CN101264455A - Preparation of photocatalysis coating supported with titanium dioxide under low temperature - Google Patents
Preparation of photocatalysis coating supported with titanium dioxide under low temperature Download PDFInfo
- Publication number
- CN101264455A CN101264455A CNA2008101042078A CN200810104207A CN101264455A CN 101264455 A CN101264455 A CN 101264455A CN A2008101042078 A CNA2008101042078 A CN A2008101042078A CN 200810104207 A CN200810104207 A CN 200810104207A CN 101264455 A CN101264455 A CN 101264455A
- Authority
- CN
- China
- Prior art keywords
- titanium dioxide
- preparation
- photocatalysis
- low temperature
- nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention relates to a method for preparing a low-temperature titanium dioxide loaded photocatalysis coating layer, belonging to the technical field of photocatalysis coating layer preparation. The method is characterized in that photocatalysis mother liquor is prepared through preparing nanometer titanium dioxide dispersion liquid and polysiloxane. The method has the advantages of easy preparation technology, easy operation, good photocatalysis effect for adopting nanometer titanium dioxide to prepare, ability to coat and solidify under normal temperature, and to release high-temperature agglomerating, ability to be used on the surface coating without high temperature resistant based material such as plastic, at the same time, the photocatalysis coating layer has good binding force of the selected polysiloxane ultraviolet with tolerance properties to metal, plastic, and glass, and simultaneously, good anti-aging property of the formed photocatalysis coating layer under the irradiation of ultraviolet.
Description
Technical field
The invention belongs to the preparing technical field of photocatalysis coating, be specifically related to a kind of preparation method of photocatalysis coating of supported with titanium dioxide under low temperature.
Background technology
The method of existing preparation titanium dichloride load type photochemical catalyst mainly contains three classes: (one) utilizes collosol and gel directly to prepare titanium deoxid film and high-temperature calcination at carrier surface; (2) be to utilize nano-powder to be dispersed into suspension, load on the method for carrier surface, also need high-temperature calcination; (3) utilize inorganic and organic gel that nano-photocatalyst is loaded on method on the woven wire.
Above-mentioned three kinds of methods respectively have its weak point,, active relatively poor in the method () because the titanium dioxide optical catalyst film of employing Prepared by Sol Gel Method is a non-porous structure, and specific surface is little, and calcining heat is generally more than 400 ℃, and this has certain high temperature resistant requirement for base material; The photochemical catalyst of method (two) preparation is because offspring is very loose with combining of base material, and catalyst is easy to come off, and its practicability is difficulty; The catalyst of method (three) preparation, because inorganic and organic gel is to the coated effect of nanocatalyst, photocatalysis efficiency is low, and its bond strength is also poor, and in addition, organic gel also the ultraviolet light decomposing phenomenon can occur.
The load of catalyst is to solve the effective way that the suspended phase catalyst separation reclaims, and can overcome shortcomings such as suspended phase poor catalyst stability and easy poisoning.Sol-gal process is owing to advantages such as its preparation technology is simple, material is easy to get have obtained extensive use in above-mentioned carrying method.Problems such as but sol-gal process exists, and the organic solvent addition is big, the loss of catalyst activity component titanium dioxide is serious, sintering temperature height cause that this method is seriously polluted, cost is higher.Therefore how to reduce the amount of the pollutant that produces in the sol-gal process production process, improve the rate of recovery of catalyst activity component, keep the high catalytic activity of catalyst to have good realistic meaning undoubtedly simultaneously.
Summary of the invention
At the defective that exists in the prior art, the preparation method who the purpose of this invention is to provide a kind of photocatalysis coating of supported with titanium dioxide under low temperature, this method prepares the photocatalysis coating of gained, photocatalysis is effective, and can under normal temperature, low temperature, apply, solidify, remove high temperature sintering from, the photocatalysis coating of Xing Chenging has good ageing-resistant performance under ultraviolet irradiation simultaneously.
