CN101760054A - Preparation method of pyrophyllite-based nanometer composite powder - Google Patents

Preparation method of pyrophyllite-based nanometer composite powder Download PDF

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Publication number
CN101760054A
CN101760054A CN200810163819A CN200810163819A CN101760054A CN 101760054 A CN101760054 A CN 101760054A CN 200810163819 A CN200810163819 A CN 200810163819A CN 200810163819 A CN200810163819 A CN 200810163819A CN 101760054 A CN101760054 A CN 101760054A
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pyrophyllite
powder
coupling agent
coupling agents
preparation
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CN101760054B (en
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刘海涛
林实俄
张景峰
翁学军
林雪青
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ZHEJIANG TAISHUN JU'E RESEARCH INSTITUTE OF POLYMER MATERIALS APPLICATION
Wenzhou University
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ZHEJIANG TAISHUN JU'E RESEARCH INSTITUTE OF POLYMER MATERIALS APPLICATION
Wenzhou University
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Abstract

The invention relates to a preparation method of pyrophyllite-based nanometer composite powder, which uses low-aluminum-content pyrophyllite, kaolin and superfine silicon dioxide powder as solid raw materials and uses silane coupling agents and titanate coupling agents as surface modifiers. The Al2O3 content in the pyrophyllite powder is smaller than 20 percent, the Al2O3 carries out the calcination at the temperature between 500 and 700 DEG C, the kaolin is powder between 200 and 300 meshes and is calcined at the temperature between 500 and 700 DEG C, the average grain diameter of the superfine silicon dioxide powder is smaller than 0.5 mum, and the superfine silicon dioxide powder are dried at the temperature between 100 and 200 DEG C. The coupling agents are silane coupling agents or titanium ester coupling agents or compounds of the silane coupling agents and the titanium ester coupling agents. The invention has a formulation consisting of the following ingredients in percentage by weight: 50 to 90 of pyrophyllite powder, 0 to 20 of kaolin, 10 to 30 of superfine silicon dioxide powder and 0.5 to 2.0 of coupling agents. The coupling agents are respectively added by two times, 10 to 50 percent of the total amount of the coupling agents are added during wet method grinding, and 50 to 90 percent of the total amount of the coupling agents are added during dry method grinding. The composite powder has the average grain diameter smaller than 2 mum.

