CN114395274A - Superfine modified magnesium hydroxide, preparation method and application thereof, and flame-retardant polyolefin cable material - Google Patents

Superfine modified magnesium hydroxide, preparation method and application thereof, and flame-retardant polyolefin cable material Download PDF

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CN114395274A
CN114395274A CN202210029510.6A CN202210029510A CN114395274A CN 114395274 A CN114395274 A CN 114395274A CN 202210029510 A CN202210029510 A CN 202210029510A CN 114395274 A CN114395274 A CN 114395274A
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magnesium hydroxide
wet
modified magnesium
dry
grinding
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宋建强
彭鹤松
邹检生
曾国元
邱文福
贺欣欣
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Haicheng Xinguangyuan Powder Material Co ltd
Henan Nanzhao New Guangyuan Material Co ltd
Jiangxi Guangyuan Chemical Co Ltd
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Haicheng Xinguangyuan Powder Material Co ltd
Henan Nanzhao New Guangyuan Material Co ltd
Jiangxi Guangyuan Chemical Co Ltd
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
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    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating

Abstract

The invention belongs to the technical field of magnesium hydroxide, and particularly relates to superfine modified magnesium hydroxide, a preparation method and application thereof, and a flame-retardant polyolefin cable material. The preparation method of the superfine modified magnesium hydroxide provided by the invention comprises the following steps: mixing the brucite raw ore and a dry grinding aid, and carrying out dry grinding to obtain dry grinding particles, wherein the mesh number of the dry grinding particles is more than or equal to 400 meshes; mixing the dry-milled particles, a dispersing agent, a wet-milled grinding aid, a composite modifier and water, and wet-milling the obtained wet-milled slurry to obtain the superfine modified magnesium hydroxide; the composite modifier comprises a silane coupling agent, a phosphate ester rare earth coupling agent and trimethyl silicon caprylate sulfonate; the mesh number of the superfine modified magnesium hydroxide is more than or equal to 8000 meshes. The preparation method provided by the invention is simple and low in cost, and the obtained superfine modified magnesium hydroxide is fine in particle size, has good flame-retardant and smoke-suppression effects, can improve the surface glossiness and mechanical properties of the flame-retardant polyolefin cable material, and is comparable to the magnesium hydroxide prepared by a chemical method.

Description

Superfine modified magnesium hydroxide, preparation method and application thereof, and flame-retardant polyolefin cable material
Technical Field
The invention belongs to the technical field of magnesium hydroxide, and particularly relates to superfine modified magnesium hydroxide, a preparation method and application thereof, and a flame-retardant polyolefin cable material.
Background
The magnesium hydroxide is a green inorganic flame-retardant material integrating three functions of flame retardance, smoke suppression and filling, releases crystallized water during combustion and absorbs a large amount of heat; the magnesium oxide generated after hydrolysis is a good refractory material, reduces the flammability of organic materials, has high decomposition temperature, chemical corrosion resistance, excellent flame retardance, smoke suppression and combustion charring property, is used as a green environment-friendly flame retardant, smoke suppressant and filler, and is widely applied to flame retardant materials such as low-smoke halogen-free flame retardant polyolefin cable materials and the like.
The magnesium hydroxide is mainly divided into mineral magnesium hydroxide and chemical magnesium hydroxide. The magnesium hydroxide prepared by the chemical method has high purity and small particle size, but has complex process and high cost. At present, magnesium hydroxide produced by a mineral method on the market is mainly produced by a dry grinding process, the average particle size is generally 3-5 mu m, and the specific surface area is 5-8 m2The magnesium hydroxide has coarse particle size, and the mineral method of the coarse particle size has low flame retardant efficiency and poor smoke suppression performance, can affect the surface gloss of the cable, and reduces the tensile strength and the elongation at break of the cable, so that the imported chemical method magnesium hydroxide is mostly adopted in the production process of some high-end low-smoke halogen-free flame retardant polyolefin cable materials, and the wide application of the magnesium hydroxide in the low-smoke halogen-free flame retardant polyolefin cable materials is seriously limited.
Disclosure of Invention
In view of the above, the present invention aims to provide an ultrafine modified magnesium hydroxide and a preparation method thereof, the preparation method provided by the present invention is simple and low in cost, and the ultrafine modified magnesium hydroxide obtained by the preparation method provided by the present invention has a fine particle size, has a good flame retardant and smoke suppression effect, and can improve the surface gloss and mechanical properties of a flame retardant polyolefin cable material, which are comparable to those of magnesium hydroxide prepared by a chemical method.
