CN106832399A - Graphene composite polyvinyl alcohol master batch and preparation method thereof, using, fibrous material - Google Patents
Graphene composite polyvinyl alcohol master batch and preparation method thereof, using, fibrous material Download PDFInfo
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- CN106832399A CN106832399A CN201610624203.7A CN201610624203A CN106832399A CN 106832399 A CN106832399 A CN 106832399A CN 201610624203 A CN201610624203 A CN 201610624203A CN 106832399 A CN106832399 A CN 106832399A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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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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- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/12—Applications used for fibers
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Abstract
The invention provides a kind of high performance Graphene composite polyvinyl alcohol master batch, mainly it is made up of graphite alkenes material and polyvinyl alcohol；In Graphene composite polyvinyl alcohol master batch, the content of graphite alkenes material is in below 6wt%；The D90 norm controllings of graphite alkenes material below 100 μm, the D90 norm controllings of graphite alkenes material below 100 μm, D10 norm controllings in below 20um, less than 20 times in D10 indexs of D90 norm controllings.The preparation method of the master batch includes：(A) the graphite alkenes material aqueous solution is pre-processed, is obtained the graphite alkenes agent particle size classification aqueous solution；(B) the PVA aqueous solution and the graphite alkenes agent particle size classification aqueous solution are mixed and obtains mixed solution, be drying to obtain.Although the Graphene composite polyvinyl alcohol master batch content of material comparing of the embodiment of the present invention is high, still dispersion ratio is more uniform for graphene particles, and granular size than more uniform, does not have any agglomerated particle to produce yet.
Description
Technical field
It is multiple in particular to a kind of high performance Graphene the present invention relates to polyvinyl alcohol master batch processing preparation field
Close polyvinyl alcohol master batch and preparation method thereof, application, and a kind of fibrous material.
Background technology
Polyvinyl alcohol (PVA) is a kind of high molecular weight water soluble polymer, and its molecular formula is [C2H4O]n.Vinal
Due to having good hydrophily, impact resistance and the features such as being easily dispersed property is good in processing and forming, can as plastics, cement with
And the reinforcing material of ceramics etc., also alternative asbestos for having a carcinogen.
Graphene is a kind of two-dimensional material of the alveolate texture being made up of individual layer sp2 hydbridized carbon atoms, with many excellent
Different performance.It has been found since 2004, Graphene just becomes a big study hotspot of scientific circles.In the thing to Graphene
While Physicochemical property is studied, the composite related to Graphene also emerges in an endless stream.On nano science direction, stone
Black alkene is also used to prepare the nano composite material of correlation, especially the nanometer of Graphene/metal or graphene/metal oxide
Composite.Due to the excellent properties of Graphene, these nano composite materials are in novel energy, bio-sensing, catalysis, optics material
There are wide Research Prospects in the fields such as material.
In the prior art, it is relatively more on the compound Related product of polyvinyl alcohol-Graphene, in view of it is widely applied,
Typically polyvinyl alcohol-Graphene can first be made function sexupara grain, so both facilitate transport, storage, be also convenient for follow-up application,
Then Related product is made as raw material by feature master batch further according to actual demand, it is thus found that feature master batch property in itself
Can be good and bad, the correlated performance of subsequent product can be directly influenced, but Graphene content in the feature master batch typically produced
Can be than relatively low, and graphene particles disperse uneven, granular size heterogeneity, are susceptible to interlayer reunion, so not
The problem that the stress concentration point brought with piece footpath graphite alkenes material can be easily broken off, the follow-up product prepared of influence
Performance.
In view of this, it is special to propose the present invention.
The content of the invention
The first object of the present invention is to provide a kind of with high performance Graphene polyvinyl alcohol master batch, stone in the master batch
Although black alkenes content of material comparing is high, still dispersion ratio is more uniform for graphene particles, and granular size is also than more uniform, group
Poly- particle produces less, properties stabilization, and after being prepared into associated materials for subsequent applications, stretching is slight, elongation at break
Etc. the raising that index has matter, and also material toughness higher, hot water resistance and antistatic behaviour additionally are imparted, further
The market range of application of material is expanded, value-added content of product is improve, is conducive to further genralrlization application.
The second object of the present invention is to provide the above-mentioned preparation with high performance Graphene composite polyvinyl alcohol master batch
Method, step linking is tight before and after preparation method, and method simple and fast can be realized seamless with existing production process equipment and flow
Docking, has the advantages that the effective ingredient that can completely retain raw material, and, operating condition temperature simply easily operated with method
With, the industrialized production of Graphene composite polyvinyl alcohol master batch is capable of achieving, economic benefit is very good.
The third object of the present invention is to provide the above-mentioned application with high performance Graphene composite polyvinyl alcohol master batch,
The master batch products application widely, is widely used in membrane product, water-absorbing resins, water imbibition sponge, plastics and undulation degree
Material aspect, the fibrous composite especially prepared by the master batch is realizing traditional high-strength, high modulus polyvinyl alcohol fibre spinning
It is further double to improve the mechanical property of fiber on Process ba- sis, while imparting fibrous material toughness higher, heat-resisting
Aqueous and antistatic behaviour.
In order to realize above-mentioned purpose of the invention, spy uses following technical scheme：
The invention provides a kind of high performance Graphene composite polyvinyl alcohol master batch product, it is mainly by graphite alkenes thing
Matter and polyvinyl alcohol are constituted, and in the master batch, the content of graphite alkenes material in below 6wt%, further for 3wt% with
Under, further between 0.05wt-1.5wt%, below 100 μm, D10 refers to the D90 norm controllings of graphite alkenes material
Mark control is in below 20um, and D90 indexs are no more than 20 times of D10 indexs, more preferably preferably less than 10 times, less than 5 times.
In the prior art, the Graphene content in general polyvinyl alcohol-Graphene master batch typically can be than relatively low, because graphite
Alkene content is too high to be susceptible to reunite, then subsequently preparing associated downstream product can accordingly influence the physical property of product,
In order to solve many technical problems present in prior art, the invention provides a kind of Graphene comparision contents are high, particle point
Dissipate again than more uniform, reunite less Graphene composite polyvinyl alcohol master batch, in the master batch, the content highest of graphite alkenes material
6wt% can be reached, the granularity of graphite alkenes material then requires to be D90 that D90 refers to 100um in 100um below 100 μm
Following particle diameter material accounts for overall 90%, i.e., this 90% the inside maximum particle diameter is 100um；D90 mentioned here 100um with
Under, can be 95um, 80um, 60um, 50um etc..The granularity for herein referring to is particle size, can be very thin thickness but area
It is very big.Similarly, D10 norm controllings are the same reason in below 20um, and D10 can be 18um, 10um, 8um, 5um, 3um,
1um etc..D90 indexs are no more than 20 times of D10 indexs, within preferably 10 times, within more preferably 5 times, it can be understood as work as D90
During for 50um, D10 is not less than 2.5um, and D10 is preferably more than 5um, more preferably more than 10um.Such feature master batch except
Ensure beyond the Graphene of high content, it is ensured that the size homogeneity of graphene particles, it is to avoid the phenomenon hair of particle agglomeration
Raw, the properties of product prepared using such feature master batch are clearly superior to Graphene composite polyvinyl alcohol common on the market
Related product.
Preferably, when Graphene composite polyvinyl alcohol master batch is used to prepare plastic products, D90 is controlled in 30-100um,
D10 is controlled in 5-20um；When Graphene composite polyvinyl alcohol master batch is used to prepare fiber, D90 controls are in 5-30um, D10 controls
System is in 0.5-3um.Because final products form is different when preparing plastic products with fiber, graphite alkenes material is caused to there is size
Difference, its purpose is to while the big chip architecture for keeping graphite alkenes material as far as possible, it is ensured that graphite alkenes material will not be sent out
Reunite between generating layer, prevent the problem of the stress concentration point fracture that different footpath graphite alkenes materials bring, if granularity it is too big or
Person is too small all may to be unfavorable for subsequently forming more homogeneous inorganic-organic bridging arrangement with PVA strands, be more held in
After the graphite alkenes material of same particle diameter is just more beneficial for subsequently being combined with PVA, the feature master batch various aspects of performance for obtaining is all
It is good, it is therefore desirable to strictly to control its particle diameter.
The graphite alkenes material that is used includes Graphene, biomass Graphene, graphene oxide, Graphene derivative
One or more mixing, the Graphene derivative is the Graphene by being modified.
Preferably, the Graphene derives any a kind included in element doping Graphene or functional group's graphite alkene thing
Or at least 2 kinds of combination.
Preferably, the element doping Graphene is including in metal-doped Graphene or nonmetal doping Graphene
Any a kind or at least 2 kinds of combination.
The metal-doped metallic element it is typical but non-limiting including potassium, sodium, gold, silver, iron, copper, nickel, chromium titanium,
Vanadium or cobalt.
The nonmetal doping Graphene is typical but non-limiting including nitrogen, phosphorus, boron or silicon.
Preferably, the nonmetal doping Graphene includes nitrogen-doped graphene, phosphorus doping Graphene or sulfur doping
Any a kind or at least 2 kinds of combination in Graphene.
Preferably, functional group's graphite alkene includes being grafted with the Graphene of functional group.
Preferably, functional group's graphite alkene includes any a kind or at least 2 be grafted with hydroxyl, carboxyl or amino
The Graphene of the combination planted.
Hydroxyl of the present invention includes that-R1-OH, the R1 include alkyl, and typical but non-limiting hydroxyl can be
Methylhydroxy, ethyl hydroxy, propyl hydroxy, butylhydroxy, amyl group hydroxyl, hexyl hydroxyl etc..
Carboxyl of the present invention includes that-R2-COOH, the R2 include alkyl, and typical but non-limiting hydroxyl can be with
It is methylhydroxy, ethyl hydroxy, propyl hydroxy, butylhydroxy, amyl group hydroxyl, hexyl hydroxyl etc..
Carboxyl of the present invention includes-R3-NH3, the R3 includes alkyl, and typical but non-limiting hydroxyl can be
Methylhydroxy, ethyl hydroxy, propyl hydroxy, butylhydroxy, amyl group hydroxyl, hexyl hydroxyl etc..
The present invention is a kind of high performance except there is provided a kind of formula of Graphene composite polyvinyl alcohol master batch, additionally providing
The preparation method of Graphene composite polyvinyl alcohol master batch, mainly comprises the following steps：
(A) the graphite alkenes material aqueous solution is pre-processed, is obtained the graphite alkenes agent particle size classification aqueous solution；
(B) the PVA aqueous solution is mixed with the graphite alkenes agent particle size classification aqueous solution and obtains mixed solution, done
It is dry to obtain final product.
It is prepared by the preparation method of the high performance Graphene composite polyvinyl alcohol master batch that the present invention is provided, this preparation method
The feature master batch for going out, the material subsequently prepared not only possesses all excellent properties of traditional polyvinyl alcohol material, Er Qiexing
The additional properties such as material toughness higher in itself, hot water resistance and antistatic behaviour are also imparted while having been lifted, it is existing
When Graphene composite polyvinyl alcohol Related product is prepared in technology, usually directly by Graphene and polyvinyl alcohol in mixed solvent
In be well mixed and be prepared, but the performance of feature master batch that this method is prepared is general, graphene particles can not be equal
Even to be dispersed in master batch, and granular size also heterogeneity, the present invention is by graphite alkenes material, (graphite alkenes material includes stone
One or more mixing, wherein Graphene derivative bag of black alkene, biomass Graphene, graphene oxide, Graphene derivative
Include the Graphene of element doping, be finally using graphene-structured therein) with polyvinyl alcohol before, specially first by graphite
The aqueous solution of alkenes material is pre-processed, and in the prior art without any record, the present invention still belongs to the method for this pretreatment
It is pioneering.
Certainly, during practical operation, the specific preprocess method for using includes：By graphite alkenes material aqueous solution ultrasound point
Retain bottom precipitation after centrifugally operated under the conditions of scattered, 2000-3000rpm, supernatant is centrifuged behaviour under the conditions of 5000-7000rpm
Secondary bottom precipitation and secondary supernatant are respectively obtained after work, wherein the Graphene class material is classified the aqueous solution being sunk including bottom
Any one in shallow lake, secondary bottom precipitation, secondary supernatant is prepared, the aqueous solution prepared by preferably secondary bottom precipitation.
The centrifugally operated speed ratio that the first step obtains bottom precipitation is relatively low, behind the further centrifugally operated of supernatant speed
It is then higher, because the material grainses degree in precipitation is general than larger, if the too fast electrodeposition substance for being unfavorable for bulky grain of speed,
Material grainses degree in follow-up supernatant is typically smaller, therefore speed needs soon, so that the small material of granularity floats
In there is supernatant.So granularity than more consistent graphite alkenes material by after classification in bottom precipitation or at secondary bottom
Portion is precipitated or in secondary supernatant, and the graphite alkenes material classification aqueous solution can select above-mentioned by any of classification treatment
A kind of material, can guarantee that with granularity than more consistent graphite alkenes material, and granularity size also than convenient, with
The homogeneity in piece footpath is fully ensured that, has been conducive to subsequently ensureing the performance of feature master batch prepared.
Wherein, the time of ultrasonic disperse be preferably controlled in 1-3h, the time of centrifugally operated is most under the conditions of 2000-3000rpm
Control between 20-40min well, the time of centrifugally operated is preferably controlled between 10-30min under the conditions of 5000-7000rpm,
Control is more conducive to the more thorough of grain size grading treatment within the preferably operating time, so that particle diameter distribution is more uniform.
In addition, the mass percent concentration of the pretreated graphite alkenes material aqueous solution is preferably controlled suitably, because such as
Fruit concentration is too high, and the reunion of piece interlayer, graphene sol liquid (the graphite alkenes material water of low concentration are susceptible in concentration process
Solution) be conducive to the PVA strands to carry out ordering orientation with Graphene as platform is sprawled, it is Graphene addition raw material with the colloidal sol
It is combined with PVA, preferably graphite alkenes material concentration of aqueous solution is below 3wt%, more preferably below 2wt%, then excellent
Select between 0.05wt-1.5wt%.
After the graphite alkenes material aqueous solution is pre-processed, first using the PVA aqueous solution and graphite alkenes material of low concentration
The aqueous solution is pre-mixed, and concentration is then stepped up again, finally obtains the mixed solution that PVA concentration is 10-20wt%, preferably
PVA concentration is controlled between 15-16wt%, to reach the complete purpose of dispersion by way of setting concentration gradient, if
The graphite alkenes material aqueous solution is directly mixed with the PVA aqueous solution, it is unfavorable that such hybrid mode is easy to generation reunion
In mixing, so as to influence the performance of product, the compound mode of setting gradient concentration of the invention is advantageously in final products
Performance, is segmented into some gradients during concrete operations, such as add the PVA aqueous solution, the PVA water of 6-8wt% of 2-5wt% successively
The PVA aqueous solution of solution, 10-12wt%, 25-40wt% etc., the number of gradient is not specifically limited, and initial concentration is controlled in 2-
Between 5wt%.During practical operation, can specifically be adjusted according to being actually needed for technique, such as the concentration of PVA sets gradient
With the addition number of times of PVA solution etc., in a word by way of compound using this gradient concentration of the invention, solve mixing molten
The incomplete problem of Dispersion of Solute Matter in liquid, and the performance of Graphene composite polyvinyl alcohol feature master batch is greatly improved.
Preferably, in 1-2h, temperature control exists the time control stirred after being added every time when adding the PVA aqueous solution several times
Between 90-100 DEG C, if the too low PVA aqueous solution of temperature cannot be with graphite alkenes material aqueous solution mixing and stirring, it may appear that
The particle of reunion, influences properties of product, therefore temperature to be preferably controlled in suitable scope.
Further, the degree of polymerization of the PVA aqueous solution is preferably controlled between 1700-2500, and alcoholysis degree is preferably controlled in 88-99%
Between, because the degree of polymerization and alcoholysis degree of PVA can significantly affect the tensile strength and stretch modulus of vinal, typically
The degree of polymerization and alcoholysis degree of PVA are higher, and the tensile strength and stretch modulus that polyvinyl alcohol master batch is made subsequent material are higher.
The Graphene composite polyvinyl alcohol master batch prepared using above-mentioned preparation method further improves subsequent product
Mechanical property, while impart toughness higher, hot water resistance and antistatic behaviour, using widely, can be used to make
Membrane product, water-absorbing resins, water imbibition sponge, plastics, there is very wide application in these areas.
When fibrous material is made using Graphene polyvinyl alcohol master batch of the invention, the tensile strength of fibrous material is reachable
To more than 2Gpa, Young's modulus is can be controlled between 3-13% in more than 45Gpa, elongation at break.
The technique for specifically preparing fiber is：Graphene composite polyvinyl alcohol master batch is dissolved in water, or the Graphene is multiple
Close polyvinyl alcohol master batch and mix soluble in water with blank polyvinyl alcohol master batch, obtain spinning solution, filtering, deaeration, spinning and
After drying, obtain final product；
Filtered in follow-up spinning solution, deaeration, before spinning and drying, preferably first added in spinning solution and handed over
After connection agent acetalization, reducing agent reduction treatment, the purpose for adding crosslinking agent be in order to PVA and Graphene crosslinking so that
Realize macromolecule in the orderly arrangement in nano-graphene piece surface, it is to avoid high molecular entanglement, the height for being conducive to spinning to post-process
Times hot-stretch, so as to improve the performance of PVA fibers., in itself as a kind of inorganic filler, addition reducing agent can for graphite alkenes material
Crosslinking agent is added to belong to preceding crosslinking to improve the hot water resistance of PVA fibers, in spinning solution, also can be after as-spun fibre be prepared
It is crosslinked again, this crosslinking belongs to post-crosslinking, either preceding crosslinking or post-crosslinking can obtain high-performance PVA fibers,
If what is added in spinning solution is graphene oxide, reduction step can be carried out in spinning solution, it is also possible to prepared
Reduced again after fiber, either preceding crosslinking or post-crosslinking, pre reduction still rear reduction is protected in patent of the invention
In the range of shield, crosslinking agent may include one or more mixtures in glyoxal, glutaraldehyde, formaldehyde, boric acid and borax, spinning
The concentration of crosslinking agent is controlled between 0.0075-0.45wt% in stoste, and reducing agent may include sodium borohydride, ascorbic acid, water
One or more mixtures in hydrazine and hydroiodic acid are closed, the concentration of reducing agent is controlled between 0.1-3wt% in spinning solution.
Also in spinning solution, during addition boric acid, the concentration of its boric acid is can be controlled between 2-5wt%, can also be
3wt%, 3.5wt%, 4wt% etc..
Finally, spinning solution filtered under conditions of 85-120 DEG C, deaeration, be to prevent from freezing the reason for 85-120 DEG C
Glue, in order to avoid being impacted to the performance of fiber, spinning solution is extrusion in the spinneret of 0.08-0.30mm by orifice diameter,
Spun silk becomes as-spun fibre into 40-45 DEG C of saltcake coagulating bath shaping, after as-spun fibre is through pickling, washing, drying, then
Processed by hot-stretch and thermal finalization, that is, obtain high performance Graphene composite polyvinyl alcohol fiber.
Preferably, deaeration mode is normal pressure discontinuous degassing or vacuum defoamation, and hot-stretch temperature control is hot at 120-250 DEG C
Draw ratio is 10-37 times, and heat-setting time is 1-15min.
Compared with prior art, beneficial effects of the present invention are：
(1) although the present invention provide with the graphite alkenes material contained by high performance Graphene polyvinyl alcohol master batch than
It is higher, but still dispersion ratio is more uniform for graphene particles, and granular size than more uniform, does not have any agglomerated particle to produce yet,
Properties stabilization；
(2) preparation method of high performance Graphene composite polyvinyl alcohol master batch of the invention, step before and after preparation method
Linking is tight, and method simple and fast can realize slitless connection with existing production process equipment and flow, with can completely retain original
The advantage of the effective ingredient of material, and it is simply easily operated with method, and operating condition is gentle, and achievable Graphene is combined poly- second
The industrialized production of enol master batch, economic benefit are good；
(3) with the application of high performance Graphene composite polyvinyl alcohol master batch widely, it is widely used in membrane product, inhales
Water-base resin, water imbibition sponge, plastics and fibrous material aspect, the fibrous composite especially prepared by the master batch exist
On the basis of traditional high-strength, the high modulus polyvinyl alcohol fibre spinning technique of realization, the mechanical property of further double lifting fiber, while
Impart fibrous material toughness higher, hot water resistance and antistatic behaviour.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
The accompanying drawing to be used needed for having technology description is briefly described.
Fig. 1 is the petrographic microscope figure of pure polyvinyl alcohol master batch；
Fig. 2 is the petrographic microscope figure of the Graphene composite polyvinyl alcohol master batch that the embodiment of the present invention 1 is prepared；
Fig. 3 is the petrographic microscope figure of the Graphene composite polyvinyl alcohol master batch that comparative example 1 is prepared.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.It is unreceipted specific in embodiment
Condition person, the condition advised according to normal condition or manufacturer is carried out.Agents useful for same or the unreceipted production firm person of instrument, are
The conventional products that can be obtained by commercially available purchase.
Embodiment 1
The preparation method of high performance Graphene composite polyvinyl alcohol master batch is as follows：
1) graphene oxide, the dispersion liquid that ultrasonic disperse is stablized is added to turn the suspension in 2000rpm in water
First time centrifugation is carried out under speed, centrifugation time 20min removes bottom precipitation, and supernatant is carried out second under 5000rpm rotating speeds
Centrifugation, centrifugation time 10min obtains secondary bottom precipitation, and the secondary bottom precipitation ultrasound that adds water is obtained into the classification oxygen of 1.5wt%
Graphite alkene sol solutionses；
2) by concentration for the graphene oxide sol solutionses of 1.5wt% are pre-mixed with the PVA aqueous solution that concentration is 5wt%
(degree of polymerization is 1700, and alcoholysis degree is 99%) to obtain premix, and the premix is mixed again with the PVA aqueous solution of 10wt%
Close (degree of polymerization is 2500, and alcoholysis degree is 88%), 1h to be stirred at 90 DEG C, adds the 25wt%PVA aqueous solution and forms mixed solution,
PVA concentration is 15wt% in mixed solution, and mixed solution evaporation solvent subsequently is dried to obtain into feature master batch；
3) in the feature master batch, graphene oxide content is 1.5wt%, and the D90 of graphite alkenes material is 100 μm,
D10 be 20 μm, the petrographic microscope figure of the master batch that the embodiment is prepared as shown in Figure 2, without adding any other
Material pure polyvinyl alcohol blank master batch petrographic microscope figure as shown in Figure 1.
Embodiment 2
Be step 1 with the distinctive points of embodiment 1) in sunk from the bottom that obtains is centrifuged under 3000rpm rotating speeds for the first time
Form sediment, the ultrasound that adds water obtains the classification graphene oxide sol solutionses of 2wt%, and in the mixed solution for obtaining, the concentration of PVA is
16wt%, evaporation solvent is dried to obtain the feature master batch that graphene oxide content is 1.5wt%, and graphite alkenes material
D90 is 70 μm, and D10 is 3.5 μm.
Embodiment 3
Be step 1 with the distinctive points of embodiment 1) in from supernatant is centrifuged under the 7000rpm rotating speeds again after
Secondary supernatant, prepares the classification graphene oxide sol solutionses of 3wt%, and in the mixed solution for obtaining for obtaining, PVA's is dense
It is 15wt% to spend, and evaporation solvent is dried to obtain the feature master batch that graphene oxide content is 1.5wt%, and graphite alkenes material
D90 be 30 μm, D10 be 5 μm.
Embodiment 4
It is the work(that final evaporation solvent is dried to obtain that graphene oxide content is 1.5wt% with the distinctive points of embodiment 1
The D90 of energy sexupara grain and graphite alkenes material is 20 μm, and D10 is 3 μm.
Embodiment 5
It is the work(that final evaporation solvent is dried to obtain that graphene oxide content is 1.5wt% with the distinctive points of embodiment 1
The D90 of energy sexupara grain and graphite alkenes material is 10 μm, and D10 is 2 μm.
Embodiment 6
It is the work(that final evaporation solvent is dried to obtain that graphene oxide content is 1.5wt% with the distinctive points of embodiment 1
The D90 of energy sexupara grain and graphite alkenes material is 5 μm, and D10 is 0.5 μm.
Embodiment 7
It is the work(that final evaporation solvent is dried to obtain that graphene oxide content is 1.5wt% with the distinctive points of embodiment 1
The D90 of energy sexupara grain and graphite alkenes material is 5 μm, and D10 is 3 μm.
Embodiment 8
Be step 1 with the distinctive points of embodiment 1) in graphene oxide is replaced with into Graphene, secondary bottom precipitation adds
Water ultrasound obtains the classification graphene sol liquid of 1wt%, and final evaporation solvent is dried to obtain graphene oxide content for 1.5wt%
Feature master batch and graphite alkenes material D90 be 10 μm, D10 be 2 μm.
Embodiment 9
Be step 1 with the distinctive points of embodiment 1) in graphene oxide is replaced with into biomass Graphene, secondary bottom
The classification graphene sol liquid that the ultrasound that adds water obtains 0.5wt% is precipitated, final evaporation solvent is dried to obtain graphene oxide content
For 1.5wt% feature master batch and graphite alkenes material D90 be 10 μm, D10 be 2 μm.
Embodiment 10
Be step 1 with the distinctive points of embodiment 1) in classification graphene oxide sol solutionses concentration be 0.05wt%；Step
It is rapid 2) in, by graphene oxide sol solutionses and mass fraction, for the PVA aqueous solution of 5wt%, (degree of polymerization is 2000, and alcoholysis degree is
88%) (degree of polymerization is 2000 to 100 DEG C of PVA aqueous solution for carrying out being pre-mixed stirring 2h, mass fraction is 10wt%, and alcoholysis degree is
99%) 95 DEG C carry out premixing 2h after obtain premix, the premix is mixed with the PVA aqueous solution of 25wt% and (is polymerized
It is 2500 to spend, and alcoholysis degree is 88%), 1.5h to be stirred at 95 DEG C, and final PVA concentration of preparing is the mixed aqueous solution of 20wt%, step
It is rapid 3) in finally give the Graphene composite polyvinyl alcohol feature master batch and graphite alkenes of graphene oxide content 0.05wt%
The D90 of material is 10 μm, and D10 is 2 μm.
Embodiment 11
Be step 1 with the distinctive points of embodiment 1) in classification graphene oxide sol solutionses concentration be 3wt%；Step 2)
In, by graphene oxide sol solutionses, (degree of polymerization is 2000, and 88%) alcoholysis degree is with the PVA aqueous solution that mass fraction is 2wt%
90 DEG C carry out premixing stirring 1h and obtain premix, are the PVA aqueous solution (degree of polymerization of 10wt% by the premix and mass fraction
Be 2000, alcoholysis degree is 99%) 95 DEG C of mixed solutions for carrying out obtaining PVA concentration 10wt% after mixing 2h, step 3) in it is final
The D90 of the Graphene composite polyvinyl alcohol feature master batch and graphite alkenes material that obtain graphene oxide content 2wt% is 10 μ
M, D10 are 2 μm.
Embodiment 12
Be step 1 with the distinctive points of embodiment 1) in from the secondary precipitation for obtaining is centrifuged again under 7000rpm rotating speeds,
The classification graphene oxide sol solutionses of 1wt% are obtained, the Graphene composite polyethylene of graphene oxide content 3wt% is finally given
The D90 of alcohol feature master batch and graphite alkenes material is 10 μm, and D10 is 2 μm.
Embodiment 13
Be step 1 with the distinctive points of embodiment 1) in from the secondary precipitation for obtaining is centrifuged again under 7000rpm rotating speeds,
The classification graphene oxide sol solutionses of 2.5wt% are obtained, the Graphene for finally giving graphene oxide content 6wt% is combined poly- second
The D90 of enol feature master batch and graphite alkenes material is 10 μm, and D10 is 2 μm.
Comparative example 1
The graphene oxide for preparing is added in water, mass fraction is the oxidation stone of 1.5wt% by ultrasonic disperse 1h
Black alkene be introduced directly into PVA solution (degree of polymerization is 2000, alcoholysis degree be 99%) in, obtain PVA concentration water-soluble for 15wt%
Liquid, stirs 1h at 95 DEG C, it is female that evaporation solvent is dried to obtain the Graphene composite polyvinyl alcohol that graphene oxide content is 1.5wt%
The D90 of grain and graphite alkenes material is 150 μm, and D10 is 6 μm.The petrographic microscope figure of the master batch that the comparative example is prepared is such as
Shown in accompanying drawing 3.In addition, as can be seen that being prepared using preparation method of the invention (such as accompanying drawing 2) from accompanying drawing of the invention
Master batch graphene particles dispersion ratio it is more uniform, granular size uses method (such as accompanying drawing of comparative example 1 also than more uniform
3) master batch for preparing has many agglomerated particles to produce, and graphene particles disperse also heterogeneity, certainly will influence whether follow-up system
The performance of the products such as standby fiber, plastics.
Application examples 1
The preparation method of Graphene polyvinyl alcohol composite fiber is as follows：
Using embodiment 1-13 and master batch obtained in comparative example 1 and/or blank polyvinyl alcohol master batch mixing it is soluble in water, add
Plus boric acid 5wt%, and ascorbic acid reducing agent 10g is introduced, and temperature is improved to 100 DEG C, continue to stir and reductase 12 h, obtain spinning
Stoste (in spinning solution, the concentration of reducing agent is 0.1wt%), by spinning solution in, by filtering, normal pressure is static de- at 90 DEG C
After bubble, it is expressed into saltcake coagulating bath through the spinneret orifice of a diameter of 0.1mm, spun silk becomes as-spun fibre, at the beginning of described
Raw fiber carries out pickling, washing, acetalization (glutaraldehyde 1%, 2min, 80 DEG C), drying, hot-stretch and thermal finalization treatment,
Hot-stretch temperature is 140 DEG C, and hot-stretch multiple is 20 times, and heat-setting time is 5min.Finally give, using embodiment 1-6,8-
13 and the master batch of comparative example 1 obtain the Graphene composite polyvinyl alcohol fiber of graphite alkenes content of material 0.5wt%；Embodiment 7
Master batch obtain the Graphene composite polyvinyl alcohol fiber of graphite alkenes content of material 0.05wt%.
Application examples 2
The preparation method of Graphene composite polyvinyl alcohol plastics is as follows：
By the additive such as the master batch (10wt%) of embodiment 1, nylon-6 master batch (86wt%) and fire retardant, stabilizer
It is heated between 200-350 DEG C in addition stirred tank, makes each material melts and mixing, form polymer melt, melt is lowered the temperature
After send into extruding machine, extrusion molding obtains final product plastic product.Embodiment 3, the master batch of comparative example 1 can also refer to above method preparation
Plastics.
Experimental example 1
The performance of the Graphene composite polyvinyl alcohol fibrous material that will be prepared in application examples 1 is contrasted, detection mark
It is accurate：Tensile strength, Young's modulus and elongation at break use GB/T19975-2005 standards.Concrete outcome is as shown in table 1 below：
The performance parameter of table 1 is contrasted
As can be seen that each side of the Graphene composite polyvinyl alcohol fiber that the embodiment of the present invention is prepared from upper table 1
Face performance is more excellent, is suitable to wide popularization and application.
Experimental example 2
The performance of the Graphene composite polyvinyl alcohol plastics batten that will be prepared in application examples 2 is contrasted, detection mark
It is accurate：Tensile strength, Young's modulus and elongation at break use GB/T19975-2005 standards.Concrete outcome is as shown in table 1 below：
The performance parameter of table 2 is contrasted
| Tensile strength (MPa) | Young's modulus (GPa) | Elongation at break (%) | |
| Embodiment 1 | 150 | 2 | 400 |
| Embodiment 3 | 200 | 2.5 | 450 |
| Comparative example 1 | 75 | 1.6 | 200 |
As can be seen that each side of the Graphene composite polyvinyl alcohol plastics that the embodiment of the present invention is prepared from upper table 2
Face performance is more excellent, is suitable to wide popularization and application.
Although illustrate and describing the present invention with specific embodiment, but will be appreciated that without departing substantially from of the invention
Many other changes and modification can be made in the case of spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (10)
1. a kind of high performance Graphene composite polyvinyl alcohol master batch, it is characterised in that main by graphite alkenes material and poly- second
Enol is constituted；
In the Graphene composite polyvinyl alcohol master batch, the content of graphite alkenes material is further in below 6wt%
Below 3wt%, further between 0.05wt-1.5wt%；
Below 100 μm, D10 norm controllings exist the D90 norm controllings of graphite alkenes material in below 20um, D90 norm controllings
Less than 20 times of D10 indexs, more preferably preferably less than 10 times, less than 5 times；
Preferably, graphite alkenes material includes Graphene, biomass Graphene, graphene oxide, one kind of Graphene derivative
Or several mixing, the wherein Graphene of Graphene derivative including element doping.
2. Graphene composite polyvinyl alcohol master batch according to claim 1, it is characterised in that when master batch is used to prepare plastics
During product, D90 controls are controlled between 5-20um in 30-100um, D10；
When master batch is used to prepare fiber, D90 controls are controlled in 0.5-3um in 5-30um, D10.
3. the preparation side of a kind of high performance Graphene composite polyvinyl alcohol master batch according to claim any one of 1-2
Method, it is characterised in that mainly comprise the following steps：
(A) the graphite alkenes material aqueous solution is pre-processed, is obtained the graphite alkenes agent particle size classification aqueous solution；
(B) the PVA aqueous solution is mixed with the graphite alkenes agent particle size classification aqueous solution and obtains mixed solution, drying is
.
4. the preparation method of Graphene composite polyvinyl alcohol master batch according to claim 3, it is characterised in that the step
(A) in, the method for pretreatment includes：Behaviour will be centrifuged under the conditions of graphite alkenes material aqueous solution ultrasonic disperse, 2000-3000rpm
Retain bottom precipitation after work, supernatant respectively obtains secondary bottom precipitation and two after centrifugally operated under the conditions of 5000-7000rpm
Secondary supernatant；
Wherein, the graphite alkenes material classification aqueous solution includes appointing in bottom precipitation, secondary bottom precipitation, secondary supernatant
Meaning one kind is prepared, preferably secondary bottom precipitation；
Preferably, in the graphite alkenes material classification aqueous solution, the concentration of graphite alkenes material is controlled in below 3wt%, more
Preferably below 2wt%.
5. the preparation method of Graphene composite polyvinyl alcohol master batch according to claim 4, it is characterised in that ultrasonic disperse
Time control in 1-3h；
Preferably, under the conditions of 2000-3000rpm the time control of centrifugally operated in 20-40min；
Preferably, under the conditions of 5000-7000rpm the time control of centrifugally operated in 10-30min.
6. the preparation method of Graphene composite polyvinyl alcohol master batch according to claim 3, it is characterised in that the step
(B) in, the PVA aqueous solution several times and gradually steps up the mode of concentration and is added, and initial concentration is controlled between 2-5wt%；
Preferably, in the mixed solution, the concentration of PVA is controlled between 10-20wt%.
7. the preparation method of Graphene composite polyvinyl alcohol master batch according to claim 6, it is characterised in that the step
(B) in, in 1-2h, temperature control is at 90-100 DEG C for the time control stirred after being added every time when adding the PVA aqueous solution several times
Between.
8. the preparation method of Graphene composite polyvinyl alcohol master batch according to claim 3, it is characterised in that the step
(B) in, the PVA degree of polymerization of the PVA aqueous solution is controlled between 1700-2500, and alcoholysis degree is controlled between 88-99%.
9. the Graphene composite polyvinyl alcohol master batch described in claim 1 or 2 membrane product, water-absorbing resins, water imbibition sponge,
Application in terms of plastics.
10. the fibrous material of the Graphene composite polyvinyl alcohol master batch described in a kind of use claim 1 or 2；
Preferably, in more than 2Gpa, Young's modulus control is in more than 45Gpa, fracture for the tensile strength control of the fibrous material
Elongation is controlled between 3-13%；
Preferably, the fibrous material is mainly made by the following method：The Graphene composite polyvinyl alcohol master batch is added water
Dissolving, or the Graphene composite polyvinyl alcohol master batch mixes soluble in water with blank polyvinyl alcohol master batch, obtains spinning solution,
After filtering, deaeration, spinning and drying, obtain final product；
It is highly preferred that in the spinning solution, adding boric acid, the concentration of boric acid is controlled between 2-5wt%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018010575A1 (en) * | 2016-07-11 | 2018-01-18 | 济南圣泉集团股份有限公司 | Graphene composite polyvinyl alcohol masterbatch and graphene composite polyvinyl alcohol fiber, preparation method for masterbatch, and applications thereof |
| CN110591209A (en) * | 2019-07-04 | 2019-12-20 | 江苏新奥碳纳米材料应用技术研究院有限公司 | Polymer heat-conducting film containing uniformly-dispersed and highly-oriented graphene and preparation method thereof |
| CN113119558A (en) * | 2021-05-10 | 2021-07-16 | 常州市顺龙宏源包装有限公司 | Three-layer co-extrusion antistatic polyethylene film and preparation method thereof |
| CN113372712A (en) * | 2021-06-25 | 2021-09-10 | 宁波石墨烯创新中心有限公司 | Pre-dispersed particles, plastic master batch and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864098A (en) * | 2010-06-03 | 2010-10-20 | 四川大学 | Preparation method of polymer/graphene composite material through in situ reduction |
| CN103224694A (en) * | 2013-04-18 | 2013-07-31 | 苏州旭光聚合物有限公司 | Conductive PBT composite material |
| CN103950919A (en) * | 2014-04-01 | 2014-07-30 | 华南理工大学 | Graphene preparation method |
| CN104328533A (en) * | 2014-11-10 | 2015-02-04 | 沙嫣 | Preparation method of high-strength and high-modulus polyvinyl alcohol-graphene nano composite fibers |
| CN104371115A (en) * | 2014-11-26 | 2015-02-25 | 上海大学 | Polymer-grafted graphene oxide master batch and preparation method thereof |
| CN105778373A (en) * | 2016-05-10 | 2016-07-20 | 四川大学 | Method for preparing melt-processable modified polyvinyl alcohol-graphene composite material |
-
2016
- 2016-08-02 CN CN201610624203.7A patent/CN106832399B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864098A (en) * | 2010-06-03 | 2010-10-20 | 四川大学 | Preparation method of polymer/graphene composite material through in situ reduction |
| CN103224694A (en) * | 2013-04-18 | 2013-07-31 | 苏州旭光聚合物有限公司 | Conductive PBT composite material |
| CN103950919A (en) * | 2014-04-01 | 2014-07-30 | 华南理工大学 | Graphene preparation method |
| CN104328533A (en) * | 2014-11-10 | 2015-02-04 | 沙嫣 | Preparation method of high-strength and high-modulus polyvinyl alcohol-graphene nano composite fibers |
| CN104371115A (en) * | 2014-11-26 | 2015-02-25 | 上海大学 | Polymer-grafted graphene oxide master batch and preparation method thereof |
| CN105778373A (en) * | 2016-05-10 | 2016-07-20 | 四川大学 | Method for preparing melt-processable modified polyvinyl alcohol-graphene composite material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018010575A1 (en) * | 2016-07-11 | 2018-01-18 | 济南圣泉集团股份有限公司 | Graphene composite polyvinyl alcohol masterbatch and graphene composite polyvinyl alcohol fiber, preparation method for masterbatch, and applications thereof |
| CN110591209A (en) * | 2019-07-04 | 2019-12-20 | 江苏新奥碳纳米材料应用技术研究院有限公司 | Polymer heat-conducting film containing uniformly-dispersed and highly-oriented graphene and preparation method thereof |
| CN113119558A (en) * | 2021-05-10 | 2021-07-16 | 常州市顺龙宏源包装有限公司 | Three-layer co-extrusion antistatic polyethylene film and preparation method thereof |
| CN113372712A (en) * | 2021-06-25 | 2021-09-10 | 宁波石墨烯创新中心有限公司 | Pre-dispersed particles, plastic master batch and preparation method thereof |
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