For reaching above purpose, the technical solution used in the present invention is: a kind of preparation method of photocatalysis coating of supported with titanium dioxide under low temperature may further comprise the steps:
(1) preparation nano titanium oxide dispersion;
Nano-titanium dioxide powder is dissolved in the solvent that has added surfactant, dispersant and defoamer, form mixed solution, above-mentioned mixed solution was tentatively disperseed 0.5-2 hour with homogenizer, mixing speed is a 2000-4000 commentaries on classics/per minute, and ultrasonic wave disperses promptly to make in 15-40 minute nano titanium oxide dispersion then;
(2) preparation polysiloxanes;
Selecting at least a is that alkyl trialkoxy silane by general structure RSi (OR ') 3 expression is as initiation material, the dialkyl dialkoxy silicane or the general structure that include general structure in the described initiation material simultaneously and be R2Si (OR ') 2 are the positive esters of silicon acis of Si (OR ') 4, wherein, R represents univalent alkyl, monovalence aryl or monovalence unsaturated group etc., and it is the alkyl of 1-4 that R ' represents carbon number;
Above-mentioned initiation material is determined proportioning by silicones R/Si value for 0.6-1.8, be incorporated as simultaneously initiation material molal quantity summation 1-4 doubly water and add the 0.1N hydrochloric acid of material gross weight 3-20ppm, 50 ℃-90 ℃ following stirring and refluxing 3-8 hour, cool off, promptly obtain the polysiloxanes of water white transparency homogeneous;
(3) preparation photocatalysis mother liquor;
With nano titanium oxide dispersion, the polysiloxanes for preparing, and solvent, polyethylene glycol at room temperature mix, and promptly makes the photocatalysis mother liquor,
(4) base material that will need to apply is immersed in the photocatalysis mother liquor, and 5-20 takes out after second, and 60 ℃-80 ℃ promptly get the nano titanium dioxide photocatalysis coating after the oven dry down;
Further, in the step (1), described nano-titanium dioxide powder is meant the titanium dioxide powder of particle size range at 5nm-30nm;
Further, in the step (1), described nano titanium dioxide crystal form is an anatase titanium dioxide;
Further, described solvent is alcohols, ketone or ester class;
Described surfactant is any or several combination in cationic cellulose, calgon, neopelex, citric acid, the sodium metasilicate;
Described dispersant is any or several combination among Disperbyk-110, Disperbyk-111, Disperbyk-160, Disperbyk-180, LD-124, HX-4010, TEGO-710, the TEGO-700;
Described defoamer is 4164;
Further, when preparing nano titanium oxide dispersion in the step (1), the consumption of each component is by weight, and is specific as follows:
Nano-titanium dioxide powder 15-30%;
Surfactant 0.01-5%;
Dispersant 0.1-5%;
Defoamer 0.1-3%;
Solvent 60-75%;
Further, when preparation prepared nano titanium oxide dispersion in the step (1), the consumption of each component is by weight, and was specific as follows:
Nano-titanium dioxide powder 25-30%;
Surfactant 0.1-5%;
Dispersant 1-3%;
Defoamer 1-2%;
Hold agent 65-70%.
Further, in the step (3), during preparation photocatalysis mother liquor, the consumption of each component is by weight, and is specific as follows:
Nano titanium oxide dispersion 1-15%
Polysiloxanes 30-60%
Solvent 20-50%
Polyethylene glycol 1-10%;
Further, in the step (3), during preparation photocatalysis mother liquor, the consumption of each component is by weight, and is specific as follows:
Nano titanium oxide dispersion 2-8%
Polysiloxanes 35-50%
Solvent 40-50%
Polyethylene glycol 1-10%;
Further, in the step (4), described base material is metal, plastics, glass, pottery.
Effect of the present invention is: adopt method of the present invention to prepare photocatalysis coating, have the following advantages:
1, adopt Nano titanium dioxide, photocatalysis is effective.
2, high temperature sintering is removed in normal temperature, low temperature coating down, curing from, can be used for the surface-coated of the base material such as the plastics of some non-refractories.
