CN102702745B - Preparation method of carbon nanotube/thermosetting resin composite material - Google Patents
Preparation method of carbon nanotube/thermosetting resin composite material Download PDFInfo
- Publication number
- CN102702745B CN102702745B CN201210198204.1A CN201210198204A CN102702745B CN 102702745 B CN102702745 B CN 102702745B CN 201210198204 A CN201210198204 A CN 201210198204A CN 102702745 B CN102702745 B CN 102702745B
- Authority
- CN
- China
- Prior art keywords
- carbon nanotube
- procuring
- prepolymer
- resin
- resin composite
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a preparation method of a carbon nanotube/thermosetting resin composite material. The preparation method comprises the following steps of: uniformly mixing 100 parts by weight of thermosetting resin and 0.1-2 parts by weight of carbon nanotube to obtain prepolymer; dividing the prepolymer into a plurality of parts; taking one part of prepolymer, precuring at certain temperature and cooling to obtain a precured sheet; taking another part of prepolymer and pouring on the precured sheet, and then precuring; precuring the rest parts of prepolymer in steps in sequence to obtain a precured body; and curing and post-treating to obtain the carbon nanotube/thermosetting resin composite material. Compared with the carbon nanotube/thermosetting resin composite material prepared by one-time forming in the prior art, the composite material provided by the invention has the advantages of higher dielectric constant, lower dielectric loss angle tangent value, simple and practical preparation method, controllable process and suitability for large-scale production.
Description
Technical field
The present invention relates to a kind of preparation method of organic high molecular compound, particularly a kind of preparation method with the carbon nanotube/thermoset ting resin composite of dielectric function.
Background technology
In all passive elements of electronic industry, electrical condenser is because multiple different functions such as having decoupling, bypass, filtering, energy transformation is paid close attention to widely.Having greater functionality needs embedded capacitor device in printed electronic circuit inner cord with the electronic product of small volume more, in order to meet this requirement, the polymer matrix composite with high-k is applied and is given birth to its good processibility with the good compatibility of circuit card.
Conductor/polymer composites is the principal mode of preparing high dielectric constant material.Wherein, carbon nanotube has high specific surface area, excellent electroconductibility and thermal conductivity becomes one of the most promising conductor; And thermosetting resin becomes conventional matrix prepared by matrix material with its good manufacturability and excellent mechanical property.Therefore carbon nanotube/thermoset ting resin composite causes people's great interest aspect high dielectric constant material.But similar to other conductor/polymer composites, carbon nanotube/thermoset ting resin composite is the higher problem of ubiquity dielectric loss also.High dielectric loss is not only wasted a large amount of energy, and shortens the work-ing life of equipment.
Before the present invention makes, bibliographical information a kind ofly utilize the technical scheme that natural sedimentation prepares the cyanate ester resin composite material of carbon nanotube (CNT) distribution gradient (referring to document: Hongyi Wu, Guozheng Liang, Aijuan Gu, Li Yuan. J. Mater. Chem. 2011,21,14838-14848), the composite material concurrent high-k and the low-dielectric loss that provide, yet, its the more difficult control of preparation technology particularly faces larger challenge in large-scale application.
Therefore, in the situation that the essentially consist of matrix material is constant, the novel method how to prepare by setting up matrix material, the matrix material that acquisition has high-k and low-dielectric loss concurrently has important using value.
Summary of the invention
In order to overcome problems of the prior art, the object of the present invention is to provide a kind of simple, technique is controlled, is suitable for the method for scale operation carbon nanotube/thermoset ting resin composite.
Realize the preparation method that technical scheme that the object of the invention takes is to provide a kind of carbon nanotube/thermoset ting resin composite, comprise the steps:
(1) by weight, 100 parts of thermosetting resins are mixed with 0.1～2.0 part of carbon nanotube, under the pre-polymerization temperature condition of described thermosetting resin, obtain prepolymer; Prepolymer is divided into n part, n >=2, every part identical in quality or not identical;
(2) portion in n part prepolymer is carried out to Procuring, obtain carbon nanotube/thermosetting resin Procuring sheet after cooling;
(3) another part of getting in prepolymer is cast on Procuring sheet, then carries out Procuring; Repeat this step, by all the other each parts proceed step by step Procuring successively in prepolymer, obtain a kind of Procuring body of carbon nanotube/thermoset ting resin composite;
(4) by the curing and aftertreatment technology condition of described thermosetting resin, the Procuring body that step (3) is obtained is cured and aftertreatment, obtains a kind of carbon nanotube/thermoset ting resin composite.
