CN101481115B - Silicon dioxide, preparation and use thereof - Google Patents
Silicon dioxide, preparation and use thereof Download PDFInfo
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- CN101481115B CN101481115B CN2009100060143A CN200910006014A CN101481115B CN 101481115 B CN101481115 B CN 101481115B CN 2009100060143 A CN2009100060143 A CN 2009100060143A CN 200910006014 A CN200910006014 A CN 200910006014A CN 101481115 B CN101481115 B CN 101481115B
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- dioxide
- silicon
- wax
- pore volume
- absorption value
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Abstract
The invention relates to silicon dioxide, a preparation method thereof and an application of the silicon dioxide to the paint. The paint obtained by adopting a flatting agent has the advantages of high flattering efficiency, good transparency, good keeping property, slippery tactility, and the like. The silicon dioxide is characterized in that the pore volume is between 0.5 and 2.0 cm<3>/g; BET is between 100 and 380<2>/g; DBP absorption value is between 200 and 350g/100g, d50 is between 4 and 15 microns, and 100*Rho*pore volume /DBP absorption value is greater than or equal to 0.50, wherein the meaning of each symbol is stated in the Description.
Description
Technical field
The present invention relates to a kind of silicon-dioxide and preparation method thereof with and application in lacquer.
Background technology
Silicon-dioxide is used for lacquer as matting agent for a long time always.Conventional matting agent mainly contains the precipitator method and gel method (opening 8-170030 referring to DE 2414478, US 6103004 and spy) with process for preparing silicon dioxide.In addition; On the basis of gel method, US 60129007 and CN02822370 etc. provide a kind of the coating through wax to handle to improve the silica flatting agent of matting agent performance, and it adopts the method for pulverizing altogether under the molten state that high molecular polymers such as polyethylene wax, paraffin is compound to silicon-dioxide; Yet; The silicon-dioxide wax coating efficiency of this art breading is low, and needs the air of heating, has therefore increased cost.CN 1418811A and CN 1644632A propose will to can be used for earlier the wax that wax coats and process the wetting ability emulsion in addition; This emulsion is added in the silica slurry that has generated; In water medium, mix spraying drying then, after pulverize the silica flatting agent that obtains the wax processing.Yet the performance of this kind matting agent is very not satisfactory yet.
Summary of the invention
The present invention provides a kind of silicon-dioxide, wherein,
Pore volume 0.5-2.0cm
3/ g;
BET 100-380m
2/g；
DBP absorption value 200-350g/100g;
d
504-15 μ m; And
100 * ρ * pore volume/DBP absorption value >=0.50,
Wherein, DBP is a Witcizer 300; The DBP absorption value is the amount that silicon-dioxide absorbs DBP, and unit is a g/100g silicon-dioxide; ρ is the density of DBP, is 1.045g/cm
3Pore volume refers to the pore volume of silicon-dioxide, and unit is cm
3/ g silicon-dioxide.
Aforesaid silicon-dioxide can use the method preparation that comprises the following steps:
(a) in sodium silicate solution, add a kind of wax emulsion, add acid for adjusting pH value again to 8-11, it is 3-4 that pH is regulated in the back that reacts completely, and is heated to 50-70 ℃, re-adjustment pH to 8-11;
(b) with reaction mixture be warming up to 80-105 ℃ of aging 2-30h (hour);
(c) the aged mixture is added acid to pH value and be 2-4, ageing 0.2-3h;
(d) filter and with deionized water wash silicon-dioxide crude product;
(e) the dry and pulverizing with the silicon-dioxide that leaches.
Silicon-dioxide of the present invention can significantly improve its performance as matting agent, compares with like product on the market, and the lacquer that adopts said matting agent to obtain has advantages such as flatting efficiency height, the transparency is good, storage property good and be smooth to the touch.
Therefore, the invention still further relates to a kind of comprise silicon-dioxide of the present invention as the lacquer of matting agent and silicon-dioxide of the present invention as the purposes of lacquer with matting agent.
Embodiment
Silicon-dioxide of the present invention is characterised in that,
Pore volume 0.5-2.0cm
3/ g;
BET 100-380m
2/g；
DBP absorption value 200-350g/100g;
d
504-15 μ m; And
100 * ρ * pore volume/DBP absorption value >=0.50.
