CN109401142B - A kind of PVDF matrix composite material with sea-island structure and preparation method thereof - Google Patents
A kind of PVDF matrix composite material with sea-island structure and preparation method thereof Download PDFInfo
- Publication number
- CN109401142B CN109401142B CN201811261852.0A CN201811261852A CN109401142B CN 109401142 B CN109401142 B CN 109401142B CN 201811261852 A CN201811261852 A CN 201811261852A CN 109401142 B CN109401142 B CN 109401142B
- Authority
- CN
- China
- Prior art keywords
- composite material
- sea
- pvdf
- island structure
- polyvinylidene fluoride
- 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
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/16—Homopolymers or copolymers or vinylidene fluoride
-
- 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
- C08K2201/001—Conductive additives
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
本发明提供一种具有海岛结构的PVDF基复合材料及其制备方法，属于复合材料制备领域。该复合材料具有海岛结构，是将聚偏氟乙烯、乙烯‑丙烯酸甲酯‑甲基丙烯酸环氧丙酯和碳纳米管先进行熔融共混，然后经过热压和冷压，脱模后得到的。本发明还提供一种具有海岛结构的PVDF基复合材料的制备方法。本发明的复合材料介电常数高达794，此时介电损耗仅为0.81。
The invention provides a PVDF-based composite material with a sea-island structure and a preparation method thereof, belonging to the field of composite material preparation. The composite material has a sea-island structure, and is obtained by melting and blending polyvinylidene fluoride, ethylene-methyl acrylate-glycidyl methacrylate and carbon nanotubes, then hot pressing and cold pressing, and demolding. . The invention also provides a preparation method of the PVDF-based composite material with sea-island structure. The dielectric constant of the composite material of the present invention is as high as 794, and the dielectric loss is only 0.81 at this time.
Description
Technical Field
The invention relates to the field of composite material preparation, in particular to a PVDF (polyvinylidene fluoride) based composite material with a sea-island structure and a preparation method thereof.
Background
In recent years, with the rapid development of the electronic industry, people have made demands for flexibility, light weight, intelligence, portability, and the like on electronic products. Embedding a large number of passive components inside a circuit board to achieve circuit board miniaturization is one of the solutions to achieve the above-described requirements. The capacitor as an important energy storage element is difficult to integrate at present, and the reason is mainly limited by the high dielectric material matched with the capacitor. The traditional high dielectric material is difficult to meet the advanced electronic technical requirements due to the harsh processing conditions, high brittleness and the like. Therefore, in order to solve the integration of the capacitor and the miniaturization of the circuit board, the development of new dielectric materials is urgent. Most high molecular polymers have a series of advantages of insulating property, excellent processability, better mechanical property, low density and the like, but the dielectric constant is lower. Accordingly, in recent years, many researchers have conducted extensive research into polymer-based dielectric composites in order to prepare high-performance dielectric materials to meet the rapidly-developing demands of the related art.
Polymer-based dielectric composites can be broadly classified into two types according to their filler differences: firstly, a polymer dielectric composite material filled with ceramic particles; the other is a conductive ion filled polymer dielectric composite. For the dielectric composite material filled with ceramic particles, the dielectric constant of the system is obviously improved when the content of the filler is generally required to be higher, and the mechanical property of the material is reduced and the processing property of the material is also reduced due to a large amount of filled ceramic particles. The dielectric constant can be obviously improved under the condition of low filler content by adding the conductive filler into the high-molecular matrix, but the dielectric loss is increased due to easy agglomeration because the surface energy of a series of nano conductive fillers such as carbon nano tubes, graphene and the like is larger. Researchers have achieved good dispersion of fillers and suppression of dielectric loss by surface treatment of fillers or preparation of composites with special structures.
Polyvinylidene fluoride (PVDF) has a relatively high dielectric constant compared with other polymers, and has the properties of chemical corrosion resistance, high temperature resistance, radiation resistance and the like, so that the PVDF is used as a collective material for the preparation and research of high-dielectric composite materials in a large number.
Disclosure of Invention
The invention aims to solve the problems that the existing composite material cannot simultaneously meet the requirements of high dielectric constant and low dielectric loss, and provides a PVDF-based composite material with an island structure and a preparation method thereof.
The invention firstly provides a PVDF-based composite material with a sea-island structure, which is prepared by firstly carrying out melt blending on polyvinylidene fluoride, ethylene-methyl acrylate-glycidyl methacrylate and carbon nano tubes, then carrying out hot pressing and cold pressing, and demoulding.
