CN111807343B - Method for controlling fine particle size in preparation of ammonium polyphosphate and application thereof - Google Patents
Method for controlling fine particle size in preparation of ammonium polyphosphate and application thereof Download PDFInfo
- Publication number
- CN111807343B CN111807343B CN202010451989.3A CN202010451989A CN111807343B CN 111807343 B CN111807343 B CN 111807343B CN 202010451989 A CN202010451989 A CN 202010451989A CN 111807343 B CN111807343 B CN 111807343B
- Authority
- CN
- China
- Prior art keywords
- ammonium polyphosphate
- particle size
- ammonia
- fine particle
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/38—Condensed phosphates
- C01B25/40—Polyphosphates
- C01B25/405—Polyphosphates of ammonium
-
- 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
- C09D131/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
- C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C09D131/04—Homopolymers or copolymers of vinyl acetate
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention provides a method for controlling the fine particle size of ammonium polyphosphate preparation and application thereof. The method comprises a reaction step, a cooling step and a crushing step. The reaction steps are as follows: mixing a mixture of 1:1, uniformly stirring the phosphorus pentoxide and the diammonium hydrogen phosphate, heating to introduce ammonia, wherein the ammonia introduction amount is 0.5 m/h-2.5 m/h, heating to 150-200 ℃, adjusting the ammonia introduction amount to 1.0 m/h-4.0 m/h, continuing to heat to 260-310 ℃, and reacting for 2-5 h; after the temperature in the reactant is stabilized for 5min to 15min, 0.5 percent to 3 percent of ammonia-deficient ammonium polyphosphate powder is added; and (3) cooling: stopping heating, reducing ammonia flow, carrying out thin film evaporation at 0.2m by year/h-1 m, and cooling for 1 to 2h to obtain a crude ammonium polyphosphate product; a crushing step: and (3) crushing the coarse ammonium polyphosphate product by adopting an air classification mill crusher to obtain a crystal II type ammonium polyphosphate product with a controlled fine particle size.
Description
Technical Field
The invention relates to the technical field of ammonium polyphosphate preparation, in particular to a fine particle size control method for ammonium polyphosphate preparation and application thereof.
Background
Ammonium phosphate (APP) is a biodegradable phosphorus and nitrogen type environment-friendly inorganic flame retardant, can be used as a flame retardant for paint, plastic and rubber, and has various crystal structures, wherein I, II is most commonly used, and the performance of crystal II is better. Therefore, the flame retardant has wide application in the flame retardant fields of fire retardant coatings, resins, rubber paper, wood, fibers and the like, and has the characteristics of low toxicity and low smoke. Ammonium polyphosphate is an important component of the steel structure intumescent fire-retardant coating, has high requirements on viscosity and storage stability, and has specific requirements on the performance and particle size of various raw materials.
The known preparation method of the electronic-grade ammonium polyphosphate flame retardant is characterized in that diammonium hydrogen phosphate and phosphorus pentoxide are ground and mixed, ammonia is introduced, a three-stage heating process is adopted, and then a polyurethane coating material is modified to obtain the electronic-grade ammonium polyphosphate with the particle size of 500 meshes. The method is mainly used for preparing the APP with the fine particle size, and meanwhile, the grinding of the raw materials has certain hygroscopicity to influence the product performance. The method of grinding ammonium polyphosphate in a solvent and modifying the ammonium polyphosphate with a triazine flame retardant is also adopted to control the particle size of the product.
Another known preparation method of high heat resistance crystal II type ammonium polyphosphate adopts the mixed reaction of diammonium hydrogen phosphate and phosphorus pentoxide, and sprays high-concentration urea solution after ammonia is introduced, and the product produced by the method has small grain size, and the average grain size is less than 10 microns. A large amount of water in the urea solution not only influences the condensation reaction in the synthesis process, but also increases the energy consumption due to the escape of a large amount of water.