Surprisingly, the contriver is surprised to find that, the lacquer that adopts silica product of the present invention to obtain as matting agent is compared advantage such as have the flatting efficiency height, the transparency is good, storage property is good and be smooth to the touch with the lacquer that adopts conventional matting agent to obtain.
In the characteristic of silicon-dioxide of the present invention, said pore volume is preferably 1.0-2.0cm
3/ g further is preferably 1.2-1.8cm
3/ g; Said BET is preferably 200-350m
2/ g further is preferably 250-300m
2/ g; Said DBP absorption value is preferably 200-300g/100g, further is preferably 250-280g/100g; Said d
50Be preferably 5-12 μ m, further be preferably 6-10 μ m; The value of said formula (100 * ρ * pore volume/DBP absorption value) is preferably more than and equals 0.55, further is preferably greater than to equal 0.63.
In the present invention, pore volume is measured according to the DIN66134 method; BET measures according to DIN66131; The DBP absorption value is measured according to the DIN53601 method; d
50Be the meso-position radius of silicon-dioxide size distribution, measure according to GB/T19077.1.
In a preferred embodiment of the invention, 0.16≤(pore volume+9.569 * 10
-3* DBP absorption value)/d
50≤2.68.
In a further preferred embodiment of the present invention, 0.29≤(pore volume+9.569 * 10
-3* DBP absorption value)/d
50≤0.82.
In the present invention, can mutual combination between wide in range characteristic of above-mentioned silicon-dioxide and the various preferred feature, constitute different embodiments; This is applicable to following preparation method, lacquer and application too.
Above-mentioned silicon-dioxide can use the method preparation that comprises the following steps:
(a) in sodium silicate solution, add a kind of wax emulsion, add acid for adjusting pH value again to 8-11, it is 3-4 that pH is regulated in the back that reacts completely, and is heated to 50-70 ℃, re-adjustment pH to 8-11;
(b) reaction mixture is warming up to 80-105 ℃ of aging 2-30h;
(c) the aged mixture is added acid to pH value and be 2-4, ageing 0.2-3h;
(d) filter and with deionized water wash silicon-dioxide crude product;
(e) the dry and pulverizing with the silicon-dioxide that leaches.
In this preparing method's step (a), said wax emulsion comprises that the wax of any routine is dispersed in the water-adds in case of necessity emulsifying agent--the emulsion of formation.Wax can be for example polyethylene wax, OPE and Microcrystalline Wax etc., is preferably OPE; Emulsifying agent is preferably by the composite mixture that forms of two or more emulsifying agent, the mixture of AEO and polyoxyethylene nonylphenol for example, and both are that 1: 1 ratio is composite with weight ratio preferably.
In this preparing method's step (a), the amount of wax emulsion preferably satisfies sodium silicate solution mesosilicic acid sodium: wax=12-25: the ratio of 1 ratio (weight ratio), more preferably water glass: wax=14-20: 1 (weight ratio).The concentration of wax emulsion is preferably 3-10wt% (weight percent), more preferably 6-8wt%.
In a preferred embodiment of the invention, the wax emulsion can prepare through following method:
I) with a kind of wax and emulsifying agent with weight ratio 9-11: 1 mixed;
Ii) the gained mixture heating up is to 80-120 ℃, the fusing continued stir 30min (minute)-1h;
Iii) with mixture after being mixed add that temperature is at least more than 85 ℃, volume is that continuously stirring 30min-2h makes the wax emulsion in the said wax volume 10-30 hot water doubly.
In the step (a) of the inventive method, said sodium silicate silicate is preferably 0.5-2M, and said acid is generally the dilute sulphuric acid of 20-40wt%, also can use Hydrogen chloride (for example, 5-25wt%) or other can reach the acid of effect of the present invention.
In the step (a) of the inventive method, water glass is preferably 15-30 ℃ with the temperature of reaction of acid.
Silicon-dioxide of the present invention can significantly improve its performance as matting agent, compares with like product on the market, and the lacquer that adopts said matting agent to obtain has advantages such as flatting efficiency height, the transparency is good, storage property is good, be smooth to the touch.
Therefore, the invention still further relates to a kind of lacquer that contains silicon-dioxide of the present invention as matting agent, and silicon-dioxide of the present invention is as the purposes of matting agent in the lacquer.
Matting agent of the present invention can be used in the lacquer, preferred paint, more preferably wood lacquer.
