CN111808133B - Diethyl phosphinate aluminum material and preparation method thereof - Google Patents
Diethyl phosphinate aluminum material and preparation method thereof Download PDFInfo
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- CN111808133B CN111808133B CN202010577627.9A CN202010577627A CN111808133B CN 111808133 B CN111808133 B CN 111808133B CN 202010577627 A CN202010577627 A CN 202010577627A CN 111808133 B CN111808133 B CN 111808133B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids R2P(=O)(OH); Thiophosphinic acids, i.e. R2P(=X)(XH) (X = S, Se)
- C07F9/301—Acyclic saturated acids which can have further substituents on alkyl
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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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to an aluminum diethyl phosphinate material and a preparation method thereof, wherein the preparation method comprises the following steps: providing a mixed acid solution and a suspension containing an aluminum source, wherein the mixed acid solution comprises diethyl phosphinic acid and a crystallization aid; mixing the mixed acid solution with the suspension, reacting to obtain diethyl aluminum phosphinate particles, and stacking a plurality of diethyl aluminum phosphinate particles to form powder with a porous structure, wherein the powder has D95 particle size distribution of 5-30 mu m; placing the powder into a mixer for mixing, adding a coupling agent into the mixer in a spraying mode and mixing the coupling agent with the powder to combine the coupling agent with the powder to obtain the diethyl phosphinate aluminum material, wherein the bulk density of the diethyl phosphinate aluminum material is 0.45g/cm 3 ‑0.70g/cm 3 . The diethyl aluminum phosphinate material can be uniformly dispersed in a polymer in the use process, so that the polymer material has excellent flame retardant property and mechanical property and has small dust pollution.
Description
Technical Field
The invention relates to the technical field of flame-retardant materials, in particular to an aluminum diethyl phosphinate material and a preparation method thereof.
Background
The superfine diethyl phosphinic acid aluminum powder has low specific surface energy, small intermolecular force, and low bulk density (only 0.20 g/cm) due to the existence of a large amount of air between the powder during production 3 -0.30g/cm 3 Rendering it unusable during useIs easy to be compatible with polymer, difficult to generate bridging phenomenon in the extrusion molding or extrusion granulation process, has poor dispersion effect, seriously affects the flame retardant property and mechanical property of polymer materials, and has large dust and seriously pollutes the environment.
Although surface modification of ultrafine aluminum diethylphosphinate powder can effectively improve bulk density, conventional ultrafine aluminum diethylphosphinate powder is usually obtained by mechanical pulverization such as wet ball milling or jet milling, and the like, and the surface is irregular and uneven coating is easily formed during surface modification. Moreover, the traditional surface modification mainly adopts a liquid phase surface treatment method, on one hand, the process is complicated, the treatment time is long, the production cost is high, and the industrial production is not facilitated, and on the other hand, the liquid phase surface treatment method generally needs to introduce acidic substances as pH regulators, and the introduction of the acidic substances is easy to corrode equipment.
Disclosure of Invention
Based on this, it is necessary to provide an aluminum diethylphosphinate material and a method for producing the same in view of the above-mentioned problems; the bulk density of the diethyl phosphinate aluminum material obtained by the preparation method is 0.45g/cm 3 -0.70g/cm 3 。
A preparation method of diethyl phosphinic acid aluminum powder comprises the following steps:
providing a mixed acid solution and a suspension comprising an aluminum source, wherein the mixed acid solution comprises diethyl phosphinic acid and a crystallization promoter;
mixing the mixed acid solution with the suspension, reacting to obtain diethyl aluminum phosphinate particles, and stacking a plurality of diethyl aluminum phosphinate particles to form powder with a porous structure, wherein the powder has D95 particle size distribution of 5-30 mu m; and
placing the powder into a mixer for mixing, adding a coupling agent into the mixer in a spraying manner and mixing with the powder, and combining the coupling agent with the powder to obtain the diethyl aluminum phosphinate material, wherein the bulk density of the diethyl aluminum phosphinate material is 0.45g/cm 3 -0.70g/cm 3 。
In one embodiment, the aluminum source comprises at least one of aluminum sulfate, aluminum hydroxide, metaaluminate, alumina, aluminum nitrate, pseudo-boehmite, boehmite.
