EP2920220A1 - Procédé de fabrication de pièces composites - Google Patents

Procédé de fabrication de pièces composites

Info

Publication number
EP2920220A1
EP2920220A1 EP13789303.8A EP13789303A EP2920220A1 EP 2920220 A1 EP2920220 A1 EP 2920220A1 EP 13789303 A EP13789303 A EP 13789303A EP 2920220 A1 EP2920220 A1 EP 2920220A1
Authority
EP
European Patent Office
Prior art keywords
polyurethane
reaction mixture
core
overpressure
polyisocyanurate reaction
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Withdrawn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
EP13789303.8A
Other languages
German (de)
English (en)
Inventor
Dirk Passmann
Klaus Franken
Stefan Lindner
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.)
Covestro Deutschland AG
Original Assignee
Bayer MaterialScience AG
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 MaterialScience AG filed Critical Bayer MaterialScience AG
Priority to EP13789303.8A priority Critical patent/EP2920220A1/fr
Publication of EP2920220A1 publication Critical patent/EP2920220A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/20—Heterocyclic amines; Salts thereof
    • C08G18/2045—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings
    • C08G18/2063—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings having two nitrogen atoms in the condensed ring system
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
    • F03D—WIND MOTORS
    • F03D1/00—Wind motors with rotation axis substantially parallel to the air flow entering the rotor 
    • F03D1/06—Rotors
    • F03D1/065—Rotors characterised by their construction elements
    • F03D1/0675—Rotors characterised by their construction elements of the blades
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2049/00—Use of polyacetylene or cyanic ester resins, i.e. polymers having one or more carbon-to-carbon triple bonds or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2120/00—Compositions for reaction injection moulding processes
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05B—INDEXING SCHEME RELATING TO WIND, SPRING, WEIGHT, INERTIA OR LIKE MOTORS, TO MACHINES OR ENGINES FOR LIQUIDS COVERED BY SUBCLASSES F03B, F03D AND F03G
    • F05B2230/00—Manufacture
    • F05B2230/20—Manufacture essentially without removing material
    • F05B2230/21—Manufacture essentially without removing material by casting
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05B—INDEXING SCHEME RELATING TO WIND, SPRING, WEIGHT, INERTIA OR LIKE MOTORS, TO MACHINES OR ENGINES FOR LIQUIDS COVERED BY SUBCLASSES F03B, F03D AND F03G
    • F05B2280/00—Materials; Properties thereof
    • F05B2280/40—Organic materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/70—Wind energy
    • Y02E10/72—Wind turbines with rotation axis in wind direction

