EP3914632A1 - Matériaux composites à base de polymères uréthanes et isocyanurates à polymérisation duale - Google Patents

Matériaux composites à base de polymères uréthanes et isocyanurates à polymérisation duale

Info

Publication number
EP3914632A1
EP3914632A1 EP20701186.7A EP20701186A EP3914632A1 EP 3914632 A1 EP3914632 A1 EP 3914632A1 EP 20701186 A EP20701186 A EP 20701186A EP 3914632 A1 EP3914632 A1 EP 3914632A1
Authority
EP
European Patent Office
Prior art keywords
isocyanate
groups
isocyanate groups
reaction mixture
reactive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20701186.7A
Other languages
German (de)
English (en)
Inventor
Richard MEISENHEIMER
Paul Heinz
Dirk Achten
Heiko Hocke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Original Assignee
Covestro Intellectual Property GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Covestro Intellectual Property GmbH and Co KG filed Critical Covestro Intellectual Property GmbH and Co KG
Publication of EP3914632A1 publication Critical patent/EP3914632A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/09—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture
    • C08G18/092—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture oligomerisation to isocyanurate groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/722—Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
    • C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
    • C08G18/165—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22 covered by C08G18/18 and C08G18/24
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1825—Catalysts containing secondary or tertiary amines or salts thereof having hydroxy or primary amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/225—Catalysts containing metal compounds of alkali or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2115/00—Oligomerisation
    • C08G2115/02—Oligomerisation to isocyanurate groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—Polyurethanes from polyethers

