CN117343401A - Preparation method of in-situ polymerization modified superfine magnesium hydroxide - Google Patents
Preparation method of in-situ polymerization modified superfine magnesium hydroxide Download PDFInfo
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- CN117343401A CN117343401A CN202311649090.2A CN202311649090A CN117343401A CN 117343401 A CN117343401 A CN 117343401A CN 202311649090 A CN202311649090 A CN 202311649090A CN 117343401 A CN117343401 A CN 117343401A
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- magnesium hydroxide
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- superfine magnesium
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 title claims abstract description 118
- 239000000347 magnesium hydroxide Substances 0.000 title claims abstract description 114
- 229910001862 magnesium hydroxide Inorganic materials 0.000 title claims abstract description 114
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 43
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 40
- 238000000576 coating method Methods 0.000 claims abstract description 120
- 239000011248 coating agent Substances 0.000 claims abstract description 113
- 230000004048 modification Effects 0.000 claims abstract description 53
- 238000012986 modification Methods 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims description 94
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 68
- 238000003756 stirring Methods 0.000 claims description 55
- 239000000126 substance Substances 0.000 claims description 28
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 27
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 27
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 22
- 235000021355 Stearic acid Nutrition 0.000 claims description 20
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 20
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 20
- 239000008117 stearic acid Substances 0.000 claims description 20
- 239000002002 slurry Substances 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 18
- 235000019441 ethanol Nutrition 0.000 claims description 16
- 239000011777 magnesium Substances 0.000 claims description 16
- 239000013118 MOF-74-type framework Substances 0.000 claims description 15
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 15
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 11
- WDFFWUVELIFAOP-UHFFFAOYSA-N 2,6-difluoro-4-nitroaniline Chemical compound NC1=C(F)C=C([N+]([O-])=O)C=C1F WDFFWUVELIFAOP-UHFFFAOYSA-N 0.000 claims description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 10
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 8
- 238000010902 jet-milling Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 238000010298 pulverizing process Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- 238000002203 pretreatment Methods 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims 1
- 238000001132 ultrasonic dispersion Methods 0.000 claims 1
- 239000003063 flame retardant Substances 0.000 abstract description 47
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 46
- 230000000694 effects Effects 0.000 abstract description 28
- 239000002245 particle Substances 0.000 abstract description 15
- 239000002861 polymer material Substances 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 11
- 238000003860 storage Methods 0.000 abstract description 9
- 230000007774 longterm Effects 0.000 abstract description 8
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 239000004743 Polypropylene Substances 0.000 description 36
- -1 polypropylene Polymers 0.000 description 27
- 239000004698 Polyethylene Substances 0.000 description 22
- 229920001155 polypropylene Polymers 0.000 description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 230000001276 controlling effect Effects 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 229920000573 polyethylene Polymers 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 238000003801 milling Methods 0.000 description 6
- 238000009776 industrial production Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000002715 modification method Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/028—Compounds containing only magnesium as metal
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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- C09C3/10—Treatment with macromolecular organic compounds
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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Abstract
The invention provides a preparation method of in-situ polymerization modified superfine magnesium hydroxide, belonging to the field of magnesium hydroxide modification. The preparation method of the in-situ polymerization modified superfine magnesium hydroxide comprises the following steps: pretreatment, modification treatment, crushing, primary coating and secondary coating. The preparation method of the in-situ polymerization modified superfine magnesium hydroxide has stable modification effect on the superfine magnesium hydroxide and small influence on the particle size uniformity of the superfine magnesium hydroxide; the modified magnesium hydroxide has small influence on the flame retardant property, and the flame retardant effect of the superfine magnesium hydroxide in the high polymer material is further improved; and further improves the stability of the modified superfine magnesium hydroxide and avoids the degradation of the modification effect in the long-term storage process.
Description
Technical Field
The invention relates to the field of magnesium hydroxide modification, in particular to a preparation method of in-situ polymerization modified superfine magnesium hydroxide.
Background
Superfine magnesium hydroxide is an inorganic nonmetallic material with important application value, and the chemical formula of the superfine magnesium hydroxide is Mg (OH) 2 Typically a white or yellowish solid powder. Ultrafine magnesium hydroxide has a crystal structure, belongs to the hexagonal system, and has a particle size generally in the micrometer scale. At present, the preparation method of the superfine magnesium hydroxide mainly comprises a chemical precipitation method, a microemulsion method, a hydrothermal method, an ultrasonic method and the like. The superfine magnesium hydroxide has higher specific surface area, so that the superfine magnesium hydroxide has higher chemical reaction activity; meanwhile, the superfine magnesium hydroxide also has good thermal stability, the decomposition temperature is 340 ℃, and the flame retardant property is good. In addition, the superfine magnesium hydroxide also has good electrical insulation and adsorption performance.
In the prior art, ultrafine magnesium hydroxide is widely applied to the fields of flame retardants, adsorbents, carriers, catalysts and the like due to the unique physical and chemical properties. The superfine magnesium hydroxide can effectively prevent flame from burning and spreading when being used as a flame retardant due to the unique performance, and no toxic and harmful gas is generated in the flame retardant process, so that the superfine magnesium hydroxide has important significance in the application of the flame retardant field (particularly the flame retardant field of high polymer materials).
