CN110818929A - Preparation method of self-cleaning intelligent temperature control nano cellulose membrane, nano cellulose membrane prepared by same and application of nano cellulose membrane - Google Patents
Preparation method of self-cleaning intelligent temperature control nano cellulose membrane, nano cellulose membrane prepared by same and application of nano cellulose membrane Download PDFInfo
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- CN110818929A CN110818929A CN201911126181.1A CN201911126181A CN110818929A CN 110818929 A CN110818929 A CN 110818929A CN 201911126181 A CN201911126181 A CN 201911126181A CN 110818929 A CN110818929 A CN 110818929A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
- C08J2491/06—Waxes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
Abstract
The invention relates to a method for preparing a phase-change temperature-controllable nano cellulose membrane by using a cellulose-based material, belonging to the technical field of preparation of green functional materials and environment-friendly energy-saving materials. The method of the invention is that tungsten is doped with vanadium dioxide (W @ VO)2) The nano-particles are added into the nano-cellulose dispersion liquid, and the nano-cellulose membrane material with the flexible phase-change temperature control function is prepared by methods such as vacuum filtration, rod (scraper) film coating, mold film casting and the like. The material can be coated on the surfaces of light-adjusting glass windows of buildings, screen glass of automobiles and airplanes and the like, and selectively absorbs or reflects external heat radiation by utilizing the thermochromic effect of the nano materialAnd the heat diffusion inside the building is prevented, so that a large amount of energy consumed by the building or the vehicle for heat preservation is reduced. The technology has the advantages of simple production process and good intelligent temperature control effect of products, and has great application potential in the process fields of intelligent home, transportation, electronics and the like.
Description
Technical Field
The invention relates to a preparation method of a self-cleaning intelligent temperature control nano cellulose membrane, a nano cellulose membrane prepared by the method and application of the self-cleaning intelligent temperature control nano cellulose membrane, and belongs to the technical field of preparation of green functional materials and environment-friendly energy-saving materials.
Background
The increasing shortage of energy makes it a worldwide problem to improve the efficiency of energy use and to develop and utilize renewable energy to be solved. In the complicated energy consumption, the energy consumption of buildings is not negligible, and the forms mainly comprise ventilation, coal burning in winter, electric heating, electric appliances in summer, air conditioning and cooling and the like. In addition, the manual temperature control consumes a large amount of non-renewable fossil fuel, increases the production cost, and generates a large amount of harmful gas polluting the environment. The research on the novel building energy-saving material can not only relieve the contradiction between energy supply and demand and waste in China, but also protect the natural environment, provide more economic and comfortable living conditions for the masses of people, has positive practical significance and important research value, and accords with the global development trend.
Vanadium dioxide (VO)2) The metal oxide is a metal oxide with phase change property, the phase change temperature is 68 ℃, the reversible transformation of infrared light from transmission to reflection is caused by the structural change before and after the phase change, and people apply the metal oxide to the field of preparing intelligent temperature control films according to the characteristic. However, since the phase transition temperature is relatively high and is much higher than the environment temperature suitable for human survival, if the material is applied to a building temperature control material, the phase transition point must be lowered.
The patent CN107188426A discloses a tungsten-doped vanadium dioxide thermochromic film and a preparation method thereof, wherein a magnetron sputtering method is adopted to deposit on the surface of a substrate in advanceAnd depositing a layer of vanadium pentoxide, depositing a metal tungsten layer on the vanadium pentoxide layer, depositing a layer of vanadium pentoxide on the tungsten layer to form a vanadium pentoxide/metal tungsten/vanadium pentoxide mixed film, oxidizing the metal tungsten into high-valence tungsten in an inert atmosphere, and reducing the vanadium pentoxide into vanadium dioxide to obtain the tungsten-doped vanadium dioxide thermochromic film. Patent CN105543810B discloses a nanometer VO with super-hydrophilic self-cleaning and intelligent temperature control functions2Firstly, preparing a precursor solution of vanadium dioxide by adopting a sol-gel method, then uniformly coating the precursor solution on a substrate, and finally carrying out one-step annealing to obtain the vanadium dioxide nano-film.
Patent CN 106957456 a discloses a method for synthesizing a temperature-sensitive material by using tungsten-doped vanadium dioxide, which utilizes the crystal form change of the tungsten-doped vanadium dioxide at different temperatures to synchronously realize the change of the LCST of hydroxymethyl cellulose, thereby causing the difference of light transmittance and achieving the purpose of reducing the LCST of the hydroxymethyl cellulose to 32-35 ℃.
