CN1631996A - Method for preparing silicon oxide/titanium dioxide composite oxide ultraviolet screening agent - Google Patents
Method for preparing silicon oxide/titanium dioxide composite oxide ultraviolet screening agent Download PDFInfo
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- CN1631996A CN1631996A CN 200410064594 CN200410064594A CN1631996A CN 1631996 A CN1631996 A CN 1631996A CN 200410064594 CN200410064594 CN 200410064594 CN 200410064594 A CN200410064594 A CN 200410064594A CN 1631996 A CN1631996 A CN 1631996A
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Abstract
A method for preparing SiO2/TiO2 compound dioxide ultraviolet shielding agent,uses butyl titanate or titanium tetrachloride as titanium source, sodium silicate or tetra ethyl ortho silicate as silicon source, by water heating method to prepare Fe ion modified SiO2/TiO2 compound dioxide ultraviolet shielding agent. The invention makes the TiO2 with diameter smaller than 20nm,outstanding dispersibility,ultraviolet ray absorportive performance and weather resistance,as well avoids blueing in the application of TiO2
Description
Affiliated field
The invention belongs to the synthetic method of inorganic nano material, the hydrothermal method that relates to a kind of silicon oxide/nano titania composite oxide ultraviolet screener of iron ion modification is specifically synthesized.
Background technology
SiO
2/ TiO
2The combined oxidation objects system is considered to have good dispersing property and thermostability.It has excellent ultravioletlight screening simultaneously, can shield long wave (380-320nm), medium wave (320-290nm) and shortwave (290-220nm) ultraviolet ray, and having erosion resistance, high chemical stability, nontoxic, the ultravioletlight screening agent that can be used as a kind of excellence is widely used in fields such as high-quality coating, rubber, fiber, paint, sun-proof skin care articles for use, printing ink, food product pack.
As a kind of ultravioletlight screening agent of excellence, SiO
2/ TiO
2The combined oxidation objects system must have outstanding dispersing property, disperses badly in base-material, and its ultraviolet screener performance is not in full use, and it also is very necessary therefore improving its dispersiveness.Important in addition one side is SiO
2/ TiO
2The combined oxidation objects system has strong photoxidation ability simultaneously can degradation of organic substances, therefore when being used for coating, makeup, to organic constituents generation photodegradation.Therefore to must reduce its photocatalytic activity as ultraviolet screening agent.In addition, titanium dioxide can occur faint blue color as ultraviolet screening agent in medium, and when being applied to makeup especially, this blueing phenomenon makes skin show unsound little blueness, therefore must be improved.
But present this composite oxides adopt sol-gel and coprecipitation method preparation usually, need through adopting the high temperature process of the unformed titania gel of calcining down.In this process, be accompanied by the conversion of hard aggregation, particle increase and crystal formation usually.And generally adopt the way of inorganic oxide coating to improve its dispersing property at present, and reducing its photocatalytic activity, the hydrate coating of JP-A 2-204326 report silicon, aluminium, iron can reduce its photocatalysis performance on the surface of titanium dioxide granule.US5,837,050 adopt on the titanium dioxide granule surface and coat the molten iron compound, the way of coating aluminium hydrate then, avoid titanium dioxide in using the blueing phenomenon, reduce its photocatalysis performance simultaneously.But step is loaded down with trivial details, and the process cycle is long, and because the particle diameter of titanium dioxide is little, is difficult to avoid a plurality of particle coatings situation together.
Summary of the invention
The method that the purpose of this invention is to provide a kind of preparation process simple oxidation silicon/titania composite oxide ultraviolet screening agent, and the screener of preparation has good dispersing property and photochemical catalysis inertia, and can avoid titanium dioxide in using the blueing phenomenon.
The present invention is the titanium source with tetrabutyl titanate or titanium tetrachloride, is the silicon source with water glass or tetraethoxy, adopts hydrothermal method directly to prepare Fe ion modification SiO
2/ TiO
2The composite oxide ultraviolet screener.