In order to further improve the flame retardant effect of the superfine magnesium hydroxide, the superfine magnesium hydroxide is generally subjected to surface modification treatment, and the compatibility of the superfine magnesium hydroxide and a high polymer material is improved by combining the superfine magnesium hydroxide with a surface modifier, so that the dispersibility of the superfine magnesium hydroxide in the high polymer material (such as PP, PE and the like) is improved, and the flame retardant effect of the superfine magnesium hydroxide is improved. The existing surface modification method of superfine magnesium hydroxide mainly comprises the following steps: chemical coating modification, coupling agent surface modification, hyper-dispersant surface modification, and the like. Among them, chemical coating modification is most widely used in industrial production.
However, the existing surface modification method of superfine magnesium hydroxide has the problem of unstable modification effect and uneven surface modification of superfine magnesium hydroxide; the particle size uniformity of the superfine magnesium hydroxide is greatly influenced; the flame-retardant effect of the superfine magnesium hydroxide in the high polymer material can be comprehensively influenced, so that the tensile strength, the elongation at break and the limiting oxygen index of the flame-retardant high polymer material are low, and the application requirements of the high-end field cannot be met. Further, the existing surface modification method of superfine magnesium hydroxide has the problem of low surface modification stability, and the problem of reduced surface modification effect of the superfine magnesium hydroxide is easy to occur in the long-term storage process.
Meanwhile, in order to obtain a better flame-retardant effect, the addition amount of the superfine magnesium hydroxide in the high polymer material is large, and effective reduction cannot be obtained.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides the preparation method of the in-situ polymerization modified superfine magnesium hydroxide, which has stable modification effect on the superfine magnesium hydroxide and small influence on the uniformity of the particle size of the superfine magnesium hydroxide; the modified magnesium hydroxide has small influence on the flame retardant property, and the flame retardant effect of the superfine magnesium hydroxide in the high polymer material is further improved; and further improves the stability of the modified superfine magnesium hydroxide and avoids the degradation of the modification effect in the long-term storage process.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the preparation method of the in-situ polymerization modified superfine magnesium hydroxide comprises the following steps: pretreatment, modification treatment, crushing, primary coating and secondary coating.
The pretreatment method comprises the steps of adding a silane coupling agent KH-550 and a silane coupling agent KH-570 into an ethanol solution, stirring for 10-20min, regulating the pH value to 4.5-5.5 by adopting acetic acid, heating to 35-40 ℃, and carrying out heat preservation and stirring for 1-2h to obtain a pretreatment liquid; then adding the superfine magnesium hydroxide into the pretreatment liquid with the volume of 1-1.5 times, stirring and heating to 50-60 ℃, and separating out solid matters after heat preservation and stirring for 2-3 hours at the stirring rotation speed of 400-500 rpm; transferring the solid into a filter press, and performing filter pressing treatment until the water content of the filter cake is 42-45wt% to obtain a pretreated substance.
In the pretreatment, the volume concentration of the ethanol solution is 15-17.5%;
the weight ratio of the silane coupling agent KH-550 to the silane coupling agent KH-570 to the ethanol solution is 0.8-0.9:2-2.5:100.
The modification treatment method comprises the steps of respectively placing MOF-74 (Mg) and ZIF-8 (Zn) in a vacuum drying oven, preserving heat at 120-130 ℃ for 80-90min under the vacuum degree of 0.08-0.09MPa, putting MOF-74 (Mg), ZIF-8 (Zn) and nano montmorillonite into absolute ethyl alcohol, uniformly dispersing by ultrasonic waves, and stirring at normal temperature for 20-40min to obtain a first liquid; putting polyvinyl alcohol PVA into deionized water, uniformly dispersing by ultrasonic waves, and stirring for 2-3 hours to prepare a second liquid; under the stirring condition, the first liquid is put into the second liquid with the volume of 0.9-1 time, and the stirring is carried out for 40-60min, so as to prepare modified slurry; and (3) putting the pretreated matter and the modified slurry into a high-speed mixer, controlling the mixing rotating speed to be 2000-2500rpm, mixing for 10-20min, transferring the materials in the high-speed mixer into a vacuum drying oven, and drying to constant weight at 80-85 ℃ under the environment of 0.05-0.07MPa of vacuum degree to obtain the modified matter.
In the modification treatment, the molecular weight of the polyvinyl alcohol PVA is 8000-10000;
in the first liquid, the weight ratio of MOF-74 (Mg), ZIF-8 (Zn), nano montmorillonite and absolute ethyl alcohol is 4-5:3-4:2-2.5:200-210;
in the second liquid, the concentration of the polyvinyl alcohol PVA is 2-2.5wt%;
the weight ratio of the pretreatment to the modified slurry is 1:0.18-0.2.
The method for pulverizing comprises the steps of putting the modified substances into a jet mill, controlling the pulverizing frequency to be 55-60Hz, pulverizing air pressure to be 0.65-0.75MPa, and performing jet milling treatment to obtain modified powder.
