CN101225249B - Method for preparing lipophilic nano SiO2 powder - Google Patents
Method for preparing lipophilic nano SiO2 powder Download PDFInfo
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- CN101225249B CN101225249B CN2007101719337A CN200710171933A CN101225249B CN 101225249 B CN101225249 B CN 101225249B CN 2007101719337 A CN2007101719337 A CN 2007101719337A CN 200710171933 A CN200710171933 A CN 200710171933A CN 101225249 B CN101225249 B CN 101225249B
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Abstract
The invention relates to a preparation method for a lipophilic nanometer powder SiO2. The procedure of the preparation method comprises: (1) the nanometer powder SiO2 is acted as an initial raw material, an activated surface treatment is applied with a hydrogen peroxide solution; (2) the surface of the nanometer powder SiO2 is modified and processed in an aqueous and oil phase mixed liquid with aGamma -(methacryloyldoxy) propyltrimethoxysilane modifying agent, a dispersion liquid of the lipophilic nanometer powder SiO2 is produced; (3) the lipophilic nanometer powder SiO2 is made after the processing of liquid separating, distilling, and drying. The lipophilic nanometer powder SiO2 has the advantages of simple process, easy industrial production, and good compatibility of the lipophilic nanometer powder SiO2 with the organic solvent and even dispersion.
Description
Technical field
The invention belongs to nanometer SiO
2Preparation field particularly relates to a kind of lipophilic nano SiO
2The preparation method of powder.
Background technology
Nanometer SiO
2Have optical characteristics such as ultraviolet absorption, infrared reflection, a large amount of unsaturated residual bond that exists in its molecular structure and the hydroxyl of different states can with some the group generation bonding action in the coating, improve the thermostability and the chemical stability of coating.In addition, nanometer SiO
2When dried coating film, can form network structure, remarkable for effects such as ageing-resistant, the smooth finish of improving coating, intensity and antiseptic properties.Though nanometer SiO
2Modified paint has the performance of a lot of excellences, but nanometer SiO
2The great amount of hydroxy group that the surface exists makes it show as wetting ability, very easily reunites, and package stability is poor.The homodisperse of nanometer in organic phase is an important step of development nano paint.E.Bourget at last report with SiO
2Be dispersed in the toluene, adopt silane coupling agent (MPS) to handle nanometer SiO
2, can effectively stop nanometer SiO
2Reunion [E.Bourget.Polymer 1995,36:4385]; Utilize ethylene glycol and tensio-active agent poly N-ethylene pyrrolidone (PVP) to nanometer SiO
2Carry out surface modification, make hydrophobic nano SiO
2, the about 39nm of particle diameter.From then on silane coupling agent is widely used in graft modification SiO
2Powder.
Silane coupling agent of a great variety, Jia Hongbing etc. adopt KH-550, KH-590, KH-792, KH-846 to SiO respectively
2Handle [Jia Hongbing etc. rubber industry 1999,46:590], studied different silane coupling agents to nanometer SiO
2Nanometer SiO in the filled rubber system
2Between interactional influence, the result shows that coupling agent has reduced interparticle interaction, influence degree is KH792>KH550>KH846>KH590.Teofil Jesionowski is at Na
2OmSiO
2NH
2In the O solution, feed CO
2Situation under made SiO
2Nanoparticle [Teofil Jesionowski.Applied Surface Science2001,172:18], and with A-189, U-13 and U-1513 to SiO
2Nanoparticle carries out modification, has studied coupling agent to SiO
2The influence of nanoparticle face pattern, and to SiO
2Dispersiveness study.People such as Shuxue Zhou adopt KH-570 modified manometer silicon dioxide [Shuxue Zhou, et al.Progress in Organic Coatings2002,45:33] at last report, make nanometer SiO by blending method and situ aggregation method
2/ vinylformic acid compound resin polyurethane coating.
