CN111777100A - Modified molybdenum trioxide sol and preparation method thereof - Google Patents
Modified molybdenum trioxide sol and preparation method thereof Download PDFInfo
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- CN111777100A CN111777100A CN202010596781.0A CN202010596781A CN111777100A CN 111777100 A CN111777100 A CN 111777100A CN 202010596781 A CN202010596781 A CN 202010596781A CN 111777100 A CN111777100 A CN 111777100A
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- C01—INORGANIC CHEMISTRY
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- C01G39/00—Compounds of molybdenum
- C01G39/02—Oxides; Hydroxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- 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
The invention discloses a modified molybdenum trioxide sol and a preparation method thereof. The molybdenum trioxide sol contains nano spherical particles with the diameter of 5-100 nm. The modified molybdenum trioxide is doped with an aluminum compound. The preparation method comprises the following steps: molybdic acid is used as a precursor, alcohols and water are used as solvents, an organic aluminum compound is used as a modification auxiliary agent, and a surfactant is used as a sol stabilizer to carry out hydrothermal reaction. The obtained product is a translucent to transparent stable liquid. The product is applied to the flame retardant field, and is a smoke suppressant with excellent performance.
Description
Technical Field
The invention relates to a modified molybdenum trioxide sol and a preparation method thereof, and the product is particularly suitable for application in water-based paint smoke inhibitors and catalysts.
Background
Molybdenum trioxide is white crystalline powder, MoO3 is a smoke-suppressing flame retardant with very excellent performance, and compared with smoke-suppressing agents such as iron compounds (ferrocene, iron oxide), copper compounds (copper oxide), metal hydroxides (aluminum hydroxide and magnesium hydroxide), zinc borate and the like, the smoke-suppressing effect of alpha-MoO 3 is the best. MoO3 can be generally prepared by evaporative crystallization of molybdic acid.
At present, industrial sublimation method produces pure molybdenum trioxide, begin to sublimate when the temperature is less than its melting point 795 ℃, get into gaseous phase with trimerization molybdenum oxide's form, conventional sublimation method adopts dust collection fan housing and sack to collect molybdenum trioxide, only obtain micron order product because of the particle coacervation, in order to prepare nanometer molybdenum trioxide, must cool sublimed molybdenum trioxide gas shock cooling, the energy consumption is high and is difficult for collecting, and the granule of collecting and obtaining is nanometer molybdenum trioxide's aggregate, be difficult to disperse in the solvent with the nanoparticle once more, bring the puzzlement for the low reaches user. Therefore, it is necessary to find a simple solution for synthesizing nano molybdenum trioxide. The addition of the modifying assistant in the synthesis process of the nano material is an effective means, and the modifier can generally make the obtained nano sol more stable and endow the nano particles with controllable and specific chemical properties.
CN 1550453A discloses a method for synthesizing antimony pentoxide by doping molybdate or tungstate, which effectively dopes the antimony pentoxide with soluble molybdate or tungstate to realize antimony pentoxide sol modification.
CN 108950653A discloses a preparation method of a graphene oxide-aluminum-molybdenum trioxide ternary nano composite energy-containing film. The GO/Al/MoO3 ternary nano composite energetic film is obtained by taking nano aluminum powder, graphene oxide and nano molybdenum trioxide as deposition phases and polyethyleneimine as an additive and adopting an electrophoretic deposition method. The invention has simple process, short period and low production cost, and is suitable for industrial large-scale production. But in application, the wide application is difficult due to equipment and process problems.
CN 108539190 a discloses molybdenum trioxide containing oxygen vacancies, an aqueous aluminum ion battery using the molybdenum trioxide as a negative electrode active material, and a preparation method thereof. The preparation method of the oxygen vacancy-containing molybdenum trioxide (MoO3-x) comprises the following steps: molybdenum trioxide is used as a precursor, and micromolecular alcohols such as ethanol, ethylene glycol or methanol are used as reducing agents to carry out hydrothermal reaction, so that MoO3-x is obtained. The aqueous aluminum ion battery taking molybdenum trioxide containing oxygen vacancies as a negative electrode material can be prepared by taking MoO3-x as a negative electrode active material, carbon materials with large specific surface area, such as graphene, activated carbon or carbon nano tubes, as a positive electrode active material, a glass fiber diaphragm, a polyethylene or polypropylene fiber diaphragm, and the like as diaphragms and an aqueous solution containing aluminum ions as an electrolyte.
CN 108147460A discloses a preparation method of a molybdenum trioxide nanotube, which comprises the following process steps: (1) molybdenum hexacarbonyl is used as a raw material, porous anodic aluminum oxide is used as a template, the template is placed above the raw material with an opening facing downwards, the crucible is sealed and then placed in a muffle furnace for heating, low-temperature sublimation is carried out to deposit the molybdenum hexacarbonyl, and the temperature is continuously raised to thermally decompose the molybdenum hexacarbonyl deposited in the porous anodic aluminum oxide template to form metal molybdenum deposition; (2) continuously heating to deposit and oxidize the molybdenum metal in the step (1); (3) removing the porous alumina template by using a dilute acid solution, then carrying out suction filtration treatment, and drying to obtain a finished product.
CN 104275890A discloses a preparation method of a high-performance nano aluminum-molybdenum trioxide composite heat insulation film, which is characterized by comprising the following process steps: (1) mixing aluminum powder, a dispersing solvent, a dispersing auxiliary agent and a ball milling medium, filling nitrogen for protection, and carrying out ball milling in a high-energy ball mill for 30-50 hours to prepare nano aluminum powder slurry; (2) mixing nano molybdenum trioxide powder, a dispersing solvent, a dispersing auxiliary agent and a ball milling medium, and ball milling for 0.5-1 hour in a high-energy ball mill to prepare nano molybdenum trioxide slurry; (3) sequentially adding the nano aluminum powder slurry and the nano molybdenum trioxide slurry into an organic solvent, respectively stirring and dispersing for 20 minutes to 1 hour, adding polyacrylate resin and an ultraviolet absorber, stirring and dispersing for 1 to 4 hours, and filtering by using a 1500-mesh filter membrane pump to obtain the heat insulation adhesive.
CN 103803650 a discloses various methods for producing molybdenum trioxide: and (3) putting molybdic acid into a flash dryer, decomposing molybdic acid into water and molybdenum trioxide, and performing cyclone dust removal and cloth bag dust removal to obtain molybdenum trioxide. The molybdenum trioxide powder obtained by the method has large particle size and is difficult to be dispersed in pure water in an ultra-fine mode.
Disclosure of Invention
Molybdenum trioxide is a flame-retardant smoke suppressant with excellent performance. The antimony bromide flame-retardant product has high-efficiency flame retardance, dense smoke released in the flame-retardant process is a problem which is difficult to solve in the industry, and molybdenum trioxide replaces part of antimony oxide in the flame retardance of part of antimony bromide, so that the high-efficiency flame retardance is realized, and the smoke is obviously reduced, so that the molybdenum trioxide becomes an optimal matching reagent for an antimony bromide flame-retardant system. In order to further improve the flame-retardant and smoke-suppressing properties of molybdenum trioxide, it is common practice to increase the composition of molybdenum trioxide, reduce the particle size of molybdenum trioxide, and improve the dispersibility of molybdenum trioxide in flame-retardant articles. For the water-based flame-retardant coating, solid particles with high molybdenum trioxide density are difficult to uniformly disperse and stably suspend in a water-based system, and the coating is easy to generate a solid-liquid layering phenomenon, so that the performance of the product is seriously influenced. In order to solve the problems, the invention provides a preparation method of a storage-stable aqueous molybdenum trioxide sol, which comprises the step of carrying out hydrothermal reaction by using molybdic acid as a precursor, alcohols and water as solvents, an organic aluminum compound as a modification auxiliary agent and a surfactant as a sol stabilizer to synthesize a light blue, transparent to semitransparent and stable liquid. The product is applied to the flame-retardant field, and is a flame-retardant smoke suppressant with excellent performance.
The technical scheme adopted by the invention is as follows: molybdic acid generates molybdenum trioxide nano particles under high-temperature hydrothermal conditions. Organic aluminum monomer (such as aluminum isopropoxide) is hydrolyzed in aqueous solution of alcohol to generate aluminum hydroxide, under specific conditions, molybdenum trioxide particles are coated and modified by the generated aluminum hydroxide, and the modified particles absorb anions with negative charges, so that the stability of the molybdenum trioxide sol in solution is improved, and the stable nano molybdenum trioxide sol from translucence to transparency is formed. The technical core point of the invention is that the generation concentration and the preparation process of the aluminum hydroxide are controlled, the preparation process comprises a medicine adding process and temperature and pressure control, and the accurate control of the reaction time is shown, which is also one of the key factors of the synthesis scheme.
The modified molybdenum trioxide sol and the preparation method thereof according to the claim, wherein the sol and the preparation method comprise the following steps:
in the step (1), water and alcohol which are prepared according to a certain proportion are added into a reaction vessel A, molybdic acid particles are added, and the temperature is raised and the molybdic acid is dissolved by stirring. Adding an alcohol solvent and a sol stabilizer into the other reaction vessel B, and stirring and adding an organic aluminum compound to completely dissolve the organic aluminum compound after the sol stabilizer is completely dissolved;
slowly dripping the liquid in the reaction container B into the reaction container A, and continuously stirring;
and (3) heating the reaction container A to a specified temperature, wherein the heat preservation time is more than or equal to 2 hours.
The modified molybdenum trioxide sol and the preparation method thereof are characterized in that in the step (1), the mass ratio of water to alcohol is 1-9: 1, preferably 4: 1; heating to 70-99 ℃, and preferably selecting 85 ℃; the mass ratio of water to alcohol to molybdic acid is 1-9: 1: 0.2 to 3.
The alcohol and alcohol solvent is one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol, preferably ethanol.
The sol stabilizer is a surfactant with water solubility or alcohol solubility characteristics, and the surfactant molecule has the characteristics of containing a hydrophilic group and a hydrophobic group. The hydrophilic group includes: one or more of-OH, -COO, - (CH 2-CH 2-O) n-, -SO 3H, -CONH 2, -SH, -NH-and-NH 2. The hydrophobic groups include: one or two of R- (each alkyl R-contains 5-18 carbon atoms), Ar- (aryl) and C6H5CH 2- (benzyl). The organoaluminum compound includes, for example, one or two or more of trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, trimethylaluminum, triethylaluminum and triisopropanolaluminum, with triisopropanolaluminum being preferred.
In the step (1), the mass ratio of the organic aluminum compound to the alcohol solvent to the sol stabilizer is 1: 2-10: 0.05 to 0.2.
In the step (2), the liquid in the reaction container B is taken out and added into the reaction container A dropwise. The mass ratio of the liquid mass of the reaction container A to the liquid mass of the reaction container B is 10: 0.2-2, preferably 10: 1.
in the step (1), the highest temperature of the reaction vessel A is not more than 100 ℃. In the step (3), the highest temperature of the temperature rise and the heat preservation of the reaction container A is less than or equal to 200 ℃.
In the step (1), the optimal reaction temperature of the reaction container A is 80-85 ℃. In the step (3), the optimal temperature for heating and heat preservation of the reaction vessel A is 105-140 ℃, and the reaction vessel is preferably a high-pressure reaction kettle.
In the specific embodiment, a specific operation flow is selected, and the method completely depends on the basic principle of synthesis and controllability of operation. Such as isopropanol, in a solvent of ethanol and water, under vigorous stirring, to form a solution, the reason why the solution can be stably present depends on temperature, concentration, alcohol-water ratio, surfactant selection, and the like. The different abovementioned influencing factors have an important significance for the stability of the resulting solution.
The flame-retardant smoke suppressant prepared by the invention has the following characteristics and advantages: the method has the advantages of simple operation, mild reaction conditions, stable and transparent prepared sol, small nano particle size and easy addition in a water-based paint system. The disadvantages are that: the process is difficult to control, and the requirement on the purity of chemical reagents is high.
The invention is described in detail below by way of examples, which are intended to be within the scope of the claims. It should be noted that the following examples are only intended to illustrate the present invention and should not be construed as limiting the scope of the present invention, and that some insubstantial modifications and adaptations made in accordance with the present invention are still within the scope of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples.
The raw materials or chemical reagents used in the examples of the present invention are commercially available unless otherwise specified.
Example 1
The main raw materials are as follows: molybdic acid, aluminum triethoxide, sodium dodecylbenzenesulfonate, water, isopropanol and polyvinyl acetate;
the preparation method comprises the following steps: in an autoclave equipped with stirring and heating, 13.9 g of molybdic acid, 149.0 g of water and 0.5 g of polyvinyl acetate were charged, and the mixture was heated to 80 ℃ and maintained at that temperature for 2 hours. A mixture of a defined amount of aluminum triethoxide, 82.5 g of water and 10.2 g of isopropanol was added to reaction vessel B and stirred for 1 hour. And (3) dropwise adding all the liquid in the reaction vessel B into the reaction vessel A, and raising the temperature to 120 ℃ for 3 hours. The prepared liquid is clear and transparent and has good fluidity.
Example 2
The main raw materials are as follows: molybdic acid, aluminum triisopropoxide, AES (surfactant), water, and ethanol;
the preparation method comprises the following steps: to a reaction vessel A with stirring and heating, 35.9 g of ethanol, 12.5 g of aluminum triethoxide and 229.5 g were sequentially added, and stirred at room temperature for 1 hour. Then 2.2 g of AES (surfactant) and 9.8 g of molybdic acid are added in sequence, the mixture is heated to 95 ℃, the temperature is kept constant for 3 hours, the temperature is raised to 120 ℃, the mixture is continuously stirred and kept warm for 2 hours, and then the reaction is finished, so that milky clear liquid is obtained.
Example 3
The main raw materials are as follows: molybdic acid, aluminum triisopropoxide, cetyltrimethylammonium chloride, water, ethanol and ammonia water;
the preparation method comprises the following steps: in a stirred and heated reaction vessel A, 27.9 g of molybdic acid and 168.0 g of water were added, and the mixture was heated to 70 ℃ and kept at the constant temperature for 5.5 hours. A mixture of a fixed amount of aluminum triisopropoxide, 60.5 g of water, 42.2 g of ethanol and 5.5 g of ammonia was added to the reaction vessel B, and stirring was continued for 1 hour. And (3) dropwise adding the liquid in the reaction vessel B into the reaction vessel A, and raising the temperature to 140 ℃ for 5 hours to obtain clear and transparent liquid with good faint yellow fluidity.
Claims (5)
1. The modified molybdenum trioxide sol and the preparation method thereof are characterized in that the sol and the preparation method thereof comprise the following steps:
adding water and alcohol prepared in proportion into a reaction vessel A, adding molybdic acid particles, and heating and stirring to dissolve molybdic acid; adding an alcohol solvent and a sol stabilizer into the other reaction vessel B, and stirring and adding an organic aluminum compound to completely dissolve the organic aluminum compound after the sol stabilizer is completely dissolved;
slowly dripping the liquid in the reaction container B into the reaction container A, and continuously stirring;
and (3) heating the reaction container A to a specified temperature, wherein the heat preservation time is more than or equal to 2 hours.
2. The modified molybdenum trioxide sol and the preparation method thereof according to claim 1 are characterized in that: in the step (1), the mass ratio of water to alcohol is 1-9: 1, preferably 4: 1; heating to 70-99 ℃, and preferably selecting 85 ℃; the mass ratio of water to alcohol to molybdic acid is 1-9: 1: 0.2 to 3; the alcohol and alcohol solvent is one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol, preferably ethanol; the sol stabilizer refers to a surfactant with water-solubility or alcohol-solubility characteristics, and the surfactant molecule has the following characteristics: containing a hydrophilic group and a hydrophobic group; the hydrophilic group includes: one or more of-OH, -COO, - (CH 2-CH 2-O) n-, -SO 3H, -CONH 2, -SH, -NH-and-NH 2; the hydrophobic groups include: one or two of R- (each alkyl R-contains 5-18 carbon atoms), Ar- (aryl) and C6H5CH 2- (benzyl); the organoaluminum compound includes, for example, one or two or more of trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, trimethylaluminum, triethylaluminum and triisopropanolaluminum, with triisopropanolaluminum being preferred.
3. The modified molybdenum trioxide sol and the preparation method thereof according to claim 1 are characterized in that: in the step (1), the mass ratio of the organic aluminum compound to the alcohol solvent to the sol stabilizer is 1: 2-10: 0.05 to 0.2.
4. The modified molybdenum trioxide sol and the preparation method thereof according to claim 1 are characterized in that: in the step (2), the liquid in the reaction container B is taken and dripped into the reaction container A; the mass ratio of the liquid mass of the reaction container A to the liquid mass of the reaction container B is 10: 0.2-2, preferably 10: 1.
5. the modified molybdenum trioxide sol and the preparation method thereof according to claim 1 are characterized in that: in the step (3), the highest temperature of the temperature rise and the heat preservation of the reaction container A is less than or equal to 200 ℃.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113896242A (en) * | 2021-11-08 | 2022-01-07 | 苏州大学附属第一医院 | Preparation method and application of oxygen vacancy molybdenum trioxide nanoparticles |
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| GB743367A (en) * | 1953-08-14 | 1956-01-11 | Exxon Research Engineering Co | Improvements in or relating to molybdena hydrosols |
| US20050239907A1 (en) * | 2004-04-21 | 2005-10-27 | Nissan Chemical Industries, Ltd. | Anhydrous zinc antimonate sol and process for producing same |
| CN101613187A (en) * | 2009-07-24 | 2009-12-30 | 同济大学 | A kind of raising WO 3The method of film gaschromic cycle performance |
| CN105060346A (en) * | 2015-07-31 | 2015-11-18 | 桂林理工大学 | Preparation method of molybdenum trioxide nanobelt colloid automatically and stably dispersed in water |
-
2020
- 2020-06-28 CN CN202010596781.0A patent/CN111777100A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB743367A (en) * | 1953-08-14 | 1956-01-11 | Exxon Research Engineering Co | Improvements in or relating to molybdena hydrosols |
| US20050239907A1 (en) * | 2004-04-21 | 2005-10-27 | Nissan Chemical Industries, Ltd. | Anhydrous zinc antimonate sol and process for producing same |
| CN101613187A (en) * | 2009-07-24 | 2009-12-30 | 同济大学 | A kind of raising WO 3The method of film gaschromic cycle performance |
| CN105060346A (en) * | 2015-07-31 | 2015-11-18 | 桂林理工大学 | Preparation method of molybdenum trioxide nanobelt colloid automatically and stably dispersed in water |
Non-Patent Citations (2)
| Title |
|---|
| XIANZHONG ZENG ET AL.: ""A facile hydrothermal method for the fabrication of one-dimensional MoO3 nanobelts"", 《MATERIALS LETTERS》 * |
| YI-BO HU ET AL.: ""Influence of a thin aluminum hydroxide coating layer on the suspension stability and reductive reactivity of nanoscale zero-valent iron"", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113896242A (en) * | 2021-11-08 | 2022-01-07 | 苏州大学附属第一医院 | Preparation method and application of oxygen vacancy molybdenum trioxide nanoparticles |
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