CN104151775A - Preparation method of three-dimensional cross-linked graphene foam structure reinforced resin composite material - Google Patents
Preparation method of three-dimensional cross-linked graphene foam structure reinforced resin composite material Download PDFInfo
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- CN104151775A CN104151775A CN201410384068.4A CN201410384068A CN104151775A CN 104151775 A CN104151775 A CN 104151775A CN 201410384068 A CN201410384068 A CN 201410384068A CN 104151775 A CN104151775 A CN 104151775A
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Abstract
The invention relates to the field of nano composite material preparation and in particular relates to a preparation method of a three-dimensional cross-linked graphene foam structure reinforced resin composite material. The preparation method comprises the following steps: (1) adding a multiamino compound, forming a flocculate of graphene oxide and the amino compound in a graphene oxide solution, centrifuging, performing freeze-drying and heating for reaction to prepare a three-dimensional cross-linked graphene foam structure; (2) filling the three-dimensional cross-linked graphene foam structure with resin by methods of vacuum pressure or negative pressure flow forming and the like, defoaming, and curing to prepare the three-dimensional cross-linked graphene foam structure reinforced resin composite material. According to the preparation method, the assembled and formed three-dimensional cross-linked graphene foam structure is filled with the resin, so that serious agglomeration phenomenon occurring in a graphene and resin mixing process is effectively avoided and the obtained three-dimensional cross-linked graphene foam structure reinforced resin composite material is excellent in performance.
Description
Technical field
The preparation method who the present invention relates to a kind of three-dimensional cross-linked grapheme foam structural reinforcing resin composite materials, belongs to Nano-composite materials field.
Background technology
Graphene is a kind of by the tightly packed bi-dimensional cellular shape crystalline structure forming of carbon atom, is the basic structural unit that builds other dimension Carbon Materials (zero dimension soccerballene, one-dimensional nano carbon pipe, three-dimensional graphite).The crystalline structure of Graphene uniqueness makes it have excellent mechanics and electric property, is considered to the desirable strongthener of matrix material.The exterior appearance of its two-dimensional sheet and super large specific surface area can contact more closely with body material generation is abundanter, have better and strengthen the property than the carbon nanotube of one dimension.
The preparation method of Graphene/resin composite materials is mainly solution mechanical blending method at present; but while adopting the method to prepare graphene composite material; be difficult to two-dimentional graphene film to be dispersed in completely uniformly in the polymkeric substance such as resin; graphene film can again be reunited conventionally in polymeric matrix; cause uneven distribution state; make the effective content of Graphene in matrix material lower than desired value, thereby have influence on the properties of Graphene enhancing polymer matrix composites.
The present invention proposes graphene nanometer sheet to be assembled into the three-dimensional cross-linked foamy structure of macroscopic view, prepares graphene composite material as the reinforcement of the polymer composites such as resin, can effectively improve Graphene content, avoids the generation of Graphene from agglomeration simultaneously.
Summary of the invention
The invention provides the preparation method that a kind of novel Graphene strengthens resin composite materials.In chemical reaction process, by the effect of intermediate, between graphene film, form certain chemical bond, construct a kind of three-dimensional cross-linked grapheme foam structure.Again by perfusion resin in the three-dimensional cross-linked grapheme foam structure of preparation, effectively overcome Graphene in composite material shaping process from the generation of reuniting, obtain the three-dimensional cross-linked grapheme foam structural reinforcing resin composite materials of excellent performance.
Technical scheme of the present invention realizes by following steps:
(1) select suitable multiamino compound as intermediate, join in graphene oxide solution, form the throw out of graphene oxide and multiamino compound, through centrifugal treating, lyophilize with add thermochemical reaction process and prepare three-dimensional cross-linked grapheme foam structure;
(2) utilize vacuum to suppress or the method such as negative pressure flowing forming, perfusion resin, fills three-dimensional cross-linked grapheme foam vesicular structure, prepares three-dimensional cross-linked grapheme foam structural reinforcing resin composite materials through deaeration, solidification process.
Multiamino compound in above-mentioned steps (1) is dendritic macromole polyamide-amine, diethylenetriamine, mphenylenediamine, triethylene tetramine, chitosan etc.
Three-dimensional cross-linked grapheme foam structure prepared by aforesaid method is the three-dimensional structure that graphene sheet layer forms under the ligation of covalent linkage, and the concentration of graphite oxide aqueous solution is 0.1～10mg/mL.
The resin of filling three-dimensional cross-linked Graphene vesicular structure in above-mentioned steps (2) is the thermosetting resins such as epoxy resin, resol, unsaturated polyester resin, terpolycyantoamino-formaldehyde resin, furane resin, silicone resin.
Embodiment
Below in conjunction with specific embodiment, the preparation method of a kind of three-dimensional cross-linked grapheme foam structural reinforcing resin composite materials provided by the invention is elaborated.
Embodiment 1:
To graphite oxide aqueous solution supersound process 3h, the graphite oxide aqueous solution 400ml that preparation concentration is 1.0mg/ml, drips 2g polyamide-amide, occurs rapidly flocculation phenomenon, after leaving standstill, occurs obvious demixing phenomenon.After high speed centrifugation is removed unnecessary solvent, throw out is placed in to mould, precooling 12h at-10 DEG C, vacuum lyophilization 24h at-50 DEG C, obtains vesicular graphene oxide and polyamide-amide mixture.And at 150 DEG C of reacting by heating 12h, in mould, forming the three-dimensional cross-linked grapheme foam structure of vesicular, this structure disperses 2h still to maintain the original state in deionized water for ultrasonic.
100: 70: 1 ratio blending epoxy, solidifying agent and promotor in mass ratio, constant temperature 30min at 60 DEG C, reduces the viscosity of resin, to increase its mobility.Sealed mold, makes the three-dimensional cross-linked grapheme foam structure preparing in totally sealed environment, under vacuum pump suction, makes mould in negative pressure state, to resin container pressurization, makes resin enter mould grapheme foam is fully infiltrated, filled simultaneously.Then the moulding that is heating and curing under 90 DEG C/3h, 120 DEG C/3h, the condition of 150 DEG C/5h, obtains the epoxy resin composite material of three-dimensional cross-linked grapheme foam structural reinforcing.
Embodiment 2:
The acetic acid/water mixed solution 50ml of preparation 2%, adds 0.2g chitosan, stirs 4h and obtain transparent chitosan solution at 40 DEG C.To graphite oxide aqueous solution supersound process 3h, the graphite oxide aqueous solution 200ml that preparation concentration is 2.0mg/ml, drips in the chitosan solution making, and occurs rapidly flocculation phenomenon.After high speed centrifugation is removed unnecessary solvent, throw out is placed in to mould, precooling 12h at-10 DEG C, vacuum lyophilization 24h at-50 DEG C, obtains the mixture of vesicular graphene oxide and chitosan.And at 100 DEG C of reacting by heating 12h, in mould, form the three-dimensional cross-linked grapheme foam structure of vesicular.
Sealed mold, make the three-dimensional cross-linked grapheme foam structure preparing in totally sealed environment, adopt vacuum pump suction mould, heat-reactive phenolic resin is sucked, infiltrate, fill the three-dimensional cross-linked grapheme foam structure under negative pressure state, at 180 DEG C, heat 2h curing molding, obtain the phenolic resin composite of three-dimensional cross-linked grapheme foam structural reinforcing.
Embodiment 3:
To graphite oxide aqueous solution supersound process 4h, the graphite oxide aqueous solution 100ml that preparation concentration is 4.0mg/mL, drips 2g triethylene tetramine, occurs rapidly flocculation phenomenon, after leaving standstill, occurs obvious demixing phenomenon.After high speed centrifugation is removed unnecessary solvent, throw out is placed in to mould, precooling 12h at-10 DEG C, vacuum lyophilization 24h at-50 DEG C, obtains the mixture of vesicular graphene oxide and triethylene tetramine.And at 150 DEG C of reacting by heating 12h, in mould, forming the three-dimensional cross-linked grapheme foam structure of vesicular, this structure disperses 2h still to maintain the original state in deionized water for ultrasonic.
Sealed mold, vacuumizes and suppresses resin container to mould, and perfusion silicone resin, in mould, is then heated to 200 DEG C of insulation 2h curing moldings from room temperature, obtains the silicone resin matrix material of three-dimensional cross-linked grapheme foam structural reinforcing.
Claims (4)
1. a preparation method for three-dimensional cross-linked grapheme foam structural reinforcing resin composite materials, is characterized in that, comprises the following steps:
(1) select suitable multiamino compound, join the throw out that forms graphene oxide and multiamino compound in graphene oxide solution, prepare three-dimensional cross-linked grapheme foam structure through centrifugal treating, lyophilize and reacting by heating process;
(2) utilize vacuum to suppress or the method such as negative pressure flowing forming, perfusion resin, fills three-dimensional cross-linked grapheme foam vesicular structure, and deaeration, the three-dimensional cross-linked grapheme foam structural reinforcing resin composite materials of preparation is heating and curing.
2. preparation method according to claim 1, is characterized in that, described multiamino compound is dendritic macromole polyamide-amine, diethylenetriamine, mphenylenediamine, triethylene tetramine, chitosan etc.
3. preparation method according to claim 1, is characterized in that, graphene oxide concentration of aqueous solution used is 0.1～10mg/mL.
4. preparation method according to claim 1, it is characterized in that, the resin of filling three-dimensional cross-linked Graphene vesicular structure and preparing matrix material is the thermosetting resins such as epoxy resin, resol, unsaturated polyester resin, terpolycyantoamino-formaldehyde resin, furane resin, silicone resin.
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Cited By (16)
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| CN105111690A (en) * | 2015-09-25 | 2015-12-02 | 天津工业大学 | Method for improving mechanics properties of three-dimensional graphene structure body/polymer composite material |
| CN105153707A (en) * | 2015-10-16 | 2015-12-16 | 天津工业大学 | Method for improving mechanical property of three-dimensional graphene structural body/resin composite |
| CN105237686A (en) * | 2015-10-18 | 2016-01-13 | 桂林理工大学 | Preparation method of mesopore-graphene oxide/unsaturated polyester molding plastic |
| CN106832758A (en) * | 2017-03-06 | 2017-06-13 | 东北大学秦皇岛分校 | A kind of Graphene/phenolic resin heat-conductive composite material and preparation method thereof |
| CN106987018A (en) * | 2017-02-04 | 2017-07-28 | 安徽理工大学 | A kind of phenolic resin graphene aerogel and its preparation, application |
| WO2017139678A1 (en) * | 2016-02-12 | 2017-08-17 | Nitto Denko Corporation | Pressure sensitive graphene-based valve element |
| CN108609603A (en) * | 2018-05-27 | 2018-10-02 | 南京航空航天大学 | A kind of carbon foam and preparation method thereof containing graphite ene coatings |
| CN108751170A (en) * | 2018-06-15 | 2018-11-06 | 复旦大学 | A kind of porous laminated graphene frame material and its preparation method and application |
| CN109775693A (en) * | 2018-06-26 | 2019-05-21 | 郑州大学 | A kind of preparation method of nitrogen-doped graphene material |
| CN110105625A (en) * | 2018-02-01 | 2019-08-09 | 中国石油化工股份有限公司 | Modified 3 D graphene and preparation method thereof and polymer composites and preparation method thereof |
| CN110373001A (en) * | 2019-08-23 | 2019-10-25 | 哈尔滨工业大学 | A kind of preparation method based on graphene enhancing carbon fibre composite |
| CN110437586A (en) * | 2019-08-23 | 2019-11-12 | 哈尔滨工业大学 | A kind of preparation method of high dispersive graphene reinforced epoxy based composites |
| CN110452415A (en) * | 2019-08-23 | 2019-11-15 | 哈尔滨工业大学 | A kind of preparation method of high dispersive graphene enhancing bismaleimide resin based composites |
| CN110452414A (en) * | 2019-08-23 | 2019-11-15 | 哈尔滨工业大学 | A kind of preparation method of high starch breeding alkene enhancing bismaleimide resin based composites |
| CN112606420A (en) * | 2020-11-27 | 2021-04-06 | 合肥艺光高分子材料科技有限公司 | Production method of solid silica gel foam |
| US11472939B2 (en) | 2016-12-15 | 2022-10-18 | Sabic Global Technologies B.V. | Thermally conductive three-dimensional (3-D) graphene polymer composite materials, methods of making, and uses thereof |
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| CN105111690A (en) * | 2015-09-25 | 2015-12-02 | 天津工业大学 | Method for improving mechanics properties of three-dimensional graphene structure body/polymer composite material |
| CN105153707A (en) * | 2015-10-16 | 2015-12-16 | 天津工业大学 | Method for improving mechanical property of three-dimensional graphene structural body/resin composite |
| CN105237686B (en) * | 2015-10-18 | 2017-12-12 | 桂林理工大学 | A kind of preparation method of mesoporous graphene oxide/unsaturated polyester die plastic |
| CN105237686A (en) * | 2015-10-18 | 2016-01-13 | 桂林理工大学 | Preparation method of mesopore-graphene oxide/unsaturated polyester molding plastic |
| US10722849B2 (en) | 2016-02-12 | 2020-07-28 | Nitto Denko Corporation | Pressure sensitive graphene-based valve element |
| WO2017139678A1 (en) * | 2016-02-12 | 2017-08-17 | Nitto Denko Corporation | Pressure sensitive graphene-based valve element |
| US20190015792A1 (en) * | 2016-02-12 | 2019-01-17 | Nitto Denko Corporation | Pressure sensitive graphene-based valve element |
| US11472939B2 (en) | 2016-12-15 | 2022-10-18 | Sabic Global Technologies B.V. | Thermally conductive three-dimensional (3-D) graphene polymer composite materials, methods of making, and uses thereof |
| CN106987018A (en) * | 2017-02-04 | 2017-07-28 | 安徽理工大学 | A kind of phenolic resin graphene aerogel and its preparation, application |
| CN106987018B (en) * | 2017-02-04 | 2020-02-14 | 安徽理工大学 | Phenolic resin-graphene aerogel and preparation and application thereof |
| CN106832758A (en) * | 2017-03-06 | 2017-06-13 | 东北大学秦皇岛分校 | A kind of Graphene/phenolic resin heat-conductive composite material and preparation method thereof |
| 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 |
| CN110105625A (en) * | 2018-02-01 | 2019-08-09 | 中国石油化工股份有限公司 | Modified 3 D graphene and preparation method thereof and polymer composites and preparation method thereof |
| CN108609603A (en) * | 2018-05-27 | 2018-10-02 | 南京航空航天大学 | A kind of carbon foam and preparation method thereof containing graphite ene coatings |
| CN108609603B (en) * | 2018-05-27 | 2022-03-22 | 南京航空航天大学 | Carbon foam containing graphene coating and preparation method thereof |
| CN108751170A (en) * | 2018-06-15 | 2018-11-06 | 复旦大学 | A kind of porous laminated graphene frame material and its preparation method and application |
| CN108751170B (en) * | 2018-06-15 | 2021-11-19 | 复旦大学 | Porous layered graphene framework material and preparation method and application thereof |
| CN109775693A (en) * | 2018-06-26 | 2019-05-21 | 郑州大学 | A kind of preparation method of nitrogen-doped graphene material |
| CN110452415A (en) * | 2019-08-23 | 2019-11-15 | 哈尔滨工业大学 | A kind of preparation method of high dispersive graphene enhancing bismaleimide resin based composites |
| CN110452414B (en) * | 2019-08-23 | 2021-02-09 | 哈尔滨工业大学 | Preparation method of highly-oriented graphene reinforced bismaleimide resin matrix composite material |
| CN110437586B (en) * | 2019-08-23 | 2021-04-13 | 哈尔滨工业大学 | Preparation method of high-dispersion graphene reinforced epoxy resin matrix composite material |
| CN110373001B (en) * | 2019-08-23 | 2021-04-13 | 哈尔滨工业大学 | Preparation method of graphene-based reinforced carbon fiber composite material |
| CN110452414A (en) * | 2019-08-23 | 2019-11-15 | 哈尔滨工业大学 | A kind of preparation method of high starch breeding alkene enhancing bismaleimide resin based composites |
| CN110437586A (en) * | 2019-08-23 | 2019-11-12 | 哈尔滨工业大学 | A kind of preparation method of high dispersive graphene reinforced epoxy based composites |
| CN110373001A (en) * | 2019-08-23 | 2019-10-25 | 哈尔滨工业大学 | A kind of preparation method based on graphene enhancing carbon fibre composite |
| CN112606420A (en) * | 2020-11-27 | 2021-04-06 | 合肥艺光高分子材料科技有限公司 | Production method of solid silica gel foam |
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Application publication date: 20141119 |