Below will combine embodiment to describe the present invention in detail.Yet, should understand these embodiment only for the purpose of illustration, scope of the present invention is not restricted to this.
Embodiment 1
To 1000ml concentration is that to inject 200g concentration in the sodium silicate solution of 1.2M be the wax emulsion of 5wt%, this sodium silicate solution is joined in the reaction kettle of band whipping appts again, and this moment, temperature was 20 ℃; Adding concentration is that the dilute sulphuric acid of 30wt% is 10 to pH under the continuous stirring state, and stirring 20min continued adds acid to pH3, is heated to 60 ℃ of adding ammoniacal liquor; Regulate pH value to 10, be warming up to 100 ℃ of aging 5h, add acid to pH value 3 behind aging the end; Ageing 1h; Filter and with deionized water wash 3 times, dry, pulverizing obtains finished product.
The method for making of wax emulsion is following: get 500g OPE, 25g AEO and 25g polyoxyethylene nonylphenol and join together in the reaction kettle of being with heating and stirring device; With gained mixture heating up to 120 ℃, the fusing continued stirs 1h, meanwhile in the another one reaction kettle, adds 10L water; And heat water to 95 ℃; The wax mixture that stirs is discharged to stirring fast in the hot water, and stirring velocity is 120r/min, continuously stirring 30min.
Embodiment 2
To 1000ml concentration is that to inject 200g concentration in the sodium silicate solution of 1.5M be the wax emulsion of the embodiment 1 of 5wt%, this sodium silicate solution is joined in the reaction kettle of band whipping appts again, and this moment, temperature was 20 ℃; Adding concentration is that the dilute sulphuric acid of 20wt% is 10 to pH under the continuous stirring state, and stirring 20min continued adds acid to pH4, is heated to 65 ℃ of adding ammoniacal liquor; Regulate pH value to 10, be warming up to 100 ℃ of aging 2h, add acid to pH value 3 behind aging the end; Ageing 1h; Filter and with deionized water wash 3 times, dry, pulverizing obtains finished product.
The comparative example
To the 1000ml temperature is 20 ℃, and concentration is in the sodium silicate solution of 1.2M, constantly stirring state add down concentration be 30wt% dilute sulphuric acid to pH be 10; Stir the complete continued of 20min question response and add acid, be heated to 60 ℃ and add ammoniacal liquor, regulate pH value to 10 to pH3; Be warming up to 100 ℃ of aging 5h, add acid to pH value 3 behind aging the end, ageing 1h; Filter and, the filter cake after filtering all is transferred in the device of a band stirring, add the wax emulsion among the embodiment 1 that 200g concentration is 5wt% with deionized water wash silicon-dioxide crude product; Mix 0.5h, mixed slurry is dry, pulverizing obtain finished product.
The foregoing description and comparative example's test result is as shown in the table.Testing method is: pore volume is measured according to the DIN66134 method; BET measures according to DIN66131; The DBP absorption value is measured according to the DIN53601 method; d
50Be meant the meso-position radius of silicon-dioxide size distribution, adopt laser particle analyzer (JL-1166, the smart new powder testing apparatus company in Chengdu produces) to measure according to GB/T19077.1.
Table 1 silicon-dioxide detected result
| The embodiment sequence number | Pore volume (cm 3/g) | BET (m 2/g) | DBP value (g/100g) | d 50 (μm) | λ * |
| Embodiment 1 | 1.4 | 200 | 261 | 6.0 | 0.56 |
| Embodiment 2 | 1.6 | 282 | 264 | 6.7 | 0.63 |
| The comparative example | 1.3 | 200 | 277 | 6.0 | 0.49 |
* λ=100 * ρ * pore volume/DBP absorption value (ρ=1.045g/cm wherein
3)
The application implementation example
(Syloid ED30 and Acematt OK412 are produced by Grace and Degussa respectively to select commercially available silicon-dioxide respectively for use; The parameter of product is as shown in table 2), comparative example's product and product of the present invention be as matting agent, presses the mute light lacquer as woodenware finish of formulation of table 3.The performance of more various lacquers, the result lists in table 4:
Table 2
| Product type | Syloid?ED30 | Acematt?OK412 |
| Manufacturer | Grace | Degussa |
| The preparation method | Conventional gel method | The conventional precipitator method |
| Pore volume (cm 3/g) | 1.6 | 1.3 |
| BET(m 2/g) | 320 | 310 |
| DBP value (g/100g) | 348 | 283 |
| d 50(μm) | 6.0 | 7.5 |
| λ | 0.48 | 0.48 |
The mute light lacquer as woodenware finish prescription of table 3
The preparation method of mute light lacquer as woodenware finish is following:
1) starting material of will filling a prescription mix, and in high speed dispersor, use the rotor of 3.5 centimetres of diameters then, use the rotating speed of 2000r/min, disperse 20min.