The primary coating method comprises the steps of adding acrylic acid, 2-hydroxyethyl methacrylate phosphate and stearic acid into absolute ethyl alcohol, uniformly dispersing by ultrasonic waves, and stirring for 20-30min; then continuously adding azodiisobutyronitrile, and uniformly stirring to obtain primary coating liquid; putting the modified powder into a high-speed mixer, preheating to 55-65 ℃ under the rotation speed condition of 700-800rpm, and preserving heat for 5-10 min; continuously adding the primary coating liquid, maintaining the temperature, stirring for 60-90min, and drying to obtain the primary coating.
In the primary coating, the weight ratio of the acrylic acid to the 2-hydroxyethyl methacrylate phosphate to the stearic acid to the absolute ethyl alcohol to the azodiisobutyronitrile is 2.5-3:1.6-1.8:2-2.5:85-90:0.2-0.25;
the volume of the modified powder and the primary coating liquid is 1:1.5-2.
The secondary coating method comprises the steps of putting the primary coating into a high-speed mixer, preheating to 130-140 ℃ under the rotation speed condition of 1300-1500rpm, controlling the spraying pressure to be 0.2-0.25MPa, and spraying secondary coating liquid; after the secondary coating liquid is sprayed, continuously mixing materials for 30-50min under the rotation speed of 2800-3000rpm, and separating by a ball mill grader to finish the preparation of the in-situ polymerization modified superfine magnesium hydroxide, thus obtaining the secondary coating.
In the secondary coating, the adding amount of the secondary coating liquid is 1.5-2.2% of the weight of the primary coating;
the preparation method of the secondary coating liquid comprises the steps of mixing vinyl triethoxysilane and stearic acid 1840 according to the weight ratio of 1:2-3, heating to 120-130 ℃, and preserving heat until the stearic acid 1840 is completely melted, and preserving heat to obtain the secondary coating liquid.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the preparation method of the in-situ polymerization modified superfine magnesium hydroxide, in the pretreatment process, specific pretreatment liquid is adopted to pretreat the superfine magnesium hydroxide, and then the pretreated product is obtained through filter pressing; in the modification treatment process, modified slurry prepared by matching the first liquid and the second liquid is combined with the pretreatment to prepare a modified substance; the preparation of the superfine magnesium hydroxide modified by in-situ polymerization is completed by primary coating and secondary coating of the crushed modified substances, and in the preparation process, the surface modification of the superfine magnesium hydroxide is uniform, the coating effect is good, the coating rate is high, and the influence on the particle size uniformity of the superfine magnesium hydroxide is small; meanwhile, the stability of the modification effect on the superfine magnesium hydroxide is good, the difference of relevant indexes of the final products prepared from different production batches is small, the product stability is good, and the preparation method is suitable for large-scale industrial production; aiming at the small influence on the flame retardant property of the modified magnesium hydroxide, the flame retardant effect of the superfine magnesium hydroxide in the high polymer material is further improved, and the addition amount of the superfine magnesium hydroxide in the high polymer material is reduced; furthermore, the stability of the modification of the superfine magnesium hydroxide is good, and the degradation of the modification effect in the long-term storage process is effectively avoided.
(2) By adopting the preparation method of the in-situ polymerization modified superfine magnesium hydroxide, the coating rate of the superfine magnesium hydroxide is 99.92-99.98%; the average particle diameter of the obtained secondary coating is 1.45-1.48 μm.
(3) Through experiments, the preparation method of the in-situ polymerization modified superfine magnesium hydroxide is repeatedly carried out for 10 times, and the maximum difference between the coating rate of the superfine magnesium hydroxide and a reference value in the 10 times of preparation is 0.07%; the maximum difference between the average particle diameter D50 and the reference value is 0.1 μm; the stability of the modification effect on the superfine magnesium hydroxide is good, the difference of the related indexes of the final products prepared from different production batches is small, the product stability is good, and the method is suitable for large-scale industrial production.
(4) By adopting the preparation method of the in-situ polymerization modified superfine magnesium hydroxide, the prepared secondary coating is used for flame retardant modification of the polypropylene PP, and when the vertical combustion grade of the prepared flame retardant polypropylene PP reaches UL 94V-1 level, the minimum addition amount of the secondary coating is 39.4wt%; the first ignition flame burning time in the vertical burning test can reach 4.9s; the tensile strength of the prepared flame-retardant polypropylene PP is 34.9-35.3MPa, the elongation at break is 119.8-120.6%, and the limiting oxygen index is 33.4-33.8%.
(5) By adopting the preparation method of the in-situ polymerization modified superfine magnesium hydroxide, the prepared secondary coating is used for flame retardant modification of polyethylene PE, and when the vertical combustion grade of the prepared flame retardant polyethylene PE reaches UL 94V-1 level, the minimum addition amount of the secondary coating is 41.0wt%; the flame burning time of the first ignition in the vertical burning test can reach 5.7s; the tensile strength of the prepared flame-retardant polyethylene PE is 22.0-22.3MPa, the elongation at break is 401.9-403.8%, and the limiting oxygen index is 32.0-32.4%.
(6) By adopting the preparation method of the in-situ polymerization modified superfine magnesium hydroxide, the prepared secondary coating is placed in a 45 ℃ temperature environment, and is used for flame retardant modification of polypropylene PP after standing and storage for 365 days, and when the vertical combustion grade of the prepared flame retardant polypropylene PP reaches UL 94V-1 level, the minimum addition amount of the secondary coating is 42.0wt%; the flame burning time of the first ignition in the vertical burning test can still reach 5.5s; the tensile strength of the prepared flame-retardant polypropylene PP is 33.6-34.1MPa, the elongation at break is 116.0-116.9%, and the limiting oxygen index is 31.7-32.2%.
