CN114134574B - High-length-diameter-ratio basic magnesium sulfate whisker and preparation method thereof - Google Patents
High-length-diameter-ratio basic magnesium sulfate whisker and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of inorganic functional materials, and particularly discloses a high-length-diameter ratio basic magnesium sulfate whisker and a preparation method thereof, wherein the preparation method comprises the following steps: slowly dripping a sodium hydroxide solution into a magnesium chloride solution, and carrying out sol-gel reaction at a constant temperature to obtain magnesium hydroxide sol; dissolving magnesium sulfate in ethanol-water solution to prepare magnesium sulfate alcohol water solution; adding sodium ethylene diamine tetracetate into a magnesium sulfate alcohol aqueous solution, and stirring for dissolving; mixing the obtained magnesium hydroxide sol and a magnesium sulfate alcohol aqueous solution, and uniformly stirring to obtain a basic magnesium sulfate whisker precursor; and (3) quickly transferring the mixture into a high-pressure reaction kettle, carrying out hydrothermal crystallization reaction, cooling to room temperature, carrying out suction filtration, washing and drying to obtain a basic magnesium sulfate whisker product. The basic magnesium sulfate whisker prepared by the invention has the advantages of good crystallinity, high length-diameter ratio, good dispersibility and the like, the yield of the whisker can reach 90 percent, the length can reach 500-1000 mu m, the length-diameter ratio can reach more than 150-300, and the basic magnesium sulfate whisker can be applied to various flame-retardant polymer materials.
Description
Technical Field
The invention belongs to the technical field of inorganic functional materials, and particularly relates to a high-length-diameter ratio basic magnesium sulfate whisker and a preparation method thereof.
Background
The magnesium salt whisker, as a novel fiber material, has excellent high temperature resistance, corrosion resistance and good mechanical strength, is commonly used for strengthening, toughening and flame retarding of polymer composite materials, and can obviously improve the tensile strength, bending strength, impact strength and flame retarding performance of the polymer composite materials. The basic magnesium sulfate whisker has higher thermal decomposition temperature (260-1150 ℃) and better flame retardant property. However, when the basic magnesium sulfate whisker is directly prepared by a hydrothermal method, the problems of more fan-shaped whiskers, lower long diameter ratio, low whisker purity and the like exist. Patent CN108277533A discloses a method for synthesizing monodisperse basic magnesium sulfate whisker, which takes magnesium sulfate and sodium hydroxide as raw materials and sodium dodecyl benzene sulfonate as an additive, and carries out hydrothermal treatment at 190 ℃ for 10-25 h. The length of the prepared whisker is 30-80 μm, and the diameter is 0.1-1 μm. The patent ZL2008101196697 uses water-soluble magnesium salt and inorganic base as raw materials, citric acid, tartaric acid and the like as chelating type morphology control agents, and is hydrothermally synthesized at 100-250 ℃ to obtain monodisperse one-dimensional basic magnesium sulfate whiskers, wherein the length of the whiskers is 40-400 microns, and the diameter of the whiskers is 0.05-0.2 microns. Lucheng et al (salt lake research, 2011,19 (3): 61-66.) add sodium edetate when synthesizing basic magneislum in hydrothermal condition at 150-210 deg.C, which effectively inhibits the generation of fan-shaped whiskers, but the obtained whiskers have an average length of only 40 μm and an aspect ratio of 30-100. Thus, it is found that the introduction of the additive can suppress the fan-shaped agglomeration of basic magnesium sulfate whiskers and improve the dispersibility of the whiskers. However, all the additives reported in the literature are single additives, and it is difficult to obtain one-dimensional whiskers with high dispersion, high aspect ratio and uniform size at the same time.
