, 250 parts of ammonium polyphosphate powder, 80 parts of melamine and 30 parts of pentaerythritol are crushed and mixed to obtain a first mixed solution;
(2) adding 100 parts of water, 110 parts of dodecyl carbonate, 2 parts of defoaming powder, 180 parts of polyacrylic acid emulsion grafted with halogen monomers, 1 part of diamino dimethyl isopropanol and 4.5 parts of acrylic acid into the first mixed solution, stirring and standing to obtain the ultrathin fireproof coating.
Comparative example 1:
a preparation method of an ultrathin fireproof coating specifically comprises the following steps:
(1) 300 parts of water, 2 parts of wetting agent, 4 parts of dispersing agent, 0.5 part of diamino dimethyl isopropanol, 2.5 parts of defoaming powder, 50 parts of titanium dioxide, 200 parts of ammonium polyphosphate powder, 75 parts of melamine and 25 parts of pentaerythritol are crushed and mixed to obtain a first mixed solution;
(2) adding 100 parts of water, 100 parts of dodecyl carbonate, 0.5 part of defoaming powder, 150 parts of polyacrylic acid emulsion grafted with halogen monomers, 1.5 parts of diamino dimethyl isopropanol and 3 parts of acrylic acid into the first mixed solution, stirring and standing to obtain the ultrathin fireproof coating.
Comparative example 2:
a preparation method of an ultrathin fireproof coating specifically comprises the following steps:
(1) 300 parts of water, 2 parts of wetting agent, 4 parts of dispersing agent, 0.5 part of diamino dimethyl isopropanol, 2.5 parts of defoaming powder, 50 parts of titanium dioxide, 75 parts of melamine and 25 parts of pentaerythritol are crushed and mixed to obtain a first mixed solution;
(2) adding 100 parts of water, 100 parts of dodecyl carbonate, 0.5 part of defoaming powder, 150 parts of polyacrylic acid emulsion grafted with halogen monomers, 1.5 parts of diamino dimethyl isopropanol and 3 parts of acrylic acid into the first mixed solution, stirring and standing to obtain the ultrathin fireproof coating.
Comparative example 3:
a preparation method of an ultrathin fireproof coating specifically comprises the following steps:
(1) crushing and mixing 300 parts of water, 2 parts of wetting agent, 4 parts of dispersing agent, 0.5 part of diamino dimethyl isopropanol, 2.5 parts of defoaming powder, 50 parts of titanium dioxide and 75 parts of melamine to obtain a first mixed solution;
(2) adding 100 parts of water, 100 parts of dodecyl carbonate, 0.5 part of defoaming powder, 150 parts of polyacrylic acid emulsion grafted with halogen monomers, 1.5 parts of diamino dimethyl isopropanol and 3 parts of acrylic acid into the first mixed solution, stirring and standing to obtain the ultrathin fireproof coating.
Comparative example 4:
a preparation method of an ultrathin fireproof coating specifically comprises the following steps:
(1) crushing and mixing 300 parts of water, 2 parts of wetting agent, 4 parts of dispersing agent, 0.5 part of diamino dimethyl isopropanol, 2.5 parts of defoaming powder, 50 parts of titanium dioxide and 75 parts of melamine to obtain a first mixed solution;
(2) adding 100 parts of water, 100 parts of dodecyl carbonate, 0.5 part of defoaming powder, 1.5 parts of diamino dimethyl isopropanol and 3 parts of acrylic acid into the first mixed solution, stirring and standing to obtain the ultrathin fireproof coating.
The fire-retardant coating materials obtained in example 1 and comparative examples 1 to 4 were prepared into samples having a thickness of 0.8mm, 1.0mm, 1.2mm and 1.5mm, and their fire-retardant properties were measured, and the results are shown in Table 1.
TABLE 1
The fire retardant coatings obtained in example 1 and comparative examples 1 to 4 were prepared into samples having a thickness of 0.8mm, 1.0mm, 1.2mm, 1.5mm, and the samples were immersed in tap water for 120 hours to test the water-proof property, and the results are shown in table 2.
TABLE 2
The fire retardant coatings obtained in example 1 and comparative examples 1 to 4 were prepared into samples having a thickness of 0.8mm, 1.0mm, 1.2mm and 1.5mm, and the adhesive strength thereof was measured, and the results are shown in Table 3.