In addition, the preparation method of crystal II type ammonium polyphosphate with high polymerization degree and narrow molecular weight distribution adopts the mixed reaction of diammonium hydrogen phosphate and phosphorus pentoxide with equal mol, and a large amount of inert gas is introduced in the initial process, and ammonium polyphosphate products (less than 12 microns) with fine particle size are obtained by introducing, stopping and repeatedly introducing ammonia gas, and carrying out reaction through surface treatment. Inert gases such as nitrogen, helium, argon and the like need to be introduced in the preparation process of the product, so that the production cost is increased, and the whole particle size of the product is small.
Disclosure of Invention
The invention aims to provide a method for controlling the fine particle size of ammonium polyphosphate preparation and application thereof.
In order to solve the technical problems, the method for controlling the fine particle size of the ammonium polyphosphate comprises a reaction step, a cooling step and a crushing step.
The reaction steps are as follows: mixing a mixture of 1:1, uniformly stirring the phosphorus pentoxide and the diammonium hydrogen phosphate, heating and introducing ammonia, carrying out high speed plantation by m-2.5 m/h, heating to 150-200 ℃, adjusting the ammonia introduction amount to 1.0m and carrying out high speed plantation by 3242-4.0 m/h, continuously heating to 260-310 ℃, and reacting for 2-5 h; when the temperature in the reactant is stabilized for 5min-15min, 0.5% -3% of ammonia-deficient ammonium polyphosphate powder is added;
and (3) cooling: stopping heating, reducing ammonia flow, carrying out thin film evaporation at 0.2m by year/h-1 m, and cooling for 1 to 2h to obtain a crude ammonium polyphosphate product;
a crushing step: and (3) crushing the coarse ammonium polyphosphate product by adopting an air classification mill crusher to obtain a crystal II type ammonium polyphosphate product with a controlled fine particle size.
Optionally, the ammonia-deficient ammonium polyphosphate powder is prepared by the following method:
adding 120 kg of phosphorus pentoxide and 113 kg of diammonium hydrogen phosphate into a kneader, uniformly stirring at the rotating speed of 60RPM, heating to introduce ammonia, wherein the introduction amount of the ammonia is 8.0m3/h, heating to 250 ℃ to form viscous syrup-like liquid, and keeping the reaction temperature at 300 ℃ for 2h; reducing the ammonia flux to 1.5m 3/h, reacting for 3h, and gradually reducing the reaction temperature to 240 ℃ to obtain white crystal II type ammonium polyphosphate solid powder; adding white crystal II type ammonium polyphosphate solid powder into a kneader, stirring at the speed of 150RPM, introducing nitrogen at the flow rate of 0.3m3/h, keeping the temperature for 3h after the temperature is raised to 220 ℃, cooling and crushing to obtain ammonium-deficient ammonium polyphosphate powder.
Optionally, the ammonia-deficient ammonium polyphosphate powder added in the reaction step is 1-1.7%.
Optionally, the D50 of the ammonia-deficient ammonium polyphosphate powder is 5-10 mu m.
Further, the D50 of the ammonia-deficient ammonium polyphosphate powder is 5-6 mu m.
Optionally, the feeding frequency of the air classification mill pulverizer is 15 HZ-20 HZ, the internal division frequency is 30 HZ-50 HZ, and the fan frequency is 30 HZ-45 HZ.
Optionally, the content of phosphorus pentoxide is more than or equal to 99.5%, the activity R value is more than or equal to 1.7, and the proportion of reducing substances is less than or equal to 0.005%.
Optionally, the proportion of the crystal II type ammonium polyphosphate product with the grain size of less than or equal to 2.19 mu m in the fine grain size is controlled to be less than or equal to 2 percent.
The invention also provides an application of the crystal II type ammonium polyphosphate product for controlling the fine particle size, the crystal II type ammonium polyphosphate product for controlling the fine particle size is prepared by any method for preparing the fine particle size from the ammonium polyphosphate, and the crystal II type ammonium polyphosphate product for controlling the fine particle size is used as a flame retardant in the steel structure fireproof coating.
Optionally, the mass ratio of the crystal II type ammonium polyphosphate product with fine particle size in the fireproof coating is controlled to be 24%.
