WO2014090105A1

WO2014090105A1 - Water-based expandable fireproof coating for steel structure and preparation method therefor

Info

Publication number: WO2014090105A1
Application number: PCT/CN2013/088591
Authority: WO
Inventors: 方章建; 郑兴才; 程宇婷; 卓之久
Original assignee: 中盈长江国际新能源投资有限公司
Priority date: 2012-12-14
Filing date: 2013-12-05
Publication date: 2014-06-19
Also published as: CN103045037A; CN103045037B

Abstract

A water-based expandable fireproof coating for steel structure. The fireproof coating consists of the components in mass percentage: 20-45% of coating matrix, 25-45% of nano-flame retardant, 0.1-10% of flame-retardant synergist, 1-10% of filler, 0.2-5% of auxiliary agent and 10-30% of water. The preparation method of the fireproof coating comprises the steps: firstly preparing the nano-flame retardant; secondly adding a water-based epoxy emulsion, a water-based epoxy curing agent and a self-crosslinking silicone acrylic emulsion in the coating matrix into a stirring barrel, and stirring uniformly; adding the nano-flame retardant, the flame-retardant synergist, the filler, the auxiliary agent and water, and stirring, then grinding and filtering the mixture. The fireproof coating has a high expansion rate, and has the fire endurance up to 120 minutes as well as the coating thickness of 2 mm.

Description

Water-based expanded steel structure fireproof coating and preparation method thereof

Technical field

The invention relates to the field of fireproof coatings, in particular to a water-based expanded steel structure fireproof coating based on comprehensive utilization of biomass power plant ash waste and a preparation method thereof. Background technique

Most of the frames of modern high-rise buildings and large buildings are made of steel. Although steel as a load-bearing component has the advantages of high strength, light weight, high load capacity, good seismic performance, easy construction, no pollution, and recyclability, The thermal conductivity is large. In the event of a fire, the temperature can rise to 700 °C within 10-15 min, far exceeding its own critical temperature (54 CTC). At this time, the yield strength of the steel drops sharply to 40 in the normal temperature state. Loss of bearing capacity around % will cause the building to collapse. At present, China uses steel fireproof coatings for coating protection. The fire-retardant coating is applied to the surface of the steel component. When exposed to fire, the coating expands and foams to form a carbonized fire-resistant thermal insulation layer, which isolates oxygen, delays the heating speed of the steel structure, avoids rapid heating of the steel component, thereby improving the fire-resisting time limit of the steel structure and reducing The speed of heat transfer, delaying the temperature rise of the steel structure, the time when the strength is weakened, and so on. But no matter what method is adopted, the principle is the same.

At present, there are two main types of steel structure fireproof coatings studied at home and abroad: intumescent fireproof coatings and non-intumescent fireproof coatings. Due to the poor fireproof performance of the latter, they have been gradually eliminated. The coating of steel itself is porous, lightweight and heated. The formation of a carbonized foam layer prevents heat from being rapidly transferred to the steel substrate, delaying the reduction of the strength of the steel substrate, thereby increasing the fire endurance of the steel structure.

Compared with thick-coated and thin-coated steel structure fire-retardant coatings, the ultra-thin expanded steel structure fire-retardant coating has finer grain size, thinner coating layer, convenient construction, economy and better decorativeness, while meeting the fire protection requirements of steel structures. It can also meet people's high decorative requirements; It can be widely used in fire protection of steel structures with high decoration requirements such as industrial plants, stadiums, terminal buildings, high-rise buildings, etc. It is also suitable for ships, underground works, power plants, computer rooms, etc. The fire protection of flammable substrates such as wood, fiberboard, plastics and cables in demanding facilities is a popular product promoted by the fire department. Patents 200810231868.7 and 01113320.1, etc. disclose ultra-thin expanded steel structure fireproof coatings and preparation methods thereof, and patent 201210008305.8 discloses a fireproof coating which can be widely used in the field of building materials. These fire retardant coatings are mostly solvent-based or halogen-containing fire retardant coatings. Although they have good fireproofing effect, they are easy. Pollution to the environment, especially the toxic gases generated by the combustion of halogens, can easily cause poisoning or suffocation. Summary of the invention

The object of the present invention is to disclose a novel type of aqueous intumescent steel structure fireproof coating based on the comprehensive utilization of biomass power plant ash and a method thereof. To overcome the shortcomings of traditional organic intumescent fire retardant coatings, such as poor high temperature resistance, poor aging resistance and poor water resistance.

