CN110305448A - A kind of preparation method of hexa-member heterocycle covalent modification graphene oxide/epoxy resin composite material - Google Patents
A kind of preparation method of hexa-member heterocycle covalent modification graphene oxide/epoxy resin composite material Download PDFInfo
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Abstract
A kind of preparation method of hexa-member heterocycle covalent modification graphene oxide/epoxy resin composite material, it is related to a kind of preparation method of modified graphene oxide/epoxy resin composite material.The invention aims to solve existing graphene bad dispersibility and poor compatibility in the epoxy, and graphene additive amount is big in Graphene epoxy resin composite material, problem at high cost.Method: one, the graphene oxide solution of hexa-member heterocycle covalent modification is prepared；Two, epoxy resin is added；Three, curing agent is added；Four, curing reaction obtains hexa-member heterocycle covalent modification graphene oxide/epoxy resin composite material.The additive amount of hexa-member heterocycle covalent modification graphene oxide is few in hexa-member heterocycle covalent modification graphene oxide/epoxy resin composite material prepared by the present invention, greatly reduces cost.The present invention can get a kind of hexa-member heterocycle covalent modification graphene oxide/epoxy resin composite material.
Description
Technical field
The present invention relates to a kind of preparation methods of modified graphene oxide/epoxy resin composite material.
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.
In addition, existing method is difficult to solve the problems, such as graphene bad dispersibility and poor compatibility in the epoxy, and existing
Graphene additive amount is big in the Graphene epoxy resin composite material for having method to prepare, and leads to the at high cost of composite material.
Summary of the invention
The invention aims to solve existing graphene bad dispersibility and poor compatibility, and graphene in the epoxy
Graphene additive amount is big in epoxy resin composite material, problem at high cost, and provides a kind of hexa-member heterocycle covalent modification oxidation
Graphene/epoxy resin composite material preparation method.
A kind of method of hexa-member heterocycle covalent modification graphene oxide, is completed by the following steps:
One, the graphene oxide of hexa-member heterocycle covalent modification is added in acetone, re-ultrasonic dispersion obtains mixed liquor；
The quality of graphene oxide and the volume ratio of acetone of hexa-member heterocycle covalent modification described in step 1 be
(0.033g~0.036g): (10mL~15mL)；
Two, epoxy resin is added into mixed liquor, then in ultrasonic disperse, is finally dried, it is mixed to obtain epoxy resin
Close object；
The graphene oxide of epoxy resin described in step 2 and hexa-member heterocycle covalent modification described in step 1
Mass ratio is (33~36): (0.033~0.036)；
Three, curing agent is added into epoxy resin composition, is stirred for, is finally dried, obtains that curing agent is added
Epoxy resin composition；
The mass ratio of epoxy resin described in curing agent described in step 3 and step 2 is (10~11): (33~
36)；
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 hexa-member heterocycle covalent modification graphene oxide/epoxy
Resin composite materials.
The principle of the present invention:
One, the present invention is able to solve graphene poor problem of dispersibility in epoxy matrix material, prepared by the present invention
The graphene oxide of hexa-member heterocycle covalent modification not only increases the active group of surface of graphene oxide, improves between polymer
Compatibility and interface cohesion, and grafted chain prevents the agglomeration of graphene oxide in the polymer, improves it in matrix
In dispersibility；
Two, hexa-member heterocycle covalent modification graphene oxide/epoxy resin composite material prepared by the present invention has better power
Performance is learned, compared with epoxy resin, tensile strength, which improves, is greater than 38%, and bending strength, which improves, is greater than 46%；
Three, hexa-member heterocycle in hexa-member heterocycle covalent modification graphene oxide/epoxy resin composite material prepared by the present invention
The additive amount of covalent modification graphene oxide is few, and additive amount is only hexa-member heterocycle covalent modification graphene oxide/epoxy resin
The 0.1% of composite material quality, greatly reduces cost.
The present invention can get a kind of hexa-member heterocycle covalent modification graphene oxide/epoxy resin composite material.
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 prepare for comparative example one
Graphene oxide/epoxy resin composite material tensile strength, 3 covalently repair for 4. hexa-member heterocycle that one step 5 of embodiment is prepared
Graphene oxide/epoxy resin composite material tensile strength of decorations；
Fig. 8 is bending strength histogram, in figure 1 be pure epoxy resin bending strength, 2 prepare for comparative example one
Graphene oxide/epoxy resin composite material bending strength, 3 covalently repair for 4. hexa-member heterocycle that one step 5 of embodiment is prepared
Graphene oxide/epoxy resin composite material bending strength of decorations；
Fig. 9 is the digital photograph figure of the GO dispersion liquid and GO-TCT-Tris aqueous dispersions after being ultrasonically treated；
Figure 10 is the digital photograph figure of the GO dispersion liquid and GO-TCT-Tris aqueous dispersions after standing for 24 hours；
Figure 11 is graphene oxide/epoxy resin composite material SEM figure prepared by comparative example one；
Figure 12 is that graphene oxide/epoxy resin of 4. hexa-member heterocycle covalent modification that one step 5 of embodiment is prepared is compound
The SEM of material schemes；
Figure 13 is graphene oxide/epoxy resin composite material TEM figure prepared by comparative example one；
Figure 14 is that graphene oxide/epoxy resin of 4. hexa-member heterocycle covalent modification that one step 5 of embodiment is prepared is compound
The TEM of material schemes.
Specific embodiment
Specific embodiment 1: a kind of method of hexa-member heterocycle covalent modification graphene oxide of present embodiment is by following
What step was completed:
One, the graphene oxide of hexa-member heterocycle covalent modification is added in acetone, re-ultrasonic dispersion obtains mixed liquor；
The quality of graphene oxide and the volume ratio of acetone of hexa-member heterocycle covalent modification described in step 1 be
(0.033g~0.036g): (10mL~15mL)；
Two, epoxy resin is added into mixed liquor, then in ultrasonic disperse, is finally dried, it is mixed to obtain epoxy resin
Close object；
The graphene oxide of epoxy resin described in step 2 and hexa-member heterocycle covalent modification described in step 1
Mass ratio is (33~36): (0.033~0.036)；
Three, curing agent is added into epoxy resin composition, is stirred for, is finally dried, obtains that curing agent is added
Epoxy resin composition；
The mass ratio of epoxy resin described in curing agent described in step 3 and step 2 is (10~11): (33~
36)；
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 hexa-member heterocycle covalent modification graphene oxide/epoxy
Resin composite materials.
The principle of present embodiment:
One, present embodiment is able to solve the graphene poor problem of dispersibility, this embodiment party in epoxy matrix material
The graphene oxide of the hexa-member heterocycle covalent modification of formula preparation not only increases the active group of surface of graphene oxide, improve with
Compatibility and interface cohesion between polymer, and grafted chain prevents the agglomeration of graphene oxide in the polymer, improves
Its dispersibility in matrix；
Two, hexa-member heterocycle covalent modification graphene oxide/epoxy resin composite material of present embodiment preparation has more preferably
Mechanical property, compared with epoxy resin, tensile strength improve be greater than 38%, bending strength improve be greater than 46%；
Three, hexa-atomic in hexa-member heterocycle covalent modification graphene oxide/epoxy resin composite material of present embodiment preparation
The additive amount of heterocycle covalent modification graphene oxide is few, and additive amount is only hexa-member heterocycle covalent modification graphene oxide/epoxy
The 0.1% of resin composite materials quality, greatly reduces cost.
Present embodiment can get a kind of hexa-member heterocycle covalent modification graphene oxide/epoxy resin composite material.
Specific embodiment 2: the differences between this implementation mode and the specific implementation mode are that: it is described in step 1 hexa-atomic
The graphene oxide of heterocycle covalent modification is prepared according to 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 be (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.Other steps and one phase of specific embodiment
Together.
Specific embodiment 3: one of present embodiment and specific embodiment one or two difference are: institute in step 1
The power for the ultrasonic disperse stated is 350W~360W, and the time of ultrasonic disperse is 0.6h~1h.Other steps and specific embodiment party
Formula one or two is identical.
Specific embodiment 4: one of present embodiment and specific embodiment one to three difference are: institute in step 2
The epoxy resin stated is E-51.Other steps are identical as specific embodiment one to three.
Specific embodiment 5: one of present embodiment and specific embodiment one to four difference are: institute in step 2
The power for the ultrasonic disperse stated is 350W~360W, and the time of ultrasonic disperse is 30min~60min.Other steps and specific reality
It is identical to apply mode one to four.
Specific embodiment 6: one of present embodiment and specific embodiment one to five difference are: institute in step 2
The drying temperature stated is 80 DEG C, and drying time is 10h~12h.Other steps are identical as specific embodiment one to five.
Specific embodiment 7: one of present embodiment and specific embodiment one to six difference are: institute in step 3
The curing agent stated is H256.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: institute in step 3
The mixing speed stated is 3000r/min, and mixing time is 15min~20min.Other steps and one to seven phase of specific embodiment
Together.
Specific embodiment 9: one of present embodiment and specific embodiment one to eight difference are: institute in step 3
The drying temperature stated is 80 DEG C~90 DEG C, and drying time is 1h~1.5h.Other steps are identical as specific embodiment one to eight.
Specific embodiment 10: one of present embodiment and specific embodiment one to nine difference are: institute in step 4
The curing process stated are as follows: solidify 2h under conditions of vacuum degree is -30kPa and temperature is 80 DEG C first, then vacuum degree be -
30kPa and temperature solidify 2h under conditions of being 100 DEG C, finally solid under conditions of vacuum degree is -30kPa and temperature is 150 DEG C
Change 4h.Other steps are identical as specific embodiment one to nine.
Embodiment one: graphene oxide/epoxy resin composite material preparation method of hexa-member heterocycle covalent modification, be by
What following steps were completed:
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；
Five, compound:
1., the graphene oxide of 0.036g hexa-member heterocycle covalent modification is added in 15mL acetone, then in ultrasonic power
For ultrasound 60min under 350W, mixed liquor is obtained；
2., into mixed liquor be added 36g epoxy resin be E-51, then ultrasonic power be 350W under ultrasound 30min, then
Dry 12h at being 80 DEG C in temperature, obtains epoxy resin composition；
3., into epoxy resin composition be added 10.8g curing agent H256, 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；
4., in the vacuum oven that temperature is 80 DEG C, vacuum degree is -30kPa the epoxy resin that curing agent is added mixed
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；
Step 5 4. described in curing process are as follows: it is solid under conditions of vacuum degree is -30kPa and temperature is 80 DEG C first
Change 2h, then solidify 2h under conditions of vacuum degree is -30kPa and temperature is 100 DEG C, is finally -30kPa and temperature in vacuum degree
Degree solidifies 4h under conditions of being 150 DEG C.
Comparative example one: a kind of preparation method of graphene oxide/epoxy resin composite material, is complete according to the following steps
At:
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.
Embodiment two: graphene oxide/epoxy resin composite material preparation method of hexa-member heterocycle covalent modification, be by
What following steps were completed:
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；
Five, compound:
1., the graphene oxide of 0.036g hexa-member heterocycle covalent modification is added in 15mL acetone, then in ultrasonic power
For ultrasound 60min under 350W, mixed liquor is obtained；
2., into mixed liquor be added 36g epoxy resin be E-51, then ultrasonic power be 350W under ultrasound 30min, then
Dry 12h at being 80 DEG C in temperature, obtains epoxy resin composition；
3., into epoxy resin composition be added 10.8g curing agent H256, 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；
4., in the vacuum oven that temperature is 80 DEG C, vacuum degree is -30kPa the epoxy resin that curing agent is added mixed
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；
Step 5 4. described in curing process are as follows: it is solid under conditions of vacuum degree is -30kPa and temperature is 80 DEG C first
Change 2h, then solidify 2h under conditions of vacuum degree is -30kPa and temperature is 100 DEG C, is finally -30kPa and temperature in vacuum degree
Degree solidifies 4h under conditions of being 150 DEG C.
