CN104559336A - Modified silica sol and preparation method thereof - Google Patents
Modified silica sol and preparation method thereof Download PDFInfo
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- CN104559336A CN104559336A CN201410843288.9A CN201410843288A CN104559336A CN 104559336 A CN104559336 A CN 104559336A CN 201410843288 A CN201410843288 A CN 201410843288A CN 104559336 A CN104559336 A CN 104559336A
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Abstract
The invention provides a preparation method of modified silica sol. The preparation method comprises steps as follows: 1), a silane coupling agent is dropwise added to silica sol, the mixture is stirred and mixed to form a silane coupling agent/silica sol mixed system, and initial silane coupling agent modified silica sol is obtained after continuous stirring; 2), the initial silane coupling agent modified silica sol is subjected to acid-alkaline adjustment, and the silane coupling agent modified silica sol is prepared. The invention further provides an application of the modified silica sol in a water-based coating and a formula of the water-based coating added with the modified silica sol. The prepared modified silica sol can greatly improve the compatibility between inorganic material silicon dioxide and organic resin and improves the coating hardness simultaneously under the condition that the coating glossiness is not influenced after the coating is dry, the technology is simple and convenient, the controllability is high, and the modified silica sol has a higher practical value.
Description
Technical field
The invention belongs to the technical field of inorganic nano material, relate to a kind of modified silicasol and preparation method thereof, be specifically related to a kind of modified silicasol and preparation method thereof and the application in water-borne coatings.
Background technology
Coating is the indispensable important materials of modern society, has a wide range of applications in various fields such as industrial production, covil construction, house decoration and anticorrosion protection.But traditional solvent based coating causes considerable damage and harm to ecotope and human health, and cause the waste of resource and the energy.Along with environmental pollution comes into one's own and the raising of China's national life level day by day, the environment amenable water-borne coatings of people is placed high hopes, and environmental friendliness is the inexorable trend of China's coating industry development from now on.Therefore, develop high-performance water-based emulsion and more become the most important thing.
Water-borne coatings has good environmental friendliness, good film-forming property, weathering resistance advantages of higher, has been widely used in the fields such as building decoration, wood paint and metallic finishes.But hardness is low after its film forming, poor water resistance, thermostability are low, greatly reduces its work-ing life and limit its application in wider field.
Silicon sol is SiO
2the aqueous solution, be a kind of green material, be widely used, with low cost.It is a kind of inexpensive take water as the colloidal solution of the inorganic poly-metasilicic acid of nano level polymer of dispersion medium, be the thermodynamic unstable system carrying out aid dispersion by electric charge or some other stablizer, in recombination process, flocculation, caking or gel may be caused because envrionment conditions changes.Its particle is easily reunited and is difficult to disperse in the polymer, makes it utilize limited.
At present, Nano-meter SiO_2
2to join in coating as auxiliary agent, but due to himself performance deficiency, need to carry out modification thus improve many-sided performance of coating.Therefore, be necessary exploitation silicon sol is studied, development of new modified silicasol, for coating industrial production and application all extremely important.
Summary of the invention
The shortcoming of prior art in view of the above, the object of the present invention is to provide a kind of modified silicasol and preparation method thereof, for the problem of silicon sol and resin compatible difference, simple by condition, easy labour-saving method obtains modified silicasol, and it can be used as additive application in water-borne coatings, under the condition not affecting coating gloss, improve the hardness of coating simultaneously.
For achieving the above object and other relevant objects, the invention provides a kind of preparation method of modified silicasol, comprise the following steps:
1) silane coupling agent is added drop-wise in silicon sol is uniformly mixed, form silane coupling agent/silicon sol mixed system, after continuing to stir, obtain initial silane coupler modified silicon sol;
Preferably, step 1) in, described silicon sol is the colloid aqueous solution containing silica dioxide granule.
More preferably, the concentration (i.e. silica dioxide granule content) of described silicon sol is 6-40wt%.
Optimally, the concentration (i.e. silica dioxide granule content) of described silicon sol is 30wt%.
More preferably, the particle diameter of described silicon sol (i.e. silica dioxide granule) is 6-100nm.
Preferably, step 1) in, described silane coupling agent is the silicone compounds containing epoxide group.
More preferably, described silane coupling agent is 3-(2,3-epoxy third oxygen) propyl trimethoxy silicane.
Preferably, described silane coupling agent consumption accounts for the 1-10wt% of silica dioxide granule content in silicon sol.
More preferably, described silane coupling agent consumption accounts for the 3-5wt% of silica dioxide granule content in silicon sol.
