EP4658695A1 - Phosphanylcarboxamides à terminaison isocyanate et réactifs vis-à-vis des isocyanates ainsi que leur production et leur utilisation pour la production de polyisocyanurates et polyuréthanes phosphoreux - Google Patents

Phosphanylcarboxamides à terminaison isocyanate et réactifs vis-à-vis des isocyanates ainsi que leur production et leur utilisation pour la production de polyisocyanurates et polyuréthanes phosphoreux

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Publication number
EP4658695A1
EP4658695A1 EP24702155.3A EP24702155A EP4658695A1 EP 4658695 A1 EP4658695 A1 EP 4658695A1 EP 24702155 A EP24702155 A EP 24702155A EP 4658695 A1 EP4658695 A1 EP 4658695A1
Authority
EP
European Patent Office
Prior art keywords
isocyanate
compounds
phenylene
phosphorus
pca
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP24702155.3A
Other languages
German (de)
English (en)
Inventor
Sivathmeehan YOGENDRA
Rolf Albach
Lutz Boehnke
Frank Richter
Jan Weigand
Kai Schwedtmann
Jan Haberstroh
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Original Assignee
Covestro Deutschland AG
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Filing date
Publication date
Application filed by Covestro Deutschland AG filed Critical Covestro Deutschland AG
Publication of EP4658695A1 publication Critical patent/EP4658695A1/fr
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
    • C07F9/4808—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof the acid moiety containing a substituent or structure which is considered as characteristic
    • C07F9/4858—Acids or derivatives containing the structure -C(=X)-P(XR)2 or NC-P(XR)2 (X = O, S, Se)
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/225—Catalysts containing metal compounds of alkali or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
    • C08G18/3889—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having nitrogen in addition to phosphorus
    • 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
    • C08G18/77—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
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8054—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/38
    • C08G18/8058—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/38 with compounds of C08G18/3819
    • 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
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

Definitions

  • Isocyanate-reactive and isocyanate-terminated phosphanylcarboxamides and their preparation and use for the production of phosphorus-containing polyurethanes and polyisocyanurates
  • the present invention relates to novel monomers and prepolymers for the production of plastics which can be used, for example, for the production of flame-retardant polyurethanes or polyurethane/polyisocyanurate polymers (hereinafter referred to individually or jointly as PUR/PIR).
  • PUR/PIR flame-retardant polyurethanes or polyurethane/polyisocyanurate polymers
  • PUR/PIR foams are often used as insulation materials and the use as foam in general increases the fire risk due to the large surface area per unit mass. In many areas where PUR/PIR foams are used, fire protection equipment using added flame retardants is therefore essential.
  • Halogen-containing compounds as well as nitrogen and phosphorus compounds are preferred as flame retardants.
  • Compounds containing halogens and low-valent phosphorus compounds are considered typical representatives of flame retardants that extinguish flames.
  • Higher-valent phosphorus compounds are said to cause a catalytic splitting of the polyurethanes and thus lead to the formation of a solid, polyphosphate-containing, charred surface. This intumescent layer protects the material from further combustion.
  • Low molecular weight flame retardant additives such as tris(2-chloroisopropyl) phosphate (TCPP) or triethyl phosphate (TEP) are chemically unbound in the polymer matrix and can act as plasticizers, affecting the product and leaching out over time.
  • TCPP tris(2-chloroisopropyl) phosphate
  • TEP triethyl phosphate
  • phosphorus-containing flame retardant additives are used for the production of inherently flame-retardant polymers.
  • hydroxy-terminated organic phosphonates or phosphates which are available under the trade names Exolit® OP560 or Nofia® OLIOOO, can be used to produce phosphorus-containing polyurethanes and polyurethane/polyisocyanurates.
  • the phosphonate- or phosphate-containing monomers or prepolymers are incorporated into the polyurethane via a polyaddition, which influences the polyurethane-characteristic structure and thus the properties of the polyurethane.
  • a class of organic phosphorus-containing compounds that has not yet been used commercially are phosphanylcarboxamides ( Figure 1, I) and phosphorus(III) acid carboxamides ( Figure 1, II).
