CN105820569A - Preparation method of graphene/polyimide composite material - Google Patents
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Abstract
The invention discloses a preparation method of a graphene/polyimide composite material, belonging to the technical field of composite materials. The preparation method comprises the following steps: performing ultrasonic dispersion of graphene oxide in a dimethyl sulfoxide solvent to obtain graphene oxide dispersion; crosslinking and coupling the graphene with 2-vinyl-5-aminothiophenol under the effect of a coupling agent vinyldimethoxysilane and a crosslinking agent N,N-methylene bisacrylamide to obtain modified graphene containing mercapto, carbon-carbon double bond and amino cross-linkable groups; condensing 4,4-diaminodiphenyl ether and pyromellitic dianhydride to obtain polyamide acid; and crosslinking the modified graphene containing different cross-linkable groups with polyamide acid to obtain a modified graphene/polyimide composite material. In the invention, the interface bonding between graphene and polyimide matrix is strong, the compatibility with a polymer is good, and the mechanical properties of the material are improved.
Description
Technical field
The invention discloses the preparation method of a kind of graphene/polyimide composite material, belong to technical field of composite materials.
Background technology
Polyimides is owing to having the electrical property of excellence, mechanical performance, excellent chemical resistance, solvent resistance, higher thermal stability, less thermal coefficient of expansion and good processing technology and be widely used in the sophisticated technology fields such as Aero-Space, electronic apparatus, military equipment field, automobile, communication.But the extension along with application, to the high-performance of product and improving constantly of product stability requirement under circumstances, traditional polyimide resin can not fully meet the demand of each field development, the mechanical property of polyimide resin must be improved further, heat stability and hydrophobicity, this is accomplished by being modified polyimide resin.Inorganic component is introduced in polyimide matrix and reach the compound of inorganic organic performance, become more effective method in its modified work.
There are some researches show, the Graphene only adding trace just can produce bigger lifting to the capacity of heat transmission of resin matrix and linear expansion coefficient, significantly strengthens and has widened its application.But, the relevant research and development for graphene/polyimide composite material are little, and its heat conductivility of the material developed at present is poor, generally less than 0.5w/m.k, it is impossible to be satisfied with the demand on market well.Its main cause can be attributed to two aspects: on the one hand, and Graphene, when with polymer composite, self is easily reunited and to cause it to disperse in the base uneven；Still further aspect, between Graphene and polymeric matrix, interface cohesion is weak, and poor with polymer compatibility, and the most as easy as rolling off a log formation stress concentration point and Stress Transfer efficiency are low, thus can not effectively improve the performance of polymer.It is proposed that interface cohesion is strong between a kind of Graphene and polymeric matrix, the graphene/polyimide composite material preparation method good with polymer compatibility is extremely important.
Summary of the invention
nullThe technical problem that present invention mainly solves: weak for interface cohesion between current Graphene and polymeric matrix，And the problem poor with polymer compatibility，Provide the preparation method of a kind of graphene/polyimide composite material，The present invention is that graphite oxide carries out ultrasonic disperse in dimethylsulfoxide solvent，Obtain graphene oxide dispersion，Then Graphene is at coupling agent vinyl dimethoxysilane、Cross-linking agent N，Carry out with 2-vinyl-5-mercaptoaniline under the effect of N-methylene-bisacrylamide cross-linking coupling，Obtain containing sulfydryl、Carbon-carbon double bond、The modified graphene of amido crosslinkable groups，Then by 4,4-diaminodiphenyl ether and pyromellitic acid anhydride carry out being condensed to yield polyamic acid，Finally the modified graphene with crosslinked group is cross-linked with polyamic acid，Make modified graphene/composite polyimide material.Between Graphene and the polyimide matrix of the present invention, interface cohesion is strong, good with polymer compatibility, and improves the mechanical property of material.
In order to solve above-mentioned technical problem, the technical solution adopted in the present invention is:
1. Weigh 10～20g graphene oxides and load the 500mL two mouthfuls of round-bottomed flasks with thermometer, and in two mouthfuls of round-bottomed flasks, add 10～15mL dimethyl sulfoxides, with 180～200W ultrasonic echography dispersions 1～2h, stablized and finely dispersed graphene oxide dispersion；
2.20～30mL vinyl dimethoxysilane, 10～20mLN it is sequentially added in above-mentioned dispersion liquid, N-methylene-bisacrylamide, 2～3mL triethylamine and 10～20mL2-vinyl-5-mercaptoanilines, it is 0～5 DEG C that ice-water bath controls dispersion liquid temperature, stirring reaction 10～12h, by reacted dispersion liquid vacuum filtration, it is thus achieved that containing the mixture of Graphene；
3.Respectively with dimethyl sulfoxide and deionized water wash above-mentioned gained mixture, and gained material after washing is placed in the vacuum drying oven of 50～60 DEG C baking 2～3h, must be containing the modified graphene of different crosslinkable groups；
4Weigh 0.01～0.02g above-mentioned modified graphene and load round-bottomed flask, and add 100～200mL dimethyl sulfoxides, use 180～200W ultrasonic echography dispersions 1～2h, stablized and finely dispersed modified graphene dispersion liquid；
5. Measure 50～60mL4 respectively, 4-diaminodiphenyl ether and 40～50mL pyromellitic acid anhydrides, be added dropwise in 20～30mL dimethylsulfoxide solvent successively with 2～3mL/min speed under condition of ice bath, and ice-water bath controls solution temperature at 0～5 DEG C, stirring reaction 2～3h, obtains polyamic acid；
6. Above-mentioned polyamic acid is joined in step 4 gained modified graphene dispersion liquid, stirring 8～10h, vacuum filtration, obtain Graphene polyimide mixture, mixture is dried as in the vacuum drying oven of 50～60 DEG C, then the mixture after drying is placed in mould chamber, it is warming up to 180～200 DEG C, it is forced into 5～7MPa, keep 30～40min, then unload and be depressed into 0 MPa, keep 1min, it is continuously heating to 300～400 DEG C, it is forced into 15 MPa, keep 1～2h, then naturally cooling to temperature is 100～120 DEG C, mould unloading, obtain a kind of modified graphene/composite polyimide material.
The method of the application of the present invention: the graphene/polyimide composite material present invention prepared makes novel lithium battery as battery diaphragm, novel lithium battery is tested its battery capacity after discharge and recharge 6000 times and still keeps more than 90%, novel lithium battery use big electric current can be full of by battery in 10 minutes again, the problem solving battery fast charging and discharging to greatest extent.
The invention has the beneficial effects as follows:
Between Graphene and the polyimide matrix of the present invention, interface cohesion is strong, good with polymer compatibility, and improves the mechanical property of material.
Present invention could apply to lithium battery diaphragm, improve battery, dramatically speed up the charging interval.
Detailed description of the invention
First weigh 10～20g graphene oxides and load the 500mL two mouthfuls of round-bottomed flasks with thermometer, and in two mouthfuls of round-bottomed flasks, add 10～15mL dimethyl sulfoxides, with 180～200W ultrasonic echography dispersions 1～2h, stablized and finely dispersed graphene oxide dispersion；20～30mL vinyl dimethoxysilane, 10～20mLN it is sequentially added in above-mentioned dispersion liquid, N-methylene-bisacrylamide, 2～3mL triethylamine and 10～20mL2-vinyl-5-mercaptoanilines, it is 0～5 DEG C that ice-water bath controls dispersion liquid temperature, stirring reaction 10～12h, by reacted dispersion liquid vacuum filtration, it is thus achieved that containing the mixture of Graphene；Respectively with dimethyl sulfoxide and deionized water wash above-mentioned gained mixture, and gained material after washing is placed in the vacuum drying oven of 50～60 DEG C baking 2～3h, must be containing the modified graphene of different crosslinkable groups；Weigh 0.01～0.02g above-mentioned modified graphene and load round-bottomed flask, and add 100～200mL dimethyl sulfoxides, use 180～200W ultrasonic echography dispersions 1～2h, stablized and finely dispersed modified graphene dispersion liquid；Measure 50～60mL4 respectively, 4-diaminodiphenyl ether and 40～50mL pyromellitic acid anhydrides, be added dropwise in 20～30mL dimethylsulfoxide solvent successively with 2～3mL/min speed under condition of ice bath, and ice-water bath controls solution temperature at 0～5 DEG C, stirring reaction 2～3h, obtains polyamic acid；Above-mentioned polyamic acid is joined in step 4 gained modified graphene dispersion liquid, stirring 8～10h, vacuum filtration, obtain Graphene polyimide mixture, mixture is dried as in the vacuum drying oven of 50～60 DEG C, then the mixture after drying is placed in mould chamber, it is warming up to 180～200 DEG C, it is forced into 5～7MPa, keep 30～40min, then unload and be depressed into 0 MPa, keep 1min, it is continuously heating to 300～400 DEG C, it is forced into 15 MPa, keep 1～2h, then naturally cooling to temperature is 100～120 DEG C, mould unloading, obtain a kind of modified graphene/composite polyimide material.
First weigh 10g graphene oxide and load the 500mL two mouthfuls of round-bottomed flasks with thermometer, and in two mouthfuls of round-bottomed flasks, add 10mL dimethyl sulfoxide, disperse 1h with 180W ultrasonic echography, stablized and finely dispersed graphene oxide dispersion；20mL vinyl dimethoxysilane, 10mLN it is sequentially added in above-mentioned dispersion liquid, N-methylene-bisacrylamide, 2mL triethylamine and 10mL2-vinyl-5-mercaptoaniline, it is 0 DEG C that ice-water bath controls dispersion liquid temperature, stirring reaction 10h, by reacted dispersion liquid vacuum filtration, it is thus achieved that containing the mixture of Graphene；Respectively with dimethyl sulfoxide and deionized water wash above-mentioned gained mixture, and gained material after washing is placed in the vacuum drying oven of 50 DEG C baking 2h, must be containing the modified graphene of different crosslinkable groups；Weigh the above-mentioned modified graphene of 0.01g and load round-bottomed flask, and add 100mL dimethyl sulfoxide, use 180W ultrasonic echography dispersion 1h, stablized and finely dispersed modified graphene dispersion liquid；Measuring 50mL4,4-diaminodiphenyl ether and 40mL pyromellitic acid anhydride respectively, be added dropwise to successively in 20mL dimethylsulfoxide solvent with 2mL/min speed under condition of ice bath, ice-water bath control solution temperature is at 0 DEG C, and 2h is reacted in stirring, obtains polyamic acid；Above-mentioned polyamic acid is joined in step 4 gained modified graphene dispersion liquid, stirring 8h, vacuum filtration, obtain Graphene polyimide mixture, being dried as in the vacuum drying oven of 50 DEG C by mixture, the mixture after then drying is placed in mould chamber, is warming up to 180 DEG C, it is forced into 5MPa, keep 30min, then unload and be depressed into 0 MPa, keep 1min, it is continuously heating to 300 DEG C, being forced into 15 MPa, keep 1h, then naturally cooling to temperature is 100 DEG C, mould unloading, obtains a kind of modified graphene/composite polyimide material.
The graphene/polyimide composite material present invention prepared makes novel lithium battery as battery diaphragm, novel lithium battery is tested its battery capacity after discharge and recharge 6000 times and still keeps more than 90%, novel lithium battery use big electric current can be full of by battery in 10 minutes again, the problem solving battery fast charging and discharging to greatest extent.Between Graphene and the polyimide matrix of the present invention, interface cohesion is strong, good with polymer compatibility, and improves the mechanical property of material.
First weigh 15g graphene oxide and load the 500mL two mouthfuls of round-bottomed flasks with thermometer, and in two mouthfuls of round-bottomed flasks, add 13mL dimethyl sulfoxide, disperse 1.5h with 190W ultrasonic echography, stablized and finely dispersed graphene oxide dispersion；25mL vinyl dimethoxysilane, 15mLN it is sequentially added in above-mentioned dispersion liquid, N-methylene-bisacrylamide, 2.5mL triethylamine and 15mL2-vinyl-5-mercaptoaniline, it is 3 DEG C that ice-water bath controls dispersion liquid temperature, stirring reaction 11h, by reacted dispersion liquid vacuum filtration, it is thus achieved that containing the mixture of Graphene；Respectively with dimethyl sulfoxide and deionized water wash above-mentioned gained mixture, and gained material after washing is placed in the vacuum drying oven of 55 DEG C baking 2.5h, must be containing the modified graphene of different crosslinkable groups；Weigh the above-mentioned modified graphene of 0.01g and load round-bottomed flask, and add 150mL dimethyl sulfoxide, use 190W ultrasonic echography dispersion 1.5h, stablized and finely dispersed modified graphene dispersion liquid；Measuring 55mL4,4-diaminodiphenyl ether and 45mL pyromellitic acid anhydride respectively, be added dropwise to successively in 25mL dimethylsulfoxide solvent with 2.5mL/min speed under condition of ice bath, ice-water bath control solution temperature is at 3 DEG C, and 2.5h is reacted in stirring, obtains polyamic acid；Above-mentioned polyamic acid is joined in step 4 gained modified graphene dispersion liquid, stirring 9h, vacuum filtration, obtain Graphene polyimide mixture, being dried as in the vacuum drying oven of 55 DEG C by mixture, the mixture after then drying is placed in mould chamber, is warming up to 190 DEG C, it is forced into 6MPa, keep 35min, then unload and be depressed into 0 MPa, keep 1min, it is continuously heating to 350 DEG C, being forced into 15 MPa, keep 1.5h, then naturally cooling to temperature is 110 DEG C, mould unloading, obtains a kind of modified graphene/composite polyimide material.
The method of the application of the present invention: the graphene/polyimide composite material present invention prepared makes novel lithium battery as battery diaphragm, novel lithium battery is tested its battery capacity after discharge and recharge 6000 times and still keeps more than 90%, novel lithium battery use big electric current can be full of by battery in 10 minutes again, the problem solving battery fast charging and discharging to greatest extent.Between Graphene and the polyimide matrix of the present invention, interface cohesion is strong, good with polymer compatibility, and improves the mechanical property of material.
First weigh 20g graphene oxide and load the 500mL two mouthfuls of round-bottomed flasks with thermometer, and in two mouthfuls of round-bottomed flasks, add 15mL dimethyl sulfoxide, disperse 2h with 200W ultrasonic echography, stablized and finely dispersed graphene oxide dispersion；30mL vinyl dimethoxysilane, 20mLN it is sequentially added in above-mentioned dispersion liquid, N-methylene-bisacrylamide, 3mL triethylamine and 20mL2-vinyl-5-mercaptoaniline, it is 5 DEG C that ice-water bath controls dispersion liquid temperature, stirring reaction 12h, by reacted dispersion liquid vacuum filtration, it is thus achieved that containing the mixture of Graphene；Respectively with dimethyl sulfoxide and deionized water wash above-mentioned gained mixture, and gained material after washing is placed in the vacuum drying oven of 60 DEG C baking 3h, must be containing the modified graphene of different crosslinkable groups；Weigh the above-mentioned modified graphene of 0.02g and load round-bottomed flask, and add 200mL dimethyl sulfoxide, use 200W ultrasonic echography dispersion 2h, stablized and finely dispersed modified graphene dispersion liquid；Measuring 60mL4,4-diaminodiphenyl ether and 50mL pyromellitic acid anhydride respectively, be added dropwise to successively in 30mL dimethylsulfoxide solvent with 3mL/min speed under condition of ice bath, ice-water bath control solution temperature is at 5 DEG C, and 3h is reacted in stirring, obtains polyamic acid；Above-mentioned polyamic acid is joined in step 4 gained modified graphene dispersion liquid, stirring 10h, vacuum filtration, obtain Graphene polyimide mixture, being dried as in the vacuum drying oven of 60 DEG C by mixture, the mixture after then drying is placed in mould chamber, is warming up to 200 DEG C, it is forced into 7MPa, keep 40min, then unload and be depressed into 0 MPa, keep 1min, it is continuously heating to 400 DEG C, being forced into 15 MPa, keep 2h, then naturally cooling to temperature is 120 DEG C, mould unloading, obtains a kind of modified graphene/composite polyimide material.
The method of the application of the present invention: the graphene/polyimide composite material present invention prepared makes novel lithium battery as battery diaphragm, novel lithium battery is tested its battery capacity after discharge and recharge 6000 times and still keeps more than 90%, novel lithium battery use big electric current can be full of by battery in 10 minutes again, the problem solving battery fast charging and discharging to greatest extent.Between Graphene and the polyimide matrix of the present invention, interface cohesion is strong, good with polymer compatibility, and improves the mechanical property of material.
Claims (1)
1. the preparation method of a graphene/polyimide composite material, it is characterised in that concrete preparation process is:
(1) weigh 10～20g graphene oxides and load the 500mL two mouthfuls of round-bottomed flasks with thermometer, and in two mouthfuls of round-bottomed flasks, add 10～15mL dimethyl sulfoxides, with 180～200W ultrasonic echography dispersions 1～2h, stablized and finely dispersed graphene oxide dispersion；
(2) in above-mentioned dispersion liquid, 20～30mL vinyl dimethoxysilane, 10～20mLN it are sequentially added into, N-methylene-bisacrylamide, 2～3mL triethylamine and 10～20mL2-vinyl-5-mercaptoanilines, it is 0～5 DEG C that ice-water bath controls dispersion liquid temperature, stirring reaction 10～12h, by reacted dispersion liquid vacuum filtration, it is thus achieved that containing the mixture of Graphene；
(3) respectively with dimethyl sulfoxide and deionized water wash above-mentioned gained mixture, and baking 2～3h will be placed in the vacuum drying oven of 50～60 DEG C by gained material after washing, must be containing the modified graphene of different crosslinkable groups；
(4) weigh 0.01～0.02g above-mentioned modified graphene and load round-bottomed flask, and add 100～200mL dimethyl sulfoxides, use 180～200W ultrasonic echography dispersions 1～2h, stablized and finely dispersed modified graphene dispersion liquid；
(5) 50～60mL4 are measured respectively, 4-diaminodiphenyl ether and 40～50mL pyromellitic acid anhydrides, be added dropwise in 20～30mL dimethylsulfoxide solvent successively with 2～3mL/min speed under condition of ice bath, and ice-water bath controls solution temperature at 0～5 DEG C, stirring reaction 2～3h, obtains polyamic acid；
(6) above-mentioned polyamic acid is joined in step 4 gained modified graphene dispersion liquid, stirring 8～10h, vacuum filtration, obtain Graphene polyimide mixture, mixture is dried as in the vacuum drying oven of 50～60 DEG C, then the mixture after drying is placed in mould chamber, it is warming up to 180～200 DEG C, it is forced into 5～7MPa, keep 30～40min, then unload and be depressed into 0 MPa, keep 1min, it is continuously heating to 300～400 DEG C, it is forced into 15 MPa, keep 1～2h, then naturally cooling to temperature is 100～120 DEG C, mould unloading, obtain a kind of modified graphene/composite polyimide material.
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| CN110350128A (en) * | 2019-06-17 | 2019-10-18 | 浙江大学衢州研究院 | A kind of preparation method of the composite diaphragm for lithium-sulfur cell |
| CN114163682A (en) * | 2021-06-24 | 2022-03-11 | 贵州航天天马机电科技有限公司 | Application of electromagnetic material modification method in preparation of polyimide foam electromagnetic shielding material |
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- 2016-04-21 CN CN201610251577.9A patent/CN105820569A/en not_active Withdrawn
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| CN108837715B (en) * | 2018-05-24 | 2020-10-16 | 南京工业大学 | Solvent-resistant polyimide film, preparation method and application |
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| CN109796592A (en) * | 2019-01-16 | 2019-05-24 | 武汉柔显科技股份有限公司 | A kind of polyimide precursor, transparent polyimide film and preparation method thereof |
| CN109971451A (en) * | 2019-05-14 | 2019-07-05 | 西南石油大学 | A kind of fracturing fluid stannic oxide/graphene nano crosslinking agent and preparation method thereof |
| CN109971451B (en) * | 2019-05-14 | 2021-07-20 | 西南石油大学 | Graphene oxide nano cross-linking agent for fracturing fluid and preparation method thereof |
| CN110350128A (en) * | 2019-06-17 | 2019-10-18 | 浙江大学衢州研究院 | A kind of preparation method of the composite diaphragm for lithium-sulfur cell |
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