In summary, most of the existing patents are based on the research of tungsten-doped vanadium dioxide films, and the phase change point of the prepared material has a large difference with the environmental temperature suitable for human life, so that the material is difficult to exert the actual temperature control effect when being directly applied to building glass. In addition, along with the improvement of requirements of people on aesthetic quality and life quality, glass is more and more popular in the fields of buildings, automobiles and the like, however, the glass brings many problems while being bright and beautiful to people, and for example, the cleaning problem of the glass curtain wall of a large building is always puzzled to people.
Disclosure of Invention
The invention aims to provide a preparation method of a self-cleaning intelligent temperature control nano cellulose membrane, which is characterized in that nano cellulose fibers are used as raw materials, tungsten-doped vanadium dioxide (W @ VO 2) nano particles and paraffin emulsion are added into nano cellulose dispersion liquid, and a nano cellulose membrane material with self-cleaning and flexible phase change temperature control functions is prepared by methods such as vacuum filtration, rod (scraper) film coating, mold film casting and the like. The product has good temperature control and color change effects and strong environmental adaptability, and has great application potential in the clean glass market.
A preparation method of a self-cleaning intelligent temperature control nano cellulose membrane comprises the following steps:
(1) adding tungsten-doped vanadium dioxide nano-particles and paraffin emulsion into the nano-cellulose dispersion liquid, and fully mixing; the nano-cellulose dispersion medium is water, and the concentration of the nano-cellulose dispersion medium is 0.05-3 wt.%; the tungsten doped vanadium dioxide nanoparticles: paraffin emulsion: the mass ratio of the nano cellulose dispersion liquid is 0.01-0.5: 0.1-5: 100, respectively;
(2) and preparing the uniformly mixed slurry into the intelligent temperature-control nano cellulose membrane.
The mixing mode of the tungsten-doped vanadium dioxide nano-particles, the paraffin emulsion and the nano-cellulose in the step (1) is at least one of mechanical stirring, magnetic stirring and ultrasonic dispersion.
The concentration of the nano-cellulose in the step (1) is 0.05-1.50 wt.%.
Preferably, the dosage of the tungsten-doped vanadium dioxide nano particles in the step (1) is 0.05-0.2%.
Preferably, the dosage of the paraffin wax emulsion in the step (1) is 0.5-3%.
The preparation method of the nano cellulose membrane in the step (2) is at least one of vacuum filtration, coating by a scraper bar (scraper plate) and casting by a mould.
The thickness of the nano cellulose membrane prepared in the step (2) is 10-300 mu m; preferably, the thickness of the nano cellulose membrane is 30-100 μm.
The quantitative ratio of the nano cellulose membrane prepared in the step (1) is 10-200 g/m2(ii) a Preferably, the quantitative amount of the nano cellulose membrane is 30-100 g/m2。
The self-cleaning intelligent temperature control nano cellulose membrane prepared by the method.
The phase transition temperature of the nano cellulose membrane is 25-40 ℃; the preferable phase transition temperature is 28-35 ℃.
The self-cleaning intelligent temperature control nano cellulose membrane prepared by the method is applied to a glass membrane.
The invention has the beneficial effects that:
1. simple process
The invention uses pure natural plant nano cellulose fiber as raw material, and loads tungsten-doped vanadium dioxide nano particles with phase-change temperature control effect on the surface of a nano cellulose film by a mechanical mixing method, and then prepares the nano cellulose film with intelligent temperature control effect.
2. Self-cleaning, low phase transition temperature
The effect of intelligently regulating and controlling the transparency, the haze and the color change of the nano cellulose membrane by the ultrahigh hydrophobic property and the external temperature change is realized through the interaction of the tungsten-doped vanadium dioxide nano particles, the paraffin emulsion and the nano cellulose.
2. Great potential of application
The product has good intelligent temperature control effect and strong environmental adaptability, and has great application potential in the technical fields of intelligent home, transportation, electronics and the like.
Drawings
FIG. 1 is a schematic diagram of an intelligent temperature-controlled nano cellulose membrane (a with W @ VO added thereto)2，b W@VO2The dosage of 0.05 percent, c W @ VO2The dosage of 0.1 percent, d W @ VO20.2% in amount);
FIG. 2 is an atomic force microscope image of a smart temperature-controlled nanocellulose membrane;
FIG. 3 Differential Scanning Calorimetry (DSC) profiles of a nanocellulose membrane before and after treatment;
FIG. 4 contact angle (150 degrees) of smart temperature controlled nanocellulose membranes;
FIG. 5X-ray diffraction patterns of the intelligent temperature-controlled nanocellulose membranes before and after processing;
FIG. 6 shows the transparency change of the nano-cellulose films with different amounts of tungsten-doped vanadium dioxide;
FIG. 7 is the haze change of the intelligent temperature control nano cellulose film at different temperatures.
