[go: up one dir, main page]

EP2614109A1 - Procédé de fabrication de composites polymère-cnt - Google Patents

Procédé de fabrication de composites polymère-cnt

Info

Publication number
EP2614109A1
EP2614109A1 EP11749861.8A EP11749861A EP2614109A1 EP 2614109 A1 EP2614109 A1 EP 2614109A1 EP 11749861 A EP11749861 A EP 11749861A EP 2614109 A1 EP2614109 A1 EP 2614109A1
Authority
EP
European Patent Office
Prior art keywords
weight
agglomerates
carbon nanotube
carbon nanotubes
polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP11749861.8A
Other languages
German (de)
English (en)
Inventor
Heiko Hocke
John Vitovsky
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer Intellectual Property GmbH
Original Assignee
Bayer Intellectual Property GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer Intellectual Property GmbH filed Critical Bayer Intellectual Property GmbH
Priority to EP11749861.8A priority Critical patent/EP2614109A1/fr
Publication of EP2614109A1 publication Critical patent/EP2614109A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/22—Thermoplastic resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/02—Polyalkylene oxides
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/016—Additives defined by their aspect ratio
    • 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

Definitions

  • the present invention relates to a process for the preparation of polymer-carbon nanotube composites, comprising the steps of the main agglomerates of carbon nanotube agglomerates with an average agglomerate size of> 0.02 mm to ⁇ 6 mm, contacting the carbon nanotube agglomerates with an infusion material and incorporating the infiltrated carbon nanotube agglomerates into a thermoplastic polymer material or a reactive resin system.
  • the invention further relates to an impregnating material contacted carbon nanotube agglomerates and a Kohlenstoffhanorschreiben comprehensive polymer composite.
  • Carbon nanotubes are known for their exceptional properties. For example, their strength is about 100 times that of steel, their thermal conductivity is about as large as that of diamond, their thermal stability reaches up to 2800 ° C in vacuum and their electrical conductivity can be many times the conductivity of copper.
  • these structure-related characteristics are often only accessible at the molecular level if it is possible to homogeneously distribute carbon nanotubes and to establish the largest possible contact between the tubes and the medium, ie to render them compatible with the medium and thus stable dispersible.
  • electrical conductivity it is furthermore necessary to form a network of tubes in which, ideally, they only touch one another at the ends or approach sufficiently closely.
  • the carbon nanotubes should be as isolated as possible, that is agglomerate-free, not aligned and present in a concentration at which such a network can just form, which is reflected by the sudden increase in electrical conductivity as a function of the concentration of carbon nanotubes (percolation limit) .
  • excellent dispersion and separation of the carbon nanotubes is required because larger agglomerates result in break points (Zhou, eXPRESS Polym. Lett. 2008, 2, 1, 40-48 ) and then rather a deterioration of the mechanical properties of such composites is observed.
  • US 2007/213450 Al describes a method for the production of nanotube composite materials, wherein first a nanotube dispersion of a plurality of nanotubes and a liquid is produced, this is contacted with a polymer melt and both are mixed together to form a nanotube composite To obtain melt and the liquid is removed by evaporation. In the process described there, the CNT agglomerates are destroyed by means of energy input in the liquid and the CNT is separated or dispersed. Preferably, in this case, the dispersion takes place by means of ultrasound.
  • the nanotube concentration in the liquid is very low, usually below 1 wt.
  • WO 2008/106572 A1 discloses a polymer composition comprising a resin matrix with a mixture of a resin and carbon nanotubes and a polymer matrix.
  • the polymer composition is obtained by melt blending the resin matrix and the polymer matrix together.
  • a dispersing step for preparing the resin matrix is considered necessary, that is, the CNTs are first singulated by energy input (extrusion) in the resin matrix, and this masterbatch is then mixed with the polymer.
  • WO 2009/001324 A2 deals with the use of nanotubes of at least one element of Groups IIIa, IVa and Va of the Periodic Table for improving the mechanical properties of a polymeric matrix comprising at least one semicrystalline thermoplastic polymer at high temperatures.
  • One possibility for mixing the nanotubes and the polymer matrix is the direct compounding in an extruder.
  • Another option is a Predispersion (singulation of nanotubes) in a solvent.
  • ultrasonic treatment or rotor-stator mills are mentioned here as possibilities for dispersing.
  • WO 2010/051942 A1 relates to a composition comprising a propylene-olefin copolymer wax and carbon nanotubes. With regard to the incorporation of the nanotubes, it is only disclosed that simultaneous mixing can take place.
  • the prior dispersing of carbon nanotubes in a dispersing medium prior to incorporation into polymers, for example by ultrasound treatment or mechanical action, is always associated with an increased expenditure of energy for the overall process.
  • the sub-mixture of a CNT-containing liquid in a polymer is due to the very different viscosities associated with considerable difficulties, especially in economically preferable mixing processes such as mixing in the kneader, extruder or mill.