Described carbon nanotube is a kind of without in surface treatment or surface treated Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, or its arbitrary combination.
Described thermosetting resin is self heat-setting resin; As bimaleimide resin, cyanate ester resin and combination thereof.
Described thermosetting resin is not for self being subject to the resin of thermofixation and the resin system that solidifying agent forms; The resin that self can not be subject to thermofixation is epoxy resin.
The mechanism of technical solution of the present invention is: adopt carbon nanotube/thermoset ting resin composite multistep Procuring forming technique, the surface of the matrix material obtaining after every step Procuring moulding is resin-rich layer, it has not only increased the generation probability of micro-electric capacity, and intercepted the direct contact of carbon nanotube, greatly reduce the probability that composite inner forms conductive path, thereby obtain having concurrently the matrix material of high-k and low-dielectric loss.
Compared with prior art, the beneficial effect that the present invention obtains is:
1,, owing to having adopted multistep forming technique, the carbon nanotube/thermoset ting resin composite making has the different microtexture of matrix material obtaining from traditional one-step moulding, has high-k and low-dielectric loss concurrently.
2, the preparation method of carbon nanotube/thermoset ting resin composite provided by the invention has the characteristics and advantages simple, technique is controlled, is suitable for scale operation.
Accompanying drawing explanation
Fig. 1 is carbon nanotube/cyanate ester resin composite material of preparing of the embodiment of the present invention and specific inductivity-frequency curve comparison diagram of layered carbon nano pipe/cyanate resin base composite material;
Fig. 2 is carbon nanotube/cyanate ester resin composite material of preparing of the embodiment of the present invention and tangent of the dielectric loss angle value-frequency curve comparison diagram of layered carbon nano pipe/cyanate resin base composite material.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described further.
Embodiment 1
By 0.02g multi-walled carbon nano-tubes, 20g bisphenol A cyanate ester mixes, and at 85 ℃, sonic oscillation stirs 1h, obtains mixed solution, then by mixed solution pre-polymerization 2h at 150 ℃.After pre-polymerization finishes, prepolymer is divided into 2 equal portions.By wherein 1 part pour in preheated mould, vacuum defoamation 30min at 140 ℃.Then mould is put into baking oven, Procuring 30min at 180 ℃, obtains carbon nanotube/cyanate ester resin composite material Procuring sheet after cooling.
Remaining 1 part of prepolymer is cast on Procuring sheet, at 140 ℃ after vacuum defoamation 30min, according to 180 ℃ of techniques/2h+200 ℃/2h+220 ℃/2h and 240 ℃/4h, is cured and aftertreatment, obtain carbon nanotube/cyanate ester resin composite material.
Embodiment 2
By 0.4g Single Walled Carbon Nanotube, 20g bisphenol A cyanate ester mixes, and at 85 ℃, sonic oscillation stirs 1h, obtains mixed solution, then by mixed solution pre-polymerization 2h at 150 ℃.After pre-polymerization finishes, prepolymer is divided into 3 parts, mass ratio is 2:1:1.By wherein 1 part pour in preheated mould, vacuum defoamation 30min at 140 ℃.Then mould is put into baking oven, Procuring 30min at 180 ℃, obtains carbon nanotube/cyanate ester resin composite material Procuring sheet A after cooling.
The 2nd part of prepolymer is cast in to above-mentioned Procuring sheet A upper, vacuum defoamation 30min at 140 ℃, obtains carbon nanotube/cyanate ester resin composite material Procuring sheet B after cooling.
The 3rd part of prepolymer is cast in to Procuring sheet B upper, at 140 ℃ after vacuum defoamation 30min, according to 180 ℃ of techniques/2h+200 ℃/2h+220 ℃/2h and 240 ℃/4h, is cured and aftertreatment, obtain carbon nanotube/cyanate ester resin composite material.
Embodiment 3
By 0.14g Single Walled Carbon Nanotube, 20g bisphenol A cyanate ester mixes, and at 85 ℃, sonic oscillation stirs 1h, obtains mixed solution, then by mixed solution pre-polymerization 2h at 150 ℃.After pre-polymerization finishes, prepolymer is divided into 4 parts, mass ratio is 2:1:2:1.By wherein 1 part pour in preheated mould, vacuum defoamation 30min at 140 ℃.Then mould is put into baking oven, Procuring 30min at 180 ℃, obtains carbon nanotube/cyanate ester resin composite material Procuring sheet A after cooling.
