CN108912350A - A kind of spherical shape aramid fiber nano material and preparation method thereof - Google Patents
A kind of spherical shape aramid fiber nano material and preparation method thereof Download PDFInfo
- Publication number
- CN108912350A CN108912350A CN201810607353.6A CN201810607353A CN108912350A CN 108912350 A CN108912350 A CN 108912350A CN 201810607353 A CN201810607353 A CN 201810607353A CN 108912350 A CN108912350 A CN 108912350A
- Authority
- CN
- China
- Prior art keywords
- aramid fiber
- preparation
- spherical
- water
- nanometer
- 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
Classifications
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/16—Powdering or granulating by coagulating dispersions
-
- 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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino carboxylic acids or of polyamines and polycarboxylic acids
Abstract
The invention belongs to the preparation technical fields of nano material, and in particular to a kind of spherical shape aramid fiber nano material and preparation method thereof.This method obtains aramid fiber nano-solution, nanometer aramid fiber then is precipitated by the way that water is added dropwise, using dispersion, freeze-drying obtains spherical aramid fiber nano material by the way that para-aramid fiber and alkali metal salt to be added in organic solvent.The preparation method is simple, and a nanometer aramid fiber can be successfully isolated from the alkaline solution of aramid fiber.The spherical shape aramid fiber nano material particle diameter distribution is uniform, can be stabilized, and be evenly dispersed into matrix under the conditions of non-alkaline as reinforcement, greatly expand the application range of para-aramid fiber.
Description
Technical field
The invention belongs to the preparation technical fields of nano material, and in particular to a kind of spherical shape aramid fiber nano material and its preparation
Method.
Background technique
The entitled poly terephthalic acid p-phenylenediamine (PPTA) of chemistry of para-aramid fiber, China is referred to as aramid fiber-
1414.Wherein, the para-aramid fiber of trade name Kevlar is the high property succeeded in developing by DuPont Corporation in 1971
It can para-aramid fiber.Para-aramid fiber strand is height-oriented along its length, and has extremely strong interchain force,
Therefore fiber has low unprecedented high intensity, high-modulus and high temperature resistance, acid and alkali-resistance, density, impact resistance, antifatigue, low swollen
The excellent performances such as swollen, thermal conductivity, non-ignitable, not molten are widely used in aerospace industry, national defense industry, automobile industry, heat-resisting
With the various fields such as protective clothes, high-strength rope.Wherein, the most prominent feature of para-aramid fiber is high-intensitive and high-modulus.
The intensity of Kevlar is 3 times of steel, is 4 times of aramid fiber industrial yarn；Its initial modulus is 4~10 times of polyester industrial yarn, is poly-
10 times or more of nylon.In addition, the stability of para-aramid fiber is fine, shrinking percentage is zero at 150 DEG C, 260
At DEG C, it is still able to maintain the 65% of former intensity.
Nano-macromolecule material because having large specific surface area, the features such as surface is easily modified and be widely used.But it has no
Preparation method about spherical aramid fiber nano material is reported.Existing research is the hydrogen extracted on PPTA molecule on amido bond by alkali
Atom forms nitrogen anion, generates electrostatic repulsion, which can contend with intermolecular hydrogen bonding, thus make PPTA with
Nm regime exists in solution.However, nitrogen anion obtains hydrogen original again when alkalinity weakens or is neutralized to neutrality
Son, electrostatic repulsion disappear, and the fiber of Nano grade is assembled again.Therefore the nanometer PPTA to exist in solution is extremely unstable, and
It is unfavorable for being used in combination with other materials.
Summary of the invention
It is in order to overcome the shortcomings of the prior art and insufficient, the primary purpose of the present invention is that providing a kind of spherical aramid fiber nanometer material
The preparation method of material.
Another object of the present invention is to provide the spherical aramid fiber nano materials obtained by above-mentioned preparation method.
To achieve the above object, the technical solution adopted by the present invention is as follows：
A kind of preparation method of spherical shape aramid fiber nano material, includes the following steps：By para-aramid fiber and alkali metal salt
It is added into organic solvent, obtains mixed solution, stir, obtain aramid fiber nano-solution, water, which is added, is precipitated nanometer aramid fiber, centrifugation
Washing, obtains a nanometer aramid fiber, adds water, a nanometer aramid fiber is made to be uniformly dispersed, obtain a nanometer aramid fiber dispersion liquid, is freeze-dried, i.e.,
Obtain the spherical aramid fiber nano material.