In order to achieve the above object, the technical solution adopted by the present invention is:

Water-based intumescent steel structure fireproof coating, each component is composed of several components in terms of mass percentage: 20-45% coating matrix, 25-45% nano flame retardant, 0.1-10% flame retardant synergist , 1-10% ± genuine, 0.2-5% auxiliary and 10-30% water.

The nano flame retardant is composed of a carbon forming agent, a carbon forming catalyst, a foaming agent, and a silica and a surfactant; they are obtained by nanometerizing a flame retardant raw material; The method of nanocrystallization is prepared by fixing a flame retardant raw material to nano silica particles by a precipitation method.

The flame retardant raw material is composed of a carbon forming catalyst, a carbon forming agent and a foaming agent.

The specific preparation step of the nano flame retardant is: adding the flame retardant raw material, the water glass of 5-50% by weight of the raw material of the flame retardant, and the surfactant of 0.5-50% by weight of the raw material of the flame retardant. After heating to 50-9 CTC in 1-5 times the weight of the flame retardant raw material, the pH is adjusted to 5-8 with acid, and after cooling for two hours, the reaction product is cooled and filtered, and the nano-resistance is obtained after drying. Burning agent.

The char forming catalyst is selected from one or more of ammonium polyphosphate, red phosphorus, strontium phosphate, urea phosphate, ammonium dihydrogen phosphate, ammonium pyrophosphate; the carbon forming agent is selected from the group consisting of starch, glucose, and trisorbitol. One or more of pentaerythritol, dipentaerythritol, and tripentaerythritol.

The blowing agent is selected from one or more of urea, dicyandiamide, and melamine.

The surfactant is selected from the group consisting of dodecyl hydroxypropyl phosphate betaine (BS-12) and alkylphenol ethoxylate (OP-10), silane coupling agent, fatty acid polyoxyethylene ester, ten One or more of sodium dialkyl sulfate (SDS), polyvinyl alcohol, polyethyleneimine, polyvinyl alcohol-polyethyleneimine-polyvinyl alcohol.

The flame retardant synergist is selected from biomass power plant ash; further, generally, the biomass ash refers to a boiler fly ash collected by a bag filter after the biomass power plant burns the agricultural and forestry solid waste as a fuel.

The filler is selected from the group consisting of titanium dioxide, chalk white powder, iron oxide, light calcium carbonate, aluminum silicate cellulose, kaolin, cloud One or more of mother powder, phthalocyanine, expandable graphite, and flake graphite.

The coating substrate is composed of 5-10% self-crosslinking silicone-acrylic emulsion, acrylate emulsion, styrene-acrylic emulsion, polyvinyl acetate emulsion, and 10%-35% aqueous epoxy emulsion, 1%- 5% waterborne epoxy curing agent, the total amount of coating matrix is 20-45%; epoxy curing agent is chemically reacted with epoxy resin to form a network of three-dimensional polymer, enveloping the composite material in the network Among the substances that contribute to the curing reaction.

The auxiliary agent is selected from the group consisting of alcohol ester-12, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, polyether modified silicone type leveling agent TEGO Flow425, polyether modified polysiloxane type stream One or more of the flat agent BYK-333 and the polyether modified silicone leveling agent JY3033.

The chemical composition of the alcohol ester-12 is 2,24-trimethyl-1,3-pentanediol monoisobutyl ester.

The preparation method of the above-mentioned aqueous expansion type steel structure fireproof coating prepared by using the raw materials comprises the following steps:

(1) Preparation of nano flame retardants:

The flame retardant raw material, water glass of 5-50% by weight of the raw material of the flame retardant, and 0.5-50% of the surfactant based on the weight of the raw material of the flame retardant are added to 1-5 times the weight of the raw material of the flame retardant. After heating to 50-9 CTC in water, the pH was adjusted to 5-8 with an acid. After reacting for two hours, the reaction product was cooled, filtered, and dried to obtain the nano-flame retardant.

