CN107325268A - A kind of graphene/PET nano composite materials and preparation method thereof - Google Patents
A kind of graphene/PET nano composite materials and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
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Abstract
The invention discloses a kind of graphene/PET nano composite materials and preparation method thereof, by adding the spherical graphene oxide of pleat and catalyst in PET presomas, while occurring polycondensation reaction, the spherical graphene oxide high degree of dispersion of pleat, and progressively it is dissociated into single-layer graphene oxide piece, partial esterification molecule can be with the hydroxyl on graphene oxide sheet surface, carboxyl reaction formation chemical bond, graphene oxide is occurred thermal reduction simultaneously, finally give the composite being made up of PET and surface grafting PET graphene film.Inventive process avoids the stacking of graphene oxide in Esterification Stage, cost is greatlyd save, production efficiency is improved.The formation of covalent bond effectively improves the performances such as mechanical property, the electrical conductivity of system between gained graphene good dispersion in polymeric matrix, and two kinds of materials.Preparation technology involved in the present invention is easy and effective, can effectively save cost, gained composite property is superior, and available for preparing high performance PET fabric.
Description
Technical field
The invention belongs to field of compound material, more particularly to a kind of graphene/PET nano composite materials and its preparation side
Method.
Background technology
Polyethylene terephtalate is a kind of very important high polymer material, in people are daily in occupation of
Very big ratio, such as disposable water bottle, packaging material, automobile plastic etc., PET spinning is just obtained into conventional in clothes wash
Synthetic fibre, therefore, PET is universally present in our life.If can further lift PET performance, or assign its new property
Can, PET application can not only be further widened, more facilities can be also brought to human society.In recent years, researchers are led to
Cross regulation and control PET molecular structures, carry out copolyreaction, introduce enhancing be mutually combined, design the microscopic appearances such as island, crystallization behavior
The means such as control are upgraded to PET performances, the achievement attracted people's attention.
Introduce reinforcing material be one kind can quickly large-scale production, the high method of cost performance, conventional reinforcing material include metal
Material (nano wire, nano-particle), inorganic filler (montmorillonite, titanium dioxide, silica, boron nitride etc.) and carbon material (charcoal
Black, graphite etc.).There are two big defects in conventional reinforcing material, on the one hand need very high addition to obtain gratifying effect
Really, but high addition along with other performances decline, it is difficult to realize the General Promotion of performance, another aspect enhancing effect is often
It is single, it is impossible to while being improved to multiple performances.These problems cause the cost performance of conventional reinforcing material relatively low, it is impossible to
It is satisfactory.
Graphene is a kind of two-dimensional material of atomic thickness, and the specific surface area with superelevation, excellent mechanical property, height are led
Electric rate, high thermal conductivity and high barrier.Also, many performances of material can be improved simultaneously by adding a small amount of graphene, with superelevation
Cost performance, this makes it be widely studied in terms of composite.But graphene is easily reunited, graphite stacking can be re-formed
Structure, reduces its enhancing effect.Although graphene can be promoted by adding dispersant and carrying out the method for surface modification
Dispersiveness and reduction graphene stacking, but these methods improve the cost of graphene, and introduce new composition.
Patent 201510514154.7《The preparation method of graphene oxide modified PET material》Graphene oxide is added using before esterification
Enter graphene oxide water solution, the addition of one side water can produce influence, the oxidation of another aspect Esterification Stage on esterification and polycondensation
Graphene is reduced, it is possible to create stacked, and reduces performance.Patent 201280033203.X《PET-stone
Black alkene nano-complex》By graphene nanometer sheet add PET polymerization systems, multi-layer graphene cause addition it is higher (2~
15%), and because no functional group is present, secondary stacking can occur in the course of the polymerization process for graphene, form incompatible lack
Trapping spot.Patent 201610111707.9《PET bases graphene composite material, its preparation method and aerostatics》First by graphene oxide
Spent glycol is modified, then is esterified or ester exchange with PET monomer, and last polycondensation obtains composite, although by modified
Mode improves the compatibility of graphene and PET polymerization systems, and graphene is produced covalence graft with PET, but in ester
During change, graphene oxide still can be stacked inevitably, and preparation process is complicated, and the cost of overall production is high,
Be not suitable for actual production.
