CN105032488B - A kind of manganese schiff bases graphene oxide compound and preparation method thereof - Google Patents
A kind of manganese schiff bases graphene oxide compound and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of manganese schiff bases（Mangansese‑Schiff base）Graphene oxide compound and preparation method thereof.Graphite oxide is added in ethylenediamine and N, N ' Dicyclohexylcarbodiimides and reacted, amidized graphene oxide is obtained；Again by amidized graphene oxide and bigcatkin willow aldehyde reaction, the graphene oxide of surface grafting schiff bases is obtained；In nitrogen protective condition, by the graphene oxide of surface grafting schiff bases and four hydration manganese acetate reactions, then through suction filtration, wash, dry, obtain a kind of manganese schiff bases graphene oxide compound.The active group of the compound institute band assigns its good dispersion in resin, the effect not only solidified with concerted catalysis cyanate, while the heat resistance of resin can also be effectively improved.The preparation method for the manganese schiff bases graphene oxide compound that the present invention is provided has technique simple, easily controllable, the features such as raw material sources are wide.
Description
Technical field
The invention belongs to technical field of inorganic nanometer material, and in particular to a kind of manganese schiff bases-graphene oxide compound
And preparation method thereof.
Background technology
Cyanate（CE）Resin is important high-performance thermosetting resin, with prominent hot property, dielectric properties, in electricity
The fields such as sub-information, insulation electrical have broad application prospects.However, as other types of heat-resisting thermosetting resin,
It is high to there is solidification temperature in CE resins（Generally higher than 220 DEG C）, hardening time length shortcoming, as limiting its engineer applied process
Bottleneck.How curing reaction temperature is reduced, the core content researched and developed as CE resins.
It is to reduce the common methods of resin cure temperature to add catalyst.It is broadly divided into vivaciously for the CE catalyst solidified
Hydrogen compound（Phenols, amine and imidazoles etc.）, organotin（Dibutyl tin laurate etc.）, transition metal salt（Zinc, iron, copper
Deng transition metal ions acetylacetonate etc.）The class of/nonyl phenol mixed catalyst system etc. three.Wherein, transition metal salt/nonyl phenol is mixed
Closing catalyst system and catalyzing has high catalytic activity, and when transition metal ions addition is 0.11mmol/mol, CE curing reactions are put
Peak temperature about reduces by 100 DEG C, and catalytic effect increases with the increase of catalyst content in system.Such catalyst system and catalyzing it is anti-
Mechanism is answered as shown in figure 1, it is in the presence of active hydrogen co-catalyst, formation metal-pi bond intermediate, intermediate is catalyzed CE
Solidification.It is noted that the presence of nonyl phenol is not only co-catalysis in mixed system, and it is to overcome transition metal salt to exist
In CE the problem of poor dispersion, play hydrotropy.But, with CE monomers side reaction can occur for nonylphenol class auxiliary agent, generate amino first
Acid esters, it decomposites CO in solidification hot stage2, bad performance often is produced to CE solidfied materials.Therefore, how to avoid using nonyl
Base phenols auxiliary agent, while dispersiveness of the transition metal ions in CE resins can be improved again into the problem of a worth thinking.
It is a method in investigation of materials to improve dispersiveness by the second component.In recent years, graphite oxide（GO）Had
Some large specific surface areas, unique three-dimensional drape structure and abundant active group, make it as carrier application（Particularly
The excellent carrier of nano-particle）Aspect shows good prospect.At present, the major metal loaded article on GO has metallic nanoparticle
Son, metal oxide and metallic compound etc..Mulhaupt et al. is by ion exchange by Pd2+It is attached to graphene oxide
Surface, then reduces Pd simultaneously with chemical reduction method2+And graphene oxide, it is prepared for nano-particle Pd/ graphene composite materials.
