CN109019583A - A kind of modified graphene oxide material and preparation method thereof for polymethyl methacrylate materials - Google Patents
A kind of modified graphene oxide material and preparation method thereof for polymethyl methacrylate materials Download PDFInfo
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- CN109019583A CN109019583A CN201811032892.8A CN201811032892A CN109019583A CN 109019583 A CN109019583 A CN 109019583A CN 201811032892 A CN201811032892 A CN 201811032892A CN 109019583 A CN109019583 A CN 109019583A
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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Abstract
The invention discloses the modified graphene oxide materials and preparation method thereof for polymethyl methacrylate materials, utilize the polarization of electric field, make graphitic molecules in oxidation process, active group is grafted on mostly along the direction of electric field line, realize the order of active group, simultaneously, add modifying agent, make surface of graphene oxide grafting largely with the better group of polymethyl methacrylate compatibility, to make modified graphene oxide, it is more preferable with the compatibility of polymethyl methacrylate materials, the modified graphene oxide material is used for the modification of polymethyl methacrylate materials, the properties of polymethyl methacrylate materials can significantly be improved, modified polymethyl methacrylate materials are made to can be suitably used for more areas.
Description
Technical field
The present invention relates to grapheme material fields, and in particular to a kind of modification oxygen for polymethyl methacrylate materials
Graphite alkene material and preparation method thereof.
Background technique
Graphene oxide is the oxidation material of graphene, has planar structure similar with graphene, since surface is contained
A large amount of active group, as hydroxyl (- OH), epoxy group [- C (O) C-], carbonyl (- C=O), carboxyl (- COOH), ester group (-
COO-) etc., so graphene oxide and most of materials all have preferable compatibility, and it has property similar with graphene
Can, the properties of multiple material can be significantly improved, are one of general composite modification materials best at present, are led in composite material
Domain is used widely.Polymethyl methacrylate materials belong to one of the most widely used high molecular material now, and
More one of material is modified with graphene oxide composite material.It has been investigated that although existing graphene oxide composite material
The multiple performance of polymethyl methacrylate can have been dramatically increased, but on the graphene oxide being prepared due to existing method
The randomness and unicity of active group lead to graphene oxide composite material and the compatibility of polymethyl methacrylate materials not
Reach best, meanwhile, unordered active group and polymethyl methacrylate it is bonded, will lead to polymethyl methacrylate chain
Flexibility decline reduces the toughness of graphene oxide enhancing composite material of polymethyl methacrylate, to make polymethyl
The application of sour methyl esters composite material is limited.
Summary of the invention
It is an object of the invention to overcome existing graphene oxide and polymethyl methacrylate materials poor compatibility, work
The property unordered defect of group, provides a kind of for the modified graphene oxide material of polymethyl methacrylate materials and its preparation
Method；The present invention utilizes the polarization of electric field, makes graphitic molecules in oxidation process, active group is grafted on mostly along electric field
On the direction of line, realize the order of active group, meanwhile, add modifying agent, make surface of graphene oxide grafting largely with
The better group of polymethyl methacrylate compatibility, to make modified graphene oxide itself and polymethyl methacrylate
The compatibility of material is more preferable, which is used for the modification of polymethyl methacrylate materials, can be significant
The properties for improving polymethyl methacrylate materials, can be suitably used for modified polymethyl methacrylate materials more
Field.
In order to achieve the above-mentioned object of the invention, the present invention provides a kind of modification oxygen for polymethyl methacrylate materials
The preparation method of graphite alkene material, comprising the following steps:
(1), graphite powder is added in mixed acid solution and is stirred to obtain the first suspension；
(2), the first suspension is placed in parallel electric field, potassium permanganate powder is added, heating stirring obtains the second suspension；
(3), after being cooled to room temperature the second suspension, hydrogenperoxide steam generator and hydrochloric acid solution is added, obtains third suspension；
(4), after third suspension being washed with deionized, is filtered dry, the ethanol water for being added 50% is dispersed, and obtains
Four suspensions；
(5), modifying agent is added in the 4th suspension, heating after the reaction was completed, obtains the 5th suspension；
(6), the 5th suspension is washed with deionized, is centrifugated, obtain sediment；
(7), sediment is dried in vacuo under constant temperature conditions, obtains the modification oxygen for polymethyl methacrylate materials
Graphite alkene.
