CN117551306B - Magnesium-aluminum composite halogen-free flame retardant, preparation method and application - Google Patents
Magnesium-aluminum composite halogen-free flame retardant, preparation method and application Download PDFInfo
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- CN117551306B CN117551306B CN202410044558.3A CN202410044558A CN117551306B CN 117551306 B CN117551306 B CN 117551306B CN 202410044558 A CN202410044558 A CN 202410044558A CN 117551306 B CN117551306 B CN 117551306B
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 118
- 239000002131 composite material Substances 0.000 title claims abstract description 92
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 title claims abstract description 85
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 94
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 94
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 94
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 52
- 239000013078 crystal Substances 0.000 claims abstract description 52
- 230000004048 modification Effects 0.000 claims abstract description 23
- 238000012986 modification Methods 0.000 claims abstract description 23
- 239000002002 slurry Substances 0.000 claims description 58
- 238000000227 grinding Methods 0.000 claims description 56
- 239000000843 powder Substances 0.000 claims description 56
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 44
- 239000007788 liquid Substances 0.000 claims description 41
- 239000000395 magnesium oxide Substances 0.000 claims description 38
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 36
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 35
- 229910000077 silane Inorganic materials 0.000 claims description 35
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 32
- 239000002994 raw material Substances 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 239000003054 catalyst Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000003607 modifier Substances 0.000 claims description 29
- 239000003960 organic solvent Substances 0.000 claims description 28
- 238000005507 spraying Methods 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 27
- 230000036571 hydration Effects 0.000 claims description 24
- 238000006703 hydration reaction Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 23
- 229920005989 resin Polymers 0.000 claims description 22
- 239000011347 resin Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 20
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000010009 beating Methods 0.000 claims description 18
- 238000004321 preservation Methods 0.000 claims description 16
- 238000010335 hydrothermal treatment Methods 0.000 claims description 14
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 14
- 239000011654 magnesium acetate Substances 0.000 claims description 14
- 235000011285 magnesium acetate Nutrition 0.000 claims description 14
- 229940069446 magnesium acetate Drugs 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- 238000004537 pulping Methods 0.000 claims description 14
- 238000001238 wet grinding Methods 0.000 claims description 14
- 239000012065 filter cake Substances 0.000 claims description 12
- 239000000376 reactant Substances 0.000 claims description 12
- 239000008234 soft water Substances 0.000 claims description 12
- 238000011049 filling Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 238000013329 compounding Methods 0.000 claims description 5
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 229920001529 polyepoxysuccinic acid Polymers 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 229920002545 silicone oil Polymers 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 230000001276 controlling effect Effects 0.000 claims 8
- 230000001105 regulatory effect Effects 0.000 claims 1
- 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 53
- 239000000463 material Substances 0.000 abstract description 38
- 239000002952 polymeric resin Substances 0.000 abstract description 12
- 229920003002 synthetic resin Polymers 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 229910052736 halogen Inorganic materials 0.000 abstract description 5
- 150000002367 halogens Chemical class 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 16
- 239000012752 auxiliary agent Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000000779 smoke Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- -1 polyoxyethylene Polymers 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000004080 punching Methods 0.000 description 4
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000011895 specific detection Methods 0.000 description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 2
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011218 binary composite Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
Classifications
-
- 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
- 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
-
- 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
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- 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
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention provides a magnesium-aluminum composite halogen-free flame retardant, a preparation method and application thereof, and relates to the field of halogen-free flame retardants. The preparation method of the magnesium-aluminum composite halogen-free flame retardant comprises the following steps: and (3) preparing superfine special crystal form high-purity magnesium hydroxide and carrying out magnesium-aluminum composite modification. The magnesium-aluminum composite halogen-free flame retardant can effectively realize composite synergistic flame retardance of aluminum hydroxide and magnesium hydroxide, and has good thermal stability, extremely low halogen content and high use cost performance; the magnesium-aluminum composite halogen-free flame retardant has good dispersibility in high polymer resin and compatibility, can further improve the flame retardant property and mechanical property of the flame retardant material prepared by application, and reduces the production cost of the flame retardant material.
Description
Technical Field
The invention relates to the field of halogen-free flame retardants, in particular to a magnesium-aluminum composite halogen-free flame retardant, a preparation method and application thereof.
Background
Aluminum hydroxide and magnesium hydroxide are two common halogen-free flame retardants at present, have the advantages of low cost, high efficiency, smoke suppression and the like, and have wide application in various fields, such as wires and cables, coating materials and the like, but the flame retardant efficiency, filling performance and the like of single-component magnesium hydroxide or aluminum hydroxide are required to be further improved.
The magnesium-aluminum composite flame retardant has good thermal stability and chemical stability, can have triple functions of flame retardance, smoke abatement and polymer filling, has high cost performance, and has wide application in the prior art. The low-smoke halogen-free cable material prepared by adding the magnesium-aluminum composite flame retardant into the polymer resin has the advantages of good flame retardant property, high tensile strength, high elongation at break strength, good machining property and the like, and can be effectively applied to the fields of low-smoke halogen-free cable materials, PVC plastic fabrics, PET plastics and the like. The magnesium-aluminum composite flame retardant has the advantages that: because the properties of the aluminum hydroxide and the magnesium hydroxide are different, the low-smoke halogen-free cable material product prepared by only using the aluminum hydroxide has low tensile strength, low oxygen index and poor flame retardant property, but has high elongation at break and high melt index; the low-smoke halogen-free cable material product prepared by only using magnesium hydroxide has low elongation at break, low melt index, high tensile strength, high oxygen index and excellent flame retardant property. After magnesium hydroxide and aluminum hydroxide are compounded to prepare the magnesium aluminum composite flame retardant, the defects of magnesium hydroxide or aluminum hydroxide with single component can be effectively overcome, and the low-smoke halogen-free cable material product prepared by adopting the magnesium hydroxide or aluminum hydroxide composite flame retardant has high tensile strength, high elongation at break, high melt index and good processability; meanwhile, the flame retardant has the characteristics of high oxygen index, small combustion smoke amount and good flame retardant property, and is an important development direction of inorganic flame retardants at present.
In the existing preparation of flame-retardant cable material particles, in order to overcome the defect of single-component magnesium hydroxide or aluminum hydroxide in flame retardance, the magnesium hydroxide and the aluminum hydroxide are generally added into high-molecular polymer resin directly according to a certain compounding proportion in a direct adding mode, so that the preparation method is complex in operation steps, complex in process and low in production efficiency; meanwhile, the thermal decomposition temperature (initial dehydration temperature) of aluminum hydroxide is 180-200 ℃, the thermal decomposition temperature after modification treatment is about 240 ℃, the thermal decomposition temperature of magnesium hydroxide is 340-380 ℃, and the two decomposition temperatures are not matched, so that the aluminum hydroxide and the magnesium hydroxide in the flame-retardant cable material prepared by the method cannot be effectively compounded and synergistically flame-retardant, the thermal stability is poor, and the actual flame-retardant effect needs to be further improved; in addition, the compatibility of magnesium hydroxide, aluminum hydroxide and high polymer resin is not ideal, and the prepared flame-retardant cable material has poor performance; and the halogen content in the flame-retardant cable material is high, the application safety is poor, and the environmental friendliness is poor.
