EP3337841A1 - Matériau composite polyuréthane - Google Patents

Matériau composite polyuréthane

Info

Publication number
EP3337841A1
EP3337841A1 EP16753886.7A EP16753886A EP3337841A1 EP 3337841 A1 EP3337841 A1 EP 3337841A1 EP 16753886 A EP16753886 A EP 16753886A EP 3337841 A1 EP3337841 A1 EP 3337841A1
Authority
EP
European Patent Office
Prior art keywords
composite material
polyurethane composite
component
material according
weight
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Withdrawn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
EP16753886.7A
Other languages
German (de)
English (en)
Inventor
Heiko Hocke
Dirk Achten
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Intellectual Property GmbH and Co KG
Original Assignee
Covestro Deutschland AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Covestro Deutschland AG filed Critical Covestro Deutschland AG
Publication of EP3337841A1 publication Critical patent/EP3337841A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
    • B29C70/46—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
    • C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
    • C08G18/7837—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing allophanate groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—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
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • 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
    • 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

Definitions

  • the present invention relates to a weatherproof polyurethane composite, to a process for its production, and to the use of the polyurethane composite as a structural component, e.g. for profiles, beams and reinforcing struts, as a reinforced lightweight component, e.g. for manhole covers, panels, housings, trunk and engine compartment covers, bumpers, screens and aprons, as well as for pipes, pressure vessels and tanks.
  • a structural component e.g. for profiles, beams and reinforcing struts
  • a reinforced lightweight component e.g. for manhole covers, panels, housings, trunk and engine compartment covers, bumpers, screens and aprons, as well as for pipes, pressure vessels and tanks.
  • Fiber-reinforced composite materials which consist of a polymeric matrix and a fas-shaped filler, are mainly used as lightweight materials, for example in vehicle construction, shipbuilding, aerospace sports, construction industry, oil industry and in the electrical and energy sector, application.
  • the polymer matrix fixes the fibrous filler, provides load transfer, and protects the fibrous filler from environmental influences
  • the purpose of the fibrous filler is to direct the load along the fiber.
  • Polyurethanes as a polymeric matrix material have so far had the disadvantage over conventionally used polymeric matrix materials, such as, for example, epoxy resins, polyesters and polyvinyl esters, that the customary aromatic isocyanates, such as D! and TDI react very quickly with polyols.
  • the pot life required for the industrial production of components in the various processes is often difficult to realize and often requires additional technical complexity and thus increased process costs.
  • the isocyanate component is sensitive to moisture and traces of water, for example in the starting materials or on surfaces such as the fibrous filler, lead in a side reaction to gas and thus blistering.
  • the components are not resistant to weathering and must be protected in outdoor applications, for example by painting.
  • polyurethanes play only a minor role as matrix material for composite materials.
  • fiber-reinforced polyurethane composite materials are known from the prior art, for example WO 2014/14166861 A1, these appear to be in need of improvement with regard to their weathering resistance, glass transition temperature and transparency of the polyurethane matrix material.
  • a high transparency of the polymeric matrix material is desirable, since even a slight haze or base color of the matrix material leads to the fact that the coloring of the composite materials is no longer optimally possible. Also, a high glass transition temperature of the matrix material is desirable to ensure optimum mechanical properties of the composite materials, even at higher temperatures.
  • WO 2012/013681 A1 describes highly functional urethane-containing polyisocyanates which have, by reacting a di- or trialkanolamine with at least one aliphatic and / or cycloaliphatic polyisocyanate having a functionality of> 2, at least one isocyanurate, biuret, uretdione and / or allophanate group be obtained, wherein the molar ratio of NCO groups to OH sipping at least 3: 1.
  • the urethane-containing polyisocyanates are used in two-component polyurethane coatings, where they are reacted as prepolymers with binders containing at least two isocyanate-reactive groups to give polyurethanes.
  • EP 0 978 523 A1 describes processes for the preparation of compact, transparent polyisocyanate polyaddition products.
  • isocyanate prepolymers are reacted with compounds which are reactive toward isocyanates, if appropriate in the presence of catalysts, auxiliary agents and additives in a mold under a pressure of from 1 to 20 MPa.
  • isocyanate-reactive compounds polyether or polyester polyoxy alcohols are used.
  • the print-produced transparent polyurethane products have a transmittance of over 90%, whereas the same composition without use of pressure leads to moldings with a transmission of only 62%.
  • a disadvantage of the process is in addition to the complicated production of the isocyanate prepolymers and the higher molecular weight polyols, also the first H! 1 method inevitably applied pressure.
  • polyurethane casting compounds comprising a relatively high molecular weight polyisocyanate component and a hydroxy-functional reactant, particularly preferably relatively high molecular weight adducts of ethylene oxide and / or propylene oxide with glycerol, trimethyloipropane, ethylenediamine and / or pentaerythritol, ie polyetherpoiyoie, as hydroxyfunctional reactants. be used.
  • the test specimens produced have a transmission of about 90%.
  • a disadvantage of the polyurethane casting compositions described is that the higher molecular weight ester and / or ether groups containing hydroxy-functional reactants must be prepared consuming in several reaction stages.
  • EP 2 016 111 Bl describes hyperbranched polyurethanes which are obtainable by reacting a di- or polyisocyanate with an alkanetriol having> 6 carbon atoms and optionally at least one further di- or polyoi, where the hydroxy- or isocyanate-functional polyurethanes are known as higher molecular weight core for the construction of dimoiekularer polymers, so be used as a prepolymer.
  • a special transparency of hyperbranched polyurethanes is not described.
  • EP 2777915 A1 describes an aliphatic polyurethane-based, fiber-reinforced composite material, which was produced by pultrusion and is characterized by good weathering properties and excellent mechanical properties.
  • additives such as Tinuvin B 75 were also added here, in particular to improve the weathering properties.
  • An evaluation of the pure aliphatic polyurethane matrix is not possible because no measured values were given for this purpose.
  • Various polyether polyols and aliphatic polyisocyanates were used, with only the rigid systems based on isophorone diisocyanate and dicyclohexylmethane-4,4'-diisocyanate achieving high Tg values.
  • an object of the present invention to provide a composite material having a combination of properties of high heat resistance and high weather resistance and its matrix material is highly transparent and colorless, can be produced easily and inexpensively and in optimally suited for the production of fiber-reinforced composite materials using industrially common manufacturing processes such as pultrusion, reaction injection molding (RIM) and fiber winding.
  • industrially common manufacturing processes such as pultrusion, reaction injection molding (RIM) and fiber winding.
  • a polyurethane composite material comprising polyurethane and at least one filler, wherein the polyurethane is composed of a polyisocyanate component and a polyol component, wherein the polyisocyanate component consists of one or more polyisocyanates and the polyisocyanate component has an average of about NCO functionality per molecule of> 2 and the polyol component has an OH content of> 30 wt .-% and a content of ester and / or ether groups of less than 20 wt. -%, and the polyol component consists of one or more polyols, wherein the average OH functionality per Molecule> 2 and wherein and the filler is a fibrous filler, dissolved.
  • polyurethane composite materials have extremely high heat resistance and weathering resistance.
  • they show weathering resistance of several thousand hours and heat resistance of> 100 ° C.
  • the polyurethanes used as polymeric matrix material, as well as the transmission measurements can be found in the experimental part, a high transparency with transmissions of about 90%. This allows optimal coloration of the polyurethane composite materials according to the invention, in particular also with very light pigments such as white and yellow, and also to ensure color adjustment of the formulation independently of the isocyanate batch used.
  • the polyurethanes used according to the invention as matrix material have the advantage that the pot life can be adapted over a larger range according to the requirements of the processing method and also the processing viscosities can easily be adjusted above the processing temperature, whereby the fiber-reinforced polyurethane composite materials according to the invention Compared to the conventional fiber-reinforced aromatic polyurethane composite materials easier and more economical to manufacture. Due to the high weathering stability of the composite materials according to the invention is a protective coating as for other conventionally produced fiber composites are not required even when used outdoors, resulting in a higher efficiency in the application.
  • the invention further relates to a method for producing the polyurethane composite material according to the invention and the use thereof as a structural component, such as profiles, rods, beams and reinforcing striving, as reinforced lightweight component, eg for stairs, ladders, manhole cover. Plates, housings, trunk or engine compartment covers. Bumpers and screens, aprons, lamellas and pipes, pressure vessels and tanks.
  • materials are understood as finished polymer products which are no longer available as educt for a further chemical reaction. Materials according to the invention are in particular no prepolymers.
  • Polyurethanes in the context of the invention are in particular understood to mean polyurethanes which are already crosslinked, have no more melting point, are in principle no longer flowable or soluble, and a conversion of the NGO groups or OH-G sip of greater than 90%, preferably greater than 95 %, particularly preferably greater than 99%, in particular 100%.
  • polyurethane is understood as meaning organic compounds which have urethane groups NH-CO-O-.
  • polyisocyanate an organic compound having NCO groups.
  • the polyisocyanate component in the sense of the invention contains more than 50% by weight, preferably more than 60% by weight, preferably more than 70% by weight, more preferably more than 80% by weight, in particular more than 90% by weight, most preferably 100 wt .-% of at least one or more polyisocyanates, each having an NCO functionality per molecule of> 2.
  • NCO functionality of the polyisocyanate component 2 more preferably> 3.
  • the NCO functionality of the polyisocyanate component can be calculated by dividing the total number of all NCO groups of the individual polyisocyanates constituting the polyisocyanate component by the number of all molecules of the polyisocyanate component.
  • Polyisocyanates which are suitable according to the invention are, for example, all organic aliphatic, cycloaliphatic aromatic or heterocyclic polyisocyanates known to the person skilled in the art.
  • the polyisocyanate is an aliphatic or cycloaliphatic compound.
  • the polyisocyanate component contains more than 80% by weight, preferably more than 85% by weight, preferably more than 90% by weight, in particular more than 95% by weight, particularly preferably more than 99% by weight, most preferably exclusively (to 100 wt .-%) consists of aliphatic and / or cycloaliphatic polyisocyanates.
  • suitable polyisocyanates are the oligomers of aliphatic di- or triisocyanates, such as hexane diisocyanate (hexamethylene-1, 6-diisocyanate, II DI).
  • Pentane-1 5-diisocyanate, butane-1, 4-diisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), 3,5,5-trimethyl-1-isocyanato-3-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 4-isocyanato - Methyl-1, 8-octane diisocyanate, 1, 3 -Bis (isocyanatomethyl) benzene (XDI), hydrogenated xylylene diisocyanate and hydrogenated toluene diisocyanate.
  • Oligomers are the adducts of the abovementioned di- and / or triisocyanates. These can be formed from the addition of isocyanate groups with one another to uretdiones and / or isocyanurates and / or from reaction products and their byproducts of isocyanate groups with water and amines and with alcohols, the number of di- or triisocyanates reacted per molecule of oligomer being at least two , The oligomers also contain reactive isocyanate groups.
  • the oligomers in the context of the present invention are also defined as compounds whose proportion is more than I I reacted di- or triisocyanates per molecule less than 40 wt .-%, preferably less than 25 wt .-%.
  • the use of oligomers of aliphatic di- or triisocyanates offers the advantage that they have a more attractive risk profile compared to the monomers.
  • the vapor pressure of the quasi-monomer-free oligomers is considerably lower than that of the monomers, so that virtually no release into the ambient air takes place. This is advantageous in terms of occupational safety and makes the handling of materials much easier.
  • the previous step of oligomerization already removes energy from the system and builds molecular weight, so that the energy density is lower, the reaction is more controllable and the volume shrinkage in the final cross-linking is low.
  • the polyisocyanate component may in particular have an NCO content of> 10% by weight and ⁇ 61% by weight, preferably of> 15% by weight and ⁇ 50% by weight and particularly preferably> 18% by weight and ⁇ 30 wt .-% have.
  • the NCO content indicates how much weight percent is the molecular weight of the NCO groups in the total molecular weight of the polyisocyanate component.
  • At least one polyisocyanate is a biuret, a uretdione, an allophanai.
  • an isocyanurate (symmetric or asymmetric) of a di- or triisocyanate.
  • Preferred is the di- or triisocyanate from the group hexane diisocyanate, isophorone diisocyanate, 4,4'-methylene-bis (cyclohexylisocyanate), xylylene diisocyanate, tetramethylxylylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, pentane diisocyanate, norbornene diisocyanate or 4-isocyanatomethyl-1,8 octanediisocyanate.
  • the polyisocyanate component may contain or consist of a urethane prepolymer, the urethane prepolymer having a content of ester and / or ether groups of less than 20% by weight, preferably less than 15% by weight. %, in particular less than 10 wt .-%, preferably less than 5 wt .-%, in particular less than 1 wt .-%. Most preferably, the urethane prepolymer has no ester and / or ether groups.
  • the isocyanurate of the di- or tri-isocyanates is used as the polyisocyanate. It is even more preferred if an isocyanurate of pentane diisocyanate, hexane diisocyanate or isophorone diisocyanate or a mixture of its isocyanurates is used as the polyisocyanate.
  • the polyisocyanates have a viscosity at 25 ° C of over 1000 centipoise, preferably above 1050 centipoise.
  • the polyol component according to the invention consists of more than 50% by weight, preferably more than 60% by weight, preferably more than 70% by weight, more preferably more than 80% by weight, in particular more than 90% by weight, most preferably 100 wt .-% of one or more Po fetch, which is essentially an average OH functionality per molecule of
  • the Poiyol component has an average OH functionality of> 2, preferably> 3, on.
  • the OH functionality of the polyol component can be calculated by dividing the total number of all OH groups of the individual polyols making up the polyol component by the number of molecules of the polyol component.
  • High functionality has the advantage that the formed polymeric matrix of the polyurethane composite material has a tight network and a high glass transition temperature (Tg). Practical tests have shown that this has an advantageous effect on the weathering stability and the mechanical property profile.
  • Suitable polyols according to the invention are, for example, all organic aliphatic, cycloaliphatic, aromatic or heterocyclic polyols known to the person skilled in the art.
  • each individual polyol which consists of the Poiyol component, an OH functionality> 2 on.
  • suitable polyols are glycol. Propanediol, butanediol, 1,2,10-decanetriol, 1,2,8-octanetriol, 1,2,3-trihydroxybenzene, glycerol (glycerol), 1,1,1-trimethylolpropane, 1,1,1-trimethylolethane, pentaerythritol or sugar alcohols.
  • Particularly preferred polyols are the purely aliphatic compounds glycol, glycerol (glycerol), 1,1,1-trimethylolpropane, 1,1,1-trimethylolethane, pentaerythritol or sugar alcohols.
  • glycerol (glycerol) is used as the polyol component.
  • the polyol component according to the invention further has an OH content of> 30 wt .-%.
  • the polyol component has an OH content of> 30% by weight and ⁇ 60% by weight, preferably of 35% by weight and ⁇ 60% by weight, particularly preferably> 40 Wt .-% and ⁇ 60 wt .-%, in particular of> 45 wt .-% and ⁇ 58 wt .-%.
  • the OH content of the polyol component indicates, in weight percent, how large the proportion of the molecular weight of the OH Sune is on the total molecular weight of the polyol component.
  • the polyol component has a content of ester and / or ether groups of less than 20% by weight, preferably less than 15% by weight, preferably less than 10% by weight, preferably less than 5% by weight. %, in particular less than 1 wt .-% to.
  • the polyol component has no ester and / or Ethergmppen.
  • Ethergmppen containing organic compounds having Ethergmppen -COC- organic compounds having Ethergmppen -COC-.
  • Ester phenomenon containing the purposes of the invention organic compounds are considered, the Ester phenomenon C 'OO- have, thus in particular by condensation of carboxylic acid and hydroxy compound (alcohol) available Ester phenomenon.
  • the polyol component can furthermore have a content of amino groups of less than 9% by weight, preferably less than 5% by weight, in particular less than 3% by weight, preferably less than 1 % By weight. Most preferably, the polyol component has no amino groups.
  • a disadvantage of primary and secondary amino groups is that they are significantly more reactive than hydroxyl groups and thus the pot life, i. the period in which the mixture of polyisocyanate and polyol component still has a sufficiently low viscosity to allow processing by means of the common industrial processes for the production of fiber-reinforced composite material components ,, significantly reduce.
  • tertiary amino groups do not react with the isocyanate, they can act catalytically and in this way greatly reduce the pot life. In addition, they show no such high weather resistance, since they tend to yellowing.
  • the pot life is defined as the time at a certain temperature at which the viscosity of the reaction mixture has doubled.
  • the pot life at 23 ° C according to an imple mentation form at least 20 minutes, preferably at least 30 minutes, more preferably at least 1 hour and in particular at least 2 hours.
  • the molecular ratio of polyisocyanate component to polyol component can be adjusted so that the ratio of NCO groups to OH groups is in the range of 0.85: 1.00 to 1, 20: 1, 00 and preferably in the range from 0.9: 1 to 1, 1: 1, 00 and more preferably at 1, 00: 1, 00 is located.
  • the polyisocyanate component has an average NCO functionality ⁇ 4 and / or the polyol component has an average OH functionality ⁇ 6.
  • the average functionality of the reaction mixture of polyisocyanate and polyol component is greater than 2.1, in particular greater than 2.2, preferably greater than 2.3, particularly preferably greater than 2.4, particularly preferably greater than 2.5, in particular greater 2.6, very particularly preferably greater than 2.7, in particular greater than 2.8, advantageously greater than 2.9.
  • the average functionality of the reaction mixture can be calculated by taking the sum of the average functionality of the polyol component and the isocyanate component and dividing the result by two.
  • Fibrous fillers suitable according to the invention are, for example, all inorganic fibers known to those skilled in the art, organic fibers, natural fibers or mixtures thereof.
  • a fiber is considered to be a fiber which has an aspect ratio of> 5.
  • the aspect ratio is defined as the ratio of the longest dimension divided by the smallest dimension of the material (e.g., length divided by diameter).
  • inorganic fibers suitable according to the invention are glass fibers, basalt fibers, boron fibers, ceramic fibers or whiskers, silica fibers and metallic reinforcing fibers.
  • organic fibers suitable according to the invention are aramid fibers, carbon fibers, polyester fibers, nylon fibers, carbon nanotubes, polyethylene fibers and plexiglass fibers.
  • natural fibers suitable according to the invention are flax fibers, hemp fibers, wood fibers, nanocellulose and sisal fibers.
  • glass fibers are used as fibrous fillers.
  • carbon fibers are used as fibrous fillers.
  • a polyurethane composite material according to the invention is a material which has a fiber content of> 5 wt .-% and ⁇ 95 wt .-%, preferably> 20 wt .-% and ⁇ 90 wt .-%, particularly preferably of> 40 wt .-% and ⁇ 90 wt .-% and in particular of> 50% by weight and ⁇ 85 wt .-%. If the fiber content is lower, the reinforcing effect is too low and the matrix properties outweigh. If the fiber content is higher, the amount of polyurethane resin is insufficient to bond the fibers together, and the mechanical properties of the polyurethane composite material deteriorate.
  • the polyurethane composite material can be modified on the surface. Due to the technical inaccuracy or by deliberate adjustment during mixing of the isocyanate or polyol Component remaining functional groups can be used for the surface modification of the polyurethane composite material. All methods of surface modification known to those skilled in the art are suitable. However, this surface modification has no significant influence on the bulk properties of the polyurethane composite, such as modulus E ', elongation or density.
  • Another object of the invention is a process for the preparation of a polyurethane composite material according to the invention, wherein e.g. the polyisocyanate component and the polyol component mixed, optionally added catalyst and / or additives, the resulting mixture is combined with the fibrous filler and optionally heated.
  • the order of mixing or contacting with the fiber may be arbitrary or, if necessary, depending on the processing process.
  • the method according to the invention is selected from infusion methods, prepreg methods, pultrusion methods, precision winding methods, i. so-called filament winding, RIM-V experienced and composite spray molding.
  • the polyisocyanate component and the polyol component can be mixed, for example, with the help of various known in the art static or dynamic mixing units.
  • the polyisocyanate component and the polyol component before mixing to a temperature of 10 to 90 ° C, preferably from 20 to 80 ° C and particularly preferably from 30 to 60 ° C heated become.
  • Suitable catalysts are the typical urethanization catalysts such as those given in Becker / Braun, Kunststoffhandbuch Volume 7, Polyurethanes, Chapter 3.4.
  • the catalyst used may in particular be a compound selected from the group of amines, metal salts and organometallic compounds, preferably from the group of tin salts, tin organyls and bismuth organyls and particularly preferably dibutyltin dilaurate and tin dioctoate.
  • the catalyst can be diluted with suitable solvents as well as added undiluted to one of the two components.
  • the catalyst is preferably premixed with one component without the addition of solvent before it is mixed with the other component.
  • the catalyst may also be deposited on the fiber, for example, by impregnating the fiber in a solvent containing the catalyst, followed by drying, and then mixing it with the resin component upon wetting the fiber.
  • additives such as flame retardants, dyes, fluorescent substances, light stabilizers, antioxidants, thixotropic agents, mold release agents, adhesion promoters, light-scattering agents, fillers and optionally other auxiliaries and additives may be added.
  • the feeds are dried and degassed prior to mixing by suitable methods to prevent undesirable side reactions and blistering.
  • the polyisocyanate component and the polyol component and optionally the other components are mixed anhydrous, since small amounts of moisture can lead to bubble formation.
  • the residual water content in the mixture is therefore kept so low that no disturbances occur.
  • the water content of the mixture may be ⁇ 1% by weight, in particular ⁇ 0.5% by weight, particularly preferably ⁇ 0.1% by weight.
  • the process according to the invention can also be carried out using up to 20% by weight of organic solvents, but it is preferred if no or only small amounts of solvents are used.
  • Preference is given to a process in which the content of solvent in the course of polymer formation is less than 10% by weight.
  • the invention further relates to the use of the polyurethane composite material as a structural component, such as e.g. for profiles, bars, beams and reinforcing struts, as a reinforced lightweight component e.g. for staircases, ladders, manhole covers, plates, housings, luggage compartments or engine compartment covers, bumpers and covers, aprons, lamellas and for pipes, pressure vessels and tanks.
  • a structural component such as e.g. for profiles, bars, beams and reinforcing struts
  • a reinforced lightweight component e.g. for staircases, ladders, manhole covers, plates, housings, luggage compartments or engine compartment covers, bumpers and covers, aprons, lamellas and for pipes, pressure vessels and tanks.
  • the property profile of a component for outdoor use usually includes many characteristics, most of which depend heavily on the exact application and the standards and tests required. Therefore, the glass transition temperature (Tg), the modulus E 'and, for the weathering, the L or b value were considered to be simpler for the assessment of the materials according to the invention.