Preparation method's concrete steps of the present invention are as follows:
(1) aqueous nitric acid of preparation 0.5-3.0mol/L adds iron nitrate then, dissolving;
(2) adding the silicon source under 30-60 ℃ then in the solution in (1) step, the mole add-on in silicon source is the silicon source: nitric acid is 1: 0.5-4.0, stir until complete hydrolysis, and get solution A;
(3) under agitation, the titanium source is dropwise added in the solution A in 5-30 minute, wherein the add-on in titanium source is the titanium source: silicon source mol ratio is 1: 0.25-4.0, continue to stir 5-30 minute, solution B;
(4) solution B is transferred in the teflon-lined water heating kettle, 120-200 ℃ following hydro-thermal reaction 6-20 hour;
(5) with the product after hydro-thermal reaction oven dry, grind, at 300-600 ℃ of following roasting 1-3 hour, i.e. Fe ion modification silicon oxide/titania nanoparticles;
Wherein the add-on of iron nitrate is the 1-15% that adds the quality summation in titanium source and silicon source,
The quality that iron nitrate adds is calculated with Fe, and the quality that the silicon source adds is with SiO
2Calculate, the quality that the titanium source adds is with TiO
2Calculate.
Aforesaid silicon source is tetraethoxy or water glass.
Aforesaid titanium source is tetrabutyl titanate or titanium tetrachloride.
Aforesaid silicon source: titanium source mol ratio is preferably 1: 1.
The present invention compared with prior art has following advantage:
1, the present invention directly prepares Fe ion modification SiO
2/ TiO
2Composite oxides, method is simple, and flow process is short.
2, the SiO of the present invention's preparation
2/ TiO
2The composite oxide particle diameter evenly, shows excellent thermal stability less than 20nm single the dispersion, the excellent light stability energy, and good UV absorbing properties and weather resisteant energy, and also the blueing phenomenon in the titanium dioxide application has been eliminated in the introducing of iron ion.Can be used as excellent ultravioletlight screening agent, be used for fields such as coating, rubber, fiber, paint, sun-proof skin care articles for use, printing ink, food product pack.
Embodiment
Embodiment 1
The 1000ml concentrated nitric acid adds in the water of 4500m1, adds Fe (NO then
3)
39H
2O70.7g, stirring and dissolving.At 50 ℃ of tetraethoxys that add 1120ml down, magnetic agitation forms solution A until complete hydrolysis then.Under vigorous stirring, the 1700ml tetrabutyl titanate is dropwise added in the above-mentioned solution A in 20 minutes.Tetrabutyl titanate adds the back and stirred 15 minutes, forms solution B.Then solution B is added in the teflon-lined water heating kettle 140 ℃ of following hydro-thermal reactions 10 hours.Product grinds 110 ℃ of oven dry down, promptly gets Fe ion modification SiO
2/ TiO
2The composite oxides nano particle.If this sample is applied in the makeup, continues 400 ℃ of 1.5h of roasting and remove wherein organism remnants.
It is 10nm that electron microscope is observed particle diameter down, the particle ball-type, evenly, good dispersity.The XRD measuring result shows that titanium dioxide is anatase titanium dioxide.Photocatalytic activity reduces greatly with respect to the sample that does not add iron ion, has reasonable photochemical catalysis inertia.Roasting to 1000 ℃, the sample crystal formation is constant, and grain diameter is lower than 20nm, does not still have hard aggregation to take place, and keeps good dispersion.
Embodiment 2
Adopt the preparation process of the foregoing description 1, difference is, adds Fe (NO then
3)
39H
2O40.4g.It is 8nm particle ball-type that electron microscope is observed this kind nanometer anatase titanium dioxide particle diameter down, evenly, and good dispersity.The XRD measuring result shows that titanium dioxide is anatase titanium dioxide.Photocatalytic activity reduces greatly with respect to the sample that does not add iron ion, has reasonable photochemical catalysis inertia.After the roasting to 1000 ℃, sample is an anatase titanium dioxide still, and particle is good distribution still, for 15nm even, ball-type.
Embodiment 3
The 1000ml concentrated nitric acid adds in the water of 3500ml, adds Fe (NO then
3)
39H
2O40.4g, stirring and dissolving.Under 30 ℃, add the tetraethoxy of 560ml then.Stirring forms solution A until complete hydrolysis.Under vigorous stirring, the 1700ml tetrabutyl titanate is dropwise added in the above-mentioned solution A in 30 minutes.Tetrabutyl titanate adds the back and stirs 15 minutes formation solution B.Then solution B is added in the teflon-lined water heating kettle 200 ℃ of following hydro-thermal reactions 15 hours.Product grinds 120 ℃ of oven dry down.Promptly get Fe ion modification SiO
2/ TiO
2The composite oxides nano particle.