In one embodiment, the pH of the suspension is 4-9.
In one embodiment, the mass percentage of the diethyl phosphinic acid in the mixed acid solution is 90.0% -99.9%.
In one embodiment, the crystallization aid comprises phosphorous acid, phosphinic acid, phosphoric acid, ethyl phosphinic acid, methylene ethyl phosphinic acid, ethyl butyl phosphinic acid, dibutyl phosphinic acid, ethylhexyl phosphinic acid, butyl hexyl phosphinic acid, ethyl octyl phosphinic acid, sec-butyl ethyl phosphinic acid, 1-ethylbutyl (butyl) phosphinic acid, ethyl (1-methylpentyl) phosphinic acid, di-sec-butyl phosphinic acid (di (1-methylpropyl) phosphinic acid), propyl (hexyl) phosphinic acid, dihexyl phosphinic acid, hexyl (nonyl) phosphinic acid, propyl (nonyl) phosphinic acid, dinonyl phosphinic acid, dipropyl phosphinic acid, butyl (octyl) phosphinic acid, hexyl (octyl) phosphinic acid, dioctyl phosphinic acid, ethyl (cyclopentylethyl) phosphinic acid, butyl (cyclopentylethyl) phosphinic acid, ethyl (cyclohexylethyl) phosphinic acid, ethyl (phenylethyl) phosphinic acid, butyl (phenylethyl) phosphinic acid, 4-methylethyl (4-methylphenyl) phosphinic acid, 4-methylethyl (phenylmethyl) phosphinic acid, 4-cyclohexylphosphinic acid, 4-methylethyl) phosphinic acid.
In one embodiment, the mixed acid solution is mixed with the suspension at a temperature of 20 ℃ to 150 ℃ and a pressure of 1bar to 100 bar.
In one embodiment, the molar ratio of the aluminum source to the diethylphosphinic acid is from 1:2 to 1:10 when the mixed acid solution is mixed with the suspension.
In one embodiment, the weight ratio of the powder to the coupling agent is 100:1-100:6.
In one embodiment, when the powder is placed in the mixer for mixing, the temperature of the mixer is 100-130 ℃, and the mixing time is 4-8 min.
In one embodiment, when the coupling agent is mixed with the powder, the rotating speed of the mixer is 700r/min-900r/min, and the mixing time is 5min-20min.
The preparation method comprises the steps of preparing the aluminum diethyl phosphinate powder, wherein the aluminum diethyl phosphinate material comprises aluminum diethyl phosphinate powder and a coupling agent layer coated on the aluminum diethyl phosphinate powder, the aluminum diethyl phosphinate powder is formed by stacking a plurality of aluminum diethyl phosphinate particles and has a porous structure, the aluminum diethyl phosphinate powder has D95 particle size distribution of 5-30 mu m, and the bulk density of the aluminum diethyl phosphinate material is 0.45g/cm 3 -0.70g/cm 3 。
According to the invention, the diethyl aluminum phosphinate particles are prepared by a chemical synthesis method, and a plurality of diethyl aluminum phosphinate particles are stacked to form the superfine diethyl aluminum phosphinate powder with a porous structure and D95 particle size distribution of 5-30 mu m. Therefore, in the process of mixing the powder with the coupling agent, the porous framework structure enables the specific surface area of the powder to be further increased, more anchoring points are provided for the coupling agent, more coupling agent can be anchored by the powder, and a more uniform and stable coupling agent coating layer is formed on the surface, so that the powder is not easy to analyze. Therefore, the bulk density of the diethyl phosphinate aluminum material obtained by the invention can reach 0.45g/cm 3 -0.70g/cm 3 Can be uniformly dispersed in the polymer in the use process, so that the polymer material has excellent flame retardant property and mechanical property and has small dust pollution.
