CN100375763C - Oleophilic modificatioon method for tiny inorganic Nano powder - Google Patents
Oleophilic modificatioon method for tiny inorganic Nano powder Download PDFInfo
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Abstract
The present invention relates to an oleophilic modification method for inorganic micro nanometer powder, which belongs to the field of an inorganic micro nanometer powder particle modification processing technology. The present invention is characterized in that the inorganic micro nanometer powder is used as a core, and the surface is evenly deposited with one layer of inorganic oxide or hydrate. The present invention comprises zirconium oxide, magnesia, alumina, silica, titania, zinc oxide, iron oxide or the hydrate. Deposit quantity is controlled within the range of 2% to 5% of the weight of the inorganic micro nanometer powder. An organic substance containing an oleophilic group is covered at a composite particle surface at the middle layer of inorganic micron oxide or inorganic nanometer powder oxide and is any kind of anionic surfactant, a silane coupling agent, a titanate coupling agent, an aluminate ester coupling agent, etc. The coverage quantity of the organic substance is 3 to 7% of weight of the inorganic micro nanometer powder. The modified inorganic micro nanometer powder is generally the powder of which the surface is coated with a hydroxyl radical and comprises any of calcium carbonate, barium carbonate, magnesium carbonate, barium sulfate and lead sulfate or two kinds or more than two kinds of compounds. Particle size is 1 to 50000 nm, and the prepared oleophilic modification micro nanometer composite powder can be widely used for the manufacture of manufactured products of paint, rubber, plastics, etc., and the performance of the manufactured products can be improved.
Description
Technical field
The present invention relates to the method for a kind of inorganic micro-nano powder oleophylic modification, belong to inorganic powder particle modification processing technology field.
Background technology
In recent years, the micro-nano filler of inorganic mineral is increasingly extensive in polymer Application for Field such as plastics, rubber, studies show that: with inorganic micro-nano powder, as micro-nano barium sulfate, lime carbonate etc., be applied in the coating and can not only improve ADHESION OF PAINTS power, mechanical properties such as impact resistance, and can also improve the functions such as radioresistance of coating.And it is applied in the high molecular polymers such as plastics, rubber, their mechanics function such as intensity, toughness can not only be improved, and the manufacturing cost of polymkeric substance can be reduced.
Because the consistency between inorganic micro-nano powder and high molecular polymer and the organic medium has determined the performance of matrix material and speciality coating, and they self polar difference has caused the uncompatibility of inorganic powder and high molecular polymer and organic medium.Therefore,, need that inorganic micro-nano powder is carried out lipophilic surface's modification and handle, thereby reach the purpose that improves product properties and reduce the goods cost by filling in order to improve inorganic micro-nano powder Surface Physical Chemistry characteristic and the dispersiveness in organic medium.
In the patent documentation, FR2800636 has reported with chemical bonding and has made nanoparticle and organic polymer compound particle mutually, and the conjugative effect of having observed this particle; US6287639 provides a kind of method with the sol-gel method modified inorganic nano-particle, but its condition is the surface of inorganic particulate the more reactive activity hydroxyl that participates in is arranged; EP0552133 has reported that use polymer precursor GOLD FROM PLATING SOLUTION belongs to positively charged ion and foam of polymers and carries out the chemical bonding reaction, calcines after adding the heat abstraction solvent, limit the ceramic powder after the modification, the dispersed homogeneity of this powder has all had very big improvement; Patent CN1380363A provides a kind of and with ultrasonic dispersion Nano diamond has been carried out the surface-treated method; This method can make different chain length and not impossible functional group be combined in the surface of Nano diamond particle by the mode of chemical bond by selecting different surface-modifying agents for use, changes the wetting ability and the lipophilicity of Nano diamond particle; Patent CN1373164A discloses by introduce organic alcohols lipophilicity inductor and organic activator in system, by chemical bonding, makes the Nano particles of calcium carbonate surface organic.
Because the realization of above cited some inorganic micro-nano powder method of modifying all has a common prerequisite, that is exactly to exist the group (mainly being hydroxyl) that is easy to the properties-correcting agent reaction on the surface of inorganic micro-nano powder, therefore, for the inorganic micro-nano powder of those surface active groups rarenesses, these methods are also inapplicable.
Yet at present in the document about the report of the inorganic micro-nano powder surface modification of some thin hydroxyls, most of technology is to make tensio-active agent directly be adsorbed on inorganic powder surface by physical action, yet, the modified particle that makes like this will the forfeiture effect under the effect of certain mechanical force, reverts to non-modified particle.What therefore, people were concerned about is that the surface chemistry oleophylic modification that how to make the surface dredge the inorganic micro-nano powder of hydroxyl becomes possible problem.
