CN101134852A - Inorganic powder organic surface modifying method - Google Patents
Inorganic powder organic surface modifying method Download PDFInfo
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- CN101134852A CN101134852A CNA2007101332767A CN200710133276A CN101134852A CN 101134852 A CN101134852 A CN 101134852A CN A2007101332767 A CNA2007101332767 A CN A2007101332767A CN 200710133276 A CN200710133276 A CN 200710133276A CN 101134852 A CN101134852 A CN 101134852A
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Abstract
The present invention provides process of organizing the surface to modify inorganic powder, and during the process, inorganic superfine particles are dispersed homogeneously in non-polar organic solvent and have the surfaces well organization modified. The process includes preparing water solution for dispersing inorganic powder, dissolving organic surface modifier, organic surface modifying, solid-liquid separating and washing, and post-treatment. The process features that oil-water interface and phase transfer are utilized for organic surface modification of inorganic superfine powder in non-polar organic solvent.
Description
Technical field
The present invention relates to a kind of powder organic surface modifying method, more specifically relate to the organise method of surface modification of a kind of inorganic powder.
Background technology
Inorganic powder surface is wetting ability, is suitable for using in the polar system.But add when it in organic systems such as plastics, rubber, chemical fibre, solvent based coating, oil-based cosmetic preparation, then be difficult to disperse, can not embody the specific function of inorganic powder material.For improving consistency and the dispersiveness of inorganic powder, must carry out organic surface modifying to inorganic powder at organic system.
According to the application system difference of inorganic powder, should select different organic surface modifying agent.The kind of organic surface modifying agent is a lot, according to its deliquescent difference, mainly can be divided into water-soluble and oil soluble organic surface modifying agent two big classes.For water-fast organic surface modifying agent, can only in organic solvent, implement the wet method organic surface modifying of inorganic powder.Since polar solvent often contain can with the active group of inorganic particulate surface reaction, or influence chemical reaction between surface-modifying agent and the inorganic particulate surface.Therefore, when using the agent of oil soluble organic surface modifying, normally be chosen in the non-polar organic solvent inorganic particulate is carried out organic surface modifying.The method of its organic surface modifying generally is: at first the organic surface modifying agent is dissolved in the nonpolar organic solvent, and then adds inorganic powder, react for some time at a certain temperature.For example: Chinese patent ZL200510045706.0 proposes nanometer SiO
2Place toluene solvant, utilize silane coupling agent that it is carried out organic surface modifying; Li Zongwei etc. are solvent with the normal hexane, are that surface-modifying agent is to nano-TiO with oleic acid
2Carry out surface modification (chemical journal, 2003 the 9th phases; Langmuir, 2000, the 16th volume); Jiang Xiaoming etc. use stearic acid and hexanodioic acid to nano-TiO in toluene solvant
2Particle carries out surface modification (petroleum journal (refining of petroleum), 2002 the 1st phases).But because the inorganic particulate surface is between strong polarity and inorganic particulate and has planar water, make that inorganic particulate is difficult to disperse in non-polar solvent, the organic surface modifying agent mostly react or the coacervate attached to inorganic particulate on, therefore, the organic surface modifying effect is unsatisfactory.The investigator who also has adopts dry method that inorganic particulate is carried out organic surface modifying, and for example: U.S. Pat 6663851 proposes with the nano-TiO of being with amino silane that vapor phase process is produced
2(P25) handle this more difficult good distribution and organic surface modifying effect of guaranteeing inorganic particulate in the organic surface modifying process.
Summary of the invention
The objective of the invention is to solve deficiency and the problem that above-mentioned prior art exists, a kind of method of inorganic powder organic surface modifying is provided, this method has overcome the difficult problem that ultrafine inorganic particle can't be dispersed in the ordinary method in the non-polar organic solvent in the organic surface modifying process, use this kind method and can make inorganic powder under good dispersion state, carry out organic surface modifying, significantly improve the organic surface modifying effect.