Meanwhile, the invention adopts the solid phase surface treatment method to carry out surface modification on the diethyl phosphinic acid aluminum powder, has simple technical process and short time, can not corrode equipment, is convenient for industrialized production and has good economic benefit.
Drawings
FIG. 1 is an SEM image of aluminum diethylphosphinate powder prepared according to example 1 of the present invention.
Detailed Description
The aluminum diethylphosphinate material and the preparation method thereof provided by the invention are further described below.
The preparation method of the diethyl phosphinate aluminum material provided by the invention comprises the following steps:
s1, providing a mixed acid solution and an aluminum-containing source suspension, wherein the mixed acid solution comprises diethyl phosphinic acid and a crystallization aid;
s2, mixing the mixed acid solution with the suspension, reacting to obtain diethyl aluminum phosphinate particles, and stacking a plurality of diethyl aluminum phosphinate particles to form powder with a porous structure, wherein the powder has D95 particle size distribution of 5-30 mu m;
s3, placing the powder into a mixer for mixing, adding a coupling agent into the mixer in a spraying manner and mixing the coupling agent with the powder, and combining the coupling agent with the powder to obtain the diethyl aluminum phosphinate material, wherein the bulk density of the diethyl aluminum phosphinate material is 0.45g/cm 3 -0.70g/cm 3 。
In step S1, the aluminum source includes at least one of aluminum sulfate, aluminum hydroxide, aluminum metaaluminate, aluminum oxide, aluminum nitrate, pseudo-boehmite, and sodium metaaluminate.
Since the aluminum source is acidic, weakly acidic, basic or weakly basic, a blend is further added to the suspension to adjust the pH of the suspension to 4 to 9, preferably to 6 to 8, in consideration of the yield and thermal stability of the reaction product aluminum diethylphosphinate particles.
Wherein the blend comprises one or more of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sulfuric acid, acetic acid, nitric acid, hydrochloric acid, phosphoric acid, phosphorous acid, hypophosphorous acid, sodium hypophosphite and sodium phosphite.
In the mixed acid solution, the crystallization aid can promote the reaction of diethyl phosphinic acid and an aluminum source to form diethyl phosphinic acid aluminum, so that the mass percentage of the crystallization aid in the mixed acid solution is preferably 0.1-10%, more preferably 1-10%, and the mass percentage of diethyl phosphinic acid in the mixed acid solution is preferably 90.0-99.9%, more preferably 90-99%.
Specifically, the crystallization aid is preferably an alkyl phosphinic acid other than diethyl phosphinic acid, including phosphorous acid, phosphinic acid, phosphoric acid, ethyl phosphinic acid, methylene ethyl phosphinic acid, ethylbutyl phosphinic acid, dibutyl phosphinic acid, ethylhexyl phosphinic acid, butyl hexyl phosphinic acid, ethyl octyl phosphinic acid, sec-butyl ethyl phosphinic acid, 1-ethylbutyl (butyl) phosphinic acid, ethyl (1-methylpentyl) phosphinic acid, di-sec-butyl phosphinic acid (di (1-methylpropyl) phosphinic acid), propyl (hexyl) phosphinic acid, dihexyl phosphinic acid, hexyl (nonyl) phosphinic acid, propyl (nonyl) phosphinic acid, dinonyl phosphinic acid, dipropyl phosphinic acid, butyl (octyl) phosphinic acid, hexyl (octyl) phosphinic acid, dioctyl phosphinic acid, ethyl (cyclopentylethyl) phosphinic acid, butyl (cyclopentylethyl) phosphinic acid, ethyl (cyclohexylethyl) phosphinic acid, butyl (cyclohexylethyl) phosphinic acid, ethyl (4-methylethyl) phosphinic acid, 4-methylphenyl (methyl) phosphinic acid, 4-methylphenyl) phosphinic acid, or at least one of butyl (methyl) phosphinic acid. So that the crystallization aid can also react with an aluminum source to generate aluminum alkyl phosphinate, thereby playing a role in flame retardant synergism when being applied as a flame retardant and further improving flame retardant effect.