3, select the polysiloxanes of ultra-violet resistance energy for use, it has good adhesion to metal, plastics, glass etc., and the photocatalysis coating of Xing Chenging has good ageing-resistant performance under ultraviolet irradiation simultaneously.
The specific embodiment
The invention will be further described below in conjunction with embodiment:
Embodiment 1
(1) preparation nano titanium oxide dispersion;
With ethanol 360g is solvent, add neopelex 2.5g, add 15g dispersant Disperbyk-110,5g defoamer 4164, the titanium dioxide powder 100g of 5 nanometers is added in the above-mentioned solvent, form mixed liquor, above-mentioned mixed solution was disperseed 1 hour with homogenizer is preliminary, ultrasonic wave disperseed 30 minutes then;
(2) preparation polysiloxanes;
MTES 1000g, dimethyldiethoxysilane 200g, distilled water 200g, 0.1N hydrochloric acid 4g, 80 ℃ of whipping temps kept 4 hours, then cooling;
(3) preparation photocatalysis mother liquor 100g;
During preparation photocatalysis mother liquor, the consumption of its each component is specific as follows:
Nano titanium oxide dispersion 10g
Polysiloxanes 50g
Ethanol 35g
Cetomacrogol 1000 5g
(4) base material that will need to apply is immersed in the photocatalysis mother liquor, takes out after 10 seconds, and 70 ℃ promptly get the nano titanium dioxide photocatalysis coating after the oven dry down.
Embodiment two
(1) preparation nano titanium oxide dispersion;
With isopropyl alcohol 375g is solvent, add calgon 5g, add 10g dispersant Disperbyk-180, add citric acid 5g, 10g defoamer 4164 adds the nano titanium oxide 100g of 15 nanometers in the above-mentioned solvent, forms mixed solution, above-mentioned mixed solution was disperseed 1.5 hours with homogenizer is preliminary, and ultrasonic wave disperseed 20 minutes then;
(2) preparation polysiloxanes;
Phenyl triethoxysilane 1000g, dimethyldimethoxysil,ne 100g, distilled water 100g, 0.1N hydrochloric acid 3g, 60 ℃ of whipping temps kept 7 hours, then cooling;
(3) preparation photocatalysis mother liquor 100g;
During preparation photocatalysis mother liquor, the consumption of its each component is specific as follows:
Nano titanium oxide dispersion 2g
Polysiloxanes 58g
Isopropyl alcohol 37g
Polyethylene glycol 800 3g
(4) base material that will need to apply is immersed in the photocatalysis mother liquor, takes out after 20 seconds, and 70 ℃ promptly get the nano titanium dioxide photocatalysis coating after the oven dry down.
Embodiment three
(1) preparation nano titanium oxide dispersion;
With cyclohexanone 372.5g is solvent, add the 2.5g calgon, add 5g dispersant LD-124, add sodium metasilicate 5g, 15g defoamer 4164 is dissolved in the nano titanium oxide 100g of 25 nanometers in the above-mentioned solvent, forms mixed solution, above-mentioned mixed solution was disperseed 0.5 hour with homogenizer is preliminary, and ultrasonic wave disperseed 40 minutes then;
(2) preparation polysiloxanes;
VTES 1000g, aminomethyl phenyl diethoxy silane 300g, distilled water 100g, 0.1N hydrochloric acid 5g, 70 ℃ of whipping temps kept 6 hours, then cooling;
(3) preparation photocatalysis mother liquor 100g;
During preparation photocatalysis mother liquor, the consumption of its each component is specific as follows:
Nano titanium oxide disperses: 15g
Polysiloxanes 55g
Isopropyl alcohol 23g
Cetomacrogol 1000 7g
(4) base material that will need to apply is immersed in the photocatalysis mother liquor, takes out after 15 seconds, and 80 ℃ promptly get the nano titanium dioxide photocatalysis coating after the oven dry down.
