CN110204929A - A kind of method of hexa-member heterocycle covalent modification graphene oxide - Google Patents
A kind of method of hexa-member heterocycle covalent modification graphene oxide Download PDFInfo
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Abstract
A kind of method of hexa-member heterocycle covalent modification graphene oxide, it is related to a kind of method for modifying graphene oxide.The invention aims to solve the problems, such as that the dispersed and boundary strength of existing graphene in the composite is poor.Method: one, graphene oxide is prepared；Two, the hydroxylating processing of graphene oxide；Three, Cyanuric Chloride modifies graphene oxide；Four, trihydroxy aminomethane modifies graphene oxide, obtains the graphene oxide of hexa-member heterocycle covalent modification.Hexa-member heterocycle covalent modification graphene oxide prepared by the present invention and epoxy resin are compounded with better mechanical property, and compared with epoxy resin, tensile strength, which improves, is greater than 38%, and bending strength, which improves, is greater than 46%.The present invention can get hexa-member heterocycle covalent modification graphene oxide.
Description
Technical field
The present invention relates to a kind of methods for modifying graphene oxide.
Background technique
Graphene is that have receiving for the excellent properties such as unique structure, layer atomic thickness, high intensity, highly conductive and thermal conductivity
Rice material, is widely used in fields such as aerospace, machine-building, buildings.In addition, having had most experiments have shown that stone
Black alkene and graphene oxide sheet material are because its excellent mechanical performance becomes most promising enhancing in polymer composites
Material.However, there are two main problems for the mechanical performance of limitation Graphene epoxy resin composite material and application: 1) due to model
De Huali is strong, and irreversible aggregation easily occurs in the composite for graphene, this will lead to poor point in the base of graphene
Dissipate property；2) weaker with the interfacial interaction of matrix due to graphene surface inertia, which also limits the loads from matrix to sheet material
Lotus transfer.To solve the above problems, the modified method of surface of graphene oxide is generallyd use, mainly including non-covalent modification and altogether
Valence modification.Non-covalent modification is by weak combination connection molecule, such as hydrogen bond, Van der Waals force or Electrostatic Absorption etc..Altogether
Valence modification is then the chemical reaction of the functional group and other compounds by surface of graphene oxide, generates strong bonding and makees
With, and whereby graphene oxide surface introduce various active group, efficiently control graphene composite material physics and
Chemical property.In recent years, existing numerous studies modified to surface of graphene oxide, but due to graphene surface grafted chain
Active group limited amount improves still limited and at high cost, low efficiency to graphene/epoxy resin composite material performance.
Therefore, it is badly in need of a kind of process for modifying surface of efficient graphene at present, is formed on its surface more active sites, improves it
Dispersibility and interfacial combined function in the epoxy expand its application range to improve the mechanical property of composite material.
Many experiments are chemically modified the surface of graphene oxide, but there are still some disadvantages, such as graphite oxide
The covalence graft of alkene leads to the destruction of the perfect structure of graphene, this causes to enhance the strength reduction of component and the heat of composite material
The disadvantages of reduced performance.
Summary of the invention
The invention aims to solve the problems, such as that the dispersed and boundary strength of existing graphene in the composite is poor,
And provide a kind of method of hexa-member heterocycle covalent modification graphene oxide.
A kind of method of hexa-member heterocycle covalent modification graphene oxide, is completed by the following steps:
One, graphene oxide is prepared:
1., graphite, sodium nitrate and the concentrated sulfuric acid be added in three-necked flask, three-necked flask is placed to 0 DEG C~5 DEG C of ice
In water-bath and low whipping speed is to be stirred to react 30min~40min under 300r/min~400r/min, obtains reaction solution I；
Step 1 1. described in the concentrated sulfuric acid mass fraction be 96%~98%；
Step 1 1. described in graphite quality and the concentrated sulfuric acid volume ratio be (6g~8g): (360mL~500mL)；
Step 1 1. described in sodium nitrate quality and the concentrated sulfuric acid volume ratio (2g~4g): (360mL~500mL)；
2., potassium permanganate is added into reaction solution I, then three-necked flask is placed in 0 DEG C~5 DEG C of ice-water bath and is being stirred
Mixing speed is to be stirred to react 2h~3h under 300r/min~400r/min, obtains reaction solution II；
Step 1 2. described in potassium permanganate and step 1 1. described in graphite mass ratio be (20~25): (6~
8)；
3., the temperature of reaction solution II is warming up to 35 DEG C~40 DEG C, and reacted at being 35 DEG C~40 DEG C in temperature 17h~
19h adds distilled water, obtains reaction solution III；
Step 1 3. described in distilled water volume and step 1 1. described in graphite mass ratio be (400mL~
600mL): (6g~8g)；
4., by III low whipping speed of reaction solution be 300r/min~400r/min under be stirred to react 1h~2h, add steaming
The hydrogenperoxide steam generator that distilled water and mass fraction are 30%, obtains reaction solution IV；
Step 1 4. described in distilled water volume and step 1 1. described in graphite mass ratio be (600mL~
800mL): (6g~8g)；
Step 1 4. described in mass fraction be 30% hydrogenperoxide steam generator volume and step 1 1. described in
The mass ratio of graphite is (40mL~60mL): (6g~8g)；
5., by IV low whipping speed of reaction solution be 300r/min~400r/min under be stirred to react 20min~40min, then
Ultrasound 30min~50min in the case where ultrasonic power is 350W~360W, is then allowed to stand 6h~8h, supernatant is outwelled, mixed
Object I；
6., the hydrochloric acid that is 14%~16% using mass fraction as cleaning agent, be 6000r/min~8000r/ in centrifugal speed
Mixture I is cleaned under the centrifugal speed of min, until the supernatant of mixture I is added 0.1mol/L~0.15mol/L's
Barium chloride solution no longer generates precipitating, the mixture I after obtaining hydrochloric acid cleaning；
7., using deionized water the mixture I after hydrogen chloride solution cleaning is cleaned, until the pH value of cleaning solution is
7, the mixture I after obtaining deionized water cleaning；
8., deionized water is cleaned after mixture I be put into freeze drier dry, obtain solids I, will finally consolidate
Body object I grinds and crosses 300 meshes, and screenings is graphene oxide；
Two, the hydroxylating processing of graphene oxide:
1., lithium aluminium hydride reduction is dissolved into tetrahydrofuran, obtain the tetrahydrofuran solution of lithium aluminium hydride reduction；
Step 2 1. described in lithium aluminium hydride reduction quality and tetrahydrofuran volume ratio be (4g~5g): (100mL~
120mL)；
2., added graphene oxide into the tetrahydrofuran solution of lithium aluminium hydride reduction first, be then in ultrasonic power
Ultrasound 0.5h~1h under 350W~360W, then reacted at room temperature with the mixing speed magnetic agitation of 300r/min~400r/min
2h~3h obtains mixture；
Step 2 2. described in graphene oxide quality and step 2 1. in tetrahydrofuran volume ratio be (2g~
3g): (100mL~120mL)；
3., into mixture be added mass fraction be 37% hydrochloric acid, until mixture supernatant become clarification, reuse
It is neutrality that deionization, which is cleaned to cleaning solution, is finally putting into dry 6h~12h in the vacuum oven that temperature is 80 DEG C~90 DEG C, obtains
To hydroxylated graphene oxide；
Three, Cyanuric Chloride modifies graphene oxide:
1., hydroxylated graphene oxide is added in tetrahydrofuran, then surpass in the case where ultrasonic power is 350W~360W
Sound 1h~2h, adds Cyanuric Chloride and triethylamine, then temperature be 70 DEG C~80 DEG C and mixing speed be 300r/min~
Heating stirring reflux for 24 hours~36h, obtains reaction product I under conditions of 400r/min；
Step 3 1. described in hydroxylated graphene oxide quality and tetrahydrofuran volume ratio be (1g~2g):
100mL；
Step 3 1. described in Cyanuric Chloride quality and tetrahydrofuran volume ratio be (3g~4g): 100mL；
Step 3 1. described in triethylamine quality and tetrahydrofuran volume ratio be (4g~6g): 100mL；
2., using tetrahydrofuran reaction product I is cleaned 3 times~5 times, reuse washes of absolute alcohol 3 times~8 times, most
Dry 4h~6h in the vacuum oven that temperature is 80 DEG C~90 DEG C afterwards obtains Cyanuric Chloride modification graphene oxide；
Four, trihydroxy aminomethane modifies graphene oxide:
1., by Cyanuric Chloride modification graphene oxide be added in acetonitrile, then ultrasonic power be 350W~360W under surpass
Sound disperses 1h~2h, adds trihydroxy aminomethane and triethylamine, then heating is stirred under conditions of temperature is 70 DEG C~80 DEG C
Reflux 12h~18h is mixed, reaction product II is obtained；
Step 4 1. described in Cyanuric Chloride modification graphene oxide quality and acetonitrile volume ratio be (0.2g~
0.4g): (30mL~60mL)；
Step 4 1. described in trihydroxy aminomethane quality and acetonitrile volume ratio be (0.4g~0.6g):
(30mL~60mL)；
Step 4 1. described in triethylamine quality and acetonitrile volume ratio be (4g~6g): (30mL~60mL)；
2., using dehydrated alcohol reaction product II is cleaned 3 times~8 times, then it is dry in the vacuum that temperature is 80 DEG C~90 DEG C
Dry 4h~6h, obtains the graphene oxide of hexa-member heterocycle covalent modification in dry case.
The principle of the present invention:
The present invention carries out hydroxylating processing to graphene oxide first, recycles the hydroxy functional group of surface of graphene oxide
It is chemically combined with chlorine active in Cyanuric Chloride, the grafting of Cyanuric Chloride is that the surface of graphene oxide increases reaction position
Point；It recycles the amino in small molecule trihydroxy aminomethane to chemically react with the unreacted chlorine of Cyanuric Chloride, generates strong
Strong chemical bond.The modification of Cyanuric Chloride and trihydroxy aminomethane to graphene oxide, not only increases graphene oxide table
The active group in face improves compatibility and interface cohesion between polymer, and grafted chain prevents graphene oxide poly-
The agglomeration in object is closed, its dispersibility in matrix is improved.
Advantages of the present invention:
One, Cyanuric Chloride has the special design features such as stable triazine ring structure and multiple active chlorine reaction sites,
A variety of possibility are provided for the modification of graphene oxide；Small molecule trihydroxy aminomethane possesses multiple active groups, improves oxygen
The surface-active of graphite alkene；The cost of Cyanuric Chloride and trihydroxy aminomethane is low, the reaction condition ratio with graphene oxide
Relatively mild, reaction process is easy, consumes energy low, economical and environmentally friendly；Small molecule will not only make the surface modification of graphene oxide
At graphene oxide structural damage itself, and it can effectively prevent the agglomeration phenomenon of graphene oxide；
Two, hexa-member heterocycle covalent modification graphene oxide and epoxy resin prepared by the present invention are compounded with better mechanical property
Can, composite material is compared with epoxy resin, and tensile strength, which improves, is greater than 38%, and bending strength, which improves, is greater than 46%.
The present invention can get hexa-member heterocycle covalent modification graphene oxide.
Detailed description of the invention
Fig. 1 is infrared spectrogram, and a is that the infrared light of 8. graphene oxide that one step 1 of embodiment obtains is set a song to music in figure
Line, b are the infrared spectrum curve that 2. Cyanuric Chloride that one step 3 of embodiment obtains modifies graphene oxide, and c is embodiment one
The infrared spectrum curve of the graphene oxide of 2. hexa-member heterocycle covalent modification that step 4 obtains；
Fig. 2 is raman spectrum, and a is the Raman curve of 8. graphene oxide that one step 1 of embodiment obtains in figure, and b is real
The Raman curve of 2. Cyanuric Chloride modification graphene oxide that one step 3 of example obtains is applied, c is 2. one step 4 of embodiment obtains
Hexa-member heterocycle covalent modification graphene oxide Raman curve；
Fig. 3 is the XPS swarming spectrogram of 8. graphene oxide that one step 1 of embodiment obtains；
Fig. 4 is the XPS swarming spectrogram of the graphene oxide of 2. hexa-member heterocycle covalent modification that one step 4 of embodiment obtains；
Fig. 5 is the SEM figure of 8. graphene oxide that one step 1 of embodiment obtains；
Fig. 6 is the SEM figure of the graphene oxide of 2. hexa-member heterocycle covalent modification that one step 4 of embodiment obtains；
Fig. 7 is tensile strength histogram, in figure 1 be pure epoxy resin tensile strength, 2 oxidations prepared for embodiment three
Graphene/epoxy resin composite material tensile strength, the graphite oxide of the 3 hexa-member heterocycle covalent modifications prepared for example IV
Alkene/epoxy resin composite material tensile strength；
Fig. 8 is bending strength histogram, in figure 1 be pure epoxy resin bending strength, 2 oxidations prepared for embodiment three
Graphene/epoxy resin composite material bending strength, the graphite oxide of the 3 hexa-member heterocycle covalent modifications prepared for example IV
Alkene/epoxy resin composite material bending strength.
Specific embodiment
Specific embodiment 1: present embodiment is a kind of method of hexa-member heterocycle covalent modification graphene oxide, be by
What following steps were completed:
One, graphene oxide is prepared:
1., graphite, sodium nitrate and the concentrated sulfuric acid be added in three-necked flask, three-necked flask is placed to 0 DEG C~5 DEG C of ice
In water-bath and low whipping speed is to be stirred to react 30min~40min under 300r/min~400r/min, obtains reaction solution I；
Step 1 1. described in the concentrated sulfuric acid mass fraction be 96%~98%；
Step 1 1. described in graphite quality and the concentrated sulfuric acid volume ratio be (6g~8g): (360mL~500mL)；
Step 1 1. described in sodium nitrate quality and the concentrated sulfuric acid volume ratio (2g~4g): (360mL~500mL)；
2., potassium permanganate is added into reaction solution I, then three-necked flask is placed in 0 DEG C~5 DEG C of ice-water bath and is being stirred
Mixing speed is to be stirred to react 2h~3h under 300r/min~400r/min, obtains reaction solution II；
Step 1 2. described in potassium permanganate and step 1 1. described in graphite mass ratio be (20~25): (6~
8)；
3., the temperature of reaction solution II is warming up to 35 DEG C~40 DEG C, and reacted at being 35 DEG C~40 DEG C in temperature 17h~
19h adds distilled water, obtains reaction solution III；
Step 1 3. described in distilled water volume and step 1 1. described in graphite mass ratio be (400mL~
600mL): (6g~8g)；
4., by III low whipping speed of reaction solution be 300r/min~400r/min under be stirred to react 1h~2h, add steaming
The hydrogenperoxide steam generator that distilled water and mass fraction are 30%, obtains reaction solution IV；
Step 1 4. described in distilled water volume and step 1 1. described in graphite mass ratio be (600mL~
800mL): (6g~8g)；
Step 1 4. described in mass fraction be 30% hydrogenperoxide steam generator volume and step 1 1. described in
The mass ratio of graphite is (40mL~60mL): (6g~8g)；
5., by IV low whipping speed of reaction solution be 300r/min~400r/min under be stirred to react 20min~40min, then
Ultrasound 30min~50min in the case where ultrasonic power is 350W~360W, is then allowed to stand 6h~8h, supernatant is outwelled, mixed
Object I；
6., the hydrochloric acid that is 14%~16% using mass fraction as cleaning agent, be 6000r/min~8000r/ in centrifugal speed
Mixture I is cleaned under the centrifugal speed of min, until the supernatant of mixture I is added 0.1mol/L~0.15mol/L's
Barium chloride solution no longer generates precipitating, the mixture I after obtaining hydrochloric acid cleaning；
7., using deionized water the mixture I after hydrogen chloride solution cleaning is cleaned, until the pH value of cleaning solution is
7, the mixture I after obtaining deionized water cleaning；
8., deionized water is cleaned after mixture I be put into freeze drier dry, obtain solids I, will finally consolidate
Body object I grinds and crosses 300 meshes, and screenings is graphene oxide；
Two, the hydroxylating processing of graphene oxide:
1., lithium aluminium hydride reduction is dissolved into tetrahydrofuran, obtain the tetrahydrofuran solution of lithium aluminium hydride reduction；
Step 2 1. described in lithium aluminium hydride reduction quality and tetrahydrofuran volume ratio be (4g~5g): (100mL~
120mL)；
2., added graphene oxide into the tetrahydrofuran solution of lithium aluminium hydride reduction first, be then in ultrasonic power
Ultrasound 0.5h~1h under 350W~360W, then reacted at room temperature with the mixing speed magnetic agitation of 300r/min~400r/min
2h~3h obtains mixture；
Step 2 2. described in graphene oxide quality and step 2 1. in tetrahydrofuran volume ratio be (2g~
3g): (100mL~120mL)；
3., into mixture be added mass fraction be 37% hydrochloric acid, until mixture supernatant become clarification, reuse
It is neutrality that deionization, which is cleaned to cleaning solution, is finally putting into dry 6h~12h in the vacuum oven that temperature is 80 DEG C~90 DEG C, obtains
To hydroxylated graphene oxide；
Three, Cyanuric Chloride modifies graphene oxide:
1., hydroxylated graphene oxide is added in tetrahydrofuran, then surpass in the case where ultrasonic power is 350W~360W
Sound 1h~2h, adds Cyanuric Chloride and triethylamine, then temperature be 70 DEG C~80 DEG C and mixing speed be 300r/min~
Heating stirring reflux for 24 hours~36h, obtains reaction product I under conditions of 400r/min；
Step 3 1. described in hydroxylated graphene oxide quality and tetrahydrofuran volume ratio be (1g~2g):
100mL；
Step 3 1. described in Cyanuric Chloride quality and tetrahydrofuran volume ratio be (3g~4g): 100mL；
Step 3 1. described in triethylamine quality and tetrahydrofuran volume ratio be (4g~6g): 100mL；
2., using tetrahydrofuran reaction product I is cleaned 3 times~5 times, reuse washes of absolute alcohol 3 times~8 times, most
Dry 4h~6h in the vacuum oven that temperature is 80 DEG C~90 DEG C afterwards obtains Cyanuric Chloride modification graphene oxide；
Four, trihydroxy aminomethane modifies graphene oxide:
1., by Cyanuric Chloride modification graphene oxide be added in acetonitrile, then ultrasonic power be 350W~360W under surpass
Sound disperses 1h~2h, adds trihydroxy aminomethane and triethylamine, then heating is stirred under conditions of temperature is 70 DEG C~80 DEG C
Reflux 12h~18h is mixed, reaction product II is obtained；
Step 4 1. described in Cyanuric Chloride modification graphene oxide quality and acetonitrile volume ratio be (0.2g~
0.4g): (30mL~60mL)；
Step 4 1. described in trihydroxy aminomethane quality and acetonitrile volume ratio be (0.4g~0.6g):
(30mL~60mL)；
Step 4 1. described in triethylamine quality and acetonitrile volume ratio be (4g~6g): (30mL~60mL)；
2., using dehydrated alcohol reaction product II is cleaned 3 times~8 times, then it is dry in the vacuum that temperature is 80 DEG C~90 DEG C
Dry 4h~6h, obtains the graphene oxide of hexa-member heterocycle covalent modification in dry case.
The principle of present embodiment:
Present embodiment carries out hydroxylating processing to graphene oxide first, recycles the hydroxyl official of surface of graphene oxide
It can roll into a ball and be chemically combined with chlorine active in Cyanuric Chloride, the grafting of Cyanuric Chloride is that the surface of graphene oxide increases instead
Answer site；It recycles the amino in small molecule trihydroxy aminomethane to chemically react with the unreacted chlorine of Cyanuric Chloride, produces
Raw strong chemical bond.The modification of Cyanuric Chloride and trihydroxy aminomethane to graphene oxide, not only increases graphite oxide
The active group on alkene surface improves compatibility and interface cohesion between polymer, and grafted chain prevents graphene oxide
Agglomeration in the polymer improves its dispersibility in matrix.
The advantages of present embodiment:
One, Cyanuric Chloride has the special design features such as stable triazine ring structure and multiple active chlorine reaction sites,
A variety of possibility are provided for the modification of graphene oxide；Small molecule trihydroxy aminomethane possesses multiple active groups, improves oxygen
The surface-active of graphite alkene；The cost of Cyanuric Chloride and trihydroxy aminomethane is low, the reaction condition ratio with graphene oxide
Relatively mild, reaction process is easy, consumes energy low, economical and environmentally friendly；Small molecule will not only make the surface modification of graphene oxide
At graphene oxide structural damage itself, and it can effectively prevent the agglomeration phenomenon of graphene oxide；
Two, the hexa-member heterocycle covalent modification graphene oxide and epoxy resin of present embodiment preparation are compounded with better power
Performance is learned, composite material is compared with epoxy resin, and tensile strength, which improves, is greater than 38%, and bending strength, which improves, is greater than 46%.
Present embodiment can get hexa-member heterocycle covalent modification graphene oxide.
Specific embodiment 2: the differences between this implementation mode and the specific implementation mode are that: step 2 1. described in hydrogen
The volume ratio of the quality and tetrahydrofuran of changing aluminium lithium is (4.5g~5g): (110mL~120mL).Other steps and specific implementation
Mode one is identical.
Specific embodiment 3: one of present embodiment and specific embodiment one or two difference are: step 2 2. in
The quality of the graphene oxide and step 2 1. in the volume ratio of tetrahydrofuran be (2.5g~3g): (110mL~
120mL).Other steps are the same as one or two specific embodiments.
Specific embodiment 4: one of present embodiment and specific embodiment one to three difference are: step 3 1. in
The quality of the hydroxylated graphene oxide and the volume ratio of tetrahydrofuran are (1.5g~2g): 100mL.Other steps with
Specific embodiment one to three is identical.
Specific embodiment 5: one of present embodiment and specific embodiment one to four difference are: step 3 1. in
The quality of the Cyanuric Chloride and the volume ratio of tetrahydrofuran are (3.5g~4g): 100mL.Other steps and specific embodiment party
Formula one to four is identical.
Specific embodiment 6: one of present embodiment and specific embodiment one to five difference are: step 3 1. in
The quality of the triethylamine and the volume ratio of tetrahydrofuran are (5g~6g): 100mL.Other steps and specific embodiment one
It is identical to five.
Specific embodiment 7: one of present embodiment and specific embodiment one to six difference are: step 4 1. in
The quality of Cyanuric Chloride modification graphene oxide and the volume ratio of acetonitrile is (0.3g~0.4g): (40mL~60mL).
Other steps are identical as specific embodiment one to six.
Specific embodiment 8: one of present embodiment and specific embodiment one to seven difference are: step 4 1. in
The quality of the trihydroxy aminomethane and the volume ratio of acetonitrile are (0.5g~0.6g): (45mL~60mL).Other steps
It is identical as specific embodiment one to seven.
Specific embodiment 9: one of present embodiment and specific embodiment one to eight difference are: step 4 1. in
The quality of the triethylamine and the volume ratio of acetonitrile are (5g~6g): (45mL~60mL).Other steps and specific embodiment party
Formula one to eight is identical.
Specific embodiment 10: one of present embodiment and specific embodiment one to nine difference are: step 3 1. in
Hydroxylated graphene oxide is added in tetrahydrofuran, then ultrasound 1h~2h in the case where ultrasonic power is 350W~360W, then
Cyanuric Chloride and triethylamine is added, then in the condition that temperature is 75 DEG C~80 DEG C and mixing speed is 300r/min~400r/min
Lower heating stirring reflux for 24 hours~32h, obtains reaction product I.Other steps are identical as specific embodiment one to nine.
Beneficial effects of the present invention are verified using following embodiment:
Embodiment one: a kind of method of hexa-member heterocycle covalent modification graphene oxide is completed by the following steps:
One, graphene oxide is prepared:
1., by 8g graphite, 3.75g sodium nitrate and 360mL mass fraction be 98% the concentrated sulfuric acid be added in three-necked flask,
Three-necked flask is placed in 0 DEG C of ice-water bath and low whipping speed is to be stirred to react 30min under 400r/min, obtains reaction solution
Ⅰ；
2., 22.5g potassium permanganate is added into reaction solution I, then three-necked flask is placed in 0 DEG C of ice-water bath and is being stirred
Mixing speed is to be stirred to react 2h under 400r/min, obtains reaction solution II；
3., the temperature of reaction solution II is warming up to 35 DEG C, and react 17h at being 35 DEG C in temperature, add 400mL distillation
Water obtains reaction solution III；
4., by III low whipping speed of reaction solution be 400r/min under be stirred to react 1h, add 660mL distilled water and 60mL
The hydrogenperoxide steam generator that mass fraction is 30%, obtains reaction solution IV；
5., be to be stirred to react 20min under 400r/min for IV low whipping speed of reaction solution, then in the case where ultrasonic power is 350W
Ultrasonic 30min, is then allowed to stand 6h, and supernatant is outwelled, and obtains mixture I；
6., the hydrochloric acid that is 14% using mass fraction as cleaning agent, it is right in the case where centrifugal speed is the centrifugal speed of 7000r/min
Mixture I is cleaned, until the barium chloride solution that 0.1mol/L is added in the supernatant of mixture I no longer generates precipitating, is obtained
Mixture I after hydrochloric acid cleaning；
7., using deionized water the mixture I after hydrogen chloride solution cleaning is cleaned, until the pH value of cleaning solution is
7, the mixture I after obtaining deionized water cleaning；
8., deionized water is cleaned after mixture I be put into freeze drier dry, obtain solids I, will finally consolidate
Body object I grinds and crosses 300 meshes, and screenings is graphene oxide；
Two, the hydroxylating processing of graphene oxide:
1., 4g lithium aluminium hydride reduction is dissolved into 100mL tetrahydrofuran, obtain the tetrahydrofuran solution of lithium aluminium hydride reduction；
2., 2g graphene oxide is added in the tetrahydrofuran solution of lithium aluminium hydride reduction first, be then in ultrasonic power
Ultrasound 0.5h under 350W, then 2h is reacted with the mixing speed magnetic agitation of 400r/min at room temperature, obtain mixture；
3., into mixture be added mass fraction be 37% hydrochloric acid, until mixture supernatant become clarification, reuse
It is neutrality that deionization, which is cleaned to cleaning solution, is finally putting into dry 6h in the vacuum oven that temperature is 80 DEG C, obtains hydroxylated
Graphene oxide；
Three, Cyanuric Chloride modifies graphene oxide:
1., the hydroxylated graphene oxide of 1g is added in 100mL tetrahydrofuran, then surpass in the case where ultrasonic power is 350W
Sound 1h adds 3.69g Cyanuric Chloride and 4.0g triethylamine, then in the condition that temperature is 70 DEG C and mixing speed is 400r/min
Lower heating stirring reflux for 24 hours, obtains reaction product I；
2., using tetrahydrofuran to reaction product I clean 4 times, reuse washes of absolute alcohol 5 times, be finally in temperature
Dry 4h in 80 DEG C of vacuum oven obtains Cyanuric Chloride modification graphene oxide；
Four, trihydroxy aminomethane modifies graphene oxide:
1., by 0.2g Cyanuric Chloride modification graphene oxide be added in 30mL acetonitrile, then ultrasonic power be 350W under
Ultrasonic disperse 1h adds 0.4g trihydroxy aminomethane and 4g triethylamine, then heating stirring under conditions of temperature is 70 DEG C
Flow back 12h, obtains reaction product II；
2., using dehydrated alcohol reaction product II is cleaned 5 times, then temperature be in 80 DEG C of vacuum oven it is dry
4h obtains the graphene oxide of hexa-member heterocycle covalent modification.
Embodiment two: a kind of method of hexa-member heterocycle covalent modification graphene oxide is completed by the following steps:
One, graphene oxide is prepared:
1., by 6g graphite, 2g sodium nitrate and mass fraction be 98% the concentrated sulfuric acid be added in three-necked flask, by three mouthfuls burn
Bottle is placed in 3 DEG C of ice-water bath and low whipping speed is to be stirred to react 40min under 300r/min, obtains reaction solution I；
2., 20g potassium permanganate is added into reaction solution I, then three-necked flask is placed in 3 DEG C of ice-water bath and is being stirred
Speed is to be stirred to react 3h under 300r/min, obtains reaction solution II；
3., the temperature of reaction solution II is warming up to 35 DEG C, and react 19h at being 35 DEG C in temperature, add 500mL distillation
Water obtains reaction solution III；
4., by III low whipping speed of reaction solution be 300r/min under be stirred to react 1.5h, add 800mL distilled water and
The hydrogenperoxide steam generator that 40mL mass fraction is 30%, obtains reaction solution IV；
5., be to be stirred to react 20min under 300r/min for IV low whipping speed of reaction solution, then in the case where ultrasonic power is 350W
Ultrasonic 50min, is then allowed to stand 7h, and supernatant is outwelled, and obtains mixture I；
6., the hydrochloric acid that is 15% using mass fraction as cleaning agent, it is right in the case where centrifugal speed is the centrifugal speed of 8000r/min
Mixture I is cleaned, until the barium chloride solution that 0.15mol/L is added in the supernatant of mixture I no longer generates precipitating, is obtained
Mixture I after hydrochloric acid cleaning；
7., using deionized water the mixture I after hydrogen chloride solution cleaning is cleaned, until the pH value of cleaning solution is
7, the mixture I after obtaining deionized water cleaning；
8., deionized water is cleaned after mixture I be put into freeze drier dry, obtain solids I, will finally consolidate
Body object I grinds and crosses 300 meshes, and screenings is graphene oxide；
Two, the hydroxylating processing of graphene oxide:
1., 5g lithium aluminium hydride reduction is dissolved into 120mL tetrahydrofuran, obtain the tetrahydrofuran solution of lithium aluminium hydride reduction；
2., 3g graphene oxide is added in the tetrahydrofuran solution of lithium aluminium hydride reduction first, be then in ultrasonic power
Ultrasound 1h under 350W, then 3h is reacted with the mixing speed magnetic agitation of 400r/min at room temperature, obtain mixture；
3., into mixture be added mass fraction be 37% hydrochloric acid, until mixture supernatant become clarification, reuse
It is neutrality that deionization, which is cleaned to cleaning solution, is finally putting into vacuum oven at a temperature of 90 °C dry 12h, obtains hydroxylated
Graphene oxide；
Three, Cyanuric Chloride modifies graphene oxide:
1., the hydroxylated graphene oxide of 2g is added in 100mL tetrahydrofuran, then surpass in the case where ultrasonic power is 350W
Sound 2h adds 4g Cyanuric Chloride and 6g triethylamine, then adds under conditions of temperature is 80 DEG C and mixing speed is 400r/min
Thermal agitation reflux 36h, obtains reaction product I；
2., using tetrahydrofuran to reaction product I clean 3 times, reuse washes of absolute alcohol 5 times, be finally in temperature
Dry 4h in 90 DEG C of vacuum oven obtains Cyanuric Chloride modification graphene oxide；
Four, trihydroxy aminomethane modifies graphene oxide:
1., by 0.4g Cyanuric Chloride modification graphene oxide be added in 60mL acetonitrile, then ultrasonic power be 350W under
Ultrasonic disperse 2h adds 0.6g trihydroxy aminomethane and 6g triethylamine, then heating stirring under conditions of temperature is 80 DEG C
Flow back 18h, obtains reaction product II；
2., using dehydrated alcohol reaction product II is cleaned 5 times, then in vacuum oven at a temperature of 90 °C it is dry
6h obtains the graphene oxide of hexa-member heterocycle covalent modification.
Fig. 1 is infrared spectrogram, and a is that the infrared light of 8. graphene oxide that one step 1 of embodiment obtains is set a song to music in figure
Line, b are the infrared spectrum curve that 2. Cyanuric Chloride that one step 3 of embodiment obtains modifies graphene oxide, and c is embodiment one
The infrared spectrum curve of the graphene oxide of 2. hexa-member heterocycle covalent modification that step 4 obtains；
From fig. 1, it can be seen that GO (graphene oxide) is in 3100cm-1、1716cm-1、1608cm-1And 1039cm-1Distinguish at the peak at place
The stretching vibration of corresponding O-H, C=O, C=C and C-O-C.This shows to show a large amount of oxygen-containing functional groups on the surface GO；By
The spectrum of the Cyanuric Chloride modification graphene oxide obtained after Cyanuric Chloride grafting is in 1714cm-1, 1568cm-1And 934cm-1Place
There are three new peaks, the skeleton peak of the C=N and C-N key corresponding to triazine ring and C-Cl stretching vibration；Hexa-member heterocycle covalent modification
Graphene oxide compared with Cyanuric Chloride modifies graphene oxide, the absorption peak of C-Cl disappears.These results tentatively show three
Polychlorostyrene cyanogen and trihydroxy aminomethane are successfully grafted on the surface GO.
Fig. 2 is raman spectrum, and a is the Raman curve of 8. graphene oxide that one step 1 of embodiment obtains in figure, and b is real
The Raman curve of 2. Cyanuric Chloride modification graphene oxide that one step 3 of example obtains is applied, c is 2. one step 4 of embodiment obtains
Hexa-member heterocycle covalent modification graphene oxide Raman curve；
As can be seen from Figure 2, the Raman difraction spectrum of (graphene oxide) GO and its derivative mainly includes D wave band (1335cm-1) and G-band (1581cm-1) two wave bands, the intensity ratio of ID/IG is the magnitude mode of disordered graphite.The ID/IG ratio of GO is
1.74.Compared with GO, the graphene oxide (GO-TCT-Tris) of 2. hexa-member heterocycle covalent modification that one step 4 of embodiment obtains
ID/IG value be slightly increased from 1.74 to 2.03, this is because 2. hexa-member heterocycle covalent modification that one step 4 of embodiment obtains
Graphene oxide and the surface GO on functional group formed chemical bond.2. hexa-member heterocycle that one step 4 of embodiment obtains covalently is repaired
Grafting of the graphene oxide of decorations on the surface GO increases its active site, but the sp2 structure of graphene is in modifying process
Apparent structural failure is not shown.
2. hexa-member heterocycle that 8. graphene oxide and one step 4 of embodiment that one step 1 of embodiment obtains obtains is covalent
The constituent content of the graphene oxide of modification is shown in Table 1.
Table 1
Note: GO is the graphene oxide that 8. obtains of one step 1 of embodiment, GO-TCT-Tris be one step 4 of embodiment 2.
The graphene oxide of obtained hexa-member heterocycle covalent modification.
As it can be seen from table 1 the surface of graphene oxide is mainly made of C (59.9%) and O (40.39%), and pass through
Modified graphene oxide (i.e. one step 4 of embodiment 2. obtain the graphene oxide of hexa-member heterocycle covalent modification) occurs
New element N (3.73%) and Cl (0.25%).
Fig. 3 is the XPS swarming spectrogram of 8. graphene oxide that one step 1 of embodiment obtains；
Fig. 4 is the XPS swarming spectrogram of the graphene oxide of 2. hexa-member heterocycle covalent modification that one step 4 of embodiment obtains；
Find out from the C1s swarming spectrogram of Fig. 3 and Fig. 4, graphene oxide contains there are five types of characteristic peak, and modified oxidation
C-OH of the graphene (i.e. one step 4 of embodiment 2. obtain the graphene oxide of hexa-member heterocycle covalent modification) at 285.3eV
Peak content reduces, and occurs C-N new peak at 285.7eV.This shows Cyanuric Chloride and trihydroxy aminomethane covalence graft
To surface of graphene oxide.
Fig. 5 is the SEM figure of 8. graphene oxide that one step 1 of embodiment obtains；
Fig. 6 is the SEM figure of the graphene oxide of 2. hexa-member heterocycle covalent modification that one step 4 of embodiment obtains；
The surface GO smooth even as can be seen from Figure 5, but assemble seriously, form three dimension layers.In Fig. 6
In, the marginal surface of the graphene oxide of 2. hexa-member heterocycle covalent modification that one step 4 of embodiment obtains is shown
More to fold, interlayer structure is loose.Because the dendrimer of surface of graphene oxide grafting is played a supporting role in interlayer,
Prevent the reunion of graphene oxide.
Embodiment three: it prepares graphene oxide/epoxy resin composite material and is completed by the following steps:
One, 8. graphene oxide that one step 1 of 0.036g embodiment obtains is added in 15mL acetone, then in ultrasound
Power is ultrasound 60min under 350W, obtains mixed liquor；
Two, it is E-51 that 36g epoxy resin is added into mixed liquor, then the ultrasound 30min in the case where ultrasonic power is 350W, then
Dry 12h at being 80 DEG C in temperature, obtains epoxy resin composition；
Three, 10.8g curing agent H256 is added into epoxy resin composition, is then stirred with the speed mechanical of 3000r/min
15min is mixed, 1h is dried in vacuo at being finally 80 DEG C in temperature, obtains the epoxy resin composition that curing agent is added；
Four, the epoxy resin that curing agent is added is mixed in the vacuum oven that temperature is 80 DEG C, vacuum degree is -30kPa
It closes object to pour into the preheated mold that temperature is 80 DEG C, then is solidified, obtain graphene oxide/epoxy resin composite material；
Curing process described in step 4 are as follows: solidify under conditions of vacuum degree is -30kPa and temperature is 80 DEG C first
Then 2h solidifies 2h under conditions of vacuum degree is -30kPa and temperature is 100 DEG C, be finally -30kPa and temperature in vacuum degree
Solidify 4h under conditions of being 150 DEG C.
Example IV: the graphene oxide/epoxy resin composite material for preparing hexa-member heterocycle covalent modification is by following step
Suddenly it completes:
One, the graphene oxide of 2. hexa-member heterocycle covalent modification that one step 4 of 0.036g embodiment obtains is added to
In 15mL acetone, then the ultrasound 60min in the case where ultrasonic power is 350W, obtain mixed liquor；
Two, it is E-51 that 36g epoxy resin is added into mixed liquor, then the ultrasound 30min in the case where ultrasonic power is 350W, then
Dry 12h at being 80 DEG C in temperature, obtains epoxy resin composition；
Three, 10.8g curing agent H256 is added into epoxy resin composition, is then stirred with the speed mechanical of 3000r/min
15min is mixed, 1h is dried in vacuo at being finally 80 DEG C in temperature, obtains the epoxy resin composition that curing agent is added；
Four, the epoxy resin that curing agent is added is mixed in the vacuum oven that temperature is 80 DEG C, vacuum degree is -30kPa
It closes object to pour into the preheated mold that temperature is 80 DEG C, then is solidified, obtain graphene oxide/ring of hexa-member heterocycle covalent modification
Epoxy resin composite material；
Curing process described in step 4 are as follows: solidify under conditions of vacuum degree is -30kPa and temperature is 80 DEG C first
Then 2h solidifies 2h under conditions of vacuum degree is -30kPa and temperature is 100 DEG C, be finally -30kPa and temperature in vacuum degree
Solidify 4h under conditions of being 150 DEG C.
Fig. 7 is tensile strength histogram, in figure 1 be pure epoxy resin tensile strength, 2 oxidations prepared for embodiment three
Graphene/epoxy resin composite material tensile strength, the graphite oxide of the 3 hexa-member heterocycle covalent modifications prepared for example IV
Alkene/epoxy resin composite material tensile strength；
Fig. 8 is bending strength histogram, in figure 1 be pure epoxy resin bending strength, 2 oxidations prepared for embodiment three
Graphene/epoxy resin composite material bending strength, the graphite oxide of the 3 hexa-member heterocycle covalent modifications prepared for example IV
Alkene/epoxy resin composite material bending strength.
From Fig. 7 and Fig. 8 it is found that compared with pure epoxy resin, the graphene oxide/epoxy resin for loading 0.10%GO is compound
21.79% and 18.40% has been respectively increased in the tensile strength and bending strength of material.For the hexa-member heterocycle containing 0.10%GO
Graphene oxide/epoxy resin composite material the tensile strength and bending strength ratio pure epoxy resin of covalent modification improve
37.11% and 46.90%.The result shows that the composite material of modified graphene oxide and epoxy resin has better mechanical property
Can, this is because preferably dispersibility and strong interface between GO-TCT-Tris and epoxy resin-base, effectively by load from base
Body is transferred on GO sheet material.
Claims (10)
1. a kind of method of hexa-member heterocycle covalent modification graphene oxide, it is characterised in that a kind of hexa-member heterocycle covalent modification oxidation
The method of graphene is completed by the following steps:
One, graphene oxide is prepared:
1., graphite, sodium nitrate and the concentrated sulfuric acid be added in three-necked flask, three-necked flask is placed to 0 DEG C~5 DEG C of ice-water bath
In and low whipping speed be 300r/min~400r/min under be stirred to react 30min~40min, obtain reaction solution I；
Step 1 1. described in the concentrated sulfuric acid mass fraction be 96%~98%；
Step 1 1. described in graphite quality and the concentrated sulfuric acid volume ratio be (6g~8g): (360mL~500mL)；
Step 1 1. described in sodium nitrate quality and the concentrated sulfuric acid volume ratio (2g~4g): (360mL~500mL)；
2., potassium permanganate is added into reaction solution I, then three-necked flask is placed in 0 DEG C~5 DEG C of ice-water bath and in stirring speed
Degree is to be stirred to react 2h~3h under 300r/min~400r/min, obtains reaction solution II；
Step 1 2. described in potassium permanganate and step 1 1. described in graphite mass ratio be (20~25): (6~8)；
3., the temperature of reaction solution II is warming up to 35 DEG C~40 DEG C, and react 17h~19h at being 35 DEG C~40 DEG C in temperature, then
Distilled water is added, obtains reaction solution III；
Step 1 3. described in distilled water volume and step 1 1. described in graphite mass ratio be (400mL~
600mL): (6g~8g)；
4., by III low whipping speed of reaction solution be 300r/min~400r/min under be stirred to react 1h~2h, add distilled water
The hydrogenperoxide steam generator for being 30% with mass fraction, obtains reaction solution IV；
Step 1 4. described in distilled water volume and step 1 1. described in graphite mass ratio be (600mL~
800mL): (6g~8g)；
Step 1 4. described in mass fraction be 30% hydrogenperoxide steam generator volume and step 1 1. described in graphite
Mass ratio be (40mL~60mL): (6g~8g)；
5., be to be stirred to react 20min~40min under 300r/min~400r/min for IV low whipping speed of reaction solution, then super
Acoustical power is ultrasound 30min~50min under 350W~360W, is then allowed to stand 6h~8h, supernatant is outwelled, obtain mixture I；
6., the hydrochloric acid that is 14%~16% using mass fraction as cleaning agent, be 6000r/min~8000r/min in centrifugal speed
Centrifugal speed under mixture I is cleaned, until mixture I supernatant be added 0.1mol/L~0.15mol/L chlorine
Change barium solution and no longer generates precipitating, the mixture I after obtaining hydrochloric acid cleaning；
7., using deionized water to hydrogen chloride solution cleaning after mixture I clean, until cleaning solution pH value be 7, obtain
Mixture I to after deionized water cleaning；
8., deionized water is cleaned after mixture I be put into freeze drier dry, solids I is obtained, finally by solids
I grinds and crosses 300 meshes, and screenings is graphene oxide；
Two, the hydroxylating processing of graphene oxide:
1., lithium aluminium hydride reduction is dissolved into tetrahydrofuran, obtain the tetrahydrofuran solution of lithium aluminium hydride reduction；
Step 2 1. described in lithium aluminium hydride reduction quality and tetrahydrofuran volume ratio be (4g~5g): (100mL~
120mL)；
2., added graphene oxide into the tetrahydrofuran solution of lithium aluminium hydride reduction first, then ultrasonic power be 350W~
Ultrasound 0.5h~1h under 360W, then at room temperature with the mixing speed magnetic agitation of 300r/min~400r/min reaction 2h~
3h obtains mixture；
Step 2 2. described in graphene oxide quality and step 2 1. in tetrahydrofuran volume ratio be (2g~3g):
(100mL~120mL)；
3., into mixture be added mass fraction be 37% hydrochloric acid, until mixture supernatant become clarification, reuse from
Son cleaning to cleaning solution is neutrality, is finally putting into dry 6h~12h in the vacuum oven that temperature is 80 DEG C~90 DEG C, obtains hydroxyl
The graphene oxide of base；
Three, Cyanuric Chloride modifies graphene oxide:
1., hydroxylated graphene oxide is added in tetrahydrofuran, then the ultrasound 1h in the case where ultrasonic power is 350W~360W
~2h, adds Cyanuric Chloride and triethylamine, then is 70 DEG C~80 DEG C in temperature and mixing speed is 300r/min~400r/
Heating stirring reflux for 24 hours~36h, obtains reaction product I under conditions of min；
Step 3 1. described in hydroxylated graphene oxide quality and tetrahydrofuran volume ratio be (1g~2g):
100mL；
Step 3 1. described in Cyanuric Chloride quality and tetrahydrofuran volume ratio be (3g~4g): 100mL；
Step 3 1. described in triethylamine quality and tetrahydrofuran volume ratio be (4g~6g): 100mL；
2., using tetrahydrofuran to reaction product I clean 3 times~5 times, reuse washes of absolute alcohol 3 times~8 times, finally exist
Dry 4h~6h in the vacuum oven that temperature is 80 DEG C~90 DEG C obtains Cyanuric Chloride modification graphene oxide；
Four, trihydroxy aminomethane modifies graphene oxide:
1., by Cyanuric Chloride modification graphene oxide be added in acetonitrile, then ultrasonic power be 350W~360W under ultrasound point
1h~2h is dissipated, adds trihydroxy aminomethane and triethylamine, then heating stirring is returned under conditions of temperature is 70 DEG C~80 DEG C
12h~18h is flowed, reaction product II is obtained；
Step 4 1. described in Cyanuric Chloride modification graphene oxide quality and acetonitrile volume ratio be (0.2g~0.4g):
(30mL~60mL)；
Step 4 1. described in trihydroxy aminomethane quality and acetonitrile volume ratio be (0.4g~0.6g): (30mL~
60mL)；
Step 4 1. described in triethylamine quality and acetonitrile volume ratio be (4g~6g): (30mL~60mL)；
2., using dehydrated alcohol reaction product II is cleaned 3 times~8 times, then in temperature be 80 DEG C~90 DEG C of vacuum oven
Middle dry 4h~6h, obtains the graphene oxide of hexa-member heterocycle covalent modification.
2. a kind of method of hexa-member heterocycle covalent modification graphene oxide according to claim 1, it is characterised in that step
Two 1. described in lithium aluminium hydride reduction quality and tetrahydrofuran volume ratio be (4.5g~5g): (110mL~120mL).
3. a kind of method of hexa-member heterocycle covalent modification graphene oxide according to claim 1, it is characterised in that step
Two 2. described in graphene oxide quality and step 2 1. in tetrahydrofuran volume ratio be (2.5g~3g): (110mL
~120mL).
4. a kind of method of hexa-member heterocycle covalent modification graphene oxide according to claim 1, it is characterised in that step
Three 1. described in hydroxylated graphene oxide quality and tetrahydrofuran volume ratio be (1.5g~2g): 100mL.
5. a kind of method of hexa-member heterocycle covalent modification graphene oxide according to claim 1, it is characterised in that step
Three 1. described in Cyanuric Chloride quality and tetrahydrofuran volume ratio be (3.5g~4g): 100mL.
6. a kind of method of hexa-member heterocycle covalent modification graphene oxide according to claim 1, it is characterised in that step
Three 1. described in triethylamine quality and tetrahydrofuran volume ratio be (5g~6g): 100mL.
7. a kind of method of hexa-member heterocycle covalent modification graphene oxide according to claim 1, it is characterised in that step
Four 1. described in Cyanuric Chloride modification graphene oxide quality and acetonitrile volume ratio be (0.3g~0.4g): (40mL~
60mL)。
8. a kind of method of hexa-member heterocycle covalent modification graphene oxide according to claim 1, it is characterised in that step
Four 1. described in trihydroxy aminomethane quality and acetonitrile volume ratio be (0.5g~0.6g): (45mL~60mL).
9. a kind of method of hexa-member heterocycle covalent modification graphene oxide according to claim 1, it is characterised in that step
Four 1. described in triethylamine quality and acetonitrile volume ratio be (5g~6g): (45mL~60mL).
10. a kind of method of hexa-member heterocycle covalent modification graphene oxide according to claim 1, it is characterised in that step
Three 1. in hydroxylated graphene oxide is added in tetrahydrofuran, then ultrasonic power be 350W~360W under ultrasound 1h~
2h, adds Cyanuric Chloride and triethylamine, then is 75 DEG C~80 DEG C in temperature and mixing speed is 300r/min~400r/min
Under conditions of heating stirring flow back for 24 hours~32h, obtain reaction product I.
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| EP2931781A1 (en) * | 2012-12-14 | 2015-10-21 | Blue Cube IP LLC | Modified epoxy resins |
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