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WO2012038200A1 - Préimprégnés à base d'une composition de polyuréthane stable au stockage, réactive ou hautement réactive - Google Patents

Préimprégnés à base d'une composition de polyuréthane stable au stockage, réactive ou hautement réactive Download PDF

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Publication number
WO2012038200A1
WO2012038200A1 PCT/EP2011/064895 EP2011064895W WO2012038200A1 WO 2012038200 A1 WO2012038200 A1 WO 2012038200A1 EP 2011064895 W EP2011064895 W EP 2011064895W WO 2012038200 A1 WO2012038200 A1 WO 2012038200A1
Authority
WO
WIPO (PCT)
Prior art keywords
dyes
reactive
prepregs
uretdione
prepregs according
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.)
Ceased
Application number
PCT/EP2011/064895
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
Priority to KR20137010206A priority Critical patent/KR20130109142A/ko
Priority to CN2011800562465A priority patent/CN103210023A/zh
Priority to MX2013003169A priority patent/MX2013003169A/es
Priority to EP11757213.1A priority patent/EP2619256A1/fr
Priority to US13/824,084 priority patent/US20130231022A1/en
Priority to BR112013006846A priority patent/BR112013006846A2/pt
Priority to RU2013118433/05A priority patent/RU2013118433A/ru
Priority to JP2013529594A priority patent/JP2013537928A/ja
Application filed by Evonik Degussa GmbH filed Critical Evonik Degussa GmbH
Priority to CA 2811063 priority patent/CA2811063A1/fr
Priority to AU2011304536A priority patent/AU2011304536B2/en
Publication of WO2012038200A1 publication Critical patent/WO2012038200A1/fr
Anticipated expiration legal-status Critical
Priority to ZA2013/02838A priority patent/ZA201302838B/en
Ceased legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • 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
    • 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
    • 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
    • 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 prepregs colored with pigment or dyestuff formulations on the basis of storage-stable reactive or highly reactive polyurethane compositions.
  • Polyurethane compositions are known from DE 102009001793, DE 102009001806,
  • the object of the present invention was to enable the production of color-adjusted prepregs based on storage-stable reactive or highly reactive polyurethane composition.
  • the object of the present invention is accomplished with pigment or dye preparations suitable for powder coating applications which are used in prepreg preparation in the matrix material composition on the basis of storage-stable reactive or highly reactive
  • Polyurethane compositions are already included.
  • the invention relates to colored prepregs
  • polyurethane compositions essentially comprising mixtures of a polymer having isocyanate-reactive functional groups b) as binder and internally blocked and / or blocked blocking agents with di- or polyisocyanate as hardener a),
  • a powdery polyurethane composition B) containing the dyes or pigments is by powder impregnation, preferably by a
  • the powder (total or fraction) is preferably spread over the fiber-shaped carrier, for. B. on webs of glass, carbon, or aramid fiber fabric / fabric, applied and then fixed.
  • the fiber-shaped carrier which is acted upon with powder, is preferably heated directly after the scattering process in a heating section (eg with IR emitters) so that the particles are sintered, whereby temperatures of 80 to 100 ° C. are not exceeded should prevent the reaction of the highly reactive matrix material.
  • a heating section eg with IR emitters
  • 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 of all a reactive or highly reactive polyurethane composition B) containing the dyes or pigments of their individual components in the
  • melt is produced.
  • This melt of the dyes or pigments containing 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 from B). Thereafter, the cooled storable prepregs can be further processed into composites at a later date.
  • direct melt impregnation method according to the invention there is a very good impregnation of the fiber-shaped carrier, due to the fact that the case of liquid low viscous reactive
  • Polyurethane compositions very well wet the fiber of the wearer.
  • the prepregs can also be produced by means of a solvent.
  • the principle of the process for the production of prepregs is then that first a solution or a dispersion which contains the dyes or pigments, reactive or highly reactive polyurethane composition B) is prepared from their individual components, in a suitable common solvent. This solution or dispersion 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 preferably completely removed at low temperature, preferably ⁇ 100 ° C., by, for example, thermal treatment or vacuum application. After that they can be freed again from the solvent storable prepregs are later processed into composites.
  • Polyurethane compositions very well wet the fiber of the wearer.
  • Polyurethane compositions are, have a sufficient solubility against the individual components of the reactive polyurethane composition used and in the process step of the solvent removal to the slightest trace ( ⁇ 0.5% by weight) of the reactive
  • Polyurethane composition impregnated prepreg can be withdrawn, with a recycling of the separated solvent is advantageous.
  • ketones acetone, methyl ethyl ketone
  • 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 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.
  • 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
  • corresponding catalysts provided highly reactive matrix materials (variant II) at temperatures above 100 ° C.
  • 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 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) used.
