CN109134824A - One kind containing graphene/nanometer TiO2Epoxy resin of composite material and preparation method thereof - Google Patents
One kind containing graphene/nanometer TiO2Epoxy resin of composite material and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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Abstract
The present invention relates to one kind to contain graphene/nanometer TiO2The epoxy resin of composite material, the graphene/nanometer TiO2Mass percentage of the composite material in the epoxy resin is 0.02%~1%.The invention further relates to the preparation methods of the epoxy resin.The present invention carries out splitting to graphene using the organic deposition method of independent research, obtains TiO2Then/graphene composite material combines the material with the preparation process of epoxy resin, a step is prepared in situ out ultra-dispersed, high performance containing graphene/nanometer TiO2The epoxy resin of composite material.This method is at low cost, simple production process, equipment requirement are low, can be produced in batches.
Description
Technical field
The present invention relates to technical field of composite materials, and in particular to one kind contains graphene/nanometer TiO2Composite material
The preparation method of epoxy resin and the epoxy resin.
Background technique
Bisphenol A type epoxy resin has preferable craftsmanship, can be used cooperatively with various curing agent and additive, Ke Yishe
Multiple formulations are counted to meet various requirement, there is the features such as low pressure molding, the performance of cured product is stablized.And because its is at low cost,
Yield obtains greatly the favor of user.But bisphenol A type epoxy resin has weak drawing force, poor impact resistance, poor toughness simultaneously, resistance to
The disadvantages of hot difference, keeps its application scenarios limited, and people only promote its machine by being modified to bisphenol A type epoxy resin
Tool performance.
The appearance of nanoparticle provides new thinking for the modification of bisphenol A type epoxy resin.This is because nanoparticle
With special natures such as skin effect, small-size effect, quantum effects, such as using nano material as added material, coating can be made
Mechanical property and corrosion resistance be all largely increased.However, interface characteristics due to inorganic nano-particle and epoxy resin
Matter is different, poor compatibility, and rigid particles surface can be in thermodynamics unsteady state, easily assemble it is agglomerating, therefore with epoxy
Easily cause that binding force is poor, the problems such as can be easily separated when resin-bonded.In addition to this, nano material itself due to preparation process it is multiple
It is miscellaneous, expensive, can not also constrain the popularization and application of nanometer modified epoxy resin the problems such as volume production.
Graphene is because having high specific surface area, heating conduction outstanding and mechanical property and its outstanding electron transmission
A series of excellent properties such as energy, cause the great interest of researcher.If mixed graphene as lubricating type material
After epoxy resin, the coefficient of friction of epoxy resin can be reduced, effectively improves its intensity, toughness, wearability and corrosion resistance.So
And since the effect of interlayer Van der Waals force causes graphene to be easy to reunite or even stack, thus lose extra specific surface area and two
Tie up advantage possessed by structure.Therefore it is used as a kind of packing material, the removing situation of graphene itself is to determine material property
Key factor.In the polymerization process of epoxy resin, the reunion situation of graphene is also the main reason for influencing its performance.Cause
This, graphene modified epoxy of good performance in order to obtain, it is desirable to provide a kind of graphene of good dispersion, to guarantee stone
Strong interface interaction occurs between black alkene and epoxy molecule.
In consideration of it, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is that providing one kind contains graphene/nanometer TiO2The epoxy resin of composite material.
The second object of the present invention is to provide the preparation method of the epoxy resin.
To achieve the above object, technical scheme is as follows:
The present invention relates to one kind to contain graphene/nanometer TiO2The epoxy resin of composite material, the graphene/nanometer
TiO2Mass percentage of the composite material in the epoxy resin is 0.02%~1%.
Contain graphene/nanometer TiO the invention further relates to described2The preparation method of the epoxy resin of composite material, it is described
Method the following steps are included:
(1) by graphene/nanometer TiO2Composite material is dispersed with stirring in epoxychloropropane, adds bisphenol-A, and stirring is filled
Heating water bath is to 75~80 DEG C after point；
(2) sodium hydroxide solution is added in the reaction system obtained to step (1), stops adding after reaction 1.5~2 hours
Heat；
(3) benzene is added in the reaction system obtained to step (2), stirs 20~30 minutes, carries out organic layer after standing
Distillation removes benzene and unreacted epoxychloropropane, obtains described containing graphene/nanometer TiO2The asphalt mixtures modified by epoxy resin of composite material
Rouge.
