CN109019584A - A kind of modified graphene oxide material and preparation method thereof for polyphenyl thioether material - Google Patents
A kind of modified graphene oxide material and preparation method thereof for polyphenyl thioether material Download PDFInfo
- Publication number
- CN109019584A CN109019584A CN201811033565.4A CN201811033565A CN109019584A CN 109019584 A CN109019584 A CN 109019584A CN 201811033565 A CN201811033565 A CN 201811033565A CN 109019584 A CN109019584 A CN 109019584A
- Authority
- CN
- China
- Prior art keywords
- suspension
- preparation
- acid solution
- graphene oxide
- added
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses the modified graphene oxide materials and preparation method thereof for polyphenyl thioether 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 polyphenylene sulfide compatibility, to make modified graphene oxide, it is more preferable with the compatibility of polyphenyl thioether material, the modified graphene oxide material is used for the modification of polyphenyl thioether material, the properties of polyphenyl thioether material can significantly be improved, modified polyphenyl thioether 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 for polyphenyl thioether 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.Polyphenyl thioether material belongs to one of the most widely used high molecular material now, and with oxidation
Grapheme material is modified more one of material.It has been investigated that although existing graphene oxide composite material can be significant
Increase polyphenylene sulfide multiple performance, but on the graphene oxide being prepared due to existing method active group randomness
And unicity, lead to the compatibility of graphene oxide composite material and polyphenyl thioether material and not up to best, meanwhile, unordered activity
Group and polyphenylene sulfide it is bonded, will lead to the decline of polyphenylene sulfide chain flexibility, it is multiple to reduce graphene oxide enhancing polyphenylene sulfide
The toughness of condensation material, to keep the application of polyphenyl thioether composite material limited.
Summary of the invention
It is an object of the invention to overcome existing graphene oxide with polyphenyl thioether material poor compatibility, active group without
The defect of sequence provides a kind of modified graphene oxide material and preparation method thereof for polyphenyl thioether material；The present invention utilizes
The polarization of electric field, makes graphitic molecules in oxidation process, and active group is grafted on mostly along the direction of electric field line, realizes
The order of active group, meanwhile, add modifying agent, make surface of graphene oxide grafting largely with polyphenylene sulfide compatibility more
Good group, to make modified graphene oxide, it is more preferable with the compatibility of polyphenyl thioether material, the modified graphite oxide
Alkene material is used for the modification of polyphenyl thioether material, can significantly improve the properties of polyphenyl thioether material, makes modified poly-
Diphenyl sulfide material can be suitably used for more areas.
In order to achieve the above-mentioned object of the invention, the present invention provides a kind of modified graphene oxides for polyphenyl thioether 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 graphite oxide for polyphenyl thioether material
Alkene.
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
Hydroxyl and epoxy group accounting are 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, hydroxyl and epoxy group 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 1 ︰ 100；Preferred ratio is to stone
The oxidation of ink is more preferable, and hydroxyl and epoxy group accounting are bigger in obtained graphene oxide, 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 6.5-
8.5KV/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, hydroxyl and epoxy group are more on obtained graphene oxide, stronger with the bonding capability of modifying agent.
Preferably, the heating temperature is 50-55 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 1.0-2.5mol/L；The hydrochloric acid solution
Concentration is 0.8-1.5mol/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 ︰, 1 ︰ 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 mixed of sulfonic acid and imidazoles, phenol and zinc dialkyl dithiophosphate
Close object；The modifying agent can be bonded with the active group on graphene oxide, thus significant modified graphene oxide and polyphenylene sulfide
The compatibility of ether material；Preferably, the mass ratio of sulfonic acid and imidazoles, phenol and zinc dialkyl dithiophosphate in the modifying agent
For 2 ︰, 1 ︰ 3；The compatibility of preferred modifying agent proportion, modified graphene oxide and polyphenylene sulfide 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 polyphenylene sulfide 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 polyphenylene sulfide is best.
A kind of modified graphene oxide material for polyphenyl thioether material, is prepared by above-mentioned preparation method
, the active group on the modified graphene oxide material has order, and has excellent compatibility with polyphenylene sulfide, fits
Modification for polyphenyl thioether composite 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 polyphenylene sulfide material
Compatibility between material.
3, preparation method of the present invention is simple, reliable, the modified graphene oxide material suitable for polyphenyl thioether material
On a large 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 1g is added to the sulfuric acid solution and 25ml mass percent by the mass percent concentration of 75ml 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 0.25g potassium permanganate powder is added in the direct current parallel electric field of 7.5KV/m by the first suspension merging electric field strength
End is heated to 52 DEG C of stirrings, obtains the second suspension；
(3), after being cooled to room temperature the second suspension, the concentration that 2ml 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 50ml is added is dispersed,
Obtain the 4th suspension；
(5), the mass ratio that 0.2g is added in the 4th suspension is the sulfonic acid and imidazoles, phenol and dialkyl dithio of 2 ︰, 1 ︰ 3
Trbasic zinc phosphate is heated to 88 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 graphite oxide for polyphenyl thioether material
Alkene.
Embodiment 2
(1), the graphite powder of 1g is added to the sulfuric acid solution and 25ml mass percent by the mass percent concentration of 75ml 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 0.25g potassium permanganate powder is added in the direct current parallel electric field of 6.5KV/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 2ml is added is 1.0mol/L hydrogenperoxide steam generator and 10ml
Concentration is 1.5mol/L hydrochloric acid solution, obtains third suspension；
(4), after third suspension being washed with deionized, 50% ethanol water that 50ml is added is dispersed, and obtains
Four suspensions；
(5), the mass ratio that 0.1g is added in the 4th suspension is the sulfonic acid and imidazoles, phenol and dialkyl dithio of 2 ︰, 1 ︰ 3
Trbasic zinc phosphate is heated to 88 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 graphite oxide for polyphenyl thioether material
Alkene.
Embodiment 3
(1), the graphite powder of 1g is added to the sulfuric acid solution and 25ml mass percent by the mass percent concentration of 75ml 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 0.25g potassium permanganate powder is added in the exchange parallel electric field of 8.5KV/m by the first suspension merging electric field strength
End is heated to 55 DEG C of stirrings, obtains the second suspension；
(3), after being cooled to room temperature the second suspension, the concentration that 2ml is added is 2.5mol/L hydrogenperoxide steam generator and 10ml
Concentration is 0.8mol/L hydrochloric acid solution, obtains third suspension；
(4), after third suspension being washed with deionized, 50% ethanol water that 50ml is added is dispersed, and obtains
Four suspensions；
(5), the mass ratio that 0.2g is added in the 4th suspension is the sulfonic acid and imidazoles, phenol and dialkyl dithio of 2 ︰, 1 ︰ 3
Trbasic zinc phosphate is heated to 88 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 graphite oxide for polyphenyl thioether material
Alkene.
Comparative example 1
(1), the graphite powder of 1g is added to the sulfuric acid solution and 25ml mass percent by the mass percent concentration of 75ml 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), 0.25g potassium permanganate powder is added in the first suspension, is heated to 52 DEG C of stirrings, obtains the second suspension；
(3), after being cooled to room temperature the second suspension, the concentration that 2ml 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 50ml is added is dispersed,
Obtain the 4th suspension；
(5), the mass ratio that 0.2g is added in the 4th suspension is the sulfonic acid and imidazoles, phenol and dialkyl dithio of 2 ︰, 1 ︰ 1
Trbasic zinc phosphate is heated to 88 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 1g is added to the sulfuric acid solution and 25ml mass percent by the mass percent concentration of 75ml 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 0.25g potassium permanganate powder is added in the direct current parallel electric field of 7.5KV/m by the first suspension merging electric field strength
End is heated to 52 DEG C of stirrings, obtains the second suspension；
(3), after being cooled to room temperature the second suspension, the concentration that 2ml 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 50ml 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 1g is added to the sulfuric acid solution and 25ml mass percent by the mass percent concentration of 75ml 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 0.25g potassium permanganate powder is added in the direct current parallel electric field of 7.5KV/m by the first suspension merging electric field strength
End is heated to 52 DEG C of stirrings, obtains the second suspension；
(3), after being cooled to room temperature the second suspension, the concentration that 2ml 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 50ml is added is dispersed,
Obtain the 4th suspension；
(5), the mass ratio that 0.2g is added in the 4th suspension is the sulfonic acid and imidazoles and zinc dialkyl dithiophosphate of 2 ︰ 3,
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.
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 polyphenyl thioether material, is obtained sample (every group of 10 samples) through twin-screw extrusion, injection molding, blank sample is pure
Polyphenyl thioether 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 | 63.21 | 62.12 | 38.24 |
| Embodiment 2 | 62.85 | 59.24 | 37.58 |
| Embodiment 3 | 62.97 | 67.25 | 38.51 |
| Comparative example 1 | 59.87 | 53.86 | 34.85 |
| Comparative example 2 | 58.68 | 54.24 | 35.03 |
| Comparative example 3 | 59.34 | 57.52 | 35.58 |
| Blank sample | 54.21 | 31.25 | 29.85 |
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 polyphenylene sulfide；And in comparative example 1, not to stone in parallel electric field
Ink carries out oxidation processes, and active group be in disordered state on obtained graphene oxide, poly-p-phenylene sulfide ether tensile strength and breaks
The humidification for splitting elongation significantly reduces；It is not added with modifying agent in comparative example 2 to be modified graphene oxide, obtained oxygen
The compatibility of graphite alkene material and polyphenylene sulfide reduces, and leads to tensile strength, elongation at break and the notch of poly-p-phenylene sulfide ether
The humidification of impact strength significantly reduces；The modifying agent added in comparative example 3 be not it is given to this invention, it is modified
Graphene oxide composite material and the compatibility of polyphenylene sulfide reduce, and lead to the tensile strength of poly-p-phenylene sulfide ether, elongation at break and lack
The humidification of mouth impact strength decreases.
Claims (10)
1. a kind of preparation method of the modified graphene oxide material for polyphenyl thioether material, which is characterized in that including following
Step:
(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 graphite oxide for polyphenyl thioether material
Alkene；
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 1.0-2.5mol/L；
The concentration of hydrochloric acid solution is 0.8-1.5mol/L；
The modifying agent is the mixture of sulfonic acid and imidazoles, phenol and zinc dialkyl dithiophosphate.
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 1 ︰ 100 than (g ︰ ml).
4. preparation method according to claim 1, which is characterized in that the parallel electric field intensity is 6.5-8.5KV/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 ︰, 1 ︰ 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, phenol and two in the modifying agent
The mass ratio of alkyl zinc dithiophosphate is 2 ︰, 1 ︰ 3.
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 polyphenyl thioether material, which is characterized in that pass through claim 1-9
Any one preparation method is prepared.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811033565.4A CN109019584A (en) | 2018-09-05 | 2018-09-05 | A kind of modified graphene oxide material and preparation method thereof for polyphenyl thioether material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811033565.4A CN109019584A (en) | 2018-09-05 | 2018-09-05 | A kind of modified graphene oxide material and preparation method thereof for polyphenyl thioether material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109019584A true CN109019584A (en) | 2018-12-18 |
Family
ID=64624198
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811033565.4A Withdrawn CN109019584A (en) | 2018-09-05 | 2018-09-05 | A kind of modified graphene oxide material and preparation method thereof for polyphenyl thioether material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109019584A (en) |
-
2018
- 2018-09-05 CN CN201811033565.4A patent/CN109019584A/en not_active Withdrawn
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI542643B (en) | Dispersing agent, its preparation method and dispersed composition of carbon-based material comprising the same | |
| CN105004773B (en) | A kind of preparation of chitosan graphene quantum dot nano composite material and its modified electrode electrochemical process detection heavy metal ion | |
| CN102898872B (en) | Functional graphene and preparation method as well as application thereof to graphene /non-polar polymer composite material | |
| CN108530643A (en) | A kind of preparation method for the graphene Polyaniline Grafted composite material can be used for electrochemical energy storage | |
| CN105802122B (en) | A kind of cable insulation material comprising nano magnesia/low density polyethylene (LDPE)/modified alta-mud and its application | |
| CN102600814A (en) | Preparation method of novel magnetic nano biosorption material | |
| CN108912659B (en) | Preparation method of crosslinked three-dimensional carbon nano composite polyurethane material | |
| CN109054349A (en) | A kind of modified graphene oxide material and preparation method thereof for polyurethane material | |
| CN102516575A (en) | Method for preparing bipolar membrane modified by heavy metal ion loaded carbon nao tube | |
| CN109233199A (en) | A kind of modified graphene oxide material and preparation method thereof for polyetheretherketonematerials materials | |
| CN109181069A (en) | A kind of graphene oxide enhancing composite polyethylene material and preparation method thereof | |
| CN112662077B (en) | Antistatic graphene-coated aluminum microsphere modified PP composite material and preparation method thereof | |
| CN109019584A (en) | A kind of modified graphene oxide material and preparation method thereof for polyphenyl thioether material | |
| CN109320904A (en) | A kind of graphene oxide reinforced polyether ether ketone composite material and preparation method | |
| Huang et al. | Electroactive polyurea/CNT composite-based electrode for detection of vitamin C. | |
| CN109181307A (en) | A kind of modified graphene oxide material and preparation method thereof for polyether sulfone materials | |
| CN109021290A (en) | A kind of modified graphene oxide material and preparation method thereof for makrolon material | |
| Amaturrahim et al. | Preparation of graphene oxide/bacterial cellulose nanocomposite via in situ process in agitated culture | |
| CN109320936A (en) | A kind of graphene oxide polycarbafil composite material and preparation method | |
| CN109233252A (en) | A kind of graphene oxide enhancing compound polyurethane material and preparation method thereof | |
| CN111394991A (en) | Method for grafting carbon nano tube on surface of carbon fiber based on plasma technology | |
| CN109019583A (en) | A kind of modified graphene oxide material and preparation method thereof for polymethyl methacrylate materials | |
| CN109081975A (en) | A kind of modified graphene oxide material and preparation method thereof for polyolefine material | |
| CN109320961A (en) | A kind of graphene oxide enhancing polyphenyl thioether composite material and preparation method thereof | |
| CN103012792B (en) | In-situ intercalation powder preparation of graphene oxide-benzoxazine nano composite resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20181218 |