Definitions

  • the present invention relates to a method for the production of composite components, comprising the steps of providing a molded core and contacting at least a portion of the molded core with a polyurethane / polyisocyanurate reaction mixture, wherein during the contacting, at least temporarily, a negative pressure pl at at least the outside of the shaped body core is applied.
  • PUR polyurethane
  • PIR polyisocyanurate
  • the ratio of the number of isocyanate groups to the number of isocyanate-reactive groups is preferably between 0.9 and 1.5.
  • the examples were carried out with a ratio of the number of isocyanate groups to the number of isocyanate-reactive groups of about 1.02.
  • a disadvantage of the method is that the viscosity of the mixture is higher and thereby makes it difficult to produce the plastic layer provided with fiber.
  • WO 201 1/081622 A1 describes polyurethane compositions for composite structures.
  • the composite structures can be used for wind turbine rotor blades.
  • the OH / NCO ratio is at least 1, i. There are at least as many OH groups as NCO groups.
  • a disadvantage of the method is that the viscosity is relatively high and the processing period is very short, which makes the filling of large components very difficult.
  • PUR / PIR in contrast to the usual resins such as EP or UP, has the property of foaming on contact with water. This is a disadvantage at first because the materials to be used for a composite core such as balsa wood and the like inevitably involve water and thus would be dry. This is associated with a higher logistic effort, drying costs, etc. This phenomenon is further enhanced by the use of a vacuum during infusion, when a resin injection method such as RTM (resin transfer molding) is performed. However, a vacuum is needed to remove trapped gases prior to infusion or to optimally position a gel buildup.
  • the present invention has the object to provide a method for producing composite components, in which polyurethane resins can be used together with moisture-containing materials.
  • the object is achieved by a method for producing composite components, comprising the steps:
  • the inventive method can be used for the production of composite components, in which a molded core is firmly connected to a resin.
  • the resin here is the polyurethane / polyisocyanurate reaction mixture.
  • fiber composite is made of fiber and resin, and that the core of the molded article is merely for molding without bonding with the resin.
  • fibers or textile surface elements are arranged on a shaped body core and the resin forms a bond with the core and the fibers or textile surface elements.
  • the shaped body core can also serve as a means for maintaining a certain distance in the composite component.
  • the composite components produced rotor blades for wind turbines.
  • Suitable materials for the shaped core are, for example, balsa wood, polyvinyl chloride (PVC), polyester (PET) or polyurethane (PUR).
  • the apparent density of foamed cores may range from 20 kg / m 3 to 600 kg / m 3 , preferably 30 kg / m 3 to 400 kg / m 3, and more preferably 50 kg / m 3 to 200 kg / m 3 lie.
  • One step of the method involves contacting at least a portion of the mold core with a polyurethane / polyisocyanurate reaction mixture, wherein at least temporarily a vacuum pl is applied to at least the exterior of the mold core during contacting.
  • the term "negative pressure" refers to an absolute pressure of less than 1013 mbar. In this way, interfering gases are removed, it is achieved a fixation of the core and possibly located on the core fibers and the propagation or infusion of the reaction mixture over the core away is facilitated.
  • the negative pressure is applied by means of an evacuable mold or other wrapping of the shaped body core.
  • an overpressure p2 is applied.
  • the term "overpressure” refers to an absolute pressure of 1013 mbar or more. This overpressure counteracts the foaming, so that, for example, formed CO 2 can go into solution again.
  • the time t1 and / or the temperature T1 are selected as a function of the spatial conditions of the composite component to be produced and of the properties of the polyurethane / polyisocyanurate reaction mixture, in particular the crosslinking or gel time.
  • polyurethane / polyisocyanurate reaction mixture denotes a reaction mixture which leads to polyurethanes and / or polyisocyanurates.
  • the NCO index (molar ratio of NCO groups to NCO-reactive groups) is preferably> 0.95, more preferably> 1.00 to ⁇ 6.00, even more preferably> 1.10 to ⁇ 6.00.
  • the polyurethane / polyisocyanurate reaction mixture comprises:
  • the polyisocyanate component A) used are the customary aliphatic, cycloaliphatic and, in particular, aromatic di- and / or polyisocyanates.
