EP2523902A1 - Verfahren zur herstellung von hydroxyalkylestergruppen aufweisenden kohlenstoffnanoröhren und diese kohlenstoffnanoröhren aufweisende werkstoffe und dispersionen - Google Patents
Verfahren zur herstellung von hydroxyalkylestergruppen aufweisenden kohlenstoffnanoröhren und diese kohlenstoffnanoröhren aufweisende werkstoffe und dispersionenInfo
- Publication number
- EP2523902A1 EP2523902A1 EP11700254A EP11700254A EP2523902A1 EP 2523902 A1 EP2523902 A1 EP 2523902A1 EP 11700254 A EP11700254 A EP 11700254A EP 11700254 A EP11700254 A EP 11700254A EP 2523902 A1 EP2523902 A1 EP 2523902A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- carbon nanotubes
- dispersion
- reaction
- process according
- polyisocyanate
- 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- Withdrawn
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B1/00—Nanostructures formed by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
- B82B1/008—Nanostructures not provided for in groups B82B1/001 - B82B1/007
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
- B82B3/0009—Forming specific nanostructures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
- B82B3/0061—Methods for manipulating nanostructures
-
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
- C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents
Definitions
- the present invention relates to a process for the preparation of hydroxyalkyl ester-containing carbon nanotubes, a process for the preparation of these carbon nanotubes having dispersions, more preferably dispersions in polyols and / or polyisocyanates, wherein optionally a portion of the carbon nanotubes may be covalently bound to the dispersant polyisocyanate, a process for the production of these carbon nanotubes having materials, more preferably polyurethane polymers, and carbon nanotubes having materials, optionally a part of the carbon nanotubes is covalently bonded to the material, in particular polyurethane polymer.
- Carbon nanotubes are known for their exceptional properties. For example, their strength is about 100 times that of steel, their thermal conductivity is about twice 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 , However, these structural characteristics are only accessible at the molecular level if it is possible to homogeneously distribute carbon nanotubes and to produce the largest possible contact between the tubes and the medium, ie to make them compatible with the medium and thus stable dispersible.
- Chemical functionalization of carbon nanotubes or carbon fibers can, among other things, improve their dispersibility.
- a review article by N. Tsubokawa (Polymer Journal 2005, 37, 637-655) lists a variety of possibilities for such functionalization.
- complex chemical reactions such as ligand exchange reactions on 1, 1 '-Dicarboxyferrocen, the living radical polymerization with styrene and the reaction with azides, the well-known in this field oxidation of carbon nanotubes with HNO 3 and corresponding modifications based on it was called.
- Tsubokawa reports three possibilities of subsequent chemistry after the oxidative introduction of carboxyl groups.
- the first variant is the reaction of the carboxyl groups of the carbon nanotubes with coupling reagents such as the known from peptide chemistry dicyclohexylcarbodiimide with subsequent reaction with a nucleophile.
- this method requires the use of an expensive coupling reagent and, depending on the coupling reagent used, produces a poorly soluble urea as a by-product.
- the second variant of this is the activation of the acid groups by thionyl chloride, followed by further reaction with a nucleophile.
- a disadvantage of this is the released by the use of thionyl chloride S0 2 and HCl.
- HCl is released again. This represents a troublesome by-product for later use of such functionalized carbon nanotubes in dispersions and would affect chemical reactions.
- VGCF vapor-grown carbon fibers
- an anionic co-polymerization of epoxides and acid anhydrides takes place by alterniernde ring opening.
- the synthesis sequence is initiated by the deprotonation of the carboxyl group by KOH.
- the polymerization must be carried out in the presence of crown ethers, which makes this chemistry very expensive and involves waste problems.
- the carboxylate group of the carbon fiber is reacted with styrene oxide and phthalic anhydride. From a table it can be seen that the reaction of the carboxylate group with styrene oxide alone leads to no reaction.
- polyester-polyol synthesis The functionalization of carboxyl groups in the polyester-polyol synthesis is disclosed in DE 36 13 875 AI.
- polyester polyols having an acid number of less than 1 a hydroxyl number of about 20 to about 400 and a functionality of preferably 2 to 3 polycarboxylic acids and / or their anhydrides and polyhydric alcohols are condensed.
- tertiary amine is selected from the group consisting of N-methylimidazole, diazabicyclo [2,2,2] octane, diazabicyclo [5,4,0] undec-7-ene and pentamethylene-diethylenetriamine.
