CN107108954A - High-strength polymer containing CNT - Google Patents
High-strength polymer containing CNT Download PDFInfo
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- CN107108954A CN107108954A CN201680004245.9A CN201680004245A CN107108954A CN 107108954 A CN107108954 A CN 107108954A CN 201680004245 A CN201680004245 A CN 201680004245A CN 107108954 A CN107108954 A CN 107108954A
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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
- C08K3/041—Carbon nanotubes
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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
- C08L101/00—Compositions of unspecified macromolecular compounds
Abstract
The invention provides a kind of high-strength polymer composite material, it contains：Thermoplastic polymer and CNT；Wherein, BET specific surface area is 40m2/ g~120m2/ g, bulk density is 10~60kg/m3, CNT is 5~15 weight % relative to the content of polymer composites gross weight.By adjusting and optimizing specific surface area and bulk density simultaneously, so as to while CNT dispersiveness is not reduced, making the content of institute's carbon nanotubes in polymer composites increases, and the high-strength polymer composite material improved is obtained so as to provide a kind of mechanical strength.
Description
Technical field
The present patent application is advocated based on the korean patent application 10-2015-0135974 submitted for 25 days 09 month in 2015
Number priority, the full content disclosed in the korean patent application document is herein incorporated by reference the application.
The present invention is a kind of multiple containing the polymer with high specific surface area and the CNT of bulk density by providing
Condensation material, so as to provide a kind of compound with the polymer for improving mechanical strength by improving the dispersiveness in composite
Material.
Background technology
Under normal circumstances, CNT (hereinafter referred to as " CNT ") refer to have about 3 to 150nm, specifically about 3~
100nm diameter, length is the several times of diameter, such as more than 100 times of cylindrical carbon pipe.Such CNT is by carbon atom arrangement
Layer composition, the core with different shape.In addition, such CNT is for example also known as carbon fiber or hollow carbon fiber.
Because such CNT has higher electric conductivity, heat endurance, tensile strength and restoration, therefore it is used as many
Plant the additive of composite.When CNT is used as the additive of composite, the scattered uniformity coefficient of CNT beams be one particularly
Important factor.When makrolon/carbon nano tube compound material, likewise as carbon in polymer substrate (matrix)
The scattered uniformity coefficient of nanotube, makes the physical property of complex change.However, for CNT, due to length and diameter phase
Than relatively longer, and the gravitation that CNT exists each other is stronger, therefore exists non-with polymer phase specific dispersion degree
Often low the problem of.
In order to which a kind of prior art for solving to use in these problems, industry is, by the way that CNT is immersed in into nitric acid, sulfuric acid
Or make its surface oxidation in their mixed solution, so that the increased technology of the decentralization of CNT.However, such
In technology, due to having used acid solution in preparation technology, therefore it there is generation safety problem or environmental problem etc. be all kinds of and ask
The problem of technology stability being difficult to ensure that in the case of topic, and a large amount of productions.
On the other hand, makrolon (polycarbonate) is a kind of engineering plastics, and transparent, mechanical strength and impact are strong
Degree is excellent and heat resistance is strong, is widely used in various fields, is got most of the attention especially as the sheathing material of electronic product.Electronics
The sheathing material of product is sometimes required electromagnetic wave shielding performance, particularly as mobile phone shell produce electromagnetic wave compared with
During the material of the shell of many electronic equipments, its electromagnetic wave shielding performance is same with mechanical strength to turn into an essential thing
Property.Technology for increasing electromagnetic wave shielding performance in the material of polymerizable material is to add and can play in fluoropolymer resin
The inorganic substances of electromagnetic wave shielding function or the technology of carbons material, but in this case, existing drops the formability of material
Low the problem of.Therefore, carrying out recently and a small amount of CNT is added in fluoropolymer resin, while meeting outstanding electromagnetic wave
The research of shielding properties and formability.
Makrolon and CNT are dissolved in a solvent Patent Document 1 discloses one kind, preparation complex is formed
Afterwards, then by the complex mixed, answered so as to prepare polymer/carbon nano-tube with polycarbonate resin again in an extruder
Fit method.
Patent document 2 is related to the preparation side that a kind of dispersiveness in polymer substrate obtains the CNT powder compositions improved
Method.Wherein include, by the way that excessive acrylic acid compared with CNT is sprayed with solution state to CNT, it is mixed into wherein
Heated afterwards, either acrylic acid and initiator are together added dropwise in CNT and carries out being thermally formed polyacrylic acid or makes third
Heat-treating methods etc. are carried out after olefin(e) acid vapor sorption, CNT powder compositions is obtained, it is mixed with all kinds of polymer,
Prepare electric conductivity and obtain the polymer composite body improved.
Patent document 3 is related to a kind of preparation method of polymer-carbon nanotube composite particles.Made using ultrasonic oscillation device
CNT and polymer disperse to obtain suspension in a solvent, are formed it into after mesomorphic state and dried using sprayer unit, prepared described
The weight ratio of composite particles, wherein CNT and polymer is 0.01:1 to 0.1:1.
Patent Document 4 discloses a kind of polymer composite body preparation method.Thermoplastic resin is dissolved in water-insoluble
Obtain adhesive resin solution in solvent, and during relative to 100 parts by weight of thermoplastic resin 100~1500 parts by weight carbon
The suspension of nanotube and water is mixed, and CNT height blended resin composition is obtained, by itself and matrix
(base) resin is mixed, and prepares polymer composite body.Wherein, adhesive resin uses polyethylene, polyvinyl chloride, matrix tree
Fat uses ABS.
Citation
Patent document
(patent document 0001) Korean Patent Application Publication the 10-2011-0000296th
(patent document 0002) Korean Patent Application Publication the 10-2008-0065688th
(patent document 0003) Korean Patent Application Publication the 10-2012-0124611st
(patent document 0004) Korean Patent Application Publication the 10-2012-0027263rd
The content of the invention
Technical task
Problem to be solved is in the present invention, by adjusting specific surface area and bulk density, contains so as to provide one kind
Dispersiveness obtains the high-strength polymer composite material of improved CNT.
Solve the scheme of problem
It is a kind of poly- containing thermoplastic polymer and CNT to solve to provide in the problem in the present invention, the present invention
Compound composite material.Wherein, BET specific surface area is 40m2/ g to 120m2/ g, bulk density is 10kg/m3To 60kg/m3, carbon receives
Mitron is 5~15 weight % relative to the content of composite gross weight.
In addition, the polymer composites in one embodiment, compared with adding before the CNT, improved strength rate
Can be more than 10%.
In addition, the aspect ratio range of the CNT can be 1~100, diameter can be 20~100nm.
In addition, the bulk density of the CNT can be 30~60g/cm3。
In addition, the mean size of contained carbon nanotube agglomerate can be less than 5 μm in the polymer composites.
In addition, the average grain diameter of the CNT used as raw material can be 100 μm~800 μm.
In addition, the CNT can have white potato shaped or spherical winding shape (entangled) two-dimensional structure.
In addition, a kind of preparation method of the CNT includes：By catalyst component and active component be carried on spherical α-
In alumina support, the supported catalyst calcined below 600 DEG C is put into inside reactor, and it is more than 650 DEG C and small
At a temperature of 800 DEG C, reactor is injected into carbon supply source or the carbon supply source with hydrogen, nitrogen or their mixed gas
Internal step；And
Decomposed by the carbon supply source of injection in the catalyst surface, so that the step of carbon nano tube growth.
In addition, the calcining heat can be 400 DEG C~600 DEG C.
In addition, on the basis of the spherical parts by weight of Alpha-alumina 100, catalyst component described in about 10~25 parts by weight can be loaded
And active component.
In addition, the weight ratio of the catalyst component and active component can be 10~30:1~14.
In addition, the catalyst component can contain the one or more in Fe, Co and Ni.
In addition, the active component can be containing the one or more in Mo and V.
In addition, a kind of preparation method of the supported catalyst, including：By spherical alpha-alumina supports with containing catalyst component
The aqueous metal solution of precursor and active component precursors is mixed, so that the step of forming the aqueous solution containing supported catalyst precursor；
Maturation, dipping are carried out to the aqueous solution containing supported catalyst precursor, so that the step of obtaining mixture；The mixture is entered
Row vacuum drying, the step of catalyst component and active component are coated on the carrier surface；And, to dry by vacuum
The product of dry acquisition is calcined at the temperature below 600 DEG C, the step of forming supported catalyst.
In addition, the concentration of the aqueous metal solution can be 0.1~0.4g/ml.
According to one embodiment, the maturation, impregnation technology can implement 30 minutes~15 at a temperature of 20 to 100 DEG C
Hour.
The present invention is in order to solve another problem there is provided a kind of preparation method of composite, and it includes：
Make the step of thermoplastic polymer is mixed with CNT；And,
The step of being melted, kneaded and extruded to the mixture using extruder.
Beneficial effect
Polymer composites in the present invention, improve the specific surface area of CNT, so that polymer composite
CNT containing high level in material, and due to larger bulk density and diameter, it is possible to increase composite
The dispersiveness of interior CNT, so as to effectively improve the mechanical strength transitivity of polymer composites, therefore it is available
In multiple fields such as energy and material, functional composite material, medicine, battery, semiconductor, display element and its manufacture methods.
Brief description of the drawings
Fig. 1 a and Fig. 1 b represent the SEM image of polymer composites extrudate/injection article in comparative example 5.
Fig. 2 a and Fig. 2 b represent the SEM image of polymer composites extrudate/injection article in embodiment 1.
Fig. 3 represents the SEM image of the improved strength CNT used in embodiment 1.
Embodiment
The explanation of term or word used in description of the invention and claim, should not be limited to normal conditions or
Implication in dictionary, inventor illustrates for the invention in the best way to he or she, based on can be to the general of term
The principle appropriately defined is read, therefore can only be explained with the meaning and concept for meeting the technology of the present invention thought.
The present invention is described in detail below.
According to the preferred embodiment of the present invention there is provided a kind of polymer composites,
It is the polymer composites containing thermoplastic polymer and CNT.Wherein, BET specific surface area is
40m2/ g~120m2/ g, bulk density is 10kg/m3~60kg/m3, content of the CNT relative to composite gross weight
For 5~15 weight %.
The polymer composites compared with adding before the CNT, tensile strength improvement rate can for 10% with
On.
That is, the specific surface area of the invention by improving CNT, receives so as to increase the carbon that can contain in polymer
The content of mitron, thus, it is possible to improve the physical property that the content of the CNT in polymer composites is raised and shown.Separately
Outside, in order to solve the problems, such as the dispersed decline caused by content of carbon nanotubes increase, while also bulk density is adjusted,
So as to suppress the phenomenon that dispersiveness declines in polymer composites.By above-mentioned characteristic, it is possible to provide a kind of mechanical strength is excellent
Elegant, i.e., by adding the CNT, so that tensile strength improves about more than 10% high-strength polymer composite wood
Material.
In addition, Inventive polymers composite can be prepared with the following method：By thermoplastic polymer and CNT
The step of being mixed；And the step of the mixture is melted, kneaded and extruded using extruder.Now, utilize
The carbon nanotube agglomerate of residual can be deposited with the size below 5 μm in the composite of extruder extrusion injection cohesion
, and this may indicate that CNT dispersiveness in polymer is outstanding.
CNT
According to one embodiment of present invention, the specific surface area of the CNT is preferably 40 to 100m2/ g, volume is close
Spend for 60kg/m3Hereinafter, for example, 10 to 60kg/m3, preferably 30 to 60kg/m3, more preferably 30~50kg/m3.Although carbon
The specific surface area of nanotube is lower, can more increase the loading content in composite, but its dispersiveness and density will be reduced.Separately
Outside, bulk density is smaller, and the dispersiveness in fluoropolymer resin is also lower, and is likely to form the aggregation of CNT, and this can
Can turn into makes the factor of mechanical electricity physical property reduction.
In addition, institute's carbon nanotubes is 5~15 weights relative to the content of composite gross weight in polymer composites
Measure %, more preferably 5~10 weight %.In the case that content is less than the 5 weight %, it is impossible to obtain mechanical strength abundant
Improve.
Therefore, the present invention is adjusted by the specific surface area and bulk density simultaneously to CNT, so as to make
The loading content and dispersiveness of the CNT are optimized, and it is outstanding, particularly mechanical strong to prepare physical property
Degree obtains the polymer composites significantly improved.
In addition, the mean size of contained carbon nanotube agglomerate can be 5 μm in the polymer composites injection article
Hereinafter, it obtains the index improved as the dispersiveness for representing composite, it is possible to visualise the physical property for going out composite is carried
High effect.
In addition, the mean aspect ratio of institute's carbon nanotubes can be 1 to 100 in the polymer composites, it is preferably
10 to 60, more preferably 10 to 30.
In addition, in the polymer composites institute's carbon nanotubes diameter can for 20 to 100nm, preferably 30 to
100nm。
The average length and length-width ratio of the CNT can pass through SEM (Scanning Electron Microscope：
SEM) or TEM (transmission electron microscope：Transmission electron microscope) photo survey
.That is, obtained by these measurement apparatus after raw material are the photo of powder formed carbon nanotube, image analyzer can be passed through
(image analyzer), such as Scandium 5.1 (Olympus soft Imaging Solutions GmbH, Germany) are right
It is analyzed, and draws average length.
According to one embodiment, the average grain diameter of the CNT used as raw material is about 5 μm to 1000 μm or 100
To 800 μm, preferably 200 μm to 600 μm, more preferably 300 μm to 4000 μm, thickness range can be 10nm to 1000 μm.
The pencil CNT of average length and thickness with above range is more beneficial for improving described containing thermoplastic polymer
The electric conductivity of composite.The CNT has in the polymer composites Medium Culture containing thermoplastic polymer
Network structure, the longer CNT of length is more beneficial for forming above-mentioned network, and its result can improve polymer composites
Physical property.
CNT of the present invention disclosure satisfy that beam diameter 10 to 50nm, can be that flat ratio 0.9 to 1.0, size distribution value are
(Dcnt) 0.5 to 1.0 white potato shaped or spherical winding shape (entangled type).
The term " bulk density " used in the present invention is defined with following formula 1, by adjusting the calcining heat of supported catalyst,
Increase reaction temperature during CNT synthesis, thus can obtain the CNT grown Density Distribution or particular range.
【Formula 1】
Bulk density=CNT weight (kg)/CNT volumes (m3)
In addition, the shape of flat ratio and beam, can pass through the above-mentioned uniqueness prepared using supported catalyst of the present invention
Technique is obtained.Now, flat ratio following formula 2 is defined.
【Formula 2】
Flat ratio=the most short diameter through CNT centers/runs through the longest diameter at CNT centers
And then, the size distribution value (Dcnt) can be defined with following formula 3.
【Formula 3】
Dcnt=[Dn90-Dn10]/Dn50
In calculating formula, Dn90 refer to by CNT be placed in distilled water place 3 hours after, utilize Microtrac grain size analyses
Instrument, the number average bead diameter measured in the case where absorbing (absorbing) pattern with 90% standard, Dn10 refers to the number measured with 10% standard
Equal particle diameter, Dn50 refers to the number average bead diameter measured with 50% standard.
It is prepared by the supported catalyst that the CNT of the present invention can be calcined using spherical alpha-alumina supports below 600 DEG C
Form, it is highly preferred that being prepared from using following preparation method.
The method used to prepare the CNT includes：By catalyst component and active component be carried on spherical α-
In alumina support, and by below 600 DEG C calcine supported catalyst put into inside reactor, and more than 650 DEG C and
At a temperature of less than 800 DEG C, carbon supply source or the carbon supply source are injected with hydrogen, nitrogen or their mixed gas and reacted
Step inside device；And by making the carbon supply source of injection be decomposed in the catalyst surface, so that carbon nano tube growth
The step of.
That is, the present invention uses alpha-alumina supports, and by adjusting catalyst calcination temperature and reaction temperature, so as to prepare
BET specific surface area is 40m2/ g to 120m2/ g, bulk density is in 60kg/m3Following CNT.
CNT synthesis supported catalyst in a specific example is characterised by, by catalyst component and activity into
Divide and be carried in spherical alpha-alumina supports, and calcined below 600 DEG C.
Under normal circumstances, chemical formula is Al2O3Aluminum oxide with multiple different phases, for example with α-, γ-, δ-, η-, θ-and
X- aluminum oxide is present.In Alpha-alumina (corundum), oxide ion formation hexahedron closed structure, oxidation aluminium ion is in octahedral
It is symmetrical in body space.Similarly, gama-alumina has " defective " spinel structure (spinelle knot of no cationic
Structure).
In addition, the carrier of the catalyst can contain Alpha-alumina.Although known gama-alumina is because it is compared with high porosity
And it is used as catalytic carrier more, but Alpha-alumina is because its porous is very low and is seldom used as catalyst carrier.It was unexpected that making
In the case of preparing supported catalyst as carrier with spherical Alpha-alumina, the calcining of the supported catalyst is formed by regulation
Temperature, can suppress the generation of amorphous carbon when synthesizing CNT, while reducing specific surface area to control diameter.
In summary, the CNT synthesis supported catalyst in the present invention, it is technically characterized in that, by catalyst component and work
Property composition is carried in spherical alpha-alumina supports, is formed by less than 600 DEG C of temperature calcination.The calcining heat for example can be with
At 400 DEG C with up to less than 600 DEG C of scope.The supported catalyst calcined in the range of said temperature, in synthesis CNT
When, the generation of amorphous carbon can be reduced, while can by the way that CNT specific surface area, diameter and bulk density are adjusted, from
And improve the decentralization in polymer.
In the spherical Alpha-alumina used in the present invention, " spherical " this term is also wrapped in addition to preferably spherical
Include actual spherical, also including such as potato shape, section for ellipse situation.
According to one embodiment, the spherical Alpha-alumina can be prepared from using method known to industry.For example, industrial
On be widely used for preparing Bayer (Bayer) method of aluminum oxide from bauxite (bauxite).Similarly, spherical alpha-oxidation
Aluminium can be by γ-Al2O3Or arbitrary aqueous (hydrous) oxide is heated to preparing more than the temperature of 1000 DEG C of degree.
In the present invention, the spherical Alpha-alumina as carrier can be made into arbitrarily suitable size.For example, in the present invention
Used spherical Alpha-alumina using BET method when being measured, for example, can have about 1m2/ g to about 50m2/ g surface
Product.In the present invention, the spherical Alpha-alumina used as carrier is different from existing carrier, and its surface is smooth, and with very
Low porosity, for example, can have 0.001 to 0.1cm3/ g pore volume.
As the spherical Alpha-alumina of carrier, can loading content than relatively low metal.As the metal of the load,
For example, when on the basis of the spherical parts by weight of Alpha-alumina 100, catalyst component and active component are about 10 to 25 weight
Part, or about 15~20 parts by weight.Sufficient catalytic activity can be shown under above-mentioned loading content.
The catalyst component and active component loaded in the spherical Alpha-alumina can be with 10 to 30:1 to 14 weight ratio
Content use, and in above-mentioned content range, more preferably CNT can be shown and prepare activity.
The catalyst component used in the present invention can be the one or more in Fe, Co and Ni.Can be for example choosing
One from Fe salt, Fe oxides, Fe compounds, Co salt, Co oxides, Co compounds, Ni salt, Ni oxides, Ni compounds
Plant or a variety of, in another example can be such as Fe (NO3)2·6H2O、Fe(NO3)2·9H2O、Ni(NO3)2·6H2O、Co(NO3)2·
6H2The nitride such as O.
In addition, the active component used in the present invention, such as can be the one or more in Mo and V, in another example can
Think Mo salt, Mo oxides, Mo compounds, V salt, V oxides, V compounds etc., then for example can be by such as (NH4)6Mo7O24·
4H2O nitride etc., which is dissolved in distilled water, to be used.
As described above, the CNT synthesis in the present invention can be prepared from supported catalyst by infusion process.
According to one embodiment, the preparation method of the CNT synthesis supported catalyst in the present invention, including：
(1) spherical alpha-alumina supports are carried out with the aqueous metal solution containing catalyst component precursor and active component precursors
Mixing, so that the step of forming the aqueous solution containing supported catalyst precursor；
(2) maturation, dipping are carried out to the aqueous solution containing supported catalyst precursor, so that the step of obtaining mixture；
(3) mixture is dried in vacuo, and coats on the carrier surface catalyst component and activity
The step of composition；And
(4) temperature of the product obtained by the vacuum drying below 600 DEG C is calcined, so as to form load
The step of catalyst.
In the preparation method, the aqueous solution containing supported catalyst precursor is formed in step (1), the aqueous solution is by inciting somebody to action
Al classes carrier is mixed and formed with the aqueous metal solution containing catalyst component precursor and active component precursors.Wherein, contain
Catalyst component, active component and spherical alpha-alumina supports, and hereinbefore illustrated for mentioned component.
The concentration of the aqueous metal solution, when in view of pickling efficiency, uses such as 0.1 to 0.4g/ml or 0.1
Scope to 0.3g/ml is highly efficient.As mentioned previously, the spherical alpha-alumina supports in above-mentioned aqueous metal solution are blended in
Use content, such as when on the basis of the spherical parts by weight of Alpha-alumina 100, the content of catalyst component and active component
It is about 10 to 25 parts by weight, or about 15 to 20 parts by weight.
The step of the preparation method in (2), maturation, dipping are carried out to the supported catalyst precursor solution, so that
Obtain mixture.Now, maturation, dipping are not limited to this, can be in 20 DEG C to 100 DEG C or 60 to 100 DEG C of temperature range
It is interior, implement 30 minutes~15 hours, or 1 to 15 hour.Above range can provide higher load efficiency.
The step of the preparation method in (3), to being mixing in the middle maturation obtained of the step (2), impregnation product
Thing is dried in vacuo, and cladding catalyst component and active component on carrier surface.The vacuum drying, refers under vacuo
Rotary evaporation makes the process that it is dried, such as within can implementing one hour at 45 to 80 DEG C, or at one minute to one hour
In the range of implement.Fail to impregnate residual metallic salt in the carrier, can be formed uniformly in oxidation aluminium surface by drying process
It is immersion film-coated.
In this specification in described vacuum drying, the implication of " vacuum " is meeting suitable for generally vacuum drying true
In the case of empty scope and it is not particularly restricted.
The step of the preparation method in (4), the product obtained to the vacuum drying by the step (3) is carried out
Calcining, so as to form the final product i.e. supported catalyst of the present invention.Above-mentioned calcining can be implemented in the range of about 400 to 600 DEG C,
It can implement in atmosphere or under inert gas conditions.It can implement in about 30 minutes to 5 hours, but the calcination time is not limited
Due to this.
According to one embodiment, after the vacuum drying in the step (3), can the calcining in the step (4) it
Before, implement precalcining at least 1 time at about 250 to 400 DEG C.In this case, being preferably in terms of reaction efficiency, described pre-calcined
Before burning, most 50% in whole supported catalyst precursor aqueous solution are immersed in the amorphous alpha-alumina supports and
Use, and after the precalcining is just implemented or before calcining, supported catalyst precursor aqueous solution residue is immersed in
Used in the spherical alpha-alumina supports.
The volume profiles of supported catalyst prepared by method described above depend on used spherical alpha-alumina supports
Bulk ＆ form, but it is not limited to this.That is, the volume profiles of described CNT synthesis supported catalyst are spherical, and are had
The structure of single or multiple lift (2 layers or more than 3 layers) catalyst component is coated on the surface of carrier.Moreover, in terms of CNT synthesis preferably
To there is continuous clad structure with it, not as with discontinuous clad structure.
The CNT preparations supported catalyst provided in the present invention, such as particle diameter or average grain diameter are about 30 to 150
μm, when being observed using SEM, surface granularity can about 10 to 50nm scope, preferably within the range regulation CNT diameters and
Catalyst activity is optimal within the range.
On the other hand, the supported catalyst of catalyst component and active component is coated on the spherical alpha-alumina supports surface
In agent, it is contemplated that when the particle diameter or average particle size range of the alumina support, be defined by mesh number grain diameter measurement, by less than 32 μm
Particle diameter when being defined as ultrasonic wave (ultrasonic) micro mist amount, the measured value of number average bead diameter can specifically may be used within 5%
Scope within 3%.
As reference, in the ultrasonic technique, catalytic specie and active matter of the micro mist as attachment on a catalyst
The aggregation of matter, will not be sifted out when being screened with sieve, but with it is good be coated on supported catalyst-active material compared with
Granularity is different, catalytic activity is also different, and island (island) the shape aggregation adhered on a catalyst by above-mentioned state causes CNT to receive
Rate is remarkably decreased.And separated because how much the material weaker adheres on a catalyst, therefore when carrying out ultrasound,
Form micro mist.
In the present invention, the ultrasonic wave micro powder amount means after ultrasonication is carried out, and is measured by Particle Size Analyzer
Number average bead diameter micro mist amount, now the carrier include multilayer carrier.
In particular according to the CNT synthesis supported catalyst that obtains of the present invention, when in view of specific surface area, preferably ball
Shape.And verified, the CNT synthesis supported catalyst that actually prepares in the present invention, also close to spherical, almost spherical or
It is actual spherical.
The technique that CNT is prepared by the supported catalyst obtained by the above method, comprises the following steps, but is not limited to
This：
Supported catalyst in the present invention is put into inside reactor, at a temperature of about 650 DEG C~about 800 DEG C,
The step of carbon supply source or the carbon supply source and hydrogen, nitrogen or their mixed gas being passed through to inside reactor；And
Decomposed by the carbon supply source being injected on the catalyst surface, so that the step of carbon nano tube growth.
According to one embodiment, unrestrictedly it can be reacted as the reactor using fixed bed reactors or thermopnore
Device.
CNT preparation methods in the present invention, such as defined in the examples below, can be prepared with non-pencil
Two-dimensional structure, and possess the CNT of spherical volume profiles.
Thermoplastic polymer
When in view of formability, the thermoplastic polymer preferably has to be measured under conditions of 25 DEG C, concentration 1g/dl
1.5 to 5, more preferably 2 to 4.5 relative viscosity.When relative viscosity is less than 1.5, because viscosity is too low, therefore melting is mixed
Processing after refining becomes difficult, it may be difficult to obtain preferred physical property.And when more than 5, then viscosity is too high, therefore forming
When mobility be deteriorated, it is impossible to apply enough injection pressures, it is thus possible to be difficult to the preparation of molded product.
In addition, being preferably 0.5 to 100g/min, more preferably according to the melt index of the thermoplastic polymer of the present invention
1.0 to 80g/min.But in the case that melt index is less than 0.5g/min, due to needing higher shearing force, therefore melting is mixed
Refining is more difficult, and CNT is not scattered good in thermoplastic polymer, in the case that melt index is more than 100g/min, molding
The impact strength of product may be reduced seriously.
Available for the thermoplastic polymer of the conductive composite material, as long as it is used for the thermoplastic in relevant industries
The material of property polymer, then it is unrestricted.It is, for example, possible to use polycarbonate resin, acrylic resin, aromatic polyamide tree
Fat, aromatic polyester resins, vistanex, polycarbonate resin, polyphenylene oxide resin, polysulfone resin, polyethersulfone resin, poly- Asia
It is aryl resin, cyclenes hydrocarbon resins, polyetherimide resin, polyacetal resin, polyvinyl acetal resin, polyketone resin, poly-
Ether ketone resin, polyether-ether-ketone resin, poly- aryl ketone resin, poly- ether nitrile resin, liquid crystalline resin, polybenzimidazole resin, poly- second two
Ureic resins, polyamide, or
By in aromatic series alkenyl compound, methacrylate, acrylate and vinyl cyanide compound at least
Vinyl class in polymer or copolymer resin that a kind of polymerization of vinyl monomer or copolymerization are obtained, or
By selected from diene aromatic alkenyl compound copolymer resin, vinyl cyanide-diene aromatic alkenyl compound
Copolymer resin, aromatic series alkenyl compound-diene-vinyl cyanide-N-phenylmaleimide copolymer resin, vinyl
Cyanogen-(ethylene-diene-propylene (EPDM))-aromatic series alkenyl compound copolymer resin, polyolefin, vinyl chloride resin, chlorination chlorine
One or more in vinyl.The specific species of these resins is common knowledge, and those skilled in the art can fit
When example of the selection available for the present composition.
As the vistanex, for example, can be polypropylene, polyethylene, polybutene and poly- (4- methyl-1-pentenes
Alkene) and their compositions, but it is not limited to this.In one embodiment, the polyolefin is selected from polypropylene homopolymer
(for example, atactic (atactic) polypropylene, isotaxy (isotactic) polypropylene and syndiotaxy
(syndiotactic) polypropylene), polypropylene copolymer (for example, polypropylene random copolymer) and their mixture.Properly
Polypropylene copolymer include be selected from ethene, but-1-ene (that is, 1- butylene) and hex- 1- alkene (that is, 1- hexenes) in copolymerization list
In the presence of body, the random copolymer prepared by propylene polymerization, but it is not limited to this.Although these polypropylene random copolymers
In may include the comonomer for the amount of setting arbitrarily, under normal circumstances comprising about below 10wt% (for example, about 1 to about
7wt%, or about 1 to about 4.5wt%) amount.
Described polyester resin, refers to the condensation polymer of dicarboxylic acid component's skeleton and diol component skeleton, i.e., equal polyester or common
Polyester.Wherein, the representative of equal polyester have PET (Polyethylene terephthalate), poly- pair
Phthalic acid propylene diester (Polypropylene terephthalate), polybutylene terephthalate (Polybutylene
Terephthalate), PEN (Polyethylene-2,6-naphthalate), poly terephthalic acid -1,
4- cyclohexanedimethylene terephthalates (Poly-1,4-cyclohexane dimethylene terephthalate), polyethylene diphenyl
(Polyethylene diphenylate) etc..Especially PET, because its is cheap, can be used for
The purposes of many aspects, thus it is more preferred.In addition, described copolyester, is defined as being selected from two in following example
The composition of carboxylic acid skeleton and 3 kinds in the composition with two ol skeletons or the condensation polymer of more than 3 kinds composition compositions.As with two
The composition of carboxylic acid skeleton, can include terephthalic acid (TPA), M-phthalic acid, phthalic acid, Isosorbide-5-Nitrae-naphthalene dicarboxylic acids, 1,5- naphthalenes two
Carboxylic acid, 2,6- naphthalene dicarboxylic acids, 4,4'- diphenyl dicarboxylic acids, 4,4'- diphenyl sulphone (DPS)s dicarboxylic acids, adipic acid, decanedioic acid, dimeric dibasic acid, hexamethylene
Derivative of alkane dicarboxylic acids and their ester etc..As the composition with two ol skeletons, ethylene glycol, 1,2- the third two can be included
Double (the 4'- beta-hydroxy ethoxies of alcohol, 1,3-BDO, BDO, 1,5-PD, diethylene glycol (DEG), PAG, 2,2-
Base phenyl) propane, Soquad (Isosorbate), Isosorbide-5-Nitrae-cyclohexanedimethanol, the spiroglycol (spiroglycol) etc..
Described polycarbonate resin, can pass through biphenyl class and phosgene (phosgene), halogenated formate (Halogen
Formate), prepared by carbonic ester or combinations thereof reaction.Described biphenyl class is enumerated, can be specifically hydroquinones, isophthalic
Double (4- hydroxy phenyls) propane of diphenol, 4,4 '-dihydroxybiphenyl, 2,2- (also known as " bisphenol-A "), 2,4- double (4- hydroxy phenyls)-
Double (the 3- chloro-4-hydroxyl benzene of 2- methybutanes, double (4- hydroxy phenyls) methane, 1,1-bis(4-hydroxyphenyl)-cyclohexane, 2,2-
Base) propane, double (3,5- dimethyl -4- hydroxy phenyls) propane of 2,2-, 2,2- double (the chloro- 4- hydroxy phenyls of 3,5- bis-) propane, 2,
2- double (the bromo- 4- hydroxy phenyls of 3,5- bis-) propane, double (4- hydroxy phenyls) sulfoxides, double (4- hydroxy phenyls) ketone, double (4- hydroxy benzenes
Base) ether etc..Wherein, preferably use double (3, the 5- bis- chloro- 4- hydroxy phenyls) propane of double (4- hydroxy phenyls) propane of 2,2-, 2,2- or
1,1- bis(4-hydroxyphenyl)cyclohexane, more preferably using double (4- hydroxy phenyls) propane of 2,2-.
Described polycarbonate resin or the mixture of the copolymer prepared by biphenyl class of more than two kinds.Separately
Outside, described polycarbonate resin can use linear polycarbonate resin, branching type (branched) polycarbonate resin, gather
Carbonate copolymer resin etc..
Described linear polycarbonate resin can enumerate bisphenol-A class polycarbonate resin etc..It is used as described branching type
Polycarbonate resin, can enumerate the multi-functional aromatic compound such as trimellitic anhydride, trimellitic acid and biphenyl class and
Product prepared by carbonate reaction.Described multi-functional aromatic compound is relative to branched polycarbonate resin total amount
Molar percentage is 0.05 to 2%.Described Copolycarbonate resin can be included difunctionality carboxylic acid and biphenyl class
And product prepared by carbonate reaction.Now, as described carbonic ester, such as biphenyl carbonate diaryl carbonate can be used
Ester, ethylene carbonate etc..
As described cycloolefin polymer, norbornene polymer, cycloolefin can be included and birdsed of the same feather flock together compound, ring-type
Conjugated diolefine polymer, vinyl alicyclic hydrocarbon polymer and their hydride.Enumerating specific example has APEL (Japan three
Well KCC (system) ethylene-cycloolefin hydrocarbon copolymer), ATON (Japanese JSR Corp.'s (system) ENB Type of Collective
Thing), ZEONOR (Zeon Corp (system) norbornene polymer) etc..
Described polyphenylene oxide resin is also referred to as polyphenylene oxide, possesses the structure that-O- is combined in repeat unit phenylene.It is described
Phenylene can have different substituents, for example, methyl, ethyl, halogen, hydroxyl etc..
As described polyamide, nylon resin, nylon multipolymer resins and their mixture can be used.Buddhist nun
Imperial resin can use the ring-opening polymerisation of the lactams such as well-known epsilon-caprolactams, omega-lauric lactam obtain polyamide-
6 (nylon 6)；The nylon polymerization that can be obtained by amino acid such as aminocaproic acid, 11- amino undecanoic acids, 12 amino dodecanoic acids
Thing；By ethylenediamine, tetra-methylenedimine, hexamethylene diamine, 11 methylene diamines, ten dimethylene diamines, 2,2,4- trimethyls six
Methylene diamine, 2,4,4- trimethylhexamethylenediamines, 5- methyl nonyl hexamethylene diamines (5-
Methylnonahexamethylenediamine), the double amino methyl hexamethylenes of m-xylene diamine, paraxylene diamines, 1,3-
Alkane, Isosorbide-5-Nitrae-bis- aminomethyl cyclohexanes, 1- amino -3- amino methyls -3,5,5- trimethyl-cyclohexanes, double (4- aminocyclohexanes)
Methane, double (4- methyl -4- aminocyclohexyls) methane, 2,2- double (4- aminocyclohexyls) propane, double (aminopropyl) piperazines, ammonia
The aliphatic such as base ethyl piperidine, alicyclic or aromatic diamine, with adipic acid, decanedioic acid (sebacicacid), azelaic acid
(azelaicacid), aliphatic, the alicyclic or fragrance such as terephthalic acid (TPA), 2- chlorine terephthalic acid (TPA), 2- methylterephthalic acids
The nylon polymer that the polymerization such as race's dicarboxylic acids is obtained；Their copolymer or mixture.Nylon copolymer, including polycaprolactam
Copolymer, polycaprolactam (nylon 6) and the polyhexamethylene adipamide of (nylon 6) and polyhexamethylene sebacamide (nylon 6,10)
The copolymer of (nylon66 fiber), polycaprolactam (nylon 6) and copolymer of nylon 12 (nylon 12) etc..
Other additives
Described conductive composite material, in the range of influence is not produced on electric conductivity transitivity, can also contain and be selected from
Fire retardant, flame retardant, lubricant, plasticizer, heat stabilizer, anti-drip agent, antioxidant, bulking agent, light stabilizer, face
One or more additives in material, dyestuff, inorganic additive and anti-dripping agent, it is to be received relative to the carbon using content
Below 5 parts by weight of the parts by weight of mitron 100.The specific species of these additives is common knowledge, and those skilled in the art
The example that can be used in the present composition can suitably be selected.
According to the conductive composite material of the present invention, it can be prepared by extruding Shooting Technique.Under normal circumstances, extrude
Technique is to be supplied raw material to extruder, and is released from the works of heating cylinder form, then is changed into a setting
The manufacturing process of the non-individual body in shape section.The raw material of the conductive composite material of extruder is fed into hot cylinder by adding
Heat, softening, melting, are conveyed simultaneously by the rotation of propeller by mixing with compression.The raw material stream of homogeneous molten mass is formed,
Continuously outwards extruded from the opening portion for the mould that target shape is made, can obtain extrusion product by cooling procedure afterwards.
In above-mentioned expressing technique, when raw material passes through the mixing process by mechanical pressure in a heated state, its physical property
It may change.For example, for the CNT of fine structure, it may appear that mechanicalness is broken, therefore remains in extrusion
CNT in product, may have the shape different from the CNT supplied as raw material thing.It is therefore preferable that keeping
Expressing technique is carried out while raw material thing physical property, needs to carry out appropriate control to the extrusion condition of extruder for this.The present invention
In, it can be controlled by the rotary speed of the rotating screw to being installed on extruder, so as to suppress the damage of raw material thing.
In the present invention, the multiple screw extruder for possessing the single axle extruding machine of 1 propeller He possessing multiple propellers can be divided into.
As described multiple screw extruder, the twin shaft for possessing 2 propellers in order to uniformly be kneaded to additive can be included and squeezed
Go out machine.
In the case of biaxial extruder is used as the extruder, the propeller of biaxial extruder is not special
Limitation, can be used the propellers such as at a fully engaged type, incomplete engagement type, non-engagement type.Examined from the angle of mixing property and reactivity
Consider, preferably at a fully engaged type propeller.
In addition, the direction of rotation of propeller can be it is in the same direction, reversely any of, but from mixing property, reactivity angle
Consider, preferably rotating Vortex.Propeller is most preferably the at a fully engaged type of rotating Vortex.
According to one embodiment, in described expressing technique, to suppress the heat deterioration of resin, it can draw in raw material throw-in part
Enter inert gas and carry out melting mixing, and inert gas now is such as can be nitrogen.
As the compounding process using above-mentioned extruder, for example, it can include and thermoplastic resin, CNT one are gone forward side by side
The method of row mixing, and produce the resin combination (Master containing high-concentration carbon nano tube in thermoplastic resin
pellet:Masterbatch) after, the described resin combination of addition, CNT reach normal concentration, then carry out melting mixing
Method (mother material) etc., can be used any compounding process.As different method, in order to suppress the breakage of CNT,
It can use and put into thermoplastic resin from extruder side, and carbon is supplied to extruder using side batcher (side feeder)
Nanotube and the method for carrying out melting mixing.
Embodiment
Being exemplified below embodiment and comparative example, the present invention is described in detail, and the present invention is not limited to this, and it is acted on
It is only that citing is carried out to the present invention more specifically bright.
Preparation example 1:The preparation of catalyst
As catalyst metal precursor, using with the Fe (NO that content is recorded in such as table 1 below3)29H2O、Co(NO3)2·
6H2O、(NH4)6Mo7O24And NH4VO3, it is dissolved completely in distilled water 15.0ml, completes the preparation in flask A.
As carrier, spherical α-Al are being filled2O3(pore volume:0.01cm3/ g, BET specific surface area:4.9m2/ g, Saint
Gobain Products) 12.5mg or α-Al2O3(pore volume:0.55cm3/ g, BET specific surface area:185m2/ g, Saint
Gobain Products) 12.5mg (comparative example 1) flask B in, add the material in the flask A, make before catalyst metals
Body is carried on spherical α-Al2O3Afterwards, stirring, maturation 15 hours in the isothermal reactor including 100 DEG C of backflashes.
In 60 DEG C of thermostats, after its drying being made in 100rpm, 150mbar rotatory vacuum device 30 minutes, addition
Ethanol 15ml, mixes be dried after disperseing at 100 rpm, and this technique repeats to implement 2 times altogether.It will be urged by dry
Agent is completed after intermediate calcination at 350 DEG C, and 3 are calcined under nitrogen (or air) atmosphere and calcining heat (400 DEG C to 600 DEG C)
Hour, prepare uniform (homogeneous) supported catalyst.The catalyst for completing to prepare forms spherical grain when drying
Shape.
Preparation example 2:It is prepared by CNT
Using the CNT synthesis catalyst prepared in the preparation example 1, in the fixed-bed reactor of laboratory scale
In, carry out the synthetic test of CNT.Specifically, the CNT synthesis prepared in the process is arranged on catalyst
After hollow bulb of the internal diameter for 55mm quartz ampoule, 650 DEG C are warming up under nitrogen atmosphere and the temperature is kept, with 60sccm stream
Speed circulation hydrogen, is synthesized 2 hours, so as to synthesize the CNT congeries of specified amount.Physical property (the body of the CNT prepared
Product density, average grain diameter, diameter, specific surface area), record in such as table 1 below.
Embodiment 1
Using biaxial extruder, it will be provided with such as CNT physical property condition, being prepared in preparation example 2 in table 1 below
(reference picture 3) 5 weight % carries out melting mixing with makrolon at 280 DEG C, thus prepares polymer composites.
Embodiment 2
Using biaxial extruder, it will be provided with such as CNT physical property condition, being prepared in preparation example 2 in table 1 below
10 weight % carry out melting mixing with makrolon at 280 DEG C, thus prepare polymer composites.
Comparative example 1
In addition to being not added with CNT, complete to prepare to be equal to the condition of embodiment 1.
Comparative example 2
In addition to adding the weight % of CNT 2 as recorded in table 1 below, to possess physical property condition in comparative example 2,
Complete to prepare to be equal to the method for embodiment 1.
Comparative example 3
In addition to adding the weight % of CNT 2 as recorded in table 1 below, to possess physical property condition in comparative example 3,
Complete to prepare to be equal to the method for embodiment 1.
Comparative example 4
In addition to the weight % of CNT 5 recorded in addition such as table 1 below, to possess physical property condition in comparative example 4, with etc.
The method for being same as embodiment 1 completes to prepare.
Comparative example 5
In addition to adding the weight % of CNT 5 as recorded in table 1 below, to possess physical property condition in comparative example 4,
Complete to prepare to be equal to the method for embodiment 1.
【Table 1】
Tensile strength is assessed
Speed at room temperature is used for 5mm/sec INSTRON companies UTM, completes to measure according to ASTM D638.
【Table 2】
Result in the table 2, the polymer composite body of embodiment 1 and 2 and compareing for comparative example 1, i.e., do not mix
The polymer composite body of compound/carbon nano pipe is compared, tensile strength increase at least 10%.It means that can be by increasing specific surface area
The height mixing of CNT is realized, and improves bulk density, so as to reduce such as the polymer in comparative example 5 in Fig. 1
Complex, i.e. issuable in the case where there is the specific surface area of CNT higher value, bulk density to have smaller value
Amount and size of the aggregation of dispersiveness reduction and generation etc., and then can prepare as shown in Fig. 2 being nearly free from aggregation
Body or the seldom high strength carbon composite of aggregation.
Industrial applicibility
According to the polymer composites of the present invention, by improving the specific surface area of CNT, so that multiple in polymer
CNT is included with higher amount in condensation material, and due to larger bulk density and diameter, it is multiple so as to make
The dispersiveness of CNT is improved in condensation material, the mechanical strength transitivity of polymer composites is obtained more effective
Improve, therefore available for energy and material, functional composite material, medicine, battery, semiconductor, display element and its manufacture method
Deng multiple fields.
Claims (13)
1. a kind of high-strength polymer composite material, it contains thermoplastic polymer and CNT, wherein,
BET specific surface area is 40m2/ g~120m2/ g, bulk density is 10~60kg/m3, CNT is relative to composite
The content of gross weight is 5~15 weight %.
2. high-strength polymer composite material according to claim 1, wherein,
Compared with adding before the CNT, the stretching that with the addition of the high-strength polymer composite material of the CNT is strong
Spend improvement rate and improve more than 10%.
3. high-strength polymer composite material according to claim 1, wherein,
The aspect ratio range of the CNT is 1~100, a diameter of 20~100nm.
4. high-strength polymer composite material according to claim 1, wherein,
The bulk density of the CNT is 30~60g/cm3。
5. high-strength polymer composite material according to claim 1, wherein,
Carbon nanotube agglomerate is included in the polymer composites, and its mean size is less than 5 μm.
6. high-strength polymer composite material according to claim 1, wherein,
The average grain diameter of the CNT used in the polymer composites as raw material is 100 μm~800 μm.
7. high-strength polymer composite material according to claim 1, wherein,
The CNT has white potato shaped or spherical winding shape two-dimensional structure.
8. a kind of preparation method of high-strength polymer composite material, it is characterised in that including by CNT and thermoplastic resin
The process of fat mixing, and the preparation method of the CNT includes：
Catalyst component and active component are carried in spherical alpha-alumina supports, the supported catalyst that will be calcined below 600 DEG C
Agent put into inside reactor, and 650 DEG C less than 800 DEG C at a temperature of, by carbon supply source or the carbon supply source
The step of inside reactor being injected with hydrogen, nitrogen or their mixed gas；And
Decomposed by the carbon supply source of injection in the catalyst surface, so that the step of carbon nano tube growth.
9. the preparation method of high-strength polymer composite material according to claim 8, wherein,
Calcining heat is 400 DEG C~600 DEG C.
10. the preparation method of high-strength polymer composite material according to claim 8, wherein,
On the basis of the spherical parts by weight of Alpha-alumina 100, the catalyst component and activity are loaded with the amount of about 10 to 25 parts by weight
Composition.
11. the preparation method of high-strength polymer composite material according to claim 8, wherein,
The catalyst component and active component are with 10 to 30:1 to 14 weight is than mixing.
12. the preparation method of high-strength polymer composite material according to claim 8, wherein,
The catalyst component contains the one or more in Fe, Co and Ni.
13. the preparation method of high-strength polymer composite material according to claim 8, in addition to：
Spherical alpha-alumina supports are mixed with the aqueous metal solution of precursor containing catalyst component and active component precursors, so that
The step of forming the aqueous solution containing supported catalyst precursor；Maturation, dipping are carried out to the aqueous solution containing supported catalyst precursor, from
And the step of obtain mixture；The mixture is dried in vacuo, and is catalyzed on the carrier surface described in cladding
Point and the step of active component；And, to being calcined by being dried in vacuo at temperature of the product obtained below 600 DEG C,
The step of forming supported catalyst.
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| CN115667138A (en) * | 2020-08-12 | 2023-01-31 | 株式会社Lg化学 | Carbon nanotubes having low density and composite materials comprising the same |
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| CN114316238B (en) * | 2021-12-10 | 2023-06-09 | 卓尔博（宁波）精密机电股份有限公司 | Bisphenol A type polycarbonate composite material for motor housing and preparation method thereof |
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