CN102500299B - Preparation method for nanoscale modified magnesium hydroxide - Google Patents
Preparation method for nanoscale modified magnesium hydroxide Download PDFInfo
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- CN102500299B CN102500299B CN201110375485.9A CN201110375485A CN102500299B CN 102500299 B CN102500299 B CN 102500299B CN 201110375485 A CN201110375485 A CN 201110375485A CN 102500299 B CN102500299 B CN 102500299B
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Abstract
The invention provides a preparation method for nanoscale modified magnesium hydroxide and aims to provide a preparation method for superfine magnesium hydroxide. By the preparation method, the yield is high; the technical process is short; no pollution exists in the production process; the grain size is distributed narrowly; and ultrafining and surface modification can be finished at one step. The preparation method is implemented by the following technical scheme: mixing, stirring and pulping 1,000 weight parts of magnesium hydroxide powder with the grain size of 325 to 8,000 meshes, 1 to 80 weight parts of surfactant and 1,000 to 5,000 weight parts of solvent; filling the pulp into a grinding cavity by using spherical medium grinding beads with the diameter of less than or equal to 0.8 mm and grinding the pulp by using the pulp grinding equipment under the conditions that the filling volume is more than 35 percent and the minimum speed of the grinding beams is more than 10 meters per second; and drying the pulp subjected to grinding by using drying equipment under the drying condition of 40 to 320 DEG C to obtain the ultrafine magnesium hydroxide powder with the average grain size of 50 to 500 nanometers and the modified surface.
Description
Technical field
The invention relates to the preparation method of nanoscale modified magnesium hydroxide, more particularly the invention relates to and can be mainly used in flame retardant area, the preparation method of the nano level modified super fine magnesium hydroxide of surface modification.
Background technology
Magnesium hydrate powder material as inorganic, press down cigarette, nontoxic fire proofing, in high molecular polymer flame retardant area, be widely used.Magnesium hydroxide has high thermal stability, high caloric receptivity, excellent cigarette ability, the soft of pressing down with it with respect to the aluminium hydroxide flame-retardant material being widely used, be considered to the most rising environmentally friendly inorganic combustion inhibitor, become the focus of various countries' research in recent years.
The fast development of nanoscale science and technology, from aspects such as theory, preparation technology and relevant devices (comprising analytical and testing instrument), has all produced great promotion to the fine research of flame retardant of magnesium hydroxide.Utilize ultra fine, the processing method that especially fine and surface treatment combine, can significantly improve the compatibility of flame retardant of magnesium hydroxide and polymer substrate, can obviously improve magnesium hydroxide flame retardant material mechanical performance and processing characteristics.In addition, fire retardant nanometer contributes to give full play to its fire resistance, as the polymeric material that is added with nano-meter flame retardants is carried out to combustion testing, the expanded foam charcoal layer that the polymeric material of known interpolation nano-sized magnesium hydroxide (compared with conventional flame retardant) forms is fine and closely woven, has high density and high strength.This is because nano-meter flame retardants size is tiny, specific area is large, particle is dispersed in polymer, in fire-retardant process, nano-sized magnesium hydroxide particle can thermally equivalent everywhere, and while having avoided particle larger, exploded causes polymeric material to become charcoal inhomogeneous with to become charcoal of poor quality.
Strengthen the preparation research of nano-sized magnesium hydroxide, promote the production of China's flame retardant of magnesium hydroxide and develop the study hotspot that has become inorganic combustion inhibitor field.In recent years, the units such as Beijing Institute of Technology, Chinese University of Science and Technology, Tsing-Hua University, the Beijing University of Chemical Technology in succession preparation technology to nano-magnesium hydrate fire retardant and application are studied, and the method for employing mainly contains metal magnesium hydration method, direct precipitation method, sluggish precipitation, precipitation-azeotropic distillation method, gravity Method etc.
Metal magnesium hydration legal system magnesium hydroxide has two kinds of techniques, and it is high especially to the requirement of raw material and equipment, and product purity is high, but cost is also high, and productive rate is low, and difficulty realizes suitability for industrialized production.
The natural brucite that the selection of shepardite pulverizing method is relatively pure etc. is raw material, under grinding aid exists, and through stirring mill wet grinding, fraction, surface treatment, obtains the superfine powder that reaches re-set target.But this preparation method consumes energy high, the size general 0.7-3 μ m of particle or larger, yardstick and distribution of shapes are wide, reach product quality low.