  • the subsequent evaporation of the liquid is associated with considerable expenditure of energy, especially in the case of very dilute nanorubile dispersions, and brings about considerable problems, in particular on an industrial scale, because of the necessary energy input.
  • the reproducible metering of the dispersions into the melt represents a technical challenge industrially.
  • the object of the present invention is therefore to improve a process for the production of electrically conductive and / or mechanically enhanced polymer-carbon nanotube composites in such a way that the overall energy consumption of the process is reduced and at the same time a high degree of separation of the nanotubes (dispersing quality) is achieved.
  • the object is achieved according to the invention by a process for the preparation of polymer-carbon nanotube composites, comprising the steps:
  • step (C) incorporating obtained with a impregnating material carbon nanotube agglomerates in step (B) in a thermoplastic polymer material or
  • step (C) it has been found that can be broken up by the inventive method when incorporated in step (C), the previously substantially intact agglomerates and thereby allow the carbon nanotubes dispersed in the polymer better than in a direct compounding without impregnating material.
  • step (C) it was found that less energy is needed during the training itself.
  • much energy is saved by avoiding predispersion, for example by sonicating a dispersion of the aggregates in a liquid.
  • the process also readily solves the incorporation and mixing of a low viscosity material with a high viscosity material, since the low viscosity liquid soaked in the carbon nanotube agglomerates is released upon dispersion of the agglomerates in the higher viscosity material and mixed immediately.
  • a further advantage of the method according to the invention is the reduction of the dusting behavior of the carbon nanotubes, which simplifies handling and reduces possible exposure to CNTs during extrusion.
  • Carbon nanotubes in the sense of the invention are all single-walled or multi-walled carbon nanotubes of the cylinder type (eg in US Pat. No. 5,747,161; WO 86/03455), scroll type, multiscroll type, cup-stacked type of unilaterally closed or open on both sides, consisting of conical cups (eg in EP-A 198,558 and US 7018601 B2), or onion-like structure.
  • Preference is given to using multi-walled carbon nanotubes of the cylinder type, scroll type, multiscroll type and cup-stacked type or mixtures thereof. It is favorable if the carbon nanotubes have a ratio of length to outer diameter of> 5, preferably> 100.
  • the individual graphene or graphite layers in these carbon nanotubes seen in cross-section, evidently run continuously from the center of the carbon nanotubes to the outer edge without interruption. This may allow, for example, improved intercalation of other materials in the tube framework, as more open edges than the entry zone of the intercalates are available compared to simple scroll structure carbon nanotubes (Carbon 1996, 34, 1301-3) or onion-like CNTs (Science 1994, 263, 1744-7).
  • the carbon nanotubes are provided in the form of agglomerates.
  • the agglomerated form is the present form of carbon nanotubes in which they are commercially available.
  • Several types of structures of agglomerates can be distinguished: the bird's nest structure (BN), the combed yarn (CY), and the open net structure (ON).
  • Other agglomerate structures are known, e.g. a, b e d e r s i c h d i e Arrange carbon nanotubes in the form of bundled yarns (Hocke, WO PCT / EP2010 / 004845).
  • agglomerate forms can either be mixed together as desired or used as a mixed hybrid, that is to say different structures within an agglomerate.
  • the agglomerates provided have an average agglomerate size of> 0.02 mm. This value can be determined by means of laser diffraction spectrometry (an example of a device is the Mastersizer MS 2000 with dispersing unit Hydro S from Malvern, in water).
  • the upper limit of the agglomerate size may be, for example, ⁇ 6 mm.
  • the average agglomerate size is> 0.05 mm to ⁇ 2 mm and more preferably> 0.1 mm to ⁇ 1 mm.
  • step (A) and step (B) no step takes place in which the agglomerates are comminuted (as is the case, for example, in high-speed stirring), so that free-flowing agglomerates are used in step (B).
  • step (B) of the process according to the invention the agglomerates are contacted with a impregnating material.
  • the impregnation material here is liquid under the conditions prevailing in step (B) and wets at least part of the surface of the carbon nanotubes.
  • the impregnating agent itself may be a substance specially selected for this purpose or else a substance which is usually incorporated into polymers. Examples of this latter case are flame retardants, mold release agents, plasticizers, stabilizers or other customary in the polymer industry additives in bulk, as a dispersion or in a solvent. Another possibility is that the impregnation agent constitutes or contains a component of a reactive system. Polyols, isocyanates, epoxides, amines and phenols, which are converted into polyurethane, epoxy or phenolic resins, are to be mentioned here in particular.
  • the impregnation material may in one embodiment be in the form of an aqueous or nonaqueous solution or dispersion.
  • the impregnation agent does not comprise any substances reactive with the carbon nanotube, e.g. Coupling agent.