In conclusion, the invention can control the proportion of the fine particle size of the final product without introducing a large amount of inert gas, urea containing a large amount of moisture and grinding the raw materials, and the crystal II type ammonium polyphosphate product with the proportion of the fine particle size of less than or equal to 2.19 mu m of less than or equal to 2 percent is used as a flame retardant in the steel structure fireproof coating.
Detailed Description
The following examples are given to further illustrate embodiments of the present invention. The following examples are intended to illustrate the invention, but are not intended to limit the scope of the invention.
The percentages referred to in the present invention are all mass percentages. For example, 0.5% -3% of the ammonia-deficient ammonium polyphosphate powder is added, which means that the ammonia-deficient ammonium polyphosphate powder accounts for 0.5% -3% of the mass of the total reactants.
Example 1
(1) And a reaction step: 125kg of phosphorus pentoxide and 116kg of diammonium hydrogen phosphate (the molar ratio is 1:1, the content of phosphorus pentoxide is more than or equal to 99.5%, the activity R value is more than or equal to 1.7, and the proportion of reducing substances is less than 0.005%) are put into a 500L kneader, the mixture is uniformly stirred and then heated and introduced with ammonia, and the ammonia introduction amount is 1.3 m/h (calculated by 100kg of reactants). Heating to 160 ℃, introducing ammonia 2.5 m/h, carrying out a melting reaction on the phosphorus pentoxide and diammonium phosphate materials to release heat, heating the reaction temperature to 280 ℃, adding 4.8kg of ammonium polyphosphate with D50 of 7 mu m ammonia deficiency after stabilizing for 10 minutes, and carrying out reaction for 3 hours at the stage;
(2) and cooling: stopping heating, reducing ammonia introduction amount, carrying out the reaction for 1m and cooling for 1h per 100kg of reactants, and discharging;
(3) and the product is ground by an air classification mill, the feeding frequency is 20HZ, the internal division frequency is 30HZ, and the fan frequency is 30HZ, so that the crystal II type ammonium polyphosphate product with the controlled fine particle size is obtained.
Example 2
(1) And (3) reaction: 125kg of phosphorus pentoxide and 116kg of diammonium hydrogen phosphate (the molar ratio is 1:1, the content of phosphorus pentoxide is more than or equal to 99.5%, the activity R value is more than or equal to 1.7, and the proportion of a reducing substance is less than 0.005%) are put into a 500L kneader, the mixture is uniformly stirred and then heated and introduced with ammonia, and the ammonia introduction amount is 0.5 m/h (calculated by 100kg of reactants). Heating to 150 ℃, introducing ammonia for 4.0 m/h, carrying out a melting reaction on the phosphorus pentoxide and diammonium phosphate materials to release heat, heating the reaction temperature to 310 ℃, stabilizing for 5 minutes, adding 7.23kg of ammonium polyphosphate lacking ammonia with D50 of 10 mu m, and carrying out reaction for 2 hours at the stage;
(2) and cooling: stopping heating, reducing ammonia introduction amount, carrying out dry distillation at the ammonia introduction amount of 0.2 m/h per 100kg of reactants, continuously carrying out reaction and cooling for 2h, and discharging;
(3) and the product is ground by an air classification mill, the feeding frequency is 20HZ, the internal division frequency is 30HZ, and the fan frequency is 30HZ, so that the crystal II type ammonium polyphosphate product with the controlled fine particle size is obtained.
Example 3
(1) And (3) reaction: 125kg of phosphorus pentoxide and 116kg of diammonium hydrogen phosphate (the molar ratio is 1:1, the content of phosphorus pentoxide is more than or equal to 99.5%, the activity R value is more than or equal to 1.7, and the proportion of a reducing substance is less than 0.005%) are put into a 500L kneader, and the phosphorus pentoxide and the diammonium hydrogen phosphate are uniformly stirred, heated and introduced with ammonia, wherein the ammonia introduction amount is 2.5m for each year (100 kg of reactants). Heating to 200 ℃, introducing ammonia for 1.0 m/h, carrying out melting reaction on the phosphorus pentoxide and diammonium hydrogen phosphate materials to release heat, raising the reaction temperature to 260 ℃, adding 1.21kg of ammonia-deficient ammonium polyphosphate with the D50 of 5 mu m after stabilizing for 15 minutes, and carrying out reaction for 5 hours at this stage;
(2) and cooling: stopping heating, reducing ammonia introduction amount, carrying out reaction and cooling for 2h continuously, and discharging, wherein the ammonia introduction amount is 1m for each 100kg of reactants;
(3) and the product is ground by an air classification mill, the feeding frequency is 20HZ, the internal division frequency is 30HZ, and the fan frequency is 30HZ, so that the crystal II type ammonium polyphosphate product with the controlled fine particle size is obtained.