Preferably, in step (1), the graphene/nanometer TiO2The quality of composite material, bisphenol-A and epoxychloropropane
Than for (0.01~0.5): (20~30): (20~40).
Preferably, in step (1) and (2), by graphene/nanometer TiO2Composite material is dispersed with stirring in epoxychloropropane
In, it adds bisphenol-A, when heating water bath is to 70 DEG C after stirring sufficiently, controls temperature-resistant, concentration, which is added, into reaction system is
20% sodium hydroxide solution then heats to 75~80 DEG C, stops heating after the reaction was continued 1.5~2 hours.
Preferably, in step (3), by organic layer, first benzene is removed in distillation under 75 DEG C of normal pressures after standing, then carries out decompression steaming
It evaporates, removes all volatile matters.
Preferably, the graphene/nanometer TiO2Composite material is prepared by the following method to obtain:
[1] graphite powder is mixed with sodium nitrate, obtains mixture；
[2] in ice-water bath, the mixture that step [1] obtains is added into the concentrated sulfuric acid, permanganic acid is added after being stirred
Potassium；
[3] reaction system that step [2] obtains is removed from ice-water bath, and is warming up to 35 DEG C, keep the temperature 30~50min；
[4] hydrogen peroxide solution is added in the reaction system obtained to step [3], and reaction is filtered after 2 hours, precipitating is washed
Wash, dry after obtain graphene oxide；
[5] graphene oxide is added in the mixed solution of ethyl alcohol and water, TiO is then added2Presoma and boron
Sodium hydride solution, ultrasonic reaction 12~filtered afterwards for 24 hours will obtain the composite material after washing of precipitate, drying.
Preferably, in step [1] and step [2], graphite powder, sodium nitrate, the concentrated sulfuric acid, potassium permanganate additional proportion be (1
~2g): (1~2g): (20~25ml): (2~3g).
Preferably, in step [5], the TiO2Presoma is prepared using following methods: by titanium salt and acyl ketone
Conjunction object, which is dissolved in alcohol, obtains solution A, and organic acid is dissolved in alcohol and obtains solution B, A, B solution are mixed to abundant precipitating
Afterwards, it is aged 20~30h, obtains the TiO2Presoma.
Preferably, in step [5], the titanium salt is titanium tetrachloride, and the acyl ketone compounds are acetylacetone,2,4-pentanedione, described to have
Machine acid is selected from least one of formic acid, acetic acid, ethanedioic acid.
Preferably, in step [5], the volume ratio of the alcohol and organic acid is (2~5): (1~2), acyl ketone compounds with
The mass ratio of titanium salt is 1:(8~10).
Preferably, in step [5], the mass ratio of sodium borohydride and graphene oxide is 1:(5~10).
Beneficial effects of the present invention:
It is at high cost for graphene, easy to reunite, in epoxy resin the problems such as difficult dispersion, the present invention is using independent research
Organic deposition method carries out splitting to graphene, obtains TiO2/ graphene composite material, then by the material and epoxy resin
Preparation process combine, a step is prepared in situ out ultra-dispersed, high performance containing graphene/nanometer TiO2The ring of composite material
Oxygen resin.This method is at low cost, simple production process, equipment requirement are low, can be produced in batches.Modified ring prepared by the present invention
The mechanical performance of oxygen resin greatly improves, and wherein impact resistance enhances 25%, and tensile property raising has been more than 35%, bendability
Can improve has been more than 47%., ingredient good as coating quality uniformly, be easy to industrialization.
Detailed description of the invention
Fig. 1-1, Fig. 1-2 and Fig. 1-3 are the graphene/nanometer TiO that embodiment 1 obtains2Composite material is in different times magnifications
Transmission electron microscope (TEM) photo under several.
Fig. 2 is the graphene/nanometer TiO that comparative example 1 obtains2The TEM photo of composite material.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, technical solution of the present invention will be carried out below
Detailed description.Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Base
Embodiment in the present invention, those of ordinary skill in the art are obtained all without making creative work
Other embodiment belongs to the range that the present invention is protected.
The present embodiments relate to one kind to contain graphene/nanometer TiO2The epoxy resin of composite material, the graphene/
Nano-TiO2Mass percentage of the composite material in the epoxy resin is 0.02%~1%.