γ-(methacryloxypropyl) propyl trimethoxy silicane is a kind of silane coupling agent commonly used, is used for the various inorganic powders of modification, yet how to make nanometer SiO
2Improve modified effect, the nanometer SiO that avoids
2Powder reuniting, the reaction times of control modification, to control cost, the recycle disperse phase is difficult to solve always, and unsuitable suitability for industrialized production.
Summary of the invention
The object of the present invention is to provide a kind of lipophilic nano SiO
2The preparation method of powder is by adopting nanometer SiO
2Powder is a raw material, uses H
2O
2Carry out surface activation process, in the organic/inorganic mixed phase, use γ-(methacryloxypropyl) propyl trimethoxy silicane nanometer SiO
2Powder carries out modification, and organic disperse phase is collected in distillation, and drying makes lipophilic nano SiO
2Powder.This method is a kind of nanometer SiO simple, with low cost
2Powder-modified method is first by using H
2O
2Solution as activator and in-situ modified method in the organic/inorganic mixed phase to nanometer SiO
2Powder carries out modification, utilizes the distillatory method to reclaim organic disperse phase, and recycle, saves cost, and the lipophilic nano SiO that obtains
2Characteristics such as powder and organic solvent have good consistency, be uniformly dispersed are suitable for suitability for industrialized production.
Lipophilic nano SiO of the present invention
2The preparation method of powder, step comprises:
(1) with nanometer SiO
2Powder is a starting raw material, adopts superoxol to carry out surface activation process;
(2) with γ-(methacryloxypropyl) propyl trimethoxy silicane properties-correcting agent in water oil phase mixed solution to nanometer SiO
2Powder carries out surface modification treatment, obtains lipophilic nano SiO
2Powder dispersion;
(3) obtain lipophilic nano SiO through separatory, distillation, drying
2Powder.
Described nanometer SiO
2The particle diameter of powder starting raw material is 10~500nm;
Described step (1) surface activation process is to contain distilled water, dehydrated alcohol, H
2O
2Solution in carry out wherein dehydrated alcohol, H
2O
2(30wt%) consumption is respectively 8~15% of dispersion liquid volume, and the activation treatment condition is to stir 10~30 minutes with 400~800rpm speed mechanical, ultrasonic 10~30 minutes, at room temperature leaves standstill 8~24 hours;
Described γ-(methacryloxypropyl) propyl trimethoxy silicane and nanometer SiO
2The mass ratio of powder is 1: 10~1: 30;
Water oil phase mixed solution in the described step (2) is distilled water and ethyl acetate, and its consumption volume ratio is 1: 1;
The surface modification treatment condition of described step (2) is ultrasonic under the room temperature, mechanical stirring 20~30 minutes, and the pH value of solution is 6~10, under 50~60 ℃ of mechanical stirring conditions, heats 5~10 hours, and mechanical stirring speed is 400~800rpm;
Described separatory, distillation, drying conditions are to leave standstill to make the layering of water oil phase in 2~8 hours, adopt separating funnel to remove water, and 80 ℃ are distilled, and remove oil phase, 45~65 ℃ of dryings 8~12 hours.
Use dehydrated alcohol, H among the present invention
2O
2The aqueous solution to nanometer SiO
2Powder activates, and utilizes electrostatic repulsion, prevents nanometer SiO
2Powder is reunited in liquid phase; In the powder-modified step of lipophilic nano, utilize the lipophilic group on γ-(methacryloxypropyl) propyl trimethoxy silicane coupling agent, make hydrophilic nanometer SiO
2Powder is converted into oil loving nanometer SiO
2Powder; In the separation and aftertreatment of lipophilic nano powder, the evaporated liquor that condensation is reclaimed can recycle.By regulating modification temperature, modification environment PH and reaction times control nanometer SiO
2Powder-modified degree, therefore, the selection of modification temperature, modification environment PH, these three parameters of reaction times has fundamental influence to the performance of modification, and these three parameters of choose reasonable are most important to the result of modification.