Purpose of the present invention is achieved through the following technical solutions:
The method of inorganic powder organic surface modifying of the present invention may further comprise the steps:
(1) preparation of inorganic powder aqueous dispersions: inorganic powder is dispersed in the water, prepares the inorganic powder aqueous dispersions, inorganic powder accounts for 3%～100% of water weight in the dispersion liquid;
(2) dissolving of organic surface modifying agent: the organic surface modifying agent is dissolved in the non-polar organic solvent, form solution, wherein the weight of organic surface modifying agent accounts for 1%～30% of the middle inorganic powder weight of step (1), and the weight of non-polar organic solvent accounts for 50%～500% of the middle water weight of step (1);
(3) organic surface modifying: above-mentioned inorganic powder aqueous dispersions and the non-polar organic solvent that contains organic surface-modifying agent are mixed, vigorous stirring and continuous heated mixt, to add the mixing steam condensation of thermogenesis by condenser, by skimmer organic solvent in the phlegma and water sepn, water is discharged system, and organic solvent is back to reaction system again, when vapor temperature rises to the boiling point of non-polar organic solvent, stop heating, the organic surface modifying reaction of inorganic powder finishes;
(4) solid-liquid separation and washing: the inorganic powder suspension behind the organic surface modifying is carried out solid-liquid separation, and remove the agent of unreacted organic surface modifying with the dehydrated alcohol repetitive scrubbing;
(5) aftertreatment: the inorganic powder drying after will washing, pulverizing.
The method of inorganic powder organic surface modifying of the present invention, the inorganic powder that it was suitable for is preferably oxide powder, oxyhydroxide powder, clay mineral powder or carbonate powder, and wherein said oxide powder is preferably titanium oxide, silicon oxide, aluminum oxide, zinc oxide, cerium oxide, zirconium white or stannic oxide; Described oxyhydroxide powder is preferably aluminium hydroxide or magnesium hydroxide; Described clay mineral powder is preferably attapulgite, polynite, kaolin, wollastonite or mica; Described carbonate powder is preferably lime carbonate or magnesiumcarbonate.
In the method for inorganic powder organic surface modifying of the present invention, its used organic surface modifying agent is the mixture of organic acid or organoalkoxysilane or organic acid and organoalkoxysilane, wherein said organic acid is preferably stearic acid, oleic acid, lauric acid, sad, the certain herbaceous plants with big flowers diacid, the mixture of one or more in the hexanodioic acid, described organoalkoxysilane are methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, ethyl triethoxysilane, the n-propyl Trimethoxy silane, the n-propyl triethoxyl silane, the sec.-propyl Trimethoxy silane, the sec.-propyl triethoxyl silane, the normal-butyl Trimethoxy silane, ne-butyltriethoxysilaneand, the n-hexyl Trimethoxy silane, the n-hexyl triethoxyl silane, the n-octyl Trimethoxy silane, the n-octyl triethoxyl silane, isooctyltrimethoxysi,ane, 3-sulfydryl propyl trimethoxy silicane, phenyl triethoxysilane, vinyltrimethoxy silane, vinyl-dimethyl base oxethyl silane, vinyltriethoxysilane, vinyltriacetoxy silane, vinyl silane triisopropoxide, the propenyl Trimethoxy silane, γ-methacryloxypropyl trimethoxy silane, N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane, N-(β one aminoethyl)-γ-An Bingjisanjiayangjiguiwan, anilinomethyl triethoxysilane, γ-An Bingjisanyiyangjiguiwan, the mixture of one or more in γ-glycidyl ether oxygen propyl trimethoxy silicane.
In the method for inorganic powder organic surface modifying of the present invention, its used non-polar organic solvent is preferably the non-polar organic solvent that can form minimum azeotrope with water, more more preferably benzene, toluene or dimethylbenzene.
The present invention is polarity according to the inorganic powder particle surface, is easier to be dispersed into these characteristics of single particle state in water, at first inorganic powder is dispersed in the water, prepares the inorganic powder aqueous dispersions.Add the non-polar organic solvent that contains organic surface-modifying agent then, form the profit two-phase.Organic surface modifying agent and inorganic particulate can carry out the surface bond reaction on profit biphase interface.In order the surface modification reaction of inorganic particulate to be carried out fully and reduce the reunion degree of product after the modification, need constantly remove the water in the system.The present invention utilizes the method dehydration of component distillation, at last inorganic particulate is transferred in the non-polar organic solvent that contains organic surface-modifying agent, and is finished the inorganic particulate organic surface modifying.