Example 4
(1) And reaction: 125kg of phosphorus pentoxide and 116kg of diammonium hydrogen phosphate (the molar ratio is 1:1, the content of phosphorus pentoxide is more than or equal to 99.5%, the activity R value is more than or equal to 1.7, and the proportion of a reducing substance is less than 0.005%) are put into a 500L kneader, and the phosphorus pentoxide and the diammonium hydrogen phosphate are uniformly stirred, heated and introduced with ammonia, wherein the ammonia introduction amount is 1.5m for each year (100 kg of reactants). Heating to 180 ℃, introducing ammonia 2.5 m/h, carrying out a melting reaction on the phosphorus pentoxide and diammonium phosphate to release heat, heating the reaction temperature to 300 ℃, adding 2.50kg of ammonia-deficient ammonium polyphosphate with D50 of 6 mu m after stabilizing for 5 minutes, and carrying out reaction for 4 hours at the stage;
(2) and cooling: stopping heating, reducing ammonia introduction amount, continuously reacting and cooling for 1.5h, wherein the ammonia introduction amount is 0.5 m/h per 100kg of reactants, and discharging;
(3) and the product is ground by an air classification mill, the feeding frequency is 20HZ, the internal division frequency is 30HZ, and the fan frequency is 30HZ, so that the crystal II type ammonium polyphosphate product with the controlled fine particle size is obtained.
Example 5
The reaction temperature is increased to 295 ℃, 4.00kg and 5 mu m ammonia-deficient ammonium polyphosphate with D50 are added after stabilization for 10 minutes, and the reaction time is 3 hours at this stage. The same as in example 4.
Example 6
(1) And (3) reaction: 125kg of phosphorus pentoxide and 116kg of diammonium hydrogen phosphate (the molar ratio is 1:1, the content of phosphorus pentoxide is more than or equal to 99.5%, the activity R value is more than or equal to 1.7, and the proportion of a reducing substance is less than 0.005%) are put into a 500L kneader, and the phosphorus pentoxide and the diammonium hydrogen phosphate are uniformly stirred, heated and introduced with ammonia, wherein the ammonia introduction amount is 1.5m for each year (100 kg of reactants). And (3) heating to 170 ℃, introducing ammonia for 3.0 m/h, carrying out melting reaction on the phosphorus pentoxide and the diammonium phosphate to release heat, heating the reaction temperature to 290 ℃, adding 4.00kg of ammonium polyphosphate with D50 of 7 mu m after stabilizing for 15 minutes, and carrying out reaction for 3.5 hours at the stage. The same as in example 4.
Comparative example 1
(1) And (3) reaction: 125kg of phosphorus pentoxide and 116kg of diammonium hydrogen phosphate (the molar ratio is 1:1, the content of phosphorus pentoxide is more than or equal to 99.5%, the activity R value is more than or equal to 1.7, and the proportion of a reducing substance is less than 0.005%) are put into a 500L kneader, and the phosphorus pentoxide and the diammonium hydrogen phosphate are uniformly stirred, heated and introduced with ammonia, wherein the ammonia introduction amount is 1.3m for each year (100 kg of reactants). Heating to 160 ℃, introducing ammonia 2.5 m/h, carrying out melt reaction on the phosphorus pentoxide and diammonium phosphate to release heat, heating the reaction temperature to 280 ℃, and carrying out reaction for 3 hours;
(2) and cooling: stopping heating, reducing ammonia introduction amount, carrying out the reaction for 1m and cooling for 1h per 100kg of reactants, and discharging;
(3) and the product is ground by an air classification mill, the feeding frequency is 20HZ, the internal division frequency is 30HZ, and the fan frequency is 30HZ, so that the crystal II type ammonium polyphosphate product is obtained.