In order to achieve the purpose of the invention, the invention provides the following technical scheme:
the invention provides a preparation method of superfine modified magnesium hydroxide, which comprises the following steps:
mixing the brucite raw ore and a dry grinding aid, and carrying out dry grinding to obtain dry grinding particles, wherein the mesh number of the dry grinding particles is more than or equal to 400 meshes;
mixing the dry-milled particles, a dispersing agent, a wet-milled grinding aid, a composite modifier and water, and wet-milling the obtained wet-milled slurry to obtain the superfine modified magnesium hydroxide; the solid content of the wet grinding slurry is 75-80%;
the grinding ball for wet grinding is a ceramic ball; the ceramic balls comprise large ceramic balls, middle ceramic balls and small ceramic balls; the particle size of the large ceramic balls is 1.8-2.5 mm, and the filling rate in a cavity of wet grinding equipment is 12-15%; the particle size of the medium ceramic ball is 1.3-1.6 mm, and the filling rate in a cavity of wet grinding equipment is 15-18%; the particle size of the small ceramic balls is 0.8-1.2 mm, and the filling rate in a cavity of wet grinding equipment is 25-28%;
the composite modifier comprises a silane coupling agent, a phosphate ester rare earth coupling agent and trimethyl silicon caprylate sulfonate;
the mesh number of the superfine modified magnesium hydroxide is more than or equal to 8000 meshes.
Preferably, the dry grinding aid comprises sodium polyacrylate;
the mass ratio of the brucite raw ore to the dry grinding auxiliary agent is 1000: (2-4).
Preferably, the wet grinding aid comprises triethanolamine.
Preferably, the mass ratio of the dry-milled particles to the wet-milling aid is 1000: (3-5).
Preferably, the composite modifier comprises a silane coupling agent, a phosphate ester rare earth coupling agent and trimethyl silicon caprylate sulfonate in a mass ratio of (3-5): (1-3): (2-4).
Preferably, the mass ratio of the dry-milled particles to the silane coupling agent is 1000: (3-5);
the mass ratio of the dry-milled particles to the phosphate rare earth coupling agent is 1000: (1-3);
the mass ratio of the dry-milled particles to the trimethyl silicon caprylate sulfonate is 1000: (2-4).
Preferably, the grinding balls for wet grinding are ceramic balls; the ceramic balls comprise large ceramic balls, middle ceramic balls and small ceramic balls;
the particle size of the large ceramic balls is 1.5-2 mm, and the filling rate in a cavity of wet grinding equipment is 12-15%;
the particle size of the medium ceramic ball is 1.3-1.8 mm, and the filling rate in a cavity of wet grinding equipment is 15-18%;
the particle size of the small ceramic balls is 0.8-1.2 mm, and the filling rate in a cavity of wet grinding equipment is 25-28%.
Preferably, the temperature of the wet grinding slurry in the wet grinding is 110-120 ℃, and the stirring speed is 2500-3000 rpm.
The invention also provides the superfine modified magnesium hydroxide obtained by the preparation method of the technical scheme, and the mesh number of the superfine modified magnesium hydroxide is more than or equal to 8000 meshes.
The invention also provides application of the superfine modified magnesium hydroxide as a flame retardant.
The invention also provides a flame-retardant polyolefin cable material which comprises the following components in parts by mass:
55-65 parts of superfine modified magnesium hydroxide, 20-25 parts of ethylene-vinyl acetate copolymer, 10-15 parts of linear low-density polyethylene, 6-12 parts of ethylene-octene thermoplastic elastomer of metallocene catalyst and 4-8 parts of compatilizer;
the superfine modified magnesium hydroxide is the superfine modified magnesium hydroxide in the technical scheme.
The invention provides a preparation method of superfine modified magnesium hydroxide, which comprises the following steps: mixing the brucite raw ore and a dry grinding aid, and carrying out dry grinding to obtain dry grinding particles, wherein the mesh number of the dry grinding particles is more than or equal to 400 meshes; mixing the dry-milled particles, a dispersing agent, a wet-milled grinding aid, a composite modifier and water, and wet-milling the obtained wet-milled slurry to obtain the superfine modified magnesium hydroxide; the solid content of the wet grinding slurry is 75-80%; the grinding ball for wet grinding is a ceramic ball; the ceramic balls comprise large ceramic balls, middle ceramic balls and small ceramic balls; the particle size of the large ceramic balls is 1.8-2.5 mm, and the filling rate in a cavity of wet grinding equipment is 12-15%; the particle size of the medium ceramic ball is 1.3-1.6 mm, and the filling rate in a cavity of wet grinding equipment is 15-18%; the particle size of the small ceramic balls is 0.8-1.2 mm, and the filling rate in a cavity of wet grinding equipment is 25-28%; the composite modifier comprises a silane coupling agent, a phosphate ester rare earth coupling agent and trimethyl silicon caprylate sulfonate; the mesh number of the superfine modified magnesium hydroxide is more than or equal to 8000 meshes. In the invention, the composite modifier reduces the polarity of the superfine magnesium hydroxide, improves the compatibility of the superfine magnesium hydroxide and resin, and improves the fluidity and the dispersibility of the superfine magnesium hydroxide; the wet grinding process is adopted, and the solid content of the slurry, the material quality, the grain diameter and the filling amount of the grinding balls in wet grinding are controlled, so that the wet grinding can break through the limit of the traditional dry grinding, and the superfine magnesium hydroxide with more than 8000 meshes can be ground and produced.