The content of the invention
The purpose of the present invention is that there is provided a kind of graphene/PET nano composite materials and its system for existing technical deficiency
Preparation Method.
The purpose of the present invention is achieved through the following technical solutions：A kind of preparation of graphene/PET nano composite materials
Method, it is characterised in that prepared and carried out by following steps：
(1) size is dried for 1~50 micron of single-layer graphene oxide dispersion liquid by atomization drying method, obtains pleat ball
Shape graphene oxide, its carbon-to-oxygen ratio is 2.5~5；
(2) 100 parts by weight terephthalic acid (TPA)s, 48~67 parts by weight ethylene glycol, 0.02g sodium acetates are sufficiently mixed stirring,
Esterification is carried out at 250 DEG C；
(3) 0.0117~5.85 spherical graphene oxide of parts by weight pleat for obtaining step (1), is urged with 0.018 parts by weight
Agent is added in step (2) obtained esterification products, and 1~3h of insulated and stirred is warming up to 285 DEG C and vacuumized afterwards, react into
Row is to system no longer heat release, and water cooling pelletizing obtains graphene/PET nano composite materials.
Further, the atomization drying temperature of the step (1) is 130~200 DEG C.
Further, mixing speed is 140~200 revs/min in the step (3).
Further, catalyst is antimony-based catalyst in the step (3), including the oxide of antimony, inorganic salts and organic
Compound.
Further, catalyst is Titanium series catalyst in the step (3), including titanyl compound, inorganic salts and organic
Compound.
Further, catalyst is germanium series catalysts in the step (3), including the oxide of germanium, inorganic salts and organic
Compound.
The beneficial effects of the present invention are：The present invention prepares the spherical oxidation stone of pleat by using atomization drying method first
Black alkene microballoon, causes the spherical graphene oxide of pleat after the completion of esterification by the carbon-to-oxygen ratio and graphene oxide size of reasonable selection
PET oligomer in can progressively deploy, be dissociated into sheet graphene oxide, the surface of graphene oxide in PET polymerization processes
Hydroxyl and carboxyl react with the PET molecules in system so that PET strands graft on graphenic surface, improve both
The raising of the performances such as mechanical property, electric conductivity is also contributed to while compatibility.Graphene oxide is added after esterification, it is to avoid
Influence to first step esterification process, in actual production process more rationally, more efficient, cost is lower, while also keeping away
Exempt from graphene oxide and form aggregate in Esterification Stage generation stacking.For whole PET polymerizations, except the spherical oxidation stone of pleat
Any material is not introduced outside black alkene, terephthalic acid (TPA), ethylene glycol, esterification catalyst and polycondensation catalyst consumption press pure PET
Polymerization technique, reduces influence of the graphene introducing to technique and equipment, has broad application prospects to greatest extent.Gained stone
Black alkene/PET composite material has excellent mechanical property and conductance, and available for the preparation of functionalization polyester fiber.
Brief description of the drawings
Fig. 1 is the photo of the graphene/PET nano composite materials prepared through the embodiment of the present invention 1.
Fig. 2 is the SEM figures of the spherical graphene oxide of pleat prepared through the embodiment of the present invention 1.
Embodiment
The method for preparing graphene/PET nano composite materials comprises the following steps：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains the spherical graphene oxide of pleat.It is described
Atomization drying temperature is 130~200 DEG C.The spherical graphene oxide of pleat is made up of single-layer fold graphene oxide sheet, oxidation
The size of graphene film is 1~50 micron, and carbon-to-oxygen ratio is 2.5~5；(2) by 100 parts by weight terephthalic acid (TPA)s, 48~67 weight
Part ethylene glycol, 0.02g sodium acetates are sufficiently mixed stirring, and esterification is carried out at 250 DEG C and is produced to anhydrous；(3) by step (1)
0.0117~5.85 obtained spherical graphene oxide of parts by weight pleat, adds what step (2) was obtained with 0.018 part by weight of catalyst
In esterification products, 1~3h of insulated and stirred is warming up to 285 DEG C and vacuumized afterwards, and reaction is carried out to system no longer heat release, water cooling
Pelletizing obtains graphene/PET nano composite materials.The mixing speed is 140~200 revs/min.The catalyst is that antimony system urges
Agent, includes oxide, inorganic salts and the organic compound of antimony.The catalyst be Titanium series catalyst, including antimony oxide,
Inorganic salts and organic compound.The catalyst is antimony-based catalyst, includes oxide, inorganic salts and the organic compound of germanium.
The present invention is specifically described below by embodiment, the present embodiment is served only for doing further the present invention
Bright, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art makes one according to the content of foregoing invention
A little nonessential changes and adjustment belong to protection scope of the present invention.
Embodiment 1：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains graphene oxide microballoon, atomization temperature
Spend for 130 DEG C, the size of graphene oxide sheet is 1~3 micron, and carbon-to-oxygen ratio is 2.5；
(2) 1000g phthalic acids, 530g ethylene glycol, 0.2 sodium acetate are sufficiently mixed stirring, are esterified at 250 DEG C
Reaction is produced to anhydrous；
(3) the spherical graphene oxide of 1.17g pleats for obtaining step (1), adds step (2) with 0.18g antimony glycols and obtains
To esterification products in, insulated and stirred 2h, mixing speed be 160 revs/min, 285 DEG C are warming up to afterwards and is vacuumized, reaction carry out
To system no longer heat release, water cooling pelletizing obtains graphene/PET nano composite materials.
Through above step, graphene/PET nano composite materials are obtained, as shown in Figure 1.The spherical graphene oxide of gained pleat
SEM figures it is as shown in Figure 2.The specific performance of composite is as shown in table 1.
Embodiment 2：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains graphene oxide microballoon, atomization temperature
Spend for 130 DEG C, the size of graphene oxide sheet is 10~15 microns, and carbon-to-oxygen ratio is 2.5；
(2) 1000g terephthalic acid (TPA)s, 530g ethylene glycol, 0.2g are sufficiently mixed stirring, carry out being esterified instead at 250 DEG C
It should be produced to anhydrous；
(3) the spherical graphene oxide of 1.17g pleats for obtaining step (1), adds step (2) with 0.18g antimony glycols and obtains
To esterification products in, insulated and stirred 2h, mixing speed be 160 revs/min, 285 DEG C are warming up to afterwards and is vacuumized, reaction carry out
To system no longer heat release, water cooling pelletizing obtains graphene/PET nano composite materials.
Through above step, graphene/PET nano composite materials are obtained, specific performance is as shown in table 1.
Embodiment 3：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains graphene oxide microballoon, atomization temperature
Spend for 130 DEG C, the size of graphene oxide sheet is 40~45 microns, and carbon-to-oxygen ratio is 2.5；
(2) 1000g terephthalic acid (TPA)s, 530g ethylene glycol, 0.2g sodium acetates are sufficiently mixed stirring, carried out at 250 DEG C
Esterification is produced to anhydrous；
(3) the 1.17 spherical graphene oxides of parts by weight pleat for obtaining step (1), step is added with 0.18g antimony glycols
(2) in the esterification products obtained, insulated and stirred 2h, mixing speed is 160 revs/min, and 285 DEG C are warming up to afterwards and is vacuumized, instead
It should carry out to system no longer heat release, water cooling pelletizing obtains graphene/PET nano composite materials.
Through above step, graphene/PET nano composite materials are obtained, specific performance is as shown in table 1.
Embodiment 4：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains graphene oxide microballoon, atomization temperature
Spend for 160 DEG C, the size of graphene oxide sheet is 10~15 microns, and carbon-to-oxygen ratio is 5；
(2) 1000g terephthalic acid (TPA)s, 530g ethylene glycol, 0.2g sodium acetates are sufficiently mixed stirring, carried out at 250 DEG C
Esterification is produced to anhydrous；
(3) the spherical graphene oxide of 1.17g pleats for obtaining step (1), adds step (2) with 0.18g antimony glycols and obtains
To esterification products in, insulated and stirred 2h, mixing speed be 160 revs/min, 285 DEG C are warming up to afterwards and is vacuumized, reaction carry out
To system no longer heat release, water cooling pelletizing obtains graphene/PET nano composite materials.
Through above step, graphene/PET nano composite materials are obtained, specific performance is as shown in table 1.
Embodiment 5：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains graphene oxide microballoon, atomization temperature
Spend for 130 DEG C, the size of graphene oxide sheet is 10~15 microns, and carbon-to-oxygen ratio is 2.5；
(2) 1000g terephthalic acid (TPA)s, 530g ethylene glycol, 0.2g sodium acetates are sufficiently mixed stirring, carried out at 250 DEG C
Esterification is produced to anhydrous；
(3) the spherical graphene oxide of 11.7g pleats for obtaining step (1), adds step (2) with 0.18g antimony glycols and obtains
To esterification products in, insulated and stirred 2h, mixing speed be 160 revs/min, 285 DEG C are warming up to afterwards and is vacuumized, reaction carry out
To system no longer heat release, water cooling pelletizing obtains graphene/PET nano composite materials.
Through above step, graphene/PET nano composite materials are obtained, specific performance is as shown in table 1.
Embodiment 6：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains graphene oxide microballoon, atomization temperature
Spend for 130 DEG C, the size of graphene oxide sheet is 10~15 microns, and carbon-to-oxygen ratio is 2.5；
(2) 1000g terephthalic acid (TPA)s, 530g ethylene glycol, 0.2g sodium acetates are sufficiently mixed stirring, carried out at 250 DEG C
Esterification is produced to anhydrous；
(3) the spherical graphene oxide of 58.5g pleats for obtaining step (1), adds step (2) with 0.18g antimony glycols and obtains
To esterification products in, insulated and stirred 2h, mixing speed be 160 revs/min, 285 DEG C are warming up to afterwards and is vacuumized, reaction carry out
To system no longer heat release, water cooling pelletizing obtains graphene/PET nano composite materials.
Through above step, graphene/PET nano composite materials are obtained, specific performance is as shown in table 1.
Comparative example 1：
PET is prepared according to the method for embodiment 1, unlike, without the spherical graphene oxide of pleat in preparation process.Property
Can be as shown in table 1.
Comparative example 2：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains graphene oxide microballoon, atomization temperature
Spend for 130 DEG C, the size of graphene oxide sheet is 0.3~0.7 micron, and carbon-to-oxygen ratio is 2.5；
(2) 1000g terephthalic acid (TPA)s, 530g ethylene glycol, 0.2g sodium acetates are sufficiently mixed stirring, carried out at 250 DEG C
Esterification is produced to anhydrous；
(3) the spherical graphene oxide of 1.17g pleats for obtaining step (1), adds step (2) with 0.18g antimony glycols and obtains
To esterification products in, insulated and stirred 2h, mixing speed be 160 revs/min, 285 DEG C are warming up to afterwards and is vacuumized, reaction carry out
To system no longer heat release, water cooling pelletizing obtains graphene/PET nano composite materials.
Through above step, graphene/PET nano composite materials are obtained, specific performance is as shown in table 1.
Comparative example 3：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains graphene oxide microballoon, atomization temperature
Spend for 130 DEG C, the size of graphene oxide sheet is 70~80 microns, and carbon-to-oxygen ratio is 2.5；
(2) 1000g terephthalic acid (TPA)s, 530g ethylene glycol, 0.2g sodium acetates are sufficiently mixed stirring, carried out at 250 DEG C
Esterification is produced to anhydrous；
(3) the spherical graphene oxide of 1.17g pleats for obtaining step (1), adds step (2) with 0.18g antimony glycols and obtains
To esterification products in, insulated and stirred 2h, mixing speed be 160 revs/min, 285 DEG C are warming up to afterwards and is vacuumized, reaction carry out
To system no longer heat release, water cooling pelletizing obtains graphene/PET nano composite materials.
Through above step, graphene/PET nano composite materials are obtained, specific performance is as shown in table 1.
Comparative example 4：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains graphene oxide microballoon, atomization temperature
Spend for 220 DEG C, the size of graphene oxide sheet is 10~15 microns, and carbon-to-oxygen ratio is 10；
(2) 1000g terephthalic acid (TPA)s, 530g ethylene glycol, 0.2g sodium acetates are sufficiently mixed stirring, carried out at 250 DEG C
Esterification is produced to anhydrous；
(3) the 1.17 spherical graphene oxides of parts by weight pleat for obtaining step (1), are added with 0.18 parts by weight antimony glycol
In the esterification products that step (2) is obtained, insulated and stirred 2h, mixing speed is 160 revs/min, and 285 DEG C are warming up to afterwards and takes out true
Sky, reaction is carried out to system no longer heat release, and water cooling pelletizing obtains graphene/PET nano composite materials.
Through above step, graphene/PET nano composite materials are obtained, specific performance is as shown in table 1.
Comparative example 5：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains graphene oxide microballoon, atomization temperature
Spend for 130 DEG C, the size of graphene oxide sheet is 10~15 microns, and carbon-to-oxygen ratio is 2.5；
(2) 1000g terephthalic acid (TPA)s, 530g ethylene glycol, 0.2g sodium acetates are sufficiently mixed stirring, carried out at 250 DEG C
Esterification is produced to anhydrous；
(3) the spherical graphene oxide of 93.6g pleats for obtaining step (1), adds step (2) with 0.18g antimony glycols and obtains
To esterification products in, insulated and stirred 2h, mixing speed be 160 revs/min, 285 DEG C are warming up to afterwards and is vacuumized, reaction carry out
To system no longer heat release, water cooling pelletizing obtains graphene/PET nano composite materials.
Through above step, graphene/PET nano composite materials are obtained, specific performance is as shown in table 1.
The embodiment design parameter of table 1 and property
Comparative example 1, comparative example 2, embodiment 1, embodiment 2, embodiment 3 and comparative example 3 are analyzed it can be found that keeping oxygen
In the case that graphite alkene carbon-to-oxygen ratio and addition are constant, suitable graphene oxide size range is selected to can obtain best performance
Composite.The graphene oxide of comparative example 2 it is undersized, itself cannot function as effective reinforcing material, and comparative example 3
Graphene oxide it is oversized, add polymerization system in after can not effectively expand into sheet graphene oxide, can only conduct
Pleat spherical filling body strengthens composite, and tensile strength and modulus incrementss are few, and elongation at break slightly has reduction.And
In 1~50 micron of size range, as size increases, graphene oxide can more efficiently play humidification.
Comparative example 1, embodiment 2, embodiment 4, comparative example 4 are analyzed it can be found that carbon-to-oxygen ratio increase, the performance of composite
Better, this is due to that carbon-to-oxygen ratio rises, and the defect of graphene is few, and the performance of itself is more excellent, so that the performance of composite is more
It is good.But carbon-to-oxygen ratio can not be too high, otherwise the adhesion between graphene oxide sheet is too strong, does not deploy during polymerization, it is impossible to effectively increase
By force, or even it is greatly reduced elongation at break (comparative example 4).
Comparative example 1, embodiment 2, embodiment 5, embodiment 6, comparative example 5 are analyzed it can be found that the addition of graphene oxide
Amount increase, the mechanical property of material gets a promotion, and electrical conductivity is substantially improved in addition.Add after excessive graphene oxide, although electricity
Conductance can further improve, and material mechanical performance declines, and this is due to that excessive graphene is stacked, and reduces enhancing effect
(comparative example 5).
Embodiment 7：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains graphene oxide microballoon, atomization temperature
Spend for 200 DEG C, the size of graphene oxide sheet is 40-50 microns, and carbon-to-oxygen ratio is 5；
(2) 1000g terephthalic acid (TPA)s, 530g ethylene glycol, 0.2g sodium acetates are sufficiently mixed stirring, carried out at 250 DEG C
Esterification is produced to anhydrous；
(3) the spherical graphene oxide of 58.5g pleats for obtaining step (1), adds step (2) with 0.18g antimony glycols and obtains
To esterification products in, insulated and stirred 3h, mixing speed be 140 revs/min, 285 DEG C are warming up to afterwards and is vacuumized, reaction carry out
To system no longer heat release, water cooling pelletizing obtains graphene/PET nano composite materials.After tested, graphene/PET nanometers is obtained again
Condensation material has good mechanical property and electrical property.
Embodiment 8：
(1) single-layer graphene oxide dispersion liquid is dried by atomization drying method, obtains graphene oxide microballoon, atomization temperature
Spend for 200 DEG C, the size of graphene oxide sheet is 40-50 microns, and carbon-to-oxygen ratio is 5；
(2) 1000g terephthalic acid (TPA)s, 530g ethylene glycol, 0.2g sodium acetates are sufficiently mixed stirring, carried out at 250 DEG C
Esterification is produced to anhydrous；
(3) the spherical graphene oxide of 0.117g pleats for obtaining step (1), adds step (2) with 0.18g antimony glycols and obtains
To esterification products in, insulated and stirred 1h, mixing speed be 200 revs/min, 285 DEG C are warming up to afterwards and is vacuumized, reaction carry out
To system no longer heat release, water cooling pelletizing obtains graphene/PET nano composite materials.After tested, graphene/PET nanometers is obtained again
Condensation material has good mechanical property and electrical property.
Claims (7)
1. a kind of graphene/PET nano composite materials, it is characterised in that be made up of single-layer graphene film and PET, the graphite
Alkene piece surface is connected with PET molecules by covalent bond.
2. the preparation method of a kind of graphene/PET nano composite materials, it is characterised in that prepared and carried out by following steps：
(1) size is dried for 1~50 micron of single-layer graphene oxide dispersion liquid by atomization drying method, obtains the spherical oxygen of pleat
Graphite alkene, its carbon-to-oxygen ratio is 2.5~5；
(2) 100 parts by weight terephthalic acid (TPA)s, 48~67 parts by weight ethylene glycol, 0.02g sodium acetates are sufficiently mixed stirring, 250
Esterification is carried out at DEG C；
(3) 0.0117~5.85 spherical graphene oxide of parts by weight pleat for obtaining step (1), with 0.018 part by weight of catalyst
Add in the esterification products that step (2) is obtained, 1~3h of insulated and stirred is warming up to 285 DEG C and vacuumized afterwards, reaction is carried out extremely
System no longer heat release, water cooling pelletizing obtains graphene/PET nano composite materials.
3. method according to claim 2, it is characterised in that the atomization drying temperature of the step (1) is 130~200
℃。
4. method according to claim 2, it is characterised in that in the step (3) mixing speed be 140~200 turns/
Point.
5. method according to claim 2, it is characterised in that catalyst is antimony-based catalyst in the step (3), including
Oxide, inorganic salts and the organic compound of antimony.
6. method according to claim 2, it is characterised in that catalyst is Titanium series catalyst in the step (3), including
Titanyl compound, inorganic salts and organic compound.
7. method according to claim 2, it is characterised in that catalyst is germanium series catalysts in the step (3), including
Oxide, inorganic salts and the organic compound of germanium.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710494501.3A CN107325268B (en) | 2017-06-26 | 2017-06-26 | graphene/PET (polyethylene terephthalate) nano composite material and preparation method thereof |
| US16/626,546 US11149129B2 (en) | 2017-06-26 | 2018-02-26 | Graphene composite material and preparation method thereof |
| PCT/CN2018/077169 WO2019000985A1 (en) | 2017-06-26 | 2018-02-26 | Graphene composite material and preparation method therefor |
| BR112019027930-0A BR112019027930B1 (en) | 2017-06-26 | 2018-02-26 | METHOD FOR PREPARING A GRAPHENOPOLYESTER NANOCOMPOSITE MATERIAL |
| KR1020207002385A KR102284847B1 (en) | 2017-06-26 | 2018-02-26 | Graphene composite material and its manufacturing method |
| EP18822649.2A EP3626758B1 (en) | 2017-06-26 | 2018-02-26 | Graphene composite material and preparation method therefor |
| JP2019571324A JP6963040B2 (en) | 2017-06-26 | 2018-02-26 | Method for manufacturing graphene composite material |
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