Beneficial effect of the present invention:
(1) the mixed phase method of modifying prepares oil loving nanometer SiO
2Powder;
(2) use H
2O
2Pre-treatment nanometer SiO
2Powder activates its surface, activatory nanometer SiO
2Surface hydroxyl increases electrostatic repulsion, prevents powder reuniting, increases the surfactivity of powder, improves modified effect;
(3) the mixed phase reaction environment has shortened the reaction times, has improved reaction efficiency, and the may command level of response, and oil phase is recyclable to be utilized again;
(4) the lipophilic nano SiO that obtains
2Powder stable and uniform in organic oil-based solvent is disperseed;
(5) simple, the required production unit of preparation technology is simple, is easy to realize suitability for industrialized production.
Description of drawings
Fig. 1 is the sedimentation experiment figure as a result that makes sample with γ-(methacryloxypropyl) propyl trimethoxy silicane under the pH=9 reaction environment;
Fig. 2 is the forward and backward sample sedimentation experiment of modification result's a comparison diagram in kind;
Fig. 3 is the infrared absorpting light spectra of the forward and backward sample of modification;
Fig. 4 is the ultraviolet absorption figure of the forward and backward sample of modification.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
Take by weighing the nanometer SiO of 4g
2The powder beaker of packing into adds the 100ml deionized water, stirs simultaneously; In beaker, add 15mlH again
2O
2(30wt%) with the 15ml ethanol solution, ultra-sonic dispersion 30min uses culture dish to seal, and puts into shady and cool place and leaves standstill 12h.This mixing suspension is added three-necked flask, use oil bath pan to be heated to 50 ℃, carry out mechanical stirring simultaneously, stirring velocity is 400rpm.Get the 120ml ethyl acetate solution and add three-necked flask.Use 0.1mol/L ammoniacal liquor that the pH value of reaction environment is adjusted to 9, get 0.5ml γ-(methacryloxypropyl) propyl trimethoxy silicane again and add three-necked flask, reaction 8h (entering organic phase fully with the lipophilicity powder after the modification is as the criterion).Question response finishes, and leaves standstill and makes the layering of water oil phase in 6 hours, separates organic phase with separating funnel then, and heating organic phase to 80 ℃ is distilled, and makes the ethyl acetate evaporation, and condensation reclaims, and powder obtained lipophilic nano SiO in 12 hours 60 ℃ of dryings
2Powder.Sample dispersion after the modification in methyl methacrylate, is tested its dispersing property.Fig. 1 is the sedimentation experiment result of sample/methyl methacrylate dispersion liquid after the modification, as can be seen: after the modification sample in organic solvent, be uniformly dispersed, not stratified all the time.Fig. 2 is the forward and backward sample of modification/ultrasonic 10 minutes of methyl methacrylate dispersion liquid, leaves standstill the photo after 2 hours, as can be seen: the nanometer SiO after the modification
2Good, not stratified with organic phase methyl methacrylate consistency, and the nanometer SiO of non-modified
2The obvious layering of powder, consistency are poor.Fig. 3 is the infrared spectrogram of sample before and after the modification, and as can be seen: the group of γ-(methacryloxypropyl) propyl trimethoxy silicane successfully has been connected nanometer SiO
2The surface.Fig. 4 is the ultraviolet spectrogram of the forward and backward sample of modification/ethyl acetate mark liquid, as can be seen: nanometer SiO after the modification
2Dispersion liquid is than the nanometer SiO that does not have modification
2Dispersion liquid is stronger to ultraviolet absorption, and nanometer SiO after the modification is described
2Particles dispersed is even, and modified effect is obvious.