Detailed Description
Specific embodiments of the present invention will now be described in order to provide a clearer understanding of the technical features, objects and effects of the present invention.
Example 1
The preparation method of the in-situ polymerization modified superfine magnesium hydroxide specifically comprises the following steps:
1. pretreatment of
Adding a silane coupling agent KH-550 and a silane coupling agent KH-570 into an ethanol solution, stirring for 10min, regulating the pH value to 4.5 by adopting acetic acid, heating to 35 ℃, and carrying out heat preservation and stirring for 1h to obtain a pretreatment liquid; then adding superfine magnesium hydroxide into the pretreatment liquid with the volume of 1 time, stirring and heating to 50 ℃, and separating out solid matters after heat preservation and stirring for 2 hours at the stirring rotation speed of 400 rpm; transferring the solid into a filter press, and performing filter pressing treatment until the water content of the filter cake is 42wt% to obtain a pretreated substance.
Wherein the volume concentration of the ethanol solution is 15%.
The weight ratio of the silane coupling agent KH-550 to the silane coupling agent KH-570 to the ethanol solution is 0.8:2:100.
2. Modification treatment
Placing MOF-74 (Mg) and ZIF-8 (Zn) in a vacuum drying oven respectively, preserving heat at 120 ℃ for 80min under the environment of 0.08MPa, putting MOF-74 (Mg), ZIF-8 (Zn) and nano montmorillonite into absolute ethyl alcohol, uniformly dispersing by ultrasonic waves, and stirring at normal temperature for 20min to obtain a first liquid; putting polyvinyl alcohol PVA into deionized water, uniformly dispersing by ultrasonic waves, and stirring for 2 hours to prepare a second liquid; under the stirring condition, the first liquid is put into the second liquid with the volume being 0.9 times of that of the first liquid, and the mixture is stirred for 40 minutes to prepare modified slurry; and (3) putting the pretreated substance and the modified slurry into a high-speed mixer, controlling the mixing rotating speed to be 2000rpm, mixing for 10min, transferring the materials in the high-speed mixer into a vacuum drying oven, and drying at 80 ℃ to constant weight under the environment of 0.05MPa of vacuum degree to obtain the modified substance.
Wherein the molecular weight of the polyvinyl alcohol PVA is 8000.
In the first liquid, the weight ratio of MOF-74 (Mg), ZIF-8 (Zn), nano montmorillonite and absolute ethyl alcohol is 4:3:2:200.
In the second liquid, the concentration of polyvinyl alcohol PVA was 2% by weight.
The weight ratio of the pretreatment to the modified slurry was 1:0.18.
3. Crushing
Putting the modified substance into a jet mill, controlling the milling frequency to be 55Hz and the milling air pressure to be 0.65MPa, and performing jet milling treatment to obtain modified powder.
4. Primary coating
Adding acrylic acid, 2-hydroxyethyl methacrylate phosphate and stearic acid into absolute ethyl alcohol, uniformly dispersing by ultrasonic, and stirring for 20min; then continuously adding azodiisobutyronitrile, and uniformly stirring to obtain primary coating liquid; putting the modified powder into a high-speed mixer, preheating to 55 ℃ under the condition of 700rpm, and preserving heat for 5min; continuously adding the primary coating liquid, keeping the temperature, stirring for 60min, and drying to obtain the primary coating.
Wherein the weight ratio of the acrylic acid to the 2-hydroxyethyl methacrylate phosphate to the stearic acid to the absolute ethyl alcohol to the azodiisobutyronitrile is 2.5:1.6:2:85:0.2.
The volume of the modified powder and the primary coating liquid is 1:1.5.
5. Secondary coating
Putting the primary coating into a high-speed mixer, preheating to 130 ℃ under the rotation speed of 1300rpm, controlling the injection pressure to be 0.2MPa, and injecting secondary coating liquid; after the secondary coating liquid is sprayed, continuously mixing for 30min under the condition of 2800rpm, separating by a ball mill grader, and preparing the in-situ polymerization modified superfine magnesium hydroxide to obtain the secondary coating.
Wherein the addition amount of the secondary coating liquid is 1.5% of the weight of the primary coating.
The preparation method of the secondary coating liquid comprises the steps of mixing vinyl triethoxysilane and stearic acid 1840 according to the weight ratio of 1:2, heating to 120 ℃, and preserving heat until the stearic acid 1840 is completely melted, and preserving heat to obtain the secondary coating liquid.
Example 2
The preparation method of the in-situ polymerization modified superfine magnesium hydroxide specifically comprises the following steps:
1. pretreatment of
Adding a silane coupling agent KH-550 and a silane coupling agent KH-570 into an ethanol solution, stirring for 15min, regulating the pH value to 5 by adopting acetic acid, heating to 38 ℃, and carrying out heat preservation and stirring for 1.5h to obtain a pretreatment liquid; then adding superfine magnesium hydroxide into the pretreatment liquid with the volume of 1.3 times, stirring and heating to 55 ℃, and separating out solid matters after heat preservation and stirring for 2.5 hours at the stirring speed of 450 rpm; transferring the solid into a filter press, and performing filter pressing treatment until the water content of the filter cake is 43wt% to obtain a pretreated substance.
