CN106517152B - Single-walled carbon nanotube method evenly dispersed in aqueous solvent - Google Patents
Single-walled carbon nanotube method evenly dispersed in aqueous solvent Download PDFInfo
- Publication number
- CN106517152B CN106517152B CN201610946073.9A CN201610946073A CN106517152B CN 106517152 B CN106517152 B CN 106517152B CN 201610946073 A CN201610946073 A CN 201610946073A CN 106517152 B CN106517152 B CN 106517152B
- Authority
- CN
- China
- Prior art keywords
- carbon nanotube
- walled carbon
- solvent
- walled
- evenly dispersed
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/02—Single-walled nanotubes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/28—Solid content in solvents
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Abstract
Method evenly dispersed in aqueous solvent that the invention discloses single-walled carbon nanotubes.First under inert atmosphere protection, keep carbon nano tube surface all positively charged using the tetrahydrofuran solution of sodium naphthalene, makes carbon nano-tube bundle thermoplastic polymer in dimethyl sulfoxide solvent with the repulsive force between electrical carbon pipe.Then polyvinylpyrrolidone protection is added to lose the carbon pipe of charge in air atmosphere and be allowed to keep dispersity.The method for recycling dialysis makes the dispersion solvent of the single-walled carbon nanotube of polyvinylpyrrolidone cladding be converted to water by dimethyl sulfoxide (DMSO).While realizing the solubility of single-walled carbon nanotube, the structural intergrity of single-walled carbon nanotube and the primitive character of itself are maintained.Under the premise of without ultrasonic and surface-functionalized, realize that single-walled carbon nanotube is evenly dispersed in aqueous solvent.Uniform, stable dispersion the carbon nanotube in water phase, to promoting application of the carbon nanotube in the fields such as biomedicine, chemistry, physics, composite material to be of great significance.
Description
Technical field
The invention belongs to carbon nanotube field of dispersions, more particularly to single-walled carbon nanotube side evenly dispersed in aqueous solvent
Method.
Background technology
Carbon nanotube can regard the hollow seamless structure curled by graphene as, and the pipe shaft of carbon nanotube is by six
Side shape graphite carbon ring structural unit composition.It is excellent that the unique structure of carbon nanotube, especially single-walled carbon nanotube creates its
The property of physics, chemistry, electricity, optics etc., therefore since rising for birth just causes the great interest of scientific circles and wide
General concern.However, the single-walled carbon nanotube prepared is generally easy to due to Van der Waals force strong between its big draw ratio and carbon pipe
Form larger tube bank, it is difficult to disperse, weaken the excellent properties of single-walled carbon nanotube, greatly constrain its subsequent applications.
Evenly dispersed single-walled carbon nanotube, researcher are continuously attempted in order to obtain, have developed a variety of carbon modifieds
Nanotube includes mainly in the method for improving dispersibility in a solvent：Covalent functionalization and non-covalent functionalization.Covalent function
Change is to make the upper functional group of carbon nanotube grafting by the method for covalent modification, therefore can be dissolved in a variety of organic and inorganic solvent
In.But it is miscellaneous to introduce many SP2 in carbon nanotube for the complete structure for destroying carbon nanotube itself while covalent functionalization
Change defect, destroys optics, the electric property of single-walled carbon nanotube essence, reduce the mechanical property of carbon nanotube.It is non-covalent
Key functionalization refers to single-walled carbon nanotube and surfactant, polymer, bioactive molecule or molecule containing big pi bond pass through
π-π interactions or Van der Waals force combine, and improve the dispersion performance of carbon nanotube.But in dispersion process, generally use strength
Ultrasonic wave realize single-walled carbon nanotube cladding and dispersion.And strong ultrasonic wave has not only blocked single-walled carbon nanotube, and
And bring a lot of defects to carbon pipe itself.Therefore, the performance of the carbon nanotube of dispersion is had a greatly reduced quality, and it is excellent to greatly restrict its
The performance of anisotropic energy and practical application.In view of the application value of single-walled carbon nanotube, the method for a milder is needed to divide
Throwaway wall carbon nano tube.
Invention content
In order to overcome above-mentioned deficiency, the present invention provides it is a kind of in a mild condition disperse single-walled carbon nanotube method,
The shortcomings that overcome functionalization destroying carbon nanometer tube structure.The present invention combines electrification single-walled carbon nanotube in aprotic solvent
Spontaneous dissolving and polymer realize the evenly dispersed of carbon nanotube to the cladding and osmotic technique of single-walled carbon nanotube.It keeps away
The destruction of ultrasound or covalent functionalization to complete carbon nano tube structure is exempted from so that single pipe surface has coated water solubility
High-molecular compound, to reach the dispersion of single-walled carbon nanotube in water.