The embodiment of the present invention further relates to the preparation method of the epoxy resin, the method includes with above-mentioned composite material,
Bisphenol-A and epoxychloropropane are reactant, and open loop and ring-closure reaction are carried out using sodium hydroxide as catalyst, is then extracted with benzene
And isolated epoxy resin.Specifically includes the following steps:
(1) by graphene/nanometer TiO2Composite material is dispersed with stirring in epoxychloropropane, adds bisphenol-A, and stirring is filled
Heating water bath is to 75~80 DEG C after point.
In one embodiment of the invention, the graphene/nanometer TiO2Composite material, bisphenol-A and epoxychloropropane
Mass ratio be (0.01~0.5): (20~30): (20~40).
(2) sodium hydroxide solution is added in the reaction system obtained to step (1), stops adding after reaction 1.5~2 hours
Heat；
In one embodiment of the invention, by graphene/nanometer TiO2Composite material is dispersed with stirring in epoxychloropropane
In, it adds bisphenol-A, when heating water bath is to 70 DEG C after stirring sufficiently, controls temperature-resistant, concentration, which is added, into reaction system is
20% sodium hydroxide solution then heats to 75~80 DEG C, stops heating after the reaction was continued 1.5~2 hours.
(3) benzene is added in the reaction system obtained to step (2), stirs 20~30 minutes.Reaction solution is moved into after cooling
Whether separatory funnel divides sub-cloud water layer after standing, then is washed with distilled water repeatedly, be in neutrality with pH test paper detection washing water,
Use AgNO3Solution checks for chloride ion, then separates organic layer.Organic layer is distilled after standing, removes benzene and not
The epoxychloropropane of reaction obtains described containing graphene/nanometer TiO2The epoxy resin of composite material.
In one embodiment of the invention, by organic layer, first benzene is removed in distillation under 75 DEG C of normal pressures after standing, then carries out
Vacuum distillation, removes all volatile matters.Stop heating when bubbling is not violent, otherwise resin is easy to burn.
The embodiment of the present invention further relates to above-mentioned graphene/nanometer TiO2The preparation method of composite material, this method include with
Lower step:
(1) graphite powder is mixed with sodium nitrate, obtains mixture.
(2) in ice-water bath, it is slowly added to the mixture that step (1) obtains into the concentrated sulfuric acid, slowly adds after being stirred
Enter potassium permanganate, is slowly stirred 20min after being preferably added to potassium permanganate.
In one embodiment of the invention, in step (1) and step (2), graphite powder, sodium nitrate, the concentrated sulfuric acid, permanganic acid
The additional proportion of potassium is (1~2g): (1~2g): (20~25ml): (2~3g).
(3) reaction system that step (2) obtains is removed from ice-water bath, and is warming up to 35 DEG C, keep the temperature 30~50min,
The process can carry out under oil bath or water bath condition.
(4) hydrogen peroxide solution that mass concentration is 30% is added in the reaction system obtained to step (3), after reaction 2 hours,
System bubble-free generates at this time.Reaction solution is filtered using miillpore filter, will filter obtained precipitating deionized water into
Row repeatedly washing, until sulfate radical-free detects.Graphene oxide is obtained after precipitating is dried in vacuo.
(5) according to 1g:(8~10ml) solid-liquid ratio, graphene oxide obtained above is added to the mixed of ethyl alcohol and water
It closes in solution, tests the pH value of mixed solution, if pH value is less than 7, the pH value of mixed solution is transferred to 7 using NaOH aqueous solution.
Then TiO is slowly added into mixed solution2Presoma and sodium borohydride solution, ultrasonic reaction 12~filtered afterwards for 24 hours will
Ultra-dispersed type porous graphene/nano-TiO is obtained after washing of precipitate, drying2Composite material.
In one embodiment of the invention, in the mixed solution of ethyl alcohol and water, the volume ratio of ethyl alcohol and water is 1:2.
It is studied by many years, a kind of method that can be prepared on a large scale at normal temperature nano-oxide of applicant's independent research
(such as TiO2、SiO2、ZrO2Deng), and it is named as " organic deposition method ", this method can homogeneously be sunk in organic solvent
Product, generates a large amount of high energy metastable state nano-oxide presomas, and then under given conditions, one step of forerunner's physical efficiency decomposes and from group
Dress is monodisperse type nano-oxide cluster.According to response characteristic, can make nano-oxide presoma between graphene layer from
Nano-oxide cluster is assembled into effectively carry out splitting to graphene to form ultra-dispersed graphene.
In one embodiment of the invention, TiO2Presoma is prepared using following methods: alcohol is as solvent, acyl ketone
Class compound is as buffer, and titanium salt is as source metal, and organic acid is as precipitating reagent.Titanium salt and acyl ketone compounds are dissolved in alcohol
In obtain solution A, organic acid is dissolved in alcohol and obtains solution B, by A, B solution be mixed, make to be uniformly distributed in system
Organic acid and alcohol reaction generates hydrone, and it is anti-that hydrolysis directly occurs with the metal salt being uniformly distributed in solvent using the hydrone
It answers, is stirred continuously until reaction generates white opacity precipitating.It sufficiently is aged 20~30h after precipitating, obtains TiO2Presoma.
In one embodiment of the invention, titanium salt is titanium tetrachloride, and acyl ketone compounds are acetylacetone,2,4-pentanedione, organic acid choosing
From at least one of formic acid, acetic acid, ethanedioic acid.
In one embodiment of the invention, the volume ratio of alcohol and organic acid is (2~5): (1~2), acyl ketone compounds
Mass ratio with titanium salt is 1:(8~10).In above-mentioned reaction, the additive amount of organic acid is more, reacts faster, generates precipitating
Time is shorter.The additional amount of pure and mild acyl ketone compounds is more, and titanium salt dissolubility is better, reacts more abundant.But it is added excessively
Pure and mild organic acid can reduce the concentration of reaction system, so that subsequent suction filtration energy consumption increases, it is therefore desirable to by above-mentioned organic reagent
Fixing fabric structure is in a certain range.
In step (5), sodium borohydride is used as the reducing agent of graphene oxide.In one embodiment of the present of invention
In, the mass ratio of sodium borohydride and graphene oxide is 1:(5~10).Sodium borohydride dosage is very few, goes back to graphene oxide
It is former insufficient, it still can residual oxygen graphene in product.Sodium borohydride dosage is excessive, can introduce excessive sodium ion and boron hydrogen radical
Ion equally increases the impurity content in product.
It in one embodiment of the invention, can be by TiO2Presoma is added in sodium borohydride solution, then slowly
It is added dropwise in the mixed liquor of graphene oxide.Due to TiO2Presoma in organic solvent can a step decompose and self assembly be single point
Dissipate type nano-TiO2Cluster, above-mentioned organic solvent is water-miscible or evenly dispersed in water, therefore in graphene oxide quilt
During reduction removing, TiO2Presoma decomposes in one step of interlayer meeting of graphene and is self-assembled into a large amount of nano-TiOs2Cluster,
These nano-TiOs2Cluster is fine and close " interlayer " in the formation between layers of graphene, has effectively carried out interlayer stripping to graphene
From having blocked the interlayer of graphene compound, to prepare stable ultra-dispersed type graphene.
In the composite material finally obtained, nano-TiO2Mass ratio with graphene is (0.5~1): 10.That is nano-TiO2
Quality account for the 5%~10% of graphene quality.
Embodiment 1
Prepare ultra-dispersed type porous graphene/nano-TiO2Composite material, comprising the following steps:
(1) 1g graphite powder is mixed with 1g sodium nitrate, obtains mixture.
(2) in ice-water bath, it is slowly added to the mixture that step (1) obtains into the 20ml concentrated sulfuric acid, delays after being stirred
It is slow that 2g potassium permanganate is added, continue to stir 20min.
(3) reaction system that step (2) obtains is removed from ice-water bath, be placed in water-bath and be warming up to 35 DEG C, heat preservation
30min。
(4) hydrogen peroxide solution that mass concentration is 30% is added in the reaction system obtained to step (3), after reaction 2 hours,
System bubble-free generates at this time.Reaction solution is filtered using miillpore filter, will filter obtained precipitating deionized water into
Row repeatedly washing, until sulfate radical-free detects.Graphene oxide is obtained after precipitating is dried in vacuo.
