EP3997149A1 - Compositions polymérisables à durée de vie en pot prolongée pour la fabrication de plastiques polyisocyanurates - Google Patents

Compositions polymérisables à durée de vie en pot prolongée pour la fabrication de plastiques polyisocyanurates

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Publication number
EP3997149A1
EP3997149A1 EP20735579.3A EP20735579A EP3997149A1 EP 3997149 A1 EP3997149 A1 EP 3997149A1 EP 20735579 A EP20735579 A EP 20735579A EP 3997149 A1 EP3997149 A1 EP 3997149A1
Authority
EP
European Patent Office
Prior art keywords
isocyanate
polymerizable composition
acid
composition
polyisocyanate
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Withdrawn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
EP20735579.3A
Other languages
German (de)
English (en)
Inventor
Richard Daniel Matthias MEISENHEIMER
Paul Heinz
Dirk Achten
Florian Golling
Hans-Josef Laas
Dieter Mager
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Intellectual Property GmbH and Co KG
Original Assignee
Covestro Intellectual Property GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Covestro Intellectual Property GmbH and Co KG filed Critical Covestro Intellectual Property GmbH and Co KG
Publication of EP3997149A1 publication Critical patent/EP3997149A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—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
    • C08G18/22—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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/721—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
    • C08G18/70—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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • 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

Definitions

  • the present invention relates to polymerizable compositions which are suitable for the production of polyisocyanurate plastics and which have a longer pot life than the compositions conventionally used for this purpose.
  • a frequently used process for the continuous production of fiber composite materials is pultrusion.
  • a fiber is drawn through an immersion bath filled with a polymerizable composition and then cured in a heated profile.
  • the polymerizable composition creates a polymer matrix in which the fiber is embedded. It is important here that the polymerizable composition shows the lowest possible reactivity at room temperature, so that the viscosity of the polymerizable composition in the immersion bath remains so low as long as possible that processing is possible.
  • the period from the provision of the polymerizable composition to the achievement of a viscosity that is unacceptably high for the application in question is also known to the person skilled in the art as the pot life. A long pot life is also desirable in other areas of application.
  • the present invention relates to a polymerizable composition having a molar ratio of isocyanate groups to isocyanate-reactive groups of at least 1.5: 1.0 a) a polyisocyanate composition A containing at least 1% by weight of isocyanate groups;
  • a “polymerizable composition” is a composition which contains at least the above-mentioned components and can be cured to a polymer by crosslinking the functional groups of the components it contains.
  • This polymer necessarily contains functional groups which are formed by the crosslinking of isocyanate groups with one another. These are preferably selected from the group consisting of isocyanurate, biuret, uretdione, iminooxadiazinedione and oxadiazinetrione structures.
  • the polymer particularly preferably contains isocyanurate groups or oxadiazinetrione groups and is therefore also referred to for simplicity in this application as "isocyanurate plastic".
  • the polymerizable composition has a molar excess of isocyanate groups over isocyanate-reactive groups, since otherwise in undesirably high proportions or even exclusively - depending on the type and amount of isocyanate-reactive groups present - urethane, amino - Or urea groups are formed.
  • the molar ratio of isocyanate groups to isocyanate-reactive groups is at least 2: 1, more preferably at least 3: 1 and even more preferably at least 5: 1.
  • "Isocyanate-reactive groups" in the context of the present application are hydroxyl and thiol - and amino groups The amino groups can be primary or secondary amino groups.
  • the polymerizable composition can contain conventional additives. These are preferably pigments, fillers, antioxidants, flame retardants, mold release agents and UV stabilizers.
  • polyisocyanate composition A denotes all compounds present in the polymerizable composition according to the invention which contain at least one free isocyanate group.
  • the polyisocyanate composition A has, based on its total weight, an isocyanate group content of at least 1% by weight, preferably at least 5% by weight, more preferably at least 10% by weight and even more preferably at least 15% by weight.
  • the polyisocyanate composition A consists of at least 70% by weight, preferably at least 80% by weight and most preferably at least 90% by weight polyisocyanates as defined below consists.
  • a “polyisocyanate” is understood to mean any compound which has an average of at least 1.8, preferably at least 2.0 and particularly preferably at least 2.1 isocyanate groups.