Preferably, the carbon nanotube is a carbon nanotube with a carboxyl group on the surface.
The invention also provides a preparation method of the PVDF-based composite material with the sea-island structure, which comprises the following steps:
the method comprises the following steps: performing melt blending on polyvinylidene fluoride, ethylene-methyl acrylate-glycidyl methacrylate and carbon nano tubes to obtain a polyvinylidene fluoride/ethylene-methyl acrylate-glycidyl methacrylate/carbon nano tube compound;
step two: and (3) placing the polyvinylidene fluoride/ethylene-methyl acrylate-glycidyl methacrylate/carbon nanotube composite obtained in the first step into a mould for hot pressing, then transferring the mould into a cold press for cold pressing, and demoulding to obtain the PVDF-based composite material with the sea-island structure.
Preferably, in the first step, the mass ratio of the polyvinylidene fluoride, the ethylene-methyl acrylate-glycidyl methacrylate and the carbon nanotubes is (87.5-90): 10: (0.5-2.5).
Preferably, in the first step, the mass ratio of the polyvinylidene fluoride, the ethylene-methyl acrylate-glycidyl methacrylate to the carbon nanotubes is 88: 10: 2.
preferably, the melt blending temperature in the first step is 190-.
Preferably, the hot pressing temperature of the second step is 190-220 ℃, the pressure is 8-13MPa, and the hot pressing time is 5-10 minutes.
Preferably, the step two is cold pressing at a pressure of 8-13 Mpa.
The invention has the advantages of
The invention provides a PVDF-based composite material with a sea-island structure and a preparation method thereof, the composite material takes polyvinylidene fluoride as a matrix, ethylene-methyl acrylate-glycidyl methacrylate (E-MA-GMA) with poor compatibility with PVDF is taken as an island phase to be distributed in the PVDF matrix, carbon nano tubes with carboxyl on the surface are taken as conductive fillers to be subjected to melt blending with PVDF and E-MA-GMA, wherein the carbon nano tubes with carboxyl on the surface can react with the E-MA-GMA in the melt blending process, so that the carbon nano tubes are selectively distributed in the E-MA-GMA phase, and E-MA-GMA molecules reacted with the carbon nano tubes can be coated on the surfaces of the carbon nano tubes, thereby effectively reducing the contact among the carbon nano tubes, and ensuring that the obtained composite material has high dielectric constant, The dielectric loss is low, and the experimental result shows that: the dielectric constant of the composite material of the invention is as high as 794(1KHz), and the dielectric loss is only 0.81. Meanwhile, the preparation method is simple and the raw materials are easy to obtain.
Drawings
FIG. 1 is a schematic diagram of the process for preparing the composite material and the sea-island structure of the composite material according to the present invention.
FIG. 2 is a scanning electron micrograph of the composite obtained in example 1;
FIG. 3 is a graph showing the relationship between the dielectric constant and the dielectric loss at 1KHz measured at room temperature for the composite materials obtained in examples 1 to 5, as a function of the mass fraction of carbon nanotubes;
FIG. 4 is a graph showing the relationship between the dielectric constant and the dielectric loss at 1KHz, measured at room temperature, of the composite material prepared in comparative example 1, and the change in the mass fraction of carbon nanotubes.
Detailed Description
The invention firstly provides a PVDF-based composite material with a sea-island structure, which is prepared by firstly carrying out melt blending on polyvinylidene fluoride, ethylene-methyl acrylate-glycidyl methacrylate and carbon nano tubes, then carrying out hot pressing and cold pressing, and demoulding.
According to the invention, the polyvinylidene fluoride, the ethylene-methyl acrylate-glycidyl methacrylate and the carbon nano tube are commercially available, and the preferable model of the polyvinylidene fluoride (PVDF) is Solef 6010; ethylene-methyl acrylate-glycidyl methacrylate (E-MA-GMA) is preferably LOTADER AX8900 of Arkema, and the carbon nanotube is preferably a carbon nanotube with carboxyl on the surface, and is preferably TNMC3 of Chengdu organic chemistry, Inc., of Chinese academy of sciences.
The composite material is prepared by taking polyvinylidene fluoride as a matrix, taking ethylene-methyl acrylate-glycidyl methacrylate which is poor in compatibility with PVDF as an island phase to be distributed in the PVDF matrix, taking carbon nanotubes with carboxyl on the surface as a conductive filler to be subjected to melt blending with PVDF and E-MA-GMA, wherein the carbon nanotubes with carboxyl on the surface can react with the E-MA-GMA in the melt blending process, so that the carbon nanotubes are selectively distributed in the E-MA-GMA phase, and E-MA-GMA molecules reacted with the carbon nanotubes can be coated on the surfaces of the carbon nanotubes, thereby effectively reducing the contact among the carbon nanotubes.