Summary of the invention
The method that the purpose of this invention is to provide the modification of a kind of inorganic micro-nano powder oleophylic, also limit is that the surface chemistry oleophylic modification that makes the surface dredge the inorganic micro-nano powder of hydroxyl is achieved.
The preparation method of the micro-nano composite granule of a kind of oleophylic modified inorganic is characterized in that having following technological process and step:
A. will needing inorganic micro-nano powder modification, that hydroxyl is dredged on the surface to add deionized water, to be mixed with weight concentration be 15～25% slurries, these slurries are put in the high shearing mixing emulsor that rotating speed is 3000-6000rpm disperseed 60～100 minutes, scatter operation divides to be carried out for 2～3 times, need add certain amount of dispersant therebetween and carry out aid dispersion, dispersion agent is mainly negatively charged ion, nonionogenic tenside, or their mixture, the consumption of dispersion agent is 1～4% of an inorganic micro-nano powder slurry weight; The thin inorganic micro-nano powder of hydroxyl in described surface comprises any in lime carbonate, barium carbonate, magnesiumcarbonate, barium sulfate, the lead sulfate, or mixture more than two kinds and two kinds, and particle size is 1～50000nm;
B. above-mentioned micro-nano powder slurries are put in the container of electronic thermostatic water-bath, begin heating and constantly stir, add then and make the powder surface introduce the precursor compound of metal oxide and hydrate middle layer zirconium white thereof, magnesium oxide, aluminum oxide, silicon oxide, titanium oxide, zinc oxide, ferric oxide; Described zirconic precursor compound is a zirconium chloride, and the precursor compound of aluminum oxide is NaAlO
2, described silica precursors compound is Na
2SiO
3, the precursor compound of titanium oxide is TiCl
4, the precursor compound of zinc oxide is ZnCl
2, the precursor compound of ferric oxide is FeCl
3, it is made into certain density solution when temperature of reaction is 40～50 ℃, adds in the reaction vessel; Simultaneously slowly drip sulfuric acid or sodium hydroxide solution while stirring, be adjusted to different pH values; Reaction finishes and is incubated 30 minutes again; Finally make metal oxide deposit amount be controlled to be 2～5% of inorganic micro-nano powder matrix weight;
C. and then at above-mentioned inorganic nanometer powder-oxide compound middle layer composite particles or inorganic micro-powder-oxide compound middle layer composite particles surface coat organism, this organism comprises any in anion surfactant, silane coupling agent, titanate coupling agent, the aluminate coupling agent, and organic covering amount is 3～7% of an inorganic micro-nano powder matrix weight; Organism is made into certain density solution joins in the above-mentioned reaction vessel, under 70～80 ℃ of temperature, make its reaction, and after reaction finishes, be incubated 30 minutes;
D. then above-mentioned reaction soln is carried out suction filtration, filter cake is after washing repeatedly, and is dry under 110 ℃, pulverizes subsequently, finally makes the micro-nano composite granule of oleophylic modified inorganic.
The mechanism of the inventive method is: by introducing metal oxide as the tundish coating, thereby less inorganic micro-nano powder of surface hydroxyl and the organism that contains lipophilic group are combined effectively, realize the surface modification of the thin hydroxyl nano-powder in surface, and make it present the lipophilicity feature.Introduce the metal oxide middle layer, can make the surface charge of SA inorganic micro-nano powder abundant, thereby can further have the organism of lipophilic group to react, realize the surperficial oleophylic modification of the thin hydroxyl inorganic nanometer powder in surface with other.Powder after modification can be widely used in the systems such as coating, rubber, plastics, can make the performance of goods obtain further to improve.
Embodiment
After now specific embodiments of the invention being described in.
Embodiment 1
Technological process and step in the present embodiment are as follows:
(particle size 400～500nm) 500g are positioned over these slurries in the high shearing mixing emulsor that rotating speed is 5500rpm and disperseed 60 minutes, and scatter operation divides to be carried out for 2 times, adds OP-10 dispersion agent 50g therebetween to get 10% barite slurries; Then slurries are positioned in the there-necked flask in the electronic thermostatic water-bath, begin heating and constantly stirring, when being warming up to 40 ℃, adding 10ml concentration is 10% titanium tetrachloride solution in the barite slurries, be heated to 50 ℃ of temperature of reaction, slowly drip the NaOH solution of 2mol/L simultaneously while stirring, regulate pH to 8.5, be controlled in 60 minutes and dropwise, reaction finishes and is incubated 30 minutes again; Add 5g calcium dodecylbenzene sulphonate solution then, insulation is 30 minutes about 75 ℃; Then this reaction soln is carried out suction filtration, filter cake is after deionization washing 2 times, and is dry under 110 ℃, pulverizes subsequently, finally makes the submicron barite powder of oleophylic modification.After tested, the modified barite particulate lipophilic degree that makes is 95%.
