CN103865298B - Preparation method of graphene filler capable of enhancing function of epoxy resin - Google Patents
Preparation method of graphene filler capable of enhancing function of epoxy resin Download PDFInfo
- Publication number
- CN103865298B CN103865298B CN201410049583.7A CN201410049583A CN103865298B CN 103865298 B CN103865298 B CN 103865298B CN 201410049583 A CN201410049583 A CN 201410049583A CN 103865298 B CN103865298 B CN 103865298B
- Authority
- CN
- China
- Prior art keywords
- graphene
- fgns
- preparation
- socl
- epoxy resin
- 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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of a graphene filler capable of enhancing a function of epoxy resin. The preparation method comprises the steps: preparing to obtain oxidized graphene by adopting a two-step oxidation process, then mixing the oxidized graphene with thionyl chloride, and adding a small amount of dimethylformamide for reflux; after the reflux is ended, removing excessive thionyl chloride, adding anhydrous dimethylformamide in a residual solid, completely ultrasonically dissolving the solid, dropwise adding a mixed solution in m-xylylenediamine, ultrasonically treating to obtain a uniform solution, heating to 120 DEG C and preserving the heat for 6-12 hours, centrifugally separating and collecting a precipitate, dispersing the precipitate in acetone to form a uniform dispersion liquid, adding epoxy resin at a certain proportion, ultrasonically treating to obtain a mixture liquid, removing bubbles and excessive acetone and cooling to a room temperature to obtain a suspension, and after adding a solidifying agent for solidifying, and cooling to a room temperature to prepare the graphene filler. The graphene filler prepared by adopting the preparation method has better compatibility and dispersity in an epoxy resin matrix, and is capable of enhancing the mechanical property of a material.
Description
Technical field
The invention belongs to functional nonmetallic composite technical field, particularly relating to can the preparation method of Graphene filler of reinforced epoxy function.
Background technology
Graphene be a kind of by carbon atom with sp
2hybridized orbital composition hexangle type is the novel material of the individual layer sheet structure of honeycomb lattice, only has the thickness of a carbon atom, it is maximum, the electroconductibility best material of intensity in the world up to now, and grapheme material or a kind of excellent properties-correcting agent, these advantages make it have huge application potential in the field such as microelectronics, new forms of energy.Research finds, by nano composite material prepared by Graphene and functional polymer compound, can improve the over-all properties of material significantly, gives the new performance of matrix material and characteristic simultaneously.
Polymer composite, high-performance epoxy resin are very important class thermosetting resins, are widely used in spacecraft, electronic product, coating, tackiness agent and other field of compounding.In recent years, relevant Graphene becomes focus for the research of reinforced epoxy material.But, simple Graphene itself has inherent Van der Waals force, and when joining in polymeric system as filler, Graphene is easy to produce reunites and stacking, thus greatly have impact on the dispersing property of Graphene in polymeric system, then affect the performance of final matrix material.Therefore by the surface modification to Graphene, make graphenic surface possess certain activity on the one hand, can well be dispersed in epoxy resin and other polymeric matrixs; Can make to produce very strong interaction force between Graphene and polymeric matrix to the surface modification of Graphene on the other hand, thus effectively produce Stress transmit.In view of this, the present invention adopts mphenylenediamine to carry out amination to graphenic surface, follow-uply finally reaches with epoxy resin compound the effect strengthened epoxy resin composite material mechanics.
Summary of the invention
The object of the invention is to: provide a kind of can the preparation method of Graphene filler of reinforced epoxy function, graphene oxide (GO) is prepared by adopting two-step penetration method, mphenylenediamine is then utilized to carry out amination modified process to its surface, make prepared Graphene modified product have good wetting ability and can be covalently bound with polymkeric substance functionalization group, and then the amalgamation improved between Graphene and polymkeric substance and dispersiveness.
