EP3472217A1 - Composition durcie à haute résistance aux chocs et haute résistance thermique à base d'une résine époxyde et d'un polyisocyanate - Google Patents

Composition durcie à haute résistance aux chocs et haute résistance thermique à base d'une résine époxyde et d'un polyisocyanate

Info

Publication number
EP3472217A1
EP3472217A1 EP17729884.1A EP17729884A EP3472217A1 EP 3472217 A1 EP3472217 A1 EP 3472217A1 EP 17729884 A EP17729884 A EP 17729884A EP 3472217 A1 EP3472217 A1 EP 3472217A1
Authority
EP
European Patent Office
Prior art keywords
hours
reaction mixture
polyisocyanate
polyol
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP17729884.1A
Other languages
German (de)
English (en)
Inventor
Christian Holtgrewe
Harald KÜSTER
Thomas Bachon
Guadalupe Sanchis Otero
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP3472217A1 publication Critical patent/EP3472217A1/fr
Withdrawn legal-status Critical Current

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    • 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
    • C08G18/58—Epoxy resins
    • C08G18/581—Reaction products of epoxy resins with less than equivalent amounts of compounds containing active hydrogen added before or during the reaction with the isocyanate component
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/24—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 characterised by the choice of material
    • B29C67/246—Moulding high reactive monomers or prepolymers, e.g. by reaction injection moulding [RIM], liquid injection moulding [LIM]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28—Shaping operations therefor
    • B29C70/40—Shaping or impregnating by compression not applied
    • B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
    • B29C70/46—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs
    • B29C70/48—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs and impregnating the reinforcements in the closed mould, e.g. resin transfer moulding [RTM], e.g. by vacuum
    • 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
    • C08G18/003—Polymeric products of isocyanates or isothiocyanates with epoxy compounds having no active hydrogen
    • 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/20—Heterocyclic amines; Salts thereof
    • C08G18/2009—Heterocyclic amines; Salts thereof containing one heterocyclic ring
    • C08G18/2027—Heterocyclic amines; Salts thereof containing one heterocyclic ring having two nitrogen atoms in the ring
    • 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
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    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/20—Heterocyclic amines; Salts thereof
    • C08G18/2045—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings
    • C08G18/2063—Heterocyclic amines; Salts thereof containing condensed heterocyclic rings having two nitrogen atoms in the condensed ring system
    • 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
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    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/20—Heterocyclic amines; Salts thereof
    • C08G18/2081—Heterocyclic amines; Salts thereof containing at least two non-condensed heterocyclic rings
    • 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
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • 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
    • C08G18/4825—Polyethers containing two 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
    • C08G18/28—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
    • C08G18/4895—Polyethers prepared from polyepoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—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
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl 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
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4028—Isocyanates; Thioisocyanates
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2063/00—Use of EP, i.e. epoxy resins or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2079/00—Use of polymers having nitrogen, with or without oxygen or carbon only, in the main chain, not provided for in groups B29K2061/00 - B29K2077/00, as moulding material
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2120/00—Compositions for reaction injection moulding processes
    • 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
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/02—Polyglycidyl ethers of bis-phenols
    • 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

  • Cured composition having high impact strength and temperature stability based on an epoxy resin and a polyisocyanate
  • the present invention relates to a process for the preparation of a cured composition having at least one Oxazolidinonring and at least one isocyanurate ring and crosslinked by these, starting from a liquid reaction mixture based on the total weight of at least one epoxy resin, at least one polyisocyanate, at least one polyol and containing at least one catalyst composition, and the hardened composition obtainable thereby.
  • Cured polymer compositions are subjected to high mechanical and thermal stresses during their manufacture and use.
  • tougheners are added to the resin systems from which the compositions are made.
  • the tougheners known in the art cause an increase in impact resistance, but also a lowering of the glass transition temperature that they are unsuitable for use at elevated temperature.
  • the present invention is based on the discovery of the inventors that oxazolidinone- and isocyanurate-crosslinked plastics which increase the impact strength can be produced in certain ratios in short curing cycles by the addition of polyols to room temperature stable polyepoxide or polyisocyanate monomers with low viscosity without lowering the glass transition temperature.
  • the plastics can be used in manufacturing processes and in their later applications in which these high temperatures are exposed.
  • the plastics thus obtainable also show advantageous mechanical properties, in particular high impact strength, which are suitable for use in the automotive industry.
