CN105543997B - A kind of resistance to ultraviolet graphene quantum dot is combined the preparation method of para-aramid fiber - Google Patents
A kind of resistance to ultraviolet graphene quantum dot is combined the preparation method of para-aramid fiber Download PDFInfo
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- CN105543997B CN105543997B CN201510943533.8A CN201510943533A CN105543997B CN 105543997 B CN105543997 B CN 105543997B CN 201510943533 A CN201510943533 A CN 201510943533A CN 105543997 B CN105543997 B CN 105543997B
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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
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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
- 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
- D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents
Abstract
The invention discloses the preparation method that a kind of resistance to ultraviolet graphene quantum dot is combined para-aramid fiber, it is characterised in that comprises the following steps：1) graphene quantum dot vinyl functionalization, 2) response type BTA graft grapheme quantum dot, 3) the quantum-dot modified p-aramid fiber of response type BTA graft grapheme, 4) the quantum-dot modified para-aramid fiber of response type BTA graft grapheme preparation.Para-aramid fiber prepared by the present invention is while having shielding and absorbing the ability of ultraviolet, there is excellent UV resistant performance, the service life in an atmosphere of aramid fiber is improved, in terms of aerospace industry, national defence, auto industry, flak jackets, communication cable and sports car.
Description
Technical field
It is specifically that a kind of resistance to ultraviolet graphene quantum dot is combined the present invention relates to the preparation field of p-aramid fiber composite fibre
The preparation method of para-aramid fiber.
Background technology
Para-aramid fiber, also known as Fanglun l414, are organic fibres that a kind of macromolecular chain is made up of aromatic rings and amido link
Dimension, with high intensity, high-modulus, low-density performance, its specific strength is 5~6 times of steel, and modulus is steel wire and glass fibre
2~3 times, toughness is 2 times of steel wire, and density is only 1/5th of steel wire, while high temperature-resistant acid-resistant alkali and the overwhelming majority
The corrosion of organic solvent, therefore aramid fiber is widely used in aerospace industry, national defence, auto industry, flak jackets, communication cable
And in terms of sports car.But aramid fiber is used in an atmosphere, it is old that the ultraviolet in sunshine can occur aramid fiber
Change degraded, mechanical property changes, generation becomes fragile, be cracked and yellowing phenomenon is even completely destroyed and can not used.Therefore such as
What, which improves the UV resistant performance of aramid fiber, turns into investigation of materials so as to extend the service life of aramid fiber, designs and use
Person's very concern.
Aramid fiber surface is very smooth and lacks active group, and itself wellability is poor, causes aramid fiber purple with tradition
Interface binding power between outer light absorber is weaker, therefore can not use directly these conventional methods such as doping or collosol and gel
Improve the UV resistant performance of aramid fiber；Nano level ultraviolet shielding material, can be to a certain degree due to bigger than surface
Conventional chemical active force is made up above, and preferable adhesion can be formed between aramid fiber, but nano material is easy in itself
Formed and reunited, be not easy to disperse (the preparation of class's swallow .TiO2 Nano sols and its old alleviating aramid fiber ultraviolet light in media as well
Application study [D] Donghua University in change, 2005.), and by the virtue of the direct coating modification of inorganic nano-particle titanium dioxide
Synthetic fibre fiber, soaks, nano-particle is easily desorbed, and aramid fiber can lose resistance to ultraviolet property in some specific use occasions such as solution
Energy.
The content of the invention
Present invention aim to address in the prior art, the problem of UV resistant performance of para-aramid fiber is poor.
To realize that the technical scheme that the object of the invention is used is a kind of such, compound pair of resistance to ultraviolet graphene quantum dot
The preparation method of position aramid fiber, it is characterised in that comprise the following steps：
1) graphene quantum dot vinyl functionalization
1.1) sequentially added in 100 parts of ethylenediamine 0.1~5 part graphene oxide quantum dot, 0.5~1 part of 4-
Dimethylamino naphthyridine and 0.5~1 part of 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, obtain mixed solution
A；
1.2) by after 30~60min of mixed solution A ultrasonic disperse, 24~48h is reacted under the conditions of being placed in 90~95 DEG C, will be anti-
Should after obtained mixture be cooled to room temperature, obtain suspension A；
1.3) suspension A suction filtrations are washed, obtains product A, 12~24h is dried under the conditions of product A is placed in into 60 DEG C, is obtained
Product B；
1.4) 0.5~1 part DMAP, 0.5~1 part of 1- (3- dimethylamino-propyls) -3- ethyls is weighed
Carbodiimide hydrochloride and 100 parts of processes remove the acrylic acid of water process, and three is mixed to get into mixed solution B；
1.5) 0.5 part of product B is added in mixed solution B, after 30~60min of ultrasonic disperse, be placed under the conditions of 50 DEG C
12~24h is reacted, suspension B is obtained；
1.6) suspension B suction filtrations are washed, obtains product C, 12~24h is dried under the conditions of product C is placed in into 60 DEG C, is obtained
The graphene quantum dot of vinyl functionalization；
2) response type BTA (BTA) graft grapheme quantum dot
2.1) by the graphene quantum dot and 50~100 parts of response type benzo three of 100~200 parts of vinyl functionalization
In azoles, the deionized water for being dissolved in 2000 parts, mixed solution C is obtained,
2.2) 50 parts of ammonium persulfates (APS) are added in 200 parts of deionized water, obtain mixed solution D；
2.3) funnel is titrated using constant pressure, mixed solution D is added in mixed solution C, rate of titration is adjusted, was made
Ammonium sulfate has been titrated in 30-120min, obtains mixed solution E；
2.4) mixed solution E is stirred, after stirring, is warming up to 80~100 DEG C, then by mixed solution E in nitrogen
12~24h is reacted under gas and magnetic agitation, suspension C is obtained；
2.5) suspension C is subjected to suction filtration washing, obtains product D, 12h is dried under the conditions of product D is placed in into 60 DEG C, is obtained
The graphene quantum dot of response type BTA grafting；
3) the quantum-dot modified p-aramid fiber of response type BTA graft grapheme
3.1) by the graphene quantum dot and 50~100 parts of pair of 0.05~0.1 part of above-mentioned response type BTA grafting
Position aramid fiber is dissolved in 200 parts of pyrovinic acid, obtains mixed solution F；
3.2) suction filtration after 60~120min of mixed solution F ultrasonic disperses is dried, obtains response type BTA grafting stone
The quantum-dot modified p-aramid fiber of black alkene；
4) preparation of the quantum-dot modified para-aramid fiber of response type BTA graft grapheme
4.1) 15~25 parts of the quantum-dot modified p-aramid fiber of response type BTA graft grapheme is dissolved in 75~85
Part concentration is in 99% concentrated sulfuric acid, stirring obtains product E；
4.2) under the conditions of 85 DEG C, product E is placed in spinning-drawing machine spinning, by coagulating bath, washes, be heat-treated and wind it
Afterwards, the enhanced para-aramid fiber of graphene quantum dot is obtained.
Further, the step 1.1) in its thickness of graphene quantum dot in 0.34~1nm, lamella diameter 1~
100nm。
Further, step 2.1) described in response type BTA include N- [(1- pi-allyl -2- pyrrolidinyls) first
Base] -6- methoxyl group -1H- BTA -5- carboxylic acid amides, 1- (allyloxy carbon epoxide) -1H- BTAs or 2- (3- allyls
Base -2- hydroxy-5-methyl bases phenyl) -2H- BTAs.
Further, step 3.1) described in p-aramid fiber inherent viscosity be 4.0~9.0dl/g.
Further, step 4) described in the quantum-dot modified p-aramid fiber sulphur of obtained response type BTA graft grapheme
After acid solution, filter and uniform and stable spinning solution is prepared after the solution, deaeration.
Further, the step 4.2) in solidification liquid used in coagulating bath be that the sulfuric acid that concentration is 15%~25% is water-soluble
Liquid, heat-treatment temperature range is 120~240 DEG C, and winding speed scope is 120~350m/min.
What deserves to be explained is, it is due to the difference of yardstick although graphene quantum dot molecular composition is identical with graphene,
There is difference substantially in the two.Graphene quantum dot is the nano material of quasi-zero dimension, fortune of its internal electron in all directions
It is dynamic all to be limited to, so quantum confinement effect is particularly significant, with many unique properties.The thickness of graphene quantum dot exists
0.34~1nm, lamella diameter is in 1~100nm, while it shows more significant small-size effect, graphene quantum dot tool
There is very big specific surface area, the active force between macromolecule caused by its skin effect is stronger, while graphene quantum
Point has strong π-πconjugation with the phenyl ring above p-aramid fiber, and graphene quantum dot absorption can on p-aramid fiber
Shielding ultraviolet rays to a certain extent, but graphene quantum dot is equally easily reunited, by graphene quantum dot graft modification energy
Enough improve its dispersibility in media as well.
The solution have the advantages that unquestionable, the present invention has advantages below：
The present invention is first by graphene quantum dot vinyl-functional, traditional ultra-violet absorber response type benzene in grafting
And triazole, improve the dispersibility of graphene quantum dot in media as well, using graphene quantum dot small-size effect and
Strong π-πconjugation between phenyl ring above graphene quantum dot and p-aramid fiber, makes response type BTA in grafting
Graphene quantum dot it is stable be attached to p-aramid fiber, graphene quantum dot is then prepared by way of fiber spinning from crystalline state and is combined
Aramid fiber, has shielding and the ability absorbed, so as to improve the UV resistance of aramid fiber simultaneously to ultraviolet.
Para-aramid fiber prepared by the present invention has excellent resistance to purple while having shielding and absorbing the ability of ultraviolet
Outside line performance, in 400W ultraviolet light and aging casees, by 168h ultraviolet radioactive, fiber can also keep initial tensile strength
50%, improve the service life in an atmosphere of aramid fiber, available for aerospace industry, national defence, auto industry, flak jackets,
In terms of communication cable and sports car.
Brief description of the drawings
Fig. 1 is the chemical equation of graphene quantum dot vinyl functionalization；
Fig. 2 is the chemical equation of response type BTA graft grapheme quantum dot.
In figure：BTA is the benzotriazole derivatives containing vinyl groups.
Embodiment
With reference to embodiment, the invention will be further described, but should not be construed above-mentioned subject area of the 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：
A kind of resistance to ultraviolet graphene quantum dot is combined the preparation method of para-aramid fiber, comprises the following steps:
1) graphene quantum dot vinyl functionalization
Take 100mg graphene oxide quantum dot to be dissolved in 100ml ethylenediamine, add 50mg DMAP
With 50mg 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, ultrasonic disperse 30min reacts 24h at 90 DEG C
After be cooled to room temperature, 12h is dried in suction filtration washing at 60 DEG C.By reaction product be added to 50mg DMAP,
50mg 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and 20ml passes through the mixing of the acrylic acid except water process
Ultrasonic disperse 30min in solution, is then reacted after 12h at 50 DEG C, is washed by suction filtration, and 12h is dried at 60 DEG C, second is obtained
The graphene quantum dot of alkenyl functionalization.
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.
2) N- [(1- pi-allyl -2- pyrrolidinyls) methyl] -6- methoxyl group -1H- BTA -5- carboxylic acid amides grafting graphite
Alkene quantum dot
Take the graphene quantum dot of the above-mentioned vinyl functionalization of 100mg and 50mg N- [(1- pi-allyl -2- pyrrolidinyls)
Methyl] -6- methoxyl group -1H- BTA -5- carboxylic acid amides is dissolved in 100ml deionized water, and add 50mg ammonium persulfates and arrive
In 30ml deionized water, graphene quantum dot and N- [(1- allyls that funnel is added to vinyl functionalization are titrated using constant pressure
Base -2- pyrrolidinyls) methyl] -6- methoxyl group -1H- BTA -5- carboxylic acid amides mixed solution, adjust rate of titration, made
Ammonium sulfate has been titrated in 30min, after stirring, and is brought rapidly up to 80 DEG C, is reacted under nitrogen and magnetic agitation
12h, suction filtration washing, 12h is dried at 60 DEG C, N- [(1- pi-allyl -2- pyrrolidinyls) methyl] -6- methoxyl group -1H- benzene is obtained
And the graphene quantum dot of triazole -5- carboxylic acid amides grafting.
3) N- [(1- pi-allyl -2- pyrrolidinyls) methyl] -6- methoxyl group -1H- BTA -5- carboxylic acid amides grafting graphite
The quantum-dot modified p-aramid fiber of alkene
Take the above-mentioned N- of 50mg [(1- pi-allyl -2- pyrrolidinyls) methyl] -6- methoxyl group -1H- BTA -5- carboxylic acid amides
The graphene quantum dot of grafting is dissolved in 500ml pyrovinic acid with 100g inherent viscosities for 4.0dl/g p-aramid fiber, ultrasound
Suction filtration is dried after scattered 60min, obtains the quantum-dot modified p-aramid fiber of response type BTA graft grapheme.
4) N- [(1- pi-allyl -2- pyrrolidinyls) methyl] -6- methoxyl group -1H- BTA -5- carboxylic acid amides grafting graphite
The preparation of the quantum-dot modified para-aramid fiber of alkene
15g N- [(1- pi-allyl -2- pyrrolidinyls) methyl] -6- methoxyl group -1H- BTA -5- carboxylic acid amides is connect
Branch graphene quantum dot is modified p-aramid fiber and is dissolved in the concentrated sulfuric acid of the 85g concentration more than 99%, will be mixed after stirring molten
Liquid temperature degree is raised to 85 DEG C, by obtained N- [(1- pi-allyl -2- pyrrolidinyls) methyl] -6- methoxyl group -1H- BTA -5- carboxylics
Acid amide-grafted graphene quantum dot is modified after p-aramid fiber sulfuric acid solution, filters the solution, and deaeration is to prepare uniform and stable spinning
Silk stock solution, then by spinning-drawing machine spinning, stretching ratio is 3 times in air gap, by coagulating bath, washing, heat treatment and after winding,
The enhanced para-aramid fiber of graphene quantum dot is obtained, solidification liquid used in coagulating bath is that the sulfuric acid that concentration is 15% is water-soluble
Liquid, heat treatment temperature is at 120 DEG C, and winding speed is in 120m/min.
Fiber is in 400W ultraviolet light and aging casees obtained by the present embodiment, and by 168h ultraviolet radioactive, fiber can also be kept
The 35% of initial tensile strength.
Embodiment 2：
A kind of resistance to ultraviolet graphene quantum dot is combined the preparation method of para-aramid fiber, comprises the following steps:
1) graphene quantum dot vinyl functionalization
Take 200mg graphene oxide quantum dot to be dissolved in 100ml ethylenediamine, add 50mg DMAP
With 50mg 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, ultrasonic disperse 30min reacts 24h at 90 DEG C
After be cooled to room temperature, 12h is dried in suction filtration washing at 60 DEG C.By reaction product be added to 50mg DMAP,
50mg 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and 20ml passes through the mixing of the acrylic acid except water process
Ultrasonic disperse 30min in solution, is then reacted after 12h at 50 DEG C, is washed by suction filtration, and 12h is dried at 60 DEG C, second is obtained
The graphene quantum dot of alkenyl functionalization.
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.
2) 1- (allyloxy carbon epoxide) -1H- BTA graft grapheme quantum dots
Take the graphene quantum dot of the above-mentioned vinyl functionalization of 100mg and 50mg 1- (allyloxy carbon epoxide) -1H- benzene
And triazole is dissolved in 100ml deionized water, 50mg ammonium persulfates are added into 30ml deionized water, are titrated and leaked using constant pressure
Bucket is added to the graphene quantum dot of vinyl functionalization and the mixed solution of 1- (allyloxy carbon epoxide) -1H- BTAs,
Adjust rate of titration, ammonium persulfate 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, suction filtration washing dries 12h at 60 DEG C, obtains 1- (allyloxy carbon epoxide) -1H- BTAs
The graphene quantum dot of grafting.
3) 1- (allyloxy carbon epoxide) the quantum-dot modified p-aramid fiber of -1H- BTA graft graphemes
Take the graphene quantum dot that the above-mentioned 1- of 50mg (allyloxy carbon epoxide) -1H- BTAs are grafted and 100g characteristics
Viscosity is dissolved in 500ml pyrovinic acid for 4.0dl/g p-aramid fiber, and suction filtration is dried after ultrasonic disperse 60min, is reacted
The quantum-dot modified p-aramid fiber of type BTA graft grapheme.
4) system of 1- (allyloxy carbon epoxide) quantum-dot modified para-aramid fiber of -1H- BTA graft graphemes
It is standby
15g 1- (allyloxy carbon epoxide) quantum-dot modified p-aramid fiber of -1H- BTA graft graphemes is dissolved in
85g concentration is more than in 99% concentrated sulfuric acid, mixed solution temperature is raised into 85 DEG C after stirring, by obtained 1- (allyl oxygen
Base carbon epoxide) after the quantum-dot modified p-aramid fiber sulfuric acid solution of -1H- BTA graft graphemes, filter the solution, deaeration with
Prepare uniform and stable spinning solution, then by spinning-drawing machine spinning, stretching ratio is 3 times in air gap, by coagulating bath, washing,
After heat treatment and winding, the enhanced para-aramid fiber of graphene quantum dot is obtained, solidification liquid used in coagulating bath is dense
The aqueous sulfuric acid for 15% is spent, heat treatment temperature is at 120 DEG C, and winding speed is in 120m/min.
Fiber is in 400W ultraviolet light and aging casees obtained by the present embodiment, and by 168h ultraviolet radioactive, fiber can also be kept
The 36.7% of initial tensile strength.
Embodiment 3：
A kind of resistance to ultraviolet graphene quantum dot is combined the preparation method of para-aramid fiber, comprises the following steps:
1) graphene quantum dot vinyl functionalization
Take 500mg graphene oxide quantum dot to be dissolved in 100ml ethylenediamine, add 50mg DMAP
With 50mg 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, ultrasonic disperse 30min reacts 24h at 90 DEG C
After be cooled to room temperature, 12h is dried in suction filtration washing at 60 DEG C.By reaction product be added to 50mg DMAP,
50mg 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and 20ml passes through the mixing of the acrylic acid except water process
Ultrasonic disperse 30min in solution, is then reacted after 12h at 50 DEG C, is washed by suction filtration, and 12h is dried at 60 DEG C, second is obtained
The graphene quantum dot of alkenyl functionalization.
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.
2) 2- (3- pi-allyl -2- hydroxy-5-methyl bases phenyl) -2H- BTA graft grapheme quantum dots
Take the graphene quantum dot of the above-mentioned vinyl functionalization of 100mg and 50mg 2- (3- pi-allyl -2- hydroxy-5-methyls
Base phenyl) -2H- BTAs are dissolved in 100ml deionized water, add 50mg ammonium persulfates into 30ml deionized water,
Graphene quantum dot and 2- (3- pi-allyl -2- hydroxy-5-methyl base benzene that funnel is added to vinyl functionalization are titrated using constant pressure
Base) -2H- BTAs mixed solution, adjust rate of titration, ammonium persulfate solution has been titrated in 30min, stir
Afterwards, it is brought rapidly up to 80 DEG C, 12h is reacted under nitrogen and magnetic agitation, suction filtration washing dries 12h at 60 DEG C, obtains 2-
The graphene quantum dot of (3- pi-allyl -2- hydroxy-5-methyl bases phenyl) -2H- BTAs grafting.
3) 2- (3- pi-allyl -2- hydroxy-5-methyl bases phenyl) the quantum-dot modified contraposition of -2H- BTAs graft grapheme
Aramid fiber
The graphene quantum for taking the above-mentioned 2- of 50mg (3- pi-allyl -2- hydroxy-5-methyl bases phenyl) -2H- BTAs to be grafted
Point is dissolved in 500ml pyrovinic acid with 100g inherent viscosities for 4.0dl/g p-aramid fiber, suction filtration after ultrasonic disperse 60min
Dry, obtain the quantum-dot modified p-aramid fiber of response type BTA graft grapheme.
4) 2- (3- pi-allyl -2- hydroxy-5-methyl bases phenyl) the quantum-dot modified contraposition of -2H- BTAs graft grapheme
The preparation of aramid fiber
15g 2- (3- pi-allyl -2- hydroxy-5-methyl bases phenyl) -2H- BTA graft graphemes is quantum-dot modified
P-aramid fiber is dissolved in the concentrated sulfuric acid of the 85g concentration more than 99%, and mixed solution temperature is raised into 85 DEG C after stirring, will be made
Obtain 2- (3- pi-allyl -2- hydroxy-5-methyl bases phenyl) quantum-dot modified p-aramid fiber sulfuric acid of -2H- BTA graft graphemes
After solution, the solution is filtered, deaeration is to prepare uniform and stable spinning solution, then by spinning-drawing machine spinning, stretching times in air gap
Rate is 3 times, after coagulating bath, washing, heat treatment and winding, obtains the enhanced para-aramid fiber of graphene quantum dot,
Solidification liquid used in coagulating bath is the aqueous sulfuric acid that concentration is 15%, and heat treatment temperature is at 120 DEG C, and winding speed exists
120m/min。
Fiber is in 400W ultraviolet light and aging casees obtained by the present embodiment, and by 168h ultraviolet radioactive, fiber can also be kept
The 37.6% of initial tensile strength.
Embodiment 4：
A kind of resistance to ultraviolet graphene quantum dot is combined the preparation method of para-aramid fiber, comprises the following steps:
1) graphene quantum dot vinyl functionalization
Take 5000mg graphene oxide quantum dot to be dissolved in 100ml ethylenediamine, add 75mg 4- dimethylamino pyrroles
Pyridine and 75mg 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, ultrasonic disperse 45min react at 93 DEG C
Room temperature is cooled to after 36h, 18h is dried in suction filtration washing at 60 DEG C.Reaction product is added to 75mg 4- dimethylamino pyrroles
Pyridine, 75mg 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and 60ml pass through the acrylic acid except water process
Ultrasonic disperse 45min in mixed solution, is then reacted after 18h at 50 DEG C, is washed by suction filtration, and 18h is dried at 60 DEG C, is obtained
To the graphene quantum dot of vinyl functionalization.
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.
2) N- [(1- pi-allyl -2- pyrrolidinyls) methyl] -6- methoxyl group -1H- BTA -5- carboxylic acid amides grafting graphite
Alkene quantum dot
Take the graphene quantum dot of the above-mentioned vinyl functionalization of 150mg and 75mg N- [(1- pi-allyl -2- pyrrolidinyls)
Methyl] -6- methoxyl group -1H- BTA -5- carboxylic acid amides is dissolved in 100ml deionized water, and add 50mg ammonium persulfates and arrive
In 30ml deionized water, graphene quantum dot and N- [(1- allyls that funnel is added to vinyl functionalization are titrated using constant pressure
Base -2- pyrrolidinyls) methyl] -6- methoxyl group -1H- BTA -5- carboxylic acid amides mixed solution, adjust rate of titration, made
Ammonium sulfate has been titrated in 30min, after stirring, and is brought rapidly up to 90 DEG C, is reacted under nitrogen and magnetic agitation
18h, suction filtration washing, 12h is dried at 60 DEG C, N- [(1- pi-allyl -2- pyrrolidinyls) methyl] -6- methoxyl group -1H- benzene is obtained
And the graphene quantum dot of triazole -5- carboxylic acid amides grafting.
3) N- [(1- pi-allyl -2- pyrrolidinyls) methyl] -6- methoxyl group -1H- BTA -5- carboxylic acid amides grafting graphite
The quantum-dot modified p-aramid fiber of alkene
Take the above-mentioned N- of 75mg [(1- pi-allyl -2- pyrrolidinyls) methyl] -6- methoxyl group -1H- BTA -5- carboxylic acid amides
The graphene quantum dot of grafting is dissolved in 750ml pyrovinic acid with 75g inherent viscosities for 7.5dl/g p-aramid fiber, ultrasound
Suction filtration is dried after scattered 90min, obtains the quantum-dot modified p-aramid fiber of response type BTA graft grapheme.
4) N- [(1- pi-allyl -2- pyrrolidinyls) methyl] -6- methoxyl group -1H- BTA -5- carboxylic acid amides grafting graphite
The preparation of the quantum-dot modified para-aramid fiber of alkene
20g N- [(1- pi-allyl -2- pyrrolidinyls) methyl] -6- methoxyl group -1H- BTA -5- carboxylic acid amides is connect
Branch graphene quantum dot is modified p-aramid fiber and is dissolved in the concentrated sulfuric acid of the 80g concentration more than 99%, will be mixed after stirring molten
Liquid temperature degree is raised to 85 DEG C, by obtained N- [(1- pi-allyl -2- pyrrolidinyls) methyl] -6- methoxyl group -1H- BTA -5- carboxylics
Acid amide-grafted graphene quantum dot is modified after p-aramid fiber sulfuric acid solution, filters the solution, and deaeration is to prepare uniform and stable spinning
Silk stock solution, then by spinning-drawing machine spinning, stretching ratio is 5 times in air gap, by coagulating bath, washing, heat treatment and after winding,
The enhanced para-aramid fiber of graphene quantum dot is obtained, solidification liquid used in coagulating bath is that the sulfuric acid that concentration is 20% is water-soluble
Liquid, heat treatment temperature is at 180 DEG C, and winding speed is in 240m/min.
Fiber is in 400W ultraviolet light and aging casees obtained by the present embodiment, and by 168h ultraviolet radioactive, fiber can also be kept
The 42% of initial tensile strength.
Embodiment 5：
A kind of resistance to ultraviolet graphene quantum dot is combined the preparation method of para-aramid fiber, comprises the following steps:
1) graphene quantum dot vinyl functionalization
Take 2500mg graphene oxide quantum dot to be dissolved in 100ml ethylenediamine, add 75mg 4- dimethylamino pyrroles
Pyridine and 75mg 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, ultrasonic disperse 45min react at 93 DEG C
Room temperature is cooled to after 36h, 18h is dried in suction filtration washing at 60 DEG C.Reaction product is added to 75mg 4- dimethylamino pyrroles
Pyridine, 75mg 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and 60ml pass through the acrylic acid except water process
Ultrasonic disperse 45min in mixed solution, is then reacted after 18h at 50 DEG C, is washed by suction filtration, and 18h is dried at 60 DEG C, is obtained
To the graphene quantum dot of vinyl functionalization.
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.
2) 1- (allyloxy carbon epoxide) -1H- BTA graft grapheme quantum dots
Take the graphene quantum dot of the above-mentioned vinyl functionalization of 150mg and 75mg 1- (allyloxy carbon epoxide) -1H- benzene
And triazole is dissolved in 100ml deionized water, 50mg ammonium persulfates are added into 30ml deionized water, are titrated and leaked using constant pressure
Bucket is added to the graphene quantum dot of vinyl functionalization and the mixed solution of 1- (allyloxy carbon epoxide) -1H- BTAs,
Adjust rate of titration, ammonium persulfate solution has been titrated in 30min, after stirring, be brought rapidly up to 90 DEG C, in nitrogen and
18h is reacted under magnetic agitation, suction filtration washing dries 12h at 60 DEG C, obtains 1- (allyloxy carbon epoxide) -1H- BTAs
The graphene quantum dot of grafting.
3) 1- (allyloxy carbon epoxide) the quantum-dot modified p-aramid fiber of -1H- BTA graft graphemes
The graphene quantum dot that the above-mentioned 1- of 75mg (allyloxy carbon epoxide) -1H- BTAs are grafted is taken to be glued with 75g characteristics
Spend and be dissolved in for 7.5dl/g p-aramid fiber in 750ml pyrovinic acid, suction filtration is dried after ultrasonic disperse 90min, obtains response type
The quantum-dot modified p-aramid fiber of BTA graft grapheme.
4) system of 1- (allyloxy carbon epoxide) quantum-dot modified para-aramid fiber of -1H- BTA graft graphemes
It is standby
20g 1- (allyloxy carbon epoxide) quantum-dot modified p-aramid fiber of -1H- BTA graft graphemes is dissolved in
80g concentration is more than in 99% concentrated sulfuric acid, mixed solution temperature is raised into 85 DEG C after stirring, by obtained 1- (allyl oxygen
Base carbon epoxide) after the quantum-dot modified p-aramid fiber sulfuric acid solution of -1H- BTA graft graphemes, filter the solution, deaeration with
Prepare uniform and stable spinning solution, then by spinning-drawing machine spinning, stretching ratio is 5 times in air gap, by coagulating bath, washing,
After heat treatment and winding, the enhanced para-aramid fiber of graphene quantum dot is obtained, solidification liquid used in coagulating bath is dense
The aqueous sulfuric acid for 20% is spent, heat treatment temperature is at 180 DEG C, and winding speed is in 240m/min.
Fiber is in 400W ultraviolet light and aging casees obtained by the present embodiment, and by 168h ultraviolet radioactive, fiber can also be kept
The 44.2% of initial tensile strength.
Embodiment 6：
A kind of resistance to ultraviolet graphene quantum dot is combined the preparation method of para-aramid fiber, comprises the following steps:
1) graphene quantum dot vinyl functionalization
Take 1000mg graphene oxide quantum dot to be dissolved in 100ml ethylenediamine, add 75mg 4- dimethylamino pyrroles
Pyridine and 75mg 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, ultrasonic disperse 45min react at 93 DEG C
Room temperature is cooled to after 36h, 18h is dried in suction filtration washing at 60 DEG C.Reaction product is added to 75mg 4- dimethylamino pyrroles
Pyridine, 75mg 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and 60ml pass through the acrylic acid except water process
Ultrasonic disperse 45min in mixed solution, is then reacted after 18h at 50 DEG C, is washed by suction filtration, and 18h is dried at 60 DEG C, is obtained
To the graphene quantum dot of vinyl functionalization.
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.
2) 2- (3- pi-allyl -2- hydroxy-5-methyl bases phenyl) -2H- BTA graft grapheme quantum dots
Take the graphene quantum dot of the above-mentioned vinyl functionalization of 150mg and 75mg 2- (3- pi-allyl -2- hydroxy-5-methyls
Base phenyl) -2H- BTAs are dissolved in 100ml deionized water, add 50mg ammonium persulfates into 30ml deionized water,
Graphene quantum dot and 2- (3- pi-allyl -2- hydroxy-5-methyl base benzene that funnel is added to vinyl functionalization are titrated using constant pressure
Base) -2H- BTAs mixed solution, adjust rate of titration, ammonium persulfate solution has been titrated in 30min, stir
Afterwards, it is brought rapidly up to 90 DEG C, 18h is reacted under nitrogen and magnetic agitation, suction filtration washing dries 12h at 60 DEG C, obtains 2-
The graphene quantum dot of (3- pi-allyl -2- hydroxy-5-methyl bases phenyl) -2H- BTAs grafting.
3) 2- (3- pi-allyl -2- hydroxy-5-methyl bases phenyl) the quantum-dot modified contraposition of -2H- BTAs graft grapheme
Aramid fiber
The graphene quantum for taking the above-mentioned 2- of 75mg (3- pi-allyl -2- hydroxy-5-methyl bases phenyl) -2H- BTAs to be grafted
Point is dissolved in 750ml pyrovinic acid with 75g inherent viscosities for 7.5dl/g p-aramid fiber, and suction filtration is done after ultrasonic disperse 90min
It is dry, obtain the quantum-dot modified p-aramid fiber of response type BTA graft grapheme.
4) 2- (3- pi-allyl -2- hydroxy-5-methyl bases phenyl) the quantum-dot modified contraposition of -2H- BTAs graft grapheme
The preparation of aramid fiber
20g 2- (3- pi-allyl -2- hydroxy-5-methyl bases phenyl) -2H- BTA graft graphemes is quantum-dot modified
P-aramid fiber is dissolved in the concentrated sulfuric acid of the 80g concentration more than 99%, and mixed solution temperature is raised into 85 DEG C after stirring, will be made
Obtain 2- (3- pi-allyl -2- hydroxy-5-methyl bases phenyl) quantum-dot modified p-aramid fiber sulfuric acid of -2H- BTA graft graphemes
After solution, the solution is filtered, deaeration is to prepare uniform and stable spinning solution, then by spinning-drawing machine spinning, stretching times in air gap
Rate is 5 times, after coagulating bath, washing, heat treatment and winding, obtains the enhanced para-aramid fiber of graphene quantum dot,
Solidification liquid used in coagulating bath is the aqueous sulfuric acid that concentration is 20%, and heat treatment temperature is at 180 DEG C, and winding speed exists
240m/min。
Fiber is in 400W ultraviolet light and aging casees obtained by the present embodiment, and by 168h ultraviolet radioactive, fiber can also be kept
The 46.7% of initial tensile strength.
Embodiment 7：
A kind of resistance to ultraviolet graphene quantum dot is combined the preparation method of para-aramid fiber, comprises the following steps:
1) graphene quantum dot vinyl functionalization
Take 500mg graphene oxide quantum dot to be dissolved in 100ml ethylenediamine, add 100mg 4- dimethylamino pyrroles
Pyridine and 100mg 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, ultrasonic disperse 60min react at 95 DEG C
Room temperature is cooled to after 48h, 24h is dried in suction filtration washing at 60 DEG C.Reaction product is added to 100mg 4- dimethylamino pyrroles
Pyridine, 100mg 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and 100ml pass through the acrylic acid except water process
Mixed solution in ultrasonic disperse 60min, then at 50 DEG C react 24h after, washed by suction filtration, at 60 DEG C dry 24h,
Obtain the graphene quantum dot of vinyl functionalization.
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.
2) N- [(1- pi-allyl -2- pyrrolidinyls) methyl] -6- methoxyl group -1H- BTA -5- carboxylic acid amides grafting graphite
Alkene quantum dot
Take the graphene quantum dot of the above-mentioned vinyl functionalization of 200mg and 100mg N- [(1- pi-allyl -2- pyrrolidines
Base) methyl] -6- methoxyl group -1H- BTA -5- carboxylic acid amides is dissolved in 100ml deionized water, adds 50mg ammonium persulfates
Into 30ml deionized water, graphene quantum dot and N- [(1- alkene that funnel is added to vinyl functionalization are titrated using constant pressure
Propyl group -2- pyrrolidinyls) methyl] -6- methoxyl group -1H- BTA -5- carboxylic acid amides mixed solution, adjust rate of titration, make
Ammonium persulfate solution has been titrated in 30min, after stirring, and is brought rapidly up to 100 DEG C, is reacted under nitrogen and magnetic agitation
24h, suction filtration washing, 12h is dried at 60 DEG C, N- [(1- pi-allyl -2- pyrrolidinyls) methyl] -6- methoxyl group -1H- benzene is obtained
And the graphene quantum dot of triazole -5- carboxylic acid amides grafting.
3) N- [(1- pi-allyl -2- pyrrolidinyls) methyl] -6- methoxyl group -1H- BTA -5- carboxylic acid amides grafting graphite
The quantum-dot modified p-aramid fiber of alkene
Take the above-mentioned N- of 100mg [(1- pi-allyl -2- pyrrolidinyls) methyl] -6- methoxyl group -1H- BTA -5- carboxylic acyls
The graphene quantum dot of amine grafting is dissolved in 1000ml pyrovinic acid with 100g inherent viscosities for 9.0dl/g p-aramid fiber,
Suction filtration is dried after ultrasonic disperse 120min, obtains the quantum-dot modified p-aramid fiber of response type BTA graft grapheme.
4) N- [(1- pi-allyl -2- pyrrolidinyls) methyl] -6- methoxyl group -1H- BTA -5- carboxylic acid amides grafting graphite
The preparation of the quantum-dot modified para-aramid fiber of alkene
25g N- [(1- pi-allyl -2- pyrrolidinyls) methyl] -6- methoxyl group -1H- BTA -5- carboxylic acid amides is connect
Branch graphene quantum dot is modified p-aramid fiber and is dissolved in the concentrated sulfuric acid of the 75g concentration more than 99%, will be mixed after stirring molten
Liquid temperature degree is raised to 85 DEG C, by obtained N- [(1- pi-allyl -2- pyrrolidinyls) methyl] -6- methoxyl group -1H- BTA -5- carboxylics
Acid amide-grafted graphene quantum dot is modified after p-aramid fiber sulfuric acid solution, filters the solution, and deaeration is to prepare uniform and stable spinning
Silk stock solution, then by spinning-drawing machine spinning, stretching ratio is 10 times in air gap, by coagulating bath, washes, is heat-treated and winds it
Afterwards, the enhanced para-aramid fiber of graphene quantum dot is obtained, solidification liquid used in coagulating bath is the sulfuric acid that concentration is 25%
The aqueous solution, heat treatment temperature is at 240 DEG C, and winding speed is in 350m/min.
Fiber is in 400W ultraviolet light and aging casees obtained by the present embodiment, and by 168h ultraviolet radioactive, fiber can also be kept
The 44% of initial tensile strength.
Embodiment 8：
A kind of resistance to ultraviolet graphene quantum dot is combined the preparation method of para-aramid fiber, comprises the following steps:
1) graphene quantum dot vinyl functionalization
Take 500mg graphene oxide quantum dot to be dissolved in 100ml ethylenediamine, add 100mg 4- dimethylamino pyrroles
Pyridine and 100mg 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, ultrasonic disperse 60min react at 95 DEG C
Room temperature is cooled to after 48h, 24h is dried in suction filtration washing at 60 DEG C.Reaction product is added to 100mg 4- dimethylamino pyrroles
Pyridine, 100mg 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and 100ml pass through the acrylic acid except water process
Mixed solution in ultrasonic disperse 60min, then at 50 DEG C react 24h after, washed by suction filtration, at 60 DEG C dry 24h,
Obtain the graphene quantum dot of vinyl functionalization.
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.
2) 1- (allyloxy carbon epoxide) -1H- BTA graft grapheme quantum dots
Take the graphene quantum dot of the above-mentioned vinyl functionalization of 200mg and 100mg 1- (allyloxy carbon epoxide) -1H-
BTA is dissolved in 100ml deionized water, is added 50mg ammonium persulfates into 30ml deionized water, is titrated using constant pressure
The mixing that funnel is added to the graphene quantum dot and 1- (allyloxy carbon epoxide) -1H- BTAs of vinyl functionalization is molten
Liquid, adjusts rate of titration, ammonium persulfate solution has been titrated in 30min, after stirring, be brought rapidly up to 100 DEG C, in nitrogen
24h is reacted under gas and magnetic agitation, suction filtration washing dries 12h at 60 DEG C, obtains 1- (allyloxy carbon epoxide) -1H- benzos
The graphene quantum dot of triazole grafting.
3) 1- (allyloxy carbon epoxide) the quantum-dot modified p-aramid fiber of -1H- BTA graft graphemes
Take the graphene quantum dot that the above-mentioned 1- of 100mg (allyloxy carbon epoxide) -1H- BTAs are grafted and 100g characteristics
Viscosity is dissolved in 1000ml pyrovinic acid for 9.0dl/g p-aramid fiber, and suction filtration is dried after ultrasonic disperse 120min, obtains anti-
The p-aramid fiber for answering type BTA graft grapheme quantum-dot modified.
4) system of 1- (allyloxy carbon epoxide) quantum-dot modified para-aramid fiber of -1H- BTA graft graphemes
It is standby
25g 1- (allyloxy carbon epoxide) quantum-dot modified p-aramid fiber of -1H- BTA graft graphemes is dissolved in
75g concentration is more than in 99% concentrated sulfuric acid, mixed solution temperature is raised into 85 DEG C after stirring, by obtained 1- (allyl oxygen
Base carbon epoxide) after the quantum-dot modified p-aramid fiber sulfuric acid solution of -1H- BTA graft graphemes, filter the solution, deaeration with
Prepare uniform and stable spinning solution, then by spinning-drawing machine spinning, stretching ratio is 10 times in air gap, by coagulating bath, washing,
After heat treatment and winding, the enhanced para-aramid fiber of graphene quantum dot is obtained, solidification liquid used in coagulating bath is dense
The aqueous sulfuric acid for 25% is spent, heat treatment temperature is at 240 DEG C, and winding speed is in 350m/min.
Fiber is in 400W ultraviolet light and aging casees obtained by the present embodiment, and by 168h ultraviolet radioactive, fiber can also be kept
The 46.9% of initial tensile strength.
Embodiment 9：
A kind of resistance to ultraviolet graphene quantum dot is combined the preparation method of para-aramid fiber, comprises the following steps:
1) graphene quantum dot vinyl functionalization
Take 800mg graphene oxide quantum dot to be dissolved in 100ml ethylenediamine, add 100mg 4- dimethylamino pyrroles
Pyridine and 100mg 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, ultrasonic disperse 60min react at 95 DEG C
Room temperature is cooled to after 48h, 24h is dried in suction filtration washing at 60 DEG C.Reaction product is added to 100mg 4- dimethylamino pyrroles
Pyridine, 100mg 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides and 100ml pass through the acrylic acid except water process
Mixed solution in ultrasonic disperse 60min, then at 50 DEG C react 24h after, washed by suction filtration, at 60 DEG C dry 24h,
Obtain the graphene quantum dot of vinyl functionalization.
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.
2) 2- (3- pi-allyl -2- hydroxy-5-methyl bases phenyl) -2H- BTA graft grapheme quantum dots
Take the graphene quantum dot of the above-mentioned vinyl functionalization of 200mg and 100mg 2- (3- pi-allyl -2- hydroxy-5-methyls
Base phenyl) -2H- BTAs are dissolved in 100ml deionized water, add 50mg ammonium persulfates into 30ml deionized water,
Graphene quantum dot and 2- (3- pi-allyl -2- hydroxy-5-methyl base benzene that funnel is added to vinyl functionalization are titrated using constant pressure
Base) -2H- BTAs mixed solution, adjust rate of titration, ammonium persulfate solution has been titrated in 30min, stir
Afterwards, it is brought rapidly up to 100 DEG C, 24h is reacted under nitrogen and magnetic agitation, suction filtration washing dries 12h at 60 DEG C, obtains 2-
The graphene quantum dot of (3- pi-allyl -2- hydroxy-5-methyl bases phenyl) -2H- BTAs grafting.
3) 2- (3- pi-allyl -2- hydroxy-5-methyl bases phenyl) the quantum-dot modified contraposition of -2H- BTAs graft grapheme
Aramid fiber
The graphene quantum for taking the above-mentioned 2- of 100mg (3- pi-allyl -2- hydroxy-5-methyl bases phenyl) -2H- BTAs to be grafted
Point is dissolved in 1000ml pyrovinic acid with 100g inherent viscosities for 9.0dl/g p-aramid fiber, is taken out after ultrasonic disperse 120min
It is filtered dry dry, obtains the quantum-dot modified p-aramid fiber of response type BTA graft grapheme.
4) 2- (3- pi-allyl -2- hydroxy-5-methyl bases phenyl) the quantum-dot modified contraposition of -2H- BTAs graft grapheme
The preparation of aramid fiber
25g 2- (3- pi-allyl -2- hydroxy-5-methyl bases phenyl) -2H- BTA graft graphemes is quantum-dot modified
P-aramid fiber is dissolved in the concentrated sulfuric acid of the 75g concentration more than 99%, and mixed solution temperature is raised into 85 DEG C after stirring, will be made
Obtain 2- (3- pi-allyl -2- hydroxy-5-methyl bases phenyl) quantum-dot modified p-aramid fiber sulfuric acid of -2H- BTA graft graphemes
After solution, the solution is filtered, deaeration is to prepare uniform and stable spinning solution, then by spinning-drawing machine spinning, stretching times in air gap
Rate is 10 times, after coagulating bath, washing, heat treatment and winding, obtains the enhanced para-aramid fiber of graphene quantum dot,
Solidification liquid used in coagulating bath is the aqueous sulfuric acid that concentration is 25%, and heat treatment temperature is at 240 DEG C, and winding speed exists
350m/min.Fiber is in 400W ultraviolet light and aging casees obtained by the present embodiment, and by 168h ultraviolet radioactive, fiber can also be kept
The 50% of initial tensile strength.
Claims (6)
1. a kind of resistance to ultraviolet graphene quantum dot is combined the preparation method of para-aramid fiber, it is characterised in that including following step
Suddenly：
1) graphene quantum dot vinyl functionalization
1.1) sequentially added in 100 parts of ethylenediamine 0.1~5 part graphene oxide quantum dot, 0.5~1 part of 4- diformazans
Aminopyridine and 0.5~1 part of 1- (3- dimethylamino-propyls) -3- ethyl-carbodiimide hydrochlorides, obtain mixed solution A；
1.2) by after 30~60min of mixed solution A ultrasonic disperse, 24~48h is reacted under the conditions of being placed in 90~95 DEG C, after reaction
Obtained mixture is cooled to room temperature, obtains suspension A；
1.3) suspension A suction filtrations are washed, obtains product A, 12~24h is dried under the conditions of product A is placed in into 60 DEG C, product is obtained
B；
1.4) 0.5~1 part of DMAP, 0.5~1 part of 1- (3- dimethylamino-propyls) -3- ethyls carbon two is weighed
Inferior amine salt hydrochlorate and 100 parts of processes remove the acrylic acid of water process, and three is mixed to get into mixed solution B；
1.5) 0.5 part of product B is added in mixed solution B, after 30~60min of ultrasonic disperse, reacted under the conditions of being placed in 50 DEG C
12~24h, obtains suspension B；
1.6) suspension B suction filtrations are washed, obtains product C, 12~24h is dried under the conditions of product C is placed in into 60 DEG C, ethene is obtained
The graphene quantum dot of base functionalization；
2) response type BTA graft grapheme quantum dot
2.1) it is molten by the graphene quantum dot and 50~100 parts of response type BTA of 100~200 parts of vinyl functionalization
In 2000 parts of deionized water, mixed solution C is obtained；
2.2) 50 parts of ammonium persulfates are added in 200 parts of deionized water, obtain mixed solution D；
2.3) funnel is titrated using constant pressure, mixed solution D is added in mixed solution C, adjusted rate of titration, make ammonium persulfate
Solution has been titrated in 30-120min, obtains mixed solution E；
2.4) mixed solution E is stirred, after stirring, is warming up to 80~100 DEG C, then by mixed solution E in nitrogen and
12~24h is reacted under magnetic agitation, suspension C is obtained；
2.5) suspension C is subjected to suction filtration washing, obtains product D, 12h is dried under the conditions of product D is placed in into 60 DEG C, is reacted
The graphene quantum dot of type BTA grafting；
3) the quantum-dot modified p-aramid fiber of response type BTA graft grapheme
3.1) by the graphene quantum dot and 50~100 parts of contraposition virtue of 0.05~0.1 part of above-mentioned response type BTA grafting
Synthetic fibre is dissolved in 200 parts of pyrovinic acid, obtains mixed solution F；
3.2) suction filtration after 60~120min of mixed solution F ultrasonic disperses is dried, obtains response type BTA graft grapheme
Quantum-dot modified p-aramid fiber；
4) preparation of the quantum-dot modified para-aramid fiber of response type BTA graft grapheme
4.1) by 15~25 parts of the quantum-dot modified p-aramid fiber of response type BTA graft grapheme be dissolved in 75~85 parts it is dense
Spend in the concentrated sulfuric acid for 99%, stir, obtain the product E；
4.2) under the conditions of 85 DEG C, product E is placed in spinning-drawing machine spinning, after coagulating bath, washing, heat treatment and winding,
Obtain the enhanced para-aramid fiber of graphene quantum dot.
2. a kind of resistance to ultraviolet graphene quantum dot according to claim 1 is combined the preparation method of para-aramid fiber, its
It is characterised by：The step 1.1) in its thickness of graphene quantum dot in 0.34~1nm, lamella diameter is in 1~100nm.
3. a kind of resistance to ultraviolet graphene quantum dot according to claim 1 or 2 is combined the preparation method of para-aramid fiber,
It is characterized in that：Step 2.1) described in response type BTA include N- [(1- pi-allyl -2- pyrrolidinyls) methyl] -6-
Methoxyl group -1H- BTA -5- carboxylic acid amides, 1- (allyloxy carbon epoxide) -1H- BTAs or 2- (3- pi-allyl -2- hydroxyls
Base -5- aminomethyl phenyls) -2H- BTAs.
4. a kind of resistance to ultraviolet graphene quantum dot according to claim 1 is combined the preparation method of para-aramid fiber, its
It is characterised by：Step 3.1) described in p-aramid fiber inherent viscosity be 4.0~9.0dl/g.
5. a kind of resistance to ultraviolet graphene quantum dot according to claim 1 is combined the preparation method of para-aramid fiber, its
It is characterised by：Step 4) described in the quantum-dot modified p-aramid fiber sulfuric acid solution of obtained response type BTA graft grapheme
Afterwards, filter and uniform and stable spinning solution is prepared after the solution, deaeration.
6. a kind of resistance to ultraviolet graphene quantum dot according to claim 1 is combined the preparation method of para-aramid fiber, its
It is characterised by：The step 4.2) in solidification liquid used in coagulating bath be aqueous sulfuric acid that concentration is 15%~25%, heat
Temperature ranges are 120~240 DEG C, and winding speed scope is 120~350m/min.
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