EP3794050A1 - Procédé pour la production de matériaux composites à partir de fibres de polyéthylène de poids moléculaire ultraélevé et des polyisocyanates réticulés - Google Patents

Procédé pour la production de matériaux composites à partir de fibres de polyéthylène de poids moléculaire ultraélevé et des polyisocyanates réticulés

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Publication number
EP3794050A1
EP3794050A1 EP19722646.7A EP19722646A EP3794050A1 EP 3794050 A1 EP3794050 A1 EP 3794050A1 EP 19722646 A EP19722646 A EP 19722646A EP 3794050 A1 EP3794050 A1 EP 3794050A1
Authority
EP
European Patent Office
Prior art keywords
crosslinking
polyisocyanate
fibers
alkyl
catalyst
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Withdrawn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
EP19722646.7A
Other languages
German (de)
English (en)
Inventor
Paul Heinz
Dirk Achten
Dirk Dijkstra
Heiko Hocke
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 Intellectual Property GmbH and Co KG
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 Intellectual Property GmbH and Co KG filed Critical Covestro Intellectual Property GmbH and Co KG
Publication of EP3794050A1 publication Critical patent/EP3794050A1/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Withdrawn legal-status Critical Current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
    • 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
    • C08G18/09—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture
    • C08G18/092—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture oligomerisation to isocyanurate groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • 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
    • C08G18/09—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture
    • 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
    • C08G18/166—Catalysts not provided for in the groups C08G18/18 - C08G18/26
    • C08G18/168—Organic compounds
    • 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
    • C08G18/225—Catalysts containing metal compounds of alkali or alkaline earth metals
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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

Definitions

  • the present invention relates to a process for the production of composites from ultra high molecular weight polyethylene fibers and crosslinked polyisocyanates, to the composites obtainable therefrom, and to the use of such composites for the production of components and components consisting of or containing a composite material according to the invention.
  • Synthetic fibers based on polymers are widely used in the chemical industry.
  • Particularly interesting members of this class are polyethylene-based (PE) fibers, e.g. the so-called high-performance polyethylene fibers (HPPE). These usually consist of linear polyethylene with very high molecular weights (> 500 kg / mol). Therefore, they are also known by the term ultrahigh molecular weight PE fibers (UHMWPE).
  • UHMWPE ultrahigh molecular weight PE fibers
  • WO 2015/059268 describes a production process for UHMWPE.
  • EP 0 504 954 moreover describes the outstanding material properties of PE with molecular weights of more than 500 kg / mol. Great attention is paid to properties such as abrasion resistance or chemical resistance.
  • UHMWPE fibers are usually obtained by the so-called gel spinning process.
  • EP 2 287 371 and WO 2012/139934 describe the production of UHMWPE fibers by this process.
  • the resulting fibers are characterized by a high crystallinity and outstanding material properties such as very high tensile strength and moduli of elasticity with extremely low weight. In fact, the fibers have the highest strength to weight ratio known so far (P.K. Mallick, Fiber-Reinforced Composites - Materials Manufacturing and Design, 2008; CRC Press - Taylor & Francis Group; Boca Raton).
  • P.K. Mallick Fiber-Reinforced Composites - Materials Manufacturing and Design, 2008; CRC Press - Taylor & Francis Group; Boca Raton
  • such fibers are available under trade names such as Dyneema or Spectra. Mainly these fibers find application in ropes, cords and slings.
  • plastics based on isocyanate formulations having a ratio of isocyanate groups to isocyanate-reactive groups of at least 200 are suitable as an encapsulating resin for UHMWPE fibers, when liquid and having an isocyanate concentration, herein defined as the weight fraction of the isocyanate group on the reactive resin component of > 10 wt.% Are brought into contact with UHMWPE fibers and reacted at reaction temperatures of ⁇ 150 ° C in the presence of UHMWPE fibers, wherein> 50% of the isocyanates used react in the form of a trimerization to symmetrical or asymmetric polyisocyanurates.
  • the present invention relates to a process for producing a composite of polymer fibers and crosslinked polyisocyanates, comprising the steps of: a) providing a polyisocyanate composition A which contains polyisocyanates, and b) catalytic crosslinking of the polyisocyanate composition A in the presence of at least one polymer fiber B. and at least one crosslinking catalyst C to the composite of polymer fibers and crosslinked polyisocyanates.
  • a composite material in the sense of the present application is characterized in that the polymer fibers B are embedded in a polymer matrix which is formed by the catalytic crosslinking of the polyisocyanates contained in the polyisocyanate composition.
  • the composite may have any shape that can be achieved with the manufacturing process used.
  • the method according to the invention is characterized in that a pretreatment of the polymer fiber B in order to compatibilize it with the polyisocyanate composition A need not occur.
  • the composite material according to the invention can be prepared by the method described above, without polymer fiber B being subjected to gas plasma treatment before carrying out process step b), irradiated with UV light having a wavelength ⁇ 400 nm or oxidatively, in particular with peroxides, oxidizing acids or Ozone, is treated.
  • a cleaning of the polymer fiber with organic solvents, inorganic solvents or by mechanical treatment is not understood in this application as compatibilization.
  • polymers for example polyurethanes, polyureas and polyisocyanurates
  • low molecular weight compounds for example those containing uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione
  • polyisocyanates for example polyurethanes, polyureas and polyisocyanurates
  • low molecular weight compounds for example those containing uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione
  • polyisocyanates When referring in general to “polyisocyanates”, they mean both monomeric and / or oligomeric polyisocyanates, but for understanding many aspects of the invention, it is important to distinguish between monomeric diisocyanates and oligomeric polyisocyanates. is talking, then it means polyisocyanates, which are composed of at least two monomeric Diisocyanatmolekülen, ie they are compounds which are or contain a reaction product of at least two monomeric diisocyanate molecules.
  • oligomeric polyisocyanates from monomeric diisocyanates is also referred to in this application as a modification of monomeric diisocyanates.
  • This "modification” as used herein means the reaction of monomeric diisocyanates to oligomeric polyisocyanates having uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structure.
  • hexamethylene diisocyanate is a "monomeric diisocyanate” because it contains two isocyanate groups and is not a reaction product of at least two polyisocyanate molecules:
  • HDI reaction products of at least two HDI molecules which still have at least two isocyanate groups
  • oligomeric polyisocyanates Representatives of such "oligomeric polyisocyanates" are, for example, HDI isocyanurate and HDI starting from the monomeric HDI Biuret, each composed of three monomeric HDI building blocks:
  • isocyanate component in the initial reaction mixture is referred to as “polyisocyanate composition A.”
  • polyisocyanate composition A is the sum of all compounds in the initial reaction mixture which have isocyanate groups.
  • Polyisocyanate Composition A in particular, “Providing Polyisocyanate Composition A”
  • polyisocyanate composition A may consist essentially of monomeric polyisocyanates or substantially of oligomeric polyisocyanates. But it can also contain oligomeric and monomeric polyisocyanates in any mixing ratios.
  • the polyisocyanate composition A used as starting material in the crosslinking is low in monomer (i.e., low in monomeric diisocyanates) and already contains oligomeric polyisocyanates.
  • the terms "low in monomer” and “low in monomeric diisocyanates” are used interchangeably herein with respect to the polyisocyanate composition A.
  • the proportion of monomeric polyisocyanates in the polyisocyanate composition is preferably adjusted so that the temperature during the catalytic crosslinking does not exceed 150 ° C., preferably 140 ° C., more preferably 130 ° C.
  • the proportion of monomeric polyisocyanates which leads to exceeding the aforementioned temperature limits depends on other parameters, in particular the shape of the workpiece to be produced, ie the ratio of surface area to volume, the proportion of the fibrous filler in the total weight of the workpiece and the reaction rate and the ability to dissipate heat of reaction. The latter in turn depends essentially on the type and concentration of the catalyst used. In individual cases, however, the maximum possible proportion of monomeric polyisocyanates can be determined simply by temperature measurements by means of temperature probes at different points of the component during the catalytic crosslinking. Thus, the critical limit can be determined experimentally by the person skilled in the art using routine methods.
  • the polyisocyanate A contains a proportion of monomeric diisocyanates in the polyisocyanate A of at most 80 wt .-%, in particular at most 50 wt .-% or at most 20 wt .-%, each based on the weight of the polyisocyanate A, has.
  • the polyisocyanate composition A has a content of monomeric diisocyanates of at most 5 wt .-%, preferably at most 2.0 wt .-%, particularly preferably at most 1.0 wt .-%, each based on the weight of the polyisocyanate A composition on.
  • Particularly good results are obtained when the polymer composition A is substantially free of monomeric diisocyanates. Substantially free means that the content of monomeric diisocyanates is at most 0.5% by weight, based on the weight of the polyisocyanate A composition.
  • the polyisocyanate composition A is completely or at least 80, 85, 90, 95, 98, 99 or 99.5 wt .-% of oligomeric polyisocyanates, each based on the weight of the monomers contained in the polyisocyanate A. and oligomeric polyisocyanates.
  • a content of oligomeric polyisocyanates of at least 99 wt .-% is preferred.
  • This content of oligomeric polyisocyanates refers to the polyisocyanate composition A as provided. That the oligomeric polyisocyanates are not formed during the process according to the invention as an intermediate, but are already present at the beginning of the reaction in the polyisocyanate A used as starting material.
  • Polyisocyanate compositions which are low in monomer or substantially free of monomeric isocyanates can be obtained by, after the actual modification reaction, in each case at least one further process step for separating the unreacted excess monomeric diisocyanates is carried out.
  • This monomer removal can be carried out in a particularly practical manner by processes known per se, preferably by thin-layer distillation under high vacuum or by extraction with suitable isocyanate-inert solvents, for example aliphatic or cycloaliphatic hydrocarbons, such as pentane, hexane, heptane, cyclopentane or cyclohexane.
  • Polyisocyanate A obtained by modifying monomeric diisocyanates with subsequent removal of unreacted monomers.
  • Polyisocyanate composition A but a monomeric foreign diisocyanate.
  • monomeric foreign diisocyanate means that it differs from the monomeric diisocyanates used to prepare the oligomeric polyisocyanates contained in the polyisocyanate composition A.
  • additive of monomeric foreign diisocyanate may be used to achieve special technical effects, such as e.g. be advantageous to a particular hardness.
  • Particularly practical results are obtained when polyisocyanate composition A has a proportion of monomeric foreign diisocyanate in polyisocyanate composition A of at most 50% by weight, preferably at most 35% by weight, more preferably at most 20% by weight, and most preferably at most 10 % By weight, based in each case on the weight of the polyisocyanate composition A.
  • the polyisocyanate composition A has a content of monomeric foreign diisocyanate of at most 5 wt .-%, preferably at most 2.0 wt .-%, particularly preferably at most 1.0 wt .-%, each based on the weight of the polyisocyanate A composition on.
  • the polyisocyanate composition A comprises monomeric monoisocyanates or monomeric isocyanates having an isocyanate functionality greater than two, ie having more than two isocyanate groups per molecule.
  • monomeric monoisocyanates or monomeric isocyanates having an isocyanate functionality greater than two has been found to be advantageous for affecting the network density of the material.
  • Particularly practical results are obtained when the polyisocyanate composition A contains a proportion of monomeric monoisocyanates or monomeric isocyanates having an isocyanate functionality greater than two in the polyisocyanate composition A of not more than 20% by weight, in particular not more than 15% by weight or not more than 10% by weight.
  • the polyisocyanate composition A has a content of monomeric monoisocyanates or monomeric isocyanates having an isocyanate functionality greater than two of at most 5 wt .-%, preferably at most 2.0 wt .-%, particularly preferably at most 1.0 wt .-%, each based on the weight the polyisocyanate A, on.
  • no monomeric monoisocyanate or monomeric isocyanate with an isocyanate functionality greater than two is used in the crosslinking reaction according to the invention.
  • the oligomeric polyisocyanates may in particular have uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structures.
  • the oligomeric polyisocyanates have at least one of the following oligomeric structural types or mixtures thereof:
  • a polymer composition A is used whose isocyanurate structure content is at least 50 mol%, preferably at least 60 mol%, more preferably at least 70 mol%, even more preferably at least 80 mol%, even more preferably at least 90 mol %, and particularly preferably at least 95 mol%, based on the sum of the oligomeric structures present from the group consisting of uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and oxadiazinetrione structure in the polyisocyanate A composition.
  • a polyisocyanate composition A which, in addition to the isocyanurate structure, contains at least one further oligomeric polyisocyanate having uretdione, biuret, allophanate, iminooxadiazinedione and oxadiazinetrione structure and mixtures thereof.
  • the proportions of the uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structures in the polyisocyanates A can be determined, for example, by NMR spectroscopy.
  • the 13 C-NMR spectroscopy, preferably proton-decoupled, can preferably be used in this case since the stated oligomeric structures provide characteristic signals.
  • the oligomeric polyisocyanate composition A to be used in the process according to the invention and / or the oligomeric polyisocyanates contained therein preferably has an (average) NCO Functionality of from 2.0 to 5.0, preferably from 2.3 to 4.5.
  • the polyisocyanate composition A to be used according to the invention has a content of isocyanate groups of from 8.0 to 28.0% by weight, preferably from 14.0 to 25.0% by weight, in each case based on the weight of the
  • Polyisocyanate A having. Said isocyanate groups may be blocked or free.
  • the above-mentioned isocyanate content then refers to the calculated proportion of isocyanate groups after removal of the blocking agent.
  • the polyisocyanate composition A according to the invention is defined as containing oligomeric polyisocyanates consisting of monomeric diisocyanates, regardless of the type of modification reaction used, while maintaining a degree of oligomerization of 5 to 45%, preferably 10 to 40% preferably 15 to 30% were obtained.
  • degree of oligomerization is meant the percentage of isocyanate groups originally present in the starting mixture which is consumed during the production process to form uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structures.
  • Suitable polyisocyanates for preparing the polyisocyanate composition A to be used in the process of the present invention and the monomeric and / or oligomeric polyisocyanates contained therein are any of various ways, for example, by liquid or gas phase phosgenation or phosgene-free route, e.g. by thermal urethane cleavage, accessible polyisocyanates. Particularly good results are obtained when the polyisocyanates are monomeric diisocyanates.
  • Preferred monomeric diisocyanates are those which have a molecular weight in the range of 140 to 400 g / mol, with aliphatic, cycloaliphatic, araliphatic and / or aromatically bonded isocyanate groups, such as. B.
  • 1,4-diisocyanatobutane BDI
  • 1,5-diisocyanatopentane PDI
  • 1,6-diisocyanatohexane HDI
  • 2-methyl-l 5-diisocyanatopentane
  • l 5-diisocyanato-2,2-dimethylpentane
  • 2,2,4- and 2,4,4-trimethyl-1,6-diisocyanatohexane 1,10-diisocyanatodecane
  • 1,3- and 1,4-diisocyanatocyclohexane 1,4-diisocyanato-3,3, 5-trimethylcyclohexane
  • 1,3-diisocyanato-2-methylcyclohexane 1,3-diisocyanato-4-methylcyclohexane
  • I PDI isophorone diisocyanate
  • H12MDI 2,4'- and 4,4'-diisocyanatodicyclohexylmethane
  • NBDI bis (isocyanatomethyl) norbornane
  • 4 , 4'-diisocyanato-3,3'-dimethyldicyclohexylmethane 4,4'-diisocyanato-3,3 ', 5,5'-tetramethyl-dicyclohexylmethane
  • Suitable monomeric monoisocyanates which can optionally be used in the polyisocyanate composition A are, for example, n-butyl isocyanate, n-amyl isocyanate, n-hexyl isocyanate, n-heptyl isocyanate, n-octyl isocyanate, undecyl isocyanate, dodecyl isocyanate, tetradecyl isocyanate, cetyl isocyanate, stearyl isocyanate, cyclopentyl isocyanate, cyclohexyl isocyanate, 3- or 4-methylcyclohexyl isocyanate or any mixtures of such monoisocyanates.
  • a monomeric isocyanate having an isocyanate functionality greater than two which may optionally be added to the polyisocyanate A
  • 4-isocyanatomethyl-l, 8-octane diisocyanate (triisocyanatononane, TIN) may be mentioned by way of example.
  • the polyisocyanate composition A contains at most 30% by weight, in particular at most 20% by weight, at most 15% by weight, at most 10% by weight, at most 5% by weight or at most 1% by weight. %, in each case based on the weight of the polyisocyanate A, of aromatic polyisocyanates.
  • aromatic polyisocyanate means a polyisocyanate having at least one aromatic-bonded isocyanate group.
  • aromatically bound isocyanate groups is meant isocyanate groups which are bonded to an aromatic hydrocarbon radical.
  • a polyisocyanate A composition which has exclusively aliphatic and / or cycloaliphatic bound isocyanate groups.
  • aliphatic or cycloaliphatic bound isocyanate groups is meant isocyanate groups which are bonded to an aliphatic or cycloaliphatic hydrocarbon radical.
  • a polyisocyanate A composition which consists of or contains one or more oligomeric polyisocyanates, wherein the one or more oligomeric polyisocyanates have exclusively aliphatically and / or cycloaliphatically bonded isocyanate groups.
  • the polyisocyanate A is at least 50, 70, 85, 90, 95, 98 or 99 wt .-%, each based on the weight of the polyisocyanate A, of polyisocyanates exclusively aliphatic and / or cycloaliphatic bound Having isocyanate groups. Practical experiments have shown that particularly good results can be achieved with polyisocyanate compositions A in which the oligomeric polyisocyanates contained therein have exclusively aliphatically and / or cycloaliphatically bonded isocyanate groups.
  • a polyisocyanate A composition which consists of or contains one or more oligomeric polyisocyanates, wherein the one or more oligomeric polyisocyanates based on 1,4-diisocyanatobutane (BDI), 1,5-diisocyanatopentane (PDI), 1,6-diisocyanatohexane (HDI), isophorone diisocyanate (IPDI) or 4,4'-diisocyanatodicyclohexylmethane (H12MDI) or mixtures thereof.
  • BDI 1,4-diisocyanatobutane
  • PDI 1,5-diisocyanatopentane
  • HDI 1,6-diisocyanatohexane
  • IPDI isophorone diisocyanate
  • H12MDI 4,4'-diisocyanatodicyclohexylmethane
  • the polyisocyanate composition A is further characterized in that before the catalytic crosslinking, it has a surface tension of at most 45 mN / m, preferably at most 40 mN / m and most preferably at most 35 mN / m and according to Crosslinking has a surface energy of at most 50 mN / m, preferably at most 45 mN / m and most preferably at most 40 mN / m.
  • the energy delta between the surface tension of the polyisocyanate composition A and the polymer obtainable therefrom after crosslinking of the polyisocyanate composition A is at least 2 mN / m and at most 20 mN / m, preferably at least 4 mN / m and at most 15 mN / m and especially preferably at least 6 mN / m and at most 12 mN / m.
  • the surface tension (energy) of the polyisocyanate composition A is at most 5 mN / m smaller and at most 10 mN / m greater than the surface energy of the polymer fiber used in the invention and the surface energy of the crosslinked polymer of the polymer composition A obtainable according to the invention is at least 1 mN / m greater and at most 20 mN / m greater based on the surface energy of the polymer fiber used in the invention.
  • the ratios of surface tension and surface energies of the polyisocyanate composition A according to the invention and the inventively obtainable therefrom Crosslinked polymers have been found to be particularly advantageous for achieving good wetting of the surface of the polymer fibers according to the invention.
  • the comparatively low surface tension (energy) of the polyisocyanate composition A used according to the invention in combination with a comparably small change in the surface energy towards the crosslinkable polymer obtainable according to the invention enables particularly good results in the initial wetting of particularly polymer fibers with low surface energies. It has also been found that the adhesion of the resulting crosslinked polymers of the polyisocyanate composition A according to the invention is particularly good if the surface energy of the resulting polymer phase changes only in the context of the invention.
  • the named surface tensions and the surface energies are determined in accordance with methods customary to the person skilled in the art each at 23 ° C.
  • the surface tension is preferably measured by dynamic methods, e.g. the bubble pressure method.
  • the surface energy of the polymeric surface of the crosslinked polyisocyanate A and the polymer fiber are preferably determined by the contact angle method using test inks or Wilhelmy method (single fiber method for fibers).
  • the shrinkage of the polyisocyanate composition A used in the crosslinking process during the formation of the polymer-phase composite in the fiber direction is by a factor of> 1.5 less than orthogonal to the fiber direction.
  • the shrinkage of the polyisocyanate A used in the crosslinking process during the formation of the polymer phase is ⁇ 10%, preferably ⁇ 6%, more preferably ⁇ 5% and most preferably ⁇ 4%.
  • polymer fiber B) is basically any synthetic fiber suitable.
  • the polymer fiber B) is selected from the group consisting of cellulose fibers, regenerated protein fibers, polylactide fibers, chitin fibers, polyester fibers, polyamide fibers, polyimide fibers, polydiimide fibers, polyacrylic fibers, polyacrylonitrile fibers, polytetrafluoroethylene fibers, polychloride fibers, polyurethane fibers, polypropylene fibers and polyethylene fibers.
  • the polymer fiber is nonpolar. Particularly preferred nonpolar polymer fibers are polyethylene and polypropylene fibers.
  • the polymer fiber B) is a polyethylene fiber.
  • the ultrahigh molecular weight polyethylene fibers (UHMWPE) defined below are preferred.
  • polymer fiber B also refers to combinations of at least two of the above-mentioned types of polymer fibers, but it is preferred to use a polymer fiber B consisting only of fibers of one of the abovementioned types.
  • ultrahigh molecular weight polyethylene fibers refers to fibers consisting of polyethylene (PE)
  • the PE has a number average molecular weight of at least 360 kg / mol, more preferably at least 500 kg / mol, even more preferably at least 1000 kg /
  • at least 1,600 kg / mol is not exceeded, more preferably the number average molecular weight is between 500 kg / mol and 8,400 kg / mol, very particularly preferably between 1,600 kg / mol and 8,400 kg / mol.
  • the polydispersity (ratio of the weight average and the number average molecular weight) of the PE fibers usable in the present invention is at most 4.0, while maintaining the number average molecular weight given above. preferably at most 3.5; more preferably at most 3.0, and most preferably at most 2.8.
  • the lower limit of polydispersity is at least 1.1.
  • the tensile strength of preferred fibers is more than 2,500 N / mm 2 .
  • the parallel orientation of the polyethylene chains is preferably at least 80%, more preferably at least 90%, most preferably at least 95%.
  • Fibers suitable according to the invention can be obtained by the methods described in EP 2 287 371, WO 2012/139934 and WO 2014/187948.
  • the fibers can be arranged unidirectionally, ie parallel to one another. However, the use of fabrics and knits is also possible according to the invention. These can be arranged in one or more layers. The combination of unidirectionally oriented fibers with fabrics and / or knitted fabrics is possible according to the invention.
  • the fiber content in the polyisocyanurate composite material is more than 3% by weight, preferably more than 10% by weight, more preferably more than 15% by weight, preferably more than 20% by weight, most preferably more than 30 wt .-%, in particular 50, 60, 70 wt .-% based on the polyisocyanurate composite material.
  • polyethylene fibers show poor binding to the polymer matrix and must be compatibilized by appropriate pretreatments.
  • This can e.g. by silanization and / or corona treatment, as in Bahramian et al., 2015, "Ultra-high molecular weight polyethylene-reinforced dental composites: Dental Materials, Vol. 31, 1022
  • no pretreatment of the PE fibers is necessary when using the isocyanurate plastics according to the invention To cause adhesion of PE fiber and matrix material.
  • catalysts C for the crosslinking reaction it is possible in principle to use all catalysts which, at reaction temperatures of not more than 150 ° C., preferably not more than 130 ° C. and more preferably not more than 100 ° C., cross-link isocyanate groups to at least one of the structures selected from the group consisting of Catalyze isocyanurate, uretdione, biuret, urea, iminooxadiazinedione, oxadiazinetrione and allophanate groups.
  • crosslinking catalysts C are compounds which accelerate the trimerization of isocyanate groups to isocyanurate or uretdione structures. Since the formation of a structure is often accompanied by side reactions, depending on the catalyst used, for example, the trimerization to form Iminoxadiazindionen (so-called asymmetric Trimerisaten) and in the presence of urethane groups in the
  • catalysts of the invention may catalyze a trimerization preferably via the intermediate step of a uretdione formation.
  • Suitable catalysts C for the process according to the invention are simple tertiary amines, for example triethylamine, tributylamine, N, N-dimethylaniline, N-ethylpiperidine or N, N'-dimethylpiperazine.
  • Suitable catalysts are also the tertiary hydroxyalkylamines described in GB 2 221 465, such as, for example, triethanolamine, N-methyl-diethanolamine, Dimethylethanolamine, N-isopropyldiethanolamine and 1- (2-hydroxyethyl) pyrrolidine, or known from GB 2 222 161, from mixtures of tertiary bicyclic amines, such as DBU, with simple low molecular weight aliphatic alcohols catalyst systems.
  • GB 2 221 465 such as, for example, triethanolamine, N-methyl-diethanolamine, Dimethylethanolamine, N-isopropyldiethanolamine and 1- (2-hydroxyethyl) pyrrolidine, or known from GB 2 222 161, from mixtures of tertiary bicyclic amines, such as DBU, with simple low molecular weight aliphatic alcohols catalyst systems.
  • trimerization catalysts C for the process according to the invention are, for example, the quaternary ammonium hydroxides known from DE-A 1 667 309, EP-A 0 013 880 and EP-A 0 047 452, such as, for example, US Pat.
  • N, N, N-trimethyl-N-2-hydroxypropylammonium p-tert-butylbenzoate and N, N, N-trimethyl-N-2-hydroxypropylammonium 2-ethylhexanoate those known from EP-A 1 229 016 quaternary Benzylammonium carboxylates, such as N-benzyl-N, N-dimethyl-N-ethylammonium pivalate, N-benzyl-N, N-dimethyl-N-ethylammonium 2-ethylhexanoate, N-benzyl-N, N, N-tributylammonium 2-ethylhexanoate, N, N-dimethyl-N-ethyl-N- (4-methoxybenzyl) ammonium 2-ethylhexanoate or N, N, N-tributyl-N- (4-methoxybenzyl) ammonium pivalate, which are known from
  • Tetraethylphosphonium fluoride or tetra-n-butylphosphonium fluoride which are known from EP-A 0 798 299, EP-A 0 896 009 and EP-A 0 962 455 known quaternary ammonium and
  • Phosphoniumpolyfluoride such as benzyl-trimethylammoniumhydrogenpolyfluorid, known from EP-A 0 668 271 Tetraalkylammoniumalkylcarbonate which are obtainable by reaction of tertiary amines with dialkyl, or betaine structured quaternary Ammonioalkylcarbonate, known from WO 1999/023128 known quaternary ammonium bicarbonates, such as choline bicarbonate, the quaternary ammonium salts known from EP 0 102 482, obtainable from tertiary amines and alkylating esters of acids of phosphorus, such as reaction products of triethylamine, DABCO or N-methylmorpholine with dimethyl methanephosphonate, or the tetra-substituted ones known from WO 2013/167404 Ammonium salts of lactams, such as trioctylammonium caprolactamate or dodecyltrimethylammonium
  • Suitable are the known sodium and potassium salts of linear or branched alkanecarboxylic acids having up to 14 carbon atoms, such as butyric acid, valeric acid, caproic acid, 2-ethylhexalic acid, heptanoic acid, caprylic acid, pelargonic acid and higher homologs.
  • trimerization catalysts C for the process according to the invention is a multiplicity of different metal compounds.
  • Suitable examples are the octoates and naphthenates described in DE-A 3 240 613 as catalysts of manganese, iron, cobalt, nickel, copper, zinc, zirconium, cerium or lead or mixtures thereof with acetates of lithium, sodium, potassium, calcium or Barium, known from DE-A 3 219 608 sodium and potassium salts of linear or branched alkanecarboxylic acids having up to 10 carbon atoms, such as of propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, pelargonic acid, capric acid and undecynic acid, the alkali metal or alkaline earth metal salts of aliphatic, cycloaliphatic or aromatic monocarboxylic and polycarboxylic acids having 2 to 20 C atoms known from EP-A 0 100 129 , such as Sodium
  • Sodium or potassium phenoxide those known from GB 809 809 alkali and alkaline earth oxides, hydroxides, carbonates, alcoholates and phenates, alkali metal salts of enolisable compounds and metal salts of weak aliphatic or cycloaliphatic carboxylic acids, such as.
