US20200190245A1 - Composite materials based on dual-curing isocyanurate polymers - Google Patents

Composite materials based on dual-curing isocyanurate polymers Download PDF

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Publication number
US20200190245A1
US20200190245A1 US16/349,322 US201716349322A US2020190245A1 US 20200190245 A1 US20200190245 A1 US 20200190245A1 US 201716349322 A US201716349322 A US 201716349322A US 2020190245 A1 US2020190245 A1 US 2020190245A1
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United States
Prior art keywords
isocyanate
component
polymerizable composition
reactive
groups
Prior art date
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US16/349,322
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English (en)
Inventor
Paul Heinz
Richard MEISENHEIMER
Jöng TILLACK
Dirk Achten
Thomas Büsgen
Michael Ludewig
Christoph Tomczyk
Roland Wagner
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Covestro Deutschland AG
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Covestro Deutschland AG
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Publication of US20200190245A1 publication Critical patent/US20200190245A1/en
Assigned to COVESTRO DEUTSCHLAND AG reassignment COVESTRO DEUTSCHLAND AG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: TOMCZYK, Christoph, MEISENHEIMER, Richard, LUDEWIG, MICHAEL, ACHTEN, DIRK, BUESGEN, THOMAS, HEINZ, PAUL, TILLACK, JOENG, WAGNER, ROLAND
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    • 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
    • C08G18/81—Unsaturated isocyanates or isothiocyanates
    • C08G18/8125—Unsaturated isocyanates or isothiocyanates having two or more isocyanate or isothiocyanate groups
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    • 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
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
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    • 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
    • C08G18/81—Unsaturated isocyanates or isothiocyanates
    • C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
    • C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
    • C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
    • C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/244—Stepwise homogeneous crosslinking of one polymer with one crosslinking system, e.g. partial curing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2475/00—Presence of polyurethane

Definitions

  • the present invention relates to polymerizable compositions comprising components which can be crosslinked either via isocyanurate bonds or by a free-radical reaction mechanism. It further describes processes by which polymers can be prepared from these compositions.
  • WO 2015/155195 describes a composite material obtainable from a reinforcing material and a polyurethane composition consisting of at least one polyisocyanate (PIC), a PIC-reactive component consisting of at least one polyol and at least one methacrylate having OH groups, and a free-radical initiator.
  • PIC polyisocyanate
  • PIC-reactive component consisting of at least one polyol and at least one methacrylate having OH groups
  • a free-radical initiator a free-radical initiator.
  • a disadvantage of the process used, in addition to the short pot lives/gel times of the polyurethane compositions, is the fact that, in the preparation of polyurethanes, the mixing ratio of the components, especially of the polyisocyanate and the polyol, is limited by the necessity of keeping the molar ratio of isocyanate and isocyanate-reactive groups close to 1:1.
  • WO 2016/087366 describes a free-radically polymerizable composition consisting of a polyurethane containing double bonds and a reactive diluent based on various methacrylates.
  • a disadvantage here is the two-stage reaction regime since a polyurethane first has to be prepared proceeding from an isocyanate and a polyol, and has to be significantly diluted. The subsequent crosslinking is effected exclusively via a free-radical polymerization in a separate step.
  • WO 2016/170057, WO 2016/170059 and WO 2016/170061 describe the production of polyisocyanurate plastics by polyaddition of oligomeric isocyanates.
  • the effect of the use of oligomeric isocyanates in place of monomeric isocyanates is that less heat of reaction arises in the polymerization and hence rapid polymerization is possible without overheating of the reaction mixture. This is important particularly in the production of shaped bodies since the heat that arises within the shaped body can be removed here via the surface only to a limited degree.
  • the low-monomer polyisocyanate compositions described as reactants in these applications have the disadvantage of a high relatively high viscosity which can be a hindrance in some applications. This is especially true for the production of composite materials with a high filler level.
  • monomeric polyisocyanates as reactive diluents is undesirable owing to the above-described problem of the heat of reaction.
  • monomeric polyisocyanates are volatile and should therefore not be used if at all possible for reasons of occupational hygiene.
  • conventional organic solvents can be used to reduce the viscosity.
  • these are disadvantageous for reasons of environmental protection since they are released into the environment during or after the polymerization.
  • the use of solvents in the production of shaped bodies can lead to material defects, for example to formation of cavities, since the volume of the evaporating solvent is missing in the material.
  • a first object of the present invention was that of providing a reaction system with a dual curing mechanism in which the mixing ratio of the reactants is adjustable within a distinctly wider range than in the case of the known polyurethane systems.
  • the present invention relates to a polymerizable composition for producing a composite material, comprising
  • a “reactive resin” is a mixture that can be cured by a combination of free-radical polymerization and crosslinking of the isocyanate groups of the isocyanate component with one another to give a solid material.
  • reaction mixture is also used synonymously hereinafter.
  • the reactive resin serves as matrix material into which the filler J is embedded.
  • Components A to I defined further down are obligatory or optional constituents of the reactive resin.
  • the isocyanate component A enables the formation of a polymer that forms through the addition of isocyanate groups. This forms isocyanurate groups in particular.
  • the crosslinking of the isocyanate groups present in the isocyanate component A endows the polymer with the majority of its mechanical and chemical stability.
  • the crosslinking of the isocyanate groups is mediated by the trimerization catalyst C.
  • Components B, D and E are each characterized by the presence of an ethylenic double bond. This double bond is a prerequisite for a second crosslinking mechanism to be available in addition to the polyaddition of the isocyanate groups in the polymerizable composition.
  • the use of these individual components or particular combinations of components has specific advantages here:
  • Component B lowers the viscosity of the polymerizable composition. It can thus advantageously serve as a reactive diluent, meaning that it becomes part of the polymer on conclusion of the polymerization process. It can also serve for the rapid buildup of viscosity if a free-radical polymerization of the ethylenic double bonds is first initiated, preferably by ionizing radiation, and the crosslinking of the isocyanate groups is conducted only thereafter.
  • component B is used in combination with a component D or E. It can also be used in combination with both components.
  • Components D and E mediate the crosslinking of the network, formed by free-radical polymerization, of component B with the polymer of isocyanate component A formed through polyaddition of the isocyanate groups. They thus ensure that there are no two separate polymer networks of components A and B present in the polymer, but rather a single polymer network.
  • components D and F enable the formation of a polymer network via free-radical polymerization.
  • the complete curing of the polymerizable composition of the invention can be effected in two different process steps separated in time.
  • the free-radical crosslinking of components D and E can firstly build up viscosity that already imparts a certain degree of dimensional stability to the product being formed, but without making further processing impossible, for example by bending, pressing or embossing. It is only the subsequent crosslinking of the isocyanate groups with one another that leads to complete curing that endows the product with its ultimate stability. What is formed here is a uniform polymer network since components B and D always also react with the isocyanate groups of isocyanate component A.
  • the polymerizable composition contains at least one of the two components D and E, but no component B.
  • composition of the invention contains a component B and at least one of the two components D and E, Particular preference is given to the combination of B and D.
  • the polymerizable composition of the invention comprises isocyanate component A and component B preferably in a quantitative ratio that lowers the viscosity of the undiluted isocyanate component to at most 75%, more preferably at most 50%, even more preferably at most 33%, of the viscosity of undiluted isocyanate component A.
  • the presence of at least one of components D and E is preferred in this embodiment, but not obligatory.
  • the quantitative ratio of component A to the total amount of components B, D and E is such that the polymerizable composition has a viscosity of at most 100000 mPas, more preferably of at most 10000 mPas, even more preferably of at most 5000 mPas and most preferably at most 2000 mPas.
  • the molar ratio of isocyanate groups and ethylenic double bonds is preferably within a range from 1:10 to 10:1, more preferably 1:5 to 8:1 and even more preferably 1:3 to 5:1.
  • the molecular ratio of these functional groups can be determined by the integration of the signals of a sample in the 13 C NMR spectrum.
  • the polymer obtainable by polymerizing the reactive resin of the invention receives its advantageous properties very substantially through crosslinking of the isocyanate groups with one another. Consequently, it is essential to the invention that the ratio of isocyanate groups to the total amount of the isocyanate-reactive groups in the reactive resin is restricted such that there is a distinct molar excess of isocyanate groups.
  • the molar ratio of isocyanate groups of the isocyanate component to isocyanate-reactive groups in the reactive resin is consequently at least 2.0:1.0, preferably at least 3.0:1,0, more preferably at least 4.0:1.0 and even more preferably at least 8.0:1.0.
  • Isocyanate-reactive groups in the context of the present application are hydroxyl, thiol, carboxyl and amino groups, amides, urethanes, acid anhydrides and epoxides.
  • the isocyanate groups present in the polymerizable composition are present in components A and—if present—E.
  • the isocyanate-reactive groups may in principle be present in all other components except for component B.
  • the use of the reactive resin of the invention enables greater flexibility in the selection of the proportions of the individual components. If a polyurethane or a polyurea is to be obtained, the molar ratio of isocyanate groups to isocyanate-reactive groups must if possible be close to 1:1. According to the present invention, however, there is a distinct excess of isocyanate groups that is consequently not just acceptable but actually desired because the polymer formed owes its advantageous properties very substantially to the reaction of isocyanate groups with other isocyanate groups.
  • the structures thus formed, especially the isocyanurate groups lead to polymers with exceptional hardness and exceptional stability to chemicals. Isocyanurate groups also have an intrinsic flame-retardant effect, and so the addition of flame retardants otherwise necessary for many applications can be dispensed with.
  • Isocyanate component A in the context of the invention refers to the isocyanate component in the reactive resin. In other words, this is the sum total of all the compounds in the reactive resin that have isocyanate groups, except for component E.
  • the isocyanate component A is thus used as reactant in the process of the invention.
  • isocyanate component A especially to “providing the isocyanate component A”, this means that the isocyanate component A exists and is used as reactant.
  • the isocyanate component A preferably contains at least one polyisocyanate.
  • polyisocyanate as used here is a collective term for compounds containing two or more isocyanate groups in the molecule (this is understood by the person skilled in the art to mean free isocyanate groups of the general structure —N ⁇ C ⁇ O).
  • the simplest and most important representatives of these polyisocyanates are the diisocyanates. These have the general structure O ⁇ C ⁇ N—R—N ⁇ C ⁇ O where R typically represents aliphatic, alicyclic and/or aromatic radicals.
  • polyisocyanates Because of the polyfunctionality ( ⁇ 2 isocyanate groups), it is possible to use polyisocyanates to produce a multitude of polymers (e.g. polyurethanes, polyureas and polyisocyanurates) and low molecular weight compounds (for example those having uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and/or oxadiazinetrione structure).
  • polymers e.g. polyurethanes, polyureas and polyisocyanurates
  • low molecular weight compounds for example those having uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and/or oxadiazinetrione structure.
  • polyisocyanates in this application refers equally to monomeric and/or oligomeric polyisocyanates. For the understanding of many aspects of the invention, however, it is important to distinguish between monomeric diisocyanates and oligomeric polyisocyanates. Where reference is made in this application to “oligomeric polyisocyanates”, this means polyisocyanates formed from at least two monomeric diisocyanate molecules, i.e. compounds that constitute or contain a reaction product formed from at least two monomeric diisocyanate molecules.
  • oligomeric polyisocyanates from monomeric diisocyanates is also referred to here as modification of monomeric diisocyanates.
  • modification means the reaction of monomeric diisocyanates to give oligomeric polyisocyanates having uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and/or oxadiazinetrione structure.
  • hexamethylene diisocyanate is a “monomeric diisocyanate” since it contains two isocyanate groups and is not a reaction product of at least two polyisocyanate molecules:
  • oligomeric polyisocyanates within the context of the invention.
  • Representatives of such “oligomeric polyisocyanates” are, proceeding from monomeric HDI, for example, HDI isocyanurate and HDI biuret, each of which is formed from three monomeric HDI units:
  • the proportion by weight of isocyanate groups based on the total amount of the isocyanate component A is at least 15% by weight.
  • the isocyanate component A may consist essentially of monomeric polyisocyanates or essentially of oligomeric polyisocyanates. It may alternatively comprise oligomeric and monomeric polyisocyanates in any desired mixing ratios.
  • the isocyanate component A used as reactant in the trimerization has a low level of monomers (i.e. a low level of monomeric diisocyanates) and already contains oligomeric polyisocyanates.
  • a low level of monomers i.e. a low level of monomeric diisocyanates
  • oligomeric polyisocyanates already contains oligomeric polyisocyanates.
  • the isocyanate component A has a proportion of monomeric diisocyanates in the isocyanate component A of not more than 20% by weight, especially not more than 15% by weight or not more than 10% by weight, based in each case on the weight of the isocyanate component A.
  • the isocyanate component A has a content of monomeric diisocyanates of not more than 5% by weight, preferably not more than 2.0% by weight, more preferably not more than 1.0% by weight, based in each case on the weight of the isocyanate component A.
  • Particularly good results are established when the isocyanate component A is essentially free of monomeric diisocyanates. “Essentially free” here means that the content of monomeric diisocyanates is not more than 0.5% by weight, based on the weight of the isocyanate component A.
  • the isocyanate component A consists entirely or to an extent of at least 80%, 85%, 90%, 95%, 98%, 99% or 99.5% by weight, based in each case on the weight of the isocyanate component A, of oligomeric polyisocyanates. Preference is given here to a content of oligomeric polyisocyanates of at least 99% by weight. This content of oligomeric polyisocyanates relates to the isocyanate component A as provided. In other words, the oligomeric polyisocyanates are not formed as intermediate during the process of the invention, but are already present in the isocyanate component A used as reactant on commencement of the reaction.
  • Polyisocyanate compositions which have a low level of monomers or are essentially free of monomeric isocyanates can be obtained by conducting, after the actual modification reaction, in each case, at least one further process step for removal of the unconverted excess monomeric diisocyanates.
  • This removal of monomers can be effected in a particularly practical manner by processes known per se, preferably by thin-film distillation under high vacuum or by extraction with suitable solvents that are inert toward isocyanate groups, for example aliphatic or cycloaliphatic hydrocarbons such as pentane, hexane, heptane, cyclopentane or cyclohexane.
  • the isocyanate component A of the invention is obtained by modifying monomeric diisocyanates with subsequent removal of unconverted monomers.
  • an isocyanate component A having a low level of monomers contains an extra monomeric diisocyanate.
  • extra monomeric diisocyanate means that it differs from the monomeric diisocyanates which have been used for preparation of the oligomeric polyisocyanates present in the isocyanate component A.
  • the isocyanate component A has a proportion of extra monomeric diisocyanate in the isocyanate component A of not more than 20% by weight, especially not more than 15% by weight or not more than 10% by weight, based in each case on the weight of the isocyanate component A.
  • the isocyanate component A has a content of extra monomeric diisocyanate of not more than 5% by weight, especially not more than 2.0% by weight, more preferably not more than 1.0% by weight, based in each case on the weight of the isocyanate component A.
  • the isocyanate component A contains monomeric monoisocyanates or monomeric isocyanates having an isocyanate functionality greater than two, i.e. 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 in order to influence the network density of the coating.
  • the isocyanate component A has a proportion of monomeric monoisocyanates or monomeric isocyanates having an isocyanate functionality greater than two in the isocyanate component A of not more than 20% by weight, especially not more than 15% by weight or not more than 10% by weight, based in each case on the weight of the isocyanate component A.
  • the isocyanate component A has a content of monomeric monoisocyanates or monomeric isocyanates having an isocyanate functionality greater than two of not more than 5% by weight, preferably not more than 2.0% by weight, more preferably not more than 1.0% by weight, based in each case on the weight of the isocyanate component A.
  • no monomeric monoisocyanate or monomeric isocyanate having an isocyanate functionality greater than two is used in the trimerization reaction of the invention.
  • the oligomeric polyisocyanates may, in accordance with the invention, especially have uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and/or oxadiazinetrione structure.
  • the oligomeric polyisocyanates have at least one of the following oligomeric structure types or mixtures thereof:
  • an isocyanate component A is used, wherein the isocyanurate structure component 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 still at least 90 mol % and especially preferably at least 95 mol %, based on the sum total of the oligomeric structures from the group consisting of uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and oxadiazinetrione structure present in the isocyanate component A, is used.
  • an isocyanate component A containing, as well as the isocyanurate structure, at least one further oligomeric polyisocyanate having uretdione, biuret, allophanate, iminooxadiazinedione and oxadiazinetrione structure and mixtures thereof is used.
  • the proportions of uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and/or oxadiazinetrione structure in the isocyanate component A can be determined, for example, by NMR spectroscopy. It is possible here with preference to use 13C NMR spectroscopy, preferably in proton-decoupled form, since the oligomeric structures mentioned give characteristic signals.
  • an oligomeric isocyanate component A for use in the process of the invention and/or the oligomeric polyisocyanates present therein preferably have/has an (average) NCO functionality of 2.0 to 5.0, preferably of 2.3 to 4.5.
  • the isocyanate component A to be used in accordance with the invention has a content of isocyanate groups of 8.0% to 28.0% by weight, preferably of 14.0% to 25.0% by weight, based in each case on the weight of the isocyanate component A.
  • the isocyanate component A of the invention is defined in that it contains oligomeric polyisocyanates which have been obtained from monomeric diisocyanates, irrespective of the nature of the modification reaction used, with observation of an oligomerization level of 5% to 45%, preferably 10% to 40%, more preferably 15% to 30%.
  • Oligomerization level is understood here to mean the percentage of isocyanate groups originally present in the starting mixture which are consumed during the preparation process to form uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and/or oxadiazinetrione structures.
  • Suitable polyisocyanates for production of the isocyanate component A for use in the process of the invention and the monomeric and/or oligomeric polyisocyanates present therein are any desired polyisocyanates obtainable in various ways, for example by phosgenation in the liquid or gas phase or by a phosgene-free route, for example by thermal urethane cleavage. Particularly good results are established when the polyisocyanates are monomeric diisocyanates.
  • Preferred monomeric diisocyanates are those having a molecular weight in the range from 140 to 400 g/mol, having a liphatically, cycloaliphatically, araliphatically and/or aromatically bonded isocyanate groups, for example 1,4-diisocyanatobutane (BDI), 1,5-diisocyanatopentane (PDI), 1,6-diisocyanatohexane (HDI), 2-methyl-1,5-diisocyanatopentane, 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- or 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-methylcyclo
  • Suitable monomeric monoisocyanates which can optionally be used in the isocyanate component 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 desired mixtures of such monoisocyanates.
  • An example of a monomeric isocyanate having an isocyanate functionality greater than two which can optionally be added to the isocyanate component A is 4-isocyanatomethyloctane 1,8-diisocyanate (triisocyanatononane; TIN).
  • the isocyanate component A contains not more than 30% by weight, especially not more than 20% by weight, not more than 15% by weight, not more than 10% by weight, not more than 5% by weight or not more than 1% by weight, based in each case on the weight of the isocyanate component A, of aromatic polyisocyanates.
  • aromatic polyisocyanate means a polyisocyanate having at least one aromatically bonded isocyanate group.
  • Aromatically bonded isocyanate groups are understood to mean isocyanate groups bonded to an aromatic hydrocarbyl radical.
  • an isocyanate component A having exclusively aliphatically and/or cycloaliphatically bonded isocyanate groups is used.
  • Aliphatically and cycloaliphatically bonded isocyanate groups are understood to mean isocyanate groups bonded, respectively, to an aliphatic and cycloaliphatic hydrocarbyl radical.
  • an isocyanate component A consisting of or comprising one or more oligomeric polyisocyanates is used, where the one or more oligomeric polyisocyanates has/have exclusively aliphatically and/or cycloaliphatically bonded isocyanate groups.
  • the isocyanate component A consists to an extent of at least 70%, 80%, 85%, 90%, 95%, 98% or 99% by weight, based in each case on the weight of the isocyanate component A, of polyisocyanates having exclusively a liphatically and/or cycloaliphatically bonded isocyanate groups. Practical experiments have shown that particularly good results can be achieved with isocyanate component A in which the oligomeric polyisocyanates present therein have exclusively aliphatically and/or cycloaliphatically bonded isocyanate groups.
  • a polyisocyanate composition A which consists of or comprises one or more oligomeric polyisocyanates, where the one or more oligomeric polyisocyanates is/are 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
  • isocyanate components A having a viscosity greater than 500 mPas and less than 200000 mPas, preferably greater than 1000 mPas and less than 100000 mPas, more preferably greater than 1000 mPas and less than 50000 mPas and even more preferably greater than 1000 mPas and less than 25000 mPas, measured according to DIN EN ISO 3219 at 21° C., are used.
  • Suitable components B are all compounds containing at least one ethylenic double bond.
  • This ethylenic double bond is crosslinkable with other ethylenic double bonds by a free-radical reaction mechanism.
  • This condition is met by preferably activated double bonds between the ⁇ carbon atom and the ⁇ carbon atom alongside an activating group.
  • the activating group is preferably a carboxyl or carbonyl group.
  • component B is an acrylate, a methacrylate, the ester of an acrylate or the ester of a methacrylate.
  • component B does not contain any isocyanate-reactive groups as defined further up in this application.
  • Preferred components B are components B1 with one, component B2 with two and component B3 with three of the above-described ethylenic double bonds. Particular preference is given to B1 and/or B2.
  • component B used is a mixture of at least one component B1 and at least one component B2.
  • component B used is a mixture of at least one component B1 and at least one component B3.
  • component B used is a mixture of at least one component B2 and at least one component B3.
  • component B used is a mixture of at least one component B1, at least one component B2 and at least one component B3, Preference is given to using a mixture of at least one component B1 with at least one component B2.
  • the mass ratio of components B1 and B2 here is preferably between 30:1 and 1:30, more preferably between 20:1 and 1:20, even more preferably between 1:10 and 10:1 and most preferably between 2:1 and 1:2.
  • Preferred components B1 are methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, octadecyl (meth)acrylate, dodecyl (meth)acrylate, tetradecyl (meth)acrylate, oleyl (meth
  • Preferred components B2 are vinyl (meth)acrylate, tetraethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, hexane-1,6-diol di(meth)acrylate, neopentyl glycol propoxylate di(meth)acrylate, tripropylene glycol di(meth)acrylate, bisphenol A ethoxylated di(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, hexamethylene glycol di(meth)acrylate, bisphenol A di(meth)acrylate and 4,4′-bis(2-(meth)acryloyloxyethoxy)diphenylpropane.
  • Preferred components B3 are ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane ethoxytri(meth)acrylate, trimethylolpropane tri(meth)acrylate, alkoxylated tri(meth)acrylate and tris(2-(meth)acryloylethyl)isocyanurate.
  • the trimerization catalyst C may be mixed from one catalyst type or different catalyst types, but contains at least one catalyst that brings about the trimerization of isocyanate groups to isocyanurates or iminooxadiazinediones.
  • Suitable catalysts for the process of the invention are, for example, 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, for example triethanolamine, N-methyldiethanolamine, dimethylethanolamine, N-isopropyldiethanolamine and 1-(2-hydroxyethyl)pyrrolidine, or the catalyst systems known from GB 2 222 161 that consist of mixtures of tertiary bicyclic amines, for example DBU, with simple aliphatic alcohols of low molecular weight.
  • trimerization catalysts for the process of the invention are a multitude of different metal compounds. Suitable examples are the octoates and naphthenates of manganese, iron, cobalt, nickel, copper, zinc, zirconium, cerium or lead or mixtures thereof with acetates of lithium, sodium, potassium, calcium or barium that are described as catalysts in DE-A 3 240 613, the sodium and potassium salts of linear or branched alkanecarboxylic acids having up to 10 carbon atoms that are known from DE-A 3 219 608, for example of propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, pelargonic acid, capric acid and undecylenoic acid, the alkali metal or alkaline earth metal salts of aliphatic, cycloaliphatic or aromatic mono- and polycarboxylic acids having 2 to 20 carbon atoms that are known from EP-A 0 100 129, for example
  • dibutyltin dichloride diphenyltin dichloride, triphenylstannanol, tributyltin acetate, tributyltin oxide, tin dioctoate, dibutyl(dimethoxy)stannane and tributyltin imidazolate.
  • trimerization catalysts suitable for the process of 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, for example tetraethylammonium hydroxide, trimethylbenzylammonium hydroxide, N,N-dimethyl-N-dodecyl-N-(2-hydroxyethyl)ammonium hydroxide, N-(2-hydroxyethyl)-N,N-dimethyl-N-(2,2′-dihydroxymethylbutyl)ammonium hydroxide and 1-(2-hydroxyethyl)-1,4-diazabicyclo[2.2.2]octane hydroxide (monoadduct of ethylene oxide and water with 1,4-diazabicyclo[2.2.2]octane), the quaternary hydroxyalkylammonium hydroxides known from EP-A 37 65 or EP-A 10 5
  • trimerization catalysts C suitable in accordance with 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.
  • carboxylates and phenoxides with metal or ammonium ions are the anions of all aliphatic or cycloaliphatic carboxylic acids, preferably those with mono- or polycarboxylic acids having 1 to 20 carbon atoms.
  • Suitable metal ions are derived from alkali metals or alkaline earth metals, manganese, iron, cobalt, nickel, copper, zinc, zirconium, cerium, tin, titanium, hafnium or lead.
  • Preferred alkali metals are lithium, sodium and potassium, more preferably sodium and potassium.
  • Preferred alkaline earth metals are magnesium, calcium, strontium and barium.
  • octoate and naphthenate catalysts described in DE-A 3 240 613 are octoates and naphthenates of manganese, iron, cobalt, nickel, copper, zinc, zirconium, cerium or lead, or mixtures thereof with acetates of lithium, sodium, potassium, calcium or barium.
  • the trimerization catalyst C preferably contains a polyether. This is especially preferred when the catalyst contains metal ions.
  • Preferred polyethers are selected from the group consisting of crown ethers, diethylene glycol, polyethylene glycols and polypropylene glycols. It has been found to be of particular practical relevance in the process of the invention to use a trimerization catalyst B containing, as polyether, a polyethylene glycol or a crown ether, more preferably 18-crown-6 or 15-crown-5.
  • the trimerization catalyst B comprises a polyethylene glycol having a number-average molecular weight of 100 to 1000 g/mol, preferably 300 g/mol to 500 g/mol and especially 350 g/mol to 450 g/mol.
  • Component D is a compound having at least one isocyanate-reactive group as defined further up in this application and at least one ethylenic double bond in one molecule.
  • the isocyanate-reactive group of component D may also be a uretdione group, Ethylenic double bonds are preferably those that are crosslinkable with other ethylenic double bonds by a free-radical reaction mechanism. Corresponding activated double bonds are defined in detail further up in this application for component B.
  • Preferred components D are alkoxyalkyl (meth)acrylates having 2 to 12 carbon atoms in the hydroxyalkyl radical. Particular preference is given to 2-hydroxyethyl acrylate, the isomer mixture formed on addition of propylene oxide onto acrylic acid, or 4-hydroxybutyl acrylate.
  • Component E is a compound having both at least one isocyanate group and at least one ethylenic double bond in one molecule. It can advantageously be obtained by crosslinking a component D described in the preceding paragraph with a monomeric or oligomeric polyisocyanate as described further up in this application. This crosslinking is effected by reaction of the isocyanate-reactive groups, in this case especially a hydroxyl, amino or thiol group, and an isocyanate group of the polyisocyanate. This is preferably catalyzed by a component G as described further down in this application. But any other suitable catalyst known to those skilled in the art is also conceivable. It is also possible to dispense with a catalyst entirely.
  • a hexamethylene diisocyanate- or pentamethylene diisocyanate-based oligomeric polyisocyanate is combined with a component D selected from the group consisting of 2-hydroxyethyl acrylate, the isomer mixture formed on addition of propylene oxide onto acrylic acid, and 4-hydroxybutyl acrylate.
  • Further preferred components E are 2-isocyanatoethyl (meth)acrylate, tris(2-hydroxyethyl) isocyanate tri(meth)acrylate, vinyl isocyanates, allyl isocyanates and 3-isopropenyl- ⁇ , ⁇ -dimethylbenzyl isocyanate.
  • free-radical polymerization of the ethylenically unsaturated compounds present in the reaction mixture can be brought about by actinic radiation with a sufficient energy content. This is especially UV-VIS radiation in the wavelength range between 200 and 500 nm.
  • the polymerizable composition of the invention need not contain any component F.
  • At least one component F suitable as an initiator for a free-radical polymerization of the ethylenic double bonds present in the polymerizable composition of the invention is required.
  • the effect of initiators of this kind is that they form, under suitable conditions, especially when heated or under the action of suitable radiation, free radicals that react with the ethylenic double bonds, forming vinyl radicals which in turn react with further ethylenic double bonds in a chain reaction.
  • Component F comprises at least one radiation-activated initiator F1 or at least one heat-activated initiator F2. But it may also comprise a mixture of at least one radiation-activated initiator F1 and at least one heat-activated initiator F2.
  • Preferred radiation-activated initiators F1 are compounds of the unimolecular type (I) and of the bimolecular type (II).
  • Suitable type (I) systems are aromatic ketone compounds, for example benzophenones in combination with tertiary amines, alkylbenzophenones, 4,4°-bis(dimethylamino)benzophenone (Michler's ketone), anthrone and halogenated benzophenones or mixtures of the recited types.
  • type (II) initiators such as benzoin and derivatives thereof, benzil ketals, acylphosphine oxides, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bisacylphosphine oxides, phenylglyoxylic esters, camphorquinone, ⁇ -aminoalkylphenones, ⁇ , ⁇ -dialkoxyacetophenones and ⁇ -hydroxyalkylphenones.
  • Irgacure®500 a mixture of benzophenone and 1-hydroxycyclohexyl phenyl ketone, from Ciba, Lampertheim, Del.
  • Irgacure®819 DW phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, from Ciba, Lampertheim, Del.
  • Esacure® KIP EM oligo-[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanones], from Lamberti, Aldizzate, Italy
  • Mixtures of these compounds may also be employed.
  • photoinitiators have a sufficient reactivity toward the radiation source used.
  • a multitude of photoinitiators is known on the market. Commercially available photoinitiators cover the wavelength range of the entire UV-VIS spectrum.
  • Preferred heat-activated initiators F2 are organic azo compounds, organic peroxides and C-C-cleaving initiators, such as benzpinacol silyl ether, N,N-diacylhydroxylamines, O-alkylated N,N-diacylhydroxylamines or O-acylated N,N-diacylhydroxylamines.
  • suitable are inorganic peroxides such as peroxodisulfates.
  • thermal free-radical initiators are azobisisobutyronitrile (AIBN), dibenzoyl peroxide (DBPO), di-tert-butyl peroxide, dicumyl peroxide (DCP) and tert-butyl peroxybenzoate.
  • AIBN azobisisobutyronitrile
  • DBPO dibenzoyl peroxide
  • DCP dicumyl peroxide
  • tert-butyl peroxybenzoate tert-butyl peroxybenzoate
  • Component G is a catalyst that catalyzes the crosslinking of an isocyanate group with an isocyanate-reactive group. This preferably gives rise to a urethane group, a thiourethane group or a urea group.
  • the polymerizable composition preferably contains a component G when a component D having at least one isocyanate-reactive group is present.
  • a component G is not obligatory in this case either, since the crosslinking of isocyanate groups with isocyanate-reactive groups can also be accelerated by the trimerization catalysts C used and also proceeds at sufficient speed even entirely without catalysis when the reaction temperature is high enough. It is possible to dispense with the addition of a component G especially when the crosslinking of the isocyanate groups present in the isocyanate component A is conducted at a temperature of at least 60° C., preferably at least 120° C.
  • Preferred components G are the typical urethanization catalysts as specified, for example, in Becker/Braun, Kunststoffhandbuch [Plastics Handbook] volume 7, Polyurethane [Polyurethanes], section 3.4.
  • the catalyst used may especially be a compound selected from the group of the tertiary amines, tertiary amine salts, metal salts and metal organyls, preferably from the group of the tin salts, tin organyls and bismuth organyls.
  • the viscosity of the polymerizable composition is preferably adjusted by the use of a component B in suitable concentration.
  • a component B act as reactive diluents and basically make it possible to dispense with the use of additional solvents to lower the viscosity of the isocyanate component A.
  • a solvent suitable for isocyanates may be added to the polymerizable composition of the invention. This may be desirable, for example, when the proportion of component B in the polymerizable composition is to be limited and the aim is a lowering of viscosity unachievable with this limited proportion of component B.
  • the polymerizable composition of the invention may contain all solvents suitable for the dilution of isocyanates that are known to the person skilled in the art, These are preferably hexane, toluene, xylene, chlorobenzene, ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl or monoethyl ether acetate, diethylene glycol ethyl and butyl ether acetate, propylene glycol monomethyl ether acetate, 1-methoxyprop-2-yl acetate, 3-methoxy-n-butyl acetate, propylene glycol diacetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, lactones such as ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -caprolactone and
  • the polymerizable composition of the invention additionally comprises at least one additive I selected from the group consisting of UV stabilizers, antioxidants, mold release agents, water scavengers, slip additives, defoamers, leveling agents, rheology additives, flame retardants and pigments.
  • additives selected from the group consisting of UV stabilizers, antioxidants, mold release agents, water scavengers, slip additives, defoamers, leveling agents, rheology additives, flame retardants and pigments.
  • auxiliaries and additives are typically present in an amount of not more than 10% by weight, preferably not more than 5% by weight and more preferably not more than 3% by weight, based on the polymerizable composition of the invention.
  • the polymerizable composition comprises at least one organic filler J1 and/or at least one inorganic filler J2, Said fillers may be present in any shape and size known to the person skilled in the art. These are especially particulate fillers having a grain size distribution of polydispersity at most 50, preferably at most 30 and most preferably at most 10, with an average grain diameter of at most 0.1 mm and preferably at most 0.05 mm.
  • fillers with an aspect ratio of at least 1000 are used.
  • particulate fillers and fillers having an aspect ratio of at least 1000 are used in a weight ratio of 1:100 to 100:1, preferably 1:80 to 50:1 and more preferably 1:50 bis 20:1.
  • the fillers are predominantly inorganic in nature, preferably based on (semi)metal salts and (semi)metal oxides.
  • Preferred organic fillers J1 are wood, pulp, paper, paperboard, fabric slivers, cork, wheat chaff, polydextrose, cellulose, aramids, polyethylene, carbon, carbon nanotubes, polyester, nylon, Plexiglass, flax, hemp and also sisal.
  • Preferred inorganic fillers J2 are AlOH 3 , CaCO 3 , silicon dioxide, magnesium carbonate, TiO 2 , ZnS, minerals containing silicates, sulfates, carbonates and the like, such as magnesite, baryte, mica, dolomite, kaolin, talc, clay minerals, and carbon black, graphite, boron nitride, glass, basalt, boron, ceramic and silica.
  • the polymerizable composition of the invention is preferably suitable for production of a composite material with high filler level.
  • a “high filler level” means that filler contents up to 50% by volume to 80% by volume, preferably 60% by volume to 80% by volume, can be attained.
  • the filler is a fibrous filler J3.
  • the fibrous filler 13 may have been produced from any of the inorganic fibers, organic fibers or natural fibers that are known to those skilled in the art, or mixtures thereof.
  • the fact that a fibrous filler has been produced from a material or a mixture of different materials does not mean that it does not contain further substances that serve as sizes, for example.
  • Preferred inorganic fibers are glass fibers, basalt fibers, boron fibers, ceramic fibers, whiskers, silica fibers and metallic reinforcing fibers.
  • Preferred organic fibers are aramid fibers, carbon fibers, carbon nanotubes, polyester fibers, nylon fibers and Plexiglass fibers,
  • Preferred natural fibers are flax fibers, hemp fibers, wood fibers, cellulose fibers and sisal fibers.
  • suitable fibrous fillers J3 are all fibers having an aspect ratio greater than 1000, preferably greater than 5000, more preferably greater than 10000 and most preferably greater than 50000.
  • the aspect ratio is defined as the length of the fibers divided by the diameter.
  • the fibrous fillers J3 preferably have a minimum length of 1 m, more preferably 50 m and most preferably 100 m.
  • the fibrous filler J3 is selected from the group consisting of glass fibers, basalt fibers, carbon fibers and mixtures thereof.
  • the fibers may be in individual form, but they can also be woven or knitted in any form known to those skilled in the art to give mats or fleeces.
  • Preferably less than 50% by weight, more preferably less than 35% by weight, even more preferably less than 20% by weight and most preferably less than 10% by weight of the fibers used are in the form of mats or fleeces.
  • the individual fibers preferably have a diameter of less than 0.1 mm, more preferably less than 0.05 mm, and even more preferably less than 0.03 mm.
  • the size is a thin polymer film which frequently contains reactive groups and which improves wetting with the resin or the binding between the matrix and the fiber.
  • the fibers used exhibit a low water content.
  • Water can be absorbed, for example, on the surface of the fibers and enter into unwanted side reactions with isocyanate groups later on. It has therefore been found to be advantageous when the water content of the fibers is less than 5% by weight, preferably less than 3% by weight, more preferably less than 2% by weight, especially less than 1% by weight and most preferably less than 0.5% by weight, based on the total weight of fibers.
  • the fibers have zero moisture content. This can be achieved if appropriate by drying of the fibers.
  • the moisture content of the fibers can be determined by gravimetric measurement before and after drying, preferably at 120° C. for 2 hours.
  • At least 50%, more preferably at least 70%, even more preferably at least 80% and most preferably at least 90% of the fibers are oriented parallel to one another. Fibers are oriented parallel to one another when the angle between them is less than 15 degrees, preferably less than 10 degrees and even more preferably less than 5 degrees over a length of 0.5 m, preferably 1 m and more preferably 2 m. Most preferably, the angle between at least 90% of the fibers over a length of 2 m is not more than 10 degrees and even more preferably not more than 5 degrees.
  • the person skilled in the art will be aware that the details above are only meaningful in the case of use of individual fibers. If the fibers used are in the form of mats or fleeces, it is clear from the arrangement of the fibers in these materials that these conditions cannot be complied with.
  • the ratio between the reactive resin, the fibrous filler J3 and all other constituents of the composite material is preferably chosen such that the fiber content makes up at least 30% by volume, preferably 45% by volume, even more preferably at least 50% by volume, even more preferably still at least 60% by volume and most preferably at least 65% by volume of the cured composite material.
  • the present invention relates to the use of at least one component selected from the group consisting of components B, D and E for production of a polymerizable composition having a ratio of isocyanate groups to isocyanate-reactive groups of at least 2.0:1.0, which contains an isocyanate component A and a filler J and is polymerizable either by free-radical polymerization or by crosslinking of isocyanate groups with one another.
  • At least one component B as defined above in this application is additionally used.
  • the present invention relates to a process for preparing a polymer, comprising the steps of
  • viscosity is first built up by process step d) before the ultimate curing of the polymer in process step e).
  • the two process steps need not follow directly on from one another in time. It is especially preferable that, between the two process steps, there is a further operating step in which the product of process step d) is shaped.
  • the polymerizable composition of the invention does not contain any heat-activated initiator F2.
  • a heat-activated initiator F2 is used since, in this case, the increase in temperature required for the crosslinking of the isocyanate groups in process step e) also brings about the crosslinking of the ethylenic double bonds in process step d).
  • the process of the invention includes a further reaction step f) in which the isocyanate-reactive group of component D is crosslinked with an isocyanate group of the isocyanate component A or of a reaction product of the isocyanate component A.
  • Said process step f) can be conducted before process step d), it can be conducted between process steps d) and e), or it can be conducted in parallel to process step d) or e) or else after process steps d) and e). But it is in any case conducted after process step c).
  • process step f) preferably proceeds in parallel to process step e) since there is already an increase in temperature therein that also brings about the reaction of components A and D.
  • the filler J is wetted in process step c) with the reactive resin mixture from process step a). Good wetting is necessary to assure transmission of force between the filler and the matrix in the finished component and to avoid inclusions, for example air.
  • the wetting step can be conducted either continuously or batchwise; preference is given to a continuous process.
  • all known processes that enable good wetting of the filler with the resin matrix are suitable. Without any claim to completeness, these include bar coating, a dipping bath, an injection box, spraying methods, resin injection methods, resin infusion methods with vacuum or under pressure, an application roll and manual lamination methods.
  • the dipping bath is used.
  • the dried fibers are pulled here through an open resin bath, with deflection of the fibers into and out of the resin bath via guide grids (bath method).
  • the fibers also can be pulled straight through the impregnation device without deflection (pull-through method).
  • the injection box in the case of a fibrous filler J, is used.
  • the fibers are pulled without deflection into the impregnation unit that already has the shape of the later profile.
  • the reactive resin mixture is pumped into the box, preferably transverse to the fiber direction.
  • the process of the invention is preferably a pultrusion process in which process step c) is conducted as described above in a dipping bath or in an injection box and process step e), without further intervening process steps, is conducted by pulling the wetted fibers of the filler through a heated mold, the profile of which corresponds to the profile of the workpiece to be manufactured.
  • preference is given to using heat-activated initiators.
  • the viscosity of the reactive resin is preferably adjusted such that it is between 10 mPas and 10000 mPas, preferably between 10 and 5000 mPas and even more preferably between 10 and 2000 mPas.
  • the ethylenic double bonds present in the polymerizable composition of the invention are crosslinked by a free-radical polymerization. If a radiation-activated initiator F1 is present, this polymerization reaction is initiated in accordance with the invention by the use of radiation suitable for activation thereof. If a heat-activated initiator F2 is present in the polymerizable composition used, the crosslinking of the ethylenic double bonds is initiated by heating the polymerizable composition to the temperature required. In principle, however—irrespective of the presence of initiators F1 or F2—the use of sufficiently high-energy radiation as defined further up in this application is also sufficient to initiate the free-radical polymerization in process step d).
  • the “crosslinking” of the isocyanate component A in process step e) is a process in which the isocyanate groups present therein react with one another or with urethane groups already present to form at least one structure selected from the group consisting of uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and oxadiazinetrione structures.
  • the isocyanate groups originally present in the isocyanate component A are consumed.
  • the formation of the aforementioned groups results in combination of the monomeric and oligomeric polyisocyanates present in the isocyanate composition A to form a polymer network.
  • the result of the crosslinking reaction is that at most 20%, preferably at most 10%, more preferably at most 5%, even more preferably at most 2% and especially at most 1% of the total nitrogen content of the isocyanate component A is present in urethane and/or allophanate groups.
  • the cured isocyanate component A is not entirely free of urethane and allophanate groups. Consequently, taking account of the upper limits defined in the preceding paragraph, it preferably contains at least 0.1% urethane and/or allophanate groups based on the total nitrogen content.
  • the crosslinking of the isocyanate groups present in the polymerizable composition of the invention proceeds predominantly via cyclotrimerization of at least 50%, preferably at least 60%, more preferably at least 70%, especially at least 80% and most preferably 90% of the free isocyanate groups present in the isocyanate component A to give isocyanurate structural units.
  • cyclotrimerization of at least 50%, preferably at least 60%, more preferably at least 70%, especially at least 80% and most preferably 90% of the free isocyanate groups present in the isocyanate component A to give isocyanurate structural units.
  • corresponding proportions of the nitrogen originally present in the isocyanate component A are bound within isocyanurate structures.
  • the crosslinking of the isocyanate groups is preferably effected at temperatures between 50° C. and 220° C., more preferably between 80° C. and 200° C. and even more preferably between 100° C. and 200° C.
  • the abovementioned temperatures are maintained in process step c) until at least 50%, preferably at least 75% and even more preferably at least 90% of the free isocyanate groups present in the isocyanate component A at the start of process step b) have been consumed.
  • the percentage of isocyanate groups still present can be determined by a comparison of the content of isocyanate groups in % by weight in the isocyanate component A present at the start of process step b) with the content of isocyanate groups in % by weight in the reaction product, for example by the aforementioned comparison of the intensity of the isocyanate band at about 2270 cm ⁇ 1 by means of IR spectroscopy.
  • process step e naturally depends on the geometry of the workpiece to be created, especially the ratio of surface area and volume, since the required temperature has to be attained for the minimum time required even in the core of the workpiece being formed.
  • the person skilled in the art is able to determine these parameters by simple preliminary tests.
  • crosslinking of the above mentioned proportions of free isocyanate groups is achieved when the abovementioned temperatures are maintained for 1 minute to 4 hours. Particular preference is given to a duration between 1 minute and 15 minutes at temperatures between 180° C. and 220° C. or a duration of 5 minutes to 120 minutes at a temperature of 120° C.
  • process step e) is preferably effected in a mold heated to the abovementioned temperatures that has a recess in the form of the profile to be produced, through which the fibrous filler J3 wetted with the reactive resin is pulled.
  • the present invention relates to a composite material obtainable by the process described above.
  • the composite material is preferably in the form of a shaped body.
  • the shaped body can preferably be obtained by casting using suitable molds.
  • the composite material takes the form of an open or closed hollow body.
  • a “shaped body” is defined in that it has an edge length of at least 0.5 mm, preferably at least 1 mm, in at least one of the three dimensions, and a dimension of at least 2 cm, preferably at least 5 cm, in at least one of the two other dimensions. It preferably has an edge length of at least 2 cm in all three dimensions.
  • the composite material of the invention is the product of a pultrusion process, meaning that it contains a fibrous filler J and has a profile.
  • a “profile” as understood in the present application is a body having the same cross section essentially over its entire length.
  • the “profile” has a length of preferably at least 2 m, more preferably at least 10 m and even more preferably at least 50 m. It is explicitly the case that the profile can be divided into multiple segments after the curing of the reactive resin. The above-specified lengths then relate to a hypothetical undivided product as originates from the process and would be present without further division.
  • a profile has “the same cross section essentially over its entire length” even when this cross section is not always attained at all times for manufacturing reasons. It is assumed here that these sections are short in relation to the total length of the profile. Said sections with a different cross section are short when the total length thereof is less than 10%, preferably less than 5% and most preferably less than 1% of the total length of the hypothetical undivided profile.
  • a different cross section is understood to mean a value that differs by at least 10% from the average value or the desired value.
  • RT room temperature
  • phase transitions were determined by means of DSC (differential scanning calorimetry) with a Mettler DSC 12E (Mettler Toledo GmbH, Giessen, Germany) in accordance with DIN EN 61006. Calibration was effected via the melt onset temperature of indium and lead. 10 mg of substance were weighed out in standard capsules. The measurement was effected by three heating runs 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. Cooling was effected by means of liquid nitrogen. The purge gas used was nitrogen. The values reported are each based on the evaluation of the 2nd heating curve. The glass transition temperature T g was obtained from the temperature at half the height of a glass transition step.
  • the infrared spectra were measured on a Bruker FT-IR spectrometer equipped with an ATR unit.
  • Polyisocyanate A1 HDI trimer (NCO functionality>3) with an NCO content of 23.0% by weight from Covestro AG.
  • the viscosity is about 1200 mPa ⁇ s at 23° C. (DIN EN ISO 3219/A.3).
  • Polyisocyanate A2 PDI trimer (NCO functionality>3) with an NCO content of 21.5% by weight from Covestro AG.
  • the viscosity is about 9500 mPa ⁇ s at 23° C. (DIN EN ISO 3219/A.3).
  • HPMA Hydroxypropyl methacrylate
  • IBOMA Isobornyl methacrylate
  • Trigonox® C (tert-butyl peroxybenzoate) was sourced with a purity of 98% by weight from Akzo Nobel.
  • Potassium acetate was sourced with a purity of >99% by weight from ACROS.
  • Polyethylene glycol (PEG) 400 was sourced with a purity of >99% by weight from ACROS.
  • the INT-1940 RTM demolding agent was acquired from Axel Plastics Research Laboratories, INC. and, according to the datasheet, is a mixture of organic fatty acids and esters.
  • the short glass fibers designated 910A-10P were supplied by Owens Corning and were in the form of bundles of about 4.5 mm in length. The diameter of the individual fibers was 0.01 mm.
  • the endless glass fiber was glass fiber bundles with standard size for UP, VE and epoxy resins with the product name ‘Advantex 399’ with 4800 tex from 3B-fiberglass. According to the datasheet, the endless glass fibers have a diameter of 24 micrometers, are boron-free and consist of E-CR glass.
  • the tensile modulus is 81-83 GPa, the tensile strength 2200-2400 MPa and the density 2.62 g/cm 3 .
  • Potassium acetate (5.0 g) was stirred in the PEG 400 (95.0 g) at RT until all of it had dissolved. In this way, a 5% by weight solution of potassium acetate in PEG 400 was obtained and was used as catalyst without further treatment.
  • the polyisocyanurate composites were produced by first preparing the isocyanate composition by mixing the appropriate isocyanate components (A1 or A2) with an appropriate amount of catalyst K, initiator and acrylate at 23° C. in a Speedmixer DAC 150.1 FVZ from Hauschild at 2750 min ⁇ 1 for 60-300 seconds. Subsequently, one tenth of the amount of short glass fibres was added at first to the isocyanate composition. The overall mixture was mixed in a Speedmixer DAC 150.1 FVZ from Hauschild at 2750 min ⁇ 1 for 60 to 300 seconds, in the course of which the short glass fiber bundles are exfoliated and the whole mixture forms a slurry-like mass. Then the remaining amount of short glass fibers is added and the mixture is mixed again in the Speedmixer at 2750 min ⁇ 1 for about 60 seconds.
  • the mixture was transferred to a mold (metal lid, about 6 cm in diameter and about 1 cm in height) and cured in an oven.
  • polyisocyanate A1 (16.13 g) was treated with initiator I (0.064 g), catalyst K (0.595 g) and HPMA (1.60 g) according to the abovementioned preparation method for reaction mixtures, and the mass was introduced into the mold without addition of glass fibers. After the preparation, the mixture had a viscosity of 929 mPas.
  • polyisocyanate A1 (16.13 g) was treated with initiator I (0.064 g), catalyst K (0.595 g) and HPMA (1.60 g) according to the abovementioned preparation method for reaction mixtures, the short glass fibers (4.0 g) were incorporated and the mass was introduced into the mold.
  • polyisocyanate A1 (32.2 g) was treated with initiator I (0.12 g), catalyst K (12.3 g), HPMA (0.29 g), HDDA (3.08 g), IBOMA (3.08 g) according to the abovementioned preparation method for reaction mixtures. After the preparation, the material had a viscosity of 611 mPas. After curing at 220° C. for 5 min, a material with a T G of 102° C. was obtained.
  • polyisocyanate A2 (29.7 g) was treated with initiator I (0.16 g), catalyst K (1.23 g), HPMA (0.41 g), HDDA (4.21 g), IBOMA (4.21 g) according to the abovementioned preparation method for reaction mixtures. After the preparation, the mixture had a viscosity of 1560 mPas. After curing at 200° C. for 10 min, a material with a T G of 126° C. was obtained.
  • the isocyanate was initially charged in an open vessel at room temperature and stirred by means of a Dispermat® and dissolver disk at 100 revolutions per minute (rpm). Subsequently, first the acrylate and then the demolding agent were added, and the stirrer speed was increased to 300 rpm and the whole mixture was stirred for a further 5 min, so as to form a homogeneous mixture. Then the catalyst solution and the initiator were metered in and the resin mixture was stirred at 300 rpm for a further 5 min. This reactive resin mixture was used without further treatment for the pultrusion.
  • polyisocyanate A1 (3.22 kg) was treated with initiator I (12 g), catalyst K (123 g), HPMA (29 g), HDDA (308 g), IBOMA (308 g) and INT-1940 RTM demolding agent (103 g) according to the abovementioned production method for resin mixture for pultrusion. After the preparation, the mixture had a viscosity of 611 mPas.
  • the glass fiber bundles (126 rovings) were oriented and guided through an injection box, which was connected to the mold in a fixed manner and was filled with the resin mixture via a window opening on the top side of the box.
  • the glass fibers that had thus been impregnated with resin were pulled directly into the heated mold.
  • the pulling speed was 0.3 m/min and 0.5 m/min.
  • the offtake forces were about 0.7 t. 5 m of profile were produced at each of the two speeds.
  • the surface of the profile was homogeneous and matt, and the glass content was 80% by mass.
  • polyisocyanate A2 (2.97 kg) was treated with initiator 1 (16 g), catalyst K (123 g), HPMA (41 g), HDDA (421 g), IBOMA (421 g) and INT-1940 RTM demolding agent (102 g) according to the abovementioned production method for resin mixture for pultrusion.
  • the glass fiber bundles (126 rovings) were oriented and guided through an injection box, which was connected to the mold in a fixed manner and was filled with the resin mixture via a window opening on the top side of the box.
  • the glass fibers that had thus been impregnated with resin were pulled directly into the heated mold.
  • the pulling speed was 0.3 m/min and 0.5 m/min.
  • the offtake forces were about 0.7 t. 5 m of profile were produced at each of the two speeds.
  • the surface of the profile was homogeneous and matt, and the glass content was 80% by mass.
  • polyisocyanate A1 93.5 g
  • catalyst K 4.0 g
  • the mass was introduced into the mold.
  • the mixture had a viscosity of 2180 mPas.
  • polyisocyanate A2 93.5 g
  • catalyst K 4.0 g
  • the mass was introduced into the mold.
  • the mixture had a viscosity of more than 10000 mPas.
  • polyisocyanate A2 (4.39 kg) was treated with catalyst K (188 g) and INT-1940 RTM demolding agent (117 g) according to the abovementioned production method for resin mixture for pultrusion. After the preparation, the mixture had a high viscosity by comparison of more than 10000 mPas. After curing at 220° C. for 3 min, a material with a T G of 126° C. was obtained.
  • the glass fiber bundles (126 rovings) were oriented and guided through an injection box, which was connected to the mold in a fixed manner and was filled with the resin mixture via a window opening on the top side of the box.
  • the glass fibers thus treated were pulled directly into the heated mold.
  • the pulling speed was 0.2 m/min and 0.3 m/min.
  • the offtake forces were between about 0.4 and 0.9 t.
  • the glass fibers came out of the mold virtually unchanged since the resin was unable to impregnate the fibers owing to the high viscosity.
  • Working examples 1, 3 and 4 show that an addition of double bond-containing (acrylate-based) monomers to polyisocyanate-based reaction mixtures leads to significantly reduced starting viscosities compared to pure polyisocyanate-based reaction mixtures (cf. comparative examples 7 and 8). Such reduced starting viscosities are often helpful in the case of use of such mixtures as resins for (fiber) composite materials since they facilitate the wetting of (fibrous) fillers (see below).
  • Working examples 1, 3 and 4 also show that a combination of the addition reaction of isocyanate groups with the free-radical polymerization of double bond-containing monomers leads in principle to cured plastics having high glass transition temperatures.
  • working example 2 shows that such mixtures are of good suitability for embedding (fibrous) fillers without undergoing losses in material properties (e.g. Tg).
  • working examples 5 and 6 show that mixtures of this kind are of good suitability for continuously producing fiber composite materials with very high filler contents (>80% by mass) by means of pultrusion, whereas comparative example 9 demonstrates that excessively high starting viscosities of polymer resins prevent the continuous production of fiber composite materials.

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022108738A1 (en) * 2020-11-18 2022-05-27 Covestro Llc Polyurethane and polyisocyanurate hybrid coatings
WO2022108737A1 (en) * 2020-11-18 2022-05-27 Covestro Llc Polyurethane and polyisocyanurate hybrid materials and method of preparing the same

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016085914A1 (en) 2014-11-24 2016-06-02 Ppg Industries Ohio, Inc. Coreactive materials and methods for three-dimensional printing
US10434704B2 (en) 2017-08-18 2019-10-08 Ppg Industries Ohio, Inc. Additive manufacturing using polyurea materials
WO2019092140A1 (de) * 2017-11-09 2019-05-16 Covestro Deutschland Ag Verfahren zur herstellung eines gegenstandes und verwendung eines radikalisch vernetzbaren harzes in einem additiven fertigungsverfahren
EP3743449B1 (de) * 2017-11-14 2024-04-17 Covestro Deutschland AG Halbzeuge basierend auf dualem vernetzungsmechanismus
GB201819984D0 (en) 2018-12-07 2019-01-23 Ge Healthcare Bio Sciences Ab Chromatography column and method of assembling the same
KR20210122823A (ko) 2019-02-01 2021-10-12 바스프 에스이 폴리우레탄 및 이를 포함하는 uv-수분 이중 경화 pu 반응성 핫멜트
JPWO2021002479A1 (zh) * 2019-07-04 2021-01-07
JP2024514474A (ja) 2021-03-29 2024-04-02 コベストロ、ドイチュラント、アクチエンゲゼルシャフト ポリイソシアヌレート－プリプレグおよびそれから製造される繊維複合コンポーネント
EP4092064A1 (en) 2021-05-17 2022-11-23 Covestro Deutschland AG Photo- and thermally curable resin useful for additive manufacturing
EP4116348A1 (en) 2021-07-09 2023-01-11 Covestro Deutschland AG Photo- and thermally curable resin useful in additive manufacturing processes
EP4166331A1 (en) * 2021-10-12 2023-04-19 Covestro Deutschland AG Photo- and thermally curable resin useful in additive manufacturing processes
CN115160908B (zh) * 2022-07-06 2023-07-07 海利得新材料研究(上海)有限公司 无溶剂uv哑光涂料及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0008170A1 (en) * 1978-07-27 1980-02-20 Ici Americas Inc. Polyisocyanurate containing moulding compositions
US4352906A (en) * 1981-08-06 1982-10-05 Ici Americas Inc. Blister resistant calcium carbonate filled polyisocyanurate resin molding compositions

Family Cites Families (119)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB809809A (en) 1956-11-16 1959-03-04 Ici Ltd Polymeric isocyanates and their manufacture
GB952931A (en) 1961-05-25 1964-03-18 Ici Ltd Improved polyisocyanate compositions
GB966338A (en) 1961-10-26 1964-08-12 Ici Ltd Polyurethane surface coatings
US3211703A (en) 1962-03-23 1965-10-12 Monsanto Res Corp Polyaliphatic polyisocyanurate laminating resin prepared in the presence of a cocatalyst system
DE1226109B (de) 1964-04-20 1966-10-06 Bayer Ag Verfahren zur Herstellung von Polyisocyanaten mit Isocyanuratstruktur
CA932333A (en) 1966-02-02 1973-08-21 Farbenfabriken Bayer Aktiengesellschaft Compounds containing the 2,4,6-triketo-1,3,5-oxadiazine ring
GB1200542A (en) 1967-01-19 1970-07-29 Takeda Chemical Industries Ltd A method for producing isocyanate trimers
DE1954093C3 (de) 1968-11-15 1978-12-21 Mobay Chemical Corp., Pittsburgh, Pa. (V.St.A.) Verfahren zur Herstellung von polymeren organischen Isocyanaten
GB1386399A (en) 1971-07-16 1975-03-05 Ici Ltd Isocyanurate polymers
GB1391066A (en) 1971-07-16 1975-04-16 Ici Ltd Urethane oils
BE795448A (nl) * 1972-02-24 1973-08-16 Shell Int Research Werkwijze voor de bereiding van hardbare composities
DE2414413C3 (de) 1974-03-26 1978-08-24 Bayer Ag, 5090 Leverkusen Verwendung von Lösungen von Polyisocyanaten mit Isocyanuratstruktur in Zweikomponenten-Polyurethan-Lacken
DE2452532C3 (de) 1974-11-06 1978-08-24 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von Polyisocyanaten mit Isocyanurat-Struktur
US4040992A (en) 1975-07-29 1977-08-09 Air Products And Chemicals, Inc. Catalysis of organic isocyanate reactions
DE2641380C2 (de) 1976-09-15 1989-11-23 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von Polyisocyanaten mit Isocyanuratstruktur
DE2722400C2 (de) * 1977-05-17 1985-05-30 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von wärmebeständigen, blasenfreien Isocyanuratgruppen aufweisenden Kunststoffen
US4145544A (en) 1977-07-27 1979-03-20 Ici Americas Inc. Preparation of isocyanurates
US4128537A (en) * 1977-07-27 1978-12-05 Ici Americas Inc. Process for preparing ethylenically unsaturated isocyanurates
DE2861054D1 (en) * 1977-07-27 1981-11-26 Ici America Inc An isocyanurate composition formed by the trimerisation of an isocyanate group containing urethane of an aromatic polyisocyanate and a vinylidenecarbonyloxyalkanol and solutions, polymers and laminates obtained therefrom.