To achieve the goals above, the present invention adopts the following technical scheme that：
A kind of method that single-walled carbon nanotube is evenly dispersed in aqueous solvent, including：
Single-walled carbon nanotube is surface-treated using sodium-naphthalene solution, obtains the single-walled carbon nanotube of electrification；
Make the single-walled carbon nanotube self-dispersing of the electrification in polar solvent, using covering it coated, dialysis,
Up to single-walled carbon nanotube aqueous solution.
Due to most inorganic agent, covalent functionalization can be generated to carbon pipe, to the original performance of destroying carbon nanometer tube.
Therefore, the present invention carries out Large-scale Screening to existing inorganic agent, finds：Using sodium-naphthalin treatment solution to carbon nanotube at
When reason, due to the chemical inertness of carbon nanotube itself, tube wall does not occur chemical reaction with sodium-naphthalin treatment solution and generates polar group
Group.And carbon nanotube can only be made positively charged, it generates [Na (THF)]nNT (sodium-tetrahydrofuran-carbon nanotube) colloidal sol, these bands
Repulsive force between electrical carbon nanotube is the basis that carbon nanotube thermoplastic polymer forms colloidal sol.The carbon nanotube of this thermoplastic polymer
Concentration in dimethyl sulfoxide (DMSO) can reach 0.4mg/g.
On the other hand, the stability of the carbon pipe colloidal sol based on preparation, the present invention have selected the PVP of non-electrolyte to coat point
Scattered carbon nanotube, the aggregation without causing carbon pipe avoid carbon nanotube sol and coagulation occur under electrolyte effect.Together
When, since PVP is not only dissolved in water, but also it is dissolved in organic solvent dimethyl sulfoxide (DMSO), therefore be suitble to dialysis, stablized in not destroying carbon nanometer tube
Property under the premise of, the solvent of carbon nanotube of PVP claddings is switched to water phase from organic phase.
Preferably, in the sodium-naphthalene solution and single-walled carbon nanotube, sodium, naphthalene, single-walled carbon nanotube mass ratio be 0.07
~00.9：0.384~0.4：0.2~0.24.When the mass ratio of naphthalene, single-walled carbon nanotube is more than 2, excessive anion is free
Base is easily assembled with positively charged carbon nanotube, and Na (THF) is destroyed]nThe stabilization of NT (sodium-tetrahydrofuran-carbon nanotube) colloidal sol
Property；When the mass ratio of naphthalene, single-walled carbon nanotube is less than 1.6, the repulsive force between carbon nanotube is smaller, molten in polar solvent
Solution property declines.
Preferably, the mass ratio of the single-walled carbon nanotube and covering of the electrification is 1~10：10~1.When single wall carbon is received
When the ratio of mitron and covering is more than 10, the stability of carbon nanotube declines, easily assembles, and dialysis effect is poor；When single wall carbon is received
When the ratio of mitron and covering is less than 1/10, covering ratio is continued growing, dissolubility is promoted not in water to carbon nanotube
Greatly.
Preferably, the polar solvent is dimethyl sulfoxide (DMSO), chloroform, dichloromethane or aromatic solvent.
Preferably, the covering is not only to be dissolved in organic solvent but also be dissolved in the polymer overmold agent of water.
It is furthermore preferred that the polymer overmold agent is polyvinylpyrrolidone PVP, poly- (propionyl ethylenimine -co- is sub-
Ethyl ethamine) PPEI-EI or polyvinylsulfonic acid salt.
Preferably, without being ultrasonically treated in each step of the method.
Preferably, the dialysis processing makes the solvent of single-walled carbon nanotube be converted to water by organic solvent.
The present invention also provides a kind of methods that preferably single-walled carbon nanotube is evenly dispersed, include the following steps：
1) in the glove box of nitrogen protection, 0.384g naphthalenes and 0.07g sodium is dissolved in 100 milliliters of tetrahydrofurans, acutely stirred
Mixing makes all solids all dissolve.
2) above-mentioned naphthalene sodium solution is added in about 200mg single-walled carbon nanotubes (HiPco, NanoIntegris, USA), stirred
After mixing 12 hours, filtering, it is colourless to be used in combination tetrahydrofuran to rinse to efflux.
3) after being dried in vacuo, by 20mg, treated that single-walled carbon nanotube is placed in 50mL dimethyl sulfoxide (DMSO)s, stirring and dissolving.