In step S2, after the suspension and the mixed acid solution are mixed, a double decomposition reaction will occur between the aluminum source and the diethyl phosphinic acid, so as to generate a precipitate of approximately spherical diethyl phosphinic acid aluminum particles, and a plurality of diethyl phosphinic acid aluminum particles will be stacked to form ultra-fine powder with a D95 particle size distribution of 5 μm-30 μm. It can be understood that pore channels are formed among the diethyl phosphinate aluminum particles in the powder, so that the powder is provided with a plurality of pore channels, and the specific surface area of the powder is increased.
Specifically, the mixed acid solution is mixed with the suspension at the temperature of 20-150 ℃ and the pressure of 1-100 bar, so that the rate of generating the aluminum diethyl phosphinate particles by reaction and the rate of stacking the aluminum diethyl phosphinate particles into powder can be better controlled, and further more uniform and regular powder can be obtained.
In view of the low solubility of diethylphosphinic acid in water, the mixed acid solution is mixed with the suspension in an excess amount in order to maintain the reaction rate, and preferably, the molar ratio of the aluminum source to diethylphosphinic acid is 1:2 to 1:10.
In step S3, when the coupling agent is added into the mixer in a spraying manner, the atomized coupling agent can enter the pore canal of the powder and uniformly adhere to the surface of the pore canal and the surface of the powder.
Since the coupling agent contains lipophilic functional groups and polar functional groups in the molecule, and the aluminum diethylphosphinate contains dialkyl, phosphonate and aluminum ions in the molecule. Therefore, after the coupling agent contacts with the powder, polar functional groups such as titanate groups, hydroxyl groups, acyloxy groups, long-chain alkoxy groups, phenolic groups, carboxyl groups, sulfuric acid groups, phosphate groups, pyrophosphoric acid groups and the like in the coupling agent molecules can chemically react with phosphonate groups in the diethyl aluminum phosphinate molecules to form chemical bonds or hydrogen bonds, so that chemical crosslinking points are generated; simultaneously, nonpolar energy groups such as vinyl, long-chain alkyl and the like in the coupling agent molecules can generate winding action with dialkyl in the diethyl aluminum phosphinate molecules through intermolecular action, and crosslinking points are formed, so that the coupling agent forms multipoint anchoring on the surface of the powder.
It should be noted that, in the process of mixing the powder with the coupling agent, the porous skeleton structure further increases the specific surface area of the powder, provides more anchoring points for the coupling agent, and further enables the powder to anchor more coupling agent, so that a more uniform and stable coupling agent coating layer can be formed on the surface of the powder, and the powder is not easy to analyze.
Therefore, the specific surface energy and intermolecular acting force of the diethyl phosphinate aluminum material obtained by coating the powder with the coupling agent are obviously improvedThereby increasing the bulk density of the diethyl phosphinate aluminum material to 0.45g/cm 3 -0.70g/cm 3 And further, the dust of the diethyl phosphinate aluminum material is obviously reduced, which is beneficial to environmental protection.
The particle size of the aluminum diethylphosphinate material after coating the coupling agent layer is equal to or substantially equal to the particle size of the aluminum diethylphosphinate powder, and the aluminum diethylphosphinate material still has a porous structure.
Specifically, when the powder is placed in the mixer for mixing, the temperature of the mixer is preferably 100-130 ℃, more preferably 110 ℃, the mixing time is preferably 4-8 min, more preferably 6min, and the rotating speed of the mixer is preferably 200-500 r/min, more preferably 400r/min, so as to remove moisture in the powder.