(5) according to the solid-liquid ratio of 1g:8ml, graphene oxide obtained above is added to 1 volume ethanol and 2 volume of water
Mixed solution in, the pH value of mixed solution is tested, if pH value is less than 7, using NaOH aqueous solution by the pH value tune of mixed solution
To 7.Then TiO is slowly added into mixed solution2The matter of presoma and sodium borohydride solution, sodium borohydride and graphene oxide
Amount is than being 1:10.It is filtered after ultrasonic reaction 12h, ultra-dispersed type porous graphene/nanometer will be obtained after washing of precipitate, drying
TiO2Composite material.
Wherein, TiO2Presoma is prepared using following methods:
The acetylacetone,2,4-pentanedione of 10.98ml titanium tetrachloride and 0.149g is dissolved in 15ml dehydrated alcohol and obtains solution A, by 20ml
Formic acid, which is dissolved in 15ml dehydrated alcohol, obtains solution B, and A, B solution are mixed, and is stirred continuously until reaction generates white opacity and sinks
It forms sediment.After being aged for 24 hours at room temperature, TiO is obtained2Presoma.
Embodiment 2
Prepare ultra-dispersed type porous graphene/nano-TiO2Composite material, comprising the following steps:
(1) 1.5g graphite powder is mixed with 1.5g sodium nitrate, obtains mixture.
(2) in ice-water bath, it is slowly added to the mixture that step (1) obtains into the 25ml concentrated sulfuric acid, delays after being stirred
It is slow that 3g potassium permanganate is added, continue to stir 20min.
(3) reaction system that step (2) obtains is removed from ice-water bath, be placed in water-bath and be warming up to 35 DEG C, heat preservation
40min。
(4) hydrogen peroxide solution that mass concentration is 30% is added in the reaction system obtained to step (3), after reaction 2 hours,
System bubble-free generates at this time.Reaction solution is filtered using miillpore filter, will filter obtained precipitating deionized water into
Row repeatedly washing, until sulfate radical-free detects.Graphene oxide is obtained after precipitating is dried in vacuo.
(5) according to the solid-liquid ratio of 1g:10ml, graphene oxide obtained above is added to 1 volume ethanol and 2 volume of water
Mixed solution in, the pH value of mixed solution is tested, if pH value is less than 7, using NaOH aqueous solution by the pH value tune of mixed solution
To 7.Then TiO is slowly added into mixed solution2The matter of presoma and sodium borohydride solution, sodium borohydride and graphene oxide
Amount is than being 1:8.It is filtered after ultrasonic reaction 12h, ultra-dispersed type porous graphene/nanometer will be obtained after washing of precipitate, drying
TiO2Composite material.
Wherein, TiO2Presoma is prepared using following methods:
The acetylacetone,2,4-pentanedione of 10.98ml titanium tetrachloride and 0.0745g is dissolved in 30ml dehydrated alcohol and obtains solution A, it will
20ml acetic acid, which is dissolved in 30ml dehydrated alcohol, obtains solution B, and A, B solution are mixed, and is stirred continuously until reaction generation white is muddy
Turbid precipitating.After being aged for 24 hours at room temperature, TiO is obtained2Presoma.
Comparative example 1
In step (5), the commercially available nanoscale TiO of 5g is slowly added into mixed solution2, other operating procedures are the same as embodiment 1.
Comparative example 2
Step does not add TiO in (5)2, other operating procedures are the same as embodiment 1.
Test case
Transmissioning electric mirror test
The graphene/nanometer TiO that embodiment 1 and comparative example 1 are obtained2Composite material carries out transmission electron microscope (TEM) test,
The result is shown in Figure 1-1,1-2,1-3 and Fig. 2.Wherein Fig. 1-1, Fig. 1-2, Fig. 1-3 are the obtained composite material of embodiment 1 in difference
Electromicroscopic photograph under amplification factor, Fig. 2 are electromicroscopic photograph of the obtained composite material of comparative example 1 under different amplification.From
As can be seen that the obtained graphene matter of embodiment 1 is thin and penetrating in figure, it can be determined that be single layer, and visible nano-TiO2In stone
Black alkene surface is uniformly distributed.The graphene stacking that comparative example 1 obtains is more serious, and due to opaque, nano-TiO2Hardly
It can be seen that.