It is 11nm that electron microscope is observed particle diameter down, the particle ball-type, evenly, good dispersity.The XRD measuring result shows that titanium dioxide is anatase titanium dioxide.
Embodiment 4
The 2000ml concentrated nitric acid adds in the water of 4500ml, adds Fe (NO then
3)
39H
2O150g, stirring and dissolving.Under 45 ℃, add the 100g water glass then, stir, form solution A until complete hydrolysis.Under vigorous stirring, the 1700ml tetrabutyl titanate is dropwise added in the above-mentioned solution A in 15 minutes.Tetrabutyl titanate adds the back and stirs 15 minutes formation solution B.Solution B adds in the teflon-lined water heating kettle then, 150 ℃ of following hydro-thermal reactions 10 hours.Product grinds 110 ℃ of oven dry down, and final sample is respectively 400 ℃ of following roastings 2 hours.Promptly get Fe ion modification SiO
2/ TiO
2The composite oxides nano particle.
It is 8nm that electron microscope is observed particle diameter down, the particle ball-type, evenly, good dispersity.The XRD measuring result shows that titanium dioxide is anatase titanium dioxide.Photocatalytic activity reduces greatly with respect to the sample that does not add iron ion, has reasonable photochemical catalysis inertia.Roasting to 1000 ℃, the sample crystal formation is constant, and grain diameter is lower than 20nm, does not still have hard aggregation to take place, and keeps good dispersion.If this sample is applied in the makeup, continues 400 ℃ of 2h of roasting and remove wherein organism remnants.
Embodiment 5
The 1000ml concentrated nitric acid adds in the water of 4500ml, adds Fe (NO then
3)
39H
2O70.7g, stirring and dissolving.The tetraethoxy that adds 1120ml then, under 45 ℃, magnetic agitation forms solution A A until complete hydrolysis.Under vigorous stirring, the 1500ml titanium tetrachloride is dropwise added in the above-mentioned solution A in 20 minutes.Tetrabutyl titanate adds the back and stirs 15 minutes formation solution B.Then solution B is added in the teflon-lined water heating kettle 120 ℃ of following hydro-thermal reactions 10 hours.Product grinds 110 ℃ of oven dry down, promptly gets Fe ion modification SiO
2/ TiO
2The composite oxides nano particle.If this sample is applied in the makeup, 500 ℃ of 1h of continuation roasting remove wherein organism remnants.
Claims (4)
1, the preparation method of a kind of silicon oxide/titania composite oxide ultraviolet screening agent is characterized in that comprising the steps:
(1) aqueous nitric acid of preparation 0.5-3.0mol/L adds iron nitrate then, dissolving;
(2) adding the silicon source under 30-60 ℃ then in the solution in (1) step, the mole add-on in silicon source is the silicon source: nitric acid is 1: 0.5-4.0, stir until complete hydrolysis, and get solution A;
(3) under agitation, the titanium source is dropwise added in the solution A in 5-30 minute, wherein the add-on in titanium source is the titanium source: silicon source mol ratio is 1: 0.25-4.0, continue to stir 5-30 minute, solution B;
(4) solution B is transferred in the teflon-lined water heating kettle, 120-200 ℃ following hydro-thermal reaction 6-20 hour;
(5) with the product after hydro-thermal reaction oven dry, grind, at 300-600 ℃ of following roasting 1-3 hour, i.e. Fe ion modification silicon oxide/titania nanoparticles;
Wherein the add-on of iron nitrate is the 1-15% that adds the quality summation in titanium source and silicon source
The quality that iron nitrate adds is calculated with Fe, and the quality that the silicon source adds is with SiO
2Calculate, the quality that the titanium source adds is with TiO
2Calculate.
2, the preparation method of a kind of silicon oxide as claimed in claim 1/titania composite oxide ultraviolet screening agent is characterized in that described silicon source is tetraethoxy or water glass.
3, the preparation method of a kind of silicon oxide as claimed in claim 1/titania composite oxide ultraviolet screening agent is characterized in that described titanium source is tetrabutyl titanate or titanium tetrachloride.
