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EP4077436A1 - Composant de catalyseur pour la modification d'isocyanate - Google Patents

Composant de catalyseur pour la modification d'isocyanate

Info

Publication number
EP4077436A1
EP4077436A1 EP20824549.8A EP20824549A EP4077436A1 EP 4077436 A1 EP4077436 A1 EP 4077436A1 EP 20824549 A EP20824549 A EP 20824549A EP 4077436 A1 EP4077436 A1 EP 4077436A1
Authority
EP
European Patent Office
Prior art keywords
optionally
nitrogen atom
charge
hydroxyl group
catalyst component
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Withdrawn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
EP20824549.8A
Other languages
German (de)
English (en)
Inventor
Frank Richter
Yoan PREUX
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 EP4077436A1 publication Critical patent/EP4077436A1/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Withdrawn legal-status Critical Current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
    • C08G18/08—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
    • C08G18/2018—Heterocyclic amines; Salts thereof containing one heterocyclic ring having one nitrogen atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
    • C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
    • C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
    • C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
    • C07D295/092—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings with aromatic radicals attached to the chain
    • 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
    • C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
    • C08G18/022—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing 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
    • C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
    • C08G18/025—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing carbodiimide 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
    • C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
    • C08G18/027—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing urethodione 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
    • C08G18/14—Manufacture of cellular products
    • 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
    • C08G18/2081—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
    • C08G18/70—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
    • C08G18/70—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
    • C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine 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
    • C08G18/77—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
    • C08G18/798—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing urethdione 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
    • C08G2101/00—Manufacture of cellular products
    • 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
    • C08G2150/00—Compositions for coatings
    • C08G2150/60—Compositions for foaming; Foamed or intumescent coatings