(2) Preparation of fire retardant coatings:

Firstly add the waterborne epoxy emulsion, waterborne epoxy curing agent and self-crosslinking silicone-acrylic emulsion in the coating matrix to the mixing tank. After mixing, add nano-flame retardant, flame retardant synergist, filler, auxiliary and water. After stirring for 10-30min, it is added to the ball mill for grinding. After uniform mixing, the fineness of the coating is checked by the scraper fineness meter. After the requirement is reached, the grinding is stopped, the filter is filtered, the grinding beads and the coating are separated, and the coating is loaded. In the specified tank, the drum is discharged.

By the above steps, the low-cost and high-efficiency water-swellable steel structure fireproof coating described in the present invention can be prepared.

The invention provides a water-based expanded steel structure fireproof coating for comprehensive utilization of biomass power plant ash and a preparation method thereof, and the nano flame retardant system is adopted in the invention, and the nano flame retardant is applied to an expanded steel structure fireproof coating. , thereby greatly improving the fire performance of fire retardant coatings. The advantages are mainly reflected in the following aspects:

Firstly, the invented steel structure fireproof coating material of the invention has a wide range of raw materials, and the use of solid waste in agriculture and industrial fields to prepare environmentally friendly, economical and multifunctional green materials is an important development of solid waste resource utilization and fireproof coating. One of the directions, with significant economic and social benefits;

Secondly, the fireproof coating of the invention has strong weather resistance, water resistance and water precipitation resistance; Thirdly, the invention adopts the nano-flame retardant technology to surface-modify the nano-flame retardant, thereby improving the dispersion performance of the flame retardant in the coating, thereby improving the physical and chemical properties of the coating;

Fourth, since the invention adopts biomass power plant ash as a flame retardant synergist, the strength of the carbonized layer and the high temperature resistance are obviously improved, thereby improving the fire endurance of the coating;

Fifthly, the invention adds a surface modifier having flame retardant property in the process of preparing the nano flame retardant, thereby enhancing the fireproof performance of the fireproof coating, thereby contributing to improving the fire endurance of the coating;

Sixth, since the coating matrix emulsion system (aqueous epoxy system and self-crosslinking silicone-acrylic emulsion) used in the invention has a micro-crosslinked structure, the density of the coating is improved, wherein the self-crosslinking silicone-acrylic emulsion contains silicon. In the flame ablation, a hard white ceramic-like substance can be formed on the surface of the carbonized layer, thereby increasing the strength of the carbonized layer and prolonging its fire endurance. detailed description

In order to better explain the present invention, the main contents of the present invention will be further clarified below with reference to specific embodiments, but the contents of the present invention are not limited only to the following embodiments. The materials listed in Table 1 of the present invention are all purchased directly from the market.

Example 1

Please refer to the fire retardant coating formulations of the present invention listed in Tables 1 and 2.

(1) Preparation of nano flame retardants:

Adding each flame retardant raw material, water glass and surfactant to the water which is 5 times the weight of the flame retardant raw material, heating to 85 ° C, adjusting the pH value to 6.5 with dilute sulfuric acid, cooling for two hours, filtering and washing the reaction product After drying, the nano-flame retardant is obtained.

(2) Preparation of fire retardant coatings:

Firstly add waterborne epoxy emulsion, waterborne epoxy curing agent and self-crosslinking silicone-acrylic emulsion into the mixing tank, stir evenly, add nano flame retardant, flame retardant synergist, filler, auxiliary agent and appropriate amount of water, stir 30 After min, add to the ball mill for grinding once. After uniform mixing, use the squeegee fineness meter to check whether the fineness of the paint meets the requirements. After the requirement is reached, stop the grinding, filter with the filter, separate the grinding beads and the paint, and put the paint into the designated tank. in. Unloading and loading.

The physical and chemical performance test was carried out according to GB14907-2002, and the performance of the obtained fireproof coating of the present invention is shown in Example 1 of Table 3. It can be seen from Table 3 that the intumescent fireproof coating prepared in this example has no agglomeration uniformly, and the fineness, drying time, adhesion, flexibility and impact resistance are all within the requirements of the technical specifications, and are water-based and fire-resistant. Sexuality To the technical preparation requirements, the overall performance of the coating is excellent.