The 2nd part of prepolymer is cast in to above-mentioned Procuring sheet A upper, vacuum defoamation 30min at 140 ℃, obtains carbon nanotube/cyanate ester resin composite material Procuring sheet B after cooling.
The 3rd part of prepolymer is cast in to above-mentioned Procuring sheet B upper, vacuum defoamation 30min at 140 ℃, obtains carbon nanotube/cyanate ester resin composite material Procuring sheet C after cooling.
The 4th part of prepolymer is cast in to Procuring sheet C upper, at 140 ℃ after vacuum defoamation 30min, according to 180 ℃ of techniques/2h+200 ℃/2h+220 ℃/2h and 240 ℃/4h, is cured and aftertreatment, obtain carbon nanotube/cyanate ester resin composite material.
Embodiment 4
By 0.14g Single Walled Carbon Nanotube, 10g N, N '-4,4 '-diphenyl methane dimaleimide and 7.4g diallyl bisphenol monomer mix, by mixture pre-polymerization 2h at 150 ℃.After pre-polymerization finishes, prepolymer is divided into n part, mass ratio is 1:2:3: ...: (n-1): n(n is positive integer, in the present embodiment, n=10).By wherein 1 part pour in preheated mould, vacuum defoamation 30min at 140 ℃.Then mould is put into baking oven, Procuring 30min at 180 ℃, obtains carbon nanotube/cyanate ester resin composite material Procuring sheet A1 after cooling.
The 2nd part of prepolymer is cast in to above-mentioned Procuring sheet A1 upper, vacuum defoamation 30min at 140 ℃, obtains carbon nanotube/cyanate ester resin composite material Procuring sheet A2 after cooling.
The 3rd part of prepolymer is cast in to above-mentioned Procuring sheet A2 upper, vacuum defoamation 30min at 140 ℃, obtains carbon nanotube/cyanate ester resin composite material Procuring sheet A3 after cooling.
Repeat above step, obtain Procuring sheet A (n-1).
N part prepolymer is cast on Procuring sheet A (n-1), at 140 ℃ after vacuum defoamation 30min, according to 180 ℃ of techniques/2h+200 ℃/2h+220 ℃/2h and 240 ℃/4h, be cured and aftertreatment, obtain carbon nanotube/cyanate ester resin composite material.
Embodiment 5
By 0.1g multi-walled carbon nano-tubes, 20g bisphenol A cyanate ester mixes, and at 85 ℃, sonic oscillation stirs 1h, obtains mixed solution, then by mixed solution pre-polymerization 2h at 150 ℃.After pre-polymerization finishes, prepolymer is divided into 2 equal portions.By wherein 1 part pour in preheated mould, vacuum defoamation 30min at 140 ℃.Then mould is put into baking oven, Procuring 30min at 180 ℃, obtains carbon nanotube/cyanate ester resin composite material Procuring sheet after cooling.
Remaining 1 part of prepolymer is cast on Procuring sheet, at 140 ℃ after vacuum defoamation 30min, according to 180 ℃ of techniques/2h+200 ℃/2h+220 ℃/2h and 240 ℃/4h, is cured and aftertreatment, obtain carbon nanotube/cyanate ester resin composite material.
Comparative example 1: by 0.1g multi-walled carbon nano-tubes, 20g bisphenol A cyanate ester mixes, and sonic oscillation stirs 1h at 85 ℃, obtains mixed solution, then by mixed solution pre-polymerization 2h at 150 ℃.After pre-polymerization finishes, prepolymer is poured in preheated mould into vacuum defoamation 30min at 140 ℃.Again mould is put into baking oven, according to 180 ℃/2h+200 ℃/2h+220 ℃/2h and 240 ℃/4h, be cured and aftertreatment, obtain multi-walled carbon nano-tubes/cyanate ester resin composite material.
Referring to accompanying drawing 1, it is the comparison diagram of specific inductivity-frequency curve of the carbon nanotube/cyanate ester resin composite material of the present embodiment and comparative example 1 preparation.As seen from Figure 1, both specific inductivity reduce along with the rising of frequency.But the matrix material that the present embodiment makes demonstrates higher specific inductivity in low frequency range, this is mainly to have formed a resin-rich layer because two steps are cast in matrix material, forms more micro-electric capacity, contributes to the raising of specific inductivity.