Advantage of the present invention is to utilize oil-water two-phase interfaces and two specific step of phase transition to realize in non-polar organic solvent ultrafine inorganic particle being carried out organic surface chemical modification, add through the powder of present method modification its performance of material that makes in the systems such as plastics, rubber, chemical fibre be better than greatly powder with proportioning through the general method modification add plastics, rubber, etc. prepared material in the system.
Because component distillation is a kind of anti-method of agglomeration of effective inorganic ultrafine powder, the present invention is treated to the novel method of one at organic surface chemical modification of collection ultrafine inorganic particle and anti-the reunion.
Embodiment
Embodiment 1:
Get the 3g attapulgite and add in the 100g distilled water,, make the aqueous dispersions of attapulgite with FS-1200 ultrasonic dispersing processing instrument ultra-sonic dispersion 60min.In the there-necked flask of 1000ml, add 500g toluene, add the n-octyl triethoxyl silane as organoalkoxysilane, the quality of n-octyl triethoxyl silane is 0.9g, stirs the n-octyl triethoxyl silane is dissolved in the toluene fully, adds above-mentioned attapulgite aqueous dispersions again.There-necked flask is placed electric mantle, vigorous stirring and heating continuously.Can produce macro-mixing steam during boiling, with the mixing steam condensation, utilize skimmer toluene in the phlegma and water sepn by condenser, water is discharged system, and toluene is back in the there-necked flask again, continues heating.When vapor temperature rises to the boiling point (about 110.8 ℃) of toluene, stop heating, the organic surface modifying end of processing.Gained behind the component distillation is contained the toluene suspension cooling of attapulgite, filter, isolated solid is used the dehydrated alcohol repetitive scrubbing again, up to graft reaction is not removed to the n-octyl triethoxyl silane of attapulgite's surface.Washing is placed on 120 ℃ of following forced air drying 4h to the gained attapulgite after finishing, and promptly gets the attapulgite through n-octyl triethoxyl silane surface modification after the pulverizing.
Embodiment 2:
50g aerosil (German Degussa company) is added in the 500g distilled water, the silica suspension of gained with FS-1200 ultrasonic dispersing processing instrument ultra-sonic dispersion 40min, is made the silicon oxide aqueous dispersions.In the there-necked flask of 1000ml, add 250g benzene, add vinyltrimethoxy silane as organoalkoxysilane, the quality of vinyltrimethoxy silane is 7.5g, stirs vinyltrimethoxy silane is dissolved in the benzene fully, adds above-mentioned silicon oxide aqueous dispersions again.There-necked flask is placed electric mantle, vigorous stirring and heating continuously.Can produce macro-mixing steam during boiling, with the mixing steam condensation, utilize skimmer benzene in the phlegma and water sepn by condenser, water is discharged system, and benzene is back in the there-necked flask again, continues heating.When vapor temperature rises to the boiling point (about 80.1 ℃) of benzene, stop heating, the organic surface modifying end of processing.With the cooling of the silica containing benzene suspension of gained behind the component distillation, filter, isolated solid is used the dehydrated alcohol repetitive scrubbing again, up to graft reaction is not removed to the vinyltrimethoxy silane of silica sphere.Washing is placed on 100 ℃ of following forced air drying 10h with gained silicon-dioxide after finishing, and promptly gets the silicon-dioxide through the vinyltrimethoxy silane surface modification after the pulverizing.
Embodiment 3:
In 400g distilled water, add the 3.2g Sodium hexametaphosphate 99, after the Sodium hexametaphosphate 99 dissolving, add 400g Rutile type Titanium Dioxide (R902, du pont company) again, be mixed with the titanium dioxide slurry.With diameter is that zirconia ball about 1mm is a grinding medium, with titanium dioxide slurry sand milling 60min, makes the titanium dioxide aqueous dispersions in the SK-2 sand Mill.In the there-necked flask of 1000ml, add 300g dimethylbenzene, add silane coupling agent KH-570 (γ-methacryloxypropyl trimethoxy silane) then as organoalkoxysilane, the mass ratio of KH-570 is 4g, stirring is dissolved in the dimethylbenzene KH-570 fully, adds above-mentioned titanium dioxide aqueous dispersions again.There-necked flask is placed electric mantle, vigorous stirring and heating continuously.Can produce macro-mixing steam during boiling, with the mixing steam condensation, utilize skimmer dimethylbenzene in the phlegma and water sepn by condenser, water is discharged system, and dimethylbenzene is back in the there-necked flask again, continues heating.When vapor temperature rises to the boiling point (about 140 ℃) of dimethylbenzene, stop heating, the organic surface modifying end of processing.Gained behind the component distillation is contained the dimethylbenzene suspension cooling of titanium dioxide, filter, isolated solid is used the dehydrated alcohol repetitive scrubbing again, up to the KH-570 to the titanium dioxide surface of graft reaction is not removed.To wash the gained titanium dioxide at 120 ℃ of following forced air drying 6h, promptly get titanium dioxide after the pulverizing through the KH-570 surface modification.