Example 2:

(1) Preparation of nano flame retardants:

Each flame retardant raw material, water glass and surfactant are added to water which is 4 times the weight of the flame retardant raw material, heated to 90 ° C, and the pH is adjusted to 7.0 with dilute hydrochloric acid. After two hours of reaction, the reaction product is cooled and filtered. After drying, the nano-flame retardant is obtained.

(2) Preparation of fire retardant coatings:

Firstly add waterborne epoxy emulsion, waterborne epoxy curing agent and self-crosslinking silicone-acrylic emulsion into the mixing tank. After stirring evenly, add nano-flame retardant, flame retardant synergist, filler, auxiliary and appropriate amount of water, stir for 15min. After grinding into the ball mill, grind once, evenly mix and use the scraper fineness meter to check whether the fineness of the paint meets the requirements. After the requirement is reached, stop the grinding, filter with the filter, separate the grinding beads and the paint, and put the paint into the designated tank. . Unloading and loading.

The physical and chemical performance test was carried out in accordance with GB 14907-2002, and the properties of the obtained fireproof coating of the present invention are shown in Example 2 of Table 3. It can be seen from Table 3 that the intumescent fireproof coating prepared in this example has no agglomeration uniformly, and the fineness, drying time, adhesion, flexibility and impact resistance are all within the requirements of the technical specifications, and are water-based and fire-resistant. The properties also meet the technical preparation requirements, so the overall performance of the coating is excellent.

Example 3:

(1) Preparation of nano flame retardants:

Adding each flame retardant raw material, water glass and surfactant to the water which is 3 times the weight of the flame retardant raw material, heating to 50 ° C, adjusting the pH value to 7.5 with dilute sulfuric acid, cooling for 2 hours, filtering and washing the reaction product After drying, the nano-flame retardant is obtained.

(2) Preparation of fire retardant coatings:

Firstly add waterborne epoxy emulsion, waterborne epoxy curing agent and self-crosslinking silicone-acrylic emulsion into the mixing tank. After stirring evenly, add nano-flame retardant, flame retardant synergist, filler, auxiliary and appropriate amount of water, stir for 20min. After grinding into the ball mill, grind once, evenly mix and use the scraper fineness meter to check whether the fineness of the paint meets the requirements. After the requirement is reached, stop the grinding, filter with the filter, separate the grinding beads and the paint, and put the paint into the designated tank. . Unloading and loading.

The physical and chemical performance test is carried out according to GB14907-2002, and the performance of the fireproof coating of the present invention is shown in Table 3. Example 3. It can be seen from Table 3 that the intumescent fireproof coating prepared in this example has no agglomeration uniformly, and the fineness, drying time, adhesion, flexibility and impact resistance are all within the requirements of the technical specifications, and are water-based and fire-resistant. The properties also meet the technical preparation requirements, so the overall performance of the coating is excellent.

Example 4:

(1) Preparation of nano flame retardants:

Adding each flame retardant raw material, water glass and surfactant to the water which is 5 times the weight of the flame retardant raw material, heating to 50 ° C, adjusting the pH value to 8.0 with dilute sulfuric acid, cooling for 2 hours, filtering and washing the reaction product After drying, the nano-flame retardant is obtained.

(2) Preparation of fire retardant coatings:

Firstly add waterborne epoxy emulsion, waterborne epoxy curing agent and self-crosslinking silicone-acrylic emulsion into the mixing tank. After stirring evenly, add nano-flame retardant, flame retardant synergist, filler, auxiliary agent and appropriate amount of water, stir for 30min. After grinding into the ball mill, grind once, evenly mix and use the scraper fineness meter to check whether the fineness of the paint meets the requirements. After the requirement is reached, stop the grinding, filter with the filter, separate the grinding beads and the paint, and put the paint into the designated tank. . Unloading and loading.

The physical and chemical performance test was carried out according to GB14907-2002, and the performance of the obtained fireproof coating of the present invention is shown in Example 4 of Table 3. It can be seen from Table 3 that the intumescent fireproof coating prepared in this example has no agglomeration uniformly, and the fineness, drying time, adhesion, flexibility and impact resistance are all within the requirements of the technical specifications, and are water-based and fire-resistant. The properties also meet the technical preparation requirements, so the overall performance of the coating is excellent.