To achieve these goals, the present invention adopts following technical scheme:
Can the preparation method of Graphene filler of reinforced epoxy function, concrete steps are as follows:
(1) the Hummers method improved is adopted to prepare graphene oxide (GO);
(2) graphene oxide (GO) that step (1) prepares is joined thionyl chloride (SOCl
2) in obtain " the GO/SOCl of certain mass concentration
2" mixing solutions, by " GO/SOCl
2" mixing solutions is placed in reflux, after adding micro-dimethyl formamide (DMF), reflux 24 ~ 36 hours at 70 DEG C, do protective tube with Calcium Chloride Powder Anhydrous;
(3), after backflow terminates, excessive SOCl is removed in distillation
2then in remaining solid, add dry DMF, remaining solid was dissolved completely in ultrasonic 10 minutes, then mixing solutions is dropwise joined in the m-xylene diamine (m-XDA) of ice-water bath, continue ultrasonic 10 minutes until obtain uniform solution, be warming up to 120 DEG C and keep 6 ~ 12 hours;
(4) centrifugal collecting precipitation: a large amount of alcohol flushing of product step (3) obtained, can obtain the derivative of the graphene oxide with amino end group, is labeled as m-xylene diamine functional graphene oxide (FGNs);
(5) FGNs of a certain amount of step (4) gained is taken, and be scattered in acetone the uniform dispersion forming finite concentration FGNs, add a certain amount of epoxy resin (EP) more in proportion, within ultrasonic 2 ~ 4 hours, obtain " FGNs/EP " mixture solution, described mixture solution removes bubble and excessive acetone in 60 DEG C of vacuum;
(6) mixture solution of removing bubble and excessive propanone in step (5) is cooled to room temperature, obtain " FGNs/EP " suspension, suspension to be transferred in open template and to add solidifying agent, suspension solidifies respectively at 60 DEG C and 150 DEG C, naturally cools to room temperature and can prepare completely crosslinked matrix material FGNs/EP.
Further, the Hummers method of described improvement refers to two-step penetration method, comprise preoxidation and two stages of oxidation, namely pass through Potassium Persulphate, Vanadium Pentoxide in FLAKES and the vitriol oil to after Graphite Powder 99 preoxidation, then obtain graphene oxide by the oxidation of vitriol oil potassium permanganate system.
" GO/SOCl described in step (2)
2" mass concentration of mixing solutions is 0.1mg/mL ~ 100mg/mL.
Know-why of the present invention and beneficial effect:
Know-why of the present invention is: adopt two-step penetration method to prepare graphene oxide (GO), mphenylenediamine is then utilized to carry out amination modified process to its surface, prepared Graphene modified product is made to have good wetting ability and functionalization group, by the chemical bond-linking graft (co) polymers of these functionalization groups, the reunion that produces due to Van der Waals force and stacking phenomenon effectively can be prevented; Simultaneously due to the existence of these functionalization groups, when graphene oxide joins in polymeric system as filler, the polymer network that interaction force is very strong can be formed, thus the amalgamation improved between Graphene and polymkeric substance and dispersiveness.
Compared with prior art, beneficial effect of the present invention is:
(1) the inventive method preparation can the Graphene packed art of reinforced epoxy function simple, equipment is simple, cost is low, be applicable to scale operation;
(2) what prepared by the inventive method the Graphene filler of reinforced epoxy function can have good amalgamation and dispersiveness in epoxy resin-base, simultaneously also can the mechanical property of reinforced epoxy.
Accompanying drawing explanation
Fig. 1 is the FT-IR spectrogram of Graphene, graphene oxide and FGNs.
Fig. 2 is the ultimate tensile strength of the FGNs/EP matrix material that EP and different FGNs content are filled and toughness (a) and greatest compressive strength (b) comparison diagram.
Embodiment
Below in conjunction with specific examples, technical scheme of the present invention is described further, but does not limit the scope of the invention.
Embodiment 1
Can the preparation method of Graphene filler of reinforced epoxy function, concrete steps are as follows:
(1) the Hummers method improved is adopted to prepare graphene oxide (GO);
(2) the 100mg graphene oxide (GO) that step (1) prepares is joined 20mL thionyl chloride (SOCl
2) in obtain the GO/SOCl of certain mass concentration
2mixing solutions, by GO/SOCl
2mixing solutions is placed in reflux, after adding 0.5mL dimethyl formamide (DMF), refluxes 24 hours, do protective tube with Calcium Chloride Powder Anhydrous at 70 DEG C;
(3), after backflow terminates, excessive SOCl is removed in distillation
2then in remaining solid, 20mL dry DMF is added, remaining solid was dissolved completely in ultrasonic 10 minutes, again mixing solutions is dropwise joined in the m-xylene diamine (m-XDA) of 20mL ice-water bath, continue ultrasonic 10 minutes until obtain uniform solution, be warming up to 120 DEG C and keep 12 hours;
(4) centrifugal collecting precipitation: a large amount of alcohol flushing of product step (3) obtained, can obtain the derivative of the graphene oxide with amino end group, is labeled as m-xylene diamine functional graphene oxide (FGNs);
(5) FGNs of a certain amount of step (4) gained is taken, and be scattered in acetone the uniform dispersion of the FGNs forming 0.125mg/mL, add a certain amount of epoxy resin (EP) more in proportion, ultrasonic 2 hours, acutely ultrasonic 2 hours again, obtain " FGNs/EP " mixture solution, described mixture solution removes bubble and excessive acetone in 60 DEG C of vacuum;
(6) mixture solution of removing bubble and excessive propanone in step (5) is cooled to room temperature, obtain " FGNs/EP " suspension, suspension to be transferred in open template and to add solidifying agent, suspension solidifies respectively at 60 DEG C and 150 DEG C, naturally cools to room temperature and can prepare completely crosslinked matrix material FGNs/EP.