  • the glass transition temperature (Tg) is a good indicator of the temperature range up to which the component retains its mechanical properties. Above the glass transition temperature, the material softens, i. the mechanical properties change dramatically, often by several orders of magnitude. Since external components are rapidly heated by solar radiation up to 80 ° C, the glass transition temperature should reach well above 80 ° C, preferably at least 90 ° C or more preferably at least 100 ° C and above.
  • the modulus E ' is a mechanical fixed value, the better the higher it is. For composite materials, it depends heavily on the fiber content, its nature and orientation. In addition, it provides information about the interaction of the fiber with the matrix and in the fiber bundle.
  • the L or b-value is a color value in the weathering test. Decisive is often less the absolute height than the relative change before and after weathering, as this is also a measure of how the hue changes. Here the lowest possible change is desired.
  • the pot-life was considered. This is the time within which the reactive material can be processed.
  • RT room temperature
  • the composite material was released from the mold and the measurement was carried out on the lower, smooth surface of the material.
  • a colorimeter from BYK-Gardner GmbH, type color-guide sphere spin with scale (IEL * a * b system, measuring geometry d / 8 ° and illuminant / observer D65 / 10 0 was used the arithmetic mean of 5 measurements.
  • the transmission of the cured polyurethane materials was determined using a Byk-Gardner haze-gard plus apparatus according to ASTM standard D-1003. The measurement was carried out on samples with a layer thickness of 1 cm.
  • the pot life was determined by means of rheometer Physica MC R 51 (plate - plate) at the appropriate temperature and a shear rate of 10 / 's.
  • the glass transition temperature (Tg) was determined by means of the DMA method (dynamic mechanical analysis) using DMA-SEIKO® EXSTAR 6100 DMS on free films or composite strips at an excitation frequency of 1 Hz.
  • the modulus E " was determined by means of the DMA method on composite strips by means of DMA-SEIKO® EXSTAR 6100 DMS at an excitation frequency of 1 Hz at 20 ° C. feedstocks
  • Desmodur ® N 3600 is an HDI trimer (NCO functionality> 3) having an NCO content of 23.0 wt .-% of the company. Covestro Germany AG. The viscosity is 1200 mPas (DIN EN IS0 3219 / A.3).
  • Desmodur ® XP 2838 is a mixture HDi oligomers and IPDI trimer (NCO functionality> 2) and having an NCO content of 21 wt .-% of the company. Covestro Germany AG. The viscosity is 3000 mPas (IN EN ISO 3219 / A.3).
  • Desmodur ® XP 2489 is an HDI / IPDI trimer (NCO functionality> 3) having an NCO content of 21.0 wt .-% of the company. Covestro Germany AG. The viscosity is 22,500 mPas (DIN EN ISO 3219 / A.3).
  • Glycerol (1,2,3-propanetriol) was obtained with a purity of 99.0% from Calbiochem.
  • TMP 1,1,1-trimethylolpropane
  • Desmophen ® 401 IT is a tri-functional polyol of the Fa. Covestro Germany AG, which is about 45 wt .-% ether, about 17 wt .-% OH-groups and less containing 0.15 wt .-% of water.
  • Desmophen VP LS 2249/1 is a branched (2 ⁇ F ⁇ 3), short-chain polyester polyol from Covestro Deutschland AG with a hydroxyl content of 15.5%.
  • Dibutyltin dilaurate (DBTL) was purchased from Acros Chemicals under the name Tinstab BL277.
  • Ethylene glycol was obtained with a purity of> 99% by weight from Bernd Kraft.
  • Hexane-1, 2,6-triol was obtained with a purity of> 97 wt .-% of the company.
  • Triethanolamine was obtained with a purity of> 98 wt .-% of the Fa. Aber GmbH.
  • D-sorbitol was obtained with a purity of> 98% by weight from Sigma.
  • the glass fiber fabric was a roving fabric of 300 g / m 2 and was purchased from PH D.