- the catalyst is expediently used in an amount of 0.001 to 1.0% by weight, based on the polycondensate weight.
- alkoxylated at temperatures of 100 ° C to 170 ° C and under a pressure of 1 to 10 bar.
- the object was to provide an improved process for the preparation of functionalized carbon nanotubes in which, based on carboxyl groups on the surface, hydroxyalkyl ester groups with a distance of at least 2 carbon atoms between the ester function and the free OH group are available.
- the invention relates to a process for the preparation of hydroxyalkyl ester-containing carbon nanotubes comprising the steps:
- step (b) reaction of the carbon nanotubes of step (a) with one or more epoxides
- R 1 and R 2 independently of one another are hydrogen, an alkyl radical or aryl radical and the epoxides are gaseous during the reaction.
- step (a) The provision of carbon nanotubes in step (a) is preferably carried out as a solid.
- alkyl in the context of this invention includes substituents from the group n-alkyl, branched alkyl and cycloalkyl.
- aryl in the context of this invention includes substituents from the group mononuclear carbo- and heteroaryl and polynuclear carbo- and heteroaryl.
- the economic synthesis route via the gas phase is the economic synthesis route via the gas phase.
- the activation as acid chloride is not necessary, so that this step carried out in the prior art is omitted.
- the starting material and the product are solids which can be introduced universally into any medium without further processing.
- the reaction of gaseous reactants with the oxidized carbon nanotubes presented as solid in the process according to the invention makes superfluous work-up steps superfluous.
- the functionalized carbon nanotubes must be isolated from a liquid reaction medium or solvent after the reaction is very expensive. The large surface of carbon nanotubes makes it difficult to completely remove the excess medium or solvent, which is why traces of this adsorbed material adhere.
- the reaction of the oxidized carbon nanotubes via the gas phase is therefore particularly advantageous, since in this case such impurities are avoided and the solid product can be used universally in any medium.
- the process according to the invention is an addition reaction which, with very small amounts, also exists in gaseous form during the reaction Catalyst manages. Esterification via acid chlorides (prior art) releases stoichiometric amounts of hydrogen chloride, which must be removed to prevent subsequent reactions.
- the process according to the invention can also be carried out uncatalyzed.
- the inventively functionalized carbon nanotubes can directly into a opposite
- the carbon nanotubes having carboxyl groups covalently bonded to the surface and used as starting material can be obtained from unfunctionalized carbon nanotubes by means of oxidative processes, such as the HNO 3 process.
- the content of surface carboxyl groups can be determined by conductometric titration and expressed in mmol of carboxyl groups per gram of carbon nanotubes.
- the content may preferably be> 0.01 mmol / g to ⁇ 50 mmol / g, more preferably> 0.1 mmol / g to ⁇ 10 mmol / g.
- the gaseous epoxide in step (b), can advantageously be used in a large excess over the carboxyl groups on the surface of the carbon nanotubes.
- the reaction pressure absolute
- the reaction temperature may preferably be between> 50 ° C and ⁇ 200 ° C, more preferably between> 80 ° C and ⁇ 150 ° C.
- the reaction may preferably be carried out under inert gas (e.g., nitrogen, argon, helium).
- inert gas e.g., nitrogen, argon, helium
- Carbon nanotubes in step (b) in the presence of a gaseous tertiary amine carried out as a catalyst is particularly preferably N, N-dimethylethylamine.
- R 1 and R 2 independently of one another are hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl or phenyl or together for - (CH 2 ) 4-
- the epoxide in step (b) is a terminal alkylene oxide.
- alkylene oxides are ethylene oxide, propylene oxide, 1, 2-butylene oxide and 2,3-butylene oxide. Particularly preferred are ethylene oxide and propylene oxide.
- the carbon nanotubes in step (a) are selected from the group consisting of single-walled carbon nanotubes, multi-walled carbon nanotubes, multi-walled carbon nanotubes of the cylinder-type, scroll-type, multiscroll-type and / or onion-like structure.
- Carbon nanotube structures consisting of several graphite layers, which are combined into a stack and rolled up, can likewise be used. This is referred to as carbon nanotubes from the multiscroll Type. (Note: These are already covered in the previous paragraph! These carbon nanotubes are described in DE 10 2007 044031 AI.