Referring to accompanying drawing 2, it is tangent of the dielectric loss angle value-frequency curve comparison diagram of the carbon nanotube/cyanate ester resin composite material of the present embodiment and comparative example 1 preparation.As seen from Figure 2, compare with the carbon nanotube/cyanate ester resin composite material of comparative example 1 preparation, matrix material prepared by the present embodiment demonstrates lower tangent of the dielectric loss angle value, for example, when 10Hz, the tangent of the dielectric loss angle value of the carbon nanotube/cyanate ester resin composite material of the present embodiment and comparative example 1 preparation is respectively 12.1 and 187.3.
Embodiment 6
By 0.2g Single Walled Carbon Nanotube, 20g bisphenol A cyanate ester mixes, and at 85 ℃, sonic oscillation stirs 1h, obtains mixed solution, then by mixed solution pre-polymerization 2h at 150 ℃.After pre-polymerization finishes, prepolymer is divided into 3 parts, mass ratio is 1:1:1.By wherein 1 part pour in preheated mould, vacuum defoamation 30min at 140 ℃.Then mould is put into baking oven, Procuring 30min at 180 ℃, obtains carbon nanotube/cyanate ester resin composite material Procuring sheet A after cooling.
The 2nd part of prepolymer is cast in to above-mentioned Procuring sheet A upper, vacuum defoamation 30min at 140 ℃, obtains carbon nanotube/cyanate ester resin composite material Procuring sheet B after cooling.
The 3rd part of prepolymer is cast in to Procuring sheet B upper, at 140 ℃ after vacuum defoamation 30min, according to 180 ℃ of techniques/2h+200 ℃/2h+220 ℃/2h and 240 ℃/4h, is cured and aftertreatment, obtain carbon nanotube/cyanate ester resin composite material.
Embodiment 7
By the multi-walled carbon nano-tubes of 0.5g acidifying, 20g epoxy resin (E-51) sonic oscillation at 60 ℃ stirs 1h, obtains mixed solution, then will add 0.8g triethylene diamine (solidifying agent).Stir after 10 minutes, by prepolymer be divided into 2 parts, mass ratio is 1:2.By wherein 1 part pour in preheated mould, vacuum defoamation 20min at 60 ℃.Then Procuring 30min at 80 ℃, obtains carbon nano tube/epoxy resin Procuring sheet after cooling.
Remaining a prepolymer is cast on Procuring sheet, at 60 ℃ after vacuum defoamation 30min, according to being cured and aftertreatment of 80 ℃ of techniques/2h+100 ℃/2h+120 ℃/2h+150 ℃/4h, obtains carbon nano tube/epoxy resin composite material.
Embodiment 8
By the epoxidised Single Walled Carbon Nanotube of 0.05g, 16g Cyclopeutadiene type cyanate and 4g N, N '-4,4 '-diphenyl methane dimaleimide mixes, pre-polymerization 2h at 150 ℃.After pre-polymerization finishes, by prepolymer be divided into 2 parts, mass ratio is 1:2.By wherein 1 part pour in preheated mould, vacuum defoamation 30min at 140 ℃.Finally mould is put into baking oven, Procuring 30min at 180 ℃, obtains carbon nanotube/bismaleimide-triazine resin Procuring sheet after cooling.
Remaining a prepolymer is cast on Procuring sheet, at 140 ℃ after vacuum defoamation 30min, according to the technique of 180 ℃/2h+200 ℃/2h+220 ℃/2h be cured and at 240 ℃ aftertreatment 4h, obtain layered carbon nano pipe/bismaleimide-triazine resin composite material.
Embodiment 9
By the epoxidised Single Walled Carbon Nanotube of 0.5g, the multi-walled carbon nano-tubes of 0.5g acidifying, 16g Cyclopeutadiene type cyanate and 4g N, N '-4,4 '-diphenyl methane dimaleimide mixes, pre-polymerization 2h at 150 ℃.After pre-polymerization finishes, prepolymer is divided into 2 equal portions.By wherein 1 part pour in preheated mould, vacuum defoamation 30min at 140 ℃.Then mould is put into baking oven, Procuring 30min at 180 ℃, obtains carbon nanotube/cyanate ester resin composite material Procuring sheet after cooling.Remaining 1 part of prepolymer is cast on Procuring sheet, at 140 ℃ after vacuum defoamation 30min, according to 180 ℃ of techniques/2h+200 ℃/2h+220 ℃/2h and 240 ℃/4h, be cured and aftertreatment, obtain carbon nanotube/bismaleimide-triazine resin composite material.