  • 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
  • Carbon fibers suitable are reinforced (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 High-performance composites are used, where the lower density in relation to the glass fiber and at the same time high strength is an important factor.
  • Carbon fibers also carbon fibers are industrially produced carbon-containing fibers
  • isotropic fibers have only low strength and less technical importance, anisotropic fibers show high strength 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 and thus 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 fiber composites Compared to carbon fiber reinforced plastics, the compressive strength of aramid fiber composites is significantly lower.
  • Known brand names for 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.
  • long fiber and short fiber materials as a carrier.
  • 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.
  • Reinforcing fibers contains "Composites Technologies, Paolo Ermanni (Version 4), Script for the Lecture ETH Zurich, August 2007, Chapter 7".
  • suitable polyurethane compositions consist of mixtures of a functional group-reactive with respect to NCO groups-containing polymers b) (binder), also referred to as a resin, and temporarily deactivated, ie internally blocked and / or blocked with blocking agents, di- or polyisocyanates, too 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.
  • each functional group of component b) contains 0.6 to 2 NCO equivalents or 0.3 to 1 uretdione group of component a).
  • 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, ethylcyclohexane diisocyanate, propylcyclohexane 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
  • H 12 MDI Diisocyanatodicyclohexylmethane
  • MPDI 2-methylpentane diisocyanate
  • TMDI 2,2,4-trimethylhexamethylene diisocyanate / 2,4,4-trimethylhexamethylene diisocyanate
  • NBDI norbornane diisocyanate
  • 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.
  • 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,
  • Methyl ethyl ketoxime, diethyl malonate, ⁇ -caprolactam, 1, 2,4-triazole, phenol or substituted phenols and 3,5-dimethylpyrazole 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
  • tin octoate bismuth neodecanoate
  • tertiary amines such as z. 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.
  • additives such as leveling agents, for.
  • leveling agents for.
  • polysilicone or acrylates light stabilizers z.
  • sterically hindered amines, or other auxiliaries such as.
  • 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) 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-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.
  • Dimerization catalysts such as dialkylaminopyridines, trialkylphosphines,
  • Catalyst can be freed.
  • the addition of catalyst poisons can be dispensed with in this case.
  • a wide range of isocyanates is suitable for the preparation of polyisocyanates containing uretdione groups.
  • the above di- and polyisocyanates can be used.
  • di- and polyisocyanates can be used.
  • di- and polyisocyanates can be used.
  • 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, HDI, TMDI and / or H 12 MDI isocyanurates also being usable.
  • IPDI and / or HDI are used for the matrix material.
  • the reaction of these polyisocyanates containing uretdione groups with uretdione-containing curing agents 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.
  • Polyurethane compositions B) additional catalysts c) may be included.
  • 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 .-%.
  • Polyurethane compositions are used under normal conditions, e.g. B. with DBTL catalysis, from 160 ° C, usually cured from about 180 ° C and referred to as variant I.
  • Polyurethane compositions may be those customary in powder coating technology
  • Additives such as leveling agents, eg. As polysilicone or acrylates, light stabilizers z. B.
  • sterically hindered amines or other adjuvants, such as. As described in EP 669 353, be added in a total amount of 0.05 to 5 wt .-%.
  • 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
  • Ammonium acetylacetonate and / or quaternary phosphonium acetylacetonate e) optionally known from polyurethane chemistry auxiliaries and additives.
  • a matrix material B is used
  • a polyurethane composition as matrix material essentially containing a) at least one uretdione group-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 has an OH number between 20 and 200 mg KOH / gram;
  • Polyurethane compositions are cured at temperatures of 100 to 160 ° C and referred to as variant II.
  • 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
  • Uretdione group-containing polyurethane compositions at low temperature.
  • the uretdione-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 Tetrapropylammonium benzoate, tetrabutylammonium formate, tetrabutylammonium acetate, tetrabutylammonium propionate, tetrabutylammonium butyrate and Tetrabutylammonium benzoate and tetrabutylphosphonium acetate, tetrabutylphosphonium formate and ethyltriphenylphosphonium acetate,
  • Tetrabutylphosphonium benzotriazolate tetraphenylphosphonium phenolate 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, benzyltriethylammonium hydroxide, tri-methylphenylammonium hydroxide, triethylmethylammonium hydroxide, tri-methylvinylammonium hydroxide,
  • Methyltributylammonium methoxide methyltriethylammonium methoxide, tetramethylammonium methoxide, tetraethylammonium methoxide,
  • Tetrapentylammonium methoxide Tetrapentylammonium methoxide, tetrahexylammonium methoxide,