The composite is applied in the heterogeneous catalysis of Suzuki-Miyaura coupling reactions, and its catalytic activity is much higher than the Pd of commercialization
Catalyst（Referring to document：Scheuermann G M, Rumi L, Steurer P. Palladium nanoparticles
on graphite oxide and its functionalized graphene derivatives as highly
active catalysts for the Suzuki− Miyaura coupling reaction. Journal of the
American Chemical S℃iety, 2009, 131(23): 8262-8270）.Document report uses self assembly skill
Art, is prepared for TiO2/ graphene composite material, it is found that the charging and discharging capabilities of the composite are higher than single TiO2, photocatalysis drop
The activity for solving methylenum careuleum is higher than TiO2Nanometer rods（Referring to document：Wang D, Choi D. Self-assembled TiO2–
graphene hybrid nanostructures for enhanced Li-ion insertion. ACS nano, 2009,
3(4): 907-914）.Document report is with coordination method by Co2+Surface of graphene oxide is modified, catalysis cyclohexene oxide is anti-
Should, it is found that GO-Salen-Co, as heterogeneous catalyst, can improve cyclohexene conversion rate, the selectivity of target product and yield
（Referring to document：Jing Sun, Jian Zhang. Co-salen functionalized on graphene as an
efficient heterogeneous catalyst for cyclohexene oxidation. Journal of
Energy, 2013, 22(1): 48-51）.Document report is respectively made using Cu-Salen and Co-Salen by coordinate bond
With GO surfaces are carried on, for styrene catalyzed epoxidation, target conversion is respectively higher than individually with Cu-Salen and Co-
Conversion ratio styrene catalyzed Salen（Referring to document：Zhifang Li, Shujie Wu. Immobilized Cu(II)
and Co(II) salen complexes on graphene oxide and their catalytic activity for
aerobic epoxidation of styrene. New Journal of Chemistry, 2013, 37(5): 1561-
1568）.
It is well known that the structure of catalyst, which must be adapted to plan catalytic reaction, i.e. catalyst, usually shows specificity.On
The metallic catalyst for stating GO loads is not suitable for being catalyzed CE curing reaction.In fact, be composited by GO and transition metal
CE solidifications catalyst is there is not yet report.
The content of the invention
There is provided both a kind of integrated manganese ion and graphene oxide for deficiency of the present invention present in existing CE catalyst
A kind of new catalyst of advantage and preparation method thereof.
To reach above-mentioned purpose, it is multiple that the technical solution adopted in the present invention is to provide a kind of manganese schiff bases-graphene oxide
The preparation method of compound, comprises the following steps：
（1）By mass, 1 part of graphite oxide is dispersed in 500~600 parts of DMFs, obtained
The dispersion liquid A of graphene oxide；45~90 parts of ethylenediamines are added in dispersion liquid A and 3~5 parts of N, N '-dicyclohexyl phosphinylidyne are sub-
Amine, 6~12h is reacted under conditions of temperature is 70~75 DEG C；After reaction terminates, by suction filtration, washing, dry, obtain amino
The graphene oxide of change；
（2）By mass, by 1 part of step（1）The amidized graphene oxide prepared is dispersed in 200~300 parts
In absolute ethyl alcohol, the dispersion liquid B of amidized graphene oxide is obtained；Under nitrogen protective condition, by 91~182 parts of salicylides
It is slowly added into dispersion liquid B, 1~2 part of acetic acid is added dropwise, 12~24h is reacted under the conditions of temperature is 80~85 DEG C；Reaction terminates
Afterwards, through suction filtration, wash, dry, obtain the graphene oxide of surface grafting schiff bases；
（3）By mass, by 1 part of step（2）The graphene oxide of the surface grafting schiff bases of preparation evenly spreads to 200
In~300 parts of absolute ethyl alcohols, uniform dispersion liquid C is obtained；Under nitrogen protection, 0.98~4.9 part of four hydration manganese acetate is added
Enter into dispersion liquid C, 6~12h is reacted under the conditions of temperature is 60~65 DEG C；After reaction terminates, through suction filtration, wash, dry, obtain
To a kind of manganese schiff bases-graphene oxide compound.
A kind of manganese schiff bases-graphene oxide that technical solution of the present invention is also obtained including being prepared as described above method is combined
Thing, the wherein load capacity of manganese schiff bases are 3.8wt%~18.5wt%.
