CN105459284A - Liquid phase continuous mixing process of high dispersion carbon nanotube masterbatch and rubber product thereof - Google Patents
Liquid phase continuous mixing process of high dispersion carbon nanotube masterbatch and rubber product thereof Download PDFInfo
- Publication number
- CN105459284A CN105459284A CN201410422228.XA CN201410422228A CN105459284A CN 105459284 A CN105459284 A CN 105459284A CN 201410422228 A CN201410422228 A CN 201410422228A CN 105459284 A CN105459284 A CN 105459284A
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- rubber
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- masterbatch
- liquid phase
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
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Abstract
The invention discloses a liquid phase continuous preparation method of a carbon nanotube masterbatch. The method includes: preparing a carbon nanotube suspension; concinuously dispersing and mixing the carbon nanotube suspension with a rubber solution/emulsion and an optional rubber compounding ingredient solution/suspension to obtain a carbon nanotube/rubber/solvent mixture; carrying out solidification and continuous extrusion on the carbon nanotube/rubber/solvent mixture simultaneously to realize carbon nanotube orientation, and removing water or the solvent to obtain the carbon nanotube/rubber mixture; and continuously drying the carbon nanotube/rubber mixture to obtain the carbon nanotube masterbatch. The invention also includes the carbon nanotube masterbatch obtained by the liquid phase continuous preparation method and the rubber product prepared from the carbon nanotube masterbatch.
Description
Technical field
The present invention relates to CNT/rubber composite field, particularly relate to the liquid phase continuous mixing technique of CNT masterbatch, the method for the CNT masterbatch of preparation high dispersive and high orientation and the application of these technique in rubber.
Background technology
In modern rubber industry, most of rubber has to pass through reinforcement just can have the practical value such as high mechanical properties and Long Service Life.Except framework material, the method for enhancing rubber the most general is at present the reinforcing agent adding various granular or other shapes, as the carbon black of nano-scale, white carbon or other hard particles, and various organic/inorganic short fiber.But carbon black, short fiber and other organic reinforcing agents place one's entire reliance upon petroleum industry, therefore the inevitable minimizing day by day along with petroleum resources, can be subject to more and more serious restriction.The white carbon of nano-scale not only has the reinforcing property close with carbon black, and more give the performance of some excellence of rubber due to surface modification and coupling, after tread rubber such as containing solution polymerized butadiene styrene rubber adds the white carbon of coupling modifier, wet-sliding resistant performance and resistance to rolling significantly improve.But when using white carbon to carry out reinforcement to rubber, need the coupling considering white carbon, rubber clone and coupling agent kind, otherwise mechanical property cannot reach significant improvement; And white carbon surface nature differs very big in mixing process with rubber, be difficult to be mixed in rubber, be difficult to be uniformly dispersed, have to pass through multistage calendering process, energy consumption is large, the cycle is long, otherwise bad point of breaking up of white carbon causes, and rubber strength reduces, hydraulic performance decline.Except above-mentioned shortcoming, the nano material such as carbon black, white carbon is because particle size is minimum, easily fly upward, and waste gas, wastewater discharge are large, in production and application, all there is serious problem of environmental pollution.Therefore, the better filler of reinforcing property and the less processing technology of environmental pollution are one of research emphasis of rubber researcher always.
CNT is a kind of single or multiple lift nanoscale tubular material primarily of carbon hexagon composition, the surface nature of its excellent physical and mechanical properties and similar carbon black, make it in rubber materials, have extremely strong using value [CN102924763A, CN102321879A, CN102344587A, CN103694505A, CN102630238A, CN102630244A etc.].The Young's modulus of CNT is about 1.8TPa, and hot strength is about 200GPa, and higher than steel 100 times, density but only has 1/6 to 1/7 of steel.The elastic strain of CNT reaches as high as about 12%, has good pliability.The electrical conductivity of CNT and thermal conductivity are also very good.Therefore CNT is the Nano filling of a kind of potential replacement carbon black or white carbon.But due to the nano material characteristic such as strong skin effect of CNT, cause being very easy between CNT occur to reunite and tangle, common mechanically milling technique is adopted to be difficult to be uniformly dispersed in rubber base material, often cause the mechanical property of rubber obviously to improve even to be deteriorated, because which limit its application in rubber industry.
In order to avoid the mixing method of standard machinery and the mixing various shortcomings of dry method, as manufacturing procedure is complicated, equipment investment is large, labour intensity is high, dust from flying, environmental pollution are serious, many novel mixed methods are applied to the mixed process of rubber and filler, such as polymer emulsion and extender paste mixed and solidify the method preparing polymer filler masterbatch, i.e. wet method mixing [CN102153792B, CN102775650B, CN102816265A etc.].Wet refining method utilizes carbon black to the demulsification of NR latex, and NR emulsion particle is coprecipitated by carbon black embedding, forms natural rubber/carbon black elastomeric compound.Compared with mixing with dry method, adopt the wet method mixing dispersion not only improving filler, can also reduce energy consumption, reduce equipment investment, but shortcoming is solidified with drying time long, production cycle long, efficiency reduction, cannot meet the Production requirement of modern rubber industry.Patent CN102153792B discloses the preparation method of the mixing white carbon filling natural rubber of a kind of wet method, by preparing slurry (white carbon 15-40%+69-85% water+coupling agent+surfactant), mixing, grinding, compound is joined in latex, be uniformly mixed into latex mixed liquor, then add acetic acid flocculation, wash glue dehydration, granulation through rubber washing machine, equipment investment is little, dust pollution is little, economize energy, and the dispersiveness of white carbon and uniformity improve.Patent CN102731874B disclose a kind of adopt rubber latex and nano silicon/poly-conjugated-diolefin complex emulsions blending after cohesion, breakdown of emulsion co-precipitation prepare the method for modified rubber.Patent 102775650B discloses the tread rubber sizing material and preparation method thereof containing solution dispersion white carbon latex mixture, effectively save the macromolecular original state of natural gum, the brute force of natural gum is retained, achieve the dispersed of rubber and white carbon, significantly improve brute force and the wearability of epoxy glue, heat generation and hysteresis loss obviously reduce, and apply the epoxy glue that this method produces and can be used alone, also can use with natural gum, rubber polymer etc. in any proportion.But the defect of the method is that when adopting solution dispersion white carbon latex mixture, white carbon has very strong delay effect to sulfuration, simultaneously because the existence of moisture and acid not only have impact on original performance of formula, and may cause producing defect in tire production.The existence of acid also reduces sulfuration effect, must just can make up by promoter increment.The open one of patent CN102816350A prepares the wet refining method of natural rubber/carbon black-nano silicon (white carbon) elastomeric compound.The present invention's carbon black dispersion and silica aqueous solution are mixed with carbon black-silicone dispersion, to mix with NR latex with it and form wet refining system, utilize Ludox to be heated and the character that condensation reaction generates white carbon gel occurs, to wet refining system heating, make silica sol in-situ generate carbon black-white carbon compound particle and be dispersed in NR latex, condense coprecipitated rear formation NR/ carbon black-white carbon elastomeric compound.
On the basis that wet method is mixing, Cabot Co., Ltd proposes liquid phase continuous mixing technique [CN98811684, CN00808002, CN02825969], simplifies rubber mixing technique, shortens mixing time.Patent CN103203810A discloses rubber masterbatch and rubber prepared by a kind of method for continuously producing of rubber masterbatch and the method, compared with existing wet method elastomeric compound technology, this method to rubber, filler without particular/special requirement, the scope of application is wide, correspondingly improves the decentralization of filler in rubber size.Carbon black directly mixes with water by this technical process, with mixing and later stage and the pure mechanical system mixed with high-speed stirred of latex of water, does not add any dispersant or surfactant.Then latex and extender paste are at room temperature carried out high speed machine to mix, the short time completes, and carries out dewatering etc. subsequent handling subsequently, improves the decentralization of filler in rubber, and production technology is continuous, reduces mixing cost.
In addition, patent CN102825674A proposes a kind of towards the in-situ modified mixing continuous extrusion apparatus of high filling white carbon black and method, and whole device is formed by 1 cover banburying unit and 1 ~ 10 cover Screw Extrusion unit combination collocation; Wherein often overlap Screw Extrusion unit to be in series by the screw extruder of head side direction head and the tail docking by 1 screw extruder or 2 ~ 10.Sizing material carries out the in-situ modified process of silane coupler dialogue carbon blacksurface can be in stationary temperature condition in screw extruder under, production efficiency significantly improves, and is conducive to the processing and forming of sizing material in subsequent production technique.
For CNT/rubber composition, most of patent or research all concentrate on the mixing (CN1803939A of dry method, CN102321879A, CN102344587A, CN102924763A, CN101381483A, CN103189310A, CN101831090B, and the mixing (CompositeStructures of discontinuous wet method CN102702591B), 2006, 75:496-500, CN1663991A, CN1673261A, CN01381483A, CompositesScienceandTechnology, 2007, 67 (9): 1813-1822.), CN1312206C discloses a kind of carbon nanotube modified powder natural rubber, acidifying is carried out to CNT, at dispersant, be distributed under hyperacoustic effect in water, after regulating pH, mix with Heveatex, then spraying dry.The sizing material that said method obtains often also exists the shortcomings such as intensity is not high, percentage elongation is low, viscosity is low, poor processability, does not reach the serviceability of rubber.In addition because CNT is without surface treatment, disperse uneven in rubber, so that the structural homogeneity of composite is poor, and the advantage of CNT in mechanical property and heat conductivility can not be played very well, the amplitude that composite property improves is little.Patent CN1554693A discloses one and utilizes LNBR or liquid XNBR to prepare rubber master batch, then by rubber master batch and the mixing method preparing carbon nano-tube modification hydrogenated nitrile-butadiene rubber of hydrogenated nitrile-butadiene rubber; These art methods ubiquities complex process, the shortcomings such as the product quality of preparation is difficult to reach requirement, and range of application is limited.
The CNT rubber obtaining high dispersive high orientation is wished in this area, but existing technology all fails to realize the high dispersive high orientation of CNT.Therefore, prior art still needs a kind of liquid phase continuous production method developing CNT masterbatch, and the method can improve the dispersiveness of CNT in rubber size, the CNT masterbatch of obtained high dispersive, high orientation.
Summary of the invention
A kind of liquid phase continuous production method that the object of this invention is to provide CNT masterbatch prepares the CNT masterbatch of high dispersive, high orientation.
Another object of the present invention is to provide a kind of liquid phase continuous mixing technique of CNT masterbatch, this process can improve the dispersiveness of CNT in rubber size and orientation, and the rubber adopting this process to prepare has that hardness is high, tensile property good, ageing-resistant performance is good, electrical and thermal conductivity advantages of higher.
Therefore, one aspect of the present invention, provide a kind of liquid phase continuous production method of CNT masterbatch, described method comprises:
1) carbon nano tube suspension is prepared;
2) suspension of described CNT disperseed continuously with rubber solutions/emulsion and optional rubber chemicals solution/suspension and mix, obtaining CNT/rubber/solvent mixture;
3) solidify with continuously extruded to described CNT/rubber/solvent mixture simultaneously, to realize CNT orientation, after removing water or solvent, obtain CNT/rubber composition;
4) continuous drying is carried out to described CNT/rubber composition, obtain CNT masterbatch.
In the present invention one preferred embodiment, the step of described preparation carbon nano tube suspension comprises and adds in oil-based solvent or aqueous dispersion medium by CNT, surfactant, stabilizing agent and dispersant, prepares stable CNT oiliness or waterborne suspension by mixing plant.
In the present invention one preferred embodiment, described CNT is the CNT of functional organic surface modification.
In the present invention one preferred embodiment, described carbon nano tube suspension is disperseed to comprise with the step mixed with rubber solutions/emulsion and optional rubber chemicals solution/suspension continuously: by high-pressure pump by carbon nano tube suspension, rubber solutions/emulsion and optional rubber chemicals solution/suspension are transported in the pipeline that cross section of fluid channel gradually becomes with certain flow velocity respectively, then impact at high pressure and runner, under the effect of mixing, be uniformly dispersed and stable CNT/rubber/solvent mixture, wherein high-pressure is 1-100MPa, preferred 10-60MPa, flow velocity is 10m/s-1000m/s, preferred 100-500m/s.
In the present invention one preferred embodiment, described CNT/rubber/solvent mixture is solidified simultaneously and comprises with continuously extruded step: the coagulating agent adding 0.01-2.00% mass concentration according to certain flow velocity in CNT/rubber/solvent mixture fluid, enter Screw Extrusion unit high pressure continuously extrude obtaining the stable coprecipitated mixture fluid of rubber/CNT after rubber quick solidification, to realize the orientation of CNT in rubber, wherein high-pressure is 2-200MPa, preferred 20-60MPa; Flow velocity is 0.1m/s-100m/s, preferred 0.1-10m/s.
In the present invention one preferred embodiment, it is 50-150 DEG C that the step of carrying out continuous drying to CNT/rubber composition is included in baking temperature, carries out drying under the condition of preferred 80-120 DEG C by heating.
In the present invention one preferred embodiment, described rubber is natural rubber or synthetic rubber, preferred Hevea rubber, gutta-percha, guayule, dandelion glue, polybutadiene rubber, polyisoprene rubber, butadiene-styrene rubber, EP rubbers, butyl rubber, acrylonitrile-butadiene rubber, neoprene, silicon rubber, polyurethane rubber, ACM, fluorubber and derivative products thereof.
Another aspect of the present invention provides the CNT masterbatch prepared according to the liquid phase continuous production method of CNT masterbatch of the present invention.
Another aspect of the present invention provides the rubber adopting CNT masterbatch of the present invention to prepare.
Another aspect of the present invention provides a kind of liquid phase continuous mixing technique of CNT masterbatch, and described technique comprises:
1) carbon nano tube suspension is prepared;
2) suspension of described CNT disperseed continuously with rubber solutions/emulsion and optional rubber chemicals solution/suspension and mix, obtaining CNT/rubber/solvent mixture;
3) solidify with continuously extruded to described CNT/rubber/solvent mixture simultaneously, to realize CNT orientation, after removing water or solvent, obtain CNT/rubber composition;
4) continuous drying is carried out to described CNT/rubber composition, obtain CNT masterbatch;
5) the CNT masterbatch through super-dry is entered continuously one to multiple banbury, one to multiple mill, one to multiple screw extruder, machine-shaping is until sulfuration.
Below, the present invention will be described by reference to the accompanying drawings.
Fig. 1 is CNT/rubber liquid phase continuous mixing process flow diagram;
Fig. 2 is uniformly dispersed and the microphotograph of stable CNT/rubber/solvent mixed system;
Fig. 3 is the size distribution curve figure of CNT/rubber/solvent mixed system;
Fig. 4 is the stereoscan photograph of the orientation of display CNT in masterbatch.
Detailed description of the invention
In the present invention, term " rubber " can be rubber or the elastomer of any kind, as natural rubber or synthetic rubber, synthetic elastomer.Described natural rubber includes but not limited to Hevea rubber, gutta-percha, guayule, dandelion glue etc.; Described synthetic rubber or elastomer, include but not limited to the polybutadiene rubber with different polymerization degree, polyisoprene rubber, butadiene-styrene rubber, EP rubbers, butyl rubber, acrylonitrile-butadiene rubber, neoprene, silicon rubber, polyurethane rubber, ACM, fluorubber and derivative products thereof that polymerisation in solution or the method such as emulsion polymerisation, polymerisation in bulk obtain.Rubber concentration range is in the solution 1-80%, preferred 20-30%.
In the present invention, term " masterbatch " refers to can for next step by the mixing sizing of formula, and " mixing " refers to the technique with rubber mixing machine, rubber or plasticate rubber and compounding ingredient being smelt elastomeric compound, is the most important production technology of rubber processing.Essence is compounding ingredient homodisperse process in rubber, and granular compounding ingredient is decentralized photo, and rubber is continuous phase.
At rubber materials, term " compounding ingredient " refers to the auxiliary agent added in rubber base material, include but not limited to that vulcanizing system (includes but not limited to Sulfur, sulfur-donor, zinc oxide, peroxide, curing resin, promoter, activating agent, auxiliary curing agent), reinforcement/infill system (includes but not limited to carbon black, white carbon, calcium carbonate, potter's clay, barium sulfate), softening/Plasticising system (includes but not limited to petroleum, coal tar system, vegetable oil system, synthesizing ester or polyesters), protection system (includes but not limited to amine, phenols, quinolines chemical antiager or antioxidant, paraffin, microwax class physical antioxidant).In the present invention, compounding ingredient does not comprise CNT itself.The exemplary compounding ingredient that the present invention uses has vulcanizing agent-Sulfur, accelerator NS, activating agent zinc oxide, stearic acid, reinforcing agent-carbon black N330, filler-calcium carbonate, softening agent-environment-friendly aromatic oil, plasticizer-dibutyl phthalate, age resistor-4010NA, microwax.
" CNT masterbatch " of the present invention refers to the sizing wherein containing pre-dispersed CNT not containing other compounding ingredients, and wherein carbon nanotube concentration is 0.1-200%.
Below the concrete steps of the liquid phase continuous mixing technique of CNT masterbatch are described:
(1)
preparation carbon nano tube suspension
In the present invention, term " CNT " represents a kind of One-dimensional Quantum material with special construction, and its radial dimension is nanometer scale, and axial dimension is micron dimension, is a kind of fibrous material of lightweight.CNT forms the coaxial pipe of several layers to tens of layers primarily of the carbon atom in hexagonal array.Keep fixing distance between layers, about 0.34nm, diameter is generally 2 ~ 20nm.
The present invention's CNT used is without particular limitation, and can be the CNT of any routine in this area, it comprises the mixture of SWCN, multi-walled carbon nano-tubes and above-mentioned CNT, and the CNT of various form; Be preferably multi-walled carbon nano-tubes.Wherein, SWCN is made up of individual layer column type graphite linings, and the distribution of its diameter is little, defect is few, has higher uniformity consistency.And multi-walled carbon nano-tubes is made up of Multi-layer graphite layer, be easy between layers become Trapping Centers and catch various defect, the tube wall of thus multi-walled pipes be covered with usually the defect of duck eye sample.Except single wall and multi-walled carbon nano-tubes, there is the inorganic material such as the carbon nano rod of similar structures, nano wire and be also applicable to the present invention.
Described CNT is preferably the CNT of functional organic surface modification, such as, and cyclopentadiene modified carbon nano-tube.
Carbon nano tube suspension comprises oily suspensions and waterborne suspension.The step of preparation carbon nano tube suspension comprises and adds in oil-based solvent or aqueous dispersion medium by CNT, surfactant, stabilizing agent and dispersant, prepares stable CNT oiliness or waterborne suspension by mixing plant.
The method preparing CNT oily suspensions comprises:
1) select can the good solvent of dissolving rubber as dispersion liquid, described good solvent includes but not limited to fat hydrocarbon, arene, chlorinated hydrocarbons, ester class, ketone or ether solvent and composition thereof;
2) stabilizing agent of the surfactant of CNT, 0.1-3.0 % by weight, 0.1-3.0 % by weight, the dispersant etc. of 0.1-3.0 % by weight are added in above-mentioned good solvent, by mixing plants such as homogenizer, colloid mill or homogenizers, prepare stable CNT oily suspensions, rotating speed 100-10000rpm, 1 minute-10000 hours time, in the suspension obtained, the concentration of CNT is 0.1-100 % by weight, above percetage by weight all in the gross weight of described oily suspensions for benchmark.
The method preparing CNT waterborne suspension comprises:
1) aqueous solution selecting water and ethylene glycol, modified cellulose etc. to form is as dispersion liquid;
2) stabilizing agent of the surfactant of CNT, 0.1-3.0 % by weight, 0.1-3.0 % by weight, the dispersant etc. of 0.1-3.0 % by weight are added in above-mentioned good solvent, by mixing plants such as homogenizer, colloid mill or homogenizers, prepare stable CNT oily suspensions, rotating speed 100-10000rpm, 1 minute-10000 hours time, in the suspension obtained, the concentration of CNT is 0.1-100 % by weight, above percetage by weight all in the gross weight of described waterborne suspension for benchmark.
Described surfactant, stabilizing agent and dispersant are all reagent conventional in wet method mixing of rubber, and those skilled in the art can select agents useful for same and appointed condition according to the performance requirement of final rubber.Exemplary surfactant includes but not limited to dodecyl sodium sulfate and derivative products, neopelex and derivative products thereof, lauryl sodium sulfate and derivative products, softex kw and derivative products, polyoxyethylene nonylphenol ether etc.; Exemplary stabilizing agent includes but not limited to the condensation product of potassium hydroxide, NaOH, ammoniacal liquor, laurate, casein, polyethylene glycol, polyglycerol, oxirane and alcohol, N-methyl-N-oleic acid acyl group ox acid sodium and the derivative products of above-mentioned substance or mixture; Exemplary dispersant includes but not limited to methylene sodium hisbenzene sulfonate, nekal, methylene diisopropyl sodium naphthalene sulfonate, sodium pyrophosphate and derivative products thereof or mixture.
(2)
continuous dispersion with mix the suspension of described CNT and rubber solutions/emulsion and optional rubber chemicals solution/suspension
In the present invention, high-efficiency and continuous dispersion comprises with the method mixing carbon nano tube suspension and rubber solutions/emulsion and optional rubber chemicals solution/suspension: pass through high-pressure pump, by carbon nano tube suspension, rubber solutions (or emulsion) and optional rubber chemicals solution/suspension are transported in the pipeline that cross section of fluid channel gradually becomes with certain flow velocity respectively, then impact at high pressure and runner, under the effect of mixing, be uniformly dispersed and stable CNT/rubber/solvent mixed system (as shown in Figure 2), and enter into next step continuous solidification and extrusion process with certain flow velocity.This step mesohigh pressure is 1-100MPa, preferred 10-60MPa; Flow velocity is 10m/s-1000m/s, preferred 100-500m/s.
As can be seen from the microphotograph shown in Fig. 2, CNT/rubber/solvent mixed system is dispersed and stable system, Fig. 3 is the grain size distribution of CNT/rubber/solvent mixed system, the D50 of CNT/rubber/solvent mixed system is 4.409um, and namely in CNT/rubber/solvent mixed system, the particle diameter of 50% is all less than 4.409um.Fig. 2 and Fig. 3 proves through step 2) CNT is dispersed in rubber solvent mixed system afterwards, and define and be uniformly dispersed and stable CNT/rubber/solvent mixed system.
Described rubber solutions/emulsion refers to rubber solutions or rubber latex.Described rubber latex is emulsion prepared by Heveatex or various rubber polymer, rubber solutions is prepare the non-desolventizing product of solution polymerized rubber or dry glue to be dissolved in product in good solvent, and the two mixes with carbon nano tube suspension after can adding other rubber chemicals co-ground.
Rubber chemicals solution/suspension is solution or the suspension of the various compounding ingredients for rubber adopting methods known in the art preparation, according to the performance requirement of final rubber, can adjust formula and the content of rubber compounding agent solution or suspension.In the present invention, rubber chemicals solution/suspension adopts and prepares CNT oiliness or the similar method of waterborne suspension is carried out.In step 2) in, rubber chemicals solution/suspension is optional.
In liquid phase continuous mixing technique of the present invention, can to step 2) add or do not add the solution/suspension of rubber chemicals in CNT/rubber composition.In step 2) in when adding rubber chemicals in CNT/rubber composition, rubber chemicals add with the liquid form of solution or suspension, prepare rubber by liquid phase wet method is mixing.The CNT masterbatch that the present invention prepares can be processed into rubber further according to the situation that adds of rubber chemicals.
(3)
solidify and continuously extruded described CNT/rubber/solvent mixture simultaneously
Present inventor finds, in liquid phase continuous mixing technique of the present invention, solidifying of CNT/rubber/solvent mixture is carried out with continuous high-pressure extrusion simultaneously, can realize the orientation of CNT in masterbatch.CNT orientation in rubber can improve intensity, the raising electrical and thermal conductivity performance of rubber, and degree of orientation is higher, and rubber performance is better.Liquid phase continuous mixing technique of the present invention can obtain the CNT masterbatch of the degree of orientation up to 80-95%.
Solidify to comprise with the step of continuously extruded described CNT/rubber/solvent mixture simultaneously and in CNT/rubber/solvent mixture fluid, add 0.01-2.00 % by weight according to certain speed, the coagulating agent of preferred 0.01-1.00 % by weight, by obtaining after rubber quick solidification, the coprecipitated mixture fluid of stable rubber/CNT enters dehydration (solvent) Screw Extrusion unit simultaneously continuously, rubber breaker group high pressure is extruded, the removal water obtained or the CNT of solvent/rubber composition blob of viscose, blob of viscose enters next step continuous drying technique through induction system.Solidify simultaneously and when comprising flow at high speed with continuously extruded step, to solidify coprecipitated, preliminary hydro-extraction, deep dehydration, screw extruder plasticate, extrude orientation, to realize the orientation of CNT in rubber (as shown in Figure 4).The stereoscan photograph of CNT masterbatch as shown in Figure 4 confirmed, through step 3) after, CNT is height-oriented in masterbatch.
This step mesohigh pressure is 2-200MPa, preferred 20-60MPa; Flow velocity is 0.1m/s-100m/s, preferred 0.1-10m/s.
Described dehydration (solvent) Screw Extrusion unit comprises one to multiple extruder, and those skilled in the art can regulate the service condition of screw extruder according to actual needs.
Exemplary coagulating agent includes but not limited to one or more mixture of the materials such as hydrochloric acid, sulfuric acid, acetic acid, formic acid, calcium chloride, calcium nitrate, cyclohexylamine acetate.
(4)
continuous drying is carried out to described CNT/rubber composition
The step of carrying out continuous drying to CNT/rubber composition comprises carries out drying by heating at elevated temperatures, obtains CNT masterbatch.Baking temperature is 50-150 DEG C, preferred 80-120 DEG C.
Specifically, the continuous drying technique of CNT/rubber composition of the present invention, comprise following content: will through dehydration (or desolventizing), kibbled CNT/rubber composition, continus convergence is in high temperature dry channel, abundant dry aft-loaded airfoil powdering, graininess or bulk, namely can be used as CNT masterbatch to use, baking temperature 50-150 DEG C, preferred 80-120 DEG C.The heating means of high temperature drying passage include but not limited to the heating processes such as saturated vapor, hot-air, microwave, far infrared, salt bath, ultrasonic wave.
The masterbatch obtained after drying is processed into powdery by rubber breaker, refiner etc., also can grind to form powdery after cryogenic freezing; Masterbatch is also processed into graininess by comminutor; Or adopt light water press to be pressed into bulk when 100-120 DEG C.
In liquid phase continuous production method of the present invention, the CNT masterbatch that rubber chemicals obtain has been added when liquid phase, can directly machine-shaping, be sulfided into rubber, therefore, for the situation having added rubber chemicals when liquid phase, the CNT masterbatch adopting the inventive method to prepare can enter one to multiple banbury, one to multiple mill, one to multiple screw extruder further continuously, and machine-shaping is until sulfuration.
For the masterbatch obtained when not adding rubber chemicals, can be used as pre-dispersed CNT during its carbon nanotube concentration height and use, the CNT masterbatch of middle low concentration can add other compounding ingredients and use as elastomeric compound.
Vulcanized rubber of the present invention and rubber thereof adopt the CNT masterbatch prepared by liquid phase continuous production method of the present invention to make, and comprise the tire tread glue of content of carbon nanotubes between 0.1-100 part, sebific duct outer layer glue, conveyer belt coating rubber, the large primer of rubber overshoes etc.
Fig. 1 is CNT/rubber liquid phase continuous mixing process flow diagram, when running this technological process, carbon nano tube suspension and other optional compounding ingredients are added in rubber solutions or emulsion, the mixture obtained is carried out dispersion continuously and mixed, continuous solidification dewaters with extruding orientation, and continuous drying, obtain CNT masterbatch, the CNT masterbatch obtained can have different concentration according to actual process condition, high concentration masterbatch can add common elastomeric compound namely in, machine-shaping sulfuration obtains rubber; Middle low concentration masterbatch can add other compounding ingredients, machine-shaping sulfuration obtains rubber; For the situation having added other compounding ingredients when preparing CNT masterbatch, the middle low concentration elastomeric compound prepared can directly machine-shaping, and sulfuration obtains rubber.
The liquid phase continuous mixing technique of CNT of the present invention, by the pre-modification of CNT, fine gtinding/dispersing apparatus, can improve the decentralization of CNT in rubber; By continuous extrusion apparatus, the degree of orientation of CNT can be improved.This technique is applicable to the solution of the rubber latexs such as Heveatex, styrene-butadiene latex, NBR latex or different rubber, the CNT masterbatch prepared or the rubber composition applied range containing other compounding ingredients, can be used for preparing tire tread glue, sebific duct outer layer glue, conveyer belt coating rubber, the large primer of rubber overshoes etc., the anti-wear performance of rubber, tear resistance, anti-puncture performance can be improved, and there is the character such as high connductivity, high heat conduction, low-density.
Below in conjunction with the drawings and specific embodiments, the present invention is further described, so that those skilled in the art more understands the present invention, but does not limit the present invention with this.The improvement make the present invention and equivalent modifications also should fall in the scope of the invention in this paper.
Raw material sources and preparation:
(1) rubber latex
Natural concentrating glue breast: purchased from Hainan Xing Matai natural rubber Co., Ltd, concentration 60 % by weight;
Styrene-butadiene latex: purchased from Shandong Qilu Petrochemical Co., Ltd, concentration 22 % by weight;
Polychloroprene latex: purchased from China Resources, Qingdao rubber and plastic Co., Ltd, concentration 50 % by weight;
(2) CNT:
CNT is provided by Shandong great Zhan nano material Co., Ltd, purity >96%, and diameter is 8-15nm, and length is about 3-15 μm, content of ashes <2.5%;
(3) stabilizing agent
Potassium hydroxide: purchased from Jinan Jin Hao Chemical Co., Ltd., purity >95%;
Sulfonated methyl enuatrol: purchased from Wald, Jinan Chemical Co., Ltd., purity >99%;
Polyethylene glycol: purchased from Jiangsu Hai'an Petrochemical Plant, molecular weight 900-3300;
(4) surfactant
Dodecyl sodium sulfate: purchased from Tianjin chemical reagent Co., Ltd, purity >97%;
All the other rubber chemicals, comprise promoter, age resistor etc. all purchased from Qingdao Hua Heng auxiliary agent Co., Ltd.
Properties of product are tested:
Following performance test is carried out to the rubber prepared:
(1) hardness test adopts Shao A hardometer to carry out according to GB/T531.1-2008 method;
(2) extension test adopts electronic tensile machine to carry out according to GB/T528-2009 method;
(3) wearability test adopts Akron abrasion machine to carry out according to GB/T1689-1998 method: result represents with Akron abrasion volume, when wherein Akron abrasion bulking value represents that sample and emery wheel rub, from the rubber volume that sample grinds off.Therefore, Akron abrasion bulking value is larger, represents that wearability is poorer;
(4) burn-in test adopts GB/T3512-2001 to carry out;
(5) resistivity measurement adopts megger to carry out according to GB/T1692-2008 method;
(6) heat conductivility test adopts guarded-plate method conductometer to carry out according to GB/T3399-1982.
Embodiment 1
(1) comparative example
Common tread rubber (being usually used in whole steel wire radial tyre) as comparative example is prepared according to following dry method compounding process: natural rubber of being plasticated by 100 weight portions, 1 weight portion accelerator N-tertiary butyl-2-[4-morpholinodithio time yellow acid amides, 5 part by weight of zinc oxide, 2 weight portion stearic acid, 1 weight portion age resistor N-isopropyl-N '-diphenyl-para-phenylene diamine, 0.5 weight portion N, a N '-penylene BMI, 50 parts by weight of carbon black per N330, 5 weight parts of calcium carbonate, 3 weight portion environment-friendly aromatic oils, 0.5 weight portion zinc soap salt, evenly mixing in banbury, 140 DEG C of binder removals, bag roller in mill is added after cooling, add 2 weight portion Sulfurs evenly mixing, bottom sheet, to park after 12 hours at 143 DEG C sulfuration 15 minutes, obtain rubber.Its properties of product test result corresponds to the comparative example in table 1.
(2) embodiment 1A
1, raw material preparation
A. Heveatex
Heveatex component
| Component | Content/weight portion |
| Concentrated latex (60%) | 100 |
| Potassium hydroxide | 0.1 |
| Water | 100 |
Stirring condition: 2000-3000rpm, 2-5 minute.
B. carbon nano tube suspension
Carbon nano tube suspension component
| Component | Content/weight portion |
| CNT | 5 |
| Dodecyl sodium sulfate | 0.8 |
| Stabilizing agent polyethylene glycol | 0.8 |
| Dispersant water | 100 |
Stirring condition: 2000-3000rpm, 2-5 minute.
C. rubber chemicals suspension
By 1 weight portion accelerator N-tertiary butyl-2-[4-morpholinodithio time yellow acid amides, 5 part by weight of zinc oxide, 2 weight portion stearic acid, 1 weight portion age resistor N-isopropyl-N '-diphenyl-para-phenylene diamine, 0.5 weight portion N, a N '-penylene BMI, 50 parts by weight of carbon black per N330,5 weight parts of calcium carbonate, 3 weight portion environment-friendly aromatic oils, 0.5 weight portion zinc soap salt, 2 weight portion Sulfurs and 100 weight parts waters are mixed with rubber chemicals suspension.
2, mix
In the present embodiment, during the mixing of Heveatex, carbon nano tube suspension and rubber chemicals suspension, the solid content ratio of each component is 100 parts by weight of rubber, 1 parts by weight of carbon nanotubes, the 1 weight portion N-tert-butyl group-2-[4-morpholinodithio time yellow acid amides, 5 part by weight of zinc oxide, 2 weight portion stearic acid, 1 weight portion N-isopropyl-N '-diphenyl-para-phenylene diamine, 0.5 weight portion N, a N '-penylene BMI, 50 parts by weight of carbon black per N330,5 weight parts of calcium carbonate, 3 weight portion environment-friendly aromatic oils, 0.5 weight portion zinc soap salt, 2 weight portion Sulfurs.
Heveatex, carbon nano tube suspension and rubber chemicals suspension are added dispersion continuously and (namely fully stirring) in mixing apparatus, by impacting with high pressure, immixture, finally obtain homodisperse CNT/rubber liquefied mixture from discharging opening.High-pressure injection pressure 50MPa; Discharging opening flow velocity 200m/s.
3, solidify, extrusion dehydration
After CNT/rubber fluid enters continuous solidification equipment, the acetum of automatic dripping 1% mass concentration, be transported into Screw Extrusion unit after rubber cement solidifies immediately, rubber breaker carries out that high pressure is extruded, high pressure broken, extrusion dehydration, and utilize the runner guide effect of extruder die to make CNT realize orientation.In block solid-state sizing material washing and after acetic acid, be transported into continuous drying equipment, liquid flux or coagulating agent are collected rear recycling.
4, dry
Micelle through dehydration is transported in the high temperature drying streamline passage of electric heating temperature control, obtains CNT masterbatch after oven dry.
5. mixing, sulfuration
By the CNT/rubber composition after oven dry, mixed refining process is shaping, sulfuration obtains rubber.The whole process of embodiment 1A adopts the mixing legal system of liquid phase to obtain rubber, and its properties of product test result corresponds to the embodiment 1A in table 1.
(3) embodiment 1B
The rubber of embodiment 1B adopts to be prepared with the dry method compounding process of the common tread rubber of above-mentioned comparative example, difference is only the masterbatch added in common tread glue formula containing 1 parts by weight of carbon nanotubes, described CNT masterbatch preparation method is identical with embodiment 1A, but wherein in CNT masterbatch, the solid content ratio of natural rubber/CNT is 60/40, and prepares the step 3 of this masterbatch) in do not add rubber chemicals suspension.Therefore, embodiment 1B adopts CNT masterbatch of the present invention through the mixing obtained rubber of common dry method.
Table 1
As can be seen from result shown in table 1, compared with the mixing obtained tread rubber of common dry method, be no matter adopt CNT masterbatch of the present invention to adopt the mixing legal system of liquid phase to obtain natural rubber products through the mixing obtained natural rubber products of common dry method or all compounding ingredients all to have better performance in hot strength, tearing strength, stress at definite elongation, wearability, electrical and thermal conductivity, wherein all to adopt the mixing legal system of liquid phase to obtain the performance of natural rubber products better for whole preparation process.
Embodiment 2
(1) comparative example
Common tread rubber (being usually used in semi-steel wire radial tire) as comparative example is prepared as follows: by 100 weight portion styrene butadiene rubber sbrs 1502, 1 weight portion accelerator N-tertiary butyl-2-[4-morpholinodithio time yellow acid amides, 3 part by weight of zinc oxide, 1.5 weight portion stearic acid, 1 weight portion age resistor N-(1, 3-dimethyl) butyl-N'-diphenyl-para-phenylene diamine, 0.5 weight portion N, a N '-penylene BMI, 50 parts by weight of carbon black per N339, 5 weight portion environment-friendly aromatic oils, 0.5 weight portion zinc soap salt, evenly mixing in banbury, 140 DEG C of binder removals, bag roller in mill is added after cooling, add 2.5 weight portion Sulfurs evenly mixing, bottom sheet, to park after 12 hours at 151 DEG C sulfuration 15 minutes, obtain rubber.Its properties of product test result corresponds to the comparative example in table 2.
(2) embodiment 2A
1, the preparation of raw material
A. styrene-butadiene latex
Styrene-butadiene latex component
| Component | Content/weight portion |
| Styrene-butadiene latex (22%) | 100 |
| Potassium hydroxide | 0.1 |
| Water | 100 |
Stirring condition: 2000-3000rpm, 2-5 minute.
B. carbon nano tube suspension
Carbon nano tube suspension component
| Component | Content/weight portion |
| CNT | 5 |
| Dodecyl sodium sulfate | 0.8 |
| Polyethylene glycol | 0.8 |
| Water | 100 |
Stirring condition: 2000-3000rpm, 2-5 minute.
C. rubber chemicals suspension
By 1 weight portion accelerator N-tertiary butyl-2-[4-morpholinodithio time yellow acid amides, 3 part by weight of zinc oxide, 1.5 weight portion stearic acid, 1 weight portion age resistor N-(1,3-dimethyl) butyl-N'-diphenyl-para-phenylene diamine, 0.5 weight portion N, a N '-penylene BMI, 50 parts by weight of carbon black per N339,5 weight portion environment-friendly aromatic oils, 0.5 weight portion zinc soap salt, 2.5 weight portion Sulfurs and 100 weight parts waters are mixed with rubber chemicals suspension.
2, mix
In the present embodiment, during the mixing of styrene-butadiene latex, carbon nano tube suspension and rubber chemicals suspension, the solid content ratio of each component is 100 weight portion styrene-butadiene latexes, 1 parts by weight of carbon nanotubes, 1 weight portion accelerator N-tertiary butyl-2-[4-morpholinodithio time yellow acid amides, 3 part by weight of zinc oxide, 1.5 weight portion stearic acid, 1 weight portion age resistor N-(1,3-dimethyl) butyl-N'-diphenyl-para-phenylene diamine, 0.5 weight portion N, a N '-penylene BMI, 50 parts by weight of carbon black per N339,5 weight portion environment-friendly aromatic oils, 0.5 weight portion zinc soap salt, 2.5 weight portion Sulfurs.
The suspension of styrene-butadiene latex and carbon nano tube suspension and rubber chemicals is added dispersion continuously and (namely fully stirring) in mixing apparatus with above-mentioned solid content ratio, by impacting with high pressure, immixture, finally obtain homodisperse CNT/rubber liquefied mixture from discharging opening.High-pressure injection pressure 40MPa; Discharging opening flow velocity 250m/s.
3, solidify, extrusion dehydration
After CNT/rubber fluid enters continuous solidification equipment, the acetum of automatic dripping 1% mass concentration, be transported into Screw Extrusion unit after rubber cement solidifies immediately, rubber breaker carries out that high pressure is extruded, orientation, extrusion dehydration, in block solid-state sizing material washing and after acetic acid, be transported into continuous drying equipment, liquid flux or coagulating agent are collected rear recycling.
4, dry
Micelle through dehydration is transported in the high temperature drying streamline passage of electric heating temperature control, stand-by after drying.
5, mixing, sulfuration
CNT/rubber composition after oven dry, mixed refining process is shaping, sulfuration obtains rubber.The whole process of embodiment 2A adopts the mixing legal system of liquid phase to obtain rubber, and its properties of product test result corresponds to the embodiment 2A in table 2.
(3) embodiment 2B
The rubber of embodiment 2B adopts to be prepared with the dry method compounding process of the common tread rubber of above-mentioned comparative example, difference is only the styrene-butadiene latex masterbatch added in common tread glue formula containing 1 parts by weight of carbon nanotubes, described CNT masterbatch preparation method is identical with embodiment 2B, but wherein in CNT masterbatch, the solid content ratio of butadiene-styrene rubber/CNT is 60/40, and prepares the step 3 of the present embodiment masterbatch) in do not add rubber chemicals suspension.Therefore, embodiment 2B adopts CNT masterbatch of the present invention through the mixing obtained rubber of common dry method.Its properties of product test result corresponds to the embodiment 2B in table 2.
Table 2
As can be seen from result shown in table 2, compared with the mixing obtained tread rubber of common dry method, be no matter adopt CNT masterbatch of the present invention to adopt the obtained tread rubber of the mixing method of liquid phase all to have better performance in hot strength, tearing strength, stress at definite elongation, wearability, electrical and thermal conductivity through the mixing obtained tread rubber of common dry method or all compounding ingredients, wherein all to adopt the mixing legal system of liquid phase to obtain the performance of butadiene-styrene rubber goods better for whole preparation process.
Embodiment 3
(1) comparative example
Common sebific duct outer layer glue as comparative example is prepared as follows: by 20 parts by weight of natural rubber, 80 parts of neoprene, 4 weight portion magnesia, 2.5 weight portion stearic acid, 1 weight portion age resistor N-(1, 3-dimethyl) butyl-N'-diphenyl-para-phenylene diamine, 1 weight portion antioxidant BLE-acetone and diphenylamines pyrocondensation thing, 20 parts by weight of carbon black per N330, 100 weight parts of calcium carbonate, 8 weight portion dibutyl phthalates, 1 weight portion accelerant N-cyclohexyl-2-[4-morpholinodithio sulfenamide, evenly mixing in banbury, 140 DEG C of binder removals, bag roller in mill is added after cooling, add 4 part by weight of zinc oxide, 0.5 weight portion Sulfur is evenly mixing, bottom sheet, to park after 12 hours at 148 DEG C sulfuration 20 minutes, obtain rubber.Its properties of product test result corresponds to the comparative example in table 3.
(2) embodiment 3A
1, the preparation of raw material
A. latex
Heveatex component
| Component | Content/part |
| Heveatex (60%) | 100 |
| Potassium hydroxide | 0.1 |
| Water | 100 |
Neoprene latex component
| Component | Content/part |
| Polychloroprene latex (50%) | 100 |
| Sulfonated methyl enuatrol | 1 |
| Water | 100 |
Stirring condition: 2000-3000rpm, 2-5 minute.
B. carbon nano tube suspension
Carbon nano tube suspension component
| Component | Content/part |
| CNT | 5 |
| Dodecyl sodium sulfate | 0.8 |
| Polyethylene glycol | 0.8 |
| Water | 100 |
Stirring condition: 2000-3000rpm, 2-5 minute.
C. rubber chemicals suspension
By 4 weight portion magnesia, 2.5 weight portion stearic acid, 1 weight portion age resistor N-(1,3-dimethyl) butyl-N'-diphenyl-para-phenylene diamine, 1 weight portion antioxidant BLE-acetone and diphenylamines pyrocondensation thing, 20 parts by weight of carbon black per N330,100 weight parts of calcium carbonate, 8 weight portion dibutyl phthalates, 1 weight portion accelerant N-cyclohexyl-2-[4-morpholinodithio sulfenamide, 4 part by weight of zinc oxide, 0.5 weight portion Sulfur and 100 weight parts waters are mixed with rubber chemicals suspension.
3, mix
Latex in the present embodiment, when carbon nano tube suspension and the mixing of rubber chemicals suspension, the solid content ratio of each component is 20 parts by weight of natural rubber, 80 parts of neoprene, 1 parts by weight of carbon nanotubes, 4 weight portion magnesia, 2.5 weight portion stearic acid, 1 weight portion age resistor N-(1, 3-dimethyl) butyl-N'-diphenyl-para-phenylene diamine, 1 weight portion antioxidant BLE-acetone and diphenylamines pyrocondensation thing, 20 parts by weight of carbon black per N330, 100 weight parts of calcium carbonate, 8 weight portion dibutyl phthalates, 1 weight portion accelerant N-cyclohexyl-2-[4-morpholinodithio sulfenamide, 4 part by weight of zinc oxide, 0.5 weight portion Sulfur.
Heveatex, neoprene latex and carbon nano tube suspension and rubber chemicals suspension are added dispersion continuously and (namely fully stirring) in mixing apparatus with above-mentioned solid content ratio, by impacting with high pressure, immixture, finally obtain homodisperse CNT/rubber liquefied mixture from discharging opening.High-pressure injection pressure 50MPa; Discharging opening flow velocity 150m/s.
4, solidify, extrusion dehydration
After CNT/rubber fluid enters continuous solidification equipment, the acetum of automatic dripping 1% mass concentration, Screw Extrusion unit, rubber breaker is transported into immediately after rubber cement solidifies, extrusion dehydration, in block solid-state sizing material washing and after acetic acid, be transported into continuous drying equipment, liquid flux or coagulating agent are collected rear recycling.
5, dry
Micelle through dehydration is transported in the high temperature drying streamline passage of electric heating temperature control, stand-by after drying.
6, mixing, sulfuration
CNT/rubber composition after oven dry, mixed refining process is shaping, sulfuration obtains rubber.The whole process of embodiment 3A adopts the mixing legal system of liquid phase to obtain rubber, and its properties of product test result corresponds to the embodiment 3A in table 3.
(3) embodiment 3B
The rubber of embodiment 3B adopts to be prepared with the dry method compounding process of the common sebific duct outer layer glue of above-mentioned comparative example, difference is only the polychloroprene latex masterbatch added in common sebific duct outer layer glue formula containing 1 parts by weight of carbon nanotubes, described CNT masterbatch preparation method is identical with embodiment 3A, but wherein in CNT masterbatch, the solid content ratio of polychloroprene latex/CNT is 60/40, and prepares the step 3 of the present embodiment masterbatch) in do not add rubber chemicals suspension.Therefore, embodiment 3B adopts CNT masterbatch of the present invention through the mixing obtained rubber of common dry method.Its properties of product test result corresponds to the embodiment 3B in table 3.
Table 3
As can be seen from result shown in table 3, compared with the mixing obtained outer layer glue of common dry method, be no matter adopt CNT masterbatch of the present invention to adopt the mixing legal system of liquid phase to obtain outer layer glue through the mixing obtained outer layer glue of common dry method or all compounding ingredients all to have better performance in hardness, tensile property, ageing-resistant performance, electrical and thermal conductivity, wherein all to adopt the mixing legal system of liquid phase to obtain the performance of neoprene neoprene better for whole preparation process.
Claims (10)
1. a liquid phase continuous production method for CNT masterbatch, comprising:
1) carbon nano tube suspension is prepared;
2) suspension of described CNT disperseed continuously with rubber solutions/emulsion and optional rubber chemicals solution/suspension and mix, obtaining CNT/rubber/solvent mixture;
3) solidify with continuously extruded to described CNT/rubber/solvent mixture simultaneously, to realize CNT orientation, after removing water or solvent, obtain CNT/rubber composition;
4) continuous drying is carried out to described CNT/rubber composition, obtain CNT masterbatch.
2. the liquid phase continuous production method of CNT masterbatch according to claim 1, it is characterized in that, the step of preparation carbon nano tube suspension comprises and adds in oil-based solvent or aqueous dispersion medium by CNT, surfactant, stabilizing agent and dispersant, prepares stable CNT oiliness or waterborne suspension by mixing plant.
3. the liquid phase continuous production method of CNT masterbatch according to claim 1 and 2, is characterized in that, described CNT is the CNT of functional organic surface modification.
4. the liquid phase continuous production method of CNT masterbatch according to claim 1, it is characterized in that, described carbon nano tube suspension is disperseed to comprise carbon nano tube suspension by high-pressure pump with the step mixed with rubber solutions/emulsion and optional rubber chemicals solution/suspension continuously, rubber solutions/emulsion and optional rubber chemicals solution/suspension are transported in the pipeline that cross section of fluid channel gradually becomes with certain flow velocity respectively, then impact at high pressure and runner, under the effect of mixing, be uniformly dispersed and stable CNT/rubber/solvent mixture, wherein high-pressure is 1-100MPa, preferred 10-60MPa, flow velocity is 10m/s-1000m/s, preferred 100-500m/s.
5. the liquid phase continuous production method of CNT masterbatch according to claim 1, it is characterized in that, described CNT/rubber/solvent mixture is solidified simultaneously and comprises with continuously extruded step: the coagulating agent adding 0.01-2.00% mass concentration according to certain flow velocity in CNT/rubber/solvent mixture fluid, enter Screw Extrusion unit high pressure continuously extrude obtaining the stable coprecipitated mixture fluid of rubber/CNT after rubber quick solidification, to realize the orientation of CNT in rubber, wherein high-pressure is 2-200MPa, preferred 20-60MPa, flow velocity is 0.1m/s-100m/s, preferred 0.1-10m/s.
6. the liquid phase continuous production method of CNT masterbatch according to claim 1, it is characterized in that, it is 50-150 DEG C that the step of carrying out continuous drying to CNT/rubber composition is included in baking temperature, carries out drying under the condition of preferred 80-120 DEG C by heating.
7. according to claim 1, the liquid phase continuous production method of the CNT masterbatch according to any one of 4-6, it is characterized in that, described rubber is natural rubber or synthetic rubber, preferred Hevea rubber, gutta-percha, guayule, dandelion glue, polybutadiene rubber, polyisoprene rubber, butadiene-styrene rubber, EP rubbers, butyl rubber, acrylonitrile-butadiene rubber, neoprene, silicon rubber, polyurethane rubber, ACM, fluorubber and derivative products thereof.
8. the CNT masterbatch that the liquid phase continuous production method of the CNT masterbatch according to claim 1-7 prepares.
9. adopt the rubber that CNT masterbatch according to claim 8 prepares.
10. a liquid phase continuous mixing technique for CNT masterbatch, comprising:
1) carbon nano tube suspension is prepared;
2) suspension of described CNT disperseed continuously with rubber solutions/emulsion and optional rubber chemicals solution/suspension and mix, obtaining CNT/rubber/solvent mixture;
3) solidify with continuously extruded to described CNT/rubber/solvent mixture simultaneously, to realize CNT orientation, after removing water or solvent, obtain CNT/rubber composition;
4) continuous drying is carried out to described CNT/rubber composition, obtain CNT masterbatch;
5) the CNT masterbatch through super-dry is entered continuously one to multiple banbury, one to multiple mill, one to multiple screw extruder, machine-shaping is until sulfuration.
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| CN118496593A (en) * | 2024-07-17 | 2024-08-16 | 中国汽车技术研究中心有限公司 | Wear-resistant elastic material for automobile collision dummy and preparation method thereof |
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| CN105459284B (en) | 2019-04-05 |
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