The present invention also provides a method for preparing a PVDF-based composite material having an island-in-sea structure, wherein the process schematic diagram of the composite material and the island-in-sea structure schematic diagram of the composite material are shown in fig. 1, and the method comprises:
the method comprises the following steps: putting polyvinylidene fluoride, ethylene-methyl acrylate-glycidyl methacrylate and carbon nano tubes into a torque rheometer for melt blending to obtain a polyvinylidene fluoride/ethylene-methyl acrylate-glycidyl methacrylate/carbon nano tube compound;
step two: placing the polyvinylidene fluoride/ethylene-methyl acrylate-glycidyl methacrylate/carbon nanotube composite obtained in the first step into a mold for hot pressing, then transferring the composite into a cold press for cold pressing until the mold is cooled to be below the deformation temperature of PVDF, and demolding to obtain the PVDF-based composite material with the sea-island structure.
According to the invention, in the first step, the mass ratio of polyvinylidene fluoride, ethylene-methyl acrylate-glycidyl methacrylate and carbon nanotubes is preferably (87.5-90): 10: (0.5-2.5), more preferably (88-89): 10: (1-2), most preferably 88: 10: 2; when the mass fraction of the carbon nanotubes is less than 2%, the dielectric loss of the material is only slightly reduced, but the dielectric constant of the material is greatly reduced. When the content of the carbon nanotubes is higher than 2%, although the dielectric constant is greatly improved, the dielectric loss is obviously improved.
According to the invention, the melt blending temperature in the first step is preferably 190-.
According to the invention, the hot-pressing temperature of the second step is preferably 190-220 ℃, the pressure is preferably 8-13MPa, and the hot-pressing time is preferably 5-10 minutes.
According to the invention, the second step is preferably carried out by cold pressing at a pressure of 8-13 MPa.
In order to make the other advantages and technical solutions of the present invention clearer, the present invention is described in detail below with reference to specific embodiments.
Example 1
Polyvinylidene fluoride, ethylene-methyl acrylate-glycidyl methacrylate and carbon nanotubes are mixed according to the mass ratio of 88: 10: 2, putting the mixture into a torque rheometer to perform melt blending, wherein the blending temperature is 200 ℃, the rotor speed is 60 revolutions per minute, and the blending time is 5 minutes, so as to obtain a polyvinylidene fluoride/ethylene-methyl acrylate-glycidyl methacrylate/carbon nanotube compound;
placing the polyvinylidene fluoride/ethylene-methyl acrylate-glycidyl methacrylate/carbon nanotube composite in a mold, heating to 200 ℃, hot-pressing for 5 minutes under the pressure of 10MPa, and demolding after the mold is cooled to be below the PVDF deformation temperature under the pressure condition to obtain the composite material.
FIG. 2 is a scanning electron micrograph of the composite obtained in example 1; wherein (a) is an image without the addition of carbon nanotubes; (b) the image is the image when the mass fraction of the carbon nano tube is 2 wt%; (c) and (d) scanning electron microscope images after etching respectively corresponding to the (a) and the (b). The existence of sea-island structure is evident from (a) in fig. 2, and the carbon nanotubes selectively distributed in the E-MA-GMA are marked by circles in (b). (c) The formation of the sea-island structure can be further confirmed after the etching of the E-MA-GMA corresponding to the electron microscope image after the etching treatment (a) and the formation of the sea-island structure can be further confirmed after the etching of the E-MA-GMA corresponding to the electron microscope image after the etching treatment (b) and the electron microscope image after the etching treatment (d) is obvious from the figure.
The dielectric constant and the dielectric loss of the composite material prepared in example 1 were measured by an ac impedance meter, and the results are shown in fig. 3, in which when the mass fraction of the carbon nanotubes is 2 wt%, the dielectric constant of the material is 794, and the dielectric loss is only 0.81.
Example 2
The procedure and conditions were the same as in example 1 except that polyvinylidene fluoride, ethylene-methyl acrylate-glycidyl methacrylate, and carbon nanotubes were mixed in a mass ratio of 89: 10: 1 is added.
The dielectric constant and the dielectric loss of the composite material prepared in example 2 were measured by an ac impedance meter, and the result is shown in fig. 3, in which the dielectric constant of the material at 1000 hz was 22, and the dielectric loss was 0.057.