TABLE 3
As can be seen from tables 1-3, when the components cellulose, ammonium polyphosphate powder, pentaerythritol and halogen emulsion are removed in sequence, the fire resistance time, the waterproof performance and the bonding strength of the sample are obviously reduced, especially after the components in the component 4 are completely removed, the fire resistance time, the waterproof performance and the bonding strength of the sample can not meet the requirements at all, and the fire resistance and the waterproof performance of the coating can be greatly improved by adding the cellulose, the ammonium polyphosphate powder, the pentaerythritol and the halogen emulsion.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (6)
1. An ultrathin fireproof coating is characterized in that: the composition comprises the following components in parts by weight: 400 parts of water 200-containing organic silicon, 2-5 parts of wetting agent, 4-7 parts of dispersing agent, 2-6 parts of pH regulator, 2-8 parts of defoaming powder, 50-60 parts of titanium dioxide, 300 parts of ammonium polyphosphate powder 200-containing organic silicon, 75-85 parts of melamine, 25-40 parts of pentaerythritol, 120 parts of film-forming assistant 100-containing organic silicon, 3-8 parts of cellulose, 200 parts of halogen emulsion 150-containing organic silicon and 3-6 parts of thickening agent;
the halogen emulsion is characterized in that: polyacrylic acid emulsion grafted with halogen monomer;
the film-forming auxiliary agent is: a dodecanoic acid ester;
the pH regulator is: diamino dimethyl isopropanol; the thickening agent is: acrylic acid;
the molecular weight of the cellulose is 30000;
the thickness of the fireproof coating is 0.8-1.5 mm.
2. The ultra-thin fire retardant coating as claimed in claim 1, which comprises the following components in parts by weight: 300 parts of water-containing organic solvent 200, 2-3.5 parts of wetting agent, 4-5 parts of dispersing agent, 2-4 parts of pH regulator, 2-5 parts of defoaming powder, 50-55 parts of titanium dioxide, 250 parts of ammonium polyphosphate powder 200, 75-80 parts of melamine, 25-30 parts of pentaerythritol, 110 parts of film-forming assistant 100, 3-5 parts of cellulose, 180 parts of halogen emulsion 150 and 3-4.5 parts of thickening agent.
3. The ultra-thin fire retardant coating as claimed in claim 1, which comprises the following components in parts by weight: 400 parts of water, 3.5-5 parts of wetting agent, 5-7 parts of dispersing agent, 4-6 parts of pH regulator, 5-8 parts of defoaming powder, 55-60 parts of titanium dioxide, 300 parts of ammonium polyphosphate powder, 80-85 parts of melamine, 30-40 parts of pentaerythritol, 120 parts of film-forming assistant 110, 5-8 parts of cellulose, 200 parts of halogen emulsion 180 and 4.5-6 parts of thickening agent.
4. The ultra-thin fire retardant coating as claimed in claim 1, which comprises the following components in parts by weight: 400 parts of water, 2 parts of wetting agent, 4 parts of dispersing agent, 2 parts of pH regulator, 3 parts of defoaming powder, 50 parts of titanium dioxide, 200 parts of ammonium polyphosphate powder, 75 parts of melamine, 25 parts of pentaerythritol, 100 parts of film-forming assistant, 3 parts of cellulose, 150 parts of halogen emulsion and 3 parts of thickening agent.
5. The method for preparing the ultra-thin type fire retardant coating according to any one of claims 1 to 4, wherein: the method specifically comprises the following steps:
(1) crushing and mixing water, cellulose, a wetting agent, a dispersing agent, a pH regulator, defoaming powder, titanium dioxide, ammonium polyphosphate powder, melamine and pentaerythritol to obtain a first mixed solution;
(2) adding water, a film-forming assistant, defoaming powder, halogen emulsion, a pH regulator and a thickening agent into the first mixed solution, stirring and standing to obtain the ultrathin fireproof coating;
in the step (1) and the step (2), the adding amount ratio of the secondary water is 3: 1;
in the step (1) and the step (2), the adding amount ratio of the two pH regulators is 1: 3;
in the step (1) and the step (2), the adding amount ratio of the two-time defoaming powder is 5: 1.
6. use of the ultra-thin fire retardant coating according to any one of claims 1 to 4 or the preparation method according to claim 5 for fire protection of metal members, building walls.
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CN1824716A (en) * | 2005-12-22 | 2006-08-30 | 北京首创纳米科技有限公司 | Aqueous environmental protection ultration expansion type steel structure fireproof paint and its preparation method |
CN101100576A (en) * | 2007-07-05 | 2008-01-09 | 湖南大学 | Water super-thin steel structure fire-proof paint and preparation method thereof |
CN101397469A (en) * | 2008-11-11 | 2009-04-01 | 中国核动力研究设计院 | Fire-resisting paint and preparation method thereof |
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CN101100576A (en) * | 2007-07-05 | 2008-01-09 | 湖南大学 | Water super-thin steel structure fire-proof paint and preparation method thereof |
CN101397469A (en) * | 2008-11-11 | 2009-04-01 | 中国核动力研究设计院 | Fire-resisting paint and preparation method thereof |
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CP03 | Change of name, title or address | ||
CP03 | Change of name, title or address |
Address after: West of the intersection of Shunxing Road and Junbu Street, Industrial Park, Hedong District, Linyi City, Shandong Province, 276000 Patentee after: Shandong hanshifu New Material Co.,Ltd. Address before: 276000 Dushutou Industrial Park, Jiuqu Street, Hedong District, Linyi City, Shandong Province Patentee before: SHANDONG HANSHIFU ADHESIVE CO.,LTD. |