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, embodiment
The marginal surface of the graphene oxide of 2. hexa-member heterocycle covalent modification that one step 4 obtains shows more to fold, interlayer knot
Structure is loose.Because the dendrimer of surface of graphene oxide grafting is played a supporting role in interlayer, graphene oxide is prevented
Reunion.
Fig. 7 is tensile strength histogram, in figure 1 be pure epoxy resin tensile strength, 2 prepare for comparative example one
Graphene oxide/epoxy resin composite material tensile strength, 3 covalently repair for 4. hexa-member heterocycle that one step 5 of embodiment is prepared
Graphene oxide/epoxy resin composite material tensile strength of decorations；
Fig. 8 is bending strength histogram, in figure 1 be pure epoxy resin bending strength, 2 prepare for comparative example one
Graphene oxide/epoxy resin composite material bending strength, 3 covalently repair for 4. hexa-member heterocycle that one step 5 of embodiment is prepared
Graphene oxide/epoxy resin composite material bending strength of decorations.
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.
Dispersibility test:
By GO (8. graphene oxide that one step 1 of embodiment obtains) and GO-TCT-Tris, (one step 4 of embodiment is 2.
The graphene oxide of obtained hexa-member heterocycle covalent modification) it is dissolved into distilled water respectively, then ultrasound is carried out, obtaining concentration is
The GO aqueous dispersions and concentration of 1mg/L are the GO-TCT-Tris aqueous dispersions of 1mg/L, and part Fig. 9 stands and sees Figure 10 afterwards for 24 hours；
Fig. 9 is the digital photograph figure of the GO dispersion liquid and GO-TCT-Tris aqueous dispersions after being ultrasonically treated；
Figure 10 is the digital photograph figure of the GO dispersion liquid and GO-TCT-Tris aqueous dispersions after standing for 24 hours；
From Fig. 9 and Figure 10 it is found that GO and GO-TCT-Tris can be easily dispersed in water, brown color is presented respectively
With the color of black.However, TCT and Tris has significant impact to its dispersibility in acetone to the modification of GO, after 24 hours,
Untreated GO generates deposited phenomenon in acetone, and on the other hand, GO-TCT-Tris keeps steady in acetone after 24 hours
Fixed dispersibility.This shows that GO-TCT-Tris compatibility in organic reagent is improved, this can increase it in polymer substrate
In dispersibility.
Figure 11 is graphene oxide/epoxy resin composite material SEM figure prepared by comparative example one；
Figure 12 is that graphene oxide/epoxy resin of 4. hexa-member heterocycle covalent modification that one step 5 of embodiment is prepared is compound
The SEM of material schemes；
Figure 13 is graphene oxide/epoxy resin composite material TEM figure prepared by comparative example one；
Figure 14 is that graphene oxide/epoxy resin of 4. hexa-member heterocycle covalent modification that one step 5 of embodiment is prepared is compound
The TEM of material schemes；
As can be seen from Figure 11, the aggregation that many GO sheet materials are shown in epoxy resin, is marked with circle；In Figure 13
TEM figure also determines the agglomerate of GO piece in epoxy composite material, it is evident that although the Peeled display of GO goes out good degree,
But GO sheet material is inevitably gathered in epoxy matrix material.In contrast, the dispersion of GO-TCT-Tris becomes more preferably,
In addition, GO-TCT-Tris sheet material seems to seem relative loose state in epoxy matrix material (such as compared with GO sheet material cluster
Shown in Figure 14), this is because the hydroxy-end capped pyrrolotriazine derivatives of grafting reduce the stream of graphene film in the polymer matrix
Dynamic property, to prevent the sheet material of dispersion from attracting each other to be formed and agglomerate again, should the result shows that, even if in the curing process, Tris official
Energyization is also very effective for improving removing and dispersion of the GO sheet material in epoxy substrate.
Claims (10)
1. a kind of preparation method of hexa-member heterocycle covalent modification graphene oxide/epoxy resin composite material, it is characterised in that one
The method of kind hexa-member heterocycle covalent modification graphene oxide is completed by the following steps:
One, the graphene oxide of hexa-member heterocycle covalent modification is added in acetone, re-ultrasonic dispersion obtains mixed liquor；
The quality of the graphene oxide of hexa-member heterocycle covalent modification described in step 1 and the volume ratio of acetone be (0.033g~
0.036g): (10mL~15mL)；
Two, epoxy resin is added into mixed liquor, then in ultrasonic disperse, is finally dried, obtains epoxy resin composition；
The quality of the graphene oxide of epoxy resin described in step 2 and hexa-member heterocycle covalent modification described in step 1
Than for (33~36): (0.033~0.036)；
Three, curing agent is added into epoxy resin composition, is stirred for, is finally dried, obtains the epoxy that curing agent is added
Resin compound；
The mass ratio of epoxy resin described in curing agent described in step 3 and step 2 is (10~11): (33~36)；
Four, the epoxy resin composition of curing agent will be added in the vacuum oven that temperature is 80 DEG C, vacuum degree is -30kPa
It pours into the preheated mold that temperature is 80 DEG C, then is solidified, obtain hexa-member heterocycle covalent modification graphene oxide/epoxy resin
Composite material.
2. a kind of system of hexa-member heterocycle covalent modification graphene oxide/epoxy resin composite material according to claim 1
Preparation Method, it is characterised in that the graphene oxide of hexa-member heterocycle covalent modification described in step 1 is to prepare according to 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 be (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.
3. a kind of system of hexa-member heterocycle covalent modification graphene oxide/epoxy resin composite material according to claim 1
Preparation Method, it is characterised in that the power of ultrasonic disperse described in step 1 is 350W~360W, and the time of ultrasonic disperse is
0.6h~1h.
4. a kind of system of hexa-member heterocycle covalent modification graphene oxide/epoxy resin composite material according to claim 1
Preparation Method, it is characterised in that epoxy resin described in step 2 is E-51.
5. a kind of system of hexa-member heterocycle covalent modification graphene oxide/epoxy resin composite material according to claim 1
Preparation Method, it is characterised in that the power of ultrasonic disperse described in step 2 is 350W~360W, and the time of ultrasonic disperse is
30min~60min.
6. a kind of system of hexa-member heterocycle covalent modification graphene oxide/epoxy resin composite material according to claim 1
Preparation Method, it is characterised in that drying temperature described in step 2 is 80 DEG C, and drying time is 10h~12h.
7. a kind of system of hexa-member heterocycle covalent modification graphene oxide/epoxy resin composite material according to claim 1
Preparation Method, it is characterised in that curing agent described in step 3 is H256.
8. a kind of system of hexa-member heterocycle covalent modification graphene oxide/epoxy resin composite material according to claim 1
Preparation Method, it is characterised in that mixing speed described in step 3 is 3000r/min, and mixing time is 15min~20min.
9. a kind of system of hexa-member heterocycle covalent modification graphene oxide/epoxy resin composite material according to claim 1
Preparation Method, it is characterised in that drying temperature described in step 3 is 80 DEG C~90 DEG C, and drying time is 1h~1.5h.
10. a kind of system of hexa-member heterocycle covalent modification graphene oxide/epoxy resin composite material according to claim 1
Preparation Method, it is characterised in that curing process described in step 4 are as follows: be first -30kPa in vacuum degree and temperature is 80 DEG C
Under the conditions of solidify 2h, then solidify 2h under conditions of vacuum degree is -30kPa and temperature is 100 DEG C, finally vacuum degree be -
30kPa and temperature solidify 4h under conditions of being 150 DEG C.
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| CN115851199A (en) * | 2022-11-18 | 2023-03-28 | 深圳市图特美高分子材料有限公司 | Preparation method of novel flame retardant modified epoxy resin adhesive film |
| CN116832785A (en) * | 2023-05-24 | 2023-10-03 | 安庆市长三角未来产业研究院 | Graphene aerogel-ammonia modified ultrahigh crosslinked adsorption resin composite adsorption material, and preparation and application thereof |
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| CN116832785A (en) * | 2023-05-24 | 2023-10-03 | 安庆市长三角未来产业研究院 | Graphene aerogel-ammonia modified ultrahigh crosslinked adsorption resin composite adsorption material, and preparation and application thereof |
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