- the hydroxyalkyl ester-containing carbon nanotubes produced according to the invention preferably have a diameter of from> 3 nm to ⁇ 100 nm, particularly preferably from> 4 nm to ⁇ 80 nm, very particularly preferably from> 5 nm to ⁇ 60 nm.
- the diameter here refers to the mean diameter of the carbon nanotubes.
- the length of the carbon nanotubes is not limited. It may preferably be in a range from> 1 ⁇ to ⁇ 100 ⁇ and particularly preferably from> 10 ⁇ to ⁇ 30 ⁇ .
- the carbon nanotubes having free OH groups and produced by the process according to the invention can, if required, be further chemically reacted at the hydroxyl groups.
- the content of free OH groups is preferably> 0.01 mmol / g to ⁇ 50 mmol / g, preferably> 0.1 mmol / g to ⁇ 10 mmol / g.
- Suitable solid-state matrices are, for example, inorganic polymers, such as ceramics, or polymeric inorganic oxides, such as, for example, aluminum oxides. Silicon carbides, silicon nitrides and boron nitrides and mixtures thereof are also suitable.
- suitable as a solid matrix for the homogeneous distribution of the carbon nanotubes according to the invention are metals such as, for example, aluminum, magnesium, lead, copper, tungsten, titanium, niobium, hafnium, vanadium, silver and mixtures thereof.
- Another object of the present invention is the use of the present invention, hydroxyalkyl ester-containing carbon nanotubes in various liquid or meltable media for the preparation of dispersions.
- the functionalized carbon nanotubes according to the invention can be covalently bound in the medium / in the matrix. It is also possible that the carbon nanotubes according to the invention are present in the medium / in the matrix without covalent bonding.
- the usual dispersing methods for incorporation are well known. The incorporation may e.g. by the application of high shear forces by a rotor-stator system, jet disperser, extruder or calender, by grinding processes by means of ball and / or bead mill or by the application of cavitation forces by ultrasound.
- Useful liquid or meltable media are, for example, raw materials for organic polymers or thermoplastic polymers or meltable thermoplastic polymers. Preference is given, for example, to polyamides, polycarbonates, polyesters, polyethers, polyimides, polyphenylenes, polysulfones, polyurethanes, epoxy resins, rubbers or mixtures thereof. Particularly preferred are dispersions in polyurethane (PUR) raw materials (as a medium). Suitable PUR raw materials are both polyols and polyisocyanates.
- the concentration of the carbon nanotubes in a dispersion is preferably in a range from> 0.01% by weight to ⁇ 10% by weight, particularly preferably from> 0.1% by weight to ⁇ 5% by weight.
- the dispersions can be obtained by using a stirrer with a rotor / stator system at high speeds, such as between> 2000 rpm and ⁇ 30,000 rpm. In addition, ultrasound can act on the dispersion.
- Suitable polyols are basically the polyols customary in polyurethane chemistry, for example polyether, polyacrylate, polycarbonate, polycaprolactone and polyester polyols. These polyols are described in "Ullmanns Enzyklopadie der ischen Chemie", 4th Edition, Volume 19, p.
- Suitable polyisocyanates are aromatic, araliphatic, aliphatic or cycloaliphatic polyisocyanates having an NCO functionality of> 2.
- suitable polyisocyanates are 1,4-butylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,2,4- and / or 2,4,4-trimethylhexamethylene diisocyanate, the isomeric bis ( isocyanatocyclohexyl) methanes or mixtures thereof of any isomer content, 1,4-cyclohexylene diisocyanate, 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), 1,5-naphthylene diisocyanate, 2,2'-diisocyanate.
- HDI 1,6-hexamethylene diisocyanate
- IPDI isophorone diisocyanate
- MDI 2,4'- and / or 4,4'-diphenylmethane diisocyanate
- TMXDI 1, 3 and / or 1,4-bis (2-isocyanato-prop-2-yl) -benzene
- XDI 1,3-bis (isocyanatomethyl) benzene
- alkyl 2,6-diisocyanatohexanoates lysine diisocyanates
- modified or diisocyanates with a uretdione, isocyanurate, urethane, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structure and non-modified polyisocyanate with more than 2 NCO groups per molecule such as 4-isocyanatomethyl-l, 8-octane diisocyanate (nonantriisocyanate) or triphenylmethane-4,4 ', 4 "-triisocyanat be used.
