CN100572456C - Nano inner core sandwich type structural silica dioxide delustring agent and preparation method thereof - Google Patents
Nano inner core sandwich type structural silica dioxide delustring agent and preparation method thereof Download PDFInfo
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- CN100572456C CN100572456C CNB2006100351408A CN200610035140A CN100572456C CN 100572456 C CN100572456 C CN 100572456C CN B2006100351408 A CNB2006100351408 A CN B2006100351408A CN 200610035140 A CN200610035140 A CN 200610035140A CN 100572456 C CN100572456 C CN 100572456C
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- flatting agent
- silica flatting
- inner core
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- silica
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 151
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 69
- 238000000034 method Methods 0.000 claims abstract description 38
- 229960001866 silicon dioxide Drugs 0.000 claims abstract description 21
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 21
- 239000011247 coating layer Substances 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 13
- 239000012716 precipitator Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims description 11
- 239000013543 active substance Substances 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 125000005372 silanol group Chemical group 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000006224 matting agent Substances 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 239000004115 Sodium Silicate Substances 0.000 description 5
- 125000002091 cationic group Chemical group 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229910052911 sodium silicate Inorganic materials 0.000 description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 5
- 238000004381 surface treatment Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 230000001143 conditioned effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000693 micelle Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
Abstract
The invention discloses silica flatting agent of a kind of sandwich type structural and preparation method thereof.The particle diameter of silica flatting agent of the present invention is between 2-30 μ m, and this silica flatting agent comprises the nano inner core that is made of silicon-dioxide and the cotton-shaped coating layer that is made of silicon-dioxide, and wherein, the diameter of nano inner core is between 10-50nm; With respect to this nano inner core, cotton-shaped coating layer has comparatively bulk structure.Matting agent of the present invention had both had the high oil-absorption(number) of silica flatting agent of precipitator method production and the advantage of high porosity, also had the firm structure and the transparency of silica flatting agent that gel method is produced simultaneously.
Description
Technical field
The present invention relates to a kind of silica flatting agent and preparation method thereof, more particularly, the present invention relates to a kind of silicon-dioxide novel material with sandwich type structural of nano inner core and cotton-shaped coating, preparation method and as the application of matting agent.
Background technology
In coatings industry, amorphous silica is used for varnish and has the good optical performance, thereby amorphous silica becomes the first-selection of high-grade paint matting agent because of the refractive index of its refractive index and the employed most of resin of the sector is close.The main characteristic parameter that influences silica flatting agent has pore volume (porosity), median size and size distribution, surface treatment etc.What early be used for matting agent is the amorphous silica that vapor phase process is produced, for example disclose a kind of silica flatting agent that comprises particulate amorphous silicon-dioxide among the Chinese patent application CN02822370.5, wherein this silica dioxide granule is handled with hydrophilic polyolefin wax.The shortcoming of amorphous silica matting agent is to cost an arm and a leg.
Liquid phase method (wet method) is compared with the amorphous silica of vapor phase process production, because with low cost and come into one's own day by day.Liquid phase method (wet method) is produced silicon-dioxide can be divided into the gel method and the precipitator method from operational path, its processing method can be with reference to disclosed method among U.S. Pat 6103,004, US 5123,964 and the US 5637,636.
Disclose a kind of precipitated silica with dressed with polythene wax emulsion among the Chinese patent application CN200410081752.1, it can be used as the matting agent in the lacquer system.This precipitated silica has following the physical-chemical parameters: the BET surface-area that records according to DIN 66131 is 351-600m
2/ g, the DBP index that records according to DIN 53601 is 300-360%, and carbon content is 1-8%, and the compacted density that records according to DIN53194 is 70-140g/l, the fineness that records according to ISO 1524 is 15-50 μ m, with particle size distribution index I<1.0 of Malvern instrument measurement.Wherein, particle size distribution index I=(d
90-d
10)/2d
50
Also disclose a kind of efficient matting agent based on precipitated silica among the Chinese patent application CN03155464.4, the BET of this precipitated silica is 350~550m
2/ g, the DBP value is 320~400g/100g, particle diameter d50 is that 5~15 μ m, compacted density are 20~90g/l.
Chinese patent application CN200380106812.4 then discloses the silicon-dioxide that a kind of structure applies, its preparation process is: in suitable mixing vessel, water and coating-forming agent spray pyrolysis method silicon-dioxide and pyrogenic silica mixed with water and coating-forming agent grind product and regulate then.
For the silicon-dioxide that liquid phase method is produced, the resulting product performance of different operational paths are different: the silicon dioxide structure that gel method is prepared is firm, and pore size distribution is narrow, and the transparency is good, but voidage is low; The silicon-dioxide voidage height of precipitator method preparation, but structural loose, structure is destroyed easily under high-shear, and the transparency is also relatively poor.
