CN110304635A - The method that non-protonic solvent extraction prepares silica polyhedron organosol - Google Patents
The method that non-protonic solvent extraction prepares silica polyhedron organosol Download PDFInfo
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- CN110304635A CN110304635A CN201910510731.3A CN201910510731A CN110304635A CN 110304635 A CN110304635 A CN 110304635A CN 201910510731 A CN201910510731 A CN 201910510731A CN 110304635 A CN110304635 A CN 110304635A
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- silica
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/145—Preparation of hydroorganosols, organosols or dispersions in an organic medium
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Abstract
The invention discloses a kind of methods that non-protonic solvent extraction prepares silica polyhedron organosol, and described method includes following steps: (1) the silica containing hydrosol is made in the ageing of polysilicate waterglass；(2) cation in cation exchange removal waterglass liquid；(3) non-protonic solvent is added, silica polyhedron colloidal sol is mutually gone in organic phase；(4) polyalcohol is added and distills the non-protonic solvent that removal step (3) is added, obtains silica polyhedron organosol.The preparation method has the characteristics that green, convenient, atom yield is high, and the silica polyhedron organosol stability of preparation is fine.
Description
Technical field
The present invention relates to the field of material preparation in physical chemistry and materials chemistry research, and in particular to a kind of to use waterglass
Coupled ion exchange removal sodium ion, with non-protonic solvent silica spe polyhedron colloidal sol, go water removal and its in water
Soluble substance adds organic polyhydric alcohol, and silica polyhedron is transferred in organic polyhydric alcohol, prepares silica multi-panel
The method of body organosol.
Background technique
Nano silica because of its brilliant optics, electricity, machinery, both thermally and chemically performance, have good dispersibility,
Thickening property and thixotropy have a wide range of applications in plastics, rubber, coating and Electronic Packaging industry.Currently, being washed to improve
The hygroscopicity and stainability of synthetic fibre fiber, while the draw ratio of ultra-fine polyester fiber is improved, dioxy is usually added in the polymerization
SiClx in-situ polymerization, it is desirable that the silica for participating in polymerization has preferable " thixotropy " and stability.
The most important method dry and wet of Superfine Silica Dioxide are prepared, dry method mainly has gas-phase decomposition method and electric arc
Method, wet process have Hydrolyze method, chemical precipitation method and sol-gel method etc..Wherein dry method and the performance of sol-gel method preparation are excellent
More, the features such as higher cost of preparation, the period of preparation is long；Chemical precipitation method has at low cost, abundant raw materials, simple process
Be easy to the preparation that the advantages that industrializing is widely used in nanoparticle.Certainly due to Superfine Silica Dioxide surface with higher
Condensation is easy by energy, between silicone hydroxyl to slough a hydrone and reunite, and needs the partial size of fine silicon dioxide in actual use
Uniformly, good dispersion and stability are high, and technology of preparing is crucial.
Key technology of the preparation for in-situ polymerization silicon dioxide gel is that silicon dioxide gel is distributed in polymerized monomer,
Such as ethylene glycol and butanediol.Improving nano silica, dispersed method mainly has repairing for coupling agent in organic solvent
Decorations, commonly use silane KH-570 coupling agent modify silica surface, reduce its reunion, this method is relatively complicated, manufacturing cycle compared with
It is long.The present invention intends not needed using inexpensive waterglass as raw material preparing silica polyhedron organosol capable of being industrialized
The high colloidal sol of good dispersion stability can be prepared with silane coupling agent.Waterglass main component is sodium metasilicate, is being diluted with water
Or under conditions of reducing alkalinity, nano-silicon dioxide particle can be formed, there are the structures such as cyclotetrasiloxane and cube eight siloxanes.
When being suitble to be dispersed in the silica polyhedron colloidal sol in polyalcohol by waterglass preparation, need to remove sodium ion in hydrolyzate and
Water commonly uses ion exchange, sour neutralization, water decomposition, electrodialysis and ultrafiltration etc. to realize.Ion-exchange removes in silica solution
Sodium ion, initially by Ondeo Nalco Co., the U.S. the forties in last century develop, after by DuPont Corporation etc. in the five, sixties
It is perfect, it is at present most mature and the most widely used technique, opens the road of silica solution industrial applications.The technique pair
Waterglass and ion exchange resin material and operating procedure have certain requirement.