  • the groups show a strong structural analogy to the urea, urethane, biuret and isocyanurate binding motifs found in polyurethanes and polyisocyanurate.
  • the 1,4-dioxane adduct Na(OCP)(l, 4-dioxane) x obtained in this way contains non-reproducible amounts of 1,4-dioxane, so that the 1,4-dioxane content of each product batch has to be quantified by NMR spectroscopy. Due to these disadvantages, the synthesis route via the adduct consisting of Na(OCP)(l,4-dioxane) x is not well suited for the production of larger quantities of the compounds with structures I or II, and a simplified production process would be of great interest.
  • phosphanylcarboxamide- or phosphorus(III) acid carboxamide-containing structures as reactive, phosphorus-containing building blocks, e.g. for incorporation into polyurethanes or polyisocyanurates, has not yet been disclosed.
  • monomers for the production of plastics, e.g. as a reactant for the polyaddition reaction with the NCO function of an isocyanate compound in the formation of polyurethane or polyisocyanurate
  • compounds that are of particular interest are those that firstly have one or more phosphanylcarboxamide structures and/or phosphoric acid carboxamide structures and secondly have at least two functional groups that are isocyanate-reactive (“NCO-reactive groups”).
  • PCA isocyanate-reactive
  • the invention also relates to the use of PCAs as monomers for the production of phosphorus-containing prepolymers and polymers, e.g. PUR/PIR.
  • the invention further relates to prepolymers, polymers and NCO-terminated compounds which can be prepared using PCA compounds and polyfunctional isocyanates.
  • the invention further relates to novel processes for preparing the PCA, wherein a) a Na(OCP) reaction solution is reacted with an amine in the presence of a Brönsted acid and optionally an oxidizing agent in a multi-step synthesis ( Figure 4a) or alternatively b) red phosphorus, sodium, organic carbonates, tert-butanol, amines are reacted in the presence of a Brönsted acid and optionally an oxidizing agent in a one-pot reaction (Figure 4b).
  • X is an NCO-reactive group
  • R is an organyl radical (optionally substituted with heteroatoms).
  • PCA compounds which are selected from the group of compounds consisting of PCA compounds with the structures VI and VII, and wherein the organyl radicals R are preferably selected from the group consisting of trimethylene, Tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, optionally heteroatom-containing cyclohexylene, phenylene, diphenylene, dimethylphenylene, 2-methylpentamethylene, 2,2,4-trimethylhexamethylene, dodecamethylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, 5-(l-methylene-(l,3,3-trimethylcyclohexane)), all regioisomers of methylenebiscyclohexylene, all regioisomers of methylenebisphenylene, methylenebis-(3,3'-dimethylcyclohexane)),
  • the organyl radical R is very particularly preferably selected from the group consisting of trimethylene, tetramethylene, pentamethylene, hexamethylene, methylene-4,4'- or 2,4'- or 2,2'-bisphenylene and their isomer mixtures.
  • R is selected from the group consisting of trimethylene, tetramethylene, pentamethylene, hexamethylene, methylene-4,4'- or 2,4'- or 2,2'-bisphenylene and their isomer mixtures and
  • PCA isocyanate-reactive compounds
  • the invention further relates to new processes for producing PCA, whereby a) a Na(OCP) reaction solution is reacted with an amine in the presence of a Brönsted acid and optionally an oxidizing agent in a multi-stage synthesis ( Figure 4a) or b) alternatively, red phosphorus, sodium, organic carbonates, tert-butanol, naphthalene, amines can be reacted in the presence of a Brönsted acid and optionally an oxidizing agent in a one-pot reaction ( Figure 4b).
  • a) Compounds VI and VII can be prepared using a newly developed process via a Na(OCP) ("sodium phosphaethynolate”) reaction solution according to the following reaction scheme:
  • Figure 4a Reaction scheme for the preparation of PCA VI and VII via a Na(OCP) reaction solution.
  • the synthesis includes the following steps:
  • a 1,4-dioxane-free, storage-stable Na(OCP) reaction solution is prepared in a solvent ( Figure 4a).
