CN109054349A - A kind of modified graphene oxide material and preparation method thereof for polyurethane material - Google Patents
A kind of modified graphene oxide material and preparation method thereof for polyurethane material Download PDFInfo
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- CN109054349A CN109054349A CN201811033608.9A CN201811033608A CN109054349A CN 109054349 A CN109054349 A CN 109054349A CN 201811033608 A CN201811033608 A CN 201811033608A CN 109054349 A CN109054349 A CN 109054349A
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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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- 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
- C08K9/00—Use of pretreated ingredients
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Abstract
The invention discloses the modified graphene oxide materials and preparation method thereof for polyurethane material, 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 polyurethane compatibility, to make modified graphene oxide, it is more preferable with the compatibility of polyurethane material, the modified graphene oxide material is used for the modification of polyurethane material, the properties of polyurethane material can significantly be improved, modified polyurethane material is set 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 polyurethane material
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.Polyurethane material belongs 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 urethane, 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 polyurethane material and not up to best, meanwhile, unordered active group with
Polyurethane it is bonded, will lead to polyurethane chain flexibility decline, reduce graphene oxide enhancing compound polyurethane material toughness,
To keep the application of compound polyurethane material limited.
Summary of the invention
It is an object of the invention to overcome the unordered with polyurethane material poor compatibility, active group of existing graphene oxide
Defect, a kind of modified graphene oxide material and preparation method thereof for polyurethane material 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 polyurethane compatibility
Group, to make modified graphene oxide, it is more preferable with the compatibility of polyurethane material, which uses
In the modification of polyurethane material, the properties of polyurethane material can be significantly improved, modified polyurethane material 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 polyurethane material
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 polyurethane material.
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 55% 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 1 ︰ 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 3.5-
6.5KV/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 ︰ 2；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 1.8mol/L；The concentration of hydrochloric acid solution
For 1.2mol/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 the mixing of aminoacrylic acid, dimethylformamide sodium and quaternary ammonium salt
Object；The modifying agent can be bonded with the active group on graphene oxide, thus significant modified graphene oxide and polyurethane material
The compatibility of material；Preferably, the mass ratio of aminoacrylic acid, dimethylformamide sodium and quaternary ammonium salt is 4 ︰, 1 ︰ in the modifying agent
2；The compatibility of preferred modifying agent proportion, modified graphene oxide and polyurethane 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 polyurethane is best.
Wherein, it is preferred that the temperature of heating reaction is 60-70 DEG C in step (5)；In preferred range, modified effect
Fruit is best, and the compatibility of obtained graphene oxide and polyurethane is best.
A kind of modified graphene oxide material for polyurethane material, is prepared by above-mentioned preparation method,
Active group on the modified graphene oxide material has order, and has excellent compatibility with polyurethane, is suitable for
The modification of compound polyurethane material.
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 polyurethane material
Between compatibility.
3, preparation method of the present invention is simple, reliable, the modified graphene oxide material suitable for polyurethane material 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 55% mixes；
It (2), is that 1g potassium permanganate powder is added in the direct current parallel electric field of 5.0KV/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 1.8mol/L hydrogenperoxide steam generator and 10ml
Concentration is 1.2mol/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 aminoacrylic acid, dimethylformamide sodium and the season of 4 ︰, 1 ︰ 2
Ammonium salt is heated to 65 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 modified graphene oxide for polyurethane material.
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 55% mixes；
It (2), is that 1g 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 1.8mol/L hydrogenperoxide steam generator and 10ml
Concentration is 1.2mol/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 aminoacrylic acid, dimethylformamide sodium and the season of 4 ︰, 1 ︰ 2
Ammonium salt is heated to 70 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 modified graphene oxide for polyurethane material.
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 55% mixes；
It (2), is that 1g potassium permanganate powder is added in the exchange parallel electric field of 6.5KV/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 1.8mol/L hydrogenperoxide steam generator and 10ml
Concentration is 1.2mol/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 aminoacrylic acid, dimethylformamide sodium and the season of 4 ︰, 1 ︰ 2
Ammonium salt is heated to 60 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 modified graphene oxide for polyurethane material.
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 55% mixes；
(2), 1g 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 1.8mol/L hydrogenperoxide steam generator and 10ml
Concentration is 1.2mol/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 aminoacrylic acid, dimethylformamide sodium and the season of 4 ︰, 1 ︰ 2
Ammonium salt is heated to 65 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 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 55% mixes；
It (2), is that 1g potassium permanganate powder is added in the direct current parallel electric field of 5.0KV/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 1.8mol/L hydrogenperoxide steam generator and 10ml
Concentration is 1.2mol/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 55% mixes；
It (2), is that 1g potassium permanganate powder is added in the direct current parallel electric field of 5.0KV/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 1.8mol/L hydrogenperoxide steam generator and 10ml
Concentration is 1.2mol/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 aminoacrylic acid and quaternary ammonium salt of 4 ︰ 2, is heated to 65 DEG C, instead
After the completion of answering, the 5th suspension is obtained；
(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 is added by 0.1% ratio column respectively
Enter into polyurethane material, obtained sample (every group of 10 samples) through twin-screw extrusion, injection molding, blank sample is pure poly- ammonia
Ester 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 | 46.21 | 262.31 | 4.86 |
| Embodiment 2 | 45.38 | 249.35 | 4.68 |
| Embodiment 3 | 46.83 | 241.95 | 4.58 |
| Comparative example 1 | 43.68 | 192.83 | 4.61 |
| Comparative example 2 | 41.86 | 216.83 | 3.98 |
| Comparative example 3 | 43.08 | 237.68 | 4.21 |
| Blank sample | 31.64 | 345.82 | 2.68 |
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
The tensile strength and notch impact strength of high polyurethane, the influence to elongation at break are small；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, stretches to polyurethane strong
Spending humidification significantly reduces, and the influence to elongation at break significantly increases；Modifying agent is not added in comparative example 2 to graphite oxide
Alkene is modified, and the compatibility of obtained graphene oxide composite material and polyurethane reduces, cause to the tensile strength of polyurethane and
The humidification of notch impact strength significantly reduces, and the influence to elongation at break significantly increases；The modification added in comparative example 3
Agent be not it is given to this invention, the compatibility of modified graphene oxide composite material and polyurethane reduces, and causes to polyurethane
Tensile strength and the humidification of notch impact strength decrease, the influence to elongation at break is reduced.
Claims (10)
1. a kind of preparation method of the modified graphene oxide material for polyurethane material, 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 polyurethane material；
The nitric acid that the sulfuric acid solution and mass percent concentration that the mixed acid solution is 45% by mass percent concentration are 55%
Solution mixes；
The concentration of the hydrogenperoxide steam generator is 1.8mol/L；The concentration of hydrochloric acid solution is 1.2mol/L；
The modifying agent is the mixture of aminoacrylic acid, dimethylformamide sodium and quaternary ammonium salt.
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 3.5-6.5KV/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 ︰ 2.
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 aminoacrylic acid, dimethyl methyl in the modifying agent
The mass ratio of amide sodium and quaternary ammonium salt 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 polyurethane material, which is characterized in that appointed by claim 1-9
One preparation method is prepared.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112852007A (en) * | 2021-01-13 | 2021-05-28 | 北京大学 | Preparation method and application of ethylenediamine grafted graphene oxide modified polyurethane carrier |
| CN113943458A (en) * | 2021-11-22 | 2022-01-18 | 万华化学（宁波）有限公司 | Polycarbonate/polypropylene alloy material and preparation method thereof |
-
2018
- 2018-09-05 CN CN201811033608.9A patent/CN109054349A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112852007A (en) * | 2021-01-13 | 2021-05-28 | 北京大学 | Preparation method and application of ethylenediamine grafted graphene oxide modified polyurethane carrier |
| CN112852007B (en) * | 2021-01-13 | 2022-04-12 | 北京大学 | Preparation method and application of ethylenediamine grafted graphene oxide modified polyurethane carrier |
| CN113943458A (en) * | 2021-11-22 | 2022-01-18 | 万华化学（宁波）有限公司 | Polycarbonate/polypropylene alloy material and preparation method thereof |
| CN113943458B (en) * | 2021-11-22 | 2023-08-11 | 万华化学（宁波）有限公司 | Polycarbonate/polypropylene alloy material and preparation method thereof |
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