Classifications

• • 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
• • 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
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
• • 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
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/0066—Use of inorganic compounding ingredients
• • 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
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
  • C09D167/07—Unsaturated polyesters having carbon-to-carbon unsaturation having terminal carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
  • C09J167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
  • C09J167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
  • C09J167/07—Unsaturated polyesters having carbon-to-carbon unsaturation having terminal carbon-to-carbon unsaturated bonds
• • 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
  • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
  • C08J2367/06—Unsaturated polyesters
• • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/22—Expanded, porous or hollow particles
  • C08K7/24—Expanded, porous or hollow particles inorganic
• • 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
  • C08K9/02—Ingredients treated with inorganic substances

Definitions

• Reaction resin based on an unsaturated polyester, free-radically curable vinyl compounds and carbon nanotubes
• the invention relates to a curable molding compound reinforced with carbon nanotubes (hereinafter also referred to as carbon nanotubes or CNTs for short) comprising at least one unsaturated polyester resin (abbreviated to UP resin) and at least one free-radically polymerizable vinyl monomer, the carbon nanotubes containing the unsaturated polyester resin covalently linked.
• carbon nanotubes hereinafter also referred to as carbon nanotubes or CNTs for short
• UP resin unsaturated polyester resin
• free-radically polymerizable vinyl monomer the carbon nanotubes containing the unsaturated polyester resin covalently linked.
• UP resins are known per se. They have a large number of polymerizable double bonds, which serve mainly as a crosslinking component in the polymerization of the miscible with them vinyl monomer and thus cause the curing of the resin (Ullmann's Encyclopedia of Industrial Chemistry, 1992 V.A21).
• the UP resins are widely used as a molding compound, especially for various applications in the construction, construction and electrical industries.
• processing methods for example, pressing and injection molding methods are used.
• the subsequent curing takes place thermally usually under the action of organic peroxides as initiators which are added to the UP molding compositions already during production.
• the molding compositions are usually provided with reinforcing agents (glass fibers, mineral fillers such as talc and calcium carbonate, carbon fibers and various carbon blacks). It is frequently noted that the improvement of a material property (e.g., strength) is associated with a significant deterioration of one or more other properties (e.g., fracture toughness).
• a material property e.g., strength
• one or more other properties e.g., fracture toughness
• Carbon nanotubes which have an outstanding combination of mechanical and physical properties, occupy a special position in this group.
• Known carbon nanotubes with the perfect crystalline structure have a diameter in the nanometer range and reach a length of up to 1 mm and more. They have a very high modulus of elasticity up to about 1 TPa and a strength of 50-100 GPa.
• they are excellent electrical and thermal conductors. It is to be expected in principle that such nanotubes, when incorporated into thermoplastic and in thermoreactive polymeric compositions, can not only positively influence their mechanical profile, but also make the material electrically conductive. In the case of UP resins this has additional This option is of particular importance because these composites based on UP resins are often used in the electrical and electronics industry.
• the published patent application WO 2005 / 108485A2 describes the possible preparation of stable dispersions from unmodified CNTs in various polymer matrices (PVC, PVCC, PVDF, PMMA, PC, PA, PE, PS, PVA, PVAc, etc.).
• the CNTs are stabilized in the polymer matrices by addition of a copolymer containing acid, amino and anhydride groups and soluble in the above polymers.
• the ratio of CNTs to polymer [m (CNT) / m (copolymer)] is between 0.001% by weight and 1.0% by weight.
• the method also includes hydrophilic CNTs, i. those which carry hydrophilic groups.
• hydrophilic groups are introduced by irradiation with UV light, by plasma treatment and / or by Najibehariulu ⁇ g with a strong oxidizing agent in CNTs.
• the resin material includes epoxy resins, phenolic resins, melamine resins, furan resins and unsaturated polyester resins.
• the CNT-reinforced raw material is further processed by injection molding and compression molding.
• Ago et. al. investigated the preparation of composites based on CNTs and unsaturated polyesters in the magnetic field.
• the object of the present invention was to find ways of using CNTs in resins of unsaturated polyesters, which bring about a further significant improvement in the mechanical properties of the resulting molded articles with the lowest possible total concentration of the CNTs used. All previous studies have one thing in common: The SWCNTs or MWSNTs used as additives are present as a physical mixture in addition to the polymer matrix.