When direct precipitation method NaOH is precipitating reagent, severe reaction conditions, wayward; While being precipitating reagent with NH3-H2O or NH3, easily contaminated environment; While being precipitation with Ca (OH) 2, product purity is low, and accessory substance calcium salt is difficult.
The feature of precipitation-hydro-thermal method is that the purity of product is high, and particle diameter and form are evenly distributed, but particle diameter is larger, generally, at 0.5～5 μ m, needs high-temperature high-pressure apparatus, intermittent operation.
High shear emulsifying reactor is similar to colloid mill, and in fact unrealized microcosmic evenly mixes, and particle size were distributes wide.
Full back-mixing liquid film reactor is in fact in the operation of precipitate-hydro-thermal method, and the long-time back-mixing of reactant operates tediously longly, and production cost is high.
Gravity Method is prepared nano-sized magnesium hydroxide and has been obtained success, has realized industrial-scale production.But, in brin, liquid film, three kinds of different reaction environments of drop, carry out precipitation reaction, be doomed particle diameter and the morphological inhomogeneity of products therefrom; Packed bed is likely stopped up by magnesium hydrate precipitate.
Percussion flow method adopts injecting type impinging stream reaction crystallizer.In this, reactor is from molecular beam reactor, when magnesium salt solution and alkali lye injection stream are when larger, will not reach microcosmic and mixes, and will occur particle diameter and the form skewness of product, and difficulty realizes industrial-scale production.
With spin disk reactor synthesis of nano magnesium hydroxide, then through roasting oxygenerating magnesium.Owing to lacking two kinds of uniform mechanisms of reactant liquor rapid mixing on spin disk, the uniformity that therefore particle diameter and form distribute is affected.
These methods all exist respectively the problems such as technical process is tediously long, cost is high, and productive rate is low, difficulty realizes industrial-scale production, and particle diameter is large and distribution of shapes is wide, product quality is low, and production process environmental pollution is serious.
Summary of the invention
The object of the invention is the weak point existing for prior art, provide that a kind of to manufacture productive rate high, technical process is short, and production process is pollution-free, and narrow diameter distribution can a step completes the preparation method of the super fine magnesium hydroxide of fine and surface modification.
Above-mentioned purpose of the present invention can reach by following measures: a kind of preparation method of nanoscale modified magnesium hydroxide, is characterized in that comprising the steps:
By the magnesium hydrate powder of 325～8000 order particle diameters, surface modifier and solvent are that 1000: 1～80: 1000～5000 (weight portion) mixes in proportion, stirring to pulp, then, above-mentioned slurry is passed through to milling apparatus, by the spherical medium grinding bead of diameter≤0.8mm, be filled in and grind in cavity, be greater than 35% at packing volume ratio, the minimum movement velocity of grinding bead is greater than under the environment of 10 meter per seconds grinds, the slurry more above-mentioned grinding being obtained, pass through drying equipment, under 40 ℃～320 ℃ drying conditions, be dried, obtain the fine magnesium hydrate powder of average particle size distribution in the process modification of the surface of 50～500 nanometers.
The present invention has following beneficial effect than prior art.
The present invention adopts magnesium hydrate powder by a certain percentage and surface modifier and solvent, grinding, under the process conditions that are different from prior art, by thick magnesium hydrate powder, by fine, surface modifier, under uniform temperature condition, dry acquisition is through the ultrafine magnesium hydroxide powder body of surface modification.Complete fine and the surface modification of magnesium hydrate powder by shorter technological process, a step, prior art metal magnesium hydration method, direct precipitation method, sluggish precipitation, precipitation-azeotropic distillation method, gravity Method are solved, dry method, technical process is tediously long, cost is high, productive rate is low, difficulty realizes industrial-scale production, the problems such as particle diameter distribution is wide, product quality is low, and production process environmental pollution is serious.
The present invention adopts efficient nano level to grind; combining nano magnesium hydroxide surface modifying technology; magnesium hydroxide superfining process and surface modification technology are combined into a step; both reduce processing step, reduced cost; also the quality that has improved the product such as degree of modification, particle diameter distribution width, becomes a reality the scale volume production of nanoscale surface modification magnesium hydroxide simultaneously.The process conditions that with simple process equipment, easily realize, realized that process costs is low, product cut size narrowly distributing, production process be environment friendly and pollution-free, a step completes the surface modification of magnesium hydrate powder and the fine of magnesium hydrate powder.For scale cheaply, the fine Magnesium Hydroxide Nano-particles of industrial production high-quality provides technology shortcut.
