CN109321021B - Fireproof expanded vermiculite and preparation method thereof - Google Patents
Fireproof expanded vermiculite and preparation method thereof Download PDFInfo
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- CN109321021B CN109321021B CN201811270667.8A CN201811270667A CN109321021B CN 109321021 B CN109321021 B CN 109321021B CN 201811270667 A CN201811270667 A CN 201811270667A CN 109321021 B CN109321021 B CN 109321021B
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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
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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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
- C08K9/00—Use of pretreated ingredients
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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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
- 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
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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Abstract
A preparation method of fire-proof expanded vermiculite comprises the following steps: (1) carrying out incomplete expansion calcination on vermiculite: removing impurities from vermiculite raw material, putting the vermiculite raw material into a rotary furnace at the temperature of 500-1000 ℃, heating and expanding for 10-20 seconds, and discharging to obtain incomplete expanded vermiculite with the bulk density of 800-1200 kg/m-3(ii) a (2) Adding the incomplete expanded vermiculite into a solvent, fully stirring and ultrasonically dispersing for 20-40 minutes to obtain a vermiculite suspension; (3) adding a fireproof modifier into the vermiculite suspension, and performing ultrasonic dispersion for 40-60 minutes; wherein the fireproof modifier consists of a low-molecular carbon source, a char forming catalyst and a foaming agent; (4) and (4) performing centrifugal separation on the solution obtained in the step (3), and primarily drying the precipitate to obtain the fireproof expanded vermiculite which has good fireproof performance and smoke suppression performance.
Description
Technical Field
The invention relates to a fireproof expanded vermiculite and a preparation method thereof, which can be used for preparing fireproof paint and fireproof plates and belongs to the field of vermiculite preparation.
Background
Vermiculite is a complex hydrous iron magnesium silicate mineral, which is a regenerated mineral formed by hydrothermal alteration or weathering of mica minerals. The vermiculite chemical composition is [ (Mg, Fe, Al)３（Ｓｉ，Ａｌ）４Ｏ１０（ＯＨ）２〕・４Ｈ２O, but the constant change is indefinite, belongs to monoclinic system, is in a sheet shape, has the hardness of 1-1.5, the density of 2400-2700 kg/m3 and the flexibility of the sheet, and has the most important property that the sheet can expand when heated, and the expansion is maximum at 800-1000 ℃, and the expansion multiple is 8-15 times, and can reach 30 times when the expansion multiple is higher. The density of the expanded vermiculite is generally 80-200 kg/m3, the thermal conductivity coefficient is 0.047-0.07W/(m seed and seed K), the sound absorption coefficient is 0.50-0.63 (the frequency is 512 Hz), and the refractoriness is 1300-1350 ℃. In addition, the expanded vermiculite has good freezing resistance in a dry state, and at the temperature of minus 20 ℃,after 15 times of freeze thawing, the grain size and the composition are unchanged. Meanwhile, because the organic fertilizer is inorganic, the organic fertilizer is not corroded by fungi, does not rot or deteriorate, and is not easy to be bitten by insects or rats. Because of such excellent properties, it is widely used. 2 application state of vermiculite is mainly used in building industry, but vermiculite has unique application in other fields. The production process of the expanded vermiculite comprises the following steps: removing impurities from vermiculite, crushing the vermiculite into particles of 1-2 mm, and screening to remove fine powder. After the raw materials are dried (preheated), the raw materials are put back to a rotary kiln or a vertical kiln for carrying out expansion heat treatment, and the thermal regulation of the expansion heat treatment has great influence on the expansion rate of the vermiculite. The vermiculite is slowly heated to 100 ℃, and then is quickly put into a heating furnace preheated to 1000 ℃ for 0.5-1.0 min. And annealing and cooling the vermiculite after the expansion heat treatment to obtain the expanded vermiculite. The expanded vermiculite coming out of the furnace is further subjected to screening to remove unexpanded impurity particles.