The test result of the embodiment shows that the superfine modified magnesium hydroxide D50 provided by the invention is 1.52-1.56 μm, the D90 is 2.49-2.55 μm, and the BET specific surface area is 22.12-22.77 m2(iv) a small particle size and a large specific surface area; the flame-retardant polyolefin cable material prepared by adopting the superfine modified magnesium hydroxide provided by the invention has the surface glossiness of 96.5-98.1 degrees and high glossiness; the oxygen index is 38.8-39.5%, the maximum smoke density is 0.46-0.91 kg/m3, and the flame-retardant and smoke-suppression effect is good; the tensile strength is 14.8-15.5 MPa, the elongation at break is 196.2-204.9 MPa, the tensile property is high, and the mechanical property is excellent.
Drawings
FIG. 1 is an SEM photograph of ultrafine modified magnesium hydroxide prepared in example 1.
Detailed Description
The invention provides a preparation method of superfine modified magnesium hydroxide, which comprises the following steps:
mixing the brucite raw ore and a dry grinding aid, and carrying out dry grinding to obtain dry grinding particles, wherein the mesh number of the dry grinding particles is more than or equal to 400 meshes;
mixing the dry-milled particles, a dispersing agent, a wet-milled grinding aid, a composite modifier and water, and wet-milling the obtained wet-milled slurry to obtain the superfine modified magnesium hydroxide; the solid content of the wet grinding slurry is 75-80%;
the grinding ball for wet grinding is a ceramic ball; the ceramic balls comprise large ceramic balls, middle ceramic balls and small ceramic balls; the particle size of the large ceramic balls is 1.8-2.5 mm, and the filling rate in a cavity of wet grinding equipment is 12-15%; the particle size of the medium ceramic ball is 1.3-1.6 mm, and the filling rate in a cavity of wet grinding equipment is 15-18%; the particle size of the small ceramic balls is 0.8-1.2 mm, and the filling rate in a cavity of wet grinding equipment is 25-28%;
the composite modifier comprises a silane coupling agent, a phosphate ester rare earth coupling agent and trimethyl silicon caprylate sulfonate;
the mesh number of the superfine modified magnesium hydroxide is more than or equal to 8000 meshes.
In the present invention, unless otherwise specified, each component in the preparation method is a commercially available product well known to those skilled in the art.
Mixing the brucite raw ore and a dry grinding aid, and carrying out dry grinding to obtain dry grinding particles, wherein the mesh number of the dry grinding particles is more than or equal to 400 meshes.
The source of the brucite raw ore is not particularly limited in the invention, and the brucite raw ore known by the person skilled in the art can be used. In the present invention, the MgO content in the brucite raw ore is preferably 62 to 64 wt.%, more preferably 62.5 to 63.5 wt.%.
In the invention, the particle size of the brucite raw ore is preferably 5-10 mm.
The brucite raw ore is preferably crushed to 5-10 mm; the crushing preferably comprises a first crushing and a second crushing in sequence. In the invention, the particle size of the crushed product obtained by the first crushing is preferably 5-10 cm.
In the present invention, the dry grinding aid preferably includes sodium polyacrylate. In the invention, the mass ratio of the brucite raw ore to the dry grinding aid is preferably 1000: (2-4), more preferably 1000: (2.5-3.5). In the invention, the stirring speed in the dry grinding is preferably 1100-1400 rpm, and more preferably 1200-1300 rpm.
In the present invention, the dry milling apparatus is preferably a ring roll mill. In an embodiment of the invention, the dry milling apparatus is preferably a 198 ring roll mill.
In the invention, the mesh number of the dry-milled particles is more than or equal to 400 meshes.
After the dry grinding particles are obtained, the dry grinding particles, the dispersing agent, the wet grinding aid, the composite modifier and water are mixed, and the obtained wet grinding slurry is subjected to wet grinding to obtain the superfine modified magnesium hydroxide.
In the present invention, the wet grinding aid preferably comprises triethanolamine. In the present invention, the mass ratio of the dry-milled particles to the wet-milling aid is preferably 1000: (3-5), more preferably 1000: (3.5-4.5).
In the present invention, the dispersant preferably includes sodium polycarboxylate and sodium dodecylbenzenesulfonate. In the invention, the mass ratio of the sodium polycarboxylate to the sodium dodecyl benzene sulfonate in the dispersant is preferably (3-5): 1, more preferably (3.5 to 4.5): 1. in the present invention, the mass ratio of the dry-milled particles to the dispersant is preferably 1000: (4-6), more preferably 1000: (4.5-5.5).
In the invention, the composite modifier comprises a silane coupling agent, a phosphate ester rare earth coupling agent and trimethyl silicon caprylate sulfonate. In the invention, the mass ratio of the silane coupling agent, the phosphate rare earth coupling agent and the trimethyl silicon caprylic acid sulfonate in the composite modifier is (3-5): (1-3): (2-4), more preferably (3.5-4.5): (1.5-2.5): (2.5-3.5). In the present invention, the mass ratio of the dry-milled particles to the silane coupling agent is preferably 1000: (3-5), more preferably 1000: (3.5-4.5). In the present invention, the mass ratio of the dry-milled particles to the phosphate rare earth coupling agent is preferably 1000: (1-3), more preferably 1000: (1.5-2.5). In the present invention, the mass ratio of the dry-milled particles to the trimethyl silicon octanoate sulfonate is preferably 1000: (2-4), more preferably 1000: (2.5-3.5).
