CN109181307A - A kind of modified graphene oxide material and preparation method thereof for polyether sulfone materials - Google Patents
A kind of modified graphene oxide material and preparation method thereof for polyether sulfone materials Download PDFInfo
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- CN109181307A CN109181307A CN201811033583.2A CN201811033583A CN109181307A CN 109181307 A CN109181307 A CN 109181307A CN 201811033583 A CN201811033583 A CN 201811033583A CN 109181307 A CN109181307 A CN 109181307A
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Abstract
The invention discloses the modified graphene oxide materials and preparation method thereof for polyether sulfone 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 polyether sulfone compatibility, to make modified graphene oxide, it is more preferable with the compatibility of polyether sulfone materials, the modified graphene oxide material is used for the modification of polyether sulfone materials, the properties of polyether sulfone materials can significantly be improved, modified polyether sulfone 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 modified graphene oxide material for polyether sulfone materials
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.Polyether sulfone materials belong to one of the most widely used high molecular material now, and with oxidation stone
Black alkene material is modified more one of material.It has been investigated that although existing graphene oxide composite material can significantly increase
The multiple performance of addition polymerization ether sulfone, but on the graphene oxide being prepared due to existing method active group randomness and list
One property leads to the compatibility of graphene oxide composite material and polyether sulfone materials and not up to best, meanwhile, unordered active group with
Polyether sulfone it is bonded, will lead to polyether sulfone chain flexibility decline, reduce graphene oxide enhancing Polyethersulfone Composites toughness,
To keep the application of Polyethersulfone Composites limited.
Summary of the invention
It is an object of the invention to overcome the unordered with polyether sulfone materials poor compatibility, active group of existing graphene oxide
Defect, a kind of modified graphene oxide material and preparation method thereof for polyether sulfone materials is provided；The present invention utilizes electric field
Polarization, make graphitic molecules in oxidation process, active group is grafted on mostly along the direction of electric field line, realizes work
Property group order, meanwhile, add modifying agent, make surface of graphene oxide grafting largely with the better base of polyether sulfone compatibility
Group, to make modified graphene oxide, it is more preferable with the compatibility of polyether sulfone materials, which uses
In the modification of polyether sulfone materials, the properties of polyether sulfone materials can be significantly improved, modified polyether sulfone materials is enable to fit
For more areas.
In order to achieve the above-mentioned object of the invention, the present invention provides a kind of modified graphene oxide materials for polyether sulfone materials
The preparation method of 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 modified graphene oxide for polyether sulfone materials.
Wherein, sulfuric acid solution and quality percentage that mixed acid solution described in step (1) is 45% by mass percent concentration
The nitric acid solution that Particle density is 35% mixes；The mixed acid is good to the oxidation of graphitic molecules, obtained oxidation stone
Black alkene epoxy group and hydroxyl accounting are bigger, stronger with the bonding capability of modifying agent.
Preferably, the volume ratio of the sulfuric acid solution and nitric acid solution is 1 ︰ 1；Preferred ratio makees the oxidation of graphite
With more preferable, epoxy group and hydroxyl are 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 obtained graphene oxide epoxy group and hydroxyl accounting is bigger, more with the bonding capability of modifying agent
By force.
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 3.5-
4.5KV/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 ︰ 4；Preferred ratio makees the oxidation of graphite
With more preferable, epoxy group and hydroxyl are 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 1.2mol/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 sulfonic acid and imidazoles, zinc dialkyl dithiophosphate and diethylene glycol (DEG) two
The mixture of methyl ether；The modifying agent can be bonded with the active group on graphene oxide, thus significant modified graphene oxide
With the compatibility of polyether sulfone materials；Preferably, sulfonic acid and imidazoles, zinc dialkyl dithiophosphate and diethylene glycol (DEG) in the modifying agent
The mass ratio of dimethyl ether is 4 ︰, 1 ︰ 2；The compatibility of preferred modifying agent proportion, modified graphene oxide and polyether sulfone is most
It is good.
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 polyether sulfone is best.
Wherein, it is preferred that the temperature of heating reaction is 85-90 DEG C in step (5)；In preferred range, modified effect
Fruit is best, and the compatibility of obtained graphene oxide and polyether sulfone is best.
A kind of modified graphene oxide material for polyether sulfone materials, is prepared by above-mentioned preparation method,
Active group on the modified graphene oxide material has order, and has excellent compatibility with polyether sulfone, is suitable for
The modification of Polyethersulfone Composites.
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 polyether sulfone materials
Between compatibility.
3, preparation method of the present invention is simple, reliable, the modified graphene oxide material suitable for polyether sulfone materials it is big
Scale, industrialized production.
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 50ml mass percent by the mass percent concentration of 50ml for 45%
The first suspension is stirred to obtain in the mixed acid solution that the nitric acid solution that concentration is 35% mixes；
It (2), is that 0.5g potassium permanganate powder is added in the direct current parallel electric field of 4.0KV/m by the first suspension merging electric field strength
End 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 1.2mol/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 sulfonic acid and imidazoles, zinc dialkyl dithiophosphate of 4 ︰, 1 ︰ 2
And diethylene glycol dimethyl ether, 88 DEG C are heated to, 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 modified graphene oxide for polyether sulfone materials.
Embodiment 2
(1), the graphite powder of 2g is added to the sulfuric acid solution and 50ml mass percent by the mass percent concentration of 50ml for 45%
The first suspension is stirred to obtain in the mixed acid solution that the nitric acid solution that concentration is 35% mixes；
It (2), is that 0.5g potassium permanganate powder is added in the direct current parallel electric field of 3.5KV/m by the first suspension merging electric field strength
End is heated to 70 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 1.2mol/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 the sulfonic acid and imidazoles, zinc dialkyl dithiophosphate of 4 ︰, 1 ︰ 2
And diethylene glycol dimethyl ether, 85 DEG C are heated to, 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 modified graphene oxide for polyether sulfone materials.
Embodiment 3
(1), the graphite powder of 2g is added to the sulfuric acid solution and 50ml mass percent by the mass percent concentration of 50ml for 45%
The first suspension is stirred to obtain in the mixed acid solution that the nitric acid solution that concentration is 35% mixes；
It (2), is that 0.5g potassium permanganate powder is added in the exchange parallel electric field of 4.5KV/m by the first suspension merging electric field strength
End is heated to 50 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 1.2mol/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 the sulfonic acid and imidazoles, zinc dialkyl dithiophosphate of 4 ︰, 1 ︰ 2
And diethylene glycol dimethyl ether, 90 DEG C are heated to, 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 modified graphene oxide for polyether sulfone materials.
Comparative example 1
(1), the graphite powder of 2g is added to the sulfuric acid solution and 50ml mass percent by the mass percent concentration of 50ml for 45%
The first suspension is stirred to obtain in the mixed acid solution that the nitric acid solution that concentration is 35% mixes；
(2), 0.5g 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 1.2mol/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 sulfonic acid and imidazoles, zinc dialkyl dithiophosphate of 4 ︰, 1 ︰ 2
And diethylene glycol dimethyl ether, 88 DEG C are heated to, 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 50ml mass percent by the mass percent concentration of 50ml for 45%
The first suspension is stirred to obtain in the mixed acid solution that the nitric acid solution that concentration is 35% mixes；
It (2), is that 0.5g potassium permanganate powder is added in the direct current parallel electric field of 4.0KV/m by the first suspension merging electric field strength
End 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 1.2mol/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 50ml mass percent by the mass percent concentration of 50ml for 45%
The first suspension is stirred to obtain in the mixed acid solution that the nitric acid solution that concentration is 35% mixes；
It (2), is that 0.5g potassium permanganate powder is added in the direct current parallel electric field of 4.0KV/m by the first suspension merging electric field strength
End 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 1.2mol/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 sulfonic acid and imidazoles and diethylene glycol dimethyl ether of 4 ︰ 2, is heated to
88 DEG C, after the reaction was completed, obtain 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 polyether sulfone materials, is obtained sample (every group of 10 samples) through twin-screw extrusion, injection molding, blank sample is pure poly-
Ether sulfone material 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 | 68.21 | 67.23 | 16.82 |
| Embodiment 2 | 68.85 | 62.86 | 16.28 |
| Embodiment 3 | 67.67 | 68.24 | 16.41 |
| Comparative example 1 | 64.87 | 52.71 | 13.68 |
| Comparative example 2 | 62.41 | 47.85 | 12.65 |
| Comparative example 3 | 64.08 | 48.57 | 12.92 |
| Blank sample | 56.38 | 27.52 | 8.95 |
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 polyether sulfone；And in comparative example 1, not to graphite in parallel electric field
Oxidation processes are carried out, active group is in disordered state on obtained graphene oxide, stretches to polyether sulfone tensile strength and fracture
The humidification of long rate significantly reduces；It is not added with modifying agent in comparative example 2 to be modified graphene oxide, obtained oxidation stone
The compatibility of black alkene material and polyether sulfone reduces, and leads to the tensile strength to polyether sulfone, elongation at break and notch impact strength
Humidification significantly reduce；The modifying agent added in comparative example 3 is not given to this invention, modified graphite oxide
The compatibility of alkene material and polyether sulfone reduces, and leads to the tensile strength to polyether sulfone, elongation at break and notch impact strength
Humidification decreases.
Claims (10)
1. a kind of preparation method of the modified graphene oxide material for polyether sulfone materials, which is characterized in that including following step
It is rapid:
(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 the 4th
Suspension；
(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 modified graphene oxide for polyether sulfone materials；
The nitric acid that the sulfuric acid solution and mass percent concentration that the mixed acid solution is 45% by mass percent concentration are 35%
Solution mixes；
The concentration of the hydrogenperoxide steam generator is 1.2mol/L；
The concentration of hydrochloric acid solution is 1.0mol/L；
The modifying agent is the mixture of sulfonic acid and imidazoles, zinc dialkyl dithiophosphate and diethylene glycol dimethyl ether.
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 1 ︰ 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 3.5-4.5KV/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 ︰ 4.
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 sulfonic acid and imidazoles, dialkyl group two in the modifying agent
The mass ratio of thiophosphoric acid zinc and diethylene glycol dimethyl ether is 4 ︰, 1 ︰ 2.
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 polyether sulfone materials, which is characterized in that appointed by claim 1-9
One preparation method is prepared.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811033583.2A CN109181307A (en) | 2018-09-05 | 2018-09-05 | A kind of modified graphene oxide material and preparation method thereof for polyether sulfone materials |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811033583.2A CN109181307A (en) | 2018-09-05 | 2018-09-05 | A kind of modified graphene oxide material and preparation method thereof for polyether sulfone materials |
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Application publication date: 20190111 |