Disclosure of Invention
Aiming at the problem that the existing method is difficult to simultaneously obtain one-dimensional whiskers with high dispersion, high length-diameter ratio and uniform size, the invention provides a high length-diameter ratio basic magnesium sulfate whisker and a preparation method thereof. The invention aims to improve the length-diameter ratio and the dispersibility of basic magnesium sulfate whiskers, provides a composite additive with a coupling effect, prepares one-dimensional basic magnesium sulfate whiskers with good crystallinity, high length-diameter ratio and good dispersibility, has the whisker yield of 90 percent, the length of 500-1000 mu m and the length-diameter ratio of 150-300, and can be applied to various flame-retardant high polymer materials.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high length-diameter ratio basic magnesium sulfate whisker and a preparation method thereof comprise the following steps:
step one, slowly dropwise adding a sodium hydroxide solution into a magnesium chloride solution at a certain temperature under stirring, and carrying out sol-gel reaction at the constant temperature to obtain magnesium hydroxide sol;
step two, dissolving magnesium sulfate in an ethanol-water solution to prepare a magnesium sulfate alcohol water solution;
step three, adding sodium ethylene diamine tetracetate into a magnesium sulfate alcohol aqueous solution, and stirring for dissolving;
step four, mixing the magnesium hydroxide sol obtained in the step two with the ethylene diamine tetraacetic acid sodium salt-containing magnesium sulfate alcohol aqueous solution obtained in the step three, and uniformly stirring to obtain a basic magnesium sulfate whisker precursor;
step five, quickly transferring the basic magnesium sulfate whisker precursor obtained in the step four into a high-pressure reaction kettle for hydrothermal crystallization reaction, then cooling to room temperature, and obtaining the basic magnesium sulfate whisker (5 Mg (OH) after suction filtration, washing and drying 2 ·MgSO 4 ·2H 2 O, 512-phase whisker for short).
Preferably, the concentration of the magnesium chloride solution in the first step is 0.5-2 mol/L, the concentration of the sodium hydroxide solution is 2mol/L, and the molar ratio of the magnesium chloride to the sodium hydroxide is 1:1-3.
Preferably, the temperature of the magnesium chloride solution in the first step is 60-80 ℃, the gel reaction time is 1-5 h, and the slow dropping speed is 5mL/min. .
Preferably, the volume fraction of ethanol in the magnesium sulfate alcohol aqueous solution in the step two is 5-30%, and the concentration of magnesium sulfate is 0.5mol/L.
Preferably, the addition amount of the sodium ethylene diamine tetracetate in the step three is 0.03-0.2% of the mass of the magnesium disulfide in the step three.
Preferably, the volume ratio of the magnesium hydroxide sol to the magnesium sulfate alcohol aqueous solution containing sodium ethylene diamine tetracetate in the step four is 1:1.
Preferably, the temperature of the hydrothermal crystallization reaction in the fifth step is 150-210 ℃, and the time is 6-12 h.
Preferably, the temperature for drying in the fifth step is 80 ℃, and the time for drying is 6h.
The invention also provides a basic magnesium sulfate whisker with high length-diameter ratio, wherein the length of the basic magnesium sulfate whisker is 500-1000 mu m, and the length-diameter ratio is 150-300.
The invention also provides application of the basic magnesium sulfate whisker with high length-diameter ratio, and the basic magnesium sulfate whisker is used for flame-retardant high polymer materials.
Compared with the prior art, the invention has the following advantages:
the invention uses sodium ethylene diamine tetracetate and ethanol as composite additives, and the sodium ethylene diamine tetracetate and the ethanol have a coupling effect in the growth process of the basic magnesium sulfate whisker. The Mg produced by decomposition of magnesium hydroxide during hydrothermal crystallization reaction 2+ Will rapidly form a large number of growth elements [ Mg (OH) 6 ]] 4- And further with free SO4 2- The combination forms a large number of tiny crystal nucleuses, and more growth centers are provided. However, these crystal nuclei are highly susceptible to agglomeration due to low surface energy, thus resulting in the formation of a large number of whisker scallops. Furthermore, since [ Mg (OH) 6 ]] 4- The basic magnesium sulfate whisker has strong interaction, and magnesium hydroxide is easily formed by precipitation, so that the basic magnesium sulfate whisker is mixed with magnesium hydroxide precipitate, and the purity of the product is reduced. When the EDTA sodium and the ethanol are added, the EDTA negative ions are firstly mixed with Mg 2+ Combined to form a complex, and reduce Mg in solution 2+ In a slow concentration of [ Mg (OH) 6 ]] 4- Thereby reducing the agglomeration caused by too fast nucleation and also hindering the [ Mg (OH) 6 ]] 4- The interaction between them and the formation of magnesium hydroxide. Secondly, ethanol molecules can be adsorbed on the surface of basic magnesium sulfate crystal nucleus, the number of hydroxyl groups on the surface of the crystal nucleus is increased, and free [ Mg (OH) 6 in the solution is attracted through hydrogen bonding] 4- And SO4 2- Promoting the whisker to grow along the b axis to form the basic magnesium sulfate whisker with high aspect ratio. Through the coupling effect of sodium ethylene diamine tetracetate and ethanol, the dispersibility of the basic magnesium sulfate whisker is improved, the length-diameter ratio of the whisker is improved, and the formation of impurity magnesium hydroxide is inhibited. The crystal whisker product has high crystallinity, smooth surface, homogeneous size, length of 500-1000 micron and length-diameter ratio of 150-300.