Description

A kind of preparation method of pyrophyllite-based nanometer composite powder
Technical field
The present invention relates to a kind of preparation method of pyrophyllite-based nanometer composite powder, belong to novel material and mineral exploration and exploitation and Application Areas.
Background technology
Agalmatolite [Al 2(OH) 2(Si 2O 5) 2] 2Be a kind of of clay mineral, mainly be made up of quartz, kaolinite, sericite that belong to 2: 1 type stratiforms of crystalline texture hydrous alumino silicates mineral, the structural unit layer is by two " silicon-oxygen tetrahedron ", one " oxyhydrogen aluminum stone layer " formed.The theoretical chemistry component is: Al 2O 328.3%, SiO 266.7%, H 2O 5.0%, contains Fe in addition, Mg, Ca, K, small amount of impurities such as Na.
The agalmatolite single crystal (oblique system) of natural output is rare, often is foliated lamellar, flakey, radial, fibrous or column aggregate, tool pearliness or wax shape gloss.That mineral have is white, pale yellow, light green, brick red and grey brown isochrome, little translucent.The fine and smooth tool soapy feeling of agalmatolite quality, hardness low (1-2), proportion 2.65-2.90g/cm 3, refractoriness>1700 ℃, heat conduction, electric conductivity are low, good insulation preformance, stable chemical performance has only at high temperature and could be decomposed by sulfuric acid.
China is pyrophyllite resource big country, and the gross annual output amount accounts for about 40% of world's gross annual output amount, but in recovery process, the wasting of resources is very serious, adopt richness and abandon poorly, the rate of recovery is low to be to be quotidian in mining, and the development and use that therefore strengthen low aluminium pyrophyllite are significant.
The 1999.09.22 of Patent Office of the People's Republic of China day disclosed " preparation method of dispersible silico-aluminate " (publication number: 1229056), relate to a kind of preparation method who is dispersed in the high purity silicon aluminate in water and/or the acid solution medium, it is realized by the hydrolysis and the thermal treatment of aluminum compound and silicate compound.
The 2005.11.02 of Patent Office of the People's Republic of China day disclosed " a kind of manufacture method of nano-silicon aluminum composite " (publication number: CN 1689971A), relate to a kind of pyrophyllite nano-dispersed emulsion that is scattered in the etoh solvent, it is raw material with the pyrophyllite, by water logging bubble pyrophyllite in powder, add silane coupling agent through hydrophobic treatment, handle with tensio-active agent parcel again, be scattered in and make the nano-dispersed emulsion in the coordinative solvent.
" a kind of method of producing the silicon-aluminium compound stopping composition with the agalmatolite manufacturing " (patent No.: ZL 2,004 1 0066103.4) of authorizing the 2007.05.02 of Patent Office of the People's Republic of China day, relate to a kind of method of producing the silicon-aluminium compound stopping composition with the agalmatolite for the raw material manufacturing, it is agalmatolite to be pulverized obtain the agalmatolite breeze, then the agalmatolite breeze is carried out technologies such as pickling, flotation, drying after calcining and makes product.
By the domestic and foreign literature data analysis of present grasp, scientific worker both domestic and external has done a large amount of research and developments for the modification and the application of mineral material.Research at present mainly still concentrates on the modification of Mineral resources such as kaolin, lime carbonate and uses, for the applied research work of agalmatolite relatively also seldom, use low aluminium pyrophyllite and kaolin, superfine silicon dioxide and be raw material calcine, composite, prepare powder through two subsurface coupling modified techniques, can be applied to reinforcing rubber again, the research and development of the industrialization pyrophyllite product that performance can compare favourably with high wear-resistant carbon black are report not also.
Summary of the invention
The technical problem that quasi-solution of the present invention is determined provides a kind of preparation method of pyrophyllite-based nanometer composite powder.This powder can replace in certain proportion that high wear-resistant carbon black is applied to the styrene-butadiene rubber(SBR) product and the main mechanical property that do not reduce rubber product.
For achieving the above object, the present invention by the following technical solutions: with low aluminium pyrophyllite, kaolin, nanometer SiO 2Powder is a main raw material, utilizes silane and titanate coupling agent to be surface-modifying agent, by technologies such as high-temperature calcination, surperficial coupling processing, prepares styrene-butadiene rubber(SBR) reinforcement pyrophyllite-based nanometer composite powder.
The present invention is a kind of preparation method of pyrophyllite-based nanometer composite powder, it is characterized in that having following technological process and step:
1. described pyrophyllite is the low aluminium pyrophyllite in powder of 200-300 order, the Al of pyrophyllite in powder 2O 3Content is less than 20%, and through 500-700 ℃ of calcining, packing, standby.
2. described kaolin is 200-300 order kaolin, through 500-700 ℃ of calcining, packing, standby.
3. described silicon-dioxide powdery is a superfine powder, and median size is less than 0.5 μ m, through 100-200 ℃ of oven dry, packing, standby.
4. described coupling agent is silane coupling agent or titanate coupling agent or the compound of the two, and the adding total amount of coupling agent is the 0.5-2% of solid base.Silane coupling agent comprises 3-aminopropyl triethoxysilane, 3-glycidyl ether oxygen base propyl trimethoxy silicane, 3-methacryloxypropyl trimethoxy silane, two-(3-(triethoxyl silane)-propyl group)-tetrasulfide, and titanate coupling agent comprises sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester, tetra isopropyl two (dioctyl phosphorous acid acyloxy) titanic acid ester.