Preferably, the para-aramid fiber is pre-processed before use, and pre-treatment step is by p-aramid fiber fibre
Dimension is cut into the chopped strand of 1~2cm, and ethyl alcohol is added and carries out ultrasound, takes out, washes with water, is dried in vacuo, it is pretreated right to obtain
Position aramid fiber, is then added with alkali metal salt into organic solvent again, carries out subsequent step.
It is furthermore preferred that the volume of addition ethyl alcohol and the mass ratio of chopped strand is 100:1~150:1mL/g.
It is furthermore preferred that when a length of 4~6h of the described ultrasound.
It is furthermore preferred that the vacuum drying condition is dry 12~48h at 25~70 DEG C.
Preferably, the organic solvent be n,N-Dimethylformamide, dimethyl sulfoxide, N-Methyl pyrrolidone and N,
One or more of N- dimethyl acetamide.
Preferably, the alkali metal salt is one or more of potassium hydroxide, calcium chloride and lithium chloride.
Preferably, in the mixed solution, the mass ratio of para-aramid fiber and alkali metal salt is 1:1~1:1.5.
Preferably, in the mixed solution, the solid-to-liquid ratio of para-aramid fiber and organic solvent is 1:500g/mL.
Preferably, the mode of the stirring is magnetic agitation, and when stirring is 7~10 days a length of.
The aramid fiber nano-solution is kermesinus stablizing solution.
Preferably, water deionized water when nanometer aramid fiber is precipitated in the addition water, additional amount are that aramid fiber nanometer is molten
1~4 times of liquid product.
Preferably, 2~6 drops/sec of rate of addition of water when nanometer aramid fiber is precipitated in the addition water.
Preferably, the mode of the centrifuge washing is that water eccentric cleaning is used under 4000~15000 revs/min of rate,
Until the water after cleaning is in neutrality, and organic solvent is cleaned.
Preferably, the amount for adding water is 6~10 times of the volume of nanometer aramid fiber.
Preferably, described to make 5~10min of the finely dispersed mode ultrasonic disperse of nanometer aramid fiber.
Preferably, the mode of the freeze-drying is to freeze nanometer aramid fiber dispersion liquid liquid nitrogen in fact, then be freeze-dried 24
~48h.
The present invention further provides the spherical aramid fiber nano material obtained by above-mentioned preparation method, the spherical shape aramid fiber nanometer
The particle size range of material is 20~500nm.
Compared with prior art, the present invention having the following advantages that and beneficial effect：
The present invention obtains aramid fiber nano-solution, so by the way that para-aramid fiber and alkali metal salt to be added in organic solvent
Nanometer aramid fiber is precipitated by the way that water is added dropwise afterwards, using dispersion, freeze-drying obtains spherical aramid fiber nano material.The preparation side
Method is simple, and a nanometer aramid fiber can be successfully isolated from the alkaline solution of aramid fiber.The spherical shape aramid fiber nano material partial size point
Cloth is uniform, can be stabilized under the conditions of non-alkaline, and be evenly dispersed into matrix as reinforcement, greatly expands pair
The application range of position aramid fiber.
Detailed description of the invention
Fig. 1 is the SEM figure of spherical aramid fiber nano material prepared by embodiment 1.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.For not specifically specified technological parameter, routine techniques progress can refer to.
Embodiment 1
The present embodiment provides a kind of spherical aramid fiber nano materials and preparation method thereof.
Kevlar fiber is cut into the chopped strand of 1~2cm, weighs the Kevlar chopped strand of 1g, 150ml second is added
Alcohol is ultrasonically treated 6h, and after taking-up plus water cleans, 48 hours dry in 60 DEG C of vacuum drying oven, obtains pretreated Kevlar
Fiber.The N,N-dimethylformamide for taking the pretreated Kevlar fiber of 0.5g and 0.75g potassium hydroxide to be added to 250ml is organic
In solvent, magnetic agitation 7 days, obtain kermesinus aramid fiber nano-solution, then deionization is added dropwise with 2 drops/sec of speed at room temperature
Nanometer aramid fiber is precipitated in water 250ml, uses water eccentric cleaning 6 times under 8000 revolutions per seconds of speed, obtains a nanometer aramid fiber, addition is received
6 times of deionized water of meter Fang Lun volume, ultrasonic disperse 5min obtain a nanometer aramid fiber dispersion liquid, are frozen in fact with liquid nitrogen, then freeze dry
Dry 48h to get arrive the spherical aramid fiber nano material.
As shown in Figure 1, the uniform particle sizes for the spherical aramid fiber nano material that the present embodiment is prepared, average grain diameter are
120nm or so.
Embodiment 2
The present embodiment provides a kind of spherical aramid fiber nano materials and preparation method thereof.