- NCO-terminated prepolymers of the abovementioned polyisocyanates and polyols are used as the polyisocyanate component.
- the carbon nanotubes produced according to the invention are particularly preferably dispersed in polyisocyanates, the dispersion is then optionally heated to temperatures between 60 ° and 150 ° C. using a catalyst, the terminal free hydroxyl groups of the carbon nanotubes reacting at least partially with the polyisocyanate, and then cooled. If necessary, additional dispersion can be carried out after the reaction.
- hydrocarbon-boron-containing hydroxyalkyl ester groups produced according to the invention can be used in the synthesis of polyurethane polymers and thus incorporated covalently into the polymer matrix. Therefore, a further subject of the present invention is a process for the preparation of functionalized carbon nanotubes according to the invention comprising polyurethane polymers, comprising the steps:
- inventively functionalized carbon nanotubes may preferably be present in both components (polyol and polyisocyanate), in which case these two dispersions are reacted with each other, optionally together with additional polyisocyanate and / or polyol.
- the molar ratio of NCO groups of the polyisocyanate to NCO-reactive OH groups is preferably> 0.90: 1 to ⁇ 4.50: 1, more preferably> 0.95: 1 to ⁇ 3.50: 1, very particularly preferably> 0.95: 1 to ⁇ 1.5: 1.
- the polyol in step (a) or (b) is preferably a polyether polyol and / or a polyester polyol.
- Preferred polyether polyols have hydroxyl numbers of> 25 mg KOH / g to ⁇ 550 mg KOH / g, more preferably from> 100 mg KOH / g to ⁇ 520 mg KOH / g.
- Preferred polyester polyols have hydroxyl numbers of> 100 mg KOH / g to ⁇ 550 mg KOH / g, more preferably from> 200 mg KOH / g to ⁇ 500 mg KOH / g.
- the stated polyols preferably have molecular weights in the range from> 250 to ⁇ 5000 g / mol, preferably> 400 to ⁇ 3500 g / mol and a functionality between> 1.8 and ⁇ 6, preferably between> 1.95 and ⁇ 3.5 on.
- the polyisocyanate in step (a) or (b) is preferably a polyisocyanate based on diphenylmethane diisocyanate (MDI).
- MDI diphenylmethane diisocyanate
- the fact that the polyisocyanate is based on MDI means that it is either monomeric, polynuclear and / or polymeric MDI. For example, it may have an NCO content of> 25% by weight to ⁇ 35% by weight. The NCO content may also be in a range from> 29% by weight to> 31% by weight.
- the proportion of carbon nanotubes in the polyurethane polymer according to the invention is preferably> 0.01% by weight to ⁇ 10% by weight, more preferably> 0.1% by weight to ⁇ 5% by weight). Such a small proportion of the inventively functionalized carbon nanotubes in the polyurethane already leads to a noticeable reinforcement of the polymer matrix.
- the polyurethane polymer according to the invention may for example have a modulus of elasticity of> 1 N / mm 2 to ⁇ 10000 N / mm 2 .
- modulus of elasticity of> 10 N / mm 2 to ⁇ 5000 N / mm 2 , preferably from> 100 N / mm 2 to ⁇ 1000 N / mm 2 .
- the modulus of elasticity is determined as a slope at the operating point of the stress-strain curve from the tensile test according to DIN 53 504 with vanishing deformation between 0.025% and 0.05% elongation.
- Desmophen® VP.PU 22HS51 bifunctional polyether polyol with an OH number of 1 12 mg
- Desmodur® CD-S modified polyisocyanate based on 4,4'-diphenylmethane diisocyanate, and an NCO content of 29.5% (Bayer MaterialScience AG)
- DABCO 33-LV amine catalyst; 1,4-diazabicyclo [2.2.2] octane; 33% solution in
- Niax AI amine catalyst; ether bis (2-dimethylaminoethyl); 70% solution in
- Oxidized CNTs Baytubes® oxidized carbon nanotubes (oxCNT)
- the viscosities of the dispersions prepared were determined using a Physica MCR 51 viscometer from Anton Paar and the corresponding electrical conductivities using a Type 703 conductivity meter from Knick using a 4-pole measuring cell.
- the stated volume resistivities were determined according to the standard ASTM D 257.
