EP2576648A1 - Verfahren zur herstellung von lagerstabilen polyurethan-prepregs und daraus hergestellte formkörper - Google Patents

Verfahren zur herstellung von lagerstabilen polyurethan-prepregs und daraus hergestellte formkörper

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Publication number
EP2576648A1
EP2576648A1 EP11719016.5A EP11719016A EP2576648A1 EP 2576648 A1 EP2576648 A1 EP 2576648A1 EP 11719016 A EP11719016 A EP 11719016A EP 2576648 A1 EP2576648 A1 EP 2576648A1
Authority
EP
European Patent Office
Prior art keywords
prepregs
fiber
reactive
uretdione
polyurethane
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Withdrawn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
EP11719016.5A
Other languages
German (de)
English (en)
French (fr)
Inventor
Friedrich Georg Schmidt
Werner Grenda
Emmanouil Spyrou
Holger Loesch
Christoph Lammers
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.)
Evonik Operations GmbH
Original Assignee
Evonik Degussa GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Evonik Degussa GmbH filed Critical Evonik Degussa GmbH
Publication of EP2576648A1 publication Critical patent/EP2576648A1/de
Withdrawn legal-status Critical Current

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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
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/50—Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
    • 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
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/1875—Catalysts containing secondary or tertiary amines or salts thereof containing ammonium salts or mixtures of secondary of tertiary amines and acids
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/798—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing urethdione groups
    • 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
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • 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
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • 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
    • 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
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/08—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns
    • B29K2105/0872—Prepregs
    • 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
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2861—Coated or impregnated synthetic organic fiber fabric
    • Y10T442/2893—Coated or impregnated polyamide fiber fabric
    • Y10T442/2902—Aromatic polyamide fiber fabric
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2926—Coated or impregnated inorganic fiber fabric
    • Y10T442/2984—Coated or impregnated carbon or carbonaceous fiber fabric
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2926—Coated or impregnated inorganic fiber fabric
    • Y10T442/2992—Coated or impregnated glass fiber fabric

Definitions

  • the invention relates to a process for the preparation of storage-stable polyurethane prepregs and molded articles (composite components) produced therefrom, obtainable by a direct melt impregnation process of fiber-reinforced materials, such as woven fabrics and loops, using reactive polyurethane compositions.
  • the reaction transfer molding (RTM) process involves incorporating the reinforcing fibers into a mold, closing the mold, placing the crosslinkable resin formulation in the mold, and
  • Fiber reinforced prepreg materials are already being used in many industrial applications because of their ease of handling and increased processing efficiency compared to the alternative wet-lay-up technology.
  • Polyurethane composites also have superior toughness over vinyl esters, unsaturated polyester resins (UPE) or UPE-urethane hybrid resins.
  • Prepregs and epoxy-based composites made therefrom are described, for example, in WO 98/5021 1, US 4,992,228, US 5,080,857, US 5,427,725, GB 2007676, GB 2182074, EP 309,221, EP 297,674, WO 89/04335 , US 5,532,296 and US 4,377,657, US 4,757,120.
  • prepregs based on powdered thermoplastics are known as matrix.
  • Polyphenylsulfone PPS
  • polyimide PI
  • polyamide PA
  • polycarbonate PC
  • thermoplastic prepreg textiles made therefrom exhibit inherent toughness, good viscoelastic damping behavior, unlimited shelf life, good
  • Particle / gas mixture are applied in a defined velocity profile.
  • the powders consist of ceramic or thermoplastic materials, including thermoplastic polyurethane.
  • WO 99/64216 describes prepregs and composites and a method for their use
  • the polymers of the particles have a viscosity of at least 5,000 centipoise and are either thermoplastics or crosslinking polyurethane polymers.
  • thermoplastic polyurethanes Pultrusion process with thermoplastic polyurethanes, called TPU, in Coatings & Composite Materials, No.19, p37 - 39, 1997.
  • thermoplastic polyurethane prepreg Ma, C.C.M., Chiang, C.L. Annual Technical Conference -Society of Plastics Engineers (1991), 49th 2065-9.
  • TPU Thermoplastic polyurethane
  • 2-component polyurethanes 2-K-PUR
  • the category of 2-component PU essentially comprises the classic reactive polyurethane resin systems. In principle, it is a system of two separate components. While the relevant constituent of one component is always a polyisocyanate, in the case of the second polyols or in the case of more recent developments, these are also amino or amine-polyol mixtures. Both parts are mixed together just before processing. Thereafter, the chemical curing is carried out by polyadition to form a network of polyurethane or polyurea. 2-component systems have a limited pot life after blending both ingredients
  • WO 2005/049301 discloses a catalytically activated 2-component PUR system, wherein the polyisocyanate component and the polyol are mixed and processed by pultrusion into a composite.