  • Sodium methoxide, sodium acetate, potassium acetate, sodium acetoacetic ester, lead 2-ethylhexanoate and lead naphthenate which are known from EP-A 0 056 158 and EP-A 0 056 159, complexed with crown ethers or polyether alcohols basic alkali metal compounds such.
  • Dibutyltin dichloride diphenyltin dichloride, triphenylstannanol, tributyltin acetate, stannous octoate, dibutyl (dimethoxy) stannane and tributyltin imidazolate.
  • crosslinking catalysts which are suitable for the process according to the invention can be found, for example, in J.H. Saunders and K.C. Frisch, Polyurethanes Chemistry and Technology, p. 94 ff (1962) and the literature cited therein.
  • the catalysts C can be used both individually and in the form of any mixtures with one another in the process according to the invention.
  • Organic phosphine catalysts of the general formula (I) are particularly suitable for the process according to the invention.
  • R 1, R 2 and R 3 are the same or different groups and each is an alkyl or
  • Cycloalkyl group of up to 10 carbon atoms preferably an alkyl group of 2 to 8 carbon atoms or a cycloalkyl group of 3 to 8 carbon atoms, an aralkyl group of 7 to 10, preferably 7 carbon atoms or an optionally alkyl radical of up to 10, preferably 1 to 6, Carbon atoms substituted aryl group having 6 to 10, preferably 6 carbon atoms, with the proviso that at most one of the radicals is an aryl group and at least one of the radicals is an alkyl or cycloalkyl group, or in which
  • RI and R2 are aliphatic in nature and, together with the
  • Phosphorus form a heterocyclic ring having 4 to 6 ring members, wherein R3 is an alkyl group having up to 4 carbon atoms, or mixtures of such tertiary organic phosphine catalysts of the general formula (I).
  • Suitable tertiary organic phosphine catalysts are, for example, tertiary phosphines with linear aliphatic substituents, such as trimethylphosphine, triethylphosphine, tri-n-propylphosphine, tripropylphosphine, dibutylethylphosphine, tri-n-butylphosphine, triisobutylphosphine, tri-tert-butylphosphine, pentyldimethylphosphine, pentyl-diethylphosphine, pentyl-di-propylphosphine, Pentyldibutylphosphin, Pentyldihexylphosphin, Dipentylmethylphosphin, Dipentylethylphosphin, Dipentylpropylphosphin, Dipentylbutylphosphin, Dipentylhexylphosphin, Dipent
  • tertiary organic phosphine catalysts which are suitable for the process according to the invention are, for example, also the tertiary phosphines known from EP 1 422 223 A1, which are at least have a directly bonded to phosphorus cycloaliphatic radical, such as.
  • Cyclopentyldiisopropylphosphin Cyclopentyldibutyl-phosphine with any isomeric butyl radicals
  • Cyclopentyldihexylphosphine with any isomeric hexyl radicals
  • the isomeric Cyclopentyldioctylphosphin with any isomeric octyl radicals Dicyclopentylmethylphosphin, Dicyclopentylethylphosphin, cyclopentyl-n-propylphosphine, Dicyclopentylisopropylphosphin, Dicyclopentylbutylphosphin with any isomeric butyl, Dicyclopentylhexylphosphin with any isomeric hexyl, Dicyclopentyloctylphosphin with any Octyl radical, tricyclopentylphosphine, cyclohexyldimethylphosphine,
  • Cyclohexyl-di-isopropylphosphin Cyclohexyldibutylphosphine with any isomeric butyl radicals
  • Cyclohexyldihexylphosphin with any isomeric hexyl radicals the isomeric octyl radicals
  • tertiary organic phosphine catalysts for the process according to the invention are, for example, the tert-phosphines known from EP 1 982 979 A1, which have one or two directly attached to phosphorus, tertiary alkyl radicals, such as. B.
  • tert-butyldimethylphosphine tert-butyldiethyl phosphine, tert-butyldi-n-propylphosphine, tert-butyldiisopropyl phosphine, tert-butyldibutylphosphine with any isomeric butyl radicals for the non-tertiary butyl
  • Di tert-Butylmethylphosphin di-tert-butylethy
  • the tertiary organic phosphine catalyst is preferably selected from the group of said tertiary phosphines with linear aliphatic substituents.
  • Very particularly preferred tertiary organic phosphine catalysts are tri-n-butylphosphine and / or trioctylphosphine.
  • the tertiary organic phosphine catalyst generally comes in a concentration of from 0.0005 to 10.0% by weight, preferably from 0.01 to 5.0% by weight and more preferably, based on the weight of the polyisocyanate composition A used from 0.1 to 3.0 wt .-%, and most preferably from 0.5 to 2.0 wt .-% for use.
  • the tertiary organic phosphine catalysts used in the process according to the invention are generally sufficiently soluble in the polyisocyanate composition A in the amounts needed to initiate the oligomerization reaction.
  • the addition of the catalyst C to the polyisocyanate A is therefore carried out in this embodiment, preferably in substance.
  • the tertiary organic phosphine catalysts can also be used dissolved in a suitable organic solvent to improve their incorporation.
  • the degree of dilution of the catalyst solutions can be freely selected within a very wide range. Catalytically effective such catalyst solutions are usually from a concentration of about 0.01 wt .-%.
  • the phosphorus-containing catalysts used are sensitive to oxidation and convert after a few hours to weeks by oxidation into no longer catalytically active and preferably colorless and preferably flame retardant compounds.
  • Such catalysts are, for example, phosphines with (cyclo) aliphatic radicals.
  • alkali metal or alkaline earth metal salts of aliphatic, cycloaliphatic or aromatic mono- and polycarboxylic acids having 2 to 20 C atoms are particularly suitable. Even more preferred is the potassium salt of one of the aforementioned carboxylic acids. Particularly preferred is potassium acetate
  • catalysts C are catalysts according to formula (II) and their adducts. If a combination of a catalyst CI and C2 is used, the abovementioned compounds are preferably used as catalyst C2.
  • R 1 and R 2 are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, branched C5-alkyl, unbranched C5-alkyl, branched C6-alkyl, unbranched C6-alkyl, branched C7 alkyl and unbranched C7 alkyl;
  • A is selected from the group consisting of O, S and NR 3 , wherein R 3 is selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl and isobutyl; and
  • B is independently of A selected from the group consisting of OH, SH NHR 4 and NH 2 , wherein R 4 is selected from the group consisting of methyl, ethyl and propyl
  • A is NR 3 , wherein R 3 is selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl and isobutyl.
  • R 3 is methyl or ethyl. More preferably R 3 is methyl.
  • B is OH and R 1 and R 2 are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, branched C 5 alkyl, unbranched C 5 alkyl, branched C 6 - Alkyl, unbranched C6-alkyl, branched C7-alkyl and unbranched C7-alkyl.
  • R 1 and R 2 are independently methyl or ethyl. More preferably, R 1 and R 2 are methyl.
  • R 1 and R 2 are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, branched C 5 alkyl, unbranched C 5 alkyl, branched C 6 - Alkyl, unbranched C6-alkyl, branched C7-alkyl and unbranched C7-alkyl.
  • R 1 and R 2 are independently methyl or ethyl. More preferably, R 1 and R 2 are methyl.
  • R 1 and R 2 are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, branched C 5 alkyl, branched C 5 alkyl, branched C6 alkyl, unbranched C6 alkyl, branched C7 alkyl and unbranched C7 alkyl.
  • R 1 and R 2 are independently methyl or ethyl. More preferably, R 1 and R 2 are methyl.
  • R4 is selected from the group consisting of methyl, ethyl and propyl.
  • R 4 is methyl or ethyl.
  • R 4 is methyl.
  • B is NH 2 and R 1 and R 2 are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, branched C 5 -alkyl, branched C 5 -alkyl, branched C6 alkyl, unbranched C6 alkyl, branched C7 alkyl and unbranched C7 alkyl.
  • R 1 and R 2 are independently methyl or ethyl. More preferably, R 1 and R 2 are methyl.
  • A is oxygen
  • B is OH and R 1 and R 2 are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, branched C 5 alkyl, unbranched C 5 alkyl, branched C 6 - Alkyl, unbranched C6-alkyl, branched C7-alkyl and unbranched C7-alkyl.
  • R 1 and R 2 are independently methyl or ethyl. More preferably, R 1 and R 2 are methyl.
  • R 1 and R 2 are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, branched C 5 alkyl, unbranched C 5 alkyl, branched C 6 - Alkyl, unbranched C6-alkyl, branched C7-alkyl and unbranched C7-alkyl.
  • R 1 and R 2 are independently methyl or ethyl. More preferably, R 1 and R 2 are methyl.
  • R 1 and R 2 are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, branched C 5 alkyl, branched C 5 alkyl, branched C6 alkyl, unbranched C6 alkyl, branched C7 alkyl and unbranched C7 alkyl.
  • R 1 and R 2 are independently methyl or ethyl. More preferably, R 1 and R 2 are methyl.
  • R 4 is selected from the group consisting of methyl, ethyl and propyl.
  • R 4 is methyl or ethyl.
  • R 4 is methyl.
  • B is NH 2 and R 1 and R 2 are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, branched C 5 -alkyl, branched C 5 -alkyl, branched C6 alkyl, unbranched C6 alkyl, branched C7 alkyl and unbranched C7 alkyl.
  • R 1 and R 2 are independently methyl or ethyl. More preferably, R 1 and R 2 are methyl.
  • A is sulfur
  • B is OH and R 1 and R 2 are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, branched C 5 alkyl, unbranched C 5 alkyl, branched C 6 - Alkyl, unbranched C6-alkyl, branched C7-alkyl and unbranched C7-alkyl.
  • R 1 and R 2 are independently methyl or ethyl. More preferably, R 1 and R 2 are methyl.
  • R 1 and R 2 are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, branched C 5 alkyl, unbranched C 5 alkyl, branched C 6 - Alkyl, unbranched C6-alkyl, branched C7-alkyl and unbranched C7-alkyl.
  • R 1 and R 2 are independently methyl or ethyl. More preferably, R 1 and R 2 are methyl.
  • R 1 and R 2 are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, branched C 5 alkyl, branched C 5 alkyl, branched C6 alkyl, unbranched C6 alkyl, branched C7 alkyl and unbranched C7 alkyl.
  • R 1 and R 2 are independently methyl or ethyl. More preferably, R 1 and R 2 are methyl.
  • R 4 is selected from the group consisting of methyl, ethyl and propyl.
  • R 4 is methyl or ethyl.
  • R 4 is methyl.
  • B is NH 2 and R 1 and R 2 are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, branched C 5 -alkyl, branched C 5 -alkyl, branched C6 alkyl, unbranched C6 alkyl, branched C7 alkyl and unbranched C7 alkyl.
  • R 1 and R 2 are independently methyl or ethyl. More preferably, R 1 and R 2 are methyl.
  • adducts of a compound according to formula (II) and a compound having at least one isocyanate group are also suitable.
  • adduct is understood to mean urethane, thiourethane and urea adducts of a compound of the formula (II) with a compound having at least one isocyanate group, a urethane adduct being particularly preferred
  • B is a thiol group
  • a thiourethane adduct is formed
  • B is NH 2 or NFIR 4
  • a fl uid adduct is formed.
  • Suitable catalyst solvents are, for example, solvents which are inert toward isocyanate groups, e.g. Hexane, toluene, xylene, chlorobenzene, ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl or ethyl ether acetate, diethylene glycol ethyl and butyl ether acetate, propylene glycol monomethyl ether acetate, 1-methoxypropyl 2-acetate, 3-methoxy n-butyl acetate, propylene glycol diacetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, lactones such as ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -caprolactone and e-methylcaprolactone, but also solvents such as N-methylpyr
  • catalyst solvents which carry isocyanate-reactive groups and can be incorporated into the polyisocyanurarate resin.
  • solvents are mono- or polyhydric simple alcohols, such as, for example, methanol, ethanol, n-propanol, isopropanol, n- Butanol, n-hexanol, 2-ethyl-l-hexanol, ethylene glycol, propylene glycol, the isomeric butanediols, 2-ethyl-l, 3-hexanediol or glycerol; Ether alcohols, such as, for example, 1-methoxy-2-propanol, 3-ethyl-3-hydroxymethyloxetane, tetrahydrofurfuryl alcohol, ethylene glycol monomethyl ether,
  • unsaturated alcohols such as e.g. Allyl alcohol, 1,1-dimethyl-allyl alcohol or oleic alcohol
  • araliphatic alcohols such as e.g. benzyl alcohol
  • N-mono-substituted amides e.g. N-methylform
  • At least one crosslinking catalyst CI and at least one crosslinking catalyst C2 are used.
  • the first catalyst CI catalyzes crosslinking of isocyanate groups to at least one of the structures selected from the group consisting of isocyanurate, uretdione, biuret, urea, iminooxadiazinedione, oxadiazinetrione and allophanate groups at reaction temperatures below 100 ° C., preferably below 80 ° C, more preferably below 60 ° C, even more preferably below 50 ° C.
  • the second catalyst C2 catalyzes at least one of the aforementioned crosslinking reactions at reaction temperatures of at least 50 ° C, more preferably at least 60 ° C, even more preferably at least 80 ° C, and most preferably at least 100 ° C. It is preferred that the catalyst C2 has only a low activity at temperatures below 100 ° C, preferably below 80 ° C, more preferably below 60 ° C and even more preferably below 50 ° C.
  • the catalyst has the desired activity at the given temperature if it catalyzes crosslinking of at least 15 mol% of the isocyanate groups present in the polyisocyanate A composition in at most one hour, preferably at most 3 hours and more preferably at most 24 hours.
  • low activity refers to a crosslinking of at most 10 mol% of the isocyanate groups present in the polyisocyanate composition A in a period of at least one hour, more preferably at least 3 hours and even more preferably at least 24 hours.
  • Said first crosslinking catalyst CI is preferably an organic phosphine catalyst of the formula (I) as described above.
  • the second catalyst C2 may be any catalyst. Preferably, one of the catalysts mentioned in WO 2016/170057, WO 2016/170059 or WO / 2016/170061 is used.
  • the second catalyst C2 is an alkali or alkaline earth metal salt of aliphatic, cycloaliphatic or aromatic mono- and polycarboxylic acids having 2 to 20 carbon atoms. Even more preferably, the second catalyst C2 is the potassium salt of one of the aforementioned carboxylic acids. Most preferably, the second catalyst is potassium acetate.