Embodiment 4:
In 300g distilled water, add the 1.8g Sodium hexametaphosphate 99, after the Sodium hexametaphosphate 99 dissolving, add the nanometer Zinc oxide powder that the 90g median size is 30nm (median size is 30nm, Jiangsu Hehai Nanometer Technology Co., Ltd.) again, be mixed with the nano zine oxide slurry.With diameter is that zirconia ball about 1mm is a grinding medium, with nano zine oxide slurry sand milling 120min, makes the nano zine oxide aqueous dispersions in the SK-2 sand Mill.In the there-necked flask of 1000ml, add 400g dimethylbenzene, add vinyltriethoxysilane then as organoalkoxysilane, the quality of vinyltriethoxysilane is 18g, stirring is dissolved in the dimethylbenzene vinyltriethoxysilane fully, adds above-mentioned nano zine oxide aqueous dispersions again.There-necked flask is placed electric mantle, vigorous stirring and heating continuously.Can produce macro-mixing steam during boiling, with the mixing steam condensation, utilize skimmer dimethylbenzene in the phlegma and water sepn by condenser, water is discharged system, and dimethylbenzene is back in the there-necked flask again, continues heating.When vapor temperature rises to the boiling point (about 140 ℃) of dimethylbenzene, stop heating, the organic surface modifying end of processing.Gained behind the component distillation is contained the dimethylbenzene suspension cooling of nano zine oxide, filter, isolated solid is used the dehydrated alcohol repetitive scrubbing again, up to graft reaction is not removed to the vinyltriethoxysilane of nano oxidized zinc surface.To wash gained zinc oxide at 150 ℃ of following forced air drying 2h, promptly get nano zine oxide after the pulverizing through the vinyltriethoxysilane surface modification.
Embodiment 5:
In 400g distilled water, add the 2.4g Sodium hexametaphosphate 99, after the Sodium hexametaphosphate 99 dissolving, add 160g nano-titanium oxide (NTG-602A, Jiangsu Hehai Nanometer Technology Co., Ltd.) again, be mixed with the nano-titanium oxide slurry.The nano-titanium oxide slurry of gained is placed the alumina-ceramic jar, add an amount of diameter again and be the zirconia ball about Imm, with the speed ball milling 60min of QM-lSP2 ball mill with 150r/min, use FS-1200 ultrasonic dispersing processing instrument ultra-sonic dispersion 40min then, make the nano-titanium oxide aqueous dispersions.Add 400g dimethylbenzene in the there-necked flask of 1000ml, add stearic acid then as organic acid, stearic quality is 48g, and heating and stirring are dissolved in the dimethylbenzene stearic acid fully, add above-mentioned nano-titanium oxide aqueous dispersions again.There-necked flask is placed electric mantle, vigorous stirring and heating continuously.Can produce macro-mixing steam during boiling, with the mixing steam condensation, utilize skimmer dimethylbenzene in the phlegma and water sepn by condenser, water is discharged system, and dimethylbenzene is back in the there-necked flask again, continues heating.When vapor temperature rises to the boiling point (about 140 ℃) of dimethylbenzene, stop heating, the organic surface modifying end of processing.Gained behind the component distillation is contained the dimethylbenzene suspension cooling of nano-titanium oxide, filter, isolated solid is used the dehydrated alcohol repetitive scrubbing again, up to graft reaction is not removed to the stearic acid on nano-titanium oxide surface.To wash the gained titanium oxide at 110 ℃ of following forced air drying 12h, promptly get nano-titanium oxide after the pulverizing through the stearic acid surface modification.