Comparative example 2
(1) And reaction: 125kg of phosphorus pentoxide and 116kg of diammonium hydrogen phosphate (the molar ratio is 1:1, the content of phosphorus pentoxide is more than or equal to 99.5%, the activity R value is more than or equal to 1.7, and the proportion of reducing substances is less than 0.005%) are put into a 500L kneader, the mixture is uniformly stirred and then heated and introduced with ammonia, and the ammonia introduction amount is 1.3 m/h (calculated by 100kg of reactants). Heating to 160 ℃, introducing ammonia 2.5 m/h, carrying out a melting reaction on the phosphorus pentoxide and diammonium phosphate materials to release heat, heating the reaction temperature to 280 ℃, adding 8kg of crystalline II-type ammonia-deficient ammonium polyphosphate with D50 of 15 mu m after stabilizing for 10 minutes, and carrying out reaction for 3 hours at the stage;
(2) and cooling: stopping heating, reducing ammonia introduction amount, counting by every 100kg of reactants, continuing to react and cool for 1h, and discharging;
(3) and (3) passing the product through an air classification mill crusher, wherein the feeding frequency is 20HZ, the internal division frequency is 30HZ and the fan frequency is 30HZ, so as to obtain a crystal II type ammonium polyphosphate product.
Comparative example 3
(1) And reaction: 125kg of phosphorus pentoxide and 116kg of diammonium hydrogen phosphate (the molar ratio is 1:1, the content of phosphorus pentoxide is more than or equal to 99.5%, the activity R value is more than or equal to 1.7, and the proportion of a reducing substance is less than 0.005%) are put into a 500L kneader, and the phosphorus pentoxide and the diammonium hydrogen phosphate are uniformly stirred, heated and introduced with ammonia, wherein the ammonia introduction amount is 1.3m for each year (100 kg of reactants). Heating to 160 ℃, introducing ammonia 2.5 m/h, carrying out a melting reaction on the phosphorus pentoxide and diammonium phosphate to release heat, heating the reaction temperature to 280 ℃, adding 8kg of crystalline II-type ammonium polyphosphate with D50 of 7μm after stabilizing for 10 minutes, and carrying out reaction for 3 hours at the stage;
(2) and cooling: stopping heating, reducing ammonia introduction amount, carrying out the reaction for 1m and cooling for 1h per 100kg of reactants, and discharging;
(3) and the product is ground by an air classification mill, the feeding frequency is 20HZ, the internal division frequency is 30HZ, and the fan frequency is 30HZ, so that the crystal II type ammonium polyphosphate product is obtained.
The fine particle size-controlled crystal form II ammonium polyphosphate products obtained in examples 1 to 6 and the crystal form II ammonium polyphosphate obtained in comparative examples 1 to 3 were each subjected to D50 particle size, number percentage of fine particle size of 2.19 μm or less, viscosity, pH, and water solubility tests, and the results of the respective performance tests are shown in Table 1.
The particle size test method adopted in the invention comprises the following steps: about 0.05 g sample was placed in a 10 ml measuring cup, and about 8 ml-10 ml absolute alcohol was added, and dispersed by sonication for 2 min after stirring. The test solutions were measured according to the procedure of the laser particle size analyzer.
The pH value test method adopted in the invention comprises the following steps: preparing 10 percent (mass percentage) of product water suspension, stirring for 30min at 25 +/-1 ℃, and testing by using a pH meter.
The water solubility test method adopted in the invention comprises the following steps: preparing 10 percent (mass percentage) of product water suspension, stirring for 30min at a specified temperature, filtering to obtain filtrate, and drying to express the gram weight of the product dissolved in 100 grams of water.
The viscosity test method adopted in the invention is as follows: preparing 10 percent (mass percentage) of product water suspension, stirring for 30min at 25 +/-1 ℃, and testing the viscosity by adopting coaxial double-cylinder rotational viscosity NDJ-79.