• the invention relates to a reaction resin based on an unsaturated polyester, one or more free-radically curable vinyl compounds and carbon nanotubes, characterized in that carbon nanotubes are covalently bonded to the unsaturated polyester.
• the invention likewise relates to the unsaturated polyester which has undergone at least one covalent bond with at least one CNT particle and in this form can be used as an essential component for the preparation of the polyester resin.
• Such products are generally prepared by melt or azeotropic condensation of polybasic, especially dibasic carboxylic acids and their esterifiable derivatives, in particular their anhydrides or alkyl esters, which are ester-linked with polyhydric, especially dihydric alcohols, and optionally contain additional radicals of monohydric carboxylic acids or monohydric alcohols, at least some of the starting materials have ethylenically unsaturated copolymerizable groups.
• Another part of the feedstocks are carbon nanotubes which are modified so that they carry at least one chemical moiety, which can enter into at least one ester bond with the other starting materials of the condensation, which connects the carbon nanotubes with the polyester backbone.
• reaction resin which is characterized in that the resin contains from 20 to 90% by weight, preferably from 30 to 80% by weight, particularly preferably from 50 to 75% by weight, of unsaturated polyester with covalently bound carbon nanotubes.
• ⁇ , ⁇ -unsaturated dicarboxylic acids or unsaturated diols are considered as carriers of the carbon-carbon double bonds, preference being given to ⁇ , ⁇ -unsaturated dicarboxylic acids.
• Citracon, fumaric, itaconic, mesaconic and maleic acid or their anhydrides or alkyl esters, preferably methyl esters, are particularly preferred as ⁇ , ⁇ -unsaturated acid components, with fumaric acid, maleic acid and their anhydride being very particularly preferred.
• acid components it is additionally possible to use aliphatic, cycloaliphatic and / or aromatic mono-, di- and / or polycarboxylic acids, such as sebacic acid, dodecanedioic acid,
• Adipic acid Adipic acid, azelaic acid, 1,4-cyclohexanedicarboxylic acid, hexahydrophthalic acid,
• Methylhexahydrophtalklare tetrahydrophthalic acid, phthalic, isophthalic, terphthalic, trimellitic and Promellit yarnren be used for the invention relevant condensation reaction.
• Acid components can be wholly or partly in the form of anhydrides or alkyl, preferably methyl esters.
• the modified carbon nanotubes are used, which carry at least one carboxyl group per carbon nanotube.
• such carbon nanotubes are understood to be single wall carbon nanotubes (SWCNTs) and multiwall carbon nanotubes (MWCNTs), preferably multiwall carbon nanotubes (MWCNTs), which are filled with a strong oxidizing agent, e.g. fuming nitric acid, are treated so that they can form carboxylic acid groups at the ends of the particles and at defect sites on the surface of the nanotubes.
• SWCNTs single wall carbon nanotubes
• MWCNTs multiwall carbon nanotubes
• MWCNTs multiwall carbon nanotubes
• Such modified carbon nanotubes per se which carry carboxylic acid groups and their production processes are basically known (H.Hu, R.C. Haddon, Chem. Phys Let., 2001, 304, 25).
• oxidizing agent for the functionalization of the carbon nanotubes preference is given to using an oxidizing agent from the series: nitric acid, hydrogen peroxide, ozone, potassium permanganate and sulfuric acid or a possible mixture of these agents. It is preferred Nitric acid or a mixture of nitric acid and sulfuric acid, more preferably nitric acid is used.
• reaction resin characterized in that the carbon nanotubes are functionalized with oxygen-containing groups of the series -OH and -COOH which at least partially form in the covalent bond to the polyester.
• reaction resin in which the proportion of functional groups -OH and / or -COOH of the carbon nanotubes is at least 5 mol%, preferably at least 10 mol%.
• Carbon nanotubes in the context of the invention are all single-walled or multi-walled carbon nanotubes of the cylinder type, scroll type or onion-like structure. Preference is given to using multi-walled carbon nanotubes of the cylinder type, scroll type or mixtures thereof.
• the carbon nanotubes are used in particular in an amount of 0.01 to 10 wt .-%, preferably 0.1 to 5 wt .-% based on the mixture of polymer and carbon nanotubes in the finished compound. In masterbatches, the concentration of carbon nanotubes may be greater.