Wherein, sulfuric acid solution and quality percentage that mixed acid solution described in step (1) is 55% by mass percent concentration
The nitric acid solution that Particle density is 45% mixes；The mixed acid is good to the oxidation of graphitic molecules, obtained oxidation stone
Carboxyl accounting is bigger in black alkene, stronger with the bonding capability of modifying agent.
Preferably, the volume ratio of the sulfuric acid solution and nitric acid solution is 3 ︰ 1；Preferred ratio makees the oxidation of graphite
With more preferable, carboxyl is more on obtained graphene oxide molecule, stronger with the bonding capability of modifying agent.
Preferably, the mass volume ratio (g ︰ ml) of the graphite powder and mixed acid solution is 2 ︰ 100；Preferred ratio is to stone
The oxidation of ink is more preferable, and carboxyl accounting is bigger in obtained graphene oxide, stronger with the bonding capability of modifying agent.
Wherein, under the effect of the parallel electric field described in step (2), polarization occurs for graphitic molecules, prolongs direction of an electric field
Graphite electronically active is stronger, so that active group more combines on the direction along electric field line when graphitic molecules are oxidized,
Meanwhile can reduce under oxidizing condition, make reaction condition milder, safety；Preferably, the parallel electric field intensity is 2.5-
3.5KV/m；Under preferred electric field strength, the active group order on graphene oxide molecule is best.
Preferably, the mass ratio of the potassium permanganate powder and graphite powder is 1 ︰ 1；Preferred ratio makees the oxidation of graphite
With more preferable, carboxyl is more on obtained graphene oxide, stronger with the bonding capability of modifying agent.
Preferably, the heating temperature is 50-70 DEG C；Preferred thermotonus speed is fast, and reaction is thorough, energy consumption
Small, production cost is low.
Wherein, in step (3), the concentration of the hydrogenperoxide steam generator is 1. 5mol/L；The concentration of hydrochloric acid solution
For 1.0mol/L；In the hydrogen peroxide and hydrochloric acid of above-mentioned concentration, the graphene oxide purity being prepared is higher.
Preferably, the volume ratio of the second suspension, hydrogenperoxide steam generator and hydrochloric acid solution is 50 ︰, 2 ︰ 5；In preferred volume
Than under, the graphene oxide purity being prepared is best.
Wherein, in step (4), 50% ethanol water and the mass volume ratio (ml ︰ g) of graphite powder are 100 ︰ 2；Dispersion
More evenly, modified effect is more preferable.
Wherein, in step (5), the modifying agent is methallyl alcohol, acrylic acid and hydro alkoxy aluminium
Mixture；The modifying agent can be bonded with the active group on graphene oxide, thus significant modified graphene oxide and poly-
The compatibility of methyl methacrylate material；Preferably, methallyl alcohol, acrylic acid and hydrogenation in the modifying agent
The mass ratio of aluminum alkoxide is 2 ︰, 4 ︰ 1；Preferred modifying agent proportion, modified graphene oxide and polymethyl methacrylate
Compatibility it is best.
Preferably, the mass ratio of the modifying agent and graphite powder is 0.1-0.3 ︰ 1；Preferred mass ratio, it is modified
The compatibility of graphene oxide and polymethyl methacrylate is best.
Wherein, it is preferred that the temperature of heating reaction is 75-80 DEG C in step (5)；In preferred range, modified effect
Fruit is best, and the compatibility of obtained graphene oxide and polymethyl methacrylate is best.
A kind of modified graphene oxide material for polymethyl methacrylate materials, is by above-mentioned preparation method system
For what is obtained, the active group on the modified graphene oxide material has order, and has with polymethyl methacrylate
Excellent compatibility, the modification suitable for composite material of polymethyl methacrylate.
Compared with prior art, beneficial effects of the present invention:
1, in preparation method of the present invention, oxidation processes is carried out to graphite in parallel electric field, make active group along electric field line
Direction is orderly grafted on graphitic molecules, so as to significantly improve influence of the active group randomness to compound material flexible.
2, in preparation method of the present invention, the modifying agent of use can further enhance graphene oxide composite material and polymethyl
Compatibility between methyl acrylate material.
3, preparation method of the present invention is simple, reliable, the modified graphite oxide suitable for polymethyl methacrylate materials
Extensive, the industrialized production of alkene material.