Up to the present, the silicon-dioxide produced of liquid phase method prior art can not satisfy not only sound construction, but also the high requirement of voidage simultaneously.
Summary of the invention
The purpose of this invention is to provide a kind of soft silica matting agent, this matting agent had both had the high oil-absorption(number) of silica flatting agent of precipitator method production and the advantage of high porosity, also had the firm structure and the transparency of silica flatting agent that gel method is produced simultaneously.
Another object of the present invention provides a kind of preparation not only to have been had the precipitated silica characteristics, but also had had the processing method of the silica flatting agent of gel method silicon-dioxide characteristics.
In order to realize above-mentioned goal of the invention, on the one hand, the invention provides a kind of silica flatting agent of sandwich type structural, the particle diameter of this silica flatting agent is preferably 2-15 μ m, more preferably 4-10 μ m between 2-30 μ m; And this silica flatting agent comprises the nano inner core that is made of silicon-dioxide and the cotton-shaped coating layer that is made of silicon-dioxide, and wherein, the diameter of nano inner core is preferably 10-20nm between 10-50nm; With respect to this nano inner core, cotton-shaped coating layer has comparatively bulk structure.
In the above-mentioned silica flatting agent, the density of nano inner core is higher than the density of cotton-shaped coating layer; The porosity of cotton-shaped coating layer then is higher than the porosity of nano inner core.
In order to make nano inner core have different structures, density and porosity etc. with cotton-shaped coating layer, the nano inner core of silica flatting agent of the present invention can form by gel method, and cotton-shaped coating layer can form by the precipitator method.
The surface of above-mentioned silica flatting agent further is connected with and can be anchored to locational polymkeric substance of surface silanol group and/or tensio-active agent; Wherein polymkeric substance can be polarity or nonpolar, as polyvinyl alcohol etc.; Tensio-active agent is preferably aniorfic surfactant.By weight percentage, the 1-15% of the gross weight of polymkeric substance and/or surfactant comprise silica flatting agent is preferably 3-8%.
Above-mentioned silica flatting agent can further be pulverized and be the particle of particle diameter between 2-4 μ m.
On the other hand, the present invention also provides a kind of processing method for preparing sandwich type structural silica dioxide delustring agent, and this method comprises:
(1) utilize gel method to form the nano inner core of silica flatting agent;
(2) utilize the precipitator method to form the cotton-shaped coating layer of formation of silica flatting agent.
Wherein, the step of utilizing gel method to form nano inner core comprises again:
A) silicate solutions with dilution passes through Zeo-karb, carries out cationic exchange, and adds the cationic stabilized agent in the reaction solution after exchange; Wherein, the cationic stabilized agent can be the inorganic salt of ammonium type, sodium type or potassium type;
B) the pH value with the reaction solution of step a) gained is adjusted to 2-6, be lower than under 100 ℃ the condition aging; The aged time can be 0.5h-5h;
C) reaction solution with the step b) gained under agitation joins in the silicate solutions continuously, and regulating the pH value is 8-10, and is incubated several minutes by several hours after adding, and forming particle diameter is the silica nanometer kernel of nanometer scale;
Utilize the precipitator method form cotton-shaped coating layer step can for:
The reaction solution that contains the silica nanometer kernel of gained is maintained the temperature at 50-100 ℃, under stirring condition, drip alkali metal silicate solutions and inorganic acid solution respectively simultaneously, generate cotton-shaped precipitation of silica, the rate of addition of control acid, and the pH value of whole reaction system is remained between the 7-10, and preserving heat after reaction ends is handled, and the time of insulation can be 0.5-3h.
Above-mentioned method can further include following step:
The precipitation of silica of gained is washed, and carry out surface treatment with being anchored to locational polymkeric substance of surface silanol group and/or tensio-active agent.This step can realize the functionalization of material.
In addition, method of the present invention also comprises some conventional method stepss of this area, for example adopts spray drying device to remove moisture in the gained silicon-dioxide, adopts that supersonic jet mill is pulverized etc.
In above-mentioned step a), silicate solutions dilution back is by Zeo-karb, by the H on the resin
+With the cationic exchange in the silicate solutions, form HSiO
3 -, the silicon-dioxide of nascent state is very active, becomes glue nuclear (SiO by particle growth
2) m, glue nuclear has extremely strong adsorptive type, adsorpting anion HSiO in the particle growth and the concentration process that anhydrates
3 -Form micelle.Micelle is electronegative, forms the neutral micelle after the agent of adding cationic stabilized, and system becomes the stabilized nano silicon dioxide granule.The reaction of this process can be expressed as follows:
2R-SO
3H+Na
2O·mSiO
2→2R-SO
3Na+mSiO
2+H
2O (1)
mSiO
2→(SiO
2)m (2)
(SiO
2)m+HSiO
3 -→SiO
2)m·HSiO
3 - (3)
(SiO
2)m·HSiO
3 -+M
+→SiO
2)m·HSiO
3 -·M
+ (4)
The present invention is a kernel with the silica dioxide gel of nano-scale, and outside surface coats the sandwich type structural of flocks silicon-dioxide, serves as matting agent anti-dispersion in the coating material production process of basis preparation with the silicon-dioxide of this structure, be difficult for broken, and eliminate optical property is good, free settling not, transparency height.