  • the performance and properties of the polymers thus obtainable can be varied over a wide range by controlling the curing conditions and the type of catalyst systems.
  • reaction mixtures which, based on their total weight, comprise at least one liquid, aromatic epoxy resin, at least one liquid, aromatic polyisocyanate, 1 to 20% by weight of at least one polyol and at least one suitable catalyst composition, where an excess when NCO groups are present in relation to the epoxide groups, curing gives oxazolidinone- and isocyanurate-crosslinked polymer compositions which have increased mechanical resistance and are therefore particularly suitable for the production of fiber-reinforced plastic moldings such as automobile parts.
  • the impact resistance of the resulting cured polymer composition is increased without lowering the glass transition temperature. This phenomenon is surprisingly enhanced by the use of a molar excess of NCO groups over epoxide groups.
  • the present invention therefore relates, in a first aspect, to a process for the preparation of a cured polymer composition comprising at least one oxazolidinone ring and at least one isocyanurate ring, which process comprises the steps:
  • the present invention in another aspect, relates to a fiber-reinforced, cured composition obtainable by the methods described herein.
  • At least one refers to 1 or more, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. It refers to constituents of the catalyst compositions described herein Indicating not the absolute amount of molecules,
  • at least one polyol means one or more different polyols, ie, one or more different types of polyols, and together with quantities, the amounts refer to the total amount of the corresponding designated type of ingredient already defined above.
  • Liquid refers to flowable compositions at room temperature (20 ° C) and normal pressure (1013 mbar).
  • the viscosity of the liquid composition described herein is low enough for the composition to be pumpable and, for example, to wet and impregnate fiber materials as used for fiber reinforced plastic parts.
  • the reaction mixture has a viscosity of ⁇ 100 mPas at a temperature of 80 ° C.
  • the resin mixture is prepared at room temperature with a suitable mixer and determined on a plate / plate rheometer in oscillation, the viscosity with increasing temperature at a heating rate of 50 K / min.
  • the epoxy resin may include epoxy group-containing monomers, prepolymers and polymers, as well as mixtures of the abovementioned and is also referred to below as epoxy or epoxide group-containing resin.
  • Suitable epoxy-group-containing resins are in particular resins having 1 to 10, preferably 2 to 10 epoxide groups per molecule.
  • Epoxide groups as used herein refers to 1,2-epoxide groups (oxiranes).
  • the epoxy resins usable herein may vary and include conventional and commercially available epoxy resins, each of which may be used individually or in combination of two or more different epoxy resins. In selecting the epoxy resins, not only the properties of the final product but also the properties of the epoxy resin, such as the viscosity and other properties that affect processability, play a role.
  • the epoxy group-containing resin is a liquid, aromatic epoxy compound.
  • suitable resins include, but are not limited to, (poly) glycidyl ethers commonly obtained by reacting epichlorohydrin or epibromohydrin with polyphenols in the presence of alkali, or also (poly) glycidyl ethers of phenol-formaldehyde novolak resins, alkyl-substituted Phenol-formaldehyde resins (epoxy novolak resins), phenol-hydroxybenzaldehyde resins, cresol-hydroxybenzaldehyde resins, dicyclopentadiene-phenolic resins, and dicyclopentadiene-substituted phenolic resins.
  • Suitable polyphenols for this purpose are, for example, resorcinol, pyrocatechol, hydroquinone, bisphenol A (2,2-bis (4-hydroxyphenyl) propane), bisphenol F (bis (4-hydroxyphenyl) methane), 1, 1-bis (4-bis (4-hydroxyphenyl) propane). hydroxyphenyl) isobutane, 4,4-dihydroxybenzophenone, 1,1-bis (4-hydroxyphenyl) ethane and 1,5-hydroxynaphthalene.
  • diglycidyl ethers of ethoxylated resorcinol DGER
  • diglycidyl ether of resorcinol pyrocatechol
  • hydroquinone bisphenol, bisphenol A, bisphenol AP (1,1-bis (4-hydroxyphenyl) -1-phenylethane), bisphenol F, bisphenol K, bisphenol S, and tetramethylbiphenol.
  • Particularly preferred epoxy group-containing compounds are aromatic glycidyl ethers, in particular diglycidyl ethers, very particularly preferably those based on aromatic glycidyl ether monomers.
  • aromatic glycidyl ethers in particular diglycidyl ethers, very particularly preferably those based on aromatic glycidyl ether monomers.
  • examples include, without limitation, di- or polyglycidyl ethers of polyhydric phenols prepared by reacting a polyhydric phenol with an excess of chlorohydrin, e.g. Epichlorohydrin, can be obtained.
  • Such polyhydric phenols include resorcinol, bis (4-hydroxyphenyl) methane (bisphenol F), 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (4'-hydroxy-3 ', 5' -dibromophenyl) propane, 1,1,2,2-tetrakis (4'-hydroxyphenyl) ethane or condensates of phenols with formaldehyde obtained under acidic conditions, such as phenol novolacs and cresol novolaks.
  • Diglycidyl ethers of bisphenol A are available, for example, as DER 331 (liquid bisphenol A epoxy resin) and DER 332 (diglycidyl ether from bisphenol A) from Dow Chemical Company, Midland, Michigan. Although not specifically mentioned, other epoxy resins available under the trade names DER and DEN from Dow Chemical Company may also be used.
  • the polyisocyanate contains two or more isocyanate groups and includes any known and suitable for the purpose of the invention isocyanate and is hereinafter also referred to in part as isocyanate or isocyanate group-containing resin.
  • isocyanates having two or more isocyanate groups are suitable.
  • the polyisocyanates preferably contain 2 to 10, preferably 2 to 5, preferably 2 to 4, in particular exactly 2 isocyanate groups per molecule.
  • isocyanates having a functionality of more than two may under certain circumstances be advantageous since such polyisocyanates are suitable as crosslinking agents.
  • an aromatic polyisocyanate As the at least one polyisocyanate of the polyisocyanate component, an aromatic polyisocyanate will be used.
  • the NCO groups are attached to aromatic carbon atoms. Examples of suitable aromatic - -
  • Polyisocyanates are 1, 5-naphthylene diisocyanate, 2,4'-, 2,2'- or 4,4'-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), m- and p-tetramethylxylylene diisocyanate (TMXDI), 2,4- or 2,6-tolylene diisocyanate (TDI), di- and tetraalkyldiphenylmethane diisocyanate, 3,3'-dimethyl-diphenyl-4,4'-diisocyanate (TODI) 1, 3-phenylenediisocyanate, 1, 4-phenylenediisocyanate, 4,4 ' - Dibenzyl diisocyanate.
  • MDI 5-naphthylene diisocyanate
  • XDI xylylene diisocyanate
  • TXDI m- and p-tetramethylxy
  • the polyisocyanate component may also contain portions of low molecular weight prepolymers, for example reaction products of MDI or TDI with low molecular weight diols or triols, such as e.g. Ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, triethylene glycol, glycerol or trimethylolpropane.
  • These prepolymers can be prepared by reacting an excess of monomeric polyisocyanate in the presence of diols of the triols.
  • the number average molecular weight of the diols and triols is generally below 1000 g / mol.
  • the reaction product can be freed by distillation of monomeric aromatic isocyanates.
  • the at least one polyisocyanate preferably has an NCO content of more than 25% by weight, more preferably more than 28% by weight, particularly preferably more than 30% by weight, particularly preferably from 30 to 50% by weight, based on the at least one polyisocyanate, on.
  • the proportion by mass refers to the amount of this polyisocyanate used, whereas, when using a mixture of polyisocyanates, it refers to the amount of the mixture of these polyisocyanates used.
  • the at least one polyisocyanate has a viscosity of less than 80 mPas, in particular from 30 to 60 mPas (DIN ISO 2555, Brookfield Viscometer RVT, Spindle No. 3, 25 ° C, 50 rpm).
  • the at least one polyisocyanate has a number average molecular weight of less than 1500 g / mol, more preferably less than 1000 g / mol.
  • isocyanate group-containing resins are methylenediphenyl diisocyanate (MDI), toluene-2,4-diisocyanate (TDI), polymeric diphenylmethane diisocyanate (PMDI) and mixtures of the abovementioned.
  • MDI methylenediphenyl diisocyanate
  • TDI toluene-2,4-diisocyanate
  • PMDI polymeric diphenylmethane diisocyanate
  • DE Desmodur® from Bayer AG
  • aromatic polyisocyanate monomers in particular aromatic diisocyanates such as MDI and TDI. - -
  • both the epoxides used and the isocyanates used are monomers, in particular at standard conditions (20 ° C., 1013 mbar), liquid, low-viscosity monomers. These are particularly advantageous because they are significantly more stable, in particular storage-stable compared to other, higher-functional epoxy resins, and must not be stored refrigerated.
  • the reaction mixture may contain a plurality of different epoxide group-containing compounds and / or a plurality of different isocyanate group-containing compounds.
  • the liquid reaction mixture further comprises at least one polyol.
  • Polyols as used herein refers to compounds having at least 2 hydroxyl groups (-OH) per molecule.
  • the at least one polyol may, for example, have 2 or more hydroxyl groups, such as 3, 4, 5, 6, 7, 8, 9, 10 or more and have a cyclic, linear or branched structure.
  • the at least one polyol particularly preferably has on average 2 to 10, in particular 2 to 6, preferably 2 to 3 hydroxyl groups. Particularly preferred are diols and / or triols.
  • the polyols of the invention may be any of the polyols known in the art and useful in the present invention.
  • the polyol may have a number average molecular weight of from 120 to 6,000 g / mol, such as from 120 to 6,000 g / mol, from 120 to 4,000 g / mol from 120 to 2,000 g / mol, from 120 g / mol to 1,000 g / mol, from 500 g / mol to 6,000 g / mol, from 500 g / mol to 4,000 g / mol, from 500 g / mol to 2,000 g / mol, from 500 g / mol to 1,000 g / mol, from 1,000 g / mol to 6,000 g / mol, from 1,000 g / mol to 4,000 g / mol, from 1,000 g / mol to 2,000 g / mol or from 2,000 g / mol.
  • the at least one polyol is a polyether polyol, a polyester polyol or mixtures thereof.
  • the polyether polyol may be a polyoxyalkylene polyol.
  • the at least one polyol may also be a glycol.
  • Glycols are compounds derived from diols, for example by reaction of at least 2 diols with elimination of water and formation of at least one ether group.
  • Diols as used herein are compounds having 2 alcohol groups
  • Diols according to the invention may be, but are not limited to, ethylene diol, propylene diol, butylene diol, pentylene diol, hexylene diol, heptylene diol and octylene diol
  • the glycols may be derived from a diol or mixtures of different diols
  • the polyol of the present invention is selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, and mixtures thereof
  • the polyol is selected from the group consisting of polyethylene glycol, polypropylene glycol or mixtures thereof, and more preferably the poly ol propylene glycol.
  • the propylene glycol may have a number average molecular weight of 120 to 6,000 g / mol.
  • Propylene glycol has a number average molecular weight of 120 to 6,000 g / mol, more preferably 1,000 to 3,000 g / mol, and most preferably 2,000 g / mol.
  • the molecular weights given herein are based on the number average molecular weight (M n ).
  • M n number average molecular weight
  • the number average molecular weight can be determined by means of gel permeation chromatography according to DIN 55672-1: 2007-08 with THF as the eluent. Unless indicated otherwise, all molecular weights given are those determined by GPC.
  • the polyol according to the invention may also be a polyol having more than 2 alcohol groups.
  • examples of such polyols include, but are not limited to, glycerin, sorbitol, mannitol, xylitol, maltitol, lactitol, erythritol, isomalt, ribitol, galactitol, iditol, arabitol and polyglycitol.
  • the proportion by weight of the at least one polyol can be varied from 1, 0 to 20.0 wt .-% based on the reaction mixture and depends on the at least one polyol and its chemical and physical properties as well as the desired physical and chemical properties of the cured composition ,
  • the liquid reaction mixture contains from 2.0 to 15.0 weight percent, more preferably from 4.0 to 12.0 weight percent polyol.
  • the polymer compositions according to the invention have an increased mechanical resistance, in particular an increased impact strength, without lowering the glass transition temperature, so that the resulting compositions can be exposed to elevated temperatures during manufacture and their expedient determination. Therefore, these are particularly suitable for the production of fiber-reinforced plastic moldings, such as automotive parts.
  • the weight ratio of the at least one polyisocyanate and the at least one epoxy resin can also be varied and depends on the particular compounds used and their chemical and physical properties and on the desired physical and chemical properties of the cured composition.
  • the polyisocyanate and the epoxide are used in amounts such that the molar equivalent ratio of isocyanate to epoxide groups is at least 1.2, in particular at least 1.25, preferably at least 1.3, even more preferably at least 1.4, more preferably at least 1, 5 is.
  • the molar equivalent ratio of isocyanate groups to epoxide groups is preferably not more than 10, in particular not more than 5, preferably not more than 3, more preferably not more than 2.
  • Molar equivalent ratio refers to the molar ratio of epoxide groups to isocyanate groups Isocyanate groups formed into epoxy groups, wherein a double number from isocyanate groups to epoxide groups correspond to a molar equivalent ratio of 2.
  • a molar equivalent ratio of at least 1.2 therefore means, for example, that 1 mol of epoxide groups contain at least 1.2 mol of isocyanate groups. This means that the isocyanate groups are present in a molar excess to the epoxide groups.
  • the molar equivalent ratio of isocyanate to epoxide groups is between 1, 2 and 10, more preferably between 1, 2 and 5, even more preferably between 1, 25 and 5, even more preferably between 1, 3 and 2. The inventors have found that By the use of such proportions particularly advantageous properties in terms of glass transition temperature, the modulus of elasticity and the impact resistance result.
  • the reaction mixture based on the total weight of the reaction mixture, from 9.0 to 82.5% by weight, preferably from 15.0 to 65.0% by weight, more preferably from 20.0 to 60.0% by weight. , Most preferably 30.0 to 50.0 wt .-% of at least one liquid, aromatic epoxy resin used. In various embodiments of the invention, based on the total weight of the reaction mixture 16.5 to 90.0 wt .-%, preferably 20.0 to 80.0 wt .-%, more preferably 30.0 to 75.0 wt .-% , most preferably 35.0 to 70.0 wt .-% of the at least one liquid, aromatic polyisocyanate used.
  • the reaction mixture comprises a catalyst composition.
  • the catalyst composition does not include curing agents, i. Compounds that undergo an epoxide polyaddition reaction, such as dicyandiamide, DDS (diaminodiphenyl sulfone) and similar compounds, but only compounds that catalyze the polymerization of polyisocyanate and epoxide.
  • the reaction mixture is therefore in preferred embodiments free of dicyandiamide or DDS, preferably a total of free of curing agents such as dicyandiamide or DDS.
  • Free from means that the amount of the corresponding substance in the reaction mixture is less than 0.05% by weight, preferably less than 0.01% by weight, more preferably less than 0.001% by weight. %, based on the total weight of the reaction mixture.
  • the catalyst composition may contain one or more catalysts. In various embodiments, it is useful for forming oxazolidinone and isocyanurate rings from the indicated ingredients.
  • the catalyst is a base, wherein the catalyst used as the base is preferably a nonionic, nitrogen-containing base comprising at least one tertiary nitrogen atom and / or an imine nitrogen atom, in particular an imidazole or - -
  • Imidazolidine is. It is further preferred that the catalyst or base is not based on an imidazolium cation.
  • the term "tertiary" as used herein indicates that to the nitrogen atom contained in the at least one base, three organic moieties are covalently linked via single bonds Alternatively, the at least one base may contain an imine nitrogen atom "Imine” as used herein refers to the known class of compounds and indicates that the nitrogen atom has a covalent double bond to an organic radical and a single covalent bond to another organic radical. Imines are Schiff bases.
  • the bases are unblocked bases. That is, the bases are used in pure or untreated or unreacted form, and not in the form of a salt or, for example, as a phenol-blocked form. By blocking the effect of the catalyst and thus the reaction rate and the resulting properties are adversely affected.
  • the catalyst composition may, in various embodiments, contain several of the nonionic bases described above, for example a base with an imine nitrogen and a base with a tertiary nitrogen atom.
  • the nonionic base may also be both a tertiary amine and an imine containing both a tertiary nitrogen atom and an imine nitrogen.
  • the base used is preferably a nonionic, nitrogen-containing base which comprises at least one tertiary nitrogen atom and / or one imine nitrogen atom and also has a cyclic structure.
  • the radicals R1 to R3 and R5 are each independently selected from the group consisting of substituted or unsubstituted, linear or branched alkyl of 1 to 20 carbon atoms, substituted or unsubstituted, linear or branched alkenyl of 3 to 20 carbon atoms and substituted or unsubstituted aryl 5 to 20 carbon atoms, or at least two of R 1 to R 3 together with the nitrogen atom to which they are attached form a 5- to 10-membered heteroalicyclic ring or heteroaryl ring optionally containing one or more further nitrogen atoms, especially 1 further Nitrogen atom.
  • At least two of R 1 to R 3 together with the nitrogen atom to which they are attached form a 5- to 10-membered heteroalicyclic ring or heteroaryl ring optionally containing one or more further nitrogen atoms, especially 1 further nitrogen atom.
  • R4 is a substituted or unsubstituted, linear or branched alkylenyl having from 3 to 20 carbon atoms, or R4 and R5 together with the nitrogen atom to which they are attached form a 5- to 10-membered heteroalicyclic ring or heteroaryl ring, optionally further Contains nitrogen atoms.
  • R4 and R5 together with the nitrogen atom to which they are attached form a 5- to 10-membered heteroalicyclic ring or heteroaryl ring optionally containing further nitrogen atoms.
  • Alkylenyl refers to an alkyl radical attached to the nitrogen atom via a double bond. When substituted, the substituents are defined as described above for alkyl radicals.
  • the tertiary amine bases or imine bases are cyclic compounds which preferably contain at least two nitrogen atoms, i. at least two of R1 to R5 combine with each other to form a ring with the nitrogen atom to which they are attached, and further contain another nitrogen atom in the form of a group -NRR ', wherein the nitrogen atom is a ring atom and the group R or R 'is involved in ring formation.
  • Particularly preferred are bases based on imidazole or imidazolidine.
  • the bases are, for example, imidazole derivatives such as, for example, 1-alkylimidazole or 2,4-dialkylimidazole.
  • the at least one nonionic base is selected from the group consisting of 1-methylimidazole, 2,4-ethylmethylimidazole (EMI), 4-dimethylaminopyridine, 1, 4-diazabicyclo [2.2.2] octane (DABCO), 1, 8 Diazabicyclo [5.4.0] undec-7-ene (DBU), 1, 5-diazobicyclo [3.4.0] non-5-ene (DBN) and mixtures thereof.
  • the base is selected from the group consisting of EMI, DBU and mixtures thereof.
  • At least two bases, of the bases described, are included, in particular exactly two.
  • the reaction can be accelerated or the reaction rate can be specifically controlled and controlled.
  • the use of two different bases can have an advantageous effect on the resulting properties.
  • “Provide” as used herein refers to mixing the constituents of the reaction mixture in any order It may be advantageous, for example, first to combine two or more ingredients and optionally to mix into a heterogeneous or homogeneous mixture before adding the remaining ingredients
  • the at least one epoxy group-containing compound and the catalyst composition may first be combined and mixed and then, for example just before curing, added the at least one isocyanate group-containing compound and mixed into the other already mixed components Combination and mixing steps, it may be advantageous to cool the reaction mixture to room temperature.
  • the individual components of the reaction mixture can be used as such or as a solution in a solvent, such as an organic solvent or a mixture of organic solvents.
  • a solvent such as an organic solvent or a mixture of organic solvents.
  • the solvent may be a high boiling organic solvent.
  • the solvent may be selected from the group consisting of petroleum, benzene, toluene, xylene, ethylbenzene and mixtures thereof. Since the epoxide and isocyanate compounds are preferably selected from liquid, low viscosity monomers, in various embodiments, the catalyst composition may be employed as a solution as described above.
  • the reaction mixture in addition to the epoxide (a), the isocyanate (b), the polyol (c), and the catalyst composition (d), the reaction mixture comprises additional ingredients known and customary in the art.
  • a modified resin can be used which imparts improved impact resistance and low temperature properties to the post cure compositions.
  • Modified epoxide group-containing resins of this type are known in the art and include reaction products of epoxy resins having an epoxy functionality of greater than 1 with carboxy-functional rubbers, dimer fatty acids or so-called core / shell polymers, the Cores have a glass transition temperature of below -30 ° C.
  • the epoxy group-containing resin in this case is preferably used in a stoichiometric excess and produces an epoxide-functional reaction product.
  • the excess of epoxide group-containing resin may also be well above the stoichiometric excess.
  • An epoxide functionality of greater than 1 means that the compounds contain more than 1, preferably at least 2, 1, 2 epoxide groups per molecule.
  • modified epoxy-containing resins having an epoxide equivalent weight between 150 and 4000 are advantageous.
  • Epoxy group-containing resins may also be modified in particular with a copolymer of a 1,3-diene or an ethylenically unsaturated co-monomer and / or with core-shell-particles (CSR core-shell-rubber). These modified resins are used in addition to the epoxy resin (a) and the isocyanate (b).
  • reaction mixture described herein may be combined with other ingredients such as the tougheners described above, in the form of an adhesive composition or an injection resin.
  • Such adhesive compositions can contain a variety of other components, all of which are well known to those skilled in the art, including, but not limited to, commonly used adjuvants and additives such as fillers, plasticizers, reactive and / or non-reactive diluents, flow agents , Coupling agents (eg silanes), adhesion promoters, wetting agents, release agents, flame retardants, wetting agents, thixotropic agents and / or rheological auxiliaries (eg fumed silica), aging and / or corrosion inhibitors, stabilizers and / or dyes.
  • the auxiliaries and additives are incorporated in different amounts in the composition.
  • the reaction mixture is applied to a substrate, for example when used as an adhesive, or filled into a mold, when used as a molding compound for producing plastic parts.
  • the process is a transfer molding (RTM) process and the reaction mixture is a reactive injection resin.
  • Reactive refers to the fact that the injection resin is chemically crosslinkable Provision of the reaction mixture, ie step (1) of the described method, which comprises filling, in particular injection (injection), of the injection resin into a mold
  • injection injection
  • reaction mixtures are particularly suitable, prior to injection into the molding tool into these fibers or semi-finished fiber products (Prewovens / Preform)
  • the fibers and / or semifinished fiber products which can be used are the materials known in the art for this application, in particular carbon fibers.
  • the invention further relates to the reaction mixtures described in connection with the methods, i. Resin compositions, based on their total weight (a) 9.0 to 82.5 wt .-% of at least one liquid, aromatic epoxy resin; (b) 16.5 to 90.0% by weight of at least one liquid, aromatic polyisocyanate; (c) 1, 0 to 20.0 wt .-% of at least one polyol; and (d) 0.01 to 10.0% by weight of at least one catalyst composition, the at least one epoxy resin being used in amounts relative to the at least one polyisocyanate such that the molar equivalent ratio of isocyanate groups to epoxide groups is greater than 1, 2, more preferably between 1, 2 and 10, even more preferably between 1, 25 and 5, even more preferably between 1, 3 and 4 and most preferably between 1, 4 and 2.
  • such resin compositions are adhesive compositions or injection resins.
  • the injection resins are preferably pumpable and particularly suitable for transfer molding (RTM process). Therefore, in various embodiments, the reaction mixture is at a temperature of 80 ° C, i. a typical infusion temperature, a viscosity of ⁇ 100 mPas. To determine the viscosity, the resin mixture is prepared at room temperature with a suitable mixer and determined on a plate / plate rheometer in oscillation, the viscosity with increasing temperature at a heating rate of 50 K / min.
  • the invention therefore also relates in one embodiment to the moldings obtainable by means of the resin systems according to the invention in the RTM process.
  • the RTM processes in which the described resin systems (polymer compositions) can be used are known as such in the prior art and can readily be adapted by the person skilled in the art such that the reaction mixture according to the invention can be used.
  • the open times of the resin compositions (reaction mixture) as described herein are preferably greater than 90 seconds and more preferably in the range of 2 to 5 minutes, more preferably about 3 minutes. "Approximately” as used herein in connection with a numerical value the numerical value means ⁇ 10%.
  • the reaction mixture in step (2) of the process according to the invention can be cured at different reaction temperatures.
  • the curing temperature between 10 ° C and 230 ° C set.
  • the curing at elevated temperature ie> 25 ° C, take place.
  • the resins are cured between 50 ° C and 190 ° C, and preferably between 90 ° C and 150 ° C.
  • the duration of curing also depends on the resins to be cured and the catalyst composition and may be between 0.01 hours to 10 hours. - -
  • the cure cycle lasts a few minutes, i. especially 1 to 5 minutes.
  • the curing can be done in one or more stages.
  • the epoxy group-containing resin reacts with the isocyanate in the presence of the catalyst to form at least one oxazolidinone which cross-links the resins and, among other things, confers to the cured composition its beneficial physical properties.
  • the at least one oxazolidinone formed on curing may contain one of 1,2-oxazolidin-3-one, 1,2-oxazolidin-4-one, 1,2-oxazolidin-5-one, 1,3-oxazolidin-2-one , 1, 3-oxazolidin-4-one, or 1, 3-oxazolidin-5-one.
  • the cured composition may also contain a plurality of different of the aforementioned oxazolidinone isomers.
  • the isocyanate groups react with each other to form at least one isocyanurate which crosslinks the resins together and also contributes to the advantageous properties of the cured composition.
  • the resins cured by the catalyst systems and methods described herein preferably have a critical stress intensity factor K1 c of> 0.8, preferably at least 1, 0, more preferably> 1, 2 and most preferably> 1.5.
  • the glass transition temperature of the cured resins (Tg (tan ⁇ ) by DTMA) is, in various embodiments, in the range of more than 100 ° C, especially more than 150 ° C, typically in the range up to 200 ° C.
  • the elastic modulus of the cured resins is preferably at least 2500 N / mm 2 , preferably at least 3000 N / mm 2 , typically in the range from 2500 to 5000 N / mm 2 .
  • the present invention relates to the cured composition obtainable by the method described herein.
  • This can, depending on the method, be present as a molded part, in particular as a fiber-reinforced plastic molded part.
  • Such moldings are preferably used in the automotive industry.
  • the cured polymer composition are particularly suitable as a matrix resin for fiber composites. These can be used in various application methods, for example in the resin transfer molding process (RTM process) or in the infusion process.
  • fiber components of fiber composites known high-strength fiber materials are suitable. These can be made of glass fibers, for example; synthetic fibers such as polyester fibers, polyethylene fibers, polypropylene fibers, polyamide fibers, polyimide fibers or - -
  • aramid fibers Carbon fibers; boron fibers; oxide or non-oxide ceramic fibers such as alumina / silica fibers, silicon carbide fibers; Metal fibers, for example of steel or aluminum; or consist of natural fibers such as flax, hemp or jute.
  • These fibers may be incorporated in the form of mats, fabrics, knits, mats, fleeces or rovings. Two or more of these fiber materials may also be used as a mixture.
  • Short cut fibers can be selected, but preferably synthetic long fibers are used, in particular fabrics and scrims. Such high strength fibers, scrims, fabrics and rovings are known to those skilled in the art.
  • the fiber composite material fibers in a volume fraction of more than 20 vol .-%, preferably more than 40 vol .-%, more preferably between 50 and 70 vol .-% based on the total fiber composite material to achieve particularly good mechanical properties .
  • the volume fraction is determined in accordance with the standard DIN EN 2564: 1998-08, in the case of glass fibers in accordance with the standard DIN EN ISO 1 172: 1998-12.
  • Such a fiber composite material is particularly suitable as an automotive component.
  • Such fiber composites have several advantages over steel, so they are lighter, are characterized by an improved crash resistance and are also more durable.

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Abstract

La présente invention concerne un procédé de production d'une composition durcie qui présente au moins un cycle oxazolidinone et au moins un cycle isocyanurate et qui est réticulée par ceux-ci, à partir d'un mélange réactionnel liquide qui contient, par rapport à son poids total, au moins une résine époxyde, au moins un polyisocyanate, au moins un polyol et au moins une composition de catalyseur. L'invention concerne également la composition durcie obtenue par ce procédé.
EP17729884.1A 2016-06-20 2017-06-16 Composition durcie à haute résistance aux chocs et haute résistance thermique à base d'une résine époxyde et d'un polyisocyanate Withdrawn EP3472217A1 (fr)

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PCT/EP2017/064740 WO2017220437A1 (fr) 2016-06-20 2017-06-16 Composition durcie à haute résistance aux chocs et haute résistance thermique à base d'une résine époxyde et d'un polyisocyanate

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EP17729884.1A Withdrawn EP3472217A1 (fr) 2016-06-20 2017-06-16 Composition durcie à haute résistance aux chocs et haute résistance thermique à base d'une résine époxyde et d'un polyisocyanate

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WO2022124191A1 (fr) * 2020-12-08 2022-06-16 東レ株式会社 Composition de résine époxyde thermodurcissable, article moulé à partir de résine époxyde thermodurcissable, matériau de moulage pour matériau composite renforcé par des fibres, matériau composite renforcé par des fibres et procédé de production de matériau composite renforcé par des fibres

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CN109312041A (zh) 2019-02-05
KR20190022655A (ko) 2019-03-06
WO2017220437A1 (fr) 2017-12-28
ES2909123T3 (es) 2022-05-05
EP3260481A1 (fr) 2017-12-27
EP3260481B1 (fr) 2022-02-23
KR102466864B1 (ko) 2022-11-14
US11566113B2 (en) 2023-01-31
CN109312041B (zh) 2022-11-29
MX2018015812A (es) 2019-04-29
JP2019521216A (ja) 2019-07-25
US20190112437A1 (en) 2019-04-18
CA3033848A1 (fr) 2017-12-28

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