Example 5

(1) Preparation of nano flame retardants:

Each flame retardant raw material, water glass and surfactant are added to water which is 5 times the weight of the flame retardant raw material, heated to 90 ° C, and the pH is adjusted to 5.0 with dilute sulfuric acid. After two hours of reaction, the reaction product is cooled and filtered. After drying, the nano-flame retardant is obtained.

(2) Preparation of fire retardant coatings:

Firstly add waterborne epoxy emulsion, waterborne epoxy curing agent and self-crosslinking silicone-acrylic emulsion into the mixing tank. After stirring evenly, add nano-flame retardant, flame retardant synergist, filler, auxiliary agent and appropriate amount of water, stir lOmin After grinding into the ball mill, grind once, evenly mix and then use the scraper fineness meter to check whether the fineness of the paint meets the requirements. After the requirement is reached, the grinding is stopped. Filter with a strainer, separate the beads and paint, and load the paint into the designated tank. Unloading and loading.

The physical and chemical performance test was carried out according to GB14907-2002, and the performance of the obtained fireproof coating of the present invention is shown in Example 5 of Table 3. It can be seen from Table 3 that the intumescent fireproof coating prepared in this example has no agglomeration uniformly, and the fineness, drying time, adhesion, flexibility and impact resistance are all within the requirements of the technical specifications, and are water-based and fire-resistant. The properties also meet the technical preparation requirements, so the overall performance of the coating is excellent.

Example 6: Comparative Example

Please refer to the fire retardant coating formulations of the present invention listed in Table 2.

Firstly add waterborne epoxy emulsion, waterborne epoxy curing agent and self-crosslinking silicone-acrylic emulsion to the mixing tank, stir evenly, add ammonium polyphosphate, melamine, pentaerythritol, flame retardant synergist, filler, auxiliary and proper amount of water. After stirring for lOmin, it is added to the ball mill for grinding once. After uniform mixing, the fineness of the coating is checked by the scraper fineness meter to meet the requirements. After the requirement is reached, the grinding is stopped, the filter is filtered, the grinding beads and the coating are separated, and the coating is filled into the specified In the can. Discharge the barrel.

The physical and chemical performance test was carried out according to GB14907-2002, and the performance of the fire-retardant coating of the present invention is shown in the comparative example of Table 3. It can be seen from Table 3 that the intumescent fireproof coating prepared in this example has no agglomeration uniformly, and the fineness, drying time, adhesion, flexibility and impact resistance are all within the requirements of the technical specifications, and are water-based and fire-resistant. The properties also meet the technical preparation requirements, so the overall performance of the coating is excellent. Table 1 The ratio of the nano flame retardant of the present invention (unit: Kg)

Flame retardant 45 25 35 37 37 48 Flame retardant synergist biomass power plant ash 3 1 0. 1 10 6

Titanium Dioxide 2 5 Filler Expandable Graphite 3 10 2

Aluminosilicate cellulose 3 5 3 1. 5 alcohol ester -12 0. 2 0. 2 4. 8 0. 3

Additive hydroxyethyl cellulose 0. 1 0. 2 0. 2 0. 2

BYK-333 0. 2 0. 2 0. 2 0. 3 Solvent water 13. 7 30 10 23. 0 16. 6 10 The flame retardant used in the examples 1-5 of the present invention is prepared according to the ratio of Table 1. Nano-flame retardant; The flame retardant used in Comparative Example 6 was 22 Kg of ammonium polyphosphate, 15 Kg of melamine, and llKg of pentaerythritol.

Table 3 Comparison of main performance of the water-swellable steel structure fireproof coating of the present invention with existing coatings

Claims

claims

1. Water-based intumescent steel structure fire retardant coating. Each component is calculated by mass percentage. It is characterized by consisting of several components: 20-45% coating matrix, 25-45% nano-flame retardant, 0.1-10% flame retardant additive. Effective agent, 1-10%±real material, 0.2-5% additives and 10-30% water.

2. The water-based intumescent steel structure fire retardant coating according to claim 1, characterized in that: the nano-flame retardant consists of a char-forming agent, a char-forming catalyst, a foaming agent, silica and a surfactant; The flame retardant raw material is composed of a carbon-forming catalyst, a carbon-forming agent and a foaming agent, and is obtained by nanonizing the flame retardant raw material; the method for nanonizing the flame retardant raw material is to use the precipitation method to make the flame retardant It is prepared by fixing the agent raw materials on nano-silica particles.