TABLE 1 comparison of ammonium polyphosphate particle size control for each example with ammonium polyphosphate performance of comparative examples
Remarks 1: fireproof coating: 20% of water; ammonium polyphosphate (examples and comparative examples) 24%; 8% of melamine; 8% of pentaerythritol; 10% of titanium dioxide; tertiary vinegar emulsion 28; and 2% of an auxiliary agent.
The preparation of the crystal II type ammonium polyphosphate comprises two steps of a reaction process and a crushing of a final product, wherein the reaction process comprises three stages of prepolymerization, ammoniation crystal transformation and ammonia introduction curing, wherein the ammoniation crystal transformation and the ammonia introduction curing have obvious influence on the final crystal form and the particle size of the ammonium polyphosphate product. In the ammonification crystal transformation process, the influence of the reaction condition and the uniformity on the final crystal form and the particle size of the ammonium polyphosphate product is obvious; the ammonia-introducing, curing and cooling process can also influence the chain growth of the product, and has certain influence on the final crystal form and particle size. The crushing process of the final product mainly has the function of crushing large-particle ammonium polyphosphate, and has little crushing function on the ammonium polyphosphate with the particle size of less than or equal to 5 micrometers. Therefore, the proportion of the particle size of the ammonium polyphosphate product is controlled to be less than 2 microns, and the raw materials and the synthesis process need to be adjusted and controlled in the reaction process.
The conventional average particle size of the crystal II type ammonium polyphosphate is about 15-25 microns, different requirements are required for the particle size of ammonium polyphosphate products in different application occasions, and the requirements for small particle size and good dispersibility in textile coatings and polyurethane foam materials are mainly developed due to the coating thickness and the foam wall thickness. However, in the steel-structure fireproof coating, the specific surface area of ammonium polyphosphate theoretically affects the oil absorption value of ammonium polyphosphate powder, further affects the viscosity of the fireproof coating, the overall performance of the powder in a medium can be affected by too coarse/too fine particle size, the smaller the particle size of ammonium polyphosphate is, the larger the oil absorption is, the higher the initial viscosity in the coating formula is, the later storage is not facilitated, the fire-resistant time of the fireproof coating is affected to a certain extent, and the part with the particle size smaller than 2 micrometers must be controlled.
As is apparent from the data of comparative examples and examples, the percentage of the fine particle size-controlled crystal form II ammonium polyphosphate product in examples 1 to 6 of less than 1.7% and the percentage of the fine particle size-controlled crystal form II ammonium polyphosphate product in comparative examples of more than 3% were almost twice as large as in the examples, and therefore, the fraction of the fine particle size-controlled crystal form II ammonium polyphosphate product in examples 1 to 6 of the present application of less than 2.19. Mu.m was small. Further, by comparing the coating viscosity of the ammonium polyphosphate crystal II product in the comparative examples 1 to 6 and 1 to 3, the percentage of the fine particle size of 2.19 μm or less in the present application is less than 1.7%, and the viscosity change rate at 28 weeks of the ammonium polyphosphate crystal II product with the controlled fine particle size is significantly reduced, the viscosity change rate at 28 weeks of the emulsion of the ammonium polyphosphate crystal II obtained in each example is controlled to be 200% or less, the change rate of the ammonium polyphosphate crystal II without the addition of the ammonium polyphosphate crystal II is over 500% in the comparative example 1 and the change rate of the ammonium polyphosphate crystal II added with the common ammonium crystal II is over 500%, and the change rate of the ammonium polyphosphate crystal II with the 15 μm large particle size D50 in the comparative example 2 is over 350%.
Furthermore, by comparing the data of each example of the second paint and the third paint of the comparative example, when the added ammonia-deficient ammonium polyphosphate powder is 1% -1.7%, and the D50 of the ammonia-deficient ammonium polyphosphate powder is 5 mu m-6 mu m, the proportion control of the fine particle size of the final product is better.
