CN106832399B - Graphene composite polyvinyl alcohol master batch and preparation method thereof, application, fibrous material - Google Patents
Graphene composite polyvinyl alcohol master batch and preparation method thereof, application, fibrous material Download PDFInfo
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- CN106832399B CN106832399B CN201610624203.7A CN201610624203A CN106832399B CN 106832399 B CN106832399 B CN 106832399B CN 201610624203 A CN201610624203 A CN 201610624203A CN 106832399 B CN106832399 B CN 106832399B
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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
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- 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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Abstract
The present invention provides a kind of high performance graphene composite polyvinyl alcohol master batches, are mainly made of with polyvinyl alcohol graphene substance；In graphene composite polyvinyl alcohol master batch, the content of graphene substance is in 6wt% or less；The D90 norm controllings of graphene substance at 100 μm hereinafter, the D90 norm controllings of graphene substance at 100 μm hereinafter, D10 norm controllings in 20um hereinafter, D90 norm controllings are at 20 times or less of D10 indexs.The preparation method of the master batch includes：(A) graphene substance aqueous solution is pre-processed, obtains graphene substance grain size grading aqueous solution；(B) it is mixed PVA aqueous solutions and graphene substance grain size grading aqueous solution to obtain mixed solution, be drying to obtain.The graphene composite polyvinyl alcohol master batch content of material of the embodiment of the present invention is although relatively high, but graphene particles still disperse it is relatively uniform, granular size also than more uniform, without any agglomerated particle generate.
Description
Technical field
The present invention relates to polyvinyl alcohol master batches to process preparation field, multiple in particular to a kind of high performance graphene
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 molecular formula is [C2H4O]n.Vinal
Due to there is the features such as being easily dispersed property is good in good hydrophily, impact resistance and processing and forming, can be used as plastics, cement with
And the reinforcing material of ceramics etc., also alternative asbestos for having carcinogen.
Graphene is a kind of two-dimensional material for the honeycomb structure being made of single layer sp2 hydbridized carbon atoms, is had many excellent
Different performance.It has been found since 2004, graphene just becomes a big research hotspot of scientific circles.In the object to graphene
While Physicochemical property is studied, also emerge one after another with the relevant composite material of graphene.On nano science direction, stone
Black alkene is also used to prepare relevant nanocomposite, the especially nanometer of graphene/metal or graphene/metal oxide
Composite material.Due to the excellent properties of graphene, these nanocomposites are in novel energy, bio-sensing, catalysis, optics material
There are wide Research Prospects in the fields such as material.
In the prior art, the Related product compound about polyvinyl alcohol-graphene is relatively more, is widely applied in view of it,
Polyvinyl alcohol-graphene generally can first be made to function sexupara grain, so both convenience in transport, storages, be also convenient for subsequent application,
Then Related product is made as raw material by functional master batch further according to actual demand, it is thus found that the property of functional master batch itself
Can be good and bad, graphene content in the functional master batch that will have a direct impact on the correlated performance of subsequent product, but generally produce
Can be relatively low, and graphene particles dispersion is uneven, and granular size is inhomogenous, is easy to happen interlayer reunion, so not
The problem of being easily broken off with the stress concentration point that piece diameter graphene substance is brought, influence the product subsequently prepared
Performance.
In view of this, special propose the present invention.
Invention content
The first object of the present invention is to provide a kind of graphene polyvinyl alcohol master batch with high performance, stone in the master batch
Black alkenes content of material is although relatively high, but graphene particles are still disperseed relatively uniform, and granular size is also than more uniform, group
Poly- particle generates less, properties stabilization, and after being prepared into associated materials for subsequent applications, stretching is slight, elongation at break
Etc. indexs have the raising of matter, and also additionally impart the higher toughness of material, hot water resistance and antistatic property, further
The market application range for expanding material, improves value-added content of product, is conducive to further genralrlization application.
The second object of the present invention is to provide the preparation of above-mentioned graphene composite polyvinyl alcohol master batch with high performance
Method, step linking is close before and after preparation method, and method is simple and fast, can be realized with existing production process equipment and flow seamless
Docking has the advantages that completely retain the effective ingredient of raw material, and, operating condition temperature simply easily operated with method
With, it can be achieved that graphene composite polyvinyl alcohol master batch industrialized production, economic benefit is very good.
The third object of the present invention is to provide the application of above-mentioned graphene composite polyvinyl alcohol master batch with high performance,
The master batch products application is very extensive, is widely used in membrane product, water-absorbing resins, water imbibition sponge, plastics and undulation degree
In terms of material, 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 the higher toughness of the fibrous material, heat-resisting
Aqueous and antistatic property.
In order to realize that the above-mentioned purpose of the present invention, spy use following technical scheme：
The present invention provides a kind of high performance graphene composite polyvinyl alcohol master batch products, mainly by graphite alkenes object
Matter and polyvinyl alcohol form, and in the master batch, the content of graphene substance in 6wt% hereinafter, further for 3wt% with
Under, further between 0.05wt-1.5wt%, the D90 norm controllings of graphene substance are at 100 μm hereinafter, D10 refers to
Mark control in 20um hereinafter, and D90 indexs be no more than 20 times of D10 indexs, preferably 10 times hereinafter, more preferable 5 times or less.
In the prior art, the graphene content in general polyvinyl alcohol-graphene master batch generally can be relatively low, because of graphite
Alkene content is too high to be easy to happen reunion, then the physical property of product can be influenced accordingly by subsequently preparing associated downstream product,
In order to solve many technical problems existing in the prior art, the present invention provides a kind of graphene comparision contents, and high, particle divides
It dissipates again than more uniform, the less graphene composite polyvinyl alcohol master batch of reuniting, in the master batch, the content highest of graphene substance
6wt% can be reached, the granularity of graphene substance then requires as D90 at 100 μm hereinafter, D90 in 100um refers to 100um
Following grain size substance accounts for whole 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 herein referred to is particle size, can be very thin thickness but area
It is very big.Similarly, D10 norm controllings are the same reason in 20um or less, and D10 can be 18um, 10um, 8um, 5um, 3um,
1um etc..D90 indexs are no more than within 20 times, preferably 10 times of D10 indexs, within more preferable 5 times, it can be understood as work as D90
For 50um when, D10 be not less than 2.5um, D10 is preferably 5um or more, more preferable 10um or more.It is such functionality master batch in addition to
Other than the graphene for ensureing high-content, it is ensured that the size homogeneity of graphene particles, the phenomenon that avoiding particle agglomeration are sent out
Raw, the properties of product prepared using such functional 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 controlled in 5-30um, D10
System is in 0.5-3um.Because final products form is different when preparing plastic products and fiber, leading to graphene substance, there are sizes
Difference, while its purpose is to keep the big chip architecture of graphene substance as possible, it is ensured that graphene substance will not be sent out
The problem of reuniting between generating layer, preventing the stress concentration point fracture that different diameter graphene substances bring, if granularity it is too big or
Person is too small may to be all unfavorable for subsequently forming more uniform inorganic-organic bridging arrangement with PVA strands, be more held in
The graphene substance of same grain size be just more advantageous to subsequently with PVA it is compound after, obtained functional master batch various aspects of performance is all
It is good, it is therefore desirable to strictly to control its grain size.
Used graphene substance includes graphene, biomass graphene, graphene oxide, Graphene derivative
One or more mixing, the Graphene derivative are graphene modified.
Preferably, it includes arbitrary a kind in element doping graphene or functional group's graphite alkene object that the graphene, which derives,
Or at least two kinds of combination.
Preferably, the element doping graphene includes in metal-doped graphene or nonmetal doping graphene
Arbitrary a kind or at least two kinds of of combination.
The metal-doped metallic element it is typical but non-limiting include potassium, sodium, gold, silver, iron, copper, nickel, chromium titanium,
Vanadium or cobalt.
The typical but non-limiting nonmetal doping graphene includes nitrogen, phosphorus, boron or silicon.
Preferably, the nonmetal doping graphene includes nitrogen-doped graphene, phosphorus doping graphene or sulfur doping
Arbitrary a kind or at least two kinds of of combination in graphene.
Preferably, functional group's graphite alkene includes the graphene for being grafted with functional group.
Preferably, functional group's graphite alkene includes arbitrary a kind or at least 2 be grafted in hydroxyl, carboxyl or amino
The graphene of the combination of kind.
Hydroxyl of the present invention includes-R1-OH, and the R1 includes alkyl, and typical but non-limiting hydroxyl can be
Methylhydroxy, ethyl hydroxy, propyl hydroxy, butylhydroxy, amyl hydroxyl, hexyl hydroxyl etc..
Carboxyl of the present invention includes-R2-COOH, and the R2 includes alkyl, and typical but non-limiting hydroxyl can be with
It is methylhydroxy, ethyl hydroxy, propyl hydroxy, butylhydroxy, amyl 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 hydroxyl, hexyl hydroxyl etc..
The present invention additionally provides a kind of high performance in addition to providing a kind of formula of graphene composite polyvinyl alcohol master batch
The preparation method of graphene composite polyvinyl alcohol master batch, mainly includes the following steps：
(A) the graphene substance aqueous solution is pre-processed, obtains graphene substance grain size grading aqueous solution；
(B) it is mixed PVA aqueous solutions and the graphene substance grain size grading aqueous solution to obtain mixed solution, do
It is dry to obtain the final product.
It is prepared by the preparation method of high performance graphene composite polyvinyl alcohol master batch provided by the invention, this preparation method
The functional master batch gone out, the material subsequently prepared not only have all excellent properties of traditional polyvinyl alcohol material, Er Qiexing
The additional properties such as the higher toughness of material itself, hot water resistance and antistatic property are also imparted while can be promoted, it is existing
When preparing graphene composite polyvinyl alcohol Related product in technology, usually directly by graphene and polyvinyl alcohol in mixed solvent
In be uniformly mixed and prepared, but the performance of functional master batch that this method is prepared is general, and graphene particles cannot be equal
Even to be dispersed in master batch, and granular size is also inhomogenous, the present invention is by graphene substance, (graphene substance includes stone
One or more of mixing of black alkene, biomass graphene, graphene oxide, Graphene derivative, wherein Graphene derivative packet
Include the graphene of element doping, be finally utilize graphene-structured therein) with polyvinyl alcohol before, specially first by graphite
The aqueous solution of alkenes substance is pre-processed, and there is no record in the prior art for this pretreated method, and the present invention still belongs to
It is pioneering.
Certainly, when practical operation, the preprocess method specifically used includes：By graphene substance aqueous solution ultrasound point
It dissipates, retain bottom precipitation after centrifugally operated under the conditions of 2000-3000rpm, supernatant centrifuges behaviour under the conditions of 5000-7000rpm
Secondary bottom precipitation and secondary supernatant are respectively obtained after work, wherein graphene substance classification aqueous solution includes that bottom is heavy
Any one in shallow lake, secondary bottom precipitation, secondary supernatant is prepared, aqueous solution prepared by preferably secondary bottom precipitation.
The centrifugally operated rate that the first step obtains bottom precipitation is relatively low, behind the further centrifugally operated of supernatant rate
It is then relatively high, because the material grains degree in precipitation is generally bigger, if the too fast electrodeposition substance for being unfavorable for bulky grain of rate,
Material grains degree in follow-up supernatant is generally smaller, therefore rate needs soon, so that the substance floating that granularity is small
There are in supernatant.In this way granularity than more consistent graphene substance after classification in bottom precipitation or at secondary bottom
Portion precipitates or in secondary supernatant, and graphene substance classification aqueous solution can select above-mentioned by the arbitrary of classification processing
A kind of substance can guarantee with granularity than more consistent graphene substance, and the size of granularity is also more suitable, with
The homogeneity for having fully ensured that piece diameter is conducive to the performance for the functional master batch for subsequently ensureing to prepare.
Wherein, the time of ultrasonic disperse is preferably controlled in 1-3h, and the time of centrifugally operated is most under the conditions of 2000-3000rpm
Good control between 20-40min, under the conditions of 5000-7000rpm the time of centrifugally operated be preferably controlled between 10-30min,
Control is more conducive to the more thorough of grain size grading processing within the preferably operating time, so that particle diameter distribution is more uniform.
In addition, the mass percent concentration of pretreated graphene substance aqueous solution preferably control it is suitable because such as
Fruit concentration is too high, and the reunion of piece interlayer, graphene sol liquid (the graphene substance water of low concentration are easy to happen in concentration process
Solution) be conducive to PVA strands with graphene to sprawl platform progress ordering orientation, add raw material by graphene of the colloidal sol
Compound with PVA progress, preferably graphene substance concentration of aqueous solution is 3wt% hereinafter, more preferably 2wt% is hereinafter, excellent again
It selects between 0.05wt-1.5wt%.
After graphene substance aqueous solution is pre-processed, the PVA aqueous solutions and graphene substance of low concentration are first used
Aqueous solution is pre-mixed, and is then stepped up concentration again, is finally obtained the mixed solution of a concentration of 10-20wt% of PVA, preferably
PVA concentration controls between 15-16wt%, and the complete purpose of dispersion is reached in a manner of by the way that concentration gradient is arranged, if it is
Graphene substance aqueous solution is directly mixed with PVA aqueous solutions, it is unfavorable that such hybrid mode is easy to occur to reunite
In mixing, to influence the performance of product, the compound mode of setting gradient concentration of the invention is more conducive to final products
Performance, is segmented into several gradients when specific operation, for example, successively the PVA aqueous solutions of addition 2-5wt%, 6-8wt% PVA water
The PVA aqueous solutions of solution, 10-12wt%, 25-40wt% etc., the number of gradient are not specifically limited, and initial concentration is controlled in 2-
Between 5wt%.It when practical operation, can specifically be adjusted according to the actual needs of technique, for example gradient is arranged in the concentration of PVA
With the addition number of PVA solution etc., in a word by using the compound mode of this gradient concentration of the present invention, it is molten to solve mixing
The incomplete problem of Dispersion of Solute Matter in liquid, and the performance of graphene composite polyvinyl alcohol functionality master batch is greatly improved.
Preferably, the time control stirred after being added every time when adding PVA aqueous solutions several times exists in 1-2h, temperature control
Between 90-100 DEG C, if the too low PVA aqueous solutions of temperature can not be mixed evenly with graphene substance aqueous solution, it may appear that
The particle of reunion influences properties of product, therefore temperature is preferably controlled in suitable range.
In addition, the degree of polymerization of PVA aqueous solutions is preferably controlled between 1700-2500, alcoholysis degree is preferably controlled in 88-99%
Between, because the degree of polymerization of PVA and alcoholysis degree can significantly affect the tensile strength and stretch modulus of vinal, generally
The degree of polymerization and alcoholysis degree of PVA is higher, polyvinyl alcohol master batch be made subsequent material tensile strength and stretch modulus it is higher.
The graphene composite polyvinyl alcohol master batch being prepared using above-mentioned preparation method further improves subsequent product
Mechanical property, while imparting higher toughness, hot water resistance and antistatic property, be widely used general, can be used for making
Membrane product, water-absorbing resins, water imbibition sponge, plastics, there is very wide application in these areas.
When fibrous material is made in graphene polyvinyl alcohol master batch using the present invention, the tensile strength of fibrous material is reachable
To 2Gpa or more, Young's modulus is can be controlled in 45Gpa or more, elongation at break between 3-13%.
The specific technique for preparing fiber is：Graphene composite polyvinyl alcohol master batch is dissolved in water or the graphene is multiple
Close polyvinyl alcohol master batch and mixed with blank polyvinyl alcohol master batch soluble in water, obtain spinning solution, filtering, deaeration, spinning and
After drying to get；
It is filtered, before deaeration, spinning and drying in follow-up spinning solution, preferably first adds and hand in spinning solution
After joining agent acetalization, reducing agent reduction treatment, the purpose of adding crosslinking agent be in order to which PVA and graphene are crosslinked, thus
It realizes the macromolecule arrangement orderly on nano-graphene piece surface, avoids high molecular entanglement, be conducive to the height of spinning post-processing
Times hot-stretch, to improve the performance of PVA fibers.Graphene substance itself is used as a kind of inorganic filler, and addition reducing agent can
Crosslinking agent is added to improve the hot water resistance of PVA fibers, in spinning solution and belongs to preceding crosslinking, it also can be after preparing as-spun fibre
It being crosslinked again, this crosslinking belongs to post-crosslinking, and either preceding crosslinking or post-crosslinking can obtain high-performance PVA fibers,
If what is be added in spinning solution is graphene oxide, reduction step can carry out in spinning solution, can also prepare
It is restored again after fiber, either preceding crosslinking or post-crosslinking, pre reduction or rear reduction are protected in patent of the invention
It protects in range, crosslinking agent may include one or more of glyoxal, glutaraldehyde, formaldehyde, boric acid and borax mixture, spinning
The concentration of crosslinking agent controls between 0.0075-0.45wt% in stoste, and reducing agent may include sodium borohydride, ascorbic acid, water
One or more of hydrazine and hydroiodic acid mixture are closed, the concentration of reducing agent controls between 0.1-3wt% in spinning solution.
Also in spinning solution, when adding boric acid, the concentration of 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, 85-120 DEG C of the reason of is to freeze in order to prevent
Glue, in order to avoid the performance to fiber impacts, spinning solution by being squeezed out in spinneret that orifice diameter is 0.08-0.30mm,
The saltcake coagulating bath forming that spun silk enters 40-45 DEG C becomes as-spun fibre, as-spun fibre through pickling, washing, it is dry after, then
By hot-stretch and thermal finalization processing to get to high performance graphene composite polyvinyl alcohol fiber.
Preferably, deaeration mode is normal pressure discontinuous degassing or vacuum defoamation, and hot-stretch temperature is controlled at 120-250 DEG C, heat
Draw ratio is 10-37 times, heat-setting time 1-15min.
Compared with prior art, beneficial effects of the present invention are：
(1) although graphene substance contained by graphene polyvinyl alcohol master batch with high performance provided by the invention than
It is higher, but graphene particles still disperse it is relatively uniform, granular size also than more uniform, without any agglomerated particle generate,
Properties are stablized；
(2) preparation method of high performance graphene composite polyvinyl alcohol master batch of the invention, step before and after preparation method
Linking is close, and method is simple and fast, and slitless connection can be realized with existing production process equipment and flow, and original can completely be retained by having
The advantages of effective ingredient of material, and it is simply easily operated with method, and operating condition is mild, it can be achieved that the compound poly- second of graphene
Industrialized production, the economic benefit of enol master batch are good；
(3) graphene composite polyvinyl alcohol master batch with high performance is widely used general, is widely used in membrane product, is inhaled
In terms of water-base resin, water imbibition sponge, plastics and fibrous material, the fibrous composite especially prepared by the master batch exists
On the basis of realizing traditional high-strength, high modulus polyvinyl alcohol fibre spinning technique, the further double mechanical property for promoting fiber, simultaneously
Impart the higher toughness of the fibrous material, hot water resistance and antistatic property.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described.
Fig. 1 is the petrographic microscope figure of pure polyvinyl alcohol master batch；
Fig. 2 is the petrographic microscope figure for the graphene composite polyvinyl alcohol master batch that the embodiment of the present invention 1 is prepared；
Fig. 3 is the petrographic microscope figure for the graphene composite polyvinyl alcohol master batch that comparative example 1 is prepared.
Specific implementation mode
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 invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
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 is added in water, ultrasonic disperse obtains stable dispersion liquid, which is turned in 2000rpm
Speed is lower to carry out first time centrifugation, and centrifugation time 20min removes bottom precipitation, and supernatant carries out second under 5000rpm rotating speeds
Centrifugation, centrifugation time 10min obtain secondary bottom precipitation, add water ultrasound to obtain the classification oxygen of 1.5wt% secondary bottom precipitation
Graphite alkene sol solutions；
2) the graphene oxide sol solutions of a concentration of 1.5wt% and the PVA aqueous solutions of a concentration of 5wt% are pre-mixed
(degree of polymerization 1700, alcoholysis degree 99%) obtains premix, and the PVA aqueous solutions of the premix and 10wt% are mixed again
It closes (degree of polymerization 2500, alcoholysis degree 88%), 1h is stirred at 90 DEG C, add 25wt%PVA aqueous solutions and form mixed solution,
Mixed solution evaporation solvent seasoning is subsequently obtained functional master batch by a concentration of 15wt% of PVA in mixed solution；
3) in the functionality master batch, graphene oxide content is 1.5wt%, and the D90 of graphene substance is 100 μm,
D10 is 20 μm, and the petrographic microscope figure for the master batch which is prepared is as shown in Fig. 2, without adding any other
Substance pure polyvinyl alcohol blank master batch petrographic microscope figure it is as shown in Fig. 1.
Embodiment 2
It is to select the bottom centrifuged for the first time under 3000rpm rotating speeds heavy in step 1) with the distinctive points of embodiment 1
It forms sediment, water ultrasound is added to obtain the classification graphene oxide sol solutions of 2wt%, in obtained mixed solution, PVA's is a concentration of
16wt%, evaporation solvent seasoning obtain graphene oxide content as the functional master batch of 1.5wt%, and graphene substance
D90 is 70 μm, and D10 is 3.5 μm.
Embodiment 3
After being that selection centrifuges supernatant again under 7000rpm rotating speeds in step 1) with the distinctive points of embodiment 1
Secondary supernatant, is prepared the classification graphene oxide sol solutions of 3wt%, and in obtained obtained mixed solution, PVA's is dense
Degree is 15wt%, and evaporation solvent seasoning obtains the functional master batch that graphene oxide content is 1.5wt%, and graphene substance
D90 be 30 μm, D10 be 5 μm.
Embodiment 4
It is that finally evaporating solvent seasoning obtains the work(that graphene oxide content is 1.5wt% with the distinctive points of embodiment 1
Energy sexupara grain and the D90 of graphene substance are 20 μm, and D10 is 3 μm.
Embodiment 5
It is that finally evaporating solvent seasoning obtains the work(that graphene oxide content is 1.5wt% with the distinctive points of embodiment 1
Energy sexupara grain and the D90 of graphene substance are 10 μm, and D10 is 2 μm.
Embodiment 6
It is that finally evaporating solvent seasoning obtains the work(that graphene oxide content is 1.5wt% with the distinctive points of embodiment 1
Energy sexupara grain and the D90 of graphene substance are 5 μm, and D10 is 0.5 μm.
Embodiment 7
It is that finally evaporating solvent seasoning obtains the work(that graphene oxide content is 1.5wt% with the distinctive points of embodiment 1
Energy sexupara grain and the D90 of graphene substance are 5 μm, and D10 is 3 μm.
Embodiment 8
It is in step 1) graphene oxide replacing with graphene with the distinctive points of embodiment 1, secondary bottom precipitation adds
Water ultrasound obtains the classification graphene sol liquid of 1wt%, and it is 1.5wt% that final evaporation solvent seasoning, which obtains graphene oxide content,
Functional master batch and graphene substance D90 be 10 μm, D10 be 2 μm.
Embodiment 9
It is in step 1) graphene oxide replacing with biomass graphene, secondary bottom with the distinctive points of embodiment 1
Precipitation plus water ultrasound obtain the classification graphene sol liquid of 0.5wt%, and final evaporation solvent seasoning obtains graphene oxide content
It it is 10 μm for the functional master batch of 1.5wt% and the D90 of graphene substance, D10 is 2 μm.
Embodiment 10
It is a concentration of 0.05wt% of classification graphene oxide sol solutions in step 1) with the distinctive points of embodiment 1；Step
It is rapid 2) in, by PVA aqueous solutions that graphene oxide sol solutions and mass fraction are 5wt%, (degree of polymerization 2000, alcoholysis degree are
88%) 100 DEG C carry out premixing stirring 2h, mass fraction be 10wt% PVA aqueous solutions (degree of polymerization 2000, alcoholysis degree are
99%) 95 DEG C carry out premixing 2h after obtain premix, which is mixed with the PVA aqueous solutions of 25wt% and (is polymerize
Degree is 2500, alcoholysis degree 88%), 1.5h is stirred at 95 DEG C, the final mixed aqueous solution for preparing a concentration of 20wt% of PVA, step
It is rapid 3) in finally obtain the graphene composite polyvinyl alcohol functionality master batch and graphite alkenes of graphene oxide content 0.05wt%
The D90 of substance is 10 μm, and D10 is 2 μm.
Embodiment 11
It is a concentration of 3wt% of classification graphene oxide sol solutions in step 1) with the distinctive points of embodiment 1；Step 2)
In, it is the PVA aqueous solutions (degree of polymerization 2000, alcoholysis degree 88%) of 2wt% by graphene oxide sol solutions and mass fraction
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 99%) 95 DEG C carry out obtaining the mixed solution of PVA concentration 10wt% after mixing 2h, it is final in step 3)
The D90 for obtaining the graphene composite polyvinyl alcohol functionality master batch of graphene oxide content 2wt% and graphene substance is 10 μ
M, D10 are 2 μm.
Embodiment 12
It is to select the secondary precipitation centrifuged again under 7000rpm rotating speeds in step 1) with the distinctive points of embodiment 1,
The classification graphene oxide sol solutions of 1wt% are obtained, the graphene composite polyethylene of graphene oxide content 3wt% is finally obtained
Alcohol functionality master batch and the D90 of graphene substance are 10 μm, and D10 is 2 μm.
Embodiment 13
It is to select the secondary precipitation centrifuged again under 7000rpm rotating speeds in step 1) with the distinctive points of embodiment 1,
The classification graphene oxide sol solutions of 2.5wt% are obtained, the compound poly- second of graphene of graphene oxide content 6wt% is finally obtained
Enol functionality master batch and the D90 of graphene substance are 10 μm, and D10 is 2 μm.
Comparative example 1
The graphene oxide being prepared, ultrasonic disperse 1h, by the oxidation stone that mass fraction is 1.5wt% are added in water
Black alkene is introduced directly into PVA solution (degree of polymerization 2000, alcoholysis degree 99%), obtains the water-soluble of a concentration of 15wt% of PVA
Liquid stirs 1h at 95 DEG C, and it is female that evaporation solvent seasoning obtains the graphene composite polyvinyl alcohol that graphene oxide content is 1.5wt%
Grain and the D90 of graphene substance are 150 μm, and D10 is 6 μm.The petrographic microscope figure for the master batch that the comparative example is prepared is such as
Shown in attached drawing 3.In addition, as can be seen that preparation method (such as attached drawing 2) using the present invention is prepared from the attached drawing of the present invention
Master batch graphene particles dispersion it is relatively uniform, granular size also than more uniform, but use comparative example 1 method (such as attached drawing
3) master batch being prepared has many agglomerated particles to generate, and graphene particles dispersion is also inhomogenous, certainly will influence whether subsequently to make
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：
It is soluble in water using master batch made from embodiment 1-13 and comparative example 1 and/or the mixing of blank polyvinyl alcohol master batch, add
Add boric acid 5wt%, and introduce ascorbic acid reducing agent 10g, improves temperature to 100 DEG C, continue stirring and reductase 12 h, obtain spinning
Stoste (in spinning solution, a concentration of 0.1wt% of reducing agent), by spinning solution by filtering at 90 DEG C, normal pressure is static de-
After bubble, the spinneret orifice through a diameter of 0.1mm is expressed into saltcake coagulating bath, and 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 processing,
Hot-stretch temperature is 140 DEG C, and hot-stretch multiple is 20 times, heat-setting time 5min.It finally obtains, utilizes embodiment 1-6,8-
13 and the master batch of comparative example 1 obtain the graphene composite polyvinyl alcohol fiber of graphene substance content 0.5wt%；Embodiment 7
Master batch obtain the graphene composite polyvinyl alcohol fiber of graphene substance content 0.05wt%.
Application examples 2
The preparation method of graphene composite polyvinyl alcohol plastics is as follows：
The additives such as master batch (10wt%), nylon-6 master batch (86wt%) and fire retardant, stabilizer by embodiment 1
It is added in stirred tank and is heated between 200-350 DEG C, make each material melts and mixing, form polymer melt, melt is cooled down
After be sent into extruding machine, extrusion molding is to get plastic product.Embodiment 3, comparative example 1 master batch can also refer to the above method preparation
Plastics.
Experimental example 1
The performance for the graphene composite polyvinyl alcohol fibrous material being prepared in application examples 1 is compared, detection mark
It is accurate：Tensile strength, Young's modulus and elongation at break are all made of GB/T19975-2005 standards.Concrete outcome is as shown in table 1 below：
1 performance parameter of table compares
As can be seen that each side for 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 for wide popularization and application.
Experimental example 2
The performance for the graphene composite polyvinyl alcohol plastics batten being prepared in application examples 2 is compared, detection mark
It is accurate：Tensile strength, Young's modulus and elongation at break are all made of GB/T19975-2005 standards.Concrete outcome is as shown in table 1 below：
2 performance parameter of table compares
| 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 for 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 for wide popularization and application.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from the present invention's
Many other change 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 (24)
1. a kind of high performance graphene composite polyvinyl alcohol master batch, which is characterized in that mainly by graphene substance and poly- second
Enol forms；
In the graphene composite polyvinyl alcohol master batch, the content of graphene substance is in 6wt% or less；
The D90 norm controllings of graphene substance at 100 μm hereinafter, D10 norm controllings in 20um hereinafter, D90 norm controllings exist
20 times or less of D10 indexs.
2. graphene composite polyvinyl alcohol master batch according to claim 1, which is characterized in that the compound poly- second of graphene
In enol master batch, the content of graphene substance is in 3wt% or less.
3. graphene composite polyvinyl alcohol master batch according to claim 1, which is characterized in that the graphene is compound poly-
In vinyl alcohol master batch, the content of graphene substance is between 0.05wt-1.5wt%.
4. graphene composite polyvinyl alcohol master batch according to claim 1, which is characterized in that D90 norm controllings refer in D10
10 times of target or less.
5. graphene composite polyvinyl alcohol master batch according to claim 1, which is characterized in that D90 norm controllings refer in D10
5 times of target or less.
6. according to claim 1-5 any one of them graphene composite polyvinyl alcohol master batches, which is characterized in that graphite alkenes object
Matter includes one or more of mixing of graphene, biomass graphene, graphene oxide, Graphene derivative, wherein graphite
Ene derivative includes the graphene of element doping.
7. graphene composite polyvinyl alcohol master batch according to claim 1, which is characterized in that when master batch is used to prepare plastics
When product, D90 controls are controlled in 30-100um, D10 between 5-20um；
When master batch is used to prepare fiber, D90 controls are controlled in 5-30um, D10 in 0.5-3um.
8. according to a kind of preparation side of high performance graphene composite polyvinyl alcohol master batch of claim 1-7 any one of them
Method, which is characterized in that mainly include the following steps：
(A) the graphene substance aqueous solution is pre-processed, obtains graphene substance grain size grading aqueous solution；
(B) it is mixed PVA aqueous solutions and the graphene substance grain size grading aqueous solution to obtain mixed solution, drying is
.
9. the preparation method of graphene composite polyvinyl alcohol master batch according to claim 8, which is characterized in that the step
(A) in, pretreated method includes：Behaviour will be centrifuged under the conditions of graphene substance aqueous solution ultrasonic disperse, 2000-3000rpm
Retain bottom precipitation after work, supernatant respectively obtains secondary bottom precipitation and two under the conditions of 5000-7000rpm after centrifugally operated
Secondary supernatant；
Wherein, the graphene substance classification aqueous solution includes appointing in bottom precipitation, secondary bottom precipitation, secondary supernatant
Meaning one kind is prepared.
10. preparation method according to claim 9, which is characterized in that the graphene substance classification aqueous solution is two
Secondary bottom precipitation.
11. preparation method according to claim 9, which is characterized in that in the graphene substance classification aqueous solution, stone
The concentration of black alkenes substance is controlled in 3wt% or less.
12. preparation method according to claim 9, which is characterized in that in the graphene substance classification aqueous solution, stone
The concentration of black alkenes substance is controlled in 2wt% or less.
13. preparation method according to claim 9, which is characterized in that the time control of ultrasonic disperse is in 1-3h.
14. preparation method according to claim 13, which is characterized in that under the conditions of 2000-3000rpm centrifugally operated when
Between control in 20-40min.
15. preparation method according to claim 13, which is characterized in that under the conditions of 5000-7000rpm centrifugally operated when
Between control in 10-30min.
16. preparation method according to claim 8, which is characterized in that in the step (B), PVA aqueous solutions are several times simultaneously
The mode that concentration is gradually increased is added, and initial concentration controls between 2-5wt%.
17. preparation method according to claim 8, which is characterized in that in the mixed solution, the concentration control of PVA exists
Between 10-20wt%.
18. preparation method according to claim 16, which is characterized in that in the step (B), add PVA water several times
The time control stirred after being added every time when solution is controlled in 1-2h, temperature between 90-100 DEG C.
19. preparation method according to claim 8, which is characterized in that in the step (B), the PVA aqueous solutions
The PVA degree of polymerization controls between 1700-2500, and alcoholysis degree controls between 88-99%.
20. claim 1-7 any one of them graphene composite polyvinyl alcohol master batches are in membrane product, water-absorbing resins, water suction
Application in terms of property sponge, plastics.
21. a kind of fibrous material using claim 1-7 any one of them graphene composite polyvinyl alcohol master batches.
22. fibrous material according to claim 21, which is characterized in that the tensile strength control of the fibrous material exists
2GP a or more, Young's modulus control more than 45GP a, and elongation at break controls between 3-13%.
23. fibrous material according to claim 21, which is characterized in that the fibrous material is mainly made by the following method
At：The graphene composite polyvinyl alcohol master batch is dissolved in water or the graphene composite polyvinyl alcohol master batch gathers with blank
The mixing of vinyl alcohol master batch is soluble in water, obtains spinning solution, filtering, deaeration, spinning and after drying to get.
24. fibrous material according to claim 23, which is characterized in that in the spinning solution, boric acid is added, boric acid
Concentration controls between 2-5wt%.
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| CN110343315A (en) * | 2019-07-04 | 2019-10-18 | 江苏新奥碳纳米材料应用技术研究院有限公司 | Containing Monodispersed, polymer bond's film of 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 |
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