Embodiment four
(1) preparation nano titanium oxide dispersion;
With ethanol 310g is solvent, add neopelex 5g, add 25g dispersant HX-4010, add the citric acid of 5g, 5g defoamer 4164 is dissolved in the nano titanium oxide 150g of 10 nanometers in the above-mentioned solvent, forms mixed solution, above-mentioned mixed solution was disperseed 2 hours with homogenizer is preliminary, and ultrasonic wave disperseed 15 minutes then;
(2) preparation polysiloxanes;
Phenyl triethoxysilane 1000g, positive tetraethyl orthosilicate 150g, distilled water 100g, 0.1N hydrochloric acid 3g, 55 ℃ of whipping temps kept 8 hours, then cooling;
(3) preparation photocatalysis mother liquor 100g;
During preparation photocatalysis mother liquor, the consumption of its each component is specific as follows:
Nano titanium oxide dispersion 8g
Polysiloxanes 42g
Isopropyl alcohol 49g
Polyethylene glycol 800 1g
(4) base material that will need to apply is immersed in the photocatalysis mother liquor, takes out after 5 seconds, and 60 ℃ promptly get the nano titanium dioxide photocatalysis coating after the oven dry down.
The foregoing description just illustrates of the present invention, and the present invention also can implement with other ad hoc fashion or other particular form, and does not depart from main idea of the present invention or substantive characteristics.Therefore, the embodiment of description all should be considered as illustrative from any aspect but not be determinate.Scope of the present invention should be by additional claim explanation, and the intention of any and claim and the variation of scope equivalence also should be within the scope of the present invention.
Claims (10)
1, a kind of preparation method of photocatalysis coating of supported with titanium dioxide under low temperature comprises the steps:
(1) preparation nano titanium oxide dispersion;
Nano-titanium dioxide powder is dissolved in the solvent that has added surfactant, dispersant and defoamer, form mixed solution, above-mentioned mixed solution was tentatively disperseed 0.5-2 hour with homogenizer, mixing speed is a 2000-4000 commentaries on classics/per minute, and ultrasonic wave disperses promptly to make in 15-40 minute nano titanium oxide dispersion then;
(2) preparation polysiloxanes;
Selecting at least a is that alkyl trialkoxy silane by general structure RSi (OR ') 3 expression is as initiation material, the dialkyl dialkoxy silicane or the general structure that include general structure in the described initiation material simultaneously and be R2Si (OR ') 2 are the positive esters of silicon acis of Si (OR ') 4, wherein, R represents univalent alkyl, monovalence aryl or monovalence unsaturated group etc., and it is the alkyl of 1-4 that R ' represents carbon number;
Above-mentioned initiation material is determined proportioning by silicones R/Si value for 0.6-1.8, be incorporated as simultaneously initiation material molal quantity summation 1-4 doubly water and add the 0.1N hydrochloric acid of material gross weight 3-20ppm, 50 ℃-90 ℃ following stirring and refluxing 3-8 hour, cool off, promptly obtain the polysiloxanes of water white transparency homogeneous;
(3) preparation photocatalysis mother liquor;
With nano titanium oxide dispersion, the polysiloxanes for preparing, and solvent, polyethylene glycol at room temperature mix, and promptly makes the photocatalysis mother liquor,
(4) base material that will need to apply is immersed in the photocatalysis mother liquor, and 5-20 takes out after second, and 60 ℃-80 ℃ promptly get the nano titanium dioxide photocatalysis coating after the oven dry down.
2, the preparation method of the photocatalysis coating of a kind of supported with titanium dioxide under low temperature as claimed in claim 1 is characterized in that: in the step (1), described nano-titanium dioxide powder is meant the titanium dioxide powder of particle size range at 5nm-30nm.
3, the preparation method of the photocatalysis coating of a kind of supported with titanium dioxide under low temperature as claimed in claim 1 or 2 is characterized in that: in the step (1), described nano-titanium dioxide powder crystal formation is an anatase titanium dioxide.
4, the preparation method of the photocatalysis coating of a kind of supported with titanium dioxide under low temperature as claimed in claim 3 is characterized in that: described solvent is alcohols, ketone or ester class; Described surfactant is any or several combination in cationic cellulose, calgon, neopelex, citric acid, the sodium metasilicate; Described dispersant is any or several combination among Disperbyk-110, Disperbyk-111, Disperbyk-160, Disperbyk-180, LD-124, HX-4010, TEGO-710, the TEGO-700; Described defoamer is 4164.