2) use 100 μ m spreaders that paint is coated on the sheet glass; The two ends of spreader splash into different paint sample respectively; Wherein an end is a standard, and the other end is for treating test sample, and change left and right sides order repeats to be coated with 2; Treat that with the naked eye relatively paint film is transparent through fluorescent lamp after the drying varniss, printing opacity is clear to be that the transparency is good.Standard in this control experiment is the mute light lacquer as woodenware finish sample that contains Syloid ED30 silicon-dioxide, treats that the test sample transparency is chosen as when being better than standard well, is chosen as during indifference generally, is chosen as relatively poor when transparency difference and standard.
3) use 100 μ m spreaders that paint is coated on the glossy paper, treat to test gloss numbers with 60 ° of glossometers after the drying varniss, same sample is coated with 5 and averages, and gloss number is low to be that extinction is good.
4) placing weight is that the counterweight of 500 grams is in step 2) on the paint film of preparation,, measure pulling force size (N) and assess the smooth degree of paint film with the speed pulling counterweight of 12mm/s.The more little expression paint film of numerical value is smooth more, and feel is also good more.
5) sampling of the paint after will disperseing is loaded in the round stopper bottle, and the storage suspensoid of preparation places in 35 degrees centigrade of thermostatic drying chambers, observes the sedimentation result after 7 days and 15 days respectively, and then storage property is good more more slowly for sedimentation and layering.
The table 4 light lacquer as woodenware finish detected result of making mute
| The silicon-dioxide source | 60 ° of gloss numbers | The transparency | Smooth degree (N) | 7 days sedimentation results | 15 days sedimentation results |
| Embodiment 1 | 14 | Well | 1.50 | Transparent homogeneous | Transparent homogeneous |
| Embodiment 2 | 12 | Well | 1.45 | Transparent homogeneous | Transparent homogeneous |
| The comparative example | 14 | Generally | 1.55 | Transparent homogeneous | The beginning sedimentation |
| Syloid?ED30 | 18 | Generally | 1.50 | Transparent homogeneous | The beginning sedimentation |
| Acematt?OK412 | 12 | Well | 1.60 | The beginning sedimentation | Sedimentation is complete, layering |
Claims (23)
1. silicon-dioxide, wherein,
Pore volume 0.5-2.0cm
3/ g;
BET 100 is to less than 250m
2/ g;
DBP absorption value 250-280g/100g;
d
504-15 μ m; And
100 * ρ * pore volume/DBP absorption value >=0.55,
Wherein, DBP is a Witcizer 300; The DBP absorption value is the amount that silicon-dioxide absorbs DBP, and unit is a g/100g silicon-dioxide; ρ is the density of DBP, is 1.045g/cm
3Pore volume refers to the pore volume of silicon-dioxide, and unit is cm
3/ g silicon-dioxide;
But, do not comprise that pore volume is 1.8cm
3/ g and DBP absorption value are 2.0 or the silicon-dioxide of 2.5ml/g.
2. the silicon-dioxide of claim 1, wherein said pore volume is 1.0-2.0cm
3/ g.
3. the silicon-dioxide of claim 1, wherein said pore volume is 1.2-1.8cm
3/ g.
4. the silicon-dioxide of claim 1, wherein said BET are 200 to less than 250m
2/ g.
5. the silicon-dioxide of claim 1, wherein said d
50Be 5-12 μ m.
6. the silicon-dioxide of claim 1, wherein said d
50Be 6-10 μ m.
7. the silicon-dioxide of claim 1, the value of wherein said formula (100 * ρ * pore volume/DBP absorption value) is more than or equal to 0.63.
8. the silicon-dioxide of one of claim 1 to 7, further satisfy following formula:
0.16≤(pore volume+9.569 * 10
-3* DBP absorption value)/d
50≤2.68.
9. the silicon-dioxide of claim 8, satisfy:
0.29≤(pore volume+9.569 * 10
-3* DBP absorption value)/d
50≤0.82.