  • the Na(OCP) reaction solution is strongly basic due to the tBuONa co-product, which promotes storage stability. Several Filtration steps and solvent changes are not necessary. Alternatively, the Na(OCP) reaction solution can be directly processed further without further processing.
  • An ether is preferably used as the solvent, with ethylene glycol dimethyl ether being particularly preferred.
  • Dioxane is preferably not used as the solvent, which means that the Na(OCP) remains in solution and does not precipitate, unlike previously known methods.
  • the OCP anion content can be quantified during and/or after the reaction using IR spectroscopy.
  • the Na(OCP) reaction solution is then reacted with a suitable amine (X) m - R-(NH 2 ) n in the presence of a suitable Brönsted acid to give PCA of structure VI.
  • a suitable Brönsted acid is added in excess.
  • the corresponding hydrochloride of the amine can also be used.
  • the PCA can be prepared by the direct reaction of red phosphorus, sodium, organic carbonates, tert-butanol, naphthalene, amines, a Brönsted acid and, if necessary, an oxidizing agent (Figure 4b) in a one-pot reaction ( Figure 4b).
  • the amine used for processes a) and b) is selected from the group of compounds consisting of organic amines of the structural formula (X) m -R-(NH 2 ) n , where the substituent R is selected from organyl radicals (optionally substituted by heteroatoms), preferably from the group consisting of trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene optionally heteroatom-containing cyclohexylene, phenylene, diphenylene, dimethylphenylene, 2-methylpentamethylene, 2,2,4-trimethylhexamethylene, dodecamethylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, 5-(l-methylene-(l,3,3-trimethylcyclohexane)), all regioisomers of methylenebiscyclohexylene,
  • the organic carbonate ( Figures 4a / 4b: “Org. Carbonate”) is preferably selected from the group of compounds consisting of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate, glycerol carbonate and mixtures thereof.
  • Brönsted acid is one or more acids, in particular selected from the group consisting of organic carboxylic acids, in particular acetic acid and/or formic acid, dihydrogen carbonate, sodium hydrogen carbonate, phosphoric acid, sodium dihydrogen phosphate,
  • the oxidizing agent is an oxygen transfer reagent that is able to convert phosphanylcarboxamides VI to phosphoric acid carboxamides VII.
  • Particularly suitable for this purpose are hydrogen peroxide (H 2 O 2 ), oxygen (O 2 ), ozone (O3), peroxyacetic acid, Peroxysulphuric acid, nitrous oxide (N 2 O), nitrogen dioxide (NO 2 ), organic peroxides such as tert-butyl peroxide, peroxybenzoic acid, chloroperoxybenzoic acid, pyridine-N-oxide. Hydrogen peroxide (H 2 O 2 ) or oxygen (O 2 ) is particularly preferred.
  • the compound PCA can be obtained as a pure substance after processing. Isolation is achieved, for example, by removing all volatile components from the reaction mixture in a vacuum, followed by extraction of the residue if necessary. Alternatively, the residue can be washed with water beforehand.
  • the PCAs can be used to prepare NCO-terminated phosphanylcarboxamides of structures VIII, IX and X ( Figure 5), or their equivalent compounds with oxidized phosphorus.
  • the substituted R 1 is an organyl radical (optionally substituted by heteroatoms) and is selected from the group consisting of the substituents hydrogen, methyl, ethyl, butyl, propyl, pentyl, hexyl, heptyl, oxytyl, phenyl, tolyl, cyclohexyl and cyclopentyl, and the substituents R are independently selected organyl radicals (optionally substituted by heteroatoms) and are preferably selected from the group consisting of from the substituents methylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, optionally heteroatom-containing cyclohexylene,
  • the isocyanate-terminated phosphanylcarboxamides of the formulas VIII, IX and X preferably have an average molecular weight determined by gel permeation chromatography of at least 300 g/mol and at most 10,000 g/mol, particularly preferably of at least 300 g/mol and at most 2000 g/mol.