US4159376A (en) 1977-07-27 1979-06-26 Ici Americas Inc. Isocyanurates from unsaturated monohydric alcohols and polyisocyanates
DE2806731A1 (de) 1978-02-17 1979-08-23 Bayer Ag Verfahren zur herstellung von isocyanuratgruppen aufweisenden polyisocyanaten
US4296215A (en) * 1978-07-27 1981-10-20 Ici Americas Inc. Method to thicken dissolved thermoset resins
CA1112243A (en) 1978-09-08 1981-11-10 Manfred Bock Process for the preparation of polyisocyanates containing isocyanurate groups and the use thereof
DE2901479A1 (de) 1979-01-16 1980-07-24 Bayer Ag Neue isocyanato-isocyanurate, ein verfahren zu ihrer herstellung, sowie ihre verwendung als isocyanatkomponente in polyurethan-lacken
CA1127644A (en) 1980-01-28 1982-07-13 Anupama Mishra Isocyanurate products and polyurethanes therefrom
DE3033860A1 (de) 1980-09-09 1982-04-15 Bayer Ag, 5090 Leverkusen Neue isocyanato-isocyanurate, ein verfahren zu ihrer herstellung, sowie ihre verwendung als isocyanatkomponente in polyurethanlacken
DE3100263A1 (de) 1981-01-08 1982-08-12 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von isocyanuratgruppen aufweisenden polyisocyanaten und ihre verwendung bei der herstellung von polyurethanen
DE3100262A1 (de) 1981-01-08 1982-08-05 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von isocyanuratgruppen aufweisenden polyisocyanaten, als katalysator-komponente fuer dieses verfahren geeignete loesungen, sowie die verwendung der verfahrensprodukte als isocyanat-komponente bei der herstellung von polyurethanen
JPS58162581A (ja) 1982-03-19 1983-09-27 Nippon Polyurethan Kogyo Kk ポリウレタン塗料用組成物
DE3227489A1 (de) 1982-07-23 1984-01-26 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von isocyanuratgruppen aufweisenden polyisocyanaten und ihre verwendung als isocyanatkomponente zur herstellung von polyurethanen
PT77070B (en) 1982-07-29 1986-01-27 Dsm Resins Bv Oligomerisation of polyisocyanates
AT375652B (de) 1982-10-29 1984-08-27 Valentina Alexandro Postnikova Verfahren zur herstellung von arylaliphatischen polyisozyanuraten
JPH0641501B2 (ja) * 1984-04-30 1994-06-01 旭オーリン株式会社 重合体生成物の製造法
JPH0641500B2 (ja) * 1984-04-30 1994-06-01 旭オーリン株式会社 重合体生成物の製造方法
DE3521618A1 (de) 1985-06-15 1986-12-18 Bayer Ag, 5090 Leverkusen In wasser dispergierbare polyisocyanat-zubereitung und ihre verwendung als zusatzmittel fuer waessrige klebstoffe
JPH0678418B2 (ja) 1986-03-10 1994-10-05 大日本インキ化学工業株式会社 樹脂組成物
JP2598391B2 (ja) * 1986-03-24 1997-04-09 三菱化学株式会社 磁気記録媒体の製造方法
DE3700209A1 (de) 1987-01-07 1988-07-21 Bayer Ag Verfahren zur herstellung von polyisocyanaten mit biuretstruktur
DE3737244A1 (de) 1987-11-03 1989-05-18 Bayer Ag Verfahren zur herstellung von isocyanuratgruppen und olefinische doppelbindungen aufweisenden verbindungen und ihre verwendung als bindemittel
DE3811350A1 (de) 1988-04-02 1989-10-19 Bayer Ag Verfahren zur herstellung von isocyanuratpolyisocyanaten, die nach diesem verfahren erhaltenen verbindungen und ihre verwendung
DE3814167A1 (de) 1988-04-27 1989-11-09 Bayer Ag Verfahren zur herstellung von isocyanuratgruppen aufweisenden polyisocyanaten und ihre verwendung
DE3819627A1 (de) 1988-06-09 1989-12-14 Bayer Ag Uv-haertbare beschichtungen fuer polycarbonatformkoerper
US5130402A (en) * 1988-07-01 1992-07-14 Sanyo Chemical Industries, Ltd. Coating composition and plastisol composition, and articles coated therewith
CA1334848C (en) 1988-08-05 1995-03-21 William E. Slack Process for the production of polyisocyanates which contain isocyanurate groups
CA1334849C (en) 1988-08-24 1995-03-21 Bayer Corporation Process for the production of polyisocyanates which contain isocyanurate groups
US4855383A (en) * 1988-09-23 1989-08-08 Ashland Oil, Inc. In situ quaternary ammonium catalyst formation for curing polymeric isocyanates
DE3900053A1 (de) 1989-01-03 1990-07-12 Bayer Ag Verfahren zur herstellung von uretdion- und isocyanuratgruppen aufweisenden polyisocyanaten, die nach diesem verfahren erhaeltlichen polyisocyanate und ihre verwendung in zweikomponenten-polyurethanlacken
DE3902078A1 (de) 1989-01-25 1990-07-26 Bayer Ag Verfahren zur herstellung von modifizierten, isocyanuratgruppen aufweisenden polyisocyanaten und ihre verwendung
US5091496A (en) * 1989-05-19 1992-02-25 Mitsui Toatsu Chemicals, Inc. Polyisocyanatoalkylphenyl-isocyanurates, method for the preparation thereof and use thereof
DE3928503A1 (de) 1989-08-29 1991-03-07 Bayer Ag Verfahren zur herstellung von loesungen von isocyanuratgruppen aufweisenden polyisocyanaten in lackloesungsmitteln und ihre verwendung
DE4005762A1 (de) 1990-02-23 1991-08-29 Bayer Ag Trimerisierungskatalysatoren, ein verfahren zu ihrer herstellung und ihre verwendung bei der herstellung von isocyanuratgruppen aufweisenden polyisocyanaten
US5234970A (en) * 1991-07-16 1993-08-10 W. R. Grace & Co.-Conn. Dual curing composition based on isocyanate trimer and use thereof
GB9116781D0 (en) * 1991-08-02 1991-09-18 Ici Plc Curable compositions
US5322861A (en) * 1991-10-01 1994-06-21 Mitsubishi Kasei Corporation Ultraviolet-hardening urethane acrylate oligomer
DE4136618A1 (de) 1991-11-07 1993-05-13 Bayer Ag Wasserdispergierbare polyisocyanatgemische
IT1255279B (it) * 1992-05-20 1995-10-26 Sir Ind Spa Composizioni poliestere/isocianato reticolabili adatte alla preparazione di manufatti in composito particolarmente con processi ad iniezione, procedimento per la loro preparazione e loro utilizzo
US5370908A (en) 1993-05-24 1994-12-06 Olin Corporation Low VOC, heat-curable, one-component and two-component coating compositions based on organic polyisocyanates
DE4405054A1 (de) 1994-02-17 1995-08-24 Basf Ag Modifizierte (cyclo)aliphatische Polyisocyanatmischungen, Verfahren zu ihrer Herstellung und ihre Verwendung
DE4405055A1 (de) 1994-02-17 1995-08-24 Basf Ag Verfahren zur Herstellung von Isocyanuratgruppen aufweisenden Polyisocyanaten und ihre Verwendung
JPH07329191A (ja) * 1994-06-09 1995-12-19 Denken Eng Kk 光造形法
DE19611849A1 (de) 1996-03-26 1997-10-02 Bayer Ag Neue Isocyanattrimerisate und Isocyanattrimerisatmischungen, deren Herstellung und Verwendung
AU727418B2 (en) * 1997-04-01 2000-12-14 Huntsman Ici Chemicals Llc Polyisocyanate based xerogels
DE19734048A1 (de) 1997-08-06 1999-02-11 Bayer Ag Verfahren zur Herstellung von Polyisocyanaten, damit hergestellte Polyisocyanate und deren Verwendung
ZA9810038B (en) 1997-11-04 2000-05-03 Rhodia Chimie Sa A catalyst and a method for the trimerization of isocyanates.
DE19818312A1 (de) * 1998-04-23 1999-10-28 Bayer Ag Wäßriges Beschichtungssytem aus UV-härtenden Isocyanatgruppen aufweisenden Urethan(meth)acrylatisocyanaten
DE59902995D1 (de) 1998-06-02 2002-11-14 Bayer Ag Verfahren zur Herstellung Iminooxadiazindiongruppen enhaltender Polyisocyanate
DE19929064A1 (de) * 1999-06-25 2000-12-28 Bayer Ag Verfahren zur Herstellung Uretdiongruppen aufweisender Polyadditionsverbindungen
PL354140A1 (en) * 1999-09-30 2003-12-29 Basf Aktiengesellschaftbasf Aktiengesellschaft Aqueous polyurethane dispersions which can be hardened with mit uv-radiation and thermally, and use thereof
EP1248772B1 (fr) * 2000-01-20 2006-03-22 Rhodia Chimie Procede d'obtention de polyisocyanate(s) ramifie(s) faiblement colore(s), et composition en decoulant
DE10016194A1 (de) * 2000-03-31 2001-10-04 Bayer Ag Beschichtungssystem enthaltend UV-härtbare, Isocyanatgruppen aufweisende Urethan(meth)acrylate und Hydroxylgruppen aufweisende Urethan(meth)acrylate
DE10041634C2 (de) * 2000-08-24 2002-10-17 Basf Coatings Ag Wäßrige Dispersion und ihre Verwendung zur Herstellung von thermisch und mit aktinischer Strahlung härtbaren Beschichtungsstoffen, Klebstoffen und Dichtungsmassen
DE10065176A1 (de) 2000-12-23 2002-06-27 Degussa Katalysator und Verfahren zur Herstellung von niedrigviskosen und farbreduzierten isocyanuratgruppenhaltigen Polyisocyanaten
JP2004217808A (ja) * 2003-01-16 2004-08-05 Mitsubishi Chemicals Corp 活性エネルギー線硬化性樹脂組成物並びにそれを用いた印刷インキ用バインダー及び積層シート
CA2516089C (en) 2003-02-28 2013-05-14 Dow Global Technologies Inc. Preparation of isocyanurate group containing polyisocyanate mixtures
JP2004315617A (ja) 2003-04-14 2004-11-11 Mitsubishi Rayon Co Ltd 立体造形用組成物、及び立体造形物
JP2005015627A (ja) 2003-06-26 2005-01-20 Jsr Corp 光硬化性液状樹脂組成物
DE102004012571A1 (de) 2004-03-12 2005-09-29 Basf Ag Verfahren zur Herstellung von Isocyanuratgruppen aufweisenden Polyisocyanaten und ihre Verwendung
DE102004043537A1 (de) * 2004-09-09 2006-03-16 Bayer Materialscience Ag Herstellung von neuen strahlenhärtenden Bindemitteln
DE102004063102A1 (de) * 2004-12-22 2006-07-13 Basf Ag Strahlungshärtbare Verbindungen
JP2009509727A (ja) * 2005-09-22 2009-03-12 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 樹脂基材上に付着コーティングを生成する方法
US8334025B2 (en) * 2005-10-27 2012-12-18 3D Systems, Inc. Antimony-free photocurable resin composition and three dimensional article
DE102005057682A1 (de) * 2005-12-01 2007-06-06 Basf Ag Strahlungshärtbare wasserelmulgierbare Polyisocyanate
US20070299242A1 (en) * 2006-06-21 2007-12-27 Bayer Materialscience Llc Pendant acrylate and/or methacrylate-containing polyether monols and polyols
DE102006051897A1 (de) 2006-10-31 2008-05-08 Bayer Materialscience Ag Bedruckte, verformbare Folien
CN101284955B (zh) * 2007-04-11 2011-03-30 比亚迪股份有限公司 一种双重固化涂料组合物及其制备方法
EP2212366A1 (en) * 2007-11-19 2010-08-04 Cytec Surface Specialties, S.A. Radiation curable compositions
EP2346919B1 (en) * 2008-11-10 2013-09-04 Dow Global Technologies LLC Isocyanate trimerisation catalyst system, a precursor formulation, a process for trimerising isocyanates, rigid polyisocyanurate/polyurethane foams made therefrom, and a process for making such foams
JP5215897B2 (ja) * 2009-02-06 2013-06-19 日本ビー・ケミカル株式会社 塗膜形成方法
CN102361947B (zh) * 2009-03-23 2013-12-25 Dic株式会社 保护粘着膜、屏板及携带电子终端
EP2489699B1 (en) * 2009-10-16 2014-07-16 Posco Radiation curable resin composition, and fingerprint-resistant resin composition containing same
US8372330B2 (en) * 2009-10-19 2013-02-12 Global Filtration Systems Resin solidification substrate and assembly
KR101995185B1 (ko) * 2009-12-17 2019-07-01 디에스엠 아이피 어셋츠 비.브이. 트라이아릴 설포늄 보레이트 양이온 광개시제를 포함하는 적층식 제작을 위한 액체 방사선 경화성 수지
US8580887B2 (en) * 2010-07-30 2013-11-12 Basf Se High-functionality polyisocyanates containing urethane groups
US9157007B2 (en) * 2011-03-09 2015-10-13 3D Systems, Incorporated Build material and applications thereof
CN102504174A (zh) * 2011-12-19 2012-06-20 烟台德邦科技有限公司 一种聚氨酯丙烯酸酯及其制备方法以及应用
ES2557567T3 (es) * 2011-12-22 2016-01-27 Covestro Deutschland Ag Dispersiones acuosas de copolímero de poliacrilato con un alto contenido de grupo OH
US9718936B2 (en) * 2012-02-08 2017-08-01 Covestro Deutschland Ag Method for producing a hard polyurethane-polyisocyanurate foamed material
EP2847246B1 (en) 2012-05-08 2016-04-20 Basf Se Preparation of polyisocyanates having isocyanurate groups and their use
CN102675590B (zh) * 2012-05-25 2014-04-02 深圳职业技术学院 一种含脂环族环氧和双键的双重固化树脂的制备方法及应用
KR101735221B1 (ko) * 2012-06-18 2017-05-12 피피지 인더스트리즈 오하이오 인코포레이티드 금속 기재 코팅에 유용한 이중-경화 조성물 및 이 조성물을 사용하는 방법
CN102977335B (zh) * 2012-11-30 2015-04-22 深圳职业技术学院 一种以环氧氯丙烷为原料制备含光-热双重固化基团树脂的方法
CN105246953B (zh) * 2013-02-08 2018-09-21 科思创德国股份有限公司 使用硬涂层的塑料基材的改进的最大加工温度
KR20150136467A (ko) * 2013-03-27 2015-12-07 디아이씨 가부시끼가이샤 활성 에너지선 경화성 조성물, 그 경화 도막, 및 당해 경화 도막을 갖는 물품
KR20160051814A (ko) * 2013-08-26 2016-05-11 바스프 에스이 방사선 경화성의 수분산성 폴리우레탄 (메트)아크릴레이트
EP3061778B1 (en) * 2013-10-21 2020-05-20 Mitsui Chemicals, Inc. Polymerizable composition for optical material and optical material
HUE035077T2 (en) 2013-12-10 2018-05-02 Covestro Deutschland Ag Polyisocyanates containing Iminoadadiazindion groups
CN104974502B (zh) 2014-04-10 2019-12-27 科思创德国股份有限公司 聚氨酯复合材料及其制备方法
JP2016002683A (ja) 2014-06-16 2016-01-12 コニカミノルタ株式会社 ３ｄ造形物の製造方法、３ｄ造形用光硬化性組成物および３ｄ造形用インクセット
EP2993195A1 (en) * 2014-09-05 2016-03-09 Huntsman International Llc A method for improving fracture toughness of polyisocyanurate comprising reaction products
CN105778005B (zh) * 2014-12-01 2020-04-28 科思创德国股份有限公司 可自由基聚合的聚氨酯组合物
JP2016135477A (ja) 2015-01-20 2016-07-28 関西ペイント株式会社 基材の被膜形成方法
GB201501965D0 (en) * 2015-02-05 2015-03-25 Lumina Adhesives Ab Polyurethane based switchable adhesives
JP6381474B2 (ja) * 2015-03-31 2018-08-29 三井化学株式会社 硬化性ポリウレタン樹脂組成物および硬化物
FR3035109B1 (fr) * 2015-04-20 2017-04-28 Arkema France Urethanes aminoacrylate-acrylates de haute fonctionnalite derives de l'addition d'un aminoalcool a amine secondaire sur un acrylate multifonctionnel.
JP7029295B2 (ja) 2015-04-21 2022-03-03 コベストロ、ドイチュラント、アクチエンゲゼルシャフト 高い熱安定性を有するポリイソシアヌレートプラスチック
TWI695020B (zh) 2015-04-21 2020-06-01 德商科思創德意志股份有限公司 於絕熱條件下所製造以聚異氰尿酸酯聚合物為主之固體
EP3424975A1 (en) 2015-04-21 2019-01-09 Covestro Deutschland AG Polyisocyanurate polymers and process for the production of polyisocyanurate polymers
CN104830222B (zh) * 2015-04-28 2017-04-12 中科院广州化学有限公司南雄材料生产基地 一种可双重固化的低表面能聚氨酯涂料及其制备方法
US20190255788A1 (en) 2016-09-20 2019-08-22 Covestro Deutschland Ag Anisotropic composite materials based on polyisocyanates

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0008170A1 (en) * 1978-07-27 1980-02-20 Ici Americas Inc. Polyisocyanurate containing moulding compositions
US4352906A (en) * 1981-08-06 1982-10-05 Ici Americas Inc. Blister resistant calcium carbonate filled polyisocyanurate resin molding compositions

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022108738A1 (en) * 2020-11-18 2022-05-27 Covestro Llc Polyurethane and polyisocyanurate hybrid coatings
WO2022108737A1 (en) * 2020-11-18 2022-05-27 Covestro Llc Polyurethane and polyisocyanurate hybrid materials and method of preparing the same

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