Drawings
FIG. 1 is an X-ray diffraction pattern of basic magnesium sulfate whiskers of the present invention, wherein a-f represent X-ray diffraction patterns of basic magnesium sulfate whiskers in comparative example 1, comparative example 2, example 1, example 2, example 3 and example 4, respectively.
FIG. 2 is a scanning electron microscope image of basic magnesium sulfate whiskers of the present invention, wherein (a) - (f) represent the scanning electron microscope images of basic magnesium sulfate whiskers in comparative example 1, comparative example 2, example 1, example 2, example 3 and example 4, respectively.
Detailed Description
The invention will now be further described with reference to the accompanying drawings and specific examples, which should not be construed as limiting the scope of the invention:
comparative example 1
The embodiment discloses a high-length-diameter ratio basic magnesium sulfate whisker and a preparation method thereof, and the preparation method comprises the following steps:
step A: 30.495g magnesium chloride hexahydrate is weighed to prepare 150mL magnesium chloride solution with the concentration of 1 mol/L; weighing 12g of sodium hydroxide to prepare 150mL of sodium hydroxide solution with the concentration of 2 mol/L; 36.970g magnesium sulfate heptahydrate is weighed and dissolved in 300mL ethanol-water solution, the concentration of the magnesium sulfate is 0.5mol/L, and the volume fraction of ethanol is 20%.
And B: heating the magnesium chloride solution to 60 ℃, dropwise adding a sodium hydroxide solution at a dropping rate of 5mL/min while stirring, and then preserving the temperature for 2h to generate white magnesium hydroxide sol.
Step C: adding the newly prepared magnesium hydroxide sol into a magnesium sulfate alcohol aqueous solution, stirring and mixing uniformly, then quickly transferring into a 1L high-pressure reaction kettle, carrying out hydrothermal reaction at 190 ℃ for 10h, and then naturally cooling to room temperature. Filtering out the hydrothermal product, washing with deionized water and ethanol for three times respectively, and drying in an oven at 80 ℃ for 6 hours to obtain 512-phase basic magnesium sulfate whisker with the yield of 85%.
The XRD spectrum and SEM image of the prepared product are shown in figure 1a and figure 2 (a).
Comparative example 2
The embodiment discloses a high-length-diameter ratio basic magnesium sulfate whisker and a preparation method thereof, and the preparation method comprises the following steps:
step A: 30.495g magnesium chloride hexahydrate is weighed to prepare 150mL magnesium chloride solution with the concentration of 1 mol/L; weighing 12g of sodium hydroxide to prepare 150mL of sodium hydroxide solution with the concentration of 2 mol/L; 36.970g magnesium sulfate heptahydrate and 0.0396g sodium ethylene diamine tetracetate are weighed and dissolved in 300mL of water solution, and the concentration of the magnesium sulfate is 0.5mol/L.
And B: heating the magnesium chloride solution to 60 ℃, dropwise adding a sodium hydroxide solution at a dropping rate of 5mL/min while stirring, and then preserving the temperature for 2h to generate white magnesium hydroxide sol.