- the method according to the HN0 3 oxidized Baytubes C150P ® had a carboxyl group concentration of 0.23 mmol / g (conductometric titration).
- the alkoxylation of the oxidized Baytubes ® was carried out via the reaction with gaseous epoxides in a steel pressure reaction under amine catalysis or uncatalyzed over a longer period with a higher excess of the epoxide.
- the alkoxylated carbon nanotubes obtained in this way were initially introduced in the polyol in the desired concentration directly before the reaction with the isocyanate and were treated with a rotor / stator
- the dispersion thus obtained was briefly degassed both before and after the addition of the catalyst at reduced pressure.
- the isocyanate was stirred briefly with the dispersion.
- This reaction mixture was poured into a metal folding mold and annealed at 70 ° C.
- the carbon nanotube-containing polyurethane elastomers thus obtained were examined for hardness and tensile strength and electronic properties.
- Example 3 (Dispersion, 1% by weight of CNT1, dispersion 1A)
- Example 4 (Dispersion, 3% by weight of CNT1, dispersion 1B) In a 150 ml beaker, 3 g of CNT1 were admixed with 97 g of Desmophen® VP.PU 22HS51.
- This mixture was stirred under ice-water cooling for 10 minutes at 24000 rpm with a rotor Stator system (T 1 8 basic ULTRA-TURRAX®, IKA Werke GmbH & Co. KG, Staufen, Germany) sheared and then also with ice-water cooling with ultrasound (Probe Sonicator HD 3200, B ⁇ NDELEST electronic GmbH & Co. KG, Berlin, Germany) up to a total energy input of 240 kJ. The resulting dispersion 1B was used immediately for further reaction with an isocyanate.
- a rotor Stator system T 1 8 basic ULTRA-TURRAX®, IKA Werke GmbH & Co. KG, Staufen, Germany
- ultrasound Probe Sonicator HD 3200, B ⁇ NDELEST electronic GmbH & Co. KG, Berlin, Germany
- Example 5 (Dispersion, 1% by weight of CNT2, dispersion 2A)
- Example 6 (Dispersion, 3% by weight of CNT2, dispersion 2B) 3.0 g of CNT2 were admixed with 97 g of Desmophen® VP.PU 22HS51 in a 150 ml beaker. This mixture was sheared under ice-water cooling for 10 minutes at 24000 U / min with a rotor / stator system (T 1 8 basic ULTRA-TURRAX®, IKA Werke GmbH & Co. KG, Staufen, Germany) and then also under Ice water cooling with ultrasound (sample Sonicator HD 3200, BANDELIN electronic GmbH & Co. KG, Berlin, Germany) treated up to a total energy input of 240 kJ. The dispersion 2B thus obtained was used directly for the further reaction with an isocyanate.
- a rotor / stator system T 1 8 basic ULTRA-TURRAX®, IKA Werke GmbH & Co. KG, Staufen, Germany
- ultrasound sample Sonicator HD 3200,
- Example 7 (dispersion, 1% by weight of CNT3, dispersion 3A)
- Example 8 (dispersion, 3% by weight of CNT3, dispersion 3B)
- CNT3 Boytubes® C150P
- 97 g Desmophen® VP.PU 22HS51 This mixture was sheared under ice-water cooling for 10 minutes at 24,000 rpm with a rotor / stator system (T 18 basic ULTRA-TURRAX®, IKA Werke GmbH & Co. KG, Staufen, Germany) and then also under ice-water cooling treated with ultrasound (Probe Sonicator HD 3200, B ⁇ NDELEST electronic GmbH & Co. KG, Berlin, Germany) up to a total energy input of 240 kJ.
- the resulting dispersion 3B was used directly for further reaction with an isocyanate.
- the polyols or carbon nanotubes containing polyol dispersions (1A, 1B, 2A, 2B, 3A or 3B) were placed in a 11-Sch.tsch pot and briefly degassed both before and after the catalyst addition.
- the isocyanate was briefly stirred in at room temperature, the reaction mixture poured into a metal folding mold and then subjected to a tempering cycle.
- compositions PUR1 to PUR8 are shown in detail in the table below.
- Elastomer PUR3 has a 3.6% greater Shore A hardness, a 15.1% higher tensile strength, and a 33.9% higher elastic modulus.
