CN108864485A - A kind of preparation method of the large volume segment modified graphene oxide of polymolecularity - Google Patents
A kind of preparation method of the large volume segment modified graphene oxide of polymolecularity Download PDFInfo
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Abstract
The present invention discloses a kind of preparation method of the large volume segment modified graphene oxide of polymolecularity, silanization grafting is carried out to the phenodiazine bisphenol fluorene surface containing heat-resisting condensed hetero ring structure first, then silanization phenodiazine bisphenol fluorene and graphene oxide is compound, large volume segment modified graphene oxide is prepared, effect observation after being stood 20 days by graphene oxide dispersion, modified graphene oxide still have preferable dispersion effect in organic solvent；Scanning electron microscope shows that modified graphene oxide and organic siliconresin compatibility are good；When being adulterated with organic siliconresin, heat resistance large volume segment in modified graphene oxide can steric effect and buffer action inside reinforced resin, the movement velocity of segment when slowing down organic siliconresin thermal degradation reduces the decomposition rate of organic siliconresin；The hydroxyl of simultaneous oxidation graphene surface can be condensed with organic siliconresin, can high crosslink material degree, effective reinforcing material heat resistance.
Description
Technical field
The present invention relates to chemical material technical field, the large volume segment of specifically a kind of polymolecularity is modified oxidized
The preparation method of graphene.
Background technique
With being constantly progressive for society, scientific rapid development, the materials demand amount that heat resistance is high, thermal stability is good is continuous
Increase, and organic siliconresin has both the characteristic of inorganic material and organic material, can realize and be widely applied in many fields.However it is more
Number organic siliconresin is to lack certain toughness after solidification using silicon oxygen bond as primary structure, add into organic siliconresin
Nanoparticle and micro particles are condensed using the silicone hydroxyl key in the hydroxyl and organic siliconresin in particle, and resin friendship can be improved
Connection degree improves material mechanical performance and thermal stability；It can be inside reinforced resin in addition, introducing the high large volume segment of heat resistance
Steric effect and buffer action, the movement velocity of segment when slowing down organic siliconresin thermal degradation, to reduce organic siliconresin
Decomposition rate；
Graphene is as the outstanding carbon material of a new generation, with unique lamellar structure, be scattered in material can delay material by
Thermogenetic deformation and flowing, and high thermal conductivity coefficient characteristic can ensure heat rapid dispersion in entire piece in the layer of graphene
Layer.Meanwhile the interlayer poor thermal conductivity of graphene, longitudinal transmitting of heat can be delayed, make material surfaces externally and internally that there is biggish temperature
Gradient is spent, helps to protect temperature sensitive device.Graphene oxide is while retaining above-mentioned advantage, the hydroxyl on surface and side
The carboxyl of edge can be reacted with organic siliconresin, so that graphene oxide is combined with silicone resin, further increase resin
Heat resistance.However, the graphene oxide hydrophily without modification is strong, lipophilic poor, it is easy to reunite in organic siliconresin,
It is difficult to preferably disperse, the application of this oxidizing graphene brings certain obstacle.
Summary of the invention
To solve the above problems, the present invention provides a kind of preparation of the large volume segment modified graphene oxide of polymolecularity
Method, when modified graphene oxide is doped into organic siliconresin, the hydroxyl of modified surface of graphene oxide can be with
Organic siliconresin condensation improves crosslink material degree, effective reinforcing material mechanical property and heat resistance, and surface of graphene oxide
After organic decoration, its dispersibility in resin can be improved；The large volume segment introduced simultaneously can be inside reinforced resin
Steric effect and buffer action, the movement velocity of segment when slowing down organic siliconresin thermal degradation, to reduce organic siliconresin
Decomposition rate.
The present invention is achieved through the following technical solutions：
A kind of preparation method of the large volume segment modified graphene oxide of polymolecularity, includes the following steps：
Step 1: by 0.5 ~ 1.0g graphene oxide be added the organic high boiling solvent of 100 ~ 150 mL in, stirring to be uniformly mixed,
Obtain mixed solution A；
Surface of graphene oxide is handled Step 2: dehydrating agent is added dropwise into mixed solution A, reacts 4 at 60~100 DEG C
After~6h, mixed solution B is obtained；
Step 3: 0.1 ~ 0.2g silanization phenodiazine bisphenol fluorene is added into mixed solution B, temperature is slowly increased to 120~140
DEG C, after reacting 4~6h, cooling, centrifugation obtains black solid；
Step 4: black solid is washed repeatedly repeatedly with washing lotion, it is dried to obtain modified graphene oxide.