Embodiment 2
Can the preparation method of Graphene filler of reinforced epoxy function, concrete steps are as follows:
(1) the Hummers method improved is adopted to prepare graphene oxide (GO);
(2) the 100mg graphene oxide (GO) that step (1) prepares is joined 20mL thionyl chloride (SOCl
2) in obtain the GO/SOCl of certain mass concentration
2mixing solutions, by GO/SOCl
2mixing solutions is placed in reflux, after adding 0.5mL dimethyl formamide (DMF), refluxes 24 hours, do protective tube with Calcium Chloride Powder Anhydrous at 70 DEG C;
(3), after backflow terminates, excessive SOCl is removed in distillation
2then in remaining solid, 20mL dry DMF is added, remaining solid was dissolved completely in ultrasonic 10 minutes, again mixing solutions is dropwise joined in the m-xylene diamine (m-XDA) of 20mL ice-water bath, continue ultrasonic 10 minutes until obtain uniform solution, be warming up to 120 DEG C and keep 12 hours;
(4) centrifugal collecting precipitation: a large amount of alcohol flushing of product step (3) obtained, can obtain the derivative of the graphene oxide with amino end group, is labeled as m-xylene diamine functional graphene oxide (FGNs);
(5) FGNs of a certain amount of step (4) gained is taken, and be scattered in acetone the uniform dispersion of the FGNs forming 0.25mg/mL, add a certain amount of epoxy resin (EP) more in proportion, ultrasonic 2 hours, acutely ultrasonic 2 hours again, obtain " FGNs/EP " mixture solution, described mixture solution removes bubble and excessive acetone in 60 DEG C of vacuum;
(6) mixture solution of removing bubble and excessive propanone in step (5) is cooled to room temperature, obtain " FGNs/EP " suspension, suspension to be transferred in open template and to add solidifying agent, suspension solidifies respectively at 60 DEG C and 150 DEG C, naturally cools to room temperature and can prepare completely crosslinked matrix material FGNs/EP.
Interpretation of result:
Fig. 1 is the FT-IR spectrogram of Graphene, graphene oxide (GO) and FGNs, and as can be seen from the figure, the characteristic peak of graphene oxide (GO) has: be positioned at 1480cm
-1and 1063cm
-1-OH the absorption peak at place; Be positioned at 1630cm
-1the C=O absorption peak at place; And be positioned at 849cm
-1the C-O-C absorption peak at place.As can be seen from the figure, the intensity through the infrared spectra peak of the oxygen-containing functional group of the modified FGNs product of m-XDA reduces, if epoxide group absorption peak is 849cm
-1place ,-OH absorption peak are then 3440cm
-1place and 1460cm
-1, meanwhile, in spectrogram, have also appeared new-CH2 stretching vibration absorption peak (2920cm
-1), the stretching vibration absorption peak (1630cm of amidocarbonylation
-1) and the flexural vibration absorption peak (1530cm of-NH
-1), these new absorption peaks prove that m-XDA successfully achieves Graphene modification.
Fig. 2 demonstrates the ultimate tensile strength of the FGNs/EP matrix material that pure EP and different FGNs content are filled and toughness and maximum compressive strength contrast, as can be seen from the figure, compared with pure epoxy resin (EP), after adding the FGNs of 0.1wt% and 0.2wt% respectively, the ultimate tensile strength of FGS/EP matrix material is corresponding improves 12% and 21%; Toughness improves 362.2% and 150.4% respectively, and ultimate compression strength adds 11.2% and 14.8% respectively.