The specific embodiment
Describe specific embodiments of the invention in detail below in conjunction with technical scheme.
In following examples, the technological process of preparation can be as follows:
Step 1: by magnesium hydrate powder by a certain percentage with surface modifier, solvent, stir into slurry; The particle diameter of magnesium hydrate powder conventionally can be within the scope of 325～8000 orders; Surface modifier can be the one in alcohol dilution, the long chain organic acid of silane coupler; Solvent is water, one or more in alcohol below C1～C4; The ratio of magnesium hydroxide, surface modifier and solvent is 1000: (1～80): (1000～5000); The process conditions of grinding are: abrasive media can adopt diameter to be less than spherical ceramic grinding bead, zirconia ball, the spherical metal grinding bead of 0.8mm, such as the grinding bead such as stainless steel, titanium alloy;
Step 2: the slurry that step 1 is obtained, grinds under the condition of grinding material in cavity and be greater than at 40 ℃～90 ℃, the minimum movement velocity of grinding bead 10 meter per seconds than being greater than in 35% milling apparatus at the packing volume of having filled diameter and be less than grinding bead in the spherical ceramic grinding bead of 0.8mm, grinding chamber.
Step 3: the slurry that step 2 is obtained, use drying equipment to be dried under 40 ℃～320 ℃ drying conditions, can obtain the magnesium hydrate powder of average particle size distribution in the process modification of the surface of 50～500 nanometers.Drying equipment can be one or both in spray drying device, flash drying equipment, pneumatic conveying dryer, trifling drying equipment.
Embodiment 1
According to said method, get 10 kilograms of the commercially available magnesium hydrate powders of 325 order, mix, stir into slurry with 3-triethoxysilyl-1-propylamine, 20 kilograms of deionized waters with ethanol dilution of 800 gram of 30% concentration.And this slurry is repeatedly flow through and filled 4.5 kilograms
the horizontal sand mill of the 3L cavity capacity of alumina balls grinds by the rotating speed of 2000 revs/min, and when grinding, temperature of charge is controlled within the scope of 40 ℃～45 ℃.Grind after 5 hours, get slurry and be dried 48 hours in the baking oven of 80 ℃, can obtain the magnesium hydroxide of fine, modification, its average grain diameter is 421 nanometers.
Embodiment 2
According to said method, get 5 kilograms of the commercially available magnesium hydrate powders of 800 order, with 200 gram of 50% concentration with ethanol by dilution 3-triethoxysilyl-1-propylamine, 7 kilograms of deionized waters mix, stir into slurry.And this slurry is repeatedly flow through and filled 5 kilograms
the horizontal sand mill of the 3L cavity capacity of zirconia ball grinds by the rotating speed of 3000 revs/min, and when grinding, temperature of charge is controlled at 60～65 ℃.Grind after 3 hours, get slurry and be dried 36 hours in the baking oven of 110 ℃, can obtain the magnesium hydroxide of fine, modification, its average grain diameter is 260 nanometers.
Embodiment 3
According to said method, get 500 grams of the commercially available magnesium hydrate powders of 2500 order, mix, stir into slurry with 17.5 grams of stearic acid, 1200 grams of ethanol.And this slurry is repeatedly flow through and filled 1.2 kilograms
the test of the 0.6L cavity capacity of zirconium oxide abrasive ball is ground by the rotating speed of 3600 revs/min with sand mill, and when grinding, temperature of charge is controlled at 30 ℃～35 ℃.Grind after 10 hours, get slurry vacuum microwave drier and be dried at 46 ℃, can obtain the magnesium hydroxide of fine, modification, its average grain diameter is 61 nanometers.
Embodiment 4
According to said method, get 10 kilograms of the commercially available magnesium hydrate powders of 3000 order, with 800 gram of 30% concentration with ethanol by dilution γ-methacryloxypropyl trimethoxy silane, 20 kilograms of deionized waters mix, stir into slurry.And this slurry is repeatedly flow through and filled 55 kilograms
the horizontal sand mill of the 30L cavity capacity of alumina balls grinds by 2000 revs/min, and when grinding, temperature of charge is controlled at 40 ℃～45 ℃, grinds after 5 hours.Under the temperature of charge condition of 60 ℃～65 ℃, grind after 2 hours afterwards, get slurry and be dried 48 hours in the baking oven of 80 ℃, can obtain the magnesium hydroxide of fine, modification, its average grain diameter is 421 nanometers.