Definitions

  • the present invention relates to reaction mixtures with a high ratio of isocyanate groups to isocyanate-reactive groups, which predominantly harden through the formation of isocyanurate groups, and the use of such reaction mixtures for the production of semi-finished products.
  • This process does not produce semi-finished products which, although they are stable in storage and transportable after a first curing step of the polyisocyanate composition, can still be processed, e.g. by forming, and only then obtain their final mechanical properties in a second hardening step.
  • the present invention therefore relates to a two-stage process in which a polyisocyanate composition with a molar deficiency of isocyanate-reactive groups is applied to a fiber and precured in a first process step with an increase in viscosity, preferably by the formation of urethane, urea or thiourethane groups.
  • the reaction of (i) isocyanate groups with isocyanate groups in relation to the reaction of (ii) isocyanate groups with isocyanate-reactive groups takes place in the first process step in a ratio of at most 1: 1, preferably at most 1: 2 and particularly preferably at most 1: 3. In this way, a semi-finished product is obtained, which can easily be further processed, stored and transported.
  • the polyisocyanate composition is finally cured predominantly with the reaction of isocyanate groups with other isocyanate groups, preferably with the formation of uretdione groups, asymmetric trimers and isocyanurate groups, particularly preferably with the formation of isocyanurate groups.
  • the production of such a semi-finished product requires reaction mixtures which contain special reactive components and catalysts matched to the two-stage process.
  • the present invention relates in a first embodiment to a reaction mixture with a molar ratio of isocyanate groups to isocyanate-reactive groups of 2: 1 to 10: 1 containing a) a polyisocyanate composition A which has a proportion of aliphatic and cycloaliphatic isocyanate groups in the total amount of contained isocyanate groups of at least 80 mol%;
  • At least one catalytic functionality CI which is the reaction of
  • At least one catalytic functionality C2 which is the reaction of
  • Isocyanate groups catalyzed to isocyanurate groups the catalytic functionalities CI and C2 being effected by the same compound or by at least two different compounds.
  • the molar ratio of isocyanate groups to groups reactive with isocyanate is preferably between 3: 1 and 9: 1 and particularly preferably between 4: 1 and 9: 1.
  • “Isocyanate-reactive groups” in the sense of this application are preferably hydroxyl, amino and thiol groups. Even if isocyanate groups are able to undergo crosslinking reactions with other isocyanate groups, isocyanate groups are not referred to in the present application as “isocyanate-reactive groups”.
  • reaction mixture after storage for 24 hours at a temperature of up to 23 ° C., has a viscosity of at least 100 Pas or a module G ' of at least 5 * 10 3 Pa.
  • the reaction mixture according to the invention is not intended for the production of rigid or flexible foams. For this reason, it contains physical and chemical blowing agents at most in an amount which, compared to a reaction mixture without blowing agent, reduces the density of the resulting polymer by at least 10%, more preferably by at least 15% and particularly preferably by at least 20%.
  • the maximum content of physical and chemical blowing agents in the reaction mixture is preferably at most 1% by weight, more preferably at most 0.5% by weight and most preferably at most 0.1% by weight, in each case based on the total amount of the reaction mixture.
  • blowing agents are understood to be constituents which react or evaporate during the selected reaction conditions with the formation of gas bubbles.
  • the reaction mixture is prepared by mixing the components defined above. All methods known to the person skilled in the art can be used here.
  • polyisocyanate composition A denotes the isocyanate component in the initial reaction mixture. In other words, it is the sum of all compounds in the initial reaction mixture which have isocyanate groups.
  • the polyisocyanate composition A is therefore used as a starting material in the process according to the invention.
  • polymers e.g. polyurethanes, polyureas and polyisocyanurates
  • oligomeric compounds e.g. those with urethane, urea, uretdione, isocyanurate, allophanate, biuret
  • Iminooxadiazinedione and / or oxadiazinetrione structure e.g. polyurethanes, polyureas and polyisocyanurates
  • oligomeric compounds e.g. those with urethane, urea, uretdione, isocyanurate, allophanate, biuret
  • polyisocyanates When generally speaking of “polyisocyanates”, this means both monomeric and / or oligomeric polyisocyanates. However, for understanding many aspects of the invention it is important to differentiate between monomeric diisocyanates and oligomeric polyisocyanates.
  • oligomeric polyisocyanates When speaking of “oligomeric polyisocyanates” then we mean polyisocyanates that are made up of at least two monomeric diisocyanate molecules, ie they are compounds which contain or consist of a reaction product of at least two monomeric diisocyanate molecules.
  • oligomeric polyisocyanates from monomeric diisocyanates is also referred to here as modification of monomeric diisocyanates.
  • This “modification”, as used here, means the reaction of monomeric diisocyanates to oligomeric polyisocyanates with urethane, urea, uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structure.
  • hexamethylene diisocyanate (HDI) is a "monomeric diisocyanate" because it contains two isocyanate groups and is not a reaction product of at least two polyisocyanate molecules:
  • reaction products of at least two HDI molecules which still have at least two isocyanate groups are "oligomeric polyisocyanates" within the meaning of the invention.
  • oligomeric polyisocyanates are based on the monomeric HDI, e.g. the HDI isocyanurate and the HDI biuret, which are each made up of three monomeric HDI building blocks:
  • the polyisocyanate composition A contains monomeric and / or oligomeric polyisocyanates.
  • the polyisocyanate composition A consists entirely or at least 25, 40, 60, 80, 85, 90, 95, 98, 99 or 99.5% by weight, in each case based on the weight of the polyisocyanate composition A.
  • monomeric polyisocyanates Mixtures of monomeric and oligomeric polyisocyanates can be used particularly advantageously in order to adjust the viscosity of the polyisocyanate composition A.
  • the monomeric polyisocyanates can be used here as reactive thinners in order to reduce the viscosity of the oligomeric polyisocyanates.
  • the polyisocyanate composition A used in the crosslinking as starting material contains predominantly oligomeric polyisocyanates and is low in monomeric polyisocyanates.
  • the polyisocyanate composition A consists entirely or at least 25, 40, 60, 80, 85, 90, 95, 98, 99 or 99.5% by weight, in each case based on the weight of the polyisocyanate composition A.
  • oligomeric polyisocyanates This content of oligomeric polyisocyanates relates to the polyisocyanate composition A, ie they are not formed as an intermediate during the process according to the invention, but are already present in the polyisocyanate composition A used as a starting material at the start of the reaction.
  • Low in monomer and low in monomeric polyisocyanates are used synonymously here in relation to the polyisocyanate composition A.
  • the polyisocyanate composition A has a proportion of monomeric polyisocyanates in the polyisocyanate composition A of at most 20% by weight, in particular at most 15% by weight or at most 10% by weight , each based on the weight of the polyisocyanate composition A.
  • the polyisocyanate composition A preferably has a monomeric polyisocyanate content of at most 5% by weight, preferably at most 2.0% by weight, particularly preferably at most 1.0% by weight, based in each case on the weight of the polyisocyanate composition A.
  • Particularly good results are obtained when polymer composition A is essentially free of monomeric polyisocyanates. “Essentially free” means that the content of monomeric polyisocyanates is at most 0.3% by weight, preferably at most 0.1% by weight. % based on the weight of the polyisocyanate composition A.
  • Low-monomer polyisocyanate compositions A can be obtained by following the modification of a monomeric starting isocyanate by a further process step to remove the unreacted excess monomeric polyisocyanates.
  • This separation of monomers can be carried out in a particularly practical manner by processes known per se, preferably by thin-film distillation under high vacuum or by extraction with suitable solvents which are inert to isocyanate groups, for example aliphatic or cycloaliphatic hydrocarbons such as pentane, hexane, heptane, cyclopentane or cyclohexane.
  • the polyisocyanate composition A according to the invention is obtained by modifying monomeric polyisocyanates with subsequent removal of unreacted monomers. It is therefore low in monomer.
  • the polyisocyanate composition A can contain a mixture of different isocyanates.
  • a mixture of isocyanates can be advantageous to achieve special technical effects, such as a particular hardness or glass transition temperature (Tg).
  • Tg glass transition temperature
  • Particularly practical results are obtained if the polyisocyanate composition A has a proportion of monomeric diisocyanates in the polyisocyanate composition A of at most 45% by weight, in particular at most 15% by weight or at most 10% by weight, in each case based on the weight of the polyisocyanate composition A.
  • the polyisocyanate composition A preferably has a monomeric diisocyanate content of at most 5% by weight, preferably at most 2.0% by weight, particularly preferably at most 1.0% by weight, based in each case on the weight of the polyisocyanate composition A.
  • the polyisocyanate composition A has a proportion of reactive isocyanate groups of the monomeric diisocyanate based on the total number of all reactive isocyanate groups in the polyisocyanate composition A of at most 45%, in particular at most 25% or at most 10%.
  • the polyisocyanate composition A preferably has a monomeric diisocyanate group content of at most 5%, preferably at most 2.0%, particularly preferably at most 1.0%, in each case based on the total number of all reactive isocyanate groups of the polyisocyanate composition A.
  • the polyisocyanate composition A can contain monomeric monoisocyanates or monomeric polyisocyanates with an isocyanate functionality greater than two or less than two, i.e. with more than two or less than two isocyanate groups per molecule.
  • monomeric monoisocyanates has proven to be advantageous in order to influence the network density of the resulting material.
  • the polyisocyanate composition A has a proportion of monomeric monoisocyanates or monomeric isocyanates with an isocyanate functionality of less than two in the polyisocyanate composition A of less than 50% by weight, in particular less than 15% by weight or less than 10% by weight , each based on the weight of the polyisocyanate composition A.
  • the polyisocyanate composition A preferably has a content of monomeric monoisocyanates or monomeric isocyanates with an isocyanate functionality of less than two of at most 5% by weight, preferably at most 2.0% by weight, particularly preferably at most 1.0% by weight, in each case based on the weight of the
  • Polyisocyanate composition A on.
  • oligomeric polyisocyanates described here are usually obtained by modifying simple aliphatic, cycloaliphatic, araliphatic and / or aromatic monomeric diisocyanates or mixtures of such monomeric diisocyanates.
  • the oligomeric polyisocyanates can have, in particular, urethane, urea, 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:
  • oligomeric polyisocyanates which are a mixture of at least two oligomeric polyisocyanates, the structure of the at least two oligomeric polyisocyanates differing.
  • This is preferably selected from the group consisting of urethane, urea, uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and oxadiazinetrione structures and mixtures thereof.
  • Starting mixtures of this type in particular in comparison to trimerization reactions with oligomeric polyisocyanates of only one defined structure, can influence the Tg value, mechanical values such as hardness, scratch resistance, or gloss and feel, which is advantageous for many applications.
  • a polyisocyanate composition A which consists of at least one oligomeric polyisocyanate having a urethane, urea, biuret, allophanate, isocyanurate and / or iminooxadiazinedione structure and mixtures thereof is preferably used in the process according to the invention.
  • the polyisocyanate composition A which contains oligomeric polyisocyanates is one which contains only a single defined oligomeric structure, for example exclusively or largely an isocyanurate structure.
  • a polyisocyanate composition A is regarded as a polyisocyanate composition of a single defined oligomeric structure if at least one oligomeric structure selected from urethane, urea, uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structures 50 mol%, preferably 60 mol%, preferably 70 mol%, particularly preferably 80 mol%, in particular 90 mol%, in each case based on the sum of the oligomeric structures present from the group consisting of urethane and urea , Uretdione, isocyanurate, allophanate, biuret, iminooxadiazine
  • the oligomeric polyisocyanates are those which mainly have isocyanurate structures and which may only contain the above-mentioned urethane, urea, uretdione, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structure as by-products.
  • One embodiment of the invention thus provides for the use of a polymer composition A of an individually defined oligomeric structure, the oligomeric structure being an isocyanurate structure and comprising at least 50 mol%, preferably 60 mol%, preferably 70 mol%, particularly preferably 80 mol%, in particular 90 mol%, in each case based on the sum of the oligomeric structures present from the group consisting of urethane, urea, uretdione, isocyanurate, allophanate and biuret -, Iminooxadiazindione- and oxadiazintrione structures in the polyisocyanate composition A, is present.
  • oligomeric polyisocyanates which largely have no isocyanurate structure and mainly contain at least one of the above-mentioned types of urethane, urea, uretdione, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structure.
  • the polyisocyanate composition A consists of 50 mol%, preferably 60 mol%, preferably 70 mol%, particularly preferably 80 mol%, in particular 90 mol%, in each case based on the sum of the oligomeric structures present from the group consisting of urethane, urea, uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and oxadiazinetrione structures in the polyisocyanate composition A, from oligomeric polyisocyanates which have a structural type selected from the group consisting of urethane, urea , Uretdione, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structures.
  • a further embodiment of the invention provides for the use of a low-isocyanurate polyisocyanate composition A which, based on the sum of the oligomeric structures present, consists of the group consisting of urethane, urea, uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and Oxadiazinetrione structures in the polyisocyanate composition A, less than 50 mol%, preferably less than 40 mol%, preferably less than 30 mol%, particularly preferably less than 20 mol%, 10 mol% or 5 mol% of isocyanurate structures.
  • a further embodiment of the invention provides for the use of a polymer composition A of an individually defined oligomeric structure type, the oligomeric structure type being selected from the group consisting of urethane, urea, uretdione, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structures and this type of structure to at least 50 mol%, preferably 60 mol%, preferably 70 mol%, particularly preferably 80 mol%, in particular 90 mol%, based on the sum of the oligomeric structures from the group consisting of urethane -, Urea, uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and oxadiazinetrione structures in the polyisocyanate composition A, is present.
  • the proportions of urethane, urea, uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structure in the polyisocyanate composition A can be determined, for example, by NMR spectroscopy. 13 CN MR spectroscopy, preferably proton-decoupled, can preferably be used here, since the oligomeric structures mentioned provide characteristic signals.
  • the polyisocyanate composition A to be used in the process according to the invention preferably has a (mean) NCO functionality of 1 , 3 to 10.0, preferably from 2.0 to 5.0, preferably from 2.3 to 4.5.
  • the polyisocyanate composition A to be used according to the invention has an isocyanate group content of 1.0 to 60.0% by weight. It has proven particularly practical if the polyisocyanate composition A according to the invention has an isocyanate group content of 8.0 to 50.0% by weight, preferably 14.0 to 30.0% by weight, based in each case on the weight of the
  • Polyisocyanate composition A has.
  • the polyisocyanate composition A is defined in that it contains oligomeric polyisocyanates which are particularly preferred from monomeric polyisocyanates, regardless of the type of modification reaction used, while maintaining a degree of oligomerization of 5 to 45%, preferably 10 to 40% 15 to 30% were obtained.
  • the “degree of oligomerization” is to be understood as the percentage of the isocyanate groups originally present in the starting mixture, which is consumed during the production process to form urethane, urea, uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structures becomes.
  • Suitable monomeric polyisocyanates for the polyisocyanate composition A or starting compounds for the oligomeric polyisocyanates are any monomeric polyisocyanates which are accessible 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 obtained when the monomeric polyisocyanates are monomeric diisocyanates.
  • Preferred monomeric diisocyanates are those which have a molecular weight in the range from 140 to 400 g / mol, with aliphatic, cycloaliphatic, araliphatic and / or aromatically bound isocyanate groups, such as, for. B.
  • 1,4-diisocyanatobutane 1,5-diisocyanatopentane (PDI), 1,6-diisocyanatohexane (HDI), 2-methyl-l, 5-diisocyanatopentane, 1,5-diisocyanato-2,2-dimethylpentane , 2,2,4- or 2,4,4-trimethyl-l, 6-diisocyanatohexane, 1,10-diisocyanatodecane, 1,3- and 1,4-diisocyanatocyclohexane, 1,4-diisocyanato-3,3, 5- trimethylcyclohexane, 1,3-diisocyanato-2-methylcyclohexane, 1,3-diisocyanato-4-methylcyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (isophorone diisocyanate; IPD
  • Diisocyanatodicyclohexylmethane H12MDI
  • 1,3- and 1,4-bis isocyanatomethyl) cyclohexane
  • bis- (isocyanatomethyl) norbornane NBDI
  • 4,4'-diisocyanato-3,3'-dimethyldicyclohexylmethane 4,4'- Diisocyanato-3,3 ', 5,5'-tetramethyldicyclohexylmethane
  • 4,4'-diisocyanato-l, l'-bi cyclohexyl
  • 4,4'-diisocyanato-3,3'-dimethyl-l, l'- bi cyclohexyl
  • 4,4'-diisocyanato-2,2 ', 5,5'-tetra-methyl-l, l'- bi 1,8-diisocyanato-p-menthan, 1,3- Diisocyanato
  • classic aliphatic or aromatic isocyanate end-group prepolymers such as aliphatic or aromatic isocyanate end group-carrying polyether, polyester, polycarbonate prepolymers, can also be used as polyisocyanates in the polyisocyanate composition A in the process according to the invention.
  • Suitable monomeric monoisocyanates which can optionally be used in the polyisocyanate composition A are, for example, n-butyl isocyanate, n-amyl isocyanate, n-hexyl isocyanate, n-heptyl isocyanate, n-octyl isocyanate, undecyl isocyanate, dodecyl isocyanate, tetradecyl isocyanate, cetyl isocyanate, stearyl isocyanate, cyclopentane 3- or 4-methylcyclohexyl isocyanate, phenyl isocyanate, alkylphenyl isocyanate, naphthyl isocyanate or any mixture of such monoisocyanates.
  • Examples of monomeric isocyanates with an isocyanate functionality greater than two, which can optionally be added to polyisocyanate composition A, are 4-isocyanatomethyl-1,8-octane diisocyanate (triisocyanatononane; TIN) or multinuclear derivatives of diphenlymethane diisocyanate (M DI), so-called polymeric MDI (pMDl) or Roh MDI called.
  • TIN 4-isocyanatomethyl-1,8-octane diisocyanate
  • M DI multinuclear derivatives of diphenlymethane diisocyanate
  • pMDl polymeric MDI
  • Roh MDI Roh MDI
  • the polyisocyanate composition A contains aromatic polyisocyanates.
  • aromatic polyisocyanate means a polyisocyanate that has at least one aromatically bound isocyanate group.
  • Aromatically bound isocyanate groups are understood to mean isocyanate groups which are bound to an aromatic hydrocarbon radical.
  • a polyisocyanate composition A which has at least 80 mol%, more preferably at least 95 mol%, of aliphatically and / or cycloaliphatically bonded isocyanate groups, based on the total amount present in the polyisocyanate composition A.
  • Isocyanate groups More preferably, the polyisocyanate composition A in this embodiment has exclusively aliphatic and / or cycloaliphatic isocyanate groups.
  • Aliphatic or cycloaliphatic isocyanate groups are understood to mean isocyanate groups which are bonded to an aliphatic or cycloaliphatic hydrocarbon radical.
  • a polyisocyanate composition A which consists of or contains one or more oligomeric polyisocyanates, the one or more oligomeric polyisocyanates having exclusively aliphatically and / or cycloaliphatically bound isocyanate groups.
  • a polyisocyanate composition A which consists of or contains one or more monomeric polyisocyanates, the one or more monomeric polyisocyanates having exclusively aliphatic and / or cycloaliphatic isocyanate groups.
  • the polyisocyanate composition A consists of at least 70, 80, 85, 90, 95, 98 or 99% by weight, based in each case on the weight of the polyisocyanate composition A, of monomeric and / or oligomeric polyisocyanates which are exclusively aliphatic and / or cycloaliphatically bound isocyanate groups. Practical tests have shown that particularly good results can be achieved with polyisocyanate compositions A) in which the oligomeric polyisocyanates contained therein have only isocyanate groups bonded aliphatically and / or cycloaliphatically.
  • a polyisocyanate composition A which consists of or contains one or more oligomeric polyisocyanates, the one or more oligomeric polyisocyanates based on 1,4-diisocyanatobutane (BDI), 1,5-diisocyanatopentane (PDI), 1,6-diisocyanatohexane (HDI), isophorone diisocyanate (IPDI) or 4,4'-diisocyanatodicyclohexylmethane (H12MDI) or mixtures thereof.
  • BDI 1,4-diisocyanatobutane
  • PDI 1,5-diisocyanatopentane
  • HDI 1,6-diisocyanatohexane
  • IPDI isophorone diisocyanate
  • H12MDI 4,4'-diisocyanatodicyclohexylmethane
  • a polyisocyanate composition A which contains one or more monomeric polyisocyanates selected from 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
  • Component B which is reactive with isocyanate is in principle any compound which has at least 1, preferably on average at least 1.5 and particularly preferably at least 2 and less than 6, isocyanate-reactive groups as defined above in this application.
  • Component B preferably has less than 5 and particularly preferably less than 4 isocyanate-reactive groups.
  • the “isocyanate-reactive groups” of component B are preferably hydroxyl groups.
  • Component B can be a monomer, but it can also itself be an oligomer or polymer. It preferably has a number average molecular weight of at most 21,000 g / mol, more preferably at most 10,000 g / mol, even more preferably at most 2,500 g / mol and most preferably at most 300 g / mol. It is preferred that their molecular weight is at least 60 g / mol.
  • an alcohol with an average OH functionality of at least 2, preferably 3 and an OH content of at least 25% by weight is used as component B. It is also possible to use a mixture of 2, 3 or more polyols if each of the polyols used meets the aforementioned conditions.
  • the use of polyols with high OH functionality increases the network density of the resulting polymer and increases properties such as the glass transition temperature, the hardness, the resistance to chemicals and the weather resistance.
  • Preferred polyols B which meet these conditions are selected from the list consisting of glycol, glycerol, propanediol, butanediol, diethylene glycol, 1,2,10-decanetriol, 1,2,8-octanetriol, 1,2,3-trihydroxybenzene, 1,1,1-trimethylolpropane, 1,1,1-trimethylolethane, pentaerythritol and sugar alcohols.
  • the polyol B is preferably a mixture which contains at least 80% by weight of glycerol.
  • Polyol B is more preferably a mixture which contains at least 90% by weight of glycerol.
  • composition of the reaction mixture which is cured in process step c) is preferably selected such that the polyols defined above to be used according to the invention have at least 90 mol%, more preferably at least 95 mol% and even more preferably 98 mol% of those present in the reaction mixture Contain isocyanate reactive groups.
  • groups reactive toward isocyanate are taken to mean hydroxyl, thiol, carboxyl and amino groups, amides, urethanes, acid anhydrides and epoxides. This means that the presence of further compounds which carry groups which are reactive toward isocyanate is possible according to the invention, but is limited in quantity.
  • polymeric polyols are understood to mean OH-functional compounds with a number-average molecular weight Mn of at least 2,000, preferably at least 10,000 and particularly preferably at least 20,000.
  • the reaction mixture contains one or more compounds with different catalytic functions.
  • the first catalytic function is to promote the reaction of isocyanate groups with isocyanate-reactive groups, referred to in the present application as functionality CI. Urethane or urea groups are preferably formed here.
  • the second catalytic function referred to as C2 in the present application, is the promotion of the trimerization and / or dimerization of isocyanate groups to at least one structure selected from the group consisting of isocyanurate groups, iminooxadiazinediione and uretdione groups.
  • Functionality C2 preferably catalyzes the trimerization of isocyanate groups to isocyanurate groups.
  • reaction of isocyanate groups with isocyanate-reactive groups can take place separately from the trimerization of isocyanate groups to isocyanurate groups. Therefore functionality C2 must be largely inactive at a temperature at which the functionality CI is already active. In this way it is possible in a first process step to stabilize the reaction mixture applied to a surface to such an extent that the semi-finished product can be stored and transported before the final curing of the reaction mixture is achieved by activating the functionality C2 at elevated temperature.
  • the type and quantity of the catalytic functionalities CI and C2 are used in such a way that the conversion of isocyanate groups to urethane and urea groups at a given temperature in the temperature range between 10 ° C. and 50 ° C. is at least twice, preferably at least five times as fast as all other reactions in which isocyanate is consumed, in particular the reaction of isocyanate groups to isocyanurate groups.
  • the catalytic functionality CI at any temperature in the range from 10 ° C to 50 ° C compared to the catalytic functionality C2 has a reaction rate coefficient for the conversion of isocyanate group groups k (T) isoci, which is preferably at least twice as large as the reaction rate coefficient k ( T) isoc - more preferred is a factor of at least 5, even more preferred of at least 10.
  • the reaction mixture contains a compound which has both catalytic functions CI and C2.
  • the reaction mixture contains at least two different compounds, of which the first compound catalyzes the reaction of isocyanate groups with isocyanate-reactive groups (functionality CI) and the second compound catalyzes the reaction of one another (functionality C2).
  • reaction rate coefficients can optionally be determined individually in solution from the rate of reaction of the isocyanate group at the desired reaction temperatures. For this purpose, the reaction is in a range up to max. 10% conversion was observed by means of IR or NIR or NMR and the degradation of the isocyanate concentration was plotted against time at a given temperature.
  • a particularly suitable compound which has both a catalytic functionality CI and a catalytic functionality C2 is a compound as defined in formula (I) or an adduct of a compound according to formula (I)
  • R 1 and R 2 are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, branched C5 alkyl, unbranched C5 alkyl, branched C6 alkyl, unbranched C6 alkyl, branched C7 alkyl and unbranched C7 alkyl;
  • A is selected from the group consisting of 0, S and NR 3 , wherein R 3 is selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl and isobutyl; and
  • B is selected independently of A from the group consisting of OH, SH NHR 4 and NH, where R 4 is selected from the group consisting of methyl, ethyl and propyl
  • A is NR 3 , where R 3 is selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl and isobutyl.
  • R 3 is preferably methyl or ethyl.
  • R 3 is particularly preferably methyl.
  • B is OH and R 1 and R 2 are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, branched C5-alkyl, unbranched C5-alkyl, branched C6 -Alkyl, unbranched C6-alkyl, branched C7-alkyl and unbranched C7-alkyl.
  • R 1 and R 2 are preferably independently of one another methyl or ethyl.
  • R 1 and R 2 are particularly preferably methyl.
  • B SH and R 1 and R 2 are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, branched C5 alkyl, unbranched C5 alkyl, branched C6 -Alkyl, unbranched C6-alkyl, branched C7-alkyl and unbranched C7-alkyl.
  • R 1 and R 2 are preferably independently of one another methyl or ethyl.
  • R 1 and R 2 are particularly preferably methyl.
  • B is NHR 4 and R 1 and R 2 are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, branched C5-alkyl, unbranched C5-alkyl, branched C6-alkyl, unbranched C6-alkyl, branched C7-alkyl and unbranched C7-alkyl.
  • R 1 and R 2 are preferably independently of one another methyl or ethyl.
  • R 1 and R 2 are particularly preferably methyl.
  • R4 is selected from the group consisting of methyl, ethyl and propyl.
  • R 4 is preferably methyl or ethyl.
  • R 4 is particularly preferably methyl.
  • B is NH and R 1 and R 2 are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, branched C5 alkyl, unbranched C5 alkyl, branched C6 -Alkyl, unbranched C6 alkyl, branched C7 alkyl and unbranched C7 alkyl.
  • R 1 and R 2 are preferably independently of one another methyl or ethyl.
  • R 1 and R 2 are particularly preferably methyl.
  • A is oxygen
  • B is OH and R 1 and R 2 are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, branched C5-alkyl, unbranched C5-alkyl, branched C6 -Alkyl, unbranched C6-alkyl, branched C7-alkyl and unbranched C7-alkyl.
  • R 1 and R 2 are preferably independently of one another methyl or ethyl.
  • R 1 and R 2 are particularly preferably methyl.
  • B SH and R 1 and R 2 are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, branched C5 alkyl, unbranched C5 alkyl, branched C6 -Alkyl, unbranched C6-alkyl, branched C7-alkyl and unbranched C7-alkyl.
  • R 1 and R 2 are preferably independently of one another methyl or ethyl.
  • R 1 and R 2 are particularly preferably methyl.
  • B is NHR 4 and R 1 and R 2 are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, branched C5-alkyl, unbranched C5-alkyl, branched C6-alkyl, unbranched C6-alkyl, branched C7-alkyl and unbranched C7-alkyl.
  • R 1 and R 2 are preferably independently of one another methyl or ethyl.
  • R 1 and R 2 are particularly preferably methyl.
  • R 4 is selected from the group consisting of methyl, ethyl and propyl.
  • R 4 is preferably methyl or ethyl.
  • R 4 is particularly preferably methyl.
  • B is NH and R 1 and R 2 are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, branched C5 alkyl, unbranched C5 alkyl, branched C6 -Alkyl, unbranched C6-alkyl, branched C7-alkyl and unbranched C7-alkyl.
  • R 1 and R 2 are preferably independently of one another methyl or ethyl.
  • R 1 and R 2 are particularly preferably methyl.
  • A is sulfur
  • B is OH and R 1 and R 2 are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, branched C5-alkyl, unbranched C5-alkyl, branched C6 -Alkyl, unbranched C6-alkyl, branched C7-alkyl and unbranched C7-alkyl.
  • R 1 and R 2 are preferably independently of one another methyl or ethyl.
  • R 1 and R 2 are particularly preferably methyl.
  • B SH and R 1 and R 2 are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, branched C5 alkyl, unbranched C5 alkyl, branched C6 -Alkyl, unbranched C6-alkyl, branched C7-alkyl and unbranched C7-alkyl.
  • R 1 and R 2 are preferably independently of one another methyl or ethyl.
  • R 1 and R 2 are particularly preferably methyl.
  • B is NHR 4 and R 1 and R 2 are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, branched C5-alkyl, unbranched C5-alkyl, branched C6-alkyl, unbranched C6-alkyl, branched C7-alkyl and unbranched C7-alkyl.
  • R 1 and R 2 are preferably independently of one another methyl or ethyl.
  • R 1 and R 2 are particularly preferably methyl.
  • R 4 is selected from the group consisting of methyl, ethyl and propyl.
  • R 4 is preferably methyl or ethyl.
  • R 4 is particularly preferably methyl.
  • B is NH and R 1 and R 2 are independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, branched C5 alkyl, unbranched C5 alkyl, branched C6 -Alkyl, unbranched C6-alkyl, branched C7-alkyl and unbranched C7-alkyl.
  • R 1 and R 2 are preferably independently of one another methyl or ethyl.
  • R 1 and R 2 are particularly preferably methyl.
  • Preferred adducts of a compound of the formula (I) are adducts of said compound and a compound having at least one isocyanate group.
  • adduct means urethane, thiourethane and urea adducts of a compound of the formula (I) with a compound having at least one isocyanate group.
  • a urethane adduct is particularly preferred.
  • the adducts according to the invention result from the fact that an isocyanate with the functional group B of the compound defined in formula (I).
  • B is a hydroxyl group
  • a urethane adduct is formed
  • B is a thiol group
  • a thiourethane adduct is formed
  • B is NH or N HR 4
  • Catalysts CI which are particularly suitable according to the invention are metal organyls, preferably selected from the group consisting of dibutyltin diacetate, dibutyltin dilaurate (DBTL) and dibutyltin bis-acetoacetonate. Tin carboxylates are also suitable. DBTL is very particularly preferably used as the catalyst CI.
  • Suitable catalysts with a catalytic functionality C2 for the process according to the invention are, for example, simple tertiary amines, such as triethylamine, tributylamine, N, N-dimethylaniline, N-ethylpiperidine or N, N'-dimethylpiperazine.
  • Suitable catalysts are also the tertiary hydroxyalkylamines described in GB 2 221 465, such as, for example, triethanolamine, N-methyldiethanolamine, dimethylethanolamine, N-isopropyldiethanolamine and 1- (2-hydroxyethyl) pyrrolidine, or those known from GB 2 222 161 catalyst systems consisting of mixtures of tertiary bicyclic amines, such as DBU, with simple low molecular weight aliphatic alcohols.
  • a large number of different metal compounds are also suitable as catalysts with a catalytic functionality C2 for the process according to the invention.
  • Suitable are, for example, the octoates and naphthenates of manganese, iron, cobalt, nickel, copper, zinc, zirconium, cerium or lead described in DE-A 3 240 613 as catalysts or mixtures thereof with acetates of lithium, sodium, potassium, calcium or Barium, the sodium and potassium salts of linear or branched alkane carboxylic acids with up to 10 carbon atoms known from DE-A 3 219 608, for example of propionic acid, butyric acid, valeric acid, caproic acid, fleptanoic acid, caprylic acid, pelargonic acid, capric acid and undecylic acid, which are derived from the alkali metal or alkaline earth metal salts known from EP-A 0 100 129 of aliphatic, cycloaliphatic or aromatic mono- and polycarboxylic acids with 2 to
  • alkali metal and alkaline earth metal oxides, hydroxides, carbonates, alcoholates and phenolates known from GB 809 809
  • alkali metal salts of enolizable compounds and metal salts of weak aliphatic or cycloaliphatic carboxylic acids such as e.g. Sodium methoxide, sodium acetate, potassium acetate, sodium acetoacetic ester, lead 2-ethylhexanoate and lead naphthenate
  • the basic alkali metal compounds known from EP-A 0 056 158 and EP-A 0 056 159
  • complexed with crown ethers or polyether alcohols such as e.g.
  • Diphenyltin dichloride triphenylstannanol, tributyltin acetate, tributyltin oxide, tin octoate, dibutyl (dimethoxy) stannane and tributyltin imidazolate.
  • catalysts suitable for the process according to the invention with a catalytic functionality C2 are, for example, the quaternary ammonium hydroxides known from DE-A 1 667 309, EP-A 0 013 880 and EP-A 0 047 452, such as, for example, tetraethylammonium hydroxide, trimethylbenzylammonium hydroxide, N, N -Dimethyl-N-dodecyl-N- (2-hydroxyethyl) ammonium hydroxide, N- (2-flydroxyethyl) -N, N-dimethylN- (2,2'-dihydroxymethylbutyl) ammonium hydroxide and 1- (2-flydroxyethyl) -l, 4-diazabicyclo- [2.2.2] octane hydroxide (monoadduct of ethylene oxide and water to 1,4-diazabicyclo- [2.2.2] octane), the quatern
  • Phosphonium polyfluorides e.g. Benzyl-trimethylammonium hydrogen polyfluoride, the tetraalkylammonium alkyl carbonates known from EP-A 0 668 271, which can be obtained by reacting tertiary amines with dialkyl carbonates, or betaine-structured quaternary ammonioalkyl carbonates, the quaternary ammonium hydrogen carbonates known from WO 1999/023128, e.g. Choline bicarbonate, the quaternary ammonium salts known from EP 0 102 482 and obtainable from tertiary amines and alkylating esters of acids of phosphorus, such as e.g.
  • Preferred catalysts with a catalytic functionality C2 are metal compounds of the type mentioned above, in particular carboxylates and alcoholates of alkali metals, alkaline earth metals, tin or zirconium, and organic tin compounds of the type mentioned.
  • catalysts with a catalytic functionality C2 are tin, sodium and potassium salts of aliphatic carboxylic acids with 2 to 20 carbon atoms.
  • Very particularly preferred catalysts with a catalytic functionality C2 for the process according to the invention are potassium acetate and tin octoate.
  • a catalyst is understood to be the combination of active substance and suitable solvents, co-activators, reactive diluents, as used in the examples.
  • the catalyst having a catalytic functionality C2 generally comes in a concentration of 0.0005 to 15.0% by weight, preferably 0.010 to 10.0% by weight and particularly based on the amount of polyisocyanate composition A used preferably from 0.1 to 5.0% by weight.
  • At least one basic compound in particular salts of carboxylic acids, is used as the catalyst with a catalytic functionality C2.
  • mixtures of different basic compounds can also be used as catalysts with a catalytic functionality C2.
  • At least one basic compound of the alkali or alkaline earth metals, in particular their salts of carboxylic acids such as potassium acetate, and a polyether are used as the catalyst with a catalytic functionality C2.
  • the polyether has at least 2, preferably at least 4, particularly preferably at least 6 and in particular at least 8 successive ethylene oxide units in the molecule.
  • the catalyst with a catalytic functionality C2 is a polyether with at least 2, preferably 4 and particularly preferably at least 6 successive ethylene oxide units in the molecule.
  • this polyether there is an alkaline potassium, lithium or sodium salt with a metal ion concentration between 0.01% by weight and 50% by weight, preferably between 0.1% by weight and 25% by weight, particularly preferably between 0.5 wt .-% and 15 wt .-% and in particular between 1 wt .-% and 10 wt .-% dissolved.
  • a polyether having at least 7 consecutive ethylene oxide units in the molecule in which at least a portion of the alkaline potassium salt is dissolved.
  • the catalyst comes with a catalytic functionality C2 when using basic salts of carboxylic acids in general in a concentration of 0.04 to 15.0% by weight, preferably 0.10, based on the amount of the polyisocyanate composition A) used to 8.0 wt .-% and particularly preferably from 0.5 to 5.0 wt .-% for use.
  • concentration only the mixture of the at least one basic compound is considered as the catalyst.
  • the catalysts with a catalytic functionality C2 can be used both individually and in the form of any mixtures with one another in the process according to the invention.
  • the catalysts with the functionalities CI and C2 used in the process according to the invention are generally sufficiently soluble or dispersible in the polyisocyanate composition A in the amounts required to initiate the crosslinking reaction.
  • the catalysts are therefore preferably added to the polyisocyanate composition A in bulk.
  • the catalysts with the catalytic functionalities CI and C2 can also be used in solution in a suitable organic solvent to improve their incorporability.
  • suitable solvents are all those which do not negatively influence the activity of the catalysts under the chosen reaction conditions, in particular do not enter into any chemical reactions with the catalysts, are deactivated or "poisoned" by them.
  • the degree of dilution of the catalyst solutions can be chosen freely within a very wide range become.
  • Suitable catalyst solvents are, for example, solvents which are inert to isocyanate groups, e.g. Hexane, toluene, xylene, chlorobenzene, ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl or - ethyl ether acetate, diethylene glycol ethyl and butyl ether acetate, ether acetate of propylene glycol mono-methyl, l-methoxypropyl-2-acetate, 3-methoxy-n-butyl acetate, propylene glycol diacetate , Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, lactones, such as ⁇ -propiolactone, y-butyrolactone, e-caprolactone and e-methyl caprolactone, but also
  • catalyst solvents which carry groups which are reactive toward isocyanates and can be incorporated into the polyisocyanurate plastic.
  • solvents are monohydric or polyhydric simple alcohols, e.g. Methanol, ethanol, n-propanol, isopropanol, n-butanol, n-hexanol, 2-ethyl-l-hexanol, ethylene glycol, propylene glycol, the isomeric butanediols, 2-ethyl-l, 3-hexanediol or glycerin; Ether alcohols, e.g. l-methoxy-2-propanol, 3-ethyl-3-hydroxymethyloxetane, tetrahydrofurfuryl alcohol, ethylene glycol monomethyl ether,
  • the present invention relates to a fiber D which is wetted with the reaction mixture according to the invention.
  • the fiber which can be used according to the invention can be selected from all inorganic fibers, organic fibers, natural fibers or mixtures thereof known to the person skilled in the art. Said fiber can contain other substances, e.g. serve as finishing.
  • 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, polyethylene fibers, nylon fibers and plexiglass fibers.
  • Preferred natural fibers are flax fibers, flanf fibers, flolz fibers, cellulose fibers and sisal fibers.
  • all fibers are suitable whose aspect ratio is greater than 1000, preferably greater than 5000, more preferably greater than 10,000 and most preferably greater than 50,000.
  • the aspect ratio is defined as the length of the fiber divided by the diameter. If the aspect ratio defined above is maintained, the fibers preferably have a minimum length of 1 m, particularly preferably 50 m and very particularly preferably 100 m.
  • 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 fibers can be present individually, but they can also be woven or knitted into mats or tiles in any form known to the person skilled in the art, or can be present as scrims.
  • the wetting of the fibers can be carried out using any of the methods known to those skilled in the art, which enable good wetting of the fibers with the reaction mixture. Squeegees, immersion baths, injection boxes, spray processes, flarz injection processes, flarz infusion processes with vacuum or pressure, application roller and fland lamination processes are mentioned here without any claim to completeness. According to a particularly preferred embodiment of the invention, an immersion bath is used. The dry fibers are drawn through an open resin bath, with the fibers being deflected into and out of the resin bath via guide screens (tub process). Alternatively, the fibers can also be drawn straight through the impregnation device without deflection (pull-through method).
  • an injection box is used.
  • the fibers are drawn into the impregnation unit, which already has the shape of the later profile, without being deflected.
  • the reactive resin mixture is pumped into the box, preferably transversely to the fiber direction, by means of pressure.
  • a doctor blade is used.
  • the reactive resin mixture is applied to a backing paper and, if necessary, the fibers are drawn into the resin mixture.
  • the wetted fibers are used to produce a semi-finished product.
  • the ratio between the reaction mixture, the fibers to be wetted and all other constituents of the semifinished product is preferably selected so that the fiber content is at least 10% by volume, preferably 20% by volume, more preferably at least 30% by volume is more preferably at least 40% by volume and most preferably at least 50% by volume of the finished semi-finished product.
  • the present invention relates to a process for producing a semifinished product comprising the steps a) providing a reaction mixture with a molar ratio of isocyanate groups to isocyanate-reactive groups of 2: 1 to 10: 1;
  • At least one catalytic functionality CI which catalyzes the reaction of isocyanate groups with isocyanate-reactive groups to form urethane groups
  • At least one catalytic functionality C2 which catalyzes the reaction of isocyanate groups to isocyanurate groups, wherein the catalytic functionalities CI and C2 are brought about by the same compound or by at least two different compounds; and b) crosslinking the polyisocyanate component A and the component B reactive with isocyanate groups by heating the reaction mixture to a temperature between 10 ° C. and 50 ° C.
  • the proportion of the cycloaliphatic and aliphatic isocyanate groups in the total amount of the isocyanate groups contained in the polyisocyanate composition A is not limited for the process according to the invention, as stated above for the polymerizable composition.
  • provision of the reaction mixture according to the invention means that the reaction mixture is in a ready-to-use form. Basically, only a mixture of its constituents is required for this. All processes known to the person skilled in the art can be used for this.
  • the reaction mixture is in one Form that the urethane formation in process step b) can be started by simple heating.
  • the crosslinking of the polyisocyanate component A and the component B reactive with isocyanate groups is brought about by tempering the reaction mixture to a temperature at which the catalytic functionality CI is already active, while the catalytic functionality C2 is essentially inactive. This is preferably in the temperature range between 10 ° C and 50 ° C, more preferably between 10 ° C and 40 ° C. This increases the viscosity of the reaction mixture. However, since the majority of the isocyanate groups are still in free form, the resulting material has not yet reached its final hardness. The resulting semi-finished product therefore remains deformable.
  • Process step b) is preferably carried out until the reaction mixture determines a viscosity in mPas in a plate-cone rotary viscometer at 23 ° C. and a shear rate of 1 / s, of at least 30,000, preferably at least 50,000 mPas and particularly preferably at least 100,000 mPas and most preferably achieved at least 500,000 mPas.
  • the mixture is preferably stirred until the reaction mixture has a module G ' determined by a plate / plate rheometer in accordance with ISO 6721-10: 2015-09 at 1 / s at 23 ° C. of at least 5 * 10 3 Pa.
  • the module G ' is determined at a temperature of 10 ° C above the glass transition temperature at a maximum of 5 * 10 5 Pa.
  • the glass transition temperature is determined using dynamic differential scanning calometry.
  • the percentage of isocyanate groups still present can be determined by comparing the content of isocyanate groups in the original polyisocyanate composition A with the content of isocyanate groups in the reaction product, for example by the aforementioned comparison of the peak maxima of the isocyanate band at approx. 2270 cm 1 by means of ATR spectroscopy .
  • reaction mixture provided in process step a) is applied to a fiber before the start of process step b). This can be done with all methods known to the person skilled in the art.
  • the fibers are present as wovens, scrims or knitted fabrics before wetting or are joined to a woven fabric, scrim or knitted fabric after component W, but before crosslinking of polyisocyanate component A and component B.
  • the reaction of functionality B with A takes place over a period of at most 7 days, preferably at most 3 days and very particularly preferably at most 24 hours at a temperature of preferably between 10 ° C. and 50 ° C., more preferably between 10 ° C. and 40 ° C and very particularly preferably between 10 ° C and 30 ° C to a degree of conversion at which the viscosity of the formulation to at least 30,000 mPas, preferably at least 50,000 mPas, particularly preferably at least 100,000 mPas and very particularly preferably at least 500,000 mPas has risen.
  • at least 30%, preferably at least 50% and very particularly preferably at least 70% of the polyol functionality is reacted after incubation in the aforementioned periods at the aforementioned temperatures.
  • the stable sheet products obtained in this way can be stored within 7 days, preferably within 30 days and very particularly preferably within 90 days at temperatures of at most 30 ° C., preferably at most 20 ° C. and very particularly preferably at at most 10 ° C. and largely without Loss of properties at temperatures of at least 60 ° C., preferably at least 80 ° C. and particularly preferably at least 100 ° C. are converted into isocyanurate plastics.
  • the isocyanate concentration is reduced to preferably at most 30%, preferably at most 20% and particularly preferably at most 10% of the starting isocyanate concentration.
  • the degradation is preferably carried out by reaction of the isocyanate groups with other isocyanate groups to form isocyanurates.
  • the process according to the invention gives a semi-finished product which can be stored and transported.
  • the present invention thus also relates to the semifinished product which can be obtained by the process according to the invention.
  • the semifinished product can still be formed using conventional methods.
  • the semifinished product according to the invention is used for the production of profiles, carriers, reinforcing struts, sports articles, manhole covers, plates, housings, trunk covers, engine compartment covers, leaf springs, bumpers, panels, aprons, pipes, pressure vessels or tanks.
  • Preferred sports articles are arrows, sports bows, skis and rackets, in particular tennis rackets.
  • the present invention relates to a process for producing a polyisocyanurate plastic, characterized in that a semi-finished product produced by the process described above is heated to a temperature of at least 60 ° C, preferably at least 80 ° C and very particularly preferably at least 100 ° C is catalytically trimerized. To avoid decomposition of the material, a temperature of 280 ° C is not exceeded.
  • catalytic trimerization denotes the crosslinking of at least two, preferably at least three, isocyanate groups with one another. It cannot be ruled out that as a side reaction, isocyanate groups may also react with any groups that are still reactive with isocyanate.
  • At least 50%, preferably at least 60% and most preferably at least 70% of the isocyanate groups crosslinked during the catalytic trimerization are converted to uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structures.
  • the weight ratio of isocyanurate to urethane groups after conversion of at least 80% of the isocyanate groups originally present in the reaction mixture at the end of process step a) is in the range between 2: 1 and 20: 1, preferably between 3: 1 and 15: 1 and particularly preferably between 5: 1 and 10: 1.
  • the proportion by weight of the isocyanurate groups, based on the total weight of components a) and b), after conversion of at least 80% of the isocyanate groups originally present in the reaction mixture at the end of process step a), is in the range between 5% by weight and 45% by weight, preferably between 7% by weight 40% by weight and particularly preferably between 10% by weight and 35% by weight.
  • the proportion by weight of the urethane groups based on the total weight of components a) and b) after conversion of at least 80% of the isocyanate groups originally present in the reaction mixture at the end of process step a) in the range between 1% by weight and 10% by weight, preferably between 1.5% by weight and 7% by weight and particularly preferably between 2% by weight and 5% by weight.
  • the isocyanurate plastic is produced from the semi-finished product at least 10 m, more preferably at least 50 m, even more preferably at least 500 m and most preferably at least 2000 m from the location at which the semi-finished product according to the invention was produced .
  • the semifinished product from which the isocyanurate plastic according to the invention is produced by catalytic trimerization is shaped before the catalytic trimerization process step. This is preferably done by bending or pressing.
  • the present invention relates to an isocyanurate plastic which can be obtained by the process described above.
  • This isocyanurate plastic is preferably a composite material which contains at least 10% by volume, more preferably at least 20% by volume and even more preferably at least 30% by volume of fibers D.
  • RT room temperature
  • phase transitions were determined by means of DSC (Differential Scanning Calorimetry) with a Mettler DSC 12E (Mettler Toledo GmbFI, G corden, DE) according to DIN EN 61006.
  • a calibration was carried out using the temperature of the melting onset of indium and lead. 10 mg of substance were weighed into normal capsules. The measurement was carried out by three heats from -50 ° C to +200 ° C at a pickling rate of 20 K / min with subsequent cooling at a cooling rate of 320 K / min. Liquid nitrogen was used for cooling. Nitrogen was used as the purge gas. The values given are based on the evaluation of the 2nd heating curve.
  • the glass transition temperature T g was obtained from the temperature at half the fleas of a glass transition stage.
  • the infrared spectra were measured on a Bruker FT-IR spectrometer equipped with an ATR unit.
  • the viscosity of a small amount of the reactive flarz mixture (including the added catalyst) was measured at 23 ° C. using a Physica MCR 51 from Anton Paar (plate / plate; shear rate is _1 ).
  • Polyisocyanate Al is an HDI trimer (NCO functionality> 3) with an NCO content of 23.0% by weight from Covestro AG. The viscosity is approx. 1200 mPa-s at 23 ° C (DIN EN ISO 3219 / A.3).
  • Polyisocyanate A2 is a PDI trimer (NCO functionality> 3) with an NCO content of 21.5% by weight from Covestro AG. The viscosity is approx. 9500 mPa-s at 23 ° C (DIN EN ISO 3219 / A.3).
  • Polyisocyanate A3 is a FIDI / IPDI polyisocyanate with an NCO content of 21.0% by weight from Covestro AG.
  • the viscosity is approx. 22,500 mPa s at 23 ° C (DIN EN ISO 3219 / A.3).
  • Potassium acetate was obtained from ACROS with a purity of> 99% by weight.
  • Polyethylene glycol (PEG) 400 was obtained from ACROS with a purity of> 99% by weight.
  • Glycerol was obtained from ACROS with a purity of> 99% by weight.
  • DBTL Dibutyltin dilaurate
  • N, N, N'-trimethylaminoethylethanolamine with an O FH number of 384 mg KOFI / g was obtained from Fluntsman Corporation.
  • N, N, N'-trimethylaminoethylethanolamine (14.6 g) was added dropwise to the isocyanate Al (18.3 g) with cooling and the mixture was stirred until the mixture was homogeneous.
  • Potassium acetate (5.0 g) was stirred in the PEG 400 (95.0 g) at RT until everything was dissolved. A 5% by weight solution of potassium acetate in PEG 400 was thus obtained and used as a catalyst without further treatment.
  • the isocyanate composition was first prepared by mixing the corresponding isocyanate components (Al, A2 or A3) with a corresponding amount of catalyst (K1-K4) and glycerol at 23 ° C in a Speed Mixer DAC 150.1 FVZ from Hauschild produced for 120 seconds at 1500 rpm. 1
  • the mixture was then placed in a mold (metal lid, approx. 6 cm in diameter and approx. 1 cm high) and stored at RT for 24 h. After-curing was then carried out in the oven.
  • the viscosity of the reaction mixtures increased during the RT pre-curing and the material became highly viscous to elastic and dry.
  • the characteristic pre-curing of the NCO reduced the height of the characteristic NCO band between 2300 and 2250 cm 1 , whereby an NCO content of> 5% in relation to the starting quantity was still discernible in each case.
  • the Tg of the cured reaction mixtures were between 83 and 146 ° C. Thermal curing reduced the characteristic NCO band between 2300 and 2250 cm 1 in height by at least 80%.
  • the T g after oven curing is 129 ° C.
  • Thermal curing reduced the characteristic NCO band between 2300 and 2250 cm 1 in height by at least 80%.

Landscapes

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

Abstract

La présente invention concerne des mélanges réactionnels ayant un rapport groupes isocyanates sur groupes réactifs vis-à-vis des isocyanates élevé, lesquels durcissent principalement par la formation de groupes isocyanurates, et l'utilisation de tels mélanges réactionnels pour la fabrication de demi-produits.
EP20701186.7A 2019-01-22 2020-01-20 Matériaux composites à base de polymères uréthanes et isocyanurates à polymérisation duale Pending EP3914632A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP19153071 2019-01-22
LU101113 2019-02-01
PCT/EP2020/051291 WO2020152107A1 (fr) 2019-01-22 2020-01-20 Matériaux composites à base de polymères uréthanes et isocyanurates à polymérisation duale

Publications (1)

Publication Number Publication Date
EP3914632A1 true EP3914632A1 (fr) 2021-12-01

Family

ID=69177169

Family Applications (1)

Application Number Title Priority Date Filing Date
EP20701186.7A Pending EP3914632A1 (fr) 2019-01-22 2020-01-20 Matériaux composites à base de polymères uréthanes et isocyanurates à polymérisation duale

Country Status (6)

Country Link
US (1) US20220041792A1 (fr)
EP (1) EP3914632A1 (fr)
JP (1) JP2022517512A (fr)
KR (1) KR20210119396A (fr)
CN (1) CN113286836B (fr)
WO (1) WO2020152107A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117136205A (zh) 2021-03-29 2023-11-28 科思创德国股份有限公司 多异氰脲酸酯预浸料及由其生产的纤维复合材料组分

Family Cites Families (55)

* 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
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
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
US4026840A (en) * 1975-06-09 1977-05-31 Air Products And Chemicals, Inc. Hydroxyalkyl tertiary amine catalysts for isocyanate reactions
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
DE2806731A1 (de) 1978-02-17 1979-08-23 Bayer Ag Verfahren zur herstellung von isocyanuratgruppen aufweisenden polyisocyanaten
CA1112243A (fr) 1978-09-08 1981-11-10 Manfred Bock Procede de fabrication de polyisocyanates contenant des groupements isocyanurates, et utilisation de ces produits
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 (fr) 1980-01-28 1982-07-13 Anupama Mishra Isocyanurate et polyurethanes derives
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
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
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
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
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
DE3700209A1 (de) 1987-01-07 1988-07-21 Bayer Ag Verfahren zur herstellung von polyisocyanaten mit biuretstruktur
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
CA1334848C (fr) 1988-08-05 1995-03-21 William E. Slack Procede de production de polyisocyanates renfermant des groupements isocyanurate
CA1334849C (fr) 1988-08-24 1995-03-21 Bayer Corporation Procede de preparation de polyisocyanates renfermant des groupements isocyanurate
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
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
US5214076A (en) * 1992-09-18 1993-05-25 Tideswell Richard B Carbodiimide-isocyanurate all water blown open celled foam
US5296516A (en) * 1992-12-09 1994-03-22 Basf Corporation Polyurethane and polyisocyanurate rigid foams prepared using ternary blowing agent mixtures
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
DE19611849A1 (de) 1996-03-26 1997-10-02 Bayer Ag Neue Isocyanattrimerisate und Isocyanattrimerisatmischungen, deren Herstellung und Verwendung
TR199900971T2 (en) * 1996-11-04 1999-07-21 Imperial Chemical Industries Plc B�k�lmez poli�retan k�p�kleri
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.
EP0962455B1 (fr) 1998-06-02 2002-11-06 Bayer Aktiengesellschaft Procédé pour la préparation de polyisocyanates contenant des groupes imino-oxadiazine-dione
DE10065176A1 (de) 2000-12-23 2002-06-27 Degussa Katalysator und Verfahren zur Herstellung von niedrigviskosen und farbreduzierten isocyanuratgruppenhaltigen Polyisocyanaten
CN1639240A (zh) * 2002-07-18 2005-07-13 胡茨曼石油化学公司 提高泡沫体中三聚物含量的催化剂组合物
BRPI0408042B1 (pt) 2003-02-28 2014-12-02 Dow Global Technology Inc "composição de poliisocianato isocianurato e processo para a preparação de uma mistura de poliisocianato isocianurato".
DE102004012571A1 (de) 2004-03-12 2005-09-29 Basf Ag Verfahren zur Herstellung von Isocyanuratgruppen aufweisenden Polyisocyanaten und ihre Verwendung
DE102005041763A1 (de) 2005-09-01 2007-03-08 Basf Ag Polyisocyanurat Hartschaum und Verfahren zur Herstellung
WO2008144158A1 (fr) 2007-05-17 2008-11-27 Dow Global Technologies Inc. Mousse de polyisocyanurate pour des structures de toit
US9234069B2 (en) * 2011-03-09 2016-01-12 Mitsui Chemicals, Inc. Pentamethylenediisocyanate, method for producing pentamethylenediisocyanate, polyisocyanate composition, polyurethane resin, and polyurea resin
CN104093759B (zh) * 2012-02-08 2016-09-21 科思创德国股份有限公司 聚氨酯-聚异氰脲酸酯-硬质泡沫材料的制备方法
JP6223431B2 (ja) 2012-05-08 2017-11-01 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ イソシアヌレート基を有するポリイソシアネートの製造およびそれらの使用
MX2015005895A (es) * 2012-11-14 2015-09-10 Bayer Materialscience Ag Procedimiento para la produccion de componentes de materiales compuestos.
RU2707290C2 (ru) * 2014-04-03 2019-11-26 Хантсмэн Интернэшнл Ллс Катализатор тримеризации изоцианата для изготовления полиизоцианурат-содержащих пеноматериалов
WO2016170058A1 (fr) * 2015-04-21 2016-10-27 Covestro Deutschland Ag Procédé de production de matières plastiques à base de polyisocyanurate
JP2019515105A (ja) 2016-05-04 2019-06-06 コベストロ、ドイチュラント、アクチエンゲゼルシャフトＣｏｖｅｓｔｒｏ Ｄｅｕｔｓｃｈｌａｎｄ Ａｇ ポリイソシアヌレート複合材料の製造方法
US11530290B2 (en) 2016-05-04 2022-12-20 Covestro Deutschland Ag Method for producing a polyisocyanurate composite material
CN105968302B (zh) * 2016-05-27 2018-09-04 江苏长顺高分子材料研究院有限公司 用于超低温lng储罐储保冷用聚氨酯喷涂组合料及其制备方法

Also Published As

Publication number Publication date
JP2022517512A (ja) 2022-03-09
WO2020152107A1 (fr) 2020-07-30
US20220041792A1 (en) 2022-02-10
CN113286836A (zh) 2021-08-20
CN113286836B (zh) 2024-02-13
KR20210119396A (ko) 2021-10-05

Similar Documents

Publication Publication Date Title
EP2883895B1 (fr) Polyisocyanates contenant des groupes iminooxadiazine diones.
EP3085718B1 (fr) Matieres synthetiques de polyisocyanurate comprenant des groupes siloxane et leur procede de production
DE69524508T2 (de) Niedrige Oberflächenenergie aufweisende Polyisocyanate, sowie ihre Verwendung in Einkomponent- oder Zweikomponenten-Beschichtungszusammensetzungen
EP1061091B1 (fr) Polyisocyanate stable à la lumière ayant une solvabilité élevée dans des solvants non polaires
WO2017191175A1 (fr) Procédé de fabrication d'un matériau composite à base de polyisocyanurate
WO2004005363A1 (fr) Produits de polymerisation par addition contenant des groupes uretdione
EP3271432B1 (fr) Composition de polyisocyanate à base de 1,5-pentaméthylène diisocyanate
EP3743449B1 (fr) Demi-produits basés sur le double mécanisme de réticulation
EP3529326B1 (fr) Revêtements durs très résistants aux produits chimiques et présentant une résistance mécanique
EP3794049B1 (fr) Procédé de fabrication d'un polymère polyisocyanate et d'une matière plastique de polyisocyanurate
EP3914632A1 (fr) Matériaux composites à base de polymères uréthanes et isocyanurates à polymérisation duale
EP3728369B1 (fr) Matériaux composites de polyuréthane à base de catalyseurs thermolatents
WO2020064631A1 (fr) Systèmes de revêtement à faible teneur en solvant pour textiles
EP3601405B1 (fr) Fabrication de couches de polyisocyanurate par application séparée de composants d'isocyanate et catalyseurs
EP2804883B1 (fr) Pièces moulées en polyuréthane compactes et stables à la lumière
WO2019219614A1 (fr) Procédé pour la production de matériaux composites à partir de fibres de polyéthylène de poids moléculaire ultraélevé et des polyisocyanates réticulés
EP1277876A2 (fr) Utilisation d'un durcissant pour des systèmes de polyuréthane à deux composants pour revêtir des substrats flexibles
EP3572446A1 (fr) Mélange réactif d'uretdiones et de catalyseurs
EP3440122A1 (fr) Matières plastiques colorées à base de polyisocyanates réticulés
WO2020156937A1 (fr) Prépolymères terminés par isocyanate pour des revêtements de textile
WO2024008544A1 (fr) Mélange de polyisocyanates

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20210823

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: COVESTRO DEUTSCHLAND AG

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20240419