CN102311561A - Modified titanium dioxide grain, super-hydrophilic transparent thin film and preparation method thereof - Google Patents
Modified titanium dioxide grain, super-hydrophilic transparent thin film and preparation method thereof Download PDFInfo
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- CN102311561A CN102311561A CN 201110106275 CN201110106275A CN102311561A CN 102311561 A CN102311561 A CN 102311561A CN 201110106275 CN201110106275 CN 201110106275 CN 201110106275 A CN201110106275 A CN 201110106275A CN 102311561 A CN102311561 A CN 102311561A
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Abstract
The invention discloses modified titanium dioxide grain, a super-hydrophilic transparent thin film and a preparation method thereof. In the invention, a ball mill is used as a modification tool; chloroacetic anhydride is used as a modifier, is added into the titanium dioxide grain through a mechanical and chemical method and is bonded with a hydroxyl group on the surface of the titanium dioxide grain with a chemical bond through mechanical stirring, vibration and collision of ball milling of the ball mill; then the prepared grain is reacted with water in a high-energy ball mill so as to prepare the hydroxyl group-modified titanium dioxide grain; finally, the grain is added into polymer in a ball milling mode to prepare suspension; the suspension is coated on a glass slide and then thermal curing is performed to obtain the super-hydrophilic transparent thin film. The super-hydrophilic transparent thin film prepared by the invention has the advantages of superior wear resistance and heat resistance, high mechanical strength, high impact resistance capacity, optical performance, anti-ultraviolet capacity and convenience in cleaning.
Description
Technical field
The present invention relates to a kind of sym-dichloroacetic anhydride modifying titanium dioxide particulate preparation method that utilizes, refer more particularly to the method for preparing a kind of nano hybridization coating (ultra-hydrophilic transparent film) of easy cleaning with the modifying titanium dioxide particle.
Background technology
Nano titanium oxide has great volume effect, surface effects, optical characteristics, colour effect; So demonstrate very superior characteristic in fields such as light, electricity, catalysis and material fillings; Nano titanium oxide these characteristics at the interface make titanium dioxide granule that the potential application prospect arranged in a lot of fields; For example photocatalytic hydrogen production by water decomposition gas, WWT, organism decompose, preparation is super-hydrophobic and have (the Marco Minella such as coating, polymer materials reinforcement and antiultraviolet coating of self-cleaning ability; Maria Giulia Faga, et al, Effect of Fluorination on the Surface Properties of Titania P25 Powder:An FTIR Study [J]; 2010,26 (4): 2521～2527).
Titanium oxide used as the filler of coating or polymer materials not only can make the indexs such as tensile strength, shock strength, hardness, thermal property and optical property of the finished product be greatly enhanced; Can also give product antiultraviolet and self-cleaning ability (Akira Nakajima; Kazuhito Hashimoto; Et al; Transparent Superhydrophobic Thin Films with Self-Cleaning Properties [J], 2000,16 (4): 7044～7047).Yet up to now, the filler that titanium oxide mainly is used to hydrophobic material uses, and has but ignored its use in the middle of hydrophilic substrate (like epoxy resin).Titanium oxide is a kind of hydrophilic granules of surperficial hydroxyl, but the simple hydrophilic ability that relies on hydroxyl to provide is very limited.A large amount of facts show, unmodified titanium dioxide granule is added in the hydrophilic polymeric matrix, are difficult to realize that homodisperse finally can cause the defective of institute's prepared material.Therefore, improve the addition of titanium oxide in the middle of hydrophilic substrate, suitable hydrophilic modifying is made on its surface, be necessary thereby improve the addition of PM for particulate matter in the middle of polymkeric substance.Research work for the hydrophilic raising of titanium oxide never was interrupted; Research is illustrated in the water-dispersion ability that titanium dioxide surface parcel one deck inorganics (zirconium white, aluminum oxide etc.) can improve titanium oxide greatly; This be since zirconium white, aluminum oxide than titanium oxide (Yunsheng Zhang; Hengbo Yin, et al, Evolution of zirconia coating layer on rutile TiO
2Surface and the pigmentary property [J], 2010,71 (2010): 1458～1466), have higher hydroxy density, therefore can improve the particulate hydrophilicity, thereby further improve dispersing property.Yet this mode operability is not strong, does not possess the prospect of industrial application.