Preferably, step 1) in, described reaction is at room temperature carried out.
Preferably, step 1) in, described in be uniformly mixed as Keep agitation mixing.
More preferably, the time of described Keep agitation mixing is 20-48 hour.Optimally, the time of described Keep agitation mixing is 24 hours.
Preferably, step 1) in, the drop rate of described silane coupling agent is 5-10ml/min.More preferably, the drop rate of described silane coupling agent is 7ml/min.
Preferably, step 1) in, the described time of continuing to stir is 20-48 hour.More preferably, the described time of continuing to stir is 24 hours.
2) by step 1) obtain initial silane coupler modified silicon sol, carry out acid-alkali accommodation, obtained silane coupler modified silicon sol.
Preferably, the pH value of described acid-alkali accommodation is 2-11.More preferably, described pH value is 8.5.
Preferably, the acid that described acid-alkali accommodation uses to be selected from glacial acetic acid, sulfuric acid any one.
The present invention further discloses a kind of modified silicasol, is prepared by preceding method.
The present invention further discloses the application of aforesaid modified silicasol in water-borne coatings.
The present invention finally also discloses a kind of water-borne coatings that with the addition of above-mentioned modified silicasol, by mass percentage, comprises following component:
Preferably, described a kind of water-borne coatings that with the addition of above-mentioned modified silicasol, by mass percentage, comprises following component:
Preferably, described water is deionized water.
Preferably, described resin is selected from the combination of any one or two kinds in styrene-acrylic resin, acrylic resin.
Preferably, described additive is the conventional additives in water-borne coatings.Described additive comprises sanitas, thickening material, dispersion agent, defoamer, wetting agent etc.
As mentioned above, a kind of modified silicasol of the present invention and preparation method thereof, prepare a kind of modified silicasol, by silica particles attachment band oxygen groups, by chemical bonding, electrostatic interaction or adsorbent laminate medium, microparticle surfaces is modified, greatly improve the consistency between inorganic materials silicon-dioxide and organic resin.Modified silicasol prepared by the preparation method of modified silicasol in the present invention had good appearance transparence and stability, be applied in water-borne coatings, as additive, after not affecting coating drying coating gloss condition under, improve the hardness of coating simultaneously, namely the time of drying of coating is longer, and the crosslinking degree between silicon-dioxide is higher, and the hardness of coating also improves thereupon.
The modified silicasol prepared in the present invention, there is the advantages such as simple process, controllability be strong, its development & application is that the development of coating is filled with new vitality, coating property can be made to be significantly improved, in paint field, there is high value of practical, the needs of development of modern industry can be met, and very important prograding is also played to the development of coating, demonstrate broad prospect of application.
Embodiment
Set forth the present invention further below in conjunction with specific embodiment, should be understood that these embodiments are only not used in for illustration of the present invention and limit the scope of the invention.
Below by way of specific specific examples, embodiments of the present invention are described, those skilled in the art can the content disclosed by this specification sheets understand of the present invention easily
Other advantages and effect.The present invention can also be implemented or be applied by embodiments different in addition, and the every details in this specification sheets also can based on different viewpoints and application, carries out various modification or change not deviating under spirit of the present invention.
The reagent used in following examples and instrument, all can commercially obtain.
Embodiment 1
The silicon sol (silica dioxide granule content is 30wt%, and particle diameter is 15nm) of 1kg to be joined in there-necked flask and to stir; In room temperature and under Keep agitation condition, 3-(2, the 3-epoxy third oxygen) propyl trimethoxy silicane (accounting for silica dioxide granule content is 1wt%) getting 3g is added drop-wise in silicon sol, and rate of addition is 7ml/min.Continue to be stirred to 24h, obtain initial modified silicasol.Glacial acetic acid is selected to regulate the pH value to 8.5 of initial modified silicasol, the required modified silicasol 1 of final acquisition.
Embodiment 2
The silicon sol (silica dioxide granule content is 30wt%, and particle diameter is 15nm) of 1kg to be joined in there-necked flask and to stir; In room temperature and under Keep agitation condition, 3-(2, the 3-epoxy third oxygen) propyl trimethoxy silicane (accounting for silica dioxide granule content is 3wt%) getting 9g is added drop-wise in silicon sol, and rate of addition is 7ml/min.Continue to be stirred to 24h, obtain initial modified silicasol.Sulfuric acid is selected to regulate the pH value to 8.5 of initial modified silicasol, the required modified silicasol 2 of final acquisition.