  • Tetradecylammoniumethanolate Tetradecylammoniumethanolate, tetradecyltrihexylammoniumethanolate, tetraoctadecylammoniumethanolate, benzyltrimethylammoniumethanolate, benzyltriethylammoniumethanolate, tri-methylphenylammoniumethanolate, triethylmethylammoniumethanolate, tri-methylvinylammoniumethanolate, methyltributylammoniumbenzylate, methyltriethylammoniumbenzylate,
  • 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 / or
  • 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 of the invention includes the attachment of such catalysts c) to the functional groups of the polymers b) with a.
  • 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.
  • cocatalysts d2 are quaternary ammonium acetylacetonates or quaternary phosphonium acetylacetonates.
  • catalysts examples include tetramethylammonium acetylacetonate,
  • Tetrabutylphosphonium acetylacetonate Benzyltrimethylphosphoniumacetylacetonat, Benzyltriethylphosphoniumacetylacetonat.
  • Tetraethylammoniumacetylacetonat and / or tetrabutylammonium acetylacetonate used.
  • 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 polyurethane compositions B can at 100 to 160 ° C. 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 B) offer a very good flow and thus a good impregnation and in the cured state an excellent
  • pigments in principle, all known pigments are suitable.
  • Pigments from known classes of natural and synthetic inorganic pigments are used.
  • natural pigments come earth colors such. As green soil, yellow ocher or umber in question, as well as mineral colors such. B.
  • Iron oxides, malachite or cinnabar In addition, inorganic synthetic pigments such. As carbon black, chromium pigments, cobalt pigments, iron pigments, ultramarine blue, or white pigments such. As titanium dioxide suitable. Also suitable are natural organic pigments and synthetic organic pigments such as azo pigments (brilliant yellow, permanent red), polycyclic pigments (phthalocyanine blue, heliogen green) or diketopyrrolopyrrole pigments. Also suitable are metallic effect pigments or pearlescent pigments.
  • Pigment Blue 27 Cl 77510 Berlin Blue (Pigment Blue 27 Cl 77510), Brilliant Yellow (Pigment Yellow 74 Cl 1 1741), Cadmium Yellow (Pigment Yellow 35 Cl 77205), Cadmium Red (Pigment Red 108 Cl 77202), Chrome Oxide Green (Pigment Green 17 Cl 77288), Cobalt Blue (Pigment Blue 28 Cl 77346), cobalt blue turquoise bright (Pigment Blue 36 Cl 77343), cobalt violet light (Pigment Violet 49 Cl 77362), iron oxide black (Pigment Black 1 1 Cl 77499), Irgazin Red (Pigment Red 254 Cl 561 10), Manganese Violet (Pigment Violet 16 Cl 77742), Phthalocyanine Blue (org.) (Pigment Blue 15 Cl 74160), titanium white (Pigment White Cl 77891), Ultramarine Blue (Pigment Blue 29 Cl 77007), Ultramarine Red A (Pigment Red 259 Cl
  • Reactive dyes disperse dyes, pigment dyes, acid dyes, and
  • classes of dyes are anthraquinone dyes, azo dyes, Dioxazinfarbstoffe, Indigo dyes, nitro dyes, nitrosofar, phthalocyanine, sulfur dyes, triphenylmethane.
  • dyes are at least one
  • the dyes are contained in an amount of 15 to wt .-% in the matrix material B).
  • Pigments are contained in an amount of 0.5 to 20 wt .-% in the matrix material B).
  • 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 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 preferably takes place in an extruder at temperatures which, although above the melting ranges of the individual
  • compositions are below but below the temperature at which the crosslinking reaction starts.
  • the use directly from the melt or after cooling and production of a powder is then possible.
  • the preparation of the polyurethane composition B) can also be carried out in a solvent by mixing in the abovementioned aggregates.
  • 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%.
  • 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.
  • Tg 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.
  • 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 preparation of the prepregs according to the invention can be carried out by means of the known systems and apparatuses according to Reaction Injection Molding (RIM), Reinforced Reaction Injection Molding (RRIM), Pultrusins vide, by applying the solution in a roll mill or by means of a hot doctor blade, or other methods.
  • RIM Reaction Injection Molding
  • RRIM Reinforced Reaction Injection Molding
  • Pultrusinsclar by applying the solution in a roll mill or by means of a hot doctor blade, or other methods.
  • 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 räd he, preferably motorcycles and bicycles, in the areas
  • Power generation plants eg. B. for rotor blades in wind turbines.
  • the invention also relates to the prepregs of the invention
  • 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. This reactive
  • 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.
  • the solvent-based process no upstream melt homogenization is required. DSC measurements
  • the glass transition temperature of the extrudate was determined to be 62 ° C., the reaction enthalpy for the crosslinking reaction in the fresh state was 65.5 J / g
  • 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 .
  • 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 composite components are produced by means of a pressing technique known to the person skilled in the art on a composite press.
  • This table press is the Polystat 200 T of the company
  • 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 180 ° C and at the same time the pressure at 350 bar until the 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 goods) with a fiber volume fraction of> 50% are in terms 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.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Textile Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Reinforced Plastic Materials (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