Take by weighing the nanometer SiO of 4g
2Powder is packed in the beaker and is added the 100ml deionized water, stirs simultaneously; In beaker, add 15mlH again
2O
2(30wt%) with the 15ml ethanol solution, ultra-sonic dispersion 30min uses culture dish to seal, and puts into shady and cool place and leaves standstill 12h.It is added three-necked flask, use oil bath pan to be heated to 55 ℃, carry out mechanical stirring simultaneously, stirring velocity is 500rpm.Get the 120ml ethyl acetate solution and add three-necked flask.Use 0.1mol/L ammoniacal liquor that the pH value of reaction environment is adjusted to 8, get 0.5ml γ-(methacryloxypropyl) propyl trimethoxy silicane again and add three-necked flask, reaction 8h (entering organic phase fully with the lipophilicity powder after the modification is as the criterion).Question response finishes, and leaves standstill the layering of water oil phase is made, and uses separating funnel to separate organic phase then, and heating organic phase to 80 ℃ is distilled, and makes the ethyl acetate evaporation, and condensation reclaims, and powder obtained lipophilic nano SiO in 12 hours 60 ℃ of dryings
2Powder.As can be seen from Figure 1: γ-(methacryloxypropyl) propyl trimethoxy silicane demonstrates good modified effect in the pH value is 8 weakly alkaline mixing solutions, disperses more even in the organic solvent methyl acrylate.
Embodiment 3
Take by weighing the nanometer SiO of 4g
2Powder is packed in the beaker and is added the 100ml deionized water, stirs simultaneously; In beaker, add 8mlH again
2O
2(30wt%) with the 8ml ethanol solution, ultra-sonic dispersion 30min uses culture dish to seal, and puts into shady and cool place and leaves standstill 12h.This mixed dispersion liquid is added three-necked flask, use oil bath pan to be heated to 60 ℃, carry out mechanical stirring simultaneously, stirring velocity is 400rpm.Get the 130ml ethyl acetate solution and add three-necked flask.Use 0.1mol/L ammoniacal liquor that the pH value of reaction environment is adjusted to 9, get 0.2ml γ-(methacryloxypropyl) propyl trimethoxy silicane again and add three-necked flask, reaction 10h (entering organic phase fully with the lipophilicity powder after the modification is as the criterion).Question response finishes, and leaves standstill the layering of water oil phase is made, and uses separating funnel to separate organic phase then, and heating organic phase to 80 ℃ is distilled, and makes the ethyl acetate evaporation, and condensation reclaims, and powder obtained lipophilic nano SiO in 12 hours 60 ℃ of dryings
2Powder.Nanometer SiO
2Particle is uniformly dispersed in organic solvent methyl acrylate solution, and modified effect is obvious.
Take by weighing the nanometer SiO of 4g
2Powder is packed in the beaker and is added the 100ml deionized water, stirs simultaneously; In beaker, add 10mlH again
2O
2(30wt%) with the 10ml ethanol solution, ultra-sonic dispersion 30min uses culture dish to seal, and puts into shady and cool place and leaves standstill 12h.This dispersion liquid is added three-necked flask, use oil bath pan to be heated to 55 ℃, carry out mechanical stirring simultaneously, stirring velocity is 800rpm.Get the 120ml ethyl acetate solution and add three-necked flask.Use 0.1mol/L ammoniacal liquor that the pH value of reaction environment is adjusted to 8, get 0.4ml γ-(methacryloxypropyl) propyl trimethoxy silicane again and add three-necked flask, reaction 8h (entering organic phase fully with the lipophilicity powder after the modification is as the criterion).Question response finishes, and leaves standstill the layering of water oil phase is made, and uses separating funnel to separate organic phase then, and heating organic phase to 80 ℃ is distilled, and makes the ethyl acetate evaporation, and condensation reclaims, and powder obtained lipophilic nano SiO in 12 hours 60 ℃ of dryings
2Powder.Nanometer SiO
2Particle is uniformly dispersed in organic solvent methyl acrylate solution, and modified effect is obvious.