  • WO 2005/106155 discloses fiber-reinforced composites for the construction industry, which are produced by means of the long fiber injection (LFI) technology with 2-polyurethane systems.
  • LFI long fiber injection
  • JP 2004196851 composites which consist of carbon fibers and organic fibers, such as. B. hemp, using a matrix of 2-K-PUR based on polymeric methylene diphenyl diisocyanate (MDI) and special OH-containing compounds.
  • MDI polymeric methylene diphenyl diisocyanate
  • EP 1 319 503 describes polyurethane composites wherein special polyurethane cover layers for a fiber-impregnated with a 2-component PUR resin fiber laminate, a
  • Core layer (eg., A paper honeycomb) wrapped, can be used.
  • the 2K PUR resin consists z. B. from MDI and a mixture of polypropylene triols and diols of ethylene oxide-propylene oxide copolymers.
  • WO 2003/101719 describes polyurethane-based composites and the methods for their preparation. These are 2-component polyurethane resins with defined
  • moisture-curing paints correspond largely to analog 2K systems, both in their composition and in their properties. In principle, the same solvents, pigments, fillers and auxiliaries are used. Unlike 2K paints, these systems tolerate before theirs
  • Urethanes of diols and diisocyanates preferably MDI, TDI, HDI and IPDI.
  • Such thermoplastic systems generally have very high viscosities and thus also very high processing temperatures. This considerably impedes the use for prepregs.
  • the use of powders in reactive systems is rather uncommon and has hitherto been limited to a few fields of application.
  • Probably the most common method for bringing a powder onto a fiber surface is fluidized bed impregnation. By an upward flow powder particles are placed in a state in which they have fluid-like properties. This method is used in EP 590,702.
  • the strands of individual fiber bundles are braided apart and coated in a fluidized bed with the powder.
  • the powder consists of a mixture of reactive and thermoplastic powder in order to optimize the properties of the matrix. Individual rovings (fiber bundles) are finally folded together and several layers pressed at a pressure of 16 bar for about 20 minutes. The temperatures vary between 250 and 350 ° C. Frequently, however, in the fluidized bed process, irregular coating occurs, especially if the strands are not pulled apart.
  • Another application WO 2006/043019 describes the use of epoxy- and amino-terminated resins in powder form.
  • the powders are mixed and added to the fibers. Subsequently, the particles are sintered.
  • the particle size is between 1 and 3000 ⁇ , but preferably between 1 and 150 ⁇ .
  • thermoset systems Pultrusion process has already been carried out with thermoset systems, so far mostly only thermoplastic systems are used in this process.
  • the object was to find a simpler process for the preparation of easily handled, that is non-toxic, polyurethane-based prepreg systems based on polyurethane compositions.
  • Another object of this invention was to find prepregs with polyurethane matrix material which can be made by a simple process, with a focus on the handling and shelf life of the prepregs.
  • the viscosity of the uncrosslinked matrix materials is low enough to ensure in the production of the composite component wetting of the fiber-shaped carrier, wherein a thixotropy may be advantageous so that a flow of the resin into vertical component segments can be prevented.
  • Polyurethane composition is possible without previously being a powder
  • Polyurethane compositions are environmentally friendly, inexpensive, have good mechanical properties, can be easily processed and are characterized by good weather resistance after hardening as well as a balance between hardness and flexibility.
  • the invention relates to a direct melt impregnation method for producing prepregs
  • polyurethane compositions essentially comprising mixtures of a polymer having isocyanate-reactive functional groups b) as binder and internally blocked and / or blocked with blocking agents di- or polyisocyanate as hardener a), I. by preparation of the reactive polyurethane composition B) in the melt, and
  • the principle of the direct melt impregnation method of the prepregs is that a reactive polyurethane composition B) is first prepared from their individual components. This melt of the reactive polyurethane composition B) is then applied directly to the fiber-shaped carrier A), that is, there is a
  • Polyurethane compositions wet the fiber of the carrier very well, whereby the thermal stress on the polyurethane composition resulting from an initial melt homogenization can be avoided, and the process steps of milling and sieving into individual particle size fractions fall away, so that a higher yield of impregnated fiber is formed Carrier is achieved.
  • Polyurethane composition B) for preparing the prepregs may be in suitable
  • Aggregates such. B. heated stirred tanks, kneaders, or extruders, carried out, with upper temperature limits of 120 ° C should not be exceeded.
  • the mixture of the individual components is preferably carried out in an extruder at temperatures of 80 to 100 ° C, which are indeed above the melting ranges of the individual components, but below the temperature at which the crosslinking reaction starts.
  • the resulting masses are not allowed to solidify and then ground, in order to be processed in a powder impregnation process with the support to prepreg, but immediately after the homogenization step in the molten state with the fiber shaped carrier brought together and to prepregs with the desired
  • Fiber volume fraction further processed.
  • the preparation of the prepregs by the direct melt impregnation method can be carried out in principle by any desired methods and by means of the known systems and apparatuses directly from the melt.
  • Filament yarns are heated by the thermoplastic melt in a heated nozzle in the pultrusion process.
  • the filament yarn is fanned out in the melt so that the filaments are evenly wetted with the melt.
  • the melt is extruded onto the semi-finished product, which is then consolidated in a heated double belt press, so that the filaments are continuously wetted with the melt.
  • the melt can also be used up in a roll mill or by means of a hot doctor blade.
  • the melt impregnation is especially for semi-crystalline thermoplastics with both low melt viscosity such. As PP and PA, as well as high melt viscosity such. B. PET and PEEK used.
  • the melt viscosity and the high processing temperature of the thermoplastic materials is very disadvantageous and requires a constant
  • Temperatures of 80 to 120 ° C are applicable to the direct melt impregnation method according to the invention. Temperatures of 80 to 120 ° C for variant I and 80 - 100 ° C for variant II should not be exceeded in order to prevent the reactive matrix material from reacting.
  • the prepregs produced in this way can be combined and cut to different shapes as needed.
  • the prepregs are cut, optionally sewn or otherwise fixed and pressed in a suitable mold under pressure and, if appropriate, by applying a vacuum.
  • this process of producing the composites from the prepregs takes place depending on the curing time at temperatures above about 160 ° C when using reactive matrix materials (variant I), or in with
  • the corresponding catalysts provided highly reactive matrix materials (variant II) at temperatures above 120 ° C. After cooling to room temperature, the prepregs produced according to the invention have a very high storage stability at room temperature as soon as the matrix material has a Tg of at least 40 ° C. This is depending on the contained reactive
  • Polyurethane composition at least a few days at room temperature, but usually the prepregs are storage stable for several weeks at 40 ° C and below.
  • the prepregs produced in this way are not sticky and therefore very easy to handle and continue to process.
  • polyurethane compositions have very good adhesion and distribution on the fiber-shaped carrier.
  • Polyurethane composition and optionally added catalysts both the speed of the crosslinking reaction in the production of the composite components and the properties of the matrix can be varied within wide ranges.
  • the reactive or highly reactive polyurethane composition used for the preparation of the prepregs is defined as the matrix material, and in the description of the prepregs, the more reactive or highly reactive ones applied to the fiber by the direct melt impregnation method according to the invention
  • the matrix is defined as the composite crosslinked matrix materials from the reactive or highly reactive polyurethane compositions.
  • the fiber-shaped carrier in the present invention consists of fiber-shaped material (also often called reinforcing fibers).
  • any material that makes up the fibers is suitable, but is preferably fiber material made of glass, carbon, plastics, such.
  • polyamide (aramid) or polyester natural fibers or mineral fiber materials such as basalt fibers or ceramic fibers (oxide fibers based on aluminum oxides and / or silicon oxides).
  • mixtures of fiber types such as. B. fabric combinations of aramid and glass fibers, or
  • Carbon and glass fibers can be used. Likewise, hybrid composite components with prepregs of different fiber-shaped carriers can be produced.
  • Glass fibers are the most commonly used fiber types mainly because of their relatively low price. In principle, here are all types of glass-based
  • Reinforcing fibers suitable E-glass, S-glass, R-glass, M-glass, C-glass, ECR-glass, D-glass, AR-glass, or hollow glass fibers.
  • Carbon fibers are generally used in high performance composites, where lower density relative to glass fiber and high strength are also important factors.
  • Carbon fibers also carbon fibers
  • isotropic fibers have only low strengths and lower technical
  • Natural fibers are here all textile fibers and fiber materials, which are derived from vegetable and animal material (eg., Wood, cellulose, cotton, hemp, jute, linen, sisal, bamboo fibers).
  • Aramid fibers have a negative, similar to carbon fibers
  • Thermal expansion coefficients so become shorter when heated. Their specific strength and elastic modulus are significantly lower than that of carbon fibers. In conjunction with the positive expansion coefficient of the matrix resin can be manufactured dimensionally stable components. Compared to carbon fiber reinforced plastics, the compressive strength of aramid fiber composites is significantly lower.
  • aramid fibers are Nomex® and Kevlar® from DuPont, or Teijinconex®, Twaron® and Technora® from Teijin. Particularly suitable and preferred are carriers made of glass fibers, carbon fibers, aramid fibers or ceramic fibers.
  • the fiber-shaped material is a textile fabric. Suitable fabrics are nonwoven fabrics, as well as so-called knits, such as knitted fabrics and knits, but also non-meshed containers such as fabrics, scrims or braids.
  • a distinction long fiber and short fiber materials as a carrier. Also
  • Suitable according to the invention are rovings and yarns. All materials mentioned are suitable in the context of the invention as a fiber-shaped carrier.
  • Polyurethane compositions are suitable as matrix materials.
  • suitable urethane compositions are suitable as matrix materials.
  • polyurethane compositions consist of mixtures of a functional group-reactive with respect to NCO-containing polymers b) (binder), also referred to as resin, and temporarily deactivated, ie internally blocked, and / or blocked with blocking agents, di- or polyisocyanates, also as Hardener a) (component a)).
  • Suitable functional groups of the polymers b) (binders) are hydroxyl groups, amino groups and thiol groups which react with the free isocyanate groups with addition and thus crosslink and harden the polyurethane composition.
  • Binder components must have a solid resin character (glass transition temperature greater than room temperature). Suitable binders are polyesters, polyethers, polyacrylates, polycarbonates and polyurethanes having an OH number of 20 to 500 mg KOH / gram and an average molecular weight of 250 to 6000 g / mol. Particularly preferred
  • hydroxyl-containing polyesters or polyacrylates having an OH number of 20 to 150 mg KOH / gram and an average molecular weight of 500 to 6000 g / mol.
  • the amount of the functional group-containing polymer b) is selected so that each functional group of component b) 0.6 to 2 NCO equivalents or 0.3 to 1, 0 uretdione groups of component a) is omitted.
  • hardener component a blocked or internally blocked (uretdione) di- and polyisocyanates are used with blocking agents.
  • the diisocyanates and polyisocyanates used according to the invention can consist of any desired aromatic, aliphatic, cycloaliphatic and / or (cyclo) aliphatic di- and / or polyisocyanates.
  • aromatic di- or polyisocyanates in principle, all known aromatic compounds are suitable. Particularly suitable are 1, 3 and 1, 4-phenylene diisocyanate, 1, 5-naphthylene diisocyanate, tolidine diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate (2,4-TDI), 2,4'-diphenylmethane diisocyanate ( 2,4'-MDI), 4,4'-diphenylmethane diisocyanate, the mixtures of monomeric diphenylmethane diisocyanates (MDI) and oligomers
  • Diphenylmethane diisocyanates (polymer-MDI), xylylene diisocyanate,
  • Tetramethylxylylene diisocyanate and triisocyanatotoluene Tetramethylxylylene diisocyanate and triisocyanatotoluene.
  • Suitable aliphatic di- or polyisocyanates advantageously have 3 to 16
  • Carbon atoms, preferably 4 to 12 carbon atoms, in the linear or branched alkylene radical and suitable cycloaliphatic or (cyclo) aliphatic diisocyanates advantageously 4 to 18 carbon atoms, preferably 6 to 15 carbon atoms, in the cycloalkylene radical.
  • (cyclo) aliphatic diisocyanates the skilled worker understands at the same time cyclic and aliphatic bound NCO groups, as z.
  • B. isophorone diisocyanate is the case.
  • Examples are cyclohexane diisocyanate, methylcyclohexane diisocyanate,
  • Methyldiethylcyclohexane diisocyanate propane diisocyanate, butane diisocyanate,
  • Nonane diisocyanate, nonane triisocyanate such as 4-isocyanatomethyl-1, 8-octane diisocyanate (TIN), decane and triisocyanate, undecanediol and triisocyanate, dodecanedi and triisocyanates.
  • TIN 4-isocyanatomethyl-1, 8-octane diisocyanate
  • decane and triisocyanate undecanediol and triisocyanate
  • dodecanedi and triisocyanates dodecanedi and triisocyanates.
  • IPDI isophorone diisocyanate
  • HDI hexamethylene diisocyanate
  • H12MDI Diisocyanatodicyclohexylmethane
  • MPDI 2-methylpentane diisocyanate
  • TMDI 2,2,4-trimethylhexamethylene diisocyanate / 2,4,4-trimethylhexamethylene diisocyanate
  • NBDI norbornane diisocyanate
  • mixtures of di- and polyisocyanates can be used.
  • oligoisocyanates or polyisocyanates which are prepared from the abovementioned diisocyanates or polyisocyanates or mixtures thereof by linking by means of urethane, allophanate, urea, biuret, uretdione, amide, isocyanurate, carbodiimide, uretonimine , Oxadiazinetrione or iminooxadiazinedione structures.
  • isocyanurates especially from IPDI and HDI.
  • the polyisocyanates used in the invention are blocked. In question come to external blocking agents such. Ethyl acetoacetate, diisopropylamine, Methyl ethyl ketoxime, diethyl malonate, ⁇ -caprolactam, 1, 2,4-triazole, phenol or substituted phenols and 3,5-dimethylpyrazole.
  • the preferred hardener components are IPDI adducts containing isocyanurate moieties and ⁇ -caprolactam blocked isocyanate structures.
  • An internal blocking is possible and this is preferably used.
  • the internal blocking takes place via a dimer formation via uretdione structures which, at elevated temperature, split back into the originally present isocyanate structures and thus initiate crosslinking with the binder.
  • the reactive polyurethane compositions may contain additional catalysts.
  • organometallic catalysts such as. B.
  • Dibutyltin dilaurate DBTL
  • Zinnoctoat bismuth neodecanoate
  • tertiary amines such as. B. 1, 4-diazabicyclo [2.2.2.] Octane, in amounts of 0.001 - 1 wt .-%.
  • reactive polyurethane compositions are used under normal conditions, for. B. with DBTL catalysis, from 160 ° C, usually cured from about 180 ° C and designated as.
  • additives such as leveling agents, for.
  • leveling agents for.
  • polysilicone or acrylates light stabilizers z.
  • sterically hindered amines, or other auxiliaries such as.
  • Fillers and pigments such. Titanium dioxide may be added in an amount of up to 30% by weight of the total composition.
  • reactive means that the reactive polyurethane compositions used according to the invention, as described above, cure at temperatures of from 160 ° C., depending on the nature of the carrier.
  • the reactive polyurethane compositions used in the invention are used under normal conditions, for. B. with DBTL catalysis, from 160 ° C, usually from about 180 ° C cured.
  • Polyurethane composition is usually within 5 to 60 minutes.
  • a matrix material B) consisting essentially of polyurethane compositions B) containing reactive uretdione groups a) at least one hardening agent containing uretdione groups, based on
  • % and a uretdione content of 3 - 25 wt .-% b) at least one hydroxyl-containing polymer which is below 40 ° C in solid form and above 125 ° C in liquid form and an OH number between 20 and 200 mg KOH / gram, c) optionally at least one catalyst, d) optionally known from polyurethane chemistry auxiliaries and additives, so that the two components a) and b) are present in the ratio that each hydroxyl group of component b) from 0.3 to 1 uretdione group of component a) is omitted, preferably 0.45 to 0.55.
  • the latter corresponds to an NCO / OH ratio of 0.9 to 1, 1 to 1.
  • Dimerization catalysts such as dialkylaminopyridines, trialkylphosphines,
  • IPDI Isophorone diisocyanate
  • HDI hexamethylene diisocyanate
  • H 12 MDI Diisocyanatodicyclohexylmethane
  • MPDI 2-methylpentane diisocyanate
  • TMDI 2,2,4-trimethylhexamethylene diisocyanate / 2,4,4-trimethylhexamethylene diisocyanate
  • NBDI Norbornane diisocyanate
  • IPDI and HDI are used for the matrix material.
  • reaction of these polyisocyanates containing uretdione groups to hardeners containing uretdione groups a) involves the reaction of the free NCO groups with
  • polyesters polythioethers, polyethers, polycaprolactams, polyepoxides, polyester amides, polyurethanes or low molecular weight di-, tri- and / or tetra alcohols as chain extenders and optionally monoamines and / or monoalcohols as chain terminators and has been frequently described (EP 669 353, EP 669 354 DE 30 30 572, EP 639 598 or EP 803 524).
  • Preferred uretdione hardeners a) have a free NCO content of less than 5% by weight and a content of uretdione groups of 3 to 25% by weight, preferably 6 to 18% by weight (calculated as C2N2O2, molecular weight 84) , Preference is given to polyesters and monomeric dialcohols. Besides the uretdione groups, the hardeners can also be used.
  • polyesters, polyethers, polyacrylates, polyurethanes and / or polycarbonates having an OH number of 20-200 in mg KOH / gram.
  • Binders have been described, for example, in EP 669 354 and EP 254 152.
  • additional catalysts c) may be present.
  • organometallic catalysts such as. As dibutyltin dilaurate, zinc octoate, bismuth neodecanoate, or tertiary amines, such as. B. 1, 4-diazabicyclo [2.2.2.] Octane, in amounts of 0.001 - 1 wt .-%.
  • These reactive polyurethane compositions used in this invention are used under normal conditions, for. B. with DBTL catalysis, from 160 ° C, usually cured from about 180 ° C and designated as variant I.
  • the customary in the powder coating technology additives d) as leveling agents for.
  • Fillers and pigments such. Titanium dioxide may be added in an amount of up to 30% by weight of the total composition.
  • the reactive polyurethane compositions used in the invention are used under normal conditions, for. B. with DBTL catalysis, from 160 ° C, usually from about 180 ° C cured.
  • the reactive polyurethane compositions used according to the invention provide a very good flow and thus a good impregnating ability and in the
  • aliphatic crosslinkers eg IPDI or H 12 MDI
  • a matrix material is used
  • Ammonium acetylacetonate and / or quaternary phosphonium acetylacetonate e) optionally known from polyurethane chemistry auxiliaries and additives.
  • a matrix material B) is used B) at least one highly reactive powdery uretdione-containing polyurethane composition as matrix material, essentially containing a) at least one uretdione-containing hardener, based on
  • cycloaliphatic uretdione groups contained polyisocyanates and
  • hydroxyl-containing compounds wherein the hardener is below 40 ° C. in solid form and above 125 ° C. in liquid form and has a free NCO content of less than 5% by weight and a uretdione content of 3 to 25% by weight, b) at least one hydroxyl-containing polymer which is in liquid form below 40 ° C in solid form and above 125 ° C and an OH number between 20 and 200 mg KOH / gram;
  • Ammonium acetylacetonate and / or quaternary phosphonium acetylacetonate e) optionally known auxiliaries and additives from polyurethane chemistry, so that the two components a) and b) are present in the ratio that 0.3 to 1 uretdione group of component a) is required for each hydroxyl group of component b), preferably 0, 6 to 0.9.
  • suitable highly reactive Uredion-containing polyurethane compositions comprise mixtures of temporarily deactivated, ie uretdione-containing (internally blocked) di- or polyisocyanates, also referred to as hardeners a), and the catalysts c) and d) present in the invention and optionally additionally
  • the catalysts ensure curing of the Uredion phenomenon termed polyurethane compositions at low temperature.
  • the Uredion phenomenon-containing polyurethane compositions are thus highly reactive.
  • component a) and b) are used as described above.
  • Tetralkylammonium salts and / or quaternary phosphonium salts with halogens Tetralkylammonium salts and / or quaternary phosphonium salts with halogens
  • Hydroxides, alcoholates or organic or inorganic acid anions as counterion used are:
  • Tetramethylammonium propionate tetramethylammonium butyrate, tetramethylammonium benzoate, tetraethylammonium formate, tetraethylammonium acetate,
  • Tetrapropylammonium benzoate tetrabutylammonium formate, tetrabutylammonium acetate, tetrabutylammonium propionate, tetrabutylammonium butyrate and
  • Trihexyltetradecylphosphonium decanoate methyltributylammonium hydroxide
  • Methyltriethylammonium hydroxide tetramethylammonium hydroxide
  • Tetraethylammonium hydroxide Tetrapropylammonium hydroxide
  • Tetrahexylammonium hydroxide Tetrahexylammonium hydroxide, tetraoctylammonium hydroxide,
  • Tetradecylammonium hydroxide Tetradecylammonium hydroxide, tetradecyltrihexylammonium hydroxide,
  • Tetraoctadecylammonium hydroxide Tetraoctadecylammonium hydroxide, benzyltrimethylammonium hydroxide,
  • Triethylmethylammonium hydroxide tri-methylvinylammonium hydroxide
  • Methyltributylammonium methoxide methyltriethylammonium methoxide
  • Tetrapentylammonium methoxide Tetrapentylammonium methoxide, tetrahexylammonium methoxide,
  • Methyltriethylammoniumethanolat Tetramethylammoniumethanolat
  • Triethylmethylammoniumethanolate tri-methylvinylammoniumethanolate
  • Methyltributylammonium chloride methyltripropylammonium chloride
  • Methyltriethylammonium chloride methyltriphenylammonium chloride
  • Methyltripropylammonium bromide methyltriethylammonium bromide
  • Methyltriphenylammonium bromide phenyltrimethylammonium bromide
  • Benzyltripropylammonium iodide benzyltributylammonium iodide, methyltributylammonium iodide, methyltripropylammonium iodide, methyltriethylammonium iodide,
  • Methyltributylammonium hydroxide methyltriethylammonium hydroxide, Tetramethylammonium hydroxide, tetraethylammonium hydroxide,
  • Tetrapropylammonium hydroxide Tetrabutylammonium hydroxide
  • Tetrapentylammonium hydroxide Tetrapentylammonium hydroxide, tetrahexylammonium hydroxide,
  • Tetradecyltrihexylammonium hydroxide Tetradecyltrihexylammonium hydroxide, tetraoctadecylammonium hydroxide,
  • Trimethylphenylammonium hydroxide triethylmethylammonium hydroxide
  • Trimethylvinylammonium hydroxide Trimethylvinylammonium hydroxide, tetramethylammonium fluoride,
  • Tetraethylammonium fluoride Tetraethylammonium fluoride, tetrabutylammonium fluoride, tetraoctylammonium fluoride and benzyltrimethylammonium fluoride. These catalysts may be added alone or in mixtures. Preference is given to tetraethylammonium benzoate and
  • Tetrabutylammonium hydroxide used.
  • the proportion of catalysts c) may be 0.1 to 5 wt .-%, preferably from 0.3 to 2 wt .-%, based on the total formulation of the matrix material.
  • a variant according to the invention includes the attachment of such catalysts c) to the functional groups of the polymers b).
  • these catalysts may be surrounded with an inert shell and encapsulated with it.
  • Glycidyl ethers and glycidyl esters aliphatic epoxides, diglycidyl ethers based on bisphenol A and glycidyl methacrylates.
  • epoxides are triglycidyl isocyanurate (TGIC, trade name ARALDIT 810, Huntsman), mixtures of terephthalic acid diglycidyl ester and trimellitic triglycidyl ester (trade name ARALDIT PT 910 and 912, Huntsman),
  • Versatic acid glycidyl ester (trade name KARDURA E10, Shell), 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate (ECC), diglycidyl ether based on bisphenol A (trade name EPIKOTE 828, Shell) ethylhexyl glycidyl ether, butyl glycidyl ether, pentaerythritol tetraglycidyl ether, (trade name POLYPOX R 16, UPPC AG) as well as other polypoctypes with free epoxy groups. It can also be used mixtures. Preference is given to using ARALDIT PT 910 and 912 used.
  • Suitable cocatalysts d2) are metal acetylacetonates. Examples of these are zinc acetylacetonate, lithium acetylacetonate and tin acetylacetonate, alone or in
  • Zinc acetylacetonate is preferably used.
  • catalysts examples include tetramethylammonium acetylacetonate,
  • Tetraethylammoniumacetylacetonat and tetrabutylammonium acetylacetonate used. Of course, mixtures of such catalysts can be used.
  • the proportion of cocatalysts d1) and / or d2) can be from 0.1 to 5% by weight, preferably from 0.3 to 2% by weight, based on the total formulation of the matrix material.
  • Curing temperature not only saves energy and curing time, but it can also use many temperature-sensitive carrier.
  • Highly reactive (variant II) in the context of this invention means that the uretdione group-containing polyurethane compositions used according to the invention cure at temperatures of 100 to 160 ° C, depending on the nature of the carrier. This curing temperature is preferably from 120 to 150.degree. C., more preferably from 130 to 140.degree. The time for curing the polyurethane composition used according to the invention is within 5 to 60 minutes.
  • Polyurethane compositions offer a very good flow and thus a good impregnation and in the cured state an excellent
  • Polyurethane compositions essentially consist of a mixture of a reactive resin and a hardener. This mixture has a Tg of at least 40 ° C after melt homogenization and usually reacts only above 160 ° C, in the reactive polyurethane compositions or above 100 ° C, in the highly reactive Polyurethane compositions to a crosslinked polyurethane and thus forms the matrix of the composite.
  • the prepregs according to the invention after their preparation, are composed of the carrier and the applied reactive polyurethane composition as matrix material, which is present in uncrosslinked, but reactive form.
  • the prepregs are thus stable in storage, usually several days and even weeks and can thus be further processed into composites at any time. This is the essential difference to the two-component systems already described above, which are reactive and not storage-stable, since they immediately begin to react and crosslink after application to polyurethanes.
  • the process according to the invention can be carried out by means of the known plants and apparatuses according to Reaction Injection Molding (RIM), Reinforced Reaction Injection Molding (RRIM), pultrusin process or others.
  • RIM Reaction Injection Molding
  • RRIM Reinforced Reaction Injection Molding
  • pultrusin process or others.
  • the melt can also be used up in a roll mill or by means of a hot doctor blade.
  • the invention also provides the use of the prepregs prepared by the novel process, in particular with fiber-shaped carriers made of glass, carbon or aramid fibers.
  • the invention also relates to the use of the prepregs produced according to the invention,
  • Power generation plants eg. B. for rotor blades in wind turbines.
  • the invention also provides the prepregs produced by the process according to the invention.
  • the invention also relates to the composite components produced from the prepregs produced according to the invention.
  • Type I is a canvas E-glass fabric 281 L, article No. 3103 of the company "Schlösser &Cramer"
  • the fabric has a basis weight of 280 g / m 2 .
  • the type II GBX 600 item number 1023 is a sewn biaxial E-glass scrim (-45 / + 45) from the company "Schlösser &Cramer", which refers to two layers of fiber bundles that lie one above the other and This structure is held together by other fibers which, however, are not made of glass
  • the surface of the glass fibers is equipped with a standard sizing which is modified with aminosilane
  • the scrim has a basis weight of 600 g / m 2 .
  • a reactive polyurethane composition having the following formulation was used to make the prepregs and composites.
  • the comminuted feedstocks from the table are intimately mixed in a premixer and then homogenized in the extruder to a maximum of 130 ° C.
  • a coating unit is flanged, are guided by the fiberglass cloth tapes and simultaneously impregnated.
  • a highly reactive polyurethane composition having the following formulation was used to make the prepregs and composites.
  • the comminuted feedstocks from the table are intimately mixed in a pre-mixer and then homogenized in the extruder to a maximum of 1 10 ° C.
  • a coating unit is flanged, are guided by the glass fiber fabric tapes and simultaneously impregnated.
  • the storage stability of the prepregs was determined on the basis of the glass transition temperatures and the reaction enthalpies of the crosslinking reaction by means of DSC investigations.
  • the cross-linking ability of the PU prepregs is not affected by storage at room temperature for a period of 7 weeks.
  • the composite components are produced by means of a pressing technique known to the person skilled in the art on a composite press.
  • the homogeneous prepregs produced by means of direct impregnation were pressed on a tabletop press into composite materials.
  • This tabletop press is the Polystat 200 T from Schwabenthan, which presses the prepregs at temperatures between 120 and 200 ° C into the appropriate composite plates. The pressure is varied between normal pressure and 450 bar.
  • Viscosity adjustment at the processing temperature for the wetting of the fibers prove to be advantageous.
  • the temperature of the press is increased from 90 ° C during the Aufschmelzphase to 1 10 ° C, the pressure is increased after a melting phase of 3 minutes to 440 bar and then dynamically (7 times with each 1 minute duration) between 150 and 440 bar varies, the temperature is continuously increased to 140 ° C. Subsequently, the temperature is raised to 170 ° C and at the same time the pressure at 350 bar until removal of the composite component from the press after 30 minutes height, is held.
  • the hard, stiff, chemical-resistant and impact-resistant composite components (Sheet material) with a fiber volume fraction of> 50% are examined for the degree of cure (determined by DSC). The determination of
  • Glass transition temperature of the cured matrix shows the progress of crosslinking at different curing temperatures.
  • Polyurethane composition is complete after about 25 minutes, the crosslinking, in which case no reaction enthalpy for the crosslinking reaction is more detectable.
  • Two composites are produced under exactly the same conditions and then their properties determined and compared. The good reproducibility of the
  • ILSF interlaminar shear strength

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EP11719016.5A 2010-05-27 2011-05-12 Verfahren zur herstellung von lagerstabilen polyurethan-prepregs und daraus hergestellte formkörper Withdrawn EP2576648A1 (de)

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DE102010029355A1 (de) 2011-12-01
WO2011147688A1 (de) 2011-12-01
BR112012030085A2 (pt) 2019-09-24
KR20130080010A (ko) 2013-07-11
CN102906140B (zh) 2015-11-25
CN102906140A (zh) 2013-01-30
MX2012013546A (es) 2013-01-24
RU2012157000A (ru) 2014-07-10
JP2013527293A (ja) 2013-06-27
AU2011257484B2 (en) 2014-01-23
US20130045652A1 (en) 2013-02-21
CA2796799A1 (en) 2011-12-01
TW201213372A (en) 2012-04-01

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