  • the contacting is carried out in such a way that> 50% by weight, preferably> 75% by weight and particularly preferably> 90% by weight, while, based on the weight of the carbon nanotubes, the agglomerates still have the agglomerate size after contact Range of> 0.02 mm. It is therefore desirable to achieve no or only a slight breakage of the aggregates when contacting. Depending on the watering agent and amount and execution, it can also lead to clumping, whereby the original agglomerates stick together to form larger agglomerates. This case is included according to the invention.
  • the contacting can be carried out, for example, in a drum mixer or tumble dryer, but other methods and apparatus known to those skilled in the art can also be used.
  • the impregnation material Upon contacting, at least a portion of the impregnation material remains on the agglomerates before being used in the subsequent step of the process.
  • the impregnant comprises a solution or dispersion of a substance - for example an oligomer or polymer in a solvent to better adjust a particular, low viscosity for better diffusion into the agglomerate -, and by evaporation, distillation or other separation processes, the solvent was removed after soaking again.
  • Step (C) of the process according to the invention involves the incorporation of the agglomerates obtained in step (B).
  • agglomerates obtained in step (B).
  • the incorporation takes place in a thermoplastic polymer material or in a reactive resin system.
  • reactive resin system is meant a reaction mixture which reacts to form a polymer. In particular, it may be polyurethanes, phenolic and epoxy resins forming systems.
  • the carbon nanotubes forming the agglomerates are multi-walled carbon nanotubes with an average outer diameter of> 3 nm to ⁇ 100 nm, preferably> 5 nm to ⁇ 25 nm and a length to diameter ratio of> 5, preferably> 100 ,
  • the impregnation material is selected such that it has a viscosity of> 0.2 mPas to ⁇ 20,000 mPas at the temperature prevailing in step (B).
  • the viscosity is> 1 mPas to ⁇ 10000 mPas and more preferably> 10 mPas to ⁇ 2000 mPas.
  • the impregnant can also better reach areas inside the aggregates and infiltrate the agglomerate better and more uniformly overall.
  • the viscosity can be determined, for example, by means of a cylinder rotary viscometer of the Haake Viscotester VT 550 type according to DIN 53019 or DIN EN ISO 3219.
  • the impregnation material is selected such that its melting point is below the temperature prevailing in step (C).
  • a solid at room temperature impregnant ensure that the agglomerates do not stick together and that nevertheless the advantages of a liquid impregnant can be used during incorporation.
  • the impregnation material comprises an aqueous solution and / or dispersion of a polymer.
  • it may be an aqueous solution of polyvinylpyrrolidone (PVP), an acrylate, a latex based on styrenes and / or acrylonitrile and similar systems.
  • the impregnation material comprises substances selected from the group comprising polyethers, esters, ketones, phosphates, phosphonates, sulfonates, sulfonamines, carbonates, carbamates, amines, amides, silicones, organic compounds with long-chain alkyl groups, waxes , Glycerides, fats, benzoates, phthalates, adipic acid derivatives, succinic acid derivatives and / or monofunctional epoxides.
  • Preferred organic compounds having long-chain alkyl groups have C 6 alkyl groups, more preferably C 12 or higher homologous alkyl groups.
  • Preferred amines are polyether monoamines.
  • An example of a preferred ester is resorcinol bis (diphenyl phosphate), which is used under the name RDP as a flame retardant.
  • the impregnation material comprises ionic liquids, in particular those which are based on nitrogen (for example ammonium, imidazolium ions) or phosphorus (for example phosphonium ions).
  • the impregnation material may be in a solvent.
  • solvents are water, acetone, nitriles, alcohols, dimethylformamide (DMF), N-methylpyrrolidone (NMP), pyrrolidone derivatives, butyl acetate, methoxypropyl acetate, alkylbenzene and cyclohexane derivatives.
  • the carbon nanotube agglomerates obtained in step (B) and contacted with the impregnation liquid are free-flowing at room temperature. Free-flowingness is the degree of free mobility or flow behavior of bulk solids. In particular, the agglomerates obtained in step (B) show a good flowability.
  • the flow rate of these agglomerates is at least> 10 mL / s, better> 15 mL / s, preferably> 20 mL / s and particularly preferably> 25 mL / s (can be determined with the free-flowing device from the company Karg-Industrietechnik (Code No. 1012,000) ) Model PM and a 15 mm nozzle according to standard ISO 6186). Free-flowing aggregates show clear advantages their dosage and processing. The degree of flowability can be controlled by the type and amount of the impregnant.
  • the weight ratio of carbon nanotube agglomerates to impregnating material in step (B) is> 1: 4 to ⁇ 10: 1.
  • this ratio is> 1: 2 to ⁇ 5: 1 and particularly preferably> 1: 1.5 to ⁇ 3: 1, to ensure a particularly good flowability.
  • the weight fraction of carbon nanotube agglomerates in the impregnated material after step (B) is> 20% by weight, preferably> 35% by weight and particularly preferably> 40% by weight of carbon nanotubes. If the carrier material remains in the polymer after incorporation, it is advantageous to maintain a high degree of flexibility with regard to its content in the polymer in order to set desired properties in the finished polymer.
  • step (C) the carbon nanotube agglomerates obtained in step (B) and contacted with the impregnating material are introduced into the thermoplastic polymer material or the reactive resin system in a proportion of> 0.01% by weight to ⁇ 50% by weight -% (based on carbon nanotubes) incorporated. Preferably, this proportion is> 0.5% by weight to ⁇ 30% by weight.