Specific embodiment
Below with reference to test example and specific embodiment, the present invention is described in further detail.But this should not be understood
It is all that this is belonged to based on the technology that the content of present invention is realized for the scope of the above subject matter of the present invention is limited to the following embodiments
The range of invention.
Embodiment 1
(1), the graphite powder of 2g is added to the sulfuric acid solution and 25ml mass percent by the mass percent concentration of 75ml for 55%
The first suspension is stirred to obtain in the mixed acid solution that the nitric acid solution that concentration is 45% mixes；
It (2), is that 2g potassium permanganate powder is added in the direct current parallel electric field of 3.0KV/m by the first suspension merging electric field strength,
60 DEG C of stirrings are heated to, the second suspension is obtained；
(3), after being cooled to room temperature the second suspension, the concentration that 4ml is added is 1.5mol/L hydrogenperoxide steam generator and 10ml
Concentration is 1.0mol/L hydrochloric acid solution, obtains third suspension；
(4), after third suspension being washed with deionized, is filtered dry, 50% ethanol water that 100ml is added is dispersed,
Obtain the 4th suspension；
(5), the mass ratio that 0.4g is added in the 4th suspension is methallyl alcohol, acrylic acid and the hydrogen of 2 ︰, 4 ︰ 1
Change aluminum alkoxide, is heated to 78 DEG C, after the reaction was completed, obtains the 5th suspension；
(6), the 5th suspension is washed with deionized, is centrifugated, obtain sediment；
(7), sediment is dried in vacuo under constant temperature conditions, obtains the modification oxygen for polymethyl methacrylate materials
Graphite alkene.
Embodiment 2
(1), the graphite powder of 2g is added to the sulfuric acid solution and 25ml mass percent by the mass percent concentration of 75ml for 55%
The first suspension is stirred to obtain in the mixed acid solution that the nitric acid solution that concentration is 45% mixes；
It (2), is that 2g potassium permanganate powder is added in the direct current parallel electric field of 3.5KV/m by the first suspension merging electric field strength,
70 DEG C of stirrings are heated to, the second suspension is obtained；
(3), after being cooled to room temperature the second suspension, the concentration that 4ml is added is 1.5mol/L hydrogenperoxide steam generator and 10ml
Concentration is 1.0mol/L hydrochloric acid solution, obtains third suspension；
(4), after third suspension being washed with deionized, 50% ethanol water that 100ml is added is dispersed, and is obtained
4th suspension；
(5), the mass ratio that 0.2g is added in the 4th suspension is methallyl alcohol, acrylic acid and the hydrogen of 2 ︰, 4 ︰ 1
Change aluminum alkoxide, is heated to 80 DEG C, after the reaction was completed, obtains the 5th suspension；
(6), the 5th suspension is washed with deionized, is centrifugated, obtain sediment；
(7), sediment is dried in vacuo under constant temperature conditions, obtains the modification oxygen for polymethyl methacrylate materials
Graphite alkene.
Embodiment 3
(1), the graphite powder of 2g is added to the sulfuric acid solution and 25ml mass percent by the mass percent concentration of 75ml for 55%
The first suspension is stirred to obtain in the mixed acid solution that the nitric acid solution that concentration is 45% mixes；
It (2), is that 2g potassium permanganate powder is added in the exchange parallel electric field of 2.5KV/m by the first suspension merging electric field strength,
50 DEG C of stirrings are heated to, the second suspension is obtained；
(3), after being cooled to room temperature the second suspension, the concentration that 4ml is added is 1.5mol/L hydrogenperoxide steam generator and 10ml
Concentration is 1.0mol/L hydrochloric acid solution, obtains third suspension；
(4), after third suspension being washed with deionized, 50% ethanol water that 100ml is added is dispersed, and is obtained
4th suspension；
(5), the mass ratio that 0.6g is added in the 4th suspension is methallyl alcohol, acrylic acid and the hydrogen of 2 ︰, 4 ︰ 1
Change aluminum alkoxide, is heated to 75 DEG C, after the reaction was completed, obtains the 5th suspension；
(6), the 5th suspension is washed with deionized, is centrifugated, obtain sediment；
(7), sediment is dried in vacuo under constant temperature conditions, obtains the modification oxygen for polymethyl methacrylate materials
Graphite alkene.