And C: adding the newly prepared magnesium hydroxide sol into a magnesium sulfate solution containing sodium ethylene diamine tetracetate, stirring and mixing uniformly, then quickly transferring into a 1L high-pressure reaction kettle, carrying out hydrothermal reaction at 190 ℃ for 10h, and then naturally cooling to room temperature. Filtering out the hydrothermal product, washing with deionized water and ethanol three times respectively, and drying in an oven at 80 ℃ for 6h to obtain 512-phase basic magnesium sulfate whiskers with the yield of 80%.
The XRD spectrum and SEM image of the product are shown in FIG. 1b and FIG. 2 (b).
Example 1
The embodiment discloses a high-length-diameter ratio basic magnesium sulfate whisker and a preparation method thereof, and the preparation method comprises the following steps:
step A: 30.495g magnesium chloride hexahydrate is weighed to prepare 150mL magnesium chloride solution with the concentration of 1 mol/L; weighing 12g of sodium hydroxide to prepare 150mL of sodium hydroxide solution with the concentration of 2 mol/L; 36.970g magnesium sulfate heptahydrate and 0.0396g sodium ethylene diamine tetracetate are weighed and dissolved in 300mL ethanol-water solution, and the volume fraction of the magnesium sulfate is 5% with the concentration of 0.5mol/L ethanol.
And B: heating the magnesium chloride solution to 60 ℃, dropwise adding a sodium hydroxide solution at a dropping rate of 5mL/min while stirring, and then preserving the temperature for 2h to generate white magnesium hydroxide sol.
And C: adding the newly prepared magnesium hydroxide sol into a magnesium sulfate solution containing sodium ethylene diamine tetracetate, stirring and mixing uniformly, then quickly transferring into a 1L high-pressure reaction kettle, carrying out hydrothermal reaction at 190 ℃ for 10h, and then naturally cooling to room temperature. Filtering out the hydrothermal product, washing with deionized water and ethanol for three times respectively, and drying in an oven at 80 ℃ for 6 hours to obtain 512-phase basic magnesium sulfate whisker with the yield of 85%.
The XRD spectrum and SEM image of the obtained product are shown in FIG. 1c and FIG. 2 (c).
Example 2
The embodiment discloses a high-length-diameter ratio basic magnesium sulfate whisker and a preparation method thereof, and the preparation method comprises the following steps:
step A: 30.495g magnesium chloride hexahydrate is weighed to prepare 150mL magnesium chloride solution with the concentration of 1 mol/L; weighing 12g of sodium hydroxide to prepare 150mL of sodium hydroxide solution with the concentration of 2 mol/L; 36.970g magnesium sulfate heptahydrate and 0.0396g sodium ethylene diamine tetracetate are weighed and dissolved in 300mL ethanol-water solution, the concentration of the magnesium sulfate is 0.5mol/L, and the volume fraction of the ethanol is 10%.
And B: heating the magnesium chloride solution to 60 ℃, dropwise adding a sodium hydroxide solution at a dropping rate of 5mL/min while stirring, and then preserving the temperature for 2h to generate white magnesium hydroxide sol.
And C: adding the newly prepared magnesium hydroxide sol into a magnesium sulfate solution containing sodium ethylene diamine tetracetate, stirring and mixing uniformly, then quickly transferring into a 1L high-pressure reaction kettle, carrying out hydrothermal reaction at 190 ℃ for 10h, and then naturally cooling to room temperature. Filtering out the hydrothermal product, washing with deionized water and ethanol for three times respectively, and drying in an oven at 80 ℃ for 6 hours to obtain 512-phase basic magnesium sulfate whisker with the yield of 88%.
The XRD spectrum and SEM image of the prepared whisker product are shown in figure 1d and figure 2 (d).
Example 3
The embodiment discloses a high-length-diameter ratio basic magnesium sulfate whisker and a preparation method thereof, and the preparation method comprises the following steps:
step A: 30.495g magnesium chloride hexahydrate is weighed to prepare 150mL magnesium chloride solution with the concentration of 1 mol/L; weighing 12g of sodium hydroxide to prepare 150mL of sodium hydroxide solution with the concentration of 2 mol/L; 36.970g magnesium sulfate heptahydrate and 0.0396g sodium ethylene diamine tetracetate are weighed and dissolved in 300mL ethanol-water solution, the concentration of the magnesium sulfate is 0.5mol/L, and the volume fraction of the ethanol is 20%.