Summary of the invention
The purpose of this invention is to provide and contain carboxyl segmental titanium dioxide granule and preparation method thereof; And this titanium dioxide granule added to be prepared into a kind of ultra-hydrophilic transparent film in the polymeric matrix; This ultra-hydrophilic transparent film is appearance transparent not only, is prone to cleaning, has anti-uv-ray; And, superior antiwear heat resisting property, high mechanical strength, high impact-resistance and optical property have been shown than simple epoxide resin material.
First purpose of the present invention provides a kind of modifying titanium dioxide particle, it is characterized in that the titanium dioxide granule surface makes the modifying titanium dioxide particle through oxygen bonding carboxyl, and modifying titanium dioxide particulate granularity is 50-100nm.
Described modifying titanium dioxide particulate preparation method is characterized in that may further comprise the steps:
(1) be the modification instrument with the ball mill, in ball grinder, add 1-2 parts by weight of titanium dioxide particle successively, 1-8 weight part sym-dichloroacetic anhydride, 25-35 weight part chloroform solvent adds the ball milling pearl, ball grinder is sealed and is fixed in carry out ball milling in the ball mill;
(2) get the product of the step (1) of 1-2 weight part, add the water of 25-35 weight part, ball milling 4-6h obtains the modifying titanium dioxide particle.
Titanium dioxide granule granularity in the described step (1) is 21-25nm.
Second purpose of the present invention, the ultra-hydrophilic transparent film is characterized in that film matrix adds the described modifying titanium dioxide particle of claim 1.
The preparation method of described ultra-hydrophilic transparent film is characterized in that:
(1) gets the 1-2 parts by weight polymer, add the 10-15 parts by weight of ethanol, be heated to 50 degree dissolvings;
(2) 0.1-0.2 weight part modifying titanium dioxide particle is added in the product of step (1),, make suspension-s through ball-milling reaction 4-6h;
(3) the suspension-s rotation that step (2) is made is applied on the slide glass, and is placed under 100 ℃ of-120 ℃ of conditions and solidifies 1h-3h, obtains the ultra-hydrophilic transparent film.
Modifying titanium dioxide particulate addition described in the step (2) is 5 ~ 10wt.% of polymkeric substance.
Described polymkeric substance is the epoxy resin of molecular weight 70000g/mol or the fiber of resol or surface hydrophilic;
The present invention is the modification instrument with the ball mill; With the sym-dichloroacetic anhydride is properties-correcting agent; Through the method for machinery with chemistry; In the middle of titanium dioxide granule, add sym-dichloroacetic anhydride,, sym-dichloroacetic anhydride is combined with the hydroxyl of chemical bond with the titanium dioxide granule surface through mechanical stirring, vibration, the collision of ball mills.And then with the preparation particle and water react at high energy ball mill, thereby make carboxy-modified titanium dioxide granule.Mode through ball milling joins the particle that obtains in the middle of the epoxy resin at last, suspension-s is applied in carries out thermofixation (100 ℃) on the slide glass then, finally obtains the ultra-hydrophilic transparent film.
The present invention is through carrying out hydrophilic modifying to titanium dioxide surface, thereby improves the addition of modifying titanium dioxide particle in the middle of polymkeric substance, and modifying titanium dioxide particulate addition reaches 5 ~ 10wt.% of polymer weight.The ultra-hydrophilic transparent film that the present invention makes is compared with simple epoxy coating, has superior antiwear heat resisting property, high mechanical strength, high impact-resistance and better optical property.In addition, based on titanium oxide under illumination condition ultra hydrophilic characteristic (contact angle is 0
o) and the intensive ultraviolet receptivity, this coating has goodish anti-uv-ray and is convenient to advantages such as cleaning compared with simple epoxy coating.Reaction raw materials of the present invention is easy to get, and preparation technology is easy, and it is good to use with industrial prospect.
Description of drawings
Fig. 1 is a modifying titanium dioxide particle reaction process synoptic diagram;
The reaction thermogravimetric graphic representation of the modifying titanium dioxide that Fig. 2 makes for instance 2;
The DSC graphic representation of the modifying titanium dioxide that Fig. 3 makes for instance 2;
Fig. 4 is the infrared graphic representation of the modifying titanium dioxide that makes of instance 2.
Embodiment
Below in conjunction with embodiment the present invention is done further explanation.
Embodiment 1:
With the ball mill is the modification instrument, in ball grinder, adds the 1g titanium dioxide granule, then in ball grinder, adds the sym-dichloroacetic anhydride of 1g; Add the ball milling pearl, with the ball grinder sealing and be fixed in the ball mill, the control drum's speed of rotation is 400 r/min; The ball milling time is 6h, gets the particle 1g that makes under this condition, adds 25ml water; Continue ball milling 4h, finally obtain carboxy-modified titanium dioxide granule.