The invention can control the proportion of fine grain size of the final product without introducing a large amount of inert gas, urea containing a large amount of moisture and grinding the raw material.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (8)
1. A method for controlling the fine particle size of ammonium polyphosphate is characterized by comprising the following steps:
the reaction steps are as follows: mixing a mixture of 1:1, stirring the phosphorus pentoxide and the diammonium hydrogen phosphate uniformly, heating and introducing ammonia, wherein the ammonia introducing amount is 0.5m 3 /h-2.5m 3 H, heating to 150-200 ℃, and adjusting the ammonia introducing amount to 1.0m 3 /h-4.0m 3 The temperature is continuously increased to 260-310 ℃ and the reaction lasts for 2-5 h; when the temperature in the reactant is stable for 5min-15min, 0.5% -3% of ammonia-deficient ammonium polyphosphate powder is added;
and (3) cooling: stopping heating, reducing ammonia flow to 0.2m 3 /h～1m 3 Cooling for 1-2 h to obtain an ammonium polyphosphate crude product;
a crushing step: crushing an ammonium polyphosphate crude product by adopting an air classification mill crusher to obtain a crystal II type ammonium polyphosphate product with a controlled fine particle size, wherein the proportion of the particle size of the crystal II type ammonium polyphosphate product with the controlled fine particle size being less than or equal to 2.19 mu m is less than or equal to 2%;
wherein the D50 of the ammonia-deficient ammonium polyphosphate powder is 5-10 mu m.
2. The fine particle size control method for preparing ammonium polyphosphate according to claim 1, wherein the ammonia-deficient ammonium polyphosphate powder is prepared by the following method:
120 kg of phosphorus pentoxide and hydrogen phosphate are added into a kneader113 kg of diammonium, stirring evenly at the rotating speed of 60RPM, heating and introducing ammonia, wherein the ammonia introduction amount is 8.0m 3 H, when the temperature is raised to 250 ℃, forming thick syrup-like liquid, and keeping the reaction for 2h when the final temperature reaches 300 ℃; the ammonia amount is reduced to 1.5m 3 Reacting for 3 hours, and gradually reducing the reaction temperature to 240 ℃ to obtain white crystal II type ammonium polyphosphate solid powder; adding white crystal II type ammonium polyphosphate solid powder into a kneader, stirring at 150RPM, introducing nitrogen gas at a flow rate of 0.3m 3 And h, keeping the temperature for 3h after the temperature is raised to 220 ℃, and cooling and crushing to obtain ammonium-deficient ammonium polyphosphate powder.
3. The fine particle size control method for ammonium polyphosphate preparation according to claim 2, wherein the ammonia-deficient ammonium polyphosphate powder added in the reaction step is 1-1.7%.
4. The fine particle size control method for preparing ammonium polyphosphate according to claim 1, wherein the D50 of the ammonia-deficient ammonium polyphosphate powder is 5-6 μm.
5. The method for controlling the particle size of ammonium polyphosphate prepared according to any one of claims 1 to 4, wherein the air classification mill pulverizer has a feeding frequency of 15HZ to 20HZ, an internal division frequency of 30HZ to 50HZ, and a blower frequency of 30HZ to 45HZ.
6. The method for controlling the particle size of the ammonium polyphosphate prepared according to any one of claims 1 to 4, wherein the content of the phosphorus pentoxide is not less than 99.5%, the active R value is not less than 1.7, and the proportion of the reducing substance is not more than 0.005%.
7. The application of the crystal II type ammonium polyphosphate product with the controlled fine particle size is characterized in that the crystal II type ammonium polyphosphate product with the controlled fine particle size is prepared by the method for controlling the fine particle size by using the ammonium polyphosphate according to any one of claims 1 to 6, and the crystal II type ammonium polyphosphate product with the controlled fine particle size is used as a flame retardant in a steel structure fireproof coating.