5, the preparation method of the photocatalysis coating of a kind of supported with titanium dioxide under low temperature as claimed in claim 3 is characterized in that: when preparing nano titanium oxide dispersion in the step (1), the consumption of each component is by weight, and is specific as follows:
Nano-titanium dioxide powder 15-30%;
Surfactant 0.01-5%;
Dispersant 0.1-5%;
Defoamer 0.1-3%;
Solvent 60-75%.
6, the preparation method of the photocatalysis coating of a kind of supported with titanium dioxide under low temperature as claimed in claim 5 is characterized in that: when preparation prepared nano titanium oxide dispersion in the step (1), the consumption of each component is by weight, and was specific as follows:
Nano-titanium dioxide powder 25-30%;
Surfactant 0.1-5%;
Dispersant 1-3%;
Defoamer 1-2%;
Solvent 65-70%.
7, the preparation method of the photocatalysis coating of a kind of supported with titanium dioxide under low temperature as claimed in claim 1 is characterized in that: when preparing polysiloxanes in the step (2), whipping temp is 60-80 ℃, and mixing time is 4-6 hour.
8, the preparation method of the photocatalysis coating of a kind of supported with titanium dioxide under low temperature as claimed in claim 1 is characterized in that: in the step (3), during preparation photocatalysis mother liquor, the consumption of each component is by weight, and is specific as follows:
Nano titanium oxide dispersion 1-15%
Polysiloxanes 30-60%
Solvent 20-50%
Polyethylene glycol 1-10%.
9, the preparation method of the photocatalysis coating of a kind of supported with titanium dioxide under low temperature as claimed in claim 8 is characterized in that: in the step (3), during preparation photocatalysis mother liquor, the consumption of each component is by weight, and is specific as follows:
Nano titanium oxide dispersion 2-8%
Polysiloxanes 35-50%
Solvent 40-50%
Polyethylene glycol 1-10%.
10, the preparation method of the photocatalysis coating of a kind of supported with titanium dioxide under low temperature as claimed in claim 1 is characterized in that: in the step (4), described base material is metal, plastics, glass, pottery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101042078A CN101264455B (en) | 2008-04-17 | 2008-04-17 | Preparation of photocatalysis coating supported with titanium dioxide under low temperature |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101042078A CN101264455B (en) | 2008-04-17 | 2008-04-17 | Preparation of photocatalysis coating supported with titanium dioxide under low temperature |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101264455A true CN101264455A (en) | 2008-09-17 |
| CN101264455B CN101264455B (en) | 2011-04-27 |
Family
ID=39987278
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101042078A Expired - Fee Related CN101264455B (en) | 2008-04-17 | 2008-04-17 | Preparation of photocatalysis coating supported with titanium dioxide under low temperature |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101264455B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102580710A (en) * | 2012-03-20 | 2012-07-18 | 哈尔滨工业大学 | Nano TiO2 composite water treatment material and preparation method thereof |
| CN104405853A (en) * | 2014-12-12 | 2015-03-11 | 常熟市明瑞针纺织有限公司 | Cam for spinning device |
| CN107177226A (en) * | 2017-05-26 | 2017-09-19 | 山东工业陶瓷研究设计院有限公司 | A kind of ceramic membrane surface modifier and method of modifying |
| CN109304224A (en) * | 2017-07-28 | 2019-02-05 | 孙梓译 | Long-acting water purification material and preparation method thereof |
-
2008
- 2008-04-17 CN CN2008101042078A patent/CN101264455B/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102580710A (en) * | 2012-03-20 | 2012-07-18 | 哈尔滨工业大学 | Nano TiO2 composite water treatment material and preparation method thereof |
| CN102580710B (en) * | 2012-03-20 | 2013-10-30 | 哈尔滨工业大学 | Nano TiO2 composite water treatment material and preparation method thereof |
| CN104405853A (en) * | 2014-12-12 | 2015-03-11 | 常熟市明瑞针纺织有限公司 | Cam for spinning device |