Manganese schiff bases-graphene oxide compound obtained by the present invention is according to ethylenediamine and surface of graphene oxide
The mechanism of epoxy radicals and carboxyl reaction, the technical scheme not only causes reaction to be easy to progress, and required reaction temperature is low, the time is short,
And to remain substantial amounts of hydroxyl in manganese schiff bases-graphene oxide compound, it can play with being helped as nonylphenol class
The effect of catalyst.In addition, as linear diamine, ethylenediamine participates in reacting as reactant, it is ensured that one end and oxidation stone
Black the alkene reaction ,-NH that the other end carries out subsequent reactions with salicylide and generation can be with polyisocyanate reactant in the reaction, these features
Compound is conducive to obtain good dispersion and good interface interaction power in resin.Due to the manganese Schiff prepared by the present invention
Manganese ion and hydroxyl containing substantial amounts of unsaturated coordination in alkali-graphene oxide compound, and both it is present in oxidation stone
Black alkene surface, apart from short.Catalytic process be by be supported on surface of graphene oxide manganese ion first with contain lone pair electrons and to
The cyanate ester monomer formation complex of electronics pi bond, cyanate ester monomer is gathered in and around formed, then on hydroxyl in compound
Active hydrogen co-catalysis, formed metal-pi bond intermediate, intermediate catalysis cyanate solidification occur nucleophilic addition generation triazine
Ring.In addition, the manganese ion in compound exists only in the surface of graphene oxide so that manganese ion can be abundant with cyanate ester resin
Contact, reaches good catalytic effect.Therefore, manganese schiff bases-graphene oxide compound prepared by the present invention is to cyanate
Solidification has concerted catalysis effect.
Based on above-mentioned principle, compared with prior art, the beneficial effects of the invention are as follows：
1st, manganese schiff bases-graphene oxide compound obtained by the present invention is that manganese ion is supported on into oxygen by coordinate bond
Graphite alkene surface, and the abundant active group of surface of graphene oxide makes it have good disperse in cyanate ester resin
Property, so that the problem of solving transition metal ions bad dispersibility in transition metal ion catalyst cyanate system, it is to avoid add
Plus phenols auxiliary agent is the problem of bring side reaction.
2nd, manganese schiff bases-graphene oxide compound prepared by the present invention can improve the heat resistance of resin simultaneously,
Because the graphene oxide layer being dispersed in cyanate ester resin can play trap heat transmission effect.
3rd, the preparation method for new manganese schiff bases-graphene oxide compound that the present invention is provided has reaction temperature temperature
With reaction condition is simple, it is easy to control, the features such as raw material sources are wide.
Brief description of the drawings
Fig. 1 is the reaction mechanism figure of catalyst system and catalyzing in the prior art.
Fig. 2 is the reaction mechanism figure that technical solution of the present invention prepares manganese schiff bases-graphene oxide compound.
Fig. 3 is graphene oxide, amidized graphene oxide, schiff bases-graphene oxide in the embodiment of the present invention 1
And the infrared spectrogram of manganese schiff bases-graphene oxide compound.
Fig. 4 is graphene oxide, schiff bases-graphene oxide and the manganese schiff bases-graphite oxide in the embodiment of the present invention 1
The X-ray diffractogram of alkene compound.
Fig. 5 is graphene oxide, schiff bases-graphene oxide and manganese schiff bases-graphene oxide in the embodiment of the present invention 1
The ultraviolet spectrogram of compound.
Fig. 6 is that the ESEM of graphene oxide and manganese schiff bases-graphene oxide compound in the embodiment of the present invention 1 shines
Piece（Amplify 15,000 times）.
Fig. 7 is the cyanate ester resin prepolymer and manganese schiff bases-graphene oxide that comparative example 1,2,3 and 4 of the present invention is provided
The differential scanning calorimetric of catalyst/cyanate ester resin prepolymer（DSC）Curve.
Fig. 8 is the cyanate ester resin prepolymer and manganese schiff bases-graphite oxide that comparative example 1,3,5,6 and 7 of the present invention is provided
The differential scanning calorimetric of alkene catalyst/cyanate ester resin prepolymer（DSC）Curve.
Fig. 9 be cyanate ester resin and comparative example 3 prepared by comparative example 1 of the present invention prepare manganese schiff bases-graphene oxide/
Cyanate ester resin thermogravimetric（TG）With thermal weight loss speed（DTG）Curve.
Specific embodiment
Technical solution of the present invention will be further described with reference to the accompanying drawings and examples.
Embodiment 1
Referring to accompanying drawing 2, it is the reaction mechanism that technical solution of the present invention prepares manganese schiff bases-graphene oxide compound
Figure.According to Fig. 2, the present embodiment is comprised the following steps that：
（1）The preparation of amidized graphene oxide
1g graphene oxides are added in 500mL N, N'- dimethylformamides, ultrasonic disperse 30min, obtain uniform
Graphene oxide dispersion A；100mL ethylenediamines and 5g N, N'- Dicyclohexylcarbodiimides are added in dispersion liquid A, in temperature
To react 12h at 70 DEG C.After reaction terminates, by suction filtration, respectively with respectively washing three times of water and ethanol, dry, obtain at 60 DEG C
To amidized graphene oxide, its infrared spectrum is referring to accompanying drawing 1.