  • the isocyanate-terminated phosphanylcarboxamides of the formula VIII, IX or X according to the invention are particularly preferably liquid and have a dynamic viscosity at 23°C, determined with a cone-plate viscometer, of at most 30,000 mPa*s, particularly preferably of at most 20,000 mPa*s.
  • phosphanylcarboxamides VI or phosphorus(III) acid carboxamides VII can be reacted with a (molar) excess of at least one di- or polyisocyanate, optionally in the presence of a catalyst, to isocyanate-terminated phosphanylcarboxamides VIII, IX or X and VIII,
  • IX or X equivalent compounds are reacted with oxidized phosphorus.
  • at least 2 times the amount of at least one di- or polyisocyanate compared to the phosphanylcarboxamide or phosphorus(III) acid carboxamide is used.
  • the reaction can be carried out in solvent or solvent-free (e.g. with excess diisocyanate or polyisocyanate as (reactive) diluent).
  • the product is obtained after distilling off the solvent or the excess diisocyanate or polyisocyanate.
  • R is selected from the group consisting of trimethylene, tetramethylene, pentamethylene, hexamethylene, methylene-4,4'- or 2,4'- or 2,2'-bisphenylene and their isomer mixtures;
  • polyisocyanates are preferably used for the production of isocyanate-terminated phosphanylcarboxamides VIII, IX and X:
  • MDI Methylene diphenyl diisocyanate
  • TDI tolyl diisocyanate
  • NDI naphthalene diisocyanate
  • HDI hexamethylene diisocyanate
  • PDI pentramethylene diisocyanate
  • IPDI isophorone diisocyanate
  • H12MDI methylenedicyclohexyl diisocyanate
  • the molar ratio of isocyanate groups to isocyanate-reactive groups of the compounds having the structures VI or VII in the reaction mixture for preparing the isocyanate-terminated phosphanylcarboxamides VIII, IX or X is > 1 and is preferably at least 2:1 and at most 40:1, particularly preferably at least 2:1 and at most 10:1.
  • the excess isocyanate can either remain in the product mixture as a reactive diluent or be distilled off.
  • the isocyanate-terminated phosphanylcarboxamides VIII, IX and X prepared in this way have in particular an average molecular weight determined by gel permeation chromatography of at least 300 g/mol and at most 10,000 g/mol, particularly preferably of at least 300 g/mol and at most 2000 g/mol. They are very particularly preferably liquid and have a dynamic viscosity determined with a cone-plate viscometer of at most 30,000 mPa*s, particularly preferably of at most 20,000 mPa*s at 23 °C.
  • nitriles such as acetonitrile, propionitrile and ethers such as tetrahydrofuran, diethyl ether and dioxane are preferably used as solvents.
  • the same polyisocyanates such as methylenediphenyl diisocyanate (MDI), tolyl diisocyanate (TDI), naphthalene diisocyanate (NDI), hexamethylene diisocyanate (HDI), pentramethylene diisocyanate (PDI), isophorone diisocyanate (IPDI), methylenedicyclohexyl diisocyanate (H12MDI) and their oligomers and prepolymers with which the phosphanylcarboxamide VI is reacted are particularly suitable as reactive diluents.
  • Lewis bases such as amine bases, in particular tertiary amines, particularly preferably triethylamine, are preferably used as catalysts. Alternatively, the reaction can also be carried out without a catalyst.
  • the di- and multifunctional PCAs with structures VI and VII as well as the isocyanate-terminated compounds VIII, IX and X can be used as monomers and prepolymers for the production of new phosphorus-containing polymers, in particular for the production of phosphorus-containing polyurethanes and polyisocyanurates.
  • the isocyanate-terminated compounds VIII, IX and X and their equivalents with oxidized phosphorus and their mixtures with polyisocyanates as reactive diluents can also be converted to PUR/PIR with corresponding isocyanate-reactive compounds, e.g. polyols.
  • the reactions can be carried out in the presence or absence of a suitable catalyst, with or without an additional solvent.
  • R is selected from the group consisting of trimethylene, tetramethylene, pentamethylene, hexamethylene, methylene-4,4'- or 2,4'- or 2,2'-bisphenylene and their isomer mixtures and
  • polyisocyanates i.e. isocyanates with an NCO functionality of > 2, alone or with other isocyanate-reactive reactants and, if necessary, other formulation components commonly used in polyurethane chemistry.
  • polyisocyanates i.e. isocyanates with an NCO functionality of > 2, alone or with other isocyanate-reactive reactants and, if necessary, other formulation components commonly used in polyurethane chemistry.
  • suitable polyisocyanates are 1,4-butylene diisocyanate,
  • 1,5-pentane diisocyanate 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,2,4- and/or 2,4,4-trimethylhexamethylene diisocyanate, the isomeric bis(4,4'-isocyanatocyclohexyl)methanes or their mixtures with any isomer content, 1,4-cyclohexylene diisocyanate, 1,4-phenylene diisocyanate, 2,4- and/or 2,6-toluene diisocyanate (TDI),
  • 1,5-naphthylene diisocyanate 2,2'- and/or 2,4'- and/or 4,4'-diphenylmethane diisocyanate (MDI) and/or higher homologues, 1,3- and/or l,4-bis-(2-isocyanato-prop-2-yl)-benzene (TMXDI), 1,3-bis-(isocyanatomethyl)benzene (XDI), and alkyl-2,6-diisocyanatohexanoates (lysine diisocyanates) with C1 to C6 alkyl groups.
  • MDI 2,2'- and/or 2,4'- and/or 4,4'-diphenylmethane diisocyanate
  • TXDI 1,3- and/or l,4-bis-(2-isocyanato-prop-2-yl)-benzene
  • XDI 1,3-bis-(isocyanatomethyl)benzene
  • mixtures of the isomers of diphenylmethane diisocyanate (“monomeric MDI”, abbreviated “mMDI”) and its oligomers (“oligomeric MDI”) are used.
  • mMDI diphenylmethane diisocyanate
  • oligomeric MDI oligomeric MDI
  • pMDI polymeric MDI
  • polyisocyanate component A) are mixtures of mMDI and/or pMDI with a maximum of up to 20% by weight, more preferably a maximum of 10% by weight, of other aliphatic, cycloaliphatic and in particular aromatic polyisocyanates known for the production of polyurethanes, very particularly TDI.
  • R is selected from organyl radicals (optionally substituted by heteroatoms), preferably selected from the group consisting of ethyl, butyl, propyl, pentyl, hexyl, isosorbide, methylenediphenyl, tolyl, aromatic radicals based on lignin, such as dimethoxyphenyl, organyl radicals based on furan and very particularly preferably selected from the group consisting of propyl, butyl and pentyl, hexyl, methylenediphenyl, tolyl, used to completely or partially replace the commonly used isocyanate component in PUR/PIR reaction mixtures.
  • the new polymers have intrinsic flame retardancy due to the built-in phosphorus and are therefore particularly suitable for applications where good and permanent flame resistance is important, e.g. PUR/PIR rigid foam applications in the construction industry.
  • PCA compounds and the polymers produced from them can also be used as additives for polymers, in particular as flame retardant additives.
  • Compounds with decomposition temperatures of > 150 °C are particularly suitable for this purpose, especially > 155 °C and ⁇ 250 °C. Examples
  • Red phosphorus (99%, amorphous powder), sodium (99%, rods in paraffin oil), ethylene carbonate (99%), diethyl carbonate (99%), tert-butanol (99.5%), triethylammonium hydrochloride (99+%), hexamethylene diisocyanate (HDI) (99%), 6-aminohexanol (98%), 1,6-
  • Diaminohexane dihydrochloride (99%), 5-aminopentanol (92%), 1,5-diaminopentane (99%), 1,4-diaminobutane dihydrochloride (99+%), 1,3-diaminopropane (99%), ethanolamine hydrochloride (99+%), diethylamine (99.5%), 4,4'-diaminodiphenylmethane (97%), meta-chloroperbenzoic acid (m-CPBA, 77+%), 1,4-diazabicyclo[2.2.2]octane (DABCO, 99+%), 1,4-butanediol (99%) and hydrogen peroxide (aqueous solution, 30%) were used without further purification.