10. the preparation method of the silicon-dioxide of claim 1 comprises:
(a) in sodium silicate solution, add a kind of wax emulsion, add acid for adjusting pH value again to 8-11, it is 3-4 that pH is regulated in the back that reacts completely, and is heated to 50-70 ℃, re-adjustment pH to 8-11;
(b) with reaction mixture be warming up to 80-105 ℃ of aging 2-30h (hour);
(c) the aged mixture is added acid to pH value and be 2-4, ageing 0.2-3h;
(d) filter and with deionized water wash silicon-dioxide crude product;
(e) the dry and pulverizing with the silicon-dioxide that leaches.
11. the method for claim 10, wherein in step (a), said wax emulsion comprises that wax is dispersed in the emulsion that forms in the water.
12. the method for claim 10, wherein in step (a), said wax emulsion comprises that wax is dispersed in the water and adds the emulsion that emulsifying agent forms.
13. the method for claim 11, wherein said wax are polyethylene wax, OPE or Microcrystalline Wax.
14. the method for claim 13, wherein said wax are OPE.
Two or more the composite mixture that forms of emulsifying agent 15. the method for claim 12, wherein said emulsifying agent are served as reasons.
16. the method for claim 12, wherein said emulsifying agent are the mixture of AEO and polyoxyethylene nonylphenol.
17. the method for claim 16, wherein said AEO and polyoxyethylene nonylphenol are that 1: 1 ratio is composite with weight ratio.
18. the method for claim 10, wherein in step (a), the amount of wax emulsion satisfies sodium silicate solution mesosilicic acid sodium: wax=12-25: 1 weight ratio.
19. the method for claim 18, wherein said water glass: wax=14-20: 1 weight ratio.
20. the method for claim 10, the concentration of wherein said wax emulsion are 3-10 weight %.
21. the method for claim 20, the concentration of wherein said wax emulsion are 6-8 weight %.
22. lacquer, the silicon-dioxide that comprises claim 1 is as matting agent.
23. the silicon-dioxide of claim 1 is as the purposes of lacquer with matting agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100060143A CN101481115B (en) | 2009-01-22 | 2009-01-22 | Silicon dioxide, preparation and use thereof |
Applications Claiming Priority (1)
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|---|---|---|---|
| CN2009100060143A CN101481115B (en) | 2009-01-22 | 2009-01-22 | Silicon dioxide, preparation and use thereof |
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|---|---|
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| CN101481115B true CN101481115B (en) | 2012-07-04 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103436058A (en) * | 2013-08-22 | 2013-12-11 | 海安县亚太助剂有限公司 | Moisture-proof and antirust silica fine sand coating |
| CN106752275A (en) * | 2017-01-11 | 2017-05-31 | 冷水江三A新材料科技有限公司 | A kind of preparation method of elastic handfeel paint Coating Matting powder |
| 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 |
| WO2021201229A1 (en) * | 2020-04-02 | 2021-10-07 | 株式会社トクヤマ | Silica, paint and silica manufacturing method |
| CN111704141B (en) * | 2020-06-18 | 2022-10-14 | 福建省三明同晟化工有限公司 | Preparation method of liquid crystal resin filler microsphere silicon dioxide |
| CN114891391B (en) * | 2022-06-15 | 2023-01-03 | 广州市印道理印刷有限公司 | Ink with matte effect and preparation process thereof |
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|---|---|---|---|---|
| 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 |
| CN1585800A (en) * | 2001-11-13 | 2005-02-23 | 伊尼奥斯硅石有限公司 | Silica matting agents |
| CN101407324A (en) * | 2008-06-02 | 2009-04-15 | 通化双龙化工股份有限公司 | Method of preparing silicon dioxide delustrant by large pore volume gel |
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2009
- 2009-01-22 CN CN2009100060143A patent/CN101481115B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1585800A (en) * | 2001-11-13 | 2005-02-23 | 伊尼奥斯硅石有限公司 | Silica matting agents |
| 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 |
| CN101407324A (en) * | 2008-06-02 | 2009-04-15 | 通化双龙化工股份有限公司 | Method of preparing silicon dioxide delustrant by large pore volume gel |
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| 陈姚等.二氧化硅消光剂的制备及在家具漆中的应用.无机盐工业.2005,37(10),47-48. * |
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