（2）The preparation of schiff bases-graphene oxide
The amidized graphene oxides of 1g are added in 300mL ethanol, ultrasonic disperse 60min obtains uniform amino
Change the dispersion liquid B of graphene oxide；In nitrogen atmosphere, 156mL salicylides are slowly added in dispersion liquid B, and add 1g second
Acid；12h is reacted in the case where temperature is 80 DEG C.After reaction terminates, by suction filtration, respectively with respectively washing three times of water and ethanol, at 60 DEG C
Lower drying, obtains surface grafting schiff bases（Schiff base）Graphene oxide, its infrared spectrum, X-ray diffraction spectrogram and
Ultraviolet spectrogram is respectively referring to accompanying drawing 2,3 and 4.
（3）The preparation of manganese schiff bases-graphene oxide
By 1g surface grafting schiff bases（Schiff base）Graphene oxide add 300mL ethanol in, ultrasonic disperse
30min, obtains uniform dispersion liquid C；In nitrogen atmosphere, 0.98g tetra- is hydrated manganese acetate and is added in dispersion liquid C, in temperature
Spend to react 12h at 60 DEG C.After reaction terminates, by suction filtration, respectively with respectively washing three times of water and ethanol, dried at 60 DEG C,
A kind of manganese schiff bases-graphene oxide compound is obtained, the load capacity of wherein manganese schiff bases is 3.8wt%.Prepared manganese Schiff
The infrared spectrum of alkali-graphene oxide compound, X-ray diffraction spectrogram, ultraviolet spectrogram, stereoscan photograph are respectively referring to attached
Fig. 2,3,4 and 5.
Referring to accompanying drawing 3, it is graphene oxide, amidized graphene oxide, the schiff bases-oxidation that the present embodiment is provided
The infrared spectrogram of graphene and manganese schiff bases-graphene oxide compound.In the spectrogram of amidized graphene oxide,
1641cm-1The absworption peak at place is 1570 cm caused by C=O vibrations by its surface amido link-1The absworption peak at place is by secondary acyl
Caused by the N-H flexural vibrations and C-N stretching vibrations of amine, illustrate that carboxyl of the ethylenediamine with surface of graphene oxide is condensed
Reaction.Meanwhile, compared with the infrared spectrum of graphene oxide, in the absence of the red of epoxy radicals in amidized graphene oxide spectrogram
Outer absworption peak（1069cm-1）, illustrate that the epoxy radicals of ethylenediamine and surface of graphene oxide also there occurs condensation reaction.The above results
Illustrate, ethylenediamine is successfully grafted to surface of graphene oxide.In the infrared spectrum of schiff bases-graphene oxide,
1639cm-1The absworption peak at place is caused by C=N vibrations in schiff bases, illustrate salicylide with amidized oxidation stone
Black alkene reacts, and generates schiff bases-graphene oxide.It can see from manganese schiff bases-graphene oxide infrared spectrum,
1590cm-1Place occurs in that new absworption peak, 1639cm-1C=N characteristic absorption peaks in place's schiff bases are moved, and this is due to
With manganese ion coordination, which occurs, for C=N in schiff bases causes；1639cm-1C=N characteristic absorption peaks at place are moved, and show manganese
Schiff bases-graphene oxide is successfully prepared.
Referring to accompanying drawing 4, it is graphene oxide, schiff bases-graphene oxide and the manganese schiff bases-oxygen that the present embodiment is provided
The X-ray diffraction spectrogram of graphite alkene compound（XRD）.As seen from the figure, three kinds of materials all only one of which diffraction maximums, illustrate chemistry
Modification does not change its lamellar structure.In the spectrogram of graphene oxide, 10.8oPlace occurs in that GO（001）Crystal face feature diffraction
Peak.As seen from the figure, the diffraction maximum of schiff bases-graphene oxide appears in 10.1oPlace, interlamellar spacing is increased to d=0.87nm, and this is
Because by chemical reaction, schiff bases is intercalation into graphene oxide interlayer so that interlamellar spacing expands, diffraction maximum is moved to small angular direction
It is dynamic.It can be seen that diffraction maximum continues to move to small angular direction in the spectrogram of manganese schiff bases-graphene oxide compound, appear in
9.3oPlace, this is due to the schiff bases generation coordination of manganese ion and graphene oxide interlayer, is intercalation into schiff bases-oxidation stone
The interlayer of black alkene so that interlamellar spacing further expands, further demonstrates manganese schiff bases and is successfully grafted to graphene oxide
Surface.