4) by 50mg polyvinylpyrrolidone (molecular weight：90,000) it is added in the dimethyl sulphoxide solution of carbon pipe, stirring
To being completely dissolved.
5) solution of carbon pipe is taken out in glove box, is exposed in air, imported semi-permeable membrane bag, be placed in and fill distilled water
Beaker in dialysis, and repeatedly replace distilled water.Uniform single-walled carbon nanotube aqueous solution is obtained after the completion of dialysis.
First under inert atmosphere protection, keep carbon nano tube surface all positively charged using the tetrahydrofuran solution of sodium naphthalene
Lotus makes carbon nano-tube bundle thermoplastic polymer in dimethyl sulfoxide solvent with the repulsive force between electrical carbon pipe.Then polyethylene is added
Pyrrolidones protection loses the carbon pipe of charge in air atmosphere and is allowed to keep dispersity.The method for recycling dialysis makes to gather
The dispersion solvent of the single-walled carbon nanotube of vinylpyrrolidone cladding is converted to water by dimethyl sulfoxide (DMSO).
The present invention also provides single-walled carbon nanotube aqueous solutions prepared by the above-mentioned method of any one.The carbon nanometer of the present invention
The concentration of pipe can keep electrification carbon nanotube in the concentration of dimethyl sulfoxide substantially, and both 0.4mg/g, was more than common carbon nanotube
Solubility.Certainly, since the dispersion of carbon nanotube is built upon on the basis with electrical carbon pipe of thermoplastic polymer,
It is dispersed more preferable, just as being shown the characterization result of atomic force microscope (Fig. 3) and transmission electron microscope (Fig. 4).
The present invention also provides above-mentioned single-walled carbon nanotube aqueous solutions to prepare in field emission display, nanoelectronic
Application in device, super-strength composite material.
Beneficial effects of the present invention
(1) the principle of the present invention be based primarily upon electrification single-walled carbon nanotube can in thermoplastic polymer to organic solvent, and
Using the method for being not only dissolved in organic solvent but also being dissolved in the non ionic polymer compound carbon coated pipe of water, and combining dialysis, reach
Single-walled carbon nanotube evenly dispersed and carbon nanotube structure in a solvent and performance are substantially unaffected.
(2) the invention avoids the ultrasound damaged to carbon pipe structure and covalent functionalizations so that complete carbon nanometer
Pipe surface has grafted the group of functionalization, realizes the solubility of single-walled carbon nanotube, while also maintaining single walled carbon nanotubes sheet
The characteristic of the structural intergrity of body and itself.The present invention is simple and practicable, is easy to carry out large-scale industrial production.
(3) preparation method of the present invention is simple, dissolution rate is high, highly practical, easy to spread.
Description of the drawings
Fig. 1 is the flow diagram of the present invention.
Fig. 2 is the photo and microscope photo of the carbon nano-tube aqueous solutions obtained in the embodiment of the present invention 1.
Fig. 3 is 1 obtained carbon nanotube of embodiment of the present invention atomic force microscope images water-dispersed.
Fig. 4 is 1 obtained carbon nanotube of embodiment of the present invention transmission electron microscope picture water-dispersed, shows single wall carbon and receives
The polymolecularity of mitron.
Fig. 5 is ultraviolet-visible-infrared absorpting light spectra of 1 obtained carbon nano-tube aqueous solutions of inventive embodiments, is shown
Obtained single-walled carbon nanotube has very high dispersibility.
Specific implementation mode
Feature of present invention and other correlated characteristics are described in further detail by the following examples, in order to the same industry
The understanding of technical staff：
Embodiment one
1) in the glove box of nitrogen protection, 0.384g naphthalenes and 0.07g sodium is dissolved in 100 milliliters of tetrahydrofurans, acutely stirred
Mixing makes all solids all dissolve.
2) above-mentioned naphthalene sodium solution is added in about 200mg single-walled carbon nanotubes (HiPco, NanoIntegris, USA), stirred
After mixing 12 hours, filtering, it is colourless to be used in combination tetrahydrofuran to rinse to efflux.
3) after being dried in vacuo, by 2.5mg, treated that single-walled carbon nanotube is placed in 50mL dimethyl sulfoxide (DMSO)s, and stirring is molten
Solution.
4) by 50mg polyvinylpyrrolidone (molecular weight：90,000) it is added in the dimethyl sulphoxide solution of carbon pipe, stirring
To being completely dissolved.