  • a “monoisocyanate” is a compound with an average of at most 1 , 6 isocyanate groups per molecule, in particular with only one isocyanate group per molecule.
  • polyisocyanates refers to monomeric and / or oligomeric polyisocyanates. To understand many aspects of the invention, however, it is important to distinguish between monomeric diisocyanates and oligomeric polyisocyanates.
  • oligomeric polyisocyanates are mentioned in this application, then this means polyisocyanates which are built up from at least two monomeric diisocyanate molecules, ie they are compounds which represent or contain a reaction product of at least two monomeric diisocyanate molecules.
  • Oligomeric isocyanates are obtained by “modifying” a monomeric isocyanate. “Modifying” here means the reaction of monomeric isocyanates to oligomeric isocyanates having a uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structure. Diisocyanates are preferably used as starting materials for the preparation of oligomeric isocyanates.
  • hexamethylene diisocyanate 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, for example the HDI isocyanurate and the HDI -Biuret, each made up of three monomeric HDI components:
  • the monomeric isocyanates defined further below in this application are particularly preferably used as starting materials for the modification.
  • the polymerizable composition according to the invention can contain oligomeric and polymeric polyisocyanates in any mixing ratio.
  • polymerizable compositions are preferred for reasons of occupational safety, their
  • the polyisocyanate component i.e. the entirety of all polyisocyanates contained in the said composition, consist of at least 90% by weight, preferably at least 95% by weight and more preferably at least 98% by weight of oligomeric polyisocyanates. If desired, for example to lower the viscosity of the polymerizable composition, the polyisocyanate component can also contain up to 20% by weight or preferably up to 50% by weight of monomeric polyisocyanates.
  • isocyanate with aliphatically bonded isocyanate groups all isocyanate groups are bonded to a carbon atom that is part of an open carbon chain. This can be unsaturated in one or more places.
  • the aliphatically bound isocyanate group or - in the case of polyisocyanates - the aliphatically bound isocyanate groups are preferably bound to the terminal carbon atoms of the carbon chain.
  • polyisocyanates with aliphatically bound isocyanate groups are 1,4-diisocyanatobutane (BDI), 1,5-diisocyanatopentane (PDI), 1,6-diisocyanatohexane (HDI), 2-methyl-1,5-diisocyanatopentane, 1,5 Diisocyanato-2,2-dimethylpentane, 2,2,4- or 2,4,4-trimethyl-1,6-diisocyanatohexane and 1,10-diisocyanatodecane.
  • BDI 1,4-diisocyanatobutane
  • PDI 1,5-diisocyanatopentane
  • HDI 1,6-diisocyanatohexane
  • 2-methyl-1,5-diisocyanatopentane 1,5 Diisocyanato-2,2-dimethylpentane, 2,2,4- or 2,4,4-trimethyl-1,6-diisocyan
  • polyisocyanates with cycloaliphatically bonded isocyanate groups are 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; (IPDI), 1- isocyanato-l-methyl-4 (3) -isocyanatomethylcyclohexane, 2,4'- and 4,4'-
  • 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'-tetramethyl-dicyclohexylmethane
  • 4,4'-diisocyanato-l, l'-bi cyclohexyl
  • Isocyanate groups are 1,3- and 1,4-bis-tiso-cyanatomethyl-benzene (xyxlylene diisocyanate; XDI), 1,3- and 1,4-bis (1- isocyanato-1-methylethyl) -benzene (TMXDI) and bis (4- (1-isocyanato-1-methylethyl) phenyl) carbonate.
  • Isocyanates with aromatically bound isocyanate groups which are particularly suitable according to the invention are 2,4- and 2,6-diisocyanate toluene (TDI), 2,4'- and 4,4'-diisocyanatodiphenylmethane (MDI) and 1,5-diisocyanatonaphthalene.
  • TDI 2,4- and 2,6-diisocyanate toluene
  • MDI 2,4'- and 4,4'-diisocyanatodiphenylmethane
  • 1,5-diisocyanatonaphthalene 1,5-diisocyanatonaphthalene.