Embodiment 3
The silicon sol (silica dioxide granule content is 30wt%, and particle diameter is 15nm) of 1kg to be joined in there-necked flask and to stir; In room temperature and under Keep agitation condition, 3-(2, the 3-epoxy third oxygen) propyl trimethoxy silicane (accounting for silica dioxide granule content is 5wt%) getting 15g is added drop-wise in silicon sol, and rate of addition is 7ml/min.Continue to be stirred to 24h, obtain initial modified silicasol.Glacial acetic acid is selected to regulate the pH value to 8.5 of initial modified silicasol, the required modified silicasol 3 of final acquisition.
Application examples 1
Do not add silicon sol described in the present invention containing styrene-acrylic resin content be 27% water-borne coatings be water-borne coatings 1.
Application examples 2
Joining containing styrene-acrylic resin content by the initial silicon colloidal sol of non-modified is in the aqueous coating formulation of 27%, and wherein mass percent shared by modified silicasol is 30%, makes each composition mix under high-speed stirring condition, final obtained water-borne coatings 2.
Application examples 3
Being joined by modified silicasol 1 containing styrene-acrylic resin content is in the aqueous coating formulation of 27%, and wherein mass percent shared by modified silicasol is 30%, makes each composition mix under high-speed stirring condition, final obtained water-borne coatings 3.
Application examples 4
Being joined by modified silicasol 2 containing styrene-acrylic resin content is in the aqueous coating formulation of 27%, and wherein mass percent shared by modified silicasol is 30%, makes each composition mix under high-speed stirring condition, final obtained water-borne coatings 4.
Application examples 5
Being joined by modified silicasol 3 containing styrene-acrylic resin content is in the aqueous coating formulation of 27%, and wherein mass percent shared by modified silicasol is 30%, makes each composition mix under high-speed stirring condition, final obtained water-borne coatings 5.
Application examples 6
Being joined by modified silicasol 3 containing acrylic resin content is in the aqueous coating formulation of 34%, and wherein mass percent shared by modified silicasol is 10%, makes each composition mix under high-speed stirring condition, final obtained water-borne coatings 6.
Test case 1
Water-borne coatings 1-6 in application examples 1-6 is brushed at clean sheet glass and wood material, carries out seasoning at ambient temperature 1 day.The performance recording film is as shown in table 1.
Table 1
| Sample | Water-borne coatings 1 | Water-borne coatings 2 | Water-borne coatings 3 | Water-borne coatings 4 | Water-borne coatings 5 | Water-borne coatings 6 |
| Hardness | 51 | 72 | 75 | 70 | 56 | 53 |
| Glossiness | 84.1 | 49.8 | 52 | 30.7 | 76.2 | 79.1 |
, water-borne coatings 1-6 in application examples 1-6 is brushed at clean sheet glass and wood material meanwhile, carry out seasoning at ambient temperature 15 days.The performance recording film is as shown in table 2.
Table 2
| Sample | Water-borne coatings 1 | Water-borne coatings 2 | Water-borne coatings 3 | Water-borne coatings 4 | Water-borne coatings 5 | Water-borne coatings 6 |
| Hardness | 93 | 109 | 108 | 106 | 106 | 99 |
| Glossiness | 79.4 | 46.7 | 49.2 | 25.7 | 71.3 | 76.2 |
From data in table 1,2, on the one hand, compared with the water-borne coatings 1 not adding silicon sol, add modified silicasol water-borne coatings 3-5 dried coating film after coating hardness all raising to a certain extent.The glossiness of film increases gradually, to water-borne coatings 5 closer to coating 1, illustrates that the water-borne coatings glossiness being added with the larger modified silicasol of modification amount is higher; On the other hand, time of drying longer (by 1 day to 15 days), the hardness of water-borne coatings 3-5 is greatly improved.
In sum, a kind of modified silicasol provided by the invention and preparation method thereof, prepare a kind of modified silicasol, greatly can improve the consistency between inorganic materials silicon-dioxide and organic resin, after not affecting coating drying coating gloss condition under, improve the hardness of coating, and simple process, controllability are strong, have high value of practical simultaneously.So the present invention effectively overcomes various shortcoming of the prior art and tool high industrial utilization.
Above-described embodiment is illustrative principle of the present invention and effect thereof only, but not for limiting the present invention.Any person skilled in the art scholar all without prejudice under spirit of the present invention and category, can modify above-described embodiment or changes.Therefore, such as have in art usually know the knowledgeable do not depart from complete under disclosed spirit and technological thought all equivalence modify or change, must be contained by claim of the present invention.