Referring to accompanying drawing 5, it is graphene oxide, schiff bases-graphene oxide and the manganese schiff bases-oxygen that the present embodiment is provided
The uv atlas of graphite alkene compound.In the spectrogram of schiff bases-graphene oxide, strong absworption peak at 258nm and 326nm
It is due to that the charge transfer transition of schiff bases is triggered, illustrates that schiff bases has been grafted to surface of graphene oxide.In manganese seat
In the spectrogram of husband's alkali-graphene oxide, 436nm and 532nm absworption peak is corresponding be ligand metal charge transfer transition and
D-d transition, further illustrates that manganese schiff bases is successfully grafted to surface of graphene oxide.
Referring to accompanying drawing 6, it is the graphene oxide of the present embodiment offer and putting for manganese schiff bases-graphene oxide compound
Big 15,000 times of stereoscan photograph.It can be seen that, graphene oxide and manganese schiff bases-graphene oxide compound are all maintained
Thin slice Rotating fields, illustrate that chemical modification does not change its thin slice Rotating fields.But manganese schiff bases-graphene oxide composite surface with
Edge occurs in that the phenomenon of rough pleats, and this is due to surface and the reactive group at edge of graphene oxide（Epoxy radicals and carboxylic
Base）Chemical reaction has been involved in, different degrees of defect sturcture is occurred in that.
Result above shows that manganese ion successfully is supported on into surface of graphene oxide, has prepared new manganese seat
Husband's alkali-graphene oxide compound.
Embodiment 2
The preparation of manganese schiff bases-graphene oxide
The step of by embodiment 1（2）Obtained 1g schiff bases-graphene oxide is added in 300mL ethanol, ultrasonic disperse
30min, obtains uniform dispersion liquid；In nitrogen atmosphere, the hydration manganese acetates of 4.9g tetra- are added, are reacted in the case where temperature is 60 DEG C
12h.After reaction terminates, by suction filtration, respectively with respectively washing three times of water and ethanol, dried at 60 DEG C, obtain a kind of manganese Schiff
Alkali-graphene oxide compound, the load capacity of wherein manganese schiff bases is 18.5wt%.
Comparative example 1：
（1）The preparation of cyanate ester resin prepolymer
By double (the 4- cyanogen oxygen phenyl) propane of 60g 2,2'-（Also known as bisphenol A cyanate ester）Stirring and ultrasound point at 90 DEG C
Dissipate 40min；Then 10min is stirred at 140 DEG C, obtains cyanate ester resin prepolymer.Its differential scans calorimetric（DSC）Curve is shown in
Accompanying drawing 7.
（2）The preparation of cyanate solidified resin
By step（1）The cyanate performed polymer of preparation is poured into mould, vacuum defoamation 30min, according to 140 DEG C/1h+
150 DEG C/2h+180 DEG C/2h+200 DEG C/2h and 220 DEG C/4h techniques are solidified and post-processed, that is, obtain ethylene rhodanate resin curing
Thing.Its thermal weight loss（TG）Curve is referring to accompanying drawing 9.
Comparative example 2：
（1）The preparation of manganese schiff bases-graphene oxide/cyanate ester resin prepolymer
0.3g manganese schiff bases-graphene oxide compound and 59.7g bisphenol A cyanate esters prepared by embodiment 2 is added
Into beaker, stirring and ultrasound 40min at 90 DEG C；Then 10min is stirred in pre-polymerization at 140 DEG C, obtains manganese schiff bases-oxidation
The content of graphen catalyst/cyanate ester resin prepolymer, wherein manganese schiff bases-graphene oxide compound is 0.5wt%.Should
Its differential scanning calorimetric of modified cyanic acid ester performed polymer（DSC）Curve is referring to Fig. 7.
Comparative example 3：
（1）The preparation of manganese schiff bases-graphene oxide/cyanate ester resin prepolymer
0.6g manganese schiff bases-graphene oxide compound and 59.3g bisphenol A cyanate esters prepared by embodiment 2 adds
Enter into beaker, stirring and ultrasound 40min at 90 DEG C；Then at 140 DEG C pre-polymerization stir 10min, obtain manganese schiff bases-
Graphene oxide catalyst/cyanate ester resin prepolymer, the wherein content of manganese schiff bases-graphene oxide compound are 1wt%.