And when the coupling agent is mixed with the powder, the rotating speed of the mixer is preferably 700r/min-900r/min, more preferably 800r/min, and the mixing time is preferably 5min-20min, more preferably 15min, so that the coupling agent is fully contacted and combined with the powder.
Specifically, the weight ratio of the powder to the coupling agent is 100:1-100:6, so that the surface and pore canal of the powder are coated with enough coupling agent layers.
Specifically, the coupling agent comprises at least one of a compound with a cyclic chain structure containing silanol ester, a silane coupling agent, a titanate coupling agent and an aluminate coupling agent.
Therefore, in the preparation method, the diethyl phosphinic acid aluminum powder is prepared by a chemical synthesis method, so that the defect of preparing the diethyl phosphinic acid aluminum powder by mechanical crushing is overcome, and meanwhile, the obtained powder also has a porous structure, and more coupling agents can be anchored, so that a better modification effect is achieved.
In addition, the invention adopts the solid phase surface treatment method to carry out surface modification on the diethyl phosphinic acid aluminum powder, has simple process, short time, no corrosion to equipment, convenient industrialized production and good economic benefit.
The invention also provides an aluminum diethyl phosphinate material, which is prepared by the preparation method and comprises aluminum diethyl phosphinate powder and a coupling agent layer coated on the aluminum diethyl phosphinate powder, wherein the aluminum diethyl phosphinate powder is formed by stacking a plurality of aluminum diethyl phosphinate particles and has a porous structure, the aluminum diethyl phosphinate powder has D95 particle size distribution of 5-30 mu m, and the bulk density of the aluminum diethyl phosphinate material is 0.45g/cm 3 -0.70g/cm 3 。
The coupling agent layer coats the outer surface of the diethyl phosphinate aluminum powder and the surface of the pore canal in the powder.
The diethyl phosphinate aluminum material provided by the invention is mainly used as a flame retardant, has the characteristics of high heat resistance, high flame retardant efficiency, good compatibility with polymers, small influence on the mechanical properties of flame retardant modified polymer materials, good color and the like, and is commonly used for manufacturing environment-friendly flame retardant engineering plastics and thermoplastic elastomer materials, such as wires and cables, sealing materials and the like.
Because the diethyl phosphinate aluminum material has high bulk density, the raise dust is obviously reduced when in use, and the diethyl phosphinate aluminum material is beneficial to environmental protection.
Meanwhile, the particle size of the diethyl phosphinic acid aluminum material is small, and when the diethyl phosphinic acid aluminum material is used, the material has high fluidity in a polymer, and can be uniformly mixed with the polymer and other auxiliary agents. Further, the polar functional groups in the coupling agent molecules can form acting forces exceeding Van der Waals forces among the diethyl aluminum phosphinate material, the polymer molecules and other auxiliary agents, so that the components have excellent wetting effect and compatibility. Therefore, the diethyl phosphinate aluminum material has better mixing effect and is convenient for processing and forming. Furthermore, in the extrusion molding or extrusion granulation process, the diethyl phosphinic acid aluminum material can generate a bridging phenomenon, so that the flame retardant property and the mechanical property of the polymer material, such as tensile strength, oxygen index and the like, are effectively improved.
Specifically, the polymer includes at least one of TPU, TPE, TPV, EVA, EPDM.
Further, the coupling agent molecule contains groups such as silane groups, hydroxyl groups and ester groups, so that in the combustion and decomposition process, the generated silicon-oxygen bond has a char formation effect, the hydroxyl groups and the ester groups can promote the diethyl phosphinate aluminum material to generate polymetaphosphoric acid with strong dehydration performance, so that a carbon layer capable of blocking air is formed on the surface of the polymer material, the polymer material is prevented from being continuously combusted, the synergistic flame-retardant effect is achieved, and the flame-retardant effect of the polymer material is further improved.
Hereinafter, the aluminum diethylphosphinate material and the method for preparing the same will be further described by the following specific examples.
Example 1:
the aluminum sulfate is pre-dispersed in water, and the pH value is regulated to 7.8 by sodium hydroxide, so as to obtain suspension.
90kg of diethylphosphinic acid was mixed with 10kg of di-sec-butylphosphinic acid (di (1-methylpropyl) phosphinic acid), a co-crystallizing agent, to form a mixed acid solution.
And mixing the mixed acid solution with the suspension at 50 ℃ and 1bar according to the molar ratio of aluminum sulfate to diethyl phosphinic acid of 1:3, and reacting to obtain the diethyl phosphinic acid aluminum powder. The aluminum diethylphosphinate powder is formed by stacking a plurality of aluminum diethylphosphinate particles, has a porous structure, has a particle diameter D95 of 15.12 mu m and a bulk density of 0.23g/cm 3 。
50kg of the prepared aluminum diethylphosphinate powder and 0.5kg of titanate coupling agent are weighed, and the weighed aluminum diethylphosphinate powder is poured into a high-speed mixer which is preheated to 120 ℃ and mixed for 6min at a rotating speed of 400 r/min. Then adding titanate coupling agent into a high-speed mixer in a spraying mode, mixing with diethyl aluminum phosphinate powder at a high speed of 17min at a rotating speed of 800r/min, discharging, and cooling to room temperature to obtain the diethyl aluminum phosphinate material. The bulk density of the aluminum diethylphosphinate material was 0.525g/cm 3 The particle diameter D95 was 15.14. Mu.m.
Example 2
Pre-dispersing sodium metaaluminate in water, and regulating the pH value to 4.1 by hydrochloric acid to obtain suspension.
99.9kg of diethyl phosphinic acid was mixed with 0.1kg of dibutyl phosphinic acid as a co-crystallizing agent to form a mixed acid solution.
And mixing the mixed acid solution with the suspension at 150 ℃ and 25bar according to the molar ratio of sodium metaaluminate to diethyl phosphinic acid of 1:10, and reacting to obtain the diethyl phosphinic acid aluminum powder. The aluminum diethylphosphinate powder is formed by stacking a plurality of aluminum diethylphosphinate particles, has a porous structure, has a particle diameter D95 of 29.21 mu m and a bulk density of 0.310g/cm 3 。
50kg of the aluminum diethylphosphinate powder prepared above and 1.5kg of the silane coupling agent were weighed, and the weighed aluminum diethylphosphinate powder was poured into a high-speed mixer which had been preheated to 110℃and mixed for 6 minutes at a rotational speed of 400 r/min. Then adding the silane coupling agent into a high-speed mixer in a spraying mode, mixing the silane coupling agent with the aluminum diethylphosphinate powder at a high speed of 800r/min for 15min, discharging, and cooling to room temperature to obtain the aluminum diethylphosphinate material. The bulk density of the aluminum diethylphosphinate material was 0.495g/cm 3 The particle diameter D95 was 29.32. Mu.m.
Example 3:
pre-dispersing aluminum nitrate in water, and regulating the pH value to 7.5 by potassium hydroxide to obtain suspension.
95kg of diethylphosphinic acid was mixed with 5kg of ethyl hexylphosphinic acid as a co-crystallizing agent to form a mixed acid solution.
Mixing the mixed acid solution with the suspension at the temperature of 80 ℃ and 5bar according to the molar ratio of aluminum nitrate to diethyl phosphinic acid of 1:5, and reacting to obtain the diethyl phosphinic acid aluminum powder shown in figure 1. The aluminum diethylphosphinate powder is formed by stacking a plurality of aluminum diethylphosphinate particles, has a porous structure, has a particle diameter D95 of 5.65 mu m and a bulk density of 0.26g/cm 3 。
60kg of the aluminum diethylphosphinate powder prepared above and 3.6kg of the aluminate coupling agent were weighed, and the weighed aluminum diethylphosphinate powder was poured into a high-speed mixer which had been preheated to 100℃and mixed for 6 minutes at a rotational speed of 200 r/min. Then adoptAnd (3) adding the aluminate coupling agent into a high-speed mixer in a spraying mode, mixing the aluminate coupling agent with the aluminum diethyl phosphinate powder at a high speed of 700r/min for 5min, discharging, and cooling to room temperature to obtain the aluminum diethyl phosphinate material. The bulk density of the aluminum diethylphosphinate material was 0.680g/cm 3 The particle diameter D95 was 5.74. Mu.m.
Example 4:
pre-dispersing pseudo-boehmite in water, and regulating the pH value to 6.5 by phosphorous acid to obtain a suspension.
92kg of diethylphosphinic acid was mixed with 8kg of ethylhexyl phosphinic acid, a co-crystallizing agent, to form a mixed acid solution.
Mixing the mixed acid solution with the suspension at 110 ℃ and 7bar according to the mol ratio of pseudo-boehmite to diethyl phosphinic acid of 1:7, and reacting to obtain the diethyl phosphinic acid aluminum powder shown in figure 1. The aluminum diethylphosphinate powder is formed by stacking a plurality of aluminum diethylphosphinate particles, has a porous structure, has a particle diameter D95 of 7.65 mu m and a bulk density of 0.26g/cm 3 。
60kg of the aluminum diethylphosphinate powder prepared above and 1.2kg of the silane coupling agent were weighed, and the weighed aluminum diethylphosphinate powder was poured into a high-speed mixer which had been preheated to 130℃and mixed for 8 minutes at a rotational speed of 500 r/min. Then adding the aluminate coupling agent into a high-speed mixer in a spraying mode, mixing the aluminate coupling agent with the diethyl aluminum phosphinate powder at a high speed of 900r/min for 20min, discharging, and cooling to room temperature to obtain the diethyl aluminum phosphinate material. The bulk density of the aluminum diethylphosphinate material was 0.55g/cm 3 The particle diameter D95 was 7.84. Mu.m.
Application example 1:
flame retardant polyether type TPU material was prepared according to the formulation shown in Table 1.
Application example 2-application example 4:
the production process was the same as in application example 1, and the formulation ratio was changed as shown in Table 1.
Comparative example 1 was applied:
the production process was the same as that of application example 1, and the pellets in example 1 were preparedDiameter D95 of 15.12 μm and bulk density of 0.23g/cm 3 The diethyl phosphinic acid aluminum powder is applied to flame retardant polyether type TPU materials.
The flame retardant polyether type TPU material prepared in application example 1-application example 4 and application comparative example 1 was subjected to performance test, and the test results are shown in Table 1.
TABLE 1
As can be seen from Table 1, when the aluminum diethylphosphinate material of the present invention is used as a flame retardant, the oxygen index is improved by 6.2% -13.6%, and the tensile strength is improved by 44.3% -61.5%, which indicates that the aluminum diethylphosphinate material of the present invention has positive effects of flame retardance and enhancement on polymer materials.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (9)
1. The preparation method of the diethyl aluminum phosphinate material is characterized by comprising the following steps:
providing a mixed acid solution and a suspension containing an aluminum source, wherein the mixed acid solution comprises diethyl phosphinic acid and a crystallization aid, and the crystallization aid is at least one selected from di-sec-butyl phosphinic acid, dibutyl phosphinic acid and ethylhexyl phosphinic acid;
mixing the mixed acid solution with the suspension, reacting to obtain diethyl aluminum phosphinate particles, and stacking a plurality of diethyl aluminum phosphinate particles to form powder with a porous structure, wherein the powder has D95 particle size distribution of 5-30 mu m; and
placing the powder into a mixer for mixing, adding a coupling agent into the mixer in a spraying manner and mixing with the powder, and combining the coupling agent with the powder to obtain the diethyl aluminum phosphinate material, wherein the coupling agent is at least one of titanate coupling agent, silane coupling agent and aluminate coupling agent, and the bulk density of the diethyl aluminum phosphinate material is 0.45g/cm 3 -0.70g/cm 3 。
2. The method of preparing an aluminum diethylphosphinate material according to claim 1, wherein the aluminum source comprises at least one of aluminum sulfate, aluminum hydroxide, metaaluminate, aluminum oxide, aluminum nitrate, pseudo-boehmite, boehmite.