Claims (10)
1. a preparation method for modified silicasol, comprises the following steps:
1) silane coupling agent is added drop-wise in silicon sol is uniformly mixed, form silane coupling agent/silicon sol mixed system, after continuing to stir, obtain initial silane coupler modified silicon sol;
2) by step 1) obtain initial silane coupler modified silicon sol, carry out acid-alkali accommodation, obtained silane coupler modified silicon sol.
2. the preparation method of a kind of modified silicasol according to claim 1, is characterized in that, step 1) in, described silicon sol is the colloid aqueous solution containing silica dioxide granule; The concentration of described silicon sol is 6-40wt%.
3. the preparation method of a kind of modified silicasol according to claim 1, is characterized in that, step 1) in, described silane coupling agent is the silicone compounds containing epoxide group; Described silane coupling agent consumption accounts for the 1-10wt% of silica dioxide granule content in silicon sol.
4. the preparation method of a kind of modified silicasol according to claim 1, is characterized in that, described step 1) in also to comprise any one of following condition or multinomial:
A) described reaction is at room temperature carried out;
B) be uniformly mixed as Keep agitation mixing described in, the time of described Keep agitation mixing is 20-48 hour;
C) drop rate of described silane coupling agent is 5-10ml/min;
D) the described time of continuing to stir is 20-48 hour.
5. the preparation method of a kind of modified silicasol according to claim 1, is characterized in that, step 2) in, the pH value of described acid-alkali accommodation is 2-11.
6. the preparation method of a kind of modified silicasol according to claim 1, is characterized in that, step 2) in, the acid that described acid-alkali accommodation uses to be selected from glacial acetic acid, sulfuric acid any one.
7. a modified silicasol, is obtained by preparation method described in claim arbitrary in claim 1-6.
8. the application of a kind of modified silicasol in water-borne coatings according to claim arbitrary in claim 1-6.
9. a water-borne coatings, by mass percentage, comprises following component:
10. a kind of water-borne coatings according to claim 9, is characterized in that, described resin is selected from the combination of any one or two kinds in styrene-acrylic resin, acrylic resin.
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Cited By (16)
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| CN105176179A (en) * | 2015-08-31 | 2015-12-23 | 福州富兰机电技术开发有限公司 | Modified silica sol, and preparation method and application thereof |
| CN105670350A (en) * | 2016-02-17 | 2016-06-15 | 上海新安纳电子科技有限公司 | Film forming silica sol and preparation method and application thereof |
| CN106854355A (en) * | 2016-12-30 | 2017-06-16 | 深圳大学 | Waterborne, polycarbonate modified silicasol emulsion and preparation method thereof |
| CN108929657A (en) * | 2018-08-20 | 2018-12-04 | 加翎加（天津）环境科技有限公司 | A kind of miberal powder dust suppressant and preparation method thereof |
| CN110282633A (en) * | 2019-04-29 | 2019-09-27 | 江苏辉迈粉体科技有限公司 | A kind of method of modifying of nano oxidized silicon materials |
| CN110364340A (en) * | 2019-07-31 | 2019-10-22 | 横店集团东磁股份有限公司 | A kind of antifreeze plate and its preparation method and application |
| CN111017935A (en) * | 2019-12-18 | 2020-04-17 | 上海新安纳电子科技有限公司 | Preparation method of silica sol and application of silica sol in ceramic coating |
| CN111171374A (en) * | 2020-01-22 | 2020-05-19 | 黎明化工研究设计院有限责任公司 | Modified silica sol, preparation method thereof and application of modified silica sol in all-water-based foaming polyurethane spraying foam |
| CN111440500A (en) * | 2020-05-09 | 2020-07-24 | 山东百特新材料有限公司 | Chain-like silica sol modified water-borne wood paint and preparation method thereof |
| CN111844090A (en) * | 2020-07-10 | 2020-10-30 | 重庆工程职业技术学院 | Aluminum alloy mechanical gripper and processing method thereof |
