CN114456620A - Ball milling method for producing superfine magnesium hydroxide fire retardant and preparation method thereof - Google Patents
Ball milling method for producing superfine magnesium hydroxide fire retardant and preparation method thereof Download PDFInfo
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- CN114456620A CN114456620A CN202110710895.8A CN202110710895A CN114456620A CN 114456620 A CN114456620 A CN 114456620A CN 202110710895 A CN202110710895 A CN 202110710895A CN 114456620 A CN114456620 A CN 114456620A
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- magnesium hydroxide
- ball milling
- titanate
- coupling agent
- flame retardant
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 title claims abstract description 80
- 239000000347 magnesium hydroxide Substances 0.000 title claims abstract description 78
- 229910001862 magnesium hydroxide Inorganic materials 0.000 title claims abstract description 78
- 238000000498 ball milling Methods 0.000 title claims abstract description 52
- 239000003063 flame retardant Substances 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 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 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 34
- 239000007822 coupling agent Substances 0.000 claims description 32
- -1 ethyloxy Chemical group 0.000 claims description 23
- 238000000227 grinding Methods 0.000 claims description 19
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 16
- 239000007983 Tris buffer Substances 0.000 claims description 15
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 239000000314 lubricant Substances 0.000 claims description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 238000003801 milling Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims description 3
- AKUGPKHOAALNSY-UHFFFAOYSA-N n-(2-aminoethoxy)-3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCNOCCN AKUGPKHOAALNSY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 3
- UMHKOAYRTRADAT-UHFFFAOYSA-N [hydroxy(octoxy)phosphoryl] octyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OP(O)(=O)OCCCCCCCC UMHKOAYRTRADAT-UHFFFAOYSA-N 0.000 claims 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- 239000000654 additive Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 239000002245 particle Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229940057995 liquid paraffin Drugs 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- KNXNFEMPRRJNKP-UHFFFAOYSA-N dioctyl phosphono phosphate propan-2-ol titanium Chemical compound [Ti].CC(C)O.CCCCCCCCOP(=O)(OP(O)(O)=O)OCCCCCCCC.CCCCCCCCOP(=O)(OP(O)(O)=O)OCCCCCCCC.CCCCCCCCOP(=O)(OP(O)(O)=O)OCCCCCCCC KNXNFEMPRRJNKP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical group O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 125000001905 inorganic group Chemical group 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010074 rubber mixing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
- 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
-
- 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
- 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
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
-
- C—CHEMISTRY; METALLURGY
- 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
- 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
- C09C3/041—Grinding
-
- C—CHEMISTRY; METALLURGY
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon 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
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention relates to the technical field of flame retardance, and particularly relates to a superfine magnesium hydroxide flame retardant produced by a ball milling method and a preparation method thereof. Comprises the following raw materials, magnesium hydroxide, an auxiliary agent, a solvent and a pH regulator; wherein the weight ratio of the magnesium hydroxide to the auxiliary agent is (90-100): (1-7). The superfine magnesium hydroxide flame retardant produced by the ball milling method and the preparation method thereof have the advantages of high activity index, good dispersibility and good flame retardant property.
Description
Technical Field
The invention relates to the technical field of flame retardance, and particularly relates to a superfine magnesium hydroxide flame retardant produced by a ball milling method and a preparation method thereof.
Background
Magnesium hydroxide is a novel inorganic flame retardant, and has the advantages of high decomposition temperature, no toxicity, no smoke, no corrosive gas generation and the like. And thus is widely used by people. The superfine magnesium hydroxide flame retardant has the defects of small binding force with a polymer, poor compatibility, influence on the processing performance and the mechanical performance of the polymer and the like, and in order to improve the compatibility with the polymer, the magnesium hydroxide is modified in the process of preparing the magnesium hydroxide flame retardant.
Patent CN201510891135.6 provides a modification method of magnesium hydroxide flame retardant, which, although further improving the performance of magnesium hydroxide flame retardant, still has the disadvantages of large particle size of the product, serious agglomeration, uneven particle size distribution, high equipment requirement, etc. The invention provides a ball milling method for producing superfine magnesium hydroxide fire retardant and a preparation method thereof. The stamping, extruding and shearing actions in the ball milling process can not only reduce the granularity of the magnesium hydroxide particles and improve the dispersibility, but also change the crystal structure of the magnesium hydroxide particles and increase the reaction activity, and has the advantages of simple process, high efficiency and the like.
Disclosure of Invention
In order to solve the technical problems, the first aspect of the invention provides a ball milling method for producing an ultrafine magnesium hydroxide flame retardant, which comprises the following raw materials: magnesium hydroxide, an auxiliary agent, a solvent and a pH regulator; wherein the weight ratio of the magnesium hydroxide to the auxiliary agent is (90-100): (1-7).
Preferably, the auxiliaries include a coupling agent and a lubricant.
Preferably, the coupling agent comprises at least one of a rare earth coupling agent, a silane coupling agent, a titanate coupling agent and an aluminate coupling agent.
Preferably, the silane coupling agent includes at least one of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, N- (beta-aminoethoxy) -gamma-aminopropyltrimethoxysilane (ethyloxy), N-beta- (aminoethoxy) -gamma-aminopropylmethyldimethoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane, vinyltrimethoxysilane, and vinyltriacetoxysilane.
Preferably, the titanate coupling agent comprises at least one of isopropyl tris (isostearoyl) titanate, isopropyl tris (dioctyl pyrophosphoryl) titanate, titanium bis (dioctyl pyrophosphoryl) oxoacetate, bis (dioctyl pyrophosphoryl) ethylene titanate, isopropyl bis (methacryloyl) isostearoyl titanate, isopropyl tris (dioctyl phosphoryl) titanate, isopropyl tris (dodecylbenzenesulfonyl) titanate, isopropyl tris (n-ethylamino) titanate.
The second aspect of the invention provides a preparation method for producing an ultrafine magnesium hydroxide flame retardant by a ball milling method, which comprises the following steps:
1) mixing magnesium hydroxide with a part of solvent, and then carrying out ultrasonic dispersion to obtain a mixture A;
2) mixing the auxiliary agent with the rest solvent, and adjusting the pH value by using a pH regulator to obtain a mixture B;
3) and uniformly mixing the mixture A and the mixture B, and performing ball milling.
Preferably, the ball milling is continuous milling, and the ball milling speed is 50-200 r/min.
Preferably, the grinding balls during ball milling are zirconia or alumina balls.
Preferably, the diameter of the grinding balls during ball milling is 2-12 mm.
Preferably, the mass ratio of the grinding balls to the magnesium hydroxide is (10-30): 1.
has the advantages that:
1) the superfine magnesium hydroxide flame retardant produced by the ball milling method and the preparation method thereof have the advantages of high activity index, small particle size, large specific surface area and good dispersibility.
2) The superfine magnesium hydroxide flame retardant produced by the ball milling method and the preparation method thereof provided by the invention have the advantages of less smoke generation amount and good flame retardant property during combustion.
3) The superfine magnesium hydroxide flame retardant produced by the ball milling method and the preparation method thereof provided by the invention are simple to prepare and simple and convenient to operate, and the prepared superfine magnesium hydroxide has excellent performance and can fully meet the requirements of consumers.
Detailed Description
In order to solve the problems, the invention provides a ball milling method for producing an ultrafine magnesium hydroxide flame retardant, which comprises the following raw materials, magnesium hydroxide, an auxiliary agent, a solvent and a pH regulator; wherein the weight ratio of the magnesium hydroxide to the auxiliary agent is (90-100): (1-7).
Further preferably, the weight ratio of the magnesium hydroxide and the auxiliary agent is (93-98): (4-6).
Magnesium hydroxide
Preferably, the magnesium hydroxide has an average particle size of 13 to 18 um. The magnesium hydroxide can be made by the self or purchased.
Auxiliary agent
Preferably, the auxiliaries include a coupling agent and a lubricant. The weight ratio of the coupling agent to the lubricant is (2-4): (6-9).
Coupling agent
Preferably, the coupling agent comprises at least one of a rare earth coupling agent, a silane coupling agent, a titanate coupling agent and an aluminate coupling agent.
Preferably, the coupling agent comprises a silane coupling agent and a titanate coupling agent, and the weight ratio of the silane coupling agent to the titanate coupling agent is (3-5): (3-5).
Preferably, the silane coupling agent includes at least one of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, N- (beta-aminoethoxy) -gamma-aminopropyltrimethoxysilane (ethyloxy), N-beta- (aminoethoxy) -gamma-aminopropylmethyldimethoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane, vinyltrimethoxysilane, and vinyltriacetoxysilane.
Preferably, the titanate coupling agent comprises at least one of isopropyl tris (isostearoyl) titanate, isopropyl tris (dioctyl pyrophosphoryl) titanate, titanium bis (dioctyl pyrophosphoryl) oxoacetate, bis (dioctyl pyrophosphoryl) ethylene titanate, isopropyl bis (methacryloyl) isostearoyl titanate, isopropyl tris (dioctyl phosphoryl) titanate, isopropyl tris (dodecylbenzenesulfonyl) titanate, isopropyl tris (n-ethylamino) titanate.
The magnesium hydroxide prepared by the method has positive surface charge, higher surface energy and poor dispersibility in polymers, and seriously influences the compatibility of the magnesium hydroxide flame retardant and the polymers. The applicant unexpectedly discovers that when magnesium hydroxide is modified by a silane coupling agent and a titanate coupling agent, particularly a modifying agent consisting of gamma- (methacryloyloxy) propyl trimethoxy silane and isopropyl tri (dioctyl pyrophosphate) titanate, the prepared magnesium hydroxide has small particle size and good dispersibility, presumably because the contained inorganic group can react with the magnesium hydroxide to form a chemical bond which is combined on the surface of the magnesium hydroxide, and the other end can be combined with a polymer, the organic relation between the magnesium hydroxide and the polymer is strengthened, and the compatibility and the dispersibility of the magnesium hydroxide in the material are improved, so that the flame retardant property of the magnesium hydroxide is enhanced, and the mechanical property of the polymer can be improved.
Lubricant agent
Preferably, the lubricant comprises at least one of polyethylene glycol, polyvinylpyrrolidone, stearic acid and salts thereof, oleic acid and salts thereof.
Solvent(s)
Preferably, the solvent is water and/or absolute ethanol.
pH regulator
Preferably, the pH regulator is acetic acid and/or ammonia water.
The second aspect of the invention provides a preparation method for producing an ultrafine magnesium hydroxide flame retardant by a ball milling method, which comprises the following steps:
1) mixing magnesium hydroxide with a part of solvent, and then carrying out ultrasonic dispersion to obtain a mixture A;
2) mixing the auxiliary agent with the rest solvent, and adjusting the pH value by using a pH regulator to obtain a mixture B;
3) and uniformly mixing the mixture A and the mixture B, and performing ball milling.
Preferably, the time of ultrasonic dispersion is 15-20 min.
Preferably, the pH is 5 to 8.
Preferably, the ball milling is continuous milling, and the ball milling speed is 50-200 r/min.
Further preferably, the ball milling speed is 100-.
Preferably, the grinding balls during ball milling are zirconia or alumina balls.
Preferably, the diameter of the grinding balls during ball milling is 2-12 mm.
Further preferably, the grinding balls comprise large balls with the diameter of 8-12mm, medium balls with the diameter of 5-7mm and small balls with the diameter of 2-4 mm. The number ratio of the large balls with the diameter of 8-12mm to the medium balls with the diameter of 5-7mm to the small balls with the diameter of 2-4mm is (1-2): (2-3): 1.
the applicant finds that the best ball milling effect cannot be obtained by steel balls with the same specification through unexpected research, the grinding balls in the patent preferably comprise large balls with the diameter of 8-12mm, medium balls with the diameter of 5-7mm and small balls with the diameter of 2-4mm for grading, a close-packed structure with higher space utilization rate and higher coordination number can be achieved, the ball milling efficiency is greatly improved, and meanwhile, the magnesium hydroxide flame retardant with better performance is obtained.
Preferably, the mass ratio of the grinding balls to the magnesium hydroxide is (10-30): 1.
more preferably, the mass ratio of the grinding balls to the magnesium hydroxide is (20-27): 1.
preferably, the filling rate during ball milling is 40-60%.
The filling rate (volume filled by the milling bodies/effective volume of the milling bodies) is 100%, which has a significant influence on the efficiency of the ball milling and on the particle size of the product.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Examples
Example 1
A ball milling method for producing superfine magnesium hydroxide flame retardant comprises the following raw materials, magnesium hydroxide, an auxiliary agent, a solvent and a pH regulator; wherein the weight ratio of the magnesium hydroxide to the auxiliary agent is 95: 5.
the average particle size of the magnesium hydroxide is 15 um. Is purchased from combined fertilizer Zhongke flame-retardant new materials Co.
The auxiliary agent comprises a coupling agent and a lubricant.
The weight ratio of the coupling agent to the lubricant is 3: 8. the coupling agent comprises a silane coupling agent and a titanate coupling agent, wherein the weight ratio of the silane coupling agent to the titanate coupling agent is 4: 4. the silane coupling agent is gamma- (methacryloyloxy) propyl trimethoxy silane. Purchased from Nanjing eosin chemical group, Inc., trade name: KH-570. The titanate coupling agent is isopropyl tri (dioctyl pyrophosphoryl) titanate. Purchased from Huai' an and Yuan chemical Co., Ltd, under the brand name: KR-38S.
The lubricant is stearic acid.
The solvent is absolute ethyl alcohol.
The pH regulator is acetic acid.
A preparation method for producing superfine magnesium hydroxide flame retardant by a ball milling method comprises the following steps:
1) mixing magnesium hydroxide with a solvent accounting for 2/3 volumes of the total solvent, and then carrying out ultrasonic dispersion to obtain a mixture A;
2) mixing the auxiliary agent with the rest solvent, and adjusting the pH value by using a pH regulator to obtain a mixture B;
3) and uniformly mixing the mixture A and the mixture B, and performing ball milling.
Preferably, the time for ultrasonic dispersion is 18 min.
The pH was 5.5.
The ball milling is continuous grinding, and the ball milling speed is 150 r/min.
And the grinding balls are zirconia during ball milling.
The grinding balls comprise large balls with the diameter of 10mm, medium balls with the diameter of 6mm and small balls with the diameter of 3 mm. The diameter is 10 mm's big ball, and the diameter is 6 mm's well ball, and the number ratio of the little ball that the diameter is 3mm is 1: 2: 1. the grinding balls were purchased from Ganzhou encyclopedia ceramics, Inc.
The mass ratio of the grinding balls to the magnesium hydroxide is 23: 1.
the filling rate during ball milling is 50%.
Example 2
The specific implementation mode of the ball milling method for producing the superfine magnesium hydroxide flame retardant is the same as that of the embodiment 1, except that the weight ratio of the magnesium hydroxide to the auxiliary agent is 98: 6.
example 3
The specific implementation mode of the ball milling method for producing the superfine magnesium hydroxide flame retardant is the same as that of the embodiment 1, except that the weight ratio of the silane coupling agent to the titanate coupling agent is 5: 3.
example 4
The specific implementation mode of the ball milling method for producing the superfine magnesium hydroxide flame retardant is the same as that of the embodiment 1, except that the mass ratio of the grinding balls to the magnesium hydroxide is 10: 1.
comparative example 1
The specific implementation mode of the ball milling method for producing the superfine magnesium hydroxide flame retardant is the same as that of the embodiment 1, except that the grinding balls are all medium balls with the diameter of 6 mm.
Comparative example 2
The specific implementation mode of the ball milling method for producing the superfine magnesium hydroxide flame retardant is the same as that of the embodiment 1, except that the weight ratio of the silane coupling agent to the titanate coupling agent is 1: 4.
comparative example 3
The specific implementation mode of the ball milling method for producing the superfine magnesium hydroxide flame retardant is the same as that of the implementation mode 1, and the difference is that the weight ratio of the magnesium hydroxide to the auxiliary agent is (93-98): (4-6).
Performance testing
1. Activity index: weighing superfine magnesium hydroxide, recorded as W1, adding into 80ml deionized water, stirring at constant speed, standing for 10h, filtering floating powder, draining, drying and weighing as W2, wherein the activity index is W2/W1.
2. Testing the settleability: placing the modified magnesium hydroxide into a measuring cylinder with the volume of 25ml, adding liquid paraffin to the scale mark, ultrasonically oscillating for 20min, and standing for 12h, wherein the suspension volume of the modified magnesium hydroxide in the liquid paraffin is V, and the settleability is V/25 × 100%.
3. Flame retardancy: and (3) uniformly mixing the POE8150 and the superfine magnesium hydroxide on a 160-DEG C double-roll rubber mixing mill, and discharging to obtain the flame-retardant POE. The test was carried out according to GB/T5169.11-1997 at a test temperature of 550 ℃.
Combustion grade: v-2: after two 10 second burn tests on the samples, the flame extinguished within 60 seconds. The burning substances fall off; v-1: after the sample is subjected to combustion test for 10 seconds twice, the flame is extinguished within 60 seconds, and no comburent falls off; v-0: after two 10 second burn tests on the samples, the flame extinguished within 30 seconds, with no combustibles falling.
Table 1 results of performance testing
| Index of activation | The sedimentation rate% | Flame retardancy | |
| Example 1 | 0.98 | 90 | V-0 |
| Example 2 | 0.976 | 87 | V-0 |
| Example 3 | 0.978 | 88 | V-0 |
| Example 4 | 0.967 | 85 | V-1 |
| Comparative example 1 | 0.951 | 78 | V-2 |
| Comparative example 2 | 0.956 | 81 | V-1 |
| Comparative example 3 | 0.944 | 74 | V-2 |
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in other forms, and any person skilled in the art may modify or change the technical content of the above disclosure into equivalent embodiments with equivalent changes, but all those simple modifications, equivalent changes and modifications made to the above embodiments according to the technical spirit of the present invention still belong to the protection scope of the present invention.
Claims (10)
1. The ball milling method for producing the superfine magnesium hydroxide flame retardant is characterized by comprising the following raw materials: magnesium hydroxide, an auxiliary agent, a solvent and a pH regulator; wherein the weight ratio of the magnesium hydroxide to the auxiliary agent is (90-100): (1-7).
2. The ball milling process for producing ultra-fine magnesium hydroxide fire retardant of claim 1 wherein the additives include coupling agents and lubricants.
3. The method for producing the ultra-fine magnesium hydroxide fire retardant through the ball milling method according to claim 2, wherein the coupling agent comprises at least one of a rare earth coupling agent, a silane coupling agent, a titanate coupling agent and an aluminate coupling agent.
4. The ultrafine magnesium hydroxide fire retardant produced by a ball milling method according to claim 3, wherein the silane coupling agent comprises at least one of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, N- (beta-aminoethoxy) -gamma-aminopropyltrimethoxysilane (ethyloxy), N-beta- (aminoethoxy) -gamma-aminopropylmethyldimethoxysilane, gamma- (2, 3-glycidoxy) propyltrimethoxysilane, vinyltrimethoxysilane, and vinyltriacetoxysilane.
5. The method of claim 3, wherein the titanate coupling agent comprises at least one of isopropyl tris (isostearyl) titanate, isopropyl tris (dioctyl pyrophosphate) titanate, bis (dioctyl pyrophosphate) oxoacetate titanium, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl bis (methacryloyl) isostearyl titanate, isopropyl tris (dioctyl phosphoryl) titanate, isopropyl tris (dodecyl benzenesulfonyl) titanate, and isopropyl tris (n-ethylamino) titanate.
6. A method for preparing superfine magnesium hydroxide flame retardant by a ball milling method according to any one of claims 1 to 5, which is characterized by comprising the following steps:
1) mixing magnesium hydroxide with a part of solvent, and then carrying out ultrasonic dispersion to obtain a mixture A;
2) mixing the auxiliary agent with the rest solvent, and adjusting the pH value by using a pH regulator to obtain a mixture B;
3) and uniformly mixing the mixture A and the mixture B, and performing ball milling.
7. The method for preparing the superfine magnesium hydroxide flame retardant according to claim 6, wherein the ball milling is continuous milling, and the ball milling speed is 50-200 r/min.
8. The method for preparing the ultrafine magnesium hydroxide flame retardant according to claim 6, wherein the grinding balls are zirconia or alumina balls during ball milling.
9. The method for preparing the ultra-fine magnesium hydroxide fire retardant according to claim 6, wherein the grinding balls have a diameter of 2-12mm during ball milling.
10. The method for preparing ultrafine magnesium hydroxide flame retardant according to claim 8 or 9, wherein the mass ratio of the grinding balls to the magnesium hydroxide is (10-30): 1.
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| CN1492005A (en) * | 2003-08-29 | 2004-04-28 | 杨治富 | Surface treating coupling agent for natural magnesium hydroxide organic flame-retardant powder |
| CN102010619A (en) * | 2010-11-24 | 2011-04-13 | 沈阳工业大学 | Method for preparing magnesium hydroxide fire retardant and prepared magnesium hydroxide fire retardant |
| CN103665939A (en) * | 2013-12-27 | 2014-03-26 | 江苏艾特克阻燃材料有限公司 | Method for integrally preparing high-dispersity ultrafine magnesium hydroxide flame retardant |
| CN106810908A (en) * | 2015-12-01 | 2017-06-09 | 池州灵芝化建材料科技有限公司 | A kind of method of modifying of flame retardant of magnesium hydroxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1492005A (en) * | 2003-08-29 | 2004-04-28 | 杨治富 | Surface treating coupling agent for natural magnesium hydroxide organic flame-retardant powder |
| CN102010619A (en) * | 2010-11-24 | 2011-04-13 | 沈阳工业大学 | Method for preparing magnesium hydroxide fire retardant and prepared magnesium hydroxide fire retardant |
| CN103665939A (en) * | 2013-12-27 | 2014-03-26 | 江苏艾特克阻燃材料有限公司 | Method for integrally preparing high-dispersity ultrafine magnesium hydroxide flame retardant |
| CN104592790A (en) * | 2013-12-27 | 2015-05-06 | 江苏艾特克阻燃材料有限公司 | Method for controlling and modifying grain diameter of magnesium hydrate |
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