CN108251907A - A kind of High-performance graphene-polyvinyl alcohol composite fiber preparation method - Google Patents
A kind of High-performance graphene-polyvinyl alcohol composite fiber preparation method Download PDFInfo
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- CN108251907A CN108251907A CN201711267292.5A CN201711267292A CN108251907A CN 108251907 A CN108251907 A CN 108251907A CN 201711267292 A CN201711267292 A CN 201711267292A CN 108251907 A CN108251907 A CN 108251907A
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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
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/50—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyalcohols, polyacetals or polyketals
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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
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Abstract
The invention discloses a kind of High-performance graphene polyvinyl alcohol composite fiber preparation methods, which is characterized in that includes the following steps：1) the blocked isocyanate base functionalization of graphene quantum dot；2) preparation of polyvinyl alcohol graphene quantum dot (PVA GQD) spinning solution；3) wet spinning；4) post processing of as-spun fibre；It is of the invention easy, flow is short, at low cost and suitable large-scale production; and without being modified to existing Wet PVA spinning technique equipment; obtained PVA GQD fibers not only have excellent mechanical property and easy dispersing characteristic; and metallic luster is presented in appearance, is ideal concrete reinforced material, packaging material and wearing fabric.
Description
Technical field
The present invention relates to the preparation field of composite fibre, specifically a kind of High-performance graphene-polyvinyl alcohol composite fiber
Preparation method.
Background technology
Polyvinyl alcohol (PVA) is a kind of function admirable, widely used polymer, and high-performance fiber prepared therefrom has
Excellent corrosion resistance, against weather and with the good adhesive property of substrate interface, can be made into tensile strength is high, creep properties is good,
Wear-resisting, resistant to chemical etching, resistance to microorganism and the excellent geotextiles of transmissibility, build for various dams, highway, railway, bridge etc.
Engineering is built, construction quality can be significantly improved, reduces engineering cost.In addition PVA fibers have shock resistance, against weather and sea water resistance
The characteristics of comprehensive performances such as corrosivity are outstanding is suitable for use as various types of fishing nets, fishing gear, hawser etc., in marine fishing and friendship
Logical transport etc. has good application market.PVA fibers also act as tire cord, car belt, high-performance simultaneously
Rope and plastics, rubber reinforcement material etc..
With the development of the society, above application field proposes the intensity and modulus of PVA higher requirement, therefore send out
The PVA fibre manufacturing technologies of exhibition high strength and modulus are of great significance.At present, the intensity and modulus for raising PVA fibers, state
It is inside and outside to put into a large amount of manpower and materials and competitively study, as the U.S., Japan and other countries develop PVA gel spinnings, the crosslinking of PVA boracics
Wet spinning, dry-wet spinning etc..
The current high strength and modulus PVA fibers in China mainly using plus boron spining technology, contain in obtained fiber compared with
A high proportion of boron element (being usually 0.4%), as environmental protection cry grows to even greater heights, cannot gradually meet the users such as Europe
The product requirement of country, therefore current manufacturing technology of the exploitation without boron, the high strength and modulus PVA fibers of low production cost is shown
It obtains particularly important.
Invention content
Present invention aim to address problems of the prior art, provide a kind of High-performance graphene-polyvinyl alcohol
Composite fibre preparation method.