Kevlar fiber is cut into the chopped strand of 1~2cm, weighs the Kevlar chopped strand of 1g, 150ml second is added
Alcohol is ultrasonically treated 6h, and after taking-up plus water cleans, 48 hours dry in 60 DEG C of vacuum drying oven, obtains pretreated Kevlar
Fiber.The pretreated Kevlar fiber of 0.5g and 0.75g potassium hydroxide is taken to be added to the dimethyl sulfoxide organic solvent of 250ml
In, magnetic agitation 7 days, obtain kermesinus aramid fiber nano-solution, then deionized water is added dropwise with 2 drops/sec of speed at room temperature
Nanometer aramid fiber is precipitated in 500ml, uses water eccentric cleaning 6 times under 15000 revolutions per seconds of speed, obtains a nanometer aramid fiber, addition is received
6 times of deionized water of meter Fang Lun volume, ultrasonic disperse 5min obtain a nanometer aramid fiber dispersion liquid, are frozen in fact with liquid nitrogen, then freeze dry
Dry 48h to get arrive the spherical aramid fiber nano material.
The partial size of resulting spherical shape aramid fiber nano material is 500nm or so.
Embodiment 3
The present embodiment provides a kind of spherical aramid fiber nano materials and preparation method thereof.
Kevlar fiber is cut into the chopped strand of 1~2cm, weighs the Kevlar chopped strand of 1g, 150ml second is added
Alcohol is ultrasonically treated 6h, and after taking-up plus water cleans, 48 hours dry in 60 DEG C of vacuum drying oven, obtains pretreated Kevlar
Fiber.The DMAC N,N' dimethyl acetamide for taking the pretreated Kevlar fiber of 0.5g and 0.57g lithium chloride to be added to 250ml is organic molten
In agent, magnetic agitation 7 days, obtain kermesinus aramid fiber nano-solution, then deionized water is added dropwise with 4 drops/sec of speed at room temperature
Nanometer aramid fiber is precipitated in 250ml, uses water eccentric cleaning 8 times under 4000 revolutions per seconds of speed, obtains a nanometer aramid fiber, and nanometer is added
8 times of deionized water of aramid fiber volume, ultrasonic disperse 5min obtain a nanometer aramid fiber dispersion liquid, are frozen in fact with liquid nitrogen, then be freeze-dried
48h to get arrive the spherical aramid fiber nano material.
The partial size of resulting spherical shape aramid fiber nano material is 200nm or so.
Embodiment 4
The present embodiment provides a kind of spherical aramid fiber nano materials and preparation method thereof.
Kevlar fiber is cut into the chopped strand of 1~2cm, weighs the Kevlar chopped strand of 1g, 100ml second is added
Alcohol is ultrasonically treated 4h, and after taking-up plus water cleans, 36 hours dry in 70 DEG C of vacuum drying oven, obtains pretreated Kevlar
Fiber.The pretreated Kevlar fiber of 0.5g and 0.74g calcium chloride is taken to be added to the N-Methyl pyrrolidone organic solvent of 250ml
In, magnetic agitation 7 days, obtain kermesinus aramid fiber nano-solution, then deionized water is added dropwise with 2 drops/sec of speed at room temperature
Nanometer aramid fiber is precipitated in 750ml, uses water eccentric cleaning 8 times under 4000 revolutions per seconds of speed, obtains a nanometer aramid fiber, and nanometer is added
6 times of deionized water of aramid fiber volume, ultrasonic disperse 8min obtain a nanometer aramid fiber dispersion liquid, are frozen in fact with liquid nitrogen, then be freeze-dried
48h to get arrive the spherical aramid fiber nano material.
The uniform particle sizes for the spherical aramid fiber nano material that the present embodiment is prepared, average grain diameter are 20nm or so.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of spherical shape aramid fiber nano material, which is characterized in that include the following steps：By para-aramid fiber and
Alkali metal salt is added into organic solvent, obtains mixed solution, and stirring obtains aramid fiber nano-solution, and water, which is added, makes a nanometer aramid fiber
It is precipitated, centrifuge washing obtains a nanometer aramid fiber, adds water, so that a nanometer aramid fiber is uniformly dispersed, obtain a nanometer aramid fiber dispersion liquid, cold
It is lyophilized dry to get to the spherical aramid fiber nano material.
2. the preparation method of spherical shape aramid fiber nano material according to claim 1, it is characterised in that：The p-aramid fiber
Fiber is pre-processed before use, and pre-treatment step is the chopped strand that para-aramid fiber is cut into 1~2cm, and second is added
Alcohol carries out ultrasound, takes out, washes with water, and is dried in vacuo, obtains pretreated para-aramid fiber, then add again with alkali metal salt
Enter into organic solvent, carries out subsequent step.