- the PUR7 elastomer with the nonfunctionalized Baytubes® C150P carbon nanotubes showed no increase in Shore hardness, a marginal reduction in tensile strength and a reduction in the modulus of elasticity compared with unfilled PUR1 elastomer.
- the reinforcing effect of the functionalized carbon nanotubes according to the invention was even more pronounced.
- the elastomer PUR4 compared to the unfilled elastomer PUR2 had a 81.5% higher modulus of elasticity.
- CNT2 carbon nanotubes were alkoxylated in the absence of the amine catalyst.
- the dispersions 2A and 2B are thus characterized by the lower increase in viscosity compared to the non-functionalized carbon nanotubes (3A and 3B) with only a slightly reduced electrical conductivity.
- the type 2A and 2B dispersions have ideal conditions to positively influence both mechanical and electronic properties of polyurethanes made therefrom.
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- Crystallography & Structural Chemistry (AREA)
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- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Carbon And Carbon Compounds (AREA)
Applications Claiming Priority (2)
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DE102010004806 | 2010-01-16 | ||
PCT/EP2011/050231 WO2011086049A1 (de) | 2010-01-16 | 2011-01-10 | Verfahren zur herstellung von hydroxyalkylestergruppen aufweisenden kohlenstoffnanoröhren und diese kohlenstoffnanoröhren aufweisende werkstoffe und dispersionen |
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US (1) | US20120292563A1 (zh) |
EP (1) | EP2523902A1 (zh) |
JP (1) | JP2013517198A (zh) |
KR (1) | KR20120118009A (zh) |
CN (1) | CN102822091A (zh) |
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US9034426B2 (en) * | 2011-11-18 | 2015-05-19 | Tuskegee University | Nanostructured thermoplastic polyimide films |
WO2013163413A1 (en) | 2012-04-26 | 2013-10-31 | Brewer Science Inc. | Multifunctional alcohol dispersions of carbon nanotubes |
CN104508056B (zh) * | 2012-06-21 | 2017-03-29 | 特斯拉纳米涂料有限公司 | 可调的材料 |
CN106009677B (zh) * | 2016-07-18 | 2018-06-26 | 深圳市尚智工程技术咨询有限公司 | 一种纳米导电橡胶传感单元及其制备方法 |
CN106753429A (zh) * | 2016-12-30 | 2017-05-31 | 深圳市华星光电技术有限公司 | 一种用于蓝相液晶中的碳点材料及蓝相液晶组合物 |
CN115433452B (zh) * | 2022-10-08 | 2023-10-31 | 盛鼎高新材料有限公司 | 高硬度热塑性聚氨酯弹性体及其制备方法 |
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DE3613875A1 (de) | 1986-04-24 | 1987-10-29 | Basf Ag | Verfahren zur herstellung von polyester-polyolen |
DE102007044031A1 (de) | 2007-09-14 | 2009-03-19 | Bayer Materialscience Ag | Kohlenstoffnanoröhrchenpulver, Kohlenstoffnanoröhrchen und Verfahren zu ihrer Herstellung |
EP2239290A1 (de) * | 2009-04-09 | 2010-10-13 | Bayer MaterialScience AG | Hydroxygruppen umfassende Kohlenstoffnanoröhren, Verfahren zu deren Herstellung und diese Kohlenstoffnanoröhren umfassende Polyurethanpolymere |
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2011
- 2011-01-10 WO PCT/EP2011/050231 patent/WO2011086049A1/de active Application Filing
- 2011-01-10 CA CA2787073A patent/CA2787073A1/en not_active Abandoned
- 2011-01-10 CN CN2011800062892A patent/CN102822091A/zh active Pending
- 2011-01-10 EP EP11700254A patent/EP2523902A1/de not_active Withdrawn
- 2011-01-10 KR KR1020127018314A patent/KR20120118009A/ko not_active Application Discontinuation
- 2011-01-10 US US13/522,438 patent/US20120292563A1/en not_active Abandoned
- 2011-01-10 JP JP2012548397A patent/JP2013517198A/ja active Pending
Non-Patent Citations (1)
Title |
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See references of WO2011086049A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO2011086049A1 (de) | 2011-07-21 |
US20120292563A1 (en) | 2012-11-22 |
KR20120118009A (ko) | 2012-10-25 |
JP2013517198A (ja) | 2013-05-16 |
CA2787073A1 (en) | 2011-07-21 |
CN102822091A (zh) | 2012-12-12 |
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