  • the process according to the invention offers the advantage that it is also possible to incorporate higher contents of carbon nanotubes than was hitherto possible.
  • the incorporation in step (C) can take place, for example, in a kneader, roll mill or extruder.
  • twin-screw extruder with an L / D ratio of> 10, preferably> 20, more preferably> 25, and most preferably> 35.
  • L / D ratio of> 10
  • co-rotating twin-screw extruder is particularly preferred.
  • steps (B) and (C) follow one another directly.
  • the steps can be combined so that the impregnation step is carried out in situ and the dispersion follows immediately after the mixing step. The process appears thereby quasi at the same time. This is possible, for example, if the impregnating agent has a lower viscosity and / or is easier to melt than the polymer.
  • the wetting of the CNT agglomerate initially takes place primarily through the impregnation material before it is wetted by the polymer.
  • the CNT agglomerates and the drench agent are first introduced (main or side feed) into a mixing unit, and then the polymer (or resin precursor) is added in a staggered step (side feed).
  • the thermoplastic polymer material comprises polyamides (for example PA.6, PA.66, PA 12 or PA11), polycarbonate (PC), homo- and copolymers of polyoxymethylene (POM-H, POM-C), thermoplastic Polyurethanes (TPU), polyolefins (for example PP, PE, HDPE, COC, LCP including modified variants), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyacrylates (for example polymethylmethacrylate PMMA), styrene polymers (for example PS, HiPS, ASA, SMA) , Polyacrylonitrile (PAN), polystyrene acrylonitrile (SAN), polyacrylonitrile butadiene styrene (ABS), polyvinylchloride (PVC), fluorinated polymers (eg polyvinylidene fluoride PVDF, ethylene tetrafluoroethylene ETFE
  • polyamides for example PA.6, PA.
  • the reactive resin system comprises epoxides (especially those of bisphenol A and / or bisphenol F), polyurethanes (especially those derived from aromatic diisocyanates such as toluene-2,4-diisocyanate TDI and / or diphenylmethane diisocyanate MDI or aliphatic diisocyanates as hexamethylene diisocyanate HDI and / or 3-isocyanato-methyl-3,5,5-trimethylcyclohexylisocyanate IPDI and / or 4,4'-diisocyanatodicyclohexylmethane Hi 2 -MDI) are constructed), phenolic resins, unsaturated polyesters and / or aminoplasts.
  • aromatic diisocyanates such as toluene-2,4-diisocyanate TDI and / or diphenylmethane diisocyanate MDI or aliphatic diisocyanates as hexamethylene diis
  • the present invention further relates to an impregnation material contacted carbon nanotube agglomerates, wherein> 50% by weight, preferably> 75% by weight and particularly preferably> 90% by weight, based on the weight of the carbon nanotubes, the carbon nanotube agglomerates an average agglomerate size of > 0, 02 mm.
  • the agglomerates are characterized in that the impregnation material comprises substances which are selected from the group comprising polyethers, esters, ketones, phosphates, Phosphonates, sulfonates, sulfonamines, carbonates, carbamates, amines, amides, silicones, organic compounds with long-chain alkyl groups, waxes, glycerides, fats, benzoates, phthalates, adipic acid derivatives, succinic acid derivatives and / or monofunctional epoxides.
  • the impregnation material comprises substances which are selected from the group comprising polyethers, esters, ketones, phosphates, Phosphonates, sulfonates, sulfonamines, carbonates, carbamates, amines, amides, silicones, organic compounds with long-chain alkyl groups, waxes, glycerides, fats, benzoates, phthalates, adipic acid derivatives, succin
  • the average agglomerate size is according to the invention> 0.02 mm. This value can be determined by means of laser diffraction spectrometry (an example of a device is the Mastersizer MS 2000 with dispersing unit Hydro S from Malvern, in water).
  • the upper limit of the agglomerate size may be, for example, ⁇ 6 mm.
  • the average agglomerate size is> 0.05 mm to ⁇ 2 mm and more preferably> 0.1 mm to ⁇ 1 mm.
  • Preferred organic compounds having long-chain alkyl groups have C 6 alkyl groups, more preferably C 12 or higher homologous alkyl groups.
  • the impregnation material may be in a solvent.
  • solvents are water, acetone, nitriles, alcohols, dimethylformamide (DMF), N-methylpyrrolidone (NMP), pyrrolidone derivatives, butyl acetate, methoxypropyl acetate, alkylbenzene and cyclohexane derivatives.
  • a further subject of the present invention is a polymer composite comprising carbon nanotubes, obtainable by a process according to the present invention, wherein the proportion of carbon nanotubes is ⁇ 50% by weight and the proportion in agglomerates having an average agglomerate size of> 0.02 mm to ⁇ 6 mm carbon nanotubes in the total amount of carbon nanotubes is ⁇ 10% by weight.
  • the proportion of carbon nanotubes is preferably ⁇ 7% by weight and more preferably ⁇ 3% by weight. It is further preferable that this proportion is> 0.01% by weight, and more preferably> 0.1% by weight.
  • the proportion of carbon nanotubes present in agglomerates having an average agglomerate size of> 0.02 mm to ⁇ 6 mm in the total amount of carbon nanotubes is preferably ⁇ 5% by weight and particularly preferably ⁇ 2% by weight.
  • the polymer of the polymer composite may be a thermoplastic polymer or a polymer obtained from a reactive resin system.
  • the composition contains no microgels after step (B) and / or after step (C).
  • Baytubes® C 150 P (Bayer MaterialScience AG) were used as CNTs. These are multi-walled CNTs with an average outer diameter of 13 nm to 16 nm and a length of over 1 ⁇ . Baytubes® C 150 P are still present as agglomerates with an average particle size of 0.1 mm to 1 mm.