Comparative example 1
(1), the graphite powder of 2g is added to the sulfuric acid solution and 25ml mass percent by the mass percent concentration of 75ml for 55%
The first suspension is stirred to obtain in the mixed acid solution that the nitric acid solution that concentration is 45% mixes；
(2), 2g potassium permanganate powder is added in the first suspension, is heated to 60 DEG C of stirrings, obtains the second suspension；
(3), after being cooled to room temperature the second suspension, the concentration that 4ml is added is 1.5mol/L hydrogenperoxide steam generator and 10ml
Concentration is 1.0mol/L hydrochloric acid solution, obtains third suspension；
(4), after third suspension being washed with deionized, is filtered dry, 50% ethanol water that 100ml is added is dispersed,
Obtain the 4th suspension；
(5), the mass ratio that 0.4g is added in the 4th suspension is methallyl alcohol, acrylic acid and the hydrogen of 2 ︰, 4 ︰ 1
Change aluminum alkoxide, is heated to 78 DEG C, after the reaction was completed, obtains the 5th suspension；
(6), the 5th suspension is washed with deionized, is centrifugated, obtain sediment；
(7), sediment is dried in vacuo under constant temperature conditions, obtains graphene oxide.
Comparative example 2
(1), the graphite powder of 2g is added to the sulfuric acid solution and 25ml mass percent by the mass percent concentration of 75ml for 55%
The first suspension is stirred to obtain in the mixed acid solution that the nitric acid solution that concentration is 45% mixes；
It (2), is that 2g potassium permanganate powder is added in the direct current parallel electric field of 3.0KV/m by the first suspension merging electric field strength,
60 DEG C of stirrings are heated to, the second suspension is obtained；
(3), after being cooled to room temperature the second suspension, the concentration that 4ml is added is 1.5mol/L hydrogenperoxide steam generator and 10ml
Concentration is 1.0mol/L hydrochloric acid solution, obtains third suspension；
(4), after third suspension being washed with deionized, is filtered dry, 50% ethanol water that 100ml is added is dispersed,
Obtain the 4th suspension；
(5), the 4th suspension is washed with deionized, is centrifugated, obtain sediment；
(6), sediment is dried in vacuo under constant temperature conditions, obtains graphene oxide.
Comparative example 3
(1), the graphite powder of 2g is added to the sulfuric acid solution and 25ml mass percent by the mass percent concentration of 75ml for 55%
The first suspension is stirred to obtain in the mixed acid solution that the nitric acid solution that concentration is 45% mixes；
It (2), is that 2g potassium permanganate powder is added in the direct current parallel electric field of 3.0KV/m by the first suspension merging electric field strength,
60 DEG C of stirrings are heated to, the second suspension is obtained；
(3), after being cooled to room temperature the second suspension, the concentration that 4ml is added is 1.5mol/L hydrogenperoxide steam generator and 10ml
Concentration is 1.0mol/L hydrochloric acid solution, obtains third suspension；
(4), after third suspension being washed with deionized, is filtered dry, 50% ethanol water that 100ml is added is dispersed,
Obtain the 4th suspension；
(5), the mass ratio that 0.4g is added in the 4th suspension is the methallyl alcohol and hydro alkoxy of 4 ︰ 1
Aluminium is heated to 78 DEG C, after the reaction was completed, obtains the 5th suspension；
(6), the 5th suspension is washed with deionized, is centrifugated, obtain sediment；
(7), sediment is dried in vacuo under constant temperature conditions, obtains graphene oxide.