In the existing special flame-retardant field (such as PVC plastic tape, etc.), although only magnesium hydroxide can be used to achieve the flame-retardant performance of the product, the special field has strict requirements on the specification of the magnesium hydroxide flame retardant used and high production cost; and the mechanical properties of the product can be influenced by the magnesium hydroxide flame retardant.
Furthermore, the dispersibility and compatibility of the existing magnesium-aluminum composite flame retardant in high polymer resin, and the flame retardant property and mechanical property of the prepared flame retardant material are required to be further improved.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides the preparation method of the magnesium-aluminum composite halogen-free flame retardant, which can effectively realize the composite synergistic flame retardance of aluminum hydroxide and magnesium hydroxide, and has the advantages of good thermal stability, extremely low halogen content and high use cost performance; the magnesium-aluminum composite halogen-free flame retardant has good dispersibility in high polymer resin and compatibility, can further improve the flame retardant property and mechanical property of the flame retardant material prepared by application, and reduces the production cost of the flame retardant material.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the preparation method of the magnesium-aluminum composite halogen-free flame retardant comprises the following steps: preparing superfine special crystal form high-purity magnesium hydroxide and compounding and modifying magnesium and aluminum;
the preparation of the superfine special crystal form high-purity magnesium hydroxide takes high-purity magnesium oxide as a raw material, and hydration is carried out in the presence of magnesium acetate to obtain hydration slurry; in the presence of a grinding aid, carrying out wet grinding on the hydrated slurry until the particle size D50 is less than 2.0 mu m to obtain grinding slurry; carrying out hydrothermal treatment, washing and drying on the grinding slurry to obtain superfine special crystal form high-purity magnesium hydroxide;
in the superfine special crystal form high-purity magnesium hydroxide, the magnesium hydroxide content is more than or equal to 99.5 weight percent, the CaO content is less than or equal to 0.05 weight percent, the acid insoluble content is less than or equal to 0.05 weight percent, the moisture content is less than or equal to 0.5 weight percent, the chloride content is less than or equal to 0.1 weight percent, and the grain diameter D50 is less than or equal to 2.0 mu m;
the magnesium-aluminum composite modification is carried out, the superfine special crystal form high-purity magnesium hydroxide and aluminum hydroxide raw powder are uniformly mixed, under the stirring condition, a modifying liquid is added in a spraying way, and stirring is continued after the modifying liquid is added; then spraying and adding a catalyst, and after the catalyst is added, carrying out heat preservation and mixing reaction at 110-140 ℃ to obtain a reactant; evaporating and desolventizing the reactant, and drying to obtain the magnesium-aluminum composite halogen-free flame retardant;
the modifying liquid is an organic solvent in which a silane modifier is dissolved;
the silane modifier is at least one of the following: trimethoxyvinylsilane, vinyltriethoxysilane, vinyltris (beta-methoxyethoxy) silane, aminosilanes, functional silicones, polyether silicone oils;
the catalyst is a methanol solution in which tetramethyl ammonium hydroxide is dissolved.
Preferably, in the magnesium-aluminum composite modification, the stirring speed is 600-900r/min;
the spraying adding time of the modifying liquid is less than 5min;
the spraying adding time of the catalyst is less than 3min;
the temperature of 110-140 ℃ is kept for 60-90min for mixing reaction.
Preferably, in the magnesium-aluminum composite modification, the weight ratio of the silane modifier to the organic solvent in the modification liquid is 1:5-8;
the addition amount of the silane modifier in the modified liquid is 1-2.5% of the total weight of the superfine special crystal form high-purity magnesium hydroxide and the aluminum hydroxide raw powder;
the concentration of the tetramethylammonium hydroxide in the catalyst is 9-10wt%;
the addition amount of the tetramethyl ammonium hydroxide in the catalyst is 0.5-1.5% of the total weight of the superfine special crystal form high-purity magnesium hydroxide and the aluminum hydroxide raw powder.
Preferably, in the magnesium-aluminum composite modification, the silane modifier is any one of the following groups:
silane modifier 1: 50% by weight of trimethoxyvinylsilane and 50% by weight of vinyltriethoxysilane;
silane modifier 2: 50wt% of functional organic silicon and 50wt% of aminosilane;
silane modifier 3: 40wt% of vinyl triethoxysilane, 20wt% of polyether silicone oil and 40wt% of aminosilane;
the organic solvent is at least one of the following: absolute ethanol, acetone, carbon tetrachloride, diethyl ether and ethyl acetate.
Preferably, in the magnesium-aluminum composite modification, the organic solvent is a mixed solvent of any one of the following groups:
organic solvent 1: 50wt% of absolute ethyl alcohol and 50wt% of carbon tetrachloride;
organic solvent 2: 30wt% of absolute ethyl alcohol, 30wt% of carbon tetrachloride and 40wt% of ethyl acetate.
Further, the hydration is carried out, the crushed high-purity magnesia and soft water are put into a reaction kettle, magnesium acetate is added, and the mixture is stirred and reacts for 1.5 to 2 hours at the temperature of 85 to 95 ℃ to obtain hydration slurry;
the weight ratio of the crushed high-purity magnesium oxide to the crushed soft water is 1:5-6;
the addition amount of the magnesium acetate is 3-5% of the weight of the crushed high-purity magnesium oxide.
Further, in the wet grinding process, the grinding aid is added dropwise;
controlling the slurry viscosity to be less than 500 mPa.s in the grinding process by controlling the dropping speed of the grinding aid;
the grinding aid is any two of the following substances: sodium dodecyl benzene sulfonate, anionic polyacrylamide, polyepoxysuccinic acid and alkylphenol ethoxylates.
Further, the hydrothermal treatment is carried out, wherein sodium hydroxide solution is adopted to adjust the alkalinity of the grinding slurry to 0.2-0.3mol/L, the temperature is raised to 180-200 ℃, the heat preservation reaction is carried out for 10-12 hours, and the hydrothermal slurry is obtained;
the water washing, after the cooled hydrothermal slurry is pressed once by a filter press, adding a first part of deionized water, controlling the temperature to be 50-60 ℃, pulping once, controlling the pulping time to be 30-40min, and the stirring speed of primary pulping to be 300-500r/min, and then pressing twice by the filter press; adding a second part of deionized water after the secondary squeezing is finished, controlling the temperature to be 50-60 ℃, carrying out secondary beating, controlling the secondary beating time to be 30-40min, controlling the secondary beating stirring rotating speed to be 300-500r/min, then carrying out tertiary squeezing in a filter press, and controlling the water content of a filter cake obtained through the tertiary squeezing to be less than or equal to 50wt%;
and (3) drying the filter cake pressed for three times until the moisture content is less than or equal to 0.5wt%, so as to obtain the superfine special crystal form high-purity magnesium hydroxide.
The magnesium-aluminum composite halogen-free flame retardant is prepared by adopting the preparation method.
The application of the magnesium-aluminum composite halogen-free flame retardant fills the magnesium-aluminum composite halogen-free flame retardant into the polymer, and controls the filling amount of the magnesium-aluminum composite halogen-free flame retardant to be not less than 50wt%;
the polymer is one of the following:
a mixture of EVA resins and PE resins;
EVA resin, PE resin and POE resin.
