CN112358653A - Preparation method of diatomite-based surface organic magnesium hydroxide flame retardant - Google Patents
Preparation method of diatomite-based surface organic magnesium hydroxide flame retardant Download PDFInfo
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- CN112358653A CN112358653A CN202011231673.XA CN202011231673A CN112358653A CN 112358653 A CN112358653 A CN 112358653A CN 202011231673 A CN202011231673 A CN 202011231673A CN 112358653 A CN112358653 A CN 112358653A
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- diatomite
- magnesium hydroxide
- flame retardant
- magnesium
- based surface
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 239000000347 magnesium hydroxide Substances 0.000 title claims abstract description 124
- 229910001862 magnesium hydroxide Inorganic materials 0.000 title claims abstract description 124
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 title claims abstract description 123
- 239000003063 flame retardant Substances 0.000 title claims abstract description 75
- 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 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000001914 filtration Methods 0.000 claims abstract description 17
- 239000004094 surface-active agent Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000011065 in-situ storage Methods 0.000 claims abstract description 11
- 238000012986 modification Methods 0.000 claims abstract description 11
- 230000004048 modification Effects 0.000 claims abstract description 11
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 32
- 239000000725 suspension Substances 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 159000000003 magnesium salts Chemical class 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 9
- 238000007873 sieving Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 5
- 229920000053 polysorbate 80 Polymers 0.000 claims description 5
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 238000007725 thermal activation Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000002689 soil Substances 0.000 claims description 2
- 239000002002 slurry Substances 0.000 abstract description 29
- 239000002861 polymer material Substances 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 8
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- 239000005909 Kieselgur Substances 0.000 description 18
- 238000005979 thermal decomposition reaction Methods 0.000 description 16
- 239000004743 Polypropylene Substances 0.000 description 15
- -1 polypropylene Polymers 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229940057995 liquid paraffin Drugs 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229940093429 polyethylene glycol 6000 Drugs 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 241000519995 Stachys sylvatica Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—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
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- 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)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method of a diatomite-based surface organic magnesium hydroxide flame retardant, belonging to the technical field of flame retardant preparation. Aiming at the problems of low flame retardant efficiency, poor compatibility with a high polymer material, poor filtering performance of magnesium hydroxide slurry and the like existing in the preparation and application processes of the existing magnesium hydroxide flame retardant, the advantages of the flame retardant performance and the filter aid performance of diatomite are utilized, the diatomite and the surfactant with good stability in water are added in the process of preparing the magnesium hydroxide to carry out in-situ modification on the magnesium hydroxide, and the synergistic flame retardant performance of the diatomite and the magnesium hydroxide is exerted while the filtering performance of the magnesium hydroxide slurry is improved and the compatibility of the flame retardant and the high polymer material is improved. The process involved in the invention is nontoxic and harmless, green and environment-friendly, and has the advantages of easily available raw materials, simple process flow, low cost and good application prospect.
Description
Technical Field
The invention belongs to the technical field of preparation of flame retardants, and particularly relates to a preparation method of a diatomite-based surface organized magnesium hydroxide flame retardant.
Background
Since nearly half a century, the development of high polymer materials such as plastics, rubber, fibers and the like is very rapid, and the high polymer materials almost permeate into various fields of national economy and people's life, thereby providing necessary new materials for medical science, electronics, aerospace industry and the like. However, the inflammability and combustion process of the high polymer material release a large amount of toxic and harmful substances, which hinders further widening of the application field. Therefore, it is very important to impart flame retardant property to polymer materials in order to ensure the life and property safety of people.
With the increasing awareness of safety and environmental protection, the development of flame retardants with no halogen, green color, low cost, high flame retardancy, and good compatibility with high polymer materials has gradually become a hot point of research in the flame retardant field. Magnesium hydroxide is used as a halogen-free and green-friendly flame retardant, and becomes the first choice of a high polymer material flame retardant due to the advantages of flame retardance, smoke suppression, no toxicity, no corrosion, good thermal stability, good function of promoting base material to form carbon and the like. However, there are some problems in the preparation and application processes: (1) the common-grade magnesium hydroxide flame retardant needs more than 60 percent of addition amount to achieve the same flame retardant effect as a halogen flame retardant, and the high addition amount can sharply reduce the mechanical property of the high polymer material; (2) because the surface of the magnesium hydroxide contains a large amount of hydrophilic groups, namely hydroxyl groups, the magnesium hydroxide has high water absorption and is easy to form aggregates, the magnesium hydroxide has poor compatibility and processing fluidity with a high polymer material, and the conditions of surface frosting, white spots or loss of luster are generated, so that the appearance, the processing performance and the like of the high polymer material are influenced; (3) the magnesium hydroxide is colloidal precipitate, so that the solid-liquid separation of the magnesium hydroxide slurry is difficult.
The diatomite is a fossil nonmetallic ore formed by piling remains of unicellular algae for 1-2 ten thousand years, the main component of the diatomite is SiO2, and less Fe is attached2O3、Al2O3MgO, etc., and a small amount of organic substances. The material has the characteristics of low density, large specific surface area, porosity, high permeability, hydroxyl contained on the surface, chemical stability and the like. In the field of flame retardance, diatomite is often used to be compounded with other flame retardants. Chinese patent CN110591387A discloses a melamine-coated ZIF-67 modified diatomite flame-retardant smoke suppressant. Research results show that the existence of the silicon dioxide in the diatomite can further enhance the catalytic carbonization effect of the metal oxide. In addition, the diatomite has good filter-aid performance, and the diatomite is introduced in the process of preparing the magnesium hydroxide flame retardant, so that the filter performance of the magnesium hydroxide slurry can be improved. However, the diatomite-magnesium hydroxide composite flame retardant still belongs to an inorganic flame retardant, has strong surface hydrophilicity and poor compatibility with high polymer materials.
Disclosure of Invention
The invention aims to provide a preparation method of a diatomite-based surface organic magnesium hydroxide flame retardant, so as to realize efficient flame-retardant modification of a high polymer material. The preparation method has the effects of strong adaptability, simple process flow, convenient operation, mild reaction conditions and high flame-retardant efficiency.
Aiming at the problems of the common magnesium hydroxide flame retardant, the invention utilizes the advantages of the flame retardant property and the filter aid property of the diatomite, adds the diatomite and the surfactant with good stability in water in the process of preparing the magnesium hydroxide, carries out in-situ modification on the magnesium hydroxide, and exerts the synergistic flame retardant property of the diatomite and the magnesium hydroxide while improving the filtration property of magnesium hydroxide slurry and the compatibility of the flame retardant and a high polymer material.
The purpose of the invention is realized by the following technical scheme:
the preparation method of the diatomite-based surface organic magnesium hydroxide flame retardant comprises the steps of adding diatomite and a surfactant with good stability in water in the preparation process of magnesium hydroxide, carrying out in-situ modification on magnesium hydroxide, carrying out structural inlaying, wrapping modification and filling modification on the diatomite, and after the modification is finished, filtering, washing, drying, grinding and sieving with a 200-mesh sieve to obtain the diatomite-based surface organic magnesium hydroxide flame retardant.
The preparation method specifically comprises the following steps:
(1) placing diatomite raw soil into a muffle furnace, roasting at 450-800 ℃ for 1-4 h, and carrying out thermal activation;
(2) putting 50-250 mL of 0.75 mol/L magnesium salt solution into a three-neck flat-bottom flask, and mixing the surfactant, diatomite and magnesium hydroxide according to a mass ratio of 1: 100-5: 100, adding a surfactant into a magnesium salt solution, and stirring at 50-80 ℃ until the surfactant is completely dissolved and uniformly dispersed in the magnesium salt solution to form a mixed solution of the surfactant and the magnesium salt solution;
the magnesium salt is one of magnesium chloride, magnesium sulfate or magnesium nitrate.
(3) According to the mass ratio of the diatomite to the magnesium hydroxide of 0.1: 1-1: adding the thermally activated diatomite into the mixed solution obtained in the step (2), and fully mixing under a stirring condition to obtain a diatomite suspension;
(4) under the magnetic stirring at 50-80 ℃, adding 50-250 mL of 1.5 mol/L alkali liquor (mainly comprising one of sodium hydroxide solution, ammonia water and calcium hydroxide aqueous solution) which is placed in a constant-pressure dropping funnel into the diatomite suspension obtained in the step (3) at the dropping speed of 3.3 mL/min, and continuing stirring and reacting for 1 h after the dropping is finished to obtain the diatomite-based surface organized magnesium hydroxide suspension;
(5) and (4) filtering, washing, drying, grinding and sieving the suspension obtained in the step (4) by a 200-mesh sieve to obtain the diatomite-based surface organic magnesium hydroxide flame retardant.
In the invention, the particle size of the diatomite is 30-40 μm.
In the invention, the average particle size of the magnesium hydroxide is 30-50 nm.
In the invention, the surfactant with good stability in water is selected as the in-situ modifier. The surfactant comprises one of sodium stearate, tween 80 or polyethylene glycol.
The invention has the beneficial effects that:
(1) the flame retardant provided by the invention has the advantages of wide raw material source, low price, simple preparation process, mild condition, low energy consumption and convenient operation, and is suitable for large-scale industrial production.
(2) In the flame retardant provided by the invention, diatomite is used as a carrier, the surface organized magnesium hydroxide is embedded, and the surface organized magnesium hydroxide is coated by a surfactant, so that the technical bottleneck that the diatomite-based magnesium hydroxide flame retardant is difficult to disperse in a high polymer material is solved, and meanwhile, the technical bottleneck that the solid-liquid separation of magnesium hydroxide slurry is difficult is solved by utilizing the filter aid performance of the diatomite.
(3) In the flame retardant provided by the invention, the concentration of combustible gas and the concentration of oxygen in a gas-phase combustion area are diluted by water vapor generated by thermal decomposition of magnesium hydroxide, so that a smoke abatement effect is achieved, and meanwhile, the magnesium oxide generated by thermal decomposition of magnesium hydroxide can promote a high polymer material to form a surface carbonization layer in a combustion process, so that the magnesium oxide and the formed carbonization layer jointly form a compact protective layer which uniformly covers the surface of the high polymer material, and the spread of flame is effectively inhibited. In addition, the diatomite and the magnesium hydroxide can generate a synergistic flame-retardant effect, so that the carbon layer structure is improved, and the flame-retardant performance of the flame retardant is greatly improved.
(4) According to the flame retardant provided by the invention, the diatomite can enhance the mechanical property of the flame-retardant engineering material, so that the problem of material mechanical property weakening caused by the introduction of the magnesium hydroxide flame retardant can be effectively avoided.
(5) The flame retardant provided by the invention has higher thermal stability and good compatibility, and the application range of the flame retardant is expanded.
Drawings
FIG. 1 is a thermogravimetric curve of a magnesium hydroxide flame retardant and a diatomaceous earth-based organized magnesium hydroxide flame retardant prepared in example 2 of the present invention under a nitrogen atmosphere;
FIG. 2 is a scanning electron micrograph of diatomaceous earth raw earth and heat-activated diatomaceous earth used in the present invention;
FIG. 3 is a scanning electron microscope photograph of the diatomite-based organized magnesium hydroxide flame retardant prepared in example 5 of the present invention;
FIG. 4 is a Fourier transform infrared spectroscopy (FTIR) profile of the diatomaceous earth-based organized magnesium hydroxide flame retardant prepared in example 5 of the present invention and the diatomaceous earth used in the present invention.
Detailed Description
The present invention will be described more fully and in detail with reference to the following specific examples, but the scope of the invention is not limited to the specific examples.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specified, the reagents and materials used in the present invention are commercially available products or products obtained by a known method.
The technical scheme adopted by the invention is further explained by combining the drawings and the embodiment.
Example 1
Adding 100 mL of magnesium chloride solution with the concentration of 0.75 mol/L into a three-neck flat-bottom flask, heating in a water bath at 80 ℃, and mixing the magnesium chloride solution and the sodium stearate with the diatomite and the magnesium hydroxide according to the mass ratio of 3: 100, adding sodium stearate into the magnesium chloride solution, magnetically stirring until the sodium stearate is completely dissolved in the magnesium chloride solution, adding 0.435 g of diatomite into the mixed solution, and uniformly stirring and mixing to form a diatomite suspension. 100 mL of 1.5 mol/L sodium hydroxide solution placed in a constant pressure dropping funnel is added into the kieselguhr suspension at the dropping speed of 3.3 mL/min, and the stirring reaction is continued for 1 h after the dropping is finished. And filtering, washing, drying, grinding and sieving the prepared white suspension by a 200-mesh sieve to obtain the diatomite-based organic magnesium hydroxide flame retardant.
The filtering speed of the diatomite-based organic magnesium hydroxide slurry subjected to in-situ synthesis is 1.8 times that of the pure magnesium hydroxide slurry, the thermal decomposition temperature of the diatomite-based organic magnesium hydroxide slurry is 377 ℃, is obviously higher than the thermal decomposition temperature of the pure magnesium hydroxide, is 340 ℃, and has good dispersibility in liquid paraffin. The prepared diatomite-based organic magnesium hydroxide flame retardant is applied to a polypropylene system, the oxygen index is 29.6% according to a test of a GB/T2406.2-2009 method, the tensile strength of the PP/diatomite-based organic magnesium hydroxide composite material is 29.93 MPa, and the tensile strength is improved by 6.5% compared with the tensile strength of PP/pure magnesium hydroxide of 28.10 MPa.
Example 2
Adding 100 mL of 0.75 mol/L magnesium chloride solution into a three-neck flat-bottom flask, heating in a water bath at 60 ℃, and mixing according to the mass ratio of Tween 80 to diatomite plus magnesium hydroxide of 3: 100, adding Tween 80 into a magnesium chloride solution, magnetically stirring until the Tween 80 is completely dissolved in the magnesium chloride solution, adding 0.435 g of diatomite into the mixed solution, and uniformly stirring and mixing to form a diatomite suspension. 100 mL of 1.5 mol/L sodium hydroxide solution in a constant pressure dropping funnel is added into the kieselguhr suspension at the dropping speed of 3.3 mL/min, and the stirring reaction is continued for 1 h after the dropping is finished. And filtering, washing, drying, grinding and sieving the prepared white suspension by a 200-mesh sieve to obtain the diatomite-based organic magnesium hydroxide flame retardant. FIG. 1 is a thermogravimetric plot of the magnesium hydroxide flame retardant and the diatomaceous earth-based organized magnesium hydroxide flame retardant prepared in this example under a nitrogen atmosphere.
The filtering speed of the diatomite-based organic magnesium hydroxide slurry subjected to in-situ synthesis is 2.1 times that of the pure magnesium hydroxide slurry, the thermal decomposition temperature of the diatomite-based organic magnesium hydroxide slurry is 361 ℃, the thermal decomposition temperature of the diatomite-based organic magnesium hydroxide slurry is obviously higher than the thermal decomposition temperature of the pure magnesium hydroxide, namely 340 ℃, and the diatomite-based organic magnesium hydroxide slurry has good dispersibility in liquid paraffin. The prepared diatomite-based organic magnesium hydroxide flame retardant is applied to a polypropylene system, the oxygen index is 29.8% according to a test of a GB/T2406.2-2009 method, the tensile strength of the PP/diatomite-based organic magnesium hydroxide composite material is 29.79 MPa, and the tensile strength is improved by 6% compared with the tensile strength of PP/pure magnesium hydroxide of 28.10 MPa.
Example 3
Adding 100 mL of 0.75 mol/L magnesium sulfate solution into a three-neck flat-bottom flask, heating in a water bath at 60 ℃, and mixing according to the mass ratio of sodium dodecyl benzene sulfonate to diatomite and magnesium hydroxide of 3: 100, adding sodium dodecyl benzene sulfonate into a magnesium chloride solution, magnetically stirring until the sodium dodecyl benzene sulfonate is completely dissolved in the magnesium chloride solution, adding 0.435 g of diatomite into the mixed solution, and uniformly stirring and mixing to form a diatomite suspension. 100 mL of 1.5 mol/L sodium hydroxide solution in a constant pressure dropping funnel is added into the kieselguhr suspension at the dropping speed of 3.3 mL/min, and the stirring reaction is continued for 1 h after the dropping is finished. And filtering, washing, drying, grinding and sieving the prepared white suspension by a 200-mesh sieve to obtain the diatomite-based organic magnesium hydroxide flame retardant.
The filtering speed of the diatomite-based organic magnesium hydroxide slurry subjected to in-situ synthesis is 1.5 times that of the pure magnesium hydroxide slurry, the thermal decomposition temperature of the diatomite-based organic magnesium hydroxide slurry is 356 ℃, the thermal decomposition temperature of the diatomite-based organic magnesium hydroxide slurry is obviously higher than the thermal decomposition temperature of the pure magnesium hydroxide, namely 340 ℃, and the diatomite-based organic magnesium hydroxide slurry has good dispersibility in liquid paraffin. The prepared diatomite-based organic magnesium hydroxide flame retardant is applied to a polypropylene system, the oxygen index is 28.1% according to a test of a GB/T2406.2-2009 method, the tensile strength of the PP/diatomite-based organic magnesium hydroxide composite material is 29.22 MPa, and the tensile strength is improved by 4% compared with the tensile strength of PP/pure magnesium hydroxide of 28.10 MPa.
Example 4
Adding 100 mL of 0.75 mol/L magnesium nitrate solution into a three-mouth flat-bottom flask, heating in a water bath at 60 ℃, and mixing the magnesium nitrate solution and the magnesium hydroxide according to the mass ratio of 3: 100, adding polyethylene glycol 6000 into a magnesium chloride solution, magnetically stirring until the polyethylene glycol 6000 is completely dissolved in the magnesium chloride solution, adding 0.435 g of diatomite into the mixed solution, and uniformly stirring and mixing to form a diatomite suspension. 100 mL of 1.5 mol/L ammonia water in a constant pressure dropping funnel is added into the kieselguhr suspension at the dropping speed of 3.3 mL/min, and the stirring reaction is continued for 1 h after the dropping is finished. And filtering, washing, drying, grinding and sieving the prepared white suspension by a 200-mesh sieve to obtain the diatomite-based organic magnesium hydroxide flame retardant.
The filtering speed of the diatomite-based organic magnesium hydroxide slurry subjected to in-situ synthesis is 1.65 times that of the pure magnesium hydroxide slurry, the thermal decomposition temperature of the diatomite-based organic magnesium hydroxide slurry is 352 ℃, the thermal decomposition temperature of the diatomite-based organic magnesium hydroxide slurry is obviously higher than the thermal decomposition temperature of the pure magnesium hydroxide, namely 340 ℃, and the diatomite-based organic magnesium hydroxide slurry has good dispersibility in liquid paraffin. The prepared diatomite-based organic magnesium hydroxide flame retardant is applied to a polypropylene system, the oxygen index is 27.8% according to a test of a GB/T2406.2-2009 method, the tensile strength of the PP/diatomite-based organic magnesium hydroxide composite material is 29.17 MPa, and the tensile strength is improved by 3.8% compared with the tensile strength of PP/pure magnesium hydroxide of 28.10 MPa.
Example 5
Adding 100 mL of 0.75 mol/L magnesium chloride solution into a three-neck flat-bottom flask, heating in a water bath at 80 ℃, and mixing according to the mass ratio of oleic acid to diatomite plus magnesium hydroxide of 3: 100, adding oleic acid into a magnesium chloride solution, magnetically stirring until the oleic acid is uniformly dispersed in the magnesium chloride solution, adding 0.435 g of diatomite into the mixed solution, and uniformly stirring and mixing to form a diatomite suspension. 100 mL of 0.75 mol/L calcium hydroxide solution in a constant pressure dropping funnel is added into the kieselguhr suspension at the dropping speed of 3.3 mL/min, and the stirring reaction is continued for 1 h after the dropping is finished. And filtering, washing, drying, grinding and sieving the prepared white suspension by a 200-mesh sieve to obtain the diatomite-based organic magnesium hydroxide flame retardant. FIG. 2 is a scanning electron micrograph of diatomaceous earth and diatomaceous earth used therein (FIG. a is a 2000-fold magnified scanning electron micrograph of diatomaceous earth, FIG. b is a 30000-fold magnified scanning electron micrograph of diatomaceous earth, FIG. b differs from FIG. a in that the pore structure of the diatomaceous earth surface can be seen more clearly, FIG. c is a 2000-fold magnified scanning electron micrograph of diatomaceous earth, FIG. d is a 30000-fold magnified scanning electron micrograph of diatomaceous earth, FIG. d differs from FIG. c in that the pores on the surface of diatomaceous earth after thermal activation can be seen more clearly, FIG. 3 is a scanning electron micrograph of diatomaceous earth-based organic magnesium hydroxide flame retardant prepared (FIG. e is a 2000-fold magnified scanning electron micrograph of diatomaceous earth-based organic magnesium hydroxide flame retardant, FIG. f is a 30000-fold magnified scanning electron micrograph of diatomaceous earth-based organic magnesium hydroxide flame retardant, the difference between the graph f and the graph e is that the surface of the diatomite is successfully loaded with the magnesium hydroxide, and the magnesium hydroxide is uniformly distributed on the surface and in the pore channels of the diatomite, and the pore structure of the diatomite is maintained); FIG. 4 is a Fourier Infrared Spectroscopy (FTIR) plot of the prepared diatomaceous earth-based organized magnesium hydroxide flame retardant and diatomaceous earth used in the present invention.
The filtering speed of the diatomite-based organic magnesium hydroxide slurry subjected to in-situ synthesis is 2.0 times that of the pure magnesium hydroxide slurry, the thermal decomposition temperature of the diatomite-based organic magnesium hydroxide slurry is 379 ℃, the thermal decomposition temperature of the diatomite-based organic magnesium hydroxide slurry is obviously higher than the thermal decomposition temperature of the pure magnesium hydroxide, namely 340 ℃, and the diatomite-based organic magnesium hydroxide slurry has good dispersibility in liquid paraffin. The prepared diatomite-based organic magnesium hydroxide flame retardant is applied to a polypropylene system, the oxygen index is 29.8% according to a test of a GB/T2406.2-2009 method, the tensile strength of the PP/diatomite-based organic magnesium hydroxide composite material is 29.87 MPa, and the tensile strength is improved by 6.3% compared with the tensile strength of PP/pure magnesium hydroxide of 28.10 MPa.
Claims (8)
1. A preparation method of a diatomite-based surface organic magnesium hydroxide flame retardant is characterized by comprising the following steps: adding diatomite and a surfactant with good stability in water in the preparation process of magnesium hydroxide, carrying out in-situ modification on the magnesium hydroxide, simultaneously carrying out structural inlaying, wrapping modification and filling modification on the diatomite, and after the modification is finished, filtering, washing, drying, grinding and sieving with a 200-mesh sieve to obtain the diatomite-based surface organic magnesium hydroxide flame retardant.
2. The method for preparing the diatomite-based surface organized magnesium hydroxide flame retardant according to claim 1, characterized by comprising the steps of:
(1) placing diatomite raw soil in a muffle furnace for thermal activation;
(2) putting the magnesium salt solution into a three-opening flat-bottom flask, and mixing the surfactant, the diatomite and the magnesium hydroxide according to a mass ratio of 1: 100-5: 100, adding a surfactant into a magnesium salt solution, and stirring at 50-80 ℃ until the surfactant is completely dissolved and uniformly dispersed in the magnesium salt solution to form a mixed solution of the surfactant and the magnesium salt solution;
(3) according to the mass ratio of the diatomite to the magnesium hydroxide of 0.1: 1-1: adding the thermally activated diatomite into the mixed solution obtained in the step (2), and fully mixing under a stirring condition to obtain a diatomite suspension;
(4) under the magnetic stirring at 50-80 ℃, adding 50-250 mL of 1.5 mol/L alkali liquor which is placed in a constant-pressure dropping funnel into the diatomite suspension obtained in the step (3) at the dropping speed of 3.3 mL/min, and continuing stirring and reacting for 1 h after the dropping is finished to obtain the diatomite-based surface organized magnesium hydroxide suspension;
(5) and (4) filtering, washing, drying, grinding and sieving the suspension obtained in the step (4) by a 200-mesh sieve to obtain the diatomite-based surface organic magnesium hydroxide flame retardant.
3. The method for preparing the diatomite-based surface organized magnesium hydroxide flame retardant according to claim 2, wherein: the particle size of the diatomite is 30-40 mu m.
4. The method for preparing the diatomite-based surface organized magnesium hydroxide flame retardant according to claim 2, wherein: the magnesium hydroxide has an average particle diameter of 30 to 50 nm.
5. The method for preparing the diatomite-based surface organized magnesium hydroxide flame retardant according to claim 2, wherein: in the step (1), the thermal activation conditions are as follows: roasting for 1-4 h at 450-800 ℃.
6. The method for preparing the diatomite-based surface organized magnesium hydroxide flame retardant according to claim 2, wherein: in the step (2), the concentration of the magnesium salt solution is 0.75 mol/L, and the magnesium salt is one of magnesium chloride, magnesium sulfate or magnesium nitrate.
7. The method for preparing the diatomite-based surface organized magnesium hydroxide flame retardant according to claim 2, wherein: selecting a surfactant with good stability in water as an in-situ modifier; the surfactant comprises one of sodium stearate, tween 80 or polyethylene glycol.
8. The method for preparing the diatomite-based surface organized magnesium hydroxide flame retardant according to claim 2, wherein: in the step (4), the alkali liquor is one of a sodium hydroxide solution, ammonia water or a calcium hydroxide solution.
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