CN105442076B - A kind of preparation method of graphene quantum dot enhancing para-aramid fiber - Google Patents
A kind of preparation method of graphene quantum dot enhancing para-aramid fiber Download PDFInfo
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 178
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 169
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 168
- 239000000835 fiber Substances 0.000 title claims abstract description 60
- 229920003235 aromatic polyamide Polymers 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 230000002708 enhancing effect Effects 0.000 title claims abstract description 19
- 229920006231 aramid fiber Polymers 0.000 claims abstract description 83
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 53
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 52
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 52
- 239000011347 resin Substances 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 28
- 150000001336 alkenes Chemical class 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 153
- 239000000243 solution Substances 0.000 claims description 122
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 claims description 110
- 239000011259 mixed solution Substances 0.000 claims description 92
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 90
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 68
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 60
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 40
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims description 38
- 229910052757 nitrogen Inorganic materials 0.000 claims description 34
- 238000005406 washing Methods 0.000 claims description 32
- 238000009987 spinning Methods 0.000 claims description 28
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 26
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 24
- 238000013019 agitation Methods 0.000 claims description 24
- 230000001112 coagulating effect Effects 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000004804 winding Methods 0.000 claims description 24
- 235000019441 ethanol Nutrition 0.000 claims description 22
- 230000004048 modification Effects 0.000 claims description 15
- 238000012986 modification Methods 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 230000004224 protection Effects 0.000 claims description 13
- 238000004448 titration Methods 0.000 claims description 13
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 12
- 241000446313 Lamella Species 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 230000006837 decompression Effects 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 12
- 238000007711 solidification Methods 0.000 claims description 12
- 230000008023 solidification Effects 0.000 claims description 12
- FBUZNPORDKVYFD-UHFFFAOYSA-N 1-bromohex-1-ene Chemical class CCCCC=CBr FBUZNPORDKVYFD-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- -1 it is stirred Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 150000002171 ethylene diamines Chemical class 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 2
- NFYSVENHRGYWJB-UHFFFAOYSA-N 6-bromohept-1-ene Chemical compound CC(Br)CCCC=C NFYSVENHRGYWJB-UHFFFAOYSA-N 0.000 claims 1
- GNYDYUQVALBGGZ-UHFFFAOYSA-N 7-bromohept-1-ene Chemical compound BrCCCCCC=C GNYDYUQVALBGGZ-UHFFFAOYSA-N 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- QCCWVNLOJADEAV-UHFFFAOYSA-N n,n-dimethyl-1h-pyrrol-3-amine Chemical class CN(C)C=1C=CNC=1 QCCWVNLOJADEAV-UHFFFAOYSA-N 0.000 claims 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims 1
- 150000003462 sulfoxides Chemical class 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 4
- 238000004891 communication Methods 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 43
- 235000011121 sodium hydroxide Nutrition 0.000 description 20
- 229920002994 synthetic fiber Polymers 0.000 description 12
- 238000001914 filtration Methods 0.000 description 11
- XNCAEAZUROUZKT-UHFFFAOYSA-N 1-bromohept-1-ene Chemical compound CCCCCC=CBr XNCAEAZUROUZKT-UHFFFAOYSA-N 0.000 description 10
- 239000002585 base Substances 0.000 description 10
- 239000007795 chemical reaction product Substances 0.000 description 10
- 125000000524 functional group Chemical group 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 239000004575 stone Substances 0.000 description 10
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- WXQDFOGZIYLEGP-UHFFFAOYSA-N C(C(C)C)#N.C(C(C)C)#N.[N] Chemical compound C(C(C)C)#N.C(C(C)C)#N.[N] WXQDFOGZIYLEGP-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- 101710129069 Serine/threonine-protein phosphatase 5 Proteins 0.000 description 2
- 101710199542 Serine/threonine-protein phosphatase T Proteins 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000470 poly(p-phenylene terephthalate) polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RLSFPQIQLKDFPA-UHFFFAOYSA-N 1,1-dibromohept-1-ene Chemical compound CCCCCC=C(Br)Br RLSFPQIQLKDFPA-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000006772 olefination reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
Classifications
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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
- 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
- D01F6/90—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 polyamides
- D01F6/905—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 polyamides of aromatic polyamides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
-
- 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
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Inorganic Fibers (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses a kind of preparation method of graphene quantum dot enhancing para-aramid fiber, comprise the following steps：1) alkene grafting p-aramid fiber resin, 2) graphene quantum dot vinyl functionalization, 3) graphene quantum dot grafting p-aramid fiber, 4) graphene quantum dot grafting para-aramid fiber preparation.Graphene quantum dot is grafted on p-aramid fiber by the present invention, solve because p-aramid fiber itself wellability is poor, interface interaction is not strong and the problems such as graphene quantum dot is difficult to uniformly be distributed in para-aramid fiber between graphene quantum dot and p-aramid fiber, the graphene quantum dot of high strength and modulus is combined with each other with aramid fiber, the intensity and modulus of para-aramid fiber is greatly improved, and without being modified to existing para-aramid fiber process equipment, obtained graphene quantum dot enhancing para-aramid fiber has excellent mechanical property, for aerospace industry, radial, flak jackets, the field such as communication cable and enhancing composite.
Description
Technical field
The present invention relates to the preparation field of para-aramid fiber, specifically a kind of graphene quantum dot enhancing p-aramid fiber is fine
The preparation method of dimension.
Background technology
Para-aramid fiber, also known as Fanglun l414, have very high intensity and modulus, at the same high temperature-resistant acid-resistant alkali and
The characteristic of the corrosion of most organic solvents, its specific strength are 5~6 times of steel, and modulus is the 2~3 of steel wire and glass fibre
Times, toughness is 2 times of steel wire, and density be only steel wire 1/5th, aramid fiber aerospace industry, radial,
Cord fabric thread, flak jackets, communication cable and enhancing composite etc. have quite varied application, increase especially as fiber
Skeleton part in strong composite.Because para-aramid fiber itself has internal flaw, the p-aramid fiber of finished product is fine at present
The maximum intensity and modulus of dimension are only 3.0Gpa and 124GPa respectively.
But with the development of the society, above-mentioned application field the intensity and modulus of para-aramid fiber is proposed it is higher
Requirement, therefore the intensity and modulus for further enhancing para-aramid fiber has highly important scientific meaning and huge warp
Ji value.In order to improve the tensile strength of aramid fiber and modulus, researcher has done substantial amounts of research work：
First, good solvent is used in the polymerization process of p-aramid fiber so as to improve the molecular weight of product, and then improves molecule
Between effective secondary bond power to improve the mechanical property of p-aramid fiber, but because dope viscosity is greatly to follow-up spinning work
Skill brings huge challenge.
2nd, Third monomer is added in the polymerization process of p-aramid fiber to carry out being copolymerized the dissolubility for improving its in a solvent,
But Third monomer destroys the regularity of aramid fiber molecular structure, cause the increase of molecule interchain secondary bond operating distance, certain
The modulus of p-aramid fiber is reduced in degree.
3rd, improve spinning technique, such as stretch, (Yu Bo p-aramid fibers produce and application technology progress (I) for heat treatment etc.
[J] synthetic technologys and application, 2005,02:22-28.), these improve technique and structure in terms of aramid fiber are had an impact.
Although the above method can lift aramid fiber mechanical property to a certain extent, the performance of aramid fiber, which improves, extremely to be had
Limit.
The content of the invention
Present invention aim to address solve in the prior art, p-aramid fiber itself wellability is poor, graphene quantum dot with
The problem of interface interaction is not strong between p-aramid fiber, and graphene quantum dot is difficult to uniformly be distributed in para-aramid fiber.