3. The method for producing an aluminum diethylphosphinate material according to claim 1, wherein the pH of the suspension is 4 to 9.
4. The method for preparing the aluminum diethylphosphinate material according to claim 1, wherein the mass percentage of the diethylphosphinic acid in the mixed acid solution is 90.0% -99.9%.
5. The method for producing an aluminum diethylphosphinate material according to claim 1, wherein the mixed acid solution is mixed with the suspension at a temperature of 20 ℃ to 150 ℃ and a pressure of 1bar to 100 bar.
6. The method for producing an aluminum diethylphosphinate material according to claim 1, wherein the molar ratio of the aluminum source to the diethylphosphinic acid is 1:2 to 1:10 when the mixed acid solution is mixed with the suspension.
7. The method for preparing an aluminum diethylphosphinate material according to claim 1, wherein the weight ratio of the powder to the coupling agent is 100:1-100:6.
8. The method for preparing the aluminum diethylphosphinate material according to claim 1, wherein the temperature of the mixer is 100-130 ℃ and the mixing time is 4-8 min when the powder is mixed in the mixer.
9. The method for preparing an aluminum diethylphosphinate material according to claim 1, wherein the rotational speed of the mixer is 700r/min-900r/min when the coupling agent is mixed with the powder, and the mixing time is 5min-20min.
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| CN112778359B (en) * | 2020-12-31 | 2022-09-16 | 浙江新化化工股份有限公司 | Dialkyl phosphinate and preparation method and application thereof |
| CN113817229B (en) * | 2021-10-25 | 2023-02-03 | 杭州捷尔思阻燃化工有限公司 | Migration-resistant modified aluminum diethylphosphinate, and preparation method and application thereof |
| CN114478625B (en) * | 2022-03-10 | 2022-11-25 | 江苏利思德新材料股份有限公司 | Aluminum diethylphosphinate crystal with low fine powder content as well as preparation method and application thereof |
| CN114806601B (en) * | 2022-05-10 | 2023-04-07 | 江苏利思德新材料有限公司 | Alkyl phosphinate composition and preparation method and application thereof |
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| CN103172664A (en) * | 2013-02-27 | 2013-06-26 | 广州金凯新材料有限公司 | Preparation method of dialkylphosphinate with excellent flowing property |
| CN103172663A (en) * | 2013-02-27 | 2013-06-26 | 广州金凯新材料有限公司 | Preparation method of dialkylphosphinate metal salt |
| CN105061500A (en) * | 2015-07-27 | 2015-11-18 | 广州金凯新材料有限公司 | Superfine particle size dialkylphosphinate, preparation method and applications thereof, and high polymer composition comprising dialkylphosphinate |
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| CN103172664A (en) * | 2013-02-27 | 2013-06-26 | 广州金凯新材料有限公司 | Preparation method of dialkylphosphinate with excellent flowing property |
| CN103172663A (en) * | 2013-02-27 | 2013-06-26 | 广州金凯新材料有限公司 | Preparation method of dialkylphosphinate metal salt |
| CN105061500A (en) * | 2015-07-27 | 2015-11-18 | 广州金凯新材料有限公司 | Superfine particle size dialkylphosphinate, preparation method and applications thereof, and high polymer composition comprising dialkylphosphinate |
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