In the prior art, a series of attempts are made to modify vermiculite to obtain higher performance, for example, a Chinese patent with publication number 100404612 discloses a preparation method of an expanded vermiculite/potassium polyacrylate-acrylamide high water absorption composite material, which directly uses the expanded vermiculite as a raw material to prepare the high water absorption composite material through graft copolymerization of potassium acrylate and acrylamide monomers; the method adopts expanded vermiculite as a raw material at normal temperature to be compounded with organic matters, and the prepared material has the characteristics of oleophobicity and hydrophilicity and cannot be used in the field of hydrophobic materials. Chinese patent application with publication number CN1800072A discloses a method for rapidly preparing intercalated vermiculite by a dry method, which takes raw vermiculite ore as raw material, is crushed by an air flow mill, takes quaternary ammonium salt as an intercalating agent, and directly synthesizes quaternary ammonium salt intercalated vermiculite by a dry method in a torque rheometer at 100-180 ℃ according to a certain proportion; the method directly modifies the unexpanded vermiculite raw material, has higher product density, and is limited to the application in the fields of light fillers, carriers, organic composite fillers and the like.
However, at present, vermiculite is adopted as a fireproof functional filler to be added into the paint or the fireproof plate, and expanded vermiculite is only directly added or is used together with other fireproof paints such as an expansion flame-retardant system and a halogen-containing flame-retardant system, so that the research on fireproof modification of the expanded vermiculite is lacked.
Disclosure of Invention
The invention provides a fireproof expanded vermiculite and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) carrying out incomplete expansion calcination on vermiculite: removing impurities from vermiculite raw material, putting the vermiculite raw material into a rotary furnace at the temperature of 500-1000 ℃, heating and expanding for 10-20 seconds, discharging to obtain incomplete expanded vermiculite, and ensuring that the stacking density of the incomplete expanded vermiculite is 1200kg/m3；
(2) Adding the incomplete expanded vermiculite into a solvent, fully stirring and ultrasonically dispersing for 20-40 minutes to obtain a vermiculite suspension;
(3) adding a fireproof modifier into the vermiculite suspension, and performing ultrasonic dispersion for 40-60 minutes; wherein the fireproof modifier consists of a low-molecular carbon source, a char forming catalyst and a foaming agent;
(4) carrying out centrifugal separation on the obtained solution obtained in the step (3), and drying the precipitate to obtain the fireproof expanded vermiculite;
wherein the carbon source is pentaerythritol, dipentaerythritol or tripentaerythritol, the char-forming catalyst is ammonium dihydrogen phosphate, ammonium monohydrogen phosphate, ammonium metaphosphate, ammonium hypophosphite, ammonium phosphite, phosphorous acid, metaphosphoric acid and/or orthophosphoric acid, and the foaming agent is dicyandiamide, ammonium oxalate, urea or hexamethylenetetramine;
wherein the weight ratio of the incompletely expanded vermiculite, the carbon source, the carbon forming catalyst and the foaming agent is about 10 (1-2) to (1-2): (0.5-1.5).
Preferably, the working temperature of the rotary kiln is 500-800 ℃, the heating expansion time is 12-15s, and the optimal time is 13 seconds.
Preferably, the bulk density of the incompletely expanded vermiculite is 900-3Most preferably 950-3。
The vermiculite is excessively expanded due to overhigh temperature and overlong heating expansion time, and the loose packing density is too low, so that the further expansion heat absorption fireproof effect cannot be exerted in case of fire; the temperature is too low, the heating expansion time is too short, the vermiculite is not fully expanded, the insertion of the fireproof modifier is not facilitated, and the insufficient fireproof modifier cannot play a synergistic fireproof and smoke-suppressing role with the expanded vermiculite.
Preferably, the drying condition is natural airing at 25 ℃. The excessive high temperature leads to excessive volatilization of the small molecule fire-proof modifier, the insufficient temperature leads to the problem of uneven dispersion of incomplete expanded vermiculite in the coating due to the fact that a large amount of solvent is attached to the surface of the vermiculite.