  • Diaminophenylmethane dihydrochloride was prepared analogously by reacting the corresponding amino alcohols or amines with ethereal or aqueous HCl solution in suitable solvents.
  • the solvents 1,2-dimethoxyethane (DME), tetrahydrofuran (THF), 1,4-dioxane, diethyl ether (Et20), dichloromethane (CH2CI2) and acetonitrile ( CH3CN ) were distilled before use and stored under protective gas over molecular sieves (3 ⁇ : CH3CN, 4 ⁇ : DME, THF, 1,4-dioxane, Et20, CH2Q2).
  • the dioxane content of the individual batches was determined by NMR methods and elemental analysis.
  • Sodium sand was prepared by melting bare sodium pieces in xylene under protective gas and finely dispersing them with a KPG stirrer.
  • Example 1 - 4 The resulting beige suspension was filtered and the filter residue was washed with CH 3 CN or warm CH 3 CN.
  • the product crystallized from the concentrated filtrate at reduced temperature (eg -30 °C) or by adding suitable solvents such as diethyl ether (Et 2 O).
  • Et 2 O diethyl ether
  • Example 5a Example 8: The resulting beige suspension was filtered and the product was obtained as a white solid by Soxhlet extraction of the filter residue with CH 2 C1 2 and subsequent drying in vacuo.
  • Example 7 The resulting beige suspension was filtered, the filter residue was washed with CH 3 CN and the filtrate was dried in vacuo to obtain the product as a yellow oil.
  • Method 2 Starting from the salts of amines and amino alcohols and with a dioxane-free NaOCP reaction solution a) Preparation and quantification of a NaOCP reaction solution
  • Red phosphorus (3 g, 97 mmol, 1 eq.), naphthalene (620 mg, 5 mmol, 0.05 eq.) and sodium sand (6.68 g, 291 mmol, 3 eq.) were suspended in 420 mL DME and stirred with a KPG stirrer for 4 h at RT.
  • the resulting black suspension was cooled to 0 °C and 30 °C warm water was added. Cert-butanol (18.53 mL, 194 mmol, 2 eq.) was slowly added.
  • a NaOCP standard solution was prepared in DME/CH 3 CN (70/30) (purity and dioxane content of the NaOCP(l,4-dioxane)22 3 used were determined by NMR spectroscopy and elemental analysis).
  • the absorbance of the CO stretching vibration of the NaOCP (1760 cm 1 ) was determined in a thin-layer liquid cuvette by a transmission measurement. The method was validated by a standard addition method. For further samples, an aliquot of the reaction solution was taken, diluted and measured in the same way.
  • Example 5b Preparation of PCA-5 starting from the NaOCP reaction solution using the example of the synthesis of N,N’-(hexane-l,6-diyl)bis(phosphanylcarboxamide)
  • Example 8b Preparation of PCA-8 starting from the NaOCP reaction solution using the example of the synthesis of (N-(6-hydroxyhexyl)phosphinocarboxamide)
  • Red phosphorus 0.5 g, 16 mmol, 1 eq.
  • naphthalene 103 mg, 1 mmol, 0.05 eq.
  • sodium sand (1.14 g, 48 mmol, 3 eq.) were suspended in 200 mL DME and stirred for 12 h at RT.
  • the resulting black suspension was cooled to 0 °C and warm tert-butanol (3.1 mL g, 32 mmol, 2 eq.) was slowly added.
  • the grey suspension was stirred for one hour at RT, to 0 °C and a solution of ethylene carbonate (1.421 g, 16 mmol, 1 eq.) in 10 mL DME was added dropwise over 1 hour.
  • the green-yellow suspension was stirred overnight at RT.
  • the suspension turned light brown when stirred overnight.
  • the suspension was filtered and the pale brown filter residue was washed with CH 3 CN (3 x 5 mL).
  • the product was precipitated from the filtrate at -30 °C as a colorless solid.