5) solution of carbon pipe is taken out in glove box, is exposed in air, imported semi-permeable membrane bag, be placed in and fill distilled water
Beaker in dialysis, and repeatedly replace distilled water.Uniform single-walled carbon nanotube aqueous solution is obtained after the completion of dialysis, solubility is
0.40mg/g。
Embodiment two
It is 0.5mg by the quality adjustment of polyvinylpyrrolidone in step 4) with embodiment 1, other reaction conditions are constant,
Evenly dispersed single-walled carbon nanotube aqueous solution is obtained, solubility is 0.39mg/g.
Embodiment three
It is 1000mg by the quality adjustment of step 4) polyvinylpyrrolidone with embodiment 1, other reaction conditions are constant,
Evenly dispersed single-walled carbon nanotube aqueous solution is obtained, solubility is 0.41mg/g.
Example IV
It is 20.0mg by the quality adjustment of step 3) single-walled carbon nanotube with embodiment 1, other reaction conditions are constant,
Aqueous solution obtains evenly dispersed single-walled carbon nanotube aqueous solution, and solubility is 0.42mg/g.
Embodiment five
It is 10.0mg by the quality adjustment of step 3) single-walled carbon nanotube with embodiment 1, other reaction conditions are constant,
Aqueous solution obtains the single-walled carbon nanotube of coagulation, and solubility is 0.40mg/g.
Embodiment six
With embodiment 1, save step 4), other reaction conditions are constant, obtain the single-walled carbon nanotube of coagulation.
Finally it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not limited to this hair
It is bright, although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still
It can modify to the technical solution recorded in previous embodiment, or equivalent replacement is carried out to which part.It is all in this hair
Within bright spirit and principle, any modification, equivalent replacement, improvement and so on should be included in protection scope of the present invention
Within.Above-mentioned, although the foregoing specific embodiments of the present invention is described with reference to the accompanying drawings, not to the scope of the present invention
Limitation, those skilled in the art should understand that, based on the technical solutions of the present invention, those skilled in the art are not required to
Make the creative labor the various modifications or changes that can be made still within protection scope of the present invention.
Claims (6)
1. a kind of single-walled carbon nanotube method evenly dispersed in aqueous solvent, which is characterized in that including：
Single-walled carbon nanotube is surface-treated using sodium-naphthalene solution, obtains the single-walled carbon nanotube of electrification；
Make the single-walled carbon nanotube self-dispersing of the electrification in polar solvent, using covering it is coated, dialysis to get
Single-walled carbon nanotube aqueous solution；
The covering is polyvinylpyrrolidone PVP；
In the sodium-naphthalene solution and single-walled carbon nanotube, sodium, naphthalene, single-walled carbon nanotube mass ratio be 0.07：0.384~
0.4：0.2~0.24；
The single-walled carbon nanotube of the electrification and the mass ratio of covering are 1 ~ 10：10~1.
2. the method as described in claim 1, which is characterized in that the polar solvent is dimethyl sulfoxide (DMSO), chloroform, dichloromethane
Or aromatic solvent.
3. the method as described in claim 1, which is characterized in that without being ultrasonically treated in each step of the method.
4. the method as described in claim 1, which is characterized in that the dialysis processing makes the solvent of single-walled carbon nanotube by organic
Solvent conversion Cheng Shui.
5. single-walled carbon nanotube aqueous solution prepared by claim 1-4 any one of them methods.
6. single-walled carbon nanotube aqueous solution described in claim 5 is preparing field emission display, nano electron device, superpower
Spend the application in composite material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610946073.9A CN106517152B (en) | 2016-11-02 | 2016-11-02 | Single-walled carbon nanotube method evenly dispersed in aqueous solvent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610946073.9A CN106517152B (en) | 2016-11-02 | 2016-11-02 | Single-walled carbon nanotube method evenly dispersed in aqueous solvent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106517152A CN106517152A (en) | 2017-03-22 |
| CN106517152B true CN106517152B (en) | 2018-08-31 |
Family
ID=58292807
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610946073.9A Active CN106517152B (en) | 2016-11-02 | 2016-11-02 | Single-walled carbon nanotube method evenly dispersed in aqueous solvent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106517152B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109592670A (en) * | 2018-12-20 | 2019-04-09 | 湖北工程学院 | The dispersing method of single-walled carbon nanotube |