Example 3
The procedure and conditions were the same as in example 1, except that polyvinylidene fluoride, ethylene-methyl acrylate-glycidyl methacrylate, and carbon nanotubes were mixed in a mass ratio of 88.5: 10: 1.5 addition.
The dielectric constant and the dielectric loss of the composite material prepared in example 3 were measured by an ac impedance meter, and the result is shown in fig. 3, in which the dielectric constant of the material at 1000 hz was 180 and the dielectric loss was 0.622.
Example 4
The procedure and conditions were the same as in example 1, except that polyvinylidene fluoride, ethylene-methyl acrylate-glycidyl methacrylate, and carbon nanotubes were mixed in a mass ratio of 88.25: 10: 1.75 is added.
The dielectric constant and the dielectric loss of the composite material obtained in example 4 were measured by an ac impedance meter, and the result is shown in fig. 3, in which the dielectric constant 563 was obtained at 1000 hz, and the dielectric loss was 0.749.
Example 5
The procedure and conditions were the same as in example 1 except that polyvinylidene fluoride, ethylene-methyl acrylate-glycidyl methacrylate, and carbon nanotubes were mixed in a mass ratio of 87.5: 10: 2.5 addition.
The dielectric constant and the dielectric loss of the composite material obtained in example 5 were measured by an ac impedance meter, and the result is shown in fig. 3, in which the dielectric constant of the material at 1000 hz was 1286, and the dielectric loss was 2.2.
Comparative example 1
The steps and conditions are the same as those of example 1, except that E-MA-GMA is not added in the steps, and the mass ratio of polyvinylidene fluoride to carbon nanotubes is (97.5-99): (1-2.5) adding.
The dielectric constant and the dielectric loss of the composite material prepared in comparative example 1 were measured by an ac impedance meter, and the results are shown in fig. 4, in which the dielectric constant of the carbon nanotube was 3326 when the carbon nanotube mass fraction was 2 wt% and the frequency was 1000 hz, but the dielectric loss was 799.
Comparative example 2
The procedure and conditions were the same as in example 1 except that polyvinylidene fluoride, ethylene-methyl acrylate-glycidyl methacrylate, and carbon nanotubes were mixed in a mass ratio of 93: 5: 2 is added.
The dielectric constant and the dielectric loss of the composite material obtained in comparative example 2 were obtained by the ac group counseling test, and the dielectric constant and the dielectric loss were 1862 and 347, respectively, when the mass fraction of the carbon nanotubes was 2% and the frequency was 1000 hz.
Comparative example 3
The procedure and conditions were the same as in example 1 except that polyvinylidene fluoride, ethylene-methyl acrylate-glycidyl methacrylate, and carbon nanotubes were mixed in a mass ratio of 83: 15: 2 is added.
The dielectric constant and the dielectric loss of the composite material obtained in comparative example 3 were obtained by the ac group counseling test, and the dielectric constant and the dielectric loss were 339 and 0.64, respectively, when the mass fraction of the carbon nanotube was 2% and the frequency was 1000 hz.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811261852.0A CN109401142B (en) | 2018-10-26 | 2018-10-26 | A kind of PVDF matrix composite material with sea-island structure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811261852.0A CN109401142B (en) | 2018-10-26 | 2018-10-26 | A kind of PVDF matrix composite material with sea-island structure and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109401142A CN109401142A (en) | 2019-03-01 |
| CN109401142B true CN109401142B (en) | 2021-04-27 |
Family
ID=65469402
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811261852.0A Active CN109401142B (en) | 2018-10-26 | 2018-10-26 | A kind of PVDF matrix composite material with sea-island structure and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109401142B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109942996B (en) * | 2019-04-03 | 2020-08-25 | 西安交通大学 | Composite material preparation method and composite material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101778903A (en) * | 2007-07-06 | 2010-07-14 | 独立行政法人产业技术综合研究所 | Structural body comprising filler and incompatible resin or elastomer, and production process or use thereof |
| CN102977524A (en) * | 2012-06-30 | 2013-03-20 | 杭州师范大学 | Polyvinylidene fluoride composite material and preparation method thereof |
| CN103289258A (en) * | 2013-06-18 | 2013-09-11 | 上海第二工业大学 | High-dielectric composite material, as well as preparation method and application thereof |
| CN105602066A (en) * | 2016-02-18 | 2016-05-25 | 四川大学 | Polyethylene/nylon composite material and preparation method thereof |