In conjunction with electromicroscopic photograph as can be seen that nano-TiO is added2It is not only that the property of its nanoparticle is utilized.By
It joined TiO in graphene preparation process in the present invention2Presoma, during graphene oxide is reduced removing, TiO2
Presoma decomposes in one step of interlayer meeting of graphene and is self-assembled into a large amount of nano-TiOs2Cluster, these nano-TiOs2Cluster is in stone
The formation between layers of black alkene is fine and close " interlayer ", has effectively carried out splitting to graphene, has blocked the layer of graphene
Between it is compound, therefore can obtain removing more sufficiently, lamellar spacing is lower, performance is more stable ultra-dispersed type graphene.
Epoxy resin preparation
The graphene/nanometer TiO that embodiment and comparative example are prepared2Addition of the composite material as epoxy resin
Agent, the specific steps are as follows:
(1) by 0.1g graphene/nanometer TiO2Composite material is dispersed with stirring in 28.02g epoxychloropropane, then will
22g bisphenol-A and above-mentioned epoxychloropropane sequentially add in the 250ml four-necked bottle equipped with blender and thermometer, heating water bath liter
For temperature to 75 DEG C, stirring is completely dissolved bisphenol-A.
(2) reaction system is cooled to 70 DEG C, the sodium hydroxide solution that 40ml mass concentration is 20% is added dropwise, is added dropwise
The reaction was continued at 75-80 DEG C afterwards 1.5-2h, solution is in milk yellow at this time, stops heating and is simultaneously down to room temperature.
(3) benzene 60ml is added into reaction system, separatory funnel is moved into after stirring, sub-cloud water layer is divided after standing, then use
It is multiple to distill water washing, whether is in neutrality with pH test paper detection washing water, uses AgNO3Solution checks for chloride ion, then will
Organic layer separates.
(4) upper layer benzole soln is poured into vacuum distillation apparatus, first benzene is removed in distillation under 75 DEG C of normal pressures, after benzene removal,
All volatile matters are removed in vacuum distillation apparatus, pour out resin while hot, are saved.
To the above-mentioned epoxy resin being prepared, GB/T1040.2-2006 carries out tensile strength test according to national standards,
And bending strength and notch impact strength are tested, and the results are shown in Table 1.
Table 1
| Embodiment/comparative example | Embodiment 1 | Embodiment 2 | Comparative example 1 | Comparative example 2 |
| Tensile strength | 58.5MPa | 59.6MPa | 54.9MPa | 50.3MPa |
| Bending strength | 230MPa | 235MPa | 221MPa | 209MPa |
| Notch impact strength | 8.3kj/m2 | 8.7kj/m2 | 7.5kj/m2 | 6.0kj/m2 |
It can be seen that the ultra-dispersed type porous stone that Examples 1 and 2 are prepared using the present invention from above-mentioned test result
Black alkene/nano-TiO2Additive of the composite material as epoxy resin, tensile strength, bending strength and notch impact strength are bright
It is aobvious to be better than comparative example 1 and 2.Illustrate to be modified epoxide resin using the composite material, its mechanical performance can be obviously improved.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (10)
1. one kind contains graphene/nanometer TiO2The epoxy resin of composite material, which is characterized in that the graphene/nanometer TiO2
Mass percentage of the composite material in the epoxy resin is 0.02%~1%.
2. the preparation method of epoxy resin according to claim 1, which is characterized in that the described method comprises the following steps:
(1) by graphene/nanometer TiO2Composite material is dispersed with stirring in epoxychloropropane, bisphenol-A is added, after stirring sufficiently
Heating water bath is to 75~80 DEG C；
(2) sodium hydroxide solution is added in the reaction system obtained to step (1), stops heating after reaction 1.5~2 hours；
(3) benzene is added in the reaction system obtained to step (2), stirs 20~30 minutes, distills organic layer after standing,
Benzene and unreacted epoxychloropropane are removed, obtains described containing graphene/nanometer TiO2The epoxy resin of composite material.
3. the preparation method of epoxy resin according to claim 1, which is characterized in that in step (1), the graphene/
Nano-TiO2The mass ratio of composite material, bisphenol-A and epoxychloropropane is (0.01~0.5): (20~30): (20~40).