Wherein the volume concentration of the ethanol solution is 16.5%.
The weight ratio of the silane coupling agent KH-550 to the silane coupling agent KH-570 to the ethanol solution is 0.85:2.3:100.
2. Modification treatment
Placing MOF-74 (Mg) and ZIF-8 (Zn) in a vacuum drying oven respectively, preserving heat at 125 ℃ for 85min under the environment of 0.085MPa, putting MOF-74 (Mg), ZIF-8 (Zn) and nano montmorillonite into absolute ethyl alcohol, uniformly dispersing by ultrasonic waves, and stirring at normal temperature for 30min to obtain a first liquid; putting polyvinyl alcohol PVA into deionized water, uniformly dispersing by ultrasonic waves, and stirring for 2.5 hours to obtain a second liquid; under the stirring condition, the first liquid is put into the second liquid with the volume of 0.95 times, and the mixture is stirred for 50 minutes to prepare modified slurry; and (3) putting the pretreated substance and the modified slurry into a high-speed mixer, controlling the mixing rotating speed to be 2200rpm, mixing for 15min, transferring the materials in the high-speed mixer into a vacuum drying oven, and drying at 82 ℃ to constant weight under the environment of 0.06MPa of vacuum degree to obtain the modified substance.
Among them, the molecular weight of the polyvinyl alcohol PVA is 9000.
In the first liquid, the weight ratio of MOF-74 (Mg), ZIF-8 (Zn), nano montmorillonite and absolute ethyl alcohol is 4.5:3.5:2.3:205.
In the second liquid, the concentration of polyvinyl alcohol PVA was 2.2wt%.
The weight ratio of the pretreatment to the modified slurry was 1:0.19.
3. Crushing
Putting the modified substance into a jet mill, controlling the milling frequency to be 58Hz and the milling air pressure to be 0.7MPa, and performing jet milling treatment to obtain modified powder.
4. Primary coating
Adding acrylic acid, 2-hydroxyethyl methacrylate phosphate and stearic acid into absolute ethyl alcohol, uniformly dispersing by ultrasonic, and stirring for 25min; then continuously adding azodiisobutyronitrile, and uniformly stirring to obtain primary coating liquid; putting the modified powder into a high-speed mixer, preheating to 60 ℃ under the rotating speed of 750rpm, and preserving heat for 8 min; continuously adding the primary coating liquid, keeping the temperature, stirring for 75min, and drying to obtain the primary coating.
Wherein the weight ratio of the acrylic acid to the 2-hydroxyethyl methacrylate phosphate to the stearic acid to the absolute ethyl alcohol to the azodiisobutyronitrile is 2.8:1.7:2.3:88:0.23.
The volume of the modified powder and the primary coating liquid is 1:1.8.
5. Secondary coating
Putting the primary coating into a high-speed mixer, preheating to 135 ℃ under the rotating speed of 1400rpm, controlling the spraying pressure to be 0.22MPa, and spraying secondary coating liquid; after the secondary coating liquid is sprayed, continuously mixing materials for 40min under the rotating speed condition of 2900rpm, separating by a ball mill grader, and preparing the in-situ polymerization modified superfine magnesium hydroxide to obtain the secondary coating.
Wherein the addition amount of the secondary coating liquid is 2% of the weight of the primary coating.
The preparation method of the secondary coating liquid comprises the steps of mixing vinyl triethoxysilane and stearic acid 1840 according to the weight ratio of 1:2.5, heating to 125 ℃, and preserving heat until the stearic acid 1840 is completely melted, and preserving heat to obtain the secondary coating liquid.
Example 3
The preparation method of the in-situ polymerization modified superfine magnesium hydroxide specifically comprises the following steps:
1. pretreatment of
Adding a silane coupling agent KH-550 and a silane coupling agent KH-570 into an ethanol solution, stirring for 20min, regulating the pH value to 5.5 by adopting acetic acid, heating to 40 ℃, preserving heat and stirring for 2h to obtain a pretreatment liquid; then adding superfine magnesium hydroxide into the pretreatment liquid with the volume of 1.5 times, stirring and heating to 60 ℃, and separating out solid matters after heat preservation and stirring for 3 hours at the stirring speed of 500 rpm; transferring the solid into a filter press, and performing filter pressing treatment until the water content of the filter cake is 45wt% to obtain a pretreated substance.
Wherein the volume concentration of the ethanol solution is 17.5%.
The weight ratio of the silane coupling agent KH-550 to the silane coupling agent KH-570 to the ethanol solution is 0.9:2.5:100.