Claims (5)
1. lipophilic nano SiO
2The preparation method of powder comprises the following steps:
(1) with nanometer SiO
2Powder is a starting raw material, adopts superoxol to carry out surface activation process; Described surface activation process is to contain distilled water, dehydrated alcohol, H
2O
2Solution in carry out wherein dehydrated alcohol, H
2O
2The 30wt% consumption is respectively 8~15% of dispersion liquid volume, and the activation treatment condition is to stir 10~30 minutes with 400~800rpm speed mechanical, ultrasonic 10~30 minutes, at room temperature leaves standstill 8~24 hours;
(2) use again γ-(methacryloxypropyl) propyl trimethoxy silicane properties-correcting agent in water oil phase mixed solution to nanometer SiO
2Powder carries out surface modification treatment, obtains lipophilic nano SiO
2Powder dispersion; Described surface modification treatment condition is ultrasonic under the room temperature, mechanical stirring 20~30 minutes, and the pH value of solution is 6~10, under 50~60 ℃ of mechanical stirring conditions, heats 5~10 hours, and mechanical stirring speed is 400~800rpm;
(3) obtain lipophilic nano SiO through separatory, distillation, drying
2Powder.
2. lipophilic nano SiO according to claim 1
2The preparation method of powder is characterized in that: described nanometer SiO
2The particle diameter of powder starting raw material is 10~500nm.
3. lipophilic nano SiO according to claim 1
2The preparation method of powder is characterized in that: described γ-(methacryloxypropyl) propyl trimethoxy silicane and nanometer SiO
2The mass ratio of powder is 1: 10~1: 30.
4. lipophilic nano SiO according to claim 1
2The preparation method of powder is characterized in that: the water oil phase mixed solution in the described step (2) is distilled water and ethyl acetate, and its consumption volume ratio is 1: 1.
5. lipophilic nano SiO according to claim 1
2The preparation method of powder is characterized in that: described separatory, distillation, drying conditions are to leave standstill to make the layering of water oil phase in 2~8 hours, adopt separating funnel to remove water, and 80 ℃ are distilled, and remove oil phase, 45~65 ℃ of dryings 8~12 hours.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1085231A (en) * | 1993-09-21 | 1994-04-13 | 锦州橡塑配合剂厂 | The production method of modified white carbon black |
CN1201046A (en) * | 1997-04-29 | 1998-12-09 | 埃勒夫阿托化学有限公司 | Modified porous silicon dioxide, its preparation method, and use as pigment and dye carrier in paint |
JP2000204355A (en) * | 1999-01-18 | 2000-07-25 | Jsr Corp | Composite particles, its production, abrasive material and its aqueous dispersion |
US6384125B1 (en) * | 1999-08-19 | 2002-05-07 | Dow Corning Corporation | Chemically modified silica fillers, process for producing, and silicone compositions containing same |
CN1407026A (en) * | 2001-08-19 | 2003-04-02 | 章浩龙 | Preparation method of superfine silicon dioxide powder |
-
2007
- 2007-12-07 CN CN2007101719337A patent/CN101225249B/en not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1085231A (en) * | 1993-09-21 | 1994-04-13 | 锦州橡塑配合剂厂 | The production method of modified white carbon black |
CN1201046A (en) * | 1997-04-29 | 1998-12-09 | 埃勒夫阿托化学有限公司 | Modified porous silicon dioxide, its preparation method, and use as pigment and dye carrier in paint |
JP2000204355A (en) * | 1999-01-18 | 2000-07-25 | Jsr Corp | Composite particles, its production, abrasive material and its aqueous dispersion |
US6384125B1 (en) * | 1999-08-19 | 2002-05-07 | Dow Corning Corporation | Chemically modified silica fillers, process for producing, and silicone compositions containing same |
CN1407026A (en) * | 2001-08-19 | 2003-04-02 | 章浩龙 | Preparation method of superfine silicon dioxide powder |
Non-Patent Citations (2)
Title |
---|
朱宛琳,王秀峰,王列松,伍媛婷,方俊.电子墨水用SiO2白色电泳颗粒的表面包裹及荷电.液晶与显示22 2.2007,22(2),140-145. |
朱宛琳,王秀峰,王列松,伍媛婷,方俊.电子墨水用SiO2白色电泳颗粒的表面包裹及荷电.液晶与显示22 2.2007,22(2),140-145. * |
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