3. the preparation method of spherical shape aramid fiber nano material according to claim 2, it is characterised in that：
The volume of addition ethyl alcohol and the mass ratio of chopped strand is 100:1~150:1mL/g；
When a length of 4~6h of the described ultrasound；
The vacuum drying condition is dry 12~48h at 25~70 DEG C.
4. the preparation method of described in any item spherical aramid fiber nano materials according to claim 1~3, it is characterised in that：
The organic solvent is N,N-dimethylformamide, dimethyl sulfoxide, N-Methyl pyrrolidone and N, N- dimethyl second
One or more of amide；
The alkali metal salt is one or more of potassium hydroxide, calcium chloride and lithium chloride.
5. the preparation method of described in any item spherical aramid fiber nano materials according to claim 1~3, it is characterised in that：
In the mixed solution, the mass ratio of para-aramid fiber and alkali metal salt is 1:1~1:1.5；
In the mixed solution, the solid-to-liquid ratio of para-aramid fiber and organic solvent is 1:500g/mL.
6. the preparation method of described in any item spherical aramid fiber nano materials according to claim 1~3, it is characterised in that：
Water deionized water when nanometer aramid fiber is precipitated in the addition water, the amount that water is added is aramid fiber nano-solution volume
1~4 times；The speed that water is added is 2~6 drops/sec.
7. the preparation method of described in any item spherical aramid fiber nano materials according to claim 1~3, it is characterised in that：It is described
The mode of stirring be magnetic agitation, when stirring, is 7~10 days a length of.
8. the preparation method of described in any item spherical aramid fiber nano materials according to claim 1~3, it is characterised in that：It is described
The mode of centrifuge washing be that water eccentric cleaning is used under 4000~15000 revs/min of rate, until the water after cleaning is in
Property, and organic solvent is cleaned.
9. the preparation method of described in any item spherical aramid fiber nano materials according to claim 1~3, it is characterised in that：
The amount for adding water is 6~10 times of the volume of nanometer aramid fiber；
Described makes 5~10min of the finely dispersed mode ultrasonic disperse of nanometer aramid fiber；
The mode of the freeze-drying is to freeze nanometer aramid fiber dispersion liquid liquid nitrogen in fact, then be freeze-dried 24~48h.
10. a kind of spherical shape aramid fiber nano material, it is characterised in that：The preparation method as described in claim 1~9 obtains.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810607353.6A CN108912350B (en) | 2018-06-13 | 2018-06-13 | Spherical aramid fiber nano material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810607353.6A CN108912350B (en) | 2018-06-13 | 2018-06-13 | Spherical aramid fiber nano material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108912350A true CN108912350A (en) | 2018-11-30 |
| CN108912350B CN108912350B (en) | 2021-05-07 |
Family
ID=64419254
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810607353.6A Active CN108912350B (en) | 2018-06-13 | 2018-06-13 | Spherical aramid fiber nano material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108912350B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111254701A (en) * | 2020-03-12 | 2020-06-09 | 鲁东大学 | Aramid nanofiber composite material, preparation method thereof and application of aramid nanofiber composite material in adsorption of Hg ions in solution |
| CN111266136A (en) * | 2020-03-12 | 2020-06-12 | 鲁东大学 | Aramid nanofiber composite material, preparation method thereof and application thereof in photocatalytic degradation of rhodamine b |
| CN113969427A (en) * | 2021-09-07 | 2022-01-25 | 华南理工大学 | Aramid micro-nanofiber with net-shaped structure and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5260846A (en) * | 1975-11-14 | 1977-05-19 | Unitika Ltd | Process for preparing aromatic polyamide powder |
| CN103937238A (en) * | 2014-04-16 | 2014-07-23 | 鲁东大学 | Novel spherical nanometer aramid fiber material and preparation method thereof |
-
2018
- 2018-06-13 CN CN201810607353.6A patent/CN108912350B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5260846A (en) * | 1975-11-14 | 1977-05-19 | Unitika Ltd | Process for preparing aromatic polyamide powder |
| CN103937238A (en) * | 2014-04-16 | 2014-07-23 | 鲁东大学 | Novel spherical nanometer aramid fiber material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| S.IFUKU ET AL.: ""Facile preparation of aramid nanofibers from Twaron fibers by a downsizing process"", 《RSC ADV.》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111254701A (en) * | 2020-03-12 | 2020-06-09 | 鲁东大学 | Aramid nanofiber composite material, preparation method thereof and application of aramid nanofiber composite material in adsorption of Hg ions in solution |