Got the carboxy-modified titanium dioxide granule of 0.05 g through Ball milling (this epoxy resin dissolved under the condition of heating and magnetic agitation through 10g ethanol) in 1g epoxy resin; Make the suspension-s that concentration is 5wt.%; Getting this suspension-s is applied on the slide glass; Solidify 3h down at 100 ℃, make the ultra-hydrophilic transparent film.Film appearance is transparent, has characteristics such as certain antiultraviolet and easy cleaning.
Embodiment 2:
With the ball mill is the modification instrument, in ball grinder, adds the 1g titanium dioxide granule, then in ball grinder, adds the sym-dichloroacetic anhydride of 1g; Add the ball milling pearl, with the ball grinder sealing and be fixed in the ball mill, the control drum's speed of rotation is 400 r/min; The ball milling time is 6h, gets the particle 1g that makes under this condition, adds 25ml water; Continue ball milling 4h, finally obtain carboxy-modified titanium dioxide granule.
Got the carboxy-modified titanium dioxide granule of 0.1 g through Ball milling (this epoxy resin dissolved under the condition of heating and magnetic agitation through 10g ethanol) in 1g epoxy resin; Make the suspension-s that concentration is 10wt.%; Getting this suspension-s is applied on the slide glass; Solidify 3h down at 100 ℃, make the ultra-hydrophilic transparent film.Film appearance is transparent, has characteristics such as certain antiultraviolet and easy cleaning.
Embodiment 3:
With the ball mill is the modification instrument, in ball grinder, adds the 1g titanium dioxide granule, then in ball grinder, adds the sym-dichloroacetic anhydride of 1g; Add the ball milling pearl, with the ball grinder sealing and be fixed in the ball mill, the control drum's speed of rotation is 400 r/min; The ball milling time is 6h, gets the particle 1g that makes under this condition, adds 25ml water; Continue ball milling 4h, finally obtain carboxy-modified titanium dioxide granule.
Got the carboxy-modified titanium dioxide granule of 0.05 g through Ball milling (this epoxy resin dissolved under the condition of heating and magnetic agitation through 10g ethanol) in 1g epoxy resin; Make the suspension-s that concentration is 5wt.%; Getting this suspension-s is applied on the slide glass; Solidify 3h down at 100 ℃, make the ultra-hydrophilic transparent film.Film appearance is transparent, has characteristics such as certain antiultraviolet and easy cleaning.
Embodiment 4:
With the ball mill is the modification instrument, in ball grinder, adds the 1g titanium dioxide granule, then in ball grinder, adds the sym-dichloroacetic anhydride of 1g; Add the ball milling pearl, with the ball grinder sealing and be fixed in the ball mill, the control drum's speed of rotation is 510 r/min; The ball milling time is 4h, gets the particle 1g that makes under this condition, adds 35ml water; Continue ball milling 6h, finally obtain carboxy-modified titanium dioxide granule.
Got the carboxy-modified titanium dioxide granule of 0.1g through Ball milling (this epoxy resin dissolved under the condition of heating and magnetic agitation through 10g ethanol) in 1g epoxy resin; Make the suspension-s that concentration is 10wt.%; Getting this suspension-s is applied on the slide glass; Solidify 3h down at 100 ℃, make the ultra-hydrophilic transparent film.Film appearance is transparent, has characteristics such as certain antiultraviolet and easy cleaning.
Claims (8)
1. the modifying titanium dioxide particle is characterized in that the titanium dioxide granule surface makes the modifying titanium dioxide particle through oxygen bonding carboxyl, and modifying titanium dioxide particulate granularity is 50-100nm.
2. modifying titanium dioxide particulate preparation method as claimed in claim 1 is characterized in that may further comprise the steps:
(1) be the modification instrument with the ball mill, in ball grinder, add 1-2 parts by weight of titanium dioxide particle successively, 1-8 weight part sym-dichloroacetic anhydride, 25-35 weight part chloroform solvent adds the ball milling pearl, ball grinder is sealed and is fixed in carry out ball milling in the ball mill;
(2) get the product of the step (1) of 1-2 weight part, add the water of 25-35 weight part, ball milling 4-6h obtains the modifying titanium dioxide particle.
3. modifying titanium dioxide particulate preparation method according to claim 2 is characterized in that the titanium dioxide granule granularity in the described step (1) is 21-25nm.