In the invention, the composite modifier is used for coating and modifying the superfine magnesium hydroxide, so that the polarity of the superfine magnesium hydroxide is reduced, the compatibility of the superfine magnesium hydroxide and resin is improved, and the fluidity and the dispersibility of the superfine magnesium hydroxide are improved.
In the invention, the solid content of the wet grinding slurry is 75-80%, and preferably 76-79%.
The content of the water is not particularly limited in the present invention, so as to ensure the solid content of the wet-milling slurry.
In the present invention, the grinding balls for wet grinding are ceramic balls, preferably zirconia ceramic balls. In the present invention, the ceramic balls include large ceramic balls, medium ceramic balls, and small ceramic balls. In the invention, the particle size of the large ceramic ball is 1.8-2.5 mm, preferably 1.9-2.4 mm; the filling rate of the large ceramic balls in the cavity of the wet grinding equipment is 12-15%, and the preferable filling rate is 12.5-14.5%. In the invention, the particle size of the medium ceramic ball is preferably 1.3-1.6 mm, and is preferably 1.4-1.5 mm; the filling rate of the medium ceramic balls in the cavity of the wet grinding equipment is 15-18%, and the preferable filling rate is 15.5-17.5%. In the invention, the particle size of the small ceramic ball is 0.8-1.2 mm, preferably 0.9-1.1 mm; the filling rate of the small ceramic balls in the cavity of the wet grinding equipment is 25-28%, and the preferable filling rate is 25.5-27.5%.
In the present invention, the wet milling apparatus is preferably a wet mill, more preferably a wet mill lined with ceramic. In an embodiment of the invention, the wet milling device is preferably a vertical mixer. In the invention, the size of the inner chamber of the wet grinding machine is as follows: the height is preferably 4.8 m; the diameter is preferably 2.4 m.
In the invention, the temperature of the wet grinding slurry in the wet grinding is preferably 110-120 ℃, and more preferably 112-118 ℃; the stirring speed in wet grinding is preferably 2500-3000 rpm, and more preferably 2550-2950 rpm.
After said wet milling, the present invention preferably further comprises: and (3) drying, collecting, depolymerizing and breaking up the wet-milled material obtained by wet milling in sequence to obtain the superfine modified magnesium hydroxide.
In the present invention, the drying is preferably flash drying.
The present invention is not particularly limited to the collection so that the flash-dried product can be collected.
In the present invention, the depolymerization break-up is preferably: the powder enters a depolymerization and scattering machine for depolymerization and scattering through a spiral reamer feeder. In the invention, the depolymerization and scattering effectively prevent the powder from agglomerating and maintain the particle size of primary particles.
In the invention, the mesh number of the superfine modified magnesium hydroxide is more than or equal to 8000 meshes.
The invention adopts a wet grinding process, and controls the solid content of slurry, the material, the grain diameter and the filling amount of grinding balls in wet grinding, so that the wet grinding can break through the limit of the traditional dry grinding and can grind and produce ultrafine magnesium hydroxide with more than 8000 meshes; furthermore, the invention sets specific grinding temperature, stirring speed and material dosage proportion to better produce the superfine modified magnesium hydroxide with more than 8000 meshes.
The invention also provides the superfine modified magnesium hydroxide obtained by the preparation method of the technical scheme, and the mesh number of the superfine modified magnesium hydroxide is more than or equal to 8000 meshes. In the invention, the coating rate of the superfine modified magnesium hydroxide is preferably more than or equal to 98 percent.
The invention also provides the application of the superfine modified magnesium hydroxide in the technical scheme as a flame retardant.
The present invention is not particularly limited to the above applications, and those known to those skilled in the art can be used.
The invention also provides a flame-retardant polyolefin cable material which comprises the following components in parts by mass:
55-65 parts of superfine modified magnesium hydroxide, 20-25 parts of ethylene-vinyl acetate copolymer, 10-15 parts of linear low-density polyethylene, 6-12 parts of ethylene-octene thermoplastic elastomer of metallocene catalyst and 4-8 parts of compatilizer;
the superfine modified magnesium hydroxide is the superfine modified magnesium hydroxide in the technical scheme.
The flame-retardant polyolefin cable material comprises, by mass, 55-65 parts of superfine modified magnesium hydroxide, preferably 56-64 parts, and more preferably 57-63 parts. In the invention, the superfine modified magnesium hydroxide in the composition of the flame-retardant polyolefin cable material is the same as the superfine modified magnesium hydroxide in the technical scheme, and is not described herein again.
Based on the mass parts of the superfine modified magnesium hydroxide, the flame-retardant polyolefin cable material provided by the invention comprises 20-25 parts of ethylene-vinyl acetate copolymer (EVA), preferably 20.5-54.5 parts, and more preferably 21-24 parts. In the invention, the melt index of the ethylene-vinyl acetate copolymer is preferably 2-6 g/10min, and more preferably 2.5-5.5 g/10 min; the density is preferably 0.92 to 0.96g/cm3More preferably 0.93 to 0.95g/cm3。
Based on the mass parts of the superfine modified magnesium hydroxide, the flame-retardant polyolefin cable material provided by the invention comprises 10-15 parts of Linear Low Density Polyethylene (LLDPE), preferably 10.5-14.5 parts, and more preferably 11-14 parts. In the present invention, the density of the linear low density polyethylene is preferably 0.92 to 0.95g/cm3More preferably 0.93 to 0.94g/cm3(ii) a The melt index is preferably 2 to 6g/10min, more preferably 2.5 to 5.5g/10 min.