Embodiment 6: among the embodiment 6, except that organic acid was oleic acid, other operation was all identical with embodiment 5, and the gained powder is the nano-titanium oxide through the oleic acid surface modification.
Embodiment 7: among the embodiment 7, except that organic acid was lauric acid, other operation was all identical with embodiment 5, and the gained powder is the nano-titanium oxide through the lauric acid surface modification.
Embodiment 8: among the embodiment 8, except that organic acid was the certain herbaceous plants with big flowers diacid, other operation was all identical with embodiment 5, and the gained powder is the nano-titanium oxide through certain herbaceous plants with big flowers diacid surface modification.
Embodiment 9: among the embodiment 9, except that organic acid was hexanodioic acid, other operation was all identical with embodiment 5, and the gained powder is the nano-titanium oxide through the adipic acid surface modification.
Embodiment 10: among the embodiment 10, except that organic acid is that the quality of n-caprylic acid, n-caprylic acid is got the 32g, other operation is all identical with embodiment 5, and the gained powder is the nano-titanium oxide through the n-caprylic acid surface modification.
Embodiment 11: among the embodiment 11, except that the organic surface modifying agent was stearic acid, other operation was all identical with embodiment 3, and the gained powder is the titanium dioxide through the stearic acid surface modification.
Embodiment 12: among the embodiment 12, except that inorganic powder was aluminium hydroxide, other operation was all identical with embodiment 5, and the gained powder is the aluminium hydroxide through the stearic acid surface modification.
Embodiment 13: among the embodiment 13, except that inorganic powder was aluminum oxide, other operation was all identical with embodiment 5, and the gained powder is the aluminum oxide through the stearic acid surface modification.
Embodiment 14: among the embodiment 14, except that inorganic powder was magnesium oxide, other operation was all identical with embodiment 5, and the gained powder is the magnesium oxide through the stearic acid surface modification.
Embodiment 15: among the embodiment 15, except that inorganic powder was nano-cerium oxide, other operation was all identical with embodiment 5, and the gained powder is the nano-cerium oxide through the stearic acid surface modification.
Embodiment 16: among the embodiment 16, except that inorganic powder was nano zircite, other operation was all identical with embodiment 5, and the gained powder is the nano zircite through the stearic acid surface modification.
Embodiment 17: among the embodiment 17, except that inorganic powder was nano zine oxide, other operation was all identical with embodiment 5, and the gained powder is the nano zine oxide through the stearic acid surface modification.
Embodiment 18: among the embodiment 18, except that inorganic powder was nano-calcium carbonate (median size 30nm), other operation was all identical with embodiment 5, and the gained powder is the nano-calcium carbonate through the stearic acid surface modification.
Embodiment 19: among the embodiment 19, except that inorganic powder is that polynite and organoalkoxysilane are the 3-sulfydryl propyl trimethoxy silicane, other operation is all identical with embodiment 1, and the gained powder is the polynite through 3-sulfydryl propyl trimethoxy silicane surface modification.
Embodiment 20: among the embodiment 20, except that inorganic powder is kaolin and organoalkoxysilane for the ethyl triethoxy silicane alkane just, other operation is all identical with embodiment 1, and the gained powder is through the kaolin of ethyl triethoxy silicane alkane surface modification just.
Embodiment 21: among the embodiment 21, except that inorganic powder is that kaolin and organoalkoxysilane are the methyltrimethoxy silane, other operation is all identical with embodiment 1, and the gained powder is the kaolin through the methyltrimethoxy silane surface modification.
Embodiment 22: among the embodiment 22, except that inorganic powder is that wollastonite and organoalkoxysilane are the methyl triethyl silicane, other operation is all identical with embodiment 2, and the gained powder is the kaolin through the Union carbide A-162 surface modification.
Embodiment 23: among the embodiment 23, except that inorganic powder is that mica powder and organoalkoxysilane are the ethyl-trimethyl silane, other operation is all identical with embodiment 2, and the gained powder is the mica powder through the ethyl trimethoxy silane surface modification.