The graphene oxide that will be prepared in above-described embodiment 1-3 and comparative example 1-3 arranges difference by 0.05% ratio
It is added in polymethyl methacrylate materials, obtains sample (every group of 10 samples), blank through twin-screw extrusion, injection molding
Sample is pure polymethyl methacrylate materials, carries out performance detection to sample respectively, and record data (average data) is as follows:
| Performance | Tensile strength (MPa) | Elongation at break (%) | Notch impact strength (kJ/m2) |
| Embodiment 1 | 71.93 | 12.83 | 21.21 |
| Embodiment 2 | 71.65 | 10.32 | 20.83 |
| Embodiment 3 | 72.16 | 9.38 | 20.24 |
| Comparative example 1 | 69.88 | 5.83 | 19.53 |
| Comparative example 2 | 67.49 | 4.83 | 16.38 |
| Comparative example 3 | 68.57 | 6.28 | 15.28 |
| Blank sample | 63.42 | 3.68 | 12.68 |
To above-mentioned analysis of experimental data it is found that the graphene oxide composite material of the present invention being prepared in embodiment 1-3, can significantly mention
Tensile strength, elongation at break and the notch impact strength of high polymethyl methacrylate；And in comparative example 1, not in parallel electricity
Oxidation processes are carried out to graphite in, active group is in disordered state on obtained graphene oxide, to polymethylacrylic acid
Methyl esters tensile strength and the humidification of elongation at break significantly reduce；Modifying agent is not added in comparative example 2 to graphene oxide
It is modified, the compatibility of obtained graphene oxide composite material and polymethyl methacrylate reduces, and causes to polymethyl
The humidification of the tensile strength of sour methyl esters, elongation at break and notch impact strength significantly reduces；It is added in comparative example 3
Modifying agent is not given to this invention, the compatibility drop of modified graphene oxide composite material and polymethyl methacrylate
It is low, lead to the humidification of the tensile strength to polymethyl methacrylate, elongation at break and notch impact strength
It reduces.
Claims (10)
1. a kind of preparation method of the modified graphene oxide material for polymethyl methacrylate materials, which is characterized in that
The following steps are included:
(1), graphite powder is added in mixed acid solution and is stirred to obtain the first suspension；
(2), the first suspension is placed in parallel electric field, potassium permanganate powder is added, heating stirring obtains the second suspension；
(3), after being cooled to room temperature the second suspension, hydrogenperoxide steam generator and hydrochloric acid solution is added, obtains third suspension；
(4), after third suspension being washed with deionized, is filtered dry, the ethanol water for being added 50% is dispersed, and obtains
Four suspensions；
(5), modifying agent is added in the 4th suspension, heating after the reaction was completed, obtains the 5th suspension；
(6), the 5th suspension is washed with deionized, is centrifugated, obtain sediment；
(7), sediment is dried in vacuo under constant temperature conditions, obtains the modification oxygen for polymethyl methacrylate materials
Graphite alkene；
The nitric acid that the sulfuric acid solution and mass percent concentration that the mixed acid solution is 55% by mass percent concentration are 45%
Solution mixes；
The concentration of the hydrogenperoxide steam generator is 1. 5mol/L；
The concentration of hydrochloric acid solution is 1.0mol/L；
The modifying agent is the mixture of methallyl alcohol, acrylic acid and hydro alkoxy aluminium.
2. preparation method according to claim 1, which is characterized in that the volume ratio of the sulfuric acid solution and nitric acid solution
For 3 ︰ 1.
3. preparation method according to claim 1, which is characterized in that the quality volume of the graphite powder and mixed acid solution
It is 2 ︰ 100 than (g ︰ ml).
4. preparation method according to claim 1, which is characterized in that the parallel electric field intensity is 2.5-3.5KV/m.
5. preparation method according to claim 1, which is characterized in that the mass ratio of the potassium permanganate powder and graphite powder
For 1 ︰ 1.
6. preparation method according to claim 1, which is characterized in that the second suspension, hydrogenperoxide steam generator and hydrochloric acid are molten
The volume ratio of liquid is 50 ︰, 2 ︰ 5.
7. preparation method according to claim 1, which is characterized in that 50% ethanol water and the quality of graphite powder
Volume ratio (ml ︰ g) is 100 ︰ 2.
8. preparation method according to claim 1, which is characterized in that methallyl alcohol in the modifying agent,
The mass ratio of acrylic acid and hydro alkoxy aluminium is 2 ︰, 4 ︰ 1.
9. preparation method according to claim 1, which is characterized in that the mass ratio of the modifying agent and graphite powder is
0.1-0.3 ︰ 1.
10. a kind of modified graphene oxide material for polymethyl methacrylate materials, which is characterized in that pass through right
It is required that any one of 1-9 preparation method is prepared.
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| CN201811032892.8A CN109019583A (en) | 2018-09-05 | 2018-09-05 | A kind of modified graphene oxide material and preparation method thereof for polymethyl methacrylate materials |
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| CN201811032892.8A CN109019583A (en) | 2018-09-05 | 2018-09-05 | A kind of modified graphene oxide material and preparation method thereof for polymethyl methacrylate materials |
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Application publication date: 20181218 |