  • Particularly suitable monoisocyanates according to the invention are preferably selected from the group consisting of n-butyl isocyanate, n-amyl isocyanate, n-hexyl isocyanate, n-heptyl isocyanate, n-octyl isocyanate, undecyl isocyanate, dodecyl isocyanate, tetradecyl isocyanate, cetyl isocyanate, stearyl isocyanate, cyclopentyl isocyanate, 3- and cyclohexyl isocyanate 4-methylcyclohexyl isocyanate, methylbenzyl isocyanate, methyl isocyanate, (trimethylsilyl) isocyanate, 1-naphthyl isocyanate, 3-methyl-2-butyl isocyanate, l- (4-methoxyphenyl) ethyl isocyanate, l- (3-methoxyphenyl)
  • Methoxyphenyl isocyanate 4-tert-butylphenyl isocyanate, 2-methoxyphenyl isocyanate, 3,4,5-
  • Ethylphenethyl isocyanate 4-methoxybenzyl isocyanate, benzenesulfonyl isocyanate, 2-
  • Biphenylyl isocyanate 3-phenylpropyl isocyanate, 2,3-dimethoxyphenethyl isocyanate, decyl isocyanate, cyclohexane methyl isocyanate, 3,4-methylenedioxyphenethyl isocyanate, 3,4-
  • Fluorophenethyl isocyanate pentafluorophenyl isocyanate, 2,4-dichlorophenethyl isocyanate, 4-
  • Chlorobenzenesulfonyl isocyanate 2-chlorobenzyl isocyanate, 3,3-diphenylpropyl isocyanate, 3,4,5-
  • Dichlorophenethyl isocyanate 4-benzylphenyl isocyanate, 4-bromobenzyl isocyanate, 4-
  • Fluorobenzopsulfonyl isocyanate mPEG5K isocyanate, 3,5-dimethylisoxazol-4-yl isocyanate, 2-methoxy-5-methylphenyl isocyanate, 2- (4-biphenyl) ethyl isocyanate, 2-ethyl-6-methylphenyl isocyanate, 2-methyl-5-phenyl-3 -furyl isocyanate, l- (l-naphthyl) ethyl isocyanate, 3,4- (methylenedioxy) phenyl isocyanate, 2,3- dihydro-l-benzofuran-5-yl isocyanate, 4-methoxy-2-nitrophenyl isocyanate, 3,5-
  • Thioisocyanates are also suitable.
  • Preferred thioisocyanates are selected from the group consisting of 4-fluorobenzyl isothiocyanate, dibutyltin diisothiocyanate, 2,6-
  • mono- or polyisocyanates which are obtained by modifying monomeric isocyanates as described above in this application.
  • Isocyanate-terminated prepolymers suitable for producing the polymerizable composition are obtained by reacting an alcohol, an amine or a thiol with a polyisocyanate. There must be a molar excess of isocyanate groups over isocyanate-reactive groups.
  • Suitable alcohols are monohydric or polyhydric monomeric alcohols, preferably selected from the group consisting of flexanol and butanediol.
  • the preferred isocyanate for the preparation of the prepolymer carrying isocyanate groups is H Dl in monomeric form, oligomerized H Dl and mixtures thereof. It is particularly preferred that the proportion of mono- and polyisocyanates with aromatically bonded isocyanate groups in the polyisocyanate component A is at most 50% by weight, more preferably at most 25% by weight, even more preferably at most 10% by weight and the strongest is preferably at most 5% by weight.
  • trimerization catalyst B is a carboxylate with a suitable counterion. Certain trimerization catalysts B are advantageously combined with catalyst solvents and / or complexing agents.
  • Carboxylates in which the conjugate acid has a pK a value from 3.5 to 5.0 are preferred. More preferably, the pK value in the range from 4.0 to 5.0. Most preferably it is in the range of 4.2 to 4.8.
  • Methylbenzoic acid (4.35), 4-phenylbutyric acid (4.76), 5,5,5-trifluoropentanoic acid (4.49), acetoacetic acid (3.58), aceturic acid (3.64), adipic acid (4.43 and 5.52), allocinnamic acid (3.96), angelic acid (4.30), Anthracene-l-carboxylic acid (3.69), anthracene-9-carboxylic acid (3.65), anthranilic acid (5.00), atropic acid (3.84), azelaic acid (4.54 and 5.52), barbituric acid (4.00), bromosuccinic acid (2.55 and 4.4), camphoric acid (4.64 ), Caprylic acid (4.85), quinic acid (3.56), chlorofumaric acid (1.78 and 3.81), chloromaleic acid (1.72 and 3.86), citric acid (3.13 and 4.76 and 6.4), crotonic acid (4.7), cyanic acid (3.66
  • Salts of acetic acid, caproic acid, formic acid, acrylic acid, benzoic acid, propionic acid, butyric acid, valeric acid, isobutyric acid and 2-ethylhexanoic acid are particularly preferred.