Embodiment 5
According to said method, get 1000 kilograms of the commercially available magnesium hydrate powders of 1500 order, mix, stir into slurry with N-(β mono-aminoethyl)-γ-aminopropyl front three (second) TMOS, 2000 kilograms of deionized waters with ethanol dilution of 10 kilogram of 20% concentration.And this slurry is repeatedly flow through and filled 50 kilograms
the horizontal sand mill of the 30L cavity capacity of zirconia ball grinds by 2500 revs/min, and when grinding, temperature of charge is controlled at 80 ℃～85 ℃.Grind after 18 hours, get slurry spray drying device dry, can obtain the magnesium hydroxide of fine, modification, its average grain diameter is 73 nanometers.
Claims (3)
1. a preparation method for nanoscale modified magnesium hydroxide, is characterized in that comprising the steps:
By the magnesium hydrate powder of 325～8000 order particle diameters, surface modifier and solvent are 1000: 1～80: 1000～5000(weight portion in proportion) mix, stirring to pulp, then, above-mentioned slurry is passed through to milling apparatus, by the spherical medium grinding bead of diameter≤0.8mm, be filled in and grind in cavity, be greater than 35% at packing volume ratio, the minimum movement velocity of grinding bead is greater than under the environment of 10 meter per seconds grinds, the slurry more above-mentioned grinding being obtained, pass through drying equipment, under 40 ℃～320 ℃ drying conditions, be dried, one step completes fine and the surface modification of magnesium hydrate powder, obtain the fine magnesium hydrate powder of average particle size distribution in the process modification of the surface of 50～500 nanometers,
Wherein, described surface modifier is the one in alcohol dilution, the long chain organic acid of silane coupler;
Wherein, described solvent is one or more in the alcohol of deionized water, C1～C4.
2. the preparation method of nanoscale modified magnesium hydroxide as claimed in claim 1, is characterized in that, described abrasive media is the one in spherical ceramic grinding bead.
3. the preparation method of nanoscale modified magnesium hydroxide as claimed in claim 1, is characterized in that, when grinding, magnesium hydroxide temperature of charge is controlled within the scope of 40 ℃～90 ℃.
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| CN201110375485.9A CN102500299B (en) | 2011-11-23 | 2011-11-23 | Preparation method for nanoscale modified magnesium hydroxide |
| CN201410161285.7A CN104031415B (en) | 2011-11-23 | 2011-11-23 | The preparation method of nanoscale modified magnesium hydroxide |
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| CN107056151A (en) * | 2017-03-03 | 2017-08-18 | 筑成联合资产管理有限公司 | A kind of fire-proof plate |
| CN108285552A (en) * | 2017-12-27 | 2018-07-17 | 江苏艾特克阻燃材料有限公司 | A kind of modified magnesium hydroxide, method of modifying and application |
| CN110229516A (en) * | 2019-07-10 | 2019-09-13 | 西北师范大学 | A kind of preparation method of the intrinsic fire-retardant Nylon 66 composite material of low smoke, zero halogen |
| CN110342552B (en) * | 2019-08-16 | 2021-12-10 | 大连环球矿产股份有限公司 | Method for preparing active micro-nano magnesium hydroxide flame retardant by chemical method |
| CN114538485B (en) * | 2022-02-25 | 2023-09-15 | 安徽大学绿色产业创新研究院 | Method for preparing flame retardant magnesium hydroxide by taking industrial magnesium hydroxide as raw material |
| CN115780035B (en) * | 2022-11-25 | 2023-09-29 | 大连亚泰科技新材料股份有限公司 | Horizontal wet ball mill with heating system and pressure control system and method for producing hexagonal flaky magnesium hydroxide by using horizontal wet ball mill |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101058429A (en) * | 2006-04-22 | 2007-10-24 | 朱晓林 | Method of preparing magnesium hydroxide superfine powder |
| CN101368009A (en) * | 2007-12-12 | 2009-02-18 | 清华大学深圳研究生院 | Modification method of nano-magnesium hydroxide |
| CN101544388A (en) * | 2008-03-26 | 2009-09-30 | 南京理工大学 | Method for preparing modified sheeted nanometer magnesium hydroxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101058429A (en) * | 2006-04-22 | 2007-10-24 | 朱晓林 | Method of preparing magnesium hydroxide superfine powder |
| CN101368009A (en) * | 2007-12-12 | 2009-02-18 | 清华大学深圳研究生院 | Modification method of nano-magnesium hydroxide |
| CN101544388A (en) * | 2008-03-26 | 2009-09-30 | 南京理工大学 | Method for preparing modified sheeted nanometer magnesium hydroxide |
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