Compared with the prior art, the invention has the beneficial effects that:
(1) In the preparation method of the magnesium-aluminum composite halogen-free flame retardant, high-purity magnesium oxide is taken as a raw material, hydration and wet grinding are carried out, then hydrothermal treatment is carried out, and then water washing and drying are carried out, thus preparing the superfine special crystal form high-purity magnesium hydroxide with specific specification; then compounding superfine special crystal form high-purity magnesium hydroxide with aluminum hydroxide, combining a modifier with the magnesium hydroxide and the aluminum hydroxide in a physical adsorption mode, and carrying out catalytic reaction on functional groups which are directly connected with silicon in silane molecules and hydroxyl groups on the surfaces of the magnesium hydroxide and the aluminum hydroxide by adopting a catalyst, wherein the composite synergistic flame retardance of the aluminum hydroxide and the magnesium hydroxide is effectively realized through the interaction between a nonpolar section of the silane and a molecular chain of a high polymer matrix, so that the thermal stability of the flame retardant is further improved, the halogen content is reduced, and the use cost performance is improved; meanwhile, the combination property of the magnesium-aluminum composite halogen-free flame retardant and the high polymer resin is further improved, and the flame retardant property and the mechanical property of the flame retardant material prepared by application are further improved under the condition that the filling amount exceeds 50 weight percent, so that the production cost of the flame retardant material is reduced.
(2) The magnesium-aluminum composite halogen-free flame retardant can be directly added into high polymer resin, so that the addition amount is easy to control, the addition process is simple, and the operation is easy; the magnesium-aluminum composite halogen-free flame retardant has good compatibility with the high polymer resin, and the prepared high polymer resin has good flame retardant property; and under the condition that the filling amount exceeds 50 weight percent, the mechanical property of the high polymer resin can be further improved.
(3) In the preparation of the magnesium-aluminum composite halogen-free flame retardant, the quality index of the adopted superfine special crystal form high-purity magnesium hydroxide is shown in the following table:
(4) The magnesium-aluminum composite halogen-free flame retardant is applied to a binary composite high polymer system of EVA resin and PE resin, and under the condition that the filling amount of the magnesium-aluminum composite halogen-free flame retardant can exceed 50wt%, the tensile strength of the prepared flame retardant polymer can reach 12.78-13.49MPa, the elongation at break can reach 181.45-206.74%, the melt index is 11.31-13.22g/10min, and the limiting oxygen index can reach 34-37%.
(5) The magnesium-aluminum composite halogen-free flame retardant is applied to ternary composite high polymer systems of EVA resin, PE resin and POE resin, and under the condition that the filling amount of the magnesium-aluminum composite halogen-free flame retardant can exceed 50wt%, the tensile strength of the prepared flame retardant polymer can reach 11.76-12.98MPa, the elongation at break can reach 367.25-498.52%, the melt index is 13.26-14.69g/10min, and the limiting oxygen index can reach 34-37%.
Drawings
FIG. 1 is an electron microscopic view of ultra-fine specific crystalline form of high purity magnesium hydroxide prepared in example 1.
In the graph, the maximum size of magnesium hydroxide raw powder crystal grain is less than 3 mu m, the particle diameter D50 of the magnesium hydroxide raw powder is 1.87 mu m, and the particle diameter D100 of the magnesium hydroxide raw powder is 7.62 mu m.
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 embodiment provides a preparation method of a magnesium-aluminum composite halogen-free flame retardant, which specifically comprises the following steps:
1. preparing superfine special crystal form high-purity magnesium hydroxide:
1) Crushing of raw materials
Mechanically crushing the high-purity magnesium oxide raw material to obtain magnesium oxide raw material powder with the particle size D50 of 4 mu m.
The high-purity magnesium oxide in the embodiment is purchased through a commercial channel, and the specific specification is as follows: 97.62wt% of magnesium oxide, 0.43% of chloride ion and a particle size D50:45.63 μm.
2) Hydration
Soft water and magnesia raw material powder are added into a reaction kettle, and a hydration auxiliary agent (magnesium acetate) is added. And (3) carrying out heat preservation and stirring reaction for 1.75h at the temperature of 90 ℃ to obtain hydrated slurry.
Wherein the weight ratio of the magnesium oxide raw material powder to the soft water is 1:5.5.
The addition amount of the hydration assistant (magnesium acetate) is 4% of the weight of the magnesium oxide raw material powder.
3) Wet milling
Wet grinding the hydrated slurry by using a grinding and peeling machine, and controlling the grinding particle diameter D50 to be less than 2.0 mu m to obtain grinding slurry; meanwhile, a grinding aid is dripped in the grinding process, and the viscosity of the slurry in the grinding process is controlled to be less than 500 mPa.s by controlling the dripping speed of the grinding aid.
Wherein the addition amount of the grinding aid is 1.3wt% (based on the weight of the magnesium hydroxide dry powder).
The grinding aid consists of the following materials in percentage by weight: 70wt% of sodium dodecyl benzene sulfonate and 30wt% of polyepoxysuccinic acid.
4) Hydrothermal treatment
Transferring the grinding slurry into a high-pressure reaction kettle, dropwise adding sodium hydroxide solution (the concentration is 30wt%) to adjust the alkalinity of the slurry to 0.25mol/L, heating the reaction kettle to 190 ℃ for hydrothermal treatment, and carrying out heat preservation reaction for 10.5h to obtain hydrothermal slurry; transferring the hydrothermal slurry into a cooling tank, and cooling until the temperature of the hydrothermal slurry is less than or equal to 60 ℃.
5) Washing:
after the cooled hydrothermal slurry is pressed once by a filter press, adding a first part of deionized water, controlling the temperature to be 55 ℃, pulping once, controlling the pulping time to be 35min, and performing secondary pressing by the filter press at the stirring rotating speed of 350 r/min; after the secondary squeezing is finished, adding a second part of deionized water, controlling the temperature to be 55 ℃, carrying out secondary beating, controlling the secondary beating time to be 35min, controlling the secondary beating stirring rotating speed to be 450r/min, then carrying out tertiary squeezing by a filter press, and controlling the water content of a filter cake obtained by the tertiary squeezing to be less than or equal to 50wt%.
Wherein the adding amount of the first deionized water is 22m 3 Per ton of magnesium hydroxide dry powder.
The addition amount of the second deionized water is 22m 3 Per ton of magnesium hydroxide dry powder.
6) Drying
And (3) drying the filter cake squeezed for three times by adopting a flash dryer, wherein the drying temperature is 160 ℃, and the moisture content of the dried material is controlled to be less than or equal to 0.5wt percent, so that the superfine special crystal form high-purity magnesium hydroxide is prepared.
The quality indexes of the superfine special crystal form high-purity magnesium hydroxide prepared by the embodiment are shown in the following table:
2. magnesium-aluminum composite modification:
uniformly mixing the prepared superfine special crystal form high-purity magnesium hydroxide and aluminum hydroxide raw powder according to the weight ratio of 6:4, heating to 90 ℃, and preserving heat; then spraying the modified liquid in a high-pressure spraying mode under the stirring condition of 750r/min, and controlling the modified liquid to be sprayed within 5min; continuously stirring for 25min after the spraying of the modifying liquid is completed; spraying the catalyst in a high-pressure spraying mode, and controlling the catalyst to be sprayed within 3min; then controlling the temperature to be 125 ℃, and carrying out heat preservation and mixing reaction for 80min to obtain a reactant; and evaporating the reactant to remove the organic solvent, and drying at 110 ℃ to obtain the magnesium-aluminum composite halogen-free flame retardant.