  • suitable poly isocyanates are 1, 4-butylene diisocyanate, 1,5-pentane diisocyanate, 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,2,4- and / or 2,4,4-trimethylhexamethylene diisocyanate, the isomeric bis (4 , 4'-isocyanatocyclohexyl) methanes or mixtures thereof any isomer content, 1,4-cyclohexylene diisocyanate, 1, 4-phenylene diisocyanate, 2,4- and / or 2,6-toluene diisocyanate (TDI), 1,5-naphthylene diisocyanate, 2.2 'and / or 2,4'- and / or 4,4'-dipheny
  • modified polyisocyanates having a uretdione, isocyanurate, urethane, carbodiimide, uretonimine, allophanate or biuret structure.
  • the isocyanate used is preferably diphenylmethane diisocyanate (MDI) and in particular mixtures of diphenylmethane diisocyanate and polyphenylenepolymethylene polyisocyanate (pMDI).
  • the mixtures of diphenylmethane diisocyanate and polyphenylenepolymethylene polyisocyanate (pMDI) have a preferred monomer content of between 60 and 100% by weight, preferably between 70 and 95% by weight, more preferably between 80 and 90% by weight.
  • the NCO content of the polyisocyanate used should preferably be above 25% by weight, preferably above 30% by weight, particularly preferably above 32% by weight.
  • the NCO content can be determined according to DIN 53185.
  • the viscosity of the isocyanate should preferably be ⁇ 150 mPas (at 25 ° C.), preferably ⁇ 50 mPas (at 25 ° C.) and particularly preferably ⁇ 30 mPas (at 25 ° C.).
  • the OH number of component B) indicates the OH number in the case of a single polyol added. In the case of mixtures, the number average OH number is given. This value can be determined using DIN 53240-2.
  • the polyol formulation preferably contains as polyols those which have a number-average OH number of 100 to 1000 mg KOH / g, preferably from 300 to 600 mg KOH / g and particularly preferably from 350 to 500 mg KOH / g.
  • the viscosity of the polyols is preferably ⁇ 800 mPas (at 25 ° C).
  • the polyols have at least 60% secondary OH groups, preferably at least 80% secondary OH groups and more preferably at least 90% secondary OH groups.
  • Polyether polyols based on propylene oxide are particularly preferred.
  • the polyols used preferably have an average functionality of 2.0 to 5.0, more preferably 2.5 to 3.5.
  • Polyether polyols, polyester polyols or polycarbonate polyols can be used according to the invention; polyether polyols are preferred.
  • Polyether polyols which can be used according to the invention are, for example, polytetramethylene glycol polyethers obtainable by polymerization of tetrahydrofuran by means of cationic ring opening.
  • suitable polyether polyols are addition products of styrene oxide, ethylene oxide, propylene oxide and / or butylene oxides to di- or polyfunctional starter molecules.
  • Suitable starter molecules are, for example, water, ethylene glycol kol, diethylene glycol, butyldiglycol, glycerol, diethylene glycol, trimethylolpropane, propylene glycol, pentaerythritol, sorbitol, sucrose, ethylenediamine, toluenediamine, triethanolamine, 1, 4-butanediol, 1,6-hexanediol and low molecular weight, hydroxyl-containing esters of such polyols with dicarboxylic acids or hydroxyl groups oils.
  • Glycerin is preferred as a starter.
  • the viscosity of the polyols is preferably ⁇ 800 mPas (at 25 ° C).
  • the polyols have at least 60% secondary OH groups, preferably at least 80% secondary OH groups and more preferably 90% secondary OH groups.
  • Polyether polyols based on propylene oxide are particularly preferred.
  • the polyols B) may also contain fibers, fillers and polymers.
  • Crosslinking catalysts C) which can be used are the crosslinking catalysts known to the person skilled in the art, for example tertiary amines and organic metal compounds such as dibutyltin dilaurate.
  • catalysts which also catalyze the trimerization are particularly preferred. These may also be bases (tertiary amines, salts of weak acids such as potassium acetate) and / or organic metal compounds. Trimerization catalysts initiate and accelerate the trimerization of isocyanate groups to isocyanurate groups.
  • additives D can be added. These include, for example, deaerators, defoamers, fillers, flame retardants and reinforcing agents. Other known additives and additives can be used as needed.
  • flame retardants may also be added to the foamable preparations, e.g. Phosphorus-containing compounds, especially phosphates and phosphonates, as well as halogenated polyesters and polyols or chlorinated paraffins.
  • non-volatile flame retardants such as melamine or expandable graphite (expandable graphite) can be added, which expands greatly under the action of flame, thereby sealing the surface from further heat.