4. the preparation method of epoxy resin according to claim 1, which is characterized in that in step (1) and (2), by graphite
Alkene/nano-TiO2Composite material is dispersed with stirring in epoxychloropropane, adds bisphenol-A, stirs sufficiently rear heating water bath to 70
DEG C when, control it is temperature-resistant, into reaction system be added concentration be 20% sodium hydroxide solution, then heat to 75~80
DEG C, stop heating after the reaction was continued 1.5~2 hours.
5. the preparation method of epoxy resin according to claim 1, which is characterized in that, will be organic after standing in step (3)
First benzene is removed in distillation to layer under 75 DEG C of normal pressures, is then evaporated under reduced pressure, removes all volatile matters.
6. epoxy resin according to claim 1, which is characterized in that the graphene/nanometer TiO2Composite material by with
Lower section method is prepared:
[1] graphite powder is mixed with sodium nitrate, obtains mixture；
[2] in ice-water bath, the mixture that step [1] obtains is added into the concentrated sulfuric acid, potassium permanganate is added after being stirred；
[3] reaction system that step [2] obtains is removed from ice-water bath, and is warming up to 35 DEG C, keep the temperature 30~50min；
[4] hydrogen peroxide solution is added in the reaction system that obtains to step [3], and reaction is filtered after 2 hours, by washing of precipitate,
Graphene oxide is obtained after drying；
[5] graphene oxide is added in the mixed solution of ethyl alcohol and water, TiO is then added2Presoma and sodium borohydride
Solution, ultrasonic reaction 12~filtered afterwards for 24 hours will obtain the composite material after washing of precipitate, drying.
7. epoxy resin according to claim 6, which is characterized in that in step [1] and step [2], graphite powder, nitric acid
Sodium, the concentrated sulfuric acid, potassium permanganate additional proportion be (1~2g): (1~2g): (20~25ml): (2~3g).
8. epoxy resin according to claim 6, which is characterized in that in step [5], the TiO2Presoma is using following
Method is prepared: titanium salt and acyl ketone compounds is dissolved in alcohol and obtains solution A, organic acid is dissolved in alcohol and obtains solution B,
After A, B solution are mixed to sufficiently precipitating, it is aged 20~30h, obtains the TiO2Presoma.
9. epoxy resin according to claim 6, which is characterized in that in step [5], the titanium salt is titanium tetrachloride, institute
Stating acyl ketone compounds is acetylacetone,2,4-pentanedione, and the organic acid is selected from least one of formic acid, acetic acid, ethanedioic acid.
10. epoxy resin according to claim 6, which is characterized in that in step [5], the volume of the alcohol and organic acid
Than for (2~5): the mass ratio of (1~2), acyl ketone compounds and titanium salt is 1:(8~10), sodium borohydride and graphene oxide
Mass ratio be 1:(5~10).
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2015040211A (en) * | 2013-08-20 | 2015-03-02 | 尾池工業株式会社 | Graphene dispersion composition, and carbon-containing resin laminated body |
| CN105551828A (en) * | 2015-12-11 | 2016-05-04 | 郑州大学 | Nano titanium dioxide/graphene composite material and preparation method thereof |
| CN105837790A (en) * | 2016-06-20 | 2016-08-10 | 山东欧铂新材料有限公司 | Preparation method of graphene modified epoxy resin |
| CN107446115A (en) * | 2016-06-01 | 2017-12-08 | 东北林业大学 | A kind of preparation method of nano modification bisphenol A type epoxy resin |
| CN107522169A (en) * | 2016-06-22 | 2017-12-29 | 东北林业大学 | A kind of normal temperature prepares pure organic homogeneous precipitation method of nano-oxide |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015040211A (en) * | 2013-08-20 | 2015-03-02 | 尾池工業株式会社 | Graphene dispersion composition, and carbon-containing resin laminated body |
| CN105551828A (en) * | 2015-12-11 | 2016-05-04 | 郑州大学 | Nano titanium dioxide/graphene composite material and preparation method thereof |
| CN107446115A (en) * | 2016-06-01 | 2017-12-08 | 东北林业大学 | A kind of preparation method of nano modification bisphenol A type epoxy resin |
| CN105837790A (en) * | 2016-06-20 | 2016-08-10 | 山东欧铂新材料有限公司 | Preparation method of graphene modified epoxy resin |
| CN107522169A (en) * | 2016-06-22 | 2017-12-29 | 东北林业大学 | A kind of normal temperature prepares pure organic homogeneous precipitation method of nano-oxide |
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