The aluminum hydroxide raw powder adopted in the embodiment is obtained through a commercial way, and the specific specification is as follows: particle diameter D50:1.74 μm, aluminum hydroxide content 99.56wt%, siO 2 The content of Fe is 0.02wt percent 2 O 3 The content was 0.015wt%.
The catalyst was a methanol solution in which tetramethylammonium hydroxide was dissolved, and the tetramethylammonium hydroxide concentration was 10wt%. The addition amount of the tetramethyl ammonium hydroxide in the catalyst is 0.9 percent of the total weight of the superfine special crystal form high-purity magnesium hydroxide and the aluminum hydroxide raw powder.
The modifying liquid is prepared by adding a silane modifying agent into an organic solvent for dissolution; the weight ratio of the silane modifier to the organic solvent is 1:6. The addition amount of the silane modifier in the modified liquid is 1.5 percent of the total weight of the superfine special crystal form high-purity magnesium hydroxide and the aluminum hydroxide raw powder.
The silane modifier in the modifying liquid consists of the following materials in percentage by weight: 50% by weight of trimethoxyvinylsilane and 50% by weight of vinyltriethoxysilane;
the organic solvent in the modified liquid consists of the following materials in percentage by weight: 50wt% of absolute ethyl alcohol and 50wt% of carbon tetrachloride.
The magnesium-aluminum composite halogen-free flame retardant prepared in the embodiment has the coating rate of 99.92wt%, the content of effective substances of 99.53wt%, the particle size of 1.78 mu m, the whiteness of 99.1 and the moisture content of 0.42wt%.
The embodiment also provides the magnesium-aluminum composite halogen-free flame retardant prepared by the method.
Example 2
The embodiment provides a preparation method of a magnesium-aluminum composite halogen-free flame retardant, which specifically comprises the following steps:
1. preparing superfine special crystal form high-purity magnesium hydroxide:
1) Crushing of raw materials
Mechanically crushing the high-purity magnesium oxide raw material to obtain magnesium oxide raw material powder with the particle size D50 of 4.5 mu m.
The high-purity magnesium oxide in the embodiment is purchased through a commercial channel, and the specific specification is as follows: 97.62wt% of magnesium oxide, 0.43% of chloride ion and a particle size D50:45.63 μm.
2) Hydration
Soft water and magnesia raw material powder are added into a reaction kettle, and a hydration auxiliary agent (magnesium acetate) is added. And (3) carrying out heat preservation and stirring reaction for 1.5h at the temperature of 85 ℃ to obtain hydrated slurry.
Wherein the weight ratio of the magnesium oxide raw material powder to the soft water is 1:5.
The addition amount of the hydration assistant (magnesium acetate) is 3% of the weight of the magnesium oxide raw material powder.
3) Wet milling
Wet grinding the hydrated slurry by using a grinding and peeling machine, and controlling the grinding particle diameter D50 to be less than 2.0 mu m to obtain grinding slurry; meanwhile, a grinding aid is dripped in the grinding process, and the viscosity of the slurry in the grinding process is controlled to be less than 500 mPa.s by controlling the dripping speed of the grinding aid.
Wherein the addition amount of the grinding aid is 1wt% (based on the weight of the magnesium hydroxide dry powder).
The grinding aid consists of the following materials in percentage by weight: 65wt% of anionic polyacrylamide and 35wt% of alkylphenol polyoxyethylene.
4) Hydrothermal treatment
Transferring the grinding slurry into a high-pressure reaction kettle, dropwise adding sodium hydroxide solution (the concentration is 30wt%) to adjust the alkalinity of the slurry to 0.2mol/L, heating the reaction kettle to 180 ℃ for hydrothermal treatment, and carrying out heat preservation reaction for 10h to obtain the hydrothermal slurry; transferring the hydrothermal slurry into a cooling tank, and cooling until the temperature of the hydrothermal slurry is less than or equal to 60 ℃.
5) Washing:
after the cooled hydrothermal slurry is pressed once by a filter press, adding a first part of deionized water, controlling the temperature to be 50 ℃, pulping once, controlling the pulping time to be 30min, and performing secondary pressing by the filter press at the stirring rotating speed of 300 r/min; after the secondary squeezing is finished, adding a second part of deionized water, controlling the temperature to be 50 ℃, carrying out secondary beating, controlling the secondary beating time to be 30min, controlling the secondary beating stirring rotating speed to be 300r/min, then carrying out tertiary squeezing by a filter press, and controlling the water content of a filter cake obtained by the tertiary squeezing to be less than or equal to 50wt%.
Wherein the adding amount of the first deionized water is 20m 3 Per ton of magnesium hydroxide dry powder.
The addition amount of the second deionized water is 20m 3 Per ton of magnesium hydroxide dry powder.
6) Drying
And (3) drying the filter cake squeezed for three times by adopting a flash dryer, wherein the drying temperature is 150 ℃, and the moisture content of the dried material is controlled to be less than or equal to 0.5wt percent, so that the superfine special crystal form high-purity magnesium hydroxide is prepared.
The quality indexes of the superfine special crystal form high-purity magnesium hydroxide prepared by the embodiment are shown in the following table:
2. magnesium-aluminum composite modification:
uniformly mixing the prepared superfine special crystal form high-purity magnesium hydroxide and aluminum hydroxide raw powder according to the weight ratio of 5:5, heating to 80 ℃, and preserving heat; then spraying the modified liquid in a high-pressure spraying mode under the stirring condition of 600r/min, and controlling the modified liquid to be sprayed within 5min; continuously stirring for 20min after the spraying of the modifying liquid is completed; spraying the catalyst in a high-pressure spraying mode, and controlling the catalyst to be sprayed within 3min; then controlling the temperature to be 110 ℃, and carrying out heat preservation and mixing reaction for 60min to obtain a reactant; and evaporating the reactant to remove the organic solvent, and drying at 80 ℃ to obtain the magnesium-aluminum composite halogen-free flame retardant.
The aluminum hydroxide raw powder adopted in the embodiment is obtained through a commercial way, and the specific specification is as follows: particle diameter D50:1.75 μm, aluminum hydroxide content 99.53wt%, siO 2 The content of Fe is 0.02wt percent 2 O 3 The content was 0.016wt%.
The catalyst was a methanol solution in which tetramethylammonium hydroxide was dissolved, and the tetramethylammonium hydroxide concentration was 9wt%. The addition amount of the tetramethyl ammonium hydroxide in the catalyst is 0.5 percent of the total weight of the superfine special crystal form high-purity magnesium hydroxide and the aluminum hydroxide raw powder.
The modifying liquid is prepared by adding a silane modifying agent into an organic solvent for dissolution; the weight ratio of the silane modifier to the organic solvent is 1:5. The addition amount of the silane modifier in the modified liquid is 2.5 percent of the total weight of the superfine special crystal form high-purity magnesium hydroxide and the aluminum hydroxide raw powder.
The silane modifier in the modifying liquid consists of the following materials in percentage by weight: 50% by weight of trimethoxyvinylsilane and 50% by weight of vinyltriethoxysilane;
the organic solvent in the modified liquid consists of the following materials in percentage by weight: 50wt% of absolute ethyl alcohol and 50wt% of carbon tetrachloride.