5. batch mixing, grinding, filtration, drying: the standby raw material in 1,2,3 is mixed in proportion, grinds after adding suitable quantity of water and part coupling agent, be ground to median size and stop to grind, filter, drying less than 2 μ m.
6. coupling processing: gained powder in 5 in the coupling machine, is carried out surface modification and promptly obtains product of the present invention under 100-120 ℃ of temperature.
7. the prescription of powder of the present invention following (wt%): base-material: pyrophyllite in powder 50-90, kaolin 0-20, silicon-dioxide powdery 10-30.Coupling agent: 0.5-2.0
Embodiment
Embodiment 1:
Starting in the stirred pot of stirring in the 50kg deionized water, add Al successively 2O 3Content is 8% pyrophyllite in powder 10kg, kaolin 2kg, silicon-dioxide powdery 2kg, back adding 0.07kg 3-aminopropyl triethoxysilane stirs, continue to stir 1 hour, grind then, be ground to median size and begin to filter, dry, pulverize less than 2 μ m.Powder after the pulverizing carries out the coupling modification with 0.1kg 3-aminopropyl triethoxysilane on the coupling machine, promptly make pyrophyllite-based nanometer composite powder.
Embodiment 2:
Starting in the stirred pot of stirring in the 50kg deionized water, add Al successively 2O 3Content is 15% pyrophyllite in powder 10kg, kaolin 2kg, silicon-dioxide powdery 2kg, back adding 0.07kg3-glycidyl ether oxygen base propyl trimethoxy silicane stirs, continue to stir 1 hour, grind then, be ground to median size and begin to filter, dry, pulverize less than 2 μ m.Powder after the pulverizing carries out the coupling modification with 0.1kg 3-glycidyl ether oxygen base propyl trimethoxy silicane on the coupling machine, promptly make pyrophyllite-based nanometer composite powder.
Embodiment 3:
Starting in the stirred pot of stirring in the 50kg deionized water, add Al successively 2O 3Content is 18% pyrophyllite in powder 10kg, kaolin 2kg, silicon-dioxide powdery 2kg, back adding 0.07kg3-methacryloxypropyl trimethoxy silane stirs, continue to stir 1 hour, grind then, be ground to median size and begin to filter, dry, pulverize less than 2 μ m.Powder after the pulverizing carries out the coupling modification with 0.1kg 3-methacryloxypropyl trimethoxy silane on the coupling machine, promptly make pyrophyllite-based nanometer composite powder.
Embodiment 4:
Starting in the stirred pot of stirring in the 60kg deionized water, add Al successively 2O 3Content is 15% pyrophyllite in powder 15kg, kaolin 3kg, silicon-dioxide powdery 2kg, back adding 0.1kg 3-aminopropyl triethoxysilane stirs, continue to stir 1 hour, grind then, be ground to median size and begin to filter, dry, pulverize less than 2 μ m.Powder after the pulverizing carries out the coupling modification with 0.15kg 3-aminopropyl triethoxysilane on the coupling machine, promptly make pyrophyllite-based nanometer composite powder.
Embodiment 5:
Starting in the stirred pot of stirring in the 50kg deionized water, add Al successively 2O 3Content is 18% pyrophyllite in powder 10kg, kaolin 3kg, silicon-dioxide powdery 2kg, back adding 0.1kg 3-methacryloxypropyl trimethoxy silane stirs, continue to stir 1 hour, grind then, be ground to median size and begin to filter, dry, pulverize less than 2 μ m.Powder after the pulverizing carries out the coupling modification with 0.15kg 3-methacryloxypropyl trimethoxy silane on the coupling machine, promptly make pyrophyllite-based nanometer composite powder.
Embodiment 6:
Starting in the stirred pot of stirring in the 50kg deionized water, add Al successively 2O 3Content is 18% pyrophyllite in powder 12kg, kaolin 3kg, silicon-dioxide powdery 2kg, back adding 0.1kg 3-methacryloxypropyl trimethoxy silane stirs, continue to stir 1 hour, grind then, be ground to median size and begin to filter, dry, pulverize less than 2 μ m.Powder after the pulverizing carries out the coupling modification with 0.12kg sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester on the coupling machine, promptly make pyrophyllite-based nanometer composite powder.
Embodiment 7:
Starting in the stirred pot of stirring in the 50kg deionized water, add Al successively 2O 3Content is 18% pyrophyllite in powder 12kg, kaolin 3kg, silicon-dioxide powdery 2kg, 0.1kg pair-(3-(triethoxyl silane)-propyl group)-tetrasulfide of back adding stirs, continue to stir 1 hour, grind then, be ground to median size and begin to filter, dry, pulverize less than 2 μ m.Powder after the pulverizing carries out the coupling modification, promptly makes pyrophyllite-based nanometer composite powder with 0.15kg pair-(3-(triethoxyl silane)-propyl group)-tetrasulfide on the coupling machine.
Embodiment 8:
Starting in the stirred pot of stirring in the 50kg deionized water, add Al successively 2O 3Content is 10% pyrophyllite in powder 12kg, kaolin 3kg, silicon-dioxide powdery 2kg, 0.1kg pair-(3-(triethoxyl silane)-propyl group)-tetrasulfide of back adding stirs, continue to stir 1 hour, grind then, be ground to median size and begin to filter, dry, pulverize less than 2 μ m.Powder after the pulverizing carries out the coupling modification with 0.15kg tetra isopropyl two (dioctyl phosphorous acid acyloxy) titanic acid ester on the coupling machine, promptly make pyrophyllite-based nanometer composite powder.
Product section of the present invention is replaced high wear-resistant carbon black use, obtained the ideal effect as strengthening agent.
The present invention compares with background technology, uses low aluminium pyrophyllite and composite kaolin and superfine silicon dioxide, so that raw material sources are more extensive, exploitation has realistic meaning for lean ore. Add surperficial coupling modifier so that powder granularity is controlled easily by process of lapping, without pickling, also need not be dispersed in and make slip in the organic solvent, optimized technology, three-waste free pollution has been realized green chemical industry technology. Product cost is lower simultaneously, is easy to industry and applies.