Detailed Description
The present invention will be further described with reference to the following specific examples; unless otherwise indicated, the parts are by mass in the examples.
Example 1
A preparation method of a self-cleaning intelligent temperature control nano cellulose membrane comprises the following steps: dispersing 5 parts of nano cellulose fiber in 95 parts of water, adding 0.01 part of tungsten-doped vanadium dioxide nano particles and 0.1 part of paraffin emulsion, starting a stirrer to adjust the rotating speed to 300r/min, stirring for 15min, and preparing the nano cellulose fiber by adopting a vacuum filtration (0.1 MPa, 1 h) and hot-pressing drying (100 ℃, 8 min).
Example 2
A preparation method of a self-cleaning intelligent temperature control nano cellulose membrane comprises the following steps: dispersing 10 parts of nano cellulose fiber in 90 parts of water, adding 0.1 part of tungsten-doped vanadium dioxide nano particles and 2 parts of paraffin emulsion, starting a stirrer to adjust the rotating speed to 300r/min, stirring for 15min, and preparing the nano cellulose fiber by vacuum filtration (0.1 MPa, 1 h) and hot-pressing drying (100 ℃ and 8 min).
Example 3
A preparation method of a self-cleaning intelligent temperature control nano cellulose membrane comprises the following steps: dispersing 15 parts of nano cellulose fiber in 85 parts of water, adding 0.05 part of tungsten-doped vanadium dioxide nano particles and 0.5 part of paraffin emulsion, starting a stirrer to adjust the rotating speed to 300r/min, stirring for 15min, and preparing the nano cellulose fiber by adopting a vacuum filtration (0.1 MPa, 1 h) and hot-pressing drying (100 ℃, 8 min).
Example 4
A preparation method of a self-cleaning intelligent temperature control nano cellulose membrane comprises the following steps: dispersing 10 parts of nano cellulose fiber in 90 parts of water, adding 0.2 part of tungsten-doped vanadium dioxide nano particles and 3 parts of paraffin emulsion, starting a stirrer to adjust the rotating speed to 300r/min, stirring for 15min, and preparing the nano cellulose fiber by vacuum filtration (0.1 MPa, 1 h) and hot-pressing drying (100 ℃ and 8 min).
Example 5
A preparation method of a self-cleaning intelligent temperature control nano cellulose membrane comprises the following steps: dispersing 30 parts of nano cellulose fiber in 70 parts of water, adding 0.5 part of tungsten-doped vanadium dioxide nano particles and 5 parts of paraffin emulsion, adding into a reaction kettle, starting a stirrer to adjust the rotating speed to 300r/min, stirring for 15min, and performing vacuum filtration (0.1 MPa for 1 h) and hot-pressing drying (100 ℃ and 8 min).
Comparative example 1
A preparation method of a self-cleaning intelligent temperature control nano cellulose membrane comprises the following steps: dispersing 10 parts of nano cellulose fiber in 90 parts of water, adding 0.3 part of paraffin emulsion, starting a stirrer to adjust the rotating speed to 300r/min, stirring for 15min, and performing vacuum filtration (0.1 MPa for 1 h) and hot-pressing drying (100 ℃ for 8 min).
Comparative example 2
A preparation method of a self-cleaning intelligent temperature control nano cellulose membrane comprises the following steps: dispersing 10 parts of nano cellulose fiber in 90 parts of water, adding 0.05 part of tungsten-doped vanadium dioxide nano particles, starting a stirrer to adjust the rotating speed to 300r/min, stirring for 15min, and performing vacuum filtration (0.1 MPa for 1 h) and hot-pressing drying (100 ℃ for 8 min).
Examples of the effects of the invention
The materials prepared in examples 1 to 5 and comparative examples 1 and 2 were analyzed for comparative properties as follows:
TABLE 1 comparison of the Properties of the materials prepared in examples 1-5 and comparative examples 1, 2
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.
Claims (10)
1. A preparation method of a self-cleaning intelligent temperature control nano cellulose membrane is characterized by comprising the following steps:
(1) adding tungsten-doped vanadium dioxide nano-particles and paraffin emulsion into the nano-cellulose dispersion liquid, and fully mixing;
(2) and preparing the uniformly mixed slurry into the intelligent temperature-control nano cellulose membrane.
2. The method according to claim 1, wherein the nanocellulose dispersion medium of step (1) is water at a concentration of 0.05 to 3 wt.%; the tungsten doped vanadium dioxide nanoparticles: paraffin emulsion: the mass ratio of the nano cellulose dispersion liquid is 0.01-0.5: 0.1-5: 100.