And B: heating the magnesium chloride solution to 60 ℃, dropwise adding a sodium hydroxide solution at a dropping rate of 5mL/min while stirring, and then preserving heat for 2 hours to generate white magnesium hydroxide sol.
And C: adding the newly prepared magnesium hydroxide sol into a magnesium sulfate solution containing sodium ethylene diamine tetracetate, stirring and mixing uniformly, then quickly transferring into a 1L high-pressure reaction kettle, carrying out hydrothermal reaction at 190 ℃ for 10h, and then naturally cooling to room temperature. Filtering out the hydrothermal product, washing with deionized water and ethanol for three times respectively, and drying in an oven at 80 ℃ for 6 hours to obtain 512-phase basic magnesium sulfate whisker with the yield of 90%.
The XRD spectrum and SEM image of the prepared whisker product are shown in figure 1e and figure 2 (e).
Example 4
The embodiment discloses a high-length-diameter ratio basic magnesium sulfate whisker and a preparation method thereof, and the preparation method comprises the following steps:
step A: 30.495g magnesium chloride hexahydrate is weighed to prepare 150mL magnesium chloride solution with the concentration of 1 mol/L; weighing 12g of sodium hydroxide to prepare 150mL of sodium hydroxide solution with the concentration of 2 mol/L; 36.970g magnesium sulfate heptahydrate and 0.0396g sodium ethylene diamine tetracetate are weighed and dissolved in 300mL ethanol-water solution, the concentration of the magnesium sulfate is 0.5mol/L, and the volume fraction of the ethanol is 30%.
And B: heating the magnesium chloride solution to 60 ℃, dropwise adding a sodium hydroxide solution at a dropping rate of 5mL/min while stirring, and then preserving the temperature for 2h to generate white magnesium hydroxide sol.
And C: adding the newly prepared magnesium hydroxide sol into a magnesium sulfate solution containing sodium ethylene diamine tetracetate, stirring and mixing uniformly, quickly transferring into a 1L high-pressure reaction kettle, carrying out hydrothermal reaction at 190 ℃ for 10h, and naturally cooling to room temperature. Filtering out the hydrothermal product, washing with deionized water and ethanol for three times respectively, and drying in an oven at 80 ℃ for 6 hours to obtain 512-phase basic magnesium sulfate whisker with the yield of 85%.
The XRD spectrum and SEM image of the prepared whisker product are shown in figure 1f and figure 2 (f).
Example 5
The embodiment discloses a high-length-diameter ratio basic magnesium sulfate whisker and a preparation method thereof, and the preparation method comprises the following steps:
step A: 60.990g magnesium chloride hexahydrate is weighed to prepare 150mL magnesium chloride solution with the concentration of 2 mol/L; weighing 12g of sodium hydroxide to prepare 150mL of sodium hydroxide solution with the concentration of 2 mol/L; 36.970g magnesium sulfate heptahydrate and 0.0396g sodium ethylene diamine tetracetate are weighed and dissolved in 300mL ethanol-water solution, the concentration of the magnesium sulfate is 0.5mol/L, and the volume fraction of the ethanol is 30%.
And B: heating the magnesium chloride solution to 80 ℃, dropwise adding a sodium hydroxide solution at a dropping rate of 5mL/min while stirring, and then preserving the temperature for 1h to generate white magnesium hydroxide sol.
Step C: adding the newly prepared magnesium hydroxide sol into a magnesium sulfate solution containing sodium ethylene diamine tetracetate, stirring and mixing uniformly, then quickly transferring into a 1L high-pressure reaction kettle, carrying out hydrothermal reaction at 190 ℃ for 10h, and then naturally cooling to room temperature. Filtering out the hydrothermal product, washing with deionized water and ethanol for three times respectively, and drying in an oven at 80 ℃ for 6 hours to obtain 512-phase basic magnesium sulfate whisker with the yield of 83%.
Example 6
The embodiment discloses a high-length-diameter ratio basic magnesium sulfate whisker and a preparation method thereof, and the preparation method comprises the following steps:
step A: 30.495g magnesium chloride hexahydrate is weighed to prepare 150mL magnesium chloride solution with the concentration of 1 mol/L; weighing 12g of sodium hydroxide to prepare 150mL of sodium hydroxide solution with the concentration of 2 mol/L; 36.970g magnesium sulfate heptahydrate and 0.0396g sodium ethylene diamine tetracetate are weighed and dissolved in 300mL ethanol-water solution, the concentration of the magnesium sulfate is 0.5mol/L, and the volume fraction of the ethanol is 30%.
And B: heating the magnesium chloride solution to 60 ℃, dropwise adding a sodium hydroxide solution at a dropping rate of 5mL/min while stirring, and then preserving the temperature for 5 hours to generate white magnesium hydroxide sol.
And C: adding the newly prepared magnesium hydroxide sol into a magnesium sulfate solution containing sodium ethylene diamine tetracetate, stirring and mixing uniformly, then quickly transferring into a 1L high-pressure reaction kettle, carrying out hydrothermal reaction at 210 ℃ for 6h, and then naturally cooling to room temperature. Filtering out the hydrothermal product, washing with deionized water and ethanol for three times respectively, and drying in an oven at 80 ℃ for 6 hours to obtain 512-phase basic magnesium sulfate whisker with the yield of 88%.
Example 7
The embodiment discloses a high-length-diameter ratio basic magnesium sulfate whisker and a preparation method thereof, and the preparation method comprises the following steps:
step A: 60.990g magnesium chloride hexahydrate is weighed to prepare 150mL magnesium chloride solution with the concentration of 2 mol/L; weighing 12g of sodium hydroxide to prepare 150mL of sodium hydroxide solution with the concentration of 2 mol/L; 36.970g magnesium sulfate heptahydrate and 0.0396g sodium ethylene diamine tetracetate are weighed and dissolved in 300mL ethanol-water solution, the concentration of the magnesium sulfate is 0.5mol/L, and the volume fraction of the ethanol is 30%.
And B: heating the magnesium chloride solution to 80 ℃, dropwise adding a sodium hydroxide solution at a dropping rate of 5mL/min while stirring, and then preserving the temperature for 1h to generate white magnesium hydroxide sol.
And C: adding the newly prepared magnesium hydroxide sol into a magnesium sulfate solution containing sodium ethylene diamine tetracetate, stirring and mixing uniformly, then quickly transferring into a 1L high-pressure reaction kettle, carrying out hydrothermal reaction at 150 ℃ for 12h, and then naturally cooling to room temperature. Filtering out the hydrothermal product, washing with deionized water and ethanol for three times respectively, and drying in an oven at 80 ℃ for 6 hours to obtain 512-phase basic magnesium sulfate whisker with the yield of 75%.
Example 8
The embodiment discloses a high-length-diameter ratio basic magnesium sulfate whisker and a preparation method thereof, and the preparation method comprises the following steps:
step A: 15.248g magnesium chloride hexahydrate is weighed to prepare 150mL magnesium chloride solution with the concentration of 0.5 mol/L; weighing 12g of sodium hydroxide to prepare 150mL of sodium hydroxide solution with the concentration of 2 mol/L; 36.970g magnesium sulfate heptahydrate and 0.0396g sodium ethylene diamine tetracetate are weighed and dissolved in 300mL ethanol-water solution, the concentration of the magnesium sulfate is 0.5mol/L, and the volume fraction of the ethanol is 30%.
And B: heating the magnesium chloride solution to 80 ℃, dropwise adding a sodium hydroxide solution at a dropping rate of 5mL/min while stirring, and then preserving the temperature for 1h to generate white magnesium hydroxide sol.
And C: adding the newly prepared magnesium hydroxide sol into a magnesium sulfate solution containing sodium ethylene diamine tetracetate, stirring and mixing uniformly, then quickly transferring into a 1L high-pressure reaction kettle, carrying out hydrothermal reaction at 190 ℃ for 10h, and then naturally cooling to room temperature. Filtering out the hydrothermal product, washing with deionized water and ethanol three times respectively, and drying in an oven at 80 ℃ for 6h to obtain 512-phase basic magnesium sulfate whiskers with the yield of 70%.