• Carbon nanotubes having a ratio of length to outer diameter of greater than 5, preferably greater than 100, are particularly preferably used.
• the carbon nanotubes are particularly preferably used in the form of agglomerates, the agglomerates in particular having an average diameter in the range of 0.05 to 5 mm, preferably 0.1 to 2 mm, particularly preferably 0.2 to 1 mm.
• the carbon nanotubes to be used have particularly preferably essentially an average diameter of 3 to 100 nm, preferably 5 to 80 nm, particularly preferably 6 to 60 nm.
• CNT structures In contrast to the initially mentioned known CNTs of the scroll type with only one continuous or interrupted graphene layer, CNT structures have recently been found which consist of several graphene layers which are combined into a stack and rolled up (multiscroll type). These carbon nanotubes and carbon nanotube agglomerates thereof, for example, are the subject of the still unpublished German patent application with the official file reference 102007044031.8. Their content is hereby incorporated with respect to the CNT and its preparation to the disclosure of this application.
• This CNT structure is related to the carbon nanotubes of the simple scroll type comparatively like the structure of multi-walled cylindrical monocarbon nanotubes (cylindrical MWNT) to the structure of single-walled cylindrical carbon nanotubes (cylindrical SWNT).
• the individual graphene or graphite layers in these carbon nanotubes seen in cross-section, evidently run continuously from the center of the CNT to the outer edge without interruption. This can be z. B. allow an improved and faster intercalation of other materials in the tube framework, as more open edges than entry zone of the intercalates are available in the
• the methods known today for producing carbon nanotubes include arc, laser ablation and catalytic processes. In many of these processes, carbon black, amorphous carbon and high diameter fibers are by-produced. In the catalytic process, a distinction can be made between the deposition of supported catalyst particles and the deposition of in-situ formed metal centers with diameters in the nanometer range (so-called flow processes).
• CCVD Catalytic Carbon Vapor Deposition
• acetylene, methane, ethane, ethylene, butane, butene, butadiene, benzene and other carbon-containing reactants Preference is therefore given to using CNTs obtainable from catalytic processes.
• the catalysts usually include metals, metal oxides or decomposable or reducible metal components.
• the metals mentioned for the catalyst are Fe, Mo, Ni, V, Mn, Sn, Co, Cu and other subgroup elements.
• the individual metals usually have a tendency to promote the formation of carbon nanotubes, according to the prior art, high yields and low levels of amorphous carbons are advantageously achieved with those metal catalysts based on a combination of the above-mentioned metals. CNTs obtainable using mixed catalysts are therefore preferred to use.
• Particularly advantageous catalyst systems for the production of CNTs are based on combinations of metals or metal compounds containing two or more elements from the series Fe, Co, Mn, Mo and Ni.
• the formation of carbon nanotubes and the properties of the tubes formed are known to depend in complex manner on the metal component used as a catalyst or a combination of several metal components, the catalyst support material optionally used and the interaction between catalyst and support, the reactant gas and partial pressure, an admixture of hydrogen or other gases, the reaction temperature and the residence time or the reactor used.
• a particularly preferred method for the production of carbon nanotubes is known from WO 2006/050903 A2.
• carbon nanotubes of various structures are produced, which can be removed from the process predominantly as carbon nanotube powder.
• Carbon nanotubes more suitable for the invention are obtained by methods basically described in the following references:
• WO86 / 03455A1 describes the preparation of carbon filaments having a cylindrical structure with a constant diameter of 3.5 to 70 nm, an aspect ratio
• These fibrils consist of many continuous layers of ordered carbon atoms arranged concentrically around the cylindrical axis of the fibrils.
• These cylindrical nanotubes were prepared by a CVD process from carbonaceous compounds by means of a metal-containing particle at a temperature between 850 0 C and 1200 0 C.
• multi-walled carbon nanotubes in the form of nested seamless cylindrical nanotubes or also in the form of the described scroll or onion structures, today takes place commercially in large quantities, predominantly using catalytic processes. These processes usually show a higher yield than the above-mentioned arc and other processes and today are typically carried out on the kg scale (several hundred kilo / day worldwide).
• the multi-walled carbon nanotubes produced in this way are generally much cheaper than the single-walled nanotubes and are therefore used, for example. used as a performance-enhancing additive in other materials.