3. the method according to claim 1, wherein the concentration of the nanocellulose in the step (1) is 0.05 to 1.50 wt.%.
4. The preparation method of claim 1, wherein the amount of the tungsten-doped vanadium dioxide nanoparticles used in the step (1) is 0.05-0.2%.
5. The method according to claim 1, wherein the amount of the paraffin emulsion used in the step (1) is 0.5 to 3%.
6. The method according to claim 1, wherein the method for preparing the nano cellulose film in step (2) is at least one of vacuum filtration, bar (blade) coating, and mold casting.
7. The method according to claim 1, wherein the thickness of the nano cellulose film prepared in the step (2) is 10 to 300 μm; preferably, the thickness of the nano cellulose membrane is 30-100 μm.
8. The self-cleaning intelligent temperature control nano cellulose membrane prepared by the method of claim 1.
9. The self-cleaning intelligent temperature control nano cellulose membrane prepared by the method of claim 1 has a phase transition temperature of 25-40 ℃.
10. The use of the self-cleaning intelligent temperature-controlled nano cellulose membrane prepared by the method of claim 1 in a glass membrane.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911126181.1A CN110818929B (en) | 2019-11-18 | 2019-11-18 | Preparation method of self-cleaning intelligent temperature control nano cellulose membrane, nano cellulose membrane prepared by same and application of nano cellulose membrane |
| AU2020101696A AU2020101696A4 (en) | 2019-11-18 | 2020-08-06 | Self-cleaning intelligent temperature control nanocellulose film, preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911126181.1A CN110818929B (en) | 2019-11-18 | 2019-11-18 | Preparation method of self-cleaning intelligent temperature control nano cellulose membrane, nano cellulose membrane prepared by same and application of nano cellulose membrane |
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| CN110818929A true CN110818929A (en) | 2020-02-21 |
| CN110818929B CN110818929B (en) | 2022-04-26 |
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| CN201911126181.1A Active CN110818929B (en) | 2019-11-18 | 2019-11-18 | Preparation method of self-cleaning intelligent temperature control nano cellulose membrane, nano cellulose membrane prepared by same and application of nano cellulose membrane |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024040429A1 (en) * | 2022-08-23 | 2024-02-29 | 中国科学院深圳先进技术研究院 | Electromagnetic shielding composite material with temperature response characteristic, and preparation method therefor and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116023800A (en) * | 2022-12-01 | 2023-04-28 | 成都先进金属材料产业技术研究院股份有限公司 | Modified vanadium dioxide nano powder and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1621459A (en) * | 2004-10-28 | 2005-06-01 | 中山大学 | Intelligent vanadium dioxide solar temperature control coating |
| CN105970603A (en) * | 2016-07-07 | 2016-09-28 | 上海大学 | Intelligent temperature-controlled textile product and preparation method thereof |
| CN206015379U (en) * | 2016-07-07 | 2017-03-15 | 上海大学 | A kind of intelligent temperature control textile |
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2019
- 2019-11-18 CN CN201911126181.1A patent/CN110818929B/en active Active
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- 2020-08-06 AU AU2020101696A patent/AU2020101696A4/en not_active Ceased
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1621459A (en) * | 2004-10-28 | 2005-06-01 | 中山大学 | Intelligent vanadium dioxide solar temperature control coating |
| CN105970603A (en) * | 2016-07-07 | 2016-09-28 | 上海大学 | Intelligent temperature-controlled textile product and preparation method thereof |
| CN206015379U (en) * | 2016-07-07 | 2017-03-15 | 上海大学 | A kind of intelligent temperature control textile |
Non-Patent Citations (1)
| Title |
|---|
| 张鑫等: "掺杂钨纳米二氧化钒控温微胶囊的合成与表征", 《塑料工业》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024040429A1 (en) * | 2022-08-23 | 2024-02-29 | 中国科学院深圳先进技术研究院 | Electromagnetic shielding composite material with temperature response characteristic, and preparation method therefor and application thereof |
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| CN110818929B (en) | 2022-04-26 |
| AU2020101696A4 (en) | 2020-09-10 |
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Effective date of registration: 20221221 Address after: Room 3115, No. 135, Ward Avenue, Ping'an Street, Changqing District, Jinan, Shandong 250300 Patentee after: Shandong Jiqing Technology Service Co.,Ltd. Address before: 250399 No. 3501 University Road, Changqing District, Jinan City, Shandong Province Patentee before: Qilu University of Technology |