After the technical scheme is adopted, the invention at least has the following beneficial effects: after vermiculite is subjected to incomplete expansion, an expansion type modifier consisting of a low-molecular carbon source, a char forming catalyst and a foaming agent can enter between layers of the incomplete expansion vermiculite, when the fireproof vermiculite is placed in a high-temperature environment such as a fire disaster, the expansion type modifier consisting of the low-molecular carbon source, the char forming catalyst and the foaming agent and the incomplete expansion vermiculite expand simultaneously, the expansion type modifier and the incomplete expansion vermiculite form thermal expansion foaming to form a carbon foam heat-insulating layer to seal a protected object, the transfer of heat and a base material is delayed, the object is prevented from being ignited and burnt or the strength is reduced due to temperature rise, meanwhile, the expanded vermiculite and the expanded vermiculite are expanded synchronously to form an organic whole with the carbon foam, the tightness, the heat insulation property and the heat insulation strength of the carbon foam are enhanced, the effects of preventing heat insulation and reducing the strength are further exerted, the two. Experiments prove that the fireproof performance of the intercalation modified incomplete expanded vermiculite is completely superior to the technical scheme of directly and simply blending the incomplete expanded vermiculite with an intumescent fireproof agent consisting of a carbon source, a char forming catalyst and a foaming agent.
And secondly, the intumescent fire-retardant filler is intercalated into the incomplete expanded vermiculite, so that the vermiculite can catalyze the carbon layer to form more carbon residue at high temperature, the generation of combustible escaping substances and the heat transfer are reduced, and meanwhile, the escaped carbon solid particles are further sealed between the vermiculite layers, so that a good smoke suppression effect is achieved.
Detailed Description
The technical solution of the invention will be described in detail with reference to the specific examples.
Example 1
The preparation method of the fireproof expanded vermiculite A comprises the following steps: (1) carrying out incomplete expansion calcination on vermiculite: removing impurities from vermiculite raw materials, putting the vermiculite raw materials into a rotary furnace at the temperature of 700 ℃, heating and expanding for 13 seconds, and discharging to obtain incomplete expanded vermiculite with the density of 1000kg/m 3;
(2) adding the incomplete expanded vermiculite into a solvent, fully stirring and ultrasonically dispersing for 30 minutes to obtain a vermiculite suspension, wherein the solvent is ethanol;
(3) adding a fireproof modifier into the vermiculite suspension, and performing ultrasonic dispersion for 50 minutes; the fireproof modifier consists of a low-molecular carbon source, a char forming catalyst and a foaming agent, wherein the carbon source is pentaerythritol, the char forming catalyst is ammonium dihydrogen phosphate, the foaming agent is ammonium oxalate, and the weight ratio of the incompletely expanded vermiculite to the carbon source to the char forming catalyst to the foaming agent is 10: 2: 2: 1;
(4) and (4) carrying out centrifugal separation on the obtained solution obtained in the step (3), and drying the precipitate to obtain the fireproof expanded vermiculite A.
Example 2
On the basis of example 1, the heating expansion time and temperature of vermiculite are changed, so that the bulk density of the expanded vermiculite obtained in step (1) is 200kg/m3And the other preparation steps are the same, so that the modified expanded vermiculite B is obtained.
Example 3
On the basis of example 1, the vermiculite heating expansion time and temperature are changed, so that the expanded vermiculite bulk density obtained in step (1) is 2000 kg/m3And the other preparation steps are the same, so that the modified expanded vermiculite C is obtained.
Example 4
The incompletely expanded vermiculite obtained in the step (1) in the embodiment 1 is directly blended with a carbon source, a char forming catalyst and a foaming agent by adopting a high-speed dispersing agent, wherein the weight ratio of the incompletely expanded vermiculite to the carbon source to the char forming catalyst to the foaming agent is 10: 2: 2: 1, obtaining the directly blended modified expanded vermiculite D.
Example 5
According to the weight percentage, 10 percent of modified expanded vermiculite, 20 percent of coating auxiliary agent and filler, 50 percent of polyurethane emulsion and 20 percent of tap water are stirred in a high-speed dispersion machine at 1000 r/min to obtain the fireproof coating, and the modified expanded vermiculite A, B, C, D prepared in the examples 1-4 is adopted to obtain the fireproof coating A, B, C, D.
Testing of fire performance
The coating is coated on a polished 150mm multiplied by 4mm wood board, the thickness of each coating is about 0.2 mm, the coating interval is 1 day, the coating is coated for 5 times to ensure that the thickness of the wood board coating is about (1 +/-0.05) mm, and the wood board is dried by air blast in a 35 ℃ oven. The test sample plate is placed on an iron ring, the coating surface faces downwards, the vertical distance between the iron ring and an alcohol burner is 7 cm, when the flame temperature rises to 1000 ℃, the burner is moved to the position below the test sample plate to burn the fireproof coating, and the temperature sensor head wrapped by the heat-insulating material is fixed on the back fire surface of the wood plate to record the back surface temperature every 5 minutes. The burn test time was 80 minutes.
The smoke density test was performed according to GB/T8627-2007 with sample sizes of 25.4mm by 4.0 mm.
According to GB 12441 + 2005 finish type fireproof paint test flame propagation ratio
TABLE 1 fire-retardant coating Properties
| Sample type | Modified expanded vermiculite type | Temperature of backfire | Amount of carbon residue | Ratio of flame propagation |
| Coating 1 | Modified expanded vermiculite A | 55 | 36% | 12 |
| Paint 2 | Modified expanded vermiculite B | 67 | 28% | 19 |
| Coating 3 | Modified expanded vermiculite C | 69 | 27% | 20 |
| Coating 4 | Modified expanded vermiculite D | 76 | 24% | 24 |
Therefore, the flame retardant property of the fire retardant coating added with the expanded vermiculite modified by a special process is greatly improved compared with the flame retardant property of the fire retardant coating added with the expanded vermiculite modified by direct blending.
Claims (7)
1. The preparation method of the fireproof expanded vermiculite is characterized by comprising the following steps:
(1) carrying out incomplete expansion calcination on vermiculite: removing impurities from vermiculite raw material, putting the vermiculite raw material into a rotary furnace at the temperature of 500-1000 ℃, heating and expanding for 10-20 seconds, and discharging to obtain incomplete expanded vermiculite with the bulk density of 800-1200-kg/m3 ；
(2) Adding the incomplete expanded vermiculite into a solvent, fully stirring and ultrasonically dispersing for 30-40 minutes to obtain a vermiculite suspension;
(3) adding a fireproof modifier into the vermiculite suspension, and performing ultrasonic dispersion for 40-60 minutes; wherein the fireproof modifier consists of a low-molecular carbon source, a char forming catalyst and a foaming agent;
(4) performing centrifugal separation on the solution obtained in the step (3), and primarily drying the precipitate to obtain the fireproof expanded vermiculite;
wherein the low molecular carbon source is pentaerythritol, dipentaerythritol or tripentaerythritol, the char-forming catalyst is ammonium dihydrogen phosphate, ammonium monohydrogen phosphate, ammonium metaphosphate, ammonium hypophosphite, ammonium phosphite, phosphorous acid, metaphosphoric acid and/or orthophosphoric acid, and the foaming agent is dicyandiamide, ammonium oxalate, urea or hexamethylenetetramine;
wherein the weight ratio of the incompletely expanded vermiculite, the low molecular carbon source, the char forming catalyst and the foaming agent is 10 (1-2) to (1-2): (0.5-1.5).
2. The method for preparing the fireproof expanded vermiculite according to claim 1, wherein the working temperature of the rotary furnace is 500-800 ℃, and the heating expansion time is 12-15 seconds.
3. The method for preparing fire-retardant expanded vermiculite according to claim 2, wherein the heating expansion time is 13 seconds.
4. The method for preparing fire-proof expanded vermiculite according to claim 1, wherein the bulk density of the incompletely expanded vermiculite is 900-3。
5. The method for preparing fire-proof expanded vermiculite according to claim 1, wherein the bulk density of the incompletely expanded vermiculite is 950-3。
6. The method for preparing fire-retardant expanded vermiculite according to claim 1, wherein the primary drying condition is natural airing.
7. A fire-resistant expanded vermiculite, characterized in that it is prepared by the method of any one of claims 1 to 6.
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| CN110527343B (en) * | 2019-09-06 | 2021-03-09 | 石家庄易辰防火保温材料有限公司 | Fireproof coating |
| CN111154145A (en) * | 2020-01-16 | 2020-05-15 | 上海工程技术大学 | Intumescent flame retardant and preparation method and application thereof |
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