| CN112320807A (en) * | 2020-11-26 | 2021-02-05 | 上海新安纳电子科技有限公司 | Modified silica sol, fireproof liquid, composite fireproof glass and preparation method and application thereof |
| CN112680000A (en) * | 2020-12-29 | 2021-04-20 | 济南百士多高分子化工技术有限公司 | Preparation method of organic silicon monomer modified nano inorganic silicon resin |
| CN113480914A (en) * | 2021-07-06 | 2021-10-08 | 浙江大学杭州国际科创中心 | Organic-inorganic hybrid three-proofing coating and preparation method thereof |
| CN113800953A (en) * | 2021-08-30 | 2021-12-17 | 湖北三江航天江北机械工程有限公司 | Method for repairing pit on surface of window of quartz composite ceramic antenna |
| CN113880096A (en) * | 2021-10-18 | 2022-01-04 | 湖北三江航天江北机械工程有限公司 | High solid content silica sol, preparation method and application thereof |
| CN114012029A (en) * | 2021-12-13 | 2022-02-08 | 山东金亿达新材料有限公司 | Amino resin modified silica sol and preparation method thereof |
-
2014
- 2014-12-29 CN CN201410843288.9A patent/CN104559336A/en active Pending
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| CN105176179A (en) * | 2015-08-31 | 2015-12-23 | 福州富兰机电技术开发有限公司 | Modified silica sol, and preparation method and application thereof |
| CN105670350A (en) * | 2016-02-17 | 2016-06-15 | 上海新安纳电子科技有限公司 | Film forming silica sol and preparation method and application thereof |
| WO2017140100A1 (en) * | 2016-02-17 | 2017-08-24 | 上海新安纳电子科技有限公司 | Film-forming silica sol, preparation method therefor and application thereof |
| US10604662B2 (en) | 2016-02-17 | 2020-03-31 | Shanghai Xinanna Electronic Technology Co., Ltd. | Film-forming silica sol, method of preparing the same, and application of the same |
| CN106854355A (en) * | 2016-12-30 | 2017-06-16 | 深圳大学 | Waterborne, polycarbonate modified silicasol emulsion and preparation method thereof |
| CN106854355B (en) * | 2016-12-30 | 2018-11-27 | 深圳大学 | Waterborne, polycarbonate modified silicasol lotion and preparation method thereof |
| CN108929657A (en) * | 2018-08-20 | 2018-12-04 | 加翎加（天津）环境科技有限公司 | A kind of miberal powder dust suppressant and preparation method thereof |
| CN110282633A (en) * | 2019-04-29 | 2019-09-27 | 江苏辉迈粉体科技有限公司 | A kind of method of modifying of nano oxidized silicon materials |
| CN110364340A (en) * | 2019-07-31 | 2019-10-22 | 横店集团东磁股份有限公司 | A kind of antifreeze plate and its preparation method and application |
| CN111017935A (en) * | 2019-12-18 | 2020-04-17 | 上海新安纳电子科技有限公司 | Preparation method of silica sol and application of silica sol in ceramic coating |
| CN111171374A (en) * | 2020-01-22 | 2020-05-19 | 黎明化工研究设计院有限责任公司 | Modified silica sol, preparation method thereof and application of modified silica sol in all-water-based foaming polyurethane spraying foam |
| CN111171374B (en) * | 2020-01-22 | 2022-05-24 | 黎明化工研究设计院有限责任公司 | Modified silica sol, preparation method thereof and application of modified silica sol in all-water-based foaming polyurethane spraying foam |
| CN111440500A (en) * | 2020-05-09 | 2020-07-24 | 山东百特新材料有限公司 | Chain-like silica sol modified water-borne wood paint and preparation method thereof |
| CN111844090A (en) * | 2020-07-10 | 2020-10-30 | 重庆工程职业技术学院 | Aluminum alloy mechanical gripper and processing method thereof |
| CN112320807A (en) * | 2020-11-26 | 2021-02-05 | 上海新安纳电子科技有限公司 | Modified silica sol, fireproof liquid, composite fireproof glass and preparation method and application thereof |
| CN112680000A (en) * | 2020-12-29 | 2021-04-20 | 济南百士多高分子化工技术有限公司 | Preparation method of organic silicon monomer modified nano inorganic silicon resin |
| CN113480914A (en) * | 2021-07-06 | 2021-10-08 | 浙江大学杭州国际科创中心 | Organic-inorganic hybrid three-proofing coating and preparation method thereof |
| CN113800953A (en) * | 2021-08-30 | 2021-12-17 | 湖北三江航天江北机械工程有限公司 | Method for repairing pit on surface of window of quartz composite ceramic antenna |
| CN113880096A (en) * | 2021-10-18 | 2022-01-04 | 湖北三江航天江北机械工程有限公司 | High solid content silica sol, preparation method and application thereof |
| CN114012029A (en) * | 2021-12-13 | 2022-02-08 | 山东金亿达新材料有限公司 | Amino resin modified silica sol and preparation method thereof |
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