The magnesium-aluminum composite halogen-free flame retardant prepared in the embodiment has the coating rate of 99.96wt%, the content of effective substances of 99.58wt%, the particle size of 1.88 mu m, the whiteness of 99.3 and the moisture content of 0.41wt%.
The embodiment also provides the magnesium-aluminum composite halogen-free flame retardant prepared by the method.
Example 3
The embodiment provides a preparation method of a magnesium-aluminum composite halogen-free flame retardant, which specifically comprises the following steps:
1. preparing superfine special crystal form high-purity magnesium hydroxide:
1) Crushing of raw materials
Mechanically crushing the high-purity magnesium oxide raw material to obtain magnesium oxide raw material powder with the particle size D50 of 5 mu m.
The high-purity magnesium oxide in the embodiment is purchased through a commercial channel, and the specific specification is as follows: 97.62wt% of magnesium oxide, 0.43% of chloride ion and a particle size D50:45.63 μm.
2) Hydration
Soft water and magnesia raw material powder are added into a reaction kettle, and a hydration auxiliary agent (magnesium acetate) is added. And (3) carrying out heat preservation and stirring reaction for 2 hours at the temperature of 95 ℃ to obtain hydration slurry.
Wherein the weight ratio of the magnesium oxide raw material powder to the soft water is 1:6.
The addition amount of the hydration assistant (magnesium acetate) is 5% of the weight of the magnesium oxide raw material powder.
3) Wet milling
Wet grinding the hydrated slurry by using a grinding and peeling machine, and controlling the grinding particle diameter D50 to be less than 2.0 mu m to obtain grinding slurry; meanwhile, a grinding aid is dripped in the grinding process, and the viscosity of the slurry in the grinding process is controlled to be less than 500 mPa.s by controlling the dripping speed of the grinding aid.
Wherein the addition amount of the grinding aid is 2wt% (based on the weight of the magnesium hydroxide dry powder).
The grinding aid consists of the following materials in percentage by weight: 70wt% of sodium dodecyl benzene sulfonate and 30wt% of polyepoxysuccinic acid.
4) Hydrothermal treatment
Transferring the grinding slurry into a high-pressure reaction kettle, dropwise adding sodium hydroxide solution (the concentration is 30wt%) to adjust the alkalinity of the slurry to 0.3mol/L, heating the reaction kettle to 200 ℃ for hydrothermal treatment, and carrying out heat preservation reaction for 12h to obtain the hydrothermal slurry; transferring the hydrothermal slurry into a cooling tank, and cooling until the temperature of the hydrothermal slurry is less than or equal to 60 ℃.
5) Washing:
after the cooled hydrothermal slurry is pressed once by a filter press, adding a first part of deionized water, controlling the temperature to be 60 ℃, pulping once, controlling the pulping time to be 40min, and performing secondary pressing by the filter press at the stirring rotating speed of 500 r/min; after the secondary squeezing is finished, adding a second part of deionized water, controlling the temperature to be 60 ℃, carrying out secondary beating, controlling the secondary beating time to be 40min, controlling the secondary beating stirring rotating speed to be 500r/min, then carrying out tertiary squeezing by a filter press, and controlling the water content of a filter cake obtained by the tertiary squeezing to be less than or equal to 50wt%.
Wherein the adding amount of the first deionized water is 25m 3 Per ton of magnesium hydroxide dry powder.
The addition amount of the second deionized water is 25m 3 Per ton of magnesium hydroxide dry powder.
6) Drying
And (3) drying the filter cake squeezed for three times by adopting a flash dryer, wherein the drying temperature is 170 ℃, and the moisture content of the dried material is controlled to be less than or equal to 0.5wt percent, so that the superfine special crystal form high-purity magnesium hydroxide is prepared.
The quality indexes of the superfine special crystal form high-purity magnesium hydroxide prepared by the embodiment are shown in the following table:
2. magnesium-aluminum composite modification:
uniformly mixing the prepared superfine special crystal form high-purity magnesium hydroxide and aluminum hydroxide raw powder according to the weight ratio of 6:4, heating to 100 ℃, and preserving heat; then spraying the modified liquid in a high-pressure spraying mode under the stirring condition of 900r/min, and controlling the modified liquid to be sprayed within 5min; continuously stirring for 30min after the spraying of the modifying liquid is completed; spraying the catalyst in a high-pressure spraying mode, and controlling the catalyst to be sprayed within 3min; then controlling the temperature to 140 ℃, and carrying out heat preservation and mixing reaction for 90min to obtain a reactant; and evaporating the reactant to remove the organic solvent, and drying at 120 ℃ to obtain the magnesium-aluminum composite halogen-free flame retardant.
The aluminum hydroxide raw powder adopted in the embodiment is obtained through a commercial way, and the specific specification is as follows: particle diameter D50:1.75 μm, aluminum hydroxide content 99.53wt%, siO 2 The content of Fe is 0.02wt percent 2 O 3 The content was 0.016wt%.
The catalyst was a methanol solution in which tetramethylammonium hydroxide was dissolved, and the tetramethylammonium hydroxide concentration was 9.5wt%. The addition amount of the tetramethyl ammonium hydroxide in the catalyst is 1.5 percent of the total weight of the superfine special crystal form high-purity magnesium hydroxide and the aluminum hydroxide raw powder.
The modifying liquid is prepared by adding a silane modifying agent into an organic solvent for dissolution; the weight ratio of the silane modifier to the organic solvent is 1:8. The addition amount of the silane modifier in the modified liquid is 1% of the total weight of the superfine special crystal form high-purity magnesium hydroxide and the aluminum hydroxide raw powder.
The silane modifier in the modifying liquid consists of the following materials in percentage by weight: 50wt% of functional organic silicon and 50wt% of aminosilane;
the organic solvent in the modified liquid consists of the following materials in percentage by weight: 30wt% of absolute ethyl alcohol, 30wt% of carbon tetrachloride and 40wt% of ethyl acetate.
The magnesium-aluminum composite halogen-free flame retardant prepared in the embodiment has the coating rate of 99.95wt%, the content of effective substances of 99.55wt%, the particle size of 1.92 mu m, the whiteness of 99.1 and the moisture content of 0.46wt%.
The embodiment also provides the magnesium-aluminum composite halogen-free flame retardant prepared by the method.
Example 4
The embodiment provides a preparation method of a magnesium-aluminum composite halogen-free flame retardant, which specifically comprises the following steps:
1. preparing superfine special crystal form high-purity magnesium hydroxide:
1) Crushing of raw materials
Mechanically crushing the high-purity magnesium oxide raw material to obtain magnesium oxide raw material powder with the particle size D50 of 4.2 mu m.
The high-purity magnesium oxide in the embodiment is purchased through a commercial channel, and the specific specification is as follows: 97.62wt% of magnesium oxide, 0.43% of chloride ion and a particle size D50:45.63 μm.
2) Hydration
Soft water and magnesia raw material powder are added into a reaction kettle, and a hydration auxiliary agent (magnesium acetate) is added. And (3) carrying out heat preservation and stirring reaction for 2 hours at the temperature of 90 ℃ to obtain hydration slurry.
Wherein the weight ratio of the magnesium oxide raw material powder to the soft water is 1:5.3.
The addition amount of the hydration assistant (magnesium acetate) is 4% of the weight of the magnesium oxide raw material powder.
3) Wet milling
Wet grinding the hydrated slurry by using a grinding and peeling machine, and controlling the grinding particle diameter D50 to be less than 2.0 mu m to obtain grinding slurry; meanwhile, a grinding aid is dripped in the grinding process, and the viscosity of the slurry in the grinding process is controlled to be less than 500 mPa.s by controlling the dripping speed of the grinding aid.
Wherein the addition amount of the grinding aid is 1.3wt% (based on the weight of the magnesium hydroxide dry powder).
The grinding aid consists of the following materials in percentage by weight: 65wt% of anionic polyacrylamide and 35wt% of alkylphenol polyoxyethylene.
4) Hydrothermal treatment
Transferring the grinding slurry into a high-pressure reaction kettle, dropwise adding sodium hydroxide solution (the concentration is 30 wt%) to adjust the alkalinity of the slurry to 0.25mol/L, heating the reaction kettle to 185 ℃ for hydrothermal treatment, and carrying out heat preservation reaction for 11h to obtain the hydrothermal slurry; transferring the hydrothermal slurry into a cooling tank, and cooling until the temperature of the hydrothermal slurry is less than or equal to 60 ℃.
5) Washing:
after the cooled hydrothermal slurry is pressed once by a filter press, adding a first part of deionized water, controlling the temperature to be 55 ℃, pulping once, controlling the pulping time to be 35min, and performing secondary pressing by the filter press at the stirring rotating speed of 400 r/min; after the secondary squeezing is finished, adding a second part of deionized water, controlling the temperature to be 55 ℃, carrying out secondary beating, controlling the secondary beating time to be 35min, controlling the secondary beating stirring rotating speed to be 400r/min, then carrying out tertiary squeezing by a filter press, and controlling the water content of a filter cake obtained by the tertiary squeezing to be less than or equal to 50wt%.
Wherein the adding amount of the first deionized water is 20m 3 Per ton of magnesium hydroxide dry powder.
The addition amount of the second deionized water is 25m 3 Per ton of magnesium hydroxide dry powder.
6) Drying
And (3) drying the filter cake squeezed for three times by adopting a flash dryer, wherein the drying temperature is 165 ℃, and the moisture content of the dried material is controlled to be less than or equal to 0.5wt percent, so that the superfine special crystal form high-purity magnesium hydroxide is prepared.
The quality indexes of the superfine special crystal form high-purity magnesium hydroxide prepared by the embodiment are shown in the following table:
2. magnesium-aluminum composite modification:
uniformly mixing the prepared superfine special crystal form high-purity magnesium hydroxide and aluminum hydroxide raw powder according to the weight ratio of 5:5, heating to 95 ℃, and preserving heat; then spraying the modified liquid in a high-pressure spraying mode under the stirring condition of 800r/min, and controlling the modified liquid to be sprayed within 5min; continuously stirring for 25min after the spraying of the modifying liquid is completed; spraying the catalyst in a high-pressure spraying mode, and controlling the catalyst to be sprayed within 3min; then controlling the temperature to be 125 ℃, and carrying out heat preservation and mixing reaction for 70min to obtain a reactant; and evaporating the reactant to remove the organic solvent, and drying at 110 ℃ to obtain the magnesium-aluminum composite halogen-free flame retardant.
The aluminum hydroxide raw powder adopted in the embodiment is obtained through a commercial way, and the specific specification is as follows: particle diameter D50:1.75 μm, aluminum hydroxide content 99.53wt%, siO 2 The content of Fe is 0.02wt percent 2 O 3 The content was 0.016wt%.
The catalyst was a methanol solution in which tetramethylammonium hydroxide was dissolved, and the tetramethylammonium hydroxide concentration was 9.2wt%. The addition amount of the tetramethyl ammonium hydroxide in the catalyst is 1.1 percent of the total weight of the superfine special crystal form high-purity magnesium hydroxide and the aluminum hydroxide raw powder.
The modifying liquid is prepared by adding a silane modifying agent into an organic solvent for dissolution; the weight ratio of the silane modifier to the organic solvent is 1:6. The addition amount of the silane modifier in the modified liquid is 2.0 percent of the total weight of the superfine special crystal form high-purity magnesium hydroxide and the aluminum hydroxide raw powder.
The silane modifier in the modifying liquid consists of the following materials in percentage by weight: 50wt% of functional organic silicon and 50wt% of aminosilane;
the organic solvent in the modified liquid consists of the following materials in percentage by weight: 30wt% of absolute ethyl alcohol, 30wt% of carbon tetrachloride and 40wt% of ethyl acetate.
The magnesium-aluminum composite halogen-free flame retardant prepared in the embodiment has the coating rate of 99.98wt%, the content of effective substances of 99.53wt%, the particle size of 1.75 mu m, the whiteness of 99.2 and the moisture content of 0.45wt%.
The embodiment also provides the magnesium-aluminum composite halogen-free flame retardant prepared by the method.
Example 5
The technical scheme of the embodiment 1 is adopted, and the difference is that: in the magnesium-aluminum composite modification step, the silane modifier in the adopted modification liquid consists of the following materials in percentage by weight: 40wt% of vinyl triethoxysilane, 20wt% of polyether silicone oil and 40wt% of aminosilane.
The magnesium-aluminum composite halogen-free flame retardant prepared in the embodiment has the coating rate of 99.93wt%, the content of effective substances of 99.56wt%, the particle size of 1.82 mu m, the whiteness of 99.2 and the moisture content of 0.44wt%.
The embodiment also provides the magnesium-aluminum composite halogen-free flame retardant prepared by the method.
Application example 1
The application of the magnesium-aluminum composite halogen-free flame retardant comprises the following specific steps:
uniformly mixing the magnesium-aluminum composite halogen-free flame retardant, resin, compatilizer, silicone and auxiliary agent, putting into an open mill, controlling the open mill temperature to 140 ℃ and the open mill time to 20min, and preparing an open mill product; the open mill is vulcanized for 30min at 150 ℃, and the flame-retardant polymer product is obtained after cooling.
Wherein, the raw materials comprise the following components in parts by weight: 25 parts of EVA resin; 6 parts of PE resin; 3 parts of a compatilizer; 2 parts of silicone; 2 parts of auxiliary agent; 40 parts of magnesium-aluminum composite flame retardant. (the filling rate of the magnesium-aluminum composite flame retardant in the magnesium-aluminum composite flame retardant is 51.3 wt%)
The compatilizer is maleic anhydride grafted modified metallocene polyethylene, with the trade mark MC218, which is produced by light and new material technology Co., ltd.
The auxiliary agent consists of the following raw materials in percentage by weight: 80% of diethyl phosphinic acid aluminum and 20% of zinc borate.
Adopting the technical scheme of application example 1, wherein the magnesium-aluminum composite halogen-free flame retardant adopts the magnesium-aluminum composite halogen-free flame retardants of examples 1-4 respectively to prepare a flame-retardant polymer product; meanwhile, the following comparative examples were respectively set and flame retardant polymer products were produced.
1) Comparative example 1, the technical scheme of example 1 was adopted, which is different in that: the preparation and the use of superfine special crystal form high-purity magnesium hydroxide are omitted, and only the aluminum hydroxide raw powder is modified.
2) Comparative example 2, the technical scheme of example 1 was adopted, which is different in that: the use of aluminum hydroxide raw powder is omitted, and only superfine special crystal form high-purity magnesium hydroxide is modified.
3) Comparative example 3, the technical scheme of example 1 was adopted, which is different in that: omitting the magnesium-aluminum composite modification step, and uniformly mixing the superfine special crystal form high-purity magnesium hydroxide and aluminum hydroxide raw powder according to the weight ratio of 6:4 to prepare the magnesium-aluminum composite halogen-free flame retardant.
4) Comparative example 4, the technical scheme of example 1 was adopted, which is different in that: the preparation and the use of superfine special crystal form high-purity magnesium hydroxide are omitted, and the magnesium-aluminum composite halogen-free flame retardant is prepared by only adopting the conventional crystal form commercial magnesium hydroxide and aluminum hydroxide to carry out composite modification according to the weight ratio of 6:4. (the Mg-Al composite halogen-free flame retardant obtained in comparative example 4 had a coating ratio of 99.9%, an active material content of 99.21% by weight, a particle diameter of 1.96. Mu.m, a whiteness of 98.5, a moisture content of 0.46% by weight.)
After the flame-retardant polymer products prepared in examples 1 to 4 and comparative examples 1 to 4 were respectively prepared into test pieces (thickness: 1 mm) by using a sheet punching machine, the tensile strength and elongation at break were measured by using a universal tester, and the melt index was measured by using a melt flow rate meter; meanwhile, after the flame retardant polymer products prepared in examples 1 to 4 and comparative examples 1 to 4 were manufactured into a test piece (thickness: 3 mm) using a sheet punching machine, limiting oxygen index was measured using an oxygen index meter. The specific detection results are as follows:
application example 2
The application of the magnesium-aluminum composite halogen-free flame retardant comprises the following specific steps:
uniformly mixing the magnesium-aluminum composite halogen-free flame retardant, resin, compatilizer, silicone and auxiliary agent, putting into an open mill, controlling the open mill temperature to 140 ℃ and the open mill time to 20min, and preparing an open mill product; the open mill is vulcanized for 30min at 150 ℃, and the flame-retardant polymer product is obtained after cooling.
Wherein, the raw materials comprise the following components in parts by weight: 10 parts of EVA resin; 5 parts of PE resin; 15 parts of POE resin; 3 parts of a compatilizer; 2 parts of silicone; 3 parts of an auxiliary agent; 40 parts of superfine high-purity magnesium hydroxide (the filling rate of the superfine high-purity magnesium hydroxide is 51.3 weight percent).
The compatilizer is maleic anhydride grafted modified metallocene polyethylene, with the trade mark MC218, which is produced by light and new material technology Co., ltd.
The auxiliary agent consists of the following raw materials in percentage by weight: 80% of diethyl phosphinic acid aluminum and 20% of zinc borate.
The technical scheme of application example 2 is adopted, wherein the magnesium-aluminum composite halogen-free flame retardant is respectively the magnesium-aluminum composite halogen-free flame retardants of examples 1-4, and the flame-retardant polymer product is prepared.
After the flame-retardant polymer products prepared in examples 1 to 4 were prepared into test pieces (thickness: 1 mm) by using a sheet punching machine, the tensile strength and elongation at break were measured by using a universal tester, and the melt index was measured by using a melt flow rate meter; meanwhile, after the flame retardant polymer products prepared in examples 1 to 4 were manufactured into a test piece (thickness of 3 mm) by using a sheet punching machine, limiting oxygen index was measured using an oxygen index meter. The specific detection results are as follows:
according to the preparation method of the magnesium-aluminum composite halogen-free flame retardant, high-purity magnesium oxide is taken as a raw material, hydration and wet grinding are carried out, hydrothermal treatment is carried out, and then water washing and drying are carried out, so that the superfine special crystal form high-purity magnesium hydroxide with specific specification is prepared; then compounding superfine special crystal form high-purity magnesium hydroxide with aluminum hydroxide, combining a modifier with the magnesium hydroxide and the aluminum hydroxide in a physical adsorption mode, and carrying out catalytic reaction on functional groups which are directly connected with silicon in silane molecules and hydroxyl groups on the surfaces of the magnesium hydroxide and the aluminum hydroxide by adopting a catalyst, wherein the composite synergistic flame retardance of the aluminum hydroxide and the magnesium hydroxide is effectively realized through the interaction between a nonpolar section of the silane and a molecular chain of a high polymer matrix, so that the thermal stability of the flame retardant is further improved, the halogen content is reduced, and the use cost performance is improved; meanwhile, the combination property of the magnesium-aluminum composite halogen-free flame retardant and the high polymer resin is further improved, and the flame retardant property and the mechanical property of the flame retardant material prepared by application are further improved under the condition that the filling amount exceeds 50 weight percent, so that the production cost of the flame retardant material is reduced.
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 (4)
1. The preparation method of the magnesium-aluminum composite halogen-free flame retardant is characterized by comprising the following steps of: preparing superfine special crystal form high-purity magnesium hydroxide and compounding and modifying magnesium and aluminum;
the preparation of the superfine special crystal form high-purity magnesium hydroxide takes high-purity magnesium oxide as a raw material, and hydration is carried out in the presence of magnesium acetate to obtain hydration slurry; in the presence of a grinding aid, carrying out wet grinding on the hydrated slurry until the particle size D50 is less than 2.0 mu m to obtain grinding slurry; carrying out hydrothermal treatment, washing and drying on the grinding slurry to obtain superfine special crystal form high-purity magnesium hydroxide;
the hydration is carried out, the crushed high-purity magnesia and soft water are put into a reaction kettle, magnesium acetate is added, and the mixture is stirred and reacts for 1.5 to 2 hours at the temperature of 85 to 95 ℃ to obtain hydration slurry;
the weight ratio of the crushed high-purity magnesium oxide to the crushed soft water is 1:5-6;
the adding amount of the magnesium acetate is 3-5% of the weight of the crushed high-purity magnesium oxide;
in the wet grinding process, the grinding aid is added dropwise;
controlling the slurry viscosity to be less than 500 mPa.s in the grinding process by controlling the dropping speed of the grinding aid;
the grinding aid is any two of the following substances: sodium dodecyl benzene sulfonate, anionic polyacrylamide, polyepoxysuccinic acid, alkylphenol ethoxylates;
the hydrothermal treatment, wherein the alkalinity of the grinding slurry is regulated to 0.2-0.3mol/L by adopting sodium hydroxide solution, the temperature is raised to 180-200 ℃, and the reaction is carried out for 10-12 hours under the heat preservation, so as to obtain the hydrothermal slurry;
the water washing, after the cooled hydrothermal slurry is pressed once by a filter press, adding a first part of deionized water, controlling the temperature to be 50-60 ℃, pulping once, controlling the pulping time to be 30-40min, and the stirring speed of primary pulping to be 300-500r/min, and then pressing twice by the filter press; adding a second part of deionized water after the secondary squeezing is finished, controlling the temperature to be 50-60 ℃, carrying out secondary beating, controlling the secondary beating time to be 30-40min, controlling the secondary beating stirring rotating speed to be 300-500r/min, then carrying out tertiary squeezing in a filter press, and controlling the water content of a filter cake obtained through the tertiary squeezing to be less than or equal to 50wt%;
the filter cake squeezed for three times is dried until the moisture content is less than or equal to 0.5 weight percent, and the superfine special crystal form high-purity magnesium hydroxide is prepared;
in the superfine special crystal form high-purity magnesium hydroxide, the magnesium hydroxide content is more than or equal to 99.5 weight percent, the CaO content is less than or equal to 0.05 weight percent, the acid insoluble content is less than or equal to 0.05 weight percent, the moisture content is less than or equal to 0.5 weight percent, the chloride content is less than or equal to 0.1 weight percent, and the grain diameter D50 is less than or equal to 2.0 mu m;
the magnesium-aluminum composite modification is carried out, the superfine special crystal form high-purity magnesium hydroxide and aluminum hydroxide raw powder are uniformly mixed, under the stirring condition, a modifying liquid is added in a spraying way, and stirring is continued after the modifying liquid is added; then spraying and adding a catalyst, and after the catalyst is added, carrying out heat preservation and mixing reaction at 110-140 ℃ for 60-90min to obtain a reactant; evaporating and desolventizing the reactant, and drying to obtain the magnesium-aluminum composite halogen-free flame retardant;
in the magnesium-aluminum composite modification, the stirring rotation speed is 600-900r/min;
the spraying adding time of the modifying liquid is less than 5min;
the spraying adding time of the catalyst is less than 3min;
in the magnesium-aluminum composite modification, the weight ratio of the silane modifier to the organic solvent in the modification liquid is 1:5-8;
the addition amount of the silane modifier in the modified liquid is 1-2.5% of the total weight of the superfine special crystal form high-purity magnesium hydroxide and the aluminum hydroxide raw powder;
the concentration of the tetramethylammonium hydroxide in the catalyst is 9-10wt%;
the addition amount of the tetramethyl ammonium hydroxide in the catalyst is 0.5-1.5% of the total weight of the superfine special crystal form high-purity magnesium hydroxide and the aluminum hydroxide raw powder;
the modifying liquid is an organic solvent in which a silane modifier is dissolved;
the silane modifier is any one of the following groups:
silane modifier 1: 50% by weight of trimethoxyvinylsilane and 50% by weight of vinyltriethoxysilane;
silane modifier 3: 40wt% of vinyl triethoxysilane, 20wt% of polyether silicone oil and 40wt% of aminosilane;
the organic solvent is at least one of the following: absolute ethyl alcohol, acetone, carbon tetrachloride, diethyl ether and ethyl acetate;
the catalyst is a methanol solution in which tetramethyl ammonium hydroxide is dissolved.
2. The method for preparing the magnesium aluminum composite halogen-free flame retardant according to claim 1, wherein in the magnesium aluminum composite modification, the organic solvent is any one of the following mixed solvents:
organic solvent 1: 50wt% of absolute ethyl alcohol and 50wt% of carbon tetrachloride;
organic solvent 2: 30wt% of absolute ethyl alcohol, 30wt% of carbon tetrachloride and 40wt% of ethyl acetate.
3. A magnesium aluminum composite halogen-free flame retardant, which is characterized by being prepared by the preparation method of claim 1 or 2.
4. The use of the magnesium aluminum composite halogen-free flame retardant according to claim 3, wherein the magnesium aluminum composite halogen-free flame retardant is filled into a polymer, and the filling amount of the magnesium aluminum composite halogen-free flame retardant is controlled to be not less than 50wt%;
the polymer is one of the following:
a mixture of EVA resins and PE resins;
EVA resin, PE resin and POE resin.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050472A (en) * | 2009-10-28 | 2011-05-11 | 中国科学院过程工程研究所 | Method for preparing submicron flaky magnesium hydroxide from magnesium oxide |
| CN102952311A (en) * | 2011-08-30 | 2013-03-06 | 苏州亨利通信材料有限公司 | Preparation method of low-smoke non-halogen flame-retardant material for high-voltage cable sheath |
| CN109749199A (en) * | 2018-12-27 | 2019-05-14 | 上海至正道化高分子材料股份有限公司 | A kind of heating cable low-smoke halogen-free flame-retardant sheath material and preparation method thereof |
| CN110951259A (en) * | 2020-01-02 | 2020-04-03 | 合肥中科阻燃新材料有限公司 | Special environment-friendly composite flame retardant for fireproof aluminum-plastic panel and preparation method thereof |
| CN114874532A (en) * | 2022-05-10 | 2022-08-09 | 江苏领瑞新材料科技有限公司 | High-performance optical cable thermoplastic sheath material and preparation method thereof |
| CN115924942A (en) * | 2022-12-30 | 2023-04-07 | 郑州大学 | Method for preparing high-purity flaky magnesium hydroxide by hydration of microcrystalline magnesite |
| CN116812953A (en) * | 2023-07-08 | 2023-09-29 | 潍坊泽隆新材料有限公司 | Preparation method of hexagonal magnesium hydroxide and application of hexagonal magnesium hydroxide in low-smoke halogen-free cable material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8703288B2 (en) * | 2008-03-21 | 2014-04-22 | General Cable Technologies Corporation | Low smoke, fire and water resistant cable coating |
-
2024
- 2024-01-12 CN CN202410044558.3A patent/CN117551306B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050472A (en) * | 2009-10-28 | 2011-05-11 | 中国科学院过程工程研究所 | Method for preparing submicron flaky magnesium hydroxide from magnesium oxide |
| CN102952311A (en) * | 2011-08-30 | 2013-03-06 | 苏州亨利通信材料有限公司 | Preparation method of low-smoke non-halogen flame-retardant material for high-voltage cable sheath |
| CN109749199A (en) * | 2018-12-27 | 2019-05-14 | 上海至正道化高分子材料股份有限公司 | A kind of heating cable low-smoke halogen-free flame-retardant sheath material and preparation method thereof |
| CN110951259A (en) * | 2020-01-02 | 2020-04-03 | 合肥中科阻燃新材料有限公司 | Special environment-friendly composite flame retardant for fireproof aluminum-plastic panel and preparation method thereof |
| CN114874532A (en) * | 2022-05-10 | 2022-08-09 | 江苏领瑞新材料科技有限公司 | High-performance optical cable thermoplastic sheath material and preparation method thereof |
| CN115924942A (en) * | 2022-12-30 | 2023-04-07 | 郑州大学 | Method for preparing high-purity flaky magnesium hydroxide by hydration of microcrystalline magnesite |
| CN116812953A (en) * | 2023-07-08 | 2023-09-29 | 潍坊泽隆新材料有限公司 | Preparation method of hexagonal magnesium hydroxide and application of hexagonal magnesium hydroxide in low-smoke halogen-free cable material |
Non-Patent Citations (2)
| Title |
|---|
| 机械球磨对煅烧菱镁矿制备纳米片状氢氧化镁颗粒的影响;杨素萍;卢旭晨;王体壮;张志敏;闫岩;;过程工程学报;20111215(06);114-120 * |
| 氧化镁水热合成氢氧化镁工艺条件研究;汪云川;鄢僖;唐博;葛方秋;;盐科学与化工;20200815(08);36-40 * |
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