  • the raw materials for the PUR Preparation of the raw materials for the PUR: the raw materials, the polyol component and the isocyanate component and, if appropriate, further liquid substances are initially charged in separate containers.
  • the raw materials are evacuated and degassed at a pressure of ⁇ 50 mbar, mainly ⁇ 1 mbar.
  • the raw materials, especially the polyol tempered (usually not above 80 ° C).
  • the raw materials are cooled to usual room conditions, such as 23 ° C.
  • the mold is prepared, cleaned, provided with release agent and it is optionally applied an "inmold coating".
  • III. The infusion structure is inserted.
  • the structure includes:
  • auxiliary materials such as hoses, clamps, flow aids, release liners, etc.
  • the infusion structure is hermetically separated from the atmosphere with a vacuum-tight foil and vacuum adhesive tape.
  • the infusion assembly is connected to a vacuum unit and evacuated. Evacuation is helpful to ensure the proper positioning of the infusion components, to achieve an optimal fiber volume fraction, and to remove interfering inclusions, primarily gases (air) during infusion, so as to prevent occlusions.
  • the infusion structure is connected to the dosing machine, primarily without realizing an increase in pressure (ventilation).
  • the infusion is usually at room temperature.
  • the infusion pressure should be above the evacuation pressure of the raw materials (so that nothing outgrows the raw materials) and the evacuation pressure of the infusion structure (so that nothing outgrows fibers, but mainly from core materials).
  • the metering machine mixes a mixing unit with the starting components in the prescribed mixing ratio and infuses the reaction product into the infusion structure. As soon as the reaction mixture leaves the filled mold, as a rule by means of a hose connection at the end of the mold, the vacuum side (Ex. Mold, in front of the vacuum pump) is closed.
  • the reaction mixture is filled from the metering machine into the infusion structure; until this, measurable by continuous flow meter, no longer flows.
  • the maximum filling pressure to be used, pressure ex. Mixing unit, should be less than the prevailing atmospheric pressure (so that the film does not lift off, too much resin is pumped into the mold, the set fiber volume fraction is not changed, etc). Once under these conditions If no more reaction mixture can be required in the infusion structure, the "pressure side" (former mixing head) is closed.
  • the infused structure should be treated energetically, primarily thermally, in order to achieve solidification of the reaction product or to be able to realize specific material properties, for example the glass transition temperature.
  • a thermal treatment can be realized by external heating of the mold, for example in a heating cabinet or by internal heating within the mold. For example, the heating can be done at a heating rate of +/- 1 ° C per minute.
  • the molar ratio of isocyanate groups to OH groups is between 1.6 and 6.0, based on the polyurethane / polyisocyanurate reaction mixture.
  • the NCO index is between 1, 8 and 4.0, and more preferably between 2.1 and 3.5.
  • the polyisocyanurate obtained preferably has a PIR conversion of more than 20%, preferably more than 40% and particularly preferably more than 60%.
  • the PIR conversion is the proportion of isocyanate groups that has reacted to PIR. It can be detected by infrared spectroscopy.
  • the polyurethane / polyisocyanurate reaction mixture comprises a latent-reactive trimerization catalyst. Particular preference is given to using latent-reactive trimerization catalysts which only begin at 50 to 100 ° C. to initiate and accelerate the trimerization of isocyanate groups to isocyanurate groups.
  • the trimerization catalyst is a salt of a tertiary amine.
  • the tertiary amine is selected from the group consisting of trimethylamine, triethylamine, tripropylamine, tributylamine, dimethylcyclohexylamine, dimethylbenzylamine, dibutylcyclohexylamine, dimethylethanolamine, triethanolamine, diethylethanolamine, ethyldiethanolamine, dimethylisopropanolamine, triisopropanolamine, triethylenediamine, tetramethyl-l, 3 butanediamine, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylethylenediamine, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylhexanediamine-1, 6, ⁇ , ⁇ , ⁇ ', ⁇ ', ⁇ '' - pentamethyldiethylenetriamine, bis (2) dimethylaminoethoxy)
  • the salt is selected from the group consisting of phenates, ethylhexanoates, oleates, acetates and / or formates.
  • PUR latent-reactive polyurethane
  • Particularly preferred as the trimerization catalyst is 1,8-diazabicyclo [5.4.0] undec-7-ene which is present as a phenolate salt, ethylhexanoate salt, oleate salt, acetate salt or formate salt.
  • the combination of a glycerol-initiated polypropylene oxide polyol having a functionality of 3 and an OH number of 350-450 mg KOH / g with the phenol salt of 1,8-diazabicyclo [5.4.0] undec-7-ene and MDI prefers.
  • the shaped body core has a water content of> 0.5% by weight to ⁇ 30% by weight.
  • the water content is> 4% by weight to ⁇ 15% by weight.
  • the easiest way to determine the water content is gravimetric: a wood sample is taken and weighed immediately.
  • fibers and / or a textile surface element are further arranged on the shaped body core, which are contacted with the polyurethane / polyisocyanurate reaction mixture.
  • a material for the fibers and / or the textile sheet element it is possible to use coated or unbleached fibers, for example glass fibers, carbon fibers, steel or iron fibers, natural fibers, aramid fibers, polyethylene fibers or basalt fibers.
  • glass fibers are particularly preferred.
  • the fibers can be used as short fibers with a length of 0.4 to 50 mm.
  • Preference is given to continuous-fiber-reinforced composite components through the use of continuous fibers.
  • the fibers in the fiber layer may be unidirectional, randomly distributed or interwoven. In components with a fiber layer of several layers, there is the possibility of fiber orientation from layer to layer.
  • semi-finished fiber products surface elements
  • surface elements such as, for example, fabrics, scrims, braids, mats, nonwovens, knits and knits or 3D fiber semi-finished products.
  • the reaction resin mixture should preferably be low-viscosity during filling and remain fluid as long as possible. This is particularly necessary for large components, since the filling time is very long (for example, up to one hour).
  • the viscosity of the reaction resin mixture according to the invention at a constant temperature of 25 ° C 30 minutes after mixing the components is less than 1000 mPas, more preferably less than 500 mPas.
  • the viscosity is determined 30 minutes after mixing the components at a constant temperature of 25 ° C with a rotary viscometer at a shear rate of 60 1 / s.
  • the time t1 is> 5 minutes to ⁇ 120 minutes, preferably> 10 minutes to ⁇ 60 minutes. In a further alternative, likewise preferred embodiment, the time t1 can be> 45 minutes to ⁇ 120 minutes. In a further embodiment of the method according to the invention, the temperature Tl> 20 ° C to ⁇ 50 ° C, preferably> 23 ° C to ⁇ 45 ° C.
  • the reduced pressure pl is> 0.1 mbar to ⁇ 500 mbar, preferably> 0.5 mbar to ⁇ 100 mbar.
  • the overpressure p 2 is> 1013 mbar to ⁇ 10 bar, preferably> 1 100 mbar to ⁇ 5 bar, further particularly preferably> 5 bar to ⁇ 10 bar.
  • FIG. 1 drying curves of balsa wood in a vacuum
  • FIG. 2 weight increases of dried balsa wood due to humidity
  • FIG. 3 shows the temperature development in the interior of an infusion structure over time
  • FIG. 4 shows a device for carrying out the method
  • FIG. 5 shows another device for carrying out the method
  • FIG. 6 shows another device for carrying out the method
  • FIG. 7 shows another device for carrying out the method
  • FIG. Figure 1 shows the weight loss of balsa wood samples by drying in vacuo.
  • the temperature at which the drying was carried out was 23 ° C.
  • Curve 1 describes the course at 50 mbar vacuum
  • curve 2 the course at 20 mbar vacuum. In these experiments it becomes clear how much water balsa wood can contain.
  • FIG. Figure 2 shows the uptake of moisture from the air of previously dried balsa wood samples.
  • Curve 3 relates to a previously dried at 20 mbar sample, curve 4 a previously dried at 50 mbar sample. From these experiments one realizes that it is not sufficient to dry balsa wood cores only once to keep them anhydrous. They will absorb moisture from the ambient air again.
  • FIG. 3 shows the temperature development in the interior of an infusion structure over time.
  • the infusion set-up was positioned after infusion in an initially unheated oven.
  • the heating cabinet was then heated at a heating rate of 1 ° C / min.
  • Curve 5 shows the oven temperature and curve 6 shows the temperature of the infusion setup. It can be seen that the resulting exotherm increases the temperature of the body to just above 80 ° C.
  • this is carried out inside a closed mold.
  • the process can be carried out in existing RTM (resin transfer molding) plants.
  • FIG. 4 shows a corresponding device.
  • the molded body core (optionally provided with fibers or textile surface elements).
  • Via valve 11 under- and overpressure can be applied to the interior of the mold.
  • the Polyurethane / polyisocyanurate reaction mixture may be introduced via valve 12 into the mold.
  • the overpressure p2 is applied by means of a flexible container into which a fluid is introduced.
  • this container presses on a mold in which the shaped body core is located.
  • the fluid may be a gas or a liquid.
  • FIG. 5 An example of this is shown in FIG. 5 shown.
  • a diagrammatically illustrated two-part mold 17 contains the provided lines for vacuum and polyurethane / polyisocyanurate reaction mixture (not shown).
  • a bracket 15 which can be opened via hinge 16
  • an inflatable bag 14 is fixed. Through valve 13, air is pumped into the bag 14.
  • the bag 14 expands, which should be symbolized by the arrows inside.
  • the fixation of the bag ensures that the pressure prevailing in the bag overpressure is transferred to the mold 17 and thus to the shaped body core.
  • FIG. 6 shows this variant as a top view in the manufacture of a rotor blade for wind turbines.
  • the bag is passed through a plurality of stirrups 19 in the same manner as in FIG. 5 fixed with bracket 15. Via valve 18, the bag 20 can be inflated.
  • the overpressure p2 is applied by means of a flexible container, into which a fluid is introduced, wherein a solid body is arranged in the interior of the flexible container.
  • a hose can be pulled over a mandrel.
  • This mandrel is then introduced into the interior of two interconnected, closed mold halves and the hose is inflated, for example by means of compressed air.
  • FIG. 7 Such a device is shown in FIG. 7 shown.
  • a closed tube 22 is pulled over a core 23 in which through holes 24 are arranged. Via valve 25 compressed air can be introduced. The compressed air leaves the core 23 through the holes 24 and inflates the tube 22.
  • shaped bodies (plates) of various Polyisocyanuratsy stemen produced and compared.
  • the Polyo mixtures containing the trimerization catalyst were degassed at a pressure of 1 mbar for 60 minutes and then added to the isocyanate. This mixture was degassed for about 5 minutes at a pressure of 1 mbar and then poured into plate molds.
  • the plates were poured at room temperature and annealed overnight in a drying oven heated to 80 ° C. The thickness of the plates was 4 mm. Optically transparent plates were obtained. The quantities and properties are shown in the table.
  • Polyol Glycerine-initiated polypropylene oxide polyol having a functionality of 3 and an OH number of 400 mg KOH / g and a viscosity of 375 mPas (at 25 ° C).
  • Polycat® SA 1/10 product of Air Products. Phenol salt of 1,8-diazabicyclo [5.4.0] undec-7-ene in dipropylene glycol. The OH number was 83 mg KOH / g.
  • Isocyanate mixture of diphenylmethane-4,4'-diisocyanate (MDI) with isomers and higher functional homologues with an NCO content of 32.5% by weight; Viscosity at 25 ° C: 20 mPas.
  • the mixture contains about 51 wt .-% diphenylmethane-4,4'-diisocyanate, 30 wt .-% diphenylmethane-2,4'-diisocyanate, 6 wt .-% diphenylmethane-2,2'-diisocyanate and 13 wt. -% higher functional homologs of MDI.
  • Isocyanate 2 mixture of diphenylmethane-4,4'-diisocyanate (MDI) with isomers and higher functional homologues with an NCO content of 32.6% by weight; Viscosity at 25 ° C: 20 mPas.
  • the mixture contains about 60 wt .-% diphenylmethane-4,4'-diisocyanate, 22 wt .-% diphenylmethane-2,4'-diisocyanate, 3 wt .-% diphenylmethane-2,2'-diisocyanate and 15 wt. -% higher functional homologs of MDI. All quantities in Table 1 are given in parts by weight.
  • Examples 1 to 4 according to the invention gave compact and optically transparent molded parts which combine very good mechanical properties such as an E-modulus of more than 2700 MPa, a strength of more than 75 MPa and an HDT value of more than 75 ° C. Above all, a very low viscosity is necessary for the production of fiber-reinforced components, as this allows the molds to be filled much faster and more uniformly. This allows shorter cycle times, the forms need only be occupied for a shorter time.
  • the latent-reactive trimerization catalyst used leads to a very rapid curing at 80 ° C.
  • Baisaho lzproben having a size of 1, 5 x 3 x 0.8 cm and a wood moisture content of 7, 1% were placed in each case a bowl and with 300 g of the polyurethane reaction mixture as Example poured. Subsequently, the samples were held at a pressure pl of 10 mbar for 45 minutes at a temperature of 23 ° C. Subsequently, an elevated pressure p2 was added to the samples and heated to a temperature of 50 ° C. After the experiment, the samples were visually inspected and the foaming was assessed. The experimental conditions and the results of the optical evaluation of the foaming are summarized in Table 2. Pressure [bar] reaction time [h] optical
  • the inventive method is ideal for efficient production of high-quality rotor blades from a composite of not necessarily pre-dried balsa wood and a polyurethane reaction mixture

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Sustainable Energy (AREA)
  • Sustainable Development (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un procédé de fabrication de pièces composites, comprenant les étapes suivantes : ‑ préparation d'une âme d'élément façonné ; ‑ mise en contact d'une partie au moins de l'âme d'élément façonné avec un mélange réactionnel à base de polyuréthane/poly­isocyanurate en appliquant pendant la mise en contact, au moins par intermittence, un vide partiel p1 au moins sur l'extérieur de l'âme d'élément façonné. Au moins sur l'extérieur de l'âme d'élément façonné, on applique une pression positive p2 lorsqu'un temps t1 s'est écoulé après le début de la mise en contact de l'âme d'élément façonné avec le mélange réactionnel à base de polyuréthane/poly­isocyanurate et/ou lorsqu'une température T1 est atteinte dans le mélange réactionnel à base de polyuréthane/poly­isocyanurate en contact avec l'âme d'élément façonné.
EP13789303.8A 2012-11-14 2013-11-11 Procédé de fabrication de pièces composites Withdrawn EP2920220A1 (fr)

Priority Applications (1)

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EP13789303.8A EP2920220A1 (fr) 2012-11-14 2013-11-11 Procédé de fabrication de pièces composites

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EP12192664 2012-11-14
EP13789303.8A EP2920220A1 (fr) 2012-11-14 2013-11-11 Procédé de fabrication de pièces composites
PCT/EP2013/073461 WO2014076022A1 (fr) 2012-11-14 2013-11-11 Procédé de fabrication de pièces composites

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CN106751737B (zh) * 2015-11-23 2019-12-13 万华化学（北京）有限公司 热固性聚氨酯复合物
EP3424707A1 (fr) * 2017-07-07 2019-01-09 Covestro Deutschland AG Procédé de fabrication d'éléments composites avec application ciblée d'un adhésif
KR20200062302A (ko) * 2017-09-29 2020-06-03 바스프 에스이 폴리우레탄 복합재
CN107903422B (zh) * 2017-11-28 2021-05-07 上海高恒材料科技有限公司 一种风机叶片前缘保护层技术
JP2022517512A (ja) * 2019-01-22 2022-03-09 コベストロ・インテレクチュアル・プロパティ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング・アンド・コー・カーゲー 二重硬化ウレタンポリマーおよび二重硬化イソシアヌレートポリマーに基づく複合材料

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DE2711958A1 (de) * 1977-03-18 1978-09-21 Bayer Ag Verfahren zur bindung oder impraegnierung lignocellulosehaltiger rohstoffe

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US6506325B1 (en) * 1999-02-05 2003-01-14 The B. F. Goodrich Company Method controlling the exotherm of a vacuum resin infusion
DK176490B1 (da) * 2006-03-03 2008-05-13 Lm Glasfiber As Fremgangsmåde og polymerforsyningsindretning til brug ved vakuuminfusion
EP2205654B1 (fr) * 2007-10-26 2011-08-17 Basf Se Résine polyuréthane de stratification, stratifié contenant la résine polyuréthane de stratification et skis ou snowboards contenant le stratifié
CN102471449B (zh) * 2009-07-30 2014-01-29 旭硝子株式会社 不饱和氨基甲酸酯低聚物、固化性树脂组合物、透明层叠体及其制造方法
DE102009058101A1 (de) * 2009-12-12 2011-06-16 Bayer Materialscience Ag Verwendung von Schichtaufbauten in Windkraftanlagen

Patent Citations (1)

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DE2711958A1 (de) * 1977-03-18 1978-09-21 Bayer Ag Verfahren zur bindung oder impraegnierung lignocellulosehaltiger rohstoffe

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WO2014076022A1 (fr) 2014-05-22
CN104768993A (zh) 2015-07-08
US20160288377A1 (en) 2016-10-06
MX2015005895A (es) 2015-09-10

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