To realize the present invention purpose and the technical solution adopted is that such, a kind of High-performance graphene-polyvinyl alcohol is multiple
Condensating fiber preparation method, which is characterized in that include the following steps：
1) the blocked isocyanate base functionalization of graphene quantum dot
1.1) load weighted graphene oxide quantum dot, diisocyanate and N,N-dimethylformamide (DMF) are mixed
Obtain mixed solution A；
The parts by weight of the graphene oxide quantum dot are 100~1000 parts；The parts by weight of the diisocyanate
It is 1000~10000 parts；The parts by weight of the N,N-dimethylformamide are 1000~10000 parts；
1.2) it after the mixed solution A obtained in step 1.1) is ultrasonically treated, is carried out under the conditions of being placed in 80~90 DEG C
Reaction, 24~48h postcoolings to room temperature obtain product A；The time of the supersound process is 30~60min；
After product A is carried out centrifugal treating, after being cleaned using ether, product B is obtained；
Product B is placed under the conditions of 60 DEG C and is dried, product C is obtained after 12~48h；
1.3) it after mixing load weighted product C and n,N-Dimethylformamide, carries out ultrasound and obtains mixing liquid B；Institute
It is 20 minutes to state ultrasonic time；
Under conditions of mixing liquid B is placed in 80~100 DEG C, sealer is added in, reaction obtains mixed liquor after 3~6 hours
Body C；
The parts by weight of the product C are 100~1000 parts；The parts by weight of the N,N-dimethylformamide are 1000
~10000 parts；The parts by weight of the sealer are 100~1000 parts；
1.4) the mixing liquid C obtained in step 1.3) is subjected to suction filtration washing, obtains product D；
Under the conditions of product D is placed in 80 DEG C, 12~48h is dried in vacuo, obtains the graphite of blocked isocyanate base functionalization
Alkene quantum dot (GQD)；
2) preparation of polyvinyl alcohol-graphene quantum dot (PVA-GQD) spinning solution
2.1) graphene quantum dot, dispersant, the polyvinyl alcohol of load weighted blocked isocyanate base functionalization are dissolved in
In water, stirring, dispersion are configured to PVA1788-GQD solution；
The degree of polymerization of the polyvinyl alcohol is 1700, alcoholysis degree 88%；
The parts by weight of the graphene quantum dot of the blocked isocyanate base functionalization are 0.005~0.02 part；It is described
The parts by weight of dispersant are 0.005~0.02 part；The parts by weight of the polyvinyl alcohol 1788 are 0.02 part；The weight of the water
It is 84.94~89.97 parts to measure number；
2.2) under the conditions of the PVA1788-GQD solution obtained in step 2.1) being placed in 95~100 DEG C, polyethylene is added in
Alcohol after stirring 5~8 hours, obtains polyvinyl alcohol-graphene quantum dot spinning solution；
The parts by weight of the polyvinyl alcohol are 10~15 parts, and the degree of polymerization of the polyvinyl alcohol is 1700~2800, point
Son amount is distributed as 1.5~2.0, alcoholysis degree 99%；
The stir speed (S.S.) is 50~200 revs/min；
3) wet spinning
Using the polyvinyl alcohol-graphene quantum dot spinning solution obtained in step 2.2) as raw material, spun using normal wet
Silk machine carries out wet spinning, prepares PVA-GQD as-spun fibres；
4) post processing of as-spun fibre
The PVA-GQD as-spun fibres obtained in step 3) are subjected to multistage hot-stretch, thermal finalization, obtain high strength and modulus
PVA-GQD composite fibres.
Further, the graphite flake layer of the graphene quantum dot in the step 1.1) be 1~3 layer, size be 10~
100nm。
Further, the diisocyanate in the step 1.1) is toluene di-isocyanate(TDI) (TDI), the own diisocyanates of 1,6-
Ester (HDI), isophorone diisocyanate (IPDI), benzene dimethylene diisocyanate (XDI), tri-methyl hexamethylene two are different
One kind in cyanate (TMDI) or 4,4 '-methyl diphenylene diisocyanate (MDI).
Further, the sealer in the step 1.3) is phenol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether or methyl ethyl ketone
One kind in oxime.
Further, after polyvinyl alcohol-graphene quantum dot spinning solution being made in the step 2), using 500 mesh screens
It is filtered, deaeration, prepares uniform and stable spinning solution.
Further, after the step 3), according to purposes difference, to PVA-GQD composite fibres carry out acetalation, on
Oil, curling and/or cut-out.
Further, the dispersant in the step 2.1) be a)~c) in state any one situation, wherein：A) polyoxy
Ethylene ethers or esters tween, b) Sulfonates, Sulfates, phosphate or phosphite anionoid activity
Agent, c) amino acids, imidazoles, oxidation one or more of amine amphoteric surfactant arbitrary proportion mixture.
Further, spinning temperature is 95~100 DEG C in the step 3), and spinneret temperature is 95~100 DEG C, spinneret hole
0.08~0.12mm of diameter；
Used wet spinning coagulating bath is supersaturated aqueous sodium persulfate solution, and coagulation bath temperature is 45~60 DEG C；
The receipts silk rate (V1) of first roller of used wet spinning is slightly less than spin rate (V0), i.e. V1/V0=
0.93~0.97, the receipts silk rate (V2) of the second roller is slightly larger than the receipts silk rate (V1) of the first roller, i.e. V2/V1=1.2~1.5.
Further, in the step 4), heat setting temperature is 210~230 DEG C, and the time is 1~3min.
What deserves to be explained is including one kind in the prior art using graphene quantum dot as template, tensile break strength is higher than
The high strength and modulus PVA fibre manufacturing technologies of 11.5cN/tex find graphene quantum dot on microcosmic by further investigation
Still there is the space that can be promoted with PVA molecules compatibility, will be helpful to further improve PVA fibers if improving the two compatibility
Tensile break strength and modulus.
The present invention on the basis of existing technology, using chemical reaction in the edge-oriented modification activities official of graphene quantum dot
It can roll into a ball and discharge functional group's activity in spinning last part technology and be allowed to bundle with orientation PVA molecules, obtain tensile break strength
Higher than the high strength and modulus graphene-PVA composite fibres that 13.5cN/tex, rupture modulus are higher than 200cN/tex.
The present invention improves the degree of orientation of the PVA molecules along fiber axial direction using the molecular template effect of graphene quantum dot；
In addition in fiber high temperature heat stretching process, the closing chemical group on graphene quantum dot is activated the isocyanates released
Group is bonded with the hydroxyl on PVA molecular side chains, enhances the interaction of graphene quantum dot and PVA molecules, graphene amount
Son puts the stacking formed between PVA textures, dislocation effect improves PVA fibrous mechanical properties.Using the technology, pass through biography
System PVA wet spinning technologies are prepared for tensile strength as 13.2~14.5cN/tex, and initial modulus is 180~210cN/tex's
PVA-Graphene Quantum Dot (PVA-GQD) composite fibre of high strength and modulus.High-strength height is prepared with wet method plus boron
Mould PVA fibers are compared, and mechanical property is more excellent, and reduce the processes such as neutralization, washing, technological process in technological process
It is short, environmental pollution is small.
The solution have the advantages that unquestionable, the present invention has the following advantages：
It is of the invention easy, flow is short, at low cost and suitable large-scale production, and without being spun to existing Wet PVA
Silk process equipment is modified, and obtained PVA-GQD fibers not only have excellent mechanical property and easy dispersing characteristic, and outer
It sees and metallic luster is presented, be ideal concrete reinforced material, packaging material and wearing fabric.
Description of the drawings
Fig. 1 is the chemical equation of the blocked isocyanate base functionalization of graphene quantum dot；
Fig. 2 is the chemical equation of graphene quantum dot and polyvinyl alcohol molecule.
Specific 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, should all be included within the scope of the present invention.
Embodiment 1：
A kind of High-performance graphene-polyvinyl alcohol composite fiber preparation method, which is characterized in that include the following steps：
1) the blocked isocyanate base functionalization of graphene oxide quantum dot
The graphene oxide quantum dot of 100mg is taken to be dissolved in the DMF of 100ml, adds in the TDI of 100mg, ultrasonic disperse
30min reacts postcooling for 24 hours at 80 DEG C and, to room temperature, product is centrifuged, is cleaned 3 times with ether, product is placed in 60 DEG C
Under the conditions of obtain the graphene quantum dot of isocyanate group functionalization after dry 12h；
The DMF mixing of the graphene quantum dot and 100ml of 100mg isocyanate group functionalization is weighed, and 20 minutes ultrasonic,
100mg phenol is added in as sealer, mixed solution is warming up to 90 DEG C, is reacted 5 hours；Mixed solution is centrifuged, is used
Ether cleans 3 times, and solid product is placed under the conditions of 80 DEG C and is dried in vacuo the stone for for 24 hours, obtaining blocked isocyanate base functionalization
Black alkene quantum dot (GQD).
As shown in Figure 1, the as chemical equation of the blocked isocyanate base functionalization of graphene quantum dot.
2) preparation of polyvinyl alcohol-graphene quantum dot (PVA-GQD) spinning solution
Take the graphene quantum dot 0.005g of blocked isocyanate base functionalization, the poly- second of dispersant 0.005g and 0.02g
Enol 1788, is mixed in the water of 84.97g, stirs at room temperature, disperses to be configured to PVA1788-GQD solution；
PVA1788-GQD solution is warming up to 98 DEG C, 15g polyvinyl alcohol 1799 is added in, is made after mechanical agitation a few hours
Polyvinyl alcohol-graphene quantum dot (PVA-GQD) spinning solution.
As shown in Fig. 2, the as chemical equation of graphene quantum dot and polyvinyl alcohol molecule.
3) wet spinning
Polyvinyl alcohol-graphene quantum dot (PVA-GQD) spinning solution prepared by step 2 is used as raw material, spinning temperature
It it is 95 DEG C, spinneret temperature is 95 DEG C, the hole diameter of spinneret 0.08mm, and coagulating bath is supersaturated aqueous sodium persulfate solution, solidifies bath temperature
Spend is 50 DEG C；The receipts silk rate (V1) of first roller is slightly less than spin rate (V0), V1/V0=0.97, the receipts silk rate of the second roller
(V2) slightly larger than the receipts silk rate (V1) of the first roller, V2/V1=1.2；Winding obtains PVA-GQD as-spun fibres；
The post processing of as-spun fibre
PVA-GQD as-spun fibres are subjected to two level hot-stretch, two level hot-stretch temperature is respectively 180 DEG C and 200 DEG C, hot-drawn
It is 12 times to stretch general times；The compound fibres of high strength and modulus PVA-GQD are obtained after multistage hot-stretch, then by thermal finalization
Dimension.Heat setting temperature is 220 DEG C, time 1min.
The fracture strength of fiber obtained by the present embodiment is 13.5cN/tex, initial modulus 180cN/tex.
Embodiment 2：
A kind of High-performance graphene-polyvinyl alcohol composite fiber preparation method, which is characterized in that include the following steps：
1) the blocked isocyanate base functionalization of graphene oxide quantum dot
The graphene oxide quantum dot of 200mg is taken to be dissolved in the DMF of 100ml, adds in the HDI of 150mg, ultrasonic disperse
30min reacts postcooling for 24 hours at 80 DEG C and, to room temperature, product is centrifuged, is cleaned 3 times with ether, product is placed in 60 DEG C
Under the conditions of obtain the graphene quantum dot of isocyanate group functionalization after dry 12h；
The DMF mixing of the graphene quantum dot and 100ml of 150mg isocyanate group functionalization is weighed, and 20 minutes ultrasonic,
100mg methyl ethyl ketoximes are added in as sealer, mixed solution is warming up to 80 DEG C, is reacted 3 hours；By mixed solution carry out from
The heart is cleaned 3 times with ether, solid product is placed under the conditions of 80 DEG C and is dried in vacuo for 24 hours, obtains blocked isocyanate base functionalization
Graphene quantum dot (GQD).
As shown in Figure 1, the as chemical equation of the blocked isocyanate base functionalization of graphene quantum dot.
2) preparation of polyvinyl alcohol-graphene quantum dot (PVA-GQD) spinning solution
Take graphene quantum dot 0.01g, the dispersant neopelex 0.01g of blocked isocyanate base functionalization
It with the polyvinyl alcohol 1788 of 0.02g, is mixed in the water of 85.96g, stirs at room temperature, disperses that be configured to PVA1788-GQD molten
Liquid；
PVA1788-GQD solution is warming up to 98 DEG C, adding in 14g polyvinyl alcohol 2099, (PVA2099 represents that polyvinyl alcohol gathers
Right is 2000, alcoholysis degree 99%), polyvinyl alcohol-graphene quantum dot (PVA-GQD) is made after mechanical agitation a few hours and spins
Silk solution.
As shown in Fig. 2, the as chemical equation of graphene quantum dot and polyvinyl alcohol molecule.
3) wet spinning
Polyvinyl alcohol-graphene quantum dot (PVA-GQD) spinning solution prepared by step 2 is used as raw material, spinning temperature
It it is 96 DEG C, spinneret temperature is 96 DEG C, the hole diameter of spinneret 0.12mm, and coagulating bath is supersaturated aqueous sodium persulfate solution, solidifies bath temperature
Spend is 55 DEG C；The receipts silk rate (V1) of first roller is slightly less than spin rate (V0), V1/V0=0.95, the receipts silk rate of the second roller
(V2) slightly larger than the receipts silk rate (V1) of the first roller, V2/V1=1.4；Winding obtains PVA-GQD as-spun fibres；
4) post processing of as-spun fibre
PVA-GQD as-spun fibres are subjected to two level hot-stretch, two level hot-stretch temperature is respectively 190 DEG C and 205 DEG C, hot-drawn
It is 14 times to stretch general times；The compound fibres of high strength and modulus PVA-GQD are obtained after multistage hot-stretch, then by thermal finalization
Dimension.Heat setting temperature is 220 DEG C, time 1.5min.
The fracture strength of fiber obtained by the present embodiment is 14.5cN/tex, initial modulus 210cN/tex.
Embodiment 3：
A kind of High-performance graphene-polyvinyl alcohol composite fiber preparation method, which is characterized in that include the following steps：
1) the blocked isocyanate base functionalization of graphene oxide quantum dot
The graphene oxide quantum dot of 300mg is taken to be dissolved in the DMF of 500ml, adds in the IPDI of 300mg, ultrasonic disperse
30min reacts postcooling for 24 hours at 80 DEG C and, to room temperature, product is centrifuged, is cleaned 3 times with ether, product is placed in 60 DEG C
Under the conditions of obtain the graphene quantum dot of isocyanate group functionalization after dry 12h；
The DMF mixing of the graphene quantum dot and 200ml of 200mg isocyanate group functionalization is weighed, and 20 minutes ultrasonic,
300mg ethylene glycol monoethyl ethers are added in as sealer, mixed solution is warming up to 90 DEG C, is reacted 5 hours；Mixed solution is carried out
Centrifugation, is cleaned 3 times with ether, solid product is placed under the conditions of 80 DEG C and is dried in vacuo 30h, obtain blocked isocyanate base function
The graphene quantum dot (GQD) of change.
As shown in Figure 1, the as chemical equation of the blocked isocyanate base functionalization of graphene quantum dot.
2) preparation of polyvinyl alcohol-graphene quantum dot (PVA-GQD) spinning solution
Take the graphene quantum dot 0.02g of blocked isocyanate base functionalization, the OP-10 of dispersant polyethenoxy ether class
The polyvinyl alcohol 1788 of 0.02g and 0.02g, is mixed in the water of 86.94g, stirs at room temperature, disperses to be configured to PVA1788-
GQD solution；
PVA1788-GQD solution is warming up to 98 DEG C, adding in 13g polyvinyl alcohol 2099, (PVA2099 represents that polyvinyl alcohol gathers
Right is 2000, alcoholysis degree 99%), polyvinyl alcohol-graphene quantum dot (PVA-GQD) is made after mechanical agitation a few hours and spins
Silk solution.
As shown in Fig. 2, the as chemical equation of graphene quantum dot and polyvinyl alcohol molecule.
3) wet spinning
Polyvinyl alcohol-graphene quantum dot (PVA-GQD) spinning solution prepared by step 2 is used as raw material, spinning temperature
It it is 96 DEG C, spinneret temperature is 96 DEG C, the hole diameter of spinneret 0.10mm, and coagulating bath is supersaturated aqueous sodium persulfate solution, solidifies bath temperature
Spend is 50 DEG C；The receipts silk rate (V1) of first roller is slightly less than spin rate (V0), V1/V0=0.96, the receipts silk rate of the second roller
(V2) slightly larger than the receipts silk rate (V1) of the first roller, V2/V1=1.3；Winding obtains PVA-GQD as-spun fibres；
4) post processing of as-spun fibre
PVA-GQD as-spun fibres are subjected to two level hot-stretch, two level hot-stretch temperature is respectively 190 DEG C and 210 DEG C, hot-drawn
It is 14 times to stretch general times；The compound fibres of high strength and modulus PVA-GQD are obtained after multistage hot-stretch, then by thermal finalization
Dimension.Heat setting temperature is 220 DEG C, time 2min.
The fracture strength of fiber obtained by the present embodiment is 14.0cN/tex, initial modulus 200cN/tex.
Embodiment 4：
A kind of High-performance graphene-polyvinyl alcohol composite fiber preparation method, which is characterized in that include the following steps：
1) the blocked isocyanate base functionalization of graphene oxide quantum dot
The graphene oxide quantum dot of 200mg is taken to be dissolved in the DMF of 200ml, adds in the MDI of 260mg, ultrasonic disperse
30min reacts postcooling for 24 hours at 90 DEG C and, to room temperature, product is centrifuged, is cleaned 3 times with ether, product is placed in 60 DEG C
Under the conditions of obtain the graphene quantum dot of isocyanate group functionalization after dry 12h；
The DMF mixing of the graphene quantum dot and 200ml of 200mg isocyanate group functionalization is weighed, and 20 minutes ultrasonic,
200mg phenol is added in as sealer, mixed solution is warming up to 100 DEG C, is reacted 6 hours；Mixed solution is centrifuged, is used
Ether cleans 3 times, and solid product is placed under the conditions of 80 DEG C and is dried in vacuo 30h, obtains the stone of blocked isocyanate base functionalization
Black alkene quantum dot (GQD).
As shown in Figure 1, the as chemical equation of the blocked isocyanate base functionalization of graphene quantum dot.
2) preparation of polyvinyl alcohol-graphene quantum dot (PVA-GQD) spinning solution
Take the graphene quantum dot 0.015g of blocked isocyanate base functionalization, the OP-10 of dispersant polyethenoxy ether class
The polyvinyl alcohol 1788 of 0.015g and 0.02g, is mixed in the water of 84.95g, stirs at room temperature, disperses to be configured to PVA1788-
GQD solution；
PVA1788-GQD solution is warming up to 98 DEG C, adding in 15g polyvinyl alcohol 2099, (PVA2099 represents that polyvinyl alcohol gathers
Right is 2000, alcoholysis degree 99%), polyvinyl alcohol-graphene quantum dot (PVA-GQD) is made after mechanical agitation a few hours and spins
Silk solution.
As shown in Fig. 2, the as chemical equation of graphene quantum dot and polyvinyl alcohol molecule.
3) wet spinning
Polyvinyl alcohol-graphene quantum dot (PVA-GQD) spinning solution prepared by step 2 is used as raw material, spinning temperature
It it is 96 DEG C, spinneret temperature is 96 DEG C, the hole diameter of spinneret 0.10mm, and coagulating bath is supersaturated aqueous sodium persulfate solution, solidifies bath temperature
Spend is 55 DEG C；The receipts silk rate (V1) of first roller is slightly less than spin rate (V0), V1/V0=0.94, the receipts silk rate of the second roller
(V2) slightly larger than the receipts silk rate (V1) of the first roller, V2/V1=1.3；Winding obtains PVA-GQD as-spun fibres；
4) post processing of as-spun fibre
PVA-GQD as-spun fibres are subjected to two level hot-stretch, two level hot-stretch temperature is respectively 190 DEG C and 200 DEG C, hot-drawn
It is 13 times to stretch general times；The compound fibres of high strength and modulus PVA-GQD are obtained after multistage hot-stretch, then by thermal finalization
Dimension.Heat setting temperature is 220 DEG C, time 1min.
The fracture strength of fiber obtained by the present embodiment is 13.8cN/tex, initial modulus 196cN/tex.
Embodiment 5：
A kind of High-performance graphene-polyvinyl alcohol composite fiber preparation method, which is characterized in that include the following steps：
1) the blocked isocyanate base functionalization of graphene oxide quantum dot
The graphene oxide quantum dot of 200mg is taken to be dissolved in the DMF of 200ml, adds in the XDI of 260mg, ultrasonic disperse
30min reacts postcooling for 24 hours at 90 DEG C and, to room temperature, product is centrifuged, is cleaned 3 times with ether, product is placed in 60 DEG C
Under the conditions of obtain the graphene quantum dot of isocyanate group functionalization after dry 12h；
The DMF mixing of the graphene quantum dot and 200ml of 200mg isocyanate group functionalization is weighed, and 20 minutes ultrasonic,
200mg ethylene glycol monobutyl ethers are added in as sealer, mixed solution is warming up to 90 DEG C, is reacted 6 hours；Mixed solution is carried out
Centrifugation, is cleaned 3 times with ether, solid product is placed under the conditions of 80 DEG C and is dried in vacuo 36h, obtain blocked isocyanate base function
The graphene quantum dot (GQD) of change.
As shown in Figure 1, the as chemical equation of the blocked isocyanate base functionalization of graphene quantum dot.
2) preparation of polyvinyl alcohol-graphene quantum dot (PVA-GQD) spinning solution
Take the graphene quantum dot 0.015g of blocked isocyanate base functionalization, the OP-10 of dispersant polyethenoxy ether class
The polyvinyl alcohol 1788 of 0.015g and 0.02g, is mixed in the water of 84.95g, stirs at room temperature, disperses to be configured to PVA1788-
GQD solution；
PVA1788-GQD solution is warming up to 98 DEG C, adding in 15g polyvinyl alcohol 2099, (PVA2099 represents that polyvinyl alcohol gathers
Right is 2000, alcoholysis degree 99%), polyvinyl alcohol-graphene quantum dot (PVA-GQD) is made after mechanical agitation a few hours and spins
Silk solution.
As shown in Fig. 2, the as chemical equation of graphene quantum dot and polyvinyl alcohol molecule.
3) wet spinning
Polyvinyl alcohol-graphene quantum dot (PVA-GQD) spinning solution prepared by step 2 is used as raw material, spinning temperature
It it is 96 DEG C, spinneret temperature is 96 DEG C, the hole diameter of spinneret 0.10mm, and coagulating bath is supersaturated aqueous sodium persulfate solution, solidifies bath temperature
Spend is 55 DEG C；The receipts silk rate (V1) of first roller is slightly less than spin rate (V0), V1/V0=0.94, the receipts silk rate of the second roller
(V2) slightly larger than the receipts silk rate (V1) of the first roller, V2/V1=1.3；Winding obtains PVA-GQD as-spun fibres；
4) post processing of as-spun fibre
PVA-GQD as-spun fibres are subjected to two level hot-stretch, two level hot-stretch temperature is respectively 190 DEG C and 200 DEG C, hot-drawn
It is 14 times to stretch general times；The compound fibres of high strength and modulus PVA-GQD are obtained after multistage hot-stretch, then by thermal finalization
Dimension.Heat setting temperature is 220 DEG C, time 1min.
The fracture strength of fiber obtained by the present embodiment is 14.0cN/tex, initial modulus 200cN/tex.
Embodiment 6：
A kind of High-performance graphene-polyvinyl alcohol composite fiber preparation method, which is characterized in that include the following steps：
1) the blocked isocyanate base functionalization of graphene oxide quantum dot
The graphene oxide quantum dot of 200mg is taken to be dissolved in the DMF of 200ml, adds in the TMDI of 260mg, ultrasonic disperse
30min reacts postcooling for 24 hours at 90 DEG C and, to room temperature, product is centrifuged, is cleaned 3 times with ether, product is placed in 60 DEG C
Under the conditions of obtain the graphene quantum dot of isocyanate group functionalization after dry 12h；
The DMF mixing of the graphene quantum dot and 200ml of 200mg isocyanate group functionalization is weighed, and 20 minutes ultrasonic,
200mg methyl ethyl ketoximes are added in as sealer, mixed solution is warming up to 100 DEG C, is reacted 6 hours；By mixed solution carry out from
The heart is cleaned 3 times with ether, and solid product is placed under the conditions of 80 DEG C and is dried in vacuo 48h, obtains blocked isocyanate base functionalization
Graphene quantum dot (GQD).
As shown in Figure 1, the as chemical equation of the blocked isocyanate base functionalization of graphene quantum dot.
2) preparation of polyvinyl alcohol-graphene quantum dot (PVA-GQD) spinning solution
Take graphene quantum dot 0.01g, the dispersant sodium metnylene bis-naphthalene sulfonate 0.01g of blocked isocyanate base functionalization
It with the polyvinyl alcohol 1788 of 0.02g, is mixed in the water of 84.96g, stirs at room temperature, disperses that be configured to PVA1788-GQD molten
Liquid；
PVA1788-GQD solution is warming up to 98 DEG C, adding in 15g polyvinyl alcohol 2099, (PVA2099 represents that polyvinyl alcohol gathers
Right is 2000, alcoholysis degree 99%), polyvinyl alcohol-graphene quantum dot (PVA-GQD) is made after mechanical agitation a few hours and spins
Silk solution.
As shown in Fig. 2, the as chemical equation of graphene quantum dot and polyvinyl alcohol molecule.
3) wet spinning
Polyvinyl alcohol-graphene quantum dot (PVA-GQD) spinning solution prepared by step 2 is used as raw material, spinning temperature
It it is 96 DEG C, spinneret temperature is 96 DEG C, the hole diameter of spinneret 0.10mm, and coagulating bath is supersaturated aqueous sodium persulfate solution, solidifies bath temperature
Spend is 60 DEG C；The receipts silk rate (V1) of first roller is slightly less than spin rate (V0), V1/V0=0.96, the receipts silk rate of the second roller
(V2) slightly larger than the receipts silk rate (V1) of the first roller, V2/V1=1.4；Winding obtains PVA-GQD as-spun fibres；
4) post processing of as-spun fibre
PVA-GQD as-spun fibres are subjected to two level hot-stretch, two level hot-stretch temperature is respectively 190 DEG C and 200 DEG C, hot-drawn
It is 14 times to stretch general times；The compound fibres of high strength and modulus PVA-GQD are obtained after multistage hot-stretch, then by thermal finalization
Dimension.Heat setting temperature is 220 DEG C, time 1min.
The fracture strength of fiber obtained by the present embodiment is 14.2cN/tex, initial modulus 206cN/tex.
Claims (9)
1. a kind of High-performance graphene-polyvinyl alcohol composite fiber preparation method, which is characterized in that include the following steps：
1) the blocked isocyanate base functionalization of graphene quantum dot
1.1) load weighted graphene oxide quantum dot, diisocyanate and N,N-dimethylformamide (DMF) are mixed to get
Mixed solution A；
The parts by weight of the graphene oxide quantum dot are 100~1000 parts；The parts by weight of the diisocyanate are
1000~10000 parts；The parts by weight of the N,N-dimethylformamide are 1000~10000 parts；
1.2) it after the mixed solution A obtained in step 1.1) is ultrasonically treated, is reacted under the conditions of being placed in 80~90 DEG C,
24~48h postcoolings obtain product A to room temperature；The time of the supersound process is 30~60min；
After product A is carried out centrifugal treating, after being cleaned using ether, product B is obtained；
Product B is placed under the conditions of 60 DEG C and is dried, product C is obtained after 12~48h；
1.3) it after mixing load weighted product C and n,N-Dimethylformamide, carries out ultrasound and obtains mixing liquid B；It is described super
The sound time is 20 minutes；
Under conditions of mixing liquid B is placed in 80~100 DEG C, sealer is added in, reaction obtains mixing liquid C after 3~6 hours；
The parts by weight of the product C are 100~1000 parts；The parts by weight of the N,N-dimethylformamide for 1000~
10000 parts；The parts by weight of the sealer are 100~1000 parts；
1.4) the mixing liquid C obtained in step 1.3) is subjected to suction filtration washing, obtains product D；
Under the conditions of product D is placed in 80 DEG C, 12~48h is dried in vacuo, obtains the graphene amount of blocked isocyanate base functionalization
Sub- point (GQD)；
2) preparation of polyvinyl alcohol-graphene quantum dot (PVA-GQD) spinning solution
It is 2.1) graphene quantum dot, dispersant, the polyvinyl alcohol of load weighted blocked isocyanate base functionalization is soluble in water,
Stirring, dispersion, are configured to PVA1788-GQD solution；
The degree of polymerization of the polyvinyl alcohol is 1700, alcoholysis degree 88%；
The parts by weight of the graphene quantum dot of the blocked isocyanate base functionalization are 0.005~0.02 part；The dispersion
The parts by weight of agent are 0.005~0.02 part；The parts by weight of the polyvinyl alcohol 1788 are 0.02 part；The parts by weight of the water
Number is 84.94~89.97 parts；
2.2) under the conditions of the PVA1788-GQD solution obtained in step 2.1) being placed in 95~100 DEG C, polyvinyl alcohol is added in, is stirred
After mixing 5~8 hours, polyvinyl alcohol-graphene quantum dot spinning solution is obtained；
The parts by weight of the polyvinyl alcohol are 10~15 parts, and the degree of polymerization of the polyvinyl alcohol is 1700~2800, molecular weight
1.5~2.0 are distributed as, alcoholysis degree 99%；
The stir speed (S.S.) is 50~200 revs/min；
3) wet spinning
Using the polyvinyl alcohol-graphene quantum dot spinning solution obtained in step 2.2) as raw material, using normal wet spinning-drawing machine
Wet spinning is carried out, prepares PVA-GQD as-spun fibres；
4) post processing of as-spun fibre
The PVA-GQD as-spun fibres obtained in step 3) are subjected to multistage hot-stretch, thermal finalization, obtain high strength and modulus PVA-
GQD composite fibres.
2. a kind of High-performance graphene-polyvinyl alcohol composite fiber preparation method according to claim 1, feature exist
In：The graphite flake layer of graphene quantum dot in the step 1.1) is 1~3 layer, size is 10~100nm.
3. a kind of High-performance graphene-polyvinyl alcohol composite fiber preparation method according to claim 1, feature exist
In：Diisocyanate in the step 1.1) is toluene di-isocyanate(TDI), hexamethylene diisocyanate, two isocyanide of isophorone
Acid esters, benzene dimethylene diisocyanate, trimethyl hexamethylene diisocyanate or 4,4 '-methyl diphenylene diisocyanate
In one kind.
4. a kind of High-performance graphene-polyvinyl alcohol composite fiber preparation method according to claim 1, feature exist
In：Sealer in the step 1.3) is one kind in phenol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether or methyl ethyl ketoxime.
5. a kind of High-performance graphene-polyvinyl alcohol composite fiber preparation method according to claim 1, feature exist
In：It after polyvinyl alcohol-graphene quantum dot spinning solution is made in the step 2), is filtered, taken off using 500 mesh screens
Bubble, prepares uniform and stable spinning solution.
6. a kind of High-performance graphene-polyvinyl alcohol composite fiber preparation method according to claim 1, feature exist
In：After the step 3), according to purposes difference, acetalation is carried out to PVA-GQD composite fibres, oils, crimp and/or cuts
It is disconnected.
7. a kind of High-performance graphene-polyvinyl alcohol composite fiber preparation method according to claim 1, feature exist
In：Dispersant in the step 2.1) is a)~c) in any one situation for stating, wherein：A) polyethenoxy ether class or ester
Class tween, b) Sulfonates, Sulfates, phosphate or phosphite anionoid activating agent, c) amino acids,
The mixture of one or more of imidazoles, oxidation amine amphoteric surfactant arbitrary proportion.
8. a kind of High-performance graphene-polyvinyl alcohol composite fiber preparation method according to claim 1, feature exist
In：Spinning temperature is 95~100 DEG C in the step 3), and spinneret temperature is 95~100 DEG C, the hole diameter of spinneret 0.08~
0.12mm；
Used wet spinning coagulating bath is supersaturated aqueous sodium persulfate solution, and coagulation bath temperature is 45~60 DEG C.
9. a kind of High-performance graphene-polyvinyl alcohol composite fiber preparation method according to claim 1, feature exist
In：In the step 4), heat setting temperature is 210~230 DEG C, and the time is 1~3min.
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| CN109294131A (en) * | 2018-08-09 | 2019-02-01 | 东华大学 | A kind of polyvinyl alcohol/graphene conductive nanocomposite and its preparation and application |
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