  • those catalysts are also preferred which are present in the form of zwitterions with a pK a value in the preferred range.
  • Examples include: 2-hydroxybutyric acid (4.04), 4-aminobutyric acid (4.54), 2-aminobenzoic acid (4.97), 3-aminobenzoic acid (4.78-4.92), 4-aminobenzoic acid (4.93).
  • Preferred metal ions are alkali metal ions, alkaline earth metal ions, ions of subgroup metals and tin ions.
  • the carboxylate is preferably combined with phosphonium, ammonium or metal ions as counterions.
  • Preferred alkali metal ions are Li + , Na + and K + .
  • Preferred alkaline earth metal ions are Mg 2+ , Ca 2+ , Sr 2+ and Ba 2+ .
  • Preferred ions of subgroup metals are Fe 2+ , Zn 2+ , Cu 2+ , Ti 2+ , Zr 2+ , Yr 2+ .
  • the concentration of the trimerization catalyst B used or of a mixture of several trimerization catalysts B is at least so high that the reaction mixture reaches the gel point at temperatures of at least 150 ° C. within 20 minutes at the most.
  • the gel point is reached when the modulus value for G ' (Pa) reaches or exceeds the modulus value for G ” (Pa), measured in oscillation at 23 ° C., 1 / s, 1% amplitude in a plate-plate rheometer.
  • the use of very high catalyst concentrations can also negate the effect of the present invention. If the catalyst concentration is high enough, the reaction mixture reaches the gel point within minutes or even seconds, even at room temperature, without the addition of CO being able to significantly influence this period.
  • the concentration of a trimerization catalyst B or a mixture of several trimerization catalysts B contained in the reaction mixture according to the invention is therefore functionally defined in a preferred embodiment of the present invention. It is dimensioned so that the reaction mixture at 23 ° C. and a CC> concentration of at most 90 ppm reaches the gel point within 1 to 22 hours, preferably 6 to 22 hours. For a given catalyst, this concentration range can be determined by a simple series of tests.
  • the gel time is identical to the pot life for the present application, since the mixture can then no longer be processed by pouring and brushing. It can be determined in a metrologically simplified manner via the increase in viscosity with so-called gel timers
  • the polymerizable composition additionally contains a polyol and / or a polyether which supports the solvation of the cation, preferably a polyether.
  • Preferred polyethers are selected from the group consisting of crown ethers, diethylene glycol, polyethylene and polypropylene glycols. The addition of a polyethylene glycol or a crown ether, particularly preferably 18-crown-6 or 15-crown-5, has proven to be particularly practical.
  • the crown ethers are preferably selected so that they complex well the metallic cation as a counterion to the preferred carboxylate catalyst. The person skilled in the art can find suitable crown ethers for the metal ion used in the literature.
  • the polymerizable composition according to the invention can contain further compounds which catalyze the crosslinking of isocyanate groups with one another. If, however, compounds are added to the polymerizable composition which already show a noteworthy catalytic activity at temperatures below 80 ° C., their presence increases the advantages of the present invention. Therefore, their proportion in the polymerizable composition must be limited. The proportion of all compounds which are not trimerization catalyst B in the context of the present application and which catalyze the reaction of isocyanate groups to isocyanurate, biuret, uretdione, iminooxadiazinedione or oxadiazinetrione structures at temperatures below 80 ° C.
  • the proportion of the aforementioned compounds must not exceed 20% by weight, preferably 10% by weight and most preferably 5% by weight, based on the total amount of all carboxylates with the properties according to the invention.
  • the C0 2 content of the polymerizable composition according to the invention is at least 150 ppm based on the total amount of the liquid constituents of the polymerizable composition. More preferably, the minimum content of CO 2 is at least 200 ppm, even more preferably at least 250 ppm and most preferably at least 300 ppm.
  • the measured values were therefore standardized to the value defined as 410 ppm for a C0 2 -saturated solution. All of the C0 2 values given in this application could therefore also be viewed as relative contents based on a C0 2 saturated system.