Definitions

  • the invention relates to a catalyst component for isocyanate modification and a method for modifying isocyanates in the presence of this catalyst component.
  • the invention also relates to modified isocyanates themselves and their use for the production of polyurethane bodies or coatings and the polyurethane bodies or coatings themselves.
  • the invention also relates to one- or two-component systems comprising the modified isocyanates.
  • the oligo- or polymerisation of isocyanates in particular with the formation of higher molecular weight oligomer mixtures with uretdione (“dimer”), isocyanurate (“trimer”) and / or iminooxadiazinedione (“asymmetric trimer”) structures in the molecular structure, has been known for a long time.
  • the oligo- or polymerization of isocyanates is based in principle on the same chemical reactions. The reaction of a smaller number of isocyanates with one another is known as oligomerization. The conversion of a large number of isocyanates is known as polymerization.
  • the oligomerization or polymerization of isocyanates described above is referred to collectively as isocyanate modification or modification of isocyanates.
  • modified polyisocyanates contain free NCO groups, which may also have been temporarily deactivated with blocking agents, they are extremely valuable starting materials for the production of a large number of polyurethane plastics and coating agents.
  • EP 1 170 283 A2 discloses a process for the preparation of polyisocyanurates, using unstable catalysts in the isocyanate environment in order to avoid stopping the catalysts with inhibitors.
  • WO 2015/124504 Al and WO 2017/029266 Al describe very stable ammonium salts in which the charge-carrying nitrogen atom is part of a ring system.
  • these compounds have the disadvantage that they cannot be incorporated into isocyanate-functional compounds and therefore remain as migratory impurities in the final process product, for example a polyurethane plastic or a polyurethane coating, and later give rise to undesirable effects such as fogging etc.
  • the invention was therefore based on the object of providing a catalyst component for isocyanate modification that can be easily prepared from inexpensive starting materials and that has high catalytic activity and selectivity with good catalyst stability and low tendency to form troublesome by-products in isocyanate modification processes.
  • a catalyst component for isocyanate modification comprising at least one cyclic ammonium salt with a cation of the formula I, (Formula I), where
  • Y for a linear or branched, optionally interrupted by heteroatoms from the series oxygen, sulfur, nitrogen and aromatic rings, optionally containing further rings, C2- which is substituted in the 2-position to the charge-carrying nitrogen atom by a hydroxyl group and optionally carrying further substituents C2o segment and the N-position substituents R 1 and R 2 either independently of one another represent identical or different, substituted or unsubstituted, optionally branched, aliphatic C1-C20 radicals, aromatic C6-C20 radicals or araliphatic C7-C20 radicals or the N-position substituents R 1 and R 2 form a ring segment X with one another for which the same or different definition given above for Y applies, with the proviso that X has a hydroxy group in the 2-position to the charge-carrying nitrogen atom as a substituent or has no hydroxy group in the 2-position to the charge-carrying nitrogen atom as a substituent.
  • the charge-bearing nitrogen atom in Formula I is presently no part of the "further rings" which is the C 2 -C 2 o-segment of the cation of formula I may optionally have. In other words, the charge-carrying nitrogen atom in formula I is not a bridgehead atom of a tricycle.
  • Y stands for a C 4 -C 6 alkylene chain segment which is substituted in the 2-position to the charge-carrying nitrogen atom by a hydroxyl group and optionally carries further substituents.
  • R 1 and R 2 independently of one another represent identical or different Ci-Cs-alkyl substituents or identical or different benzyl radicals, optionally substituted on the aromatic nucleus, preferably identical or different C I -C ⁇ - alkyl substituents and particularly preferably identical or different, linear construction Ci C ⁇ - alkyl substituents.
  • R 1 and R 2 form a ring segment X with one another, where X is a C 4 -C 6 alkylene chain segment optionally bearing further substituents, with the proviso that X is substituted by a hydroxyl group in the 2-position to the charge-bearing nitrogen atom is or is not substituted by a hydroxyl group in the 2-position to the charge-carrying nitrogen atom.
  • segment Y and / or the ring segment X are linear.
  • only Y has a hydroxyl group.
  • X and Y in formula I can preferably stand independently of one another for optionally substituted alkylene groups, C 4 -C 6 alkylene chains being preferred, in particular in both N-centered rings, and at least one of the two substituents X and / or Y carrying an OH group.
  • the C 4 -C 6 alkylene chains are preferably constructed linearly.
  • the present invention therefore also provides a process for the preparation of the catalyst components according to the invention, comprising the steps a) reaction of an optionally cyclic secondary amine R ', R 2 NH, in which R 1 and R 2 have the same substituents as in formula I stand, b) optionally in the presence of a solvent c) with epoxy-functional haloalkanes to form the quaternary ammonium halides according to the invention, which optionally can then be converted into ammonium compounds with any other anion in a step d) by exchanging the halogen atom.
  • JP 2012056897 describes the synthesis of cyclic, quaternary ammonium salts which have a hydroxy function on the ring by reaction of OH-functional, secondary, cyclic amines with alpha, omega-dihaloalkanes in poor yields.
  • the disadvantage here is that the OH-functional, secondary, cyclic amines required for this are significantly more difficult to obtain commercially than the OH-free basic substances such as pyrrolidine or piperidine, while the haloalkyloxiranes to be used in the synthesis according to the invention are simply oxidized (epoxidized). technically readily available or easily producible halogen olefins of suitable structure are easily accessible (see embodiment 1 of the present invention).
  • Hal stands for chlorine, bromine or iodine, preferably for chlorine or bromine, particularly preferably for chlorine.
  • reaction products with an OH-functional 5-ring segment are accessible from 1,2-epoxy-4-haloalkanes. Only the cations are mentioned below (IPAC names were generated with the program BioVia / Draw, MDL.Draw.Editor 16.1.0.693): 1,1-Dimethylpyrrolidin-1-ium-3-ol, 1,1-Diethylpyrrolidin-1 -ium-3-ol, l, l-dibutylpyrrolidin-l-ium-3-ol, 5-
  • reaction products with an OH-functional 6-ring segment are: l, l-dimethylpiperidin-l-ium-3-ol, l, l-diethylpiperidin-l-ium- 3-ol, 1,1-dibutylpiperidin-l-ium-3-ol, 5-azoniaspiro [4.5] decan-9-ol, 6-azoniaspiro [5.5] undecan-4-ol, 6- azoniaspiro [5.6] dodecan 4-ol, 4,6,6-trimethylspiro [2-azoniabicyclo [2.2.2] octane-2, r-azinan-l-ium] -3'-ol, 3-oxa-6-azoniaspiro [5.5] undecane 10-ol, 3-methyl-3-aza-6-azoniaspiro [5.5] undecan-10-ol and 6,9-diazoniadispiro [5.2.59.
  • all structure types known to be catalytically active towards isocyanates can be used as anions in the compounds of the formula I; preference is given to hydroxide, alkanoate, carboxylate, heterocycles with at least one negatively charged nitrogen atom in the ring, in particular azolate, imidazolate, triazolate , Tetrazolate, fluoride, hydrogen difluoride, higher polyfluorides or mixtures of these (adducts of more than one equivalent of HF to compounds containing fluoride ions), the fluorides, hydrogen difluorides and higher polyfluorides according to the invention leading to products with a high content of iminooxadiazinedione groups.
  • the catalyst component according to the invention is particularly suitable for isocyanate modification, since in particular there it shows a high catalytic activity and selectivity combined with good catalyst stability and a low tendency to form troublesome by-products.
  • the present invention therefore also provides a process for modifying isocyanates, in which at least one organic isocyanate with an NCO functionality> 1 is oligomerized in the presence of a catalyst component, characterized in that the catalyst component has at least one cyclic ammonium salt with a cation of the formula I, (Formula I), where
  • Y for a linear or branched, optionally interrupted by heteroatoms from the series oxygen, sulfur, nitrogen and aromatic rings, optionally containing further rings, C2- which is substituted in the 2-position to the charge-carrying nitrogen atom by a hydroxyl group and optionally carrying further substituents C2o segment stands and the N-position substituents R 1 and R 2 either independently represent the same or different, substituted or unsubstituted, optionally branched, aliphatic C1-C20 radicals, aromatic C6-C20 radicals or araliphatic C7-C20 radicals, or the N positions
  • Substituents R 1 and R 2 with one another form a ring segment X for which the same or different definition given above for Y applies, with the proviso that X has a hydroxy group in the 2-position to the charge-bearing nitrogen atom or none in the 2-position to the charge-bearing nitrogen atom has a hydroxyl group as a substituent.
  • the catalysts of the invention can be used individually or in any desired mixtures with one another.
  • the solutions of quaternary ammonium hydroxides in various alcohols, depending on the pKa value of the base and the alcohol used are partly or completely as ammonium salts with alcoholate anion. This equilibrium can be shifted entirely to the side of complete alcoholate formation by removing the water of reaction resulting from this reaction, whereby in individual cases the ring-bound OH function can also be involved (betaine formation).
  • Suitable methods for removing water are all the methods known for this purpose from the literature, in particular azeotropic distillation, if necessary with the aid of a suitable entrainer.
  • the oligomerization is carried out in the presence of a solvent.
  • Examples include: pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), 2-methylpentane-1,5-diisocyanate (MPDI), 2,4,4-trimethyl-1,6-hexane diisocyanate and 2,2,4-trimethyl-1 , 6-hexane diisocyanate (TMDI), 4-isocyanatomethyl-l, 8-octane diisocyanate (nonane triisocyanate, NTI), 3 (4) -isocyanatomethyl-l-methylcyclohexyl isocyanate (IMCI), isophorone diisocyanate (IPDI), 1,3 and 1,4 -Bis (isocyanatomethyl) benzene (XDI), 1,3- and 1,4-bis (isocyanatomethyl) cyclohexane (H 6 XDI), norbornane diisocyanate (NBDI), 2,4- and 2,6-toly
  • Aromatic diisocyanates ie diisocyanates in which both NCO groups are bonded to an sp 2 -hybridized carbon atom, or aliphatic diisocyanates, ie diisocyanates in which both NCO groups are bonded to an sp 3 -hybridized carbon atom, are preferred.
  • PDI, HDI, MPDI, TMDI, NTI, IPDI, IMCI, XDI, H 6 XDI, MDI, TDI or NBDI are particularly preferred.
  • HDI, PDI or IPDI are very particularly preferred.
  • the amount of the catalyst to be used in the process according to the invention depends primarily on the organic isocyanate used and the desired reaction rate and is preferably between> 0.001 and ⁇ 5 mol%, preferably between> 0.002 and ⁇ 2 mol%, based on the total the amounts of the isocyanate used and the catalyst.
  • the catalyst can be used undiluted or dissolved in solvents. All compounds that do not react with the catalyst and are able to dissolve it to a sufficient extent can be used as solvents, e.g. halogenated, aliphatic or aromatic hydrocarbons, alcohols, ketones, esters and ethers. Alcohols are preferably used.
  • the process according to the invention can be carried out in the temperature range from 0 ° C to + 250 ° C, preferably 20 ° C to 200 ° C, particularly preferably 40 ° C to 150 ° C, and at any degree of conversion, preferably after 5 to 80%, particularly preferably 10 up to 60% of the isocyanate used have been reacted, interrupted.
  • unreacted organic isocyanate is separated off by any process of the prior art, for example by (thin-layer) distillation or extraction, and preferably then reused.
  • hydroxy-functional ammonium salts in which the charge-carrying nitrogen atom is not part of a ring system (cf., for example, EP 10589), surprisingly no significant decrease in catalytic activity is observed when using the catalysts of the invention, even at higher reaction temperatures.
  • the catalysts according to the invention are substantially more stable in the organic isocyanate to be converted than the derivatives of the prior art known from the literature.
  • the oligomerization can be carried out continuously, for example in a tubular reactor.
  • the present invention also provides a modified isocyanate, obtainable or produced by the process according to the invention.
  • the catalyst component according to the invention reacts via the OH group with the formation of a covalent bond in the modified isocyanate.
  • the present invention thus likewise provides a modified isocyanate containing at least one structural element covalently bonded via the OH group of the cation of the formula I from the catalyst component according to the invention as a urethane and / or allophanate group.
  • the embodiments of the cation of the formula I mentioned above as being preferred for the catalyst component are also preferred embodiments of the modified isocyanate according to the invention.
  • polyisocyanates of the so-called isocyanate trimer type i.e. containing isocyanurate and / or iminooxadiazinedione structures
  • isocyanate dimers uretdione groups
  • the products or product mixtures obtainable by the process according to the invention are therefore versatile starting materials for the production of, optionally foamed (s), plastics (s) as well as paints, coating agents, adhesives and additives.
  • the modified isocyanates according to the invention are therefore used for production of foamed or unfoamed plastics and paints, coating agents, adhesives and aggregates are another object of the present invention.
  • the catalysts of the invention for the production of optionally foamed polyurethane bodies are under proportionate polyisocyanurate formation (so-called PIR foams), since they can practically not migrate from the finished products, which is important from the point of view of freedom from migration (leaching, fogging).
  • polyurethane bodies obtainable or produced by reacting at least one monomeric diisocyanate and / or polyisocyanate with at least one polyol component in the presence of the catalyst component according to the invention are a further subject of the invention.
  • PIR foams are preferred.
  • the products of the process according to the invention can be used as such or in conjunction with other isocyanate derivatives of the prior art, such as uretdione, biuret, allophanate, isocyanurate and / or urethane groups containing polyisocyanates, the free NCO groups of which have optionally been deactivated with blocking agents , can be used.
  • isocyanate derivatives of the prior art such as uretdione, biuret, allophanate, isocyanurate and / or urethane groups containing polyisocyanates, the free NCO groups of which have optionally been deactivated with blocking agents , can be used.
  • a one- or two-component system comprising a component A), comprising at least one modified isocyanate according to the invention, and a component B), comprising at least one NCO-reactive compound, and a coating, obtainable or produced by, optionally under the action of heat and / or in the presence of a catalyst, curing of a one- or two-component system according to the invention, but also the substrates coated with at least one one- or two-component system according to the invention, optionally cured under the action of heat.
  • modified isocyanates according to the invention are also found in the covalently bonded catalyst component according to the invention in the cured or foamed polyurethane bodies, a composite component comprising a material which is at least partially connected to a polyurethane body according to the invention or a coating according to the invention is also the subject of the invention.
  • modified isocyanate has the meaning defined at the outset and preferably stands for a polyisocyanate which, on a statistical average, has at least 1.5 NCO groups.
  • Mol% data were determined by NMR spectroscopy and, unless stated otherwise, always relate to the sum of the NCO secondary products.
  • the measurements were carried out on DPX 400 and DRX 700 strength of Fa. Jumpers to about 5% ( 'H-NMR), or approximately 50% (13 C-NMR) in dry sample C E D E at a Frequency of 400 or 700 MHz ('H-NMR) or 100 or 176 MHz ( 13 C-NMR).
  • ppm scale small amounts of tetramethyl silane in the solvent with 0 ppm 'H-NMR-chem. Shift used.
  • the dynamic viscosities were determined at 23 ° C. using a VT 550 viscometer from Haake in accordance with DIN EN ISO 3219: 1994-10. Measurements at different shear rates ensured that the flow behavior of the polyisocyanate mixtures according to the invention described, as well as that of the comparison products, corresponds to that of ideal Newtonian liquids. The specification of the shear rate can therefore be omitted.
  • the NCO content was determined by titration in accordance with DIN EN ISO 11909: 2007-05.
  • the residual monomer content was determined by gas chromatography in accordance with DIN EN ISO 10283: 2007-11 with an internal standard.
  • the diisocyanates used are products from Covestro AG, D-51365 Leverkusen, all other commercially available chemicals were obtained from Aldrich, D-82018 Taufmaschinen.
  • the optimal catalyst concentration for the isocyanate trimerization was determined in preliminary tests at 60 ° C with HDI (see Example 2) and the concentration of the catalyst solution was adjusted by diluting with 2-EH so that no or only negligibly small gel particles were formed during the addition the catalyst solution to the HDI was observed.
  • An overview of the catalysts used can be found in Table 1.
  • Table 1 Overview of the catalysts produced (the catalyst concentration relates to the active ingredient (cation and anion)) WO 2021/122508 PCT / EP2020 / 086087
  • the work-up was carried out by vacuum distillation in a thin-film evaporator, type Kurzwegverdampfer (KWV), with an upstream pre-evaporator (VV) (distillation data: pressure: 0.08 +/- 0.04 mbar, VV temperature: 120 ° C, HV temp .: 140 ° C), with unreacted monomer being separated as distillate and the low-monomer polyisocyanate resin as bottom product (starting run).
  • the polyisocyanate resin was separated and the distillate was collected in a second flat-joint stirrer, which is constructed identically to the first, and made up to the initial amount (1000 g) with freshly degassed HDI. It was then catalyzed again and the procedure described at the beginning. This procedure was repeated several times, if necessary with variation of the reaction temperature (experiments A, B, C, etc.). The results are shown in Table 2.
  • distillate composition was determined by gas chromatography. In no case could decomposition products of the catalyst cation be detected (detection limit approx. 20 ppm).
  • Stopper 1: dibutyl phosphate, 2: toluenesulphonic acid, 40% in 2-PrOH, 3: dodecylbenzenesulphonic acid, 70% in 2-PrOH
  • the resins obtained were all light-colored, clear, viscous liquids with no perceptible amine odor and no extractable catalyst by-products or secondary products.
  • fluorine-containing catalysts mixtures of isocyanurate and iminooxadiazinedione resulted in addition to a little uretdione.
  • the catalysts with oxygen-containing anions produce products of the isocyanurate type, with the alcohol (2-EH) used as catalyst solvent being completely converted to the allophanate, as is also the case when the fluorine-containing catalysts are used.
  • the recovered HDI is free from impurities that result from the decomposition of the catalyst cation and can be reused without problems in the same or in different processes.

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

Abstract

La présente invention concerne un composant de catalyseur pour la modification d'isocyanate, comprenant au moins un sel d'ammonium cyclique comportant un cation de formule I où Y est un segment en C2-C20 linéaire ou ramifié qui est substitué par un groupe hydroxyle en position 2 au niveau de l'atome d'azote porteur de charge et porte facultativement d'autres substituants et est facultativement interrompu par des hétéroatomes du groupe de l'oxygène du soufre et de l'azote et des cycles aromatiques et facultativement d'autres cycles, et les substituants liés à N R1 et R2 sont indépendamment des radicaux en C1-C20 aliphatiques, facultativement ramifiés, substitués ou non substitués, identiques ou différents, des radicaux en C6-C20 aromatiques ou des radicaux en C7-C20 araliphatiques ou les substituants liés à N R1 et R2 forment un segment de cycle X l'un avec l'autre pour lequel la même définition ou une définition différente donnée ci-dessus pour Y est applicable, à condition que X comporte un groupe hydroxyle en tant que substituant en position 2 au niveau de l'atome d'azote porteur de charge ou ne comporte pas de groupe hydroxyle en tant que substituant en position 2 au niveau de l'atome d'azote porteur de charge.
EP20824549.8A 2019-12-19 2020-12-15 Composant de catalyseur pour la modification d'isocyanate Withdrawn EP4077436A1 (fr)

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EP4166589A4 (fr) * 2020-09-25 2024-03-06 Wanhua Chemical Group Co., Ltd Composition de polyisocyanate contenant un isocyanurate ayant une chromaticité stable, et procédé de préparation associé
US20250019483A1 (en) * 2021-11-16 2025-01-16 Basf Se Preparation of polyisocyanates containing iminooxadiazinedione groups and their use
WO2023138938A1 (fr) 2022-01-18 2023-07-27 Basf Se Préparation de polyisocyanates contenant des groupes iminooxadiazinedione et utilisation associée
EP4414400A1 (fr) 2023-02-09 2024-08-14 Covestro Deutschland AG Polyisocyanates à propriétés améliorées
WO2024165361A1 (fr) 2023-02-09 2024-08-15 Basf Se Préparation de polyisocyanates contenant des groupes iminooxadiazinedione et leur utilisation
CN117402066A (zh) * 2023-10-17 2024-01-16 郑州中科新兴产业技术研究院 一种无水高纯非四正烷基氟化铵的制备方法

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DE946708C (de) 1953-10-16 1956-08-02 Basf Ag Verfahren zur Herstellung von ª‰-Oxypyrrolidinen
CA1112243A (fr) 1978-09-08 1981-11-10 Manfred Bock Procede de fabrication de polyisocyanates contenant des groupements isocyanurates, et utilisation de ces produits
DE19734048A1 (de) 1997-08-06 1999-02-11 Bayer Ag Verfahren zur Herstellung von Polyisocyanaten, damit hergestellte Polyisocyanate und deren Verwendung
DE10033099A1 (de) * 2000-07-07 2002-01-17 Degussa Verfahren zur Herstellung von geruchsarmen und lagerstabilen monomerhaltigen Polyisocyanuraten aus Isophorondiisocyanat
DE10123416A1 (de) * 2001-05-14 2002-11-21 Bayer Ag Verfahren zur Herstellung von Polyisocyanaten
JP5608019B2 (ja) 2010-09-09 2014-10-15 大塚化学株式会社 環状第４級アンモニウム塩、それを用いた電解質組成物、及び該電解質組成物を用いた電気化学デバイス
WO2015124504A1 (fr) 2014-02-18 2015-08-27 Bayer Materialscience Ag Procédé de modification d'isocyanates en utilisant des sels d'ammonium spirocycliques comme catalyseur
EP3085720A1 (fr) * 2015-04-21 2016-10-26 Covestro Deutschland AG Matieres synthetiques de polyisocyanurate a modification hydrophile et leur procede de production
US10167358B2 (en) 2015-08-17 2019-01-01 Covestro Deutschland Ag Process for modifying isocyanates with use of cyclic ammonium salts as catalyst
CN105151266A (zh) 2015-08-17 2015-12-16 南通航运职业技术学院 一种基于变频技术的泵阀联控液压舵机装置及控制方法

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US20230023659A1 (en) 2023-01-26
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CN114787215A (zh) 2022-07-22

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