4. modifying titanium dioxide particulate preparation method according to claim 2; It is characterized in that described ball mill is a planetary ball mill; The rotating speed of ball mill is 400 ~ 510 r/min; The ball milling time is 4-8h, and described ball milling pearl is the mixture that particle diameter is respectively 1.5-5mm ball milling pearl, and the ball milling pearl is compared 3:1-5:1 with quality of material.
5. the ultra-hydrophilic transparent film is characterized in that film matrix adds the described modifying titanium dioxide particle of claim 1.
6. the preparation method of ultra-hydrophilic transparent film as claimed in claim 5 is characterized in that:
(1) gets the 1-2 parts by weight polymer, add the 10-15 parts by weight of ethanol, be heated to 50 degree dissolvings;
(2) 0.1-0.2 weight part modifying titanium dioxide particle is added in the product of step (1),, make suspension-s through ball-milling reaction 4-6h;
(3) the suspension-s rotation that step (2) is made is applied on the slide glass, and is placed under 100 ℃ of-120 ℃ of conditions and solidifies 1h-3h, obtains the ultra-hydrophilic transparent film.
7. the preparation method of ultra-hydrophilic transparent film according to claim 6 is characterized in that the modifying titanium dioxide particulate addition described in the step (2) is 5 ~ 10wt.% of polymkeric substance.
8. according to the preparation method of claim 6 or 7 described ultra-hydrophilic transparent films, it is characterized in that described polymkeric substance is the epoxy resin of molecular weight 70000g/mol or the fiber of resol or surface hydrophilic.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151869A (en) * | 2014-07-10 | 2014-11-19 | 池州市英派科技有限公司 | Modified nano-titanium dioxide with tenacity and good damp-proof effect, and preparation method of modified nano-titanium dioxide |
| CN108822712A (en) * | 2018-06-26 | 2018-11-16 | 江南大学 | A kind of super-hydrophilic coating agent and preparation method thereof |
| CN110600662A (en) * | 2019-09-19 | 2019-12-20 | 湘潭大学 | Polyvinylidene fluoride-hexafluoropropylene/titanium dioxide composite membrane and preparation method and application thereof |
| CN111330560A (en) * | 2019-12-31 | 2020-06-26 | 沈阳中科碧奥能源科技有限公司 | Preparation method of natural lignin-based photocatalytic material |
| CN116891622A (en) * | 2023-09-11 | 2023-10-17 | 淄博鑫业达新材料科技有限公司 | Long-acting anti-aging master batch and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792116A (en) * | 2009-05-25 | 2010-08-04 | 中国科学院等离子体物理研究所 | Method for preparing carboxylic acid-chemically modified metal oxide nanoparticles |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101792116A (en) * | 2009-05-25 | 2010-08-04 | 中国科学院等离子体物理研究所 | Method for preparing carboxylic acid-chemically modified metal oxide nanoparticles |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151869A (en) * | 2014-07-10 | 2014-11-19 | 池州市英派科技有限公司 | Modified nano-titanium dioxide with tenacity and good damp-proof effect, and preparation method of modified nano-titanium dioxide |
| CN104151869B (en) * | 2014-07-10 | 2016-01-20 | 池州市英派科技有限公司 | A kind of have modified nano-titanium dioxide of good toughness moisture effect and preparation method thereof |
| CN108822712A (en) * | 2018-06-26 | 2018-11-16 | 江南大学 | A kind of super-hydrophilic coating agent and preparation method thereof |
| CN108822712B (en) * | 2018-06-26 | 2019-09-17 | 江南大学 | A kind of super-hydrophilic coating agent and preparation method thereof |
| CN110600662A (en) * | 2019-09-19 | 2019-12-20 | 湘潭大学 | Polyvinylidene fluoride-hexafluoropropylene/titanium dioxide composite membrane and preparation method and application thereof |
| CN111330560A (en) * | 2019-12-31 | 2020-06-26 | 沈阳中科碧奥能源科技有限公司 | Preparation method of natural lignin-based photocatalytic material |
| CN111330560B (en) * | 2019-12-31 | 2023-05-16 | 沈阳中科碧奥能源科技有限公司 | Preparation method of natural lignin-based photocatalytic material |
| CN116891622A (en) * | 2023-09-11 | 2023-10-17 | 淄博鑫业达新材料科技有限公司 | Long-acting anti-aging master batch and preparation method thereof |
| CN116891622B (en) * | 2023-09-11 | 2023-11-10 | 淄博鑫业达新材料科技有限公司 | Long-acting anti-aging master batch and preparation method thereof |
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