  • catalytic crosslinking of the isocyanate composition A refers to a process in which the isocyanate groups contained in the polyisocyanate composition A react with each other to crosslink the monomeric and / or oligomeric isocyanates contained in the polyisocyanate composition A. Since this reaction is effected by the crosslinking catalyst C It is also called “catalytic networking”.
  • the crosslinking is preferably carried out to form at least one structure selected from the group consisting of isocyanurate, uretdione, biuret, urea, iminooxadiazinedione, oxadiazinetrione and allophanate groups.
  • the crosslinking takes place with formation of isocyanurate groups and at least one further of the abovementioned structures.
  • catalytic crosslinking is at least 30 mol%, more preferably at least 40 mol%, even more preferably at least 50 mol%, even more preferably at least 60 mol%, most preferably at least 70 mol%. % and most preferably at least 80 mol% by formation of isocyanurate groups.
  • the abovementioned values are determined by relating the number of isocyanurate groups in the cured material to the total number of isocyanurate, uretdione, biuret, urea, iminooxadiazinedione, oxadiazinetrione and allophanate groups.
  • isocyanate-reactive groups are amino, thiol and hydroxyl groups, particularly preferably hydroxyl groups, whereby it does not matter by which route the abovementioned groups are introduced into the mixture present at the beginning of process step b) can be carried out via impurities of the fiber B, via additives, for example catalyst solvents, to the crosslinking catalyst C or by direct addition In any case, it is essential that the abovementioned conditions are observed at the beginning of process step b).
  • Example 2 shows that the presence of high concentration polyols or the formation of a large number of urethane groups results in the polymer fibers not becoming stably embedded in the matrix. Therefore, it makes sense to limit the concentration of isocyanate-reactive groups in the reaction mixture.
  • the temperature ranges defined below during process step b) are maintained at all points of the resulting composite material.
  • This temperature is also referred to as the "reaction temperature.” It is to be distinguished from the temperature that exists outside of the resulting composite, the “ambient temperature.”
  • the catalytic crosslinking is preferably carried out at a reaction temperature of -20 ° C to 150 ° C.
  • the curing is particularly preferably carried out in the temperature range from 0 ° C to 130 ° C and most preferably from 20 ° C to 120 ° C.
  • the catalytic crosslinking is preferably carried out at reaction temperatures between 100 ° C and 140 ° C.
  • the temperature of the reaction during catalytic crosslinking does not only depend on the ambient temperature. Among other things, it is influenced by the following parameters: isocyanate content per weight unit of the resulting composite, size and shape of the workpiece (ie ratio of heat generation and heat dissipation across the surface), active cooling of the workpiece (or, where necessary, active heating) and selection of the catalyst (faster reactions lead to more heating with the same heat dissipation).
  • the heat profile of the reaction can be monitored with temperature probes, so that it is possible in simple preliminary experiments to adjust the above parameters so that the desired temperature range is maintained.
  • the temperature profile and catalyst selection of the catalytic crosslinking of the matrix to at least 50 mol% isocyanurate structures for each component is optimized based on a process simulation.
  • a process simulation for the desired component / Flalbzeug such as a Pultrusionsprofil, a prepreg, an infusion mold, an SMC form at different catalyst concentrations or catalyst compositions and different temperature profiles driven, where appropriate, the matrix temperature via thermocouples or thermocouples over the course of the reaction is measured. From this parameter set, an ideal processing strategy with regard to temperature and catalyst is developed.
  • the catalytic trimerization in the temperature ranges defined above is preferably carried out using the phosphines described above as at least one catalyst component. However, it is also suitable any other catalyst which causes crosslinking of isocyanate groups in these temperature ranges.
  • the catalytic crosslinking of the isocyanate groups of the polyisocyanate A preferably results in that at the end of the reaction, at least 70%, preferably at least 80%, more preferably at least 90% and most preferably at least 95% of the free isocyanate groups originally present in the polyisocyanate A have reacted. In other words, preferably only at most 30%, at most 20%, particularly preferably at most 10%, very particularly preferably at most 5% of the isocyanate groups originally present in the polyisocyanate composition A are present in the matrix of the composite material obtained by the process according to the invention.
  • the course of the crosslinking reaction can initially be determined by titrimetric determination of the NCO content, but as the reaction progresses, gelling and solidification of the reaction mixture rapidly sets in, which makes wet-chemical analysis methods impossible.
  • the further conversion of the isocyanate groups can then be followed only by spectroscopic methods, for example by IR spectroscopy based on the intensity of the isocyanate at about 2270 cm-1 or the increase of the matrix Tg by means of DSC / DMA.
  • the catalytic crosslinking in process step b) takes place in two stages.
  • the lower limit of the temperature of the polyisocyanate composition A during process step bl) is at least at -20 ° C, more preferably at 0 ° C, even more preferably at 20 ° C, and most preferably at 30 ° C.
  • the temperature range between at least 20 ° C. and at most 120 ° C. is preferred for process step b1).
  • the process step b1) is preferably carried out for at least 30 minutes.
  • the temperature of the polyisocyanate A is increased in a process step b2) compared to the process step bl) by at least 20 ° C. This achieves the Temperature of the polyisocyanate A at least 50 ° C, but preferably a temperature of 150 ° C is not exceeded. At this temperature, the crosslinking is continued. Since higher crosslinking temperatures lead to higher glass transition temperatures of the cured polyisocyanate composition A, it is possible in this way to obtain composites whose matrix has an increased glass transition temperature.
  • the process step b2) is preferably carried out for at least 5 minutes.
  • a "catalytic crosslinking of the polyisocyanate composition A in the presence of at least one polymer fiber B" does not exclude that other organic or inorganic fillers are present in addition to the polymer fiber B to be used in accordance with the invention.
  • the volume fraction of polymer fiber B based on the sum of all organic and inorganic, fibrous and non-fibrous fillers is at least 20% by volume, more preferably at least 40% by volume, more preferably at least 50% by volume. even more preferably at least 70% by volume and most preferably at least 90% by volume.
  • the above-defined volume fraction of the polymer fiber B is at least 95% by volume.
  • the present invention relates to a composite material, characterized in that the composite has a density of at most 1.2 kg / l, preferably at most 1.15, more preferably at most 1.1, most preferably at most 1.05 determined according to DIN EN ISO 1183 - 1 has.
  • the modulus of elasticity is at least 3 GPa, preferably at least 5 GPa, more preferably at least 10 GPal, and most preferably at least 15 GPa.
  • the modulus of elasticity is preferably determined in a 3-point bending test in accordance with DIN EN ISO 14125: 2011-05.
  • said composite is characterized by containing polymer fibers, preferably polyethylene fibers, and most preferably ultra-high molecular weight polyethylene fibers B which have not been compatibilized.
  • the matrix of the composite is preferably constructed of a catalytically crosslinked polyisocyanate composition A having an isocyanate index of at least 100, more preferably at least 150, and most preferably at least 200.
  • the proportion of polyisocyanurate groups in the polymer matrix based on the total number of isocyanurate, uretdione, biuret, urea, iminooxadiazinedione, oxadiazinetrione and allophanate groups is at least 20 mol%, preferably at least 25 mol%, in the material defined above preferably at least 30 mol% and most preferably at least 35% mol%.
  • Proportion of polyisocyanurate groups in the polymer matrix of at least 30 mol% based on the total number of isocyanurate, uretdione, biuret, urea, Iminooxadiazindion-, Oxadiazintrion- and allophanate groups
  • the present invention relates to a composite obtainable by the method according to the invention.
  • the present invention relates to the use of a composite material obtainable by the process according to the invention for producing a semifinished product or component.
  • Components produced by the method according to the invention are preferably profiles, tubes, plates or any other shaped bodies. These can be used in various fields such as automotive and shipbuilding, aerospace, home and plant construction, personal protection, electronics, furniture, oil production, medical technology or sporting goods. In particular, structural, ballistic and / or crash-relevant components in aircraft, trains, automobiles, boats, etc. must be mentioned here.
  • Preferred embodiments are any three-dimensional molded articles from the "sheet-molding-compound process" (SMC), for example, housings, doors, roof modules, bumpers, moldings of the pultrusion process such as profiles, tubes and rods, as well as any shaped bodies or reinforcing elements that come out of the insert of prepregs, such as pipes, sashes, as well as any shaped bodies resulting from infusion processes, such as wind turbine blades, structural elements in bridges and buildings, as well as any rotationally symmetric elements such as those produced by filament winding, such as masts, pressure vessels, pipes, as well as any shaped bodies as they arise by reaction injection molding.
  • SMC sheet-molding-compound process
  • the present invention relates to one of the above components which contains or consists of a composite material obtainable by the method according to the invention.
  • the present invention relates to the use of the composite materials according to the invention for the production of moldings as well as moldings which consist of or contain the composite materials according to the invention.
  • a "shaped body” as used herein is a body having a thickness of at least 0.5 mm, preferably at least 1 mm, more preferably at least 2 mm in its smallest extension direction, in particular a "shaped body” as used herein , no foil or membrane.
  • RT room temperature
  • phase transitions were determined by means of DSC (Differential Scanning Calorimetry) using a Mettler DSC 12E (Mettler Toledo GmbH, Giessen, Germany) in accordance with DIN EN 61006. Calibration was performed by the temperature of the indium-lead melted on-set. 10 mg of substance were weighed into normal capsules. The measurement was carried out by three heats from -50 ° C to +200 ° C at a heating rate of 20 K / min with subsequent cooling at a cooling rate of 320 K / min. The cooling was carried out by liquid nitrogen. Nitrogen was used as purge gas.
  • the values given are based on the evaluation of the 1st heating curve, since the temperature changes in the investigated reactive systems in the DSC make it possible to change the sample in the measurement process at high temperatures.
  • the melting temperatures T m were obtained from the temperatures at the maxima of the heat flow curves.
  • the glass transition temperature T g was obtained from the temperature at half the height of a glass transition stage.
  • the infrared spectra were measured on a Bruker FT-IR spectrometer equipped with an ATR unit.
  • Polyisocyanate Al HDI trimer (NCO functionality> 3) with an NCO content of 23.0 wt .-% of the company. Covestro AG. The viscosity is about 1200 mPa-s at 23 ° C (DIN EN ISO 3219 / A.3).
  • Catalyst K1 Trioctylphosphine was obtained with a purity of 97% by weight from Sigma-Aldrich
  • Catalyst K2 Dibutyltin dilaurate was obtained with a purity of 95% by weight from Sigma-Aldrich
  • Polyethylene glycol (PEG) 400 was obtained with a purity of> 99 wt .-% of the company. ACROS.
  • Potassium acetate was obtained with a purity of> 99 wt .-% of the company. ACROS.
  • Glycerol was obtained with a purity of> 99 wt .-% of the company. ACROS.
  • the PE fiber was a Dyneema brand UFIMWPE gel-spun fiber from DSM.
  • the PE fabric was a woven material (0 ° / 90 °) of gel spun UFIMWPE Dyneema fibers from DSM.
  • the thermal properties of the PE fiber were determined by DSC. From the first Fleizkurve a melting temperature T m of 151.5 ° C was obtained with a heat of fusion AH m of 269.4 J / g, while from the second Fleizkurve a melting temperature T m of 137.7 ° C with a heat of fusion AH m of 147.1 J / g was obtained. This behavior is due to the high crystallinity of the gel-spun fiber and allows higher temperatures in the cross-linking of the polymer resin than in other produced PE fibers.
  • reaction mixture was, unless otherwise indicated, by mixing polyisocyanate Al with an appropriate amount of catalyst (Kl-4) and optionally an appropriate amount of glycerol at 23 ° C in a Speed Mixer DAC 150.1 FVZ Fa. Hauschild at 2750 min-1 produced. This was then either cast into a suitable mold for crosslinking without further treatment, or added to the corresponding PE fibers or PE fabrics for further processing.
  • the fibers are cleaned prior to use by placing in acetone for 30 minutes and then rinsing and drying at RT.
  • the polyisocyanurate composites are obtained by mixing the PE fibers with the appropriate reaction mixture or pouring over the PE fabrics with the reaction mixture and then curing the reaction mixture.
  • the exemplary embodiments show that exclusively the use of polyisocyanates as the reactive component and their catalytic conversion to crosslinked polyisocyanurates in the presence of one or more trimerization catalysts leads to a sufficient wetting of fillers based on polyethylene fibers and thus enables the production of composite materials based on polymer fibers ( Example 1).
  • Comparative Example 2 shows that the simultaneous use of polyisocyanates and polyols as well as their catalytic conversion into crosslinked polyurethanes leads to compatibility problems between filler and matrix. This results in a separation of the filler and thus does not lead to composite materials. Composites based on polyurethanes are not available without prior compatibilization.
  • Example 1 both in the pre-crosslinking at 100 ° C and in the subsequent post-crosslinking at 140 ° C, the heat release by the exotherm of the individual process steps was not sufficient to exceed the melting temperature of the PE fiber
  • Comparative Example 3 shows that, although the ambient temperature of 140 ° C below the melting point of the PE fiber was the heat release by the exotherm of the individual process step to an exceeding of the melting point of the PE fiber resulted because the heat of reaction could not be dissipated sufficiently quickly.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Civil Engineering (AREA)
  • Composite Materials (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne un procédé pour la production de matériaux composites à partir de fibres de polyéthylène de poids moléculaire ultraélevé et des polyisocyanates réticulés, les matériaux composites pouvant être obtenus de celui-ci ainsi que l'utilisation de tels matériaux composites pour la fabrication de composants ainsi que composants, consistant en ou contenant un matériau composite selon l'invention.
EP19722646.7A 2018-05-17 2019-05-13 Procédé pour la production de matériaux composites à partir de fibres de polyéthylène de poids moléculaire ultraélevé et des polyisocyanates réticulés Withdrawn EP3794050A1 (fr)

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EP18172971 2018-05-17
PCT/EP2019/062218 WO2019219614A1 (fr) 2018-05-17 2019-05-13 Procédé pour la production de matériaux composites à partir de fibres de polyéthylène de poids moléculaire ultraélevé et des polyisocyanates réticulés

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EP3794050A1 true EP3794050A1 (fr) 2021-03-24

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WO2023001848A1 (fr) * 2021-07-23 2023-01-26 Sika Technology Ag Plastiques de polyisocyanurate à transparence élevée

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WO2019219614A1 (fr) 2019-11-21
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