Based on the mass parts of the superfine modified magnesium hydroxide, the flame-retardant polyolefin cable material provided by the invention comprises 6-12 parts of metallocene catalyst ethylene-octene thermoplastic elastomer (POE), preferably 6.5-11.5 parts, and more preferably 7-11 parts. In the invention, the melt index of the ethylene-octene thermoplastic elastomer is preferably 2-4 g/10min, and more preferably 2.5-3.5 g/10 min; the density is preferably 0.88 to 0.92g/cm3More preferably 0.89 to 0.91g/cm3。
Based on the mass parts of the superfine modified magnesium hydroxide, the flame-retardant polyolefin cable material provided by the invention comprises 4-8 parts of a compatilizer, preferably 4.5-7.5 parts, and more preferably 5-7 parts. In the present invention, the compatibilizer is preferably a maleic anhydride graft. In the invention, the melt index of the compatilizer is preferably 2-4 g/10min, and more preferably 2.5-3.5 g/10 min; the density is preferably 0.92 to 0.95g/cm3More preferably 0.93 to 0.94g/cm3。
The flame-retardant polyolefin cable material is not particularly limited in use, and can be used by methods well known to those skilled in the art.
In order to further illustrate the present invention, the following examples are provided to describe the ultrafine modified magnesium hydroxide, its preparation method and application, and the flame retardant polyolefin cable material in detail, but they should not be construed as limiting the scope of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Mixing brucite raw ore with the particle size of 5-10 mm and the MgO content of 62 wt.% and sodium polyacrylate according to the mass ratio of 1000: 2, mixing, and carrying out dry grinding in a 198 type ring roller mill at a stirring speed of 1250rpm to obtain dry grinding particles with the mesh number of more than or equal to 400;
mixing the dry-milled particles, a dispersing agent, triethanolamine, a composite modifier and water to obtain wet-milled slurry with the solid content of 77%, wherein the mass ratio of the dry-milled particles to the triethanolamine to the dispersing agent to the composite modifier is 1000: 3: 4: 6, the dispersant is sodium polycarboxylate and sodium dodecyl benzene sulfonate according to the mass ratio of 3: 1, and the composite modifier is a silane coupling agent, a phosphate ester rare earth coupling agent and trimethyl silicon caprylate sulfonate according to a mass ratio of 3: 1: 2;
controlling the obtained wet grinding slurry at 110-120 ℃, and carrying out wet grinding for 2h under the stirring rotation speed condition of 2800rpm, wherein grinding balls used in the wet grinding are large ceramic balls, medium ceramic balls and small ceramic balls; the particle size of the large ceramic balls is 1.5-2 mm, and the filling rate in a cavity of wet grinding equipment is 13%; the particle size of the medium ceramic ball is 1.3-1.8 mm, and the filling rate in a cavity of wet grinding equipment is 16%; the particle size of the small ceramic balls is 0.8-1.2 mm, and the filling rate in a cavity of wet grinding equipment is 26%; and carrying out flash drying, collection, depolymerization and scattering on the obtained slurry with the mesh number of more than or equal to 8000 to obtain the superfine modified magnesium hydroxide with the mesh number of more than or equal to 8000.
Scanning electron microscopy tests were performed on the ultra-fine modified magnesium hydroxide obtained in example 1, and the SEM image obtained is shown in FIG. 1. As can be seen from FIG. 1, the diameters of the ultrafine modified magnesium hydroxide particles are less than or equal to 2 μm.
Example 2
Mixing brucite raw ore with the particle size of 5-10 mm and the MgO content of 62 wt.% and sodium polyacrylate according to the mass ratio of 1000: 3, mixing, and carrying out dry grinding in a 198 type ring roller mill at a stirring speed of 1250rpm to obtain dry grinding particles with the mesh number of more than or equal to 400;
mixing the dry-milled particles, a dispersing agent, triethanolamine, a composite modifier and water to obtain wet-milled slurry with the solid content of 77%, wherein the mass ratio of the dry-milled particles to the triethanolamine to the dispersing agent to the composite modifier is 1000: 4: 5: 9, the dispersant is sodium polycarboxylate and sodium dodecyl benzene sulfonate according to a mass ratio of 4: 1, and the composite modifier is a silane coupling agent, a phosphate ester rare earth coupling agent and trimethyl silicon caprylate sulfonate according to a mass ratio of 4: 2: 3;
controlling the obtained wet grinding slurry at 110-120 ℃, and carrying out wet grinding for 2h under the stirring rotation speed condition of 2800rpm, wherein grinding balls used in the wet grinding are large ceramic balls, medium ceramic balls and small ceramic balls; the particle size of the large ceramic balls is 1.5-2 mm, and the filling rate in a cavity of wet grinding equipment is 13%; the particle size of the medium ceramic ball is 1.3-1.8 mm, and the filling rate in a cavity of wet grinding equipment is 16%; the particle size of the small ceramic balls is 0.8-1.2 mm, and the filling rate in a cavity of wet grinding equipment is 26%; and carrying out flash drying, collection, depolymerization and scattering on the obtained slurry with the mesh number of more than or equal to 8000 to obtain the superfine modified magnesium hydroxide with the mesh number of more than or equal to 8000.
Example 3
Mixing brucite raw ore with the particle size of 5-10 mm and the MgO content of 62 wt.% and sodium polyacrylate according to the mass ratio of 1000: 4, mixing, and carrying out dry grinding in a 198 type ring roller mill at a stirring speed of 1250rpm to obtain dry grinding particles with the mesh number of more than or equal to 400;
mixing the dry-milled particles, a dispersing agent, triethanolamine, a composite modifier and water to obtain wet-milled slurry with the solid content of 77%, wherein the mass ratio of the dry-milled particles to the triethanolamine to the dispersing agent to the composite modifier is 1000: 5: 6: 12, the dispersing agent is sodium polycarboxylate and sodium dodecyl benzene sulfonate according to the mass ratio of 5: 1, and the composite modifier is a silane coupling agent, a phosphate ester rare earth coupling agent and trimethyl silicon caprylate sulfonate according to a mass ratio of 5: 3: 4;
controlling the obtained wet grinding slurry at 110-120 ℃, and carrying out wet grinding for 2h under the stirring rotation speed condition of 2800rpm, wherein grinding balls used in the wet grinding are large ceramic balls, medium ceramic balls and small ceramic balls; the particle size of the large ceramic balls is 1.5-2 mm, and the filling rate in a cavity of wet grinding equipment is 13%; the particle size of the medium ceramic ball is 1.3-1.8 mm, and the filling rate in a cavity of wet grinding equipment is 16%; the particle size of the small ceramic balls is 0.8-1.2 mm, and the filling rate in a cavity of wet grinding equipment is 26%; and carrying out flash drying, collection, depolymerization and scattering on the obtained slurry with the mesh number of more than or equal to 8000 to obtain the superfine modified magnesium hydroxide with the mesh number of more than or equal to 8000.
Index tests were performed on the ultrafine modified magnesium hydroxide obtained in examples 1 to 3, and the test methods and test results are shown in table 1.
TABLE 1 results of index test of ultrafine modified magnesium hydroxide obtained in examples 1 to 3
Test method Example 1 Example 2 Example 3
MgO content (%) HG/T 3607-2007 62.9 63.2 63.4
Whiteness (degree) GB/T 19281-2014 93.7 93.6 93.5
Oil absorption number (mL/100g) GB/T 19281-2014 33 32 31
D50(μm) GB/T 19077-2016 1.56 1.53 1.52
D90(μm) GB/T 19077-2016 2.55 2.52 2.49
BET specific surface area (m)2/g) GB/T 19587-2017 22.12 22.28 22.77
Coating ratio (%) By X-ray photoelectron spectroscopy 98.1 98.3 98.5
Moisture (%) GB/T 19281-2014 0.21 0.19 0.18
Fe2O3(％) GB/T 19281-2014 Not detected out Not detected out Not detected out
Mn2+(％) GB/T 19281-2014 Not detected out Not detected out Not detected out
Cr6+(％) GB/T 19281-2014 Not detected out Not detected out Not detected out
Pb2+(％) GB/T 19281-2014 Not detected out Not detected out Not detected out
Cd2+(％) GB/T 19281-2014 Not detected out Not detected out Not detected out
As can be seen from Table 1, the whiteness of the superfine modified magnesium hydroxide is 93.5-93.7, and the whiteness is high; the oil absorption value is 31-33 mL/100g, and the oil absorption value is low; d50 is 1.52 to 1.56 μm, D90 is 2.49 to 2.55 μm, and BET specific surface area is 22.12 to 22.77m2(iv) a small particle size and a large specific surface area; the coating rate is 98.1-98.5%, and the coating rate is high; the water content is 0.18-0.21%, and the water content is low; no Fe detected2O3、Mn2+、Cr6+、Pb2+And Cd2+And is environment-friendly.
Application example 1
The flame-retardant polyolefin cable material comprises the following components in parts by mass:
60 parts of superfine modified magnesium hydroxide prepared in example 1, 20 parts of ethylene-vinyl acetate copolymer, 10 parts of linear low-density polyethylene, 8 parts of metallocene catalyst ethylene-octene thermoplastic elastomer and 5 parts of compatilizer.
Application example 2
The superfine modified magnesium hydroxide prepared in the example 2 is used for replacing the superfine modified magnesium hydroxide prepared in the example 1, and the rest technical means are the same as those in the application example 1, so that the flame-retardant polyolefin cable material is obtained.
Application example 3
The superfine modified magnesium hydroxide prepared in the example 3 is used for replacing the superfine modified magnesium hydroxide prepared in the example 1, and the rest technical means are the same as those in the application example 1, so that the flame-retardant polyolefin cable material is obtained.
Comparative application example 1
Replacing the superfine modified magnesium hydroxide prepared in the example 1 with commercially available magnesium hydroxide, and obtaining the flame-retardant polyolefin cable material by the same technical means as the application example 1; wherein, the magnesium hydroxide sold in the market is purchased from the Dalian Yipu flame retardant material science and technology Limited company, the indexes are that D50 is 3.46 μm, and D97 is 14.76 μm.
The performance of the flame-retardant polyolefin cable material provided by the application examples 1-3 and the comparative application example 1 was tested, and the test results are shown in table 2.
Table 2 Performance test results of flame-retardant polyolefin cable materials of application examples 1-3 and comparative application example 1
Figure BDA0003465715600000111
As can be seen from Table 2, the flame-retardant polyolefin cable material prepared by using the superfine modified magnesium hydroxide provided by the invention has the surface glossiness of 96.5-98.1 degrees and high glossiness; the oxygen index is 38.8-39.5%, the maximum smoke density is 0.46-0.91 kg/m3, and the flame-retardant and smoke-suppression effect is good; the tensile strength is 14.8-15.5 MPa, the elongation at break is 196.2-204.9 MPa, the tensile property is high, and the mechanical property is excellent. Compared with comparative application example 1, the flame-retardant polyolefin cable material provided by the invention has better surface gloss, flame-retardant smoke-suppression performance and mechanical property, and shows that the superfine modified magnesium hydroxide provided by the invention has more excellent comprehensive performance than the magnesium hydroxide product on the market at present.
Comparative example 1
Mixing brucite raw ore with the particle size of 5-10 mm and the MgO content of 62 wt.% and sodium polyacrylate according to the mass ratio of 1000: 4, mixing, and carrying out dry grinding in a 198 type ring roller mill at a stirring speed of 1250rpm to obtain dry grinding particles with the mesh number of more than or equal to 400;
mixing the dry-milled particles, a dispersing agent, triethanolamine, a composite modifier and water to obtain wet-milled slurry with the solid content of 77%, wherein the mass ratio of the dry-milled particles to the triethanolamine to the dispersing agent to the composite modifier is 1000: 5: 6: 12, the dispersing agent is sodium polycarboxylate and sodium dodecyl benzene sulfonate according to the mass ratio of 5: 1, and the composite modifier is a silane coupling agent, a phosphate ester rare earth coupling agent and trimethyl silicon caprylate sulfonate according to a mass ratio of 5: 3: 4;
controlling the obtained wet grinding slurry at 110-120 ℃, and carrying out wet grinding for 2h under the stirring rotation speed condition of 2800rpm, wherein grinding balls used in the wet grinding are large ceramic balls, medium ceramic balls and small ceramic balls; the particle size of the large ceramic balls is 1.5-2 mm, and the filling rate in a cavity of wet grinding equipment is 18%; the particle size of the medium ceramic ball is 1.3-1.8 mm, and the filling rate in a cavity of wet grinding equipment is 19%; the particle size of the small ceramic balls is 0.8-1.2 mm, and the filling rate in a cavity of wet grinding equipment is 20%; and carrying out flash evaporation drying, collection, depolymerization and scattering on the obtained slurry to obtain the superfine modified magnesium hydroxide.
Comparative example 2
Mixing brucite raw ore with the particle size of 5-10 mm and the MgO content of 62 wt.% and sodium polyacrylate according to the mass ratio of 1000: 4, mixing, and carrying out dry grinding in a 198 type ring roller mill at a stirring speed of 1250rpm to obtain dry grinding particles with the mesh number of more than or equal to 400;
mixing the dry-milled particles, a dispersing agent, triethanolamine, a composite modifier and water to obtain wet-milled slurry with the solid content of 77%, wherein the mass ratio of the dry-milled particles to the triethanolamine to the dispersing agent to the composite modifier is 1000: 4: 8: 10, the dispersing agent is sodium polycarboxylate and sodium dodecyl benzene sulfonate according to the mass ratio of 5: 1, and the composite modifier is a silane coupling agent, a phosphate ester rare earth coupling agent and trimethyl silicon caprylate sulfonate according to a mass ratio of 5: 3: 4;
controlling the obtained wet grinding slurry at 110-120 ℃, and carrying out wet grinding for 2h under the stirring rotation speed condition of 2800rpm, wherein grinding balls used in the wet grinding are large ceramic balls, medium ceramic balls and small ceramic balls; the particle size of the large ceramic balls is 1.5-2 mm, and the filling rate in a cavity of wet grinding equipment is 13%; the particle size of the medium ceramic ball is 1.3-1.8 mm, and the filling rate in a cavity of wet grinding equipment is 16%; the particle size of the small ceramic balls is 0.8-1.2 mm, and the filling rate in a cavity of wet grinding equipment is 26%; and carrying out flash evaporation drying, collection, depolymerization and scattering on the obtained slurry to obtain the superfine modified magnesium hydroxide.
Comparative example 3
Mixing brucite raw ore with the particle size of 5-10 mm and the MgO content of 62 wt.% and sodium polyacrylate according to the mass ratio of 1000: 4, mixing, and carrying out dry grinding in a 198 type ring roller mill at a stirring speed of 1250rpm to obtain dry grinding particles with the mesh number of more than or equal to 400;
mixing the dry-milled particles, a dispersing agent, triethanolamine, a composite modifier and water to obtain wet-milled slurry with the solid content of 77%, wherein the mass ratio of the dry-milled particles to the triethanolamine to the dispersing agent to the composite modifier is 1000: 5: 6: 12, the dispersing agent is sodium polycarboxylate and sodium dodecyl benzene sulfonate according to the mass ratio of 5: 1, and the composite modifier is a silane coupling agent, a phosphate ester rare earth coupling agent and trimethyl silicon caprylate sulfonate according to a mass ratio of 3: 1: 2;
controlling the obtained wet grinding slurry at 110-120 ℃, and carrying out wet grinding for 2h under the stirring rotation speed condition of 2800rpm, wherein grinding balls used in the wet grinding are large ceramic balls, medium ceramic balls and small ceramic balls; the particle size of the large ceramic balls is 1.5-2 mm, and the filling rate in a cavity of wet grinding equipment is 13%; the particle size of the medium ceramic ball is 1.3-1.8 mm, and the filling rate in a cavity of wet grinding equipment is 16%; the particle size of the small ceramic balls is 0.8-1.2 mm, and the filling rate in a cavity of wet grinding equipment is 26%; and carrying out flash evaporation drying, collection, depolymerization and scattering on the obtained slurry to obtain the superfine modified magnesium hydroxide.
Indexes of the superfine modified magnesium hydroxide obtained in the comparative examples 1-3 are tested, and compared with the indexes in the example 3, the test method and the test result are shown in the table 3.
TABLE 3 results of index test of ultrafine modified magnesium hydroxide obtained in examples 1 to 3
Figure BDA0003465715600000131
Figure BDA0003465715600000141
As can be seen from Table 3, the superfine modified magnesium hydroxide of comparative examples 1-3 is obtained by adjusting the process parameters, and the phenomena of coarsening of the particle size, increase of the BET surface area and reduction of the coating rate of the superfine modified magnesium hydroxide product are found in comparative example 3, which proves that the technical means in the process are synergistic, important and necessary, and the technical effect is not simple and can be expected.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The preparation method of the superfine modified magnesium hydroxide is characterized by comprising the following steps:
mixing the brucite raw ore and a dry grinding aid, and carrying out dry grinding to obtain dry grinding particles, wherein the mesh number of the dry grinding particles is more than or equal to 400 meshes;
mixing the dry-milled particles, a dispersing agent, a wet-milled grinding aid, a composite modifier and water, and wet-milling the obtained wet-milled slurry to obtain the superfine modified magnesium hydroxide; the solid content of the wet grinding slurry is 75-80%;
the grinding ball for wet grinding is a ceramic ball; the ceramic balls comprise large ceramic balls, middle ceramic balls and small ceramic balls; the particle size of the large ceramic balls is 1.8-2.5 mm, and the filling rate in a cavity of wet grinding equipment is 12-15%; the particle size of the medium ceramic ball is 1.3-1.6 mm, and the filling rate in a cavity of wet grinding equipment is 15-18%; the particle size of the small ceramic balls is 0.8-1.2 mm, and the filling rate in a cavity of wet grinding equipment is 25-28%;
the composite modifier comprises a silane coupling agent, a phosphate ester rare earth coupling agent and trimethyl silicon caprylate sulfonate;
the mesh number of the superfine modified magnesium hydroxide is more than or equal to 8000 meshes.
2. The method of claim 1, wherein the dry-milled grinding aid comprises sodium polyacrylate;
the mass ratio of the brucite raw ore to the dry grinding auxiliary agent is 1000: (2-4).
3. The method of claim 1, wherein the wet grinding aid comprises triethanolamine.
4. The production method according to claim 1, wherein the mass ratio of the dry-milled particles to the wet-milling aid is 1000: (3-5).
5. The preparation method according to claim 1, wherein the composite modifier comprises a silane coupling agent, a phosphate ester rare earth coupling agent and trimethyl silicon caprylic acid sulfonate in a mass ratio of (3-5): (1-3): (2-4).
6. The production method according to claim 1, wherein the mass ratio of the dry-milled particles to the silane coupling agent is 1000: (3-5);
the mass ratio of the dry-milled particles to the phosphate rare earth coupling agent is 1000: (1-3);
the mass ratio of the dry-milled particles to the trimethyl silicon caprylate sulfonate is 1000: (2-4).
7. The preparation method according to claim 1, wherein the temperature of the wet-milling slurry in the wet milling is 110 to 120 ℃, and the stirring speed is 2500 to 3000 rpm.
8. The superfine modified magnesium hydroxide obtained by the preparation method of any one of claims 1 to 7, wherein the mesh number of the superfine modified magnesium hydroxide is more than or equal to 8000 meshes.
9. Use of the ultrafine modified magnesium hydroxide according to claim 8 as a flame retardant.
10. The flame-retardant polyolefin cable material is characterized by comprising the following components in parts by mass:
55-65 parts of superfine modified magnesium hydroxide, 20-25 parts of ethylene-vinyl acetate copolymer, 10-15 parts of linear low-density polyethylene, 6-12 parts of ethylene-octene thermoplastic elastomer of metallocene catalyst and 4-8 parts of compatilizer;
the ultrafine modified magnesium hydroxide according to claim 8.
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