L'invention concerne des préimprégnés à réglage chromatique par préparations de pigments ou de colorants, ces préimprégnés étant à base d'une composition de polyuréthane stable au stockage, réactive ou hautement réactive.
PCT/EP2011/064895 2010-09-23 2011-08-30 Préimprégnés à base d'une composition de polyuréthane stable au stockage, réactive ou hautement réactive Ceased WO2012038200A1 (fr)

Priority Applications (11)

Application Number Priority Date Filing Date Title
RU2013118433/05A RU2013118433A (ru) 2010-09-23 2011-08-30 Препреги на основе стабильных при хранении реакционноспособных или высокореакционноспособных полиуретановых композиций
MX2013003169A MX2013003169A (es) 2010-09-23 2011-08-30 Preimpregnados con base en una composicion de poliuretano reactiva o altamente reactiva estable al almacenamiento.
EP11757213.1A EP2619256A1 (fr) 2010-09-23 2011-08-30 Préimprégnés à base d'une composition de polyuréthane stable au stockage, réactive ou hautement réactive
US13/824,084 US20130231022A1 (en) 2010-09-23 2011-08-30 Prepregs based on a storage-stable reactive or highly reactive polyurethane composition
BR112013006846A BR112013006846A2 (pt) 2010-09-23 2011-08-30 pré-impregnados à base de uma composição de poliuretano reativa ou altamente reativa estável ao armazenamento
KR20137010206A KR20130109142A (ko) 2010-09-23 2011-08-30 저장-안정성인 반응성 또는 고반응성 폴리우레탄 조성물을 기재로 하는 프리프레그
AU2011304536A AU2011304536B2 (en) 2010-09-23 2011-08-30 Prepregs on the basis of a storage-stable reactive or highly reactive polyurethane composition
JP2013529594A JP2013537928A (ja) 2010-09-23 2011-08-30 貯蔵安定性の反応性のまたは高反応性のポリウレタン組成物を基礎とするプリプレグ
CA 2811063 CA2811063A1 (fr) 2010-09-23 2011-08-30 Preimpregnes a base d'une composition de polyurethane stable au stockage, reactive ou hautement reactive
CN2011800562465A CN103210023A (zh) 2010-09-23 2011-08-30 基于储存稳定的反应性或高反应性聚氨酯组合物的预浸料
ZA2013/02838A ZA201302838B (en) 2010-09-23 2013-04-19 Prepregs based on a storage-stable reactive or highly reactive polyurethane composition