Claims (6)
1. a preparation method for carbon nanotube/thermoset ting resin composite, is characterized in that comprising the steps:
(1) by weight, 100 parts of thermosetting resins are mixed with 0.1～2.0 part of carbon nanotube, under the pre-polymerization temperature condition of described thermosetting resin, obtain prepolymer; Prepolymer is divided into n part, n >=2, every part identical in quality or not identical;
(2) portion in n part prepolymer is carried out to Procuring, obtain carbon nanotube/thermosetting resin Procuring sheet after cooling;
(3) another part of getting in prepolymer is cast on Procuring sheet, then carries out Procuring; Repeat this step, by all the other each parts proceed step by step Procuring successively in prepolymer, obtain a kind of Procuring body of carbon nanotube/thermoset ting resin composite;
(4) by the curing and aftertreatment technology condition of described thermosetting resin, the Procuring body that step (3) is obtained is cured and aftertreatment, obtains a kind of carbon nanotube/thermoset ting resin composite.
2. the preparation method of a kind of carbon nanotube/thermoset ting resin composite according to claim 1, it is characterized in that: a kind of for without in surface treatment or surface treated Single Walled Carbon Nanotube, multi-walled carbon nano-tubes of described carbon nanotube, or its arbitrary combination.
3. the preparation method of a kind of carbon nanotube/thermoset ting resin composite according to claim 1, is characterized in that: described thermosetting resin is self heat-setting resin.
4. the preparation method of a kind of carbon nanotube/thermoset ting resin composite according to claim 3, is characterized in that: described self heat-setting resin is bimaleimide resin, cyanate ester resin and combination thereof.
5. the preparation method of a kind of carbon nanotube/thermoset ting resin composite according to claim 1, is characterized in that: described thermosetting resin is not for self being subject to the resin of thermofixation and the resin system that solidifying agent forms.
6. the preparation method of a kind of carbon nanotube/thermoset ting resin composite according to claim 5, is characterized in that: the described resin that self can not be subject to thermofixation is epoxy resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210198204.1A CN102702745B (en) | 2012-06-15 | 2012-06-15 | Preparation method of carbon nanotube/thermosetting resin composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210198204.1A CN102702745B (en) | 2012-06-15 | 2012-06-15 | Preparation method of carbon nanotube/thermosetting resin composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102702745A CN102702745A (en) | 2012-10-03 |
| CN102702745B true CN102702745B (en) | 2014-03-19 |
Family
ID=46895818
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210198204.1A Expired - Fee Related CN102702745B (en) | 2012-06-15 | 2012-06-15 | Preparation method of carbon nanotube/thermosetting resin composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102702745B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073847B (en) * | 2013-01-23 | 2015-01-21 | 苏州大学 | Modified carbon nano tube/thermosetting resin composite material and preparation method thereof |
| CN103194858B (en) * | 2013-04-23 | 2015-08-05 | 北京化工大学 | Elastic composite of a kind of high dielectric constant and low dielectric loss and preparation method thereof |
| CN104893287B (en) * | 2015-06-01 | 2017-06-13 | 苏州大学 | A kind of CNT/polyethersulfone with cardo/cyanate ester resin composite material and preparation method |
| CN105482339B (en) * | 2016-01-16 | 2017-10-13 | 苏州大学 | A kind of lithium salts/polyacrylonitrile/thermoset ting resin composite and preparation method thereof |
| CN107141793A (en) * | 2017-06-15 | 2017-09-08 | 铜陵安博电路板有限公司 | A kind of low-dielectric loss type polymer matrix composites of ZnOw filling and preparation method thereof |
| CN107538661B (en) * | 2017-09-11 | 2019-05-28 | 苏州大学 | Four-layer structure polymer matrix composites and preparation method thereof |
| CN110076946B (en) * | 2017-09-11 | 2021-08-27 | 苏州大学 | Precursor for three-layer structure resin-based composite material and preparation method thereof |
| CN109161195A (en) * | 2018-08-02 | 2019-01-08 | 北京空间飞行器总体设计部 | A kind of conductivity type carbon nanotube/cyanate composite material and preparation method thereof |
| CN109776832B (en) * | 2019-01-15 | 2021-03-02 | 苏州大学 | Three-layer structure resin-based composite material and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1785658A (en) * | 2005-11-08 | 2006-06-14 | 浙江大学 | Preparation method of reinforced polymer base composite material for high volume fraction carbon nano-pipe |
| CN102199351A (en) * | 2011-04-08 | 2011-09-28 | 苏州生益科技有限公司 | Thermosetting resin composition, prepreg and laminated board |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100280151A1 (en) * | 2009-05-04 | 2010-11-04 | Toray Industries, Inc. | Toughened fiber reinforced polymer composite with core-shell particles |
-
2012
- 2012-06-15 CN CN201210198204.1A patent/CN102702745B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1785658A (en) * | 2005-11-08 | 2006-06-14 | 浙江大学 | Preparation method of reinforced polymer base composite material for high volume fraction carbon nano-pipe |
| CN102199351A (en) * | 2011-04-08 | 2011-09-28 | 苏州生益科技有限公司 | Thermosetting resin composition, prepreg and laminated board |
Non-Patent Citations (4)
| Title |
|---|
| Hongyi Wu.Novel permittivity gradient carbon nanotubes/cyanate ester composites with high permittivity and extremely low dielectric loss.《Journal of Materials Chemistry》.2011,第21卷(第38期), |
| Novel permittivity gradient carbon nanotubes/cyanate ester composites with high permittivity and extremely low dielectric loss;Hongyi Wu;《Journal of Materials Chemistry》;20110818;第21卷(第38期);第14839页第2.2节，2.3节，第1486页图12 * |
| Reinforced Cyanate Ester Resins with Carbon Nanotubes: Surface Modification, Reaction Activity and Mechanical Properties Analyses;Yu-Sheng Tang等;《Polymer-Plastics Technology and Engineering》;20090331;第48卷(第4期);第359-366页 * |
| Yu-ShengTang等.ReinforcedCyanateEsterResinswithCarbonNanotubes:SurfaceModification Reaction Activity and Mechanical Properties Analyses.《Polymer-Plastics Technology and Engineering》.2009 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102702745A (en) | 2012-10-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102702745B (en) | Preparation method of carbon nanotube/thermosetting resin composite material | |
| CN102443247B (en) | Preparation method of graphene oxide grafted POSS (polyhedral oligomeric silsesquioxane) modified epoxy resin | |
| CN110550956A (en) | preparation method of graphene-polyimide-based composite sponge precursor heat-conducting film | |
| CN101937737B (en) | Low-temperature curing conductive slurry and preparation method thereof | |
| CN102675779B (en) | High-dielectric-constant three-phase composite material containing modified graphene and preparation method thereof | |
| CN103030974A (en) | Light flexible graphene/polymer foam electromagnetic shielding material, preparation method and application thereof | |
| CN103147226A (en) | Method for preparing high dielectric constant polymer-based nano composite material | |
| CN100523087C (en) | Thermostable benzoxazine resin compound and its preparation method and uses | |
| CN113004474A (en) | Multi-walled carbon nanotube/barium titanate/polydicyclopentadiene composite material based on front-end ring-opening metathesis polymerization and preparation method thereof | |
| CN114854087A (en) | Polyimide composite material with double heat-conducting networks and preparation method thereof | |
| CN102010218A (en) | Preparation method of graphene oxide doped unidirectional C/C composite material | |
| CN101885901A (en) | Biphenyl-structure-contained epoxy resin/montmorillonite nano composite material | |
| CN108164268B (en) | Preparation method of graphene composite silicon-carbon-nitrogen precursor ceramic | |
| CN101864076A (en) | Cyanate resin modified by phenylacetylene base silane resin and preparation method thereof | |
| CN106751534A (en) | A kind of copper-clad plate heat resistant type epoxy resin composite material containing polyetheramine and preparation method thereof | |
| CN107901451A (en) | A kind of technology of preparing of high-temperature resistant resin base copper-clad plate | |
| CN106751711A (en) | Fluorine substituted ethylene based polyalcohol resin combination, prepreg and laminate | |
| CN103435831A (en) | Method for preparing polyetherketone foaming material by using supercritical CO2 | |
| CN101921479B (en) | Cyanate resin base composite material and preparation method thereof | |
| CN102673070B (en) | Asymmetrical layer-shaped resin matrix composite material and preparation method thereof | |
| You et al. | Design and preparation of low-filled magnetic oriented BN@ Fe3O4/EP insulating composite with improved thermal conductivity and thermal stability | |
| CN105235318A (en) | Preparation method for copper-clad plate with large dielectric constant | |
| CN108285642B (en) | Polyphenyl ether filled oriented carbon nanotube bundle/thermosetting resin | |
| CN104402487A (en) | Preparation method of vapor growth carbon fiber (VGCF)/mesophase asphalt composite material | |
| CN103756258A (en) | Preparation method of Ti3AlC2 epoxy resin conductive composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140319 Termination date: 20200615 |