  • the two components (polyisocyanate and polyol) were heated to 23 ° C, mixed in the ratio 1, 0: 1, 0 NCO: OH, the catalyst added in the stated amount and the entire mass in one to prepare the polyurethanes Hauschild speed mixer DAC 150.1 FVZ for 60 seconds at 2750 min "1 mixed.
  • the mixture was then poured into a suitable mold and cured in the oven.
  • the following heating program was used: 1 hour at 80 ° C + 2 hours at 150 ° C.
  • the glass transition temperature was 98 ° C, the transmission 92%.
  • the panels were weathered (UVB according to DIN EN I SO 1 1507).
  • Embodiment 3
  • the glass transition temperature was 160 ° C, the transmission 89%.
  • the final reaction mixture showed a pot life at 23 ° C of> 2 hours.
  • the Gias transition temperature was 109 ° C, the transmission 2%.
  • the final reaction mixture showed a pot life at 23 ° C of> 2 hours.
  • the glass transition temperature was 66 ° C, the transmission 92%.
  • the boards were weathered for 1000 hours (UVB according to DIN EN ISO 1 1507). The L value deteriorated significantly from 96.9 to 84.4.
  • Desmodur N 3600 and glycerol (NCO: OH 1.5) were mixed with DBTL (0.005 wt%), a plate cast and cured.
  • Desmodur N 3600 and triethanolamine (NCO: OH 1) were mixed with DBTL (0.005 wt%). The mixture warmed up immediately (reaction, pot life less than 1 minute) and could not be processed further.
  • the glass transition temperature was 56 ° C, the transmission 93%.
  • the DMA Measurement revealed a glass transition temperature of 95 ° C and a modulus E '(20 ° C) of 8.4 GPa.
  • the DMA measurement gave a glass transition temperature of 95 ° C and a modulus E '(20 ° C) of
  • the DMA measurement gave a first glass transition temperature at 25 ° C and a further glass transition temperature at 99 ° C.
  • the modulus E '(20 ° C) was 4.0 GPa.

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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
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Abstract

L'invention concerne un matériau composite polyuréthane renfermant du polyuréthane et au moins une charge, le polyuréthane étant composé d'un composant polyisocyanate et d'un composant polyol, et la charge étant une charge fibreuse. L'invention porte en outre sur un procédé de production du matériau composite polyuréthane selon l'invention et sur l'utilisation de celui-ci comme élément structural.
EP16753886.7A 2015-08-21 2016-08-12 Matériau composite polyuréthane Withdrawn EP3337841A1 (fr)

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US10941292B2 (en) * 2016-09-29 2021-03-09 Boral Ip Holdings (Australia) Pty Limited Filled composites comprising glass and polyester fibers
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CN109320945A (zh) * 2018-09-21 2019-02-12 宁波雅致机械有限公司 一种用于公交车把手的聚氨酯复合材料及其制备方法
CN111393599A (zh) * 2018-12-13 2020-07-10 北京汉能光伏投资有限公司 氟改性热塑性聚氨酯复合材料及制备方法、太阳能电池组件及制备方法
WO2021048334A1 (fr) * 2019-09-12 2021-03-18 Basf Se Résines pu composites
IT202100030767A1 (it) * 2021-12-06 2023-06-06 Mitsui Chemicals Inc Composizione polimerizzabile per fabbricare un articolo stampato, articolo stampato e relativo metodo di fabbricazione.

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US20140265000A1 (en) * 2013-03-14 2014-09-18 Bayer Materialscience, Llc Water-clear aliphatic polyurethane pultrusion formulations and processes
JP6316928B2 (ja) * 2013-03-14 2018-04-25 ピーピージー・インダストリーズ・オハイオ・インコーポレイテッドＰＰＧ Ｉｎｄｕｓｔｒｉｅｓ Ｏｈｉｏ，Ｉｎｃ． ポリウレタンおよびそれから調製される物品およびコーティング、ならびにそれらを作製する方法。
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KR20180044900A (ko) 2018-05-03

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