To realize that the technical scheme that the object of the invention uses is such, a kind of graphene quantum dot strengthens p-aramid fiber
The preparation method of fiber, it is characterised in that comprise the following steps：
1) alkene grafting p-aramid fiber resin
1.1) weigh 1~5 part hydrofining and 95~99 parts water removal after dimethyl sulfoxide (DMSO) (DMSO), hydrofining is dissolved in
In dimethyl sulfoxide (DMSO) (DMSO), mixed solution A is obtained, mixed solution A is placed under 70 DEG C of constant temperatures, after stirring 0.5~3h
Room temperature is cooled to, obtains DMSO negative solution；
1.2) 10~20 parts of p-aramid fiber resins (PPTA) are weighed to be placed under nitrogen protection, p-aramid fiber resin is added to
In the DMSO negative solutions obtained in step 1.1), mixed solution B is obtained, mixed solution B is placed under 40 DEG C of constant temperatures,
Room temperature is cooled to after 2~6h of stirring, obtains PPTA negative solution；
1.3) 3~10 parts of alkene will be added in the PPTA obtained in step 1.2) negative solution, is placed in 30 DEG C of perseverance
Under the conditions of temperature, 12~48h is reacted, obtains mixed solution C；
1.4) water, ethanol and acetone are mixed according to the ratio that volume ratio is 1: 1: 1, obtains mixed solution D；
1.5) mixed solution D is added in mixed solution C, until target product separates out；
1.6) target product obtained in step 1.5) is washed 3 times with absolute ethyl alcohol, the target product after washing is put
12~48h is dried under the conditions of 80 DEG C, obtains the PPTA of alkene grafting；
2) graphene quantum dot vinyl functionalization
2.1) 100~1000 parts of graphene quantum dots, 1000~10000 parts of ethylenediamines, 10~100 parts of 4- diformazan ammonia are weighed
Yl pyridines (DMAP) and 10~100 parts of 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides (EDCHCl), by stone
Black alkene quantum dot, DMAP and EDCHCl are added sequentially in ethylenediamine, obtain mixed solution E；
2.2) mixed solution E is subjected to 30~60min of ultrasonic disperse, the mixed solution E after the completion of ultrasound is placed in 90~
24~48h is reacted at 95 DEG C, room temperature is cooled to after the completion of reaction, obtains product A, produced after product A is carried out into suction filtration washing
Thing B, product C is obtained after drying 12~48h under the conditions of product B is placed in into 60 DEG C；
2.3) 10~100 parts of DMAPs, 10~100 parts of 1- (3- dimethylamino-propyls) -3- ethyl carbon are weighed
Diimmonium salt hydrochlorate and 1000 parts of acrylic acid, mixed solution F is obtained after above-mentioned three kinds of compounds are mixed, product C is added to
In mixed solution F, mixed solution G is obtained；
2.4) it is anti-under the conditions of the mixed solution G after ultrasound is placed in into 50 DEG C by mixed solution G 30~60min of ultrasonic disperse
24~48h is answered, obtains product D, product D is subjected to suction filtration washing, obtains product E, 12 are dried under the conditions of product E is placed in into 60 DEG C
~48h, obtain the graphene quantum dot of vinyl functionalization；
3) graphene quantum dot grafting p-aramid fiber
3.1) graphene quantum dot of PPTA and 0.1~1 part of vinyl functionalization of 10~20 parts of alkene grafting is weighed, according to
It is secondary to be added in the dimethyl sulphoxide solution that 100 parts of sodium hydroxide mass fractions are 5%, by mixed solution H, it is placed in 50 DEG C of nitrogen
Under protective condition, mechanical agitation (speed 300rpm) 30-60min is carried out, during magnetic agitation, adds 0.05~0.1 part
Azodiisobutyronitrile (AIBN), then heats to 80~90 DEG C, and (speed 300rpm) reacts under nitrogen atmosphere and mechanical agitation
12~24h, obtain product F；
3.2) mixed solution D is added in product F, until target product separates out；
3.3) target product of gained in step 3.2) is washed 3 times with absolute ethyl alcohol, the target product after washing is put
In drying 12~48h under the conditions of 60 DEG C, the PPTA of graphene quantum dot grafting is obtained；
4) preparation of graphene quantum dot grafting para-aramid fiber
4.1) PPTA, 5~20 parts of pure PPTA and 75 without graft modification of 1~5 part of graphene quantum dot grafting are weighed
The concentrated sulfuric acid that~90 parts of concentration are 99%, the PPTA of graphene quantum dot grafting and the pure PPTA without graft modification are added successively
Enter into the concentrated sulfuric acid, be stirred, mixed solution is placed in firing equipment after stirring, by the mixed solution temperature liter
To 85 DEG C, product G is obtained；
4.2) product G is placed in spinning-drawing machine and carries out spinning, stretching ratio is 3~10 times in air gap, by coagulating bath, water
After washing, be heat-treated and winding, the para-aramid fiber of graphene quantum dot enhancing is obtained.
Further, the alkene in the step 1.3) is the bromo- 1- propylene of 3-, the bromo- 1- butylene of 4-, the bromo- 1- amylenes of 5-, 6-
The bromo- bromo- 1- heptene of 1- hexenes or 7-.
Further, the thickness range of the graphene quantum dot described in step 2.1) is 0.34~1nm, lamella diameter range
For 1~100nm.
Further, the acrylic acid described in the step 2.3) have passed through decompression and remove water process.
Further, the feed postition of the azodiisobutyronitrile described in step 3.1) is：Azodiisobutyronitrile is dissolved in
In 30mL dimethyl sulphoxide solution, the mass fraction of sodium hydroxide is 5% in the dimethyl sulphoxide solution, obtains mixing molten
Liquid, funnel is titrated using constant pressure, mixed solution is titrated to the PPTA and the graphene quantum of vinyl functionalization of alkene grafting
In the mixture of point, rate of titration is adjusted, azodiisobutyronitrile solution has been titrated in 30min-120min.
Further, after the obtained graphene quantum dot grafting p-aramid fiber sulfuric acid solution described in step 4.1), filtering should
Solution (ie in solution G), deaeration is to prepare uniform and stable spinning solution.
Further, solidification liquid used in coagulating bath is that the sulfuric acid that concentration is 10%~30% is water-soluble in the step 4.2)
Liquid, heat treatment temperature is at 150~220 DEG C, and winding speed is in 150~300m/min.
The solution have the advantages that unquestionable, the present invention is first by p-aramid fiber alkene functionalization, then by graphite
Alkene quantum dot vinyl functionalization, then by the p-aramid fiber for obtaining Olefination and the graphene quantum dot of vinyl functionalization
It is copolymerized, then the p-aramid fiber that graphene quantum dot is grafted is added to the spinning solution of p-aramid fiber in a manner of adding master batch
In, obtain the para-aramid fiber of graphene quantum dot modification finally by the method for fiber spinning from crystalline state.
Graphene quantum dot is grafted on p-aramid fiber by the above method, solved because p-aramid fiber itself infiltrates
Property is poor, and interface interaction is not strong between graphene quantum dot and p-aramid fiber, and graphene quantum dot is difficult to uniformly be distributed to contraposition
Problem in aramid fiber, the graphene quantum dot of high strength and modulus is combined with each other with aramid fiber, greatly improves contraposition
The intensity and modulus of aramid fiber.This method obtains fiber ultimate tensile strength and modulus difference 4.0Gpa and 163GPa, draws
Stretch intensity and 25% and 31.5% has been respectively increased with modular ratio prior art.
The present invention to existing para-aramid fiber process equipment without being modified, obtained graphene quantum dot enhancing pair
Position aramid fiber has excellent mechanical property, available for aerospace industry, radial, cord fabric thread, flak jackets, communication cable
With enhancing composite etc. field.
Brief description of the drawings
Fig. 1 is the chemical equation that alkene is grafted p-aramid fiber resin；
Fig. 2 is the chemical equation of graphene quantum dot vinyl functionalization；
Fig. 3 is the chemical equation that graphene quantum dot is grafted p-aramid fiber.
Embodiment
With reference to embodiment, the invention will be further described, but should not be construed the above-mentioned subject area of the present invention only
It is limited to following embodiments.Without departing from the idea case in the present invention described above, according to ordinary skill knowledge and used
With means, various replacements and change are made, all should be included within the scope of the present invention.
Embodiment 1：
1) the bromo- 1- propylene grafts p-aramid fiber resins of 3-
Take 1g hydrofining to be dissolved in 99g to be dissolved in the dimethyl sulfoxide (DMSO) by water removal (DMSO), 0.5h is stirred at 70 DEG C
Room temperature is cooled to afterwards obtains DMSO negative solution；10g p-aramid fiber resin (PPTA) is taken, adds match somebody with somebody under nitrogen protection
The DMSO negative solutions put, 40 DEG C stirring 2h after be cooled to room temperature, obtain PPTA negative solution；Above-mentioned PPTA's
The 3g bromo- 1- propylene of 3- is added in negative solution, 12h is reacted at 30 DEG C, then adds 100ml water, ethanol and acetone body
Product ratio 1：1：In 1 mixed solution, target product separates out, and after repeatedly being washed by absolute ethyl alcohol, in 80 DEG C of dry 12h, obtains
To the PPTA of the bromo- 1- propylene grafts of 3-.
2) graphene quantum dot vinyl functionalization
Take 100mg graphene quantum dot to be dissolved in 100ml ethylenediamine, add 10mg DMAP and
10mg 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, ultrasonic disperse 30min, after reacting 24h at 90 DEG C
Room temperature is cooled to, filters washing, 12h is dried at 60 DEG C.Reaction product is added to 10mg DMAP, 10mg
1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and 20ml acrylic acid mixed solution in ultrasonic disperse
30min, after then reacting 24h at 50 DEG C, washed by filtering, 12h is dried at 60 DEG C, obtains the stone of vinyl functionalization
Black alkene quantum dot.
Its thickness of graphene quantum dot contains carboxylic in 0.34~1nm, lamella diameter on 1~100nm, graphene quantum dot
The functional group such as base and hydroxyl, described acrylic acid have passed through decompression and removes water process.
3) graphene quantum dot grafting p-aramid fiber
The graphene quantum dot of PPTA and 100mg the vinyl functionalization of the 10g bromo- 1- propylene grafts of 3- is taken, is dissolved in
100ml sodium hydroxides mass fraction is in 5% dimethyl sulphoxide solution, is protected in 50 DEG C of nitrogen, under magnetic agitation, is added
50mg azodiisobutyronitriles to 30ml sodium hydroxide mass fraction are in 5% dimethyl sulphoxide solution, are titrated using constant pressure
Funnel is added to the mixed solution of the PPTA of the bromo- 1- propylene grafts of 3- and the graphene quantum dot of vinyl functionalization, regulation drop
Constant speed degree, azodiisobutyronitrile solution has been titrated in 30min, after stirring, be brought rapidly up to 80~90 DEG C, in nitrogen
With 12~24h of reaction under magnetic agitation, 100ml water, ethanol and acetone volume ratio 1 are then added：1：In 1 mixed solution, mesh
Mark product to separate out, after repeatedly being washed by absolute ethyl alcohol, 12h is dried at 60 DEG C, obtain graphene quantum dot grafting
PPTA。
4) preparation of graphene quantum dot grafting para-aramid fiber
Pure PPTAs of the PPTA that 1g graphene quantum dots the are grafted and 20g without graft modification is dissolved in into 75g concentration to be more than
In 99% concentrated sulfuric acid, mixed solution temperature is raised to 85 DEG C after stirring, graphene quantum dot grafting contraposition virtue is made
After synthetic fibre sulfuric acid solution, the solution is filtered, deaeration is to prepare uniform and stable spinning solution, then by spinning-drawing machine spinning, in air gap
Stretching ratio is 3 times, after coagulating bath, washing, heat treatment and winding, obtains the p-aramid fiber of graphene quantum dot grafting
Fiber, solidification liquid used in coagulating bath are the aqueous sulfuric acid that concentration is 10%, and heat treatment temperature is at 150 DEG C, winding speed
In 150m/min.
The fracture strength of fiber is 3.2GPa, stretch modulus 130GPa obtained by the present embodiment.
Embodiment 2：
1) the bromo- 1- butylene grafting p-aramid fiber resins of 4-
Take 2g hydrofining to be dissolved in 98g to be dissolved in the dimethyl sulfoxide (DMSO) by water removal (DMSO), after stirring 1h at 70 DEG C
It is cooled to room temperature and obtains DMSO negative solution；15g p-aramid fiber resin (PPTA) is taken, adds configuration under nitrogen protection
Good DMSO negative solutions, room temperature is cooled to after 40 DEG C of stirring 3h, obtains PPTA negative solution；In the negative of above-mentioned PPTA
The 5g bromo- 1- butylene of 4- is added in solion, 24h is reacted at 30 DEG C, then adds 150ml water, ethanol and acetone volume
Than 1：1：In 1 mixed solution, target product separates out, and after repeatedly being washed by absolute ethyl alcohol, in 80 DEG C of dry 24h, obtains
The PPTA of the bromo- 1- butylene grafting of 4-.
2) graphene quantum dot vinyl functionalization
Take 200mg graphene quantum dot to be dissolved in 100ml ethylenediamine, add 50mg DMAP and
50mg 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, ultrasonic disperse 40min, after reacting 48h at 95 DEG C
Room temperature is cooled to, filters washing, 24h is dried at 60 DEG C.Reaction product is added to 50mg DMAP, 50mg
1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and 30ml acrylic acid mixed solution in ultrasonic disperse
40min, after then reacting 48h at 50 DEG C, washed by filtering, 24h is dried at 60 DEG C, obtains the stone of vinyl functionalization
Black alkene quantum dot.
Its thickness of graphene quantum dot contains carboxylic in 0.34~1nm, lamella diameter on 1~100nm, graphene quantum dot
The functional group such as base and hydroxyl, described acrylic acid have passed through decompression and removes water process.
3) graphene quantum dot grafting p-aramid fiber
The graphene quantum dot of PPTA and 200mg the vinyl functionalization of the 15g bromo- 1- butylene of 4- is taken, is dissolved in 100ml hydrogen
Sodium oxide molybdena mass fraction is in 5% dimethyl sulphoxide solution, is protected in 50 DEG C of nitrogen, under magnetic agitation, adds 80mg idol
Nitrogen bis-isobutyronitrile to 30ml sodium hydroxide mass fraction are in 5% dimethyl sulphoxide solution, are added using constant pressure titration funnel
Enter the mixed solution of the PPTA and the graphene quantum dot of vinyl functionalization to the bromo- 1- butylene grafting of 4-, adjust rate of titration,
Azodiisobutyronitrile solution has been titrated in 30min, after stirring, be brought rapidly up to 90 DEG C, in nitrogen and magnetic agitation
Lower reaction 24h, then add 150ml water, ethanol and acetone volume ratio 1：1：In 1 mixed solution, target product separates out, and passes through
Absolute ethyl alcohol repeatedly after washing, dries 24h at 60 DEG C, obtains the PPTA of graphene quantum dot grafting.
4) preparation of graphene quantum dot grafting para-aramid fiber
Pure PPTAs of the PPTA that 5g graphene quantum dots the are grafted and 20g without graft modification is dissolved in into 90g concentration to be more than
In 99% concentrated sulfuric acid, mixed solution temperature is raised to 85 DEG C after stirring, graphene quantum dot grafting contraposition virtue is made
After synthetic fibre sulfuric acid solution, the solution is filtered, deaeration is to prepare uniform and stable spinning solution, then by spinning-drawing machine spinning, in air gap
Stretching ratio is 10 times, after coagulating bath, washing, heat treatment and winding, obtains the contraposition virtue of graphene quantum dot grafting
Synthetic fibre fiber, solidification liquid used in coagulating bath are the aqueous sulfuric acid that concentration is 30%, and heat treatment temperature is at 220 DEG C, winding speed
Degree is in 300m/min.
The fracture strength of fiber is 3.5GPa, stretch modulus 140GPa obtained by the present embodiment.
Embodiment 3：
1) the bromo- 1- amylenes grafting p-aramid fiber resins of 5-
Take 5g hydrofining to be dissolved in 95g to be dissolved in the dimethyl sulfoxide (DMSO) by water removal (DMSO), after stirring 3h at 70 DEG C
It is cooled to room temperature and obtains DMSO negative solution；20g p-aramid fiber resin (PPTA) is taken, adds configuration under nitrogen protection
Good DMSO negative solutions, room temperature is cooled to after 40 DEG C of stirring 6h, obtains PPTA negative solution；In the negative of above-mentioned PPTA
The 10g bromo- 1- amylenes of 5- are added in solion, 48h is reacted at 30 DEG C, then add 500ml water, ethanol and acetone volume
Than 1：1：In 1 mixed solution, target product separates out, and after repeatedly being washed by absolute ethyl alcohol, in 80 DEG C of dry 48h, obtains
The PPTA of the bromo- 1- amylenes grafting of 5-.
2) graphene quantum dot vinyl functionalization
Take 1000mg graphene quantum dot to be dissolved in 100ml ethylenediamine, add 100mg DMAP and
100mg 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, ultrasonic disperse 60min, react 48h at 95 DEG C
After be cooled to room temperature, filter washing, 48h dried at 60 DEG C.By reaction product be added to 100mg DMAP,
It is ultrasonic in the mixed solution of 100mg 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and 50ml acrylic acid
Scattered 60min, after then reacting 48h at 50 DEG C, washed by filtering, 48h is dried at 60 DEG C, obtains vinyl functionalization
Graphene quantum dot.
Its thickness of graphene quantum dot contains carboxylic in 0.34~1nm, lamella diameter on 1~100nm, graphene quantum dot
The functional group such as base and hydroxyl, described acrylic acid have passed through decompression and removes water process.
3) graphene quantum dot grafting p-aramid fiber
The 20g PPTA of the bromo- 1- amylenes grafting of 5- and the graphene quantum dot of 100~1000mg vinyl functionalization is taken,
It is dissolved in the dimethyl sulphoxide solution that 100ml sodium hydroxides mass fraction is 5%, is protected in 50 DEG C of nitrogen, under magnetic agitation, is added
The sodium hydroxide mass fraction for entering 100mg azodiisobutyronitrile to 30ml is in 5% dimethyl sulphoxide solution, uses constant pressure
Titration funnel is added to the PPTA and the graphene quantum dot of vinyl functionalization of the bromo- 1- amylenes grafting of 5- mixed solution, adjusts
Rate of titration is saved, azodiisobutyronitrile solution has been titrated in 30min, after stirring, is brought rapidly up to 90 DEG C, in nitrogen
With 24h is reacted under magnetic agitation, then add 500ml water, ethanol and acetone volume ratio 1：1：In 1 mixed solution, target production
Thing is separated out, and after repeatedly being washed by absolute ethyl alcohol, 48h is dried at 60 DEG C, obtains the PPTA of graphene quantum dot grafting.
4) preparation of graphene quantum dot grafting para-aramid fiber
Pure PPTAs of the PPTA that 5g graphene quantum dots the are grafted and 20g without graft modification is dissolved in into 90g concentration to be more than
In 99% concentrated sulfuric acid, mixed solution temperature is raised to 85 DEG C after stirring, graphene quantum dot grafting contraposition virtue is made
After synthetic fibre sulfuric acid solution, the solution is filtered, deaeration is to prepare uniform and stable spinning solution, then by spinning-drawing machine spinning, in air gap
Stretching ratio is 10 times, after coagulating bath, washing, heat treatment and winding, obtains the contraposition virtue of graphene quantum dot grafting
Synthetic fibre fiber, solidification liquid used in coagulating bath are the aqueous sulfuric acid that concentration is 10%~30%, heat treatment temperature at 220 DEG C,
Winding speed is in 300m/min.
The fracture strength of fiber is 4.0GPa, stretch modulus 163GPa obtained by the present embodiment.
Embodiment 4：
1) the bromo- 1- hexenes grafting p-aramid fiber resins of 6-
Take 3g hydrofining to be dissolved in 97g to be dissolved in the dimethyl sulfoxide (DMSO) by water removal (DMSO), after stirring 2h at 70 DEG C
It is cooled to room temperature and obtains DMSO negative solution；15g p-aramid fiber resin (PPTA) is taken, adds configuration under nitrogen protection
Good DMSO negative solutions, room temperature is cooled to after 40 DEG C of stirring 5h, obtains PPTA negative solution；In the negative of above-mentioned PPTA
The 8g bromo- 1- hexenes of 6- are added in solion, 36h is reacted at 30 DEG C, then add 250ml water, ethanol and acetone volume
Than 1：1：In 1 mixed solution, target product separates out, and after repeatedly being washed by absolute ethyl alcohol, in 80 DEG C of dry 36h, obtains
The PPTA of the bromo- 1- hexenes grafting of 6-.
2) graphene quantum dot vinyl functionalization
Take 750mg graphene quantum dot to be dissolved in 100ml ethylenediamine, add 75mg DMAP and
75mg 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, ultrasonic disperse 45min, after reacting 36h at 92 DEG C
Room temperature is cooled to, filters washing, 36h is dried at 60 DEG C.Reaction product is added to 75mg DMAP, 75mg
1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and 30ml acrylic acid mixed solution in ultrasonic disperse
45min, after then reacting 36h at 50 DEG C, washed by filtering, 36h is dried at 60 DEG C, obtains the stone of vinyl functionalization
Black alkene quantum dot.
Its thickness of graphene quantum dot contains carboxylic in 0.34~1nm, lamella diameter on 1~100nm, graphene quantum dot
The functional group such as base and hydroxyl, described acrylic acid have passed through decompression and removes water process.
3) graphene quantum dot grafting p-aramid fiber
The PPTA and the graphene quantum dot of 500mg vinyl functionalization of the 15g bromo- 1- hexenes grafting of 6- are taken, is dissolved in
100ml sodium hydroxides mass fraction is in 5% dimethyl sulphoxide solution, is protected in 50 DEG C of nitrogen, under magnetic agitation, is added
80mg azodiisobutyronitrile to 30ml sodium hydroxide mass fraction are in 5% dimethyl sulphoxide solution, are dripped using constant pressure
Determine the mixed solution that funnel is added to the PPTA and the graphene quantum dot of vinyl functionalization of the bromo- 1- hexenes grafting of 6-, regulation
Rate of titration, azodiisobutyronitrile solution has been titrated in 30min, after stirring, be brought rapidly up to 85 DEG C, in nitrogen and
18h is reacted under magnetic agitation, then adds 250ml water, ethanol and acetone volume ratio 1：1：In 1 mixed solution, target product
Separate out, after repeatedly being washed by absolute ethyl alcohol, 36h is dried at 60 DEG C, obtains the PPTA of graphene quantum dot grafting.
4) preparation of graphene quantum dot grafting para-aramid fiber
It is big that pure PPTAs of the PPTA that 2.5g graphene quantum dots the are grafted and 15g without graft modification is dissolved in 82.5g concentration
In 99% concentrated sulfuric acid, mixed solution temperature is raised to 85 DEG C after stirring, graphene quantum dot grafting contraposition is made
After aramid fiber sulfuric acid solution, the solution is filtered, deaeration is to prepare uniform and stable spinning solution, then passes through spinning-drawing machine spinning, air gap
Middle stretching ratio is 6 times, after coagulating bath, washing, heat treatment and winding, obtains the contraposition virtue of graphene quantum dot grafting
Synthetic fibre fiber, solidification liquid used in coagulating bath are the aqueous sulfuric acid that concentration is 25%, and heat treatment temperature is at 170 DEG C, winding speed
Degree is in 225m/min.
The fracture strength of fiber is 3.7GPa, stretch modulus 140GPa obtained by the present embodiment.
Embodiment 5：
1) the bromo- 1- heptene grafting p-aramid fiber resins of 7-
Take 2g hydrofining to be dissolved in 99g to be dissolved in the dimethyl sulfoxide (DMSO) by water removal (DMSO), 0.5h is stirred at 70 DEG C
Room temperature is cooled to afterwards obtains DMSO negative solution；20g p-aramid fiber resin (PPTA) is taken, adds match somebody with somebody under nitrogen protection
The DMSO negative solutions put, 40 DEG C stirring 4h after be cooled to room temperature, obtain PPTA negative solution；Above-mentioned PPTA's
The 4g bromo- 1- heptene of 7- is added in negative solution, 18h is reacted at 30 DEG C, then adds 300ml water, ethanol and acetone body
Product ratio 1：1：In 1 mixed solution, target product separates out, and after repeatedly being washed by absolute ethyl alcohol, in 80 DEG C of dry 18h, obtains
To the PPTA of the bromo- 1- heptene grafting of 7-.
2) graphene quantum dot vinyl functionalization
Take 600mg graphene quantum dot to be dissolved in 100ml ethylenediamine, add 70mg DMAP and
70mg 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, ultrasonic disperse 60min, after reacting 36h at 95 DEG C
Room temperature is cooled to, filters washing, 24h is dried at 60 DEG C.Reaction product is added to 50mg DMAP, 50mg
1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and 30ml acrylic acid mixed solution in ultrasonic disperse
45min, after then reacting 36h at 50 DEG C, washed by filtering, 36h is dried at 60 DEG C, obtains the stone of vinyl functionalization
Black alkene quantum dot.
Its thickness of graphene quantum dot contains carboxylic in 0.34~1nm, lamella diameter on 1~100nm, graphene quantum dot
The functional group such as base and hydroxyl, described acrylic acid have passed through decompression and removes water process.
3) graphene quantum dot grafting p-aramid fiber
The PPTA and the graphene quantum dot of 800mg vinyl functionalization of the 16g bromo- 1- heptene grafting of 7- are taken, is dissolved in
100ml sodium hydroxides mass fraction is in 5% dimethyl sulphoxide solution, is protected in 50 DEG C of nitrogen, under magnetic agitation, is added
75mg azodiisobutyronitrile to 30ml sodium hydroxide mass fraction are in 5% dimethyl sulphoxide solution, are dripped using constant pressure
Determine the mixed solution that funnel is added to the PPTA and the graphene quantum dot of vinyl functionalization of the bromo- 1- heptene grafting of 7-, regulation
Rate of titration, azodiisobutyronitrile solution has been titrated in 30min, after stirring, be brought rapidly up to 90 DEG C, in nitrogen and
24h is reacted under magnetic agitation, then adds 300ml water, ethanol and acetone volume ratio 1：1：In 1 mixed solution, target product
Separate out, after repeatedly being washed by absolute ethyl alcohol, 36h is dried at 60 DEG C, obtains the PPTA of graphene quantum dot grafting.
4) preparation of graphene quantum dot grafting para-aramid fiber
It is big that pure PPTAs of the PPTA that 2.5g graphene quantum dots the are grafted and 10g without graft modification is dissolved in 87.5g concentration
In 99% concentrated sulfuric acid, mixed solution temperature is raised to 85 DEG C after stirring, graphene quantum dot grafting contraposition is made
After aramid fiber sulfuric acid solution, the solution is filtered, deaeration is to prepare uniform and stable spinning solution, then passes through spinning-drawing machine spinning, air gap
Middle stretching ratio is 8 times, after coagulating bath, washing, heat treatment and winding, obtains the contraposition virtue of graphene quantum dot grafting
Synthetic fibre fiber, solidification liquid used in coagulating bath are the aqueous sulfuric acid that concentration is 15%, and heat treatment temperature is at 175 DEG C, winding speed
Degree is in 300m/min.
The fracture strength of fiber is 3.3GPa, modulus 130GPa obtained by the present embodiment.
Embodiment 6：
1) the bromo- 1- propylene grafts p-aramid fiber resins of 3-
Take 2.5g hydrofining to be dissolved in 97.5g to be dissolved in the dimethyl sulfoxide (DMSO) by water removal (DMSO), stirred at 70 DEG C
Room temperature is cooled to after 1.5h and obtains DMSO negative solution；15g p-aramid fiber resin (PPTA) is taken, is added under nitrogen protection
Enter the DMSO negative solutions configured, be cooled to room temperature after 40 DEG C of stirring 4h, obtain PPTA negative solution；Above-mentioned
The 6g bromo- 1- propylene of 3- is added in PPTA negative solution, 24h is reacted at 30 DEG C, then add 250ml water, ethanol with
Acetone volume ratio 1：1：In 1 mixed solution, target product separates out, after repeatedly being washed by absolute ethyl alcohol, in 80 DEG C of dryings
24h, obtain the PPTA of the bromo- 1- propylene grafts of 3-.
2) graphene quantum dot vinyl functionalization
Take 500mg graphene quantum dot to be dissolved in 100ml ethylenediamine, add 50mg DMAP and
50mg 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, ultrasonic disperse 45min, after reacting 36h at 93 DEG C
Room temperature is cooled to, filters washing, 36h is dried at 60 DEG C.Reaction product is added to 50mg DMAP, 50mg
1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and 40ml acrylic acid mixed solution in ultrasonic disperse
45min, after then reacting 36h at 50 DEG C, washed by filtering, 36h is dried at 60 DEG C, obtains the stone of vinyl functionalization
Black alkene quantum dot.
Its thickness of graphene quantum dot contains carboxylic in 0.34~1nm, lamella diameter on 1~100nm, graphene quantum dot
The functional group such as base and hydroxyl, described acrylic acid have passed through decompression and removes water process.
3) graphene quantum dot grafting p-aramid fiber
The graphene quantum dot of PPTA and 500mg the vinyl functionalization of the 15g bromo- 1- propylene grafts of 3- is taken, is dissolved in
100ml sodium hydroxides mass fraction is in 5% dimethyl sulphoxide solution, is protected in 50 DEG C of nitrogen, under magnetic agitation, is added
75mg azodiisobutyronitrile to 30ml sodium hydroxide mass fraction are in 5% dimethyl sulphoxide solution, are dripped using constant pressure
Determine the mixed solution that funnel is added to the PPTA of the bromo- 1- propylene grafts of 3- and the graphene quantum dot of vinyl functionalization, adjust
Rate of titration, azodiisobutyronitrile solution has been titrated in 30min, after stirring, be brought rapidly up to 85 DEG C, in nitrogen and
18h is reacted under magnetic agitation, then adds 250ml water, ethanol and acetone volume ratio 1：1：In 1 mixed solution, target product
Separate out, after repeatedly being washed by absolute ethyl alcohol, 24h is dried at 60 DEG C, obtains the PPTA of graphene quantum dot grafting.
4) preparation of graphene quantum dot grafting para-aramid fiber
Pure PPTs of the PPTA that 2.5g graphene quantum dots the are grafted and 10g without graft modification is dissolved in into 87.5g concentration to be more than
In 99% concentrated sulfuric acid, mixed solution temperature is raised to 85 DEG C after stirring, graphene quantum dot grafting contraposition virtue is made
After synthetic fibre sulfuric acid solution, the solution is filtered, deaeration is to prepare uniform and stable spinning solution, then by spinning-drawing machine spinning, in air gap
Stretching ratio is 8 times, after coagulating bath, washing, heat treatment and winding, obtains the p-aramid fiber of graphene quantum dot grafting
Fiber, solidification liquid used in coagulating bath are the aqueous sulfuric acid that concentration is 15%, and heat treatment temperature is at 200 DEG C, winding speed
In 250m/min.
The fracture strength of fiber is 3.5GPa, modulus 140GPa obtained by the present embodiment.
Embodiment 7：
1) the bromo- 1- butylene grafting p-aramid fiber resins of 4-
Take 1g hydrofining to be dissolved in 95g to be dissolved in the dimethyl sulfoxide (DMSO) by water removal (DMSO), 0.5h is stirred at 70 DEG C
Room temperature is cooled to afterwards obtains DMSO negative solution；10g p-aramid fiber resin (PPTA) is taken, adds match somebody with somebody under nitrogen protection
The DMSO negative solutions put, 40 DEG C stirring 2h after be cooled to room temperature, obtain PPTA negative solution；Above-mentioned PPTA's
The 3g bromo- 1- butylene of 4- is added in negative solution, 12~48h is reacted at 30 DEG C, then adds 100~500ml water, ethanol
With acetone volume ratio 1：1：In 1 mixed solution, target product separates out, dry at 80 DEG C after repeatedly being washed by absolute ethyl alcohol
Dry 12~48h, obtain the PPTA of the bromo- 1- butylene grafting of 4-.
2) graphene quantum dot vinyl functionalization
Take 100mg graphene quantum dot to be dissolved in 100ml ethylenediamine, add 10mg DMAP and
10mg 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, ultrasonic disperse 30min, after reacting 24h at 90 DEG C
Room temperature is cooled to, filters washing, 12h is dried at 60 DEG C.Reaction product is added to 10mg DMAP, 10mg
1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and 20ml acrylic acid mixed solution in ultrasonic disperse
30min, after then reacting 24h at 50 DEG C, washed by filtering, 12h is dried at 60 DEG C, obtains the stone of vinyl functionalization
Black alkene quantum dot.
Its thickness of graphene quantum dot contains carboxylic in 0.34~1nm, lamella diameter on 1~100nm, graphene quantum dot
The functional group such as base and hydroxyl, described acrylic acid have passed through decompression and removes water process.
3) graphene quantum dot grafting p-aramid fiber
The PPTA and the graphene quantum dot of 100mg vinyl functionalization of the 10g bromo- 1- butylene grafting of 4- are taken, is dissolved in
100ml sodium hydroxides mass fraction is in 5% dimethyl sulphoxide solution, is protected in 50 DEG C of nitrogen, under magnetic agitation, is added
50mg azodiisobutyronitrile to 30ml sodium hydroxide mass fraction are in 5% dimethyl sulphoxide solution, are dripped using constant pressure
Determine the mixed solution that funnel is added to the PPTA and the graphene quantum dot of vinyl functionalization of the bromo- 1- butylene grafting of 4-, regulation
Rate of titration, azodiisobutyronitrile solution has been titrated in 30min, after stirring, be brought rapidly up to 80 DEG C, in nitrogen and
12h is reacted under magnetic agitation, then adds 100~500ml water, ethanol and acetone volume ratio 1：1：In 1 mixed solution, target
Product is separated out, and after repeatedly being washed by absolute ethyl alcohol, 12h is dried at 60 DEG C, obtains the PPTA of graphene quantum dot grafting.
4) preparation of graphene quantum dot grafting para-aramid fiber
The PPTA that 1g graphene quantum dots are grafted and pure PPTs of the 20g without graft modification is dissolved in 79g concentration more than 99%
The concentrated sulfuric acid in, mixed solution temperature is raised to 85 DEG C after stirring, be made graphene quantum dot grafting p-aramid fiber sulphur
After acid solution, the solution is filtered, deaeration stretches to prepare uniform and stable spinning solution, then by spinning-drawing machine spinning in air gap
Multiplying power is 3 times, and after coagulating bath, washing, heat treatment and winding, the p-aramid fiber for obtaining graphene quantum dot grafting is fine
Dimension, solidification liquid used in coagulating bath is the aqueous sulfuric acid that concentration is 10%, and at 150 DEG C, winding speed exists heat treatment temperature
150m/min。
The fracture strength of fiber is 3.1GPa, modulus 129GPa obtained by the present embodiment.
Embodiment 8：
1) the bromo- 1- amylenes grafting p-aramid fiber resins of 5-
Take 3.3g hydrofining to be dissolved in 96.7g to be dissolved in the dimethyl sulfoxide (DMSO) by water removal (DMSO), stirred at 70 DEG C
Room temperature is cooled to after 2h and obtains DMSO negative solution；17g p-aramid fiber resin (PPTA) is taken, is added under nitrogen protection
The DMSO negative solutions configured, 40 DEG C stirring 3.5h after be cooled to room temperature, obtain PPTA negative solution；Above-mentioned
The 6g bromo- 1- amylenes of 5- are added in PPTA negative solution, 18h is reacted at 30 DEG C, then add 200ml water, ethanol with
Acetone volume ratio 1：1：In 1 mixed solution, target product separates out, after repeatedly being washed by absolute ethyl alcohol, in 80 DEG C of dryings
16h, obtain the PPTA of the bromo- 1- amylenes grafting of 5-.
2) graphene quantum dot vinyl functionalization
Take 600mg graphene quantum dot to be dissolved in 100ml ethylenediamine, add 70mg DMAP and
70mg 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, ultrasonic disperse 45min, after reacting 48h at 95 DEG C
Room temperature is cooled to, filters washing, 30h is dried at 60 DEG C.Reaction product is added to 60mg DMAP, 60mg
1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and 30ml acrylic acid mixed solution in ultrasonic disperse
50min, after then reacting 30h at 50 DEG C, washed by filtering, 24h is dried at 60 DEG C, obtains the stone of vinyl functionalization
Black alkene quantum dot.
Its thickness of graphene quantum dot contains carboxylic in 0.34~1nm, lamella diameter on 1~100nm, graphene quantum dot
The functional group such as base and hydroxyl, described acrylic acid have passed through decompression and removes water process.
3) graphene quantum dot grafting p-aramid fiber
The PPTA and the graphene quantum dot of 600mg vinyl functionalization of the 12g bromo- 1- amylenes grafting of 5- are taken, is dissolved in
100ml sodium hydroxides mass fraction is in 5% dimethyl sulphoxide solution, is protected in 50 DEG C of nitrogen, under magnetic agitation, is added
70mg azodiisobutyronitrile to 30ml sodium hydroxide mass fraction are in 5% dimethyl sulphoxide solution, are dripped using constant pressure
Determine the mixed solution that funnel is added to the PPTA and the graphene quantum dot of vinyl functionalization of the bromo- 1- amylenes grafting of 5-, regulation
Rate of titration, azodiisobutyronitrile solution has been titrated in 30min, after stirring, be brought rapidly up to 80 DEG C, in nitrogen and
24h is reacted under magnetic agitation, then adds 200ml water, ethanol and acetone volume ratio 1：1：In 1 mixed solution, target product
Separate out, after repeatedly being washed by absolute ethyl alcohol, 48h is dried at 60 DEG C, obtains the PPTA of graphene quantum dot grafting.
4) preparation of graphene quantum dot grafting para-aramid fiber
Pure PPTAs of the PPTA that 5g graphene quantum dots the are grafted and 15g without graft modification is dissolved in into 85g concentration to be more than
In 99% concentrated sulfuric acid, mixed solution temperature is raised to 85 DEG C after stirring, graphene quantum dot grafting contraposition virtue is made
After synthetic fibre sulfuric acid solution, the solution is filtered, deaeration is to prepare uniform and stable spinning solution, then by spinning-drawing machine spinning, in air gap
Stretching ratio is 7 times, after coagulating bath, washing, heat treatment and winding, obtains the p-aramid fiber of graphene quantum dot grafting
Fiber, solidification liquid used in coagulating bath are the aqueous sulfuric acid that concentration is 25%, and heat treatment temperature is at 180 DEG C, winding speed
In 290m/min.
The fracture strength of fiber is 3.8GPa, modulus 130GPa obtained by the present embodiment.
Embodiment 9：
1) the bromo- 1- hexenes grafting p-aramid fiber resins of 6-
Take 1g hydrofining to be dissolved in 99g to be dissolved in the dimethyl sulfoxide (DMSO) by water removal (DMSO), 0.5h is stirred at 70 DEG C
Room temperature is cooled to afterwards obtains DMSO negative solution；10g p-aramid fiber resin (PPTA) is taken, adds match somebody with somebody under nitrogen protection
The DMSO negative solutions put, 40 DEG C stirring 2h after be cooled to room temperature, obtain PPTA negative solution；Above-mentioned PPTA's
The 3g bromo- 1- hexenes of 6- are added in negative solution, 12h is reacted at 30 DEG C, then add 100ml water, ethanol and acetone body
Product ratio 1：1：In 1 mixed solution, target product separates out, and after repeatedly being washed by absolute ethyl alcohol, in 80 DEG C of dry 12h, obtains
To the PPTA of the bromo- 1- hexenes grafting of 6-.
2) graphene quantum dot vinyl functionalization
Take 100mg graphene quantum dot to be dissolved in 100ml ethylenediamine, add 10mg DMAP and
10mg 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, ultrasonic disperse 30min, after reacting 24h at 90 DEG C
Room temperature is cooled to, filters washing, 12h is dried at 60 DEG C.Reaction product is added to 10mg DMAP, 10mg
1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and 20ml acrylic acid mixed solution in ultrasonic disperse
30min, after then reacting 24h at 50 DEG C, washed by filtering, 12h is dried at 60 DEG C, obtains the stone of vinyl functionalization
Black alkene quantum dot.
Its thickness of graphene quantum dot contains carboxylic in 0.34~1nm, lamella diameter on 1~100nm, graphene quantum dot
The functional group such as base and hydroxyl, described acrylic acid have passed through decompression and removes water process.
3) graphene quantum dot grafting p-aramid fiber
The PPTA and the graphene quantum dot of 100mg vinyl functionalization of the 10g bromo- 1- hexenes grafting of 6- are taken, is dissolved in
100ml sodium hydroxides mass fraction is in 5% dimethyl sulphoxide solution, is protected in 50 DEG C of nitrogen, under magnetic agitation, is added
50mg azodiisobutyronitriles to 30ml sodium hydroxide mass fraction are in 5% dimethyl sulphoxide solution, are titrated using constant pressure
Funnel is added to the PPTA and the graphene quantum dot of vinyl functionalization of the bromo- 1- hexenes grafting of 6- mixed solution, regulation drop
Constant speed degree, azodiisobutyronitrile solution has been titrated in 30min, after stirring, be brought rapidly up to 90 DEG C, in nitrogen and magnetic
The lower reaction 18h of power stirring, then adds 100ml water, ethanol and acetone volume ratio 1：1：In 1 mixed solution, target product analysis
Go out, after repeatedly being washed by absolute ethyl alcohol, 12h is dried at 60 DEG C, obtains the PPTA of graphene quantum dot grafting.
4) preparation of graphene quantum dot grafting para-aramid fiber
Pure PPTAs of the PPTA that 1g graphene quantum dots the are grafted and 20g without graft modification is dissolved in into 75g concentration to be more than
In 99% concentrated sulfuric acid, mixed solution temperature is raised to 85 DEG C after stirring, graphene quantum dot grafting contraposition virtue is made
After synthetic fibre sulfuric acid solution, the solution is filtered, deaeration is to prepare uniform and stable spinning solution, then by spinning-drawing machine spinning, in air gap
Stretching ratio is 3 times, after coagulating bath, washing, heat treatment and winding, obtains the p-aramid fiber of graphene quantum dot grafting
Fiber, solidification liquid used in coagulating bath are the aqueous sulfuric acid that concentration is 10%, and heat treatment temperature is at 150 DEG C, winding speed
In 150m/min.
The fracture strength of fiber is 3.5GPa, stretch modulus 140GPa obtained by the present embodiment.
Embodiment 10：
1) the bromo- 1- heptene grafting p-aramid fiber resins of 7-
Take 2g hydrofining to be dissolved in 98g to be dissolved in the dimethyl sulfoxide (DMSO) by water removal (DMSO), after stirring 1h at 70 DEG C
It is cooled to room temperature and obtains DMSO negative solution；15g p-aramid fiber resin (PPTA) is taken, adds configuration under nitrogen protection
Good DMSO negative solutions, room temperature is cooled to after 40 DEG C of stirring 3h, obtains PPTA negative solution；In the negative of above-mentioned PPTA
The 5g bromo- 1- heptene of 7- is added in solion, 24h is reacted at 30 DEG C, then adds 150ml water, ethanol and acetone volume
Than 1：1：In 1 mixed solution, target product separates out, and after repeatedly being washed by absolute ethyl alcohol, in 80 DEG C of dry 24h, obtains
The PPTA of the bromo- 1- heptene grafting of 7-.
2) graphene quantum dot vinyl functionalization
Take 200mg graphene quantum dot to be dissolved in 100ml ethylenediamine, add 50mg DMAP and
50mg 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, ultrasonic disperse 40min, after reacting 48h at 95 DEG C
Room temperature is cooled to, filters washing, 24h is dried at 60 DEG C.Reaction product is added to 50mg DMAP, 50mg
1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and 30ml acrylic acid mixed solution in ultrasonic disperse
40min, after then reacting 48h at 50 DEG C, washed by filtering, 24h is dried at 60 DEG C, obtains the stone of vinyl functionalization
Black alkene quantum dot.
Its thickness of graphene quantum dot contains carboxylic in 0.34~1nm, lamella diameter on 1~100nm, graphene quantum dot
The functional group such as base and hydroxyl, described acrylic acid have passed through decompression and removes water process.
3) graphene quantum dot grafting p-aramid fiber
The graphene quantum dot of PPTA and 200mg the vinyl functionalization of the 15g bromo- 1- heptene of 7- is taken, is dissolved in 100ml hydrogen
Sodium oxide molybdena mass fraction is in 5% dimethyl sulphoxide solution, is protected in 50 DEG C of nitrogen, under magnetic agitation, adds 80mg idol
Nitrogen bis-isobutyronitrile to 30ml sodium hydroxide mass fraction are in 5% dimethyl sulphoxide solution, are added using constant pressure titration funnel
Enter the mixed solution of the PPTA and the graphene quantum dot of vinyl functionalization to the bromo- 1- heptene grafting of 7-, adjust rate of titration,
Azodiisobutyronitrile solution has been titrated in 30min, after stirring, be brought rapidly up to 90 DEG C, in nitrogen and magnetic agitation
Lower reaction 24h, then add 150ml water, ethanol and acetone volume ratio 1：1：In 1 mixed solution, target product separates out, and passes through
Absolute ethyl alcohol repeatedly after washing, dries 24h at 60 DEG C, obtains the PPTA of graphene quantum dot grafting.
4) preparation of graphene quantum dot grafting para-aramid fiber
Pure PPTAs of the PPTA that 5g graphene quantum dots the are grafted and 20g without graft modification is dissolved in into 90g concentration to be more than
In 99% concentrated sulfuric acid, mixed solution temperature is raised to 85 DEG C after stirring, graphene quantum dot grafting contraposition virtue is made
After synthetic fibre sulfuric acid solution, the solution is filtered, deaeration is to prepare uniform and stable spinning solution, then by spinning-drawing machine spinning, in air gap
Stretching ratio is 10 times, after coagulating bath, washing, heat treatment and winding, obtains the contraposition virtue of graphene quantum dot grafting
Synthetic fibre fiber, solidification liquid used in coagulating bath are the aqueous sulfuric acid that concentration is 30%, and heat treatment temperature is at 220 DEG C, winding speed
Degree is in 300m/min.
The fracture strength of fiber is 3.7GPa, stretch modulus 148GPa obtained by the present embodiment.
Claims (7)
1. a kind of preparation method of graphene quantum dot enhancing para-aramid fiber, it is characterised in that comprise the following steps：
1) alkene grafting p-aramid fiber resin
1.1) weigh 1~5 part hydrofining and 95~99 parts water removal after dimethyl sulfoxide (DMSO) (DMSO), hydrofining is dissolved in diformazan
In base sulfoxide (DMSO), mixed solution A is obtained, mixed solution A is placed under 70 DEG C of constant temperatures, is cooled down after stirring 0.5~3h
To room temperature, DMSO negative solution is obtained；
1.2) 10~20 parts of p-aramid fiber resins (PPTA) are weighed to be placed under nitrogen protection, p-aramid fiber resin is added to step
1.1) in the DMSO negative solutions obtained in, mixed solution B is obtained, mixed solution B is placed under 40 DEG C of constant temperatures, is stirred
Room temperature is cooled to after 2~6h, obtains PPTA negative solution；
1.3) 3~10 parts of alkene will be added in the PPTA obtained in step 1.2) negative solution, is placed in 30 DEG C of constant temperature bar
Under part, 12~48h is reacted, obtains mixed solution C；
1.4) water, ethanol and acetone are mixed according to the ratio that volume ratio is 1: 1: 1, obtains mixed solution D；
1.5) mixed solution D is added in mixed solution C, until target product separates out；
1.6) target product obtained in step 1.5) is washed 3 times with absolute ethyl alcohol, the target product after washing is placed in 80
12~48h is dried under the conditions of DEG C, obtains the PPTA of alkene grafting；
2) graphene quantum dot vinyl functionalization
2.1) 100~1000 parts of graphene quantum dots, 1000~10000 parts of ethylenediamines, 10~100 parts of 4- dimethylamino pyrroles are weighed
Pyridine (DMAP) and 10~100 parts of 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides (EDCHCl), by graphene
Quantum dot, DMAP and EDCHCl are added sequentially in ethylenediamine, obtain mixed solution E；
2.2) mixed solution E is subjected to 30~60min of ultrasonic disperse, the mixed solution E after the completion of ultrasound is placed in 90~95 DEG C
24~48h of lower reaction, is cooled to room temperature after the completion of reaction, obtains product A, and product B is obtained after product A is carried out into suction filtration washing,
Product C is obtained after drying 12~48h under the conditions of product B is placed in into 60 DEG C；
2.3) it is sub- that 10~100 parts of DMAPs, 10~100 parts of 1- (3- dimethylamino-propyls) -3- ethyls carbon two are weighed
Amine hydrochlorate and 1000 parts of acrylic acid, mixed solution F is obtained after above-mentioned three kinds of compounds are mixed, product C is added to mixing
In solution F, mixed solution G is obtained；
2.4) by mixed solution G 30~60min of ultrasonic disperse, the mixed solution G after ultrasound is placed under the conditions of 50 DEG C and reacts 24
~48h, product D is obtained, product D is subjected to suction filtration washing, obtains product E, dry 12 under the conditions of product E is placed in into 60 DEG C~
48h, obtain the graphene quantum dot of vinyl functionalization；
3) graphene quantum dot grafting p-aramid fiber
3.1) graphene quantum dot of PPTA and 0.1~1 part of vinyl functionalization of 10~20 parts of alkene grafting is weighed, is added successively
It is in 5% dimethyl sulphoxide solution to enter to 100 parts of sodium hydroxide mass fractions, by mixed solution H, is placed in 50 DEG C of nitrogen protections
Under the conditions of, mechanical agitation 30-60min is carried out, in whipping process, adds 0.05~0.1 part of azodiisobutyronitrile (AIBN), so
After be warming up to 80~90 DEG C, under nitrogen atmosphere and mechanical agitation react 12~24h, obtain the product F；
The churned mechanically speed is 300rpm；
3.2) mixed solution D is added in product F, until target product separates out；
3.3) target product of gained in step 3.2) is washed 3 times with absolute ethyl alcohol, the target product after washing is placed at
12~48h is dried under the conditions of 60 DEG C, obtains the PPTA of graphene quantum dot grafting；
4) preparation of graphene quantum dot grafting para-aramid fiber
4.1) PPTA, 5~20 parts of pure PPTA and 75~90 without graft modification of 1~5 part of graphene quantum dot grafting are weighed
Part concentration is more than 99% concentrated sulfuric acid, and the PPTA of graphene quantum dot grafting and the pure PPTA without graft modification are sequentially added
Into the concentrated sulfuric acid, it is stirred, mixed solution is placed in firing equipment after stirring, the mixed solution temperature is risen to
85 DEG C, obtain product G；
4.2) product G is placed in spinning-drawing machine and carries out spinning, in air gap stretching ratio be 3~10 times, by coagulating bath, washing,
After heat treatment and winding, the para-aramid fiber of graphene quantum dot enhancing is obtained.
2. a kind of preparation method of graphene quantum dot enhancing para-aramid fiber according to claim 1, its feature exist
In：Alkene in the step 1.3) is the bromo- 1- propylene of 3-, the bromo- 1- butylene of 4-, the bromo- 1- amylenes of 5-, the bromo- 1- hexenes of 6- or 7-
Bromo- 1- heptene.
3. a kind of preparation method of graphene quantum dot enhancing para-aramid fiber according to claim 1 or 2, its feature
It is：The thickness range of graphene quantum dot described in step 2.1) is 0.34~1nm, lamella diameter range is 1~
100nm。
4. a kind of preparation method of graphene quantum dot enhancing para-aramid fiber according to claim 1, its feature exist
In：Acrylic acid described in the step 2.3) have passed through decompression and remove water process.
5. a kind of preparation method of graphene quantum dot enhancing para-aramid fiber according to claim 1, its feature exist
In：The feed postition of azodiisobutyronitrile described in step 3.1) is：The dimethyl that azodiisobutyronitrile is dissolved in 30mL is sub-
In sulfolane solution, the mass fraction of sodium hydroxide is 5% in the dimethyl sulphoxide solution, obtains mixed solution, is dripped using constant pressure
Determine funnel, mixed solution be titrated in the PPTA of alkene grafting and the mixture of the graphene quantum dot of vinyl functionalization,
Rate of titration is adjusted, azodiisobutyronitrile solution has been titrated in 30min~120min.
6. a kind of preparation method of graphene quantum dot enhancing para-aramid fiber according to claim 1, its feature exist
In：After obtained graphene quantum dot grafting p-aramid fiber sulfuric acid solution described in step 4.1), the solution i.e. product G is filtered,
Deaeration is to prepare uniform and stable spinning solution.
7. a kind of preparation method of graphene quantum dot enhancing para-aramid fiber according to claim 1, its feature exist
In：Solidification liquid used in coagulating bath is the aqueous sulfuric acid that concentration is 10%~30% in the step 4.2), heat treatment temperature
Degree is at 150~220 DEG C, and winding speed is in 150~300m/min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103966844A (en) * | 2014-05-23 | 2014-08-06 | 青岛大学 | Preparation method of graphene electroconductive composite fiber |
| CN104047160A (en) * | 2014-06-17 | 2014-09-17 | 哈尔滨工业大学 | Method for grafting modified aramid fiber on surface of graphene oxide |
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| CN103966844A (en) * | 2014-05-23 | 2014-08-06 | 青岛大学 | Preparation method of graphene electroconductive composite fiber |
| CN104047160A (en) * | 2014-06-17 | 2014-09-17 | 哈尔滨工业大学 | Method for grafting modified aramid fiber on surface of graphene oxide |
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| Title |
|---|
| Electrospinning graphene quantum dots into a nanofibrous membrane for dual-purpose fluorescent and electrochemical biosensors;Panpan Zhang，et al;《J.Mater.Chem.B.》;20150202(第3期);2487-2496 * |
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