  • a measured value of 205 ppm corresponds to 50% of the saturation achievable under an air atmosphere at normal pressure.
  • the threshold value of 150 ppm defined in the claims corresponds to 37% of this saturation. All other C0 2 values given in this patent application can be converted accordingly into a percentage of the achievable saturation under an air atmosphere at normal pressure. Since different methods of CO 2 measurement for the same sample can lead to different values expressed in ppm under certain circumstances, a comparability can be established in this way.
  • the exemplary embodiments show that the C0 2 content of a polymerizable composition can be adjusted in various ways.
  • C0 2 can be added in frozen form as dry ice will. It is also possible to pass gaseous CO 2 through a liquid.
  • the CO 2 can be dissolved in one or more of the components of the polymerizable composition before mixing with the other components.
  • the polyisocyanate component A is preferred here because it has the largest volume fraction.
  • CO 2 is generated in situ by adding a compound such as water.
  • the polymerizable composition contains at least one filler F.
  • This can be organic or inorganic and be in any shape and size known to the person skilled in the art.
  • Preferred organic fillers are wood, cellulose, paper, cardboard, shredded tissue, cork, wheat chaff, polydextrose, cellulose, aramids, polyethylene, carbon, carbon nanotubes, polyester, nylon, plexiglass, flax, hemp and sisal.
  • Preferred inorganic fillers are AIOH 3 , CaCC> 3 , silicon dioxide, magnesium carbonate, T1O 2 , ZnS, minerals containing silicates, sulfates, carbonates and the like such as magnesite, barite, mica, dolomite, kaolin, talc, clay minerals, as well as carbon black, graphite, boron nitride , Glass, basalt, boron, ceramics and silica.
  • the polymerizable composition according to the invention contains a fibrous filler e consisting of organic fibers, inorganic fibers or mixtures thereof.
  • 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, polyethylene fibers, carbon fibers, carbon nanotubes, polyester fibers, nylon fibers and Plexiglas fibers.
  • Preferred natural fibers are flax fibers, hemp fibers, wood fibers, cellulose fibers and sisal fibers. benefits
  • the polymerizable composition according to the invention shows a significantly slower increase in viscosity compared to otherwise identical compositions with a lower CCh content. Nevertheless, rapid hardening is still possible after increasing the temperature. This extends the period of time in which a ready-to-use composition can be stored (pot life, the pot life in this case being determined by the gel time measured with a gel timer according to the method given below). This effect also helps to avoid waste, since a higher proportion of the composition can be used as intended and a smaller proportion has to be disposed of after a critical viscosity has been exceeded.
  • the present invention thus offers ecological and economic advantages.
  • the polymerizable composition according to the invention shows an at least doubled gel time compared to otherwise identical polymerizable compositions whose CCh content is below 100 ppm. It is particularly preferred that a polymerizable composition with a CCh content of at least 300 ppm has an at least doubled gel time compared to an otherwise identical polymerizable composition with a CC content of at most 100 ppm. This effect is particularly preferred when comparing a polymerizable composition with a CC content of at least 380 ppm with an otherwise identical polymerizable composition with a CCh content of at most 100 ppm.
  • the present invention relates to the use of CO to increase the gel time of a polymerizable composition with a molar ratio of isocyanate groups to isocyanate-reactive groups of at least 1.5: 1.0 containing a) a polyisocyanate composition A containing at least 1% by weight Isocyanate groups; and b) at least one trimerization catalyst B, which is a carboxylate.
  • the use according to the invention preferably consists in the addition of at least 150 ppm CO based on the total amount of the liquid constituents of the polymerizable composition. More preferred are at least 200, even more preferred at least 250 ppm, and most preferred at least 300 ppm CO.
  • the present invention relates to the use of the polymerizable composition according to the invention for producing a polymer.
  • This use is preferably characterized by increasing the temperature of the polymerizable composition to 80 ° C to 300 ° C. This temperature is maintained until the polymerizable composition has hardened, preferably for at least 5 minutes.
  • the use according to the invention is particularly preferably characterized in that at least 80% of the isocyanate groups originally present in the polymerizable composition are converted during the preparation of the polymer. Conversely, this means that the free isocyanate group content of the polymer is at most 20% of the isocyanate groups originally present in the polymerizable composition.
  • the polymer formed is preferably a polymer that is formed by the crosslinking of isocyanate groups to form isocyanurate groups. The formation of further groups, in particular biuret, uretdione, iminooxadiazindione, oxadiazintrione, urethane and allophanate groups, is not excluded.
  • the present invention relates to a process for producing a polymer comprising the process steps a) providing a reaction mixture which (i) a polyisocyanate composition A containing at least 1% by weight of isocyanate groups, (ii) at least one trimerization catalyst B containing a carboxylate and (iii) contains at least 150 ppm CO based on the total amount of the liquid components of the polymerizable composition; and b) The curing of the reaction mixture at a temperature between 80 ° C and 300 ° C.
  • the polyisocyanate composition A consists of at least 80% by weight, more preferably at least 90% by weight, of oligomeric polyisocyanates.
  • the curing in process step b) leads to at least 80% of the isocyanate groups originally present in the polyisocyanate composition A being converted.
  • reaction mixture is stored between the provision in process step a) and the curing in process step b) for at least 2 hours and more preferably at least 4 hours at a temperature between 10 ° C and 40 ° C.
  • the aforementioned storage time is particularly preferably a maximum of 20 hours.
  • the present invention relates to a process for producing a polymerizable composition with an increased gel time, in which a polyisocyanate composition A, a catalyst composition which contains a trimerization catalyst B and CO are combined, characterized in that a) the polymerizable in the Composition reached CC concentration is at least 150 ppm based on the total amount of the polymerizable composition; and b) isocyanate-reactive compounds are only used in an amount such that a molar ratio of isocyanate groups to isocyanate-reactive groups of at least 1.5: 1.0 is achieved in the polymerizable composition.
  • the CO 2 can be contained in one of the components to be used to produce the polymerizable composition, preferably the polyisocyanate composition. However, it is also possible to first mix the polyisocyanate composition A and the catalyst composition B and then, preferably within 30 minutes at most after the two components have been added to one another, to add the CO 2.
  • gaseous CO2 is added, combining and mixing coincide here. If it is added in the form of dry ice, a subsequent mixing of the CO2 with the liquid, for example by stirring, is preferred.
  • the present invention relates to the use of the method defined above for the production of composite materials, casting compounds, paints, adhesives or three-dimensional printed components.
  • RT room temperature
  • phase transitions were determined by means of DSC (differential scanning calorimetry) with a Mettler DSC 12E (Mettler Toledo GmbH, Giessen, DE) in accordance with DIN EN 61006.
  • a calibration was carried out by 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 means of three heatings from -50 ° C to +200 ° C at a heating rate of 20 K / min with subsequent cooling at a cooling rate of 320 K / min. Liquid nitrogen was used for cooling. Nitrogen was used as the purge gas.
  • the values given are based on the evaluation of the 1st heating curve, since in the case of the reactive systems investigated, the temperature load in the DSC may result in changes in the sample in the measurement process at high temperatures.
  • the glass transition temperature T g was obtained from the temperature at half the height of a glass transition step.
  • the infrared spectra were measured on an FT-IR spectrometer from Bruker equipped with an ATR unit.
  • the device 100.50 Geltimer GT-SP from Gelnorm with measuring stamps made of steel and a length of L 150 mm was used.
  • Polyisocyanate Al 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 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 purchased from ACROS with a purity of> 99% by weight.
  • Polyethylene glycol (PEG) 400 was obtained from ACROS with a purity of> 99% by weight.
  • Zinc stearate with a zinc content of 10-12% was obtained from Sigma-Aldrich.
  • the release agent INT-1940 RTM was obtained from AXEL PLASTICS.
  • Catalyst Kl is a mixture of 10-30% potassium 2-ethylhexanoate in ethylene glycol and diethylene glycol from Evonik Industries AG.
  • Glass fiber mat The glass fiber mat 90070 (US type 1610) in a plain weave from the company PD INTERGLAS TECFINOLOGIES GmbH and weighing 82 g / m 2 was used.
  • 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 obtained in this way and used as a catalyst without further treatment.
  • the isocyanate composition was initially prepared by mixing the appropriate isocyanate components (Al or A2) with an appropriate amount of catalyst (K1-K2) and additives at 23 ° C in a Speedmixer DAC 150.1 FVZ from Hauschild for 120 Seconds at 1500 rpm.
  • Part of the mixture was then placed in a mold (metal lid, approx. 6 cm in diameter and approx. 1 cm high) and cured in the oven.
  • the remainder of the mixture was examined for gel time using a gel bucket.
  • a resin mixture consisting of degassed polyisocyanate Al (85.0 g), catalyst K2 (3.64 g), zinc stearate (0.23 g), INT-1940RTM (2.04 g) and dry ice (9.09 g) such as as described above (acid number: 27.4 mg KOH / g). Curing in the oven gave a solid material with a T g of 98 ° C. The thermal curing reduced the height of the characteristic NCO band between 2300 and 2250 cm 1 by at least 80%. The gel time of the resin mixture at room temperature was more than 22 hours. After 24 hours of open storage at room temperature, a liquid material with a film gelled on the surface was obtained.
  • the gel time of the resin mixture at room temperature was more than 22 hours. After 24 hours of storage at room temperature, a liquid material with a film gelled on the surface was obtained.
  • the gel time of the resin mixture at room temperature was more than 22 hours. After 24 hours of storage at room temperature, a liquid material with a film gelled on the surface was obtained.
  • Freshly opened polyisocyanate was left open at room temperature for 24 hours.
  • the gel time of the resin mixture at room temperature was more than 22 hours. After 24 hours of storage at room temperature, a liquid material with a film gelled on the surface was obtained.
  • a resin mixture consisting of degassed polyisocyanate A2 (93.5 g), catalyst K2 (4.0 g), zinc stearate (0.25 g), INT-1940RTM (2.25 g) and dry ice (0.5 g) such as manufactured as described above. Curing in the oven gave a solid material with a T g of 148 ° C. The thermal curing reduced the height of the characteristic NCO band between 2300 and 2250 cm 1 by at least 80%. The gel time of the resin mixture at room temperature was more than 22 hours. After 24 hours of storage at room temperature, a liquid material with a film gelled on the surface was obtained.
  • a resin blend of freshly opened polyisocyanate Al (93.5 g), zinc stearate (0.25 g) and INT-1940R TM (2.25 g) was prepared as described above. The mixture was then stirred openly for 10 min with a dissolver at 1500 rpm. The catalyst K2 (4.0 g) was then added and the mixture was again stirred openly for 10 min with a dissolver at 1500 rpm. The gel time of the resin mixture at room temperature was more than 22 hours. After 24 hours of storage at room temperature, a liquid material with a film gelled on the surface was obtained.
  • the gel time of the resin mixture at room temperature was more than 22 hours. After 24 hours of storage at room temperature, a liquid material with a slightly increased viscosity was obtained.
  • a resin blend of degassed polyisocyanate Al (93.5 g), catalyst K2 (4.0 g), zinc stearate (0.25 g) and INT-1940RTM (2.25 g) was prepared as described above. Curing in the oven gave a solid material with a T g of 93 ° C. The thermal curing reduced the height of the characteristic NCO band between 2300 and 2250 cm 1 by at least 80%. The gel time of the resin mixture at room temperature was less than 22 hours. After 24 hours of storage at room temperature, a fully gelled material was obtained.
  • a resin blend of degassed polyisocyanate A2 (93.5 g), catalyst K2 (4.0 g), zinc stearate (0.25 g) and INT-1940R TM (2.25 g) was prepared as described above. Curing in the oven gave a solid material with a T g of 149 ° C. The thermal curing reduced the height of the characteristic NCO band between 2300 and 2250 cm 1 by at least 80%. The gel time of the resin mixture at room temperature was less than 22 hours. After 24 hours of storage at room temperature, a fully gelled material was obtained.

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Engineering & Computer Science (AREA)
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Abstract

La présente invention concerne des compositions polymérisables qui sont appropriées pour la fabrication de plastiques polyisocyanurates et qui présentent une durée de vie en pot prolongée par rapport aux compositions classiquement utilisées à de telles fins.
EP20735579.3A 2019-07-08 2020-07-01 Compositions polymérisables à durée de vie en pot prolongée pour la fabrication de plastiques polyisocyanurates Withdrawn EP3997149A1 (fr)

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PCT/EP2020/068438 WO2021004842A1 (fr) 2019-07-08 2020-07-01 Compositions polymérisables à durée de vie en pot prolongée pour la fabrication de plastiques polyisocyanurates

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