As seen from FIG. 1, the diffraction peaks at 12.94 °, 17.32 ° and 22.86 ° are (201), (202) and (203) crystal planes of the 512-phase basic magnesium sulfate whisker, wherein the corresponding diffraction peaks in FIGS. 1e and 1f are sharper, which indicates that the whisker has better crystallinity and larger aspect ratio.
As can be seen from the whisker morphology shown in FIG. 2, when ethanol is added alone, the whiskers are mainly in a sector shape (a); when the disodium ethylene diamine tetraacetate is added singly, the whiskers are still agglomerated in a fan shape and reduced, and the dispersibility is improved; when the two are added in a composite way, the size of the whisker is gradually increased along with the increase of the addition amount of ethanol ((c) to (e)), and the dispersibility and uniformity are improved, wherein the length of the whisker in (e) reaches 500-1200 mu m, the length-diameter ratio reaches 150-300, and the dispersibility is best; however, when the amount of ethanol added is 30%, the dispersibility and uniformity of whiskers are deteriorated (f).
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (8)
1. A preparation method of basic magnesium sulfate whisker with high length-diameter ratio is characterized by comprising the following steps:
step one, slowly dropwise adding a sodium hydroxide solution into a magnesium chloride solution at a certain temperature under stirring, and carrying out sol-gel reaction at the constant temperature to obtain magnesium hydroxide sol;
dissolving magnesium sulfate in an ethanol-water solution to prepare a magnesium sulfate alcohol water solution; the volume fraction of ethanol in the magnesium sulfate alcohol aqueous solution is 5-30%;
step three, adding sodium ethylene diamine tetracetate into a magnesium sulfate alcohol aqueous solution, and stirring for dissolving;
step four, mixing the magnesium hydroxide sol obtained in the step one with the ethylene diamine tetraacetic acid sodium salt-containing magnesium sulfate alcohol aqueous solution obtained in the step three, and uniformly stirring to obtain a basic magnesium sulfate whisker precursor;
and step five, quickly transferring the basic magnesium sulfate whisker precursor obtained in the step four into a high-pressure reaction kettle, carrying out hydrothermal crystallization reaction, then cooling to room temperature, and carrying out suction filtration, washing and drying to obtain a basic magnesium sulfate whisker product.
2. The preparation method of the basic magnesium sulfate whisker with the high length-diameter ratio according to claim 1, wherein the concentration of the magnesium chloride solution in the first step is 0.5 to 2mol/L, the concentration of the sodium hydroxide solution is 2mol/L, and the molar ratio of the magnesium chloride to the sodium hydroxide is 1 to 3.
3. The preparation method of the basic magnesium sulfate whisker with the high length-diameter ratio according to claim 1, wherein the temperature of the magnesium chloride solution in the first step is 60 to 80 ℃, the gel reaction time is 1 to 5 hours, and the slow dropping speed is 5mL/min.
4. The method for preparing high aspect ratio basic magnesium sulfate whiskers as recited in claim 1, wherein the concentration of magnesium sulfate is 0.5mol/L.
5. The preparation method of the high-aspect-ratio basic magnesium sulfate whisker according to claim 1, wherein the addition amount of sodium ethylene diamine tetracetate in the step three is 0.03-0.2% of the mass of magnesium sulfate.
6. The method for preparing the high-aspect-ratio basic magnesium sulfate whisker according to claim 1, wherein the volume ratio of the magnesium hydroxide sol to the magnesium sulfate alcohol aqueous solution containing sodium ethylene diamine tetracetate in the step four is 1:1.
7. the preparation method of the basic magnesium sulfate whisker with the high length-diameter ratio according to claim 1, wherein the hydrothermal crystallization reaction temperature in the fifth step is 150 to 210 ℃ and the time is 6 to 12 hours.
8. The method for preparing high aspect ratio basic magnesium sulfate whiskers as claimed in claim 1, wherein the drying temperature in step five is 80 ℃ and the drying time is 6h.
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