3. The water-based intumescent steel structure fire retardant coating according to claim 2, characterized in that: the specific preparation steps of the nano flame retardant are: adding the flame retardant raw material, accounting for 5-50% of the weight of the flame retardant raw material Water glass and surfactant accounting for 0.5-50% of the weight of the flame retardant raw material are added to water that is 1-5 times the weight of the flame retardant raw material. After heating to 50-9CTC, use acid to adjust the pH value to 5-8 , after reacting for two hours, the reaction product is cooled, filtered and washed, and dried to obtain the nano-flame retardant.

4. The water-based intumescent steel structure fire retardant coating according to claim 2, characterized in that: the carbon-forming catalyst is selected from ammonium polyphosphate, red phosphorus, guanidine phosphate, urea phosphate, ammonium dihydrogen phosphate, and ammonium pyrophosphate. One or more; the char-forming agent is selected from one or more of starch, glucose, tricyanide, pentaerythritol, dipentaerythritol, and tripentaerythritol; the foaming agent is selected from urea, dicyandiamide, and melamine of one or more.

5. The water-based intumescent steel structure fire retardant coating according to claim 2, characterized in that: the surfactant is selected from dodecyl hydroxypropyl phosphate betaine, alkylphenol polyoxyethylene ether, silane coupling agent One or more combinations of coupling agent, fatty acid polyoxyethylene ester, sodium lauryl sulfate, polyvinyl alcohol, polyethyleneimine, polyvinyl alcohol-polyethyleneimine-polyvinyl alcohol.

6. The water-based intumescent steel structure fire retardant coating according to claim 1, characterized in that: the flame retardant synergist is selected from biomass power plant ash.

7. The water-based intumescent steel structure fire retardant coating according to claim 1, characterized in that: the filler is selected from titanium dioxide, antimony white powder, iron oxide, light calcium carbonate, aluminum silicate cellulose, kaolin, mica powder, One or more of phthalocyanine, expandable graphite, and flake graphite.

8. The water-based intumescent steel structure fireproof coating according to claim 1, characterized in that: the coating matrix is composed of 5-10% self-crosslinking silicone acrylic emulsion, acrylate emulsion, styrene acrylic emulsion, polyvinyl acetate emulsion It is composed of one or more kinds of paints, 10%-35% water-based epoxy emulsion, 1%-5% water-based epoxy curing agent, and the total coating matrix is 20-45%.

9. The water-based intumescent steel structure fire retardant coating according to claim 1, characterized in that: the additive is selected from the group consisting of 2,24-trimethyl-1,3-pentanediol monoisobutyl ester and hydroxyethyl fiber Cellulose, methylhydroxyethyl cellulose, polyether modified polysiloxane leveling agent TEGO Flow425, polyether modified polysiloxane leveling agent BYK-333, polyether modified polysiloxane One or more leveling agents JY3033.

10. The preparation method of water-based intumescent steel structure fire retardant coating according to any one of claims 1 to 9, characterized by comprising the following steps:

(1) Preparation of nano-flame retardant:

Add the flame retardant raw materials, water glass accounting for 5-50% of the weight of the flame retardant raw materials, and surfactant accounting for 0.5-50% of the weight of the flame retardant raw materials into 1-5 times the weight of the flame retardant raw materials. After heating the water to 50-9 CTC, use acid to adjust the pH value to 5-8, react for two hours, cool, filter and wash the reaction product, and obtain the nano-flame retardant after drying;

(2) Preparation of fire retardant coating:

First add the water-based epoxy emulsion, water-based epoxy curing agent and self-crosslinking silicone acrylic emulsion in the coating matrix into the mixing barrel. After stirring evenly, add the nano flame retardant, flame retardant synergist, fillers, additives and water. , stir for 10-30 minutes, then add it to the ball mill and grind it once. After evenly mixing, use a scraper fineness meter to check whether the fineness of the paint meets the requirements. Stop grinding when the requirements are met, filter with a filter, separate the grinding beads and paint, and pack the paint. Put it into the designated tank, discharge it into barrels.