• Preferred alcohol components are polyhydric alcohols from the series: linear and / or branched aliphatic and / or cycloaliphatic and / or aromatic diols and / or polyols, such as ethylene glycol, 1,2- and / or 1,3-propanediol, 1,2- and / or 1,4-butanediol, 1,3-butylethylpropanediol, 1,3-methylpropanediol, 1,5-pentanediol, 1,6-hydroxyanediol, diethylene, triethylene, tetraethylene glycol, cyclohexanedimethanol, glycerol, neopentyl glycol, trimethylolethane, trimethylolpropane, Pentaerythritol, bisphenol A, B, C, F, neobornylene glycol, 1,4-benzyldimethanol and 1,4-benzyldiethanol, most
• the alcohol component is used in particular in a molar ratio of 0.8 to 1.5 to 1 to the sum of the acid components including the carbon nanotubes. Prefers the ratio of the alcohol component to the sum of the acid components is from 0.9 to 1.1 to 1.
• the unsaturated polyesters are prepared by melt condensation or condensation under azeotropic conditions at a temperature of 80 to 220 0 C from their above-mentioned starting components by continuous or batch processes by processes known in the art.
• At least one polymerizable vinyl monomer is usually added to the unsaturated polyester.
• styrene, D-methylstyrene, vinyltoluene, methyl methacrylate, vinyl acetate, diallyl phthalate and diallyl isophthalate are added.
• Particularly preferred is styrene.
• the proportion by weight of the vinyl monomer added is preferably from 5 to 70% of the total molding composition. Particularly preferred is a weight proportion of the added vinyl monomer of 30 to 60 wt.%.
• a further constituent of the curable molding composition is a polymerization initiator.
• a polymerization initiator Conventional above 50 0 C decomposing into peroxide peroxides such as diacyl peroxides, peroxydicarbonates, peroxyesters, perketals, hydroxyperoxides, ketoperoxides and dialkyl peroxides can be used as initiators. Also suitable are typical azo initiators.
• the new reaction resin can further components from the group: fillers, pigments, dispersants, stabilizers, lubricants and flame retardants; Liquid additives, in particular water or oils and / or gaseous fillers, in particular air, nitrogen or carbon dioxide are admixed.
• dyes and pigments can be added in amounts of from 0 to 300% by weight.
• Liquid additives such as water or oils, and / or gaseous fillers, such as air, nitrogen, carbon dioxide, are optionally also used.
• thermoplastic polymers such as polystyrene, polymethyl methacrylate, polyvinyl acetate, saturated polyesters and thermoplastic polyurethanes are preferably added in amounts of from 5 to 50% by weight (based on the total UP resin).
• Oxides and hydroxides of magnesium, zinc or calcium may optionally be added as thickening agents of the molding composition.
• thickening agents are isocyanates, optionally in combination with amine.
• Other substances that can be added to the molding composition are inhibitors, lubricants, accelerators, mold release agents and flame retardants.
• inorganic and / or organic fibers of glass, cellulose, polyethylene, polyamide or also carbon fibers in the form of short fibers or long fibers, webs, fabrics or mats can be presented to the molding composition (reaction resin) or incorporated during processing.
• the prefabricated molding compound (reaction resin) is brought into a mold by filling, pressing or injection molding and cured at temperatures between 60 and 200 0 C.
• the preformed molding compounds can be applied and cured from reactive resin as coatings, fillers, adhesives or as foams.
• Another object of the invention is a process for preparing the inventive curable molding compositions of unsaturated polyester resin (UP resin), which includes the covalently bonded modified carbon nanotubes.
• UP resin unsaturated polyester resin
• the novel process for preparing the novel reaction resin is characterized in that carbon nanotubes are functionalized by one or more carboxylic acid or alcohol groups by oxidation, the functionalized carbon nanotubes being dispersed in one or more polyhydric alcohols, especially in a diol, with an unsaturated acid component in particular Maleic acid, fumaric acid or maleic anhydride, mixed and condensed to form an unsaturated polyester, wherein the functionalized carbon nanotubes are covalently bonded and this polyester one or more vinyl monomers selected from the series: styrene, D-methyl styrene, methyl methacrylate, vinyl toluene, vinyl acetate, diallyl phthalate and diallyl isophthalate and a radical initiator added.
• the new method consists in particular of the following steps described below:
• step 1 chemical modification of the carbon nanotubes (step 1), which serves to bring to the surface of the particles the carboxylic acid groups.
• Carbon nanotubes are carried out at elevated temperature in an oxidizing acid, e.g.
• step 2 Preparation of the unsaturated polyester by the condensation reaction of a reaction mixture (step 2) consisting of the modified in step 1 CNTs dispersed in a diol, and an unsaturated dicarboxylic acid or its anhydride, which serves to covalently connect the carbon nanotubes with the unsaturated polyester ,
• step 2 a reaction mixture
• step 2 consisting of the modified in step 1 CNTs dispersed in a diol, and an unsaturated dicarboxylic acid or its anhydride, which serves to covalently connect the carbon nanotubes with the unsaturated polyester
• the CNTs modified in step 1 in an amount of in particular from 0.001 to 1% by weight, based on the total weight of the reaction mixture, are e.g. with an ultrasonic disintegrator (e.g., Branson) very finely suspended in a diol.
• the sonication proceeds in particular in several steps, the breaks serving for the cooling of the dispersion.
• the resulting stable suspension is at a deficit, in particular a 5%
• Subcutaneous anhydride of an unsaturated dibasic carboxylic acid added and rinsed in particular at 80 0 C with nitrogen. After up to 16h precondensation eg at 100 0 C is the
• the so-formed nanotube polyester reaction product is in particular cooled down to 140 0 C and in a weight ratio of preferably 1: 2 to 2: 1 with a vinyl monomer added (Step 3). To ensure complete mixing of the components, the reaction mixture is stirred, in particular for 1 min at 14O 0 C and then cooled to room temperature.
• the molding material is then added to form the reaction resin with a peroxide initiator and optionally poured into molds.
• the crosslinking of the resin may be carried out at elevated temperature, e.g. at 80 ° C follow.
• comparative samples were prepared after basically the same measures, which contain unmodified CNTs or no CNTs.
• a particularly preferred embodiment of the invention are unsaturated polyesters with covalently bound carbon nanotubes and the resulting curable molding compositions which are prepared from the following components by the method described above, wherein
• DBPO Dibenzoyl peroxide
• the suspension thus formed was transferred as completely as possible to a two-necked flask with septum, stirrer, water separator, reflux condenser and bubble counter. Based on the mass of the suspension, a 5% molar deficit of the anhydride component, in this case maleic anhydride, was added thereto.
• the suspension was heated to 8O 0 C with stirring.
• the suspension was stirred for 3 h at this temperature. Nitrogen was passed through the suspension for one hour during this time. It was then heated to 100 0 C and stirred for 18 h. It was then heated to 19O 0 C and stirred for a further 6 h. During this time, 1-1.2 ml of water separated from the water separator. The suspension could now be cooled. It is recommended to store in the freezer.
• the polyester was heated to 140 0 C. At this temperature, distilled styrene (in the molar ratio 1: 1 to the anhydride component) was added with vigorous stirring. The mixture was stirred for 1 minute at this temperature and then cooled to room temperature as quickly as possible. The dispersion is then liquid enough to be further processed. It was admixed with 4% by weight (based on the total mass of the suspension incl. Vinyl component) of dibenzoyl peroxide, stirred briefly and poured into Teflon molds to produce the test specimens. The molds were placed in a desiccator, the closed rinsed for 3 minutes with nitrogen and then H was placed in the oven at 80 0 C for 16 h. The finished specimens were lifted by gentle lifting with a spatula and removed from the Teflon molds. Table 1:
• MWCNTs MWCNTs Diol Comp Acid Anh. Styrene DBPO
• Example 2 Analogously to Example 1, a sample was prepared which incorporated the non-modified Köhlenstoffhanoröchen Baytubes C 150 P incorporated.
• the composition can be taken from Table 2.
• the tensile yield strength was tested on the tensile drawing machine from Zwick based on DIN 53504. (Force transducer 500 N, Wegaufhehmer: traverse, temperature: room temperature, determination of the film dimensions with caliper). The results are shown in Tab.3.
• the unsaturated polyester resins with modified CNT show a significantly higher tensile strength in the standard test.
• the bending test shows a comparatively much higher flexural strength of unsaturated polyester resins with modified CNT as additive to unsaturated polyester resins with unmodified CNT as additive.

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