| CN111266136A (en) * | 2020-03-12 | 2020-06-12 | 鲁东大学 | Aramid nanofiber composite material, preparation method thereof and application thereof in photocatalytic degradation of rhodamine b |
| CN111266136B (en) * | 2020-03-12 | 2022-08-12 | 鲁东大学 | Aramid nanofiber composite material, preparation method thereof and application thereof in photocatalytic degradation of rhodamine b |
| CN113969427A (en) * | 2021-09-07 | 2022-01-25 | 华南理工大学 | Aramid micro-nanofiber with net-shaped structure and preparation method and application thereof |
| CN113969427B (en) * | 2021-09-07 | 2022-09-06 | 华南理工大学 | Aramid micro-nanofiber with net-shaped structure and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108912350B (en) | 2021-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108912350A (en) | A kind of spherical shape aramid fiber nano material and preparation method thereof | |
| WO2017050220A1 (en) | Preparation method for para-aramid fiber | |
| Gore et al. | Functionalized aramid fibers and composites for protective applications: a review | |
| Kausar | Advances in carbon fiber reinforced polyamide-based composite materials | |
| CN105219018A (en) | A kind of preparation method of modified carbon fiber reinforced polyether ether ketone matrix material | |
| CN103739903B (en) | A kind of High-conductivity carbon nanotube/rubber nanocomposite and preparation method thereof | |
| CN103808210A (en) | Low-cost high-strength flexible protective material and preparation method thereof | |
| Chuah et al. | Phase separation in poly (p-phenylene benzobisthiazole)/nylon 66 molecular composite | |
| CN108316039B (en) | A kind of method that mechanical couplings chemistry alkali soluble method prepares aramid nano-fiber | |
| CN101899723A (en) | Manufacturing has the method for the conductibility composite fibre of nanotube at high proportion | |
| CN104211056B (en) | A kind of preparation method of high strength graphite alkene film | |
| CN110358113B (en) | Preparation method of aramid nanofiber aqueous dispersion | |
| WO2019066028A1 (en) | Fiber-reinforced composite material, additive for fiber-reinforced composite material, and method for producing fiber-reinforced composite material | |
| CN108864445A (en) | Nanometer chitin hydrogel, aeroge and its preparation method and application | |
| CN108424563A (en) | The high-performance rubber composite material and preparation method of nanofiber is drawn containing Kev | |
| CN110373814A (en) | P-aramid fiber nano fibrous membrane and preparation method thereof | |
| CN108277546A (en) | A kind of preparation method of anti-cutting polyethylene fibre | |
| Wang et al. | Evolution of anisotropic bubbles and transition of the mechanical and electrical properties during a non-continuous two-step foaming of epoxy/carbon nanofiber composites | |
| Patil et al. | Review on fabrication and applications of ultrafine particles from animal protein fibres | |
| WO2015049567A1 (en) | Sizing agent for carbon fiber, carbon fiber, carbon fiber-reinforced composite material, and method of producing carbon fiber-reinforced composite material | |
| WO2005108497A1 (en) | Nano-wool emulsion and nano-wool powders, the manufacturing method for them and their uses | |
| CN101476173A (en) | Direct spinning process for preparing PPTA fibre by end capping resin method | |
| CN106147210A (en) | A kind of composite glass fiber strengthens resin material and preparation method thereof | |
| Hu et al. | Chitin nanocrystals reticulated self‐assembled architecture reinforces deproteinized natural rubber latex film | |
| CN106046766B (en) | A kind of automobile plastic high intensity modified nylon materials |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 400700 5, No. 74 Yun He road, Beibei District, Chongqing. Applicant after: ZHONGKE GUANGHUA (CHONGQING) NEW MATERIAL RESEARCH INSTITUTE Co.,Ltd. Applicant after: Zhongke Testing Technology Service (Guangzhou) Co.,Ltd. Applicant after: CAS GUANGZHOU CHEMISTRY Co.,Ltd. Applicant after: University OF CHINESE ACADEMY OF SCIENCES Address before: 400700 5, No. 74 Yun He road, Beibei District, Chongqing. Applicant before: ZHONGKE GUANGHUA (CHONGQING) NEW MATERIAL RESEARCH INSTITUTE Co.,Ltd. Applicant before: GUANGZHOU CAS TESTING TECHNOLOGY SERVICE Co.,Ltd. Applicant before: CAS GUANGZHOU CHEMISTRY Co.,Ltd. Applicant before: University OF CHINESE ACADEMY OF SCIENCES |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |