CN108794999A - A kind of preparation method of graphene terylene composite material master batch and fiber - Google Patents
A kind of preparation method of graphene terylene composite material master batch and fiber Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 177
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 143
- 239000005020 polyethylene terephthalate Substances 0.000 title claims abstract description 73
- 229920004933 Terylene® Polymers 0.000 title claims abstract description 69
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 239000000835 fiber Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 238000000498 ball milling Methods 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 31
- 229920000728 polyester Polymers 0.000 claims abstract description 31
- 238000001914 filtration Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 16
- 238000007873 sieving Methods 0.000 claims abstract description 15
- 239000002270 dispersing agent Substances 0.000 claims abstract description 14
- 239000004014 plasticizer Substances 0.000 claims abstract description 8
- 239000007822 coupling agent Substances 0.000 claims abstract description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 44
- 229910002804 graphite Inorganic materials 0.000 claims description 38
- 239000010439 graphite Substances 0.000 claims description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 150000001448 anilines Chemical class 0.000 claims description 30
- 238000000227 grinding Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 28
- 230000032050 esterification Effects 0.000 claims description 25
- 238000005886 esterification reaction Methods 0.000 claims description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- 238000005516 engineering process Methods 0.000 claims description 19
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 15
- 238000002074 melt spinning Methods 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 10
- 229920002521 macromolecule Polymers 0.000 claims description 9
- 235000011187 glycerol Nutrition 0.000 claims description 6
- 229920002994 synthetic fiber Polymers 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 239000002480 mineral oil Substances 0.000 claims description 4
- 235000010446 mineral oil Nutrition 0.000 claims description 4
- 239000013081 microcrystal Substances 0.000 claims description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 3
- 235000013772 propylene glycol Nutrition 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims 1
- 238000006068 polycondensation reaction Methods 0.000 description 14
- 150000001336 alkenes Chemical class 0.000 description 11
- 238000009833 condensation Methods 0.000 description 11
- 230000005494 condensation Effects 0.000 description 11
- 238000010025 steaming Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000004575 stone Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- -1 polyethylene terephthalate Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 229920004934 Dacron® Polymers 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000000686 essence Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
- C08J2491/06—Waxes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/12—Applications used for fibers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Artificial Filaments (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of preparation methods of graphene terylene composite material master batch, specifically comprise the following steps：Step 1,8-12 parts of graphene oxide, 0.2-1 parts of dispersant, 5-8 parts of coupling agent, 3-6 parts of plasticizer are weighed；Step 2, each component that the step 1 weighs is uniformly mixed, press filtration is carried out after heating, obtain graphene mixture；Step 3, the graphene mixture of the step 2 and terylene particle are obtained into graphene terylene composite material master batch by ball milling mixing after sieving；The invention also discloses a kind of preparation methods of graphene polyester fiber；The preparation method of graphene polyester fiber prepared by the present invention has good fracture strength and electric conductivity.
Description
Technical field
The invention belongs to grapheme material technical fields, and in particular to a kind of graphene terylene composite material master batch and fiber
Preparation method.
Background technology
Graphene is the two-dimensional sheet nano material being made of single layer of carbon atom, is carbon atom with sp2What hydridization was bonded to,
Flat film with hexagonal honeycomb lattice structure has superior light, electrical, thermal and mechanical properties, causes numerous researchs
The interest of person shoots up as the research hotspot of material and theoretical research field, is only just achieved between several years and much rouse oneself people
The progress of the heart.Graphene is another star's carbon nanomaterial being born after carbon nanotube, it possesses the theoretical ratio of superelevation
It the features such as surface area, high intrinsic mobility, high Young's modulus and Theory Conductivity and high transparency and conductivity, is deposited in energy
Storage, transparent electrode etc. have great application potential；So far, graphene has become the representative of two-dimension nano materials
Promote the progress and innovation in the fields such as nanocomposite, sensor, the energy, catalysis, electronics and optical device.
Terylene is an important kind in synthetic fibers, is the trade name of China's polyester fiber, is with essence to benzene two
Formic acid or dimethyl terephthalate (DMT) and ethylene glycol are raw material through poly- at fine height prepared by esterification or transesterification and polycondensation reaction
Object --- polyethylene terephthalate (PET), through fiber made of spinning and post-processing.Terylene has many uses, largely
For manufacturing clothing fabric and industrial product.
However, the surface smoothness of existing graphene polyester fiber, electric conductivity and fibrous fracture strength are all poor,
Influence the function of later product.
Invention content
The object of the present invention is to provide a kind of preparation methods of graphene terylene composite material master batch, solve the prior art
The poor problem of middle graphene dacron master grain character consistency.
It is a further object to provide a kind of preparation methods of graphene polyester fiber.
The technical solution adopted in the present invention is:
A kind of preparation method of graphene terylene composite material master batch, specifically implements in accordance with the following steps：
Step 1,8-12 parts of graphene oxide, 0.2-1 parts of dispersant, 5-8 parts of coupling agent, 3-6 parts of plasticizer are weighed；
Step 2, each component that the step 1 weighs is uniformly mixed, press filtration is carried out after heating, obtain graphene mixing
Object；
Step 3, the graphene mixture of the step 2 and terylene particle are obtained into graphite by ball milling mixing after sieving
Alkene terylene composite material master batch.
The features of the present invention also characterized in that
The dispersant includes oligomer of phenylamine or oligomer of phenylamine derivative, the oligomer of phenylamine or oligomer of phenylamine
Derivative is electroactive macromolecule.
It is combined by pi-pi bond between the oligomer of phenylamine or oligomer of phenylamine derivative and graphene oxide.
The coupling agent is one kind in KH-550, KH-560, KH-570, A-171, KH-792 or KH-602.
The plasticizer is one kind in ethylene glycol, propylene glycol, glycerine, polyvinyl alcohol or mineral oil.
It is heated in a nitrogen environment in the step 2, the temperature of heating is 30-60 DEG C, and the time of heating is
30min-60min。
Ball milling is carried out using mechanical ball grinding machine in the step 3, ball milling pearl, the ball are provided in the mechanical ball grinding machine
Grind a diameter of 0.3-4mm of pearl.
A kind of preparation method of graphene polyester fiber, simultaneously with graphite by above-mentioned graphene terylene composite material master batch
It is added in high speed mixer, carries out esterification technique, polycondensating process and melt-spinning technology after mixing and washed to get graphene
Synthetic fibre fiber.
The features of the present invention also characterized in that
The mass ratio of the graphene terylene composite material master batch and graphite is 10：0.5-2.5.
The graphite is one or more in crystalline flake graphite, micro crystal graphite or expanded graphite.
Compared with prior art, dispersant of the invention includes that oligomer of phenylamine or oligomer of phenylamine derivative, aniline are low
Polymers or oligomer of phenylamine derivative are electroactive macromolecule, oligomer of phenylamine or oligomer of phenylamine derivative and graphene oxide
Between combined by pi-pi bond, to make the oligomer of phenylamine or oligomer of phenylamine derivative be bonded together with graphene, and
Oligomer of phenylamine or oligomer of phenylamine derivative are electroactive macromolecule, and adjacent two oligomer of phenylamine or oligomer of phenylamine spread out
Since charge is identical and mutually exclusive between biomolecule, so two adjacent oligomer of phenylamine or oligomer of phenylamine derivative
It is not easy to be overlapped between molecule, the graphene being bonded thereon also avoids agglomeration therewith evenly dispersed.Therefore, of the invention
Dispersant improves the dispersibility and chemical stability of graphene so that graphene is readily dispersed in various media or covers
In base material surface layer, the application of graphene is improved.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
The embodiment of the present invention provides a kind of preparation method of graphene terylene composite material master batch, specifically in accordance with the following steps
Implement：
Step 1,8-12 parts of graphene oxide, 0.2-1 parts of dispersant, 5-8 parts of coupling agent, 3-6 parts of plasticizer are weighed；
Wherein, dispersant includes oligomer of phenylamine or oligomer of phenylamine derivative, and oligomer of phenylamine or oligomer of phenylamine spread out
Biology is electroactive macromolecule, is combined by pi-pi bond between oligomer of phenylamine or oligomer of phenylamine derivative and graphene oxide；
Coupling agent is one kind in KH-550, KH-560, KH-570, A-171, KH-792 or KH-602；
Plasticizer is one kind in ethylene glycol, propylene glycol, glycerine, polyvinyl alcohol or mineral oil；
Step 2, each component that step 1 weighs is uniformly mixed, it is laggard carries out heating 30min-60min in a nitrogen environment
Row press filtration obtains graphene mixture, wherein the temperature of heating is 30-60 DEG C；
Step 3, the graphene mixture of step 2 is mixed with terylene particle by mechanical ball grinding machine, stone is obtained after sieving
Black alkene terylene composite material master batch, wherein ball milling pearl, a diameter of 0.3-4mm of ball milling pearl are provided in mechanical ball grinding machine.
The embodiment of the present invention also provides a kind of preparation method of graphene polyester fiber, and above-mentioned graphene terylene is compound
Material master batch is added in high speed mixer simultaneously with graphite, carries out esterification technique, polycondensating process and melting after mixing and spins
Silk technique is to get graphene polyester fiber；
Wherein, the mass ratio of graphene terylene composite material master batch and graphite is 10：0.5-2.5；Graphite be crystalline flake graphite,
It is one or more in micro crystal graphite or expanded graphite；
The detailed process of melt-spinning technology is：1g polymer beads are weighed every time, are added in spinning equipment, are warming up to
It 270 DEG C, after being completely melt, is squeezed out by applying pressure, under external pulled out condition, melt stream thins down to silk.
Then allow filament by hot-stretch device, the temperature of cartridge heater is set as 110 DEG C, and under the action of draw roll, fiber is stretched 4
Times, it is finally wound in take-up roll, winding speed is set as 150r/min.A kind of modified dacron material of ratio is often finished, all
Spinning equipment is cleaned up, prevents from polluting.
The dispersant of the present invention includes oligomer of phenylamine or oligomer of phenylamine derivative, oligomer of phenylamine or oligomer of phenylamine
Derivative is electroactive macromolecule, passes through pi-pi bond knot between oligomer of phenylamine or oligomer of phenylamine derivative and graphene oxide
It closes, to make the oligomer of phenylamine or oligomer of phenylamine derivative be bonded together with graphene, and oligomer of phenylamine or benzene
Amine oligomer derivative be electroactive macromolecule, adjacent two between oligomer of phenylamine or oligomer of phenylamine derivative molecular by
It is identical and mutually exclusive in charge, so being not easy weight between two adjacent oligomer of phenylamine or oligomer of phenylamine derivative molecular
Folded, the graphene being bonded thereon also avoids agglomeration therewith evenly dispersed.Therefore, dispersant of the invention improves stone
The dispersibility and chemical stability of black alkene so that graphene is readily dispersed in various media or is covered in base material surface layer, carries
The high application of graphene.
Embodiment 1：
The embodiment of the present invention 1 provides a kind of preparation method of graphene polyester fiber, specifically implements in accordance with the following steps：
First, 8 parts of graphene oxide, 0.2 part of oligomer of phenylamine are weighed, KH-5505 parts, 3 parts of ethylene glycol is each by what is weighed
Component is uniformly mixed, and is carried out press filtration after carrying out heating 30min in a nitrogen environment, is obtained graphene mixture, wherein heating
Temperature is 30 DEG C；Then, graphene mixture is mixed with terylene particle by mechanical ball grinding machine, graphene is obtained after sieving and is washed
Synthetic fibre composite material master batch, wherein ball milling pearl, a diameter of 0.3mm of ball milling pearl are provided in mechanical ball grinding machine；Finally, by graphite
Alkene terylene composite material master batch is 10 according to mass ratio with crystalline flake graphite:0.5 is added in high speed mixer simultaneously, after mixing
Esterification technique is carried out at 260 DEG C, waits for that the amount of steaming of water reaches the 90% of theoretical value, pressure release to normal pressure, esterification terminates to contract
Polymerizing technology, condensation temperature are 260 DEG C, and the polycondensation time is 180min, and it is fine to get graphene terylene finally to carry out melt-spinning technology
Dimension.
Embodiment 2：
The embodiment of the present invention 2 provides a kind of preparation method of graphene polyester fiber, specifically implements in accordance with the following steps：
First, 9 parts of graphene oxide, 0.5 part of oligomer of phenylamine are weighed, KH-560 accounts for 6 parts, 4 parts of propylene glycol, by what is weighed
Each component is uniformly mixed, and is carried out press filtration after carrying out heating 40min in a nitrogen environment, is obtained graphene mixture, wherein heating
Temperature be 40 DEG C；Then, graphene mixture is mixed with terylene particle by mechanical ball grinding machine, graphene is obtained after sieving
Terylene composite material master batch, wherein ball milling pearl, a diameter of 1mm of ball milling pearl are provided in mechanical ball grinding machine；Finally, by graphite
Alkene terylene composite material master batch is 10 according to mass ratio with crystalline flake graphite:1 is added in high speed mixer simultaneously, exists after mixing
Esterification technique is carried out at 280 DEG C, waits for that the amount of steaming of water reaches the 95% of theoretical value, pressure release to normal pressure, esterification terminates to carry out polycondensation
Technique, condensation temperature are 290 DEG C, and the polycondensation time is 170min, and it is fine to get graphene terylene finally to carry out melt-spinning technology
Dimension.
Embodiment 3：
The embodiment of the present invention 3 provides a kind of preparation method of graphene polyester fiber, specifically implements in accordance with the following steps：
First, 12 parts of graphene oxide, 1 part of oligomer of phenylamine derivative are weighed, KH-602 accounts for 7 parts, and 6 parts of glycerine will
The each component weighed is uniformly mixed, and is carried out press filtration after carrying out heating 50min in a nitrogen environment, is obtained graphene mixture,
In, the temperature of heating is 50 DEG C；Then, graphene mixture is mixed with terylene particle by mechanical ball grinding machine, after sieving
To graphene terylene composite material master batch, wherein be provided with ball milling pearl, a diameter of 2mm of ball milling pearl in mechanical ball grinding machine；Most
Afterwards, it is 10 according to mass ratio by graphene terylene composite material master batch and crystalline flake graphite:2 are added in high speed mixer simultaneously, mix
Esterification technique is carried out at 250 DEG C after closing uniformly, waits for that the amount of steaming of water reaches the 93% of theoretical value, pressure release to normal pressure, esterification knot
Shu Jinhang polycondensating process, condensation temperature are 250 DEG C, and the polycondensation time is 170min, finally carry out melt-spinning technology to get graphite
Alkene polyester fiber.
Embodiment 4：
The embodiment of the present invention 4 provides a kind of preparation method of graphene polyester fiber, specifically implements in accordance with the following steps：
First, 11 parts of graphene oxide, 0.8 part of oligomer of phenylamine are weighed, A-171 accounts for 7 parts, and 5 parts of polyvinyl alcohol will weigh
Each component be uniformly mixed, carry out press filtration after carrying out heating 36min in a nitrogen environment, obtain graphene mixture, wherein add
The temperature of heat is 40 DEG C；Then, graphene mixture is mixed with terylene particle by mechanical ball grinding machine, graphite is obtained after sieving
Alkene terylene composite material master batch, wherein ball milling pearl, a diameter of 4mm of ball milling pearl are provided in mechanical ball grinding machine；Finally, by stone
Black alkene terylene composite material master batch is 10 according to mass ratio with crystalline flake graphite:1.5 are added in high speed mixer simultaneously, are uniformly mixed
Esterification technique is carried out at 273 DEG C afterwards, waits for that the amount of steaming of water reaches the 92% of theoretical value, pressure release to normal pressure, esterification terminates to carry out
Polycondensating process, condensation temperature are 268 DEG C, and the polycondensation time is 185min, finally carry out melt-spinning technology to get graphene terylene
Fiber.
Embodiment 5：
The embodiment of the present invention 5 provides a kind of preparation method of graphene polyester fiber, specifically implements in accordance with the following steps：
First, 10.5 parts of graphene oxide, 0.9 part of oligomer of phenylamine derivative are weighed, KH-792 accounts for 8 parts, mineral oil 5
Part, each component weighed is uniformly mixed, press filtration is carried out after carrying out heating 60min in a nitrogen environment, obtains graphene mixing
Object, wherein the temperature of heating is 60 DEG C；Then, graphene mixture is mixed with terylene particle by mechanical ball grinding machine, is sieved
After obtain graphene terylene composite material master batch, wherein ball milling pearl, a diameter of 3mm of ball milling pearl are provided in mechanical ball grinding machine；
Finally, it is 10 according to mass ratio by graphene terylene composite material master batch and crystalline flake graphite:2.5 are added high speed mixer simultaneously
In, esterification technique is carried out at 278 DEG C after mixing, waits for that the amount of steaming of water reaches the 86% of theoretical value, pressure release to normal pressure, ester
Change terminate carry out polycondensating process, condensation temperature be 282 DEG C, the polycondensation time be 177min, finally carry out melt-spinning technology to get
Graphene polyester fiber.
Embodiment 6：
The embodiment of the present invention 6 provides a kind of preparation method of graphene polyester fiber, specifically implements in accordance with the following steps：
First, 12 parts of graphene oxide, 0.6 part of oligomer of phenylamine are weighed, KH-560 accounts for 6 parts, and 4 parts of polyvinyl alcohol will claim
The each component taken is uniformly mixed, and is carried out press filtration after carrying out heating 50min in a nitrogen environment, is obtained graphene mixture, wherein
The temperature of heating is 50 DEG C；Then, graphene mixture is mixed with terylene particle by mechanical ball grinding machine, stone is obtained after sieving
Black alkene terylene composite material master batch, wherein ball milling pearl, a diameter of 2.2mm of ball milling pearl are provided in mechanical ball grinding machine；Finally,
According to mass ratio it is 10 by graphene terylene composite material master batch and crystalline flake graphite:2.6 are added in high speed mixer simultaneously, mixing
Esterification technique is carried out at 264 DEG C after uniformly, waits for that the amount of steaming of water reaches the 90% of theoretical value, pressure release to normal pressure, esterification terminates
Polycondensating process is carried out, condensation temperature is 266 DEG C, and the polycondensation time is 182min, finally carries out melt-spinning technology to get graphene
Polyester fiber.
Embodiment 7：
The embodiment of the present invention 7 provides a kind of preparation method of graphene polyester fiber, specifically implements in accordance with the following steps：
First, 9 parts of graphene oxide, 0.9 part of oligomer of phenylamine are weighed, KH-570 accounts for 5 parts, 4 parts of ethylene glycol, by what is weighed
Each component is uniformly mixed, and is carried out press filtration after carrying out heating 40min in a nitrogen environment, is obtained graphene mixture, wherein heating
Temperature be 50 DEG C；Then, graphene mixture is mixed with terylene particle by mechanical ball grinding machine, graphene is obtained after sieving
Terylene composite material master batch, wherein ball milling pearl, a diameter of 0.8mm of ball milling pearl are provided in mechanical ball grinding machine；Finally, by stone
Black alkene terylene composite material master batch is 10 according to mass ratio with crystalline flake graphite:2.6 are added in high speed mixer simultaneously, are uniformly mixed
Esterification technique is carried out at 269 DEG C afterwards, waits for that the amount of steaming of water reaches the 90% of theoretical value, pressure release to normal pressure, esterification terminates to carry out
Polycondensating process, condensation temperature are 263 DEG C, and the polycondensation time is 181min, finally carry out melt-spinning technology to get graphene terylene
Fiber.
Embodiment 8：
The embodiment of the present invention 8 provides a kind of preparation method of graphene polyester fiber, specifically implements in accordance with the following steps：
First, 10 parts of graphene oxide, 1 part of oligomer of phenylamine derivative are weighed, KH-550 accounts for 8 parts, and 6 parts of ethylene glycol will
The each component weighed is uniformly mixed, and is carried out press filtration after carrying out heating 40min in a nitrogen environment, is obtained graphene mixture,
In, the temperature of heating is 40 DEG C；Then, graphene mixture is mixed with terylene particle by mechanical ball grinding machine, after sieving
To graphene terylene composite material master batch, wherein be provided with ball milling pearl, a diameter of 3mm of ball milling pearl in mechanical ball grinding machine；Most
Afterwards, it is 10 according to mass ratio by graphene terylene composite material master batch and crystalline flake graphite:1.6 are added in high speed mixer simultaneously,
Esterification technique is carried out at 275 DEG C after mixing, waits for that the amount of steaming of water reaches the 95% of theoretical value, pressure release to normal pressure, esterification
Terminate to carry out polycondensating process, condensation temperature is 269 DEG C, and the polycondensation time is 183min, finally carries out melt-spinning technology to get stone
Black alkene polyester fiber.
Embodiment 9：
The embodiment of the present invention 9 provides a kind of preparation method of graphene polyester fiber, specifically implements in accordance with the following steps：
First, 9.5 parts of graphene oxide, 0.6 part of oligomer of phenylamine are weighed, A-171 accounts for 7 parts, and 5 parts of glycerine will weigh
Each component be uniformly mixed, carry out press filtration after carrying out heating 45min in a nitrogen environment, obtain graphene mixture, wherein add
The temperature of heat is 55 DEG C；Then, graphene mixture is mixed with terylene particle by mechanical ball grinding machine, graphite is obtained after sieving
Alkene terylene composite material master batch, wherein ball milling pearl, a diameter of 2mm of ball milling pearl are provided in mechanical ball grinding machine；Finally, by stone
Black alkene terylene composite material master batch is 10 according to mass ratio with crystalline flake graphite:1 is added in high speed mixer simultaneously, after mixing
Esterification technique is carried out at 275 DEG C, waits for that the amount of steaming of water reaches the 86% of theoretical value, pressure release to normal pressure, esterification terminates to contract
Polymerizing technology, condensation temperature are 270 DEG C, and the polycondensation time is 170min, and it is fine to get graphene terylene finally to carry out melt-spinning technology
Dimension.
Comparative example 1：
The embodiment of the present invention 1 provides a kind of preparation method of graphene polyester fiber, specifically implements in accordance with the following steps：
First, 8 parts of graphene oxide, 0.2 part of calgon are weighed, KH-5505 parts, 3 parts of ethylene glycol is each by what is weighed
Component is uniformly mixed, and is carried out press filtration after carrying out heating 30min in a nitrogen environment, is obtained graphene mixture, wherein heating
Temperature is 30 DEG C；Then, graphene mixture is mixed with terylene particle by mechanical ball grinding machine, graphene is obtained after sieving and is washed
Synthetic fibre composite material master batch, wherein ball milling pearl, a diameter of 0.3mm of ball milling pearl are provided in mechanical ball grinding machine；Finally, by graphite
Alkene terylene composite material master batch is 10 according to mass ratio with crystalline flake graphite:0.5 is added in high speed mixer simultaneously, after mixing
Esterification technique is carried out at 260 DEG C, waits for that the amount of steaming of water reaches the 90% of theoretical value, pressure release to normal pressure, esterification terminates to contract
Polymerizing technology, condensation temperature are 260 DEG C, and the polycondensation time is 180min, and it is fine to get graphene terylene finally to carry out melt-spinning technology
Dimension.
Comparative example 2：
The embodiment of the present invention 2 provides a kind of preparation method of graphene polyester fiber, specifically implements in accordance with the following steps：
First, 9 parts of graphene oxide, 0.5 part of oligomer of phenylamine are weighed, KH-560 accounts for 6 parts, 8 parts of propylene glycol, by what is weighed
Each component is uniformly mixed, and is carried out press filtration after carrying out heating 40min in a nitrogen environment, is obtained graphene mixture, wherein heating
Temperature be 40 DEG C；Then, graphene mixture is mixed with terylene particle by mechanical ball grinding machine, graphene is obtained after sieving
Terylene composite material master batch, wherein ball milling pearl, a diameter of 1mm of ball milling pearl are provided in mechanical ball grinding machine；Finally, by graphite
Alkene terylene composite material master batch is 10 according to mass ratio with crystalline flake graphite:1 is added in high speed mixer simultaneously, exists after mixing
Esterification technique is carried out at 280 DEG C, waits for that the amount of steaming of water reaches the 95% of theoretical value, pressure release to normal pressure, esterification terminates to carry out polycondensation
Technique, condensation temperature are 290 DEG C, and the polycondensation time is 170min, and it is fine to get graphene terylene finally to carry out melt-spinning technology
Dimension.
Comparative example 3：
The embodiment of the present invention 3 provides a kind of preparation method of graphene polyester fiber, specifically implements in accordance with the following steps：
First, 12 parts of graphene oxide, 1 part of oligomer of phenylamine derivative are weighed, KH-602 accounts for 7 parts, and 6 parts of glycerine will
The each component weighed is uniformly mixed, and is carried out press filtration after carrying out heating 50min in a nitrogen environment, is obtained graphene mixture,
In, the temperature of heating is 50 DEG C；Then, graphene mixture is mixed with terylene particle by mechanical ball grinding machine, after sieving
To graphene terylene composite material master batch, wherein be provided with ball milling pearl, a diameter of 2mm of ball milling pearl in mechanical ball grinding machine；Most
Afterwards, it is 10 according to mass ratio by graphene terylene composite material master batch and crystalline flake graphite:2 are added in high speed mixer simultaneously, mix
Melt-spinning technology is carried out to get graphene polyester fiber at 250 DEG C after closing uniformly.
To above-described embodiment 1-9, graphene polyester fiber prepared by comparative example 1-3 carry out fracture strength, fault number and
The test of electric conductivity, test result such as table 1：
Table 1
As it can be seen from table 1 graphene polyester fiber prepared by embodiment 1-9 has preferable fracture strength and electric conductivity
Can, fault number is less；But after changing the type of dispersant, the accounting of plasticizer and the technique of fiber be made, fracture strength
Can all it decline with electric conductivity, and fault number increases simultaneously.
The dispersant of the present invention includes oligomer of phenylamine or oligomer of phenylamine derivative, oligomer of phenylamine or oligomer of phenylamine
Derivative is electroactive macromolecule, passes through pi-pi bond knot between oligomer of phenylamine or oligomer of phenylamine derivative and graphene oxide
It closes, to make the oligomer of phenylamine or oligomer of phenylamine derivative be bonded together with graphene, and oligomer of phenylamine or benzene
Amine oligomer derivative be electroactive macromolecule, adjacent two between oligomer of phenylamine or oligomer of phenylamine derivative molecular by
It is identical and mutually exclusive in charge, so being not easy weight between two adjacent oligomer of phenylamine or oligomer of phenylamine derivative molecular
Folded, the graphene being bonded thereon also avoids agglomeration therewith evenly dispersed.Therefore, dispersant of the invention improves stone
The dispersibility and chemical stability of black alkene so that graphene is readily dispersed in various media or is covered in base material surface layer, carries
The high application of graphene.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, although with reference to aforementioned reality
Applying example, invention is explained in detail, for those skilled in the art, still can be to aforementioned each implementation
Technical solution recorded in example is modified or equivalent replacement of some of the technical features.All essences in the present invention
With within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention god.
Claims (10)
1. a kind of preparation method of graphene terylene composite material master batch, which is characterized in that specifically implement in accordance with the following steps：
Step 1,8-12 parts of graphene oxide, 0.2-1 parts of dispersant, 5-8 parts of coupling agent, 3-6 parts of plasticizer are weighed；
Step 2, each component that the step 1 weighs is uniformly mixed, press filtration is carried out after heating, obtain graphene mixture；
Step 3, the graphene mixture of the step 2 and terylene particle graphene is obtained by ball milling mixing, after sieving to wash
Synthetic fibre composite material master batch.
2. a kind of preparation method of graphene terylene composite material master batch according to claim 1, which is characterized in that described
Dispersant includes oligomer of phenylamine or oligomer of phenylamine derivative, and the oligomer of phenylamine or oligomer of phenylamine derivative are that electricity is living
Property macromolecule.
3. a kind of preparation method of graphene terylene composite material master batch according to claim 2, which is characterized in that described
It is combined by pi-pi bond between oligomer of phenylamine or oligomer of phenylamine derivative and graphene oxide.
4. a kind of preparation method of graphene terylene composite material master batch according to claim 3, which is characterized in that described
Coupling agent is one kind in KH-550, KH-560, KH-570, A-171, KH-792 or KH-602.
5. a kind of preparation method of graphene terylene composite material master batch according to claim 4, which is characterized in that described
Plasticizer is one kind in ethylene glycol, propylene glycol, glycerine, polyvinyl alcohol or mineral oil.
6. a kind of preparation method of graphene terylene composite material master batch according to claim 5, which is characterized in that described
It is heated in a nitrogen environment in step 2, the temperature of heating is 30-60 DEG C, and the time of heating is 30min-60min.
7. according to a kind of preparation method of graphene terylene composite material master batch of claim 1-6 any one of them, feature
It is, ball milling is carried out using mechanical ball grinding machine in the step 3, ball milling pearl, the ball milling are provided in the mechanical ball grinding machine
A diameter of 0.3-4mm of pearl.
8. a kind of preparation method of graphene polyester fiber, which is characterized in that by claim 1-7 any one of them graphenes
Terylene composite material master batch and graphite are added in high speed mixer simultaneously, carry out after mixing esterification technique, polycondensating process with
And melt-spinning technology is to get graphene polyester fiber.
9. a kind of preparation method of graphene polyester fiber according to claim 8, which is characterized in that the graphene is washed
The mass ratio of synthetic fibre composite material master batch and graphite is 10：0.5-2.5.
10. according to a kind of preparation method of graphene polyester fiber of claim 7-9 any one of them, which is characterized in that institute
It is one or more in crystalline flake graphite, micro crystal graphite or expanded graphite to state graphite.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110656502A (en) * | 2019-08-23 | 2020-01-07 | 唐雪金 | Preparation process of soft anti-static textile fabric |
| CN114150393A (en) * | 2021-12-09 | 2022-03-08 | 南通强生光电科技有限公司 | High-strength wear-resistant composite fiber for wires and cables and preparation method thereof |
| CN115651313A (en) * | 2022-11-03 | 2023-01-31 | 山东金利特新材料有限责任公司 | Preparation method of carbon composite material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110315934A1 (en) * | 2010-06-24 | 2011-12-29 | National Tsing Hua University | Method for fabrication of functionalized graphene reinforced composite conducting plate |
| CN105778572A (en) * | 2014-12-24 | 2016-07-20 | 中国科学院宁波材料技术与工程研究所 | Composite graphene powder and preparation method thereof |
| CN105778571A (en) * | 2014-12-24 | 2016-07-20 | 中国科学院宁波材料技术与工程研究所 | Graphene composite slurry and preparation method thereof |
| CN107447286A (en) * | 2017-08-21 | 2017-12-08 | 郑行良 | A kind of preparation method of graphene terylene composite master batch and fiber |
-
2018
- 2018-05-02 CN CN201810409020.2A patent/CN108794999A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110315934A1 (en) * | 2010-06-24 | 2011-12-29 | National Tsing Hua University | Method for fabrication of functionalized graphene reinforced composite conducting plate |
| CN105778572A (en) * | 2014-12-24 | 2016-07-20 | 中国科学院宁波材料技术与工程研究所 | Composite graphene powder and preparation method thereof |
| CN105778571A (en) * | 2014-12-24 | 2016-07-20 | 中国科学院宁波材料技术与工程研究所 | Graphene composite slurry and preparation method thereof |
| CN107447286A (en) * | 2017-08-21 | 2017-12-08 | 郑行良 | A kind of preparation method of graphene terylene composite master batch and fiber |
Non-Patent Citations (2)
| Title |
|---|
| 王新龙等: "《高分子科学与工程实验》", 31 December 2012, 东南大学出版社 * |
| 陈葵阳: "《纺织纤维与面料分析》", 30 April 2012, 东华大学出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110656502A (en) * | 2019-08-23 | 2020-01-07 | 唐雪金 | Preparation process of soft anti-static textile fabric |
| CN114150393A (en) * | 2021-12-09 | 2022-03-08 | 南通强生光电科技有限公司 | High-strength wear-resistant composite fiber for wires and cables and preparation method thereof |
| CN115651313A (en) * | 2022-11-03 | 2023-01-31 | 山东金利特新材料有限责任公司 | Preparation method of carbon composite material |
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