Claims (2)
1. can the preparation method of Graphene filler of reinforced epoxy function, it is characterized in that: the concrete steps of the method are as follows:
(1) the Hummers method improved is adopted to prepare graphene oxide (GO), the Hummers method of described improvement refers to two-step penetration method, comprise preoxidation and two stages of oxidation, namely pass through Potassium Persulphate, Vanadium Pentoxide in FLAKES and the vitriol oil to after Graphite Powder 99 preoxidation, then obtain graphene oxide by the oxidation of vitriol oil potassium permanganate system;
(2) graphene oxide (GO) that step (1) prepares is joined thionyl chloride (SOCl
2) in obtain " the GO/SOCl of certain mass concentration
2" mixing solutions, by " GO/SOCl
2" mixing solutions is placed in reflux, after adding micro-dimethyl formamide (DMF), reflux 24 ~ 36 hours at 70 DEG C, do protective tube with Calcium Chloride Powder Anhydrous;
(3), after backflow terminates, excessive SOCl is removed in distillation
2then in remaining solid, add dry DMF, remaining solid was dissolved completely in ultrasonic 10 minutes, then mixing solutions is dropwise joined in the m-xylene diamine (m-XDA) of ice-water bath, continue ultrasonic 10 minutes until obtain uniform solution, be warming up to 120 DEG C and keep 6 ~ 12 hours;
(4) centrifugal collecting precipitation: a large amount of alcohol flushing of product step (3) obtained, can obtain the derivative of the graphene oxide with amino end group, is labeled as m-xylene diamine functional graphene oxide (FGNs);
(5) FGNs of a certain amount of step (4) gained is taken, and be scattered in acetone the uniform dispersion forming finite concentration FGNs, add a certain amount of epoxy resin (EP) more in proportion, within ultrasonic 2 ~ 4 hours, obtain " FGNs/EP " mixture solution, described mixture solution removes bubble and excessive acetone in 60 DEG C of vacuum;
(6) mixture solution of removing bubble and excessive propanone in step (5) is cooled to room temperature, obtain " FGNs/EP " suspension, suspension to be transferred in open template and to add solidifying agent, suspension solidifies respectively at 60 DEG C and 150 DEG C, naturally cools to room temperature and can prepare completely crosslinked matrix material FGNs/EP.
2. as claimed in claim 1 can the preparation method of Graphene filler of reinforced epoxy function, it is characterized in that: " the GO/SOCl described in step (2)
2" mass concentration of mixing solutions is 0.1mg/mL ~ 100mg/mL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410049583.7A CN103865298B (en) | 2014-02-13 | 2014-02-13 | Preparation method of graphene filler capable of enhancing function of epoxy resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410049583.7A CN103865298B (en) | 2014-02-13 | 2014-02-13 | Preparation method of graphene filler capable of enhancing function of epoxy resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103865298A CN103865298A (en) | 2014-06-18 |
| CN103865298B true CN103865298B (en) | 2015-06-17 |
Family
ID=50904337
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410049583.7A Active CN103865298B (en) | 2014-02-13 | 2014-02-13 | Preparation method of graphene filler capable of enhancing function of epoxy resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103865298B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104212295B (en) * | 2014-09-12 | 2016-06-08 | 陕西科技大学 | Ultrasonic wave added method prepares the method for polyacrylate/amino modified graphene oxide composite leather coating agent |
| CN106145093A (en) * | 2015-04-03 | 2016-11-23 | 天津工业大学 | A kind of preparation method of the modified graphene oxide material of strong-hydrophobicity |
| CN105001451A (en) * | 2015-06-12 | 2015-10-28 | 同济大学 | Graphene containing DOPO group and preparation method thereof |
| CN105802133B (en) * | 2016-04-14 | 2018-03-06 | 常州大学 | A kind of preparation method of graphene-based epoxy resin composite heat interfacial material |
| CN108929060B (en) * | 2018-07-27 | 2020-12-15 | 青岛理工大学 | Geopolymer cement modified based on graphene and epoxy resin and preparation method thereof |
| WO2020082297A1 (en) * | 2018-10-25 | 2020-04-30 | 苏州吉人高新材料股份有限公司 | Composite water-based epoxy resin and manufacturing method therefor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775241A (en) * | 2009-12-31 | 2010-07-14 | 国家复合改性聚合物材料工程技术研究中心 | Stearic acid modified graphene and application thereof |
| CN102061109A (en) * | 2010-12-10 | 2011-05-18 | 华东理工大学 | Method for preparing benzoxazole functionalized graphene hybrid materials |