  • the bulk density is according to EN ISO 60 120 kg / m 3 to 170 kg / m 3 .
  • the CNT agglomerates were contacted with the impregnating material shown in Table 1-1 in a ratio of 2 parts by weight of CNTs and 1 part by weight of impregnating material in a drum mixer for at least 12 hours. Where necessary, this was additionally heated. In the comparative experiments, the CNT agglomerates were incorporated dry (without impregnation step).
  • the CNT agglomerates were contacted with the impregnating material shown in Tables 1-2 and 1-4 in a ratio of 1 part by weight of CNTs and 2 parts by weight of impregnating material in a tumble tumble dryer for at least one hour. This step was omitted in the comparative experiments.
  • the CNT agglomerates were contacted with the impregnating material shown in Table 1-3 in a ratio of 1 part by weight of CNTs and 2 parts by weight of impregnating material in a tumbler mixer for at least 12 hours. Where necessary, this was additionally heated. In the comparative experiments, the CNT agglomerates were incorporated dry (without impregnation step).
  • PA6 polyamide 6
  • PA12 polyamide 12
  • the polymer was dried before extrusion. The drying details are in Table 5. Polymer and filler were metered into the main entrance of the extruder. Details of the extrusion conditions can be found in Tables 2-1 to 2-3.
  • TM1 denotes the processing temperature in the extruder.
  • the screw set "A” consists of approx.
  • the screw bed “B” consists of approx. 15% kneading and mixing elements and approx. 85% conveyor elements.
  • the compound came as strands from the nozzle plate of the extruder. It was cooled after extrusion in a water bath, dried with a stream of air and finally granulated.
  • TM1 refers to the processing temperature in the extruder.
  • the screw bed “C” consists of approx. 15% kneading elements and approx. 85% conveyor elements. The compound came as strands from the nozzle plate of the extruder. It was cooled after extrusion in a water bath, dried with a stream of air and finally granulated.
  • the polymer was dried (the drying details are in Table 5) and metered into the main inlet of the extruder. Details of the extrusion conditions can be found in Table 2-3.
  • "TM 1" denotes the processing temperature in the extruder.
  • the screw set "B" was used, which consists of approx. 15% kneading and mixing elements and approx. 85% conveying elements.
  • the compound came in strands from the nozzle plate of the extruder. It was cooled after extrusion in a water bath, dried with a stream of air and finally granulated. The masterbatch was diluted with pure PA 12 in a next extrusion step. The dilution was again carried out on the ZSK-26 Megacompounder. The polymer and masterbatch were dried under the same conditions (see Table 5) and metered together into the main entrance of the extruder. The extrusion was carried out as described above. Testing
  • a portion of the compounded polymer was molded into a squeeze plate (80 mm diameter, 2 mm thick) in a heated press (Polystat 400S from Schwabenthan).
  • the manufacturing process of the press plates was documented for each type of polymer in Table 6.
  • the press plate was provided in the middle with 2 parallel strips of a silver paint so as to form a square open on 2 opposite sides with a side length of 2.5 cm. It was dried again and the surface resistance was measured with a resistance meter.
  • Another portion of the compounded polymer was molded by injection molding into a plate called an injection plate. The surface resistance was measured according to ASTM D-257 with a ring electrode (Monroe model 272A measuring device) placed on the plate. The results are documented in Tables 3-1 to 3-4.
  • PA6X04 Surfonamine B200 polyether monoamine, Huntsman company
  • PA6X06 Surfonamine B200 polyether monoamine, Huntsman company
  • PA6X11 Surfonamine L200 (polyether monoamine, Huntsman company)
  • PA6X12 Surfonamine L200 polyether monoamine, Huntsman company
  • PA 12X04 Comparative Experiment - Masterbatch in PA 12
  • PA 12X05 Comparative Experiments - Dilution of Masterbatch in PA 12
  • PA 12X06 Comparative Experiments - Dilution of Masterbatch in PA 12
  • PA12X08 Reofos® RDP resorcinol bis (diphenyl phosphate)
  • Chemtura Corporation PA 12X09 Reofos® RDP (resorcinol bis (diphenyl phosphate)), Chemtura Corporation
  • PA12X10 Reofos® RDP resorcinol bis (diphenyl phosphate)
  • HDPEX04 Reofos® RDP resorcinol bis (diphenyl phosphate)
  • Chemtura Corporation HDPEX05 Reofos® RDP (resorcinol bis (diphenyl phosphate)), Chemtura Corporation
  • PA6X02 25.3 400.0 72.5 0.255 283.0 A
  • PA6X10 25, 1 400.0 64.5 0.228 280.0 A
  • PA6X12 26.9 400.0 67.0 0.221 283.0 A
  • PA6X14 3590 0 0 90.9 90.5 3, 1 66
  • the electrically conductive compounds according to the invention prepared by impregnation of CNT agglomerates and subsequent direct compounding, are superior to the compounds from the comparative experiments prepared either by direct compounding or else via masterbatch and dilution, but without impregnation of the CNT.
  • the degree of dispersion of the compounds according to the invention is improved compared to the comparative experiments.
  • an improvement in the mechanical characteristics and / or the electrical conductivity values is found in part. In all cases, fewer defects were observed on the surface of the injection moldings in the compounds according to the invention than in the compounds of the comparative experiments.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Composite Materials (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