20100233061 A1 of United States Patent (USP) discloses a kind of super-hydrophobic silica raw powder's production technology, using water
Glass as silica material, be added after waterglass is diluted alkaline ph values organosilan (such as hexamethyldisiloxane) and
Inorganic acid, organosilan obtain hydrogel as modifying agent；Then organic solvent replaces water therein, and sodium ion is then dissolved in
It is removed in water；Super-hydrophobic silica will be obtained after silica dioxide gel drying containing organic solvent.
Summary of the invention
For the problems in background technique, the present invention provides a kind of non-protonic solvent extractions to prepare silica multi-panel
The method of body organosol.With waterglass hydrolysis coupled ion exchange process removal cation, non-protonic solvent is added using extraction
It follows the example of and removes water, and silica polyhedron colloidal sol is transferred in polyalcohol.The preparation method has green, convenient, atom
The silica polyhedron colloidal sol of the features such as yield is high, preparation can be steadily in the long term in liquid polyol.
To achieve the above object, the following technical solutions are proposed by the present invention:
A kind of method that non-protonic solvent extraction prepares silica polyhedron organosol, the method includes as follows
Step:
(1) dilution and ageing of polysilicate waterglass forms silicon using the hydroxyl condensation of silicic acid in sodium silicate solution
The polyhedral hydrosol of nano-silica-containing is made in the characteristic of oxygen alkane, such as cyclotetrasiloxane and cube eight siloxanes；
By adjusting the concentration and digestion time of waterglass, the size of silica polyhedron colloidal sol is controlled；Waterglass is dense
Degree is bigger, and the size for generating silica is smaller；Digestion time is longer, and partial size is bigger；
(2) water glass solution is removed into the cation in mixed liquor by storng-acid cation exchange resin thermopnore；
(3) non-protonic solvent is added, has been transferred to the silica polyhedron colloidal sol in water phase with the method for extraction
In machine phase, the inorganic matter dissolved in water removal and water phase is removed；
(4) polyalcohol is added and distills the organic solvent that removal step (3) is added, obtains being distributed to titanium dioxide in polyalcohol
Silicon polyhedron organosol.
As a preferred solution, in step (1), the polysilicate waterglass is sodium polysilicate waterglass；
The modulus of the waterglass is 3.0~3.4, concentration 40%.
As a preferred solution, in step (1), the additional amount of water is 1~3.5 times of waterglass, control ageing
The size of time adjustment silicon dioxide gel partial size, using silicic acid in sodium silicate solution hydroxyl condensation at nanoparticle spy
Property, the silica containing hydrosol is made；
In step (1), waterglass is diluted with water to the water glass solution that mass percent concentration is 10~20%, and
Ageing 15~24 hours；
As a preferred solution, in step (3), the non-protonic solvent with boiling point lower than 100 DEG C carries out phase and turns
It moves, can be compatible with silica polyhedron colloidal sol, such as tetrahydrofuran, the silica polyhedron extracted in waterglass ageing liquid is molten
Glue, go water removal and its in water-soluble substances, obtain the polyhedral organosol of silica.
As a preferred solution, in step (4), the polyalcohol is selected from ethylene glycol, propylene glycol, butanediol and sweet
Any one of oil.
As a preferred solution, in step (4), distillation removal step (3) is added under conditions of less than 100 DEG C
Organic solvent, obtain the silica polyhedron colloidal sol of high stable being dispersed in polyalcohol.
Silica polyhedron prepared by the present invention is the polyhedrons such as tetrahedron, octahedron, dodecahedron and its corresponding
The polyhedral mixture of rescinded angle.
Principle: in the present invention, after the dilution and ageing of polysilicate waterglass, the hydroxyl contracting of silicic acid in sodium silicate solution
Conjunction forms siloxanes, such as cyclotetrasiloxane and cube eight siloxanes, and the polyhedral hydrosol of nano-silica-containing is made.It is non-
Proton solvent can be miscible with water, after the polyhedral hydrosol of silica is added in aprotic solvent, what hydroxyl condensation was formed
Siloxanes can be transferred in aprotic solvent phase.
Compared with the existing technology, beneficial effects of the present invention are as follows:
The present invention using cheap waterglass as raw material, using the spontaneous aggregation procedure of the silicic acid in water glass solution,
By adjusting the concentration and digestion time of waterglass, control silica forms the size of polyhedron colloidal sol.With boiling point less than 100
Silicon dioxide gel in DEG C non-protonic solvent aqueous phase extracted, does not need organosilicon modifier, can make silicon dioxide gel
It is transferred in polyalcohol.Less than 100 DEG C non-protonic solvents can be recycled by the method for distillation, the silica multi-panel of preparation
Body colloidal dispersion can be used directly for the modification of polymer material in polyalcohol with long term storage.