-
2014
- 2014-02-13 CN CN201410049583.7A patent/CN103865298B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775241A (en) * | 2009-12-31 | 2010-07-14 | 国家复合改性聚合物材料工程技术研究中心 | Stearic acid modified graphene and application thereof |
| CN102061109A (en) * | 2010-12-10 | 2011-05-18 | 华东理工大学 | Method for preparing benzoxazole functionalized graphene hybrid materials |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103865298A (en) | 2014-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103865298B (en) | Preparation method of graphene filler capable of enhancing function of epoxy resin | |
| Wei et al. | Influence of graphene oxide with different oxidation levels on the properties of epoxy composites | |
| Chhetri et al. | Functionalized reduced graphene oxide/epoxy composites with enhanced mechanical properties and thermal stability | |
| Kim et al. | Amine-terminated chain-grafted nanodiamond/epoxy nanocomposites as interfacial materials: Thermal conductivity and fracture resistance | |
| Rajadurai | Thermo-mechanical characterization of siliconized E-glass fiber/hematite particles reinforced epoxy resin hybrid composite | |
| Wang et al. | Carboxyl-terminated butadiene-acrylonitrile-toughened epoxy/carboxyl-modified carbon nanotube nanocomposites: Thermal and mechanical properties. | |
| CN105714138B (en) | A kind of method for preparing graphene enhancing Cu-base composites | |
| CN102040714B (en) | Preparation method of polymer-grafted graphene | |
| CN104262588A (en) | Graphene oxide-based curing agent as well as preparation and use thereof | |
| CN112778703B (en) | High-toughness and heat-conducting epoxy resin composite material and preparation method thereof | |
| CN104231624A (en) | Modified cyanate resin heat-conducting composite material and preparation method thereof | |
| Saadatmandi et al. | Effective epoxy composite coating mechanical/fracture toughness properties improvement by incorporation of graphene oxide nano-platforms reduced by a green/biocompataible reductant | |
| CN105907042B (en) | A kind of functionalized carbon nano-tube epoxy resin nano composites and preparation method thereof | |
| Martin‐Gallego et al. | Epoxy nanocomposites filled with carbon nanoparticles | |
| CN104261385A (en) | Modified carbon material as well as preparation method and application thereof | |
| CN112375369A (en) | Interface supermolecule reinforced nano composite material and preparation method thereof | |
| CN102660097B (en) | Preparation method of reinforced polyvinyl alcohol compound | |
| Shen et al. | Efficient reinforcement of epoxy resin with amine‐rich rigid short‐chain grafted graphene oxide | |
| CN103073930A (en) | Preparation method and application of alkylated functional graphene | |
| CN103589113A (en) | Heat-conducting packaging electric-insulating material and preparation method thereof | |
| Kim et al. | Effect of graphene oxide on interfacial interactions and fracture toughness of basalt fiber-reinforced epoxy composites | |
| CN104151827A (en) | Preparation method of carbon fiber/carbon nanotube/organic silicone resin multidimensional hybrid composite material | |
| CN104031290A (en) | Preparation method of graphene/polymer composite material with high strength and high low-temperature toughness | |
| Wu et al. | The comparison of mechanical and thermal properties of carbon nanotubes and graphene naonosheets enhanced phenol-formaldehyde resin | |
| CN106519586A (en) | Glass fiber/vinyl ester resin composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent of invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Tang Bo Inventor after: Cao Guoxin Inventor after: Zang Lijing Inventor after: Ma Yingtao Inventor after: Yang Xiaorui Inventor after: Zhou Yang Inventor after: He Chaoqi Inventor after: Shang Tianbao Inventor after: Zhu Ming Inventor before: Tang Bo Inventor before: Cao Guoxin Inventor before: Zang Lijing Inventor before: Ma Yingtao |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: TANG BO CAO GUOXIN ZANG LIJING MA YINGTAO TO: TANG BO CAO GUOXIN ZANG LIJING MA YINGTAO YANG XIAORUI ZHOU YANG HE CHAOQI SHANG TIANBAO ZHU MING |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230724 Address after: No. 163, Group 1, Shilipu Village, Shilipu Town, Kongtong District, Pingliang, Gansu Province, 744000 Patentee after: Pingliang Lingken Zhongjing New Materials Co.,Ltd. Address before: 744000 Pingliang Industrial Park, Gansu Province Patentee before: GANSU KANGBOSITE NEW MATERIAL Co.,Ltd. |