L'invention concerne un procédé de fabrication de composites polymère-nanotubes de carbone (CNT) qui comprend les étapes: (A) produire des agglomérats de nanotubes de carbone ayant une grandeur moyenne d'agglomérat de ≥ 0,02 mm à ≤ 6 mm; (B) mettre en contact les agglomérats de nanotubes de carbone avec un matériau d'imprégnation, la mise en contact étant effectuée de telle manière que ≥ 50 % en poids des agglomérats de nanotubes par rapport au poids des nanotubes de carbone présentent encore toujours après la mise en contact une grandeur moyenne d'agglomérat de ≥ 0,02 mm; et (C) incorporer les agglomérats de nanotubes de carbone mis en contact avec un matériau d'imprégnation, obtenus à l'étape (B) dans un matériau polymère thermoplastique ou dans un système de résine réactive. L'invention concerne également des agglomérats de nanotubes de carbone mis en contact avec un matériau d'imprégnation et un composite polymère comprenant des nanotubes de carbone.
EP11749861.8A 2010-09-07 2011-09-02 Procédé de fabrication de composites polymère-cnt Withdrawn EP2614109A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP11749861.8A EP2614109A1 (fr) 2010-09-07 2011-09-02 Procédé de fabrication de composites polymère-cnt

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP10175594A EP2426163A1 (fr) 2010-09-07 2010-09-07 Procédé destiné à la fabrication de composites polymères CNT
EP11749861.8A EP2614109A1 (fr) 2010-09-07 2011-09-02 Procédé de fabrication de composites polymère-cnt
PCT/EP2011/065215 WO2012031989A1 (fr) 2010-09-07 2011-09-02 Procédé de fabrication de composites polymère-cnt