4, the preparation method of a kind of silicon oxide as claimed in claim 1/titania composite oxide ultraviolet screening agent, it is characterized in that the silicon source: titanium source mol ratio is 1: 1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410064594 CN1288213C (en) | 2004-12-07 | 2004-12-07 | Method for preparing silicon oxide/titanium dioxide composite oxide ultraviolet screening agent |
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|---|---|---|---|
| CN 200410064594 CN1288213C (en) | 2004-12-07 | 2004-12-07 | Method for preparing silicon oxide/titanium dioxide composite oxide ultraviolet screening agent |
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|---|---|
| CN1631996A true CN1631996A (en) | 2005-06-29 |
| CN1288213C CN1288213C (en) | 2006-12-06 |
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|---|---|---|---|
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101549285B (en) * | 2009-05-13 | 2011-02-02 | 西安理工大学 | A method for preparing nano TiO2*/SiO2* photocatalytic material |
| CN102154829A (en) * | 2010-12-20 | 2011-08-17 | 北京服装学院 | Fuzzing, pilling and ultraviolet-prevention finishing agent and preparation method and application |
| CN102205418A (en) * | 2010-03-31 | 2011-10-05 | 中国科学院化学研究所 | Method for preparing nanometer particle with iron-doped nanometer titanium dioxide/silicon dioxide nuclear shell structure |
| CN102039117B (en) * | 2009-10-15 | 2012-08-08 | 中国矿业大学(北京) | Method for preparing loaded nano TiO2 composite material by using precipitated white carbon black as carrier |
| CN101146872B (en) * | 2005-03-23 | 2012-08-29 | 帝斯曼知识产权资产管理有限公司 | Chromophore coated metal oxide particles |
| CN105238071A (en) * | 2015-10-30 | 2016-01-13 | 宣城硅鑫新材料有限公司 | Preparation method for titanium-containing organic silicon resin for cosmetics |
| CN108707389A (en) * | 2018-05-21 | 2018-10-26 | 无锡尊丰新材料科技有限公司 | A kind of environment-friendly type waterproof and oilproof joint trimming agent |
| CN109235023A (en) * | 2018-08-31 | 2019-01-18 | 黄勇 | A kind of preparation method of high-affinity Anti-ultraviolet true silk textile finishing agent material |
-
2004
- 2004-12-07 CN CN 200410064594 patent/CN1288213C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101146872B (en) * | 2005-03-23 | 2012-08-29 | 帝斯曼知识产权资产管理有限公司 | Chromophore coated metal oxide particles |
| CN101549285B (en) * | 2009-05-13 | 2011-02-02 | 西安理工大学 | A method for preparing nano TiO2*/SiO2* photocatalytic material |
| CN102039117B (en) * | 2009-10-15 | 2012-08-08 | 中国矿业大学(北京) | Method for preparing loaded nano TiO2 composite material by using precipitated white carbon black as carrier |
| CN102205418A (en) * | 2010-03-31 | 2011-10-05 | 中国科学院化学研究所 | Method for preparing nanometer particle with iron-doped nanometer titanium dioxide/silicon dioxide nuclear shell structure |
| CN102205418B (en) * | 2010-03-31 | 2012-11-14 | 中国科学院化学研究所 | Method for preparing nanometer particle with iron-doped nanometer titanium dioxide/silicon dioxide nuclear shell structure |
| CN102154829A (en) * | 2010-12-20 | 2011-08-17 | 北京服装学院 | Fuzzing, pilling and ultraviolet-prevention finishing agent and preparation method and application |
| CN102154829B (en) * | 2010-12-20 | 2012-11-07 | 北京服装学院 | Fuzzing, pilling and ultraviolet-prevention finishing agent and preparation method and application |
| CN105238071A (en) * | 2015-10-30 | 2016-01-13 | 宣城硅鑫新材料有限公司 | Preparation method for titanium-containing organic silicon resin for cosmetics |
| CN108707389A (en) * | 2018-05-21 | 2018-10-26 | 无锡尊丰新材料科技有限公司 | A kind of environment-friendly type waterproof and oilproof joint trimming agent |
| CN109235023A (en) * | 2018-08-31 | 2019-01-18 | 黄勇 | A kind of preparation method of high-affinity Anti-ultraviolet true silk textile finishing agent material |
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| Publication number | Publication date |
|---|---|
| CN1288213C (en) | 2006-12-06 |
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Granted publication date: 20061206 Termination date: 20121207 |