| WO2017155106A1 (en) * | 2016-03-11 | 2017-09-14 | 旭硝子株式会社 | Fluororesin composition, molding material, and molded object |
-
2018
- 2018-10-26 CN CN201811261852.0A patent/CN109401142B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101778903A (en) * | 2007-07-06 | 2010-07-14 | 独立行政法人产业技术综合研究所 | Structural body comprising filler and incompatible resin or elastomer, and production process or use thereof |
| CN102977524A (en) * | 2012-06-30 | 2013-03-20 | 杭州师范大学 | Polyvinylidene fluoride composite material and preparation method thereof |
| CN103289258A (en) * | 2013-06-18 | 2013-09-11 | 上海第二工业大学 | High-dielectric composite material, as well as preparation method and application thereof |
| CN105602066A (en) * | 2016-02-18 | 2016-05-25 | 四川大学 | Polyethylene/nylon composite material and preparation method thereof |
| WO2017155106A1 (en) * | 2016-03-11 | 2017-09-14 | 旭硝子株式会社 | Fluororesin composition, molding material, and molded object |
Non-Patent Citations (1)
| Title |
|---|
| "A Facile Strategy to Enhance the Dielectric and Mechanical Properties of MWCNTs/PVDF Composites with the Aid of MMA-co-GMA Copolymer";shixin，song等;《MATERIALS》;20180227;第11卷(第3期);第1页摘要，第2页第3段，第3页4-5段，第12页结论部分，图5及其附图说明，图8及其附图说明 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109401142A (en) | 2019-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109913185B (en) | A kind of multi-layer structure thermally conductive composite material containing thermally conductive film and preparation method thereof | |
| CN110452418A (en) | A kind of high thermal conductivity Kapton and preparation method thereof of core-shell structure heat filling preparation | |
| CN103147226B (en) | A kind of method preparing polymer base height dielectric nano composite | |
| CN101712784B (en) | A kind of core-shell structure filler/polymer matrix composite material and preparation method thereof | |
| CN106633153A (en) | Polymer-based dielectric energy storage nanocomposite material in three-layer structure and preparation method thereof | |
| CN102173155A (en) | Polymer-base ceramic composite dielectric material and preparation method thereof | |
| Su et al. | Fabrication and dielectric properties of Na 0.5 Bi 0.5 Cu 3 Ti 4 O 12/poly (vinylidene fluoride) composites | |
| Zhou et al. | High dielectric permittivity and low loss in PVDF filled by core-shell Zn@ ZnO particles | |
| CN101508841B (en) | Flexible polymer dielectric material for capacitors and its preparation | |
| CN108794941A (en) | A kind of high-dielectric constant inorganic/organic composite material film and preparation method thereof | |
| CN103087449A (en) | Preparation method of polymer nanometer composite material with high heat conduction, high dielectric and low loss | |
| CN104194335A (en) | Preparation method of polyimide/graphene composite material and product of material | |
| CN116675983B (en) | Preparation method and application of a fully organic polyetherimide-fluorene polyester blend energy storage composite material | |
| CN103951915B (en) | Light flexible polymer-based high energy storage density material and its preparation method | |
| CN113121887A (en) | Nano-cellulose heat-conducting composite film and preparation method thereof | |
| CN109401142B (en) | A kind of PVDF matrix composite material with sea-island structure and preparation method thereof | |
| CN101955667A (en) | Heat-resisting high-dielectric constant inorganic/polymer composite film | |
| CN102627817A (en) | High-energy-storage density dielectric material and preparation method thereof | |
| CN102775626A (en) | Preparation method of high-energy storage density solid dielectric composite material | |
| CN103289258B (en) | A kind of high-dielectric composite material, Preparation Method And The Use | |
| CN108003520A (en) | A kind of preparation method of high dielectric property Kynoar titanium carbide nanosheet composite material | |
| CN112778744A (en) | High-energy-storage-density poly (arylene ether nitrile) composite material and preparation method and application thereof | |
| Liu et al. | Polyamide-imide/polyimide alloy with enhanced energy density and efficiency | |
| CN101921479B (en) | Cyanate resin base composite material and preparation method thereof | |
| CN105153604A (en) | Dielectric composite material based on carbon nanotube |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231113 Address after: 130299 East Gate 25, Floor 1, Longyi Complex Building, west side of Gucheng Street, Nong'an Town, Nong'an County, Changchun City, Jilin Province Patentee after: Changchun Lianyu Chemical Technology Co.,Ltd. Address before: 130000 No. 2055 Yan'an Street, Chaoyang District, Changchun City, Jilin Province Patentee before: Changchun University of Technology |
|
| TR01 | Transfer of patent right |