Detailed description of the invention
Fig. 1 is the flow chart for preparing superstability silica polyhedron colloidal sol；
Fig. 2 is the transmission electron microscope picture for being dispersed in silica polyhedron colloidal sol in ethylene glycol of embodiment 1；
Fig. 3 is the transmission electron microscope picture for being dispersed in silica polyhedron colloidal sol in ethylene glycol of embodiment 2.
Specific embodiment
Below with reference to embodiment, detailed elaboration is made to specific embodiments of the present invention.Following embodiment is for illustrating
The present invention, but be not intended to limit the scope of the invention.
Embodiment 1:
A kind of method that non-protonic solvent extraction prepares silica polyhedron organosol is present embodiments provided, is made
Standby process is as shown in Figure 1.Waterglass, modulus 3.1~3.4, technical grade, 40% water glass solution, Jiangsu are taken on auspicious omen industrial and trading company
It produces.10 grams of liquid soluble glass (modulus 3.1, solid content 31%) is taken, is dissolved in 30 milliliters of water, forms mass percent concentration about
For 10% water glass solution.After the solution is aged 24H, 732 cation exchange resin fixed beds are flowed through under agitation,
Obtain the poly silicate solution of removal sodium ion.15 milliliters of tetrahydrofuran are added every time in two times into poly silicate aqueous solution
Except sodium ion is removed water phase and is obtained 27.5 grams of tetrahydrofuran titanium dioxides with the poly silicic acid in tetrahydrofuran extraction aqueous solution
Silica solution, is finally added 10 grams of polyalcohol 1,4-butanediol into tetrahydrofuran extract liquor again, and distillation removal tetrahydrofuran obtains
12.3 grams of butanediol silicon dioxide gels, dioxide-containing silica 20%, particle size is in 12~21nm.Prepare silica multi-panel
The transmission electron microscope picture of body colloidal sol is as shown in Fig. 2, it can be seen that having silica polyhedron, such as tetrahedron, octahedron, 12 in figure
Face body and its polyhedral mixture of corresponding rescinded angle.It is different from the nano spherical particle reported in general literature.
Embodiment 2:
10 grams of waterglass (modulus 3.1, solid content 31%) in Example 1, is dissolved in 10 milliliters of water, forms quality
The water glass solution that percent concentration is about 16%.After the solution is aged 17H, 732 cations are flowed through under agitation and are handed over
Resin fixed bed is changed, the poly silica sol of removal sodium ion is obtained.15 milliliters of tetrahydrofuran are added in two portions, removal is added to
In the poly silicate aqueous solution of sodium ion, 13.5 grams of tetrahydrofuran silicon dioxide gels are obtained by extraction, finally again to tetrahydrofuran
Suitable polyalcohol glycerol is added in extract liquor, distillation removal tetrahydrofuran obtains 12.5 grams of nanometer butanediol colloidal sols, by testing,
Particle size is in 4~8nm range.The transmission electron microscope picture of product is prepared as shown in figure 3, it can be seen that there is silica multi-panel in figure
Body.
Embodiment 3:
10 grams of waterglass (modulus 3.1, solid content 31%) in Example 1, is dissolved in 6 milliliters of water, forms quality
The water glass solution that percent concentration is about 20%；It is aged 20H；The polyalcohol being finally added into tetrahydrofuran extract liquor is second
Glycol；Other conditions are same as Example 1, silica polyhedron organosol are prepared, particle size is in 3~6nm.
Obviously, above-mentioned case study on implementation made by clearly explanation just for the sake of enumerating, and is not the limit to embodiment
It is fixed.For those of ordinary skill in the art, it is various forms of that other can also be made on the basis of the above description
Variation changes.There is no necessity and possibility to exhaust all the enbodiments.And it thus amplifies out obvious
Variation or variation are still fallen among the protection scope of the claims in the present invention.
Claims (7)
1. a kind of method that non-protonic solvent extraction prepares silica polyhedron organosol, which is characterized in that the side
Method includes the following steps:
(1) the polyhedral hydrosol of nano-silica-containing is made in the dilution and ageing of polysilicate waterglass；Step on human feelings
(2) hydrosol of silica is removed into the cation in mixed liquor by storng-acid cation exchange resin fixed bed；
(3) non-protonic solvent is added, the silica polyhedron colloidal sol in water phase is transferred to organic phase with the method for extraction
In, remove the inorganic matter dissolved in water removal and water phase；
(4) polyalcohol is added and distills the non-protonic solvent that removal step (3) is added, it is organic molten to obtain silica polyhedron
Glue.
2. the method that non-protonic solvent extraction according to claim 1 prepares silica polyhedron organosol,
It is characterized in that, in step (1), the polysilicate waterglass is sodium polysilicate waterglass, the modulus of waterglass is 3.0~
3.4, concentration 40%.
3. the method that non-protonic solvent extraction according to claim 1 prepares silica polyhedron organosol,
It is characterized in that, in step (1), waterglass is diluted with water to the water glass solution that mass percent concentration is 10~20%,
And it is aged 15~24 hours；Control the size that digestion time adjusts silica polyhedron aerosol particle size.
4. the method that non-protonic solvent extraction according to claim 1 prepares silica polyhedron organosol,
It is characterized in that, in step (3), the boiling point of the non-protonic solvent is lower than 100 DEG C.
5. the method that non-protonic solvent extraction according to claim 1 prepares silica polyhedron organosol,
It is characterized in that, in step (3), the non-protonic solvent is tetrahydrofuran.
6. the method that non-protonic solvent extraction according to claim 1 prepares silica polyhedron organosol,
It is characterized in that, in step (4), the polyalcohol is selected from any one of ethylene glycol, propylene glycol, butanediol and glycerol.
7. the method that non-protonic solvent extraction according to claim 1 prepares silica polyhedron organosol,
It is characterized in that, in step (4), the organic solvent that distillation removal step (3) is added under conditions of less than 100 DEG C obtains height
The stable silica polyhedron colloidal sol being dispersed in polyalcohol.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3855145A (en) * | 1971-01-28 | 1974-12-17 | Nalco Chemical Co | Preparation of concentrated silica organosols |
| CN1699166A (en) * | 2005-05-23 | 2005-11-23 | 电子科技大学 | Nano organic solvent silicasol and preparation method thereof |
| US20070032560A1 (en) * | 2005-08-02 | 2007-02-08 | Nissan Chemical Industries, Ltd. | Organosol of silica and process for producing same |
| WO2009147025A2 (en) * | 2008-06-04 | 2009-12-10 | Basf Se | Method for the production of organosols |
| CN102245667A (en) * | 2008-10-15 | 2011-11-16 | 巴斯夫欧洲公司 | Method for producing polyol dispersions containing silica and use thereof for producing polyurethane materials |
| US20120071682A1 (en) * | 2008-02-14 | 2012-03-22 | The Curators Of The University Of Missouri | Organosilica nanoparticles and method for making |
-
2019
- 2019-06-13 CN CN201910510731.3A patent/CN110304635A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3855145A (en) * | 1971-01-28 | 1974-12-17 | Nalco Chemical Co | Preparation of concentrated silica organosols |
| CN1699166A (en) * | 2005-05-23 | 2005-11-23 | 电子科技大学 | Nano organic solvent silicasol and preparation method thereof |
| US20070032560A1 (en) * | 2005-08-02 | 2007-02-08 | Nissan Chemical Industries, Ltd. | Organosol of silica and process for producing same |
| US20120071682A1 (en) * | 2008-02-14 | 2012-03-22 | The Curators Of The University Of Missouri | Organosilica nanoparticles and method for making |
| WO2009147025A2 (en) * | 2008-06-04 | 2009-12-10 | Basf Se | Method for the production of organosols |
| CN102245667A (en) * | 2008-10-15 | 2011-11-16 | 巴斯夫欧洲公司 | Method for producing polyol dispersions containing silica and use thereof for producing polyurethane materials |
Non-Patent Citations (4)
| Title |
|---|
| 丁志平 主编: "《精细化工工艺 无机篇》", 31 May 1998, 化学工业出版社 * |
| 任之君 等: "乙二醇纳米硅溶胶的制备及应用", 《电子元件与材料》 * |
| 张超灿 等: "酯化改性纳米二氧化硅及其在聚酯漆中应用", 《武汉理工大学学报》 * |
| 文俊: "相转移法制备油溶纳米二氧化硅", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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