Below; in conjunction with embodiment, further specify content of the present invention and characteristics, but the present invention is not limited to these embodiments; any on essence spirit of the present invention improvement or substitute, still belong to scope required for protection in claims of the present invention.
Embodiment
Embodiment 1
10% silicate solutions of 1L is carried out ion-exchange by ion exchange resin, the pH value of conditioned reaction liquid is 2.5 then, 60 ℃ of aging 2h, under agitation condition, join in the reactor that 15% silicate solutions is housed then, regulating the pH value is 9, add the back insulation 1h that finishes, prepare the nano silicon kernel; Being warming up to 80 ℃ under stirring condition, dripping 15% sodium silicate solution and 7% hydrochloric acid soln simultaneously, is 8.5 by the dripping quantity conditioned reaction system pH of controlling acid, dropwises back insulation 1h.Filter, washing is carried out surface treatment with polymkeric substance.Adopt spray drying device to remove the contained moisture of silicon-dioxide, adopt supersonic jet mill that silicon-dioxide is crushed to 3 microns.
Embodiment 2
Substantially prepare silica flatting agent by embodiment 1 described identical method, but as different from Example 1: under agitation condition, be warming up to 70 ℃, add 10% sodium silicate solution and hydrochloric acid soln again.
Embodiment 3
Substantially prepare silica flatting agent by embodiment 1 described identical method, but as different from Example 1: drip 10% sodium silicate solution and 7% salpeter solution simultaneously.
Embodiment 4
Substantially prepare silica flatting agent by embodiment 1 described identical method, but as different from Example 1: drip 15% sodium silicate solution and 7% hydrochloric acid soln simultaneously, the conditioned reaction system pH is 9.
Embodiment 5
Substantially prepare silica flatting agent by embodiment 1 described identical method, but as different from Example 1: drip and be incubated 2h after 15% sodium silicate solution and 7% hydrochloric acid soln finish.
The prepared sample of the foregoing description is tested, be the results are shown in Table 1:
Table 1
Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
Porosity (milliliter/gram) | 2.0 | 1.8 | 1.7 | 1.9 | 1.7 |
Oil number (gram/100 grams) | 280 | 260 | 270 | 250 | 220 |
Median size (Coulter method μ) | 3 | 3 | 3 | 3 | 3 |
BET specific surface (m 2/g) | 300 | 280 | 270 | 260 | 240 |
Weight loss on heating (%) | 2.5 | 2.5 | 2.5 | 2.4 | 2.4 |
Calcination loss (%) | 3 | 4 | 4 | 3 | 3 |
Whiteness | 97 | 96 | 96 | 97 | 97 |
The physico-chemical property of the silica flatting agent (sample A and sample B) of the present invention preparation is compared with matting agent product both at home and abroad, wherein the contrast of physical parameter sees Table 2 and table 4, the contrast of performance index sees Table 3 (PU coating systems) and table 5 (NC coating system), and other contrast sees Table 6:
Table 2
Sample A of the present invention | Grace ED-30 | Home products A | |
Porosity (milliliter/gram) | 2.0 | 1.8 | 1.7 |
Oil number (gram/100 grams) | 280 | 260 | 220 |
Median size (Coulter method μ) | 3 | 3 | 3 |
Surface treatment amount (%) | 6 | 7 | 0 |
BET specific surface (m 2/g) | 300 | 280 | 240 |
Weight loss on heating (%) | 2.0 | 2.5 | 4.0 |
Calcination loss (%) | 3 | 4 | 1 |
Whiteness | 97 | 96 | 97 |
Table 3
Sample A of the present invention | Grace ED-30 | Home products A | |
Matting agent addition (%) | 4.0 | 4.0 | 4.0 |
Glossiness | 38 | 40 | 67 |
Fineness of dispersion | ≤15μ | ≤15μ | ≤20μ |
Transparency (%) | 51 | 53 | 57 |
Resistance to settling | 1 grade | 1 grade | 3 grades |
Paint viscosity (being coated with-4 glasss) | 3’15” | 3’18” | 3’27” |
Levelling property | 1 grade | 1 grade | 2 grades |
Recoatability | 1 grade | 1 grade | 3 grades |
Table 4
Sample B of the present invention | Degussa OK-607 | Home products B | |
Porosity (milliliter/gram) | 2.0 | 2.0 | 1.7 |
Oil number (gram/100 grams) | 240 | 220 | 180 |
Median size (Malvern method μ) | 4.0 | 4.5 | 4.0 |
Surface treatment amount (%) | 6 | 6 | 0 |
BET specific surface (m 2/g) | 320 | 340 | 280 |
Weight loss on heating (%) | 2.0 | 2.5 | 4.0 |
Calcination loss (%) | 3 | 4 | 1 |
Whiteness | 97 | 98 | 97 |
Table 5
Sample B of the present invention | Degussa OK-607 | Home products B | |
Matting agent addition (%) | 3.0 | 3.0 | 3.0 |
Glossiness | 22 | 19 | 42 |
Fineness of dispersion | ≤15μ | ≤15μ | ≤25μ |
Transparency (%) | 34 | 30 | 26 |
Resistance to settling | 1 grade | 1 grade | 3 grades |
Paint viscosity (being coated with-4 glasss) | 2’21” | 2’25” | 2’56” |
Levelling property | 1 grade | 1 grade | 2 grades |
Recoatability | 1 grade | 1 grade | 3 grades |
Table 6
Claims (7)
1, a kind of silica flatting agent of sandwich type structural, the particle diameter of this silica flatting agent is characterized in that between 2-30 μ m described silica flatting agent comprises nano inner core that is made of silicon-dioxide and the cotton-shaped coating layer that is made of silicon-dioxide; Described nano inner core forms by gel method, and described cotton-shaped coating layer forms by the precipitator method; The diameter of described nano inner core is between 10-50nm; With respect to described nano inner core, described cotton-shaped coating layer has comparatively bulk structure; The surface of described silica flatting agent further is connected with and can be anchored to locational polymkeric substance of surface silanol group and/or tensio-active agent.
2, silica flatting agent as claimed in claim 1 is characterized in that, the density of described nano inner core is higher than the density of described cotton-shaped coating layer; The porosity of described cotton-shaped coating layer is higher than the porosity of described nano inner core.
3, silica flatting agent as claimed in claim 1 is characterized in that, described polymkeric substance is a polyvinyl alcohol.
4, silica flatting agent as claimed in claim 1 is characterized in that, described tensio-active agent is an aniorfic surfactant.
5, silica flatting agent as claimed in claim 1 is characterized in that, by weight percentage, and the 1-15% of the gross weight of described polymkeric substance and/or the described silica flatting agent of surfactant comprise.
6, silica flatting agent as claimed in claim 5 is characterized in that, by weight percentage, and the 3-8% of the gross weight of described polymkeric substance and/or the described silica flatting agent of surfactant comprise.
As the described silica flatting agent of one of claim 1-6, it is characterized in that 7, described silica flatting agent is pulverized is the particle of particle diameter between 2-4 μ m.
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CN109627835A (en) * | 2018-11-19 | 2019-04-16 | 湖北黄冈同轩高分子材料有限公司 | A kind of high penetration self-dispersing flatting silica and preparation method thereof |
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US5123964A (en) * | 1988-05-07 | 1992-06-23 | Degussa Aktiengesellschaft | Finely divided, precipitated silica with high structure, method of its preparation and use |
US5637636A (en) * | 1992-11-12 | 1997-06-10 | Crosfield Limited | Silicas |
CN1203191A (en) * | 1997-06-13 | 1998-12-30 | 水泽化学工业株式会社 | Amorphous silica particles having double structure, process for producing same and use |
US6103004A (en) * | 1995-04-26 | 2000-08-15 | Grace Gmbh | Matting agent based on aggregated silica |
CN1418811A (en) * | 2002-12-18 | 2003-05-21 | 天津化工研究设计院 | Macroporous precipitation silicon dioxide used for achromatic colours, and its prepn. method |
CN1563574A (en) * | 2004-04-09 | 2005-01-12 | 苏州天马医药集团有限公司 | Method for fabricating nano sol of silicon dioxide in use for papermaking |
-
2006
- 2006-04-24 CN CNB2006100351408A patent/CN100572456C/en not_active Expired - Fee Related
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5123964A (en) * | 1988-05-07 | 1992-06-23 | Degussa Aktiengesellschaft | Finely divided, precipitated silica with high structure, method of its preparation and use |
US5637636A (en) * | 1992-11-12 | 1997-06-10 | Crosfield Limited | Silicas |
US6103004A (en) * | 1995-04-26 | 2000-08-15 | Grace Gmbh | Matting agent based on aggregated silica |
CN1203191A (en) * | 1997-06-13 | 1998-12-30 | 水泽化学工业株式会社 | Amorphous silica particles having double structure, process for producing same and use |
CN1418811A (en) * | 2002-12-18 | 2003-05-21 | 天津化工研究设计院 | Macroporous precipitation silicon dioxide used for achromatic colours, and its prepn. method |
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