Its differential scanning calorimetric of the modified cyanic acid ester performed polymer（DSC）Curve is referring to Fig. 7.
（2）The preparation of manganese schiff bases-graphene oxide/ethylene rhodanate resin curing resin
By step（1）Manganese schiff bases-graphene oxide/cyanate ester resin prepolymer of preparation is poured into grinding tool, at 140 DEG C
De-bubbled 40min under vacuum condition, according to+200 DEG C/2h and 220 DEG C/4h of 140 DEG C/1h+150 DEG C/2h+180 DEG C/2h of technique
Technique is solidified and post-processed, that is, obtains manganese schiff bases-graphene oxide/cyanate ester resin.Its thermal weight loss（TG）Curve is joined
See accompanying drawing 9.
Comparative example 4：The preparation of manganese schiff bases-graphene oxide/cyanate ester resin prepolymer
1.2g manganese schiff bases-graphene oxide compound and 58.8g bisphenol A cyanate esters prepared by embodiment 2 adds
Enter into beaker, stirring and ultrasound 40min at 90 DEG C；Then 10min is stirred in pre-polymerization at 140 DEG C, obtains manganese schiff bases-oxygen
Graphite alkene catalyst/cyanate ester resin prepolymer, the wherein content of manganese schiff bases-graphene oxide compound are 2wt%.Should
Its differential scanning calorimetric of modified cyanic acid ester performed polymer（DSC）Curve is referring to Fig. 7.
Comparative example 5：The preparation of graphene oxide/cyanate ester resin prepolymer
0.4887g graphene oxides and 59.5g bisphenol A cyanate esters are added in beaker, stirs and surpasses at 90 DEG C
Sound 40min；Then 10min is stirred in pre-polymerization at 140 DEG C, obtains uniform mixture, as 0.8145wt% graphene oxides/
Cyanate ester resin prepolymer, the scanning calorimetric of its differential（DSC）Curve is referring to Fig. 8.
Comparative example 6：The preparation of manganese acetate/cyanate ester resin prepolymer
0.2373g manganese acetates and 59.8g bisphenol A cyanate esters are added in beaker, stirring and ultrasound at 90 DEG C
40min；Then 10min is stirred in pre-polymerization at 140 DEG C, obtains uniform mixture, as manganese acetate/cyanate ester resin pre-polymerization
The content of body, wherein manganese ion is 0.08865wt%.The differential scanning calorimetric of manganese acetate/cyanate ester resin prepolymer（DSC）It is bent
Line is referring to Fig. 8.
Comparative example 7：The preparation of graphene oxide/manganese acetate/cyanate ester resin prepolymer
0.2373g manganese acetates, 0.4887g graphene oxides and 59.4g bisphenol A cyanate esters are added in beaker,
Stirring and ultrasound 40min at 90 DEG C；Then 10min is stirred in pre-polymerization at 140 DEG C, is obtained uniform mixture, is as aoxidized
Graphene/manganese acetate/cyanate ester resin prepolymer, wherein graphene oxide content are 0.8145wt%, and manganese ion content is
0.08865wt%.Graphene oxide/the manganese acetate/cyanate ester resin prepolymer differential scanning calorimetric（DSC）Curve is referring to accompanying drawing
8。
Referring to accompanying drawing 7, it is the differential scanning calorimetric of each performed polymer prepared by comparative example 1,2,3 and 4 of the present invention（DSC）
Curve.It can be seen that, compared with cyanate performed polymer prepared by comparative example 1, modified cyanic acid ester resin prepared by comparative example 2~4
The overall substantially reduction, and summit temperature is with manganese schiff bases-graphene oxide complex content in the exothermic heat of reaction peak of performed polymer
Increase and reduce.With comparative example 1 prepare cyanate performed polymer exothermic heat of reaction peak summit temperature compared with, when manganese schiff bases-
Graphene oxide complex content be 1wt% when, the summit temperature at exothermic heat of reaction peak reduces about 135 DEG C, show manganese schiff bases-
Graphene oxide compound has significant catalytic action to the curing reaction of cyanate.