Applications Claiming Priority (2)

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DE201010041239 DE102010041239A1 (de) 2010-09-23 2010-09-23 Prepregs auf der Basis lagerstabiler reaktiven oder hochreaktiven Polyurethanzusammensetzung
DE102010041239.2 2010-09-23

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WO2012038200A1 true WO2012038200A1 (fr) 2012-03-29

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US (1) US20130231022A1 (fr)
EP (1) EP2619256A1 (fr)
JP (1) JP2013537928A (fr)
KR (1) KR20130109142A (fr)
CN (1) CN103210023A (fr)
AU (1) AU2011304536B2 (fr)
BR (1) BR112013006846A2 (fr)
CA (1) CA2811063A1 (fr)
DE (1) DE102010041239A1 (fr)
MX (1) MX2013003169A (fr)
RU (1) RU2013118433A (fr)
TW (1) TW201226453A (fr)
WO (1) WO2012038200A1 (fr)
ZA (1) ZA201302838B (fr)

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US10029427B2 (en) 2010-09-23 2018-07-24 Evonik Degussa Gmbh Process for the production of storage-stable polyurethane prepregs and mouldings produced therefrom from dissolved polyurethane composition
US10633519B2 (en) 2011-03-25 2020-04-28 Evonik Operations Gmbh Storage-stable polyurethane prepregs and mouldings produced therefrom composed of a polyurethane composition with liquid resin components

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DE102014208415A1 (de) 2014-05-06 2015-11-12 Evonik Degussa Gmbh Herstellung eines auf Stahl und Polyurethan basierenden Faserverbundbauteils
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ES2736530T3 (es) 2015-10-30 2020-01-02 Evonik Operations Gmbh Productos preimpregnados con adherencia controlable
JP6452903B1 (ja) 2015-12-02 2019-01-16 カービテックス インコーポレイテッド 調整可能異方性特質を有する接合繊維強化型複合材料アセンブリ
CN107675531B (zh) * 2016-04-19 2018-10-12 苏州大学 一种涤纶连续热熔染色用染色溶液
EP3330311B1 (fr) 2016-12-02 2021-05-05 Evonik Operations GmbH Préimprégné de monocomposant polyuréthane stable au stockage et corps moulés ainsi fabriqués à partir de ladite composition de polyuréthane
CN109517361B (zh) * 2017-09-20 2021-12-03 科沃斯机器人股份有限公司 一种tpu共混物及其用途
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KR102596533B1 (ko) 2023-06-16 2023-11-01 주식회사 태건리너텍 하수 오니를 처리한 부숙 연료 및 그 처리 방법과 시스템

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AU2011304536B2 (en) 2014-03-13
DE102010041239A1 (de) 2012-03-29
AU2011304536A1 (en) 2013-04-04
CA2811063A1 (fr) 2012-03-29
EP2619256A1 (fr) 2013-07-31
BR112013006846A2 (pt) 2016-06-07
KR20130109142A (ko) 2013-10-07
TW201226453A (en) 2012-07-01
JP2013537928A (ja) 2013-10-07
MX2013003169A (es) 2013-05-06
ZA201302838B (en) 2013-12-23
US20130231022A1 (en) 2013-09-05
RU2013118433A (ru) 2014-10-27

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