Further, organic high boiling solvent described in step 1 is n,N-Dimethylformamide, N, N- dimethylacetamide
One or more of amine, N-Methyl pyrrolidone, dimethyl sulfoxide.
Further, dehydrating agent described in step 2 is the concentrated sulfuric acid.
Further, the synthesis step of the bisphenol fluorene of silanization phenodiazine described in step 3 is as follows：
A, under magnetic stirring, alkaline aqueous solution is slowly added into the container for filling 0.1 ~ 0.15mol phenodiazine bisphenol fluorene,
It is stirred at 50~60 DEG C to being completely dissolved, obtains mixed solution C；
B, it is slowly added to 0.05 ~ 0.075 mol dichlorosilane into mixed solution C, is added dropwise in 10 ~ 20min, is added dropwise
The reaction was continued after the completion 5~8 h, thin-layer chromatography detection reaction process obtain reaction solution after completion of the reaction；
C, acid solution is added into reaction solution and is adjusted to pH=7~8, there is solid precipitation, the solid of precipitation is filtered, it is anti-with washing lotion
After backwashing is washed repeatedly, and silanization phenodiazine bisphenol fluorene is dried to obtain.
Further, alkaline aqueous solution described in step a is potassium hydroxide aqueous solution, sodium hydrate aqueous solution, bicarbonate
One or more of sodium water solution.
Further, dichlorosilane described in step b be one of dimethyldichlorosilane, diphenyl dichlorosilane or
It is several.
Further, acid solution described in step c is one or more of dilute sulfuric acid, dilute hydrochloric acid, glacial acetic acid.
Further, the washing lotion is one or more of deionized water, methanol, ethyl alcohol.
The beneficial effects of the present invention are：
The present invention contains heat resistance condensed hetero ring structure and special substantially product space structure using it by introducing phenodiazine bisphenol fluorene
Type structure, and it is modified to carry out Silane Grafted to it, it is finally compound with graphene oxide, improve graphene oxide hydrophily it is strong but
Lipophilicity is poor and is easy the shortcomings that reuniting, it is efficient in organic resin to realize graphene oxide in organic siliconresin
Dispersion, obtains a kind of large volume segment modified graphene oxide of polymolecularity, this process employs large volume segment and micro-nanos
Rice corpuscles can enhance the characteristic of organic siliconresin hot property, while can be effectively improved the heat resistance of organic siliconresin.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of modified graphene oxide；
Fig. 2 is synthetic route of the invention；
Fig. 3 be silylation phenodiazine bisphenol fluorene structure chart and1H-NMR spectrum；
Fig. 4 is modified graphene oxide/organic siliconresin composite material scanning electron microscope (SEM) photograph；
Fig. 5 is modified graphene oxide/organic siliconresin composite material and pure organic siliconresin thermal weight loss comparison diagram.
Specific embodiment
Below in conjunction with attached drawing of the invention, technical scheme in the embodiment of the invention is clearly and completely described.
Embodiment 1：
（1）The synthesis step of synthesizing methyl silanization phenodiazine bisphenol fluorene first, silylation phenodiazine bisphenol fluorene is：
A, into the three-necked flask of 250mL be added 0.1mol phenodiazine bisphenol fluorene, under magnetic stirring, be slowly added dropwise containing
The aqueous solution of 0.2molNaOH is heated to 50 DEG C of stirrings and is completely dissolved to phenodiazine bisphenol fluorene, obtains mixed solution C；
B, it is slowly added to 0.05mol dimethyldichlorosilane into mixed solution C, is added dropwise in 10min, after being added dropwise to complete
The reaction was continued 6h, thin-layer chromatography detection reaction process obtain reaction solution after completion of the reaction；
C, dilute sulfuric acid is added into reaction solution and is adjusted to pH=7, there is faint yellow solid precipitation, the solid of precipitation is filtered, with water and second
Alcohol washs repeatedly repeatedly, obtains solid methyl silanization phenodiazine bisphenol fluorene after dry 10h.
（2）The preparation method of synthesis modification graphene oxide, includes the following steps：
Step 1: to 100mL DMAc is contained（DMAC N,N' dimethyl acetamide）250mL three-necked flask in be added 0.5g aoxidize stone
Black alkene, stirring to graphene oxide are uniformly mixed, and obtain mixed solution A；
Surface of graphene oxide is handled as dehydrating agent Step 2: the 3 drop concentrated sulfuric acids are added dropwise into mixed solution A, 80
After reacting 6h at DEG C, mixed solution B is obtained；
Step 3: 0.1g silylation phenodiazine bisphenol fluorene is added into mixed solution B, temperature is slowly increased to 120 DEG C, is reacted
After 4h, cooling, centrifugation obtains black solid；
Repeatedly no longer contain organic matter into the solution filtered Step 4: black solid water and ethyl alcohol are washed repeatedly, it is dry
Modified graphene oxide is obtained after 10h.