Referring to accompanying drawing 8, it is the differential scanning calorimetric of performed polymer prepared by comparative example 1,3,5,6,7 of the present invention（DSC）It is bent
Line.Compared with performed polymer prepared by comparative example 1,5,6,7, the solidification of modified cyanic acid ester resin performed polymer prepared by comparative example 3 is anti-
Answer exothermic peak to be unimodal and peak temperature is relatively low, show that manganese schiff bases-graphene oxide compound is anti-to ethylene rhodanate resin curing
The catalytic action answered is most strong, and be not the simple of graphene oxide and manganese acetate plus and, with significantly acting synergistically.
Referring to accompanying drawing 9, it is modification prepared by cyanate solidified resin and comparative example 3 prepared by comparative example 1 of the present invention
The thermogravimetric curve of cyanate solidified resin, the characteristic parameter of gained is listed in Table 1 below.Initial decomposition temperature（Tdi, weightless 5wt%'s
Temperature）It is considered as often the index for weighing resin heat endurance, from Fig. 8 and table 1 as can be seen that solidification prepared by comparative example 1 and 3
Resin Tdi is respectively 435.0 DEG C and 449.7 DEG C, shows that manganese schiff bases-graphene oxide/cyanate ester resin has than cyanate
The higher heat endurance of resin.In addition, modified resin prepared by comparative example 3 also has corresponding to higher maximum heat weight loss rate
Temperature（Tmax）With the carbon yield at 800 DEG C（Yc）, it was demonstrated that the presence of manganese schiff bases-graphene oxide compound can show
Write the heat endurance for improving cyanate.
Table 1：The Thermal Decomposition Characteristics parameter of solidified resin prepared by comparative example 1 and 3
| Solidified resin | Tdi (℃) | Tmax (℃) | Yc at 800℃（wt%) |
| Comparative example 1 | 435.0 | 452.8 | 36.7 |
| Comparative example 3 | 449.7 | 461.3 | 40.2 |
Embodiment 3
The preparation of manganese schiff bases-graphene oxide compound
By the step of embodiment 1（2）Obtained 1g schiff bases-graphene oxide is added in 300mL ethanol, ultrasonic disperse
30min, obtains uniform dispersion liquid, in nitrogen atmosphere, adds the hydration manganese acetates of 1.96g tetra-, is reacted in the case where temperature is 60 DEG C
12h.After reaction terminates, by suction filtration, respectively with respectively washing three times of water and ethanol, dried at 60 DEG C, obtain manganese schiff bases-oxygen
Graphite alkene compound.
Embodiment 4
The preparation of manganese schiff bases-graphene oxide compound
By the step of embodiment 1（2）Obtained 1g schiff bases-graphene oxide is added in 300mL ethanol, ultrasonic disperse
30min, obtains uniform dispersion liquid；In nitrogen atmosphere, the hydration manganese acetates of 2.94g tetra- are added, are reacted in the case where temperature is 60 DEG C
12h.After reaction terminates, by suction filtration, respectively with respectively washing three times of water and ethanol, dried at 55 DEG C, obtain manganese schiff bases-oxygen
Graphite alkene compound.
Embodiment 5
The preparation of manganese schiff bases-graphene oxide compound
By the step of embodiment 1（2）Obtained 1g schiff bases-graphene oxide is added in 300mL ethanol, ultrasonic disperse
30min, obtains uniform dispersion liquid;In nitrogen atmosphere, the hydration manganese acetates of 3.92g tetra- are added, are reacted in the case where temperature is 60 DEG C
12h.After reaction terminates, by suction filtration, respectively with respectively washing three times of water and ethanol, dried at 65 DEG C, obtain manganese schiff bases-oxygen
Graphite alkene compound.
Embodiment 6
（1）The preparation of amidized graphene oxide
1g graphene oxides are added in 600mL N, N'- dimethylformamides, 40min is thoroughly mixed, obtains oxygen
The dispersion liquid A of graphite alkene；50mL ethylenediamines and 3g N, N'- Dicyclohexylcarbodiimides are added in dispersion liquid A, in temperature
To react 6h at 75 DEG C；After reaction terminates, by suction filtration, respectively with respectively washing three times of water and ethanol, dry, obtain at 70 DEG C
Amidized graphene oxide.
（2）The preparation of schiff bases-graphene oxide
The amidized graphene oxides of 1g are added in 200mL ethanol, 50min is sufficiently mixed, amidized oxygen is obtained
The dispersion liquid B of graphite alkene；In nitrogen atmosphere, 78mL salicylides are slowly added in dispersion liquid B, and add 2g acetic acid；
Temperature be 85 DEG C at react 24h；After reaction terminates, by suction filtration, respectively with respectively washing three times of water and ethanol, done at 70 DEG C
It is dry, obtain surface grafting schiff bases（Schiff base）Graphene oxide.
