CN107245224A - A kind of graphene nanocomposite material and preparation method thereof - Google Patents
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Abstract
The invention discloses a kind of graphene nanocomposite material, its preparation method comprises the following steps：（1）Prepare graphite oxide suspension；（2）Graphite oxide suspension and Copper lysinate reaction, add water conjunction hydrazine and NaBH4Reduction；（3）Add disodium ethylene diamine tetraacetate copper removal；（4）By step（3）Gains, the epoxy resin of E 42, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, KH560 and nm boehmite mixing, ultrasonic disperse；（5）By step（4）Gains, the fatty glycidyl ethers of C12 14, nano titanium oxide, glass microballoon and camphor react 2 3h in 70 80 DEG C.Graphene nanocomposite material produced by the present invention efficiently solves the dispersion problem of graphene, improves the adhesive force of composite, anti-wear performance, fungistatic effect, the preparation available for environmental protection coating material.
Description
Technical field
The invention belongs to graphene composite material technical field, and in particular to a kind of graphene nanocomposite material and its system
Preparation Method.
Background technology
A kind of new carbonaceous material that it is in the arrangement of bi-dimensional cellular shape lattice structure by single layer of carbon atom that graphene, which is, is considered as
It is the basic component units of every other dimension carbonaceous material, such as can be bundled into the fullerene of zero dimension, is curled into one-dimensional carbon and receives
Mitron, is piled into graphite of three-dimensional etc..Graphene is with sp by carbon atom2The monatomic carbon-coating that hydridization is combined into, structure is very
It is stable, with excellent mechanical property, peculiar electrical properties and good thermal property.But it is combined preparing graphene nano
During material, because there is intrinsic Van der Waals force between graphenic surface super-hydrophobicity and graphene sheet layer, graphene layer is very
Easily reunite, therefore, its mechanical property of obtained composite etc. improves unobvious.
The content of the invention
For above-mentioned deficiency of the prior art, the invention provides a kind of graphene nanocomposite material and its preparation side
Method, can effectively solve graphene in the prior art and easily reunite to cause asking for graphene nanocomposite material poor mechanical property
Topic.
To achieve the above object, the technical solution adopted for the present invention to solve the technical problems is：
A kind of graphene nanocomposite material, its preparation method comprises the following steps：
（1）Graphite oxide is dispersed in water under the conditions of ultrasonication, finely dispersed graphite oxide suspension is obtained；
（2）Copper lysinate is added into graphite oxide suspension, is stirred, regulation solution ph is 9-10, in 75-85 DEG C of oil
The lower back flow reaction 20-24h of bath, then adds hydrazine hydrate and NaBH4, in back flow reaction 1-2h under 75-85 DEG C of oil bath；Wherein, oxygen
Graphite, Copper lysinate, hydrazine hydrate and NaBH4Mass ratio be 1:3-6:1-2:10-12；
（3）By step（2）Gains are dispersed in water, and add disodium ethylene diamine tetraacetate, 12-13h is reacted at room temperature, are filtered,
Washing, is dried；Wherein, step（2）Gains are 1 with disodium ethylene diamine tetraacetate mass ratio:3-5；
（4）By step（3）Gains, E-42 epoxy resin, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether,
KH560 and nm boehmite are 2-4 in mass ratio:40-50:2-4:2-4:1-2:0.3-0.8 is mixed, then ultrasonic disperse 30-
40min；
（5）By step（4）Gains, C12-14 fatty glycidyls ether, nano titanium oxide, glass microballoon and camphor press quality
Than for 2-5:10-12:3-5:1-3:0.2-0.5 is mixed, and 2-3h is reacted in 70-80 DEG C, is made.
Further, step（1）Middle graphite oxide, which is prepared by the following method, to be obtained：Under the conditions of 0 DEG C, graphite is added
Stirring reaction 20-30min in 95% concentrated sulfuric acid, then adds sodium nitrate, and stirring reaction 20-30min adds potassium permanganate, stirred
Moved into after mixing reaction 1.5-2h in 35-38 DEG C of water bath with thermostatic control, stirring reaction 40-60min adds deionized water, made in temperature
95-98 DEG C is risen to, 20-30min is reacted, then instill 10% H2O2, stirring reaction to system color adds by golden yellow during blackening
Enter 0.5mol/L HCl, stir 10-20min, then suction filtration, washing filter cake is into filtrate without SO4 2–, filter cake is added into deionization
In water, ultrasonic disperse 20-30min, then rotate, 24h most is dried in vacuo after 50-60 DEG C, is made.
Further, step（1）The concentration of middle graphite oxide suspension is 1-2.5mg/mL.
Further, step（2）It is middle to adjust pH with 2% NaOH solution.
Further, step（2）Middle graphite oxide, Copper lysinate, hydrazine hydrate and NaBH4Mass ratio be 1:5:1.5:
10。
Further, step（2）Then middle regulation solution ph adds hydration after back flow reaction 24h under 80 DEG C of oil baths
Hydrazine and NaBH4, in back flow reaction 1.5h under 80 DEG C of oil baths.
Further, step（3）Middle step（2）Gains are 1 with disodium ethylene diamine tetraacetate mass ratio:4.
Further, step（4）Middle step（3）Gains, E-42 epoxy resin, ethylene glycol diglycidylether, poly- second
The mass ratio of Hexanediol diglycidyl ether, KH560 and nm boehmite is 3:45:3:3:1.5:0.5.
Further, step（5）Middle step（4）Gains, C12-14 fatty glycidyls ether, nano titanium oxide, glass
Glass microballon, the mass ratio of camphor are 4:11:4:2:0.3.
Graphene nanocomposite material that the present invention is provided and preparation method thereof, has the advantages that：
（1）Copper lysinate is the lysine metallo-chelate with cyclic structure that lysine reacts generation with trace copper,
The alpha-amido and carboxyl of lysine can be protected, and Amino End Group can be used for participating in organic reaction and with less space bit
Resistance, Copper lysinate is combined with graphite oxide, is using in the less steric hindrance of Copper lysinate Amino End Group and graphite oxide
Epoxy radicals reacts, and controllable graphite oxide is difficult to dispersed problem in aqueous.
（2）The reducible graphite oxide of hydrazine hydrate, makes graphite oxide surface negatively charged, and faint electrostatic row is produced in piece interlayer
Reprimand, in conjunction with reducing agent NaBH4Effect, can offset graphite oxide surface hydrophobic effect and piece interlayer π-π effect, make to rely
Functional group in propylhomoserin can be combined together with graphite oxide well, and graphite oxide is reduced into graphene, passes through second two
Amine tetraacethyl disodium removes copper ion, obtains the compound of favorable dispersibility.
（3）Epoxy resin is the organic compound containing two or more active epoxide groups in molecule；KH560 is
Graphene, can be coupled, further increase by the chain molecule of all active group in two ends with nm boehmite
The dispersiveness of graphene, while can also have film protective effect and ball effect in friction surface, is effectively reduced material list
The abrasion in face.
Ethylene glycol diglycidylether and polyethyleneglycol diglycidylether are difunctional epoxy active diluent, second two
Alcohol diglycidyl ether can improve the flexibility of compound, and not only flexibility is good for polyethyleneglycol diglycidylether, but also can
To improve the elongation and impact strength of compound.
Glass microballoon has the characteristics such as heat-insulated, sound insulation, insulation, high intensity, moreover it is possible to the toughness of reinforcing material, increase material
Mobility, there is very strong resistance to acids and bases.
The toughness of C12-14 fatty glycidyl ether energy reinforced epoxies, is being reduced with nm boehmite and glass microballoon
Synergy can be played in terms of material abrasion.
Nano titanium oxide can degrade the harmful organic substance in air, with photocatalysis performance and Superhydrophilic, super close
Oiliness, can not only kill the bacterium in environment, can degrade the poisonous compound discharged by bacterium, but also with automatically cleaning
Effect, improves the antifouling property of material；Nano titanium oxide has synergy with camphor in restraining and sterilizing bacteria method.
（4）Graphene nanocomposite material produced by the present invention efficiently solves the dispersion problem of graphene, improves
The adhesive force of composite, anti-wear performance, fungistatic effect, the preparation available for environmental protection coating material.
Embodiment
Embodiment 1
A kind of graphene nanocomposite material, its preparation method comprises the following steps：
（1）Graphite oxide is dispersed in water under the conditions of ultrasonication, concentration is obtained for the finely dispersed oxidations of 1mg/mL
Graphite suspension；
Wherein, graphite oxide, which is prepared by the following method, obtains：Under the conditions of 0 DEG C, 1g graphite is slowly arrived into addition under agitation
In the concentrated sulfuric acids of 25mL 95%, then stirring reaction 20min adds 0.8 sodium nitrate, and stirring reaction 20min adds 4g permanganic acid
Moved into after potassium, stirring reaction 1.5h in 35 DEG C of thermostat water baths, stirring reaction 60min adds 50mL deionized waters, makes temperature
95 DEG C are risen to, 30min is reacted, then instill the H of 120mL 10%2O2, stirring reaction to system color is by golden yellow during blackening
50mL 0.5mol/L HCl is added, 10min is stirred, then suction filtration, filter cake nothing into filtrate is washed with 0.5mol/L HCl
SO4 2–, filter cake is dissolved in deionized water, ultrasonic disperse 30min, then rotate, 24h most is dried in vacuo after 60 DEG C, is made.
（2）Copper lysinate is added into graphite oxide suspension, is stirred, solution ph is adjusted with 2% NaOH solution
For 9-10, in back flow reaction 24h under 75 DEG C of oil baths, hydrazine hydrate and NaBH are then added4, in back flow reaction 2h under 75 DEG C of oil baths；
Wherein, graphite oxide, Copper lysinate, hydrazine hydrate and NaBH4Mass ratio be 1:3:1:10；
（3）By step（2）Gains are dispersed in water, and add disodium ethylene diamine tetraacetate, 12h is reacted at room temperature, are filtered, are washed
Wash, dry；Wherein, step（2）Gains are 1 with disodium ethylene diamine tetraacetate mass ratio:3；
（4）By step（3）Gains, E-42 epoxy resin, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether,
KH560 and nm boehmite are 2 in mass ratio:40:2:2:1:0.3 mixes, then ultrasonic disperse 30min；
（5）By step（4）Gains, C12-14 fatty glycidyls ether, nano titanium oxide, glass microballoon and camphor press quality
Than for 2:10:3:1:0.2 is mixed, and 3h is reacted in 70 DEG C, is made.
Embodiment 2
A kind of graphene nanocomposite material, its preparation method comprises the following steps：
（1）Graphite oxide is dispersed in water under the conditions of ultrasonication, concentration is obtained for the finely dispersed oxygen of 2.5mg/mL
Graphite suspension；
Wherein, graphite oxide, which is prepared by the following method, obtains：Under the conditions of 0 DEG C, 1g graphite is slowly arrived into addition under agitation
In the concentrated sulfuric acids of 25mL 95%, then stirring reaction 20min adds 0.8 sodium nitrate, and stirring reaction 20min adds 4g permanganic acid
Moved into after potassium, stirring reaction 1.5h in 35 DEG C of thermostat water baths, stirring reaction 60min adds 50mL deionized waters, makes temperature
95 DEG C are risen to, 30min is reacted, then instill the H of 120mL 10%2O2, stirring reaction to system color is by golden yellow during blackening
50mL 0.5mol/L HCl is added, 10min is stirred, then suction filtration, filter cake nothing into filtrate is washed with 0.5mol/L HCl
SO4 2–, filter cake is dissolved in deionized water, ultrasonic disperse 30min, then rotate, 24h most is dried in vacuo after 60 DEG C, is made.
（2）Copper lysinate is added into graphite oxide suspension, is stirred, solution ph is adjusted with 2% NaOH solution
For 9-10, in back flow reaction 24h under 85 DEG C of oil baths, hydrazine hydrate and NaBH are then added4, in back flow reaction 1h under 85 DEG C of oil baths；
Wherein, graphite oxide, Copper lysinate, hydrazine hydrate and NaBH4Mass ratio be 1:6:2:12；
（3）By step（2）Gains are dispersed in water, and add disodium ethylene diamine tetraacetate, 13h is reacted at room temperature, are filtered, are washed
Wash, dry；Wherein, step（2）Gains are 1 with disodium ethylene diamine tetraacetate mass ratio:5；
（4）By step（3）Gains, E-42 epoxy resin, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether,
KH560 and nm boehmite are 4 in mass ratio:50:4:4:2:0.8 mixes, then ultrasonic disperse 40min；
（5）By step（4）Gains, C12-14 fatty glycidyls ether, nano titanium oxide, glass microballoon and camphor press quality
Than for 5:12:5:3:0.5 is mixed, and 3h is reacted in 80 DEG C, is made.
Embodiment 3
A kind of graphene nanocomposite material, its preparation method comprises the following steps：
（1）Graphite oxide is dispersed in water under the conditions of ultrasonication, concentration is obtained for the finely dispersed oxygen of 1.5mg/mL
Graphite suspension；
Wherein, graphite oxide, which is prepared by the following method, obtains：Under the conditions of 0 DEG C, 1g graphite is slowly arrived into addition under agitation
In the concentrated sulfuric acids of 25mL 95%, then stirring reaction 20min adds 0.8 sodium nitrate, and stirring reaction 20min adds 4g permanganic acid
Moved into after potassium, stirring reaction 1.5h in 35 DEG C of thermostat water baths, stirring reaction 60min adds 50mL deionized waters, makes temperature
95 DEG C are risen to, 30min is reacted, then instill the H of 120mL 10%2O2, stirring reaction to system color is by golden yellow during blackening
50mL 0.5mol/L HCl is added, 10-2min is stirred, then suction filtration, filter cake nothing into filtrate is washed with 0.5mol/L HCl
SO4 2–, filter cake is dissolved in deionized water, ultrasonic disperse 30min, then rotate, 24h most is dried in vacuo after 60 DEG C, is made.
（2）Copper lysinate is added into graphite oxide suspension, is stirred, solution ph is adjusted with 2% NaOH solution
For 9-10, in back flow reaction 22h under 80 DEG C of oil baths, hydrazine hydrate and NaBH are then added4, in back flow reaction under 80 DEG C of oil baths
1.5h；Wherein, graphite oxide, Copper lysinate, hydrazine hydrate and NaBH4Mass ratio be 1:4:1.2:11；
（3）By step（2）Gains are dispersed in water, and add disodium ethylene diamine tetraacetate, 12h is reacted at room temperature, are filtered, are washed
Wash, dry；Wherein, step（2）Gains are 1 with disodium ethylene diamine tetraacetate mass ratio:4；
（4）By step（3）Gains, E-42 epoxy resin, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether,
KH560 and nm boehmite are 3 in mass ratio:42:2.5:2.5:1.2:0.4 mixes, then ultrasonic disperse 40min；
（5）By step（4）Gains, C12-14 fatty glycidyls ether, nano titanium oxide, glass microballoon and camphor press quality
Than for 3:11:3.5:1.5:0.3 is mixed, and 3h is reacted in 80 DEG C, is made.
Embodiment 4
A kind of graphene nanocomposite material, its preparation method comprises the following steps：
（1）Graphite oxide is dispersed in water under the conditions of ultrasonication, concentration is obtained for the finely dispersed oxygen of 2.2mg/mL
Graphite suspension；
Wherein, graphite oxide, which is prepared by the following method, obtains：Under the conditions of 0 DEG C, 1g graphite is slowly arrived into addition under agitation
In the concentrated sulfuric acids of 25mL 95%, then stirring reaction 20min adds 0.8 sodium nitrate, and stirring reaction 20min adds 4g permanganic acid
Moved into after potassium, stirring reaction 1.5h in 35 DEG C of thermostat water baths, stirring reaction 60min adds 50mL deionized waters, makes temperature
95 DEG C are risen to, 30min is reacted, then instill the H of 120mL 10%2O2, stirring reaction to system color is by golden yellow during blackening
50mL 0.5mol/L HCl is added, 10-2min is stirred, then suction filtration, filter cake nothing into filtrate is washed with 0.5mol/L HCl
SO4 2–, filter cake is dissolved in deionized water, ultrasonic disperse 30min, then rotate, 24h most is dried in vacuo after 60 DEG C, is made.
（2）Copper lysinate is added into graphite oxide suspension, is stirred, solution ph is adjusted with 2% NaOH solution
For 9-10, in back flow reaction 24h under 85 DEG C of oil baths, hydrazine hydrate and NaBH are then added4, in back flow reaction under 85 DEG C of oil baths
1.5h；Wherein, graphite oxide, Copper lysinate, hydrazine hydrate and NaBH4Mass ratio be 1:5:1.8:11；
（3）By step（2）Gains are dispersed in water, and add disodium ethylene diamine tetraacetate, 12h is reacted at room temperature, are filtered, are washed
Wash, dry；Wherein, step（2）Gains are 1 with disodium ethylene diamine tetraacetate mass ratio:4.5；
（4）By step（3）Gains, E-42 epoxy resin, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether,
KH560 and nm boehmite are 3.5 in mass ratio:48:3.5:3.5:1.8:0.7 mixes, then ultrasonic disperse 40min；
（5）By step（4）Gains, C12-14 fatty glycidyls ether, nano titanium oxide, glass microballoon and camphor press quality
Than for 4:11:4.5:2.5:0.4 is mixed, and 3h is reacted in 80 DEG C, is made.
Embodiment 5
A kind of graphene nanocomposite material, its preparation method comprises the following steps：
（1）Graphite oxide is dispersed in water under the conditions of ultrasonication, concentration is obtained for the finely dispersed oxygen of 2.5mg/mL
Graphite suspension；
Wherein, graphite oxide, which is prepared by the following method, obtains：Under the conditions of 0 DEG C, 1g graphite is slowly arrived into addition under agitation
In the concentrated sulfuric acids of 25mL 95%, then stirring reaction 20min adds 0.8 sodium nitrate, and stirring reaction 20min adds 4g permanganic acid
Moved into after potassium, stirring reaction 1.5h in 35 DEG C of thermostat water baths, stirring reaction 60min adds 50mL deionized waters, makes temperature
95 DEG C are risen to, 30min is reacted, then instill the H of 120mL 10%2O2, stirring reaction to system color is by golden yellow during blackening
50mL 0.5mol/L HCl is added, 10-2min is stirred, then suction filtration, filter cake nothing into filtrate is washed with 0.5mol/L HCl
SO4 2–, filter cake is dissolved in deionized water, ultrasonic disperse 30min, then rotate, 24h most is dried in vacuo after 60 DEG C, is made.
（2）Copper lysinate is added into graphite oxide suspension, is stirred, solution ph is adjusted with 2% NaOH solution
For 9-10, in back flow reaction 24h under 80 DEG C of oil baths, hydrazine hydrate and NaBH are then added4, in back flow reaction under 80 DEG C of oil baths
1.5h；Wherein, graphite oxide, Copper lysinate, hydrazine hydrate and NaBH4Mass ratio be 1:5:1.5:10；
（3）By step（2）Gains are dispersed in water, and add disodium ethylene diamine tetraacetate, 12h is reacted at room temperature, are filtered, are washed
Wash, dry；Wherein, step（2）Gains are 1 with disodium ethylene diamine tetraacetate mass ratio:4；
（4）By step（3）Gains, E-42 epoxy resin, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether,
KH560 and nm boehmite are 3 in mass ratio:45:3:3:1.5:0.5 mixes, then ultrasonic disperse 40min；
（5）By step（4）Gains, C12-14 fatty glycidyls ether, nano titanium oxide, glass microballoon and camphor press quality
Than for 4:11:4:2:0.3 is mixed, and 3h is reacted in 80 DEG C, is made.
Claims (10)
1. a kind of preparation method of graphene nanocomposite material, it is characterised in that comprise the following steps：
（1）Graphite oxide is dispersed in water under the conditions of ultrasonication, finely dispersed graphite oxide suspension is obtained；
（2）Copper lysinate is added into graphite oxide suspension, is stirred, regulation solution ph is 9-10, in 75-85 DEG C of oil
The lower back flow reaction 20-24h of bath, then adds hydrazine hydrate and NaBH4, in back flow reaction 1-2h under 75-85 DEG C of oil bath；Wherein, oxygen
Graphite, Copper lysinate, hydrazine hydrate and NaBH4Mass ratio be 1:3-6:1-2:10-12；
（3）By step（2）Gains are dispersed in water, and add disodium ethylene diamine tetraacetate, 12-13h is reacted at room temperature, are filtered,
Washing, is dried；Wherein, step（2）Gains are 1 with disodium ethylene diamine tetraacetate mass ratio:3-5；
（4）By step（3）Gains, E-42 epoxy resin, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether,
KH560 and nm boehmite are 2-4 in mass ratio:40-50:2-4:2-4:1-2:0.3-0.8 is mixed, then ultrasonic disperse 30-
40min；
（5）By step（4）Gains, C12-14 fatty glycidyls ether, nano titanium oxide, glass microballoon and camphor press quality
Than for 2-5:10-12:3-5:1-3:0.2-0.5 is mixed, and 2-3h is reacted in 70-80 DEG C, is made.
2. the preparation method of graphene nanocomposite material according to claim 1, it is characterised in that step（1）Middle oxygen
Graphite, which is prepared by the following method, to be obtained：Under the conditions of 0 DEG C, graphite is added into stirring reaction 20-30min in 95% concentrated sulfuric acid,
Then sodium nitrate is added, stirring reaction 20-30min adds 35-38 DEG C of ring of immigration after potassium permanganate, stirring reaction 1.5-2h
In border, stirring reaction 40-60min adds deionized water, temperature is risen to 95-98 DEG C, reacts 20-30min, then instill
10% H2O2, stirring reaction to system color addition 0.5mol/L during blackening by golden yellow HCl, stirring 10-20min, so
Suction filtration, washs filter cake into filtrate without SO afterwards4 2–, filter cake is added in deionized water, ultrasonic disperse 20-30min, then rotate, most
24h is dried in vacuo after 50-60 DEG C, is made.
3. the preparation method of graphene nanocomposite material according to claim 1, it is characterised in that step（1）Middle oxygen
The concentration of graphite suspension is 1-2.5mg/mL.
4. the preparation method of graphene nanocomposite material according to claim 1, it is characterised in that step（2）It is middle to use
2% NaOH solution regulation pH.
5. the preparation method of graphene nanocomposite material according to claim 1, it is characterised in that step（2）Middle oxygen
Graphite, Copper lysinate, hydrazine hydrate and NaBH4Mass ratio be 1:5:1.5:10.
6. the preparation method of graphene nanocomposite material according to claim 1, it is characterised in that step（2）It is middle to adjust
Solution ph is saved after back flow reaction 24h under 80 DEG C of oil baths, hydrazine hydrate and NaBH is then added4, it is anti-in being flowed back under 80 DEG C of oil baths
Answer 1.5h.
7. the preparation method of graphene nanocomposite material according to claim 1, it is characterised in that step（3）Middle step
Suddenly（2）Gains are 1 with disodium ethylene diamine tetraacetate mass ratio:4.
8. the preparation method of graphene nanocomposite material according to claim 1, it is characterised in that step（4）Middle step
Suddenly（3）Gains, E-42 epoxy resin, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, KH560 and nanometer
The mass ratio of boehmite is 3:45:3:3:1.5:0.5.
9. the preparation method of graphene nanocomposite material according to claim 1, it is characterised in that step（5）Middle step
Suddenly（4）Gains, C12-14 fatty glycidyls ether, nano titanium oxide, glass microballoon, the mass ratio of camphor are 4:11:4:
2:0.3。
10. graphene nanocomposite material made from any one of claim 1-9 methods described.
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