| CN109603697B (en) * | 2018-12-24 | 2022-02-15 | 施柏山 | Nano carbon hybrid aerogel and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2494961C2 (en) * | 2011-03-04 | 2013-10-10 | Общество с ограниченной ответственностью "НаноТехЦентр" | Dispersion of carbon nanotubes |
| CN103400991A (en) * | 2013-08-13 | 2013-11-20 | 天奈(镇江)材料科技有限公司 | Water-based carbon nanotube slurry and preparation method thereof |
| CN104445151A (en) * | 2014-12-02 | 2015-03-25 | 张满锦 | Method for preparing water-soluble multi-walled carbon nanotube |
-
2016
- 2016-11-02 CN CN201610946073.9A patent/CN106517152B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2494961C2 (en) * | 2011-03-04 | 2013-10-10 | Общество с ограниченной ответственностью "НаноТехЦентр" | Dispersion of carbon nanotubes |
| CN103400991A (en) * | 2013-08-13 | 2013-11-20 | 天奈(镇江)材料科技有限公司 | Water-based carbon nanotube slurry and preparation method thereof |
| CN104445151A (en) * | 2014-12-02 | 2015-03-25 | 张满锦 | Method for preparing water-soluble multi-walled carbon nanotube |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106517152A (en) | 2017-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Al-Hamadani et al. | Stabilization and dispersion of carbon nanomaterials in aqueous solutions: A review | |
| Hu et al. | Non‐covalent functionalization of carbon nanotubes with surfactants and polymers | |
| Li et al. | Nanocellulose as green dispersant for two-dimensional energy materials | |
| KR101812536B1 (en) | Wet spinningMethod for preparing GO-CNT composite fibers, GO-Graphene composite fibers, GO-Grephene-CNT composite fibers | |
| KR101812534B1 (en) | Method for preparing GO-CNT composite fibers, GO-Graphene composite fibers, GO-Graphene-CNT composite fibers | |
| Zhang et al. | Low percolation threshold in single-walled carbon nanotube/high density polyethylene composites prepared by melt processing technique | |
| Zhang et al. | A review on hybridization modification of graphene and its polymer nanocomposites | |
| JP2004531442A (en) | Method for producing stable suspension and powder of single carbon nanotubes | |
| CN104852021B (en) | Preparation method of graphene/carbon nanotube composite material | |
| Zhao et al. | Electrical conductivity of poly (vinylidene fluoride)/carbon nanotube composites with a spherical substructure | |
| CN108585544B (en) | Method for surface modification of substrate material based on carbon nanotube assembly composite material | |
| CN104845381B (en) | A kind of preparation method of modified multiwalled carbon nanotube material | |
| CN106029564B (en) | High content of carbon nanotubes fluid | |
| CN106517152B (en) | Single-walled carbon nanotube method evenly dispersed in aqueous solvent | |
| CN101177261B (en) | Method for preparing biocompatible cellulose functionalized carbon nano tube | |
| CN105733317A (en) | Preparation method of functionalized carbon nanotube powder | |
| Nicharat et al. | Pre-mixing and masterbatch approaches for reinforcing poly (vinyl acetate) with cellulose based fillers | |
| Pradhan et al. | Oxygen barrier of multiwalled carbon nanotube/polymethyl methacrylate nanocomposites prepared by in situ method | |
| Wu et al. | Length reduction of multi-walled carbon nanotubes via high energy ultrasonication and its effect on their dispersibility | |
| Im et al. | Wet spinning of multi-walled carbon nanotube fibers | |
| CN113620284A (en) | Composite film preparation method, composite film and application | |
| Zhao et al. | Preparation and electrochemical property of CMC/MWCNT composite using ionic liquid as solvent | |
| Cao et al. | The effects of surface modifications of multiwalled carbon nanotubes on their dispersibility in different solvents and poly (ether ether ketone) | |
| Kumar et al. | Novel amino-acid-based polymer/multi-walled carbon nanotube bio-nanocomposites: highly water dispersible carbon nanotubes decorated with gold nanoparticles | |
| PL217280B1 (en) | Method of obtaining the cellulose nanocomposite with in-built carbon nanotubes and the cellulose nanocomposite with the in-built carbon nanotubes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP02 | Change in the address of a patent holder | ||
| CP02 | Change in the address of a patent holder |
Address after: 266590 No. 579, Qian Wan Gang Road, Qingdao economic and Technological Development Zone, Shandong Patentee after: SHANDONG University OF SCIENCE AND TECHNOLOGY Address before: 250031 17 Shengli Zhuang Road, Tianqiao District, Ji'nan, Shandong Patentee before: SHANDONG University OF SCIENCE AND TECHNOLOGY |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230418 Address after: Building 17, No. 1 Liuyanghe Road, Jiaozhou Economic Development Zone, Qingdao, Shandong 266000 Patentee after: Qingdao Hailiwei Nanotechnology Co.,Ltd. Address before: 266590 No. 579, Qian Wan Gang Road, Qingdao economic and Technological Development Zone, Shandong Patentee before: SHANDONG University OF SCIENCE AND TECHNOLOGY |