（3）The preparation of manganese schiff bases-graphene oxide
By 1g surface grafting schiff bases（Schiff base）Graphene oxide add 200mL ethanol in, ultrasonic disperse
30min, obtains uniform dispersion liquid C；In nitrogen atmosphere, 0.98 g tetra- is hydrated manganese acetate and is added in dispersion liquid C, in temperature
Spend to react 6h at 65 DEG C；After reaction terminates, by suction filtration, respectively with respectively washing three times of water and ethanol, dry, obtain at 70 DEG C
To a kind of manganese schiff bases-graphene oxide compound.
Embodiment 7
（1）The preparation of amidized graphene oxide
1g graphene oxides are added in 560mL N, N'- dimethylformamides, 45min is thoroughly mixed, obtains oxygen
The dispersion liquid A of graphite alkene；70mL ethylenediamines and 4g N, N'- Dicyclohexylcarbodiimides are added in dispersion liquid A, in temperature
To react 10h at 72 DEG C；After reaction terminates, by suction filtration, respectively with respectively washing three times of water and ethanol, dry, obtain at 62 DEG C
To amidized graphene oxide.
（2）The preparation of schiff bases-graphene oxide
The amidized graphene oxides of 1g are added in 260mL ethanol, ultrasonic disperse 70min obtains amidized oxygen
The dispersion liquid B of graphite alkene；In nitrogen atmosphere, 100mL salicylides are slowly added in dispersion liquid B, and add 1.4g acetic acid；
20h is reacted in the case where temperature is 82 DEG C；After reaction terminates, by suction filtration, respectively with respectively washing three times of water and ethanol, done at 65 DEG C
It is dry, obtain surface grafting schiff bases（Schiff base）Graphene oxide.
（3）The preparation of manganese schiff bases-graphene oxide
By 1g surface grafting schiff bases（Schiff base）Graphene oxide add 240mL ethanol in, ultrasonic disperse
50min, obtains uniform dispersion liquid C；In nitrogen atmosphere, 2.5g tetra- is hydrated manganese acetate and is added in dispersion liquid C, in temperature
To react 10h at 62 DEG C；After reaction terminates, by suction filtration, respectively with respectively washing three times of water and ethanol, dry, obtain at 60 DEG C
To a kind of manganese schiff bases-graphene oxide compound.
Claims (2)
1. a kind of preparation method of manganese schiff bases-graphene oxide compound, it is characterised in that comprise the following steps：
（1）By mass, 1 part of graphite oxide is dispersed in 500~600 parts of DMFs, aoxidized
The dispersion liquid A of graphene；45~90 parts of ethylenediamines and 3~5 parts of N, N '-Dicyclohexylcarbodiimide are added in dispersion liquid A,
Temperature is 6~12h of reaction under conditions of 70~75 DEG C；After reaction terminates, by suction filtration, washing, dry, obtain amidized oxygen
Graphite alkene；
（2）By mass, by 1 part of step（1）Prepare amidized graphene oxide be dispersed in 200~300 parts it is anhydrous
In ethanol, the dispersion liquid B of amidized graphene oxide is obtained；It is under nitrogen protective condition, 91~182 parts of salicylides are slow
It is added in dispersion liquid B, 1~2 part of acetic acid is added dropwise, 12~24h is reacted under the conditions of temperature is 80~85 DEG C；After reaction terminates,
Through suction filtration, wash, dry, obtain the graphene oxide of surface grafting schiff bases；
（3）By mass, by 1 part of step（2）The graphene oxide of the surface grafting schiff bases of preparation evenly spreads to 200~
In 300 parts of absolute ethyl alcohols, uniform dispersion liquid C is obtained；Under nitrogen protection, 0.98~4.9 part of four hydration manganese acetate is added
Into dispersion liquid C, 6~12h is reacted under the conditions of temperature is 60~65 DEG C；After reaction terminates, through suction filtration, wash, dry, obtain
A kind of manganese schiff bases-graphene oxide compound.
2. a kind of manganese schiff bases that a kind of preparation method as described in claim 1 is obtained-graphene oxide compound, wherein manganese
The load capacity of schiff bases is 3.8wt%~18.5wt%.
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