  • Example 5c Preparation of PCA-5 in one step using the example of the synthesis of N,N’-(hexane-l,6-diyl)bis(phosphanylcarboxamide) (work-up by Soxhle extraction)
  • Red phosphorus 250 mg, 8 mmol, 1 eq.
  • naphthalene 52 mg, 0.4 mmol, 0.05 eq.
  • sodium sand 557 mg, 24 mmol, 3 eq.
  • the resulting black suspension was cooled to 0 °C and a solution of tert-butanol (1.55 mL, 16 mmol, 2 eq.) and diethyl carbonate (0.98 mL, 8 mmol, 1 eq.) in 15 mL DME was added dropwise.
  • the green-yellow suspension was stirred for 16 h at RT.
  • the NaOCP content of the supernatant yellow solution was determined by IR spectroscopy using a calibration curve.
  • the required amounts of 1,6-diaminohexanedihydrochloride and triethylammonium hydrochloride were determined according to the NaOCP concentration.
  • First 1,6-diaminohexanedihydrochloride (565 mg, 2.98 mmol, 0.37 eq.) and then triethylammonium hydrochloride (2.51 g, 18.25 mmol, 2.26 eq.) were rapidly added to the suspension with vigorous stirring.
  • the suspension quickly turns black upon addition of triethylammonium hydrochloride and changes color to brown-orange a few seconds after the end of the addition.
  • the suspension was stirred overnight at RT and then dried in vacuo to obtain a brown solid.
  • the product was obtained as a pale yellow solid by Soxhlet extraction with CH2Q2 and subsequent drying in vacuo.
  • Example 5d Preparation of PCA-5 in one step using the example of the synthesis of N,N '-(hexane-l,6-diyl)bis(phosphinocarboxamide)
  • Red phosphorus (7.03 g, 0.23 mol, 1 eq.), naphthalene (1.45 g, 0.4 mmol, 0.05 eq.) and sodium (15.7 g, 0.68 mol, 3 eq.) were suspended in 120 mL DME and stirred vigorously for 16 h at RT.
  • the resulting black suspension was cooled to 0 °C and a solution of tert-butanol (43.43 mL, 0.46 mol, 2 eq.) and diethyl carbonate (27.5 mL, 0.23 mol, 1 eq.) in 120 mL DME was added dropwise.
  • the green-yellow suspension was stirred for 16 h at RT.
  • the NaOCP content of the supernatant yellow solution was determined by IR spectroscopy using a calibration curve.
  • the required amounts of 1,6-diaminohexane dihydrochloride and triethylammonium hydrochloride were determined according to the NaOCP concentration.
  • To NaOCP suspension 0.538 M, 310 mL, 0.167 mol, 0.74 eq.
  • the suspension rapidly turns black upon addition of triethylammonium hydrochloride and changes color to brown-orange a few seconds after the end of the addition.
  • the suspension was stirred overnight at RT and then dried in vacuo to obtain a brown solid.
  • the dried suspension was washed with water and extracted by Soxhlet extraction with CH2Q2 to obtain the product PCA-5.
  • Bis(phosphinocarboxamide) (1 eq.) or hydroxy-R-phosphinocarboxamide (2 eq.) was dissolved or suspended in CEbCh (only for meta-chloroperbenzoic acid (m-CPBA)), CH3CN or water and an oxidizing agent such as m-CPBA or aqueous hydrogen peroxide solution (H2O2; 2 or 4 eq.) was added.
  • CEbCh meta-chloroperbenzoic acid
  • CH3CN aqueous hydrogen peroxide solution
  • H2O2 aqueous hydrogen peroxide solution
  • Example 9b By oxidation of PCA-5 with aqueous H2O2 solution:
  • PCA-10 Preparation of (N-(6-hydroxyhexyl)phosphoric acid carboxamide (PCA-10) by oxidation of PCA-8 with aqueous H2O2 solution:
  • Example 11 Isocyanate-terminated NCO-PCA-5 (structure IX) :
  • Example 12 Isocyanate-terminated NCO-PCA-8 (structure X):
  • T GA analyses were carried out under protective gas.