Embodiment 24:
With the 100g median size is in Sb-doped nano stannic oxide (ATO powder) the adding 400g distilled water of 15nm, preparation of nano stannic oxide slurry, the slurry of gained is placed the alumina-ceramic jar, add an amount of diameter again and be the zirconia ball about 1mm, with the speed ball milling 180min of QM-1SP2 ball mill, make the nano tin dioxide aqueous dispersions with 200r/min.In the there-necked flask of 1000ml, add 400ml dimethylbenzene, add 8g stearic acid and 12g vinyl-dimethyl base oxethyl silane then, heating and stirring are dissolved in the dimethylbenzene stearic acid and vinyl-dimethyl base oxethyl silane fully, add above-mentioned nano tin dioxide aqueous dispersions again.There-necked flask is placed electric mantle, vigorous stirring and heating continuously.Can produce macro-mixing steam during boiling, with the mixing steam condensation, utilize skimmer dimethylbenzene in the phlegma and water sepn by condenser, water is discharged system, and dimethylbenzene is back in the there-necked flask again, continues heating.When vapor temperature rises to the boiling point (about 140 ℃) of dimethylbenzene, stop heating, the organic surface modifying end of processing.Gained behind the component distillation is contained the dimethylbenzene suspension cooling of nano tin dioxide, filter, isolated solid is used the dehydrated alcohol repetitive scrubbing again, up to graft reaction is not removed to the surface-modifying agent of nano oxidized tin surfaces.To wash gained stannic oxide at 110 ℃ of following forced air drying 12h, promptly get nano tin dioxide powder after the pulverizing through stearic acid and vinyl-dimethyl base oxethyl silane associating surface modification.
Embodiment 25: among the embodiment 25, except that organic acid was oleic acid, other operation was all identical with embodiment 24, and the gained powder is the nano tin dioxide powder through oleic acid and vinyl-dimethyl base oxethyl silane associating surface modification.
Embodiment 26: among the embodiment 26, except that organic acid was lauric acid, other operation was all identical with embodiment 24, and the gained powder is the nano tin dioxide powder through lauric acid and vinyl-dimethyl base oxethyl silane associating surface modification.
Embodiment 27: among the embodiment 27, except that organic acid was hexanodioic acid, other operation was all identical with embodiment 24, and the gained powder is the nano tin dioxide powder through hexanodioic acid and vinyl-dimethyl base oxethyl silane associating surface modification.
Embodiment 28: among the embodiment 28, except that organoalkoxysilane was the n-octyl triethoxyl silane, other operation was all identical with embodiment 24, and the gained powder is the nano tin dioxide powder through stearic acid and n-octyl triethoxyl silane associating surface modification.
Embodiment 29:
With the 100g median size is in Sb-doped nano stannic oxide (ATO powder) the adding 400g distilled water of 15nm, preparation of nano stannic oxide slurry, the slurry of gained is placed the alumina-ceramic jar, add an amount of diameter again and be the zirconia ball about 1mm, with the speed ball milling 180min of QM-1SP2 ball mill, make the nano tin dioxide aqueous dispersions with 200r/min.In the there-necked flask of 1000ml, add 400ml dimethylbenzene, add 8g n-octyl triethoxyl silane and 12g vinyl-dimethyl base oxethyl silane then, heating and stirring are dissolved in the dimethylbenzene organic surface modifying agent fully, add above-mentioned nano tin dioxide aqueous dispersions again.There-necked flask is placed electric mantle, vigorous stirring and heating continuously.Can produce macro-mixing steam during boiling, with the mixing steam condensation, utilize skimmer dimethylbenzene in the phlegma and water sepn by condenser, water is discharged system, and dimethylbenzene is back in the there-necked flask again, continues heating.When vapor temperature rises to the boiling point (about 140 ℃) of dimethylbenzene, stop heating, the organic surface modifying end of processing.Gained behind the component distillation is contained the dimethylbenzene suspension cooling of nano tin dioxide, filter, isolated solid is used the dehydrated alcohol repetitive scrubbing again, up to graft reaction is not removed to the surface-modifying agent of nano oxidized tin surfaces.To wash gained stannic oxide at 110 ℃ of following forced air drying 12h, promptly get nano tin dioxide powder after the pulverizing through n-octyl triethoxyl silane and vinyl-dimethyl base oxethyl silane associating surface modification.
Embodiment 30:
With the 100g median size is in Sb-doped nano stannic oxide (ATO powder) the adding 400g distilled water of 15nm, preparation of nano stannic oxide slurry, the slurry of gained is placed the alumina-ceramic jar, add an amount of diameter again and be the zirconia ball about 1mm, with the speed ball milling 180min of QM-1SP2 ball mill, make the nano tin dioxide aqueous dispersions with 200r/min.Add 400ml dimethylbenzene in the there-necked flask of 1000ml, add 8g n-caprylic acid and 12g oleic acid then, heating and stirring are dissolved in the dimethylbenzene organic surface modifying agent fully, add above-mentioned nano tin dioxide aqueous dispersions again.There-necked flask is placed electric mantle, vigorous stirring and heating continuously.Can produce macro-mixing steam during boiling, with the mixing steam condensation, utilize skimmer dimethylbenzene in the phlegma and water sepn by condenser, water is discharged system, and dimethylbenzene is back in the there-necked flask again, continues heating.When vapor temperature rises to the boiling point (about 140 ℃) of dimethylbenzene, stop heating, the organic surface modifying end of processing.Gained behind the component distillation is contained the dimethylbenzene suspension cooling of nano tin dioxide, filter, isolated solid is used the dehydrated alcohol repetitive scrubbing again, up to graft reaction is not removed to the surface-modifying agent of nano oxidized tin surfaces.To wash gained stannic oxide at 110 ℃ of following forced air drying 12h, promptly get nano tin dioxide powder after the pulverizing through n-caprylic acid and oleic acid associating surface modification.
Comparative Examples:
Add 600g benzene in the there-necked flask of 1000ml, add vinyltrimethoxy silane then as organoalkoxysilane, the quality of vinyltrimethoxy silane is 15g, stirs to make vinyltrimethoxy silane be dissolved in the benzene fully; Add aerosil 100g again, with FS-1200 ultrasonic dispersing processing instrument ultra-sonic dispersion 40min.There-necked flask is placed electric mantle, and vigorous stirring and heating continuously will add the benzene vapour condensation of thermogenesis by condenser, and be back to again in the there-necked flask, and so continuous boiling reaction 8h stops heating, the organic surface modifying end of processing.Benzene suspension cooling that will reaction gained nano-silica-containing is filtered, and isolated solid is used the dehydrated alcohol repetitive scrubbing again, up to graft reaction is not removed to the vinyltrimethoxy silane of nano-silica surface.To wash gained silicon-dioxide at 100 ℃ of following forced air drying 10h, promptly get nano silicon after the pulverizing through the vinyltrimethoxy silane surface modification.
The mechanical property experiment:
Experimental raw: styrene-butadiene rubber(SBR) (SBR1502, combined styrene content 23.5%, Qilu Co., Ltd., China Petrochemical Corp); Aerosil behind the embodiment 2 gained organic surface modifyings; Aerosil behind the Comparative Examples gained organic surface modifying.
Experimentation: in the two roller mills of SK-160B type, carry out the mixing of sizing material and Synergist S-421 95, nano silicon.Order of addition(of ingredients) is: other the Synergist S-421 95 → nano silicon → sulphur of rubber → except that sulphur.Rubber mixing machine roller temperature is 45～50 ℃.Carry out the sulfuration of SBR rubber unvulcanizate with vulcanizing press, curing temperature is 160 ℃, and curing time is 20min.
Testing method: the mensuration reference standard GB/T528 of nano-silica filled styrene-butadiene rubber(SBR) tensile strength; The mensuration of tear strength adopts the sample preparation of perpendicular type cut-off knife with reference to GB/T529-1999.
Experimental result is as shown in table 1, and by table 1 as seen, organic surface effect of the present invention is better than ordinary method.
The mechanical property of table 1 nano-attapulgite stone/SBR matrix material
| The silicon-dioxide quality accounts for the per-cent/% of styrene-butadiene rubber(SBR) quality in the Comparative Examples matrix material | The silicon-dioxide quality accounts for the per-cent/% of styrene-butadiene rubber(SBR) quality in embodiment 2 matrix materials | ||||||||||
| 0 | 10％ | 20％ | 30％ | 40％ | 50％ | 10％ | 20％ | 30％ | 40％ | 50％ | |
| Tensile strength/MPa | 2.10 | 3.31 | 4.97 | 6.88 | 7.34 | 7.89 | 4.59 | 6.85 | 7.96 | 9.41 | 10.33 |
| Elongation at break (%) | 300 | 351 | 448 | 609 | 654 | 696 | 598 | 688 | 868 | 998 | 1073 |
| Tear strength (KN/m) | 15.4 | 21.3 | 25.2 | 30.8 | 34.7 | 41.2 | 31.3 | 38.4 | 43.5 | 47.3 | 52.1 |
Claims (8)
1. the method for an inorganic powder organic surface modifying is characterized in that may further comprise the steps:
(1) preparation of inorganic powder aqueous dispersions: inorganic powder is dispersed in the water, prepares the inorganic powder aqueous dispersions, inorganic powder accounts for 3%～100% of water weight in the dispersion liquid;
(2) dissolving of organic surface modifying agent: the organic surface modifying agent is dissolved in the non-polar organic solvent, form solution, wherein the weight of organic surface modifying agent accounts for 1%～30% of the middle inorganic powder weight of step (1), and the weight of non-polar organic solvent accounts for 50%～500% of the middle water weight of step (1);
(3) organic surface modifying: above-mentioned inorganic powder aqueous dispersions and the non-polar organic solvent that contains organic surface-modifying agent are mixed, vigorous stirring and continuous heated mixt, to add the mixing steam condensation of thermogenesis by condenser, by skimmer organic solvent in the phlegma and water sepn, water is discharged system, and organic solvent is back to reaction system again, when vapor temperature rises to the boiling point of non-polar organic solvent, stop heating, the organic surface modifying reaction of inorganic powder finishes;
(4) solid-liquid separation and washing: the inorganic powder suspension behind the organic surface modifying is carried out solid-liquid separation, and remove the agent of unreacted organic surface modifying with the dehydrated alcohol repetitive scrubbing;
(5) aftertreatment: the inorganic powder drying after will washing, pulverizing.
2. the method for inorganic powder organic surface modifying according to claim 1 is characterized in that described inorganic powder is oxide powder, oxyhydroxide powder, clay mineral powder or carbonate powder.
3. the method for inorganic powder organic surface modifying according to claim 2 is characterized in that described oxide powder is titanium oxide, silicon oxide, aluminum oxide, zinc oxide, cerium oxide, zirconium white or stannic oxide; Described oxyhydroxide powder is aluminium hydroxide or magnesium hydroxide; Described clay mineral powder is attapulgite, polynite, kaolin, wollastonite or mica; Described carbonate powder is lime carbonate or magnesiumcarbonate.
4. the method for inorganic powder organic surface modifying according to claim 1 is characterized in that described organic surface modifying agent is the mixture of organic acid or organoalkoxysilane or organic acid and organoalkoxysilane.
5. the method for inorganic powder organic surface modifying according to claim 4 is characterized in that described organic acid is one or more the mixture in stearic acid, oleic acid, lauric acid, sad, certain herbaceous plants with big flowers diacid, the hexanodioic acid.
6. the method for inorganic powder organic surface modifying according to claim 4 is characterized in that described organoalkoxysilane is a methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, ethyl triethoxysilane, the n-propyl Trimethoxy silane, the n-propyl triethoxyl silane, the sec.-propyl Trimethoxy silane, the sec.-propyl triethoxyl silane, the normal-butyl Trimethoxy silane, ne-butyltriethoxysilaneand, the n-hexyl Trimethoxy silane, the n-hexyl triethoxyl silane, the n-octyl Trimethoxy silane, the n-octyl triethoxyl silane, isooctyltrimethoxysi,ane, 3-sulfydryl propyl trimethoxy silicane, phenyl triethoxysilane, vinyltrimethoxy silane, vinyl-dimethyl base oxethyl silane, vinyltriethoxysilane, vinyltriacetoxy silane, vinyl silane triisopropoxide, the propenyl Trimethoxy silane, γ-methacryloxypropyl trimethoxy silane, N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxysilane, N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan, anilinomethyl triethoxysilane, γ-An Bingjisanyiyangjiguiwan, the mixture of one or more in γ-glycidyl ether oxygen propyl trimethoxy silicane.
7. the method for inorganic powder organic surface modifying according to claim 1 is characterized in that described non-polar organic solvent is for forming the non-polar organic solvent of minimum azeotrope with water.
8. the method for inorganic powder organic surface modifying according to claim 7 is characterized in that described non-polar organic solvent is benzene, toluene or dimethylbenzene.
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