CN103965389B - The gas-phase polymerization production method of CNT-polymer composite and device - Google Patents
The gas-phase polymerization production method of CNT-polymer composite and device Download PDFInfo
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Abstract
The invention discloses the gas-phase polymerization production method of a kind of CNT polymer composite, including: catalyst and CNT are provided；Polymerization monomer is provided；Polymerization monomer, catalyst and CNT carry out gas-phase polymerization under anhydrous and oxygen-free environment and obtain CNT polymer composite in situ.CNT is One-dimensional nanoreticular carbon materials, has high intensity and good conduction, heat conductivility.Being obtained in CNT polymer composite in situ by the method gas-phase polymerization, CNT both can play the effect preventing polymer bond vitrified because of exothermic heat of reaction with alternative carbon black, and composite can be made again to have good intensity and electrical and thermal conductivity performance.The method is particularly suited for gas-phase polymerization and produces macromolecular material (such as the EP rubbers etc.) complex of low softening temperature.The invention also discloses the gas-phase polymerization process units of a kind of CNT polymer composite.
Description
Technical field
The present invention relates to basic chemical industry field, be specifically related to the gas-phase polymerization producer of a kind of CNT-polymer composite
Method and device.
Background technology
EP rubbers (EPR) is the binary polymer (EPM) obtained by ethylene and propylene copolymerization or is added non-co-by ethylene, propylene and grip
The general name of the terpolymer (EPDM) that diolefinic monomer copolymerization obtains, has been since the eighties in 20th century in synthetic rubber kind
One with fastest developing speed, its yield, production capacity and consumption figure are only second to butadiene-styrene rubber and polybutadiene rubber occupies the world seven
In big synthetic rubber kind the 3rd.
At present, liquid phase method is the major technique producing EP rubbers, but owing to polyreaction is carried out in a solvent, polyreaction
Yield is relatively low, and polymer quality mark general control, at 6-9%, the highest only reaches 11-14%.After generally more than 10%, instead
Answer thing viscosity significantly to rise, have impact on mass transfer and the heat transfer of polymerization system, can occur sudden and violent poly-time serious.Additionally, polymerisation in solution
Technique there is also that solvent recovery is refined and the postprocessing working procedures such as catalyst removal, makes the technological process of production long, equipment investment and life
Produce relatively costly.
Vapor phase method is the manufacture of polyolefins technology that a kind of new development is got up, its technological process is short, need not solvent or diluent,
Almost without three waste discharge, beneficially ecological environmental protection, and device gross investment and total cost of production can be greatly lowered,
The most increasingly come into one's own, and be applied in EP rubbers produces.1999, front union carbide corporation of the U.S. was (existing
Purchased by DOW Chemical) build up the vapor phase method EP rubbers process units of a set of 91kt/a.Vapor phase method produces EP rubbers
Subject matter be in polymerization process that initial reaction rate is higher, thermal discharge is big, and reaction starting stage temperature rise is violent,
And production temperature will be typically higher than the temperature that polymer starts to soften, thus causing polymer beads agglomerate, bonding, situation is tight
Defluidization can be caused during weight, cause danger.Adding fluidization auxiliary agent is the effective ways preventing sticky polymers from boning.Front
Carbon company prevents by adding the inert particles such as white carbon black, clay or the silicon dioxide of 5-30% (mass fraction) in fluid bed
The only bonding of polymer beads in course of reaction.Except preventing the bonding of polymer beads, these inert particles are filled out as reinforcement
Fill agent and also improve the physical and mechanical properties of EP rubbers, but the space that performance is still improved.
CNT (Carbonnanotubes, CNTs) is a kind of one-dimensional nano material, in 1991 by Japanese Scientists
Iijima finds.CNT can be regarded as by carbon atom sp2It is seamless, hollow that the graphite flake layer of hydridization composition is wound into
Tubular structure, is divided into SWCN and multi-walled carbon nano-tubes (containing double-walled carbon nano-tube) to pass through according to the difference of carbon-coating number
Fluidization has been realized in volume production.CNT has the most excellent mechanical property, high draw ratio, thermally-stabilised
Property and electric conductivity: the Young's modulus average out to 1.8TPa of CNT, bending strength is 14.2GPa, and strength ratio steel is high by 100
Times, and density is only 1/6th of steel；The air of 700 DEG C does not aoxidizes；The electrical conductivity of CNT is high
Reaching 1000-2000S/cm, the electric current density that can carry is high.CNT can not only be used for high added value functional material (such as:
Catalyst carrier, electronic component, electromagnetic shielding material, energy storage material and adsorbing material etc.), again can be as high performance composite
The reinforcing agent (such as: strengthen rubber, plastics, pottery and metal etc.) of material.
Summary of the invention
It is contemplated that solve polymer bonding problem the most to a certain extent or enhance product performance.To this end, the present invention
One purpose is to propose the gas phase of CNT-polymer composite that a kind of technique is simple, productivity is high, product quality is good
Polymerization method.Further object is that the gas-phase polymerization proposing a kind of CNT-polymer composite is raw
Produce device.
The gas-phase polymerization production method of the CNT-polymer composite of embodiment according to a first aspect of the present invention, including with
Lower step: catalyst and CNT are provided；Polymerization monomer is provided；Described polymerization monomer, catalyst and CNT are in nothing
Carry out gas-phase polymerization under water oxygen-free environment and obtain CNT-polymer composite in situ.
In one embodiment of the invention, the external diameter of described CNT is less than 100nm, and average aspect ratio is not less than 100.
In one embodiment of the invention, described CNT before gas-phase polymerization through pre-dispersed process, pre-dispersed rear institute
The average aggregate particle diameter stating CNT is less than or equal to 5 μm, and bulk density is 20-500kg/m3。
In one embodiment of the invention, described CNT processes through dehydration, deoxidation and demetalization before gas-phase polymerization.
In one embodiment of the invention, described polymerization monomer includes the mixed of one or more in alkene, alkynes and aromatic hydrocarbons
Compound.
In one embodiment of the invention, described polymerization monomer includes ethylene, propylene and the 3rd comonomer, it is thus achieved that institute
Stating CNT-polymer composite is CNT-EP rubbers composite.
In one embodiment of the invention, the reaction temperature of described gas-phase polymerization is 25-100 DEG C, and reaction pressure is 0.3-10
MPa。
In one embodiment of the invention, CNT, catalyst (without solvent), the mass ratio of polymerization monomer three are
10-106:1:104-107。
In one embodiment of the invention, before carrying out gas-phase polymerization, part CNT is divided jointly with whole catalyst
Dissipate premix in a solvent, the addition when carrying out gas-phase polymerization processes of remaining CNT, wherein participate in premix CNT with
The mass ratio of catalyst (without solvent) is 0-10:1.
In one embodiment of the invention, first partially polymerized monomer is carried out prepolymerization with CNT and whole catalyst,
Then residue polymerization monomer is proceeded with prepolymerization product main polymerization, wherein, the CNT of input in pre-polymerization process:
Catalyst (without solvent): the mass ratio of polymerization monomer is 10-106:1:1-103。
In one embodiment of the invention, described prepolymerized reaction temperature is 25-40 DEG C, and reaction pressure is 0.3-1MPa；
The reaction temperature of described main polymerization is 50-100 DEG C, and reaction pressure is 1-10MPa.
In one embodiment of the invention, described gas-phase polymerization is semi-continuous process or continuous process.
The gas-phase polymerization process units of the CNT-polymer composite of embodiment, described life according to a second aspect of the present invention
Producing device is to include being polymerized raw material monomer entrance, CNT filler, catalyst filler, discharging opening and offgas outlet
Stirred tank, endless tube or fluid bed.
In one embodiment of the invention, when described process units is fluid bed, CNT inlet and catalyst note
Entrance is positioned on gas distributor, and distance d away from gas distributor meet min{50cm, 0.25H}≤d≤
Max{100cm, 0.5H}, wherein H is fluidized bed layer height.
In one embodiment of the invention, described CNT filler be close to described catalyst filler, be positioned at described in urge
Above agent filler, lower section or outside.
In one embodiment of the invention, CNT inlet and catalyst inlet oblique cutting from top to bottom enter process units,
With vertical direction angle less than or equal to 90 °.
In one embodiment of the invention, described discharging opening is positioned in emulsion zone, and described discharging opening is less than described carbon nanometer
Pipe filler and catalyst filler.
Production method and/or process units gas-phase polymerization by the present invention obtain CNT-polymer composite in situ
In, CNT both can play the effect preventing polymer bond vitrified because of exothermic heat of reaction with alternative carbon black, can make again multiple
Condensation material has good intensity and electrical and thermal conductivity performance.The method is particularly suited for gas-phase polymerization and produces the height of low softening temperature
Molecular material (such as EP rubbers etc.) complex.
Accompanying drawing explanation
Fig. 1 is the flow chart of the gas-phase polymerization production method of the CNT-polymer composite of the embodiment of the present invention.
Fig. 2 is the flow process of the gas fluidised bed polymerisation process units of the CNT-polymer composite of the embodiment of the present invention
Figure.
Fig. 3 is CNT filler and the position relationship schematic diagram of catalyst filler, wherein (a) CNT in Fig. 2
Filler is positioned at above catalyst filler, and (b) CNT filler is positioned at below catalyst filler, (b) carbon nanometer
Pipe filler is positioned at outside catalyst filler.
Fig. 4 is the material stress strain curve figure of different antiseized auxiliary agent-EP rubbers composite sample.
Detailed description of the invention
Embodiments of the invention are described below in detail, and the example of described embodiment is shown in the drawings, the most identical
Or similar label represents same or similar element or has the element of same or like function.Retouch below with reference to accompanying drawing
The embodiment stated is exemplary, it is intended to is used for explaining the present invention, and is not considered as limiting the invention.
In describing the invention, it is to be understood that term " " center ", " longitudinally ", " laterally ", " length ", " width ",
" highly ", " on ", D score, "front", "rear", " vertically ", " level ", " interior ", " outward ", " axially ", " radially " etc.
Orientation or the position relationship of instruction are based on orientation shown in the drawings or position relationship, are for only for ease of the description present invention and Jian
Change describe rather than instruction or the hint device of indication or element must have specific orientation, with specific azimuth configuration and
Operation, is therefore not considered as limiting the invention.
Introduce below in conjunction with the accompanying drawings the CNT-polymer composite of the embodiment of the present invention gas-phase polymerization production method and
Device.
Fig. 1 is the stream of the gas-phase polymerization production method of the CNT-polymer composite of first aspect present invention embodiment
Cheng Tu.As described in Figure 1, the method may comprise steps of: A. provides catalyst and CNT；B. provide polymerization single
Body；C. be polymerized monomer, catalyst and CNT carry out under anhydrous and oxygen-free environment gas-phase polymerization obtain in situ CNT-
Polymer composite.In the method, CNT is not only used as antiseized auxiliary agent and solves granule bonding in polymerization process
Problem, also serve as product modifying agent and make composite have good intensity and electrical and thermal conductivity performance.The heap of CNT
Density is only 1/3rd of white carbon black, therefore reaches the CNT required for same antiseized effect and adds quality less than white carbon black
Add quality, auxiliary agent cost can be saved.Further, since every physicochemical property of CNT is also superior to tradition materials such as white carbon blacks
Material, therefore material modification effect is the most preferable.
It should be noted that owing to oxygen and water are unfavorable for polyreaction, it is therefore desirable under anhydrous and oxygen-free environment, carry out gas phase
Polymerization.Air tight in order to ensure response system, observe vacuum after evacuation or pressurising can be used or pressure changes over
Method carry out system leak detection.Use repeatedly switching evacuation after leak detection and be filled with the behaviour of noble gas (such as: high pure nitrogen)
Make method to get rid of the water in process units and oxygen to below 100ppm before feeding intake, preferably up to below 5ppm.
Also, it should be noted the polymerization monomer provided is usually gas phase.But some gas-phase polymerization processes can also be noted
Enter Partial Liquid Phase polymerization monomer, its role is to consume polymerization reaction heat by liquid-phase vaporization, thus suppress reaction temperature to rise.
Due to Quick-gasifying after a small amount of liquid monomer addition process units, it is the most still gas-phase polymerization, does not change the principle of the present invention.
In one embodiment of the invention, CNT used is to be passed through sp by carbon atom2The 1-dimention nano pipe that hydridization is constituted
Shape material, tube wall is that single or multiple lift all may be used.Considering from composite property angle, preferably external diameter is less than 100nm, average
Draw ratio is not less than the CNT of 100.
Owing to the temperature rise of polymerization process starting stage is violent, therefore catalyst is entering process units moment with carbon nanotube dust
Mix particularly significant.For the conduction of utilization rate and composite improving CNT, heat conduction, strength character, carbon nanometer
Pipe powder body through pre-dispersed process, can use the solvent dispersion-freezing of high speed shear, ultrasonic wave added to do before injecting process units
Dry process for dispersing such as grade, the average aggregate particle diameter of pre-dispersed rear CNT is less than or equal to 5 μm, the bulk density of CNT
For 20-500kg/m3。
Owing to CNT has stronger absorption property, in order to avoid polyreaction is caused bad by its adsorption moisture and oxygen
Impact, CNT can carry out being dehydrated through the purging of high temperature inert gas before carrying out gas-phase polymerization, deoxidation treatment, is inhaled
Attached water and oxygen content are down to below 100ppm.And owing to CNT preparation process needing employing metallic catalyst,
In order to avoid kish catalyst produces harmful effect to the performance of CNT-polymer composite, vacuum can be used high
Temperature or inertia flowing atmosphere high-temperature processing method, be down to below 10ppm by metal volatilization by the tenor in CNT.
Actual degree of purification can be depending on composite requires.
In one embodiment of the invention, polymerization monomer can be to include one or more in alkene, alkynes and aromatic hydrocarbons
Mixture.Preferably, polymerization monomer includes ethylene, propylene and the 3rd comonomer, the CNT-macromolecule now obtained
Composite is CNT-EP rubbers composite.
In one embodiment of the invention, CNT, catalyst (without solvent), the mass ratio of polymerization monomer three are
10-106:1:104-107.Desired product can be obtained in theory according to this rate of charge.
In one embodiment of the invention, the reaction temperature of gas-phase polymerization preferably controls in the range of 25-65 DEG C, reaction pressure
In the range of 0.3-10MPa.Desired product can be obtained in theory according to this reaction condition.
In one embodiment of the invention, for ensureing that catalyst can be sufficiently mixed with carbon nanotube dust, can be first by part carbon
Nanotube premixes in atent solvent (such as hexane) with whole catalyst common distribution, and remaining CNT is still with powder body
Form addition when carrying out gas-phase polymerization processes, wherein participates in the CNT of premix and the quality of catalyst (without solvent)
Ratio is 0-10:1.
In one embodiment of the invention, first partially polymerized monomer is carried out prepolymerization with CNT and whole catalyst,
Then residue polymerization monomer is proceeded with prepolymerization product main polymerization, wherein, the CNT of input in pre-polymerization process:
Catalyst (without solvent): the mass ratio of polymerization monomer is 10-106:1:1-103.Pre-polymerization process can make CNT fill
Subpackage is rolled in catalyst particle surface.It should be noted that the polymerization monomer put in pre-polymerization process is the most all converted to
Polymer, the polymer obtained after usual prepolymerization is only 1-200:1 with the ratio of catalyst quality.In addition it should be noted that
Prepolymerization consumes whole catalyst, but has not necessarily consumed whole CNT.Therefore according to final composite
Content of carbon nanotubes require to determine in main polymerization process the need of continuously adding CNT.
In one embodiment of the invention, the reaction condition of prepolymerization and main polymerization can have difference.To produce carbon nanometer
As a example by pipe-EP rubbers composite, prepolymerized reaction temperature is 25-40 DEG C, and reaction pressure is 0.3-1MPa；Main polymerization
Reaction temperature be 50-100 DEG C, reaction pressure is 1-10MPa.
In one embodiment of the invention, gas-phase polymerization can be semi-continuous process (be intermittently added catalyst and CNT,
Being continuously added to be polymerized monomer, interval draws off the product of CNT-polymer composite), it is also possible to for continuous process (even
Add catalyst, CNT and polymerization monomer continuously, simultaneously continuously draw off the product of CNT-polymer composite
Thing).
The gas-phase polymerization process units of the CNT-polymer composite of second aspect present invention embodiment is described device
Including CNT filler, catalyst filler, polymerization raw material monomer entrance, discharging opening and the stirred tank of offgas outlet,
Endless tube or fluid bed.The showing of gas-phase polymerization process units such as CNT-polymer composite that Fig. 2 is fluid bed form
It is intended to.As in figure 2 it is shown, this fluid bed process units interface includes: polymerization raw material monomer entrance 1, CNT filler
2-1, catalyst filler 2-2, discharging opening 3 and offgas outlet 4.It should be noted that technical staff can also be according to reality
Border needs to do following detailed design: arrange gas distributor in process units bottom, and the polymerization monomer after purification is distributed from gas
Device is even in fluid bed.Polyreaction, reaction is there is in polymerization monomer while making catalyst granules fluidisation as unstripped gas
Heat is removed by gas heat difference or the Partial Liquid Phase feed vaporization of turnover process units.The top design of process units becomes to expand
Shape, so that granule deposition, reduces gas entrained particles amount.Unpolymerized polymerization monomer and diluent gas are through gas-solid separator
Separate Posterior circle to utilize with solid particle.For ease of safeguarding, gas-solid separator may be provided in outside process units, consolidating after separation
Body granule loops back process units.Throughput rate depends on the concentration of monomer in the speed of injecting catalyst and circulating system, logical
The most only controlled throughput rate by the charge velocity of catalyst.
In one embodiment of the invention, when process units is fluid bed, CNT inlet 2-1 and catalyst note
Entrance 2-2 is positioned on gas distributor, and the distance away from gas distributor is not less than 50cm or fluidized bed layer height
/ 2nd of/4th (taking smaller value in two data), not higher than 100cm or fluidized bed layer height (take two data
Middle higher value).
In one embodiment of the invention, catalyst filler 2-1 and CNT filler 2-2 oblique cutting from top to bottom enter
Process units, with vertical direction angle less than or equal to 90 °.It is to say, process units can be horizontally inserted.Generally preferably
Insert less than 45 degree of modes with vertical direction angle.
In one embodiment of the invention, CNT carries in addition process units by air-flow.In order to ensure CNT
Powder body Fast Packet is rolled in catalyst particle surface, and CNT filler 2-1 should be close to catalyst filler 2-2.Carbon is received
Mitron filler 2-1 can be located at the top of catalyst filler 2-2, lower section or outside, as shown in Figure 3.Wherein, carbon is worked as
When nanotube filler 2-1 is positioned at catalyst filler 2-2 outside, using sleeve structure, catalyst injects in pipe, carbon
Nanotube is brought into by air-flow from shell.Although it should be noted that the filler shown in Fig. 3 is the filler of horizontal direction,
But this is merely to the convenience of example, and it is not to be regarded as the restriction of the present invention.Can also adjust as required in actual applications
The whole filler for incline direction.
In one embodiment of the invention, discharging opening 3 is positioned in emulsion zone, and discharging opening 3 is less than CNT filler
2-1 and catalyst filler 2-2.At emulsion zone, the composite material granular that discharging opening 3, beneficially extraction are bigger is set.
The method according to the invention and/or the CNT-macromolecule utilizing assembly of the invention gas-phase polymerization to prepare in situ are combined
Material has the electrical and mechanical performance of excellence, and this is to add the effect that the antitack agents such as white carbon black do not have.Table 1 shows tool
There is the conductive test result of the EP rubbers composite sample of different content dissimilar antiseized auxiliary agent auxiliary production.
The electric conductivity test result of the different sample of table 1
As shown in Table 1, drastically decline along with the resistivity increasing composite of content of carbon nanotubes.Content of carbon nanotubes
CNT-EP rubbers the composite of 2.25% (mass percent, lower same) can reach the standard (resistance of antistatic
Rate 104～107Ωcm).When content of carbon nanotubes is higher than 6.76%, composite has become conductive material, and (resistivity is less than
104Ωcm).The electric conductivity of CNT-EP rubbers composite is better than conductive black-EP rubbers composite.Carbon nanometer
Pipe content is that the composite of 6.76% is close with the resistivity of the composite that conductive black content is 20.04%.I.e. it is intended to obtain
Conducing composite material, the addition of conductive black is 3 times of CNT.The excellence of CNT-EP rubbers composite
Electric conductivity comes from the nano material that CNT is one-dimensional tubulose, except the electric conductivity of itself excellence, CNT it
Between can mutually be wound around, compared to spherical conductive black be easier to constitute conductive network.
Fig. 4 gives by the mechanical experimental results of above-mentioned sample segment.It can be seen that CNT and conductive black are equal
The mechanical property of EP rubbers there is potentiation.It is suitably added CNT or conductive black, EP rubbers can be increased
Tensile strength and elongation at break.When content of carbon nanotubes is 6.76% or the content of conductive black is 20.04%, composite wood
The hot strength of material is respectively 1.3 and 1.2 times of blank sample, and elongation at break increases by 17% and 40% respectively.Imitate in reinforcement
In the case of the most essentially identical, the consumption of CNT is only 1/3rd of conductive black.When content of carbon nanotubes reaches
When 14.24%, composite more rigidity, showing as hot strength is 2.5 times of blank sample, and elongation at break is only
The 15% of EP rubbers.Although such composite is more solid, but elastic variation, can be used for what intensity was required by making
Parts.
In order to make those skilled in the art be more fully understood that, the present invention, applicant are described in detail below five embodiments.Need explanation
Be embodiment be part preferable example, scope with application claim be as the criterion.
Embodiment 1
Polymerization CNT-EP rubbers composite in bubble agitation still.
Select average tube external diameter 20nm, the average aspect ratio multi-walled carbon nano-tubes more than 100.Processed carbon by vacuum high-temperature
Nanotube is purified process, temperature 1800 DEG C, and vacuum is higher than 10-2Pa, 5 hours time；Utilize high speed shear to pure
CNT after change carries out dispersion process, rotating speed 20,000 revs/min, 5 minutes time, the average aggregate grain of powder body after dispersion
Footpath is less than 5 μm, bulk density 20kg/m of powder body3.Carbon nanotube dust 2.0g after being disperseed by purification adds stirring
In still reactor, in reactor, it is placed in advance in 120g PP GRANULES (as matrix bed), average diameter of particles 2.5mm.
The employing adding reactor repeatedly switches evacuation and is filled with the operational approach of high pure nitrogen, by the aqueous vapor in reactor and oxygen
Concentration is reduced to below 100ppm.Stirred tank water-bath jacket temperature is set to 50 DEG C, by 5.2mg Titanium series catalyst and 3mmol
Triethyl aluminum successively add in stirred tank reactor, be passed through the gaseous mixture (mol ratio of second third is 1.7) of ethylene and propylene,
Make the pressure in reactor maintain 0.3MPa (absolute pressure), after reaction 1h, obtain CNT-EP rubbers and be combined
Thing 9.7g, product is black powder, and wherein the content of CNT is 14.2%.Powdery product mean diameter 100 μm,
It is prone to separate with millimetre-sized PP GRANULES.
Embodiment 2
CNT-EP rubbers composite wood is produced by gas phase polymerisation in bulk in pre-polymerization reactor and main polymer reactor
Material.
First in gas-phase fluidized-bed, carbon nanotube dust is carried out high temperature purification, temperature 1800 DEG C, flowing nitrogen atmosphere.Even
Continuously CNT after purification is added in prepolymerization gas-solid fluidized bed reactor.25 DEG C, be passed through under the conditions of 0.3MPa and urge
Agent and ethylene, propylene monomer carry out prepolymerization, add CNT and the catalyst (without solvent) of prepolymerization reactor
Mass ratio is 10, and catalyst (without solvent) is 10 with the mass ratio of monomer-3.In prepolymerization kettle growth polymer with urge
Agent (without solvent) mass ratio is 1.Continuously by the solid phase (CNT+catalyst+a small amount of in pre-polymerization reactor
Polymer) introduce in main polymerization gas-solid fluidized bed reactor.50 DEG C, to be passed through ethylene, propylene and the 3rd under the conditions of 1MPa single
Body is polymerized, and prepolymer is 10 with the mass ratio of monomer-5, discharge port above distributor draw off continuously CNT-
EP rubbers composite products.
Embodiment 3
CNT-EP rubbers composite wood is produced by gas phase polymerisation in bulk in pre-polymerization reactor and main polymer reactor
Material.
Pre-polymerization reactor, main polymer reactor and CNT preprocess method are with embodiment 2.Continuously by after purification
CNT adds pre-polymerization reactor.40 DEG C, be passed through catalyst and ethylene under the conditions of 1MPa, propylene monomer carries out pre-
Polymerization, adding the CNT of prepolymerization reactor with the mass ratio of catalyst (without solvent) is 106, catalyst is (without molten
Agent) it is 10 with the mass ratio of monomer-3.In prepolymerization kettle, the polymer of growth is 200 with the ratio of catalyst quality.Continuously will
Solid phase (CNT+catalyst+a small amount of polymer) in pre-polymerization reactor introduces main polymer reactor.At 65 DEG C, 10MPa
Under the conditions of be passed through ethylene, propylene and Third monomer and be polymerized, prepolymer is 10 with the mass ratio that is passed through of monomer-4, from distribution
Discharge port above device draws off CNT-EP rubbers composite products continuously.
Embodiment 4
Polymerization CNT-PP composite material in gas-phase fluidized-bed reactor.
Carbon nanotube-sample is ground to fine-powdered, processes 10 hours under 1500 DEG C of flowing Ar atmosphere.By fluidized-bed reaction
Device flowing nitrogen is replaced to aqueous vapor and below oxygen content 100ppm, heats nitrogen in order to be warming up to by reactor simultaneously
70 DEG C, maintain fluid bed top 10MPa pressure.Propylene feedstocks gas is utilized to replace nitrogen from fluidized-bed bottom through gas distributor
Enter reactor.Use sleeve type structure injecting catalyst and CNT in fluid bed.Catalyst activity component and auxiliary agent
Be dissolved in hexamethylene, from the central canal of sleeve pipe to inject fluidized-bed reactors with a vertical 30 degree of angles, CNT with
Ar carries from the shell of sleeve pipe with same angle injecting reactor.For the ease of CNT and catalyst fully, quickly mix,
Part CNT is dispersed in cyclohexane solution and together adds reactor with catalyst, and the quality of this part CNT is for urging
10 times of agent quality (without solvent).Add the CNT total amount of reactor and the quality of catalyst (without solvent)
Ratio is 106, catalyst (without solvent) is 10 with the mass ratio of monomer-7.Catalyst and CNT inlet divide at gas
50cm position on cloth device.Fluidized-bed layer height is more than 100cm.On distributor, 20cm goes out to have a solids
Material unloads outlet (i.e. discharging opening), intermittently or continuously draws off CNT-PP composite material product.
Embodiment 5
Carry out gas-phase polymerization in a loop reactor and produce CNT-composite polyethylene material.
Reaction temperature 100 DEG C, reaction pressure 10MPa, CNT is 10 with the mass ratio of catalyst (without solvent),
Catalyst (without solvent) is 10 with the mass ratio of vinyl monomer-7。
In the description of this specification, reference term " embodiment ", " some embodiments ", " example ",
The description of " concrete example " or " some examples " etc. means to combine this embodiment or example describes specific features,
Structure, material or feature are contained at least one embodiment or the example of the present invention.In this manual, to above-mentioned
The schematic representation of term is necessarily directed to identical embodiment or example.And, the specific features of description, structure,
Material or feature can be to combine in one or more embodiments in office or example in an appropriate manner.Additionally, at not mutual lance
In the case of shield, those skilled in the art can be by the different embodiments described in this specification or example and different implement
The feature of example or example is combined and combines.
Although above it has been shown and described that embodiments of the invention, it is to be understood that above-described embodiment is exemplary,
Being not considered as limiting the invention, those of ordinary skill in the art within the scope of the invention can be to above-described embodiment
It is changed, revises, replaces and modification.
Claims (25)
1. the gas-phase polymerization production method of CNT-polymer composite, it is characterised in that comprise the following steps:
Catalyst and CNT are provided；
Polymerization monomer is provided；
Described polymerization monomer, catalyst and CNT carry out under anhydrous and oxygen-free environment gas-phase polymerization obtain in situ CNT-
Polymer composite, wherein, before carrying out gas-phase polymerization by part CNT with whole catalyst common distribution molten
Agent premixes, the addition when carrying out gas-phase polymerization processes of remaining CNT.
2. the method for claim 1, it is characterised in that the external diameter of described CNT is less than 100nm, averagely
Draw ratio is not less than 100.
3. the method for claim 1, it is characterised in that described CNT before gas-phase polymerization through pre-dispersed place
Reason, the average aggregate particle diameter of pre-dispersed rear described CNT is less than or equal to 5 μm, and bulk density is 20-500kg/m3。
4. the method for claim 1, it is characterised in that described CNT passes through dehydration before gas-phase polymerization, takes off
Oxygen and demetalization process.
5. the method as described in any one of claim 1-4, it is characterised in that the reaction temperature of described gas-phase polymerization is
25-100 DEG C, reaction pressure is 0.3-10MPa.
6. the method for claim 1, it is characterised in that CNT, catalyst, the quality of polymerization monomer three
Ratio is 10-106:1:104-107, wherein, described catalyst does not contains solvent.
7. method as claimed in claim 6, it is characterised in that the mass ratio of the CNT and catalyst that participate in premix is
0-10:1, wherein, described catalyst does not contains solvent.
8. the method for claim 1, it is characterised in that described gas-phase polymerization is semi-continuous process or continuous process.
9. the gas-phase polymerization production method of CNT-polymer composite, it is characterised in that comprise the following steps:
Catalyst and CNT are provided；
Polymerization monomer is provided；
Described polymerization monomer, catalyst and CNT carry out under anhydrous and oxygen-free environment gas-phase polymerization obtain in situ CNT-
Polymer composite, wherein, first carries out prepolymerization by partially polymerized monomer with CNT and whole catalyst, then will
Residue polymerization monomer proceeds main polymerization with prepolymerization product.
10. method as claimed in claim 9, it is characterised in that the external diameter of described CNT is less than 100nm, averagely
Draw ratio is not less than 100.
11. methods as claimed in claim 9, it is characterised in that described CNT before gas-phase polymerization through pre-dispersed
Processing, the average aggregate particle diameter of pre-dispersed rear described CNT is less than or equal to 5 μm, and bulk density is 20-500kg/m3。
12. methods as claimed in claim 9, it is characterised in that the process dehydration before gas-phase polymerization of described CNT,
Deoxidation and demetalization process.
13. methods as claimed in claim 9, it is characterised in that described polymerization monomer includes in alkene, alkynes and aromatic hydrocarbons
The mixture of one or more.
14. methods as claimed in claim 13, it is characterised in that described polymerization monomer includes that ethylene, propylene and the 3rd are altogether
Poly-monomer, it is thus achieved that described CNT-polymer composite be CNT-EP rubbers composite.
15. methods as described in any one of claim 9-14, it is characterised in that the reaction temperature of described gas-phase polymerization is
25-100 DEG C, reaction pressure is 0.3-10MPa.
16. methods as claimed in claim 9, it is characterised in that CNT: catalyst: the mass ratio of polymerization monomer
For 10-106:1:104-107, wherein, described catalyst does not contains solvent.
17. methods as claimed in claim 16, it is characterised in that the CNT put in pre-polymerization process: catalyst:
The mass ratio of polymerization monomer is 10-106:1:1-103, wherein, described catalyst does not contains solvent.
18. methods as claimed in claim 17, it is characterised in that described prepolymerized reaction temperature is 25-40 DEG C, instead
Answering pressure is 0.3-1MPa；The reaction temperature of described main polymerization is 50-100 DEG C, and reaction pressure is 1-10MPa.
19. methods as claimed in claim 9, it is characterised in that described gas-phase polymerization is semi-continuous process or continuous process.
The gas-phase polymerization process units of 20. 1 kinds of CNT-polymer composites, it is characterised in that described process units
Be include being polymerized raw material monomer entrance, CNT filler, catalyst filler, discharging opening and the stirred tank of offgas outlet,
Endless tube or fluid bed.
21. devices as claimed in claim 20, it is characterised in that when described process units is fluid bed, CNT
Filler and catalyst filler are positioned on gas distributor, and distance d away from gas distributor meets
Min{50cm, 0.25H}≤d≤max{100cm, 0.5H}, wherein H is fluidized bed layer height.
22. devices as described in claim 20 or 21, it is characterised in that urge described in described CNT filler next-door neighbour
Agent filler, is positioned at above described catalyst filler, lower section or outside.
23. devices as claimed in claim 22, it is characterised in that CNT filler and catalyst filler from upper and
Declivity inserts process units, with vertical direction angle less than or equal to 90 °.
24. devices as claimed in claim 20, it is characterised in that described discharging opening is positioned in emulsion zone, and described discharging
Mouth is less than described CNT filler and catalyst filler.
25. 1 kinds of CNT-EP rubbers composites, it is characterised in that described CNT-EP rubbers composite
Gas-phase polymerization production method with the CNT-polymer composite in claim 1-8 or according to any one of 9-19
Or prepared by the gas-phase polymerization process units of the CNT-polymer composite according to any one of claim 20-24.
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| DE102004054959A1 (en) * | 2004-11-13 | 2006-05-18 | Bayer Technology Services Gmbh | Catalyst for producing carbon nanotubes by decomposition of gaseous carbon compounds on a heterogeneous catalyst |
| CN2885864Y (en) * | 2005-12-05 | 2007-04-04 | 武晋强 | Gas distributor for use in fluidized-bed gasification furnace |
| DE102006035773A1 (en) * | 2006-08-01 | 2008-02-07 | Bayer Technology Services Gmbh | Process for the preparation of carbon nanoparticle-polymer mixtures by gas phase polymerization |
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