Embodiment 2：
（1）The synthesis step of synthesizing methyl silanization phenodiazine bisphenol fluorene first, silylation phenodiazine bisphenol fluorene is：
A, into the three-necked flask of 250mL be added 0.15mol phenodiazine bisphenol fluorene, under magnetic stirring, be slowly added dropwise containing
The aqueous solution of 0.3molKOH is heated to 60 DEG C of stirrings and is completely dissolved to phenodiazine bisphenol fluorene, obtains mixed solution C；
B, it is slowly added to 0.075mol dimethyldichlorosilane into mixed solution C, is added dropwise in 20min, is added dropwise to complete
The reaction was continued afterwards 6h, thin-layer chromatography detection reaction process obtain reaction solution after completion of the reaction；
C, dilute sulfuric acid is added into reaction solution and is adjusted to pH=8, there is faint yellow solid precipitation, the solid of precipitation is filtered, with water and second
Alcohol washs repeatedly repeatedly, obtains solid methyl silanization phenodiazine bisphenol fluorene after dry 10h.
（2）The preparation method of synthesis modification graphene oxide, includes the following steps：
Step 1: to 150mL DMF is contained（N,N-dimethylformamide）250mL three-necked flask in be added 1.0g graphite oxide
Alkene, stirring to graphene oxide are uniformly mixed, and obtain mixed solution A；
Surface of graphene oxide is handled as dehydrating agent Step 2: the 5 drop concentrated sulfuric acids are added dropwise into mixed solution A, 80
After reacting 6h at DEG C, mixed solution B is obtained；
Step 3: 0.2g silylation phenodiazine bisphenol fluorene is added into mixed solution B, temperature is slowly increased to 140 DEG C, herein
At a temperature of react 4h after, cooling, centrifugation obtains black solid；
Repeatedly no longer contain organic matter into the solution filtered Step 4: black solid water and ethyl alcohol are washed repeatedly, it is dry
Modified graphene oxide is obtained after 10h.
Embodiment 3：
（1）The synthesis step of synthesis of phenyl silanization phenodiazine bisphenol fluorene first, phenyl silane phenodiazine bisphenol fluorene is：
A, into the three-necked flask of 250mL be added 0.1mol phenodiazine bisphenol fluorene, under magnetic stirring, be slowly added dropwise containing
The aqueous solution of 0.2molKOH is heated to 50 DEG C of stirrings and is completely dissolved to phenodiazine bisphenol fluorene, obtains mixed solution C；
B, it is slowly added to 0.05mol diphenyl dichlorosilane into mixed solution C, is added dropwise in 15min, after being added dropwise to complete
The reaction was continued 5h, thin-layer chromatography detection reaction process obtain reaction solution after completion of the reaction；
C, dilute sulfuric acid is added into reaction solution and is adjusted to pH=8, there is yellow solid precipitation, the solid of precipitation is filtered, with water and ethyl alcohol
Washing repeatedly, obtains solid phenyl silane phenodiazine bisphenol fluorene after dry 10h repeatedly.
（2）The preparation method of synthesis modification graphene oxide, includes the following steps：
Step 1: to 100mL NMP is contained（N-Methyl pyrrolidone）250mL three-necked flask in be added 0.5g graphite oxide
Alkene, stirring to graphene oxide are uniformly mixed, and obtain mixed solution A；
Surface of graphene oxide is handled as dehydrating agent Step 2: the 5 drop concentrated sulfuric acids are added dropwise into mixed solution A, 100
After reacting 4h at DEG C, mixed solution B is obtained；
Step 3: into mixed solution B be added 0.15g phenyl silane phenodiazine bisphenol fluorene, slowly increase temperature to 130 DEG C,
After reacting 6h at a temperature of this, cooling, centrifugation obtains black solid；
Repeatedly no longer contain organic matter into the solution filtered Step 4: black solid water and ethyl alcohol are washed repeatedly, it is dry
Modified graphene oxide is obtained after 10h.
Test result：
（1）The silylation phenodiazine bisphenol fluorene of acquisition is carried out1H-NMR characterization, as shown in figure 3, certification structure is methyl silicon
Alkanisation phenodiazine bisphenol fluorene, compound structure is correct, and purity is higher；
（2）It disperses modified graphene oxide obtained in organic solvent, modified graphene oxide is still able to maintain surely after 20 days
Fixed dispersion shows that surface of graphene oxide modification enhances graphene oxide interlayer active force, effectively reduces graphene oxide
The generation of agglomeration；
（3）Modified graphene oxide and organic siliconresin are adulterated, as Fig. 4 scanning electron microscope shows that graphene oxide can in resin
High efficiency dispersion is realized, without obvious agglomeration, it was demonstrated that improve the phase with organic siliconresin after graphene oxide is surface-modified
Capacitive；
（4）By after the doping of modified graphene oxide and organic siliconresin modified graphene oxide/organic silicon composite with it is pure
Organic siliconresin thermal weight loss effect compares, as shown in figure 5, modified graphene oxide/organic silicon composite is after 800 DEG C
The residual mass of material is initial 49%, and the residual mass of material is initial 32% after 800 DEG C of pure organic siliconresin, explanation
After adulterating large volume segment modified graphene oxide in organic siliconresin, the heat resistance of material is improved significantly, hence it is evident that
Better than pure organic siliconresin.
The basic principles, main features and advantages of the invention have been shown and described above, and the technical staff of the industry should
Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention
Reason, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes and improvements
It all fall within the protetion scope of the claimed invention, the claimed scope of the invention is by appended claims and its equivalent circle
It is fixed.
Claims (8)
1. a kind of preparation method of the large volume segment modified graphene oxide of polymolecularity, it is characterised in that：Including following step
Suddenly：
Step 1: by 0.5 ~ 1.0g graphene oxide be added the organic high boiling solvent of 100 ~ 150 mL in, stirring to be uniformly mixed,
Obtain mixed solution A；
Surface of graphene oxide is handled Step 2: dehydrating agent is added dropwise into mixed solution A, reacts 4 at 60~100 DEG C
After~6h, mixed solution B is obtained；
Step 3: 0.1 ~ 0.2g silanization phenodiazine bisphenol fluorene is added into mixed solution B, temperature is slowly increased to 120~140
DEG C, after reacting 4~6h, cooling, centrifugation obtains black solid；
Step 4: black solid is washed repeatedly repeatedly with washing lotion, it is dried to obtain modified graphene oxide.
2. a kind of preparation method of the large volume segment modified graphene oxide of polymolecularity according to claim 1,
It is characterized in that：Organic high boiling solvent described in step 1 is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N- methyl
One or more of pyrrolidones, dimethyl sulfoxide.
3. a kind of preparation method of the large volume segment modified graphene oxide of polymolecularity according to claim 1,
It is characterized in that：Dehydrating agent described in step 2 is the concentrated sulfuric acid.
4. a kind of preparation method of the large volume segment modified graphene oxide of polymolecularity according to claim 1,
It is characterized in that：The synthesis step of the bisphenol fluorene of silanization phenodiazine described in step 3 is as follows：
A, under magnetic stirring, alkaline aqueous solution is slowly added into the container for filling 0.1 ~ 0.15mol phenodiazine bisphenol fluorene,
It is stirred at 50~60 DEG C to being completely dissolved, obtains mixed solution C；
B, it is slowly added to 0.05 ~ 0.075 mol dichlorosilane into mixed solution C, is added dropwise in 10 ~ 20min, is added dropwise
The reaction was continued after the completion 5~8 h, thin-layer chromatography detection reaction process obtain reaction solution after completion of the reaction；
C, acid solution is added into reaction solution and is adjusted to pH=7~8, there is solid precipitation, the solid of precipitation is filtered, it is anti-with washing lotion
After backwashing is washed repeatedly, and silanization phenodiazine bisphenol fluorene is dried to obtain.
5. a kind of preparation method of the large volume segment modified graphene oxide of polymolecularity according to claim 4,
It is characterized in that：Alkaline aqueous solution described in step a is potassium hydroxide aqueous solution, sodium hydrate aqueous solution, sodium bicarbonate aqueous solution
One or more of.
6. a kind of preparation method of the large volume segment modified graphene oxide of polymolecularity according to claim 4,
It is characterized in that：Dichlorosilane described in step b is one or more of dimethyldichlorosilane, diphenyl dichlorosilane.
7. a kind of preparation method of the large volume segment modified graphene oxide of polymolecularity according to claim 4,
It is characterized in that：Acid solution described in step c is one or more of dilute sulfuric acid, dilute hydrochloric acid, glacial acetic acid.
8. a kind of preparation method of the large volume segment modified graphene oxide of polymolecularity according to claim 1 or 4,
It is characterized in that：The washing lotion is one or more of deionized water, methanol, ethyl alcohol.
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