Embodiment 2
Technological process and step in the present embodiment are as follows:
(particle size 100～200nm) is positioned over these slurries in the high shearing mixing emulsor that rotating speed is 5500rpm and disperseed 60 minutes, adds sodium polyacrylate dispersion agent 50g therebetween at first to take by weighing 200g20% nano-calcium carbonate magnesium slurry; When being warming up to 45 ℃, adding 10ml concentration is 10% FeCl3 solution, and slowly dripping 40ml concentration while stirring is the NaOH solution of 2mol/L, regulates pH to 8.5, and reaction finishes and is incubated 30 minutes again; Then the 5g sodium stearate is made into 5% solution, is added in the slurry of reaction, under 75 ℃ of temperature, react, and be incubated 30 minutes; Then this reaction soln is carried out suction filtration, filter cake is after deionization washing 2 times, and is dry under 110 ℃, pulverizes subsequently, finally makes the magnesiumcarbonate nano-powder of oleophylic modification.The lipophilic degree of the modification hydrotalcite particle that makes after tested, is 90%.
Embodiment 3
Technological process and step in the present embodiment are as follows:
(particle size 10～50nm) is positioned over these slurries in the high shearing mixing emulsor that rotating speed is 5500rpm and disperseed 60 minutes, adds sodium polyacrylate dispersion agent 50g therebetween at first to take by weighing 200g20% nano-calcium carbonate slurry; When being warming up to 50 ℃, adding 15ml concentration is 10% Na
2SiO
3Solution, slowly dripping 40ml concentration while stirring is the H2SO4 solution of 1mol/L, regulates pH to 4, reaction finishes and is incubated 30 minutes again; Then the 5g silane coupling agent is made into 5% solution, is added in the slurry of reaction, under 75 ℃ of temperature, react, and be incubated 30 minutes; Then this reaction soln is carried out suction filtration, filter cake is after deionization washing 2 times, and is dry under 110 ℃, pulverizes subsequently, finally makes the calcium carbonate nano powder of oleophylic modification.After tested, the modified calcium carbonate particulate lipophilic degree that makes is 90%.
Embodiment 4
The technological process of present embodiment and step and the foregoing description 1 are identical.Different is to replace calcium dodecylbenzene sulphonate solution with aluminate coupling agent, with aluminate coupling agent the nano barite particle is carried out the surface and coats, and makes oleophylic modified barite micro-powder.After tested, the modified barite particulate lipophilic degree that makes is 60%.
Claims (1)
1. the preparation method of the micro-nano composite granule of oleophylic modified inorganic is characterized in that having following technological process and step:
A. will needing inorganic micro-nano powder modification, that hydroxyl is dredged on the surface to add deionized water, to be mixed with weight concentration be 15～25% slurries, these slurries are put in the high shearing mixing emulsor that rotating speed is 3000-6000rpm disperseed 60～100 minutes, scatter operation divides to be carried out for 2～3 times, need add certain amount of dispersant therebetween and carry out aid dispersion, dispersion agent is mainly negatively charged ion, nonionogenic tenside, or their mixture, the consumption of dispersion agent is 1～4% of an inorganic micro-nano powder slurry weight; The thin inorganic micro-nano powder of hydroxyl in described surface comprises any in lime carbonate, barium carbonate, magnesiumcarbonate, barium sulfate, the lead sulfate, or mixture more than two kinds and two kinds, and particle size is 1～50000nm;
B. above-mentioned micro-nano powder slurries are put in the container of electronic thermostatic water-bath, begin heating and constantly stir, add then and make the powder granule surface introduce the precursor compound of metal oxide and hydrate middle layer zirconium white thereof, magnesium oxide, aluminum oxide, silicon oxide, titanium oxide, zinc oxide, ferric oxide; Described zirconic precursor compound is a zirconium chloride, and the precursor compound of aluminum oxide is NaAlO
2, described silica precursors compound is Na
2SiO
3, the precursor compound of titanium oxide is TiCl
4, the precursor compound of zinc oxide is ZnCl
2, the precursor compound of ferric oxide is FeCl
3, it is made into certain density solution when temperature of reaction is 40～50 ℃, adds in the reaction vessel; Simultaneously slowly drip sulfuric acid or sodium hydroxide solution while stirring, be adjusted to different pH values; Reaction finishes and is incubated 30 minutes again; Finally make metal oxide deposit amount be controlled to be 2～5% of inorganic micro-nano powder matrix weight;
C. and then at above-mentioned inorganic nanometer powder-oxide compound middle layer composite particles or inorganic micro-powder-oxide compound middle layer composite particles surface coat organism, this organism comprises any in anion surfactant, silane coupling agent, titanate coupling agent, the aluminate coupling agent, and organic covering amount is 3～7% of an inorganic micro-nano powder matrix weight; Organism is made into certain density solution joins in the above-mentioned reaction vessel, under 70～80 ℃ of temperature, make its reaction, and after reaction finishes, be incubated 30 minutes;
D. then above-mentioned reaction soln is carried out suction filtration, filter cake is after washing repeatedly, and is dry under 110 ℃, pulverizes subsequently, finally makes the micro-nano composite granule of oleophylic modified inorganic.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101412818B (en) * | 2008-11-11 | 2012-07-25 | 上海卓越纳米新材料股份有限公司 | Industrialized preparation of nano-calcium carbonate for antibacterial fungistatic silicon rubber |
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| CN100528977C (en) * | 2006-12-20 | 2009-08-19 | 中国科学院山西煤炭化学研究所 | Titanium white surface inorganic-organic coating method |
| CN101469194B (en) * | 2007-12-29 | 2012-06-06 | 比亚迪股份有限公司 | Coating composition for polypropylene substrate and method for preparation thereof |
| CN101525450B (en) * | 2009-03-26 | 2011-06-08 | 上海大学 | Method of using inorganic nanometer functional powder for reinforcing medium resistance of vulcanized rubber |
| CN102352132A (en) * | 2011-08-22 | 2012-02-15 | 西南科技大学 | Method for preparing hydrophobic barium carbonate |
| CN102585557B (en) * | 2012-01-05 | 2013-12-25 | 池州凯尔特纳米科技有限公司 | Method for industrially preparing transparent filler nano calcium carbonate for agricultural polyethylene (PE) film |
| CN102675918B (en) * | 2012-05-04 | 2014-06-18 | 安徽江东科技粉业有限公司 | Preparation method of low-yellowness antibacterial calcium carbonate functional composite powder for ventilated membrane |
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| CN104497639A (en) * | 2015-01-15 | 2015-04-08 | 荆门市磊鑫石膏制品有限公司 | Preparation method of zinc white composite powder |
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| CN110317474A (en) * | 2019-06-28 | 2019-10-11 | 广西新晶科技有限公司 | A kind of ferric oxide powder and preparation method thereof that nano inorganic-is organic coated |
| CN111926560B (en) * | 2020-07-21 | 2023-08-18 | 上海弘睿生物科技有限公司 | Polymer fiber product with rejection separation structure and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5811070A (en) * | 1996-05-03 | 1998-09-22 | You; Kyu Jae | Process for producing calcium carbonate particles having a size of 0.1 to 1.0 μm |
| US6287639B1 (en) * | 1996-11-15 | 2001-09-11 | Institut für Neue Materialien Gemeinnützige GmbH | Composite materials |
| CN1373164A (en) * | 2002-04-05 | 2002-10-09 | 中山大学 | Organic hybridization process for processing surface of nano CaCo3 |
-
2006
- 2006-06-27 CN CNB2006100281674A patent/CN100375763C/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5811070A (en) * | 1996-05-03 | 1998-09-22 | You; Kyu Jae | Process for producing calcium carbonate particles having a size of 0.1 to 1.0 μm |
| US6287639B1 (en) * | 1996-11-15 | 2001-09-11 | Institut für Neue Materialien Gemeinnützige GmbH | Composite materials |
| CN1373164A (en) * | 2002-04-05 | 2002-10-09 | 中山大学 | Organic hybridization process for processing surface of nano CaCo3 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101412818B (en) * | 2008-11-11 | 2012-07-25 | 上海卓越纳米新材料股份有限公司 | Industrialized preparation of nano-calcium carbonate for antibacterial fungistatic silicon rubber |
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Assignee: Jiangsu Bingcheng Electrical Material Co., Ltd. Assignor: Shanghai University Contract fulfillment period: 2008.4.26 to 2017.4.26 contract change Contract record no.: 2009320000971 Denomination of invention: Oleophilic modificatioon method for tiny inorganic Nano powder Granted publication date: 20080319 License type: Exclusive license Record date: 2009.6.2 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.4.26 TO 2017.4.26; CHANGE OF CONTRACT Name of requester: JIANGSU BINGCHENG ELECTRIC EQUIPMENT CO., LTD. Effective date: 20090602 |