Publications (1)

Publication Number Publication Date
EP2614109A1 true EP2614109A1 (fr) 2013-07-17

Family

ID=43478165

Family Applications (2)

Application Number Title Priority Date Filing Date
EP10175594A Ceased EP2426163A1 (fr) 2010-09-07 2010-09-07 Procédé destiné à la fabrication de composites polymères CNT
EP11749861.8A Withdrawn EP2614109A1 (fr) 2010-09-07 2011-09-02 Procédé de fabrication de composites polymère-cnt

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP10175594A Ceased EP2426163A1 (fr) 2010-09-07 2010-09-07 Procédé destiné à la fabrication de composites polymères CNT

Country Status (7)

Country Link
US (1) US20130203928A1 (fr)
EP (2) EP2426163A1 (fr)
JP (1) JP2013536893A (fr)
KR (1) KR20140009139A (fr)
CN (1) CN103201321A (fr)
TW (1) TW201226166A (fr)
WO (1) WO2012031989A1 (fr)

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012022482A1 (de) * 2012-11-19 2014-05-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Polymerzusammensetzung mit verbesserter Langzeitstabilität, hieraus hergestellte Formteile sowie Verwendungszwecke
DE102013005307A1 (de) 2013-03-25 2014-09-25 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verwendung von organischen Oxyimiden als Flammschutzmittel für Kunststoffe sowie flammgeschützte Kunststoffzusammensetzung und hieraus hergestelltem Formteil
EP2810977A1 (fr) 2013-06-07 2014-12-10 Bayer MaterialScience AG Composition et procédé pour la préparation de composites polymer-CNT
EP2810978B1 (fr) 2013-06-07 2017-12-27 Future Carbon GmbH Retrait d'un support de faible viscosité à partir d'un composite polymère avec un matériau thermoplastique
US20170058105A1 (en) * 2013-11-27 2017-03-02 Polyone Corporation Electrically conductive polycarbonate compounds
JP6310736B2 (ja) * 2014-03-12 2018-04-11 日信工業株式会社 熱可塑性樹脂組成物の製造方法及び熱可塑性樹脂組成物
DE102014210214A1 (de) 2014-05-28 2015-12-03 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verwendung von Oxyimid-enthaltenden Copolymeren oder Polymeren als Flammschutzmittel, Stabilisatoren, Rheologiemodifikatoren für Kunststoffe, Initiatoren für Polymerisations- und Pfropfprozesse, Vernetzungs- oder Kopplungsmittel sowie solche Copolymere oder Polymere enthaltende Kunststoffformmassen
DE102014211276A1 (de) 2014-06-12 2015-12-17 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verwendung von Hydroxybenzotriazol-Derivaten und/oder Hydroxy-Indazol-Derivaten als Flammschutzmittel für Kunststoffe sowie flammgeschützte Kunststoffformmasse
KR101903300B1 (ko) 2014-07-22 2018-10-01 어드밴스드 테크놀러지 머티리얼즈, 인코포레이티드 연성 재료를 갖는 성형 플루오로중합체 브레이크 실
CN106164151B (zh) 2014-08-29 2018-03-02 株式会社Lg化学 具有提高的机械性能的复合材料和包括该复合材料的模制品
WO2016032307A1 (fr) * 2014-08-29 2016-03-03 주식회사 엘지화학 Composite présentant des propriétés mécaniques améliorées et objet moulé le contenant
CN105153463B (zh) * 2015-03-05 2018-02-09 贵州一当科技有限公司 一种改性碳纳米管的处理方法
CN104987659A (zh) * 2015-08-10 2015-10-21 广州索润环保科技有限公司 一种耐高温抗静电的导电聚合物复合材料及其制备方法和应用
CN105111467B (zh) * 2015-08-27 2018-02-23 北京化工大学 一种粒径可控的聚醚酰亚胺超微粉体的制备方法
CN106243622A (zh) * 2016-09-27 2016-12-21 广东银禧科技股份有限公司 用于sls的碳纳米管/聚醚醚酮复合粉末材料及制备方法
US12187871B2 (en) * 2017-08-25 2025-01-07 The Boeing Company Carbon nanotube enhanced polymers and methods for manufacturing the same
WO2019165359A1 (fr) * 2018-02-23 2019-08-29 Frx Polymers, Inc. Compositions de polyphosphonates et de nanotubes de carbone
WO2020203726A1 (fr) * 2019-03-29 2020-10-08 古河電気工業株式会社 Moteur sans noyau
CN111499834A (zh) * 2020-04-22 2020-08-07 青岛爱尔家佳新材料股份有限公司 一种阻燃型聚脲抗爆防护材料及其制备方法
CN113403849A (zh) * 2021-06-29 2021-09-17 哈尔滨工业大学 一种耐高温碳纤维热塑性上浆剂的制备方法
CN119019836B (zh) * 2024-10-25 2025-02-14 安徽观唐橡塑制品有限公司 一种耐磨抗菌tpe复合材料及其在瑜伽垫中的应用

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4663230A (en) 1984-12-06 1987-05-05 Hyperion Catalysis International, Inc. Carbon fibrils, method for producing same and compositions containing same
US4855091A (en) 1985-04-15 1989-08-08 The Dow Chemical Company Method for the preparation of carbon filaments
JP2687794B2 (ja) 1991-10-31 1997-12-08 日本電気株式会社 円筒状構造をもつ黒鉛繊維
CA2364075A1 (fr) 1992-05-22 1993-12-09 Hyperion Catalysis International, Inc. Methodes et catalyseurs ameliores pour la fabrication de fibrilles de carbone
US6232706B1 (en) 1998-11-12 2001-05-15 The Board Of Trustees Of The Leland Stanford Junior University Self-oriented bundles of carbon nanotubes and method of making same
JP3981567B2 (ja) 2001-03-21 2007-09-26 守信 遠藤 炭素繊維の長さ調整方法
US7285591B2 (en) 2003-03-20 2007-10-23 The Trustees Of The University Of Pennsylvania Polymer-nanotube composites, fibers, and processes
US7744793B2 (en) 2005-09-06 2010-06-29 Lemaire Alexander B Apparatus and method for growing fullerene nanotube forests, and forming nanotube films, threads and composite structures therefrom
EP2115041A4 (fr) 2007-03-01 2012-09-05 Arkema Inc Procédé et auxiliaire de performance de nanotubes en carbone
KR20100027164A (ko) 2007-06-27 2010-03-10 아르끄마 프랑스 중합체 매트릭스의 고온 기계적 특성을 개선하기 위한, 나노튜브, 특히 탄소 나노튜브의 용도
DE102007044031A1 (de) 2007-09-14 2009-03-19 Bayer Materialscience Ag Kohlenstoffnanoröhrchenpulver, Kohlenstoffnanoröhrchen und Verfahren zu ihrer Herstellung
EP2285874B1 (fr) * 2008-05-23 2016-12-07 Future Carbon GmbH Nanotubes de carbone et milieux organiques contenant des microgels
EP2184324A1 (fr) 2008-11-06 2010-05-12 Clariant International Ltd. Compositions comportant des cires de propylène-oléfine-copolymère et nanotubes en carbone
CN101580243B (zh) * 2009-06-03 2013-03-27 惠州市沃特新材料有限公司 一种碳纳米管的表面处理方法及用其制备复合塑料的方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2012031989A1 *

Also Published As

Publication number Publication date
US20130203928A1 (en) 2013-08-08
CN103201321A (zh) 2013-07-10
KR20140009139A (ko) 2014-01-22
WO2012031989A1 (fr) 2012-03-15
JP2013536893A (ja) 2013-09-26
TW201226166A (en) 2012-07-01
EP2426163A1 (fr) 2012-03-07

Similar Documents

Publication Publication Date Title
WO2012031989A1 (fr) Procédé de fabrication de composites polymère-cnt
EP2501746B1 (fr) Procédé de production de matériaux composites à base de polymères et de nanotubes de carbone (cnt), et matériaux composites ainsi produits, ainsi que leur utilisation
EP2533913B1 (fr) Procédé de fabrication de pièces moulées en un matériau en carbone à l'aide de fibres de carbone recyclees
Jacob et al. Mechanical properties of sisal/oil palm hybrid fiber reinforced natural rubber composites
DE3280480T2 (de) Granulat aus faserverstärkten Verbundstoffen und deren Herstellungsverfahren
EP2266786B1 (fr) Fabrication de matières composites à partir de nano-composites
DE102010042209A1 (de) Herstellung von Kohlenstoffnanoröhren -haltigen Dispersionen
DE112016003169B4 (de) Verfahren zum herstellen eines elastomerkomposits, nach diesem verfahren erhältlicher fester silica-haltiger kontinuierlicher kautschukphasenartikel sowie verfahren zur herstellung einer kautschukmischung und eines kautschukartikels
EP2902433B2 (fr) Procédé de fabrication de granules en fibres de carbone
EP3356591B1 (fr) Procede de fabrication d'un semi-produit fibre/matrice
EP2328736A1 (fr) Procédé de fabrication de matériaux composites contenant des nanotubes de carbone, ayant une résistance réduite
EP3098254B1 (fr) Matériau de moulage renforcé par des fibres de carbone pour moulage par injection, moulage par extrusion ou moulage par pultrusion.
EP2427520B1 (fr) Composition de granulés et son procédé de production
EP2154177B1 (fr) Procédé de fabrication de polymères thermoplastiques contenant des particules d'hydroxyde de magnésium à grosse échelle et/ou nano-échelle, revêtues, désagglomérées et un dispositif correspondant
DE60110605T2 (de) Verbundmaterial mit polymermatrix
EP2607407B1 (fr) Procédé de fabrication de mélanges maîtres avec CNT dans du caoutchouc liquide à l'aide d'un appareil à trois cylindres
DE10348548A1 (de) Extrusionsverfahren zur Herstellung von zähmodifizierten und schichtsilikatverstärkten thermoplastischen Systemen
EP0627301B1 (fr) Matériau composite renforcé par des fibres de verre et son procédé de fabrication
EP2810977A1 (fr) Composition et procédé pour la préparation de composites polymer-CNT
EP3970933A1 (fr) Procédé de fabrication de granulés, granulés, procédé d'impression 3d, procédé de fabrication d'un composant céramique et composant céramique
WO2014009163A1 (fr) Composites fibreux polymères modifiés avec des nanotubes de carbone à simple paroi
AT515234A1 (de) Verfahren zur Herstellung von Carbonpartikeln
EP3049231A1 (fr) Procédé d'utilisation de résidus de coupe de structures fibreuses
DE102017209689A1 (de) Aggregate von Ionenleiter-Nanoteilchen und Verbundwerkstoffe, die Ionenleiter-Nanoteilchen enthalten
WO2012052476A1 (fr) Granulés et le procédé de fabrication

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20130408

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20131030