8. The use of a controlled fine particle size crystalline form II ammonium polyphosphate product according to claim 7 wherein the controlled fine particle size crystalline form II ammonium polyphosphate product is present in a fire retardant coating in an amount of 24% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010451989.3A CN111807343B (en) | 2020-05-25 | 2020-05-25 | Method for controlling fine particle size in preparation of ammonium polyphosphate and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010451989.3A CN111807343B (en) | 2020-05-25 | 2020-05-25 | Method for controlling fine particle size in preparation of ammonium polyphosphate and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111807343A CN111807343A (en) | 2020-10-23 |
| CN111807343B true CN111807343B (en) | 2023-02-14 |
Family
ID=72848472
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010451989.3A Active CN111807343B (en) | 2020-05-25 | 2020-05-25 | Method for controlling fine particle size in preparation of ammonium polyphosphate and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111807343B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113860279A (en) * | 2021-10-20 | 2021-12-31 | 宿迁联盛科技股份有限公司 | Preparation method of crystal II type ammonium polyphosphate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058161A (en) * | 2012-12-21 | 2013-04-24 | 杭州捷尔思阻燃化工有限公司 | Lack-ammonium crystalline II type ammonium polyphosphate product and preparation method thereof |
| CN109019548A (en) * | 2018-09-29 | 2018-12-18 | 杭州捷尔思阻燃化工有限公司 | The preparation method of high linearity crystal form II ammonium polyphosphate |
-
2020
- 2020-05-25 CN CN202010451989.3A patent/CN111807343B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058161A (en) * | 2012-12-21 | 2013-04-24 | 杭州捷尔思阻燃化工有限公司 | Lack-ammonium crystalline II type ammonium polyphosphate product and preparation method thereof |
| CN109019548A (en) * | 2018-09-29 | 2018-12-18 | 杭州捷尔思阻燃化工有限公司 | The preparation method of high linearity crystal form II ammonium polyphosphate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111807343A (en) | 2020-10-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10400088B2 (en) | Efficient halogen-free flame retardant masterbatch for polypropylene and preparation method and use thereof | |
| US4043987A (en) | Substituted ammonium polyphosphate composition | |
| CN111807343B (en) | Method for controlling fine particle size in preparation of ammonium polyphosphate and application thereof | |
| CN112175242B (en) | Microcapsule intumescent flame retardant and preparation method and application thereof | |
| EP3988504A1 (en) | Crystalline aluminum phosphite, preparation method and use thereof | |
| EP1819758A1 (en) | Expandable styrol polymers rendered flame-proof without using halogen | |
| EP0494778B2 (en) | A process for producing finely divided particles of II type ammonium polyphosphate | |
| CN114015060B (en) | Ammonium polyphosphate flame retardant, and preparation method and application thereof | |
| CN114015230A (en) | Fireproof flame-retardant nylon material and preparation method thereof | |
| CN112898912A (en) | Preparation process of flame-retardant hot melt adhesive film | |
| CN103252200A (en) | Microencapsulation ammonium polyphosphate fire retardant and preparation method thereof | |
| CN111690207A (en) | Production method of halogen-free flame-retardant master batch | |
| CN114539621B (en) | Phosphorus-aluminum salt-containing complex and preparation method and application thereof | |
| CN116835549A (en) | Preparation method of fine-particle-size ammonium polyphosphate | |
| CN107746043B (en) | Preparation method of low-viscosity and low-water-solubility crystal form II ammonium polyphosphate | |
| CN116715901A (en) | Preparation method of ammonium polyphosphate flame retardant based on epoxy resin microencapsulation coating | |
| CN109019548B (en) | Preparation method of high-linearity crystal II type ammonium polyphosphate | |
| JP2918127B2 (en) | Method for producing fine particles of type II ammonium polyphosphate | |
| CN114478625B (en) | Aluminum diethylphosphinate crystal with low fine powder content as well as preparation method and application thereof | |
| DE102004001125A1 (en) | Process for the preparation of cyclic chlorophosphazene oligomers | |
| JP4524422B2 (en) | Method for producing type II ammonium polyphosphate | |
| CN109181109A (en) | A kind of the double-coating fire retardant plastic mastre batch and preparation method of containing graphene | |
| CN220048152U (en) | Preparation facilities of fine particle diameter ammonium polyphosphate | |
| JPH11240704A (en) | Production of fine particle of type ii ammonium polyphosphate | |
| US4239542A (en) | Water-soluble flame retarder and process for preparing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |