CN103483516B - Preparation method of graphene oxide-boron-modified phenolic resin - Google Patents
Preparation method of graphene oxide-boron-modified phenolic resin Download PDFInfo
- Publication number
- CN103483516B CN103483516B CN201310450626.8A CN201310450626A CN103483516B CN 103483516 B CN103483516 B CN 103483516B CN 201310450626 A CN201310450626 A CN 201310450626A CN 103483516 B CN103483516 B CN 103483516B
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- phenolic resin
- boron
- preparation
- modifiedphenolic
- 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
Abstract
The invention discloses a preparation method of graphene oxide-boron-modified phenolic resin, and relates to the phenolic resin. The preparation method comprises the following steps: firstly, preparing graphene oxide by an improved Hummers method; secondly, ultrasonically dispersing the obtained graphene oxide in a mixture of phenol and formaldehyde; thirdly, adding sodium hydroxide as a catalyst, and smoothly inserting small molecules of the phenolic resin into the middle of the graphene oxide through reaction between reactive groups of the graphene oxide itself and the phenol and the formaldehyde; finally, introducing boric acid, initiating the polymerization reaction between the small molecules in the phenolic resin in the graphene oxide and the boric acid by varying reaction conditions, and thus preparing the high-performance graphite oxide-boron-modified phenolic resin. With the preparation method, not only are the structure and the properties of grapheme maintained, but also certain retained oxygen-containing functional groups can well solve the problems of poor dispersion, solubility and processability of graphene and the like.
Description
Technical field
The present invention relates to resol, especially relate to a kind of preparation method of graphene oxide-boron-modifiedphenolic phenolic resin.
Background technology
Resol synthesizes one of thermosetting resin greatly as three, experienced by and exceedes century-old history, be widely used in sizing agent, moulding compound, coating, porous plastics etc. so far.Although amount ratio unsaturated polyester resin and epoxy resin less, also play huge effect in military industry field, building trade, automobile industry etc., not only as a resin, and with the form of matrix material obtain application.In the application of more wide spectrum, various material can be added with regard to needs in resol and carries out modification, improve its over-all properties to make resol.Inorganic nano material (Nano-meter SiO_2 is added in the oriented resol of modification technology of extensive employing
2, nano-TiO
2, nano imvite (MMT) etc.), organic compound (organosilicon, organic boron, cashew nut shell oil etc.), mineral compound (boride, molybdenum etc.) etc.But a lot of modifications solely can only improve thermal characteristics or the mechanical property of resol, and can not improve its thermal characteristics and mechanical property simultaneously.In addition, inorganic particulate cannot fully disperse in organic polymer, affects the performance of material.At present, the method that raising inorganic particulate disperses in organic polymer has ultrasonic method, mechanical process and surface-modification method etc., but is still difficult to the compound realizing polymkeric substance and inorganic particulate.
Research about boride modified phenolic resins shows, in raising resol resistance toheat and ablation resistance, the effect of boron is remarkable.No matter introduce inorganic boride or organic boride in the molecular structure, resol thermotolerance and Residual carbon ([1] Xu Peijun can both be significantly improved, Liu Yuhong, well is newly sharp. boride Progress On Modified Pf Resin [J]. and aerospace material technique,, but inorganic boride modified phenolic resins defect in manufacturability and mechanical property is still comparatively obvious 2009 (6): 1-5).Therefore, need to add other compound and carry out modification, thus improve the mechanical property of modified phenolic resins.
Graphene is one the thinnest in known at present material, and its thickness only has an atom, but because the singularity of this body structure makes it have very large hardness, harder than iron and steel 300 times.In addition, Graphene also has much peculiar character in electricity and magnetic property, as room-temperature quantum Hall effect, bipolarity electrical effect, ferromegnetism, supraconductivity and high electronic mobility, especially its thermal conductivity can reach 5300W/ (mK), is more than 10 times of copper thermal conductivity.Therefore, Graphene has quite wide application prospect.And Graphene is applied in the middle of macromolecular material, be one of its application.Although Graphene has the huge market space, because the singularity of itself structure makes its suitability for industrialized production and the market requirement all be in the junior stage, a lot of research is also in development.In the end of the year 2012, European Union is following gives Nokia 13.5 hundred million dollars of reasearch funds, for the research of grapheme material (Graphene) with emerging technology tissue (Future Emerging Technologies).That to have made it contain many is peculiar and be better than the physicochemical property of Today, most material, as high specific surface area and excellent heat conductivility, mechanical property and electron transmission ability for this special hexagonal structure of Graphene.At present, the main method preparing Graphene has: mechanically peel method, chemical Vapor deposition process, epitaxial growth method, oxidation reduction process ([2] Chen Ruican, Wang Haiyan, Han Yonggang, Deng. oxidation reduction process prepares Graphene and sign [J] thereof. material Leader B: a research section, 26 (6): 114-117).
One of approach of using mineral carbon alkene excellent properties is that graphene film and superpolymer compound are prepared matrix material.Produce such matrix material and require that Graphene can be evenly distributed on matrix.But the structural stability of Graphene own and Van der Waals force stronger between layers, make it can not carry out compound with other body materials well, thus the further research and development of restriction Graphene and utilization.Therefore, general by carrying out chemical modification to Graphene, the method of usual employing is Hummers method, principle is similar to above-mentioned oxidation reduction process, graphite strong acid is obtained containing enriching oxy radical graphite oxide through the oxidation of row intercalation under cryogenic, graphene oxide is obtained again by the ultrasonic graphene oxide obtaining nitrogen-atoms layer thickness, consistency ([3] Deng Yao between itself and polymer monomer or polymkeric substance is improved by introducing active group, Huang Xiaorong, Wu Xiaoling. the progress [J] of graphene oxide composite material. material Leader A: a summary section, 2012, 26 (8): 84-87).
Summary of the invention
The object of the present invention is to provide a kind of preparation method of graphene oxide-boron-modifiedphenolic phenolic resin.
The present invention includes following steps:
1) in three mouthfuls of round-bottomed flasks, the vitriol oil is added, then be placed in ice-water bath, add graphite and SODIUMNITRATE, then add solid potassium permanganate, keep the temperature of ice-water bath to be no more than 5 DEG C, then deionized water is added, holding temperature is reacted between 32 ~ 38 DEG C, when reacting close to terminal, at room temperature places, again with warm water dilution, then add H
2o
2reduce remaining value Mn ion, to solution becomes glassy yellow, then centrifuge washing to solution in neutral and detect in supernatant liquor without SO with barium salt
4 2-till, then use absolute ethanol washing, after drying, namely obtain graphene oxide;
2) phenol and formaldehyde are added in the there-necked flask that agitator, thermometer, prolong are housed, then add graphene oxide, add flaky sodium hydrate after ultrasonic disperse, after temperature rising reflux reaction, decompression dehydration, obtains graphene oxide Phenolic resin emulsion;
3) to step 2) add boric acid in the graphene oxide Phenolic resin emulsion of gained, after temperature rising reflux reaction, pour out blackish green dope, be cooled to room temperature, after vacuum-drying, namely obtain graphene oxide-boron-modifiedphenolic phenolic resin.
In step 1), described graphite, the vitriol oil, SODIUMNITRATE, solid potassium permanganate, deionized water, H
2o
2mass ratio can be 1: (35 ~ 45): (0.3 ~ 0.6): (2.5 ~ 3.5): (40 ~ 60): (15 ~ 20); The time of described reaction can be 30 ~ 60min; The described time of at room temperature placing can be 72 ~ 96h; The temperature of described warm water can be 50 ~ 60 DEG C; The condition of described centrifuge washing can be speed 10000 ~ 12000rpm, time 10 ~ 20min.
In step 2) in, the mass ratio of described phenol, formaldehyde, graphene oxide, flaky sodium hydrate can be 1: (0.97 ~ 1.14): (0.005 ~ 0.01): (0.01 ~ 0.03); The condition of described ultrasonic disperse can be temperature 50 ~ 60 DEG C, time 20 ~ 30min; The condition of described temperature rising reflux reaction can be temperature 60 ~ 65 DEG C, time 1 ~ 2h.
In step 3), the mass ratio of the phenol in the add-on of described boric acid and step 1) can be 1: (0.13 ~ 0.27); The condition of described temperature rising reflux reaction can be temperature 90 ~ 100 DEG C, time 1 ~ 2h; Described vacuum drying condition can be temperature 50 ~ 60 DEG C, time 24 ~ 36h.
Principle of the present invention is: the Hummers method first utilizing improvement, prepares graphene oxide; Again by the graphene oxide of gained ultrasonic disperse in the mixed solution of phenol and formaldehyde; Add sodium hydroxide subsequently as catalyzer, utilize the reaction between the active group of graphene oxide itself and phenol, formaldehyde, make resol small molecules be inserted in the middle of graphene oxide layer smoothly; Finally introduce boric acid, by changing reaction conditions, making the resol small molecular in graphene oxide and boric acid initiated polymerization, thus preparing High-performance graphite oxide alkene-boron modified phenolic resin.
Principal feature of the present invention is: the controlled reduction of graphene oxide not only maintains the stuctures and properties of Graphene (as excellent thermostability and mechanical property), but also gives its some new performance: the part oxygen-containing functional group of reservation can solve the difficult problems such as graphene dispersion, solvability and poor in processability well.The carbon yield of this method is 70.41%, and more common boron modified phenolic resin thermal characteristics improves 2.1%.And its flexural strength be 96.5MPa, tensile strength is 48.3MPa, shock strength is 9.7kJ/m
2, more common boron modified phenolic resin flexural strength adds 46%, tensile strength adds 38%, shock strength is high by 53%.
Accompanying drawing explanation
Fig. 1 is the carbon yield of Graphene and graphene oxide in embodiment 2.In FIG, marking ■ is graphene oxide; ● be Graphene.
Fig. 2 is the thermal destruction curve of the carbon yield graphene oxide-boron-modifiedphenolic phenolic resin of graphene oxide-boron-modifiedphenolic phenolic resin in embodiment 2, Graphene-boron modified phenolic resin and common boron modified phenolic resin.In fig. 2, marking ■ is Graphene-boron modified phenolic resin; ● be graphene oxide-boron-modifiedphenolic phenolic resin;
for boron modified phenolic resin.
Fig. 3 is that the shock strength of graphene oxide-boron-modifiedphenolic phenolic resin and common boron modified phenolic resin in embodiment 2 compares.In figure 3, a is graphene oxide-boron-modifiedphenolic phenolic resin, and b is common boron modified phenolic resin.
Fig. 4 is that the tensile strength of graphene oxide-boron-modifiedphenolic phenolic resin and common boron modified phenolic resin in embodiment 2 compares.In the diagram, a is graphene oxide-boron-modifiedphenolic phenolic resin, and b is common boron modified phenolic resin.
Fig. 5 is that the flexural strength of graphene oxide-boron-modifiedphenolic phenolic resin and common boron modified phenolic resin in embodiment 2 compares.In Figure 5, a is graphene oxide-boron-modifiedphenolic phenolic resin, and b is common boron modified phenolic resin.
Embodiment
Embodiment 1
The first step, graphene oxide preparation;
In three mouthfuls of round-bottomed flasks, add the vitriol oil of 75ml98%, be then placed in ice-water bath, then add the graphite of 3.5g and the SODIUMNITRATE of 1.6g, after stirring, slowly add solid potassium permanganate, keep stirring 2h, keep the temperature of ice-water bath to be no more than 5 DEG C; Then, slowly add deionized water, around here can very exothermic and with a small amount of bubble produce, holding temperature reacts 45min between 32 ~ 38 DEG C, and when reacting close to terminal, the suspension liquid of black becomes the dope of beige, then at room temperature places 72h.Be finally the dilutions of 60 DEG C of warm water by 500ml temperature, then drip 60mlH
2o
2reduce remaining value Mn ion (because excessive high manganese ion can to environment), to solution becomes glassy yellow.Centrifuge washing (11000rpm, 20min), is washed till solution and is neutrality and detects in supernatant liquor without SO with barium salt
4 2-till, then use absolute ethanol washing twice, the product after washing is dry in vacuum drying oven.Namely graphene oxide is obtained after drying.
Second step, the preparation of graphene oxide liquid phenolic resin;
First 47g phenol and 56.8g formaldehyde are added in the there-necked flask that agitator, thermometer, prolong are housed, add the graphene oxide 0.47g of 1% phenol quality again, 1.4g flaky sodium hydrate (catalyzer) is added after 60 DEG C of ultrasonic disperse 30min, continue to be warmed up to 65 DEG C lentamente, after continuing back flow reaction 1.5h, decompression dehydration 15min.
3rd step, the preparation of graphene oxide-boron-modifiedphenolic phenolic resin;
In reaction vessel on last stage, add 9.3g boric acid, be warmed up to 95 DEG C, back flow reaction 2h, pour out blackish green dope while hot, be cooled to room temperature and obtain graphene oxide-boron-modifiedphenolic phenolic resin, vacuum-drying 24h under 60 DEG C of conditions.
Embodiment 2
The first step, graphene oxide preparation;
In three mouthfuls of round-bottomed flasks, add the vitriol oil of about 75ml98%, be then placed in ice-water bath, then add 3.5g graphite and 1.6g SODIUMNITRATE, after stirring, slowly add solid potassium permanganate, keep stirring 2h, keep the temperature of ice-water bath to be no more than 5 DEG C; Then, slowly add deionized water, around here can very exothermic and with a small amount of bubble produce, holding temperature reacts 45min between 32 ~ 38 DEG C, and when reacting close to terminal, the suspension liquid of black becomes the dope of beige, then at room temperature places 72h.Be finally the dilutions of 60 DEG C of warm water by 500ml temperature, then drip 60mlH
2o
2reduce remaining value Mn ion (because excessive high manganese ion can to environment), to solution becomes glassy yellow.Centrifuge washing (10000rpm, 15min), is washed till solution and is neutrality and detects in supernatant liquor without SO with barium salt
4 2-till, then use absolute ethanol washing twice, the product after washing is dry in vacuum drying oven.Namely graphene oxide is obtained after drying.
Second step, the preparation of graphene oxide liquid phenolic resin;
First 47g phenol and 56.8g formaldehyde are added in the there-necked flask that agitator, thermometer, prolong are housed, add the graphene oxide 0.235g of 0.5% phenol quality again, 1.4g flaky sodium hydrate (catalyzer) is added after 60 DEG C of ultrasonic disperse 30min, continue to be warmed up to 65 DEG C lentamente, after continuing back flow reaction 1.5h, decompression dehydration 15min.
3rd step, the preparation of graphene oxide-boron-modifiedphenolic phenolic resin;
In reaction vessel on last stage, add 9.3g boric acid, be warmed up to 95 DEG C, back flow reaction 2h, pour out blackish green dope while hot, be cooled to room temperature and obtain graphene oxide-boron-modifiedphenolic phenolic resin, vacuum-drying 24h under 60 DEG C of conditions.
The residual rate of Graphene is 85.44% as can be seen from Figure 1, and weightless reason may be the moisture that Graphene also has the unreduced oxy radical of small part and interlayer, makes Graphene create weightlessness 0 ~ 200 DEG C of stage.And the carbon yield of graphene oxide is 44.49%, its thermolysis is divided into two stages: cause containing losing of moisture in the mass loss in 0 ~ 100 DEG C of stage is mainly due to graphene oxide; Be mass loss at 150 ~ 240 DEG C may be oxy radical generation thermolysis in graphene oxide, produce CO, CO
2and H
2o caused.
As can be seen from Figure 2, graphene oxide-boron-modifiedphenolic phenolic resin is mild compared with other two groups, and its carbon yield is 70.41%.Obviously be better than Graphene modified phenolic resins 53.08% and common boron modified phenolic resin 68.31%.
As can be seen from Fig. 3 ~ 5, when being doped into a small amount of graphene oxide, the flexural strength of graphene oxide-boron-modifiedphenolic phenolic resin has been 96.5MP
a, tensile strength is 48.3MP
a, shock strength is 9.7kJ/m
2, more common boron modified phenolic resin flexural strength adds 46%, and tensile strength adds 38%, and shock strength is high by 53%.
Claims (8)
1. a preparation method for graphene oxide-boron-modifiedphenolic phenolic resin, is characterized in that comprising the following steps:
1) in three mouthfuls of round-bottomed flasks, the vitriol oil is added, then be placed in ice-water bath, add graphite and SODIUMNITRATE, then add solid potassium permanganate, keep the temperature of ice-water bath to be no more than 5 DEG C, then deionized water is added, holding temperature is reacted between 32 ~ 38 DEG C, when reacting close to terminal, at room temperature places, again with warm water dilution, then add H
2o
2reduce remaining value Mn ion, to solution becomes glassy yellow, then centrifuge washing to solution in neutral and detect in supernatant liquor without SO with barium salt
4 2-till, then use absolute ethanol washing, after drying, namely obtain graphene oxide; Described graphite, the vitriol oil, SODIUMNITRATE, solid potassium permanganate, deionized water, H
2o
2mass ratio be 1: (35 ~ 45): (0.3 ~ 0.6): (2.5 ~ 3.5): (40 ~ 60): (15 ~ 20);
2) phenol and formaldehyde are added in the there-necked flask that agitator, thermometer, prolong are housed, then add graphene oxide, add flaky sodium hydrate after ultrasonic disperse, after temperature rising reflux reaction, decompression dehydration, obtains graphene oxide Phenolic resin emulsion; The mass ratio of described phenol, formaldehyde, graphene oxide, flaky sodium hydrate is 1: (0.97 ~ 1.14): (0.005 ~ 0.01): (0.01 ~ 0.03);
3) to step 2) add boric acid in the graphene oxide Phenolic resin emulsion of gained, after temperature rising reflux reaction, pour out blackish green dope, be cooled to room temperature, after vacuum-drying, namely obtain graphene oxide-boron-modifiedphenolic phenolic resin; The add-on of described boric acid and step 1) in the mass ratio of phenol be 1: (0.13 ~ 0.27).
2. the preparation method of a kind of graphene oxide-boron-modifiedphenolic phenolic resin as claimed in claim 1, is characterized in that in step 1) in, the time of described reaction is 30 ~ 60min.
3. the preparation method of a kind of graphene oxide-boron-modifiedphenolic phenolic resin as claimed in claim 1, is characterized in that in step 1) in, the described time of at room temperature placing is 72 ~ 96h.
4. the preparation method of a kind of graphene oxide-boron-modifiedphenolic phenolic resin as claimed in claim 1, is characterized in that in step 1) in, the temperature of described warm water is 50 ~ 60 DEG C.
5. the preparation method of a kind of graphene oxide-boron-modifiedphenolic phenolic resin as claimed in claim 1, is characterized in that in step 1) in, the condition of described centrifuge washing is speed 10000 ~ 12000rpm, time 10 ~ 20min.
6. the preparation method of a kind of graphene oxide-boron-modifiedphenolic phenolic resin as claimed in claim 1, is characterized in that in step 2) in, the condition of described ultrasonic disperse is temperature 50 ~ 60 DEG C, time 20 ~ 30min.
7. the preparation method of a kind of graphene oxide-boron-modifiedphenolic phenolic resin as claimed in claim 1, is characterized in that in step 2) in, the condition of described temperature rising reflux reaction is temperature 60 ~ 65 DEG C, time 1 ~ 2h.
8. the preparation method of a kind of graphene oxide-boron-modifiedphenolic phenolic resin as claimed in claim 1, is characterized in that in step 3) in, the condition of described temperature rising reflux reaction is temperature 90 ~ 100 DEG C, time 1 ~ 2h; Described vacuum drying condition is temperature 50 ~ 60 DEG C, time 24 ~ 36h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310450626.8A CN103483516B (en) | 2013-09-27 | 2013-09-27 | Preparation method of graphene oxide-boron-modified phenolic resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310450626.8A CN103483516B (en) | 2013-09-27 | 2013-09-27 | Preparation method of graphene oxide-boron-modified phenolic resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103483516A CN103483516A (en) | 2014-01-01 |
| CN103483516B true CN103483516B (en) | 2015-06-03 |
Family
ID=49824147
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310450626.8A Active CN103483516B (en) | 2013-09-27 | 2013-09-27 | Preparation method of graphene oxide-boron-modified phenolic resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103483516B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104628404B (en) * | 2015-03-02 | 2016-08-24 | 新乡市炬能耐材有限公司 | A kind of preparation method of carbon-to-carbon combined fire-resistant material bonding agent |
| CN104693678B (en) * | 2015-03-12 | 2016-08-24 | 中国科学院长春应用化学研究所 | Phenolic resin-base composite containing Graphene and preparation method thereof |
| CN105038113B (en) * | 2015-07-23 | 2017-11-17 | 安徽瑞侃电缆科技有限公司 | A kind of anti-tear cable of heat-resisting heat conduction |
| CN105038112B (en) * | 2015-07-23 | 2017-11-17 | 安徽瑞侃电缆科技有限公司 | A kind of anti-tear cable of thermostable heat-conductive |
| RU2618881C1 (en) * | 2016-05-16 | 2017-05-11 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Тамбовский государственный технический университет" ФГБОУ ВО "ТГТУ" | Method of producing dispersions of carbon nanomaterials |
| CN106832757B (en) * | 2016-08-12 | 2019-06-18 | 山东圣泉新材料股份有限公司 | A kind of composite material and preparation method of graphene phenol-formaldehyde resin modified, application |
| CN106832758B (en) * | 2017-03-06 | 2019-04-12 | 东北大学秦皇岛分校 | A kind of graphene/phenolic resin heat-conductive composite material and preparation method thereof |
| CN107177162A (en) * | 2017-06-15 | 2017-09-19 | 铜陵安博电路板有限公司 | A kind of conductive phenol formaldehyde resin of copper powder hollow glass microballoon blending and modifying and preparation method thereof |
| CN107880484B (en) * | 2017-12-05 | 2020-07-03 | 中北大学 | Nano particle/graphene oxide composite modified high polymer material and preparation thereof |
| CN108504031A (en) * | 2018-04-20 | 2018-09-07 | 宿迁南航新材料与装备制造研究院有限公司 | A kind of preparation method of graphene oxide/phenolic resin film |
| CN109183434A (en) * | 2018-08-20 | 2019-01-11 | 苏州宏久航空防热材料科技有限公司 | A kind of organic cloth of functionalization |
| CN109553918A (en) * | 2018-11-20 | 2019-04-02 | 苏州宏久航空防热材料科技有限公司 | A kind of urea and melamine activeness and quietness graphene oxide phenol-formaldehyde resin modified foam and preparation method thereof |
| CN112778868A (en) * | 2021-01-04 | 2021-05-11 | 张茜茜 | Graphene modified phenolic resin composite coating with high thermal stability and preparation method thereof |
| CN114479328A (en) * | 2022-02-24 | 2022-05-13 | 杭州高烯科技有限公司 | Preparation method of acetal polymer-graphene composite material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502612A (en) * | 2011-11-21 | 2012-06-20 | 南京工业大学 | Method for preparing grapheme through oxidation reduction |
| CN102786045A (en) * | 2012-07-27 | 2012-11-21 | 中国航空工业集团公司北京航空材料研究院 | Method for preparing oxidized graphene |
-
2013
- 2013-09-27 CN CN201310450626.8A patent/CN103483516B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502612A (en) * | 2011-11-21 | 2012-06-20 | 南京工业大学 | Method for preparing grapheme through oxidation reduction |
| CN102786045A (en) * | 2012-07-27 | 2012-11-21 | 中国航空工业集团公司北京航空材料研究院 | Method for preparing oxidized graphene |
Non-Patent Citations (2)
| Title |
|---|
| 氧化石墨烯/ 酚醛树脂原位复合材料的热性能和动态力学性能;徐伟华等;《高分子材料科学与工程》;20130531;第29卷(第5期);摘要及1.2合成部分 * |
| 王晓威等.硼改性酚醛树脂的合成及其热性能研究.《厦门大学学报(自然科学版)》.2013,第52卷(第2期),第226-231页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103483516A (en) | 2014-01-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103483516B (en) | Preparation method of graphene oxide-boron-modified phenolic resin | |
| Yang et al. | Synchronously improved electromagnetic interference shielding and thermal conductivity for epoxy nanocomposites by constructing 3D copper nanowires/thermally annealed graphene aerogel framework | |
| Li et al. | Multifunctional MXene-based fireproof electromagnetic shielding films with exceptional anisotropic heat dissipation capability and joule heating performance | |
| Liu et al. | Ultrastrong and highly conductive MXene‐based films for high‐performance electromagnetic interference shielding | |
| Wang et al. | Hydro-sensitive sandwich structures for self-tunable smart electromagnetic shielding | |
| Qi et al. | Highly conductive calcium ion-reinforced MXene/sodium alginate aerogel meshes by direct ink writing for electromagnetic interference shielding and Joule heating | |
| CN103396586B (en) | Graphene oxide fiber, preparation method, and preparation method of graphene oxide fiber composite material | |
| Pan et al. | Highly thermally conductive 3D BN/MWCNTs/C spatial network composites with improved electrically insulating and flame retardancy prepared by biological template assisted method | |
| CN104262588B (en) | A kind of epoxide resin conductive adhesive comprising graphite oxide thiazolinyl firming agent | |
| CN104693678A (en) | Phenolic resin-based composite material containing graphene and preparation method thereof | |
| Liu et al. | Thermally conductive and electrically insulating alumina-coated graphite/phthalonitrile composites with thermal stabilities | |
| CN111925630B (en) | High-strength electromagnetic shielding and heat conducting PBT/PET nano composite material and preparation method thereof | |
| CN102850717A (en) | High thermal conductivity phenolic resin and preparation method | |
| CN105622983A (en) | Method for preparing graphene nanoplatelets special for thermal conductive plastic | |
| CN113416334B (en) | Hydroxyethyl cellulose/boron nitride nano composite film and preparation method thereof | |
| CN103951916A (en) | RGO (Reduced Graphene oxide)/ferric oxide-filled polyvinylidene fluoride composite wave-absorbing material and preparation method thereof | |
| CN102796373B (en) | Graphene/cyanate ester/bimaleimide composite material and preparation method thereof | |
| He et al. | Excellent thermally conducting modified graphite nanoplatelets and MWCNTs/poly (phenylene sulfone) composites for high-performance electromagnetic interference shielding effectiveness | |
| Luo et al. | Synergistic effect of multiscale BNs/CNT and 3D melamine foam on the thermal conductive of epoxy resin | |
| Liu et al. | Construction of 3D interconnected and aligned boron nitride nanosheets structures in phthalonitrile composites with high thermal conductivity | |
| JP2008166641A (en) | Expanded carbon fiber composite material for electromagnetic shield with thermal conductivity and electric conductivity, and manufacturing method thereof | |
| CN111621253A (en) | Graphite-based high-strength heat-conducting epoxy resin adhesive and preparation method thereof | |
| CN108929521B (en) | High-thermal-conductivity and high-electric-conductivity graphene-based composite material and preparation method thereof | |
| Vidyashree et al. | Mimicking ‘sea-urchin’like heirarchical carbon structures self-assembled from carbon fibers for green EMI shielding | |
| CN107686635B (en) | Preparation method of graphene/solid epoxy resin high-thermal-conductivity 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 | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP02 | Change in the address of a patent holder | ||
| CP02 | Change in the address of a patent holder |
Address after: 363000 the southern tip of Xiamen University Zhangzhou campus, Zhangzhou, Fujian Patentee after: XIAMEN University Address before: Xiamen City, Fujian Province, 361005 South Siming Road No. 422 Patentee before: XIAMEN University |