2. Modification treatment
Placing MOF-74 (Mg) and ZIF-8 (Zn) in a vacuum drying oven respectively, preserving heat at 130 ℃ for 90min under the environment of 0.09MPa, putting MOF-74 (Mg), ZIF-8 (Zn) and nano montmorillonite into absolute ethyl alcohol, uniformly dispersing by ultrasonic waves, and stirring at normal temperature for 40min to obtain a first liquid; putting polyvinyl alcohol PVA into deionized water, uniformly dispersing by ultrasonic waves, and stirring for 3 hours to prepare a second liquid; under the stirring condition, the first liquid is put into the second liquid with the same volume, and the mixture is stirred for 60 minutes to prepare modified slurry; and (3) putting the pretreated substance and the modified slurry into a high-speed mixer, controlling the mixing rotating speed to 2500rpm, mixing for 20min, transferring the materials in the high-speed mixer into a vacuum drying oven, and drying at 85 ℃ to constant weight under the environment of 0.07MPa of vacuum degree to obtain the modified substance.
Wherein the molecular weight of the polyvinyl alcohol PVA is 10000.
In the first liquid, the weight ratio of MOF-74 (Mg), ZIF-8 (Zn), nano montmorillonite and absolute ethyl alcohol is 5:4:2.5:210.
In the second liquid, the concentration of polyvinyl alcohol PVA was 2.5wt%.
The weight ratio of the pretreatment to the modified slurry was 1:0.2.
3. Crushing
Putting the modified substance into a jet mill, controlling the milling frequency to be 60Hz and the milling air pressure to be 0.75MPa, and performing jet milling treatment to obtain modified powder.
4. Primary coating
Adding acrylic acid, 2-hydroxyethyl methacrylate phosphate and stearic acid into absolute ethyl alcohol, uniformly dispersing by ultrasonic, and stirring for 30min; then continuously adding azodiisobutyronitrile, and uniformly stirring to obtain primary coating liquid; putting the modified powder into a high-speed mixer, preheating to 65 ℃ under the condition of 800rpm, and preserving heat for 10 min; continuously adding the primary coating liquid, keeping the temperature, stirring for 90min, and drying to obtain the primary coating.
Wherein the weight ratio of the acrylic acid to the 2-hydroxyethyl methacrylate phosphate to the stearic acid to the absolute ethyl alcohol to the azodiisobutyronitrile is 3:1.8:2.5:90:0.25.
The volume of the modified powder and the primary coating liquid is 1:2.
5. Secondary coating
Putting the primary coating into a high-speed mixer, preheating to 140 ℃ under the condition of 1500rpm, controlling the spraying pressure to be 0.25MPa, and spraying secondary coating liquid; after the secondary coating liquid is sprayed, the mixture is continuously mixed for 50min under the condition of 3000rpm, and then the mixture is separated by a ball mill grader, so that the preparation of the in-situ polymerization modified superfine magnesium hydroxide is completed, and the secondary coating is prepared.
Wherein the addition amount of the secondary coating liquid is 2.2% of the weight of the primary coating.
The preparation method of the secondary coating liquid comprises the steps of mixing vinyl triethoxysilane and stearic acid 1840 according to the weight ratio of 1:3, heating to 130 ℃, and preserving heat until the stearic acid 1840 is completely melted, and preserving heat to obtain the secondary coating liquid.
Comparative example 1
Comparative example 1 adopts the technical scheme of example 2, which is different in that: 1) Omitting a pretreatment step, and simultaneously adopting 0.57 weight parts of superfine magnesium hydroxide to replace a pretreatment substance in a modification treatment step, and mixing the superfine magnesium hydroxide with the modification slurry to prepare a modified substance; 2) The primary coating step is omitted.
Comparative example 2
Comparative example 2 the technical scheme of example 2 was adopted, with the following differences: 1) In the pretreatment step, the addition of a silane coupling agent KH-570 is omitted; 2) The modification treatment step is omitted, and the pretreated matter is directly used for the jet milling step after being dried.
The preparation methods of in-situ polymerization modified ultrafine magnesium hydroxide of examples 1-3 and comparative examples 1-2 were respectively used to prepare secondary coatings, and the coating rate of ultrafine magnesium hydroxide and the average particle diameter D50 of the secondary coatings were respectively examined, and the specific results are as follows:
the preparation method of the in-situ polymerization modified superfine magnesium hydroxide has the advantages of uniform surface modification of the superfine magnesium hydroxide, good coating effect and high coating rate; meanwhile, the influence on the particle size uniformity of the superfine magnesium hydroxide is small.
Further, the preparation method of the in-situ polymerization modified ultra-fine magnesium hydroxide of example 2 was continuously repeated 10 times, and the coating ratio of the ultra-fine magnesium hydroxide in each preparation and the average particle diameter D50 of the secondary coating were examined, respectively. The coating ratio and the average particle diameter D50 index of the above-mentioned example 2 were used as the reference value (i.e., the coating ratio was 99.98%, the average particle diameter D50 was 1.45 μm), the difference between the coating ratio and the average particle diameter D50 of the ultrafine magnesium hydroxide in each preparation and the reference value was calculated, and the maximum value was retained after taking the absolute value. The stability of the modification effect of the preparation method of the in-situ polymerization modified superfine magnesium hydroxide on the superfine magnesium hydroxide is reflected by the maximum fluctuation value of the coating rate and the average particle diameter D50 in the 10 preparation. The specific results are as follows:
the preparation method of the in-situ polymerization modified superfine magnesium hydroxide has the advantages of good stability of the modification effect of the superfine magnesium hydroxide, small difference of relevant indexes of the final products prepared from different production batches, good product stability and suitability for large-scale industrial production.
Further, the secondary coatings prepared in examples 1-3 and comparative examples 1-2 were used for flame retardant modification of polypropylene PP and polyethylene PE, respectively. Specifically, the preparation method of the in-situ polymerization modified superfine magnesium hydroxide is characterized in that the prepared secondary coating is respectively added into flame retardant modification of polypropylene PP and polyethylene PE, when the vertical combustion grade of the prepared flame retardant polypropylene PP and flame retardant polyethylene PE reaches UL 94V-1 level, the minimum addition amount of the secondary coating is detected, and the flame combustion time of first ignition in a vertical combustion test is recorded; meanwhile, the flame-retardant polypropylene PP and the flame-retardant polyethylene PE are manufactured into detection sheets with the thickness of 1mm, and the tensile strength, the elongation at break and the limiting oxygen index of the flame-retardant polypropylene PP and the flame-retardant polyethylene PE are respectively detected.
The specific results of flame retardant polypropylene PP are as follows:
the specific results of the flame retardant polyethylene PE are as follows:
the preparation method of the in-situ polymerization modified superfine magnesium hydroxide can avoid the influence of modification on the flame retardant property of the magnesium hydroxide, effectively improve the flame retardant effect of the superfine magnesium hydroxide in PP and PE, reduce the addition amount of the superfine magnesium hydroxide in a high polymer material, and has the advantages of low addition amount when the vertical combustion grade reaches V-1 level, high limiting oxygen index, and no obvious attenuation of the physical properties (such as tensile strength and elongation at break) of the flame retardant polypropylene PP and the flame retardant polyethylene PE.
Further, the secondary coating prepared in the examples 1-3 and the comparative examples 1-2 are respectively placed in a temperature environment of 45 ℃, kept stand and stored for 365 days, and then used for flame retardant modification of polypropylene PP, when the vertical burning grade of the prepared flame retardant polypropylene PP reaches UL 94V-1 grade, the minimum addition amount of the secondary coating after long-term storage is detected, and the flame burning time of first ignition in a vertical burning test is recorded; meanwhile, the flame-retardant polypropylene PP is manufactured into a detection sheet with the thickness of 1mm, and the tensile strength, the elongation at break and the limiting oxygen index of the flame-retardant polypropylene PP are respectively detected. The specific results are as follows:
the preparation method of the in-situ polymerization modified superfine magnesium hydroxide has good stability for modifying the superfine magnesium hydroxide, and effectively avoids the degradation of the modification effect in the long-term storage process; in a higher temperature environment, the flame retardant property is less attenuated after long-term storage.
In summary, it can be seen that the preparation method of the in-situ polymerization modified superfine magnesium hydroxide of the invention obtains a pretreated substance by adopting a specific pretreatment liquid to pretreat the superfine magnesium hydroxide in the pretreatment process and then press-filtering; in the modification treatment process, modified slurry prepared by matching the first liquid and the second liquid is combined with the pretreatment to prepare a modified substance; the preparation of the superfine magnesium hydroxide modified by in-situ polymerization is completed by primary coating and secondary coating of the crushed modified substances, and in the preparation process, the surface modification of the superfine magnesium hydroxide is uniform, the coating effect is good, the coating rate is high, and the influence on the particle size uniformity of the superfine magnesium hydroxide is small; meanwhile, the stability of the modification effect on the superfine magnesium hydroxide is good, the difference of relevant indexes of the final products prepared from different production batches is small, the product stability is good, and the preparation method is suitable for large-scale industrial production; aiming at the small influence on the flame retardant property of the modified magnesium hydroxide, the flame retardant effect of the superfine magnesium hydroxide in the high polymer material is further improved, and the addition amount of the superfine magnesium hydroxide in the high polymer material is reduced; furthermore, the stability of the modification of the superfine magnesium hydroxide is good, and the degradation of the modification effect in the long-term storage process is effectively avoided.
The percentages used in the present invention are mass percentages unless otherwise indicated.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the in-situ polymerization modified superfine magnesium hydroxide is characterized by comprising the following steps of: pretreatment, modification treatment, crushing, primary coating and secondary coating;
the pretreatment method comprises the steps of putting superfine magnesium hydroxide into pretreatment liquid, stirring and heating to 50-60 ℃, preserving heat and stirring for 2-3 hours, and separating out solid matters; filter-pressing the solid until the water content of the filter cake is 42-45wt% to obtain a pretreated substance;
the pretreatment liquid is ethanol solution of a silane coupling agent KH-550 and a silane coupling agent KH-570;
the modification treatment method comprises the steps of preserving heat of MOF-74 (Mg) and ZIF-8 (Zn) at 120-130 ℃ in a vacuum environment, adding MOF-74 (Mg), ZIF-8 (Zn) and nano montmorillonite into absolute ethyl alcohol, uniformly dispersing by ultrasonic waves, and stirring at normal temperature to obtain a first liquid; adding polyvinyl alcohol into deionized water, uniformly dispersing by ultrasonic waves, and stirring to obtain a second liquid; under the stirring condition, the first liquid is put into the second liquid, and the mixture is stirred uniformly to prepare modified slurry; putting the pretreated matter and the modified slurry into a high-speed mixer, mixing and vacuum drying to obtain a modified matter;
the crushing method is that the modified substance is crushed to prepare modified powder;
the primary coating method comprises the steps of adding acrylic acid, 2-hydroxyethyl methacrylate phosphate and stearic acid into absolute ethyl alcohol, stirring after ultrasonic dispersion is uniform, and then continuously adding azodiisobutyronitrile, and stirring uniformly to obtain primary coating liquid; adding the modified powder into a high-speed mixer, continuously adding primary coating liquid at 55-65 ℃, preserving heat, stirring, and drying to obtain primary coating;
the secondary coating method comprises the steps of putting the primary coating into a high-speed mixer, and spraying secondary coating liquid under the conditions that the rotating speed is 1300-1500rpm and the temperature is 130-140 ℃; after the secondary coating liquid is sprayed, continuously mixing materials under the rotation speed condition of 2800-3000rpm, and performing ball milling classification to prepare the in-situ polymerization modified superfine magnesium hydroxide, thereby preparing the secondary coating.
2. The method for preparing the in-situ polymerization modified superfine magnesium hydroxide according to claim 1, wherein in the pretreatment, the preparation method of the pretreatment liquid comprises the steps of adding a silane coupling agent KH-550 and a silane coupling agent KH-570 into an ethanol solution, stirring, adjusting the pH value to 4.5-5.5, heating to 35-40 ℃, and carrying out heat preservation and stirring to obtain the pretreatment liquid;
the weight ratio of the silane coupling agent KH-550 to the silane coupling agent KH-570 to the ethanol solution is 0.8-0.9:2-2.5:100;
the volume concentration of the ethanol solution is 15-17.5%.
3. The method for preparing in-situ polymerization modified superfine magnesium hydroxide according to claim 1, wherein in the pretreatment, the volume ratio of superfine magnesium hydroxide to pretreatment liquid is 1:1-1.5.
4. The method for preparing in-situ polymerized modified ultrafine magnesium hydroxide according to claim 1, wherein in the modification treatment, the volume ratio of the first liquid to the second liquid is 1:0.9-1;
in the first liquid, the weight ratio of MOF-74 (Mg), ZIF-8 (Zn), nano montmorillonite and absolute ethyl alcohol is 4-5:3-4:2-2.5:200-210;
in the second liquid, the concentration of the polyvinyl alcohol is 2-2.5wt%;
the molecular weight of the polyvinyl alcohol is 8000-10000.
5. The method for preparing in-situ polymerized modified ultrafine magnesium hydroxide according to claim 1, wherein the weight ratio of the pretreatment to the modified slurry in the modification treatment is 1:0.18-0.2;
the mixing speed of the pretreated matters and the modified slurry in a high-speed mixer is 2000-2500rpm, and the mixing time is 10-20min.
6. The method for preparing in-situ polymerization modified superfine magnesium hydroxide according to claim 1, wherein in the pulverization, the pulverization frequency is controlled to be 55-60Hz, the pulverization air pressure is controlled to be 0.65-0.75MPa, and the modified powder is prepared by jet milling the modified substance.
7. The method for preparing in-situ polymerized modified superfine magnesium hydroxide according to claim 1, wherein in the primary coating, the mixing speed of the modified powder and the primary coating liquid is 700-800rpm, and the mixing time is 60-90min;
the volume of the modified powder and the primary coating liquid is 1:1.5-2.
8. The method for preparing in-situ polymerization modified superfine magnesium hydroxide according to claim 1, wherein the weight ratio of acrylic acid, 2-hydroxyethyl methacrylate phosphate, stearic acid, absolute ethyl alcohol and azodiisobutyronitrile in the primary coating is 2.5-3:1.6-1.8:2-2.5:85-90:0.2-0.25.
9. The method for preparing in-situ polymerization modified ultrafine magnesium hydroxide according to claim 1, wherein in the secondary coating, the spraying pressure of the secondary coating liquid is 0.2 to 0.25MPa;
the addition amount of the secondary coating liquid is 1.5-2.2% of the weight of the primary coating.
10. The method for preparing the in-situ polymerization modified superfine magnesium hydroxide according to claim 1, wherein in the secondary coating, the preparation method of the secondary coating liquid is that the vinyl triethoxysilane and the stearic acid 1840 are mixed according to the weight ratio of 1:2-3, then heated to 120-130 ℃, and the temperature is kept until the stearic acid 1840 is completely melted, and the secondary coating liquid is prepared.
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| KUNPENG WANG等: "Superior extreme pressure properties of different layer LDH nanoplatelets used as boundary lubricants", 《APPLIED SURFACE SCIENCE》, pages 1 - 14 * |
| 刘生鹏: "原位共聚改性Mg（OH）2/PP复合材料的微观结构与性能", 《武汉工程大学学报》, pages 24 - 32 * |
| 吴湘锋;杨云峰;程国丽;胡国胜;: "氢氧化镁阻燃剂的表面改性", 中国粉体工业, no. 03, pages 11 - 13 * |
| 王乃军;谢辉;连媛;: "氢氧化镁阻燃剂的表面改性及应用研究", 科技视界, no. 04, pages 23 - 24 * |
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