Claims (6)

1. the preparation method of a pyrophyllite-based nanometer composite powder, it is characterized in that, main raw material is low aluminium pyrophyllite, kaolin, micro-size silica powder, silane and titanate coupling agent, solid material all carries out pre-treatment through differing temps, grind then and surface modification, make powder of the present invention.
2. the preparation method of pyrophyllite-based nanometer composite powder according to claim 1 is characterized in that the Al of pyrophyllite 2O 3Content is 5-20%, and through 500-700 ℃ of calcining, kaolin is 200-300 order powder, and through 500-700 ℃ of calcining, the micro-size silica powder median size is less than 0.5 μ m, through 100-200 ℃ of oven dry.
3. the preparation method of pyrophyllite-based nanometer composite powder according to claim 1 is characterized in that the compositing range of composition of raw materials is (wt%): base-material: pyrophyllite in powder 50-90, kaolin 0-20, micro-size silica powder 10-30.Coupling agent: 0.5-2.0.
4. the preparation method of pyrophyllite-based nanometer composite powder according to claim 1 is characterized in that the coupling agent that uses is silane coupling agent or titanate coupling agent or the compound of the two, and the adding total amount of coupling agent is the 0.5-2.0% of solid base.Silane coupling agent comprises 3-aminopropyl triethoxysilane, 3-glycidyl ether oxygen base propyl trimethoxy silicane, 3-methacryloxypropyl trimethoxy silane, two-(3-(triethoxyl silane)-propyl group)-tetrasulfide.Titanate coupling agent is sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester, tetra isopropyl two (dioctyl phosphorous acid acyloxy) titanic acid ester.
5. according to the preparation method of claim 1,4 described pyrophyllite-based nanometer composite powders, it is characterized in that coupling agent adds at twice, add the 10-50% of coupling agent total amount during wet grinding, add the 50-90% of coupling agent total amount during the dry method coupling.
6. the preparation method of pyrophyllite-based nanometer composite powder according to claim 1, the median size that it is characterized in that composite granule is less than 2 μ m.
CN 200810163819 2008-12-25 2008-12-25 Preparation method of pyrophyllite-based nanometer composite powder Expired - Fee Related CN101760054B (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103333527A (en) * 2013-06-04 2013-10-02 广东新会美达锦纶股份有限公司 Manufacture method for surface-modified flatting agent for polyamide chemical fiber
CN105001679A (en) * 2014-11-26 2015-10-28 安徽池州博源非金属矿研发中心有限公司 Composite titanium dioxide
CN105017812A (en) * 2014-11-26 2015-11-04 安徽池州博源非金属矿研发中心有限公司 Composite titanium dioxide
CN105038327A (en) * 2014-11-26 2015-11-11 安徽池州博源非金属矿研发中心有限公司 Preparation method of dolomite composite titanium dioxide
CN106883458A (en) * 2017-03-09 2017-06-23 浙江皓翔矿业有限公司 A kind of preparation method of modified pyrophyllite powder
WO2018160102A1 (en) * 2017-03-03 2018-09-07 Дмитрий Николаевич ЗАДОРИН Smooth lamellar pyrophyllite-based substrate, and method for producing same
CN109135346A (en) * 2018-09-05 2019-01-04 中建材蚌埠玻璃工业设计研究院有限公司 Modified silicon powder of a kind of high pure and ultra-fine and preparation method thereof
CN111437793A (en) * 2020-03-27 2020-07-24 浙江工业大学 Pyrophyllite-carbon composite adsorption material and liquid phase preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN100497456C (en) * 2007-05-30 2009-06-10 中南大学 Method of preparing inorganic composition particles for polymer composite material

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103333527A (en) * 2013-06-04 2013-10-02 广东新会美达锦纶股份有限公司 Manufacture method for surface-modified flatting agent for polyamide chemical fiber
CN105001679A (en) * 2014-11-26 2015-10-28 安徽池州博源非金属矿研发中心有限公司 Composite titanium dioxide
CN105017812A (en) * 2014-11-26 2015-11-04 安徽池州博源非金属矿研发中心有限公司 Composite titanium dioxide
CN105038327A (en) * 2014-11-26 2015-11-11 安徽池州博源非金属矿研发中心有限公司 Preparation method of dolomite composite titanium dioxide
WO2018160102A1 (en) * 2017-03-03 2018-09-07 Дмитрий Николаевич ЗАДОРИН Smooth lamellar pyrophyllite-based substrate, and method for producing same
RU2676060C2 (en) * 2017-03-03 2018-12-25 Дмитрий Николаевич Задорин Smooth scaled pyrophyllite-based substrate and method for production thereof
CN106883458A (en) * 2017-03-09 2017-06-23 浙江皓翔矿业有限公司 A kind of preparation method of modified pyrophyllite powder
CN109135346A (en) * 2018-09-05 2019-01-04 中建材蚌埠玻璃工业设计研究院有限公司 Modified silicon powder of a kind of high pure and ultra-fine and preparation method thereof
CN111437793A (en) * 2020-03-27 2020-07-24 浙江工业大学 Pyrophyllite-carbon composite adsorption material and liquid phase preparation method thereof

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