| CN107177226A (en) * | 2017-05-26 | 2017-09-19 | 山东工业陶瓷研究设计院有限公司 | A kind of ceramic membrane surface modifier and method of modifying |
| CN107177226B (en) * | 2017-05-26 | 2019-07-19 | 山东工业陶瓷研究设计院有限公司 | A kind of ceramic membrane surface modifier and method of modifying |
| CN109304224A (en) * | 2017-07-28 | 2019-02-05 | 孙梓译 | Long-acting water purification material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101264455B (en) | 2011-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hu et al. | A self-templated approach to TiO2 microcapsules | |
| CN101537349B (en) | Preparation of core/shell structural polystyrene/titanium dioxide composite photo catalyst | |
| CN106492849B (en) | A kind of preparation method of BiOCl ultrathin nanometer piece photochemical catalyst | |
| CN109647480A (en) | A kind of g-C3N4-TiO2The preparation method of/AC catalysis material | |
| CN101264455B (en) | Preparation of photocatalysis coating supported with titanium dioxide under low temperature | |
| CN106010036B (en) | A kind of heat-insulated water paint of double Shell microcapsules and preparation method thereof | |
| CN101752093B (en) | Preparation method for photonic crystal structure film electrode of dye solar cell | |
| CN103031008B (en) | A kind of preparation method of antireflective plated film colloidal sol of self-cleaning high permeability bilayer | |
| CN106582331A (en) | Preparation method of photocatalytic ultrafilter membrane material with visible light activity | |
| CN102527410B (en) | Preparation method of composite photocatalytic material with CdS/TiO2 load on carbon fiber felt | |
| CN102219555A (en) | Multifunctional concrete structure endurance protective agent, preparation and application method thereof | |
| CN101602933A (en) | Self-cleaning super-hydrophilic thin film and preparation method thereof | |
| CN102585700B (en) | Method for preparing UV (ultraviolet)-curable high-temperature-resistant and corrosion-resistant organic silicon/silica hybrid coating | |
| CN105789339A (en) | Perovskite solar cell nano silicon dioxide coating liquid and application thereof | |
| CN101429350A (en) | Method for producing nano-organic/inorganic composite atom resistant oxygen coating | |
| CN106882811A (en) | A kind of sea urchin shape bivalve layer hollow microsphere and preparation method thereof | |
| CN101721986A (en) | Method for preparing glass-loaded titanium dioxide photocatalyst | |
| CN108841005A (en) | Si―H addition reaction type silicone resin high-temperature catalytic inhibition system and its preparation method and application | |
| CN105268400A (en) | Method for supporting nanometer titanium dioxide on active carbon fibers | |
| CN104925816B (en) | A kind of titania modified bar-shaped silica core shell material and preparation method thereof | |
| CN107090200A (en) | A kind of preparation method of ultraviolet light screener | |
| CN103555198A (en) | Preparation method of modified organic silicon resin coating liquid and method for manufacturing solar battery packaging glass by using modified organic silicon resin coating liquid | |
| CN108034285A (en) | A kind of normal temperature cured type nano self-cleaning antireflective coating liquid and preparation method thereof | |
| CN105153863B (en) | A kind of preparation method of photocatalyst organosilicon-modified acrylate emulsion paint | |
| CN101567270A (en) | Method for preparing meso-porous ZnO/TiO* composite film with high zinc content |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: BEIJING ECO-BAO CO., LTD. Free format text: FORMER OWNER: BEIJING SHOUCHUANG NANO TECHN CO., LTD. Effective date: 20140605 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20140605 Address after: 100085, D building 205D, 2 information road, Beijing, Haidian District Patentee after: ECO-BAO CO., LTD. Address before: 100085, room 701, building D, Pioneer Park, 2 information road, Beijing, Haidian District Patentee before: Beijing Shouchuang Nano Techn Co., Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110427 Termination date: 20200417 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |