EP2619257A1 - Préimprégnés à base d'une composition de polyuréthane stable au stockage, réactive ou hautement réactive, comportant une feuille fixée, et élément composite comportant ces préimprégnés - Google Patents

Préimprégnés à base d'une composition de polyuréthane stable au stockage, réactive ou hautement réactive, comportant une feuille fixée, et élément composite comportant ces préimprégnés

Info

Publication number
EP2619257A1
EP2619257A1 EP11757214.9A EP11757214A EP2619257A1 EP 2619257 A1 EP2619257 A1 EP 2619257A1 EP 11757214 A EP11757214 A EP 11757214A EP 2619257 A1 EP2619257 A1 EP 2619257A1
Authority
EP
European Patent Office
Prior art keywords
prepregs
reactive
uretdione
groups
diisocyanate
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Withdrawn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
EP11757214.9A
Other languages
German (de)
English (en)
Inventor
Friedrich Georg Schmidt
Sandra Reemers
Arnim Kraatz
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 EP2619257A1 publication Critical patent/EP2619257A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • 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
    • B29C70/06—Fibrous reinforcements only
    • B29C70/08—Fibrous reinforcements only comprising combinations of different forms of fibrous reinforcements incorporated in matrix material, forming one or more layers, and with or without non-reinforced layers
    • B29C70/086—Fibrous reinforcements only comprising combinations of different forms of fibrous reinforcements incorporated in matrix material, forming one or more layers, and with or without non-reinforced layers and with one or more layers of pure plastics material, e.g. foam layers
    • 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
    • B29C70/06—Fibrous reinforcements only
    • B29C70/08—Fibrous reinforcements only comprising combinations of different forms of fibrous reinforcements incorporated in matrix material, forming one or more layers, and with or without non-reinforced layers
    • B29C70/088—Fibrous reinforcements only comprising combinations of different forms of fibrous reinforcements incorporated in matrix material, forming one or more layers, and with or without non-reinforced layers and with one or more layers of non-plastics material or non-specified material, e.g. supports
    • 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
    • B29C70/68—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts by incorporating or moulding on preformed parts, e.g. inserts or layers, e.g. foam blocks
    • B29C70/86—Incorporated in coherent impregnated reinforcing layers, e.g. by winding
    • 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
    • C08J5/24—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
    • 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
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • 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
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • 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
    • B29K2275/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as reinforcement
    • 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
    • B29K2475/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as filler
    • 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
    • B29K2675/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, for preformed parts, e.g. for inserts
    • 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
    • B29K2875/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as mould material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/07—Parts immersed or impregnated in a matrix
    • B32B2305/076—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
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • 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
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/269—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension including synthetic resin or polymer layer or component

Definitions

  • Composite component The invention relates to prepregs based on storage-stable reactive or highly reactive
  • Polyurethane composition with a fixed film and the composite component produced therefrom Polyurethane composition with a fixed film and the composite component produced therefrom.
  • composite components are often post-coated to achieve a particular surface finish in terms of smoothness, color, texture or other desired properties.
  • Composite (molded parts) made of fiber composite materials are painted to finish or color the surfaces. In most cases, the coating is done by painting the components, as well as highly automated with SMC components in the production of
  • the painting is very complex because associated with high workload.
  • DE 103 09 81 1 describes a method in which a preformed film is placed in a mold such that a fiber-reinforced prepreg, for. B. with a thermoset or Thermoplastic matrix, with one on which the side of the preformed film is applied, and that after curing and cooling of the plastic of the fiber-reinforced prepreg, the finished composite of the mold is removed.
  • the fixing of a film on the surface of the composite can be done with the film-backpressing or the film-resin-transfer-molding (film RTM).
  • a preformed film is placed on one of the forming tools of a press, placed the fibrous carrier in the form of a mat on the counterpart of the tool of the press and connected with a tailored to the composition of this semi-finished pressing the preformed film with the carrier.
  • Fiber reinforcement inserted.
  • the evacuated mold is filled in a known manner with a mixture of resin and hardener, the mat is soaked and the cavity is filled under the film. The mold remains closed until the injected resin has cured.
  • open processes such as hand lamination or vacuum process, this technique is also conceivable.
  • Such a method is known, for example, from EP 0 819 516.
  • a fiber composite material is already known from EP 590 702, wherein a flexible film of a thermoplastic polymer covers a multifiber filament impregnated with a powder.
  • the powder has as an essential component thermoplastic polymers.
  • the fiber composite material should have a high flexibility, in particular for the formation of highly flexible mats. Storage-stable PU compositions containing uretdione groups are not mentioned.
  • Prepregs based on storage-stable reactive or highly reactive polyurethane compositions are known from DE 102009001793, DE 102009001806 and DE 10201029355. However, these have no film coating.
  • the task was to find new prepregs with a refined surface and to simplify the production of prepregs and composite components.
  • a storage-stable, polyurethane-based prepreg having a film which is intimately bonded to the surface of the prepregs and which, for the required surface functionality, is already fixed to the surface during the production of the prepregs Film which produces the required surface functionality of the composite component, and which tolerates temperature conditions and pressure conditions in composite component production.
  • the prepregs according to the invention can be used to simplify the production of PU composite components which have a colored, matt, particularly smooth, scratch-resistant or antistatically finished surface.
  • the invention relates to prepregs
  • polyurethane compositions essentially mixtures of a polymer having isocyanate-reactive functional groups b) as a binder and internally blocked and / or blocked with blocking agents di- or
  • a powdered polyurethane composition is passed through
  • prepregs can be combined and cut to different shapes as needed.
  • the prepregs can also be produced by the direct melt impregnation method.
  • the principle of the direct melt impregnation method of the prepregs is that first a reactive polyurethane composition B) of their individual
  • This melt of the reactive polyurethane composition B) is then applied directly to the fiber-shaped carrier A), that is, there is an impregnation of the fiber-shaped carrier A) with the melt of B). Thereafter, the cooled, storable prepregs can be composites at a later date
  • direct melt impregnation method according to the invention is a very good impregnation of the fiber-shaped carrier, due to the fact that the liquid low viscous reactive polyurethane compositions wet the fiber of the carrier very well.
  • the prepregs can also be produced by means of a solvent.
  • the principle of the process for producing prepregs is then that first a solution of the reactive polyurethane composition B) is prepared from their individual components in a suitable common solvent. This solution of the reactive polyurethane composition B) is prepared from their individual components in a suitable common solvent. This solution of the reactive polyurethane composition B) is prepared from their individual components in a suitable common solvent. This solution of the reactive
  • Polyurethane composition B) is then applied directly to the fiber-shaped carrier A), wherein the fiber-shaped carrier is impregnated / impregnated with this solution. Subsequently, the solvent is removed.
  • the solvent is completely at low temperature, preferably ⁇ 100 ° C, by e.g. thermal treatment or
  • Suitable aprotic solvents for the process according to the invention are any aprotic
  • Liquids are used that are not reactive to the reactive ones
  • Polyurethane compositions are sufficient dissolving power against the used individual components of the reactive polyurethane composition and in the process step of the solvent removal to small traces ( ⁇ 0.5% by weight) can be deducted from the impregnated with the reactive polyurethane composition prepreg, wherein a recycling of the separated solvent is advantageous.
  • Examples include: ketones (acetone, methyl ethyl ketone,
  • the prepregs according to the invention are preferably prepared by this solvent process.
  • the prepregs according to the invention After cooling to room temperature, the prepregs 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 at least a few days at room temperature, depending on the reactive polyurethane composition contained, but typically the prepregs are shelf 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.
  • the reactive or highly reactive polyurethane compositions used according to the invention therefore have a very good adhesion and distribution on the fiber-shaped carrier.
  • 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 provided with appropriate catalysts highly reactive matrix materials (variant II) at temperatures of over 100 ° C.
  • reactive matrix materials variant I
  • variant II highly reactive matrix materials
  • 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 producing the prepregs is defined as matrix material, and in the description of the prepregs, the still reactive or highly reactive polyurethane composition applied to the fiber by the process 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).
  • fiber-shaped material also often called reinforcing fibers.
  • any material that makes up the fibers is suitable, but fiber-shaped material made of glass is preferred,
  • 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) used.
  • mixtures of fiber types such as. B. fabric combinations of aramid and glass fibers, or carbon and glass fibers can be used.
  • 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
  • Carbon fibers suitable E-glass, S-glass, R-glass, M-glass, C-glass, ECR-glass, D-glass, AR-glass, or hollow glass fibers.
  • Carbon fibers generally come in
  • Carbon fibers are industrially produced carbon-containing fibers
  • isotropic fibers have only low strength and less technical importance, anisotropic fibers show high Strengths and stiffness with low elongation at break.
  • 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). Similar to carbon fibers, aramid fibers have a negative coefficient of thermal expansion, ie 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.
  • 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.
  • rovings and yarns are also suitable according to the invention. All materials mentioned are suitable in the context of the invention as a fiber-shaped carrier. An overview of reinforcing fibers can be found in "Composites Technologies, Paolo Ermanni (Version 4), Script for the lecture ETH Zurich, August 2007, Chapter 7".
  • Polyurethane compositions according to the invention consist of mixtures of a functional group - reactive with NCO groups - having polymers b) (binder), also referred to as resin, and temporarily deactivated, that is 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.
  • the binder components must have a solid resin character (glass transition temperature greater than room temperature).
  • Suitable binders are polyesters, polyethers, polyacrylates, polycarbonates and polyurethanes with an OH number of 20 to 500 mg KOH / gram and an average molecular weight of 250 to 6000 g / mol. Particularly preferred are 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. Of course, mixtures of such polymers can be used.
  • the amount of polymers b) containing the functional groups is selected such that each functional group of component b) contains 0.6 to 2 NCO equivalents or 0.3 to 1 uretdione group of component a).
  • the diisocyanates and polyisocyanates used according to the invention can be obtained from any desired
  • Compounds 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
  • 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
  • Isophorone diisocyanate is the case.
  • cycloaliphatic diisocyanates those which have only directly attached to the cycloaliphatic ring NCO groups, for. B. H 12 MDI.
  • Examples are cyclohexane diisocyanate, methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclohexane diisocyanate, propane diisocyanate, butane diisocyanate, pentane diisocyanate, hexane diisocyanate, Heptane diisocyanate, octane diisocyanate, nonane diisocyanate, nonane triisocyanate, such as 4-isocyanatomethyl-1, 8-octane diisocyanate (TIN), decane and triisocyanate, undecane
  • H 12 MDI Diisocyanatodicyclohexylmethane
  • MPDI 2-methylpentane diisocyanate
  • TMDI 2,2,4-trimethylhexamethylene diisocyanate / 2,4,4-trimethylhexamethylene diisocyanate
  • NBDI Norbornane diisocyanate
  • IPDI IPDI, HDI, TMDI and / or H 12 MDI
  • isocyanurates also being usable.
  • 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.
  • Particularly suitable are isocyanurates, especially from IPDI and / or HDI.
  • the polyisocyanates used in the invention are blocked. In question come to external blocking agents such. Ethyl acetoacetate, diisopropylamine,
  • 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 blockage occurs via a dimer formation via uretdione structures, which at elevated
  • the reactive polyurethane compositions may contain additional catalysts. These are 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 .-%.
  • 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.
  • Powder coating technology customary additives, such as leveling agents, z. As polysilicone or acrylates, light stabilizers z. As sterically hindered amines, antioxidants, or other aids, such as. As described in EP 669 353, be added in a total amount of 0.05 to 5 wt .-%. 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 are as described above
  • Polyurethane composition is usually within 5 to 60 minutes.
  • a matrix material B) is preferably used in the present invention, from a polyurethane compositions B) containing reactive uretdione groups, essentially containing a) at least one curing agent containing uretdione groups, based on
  • Hydroxyl group of component b) 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.
  • Uretdione group-containing polyisocyanates are well known and are described, for example, in US 4,476,054, US 4,912,210, US 4,929,724 and EP 417,603.
  • a comprehensive review of industrially relevant processes for the dimerization of isocyanates to uretdiones is provided by J. Prakt. Chem. 336 (1994) 185-200.
  • the reaction of isocyanates to uretdiones in the presence of soluble dimerization catalysts such.
  • Dialkylaminopyridinen, trialkylphosphines, Phosphorigklad or imidazoles optionally carried out in solvents, but preferably in the absence of solvents - is stopped when a desired conversion is achieved by addition of catalyst poisons. Excess monomeric isocyanate is followed by
  • catalyst poisons can be dispensed with in this case. Basically, a wide range of. Is to produce polyisocyanates containing uretdione groups
  • the above di- and polyisocyanates can be used. However, preference is given to diisocyanates and polyisocyanates of any aliphatic,
  • 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
  • uretdione hardeners a) have a free NCO content of less than 5 wt .-% and a content of uretdione groups from 3 to 25 wt .-%, preferably 6 to 18 wt .-% (calculated as C 2 N 2 0 2 , molecular weight 84). Preference is given to polyesters and monomeric dialcohols.
  • the hardeners may also have isocyanurate, biuret, allophanate, urethane and / or urea structures.
  • hydroxyl-containing polymers b) is chosen so that each hydroxyl group of component b) 0.3 to 1 uretdione group of component a), preferably 0.45 to 0.55, is omitted.
  • additional catalysts c) may be present in the reactive polyurethane compositions B) according to the invention.
  • 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 .-%.
  • the customary in the powder coating technology additives d) as leveling agents for.
  • sterically hindered amines, antioxidants, 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.
  • 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 have a very good flow and thus a good impregnation ability and in the cured state an excellent chemical resistance.
  • aliphatic crosslinkers eg IPDI or H12MDI
  • a good weather resistance is additionally achieved.
  • 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 containing at least one highly reactive powdered Uretdion phenomenon
  • Polyurethane composition as matrix material substantially containing
  • 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 has an OH number between 20 and 200 mg KOH / gram;
  • Ammonium acetylacetonate and / or quaternary phosphonium acetylacetonate e) optionally known from polyurethane chemistry auxiliaries and additives, so that the two components a) and b) are present in the ratio that on each
  • suitable highly reactive uretdione-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 a functional one Groups - polymer reactive to NCO groups - (Binder), also referred to as Resin b).
  • the catalysts ensure curing of the uretdione-group-containing polyurethane compositions at low temperature. Contain the uretdione groups
  • Polyurethane compositions are thus highly reactive.
  • Methyltributylammonium hydroxide methyltriethylammonium hydroxide
  • Methyltriethylammonium methoxide tetramethylammonium methoxide
  • Tetrahexylammonium methoxide Tetraoctylammonium methoxide, Tetradecylammonium methoxide, tetradecyltrihexylammonium methoxide,
  • Triethylmethylammonium methoxide trimethylvinylammonium methoxide
  • Tri-methylphenylammoniumethanolate triethylmethylammoniumethanolate
  • Triethylmethylammonium benzylate Tri-methylvinylammonium benzylate,
  • Tetramethylammonium fluoride Tetramethylammonium fluoride, tetraethylammonium fluoride, tetrabutylammonium fluoride,
  • Tetraoctylammonium fluoride Tetraoctylammonium fluoride, benzyltrimethylammonium fluoride, tetrabutylphosphonium hydroxide,
  • Tetrabutylphosphonium fluoride Tetrabutylphosphonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide,
  • Methyltributylammonium chloride methyltripropylammonium chloride
  • Methyltriethylammonium chloride methyltriphenylammonium chloride
  • Methyltriethylammonium hydroxide tetramethylammonium hydroxide
  • Tetraethylammonium hydroxide Tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, tetradecylammonium hydroxide, tetradecyltrihexylammonium hydroxide,
  • Tetraoctadecylammonium hydroxide Tetraoctadecylammonium hydroxide, benzyltrimethylammonium hydroxide,
  • Tetramethylammonium fluoride Tetramethylammonium fluoride, tetraethylammonium fluoride, tetrabutylammonium fluoride, tetraoctylammonium fluoride and benzyltrimethylammonium fluoride. These catalysts may be added alone or in mixtures. Preference is given to using tetraethylammonium benzoate and / or tetrabutylammonium hydroxide.
  • the proportion of catalysts c) may 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.
  • a variant according to the invention includes the attachment of such catalysts c) to the functional groups of the polymers b). In addition, 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,
  • ARALDIT 810 Huntsman
  • mixtures of terephthalic acid diglycidyl ester and trimellitic triglycidyl ester trade name ARALDIT PT 910 and 912, Huntsman
  • glycidyl ester of versatic acid trade name KARDURA E10, Shell
  • ECC 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxyeyclohexanecarboxylate
  • ECC 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxyeyclohexanecarboxylate
  • 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 are
  • Zinc acetylacetonate lithium acetylacetonate and tin acetylacetonate, alone or in mixtures.
  • Zinc acetylacetonate is preferably used.
  • Also suitable as cocatalysts d2) are quaternary ammonium acetylacetonates or quaternary phosphonium acetylacetonates.
  • catalysts examples include tetramethylammonium acetylacetonate,
  • 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.
  • 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. Preferably, this is
  • Polyurethane compositions provide a very good flow and thus a good Impregnation and in the cured state an excellent
  • the preparation of the Matixmaterials can be carried out as follows: The homogenization of all components for the preparation of the polyurethane composition B) can be carried out in suitable aggregates, such as. As heated stirred tanks, kneaders, or extruders, carried out, with upper temperature limits of 120 to 130 ° C should not be exceeded. The mixture of the individual components is preferably carried out in an extruder at temperatures which, although above the melting ranges of the individual components, but below the
  • Polyurethane composition B) can also be carried out in a solvent by mixing in the abovementioned aggregates.
  • 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 a 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 form a crosslinked polyurethane and thus forms the matrix of Composites. This means that the prepregs of the invention after their preparation from the carrier and the applied reactive polyurethane composition as
  • Matrix material which is present in uncrosslinked but reactive form, are constructed.
  • 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 prepregs according to the invention and the composite components have a fiber volume fraction of greater than 50%, preferably greater than 50-70%, particularly preferably from 50 to 65%.
  • Laminated films based on thermoplastics or their mixtures or compounds for example of thermoplastic polyurethanes (TPU), thermoplastic polyolefins (TPO), (meth) acrylic polymers, polycarbonate films (eg Lexan SLX from Sabic Innovative Plastics), can be used as (multilayer) films.
  • TPU thermoplastic polyurethanes
  • TPO thermoplastic polyolefins
  • acrylic polymers polycarbonate films
  • polycarbonate films eg Lexan SLX from Sabic Innovative Plastics
  • the laminating films based on thermoplastic materials can be dyed as a whole by pigments and / or dyes as well as printed or painted on the outer surface.
  • the laminating film has a thickness between 0.2 and 10 mm, preferably between 0.5 and 4 mm.
  • the softening point is between 80 and 260 ° C, preferably between 1 10 and 180 ° C, more preferably between 130 and 180 ° C for the storage-stable highly reactive
  • Polyurethane compositions and more preferably between 160 and 220 ° C. Suitable films are e.g. also described in WO 2004/067246.
  • the fixing of the laminating film on the prepreg is carried out according to the invention directly in the preparation of the prepreg.
  • the fixation of the film by the adhesion through the matrix exemplified shown in Figure 1
  • this fixation is carried out at temperatures of 50 to 1 10 ° C.
  • the fixing of the laminating film on the prepreg can also be carried out by first preparing a prepreg in a first step and, in a second step, applying and fixing the film to the prepreg which has already been prepared separately.
  • the storage-stable prepregs provided in this way with laminating films can also be combined with further prepregs (unbacked) into laminates or to sandwich components by means of suitable methods, e.g. Autoclave or Pressmold process are processed, see Figure 3.
  • An alternative to the use of a laminating film is the separate production of a decorative coating layer or film, from the same or formulation-like material based on reactive or highly reactive polyurethane compositions B), with which the storage-stable prepregs of the invention are prepared.
  • a further alternative (and embodiment of the invention) of a prepreg according to the invention has a special surface quality due to a significantly increased matrix-to-fiber ratio. It therefore has a very low fiber volume fraction.
  • a particularly smooth and / or colored composite component surface is in this embodiment a
  • the exemplary preparation of such a prepreg is shown in FIG.
  • the production of the laminated prepregs or the double-layer prepregs according to the invention can be effected by means of the known systems and apparatuses according to Reaction Injection Molding (RIM), Reinforced Reaction Injection Molding (RRIM), pultrusion processes, by application of the solution in a roll mill or by means of a hot doctor blade , or other procedures are performed.
  • RIM Reaction Injection Molding
  • RRIM Reinforced Reaction Injection Molding
  • pultrusion processes by application of the solution in a roll mill or by means of a hot doctor blade , or other procedures are performed.
  • the invention also relates to the use of prepregs, in particular with fiber-shaped carriers made of glass, carbon or aramid fibers.
  • the invention also provides the use of the prepregs according to the invention, for the production of composites in boat and shipbuilding, in aerospace engineering, in the automotive industry, for two-wheelers, preferably motorcycles and bicycles, in the areas
  • Power generation plants eg. B. for rotor blades in wind turbines.
  • the invention also relates to the composite components produced from the prepregs according to the invention.
  • the finished composite components produced from the prepregs according to the invention have a colored, matt, particularly smooth, scratch-resistant or antistatically finished surface.
  • 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 .
  • a reactive polyurethane composition having the following formulation was used to make the prepregs and composites.
  • Example 1 Formulation [Variant I]
  • this reactive polyurethane composition can be used to prepare the prepregs depending on the manufacturing method.
  • Polyurethane composition can then be used after milling to prepare the prepregs after the powder impregnation process.
  • the homogenized melt mixture produced in the extruder can be used directly.
  • a highly reactive polyurethane composition having the following formulation was used to make the prepregs and composites.
  • VESTAGON BF 9030 (uretdione group-containing 33.05
  • Polyester resin component b) Polyester resin component b)), DIC company
  • the fixing of the films takes place directly after the melt impregnation of the fibrous carrier, wherein care is taken that the, when fixing the film on the prepreg existing temperature of the impregnated matrix material between 5 and 20 ° C above the glass transition temperature of the film, so Adhesion between film and prepreg when pressed.
  • the films used are, for example, FLUOREX 2010 (ABS support material) (Soliant) or SENOTOP films (Senoplast GmbH).
  • the Senotop film itself consists of several coextruded layers of thermoplastic material and is characterized by a Class A surface. DSC measurements
  • 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 melt impregnation were pressed on a table 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.
  • dynamic compression ie changing pressurizations, can prove advantageous for the wetting of the fibers.
  • 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.
  • Fiber volume fraction of> 50% are examined with regard to the degree of hardening (determination by DSC).
  • the determination of the glass transition temperature of the cured matrix shows the progress of the crosslinking at different curing temperatures.
  • the crosslinking is complete after about 25 minutes, in which case no reaction enthalpy for the crosslinking reaction is detectable any more.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Reinforced Plastic Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des préimprégnés à base d'une composition de polyuréthane stable au stockage, réactive ou hautement réactive, comportant une feuille fixée, ainsi que l'élément composite comportant ces préimprégnés.
EP11757214.9A 2010-09-23 2011-08-30 Préimprégnés à base d'une composition de polyuréthane stable au stockage, réactive ou hautement réactive, comportant une feuille fixée, et élément composite comportant ces préimprégnés Withdrawn EP2619257A1 (fr)

Applications Claiming Priority (2)

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DE201010041256 DE102010041256A1 (de) 2010-09-23 2010-09-23 Prepregs auf der Basis lagerstabiler reaktiven oder hochreaktiven Polyurethanzusammensetzung mit fixierter Folie sowie die daraus hergestellten Composite-Bauteil
PCT/EP2011/064905 WO2012038201A1 (fr) 2010-09-23 2011-08-30 Préimprégnés à base d'une composition de polyuréthane stable au stockage, réactive ou hautement réactive, comportant une feuille fixée, et élément composite comportant ces préimprégnés

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AU2011304537B2 (en) 2014-01-23
BR112013006856A2 (pt) 2016-06-14
CN103210022A (zh) 2013-07-17
CA2811665A1 (fr) 2012-03-29
AU2011304537A1 (en) 2013-04-11
DE102010041256A1 (de) 2012-03-29
MX2013003170A (es) 2013-05-06
KR20140002633A (ko) 2014-01-08
JP2013544899A (ja) 2013-12-19
RU2013118434A (ru) 2014-10-27
WO2012038201A1 (fr) 2012-03-29
US20130230716A1 (en) 2013-09-05
TW201226454A (en) 2012-07-01

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