  • HDI was measured for comparison and has a decomposition temperature of 180 °C.
  • Cotton Lawn Rubbing Fabric (BS EN ISO 105-109) test strips in 20 cm x 8 cm strips were prepared. For impregnation, the cotton strips were dipped in CH 3 CN solutions of the samples. The cotton samples were dried at 60 °C for 1 h before and after impregnation and conditioned in atmosphere for 24 h. Samples and loadings are summarized in Table 3. Blank samples were treated with pure CH 3 CN. For the other samples, solutions of HDI (approx. 4.00 g), NCO-PCA-8 (approx. 4.00 g) and NCO-PCA-5 (approx. 2.00 g) in 30 - 50 mL CH 3 CN were used. HDI apparently evaporated completely during the treatment of the samples. Table 3 shows the mass fraction of phosphorus as well as the masses of selected samples before and after combustion.
  • the samples impregnated with NCO-PCA-5 and NCO-PCA-8 also ignited quickly and the flames spread over the entire surface within about 20 seconds. However, the samples did not burn completely. The flames extinguished very quickly and without afterglow, leaving the blackened samples in a recognizable (rectangular) shape. The residual mass of the charred samples was on average 30 mg.
  • Trimerization catalysts Desmorapid® 30HB14 (36 wt.% potassium formate, 64 wt.% ethylene glycol)
  • Ethylene glycol Foam stabilizers polyether-polydimethylsiloxane copolymers
  • Iso- and polyisocyanates B used Desmodur® N3600 (polyisocyanate containing isocyanurate groups based on 1,6-diisocyanatohexane (HDI) with an NCO content of 23.2% by weight, an average NCO functionality of 3.2 (according to GPC), a monomeric HDI content of maximum 0.2% by weight and a viscosity of 1200 mPas (23 °C)), Bayhydur® 3100 (hydrophilic polyisocyanate containing isocyanurate groups based on 1,6-diisocyanatohexane (HDI) with an NCO content of 17.4% by weight, an average NCO functionality of 3.2 (according to GPC), a monomeric HDI content of maximum 0.1% by weight and a viscosity of 2800 mPa*s (23 °C)), NCO-PCA-5 (viscosity of 3600 mPa*s (23 °C))
  • Example 14 Translucent foam containing NCO-PCA-5
  • An isocyanate-reactive composition of 0.18 g ethylene glycol, 0.22 g water, 0.18 g foam stabilizer Tegostab B8490 and 0.38 g catalyst Desmorapid® 30HB14 as well as 0.13 g Formrez UL-28 was mixed with an isocyanate mixture of 10.76 g Desmodur® ultra N3600, 2.39 g Bayhydur® 3100 and 10.76 g NCO-PCA-5 for 15 seconds with a speed mixer at 3540 rpm until virtually bubble-free and carefully poured into a mold. The mold was then placed in an oven at 74°C. The foam had set after 240 seconds. The foam was then annealed in the oven at 74° for a further 120 minutes.
  • the cell size was approximately 1 to 3 mm.
  • Example 15 Translucent foam without NCO-PCA-5
  • An isocyanate-reactive composition of 0.34 g ethylene glycol, 0.22 g water, 0.18 g foam stabilizer Tegostab B8490 and 0.38 g catalyst Desmorapid® 30HB14 as well as 0.13 g Formrez UL-28 was mixed with an isocyanate mixture of 21.38 g Desmodur® ultra N3600 and 2.38 g Bayhydur® 3100 for 15 seconds with a speed mixer at 3540 rpm until virtually bubble-free and carefully poured into a mold. The mold was then placed in an oven at 73°C. The foam had set after 540 seconds. The foam was then annealed in the oven at 74° for a further 120 minutes.
  • the cell size was approximately 1 to 3 mm.
  • the heat release rate of the product to be tested is determined in the “Cone Calorimeter” test device according to ISO 5660-1. Table 3: Fire test results

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

La présente invention concerne des phosphanylcarboxamides à terminaison isocyanate et réactifs vis-à-vis des isocyanates en tant que nouveaux monomères et prépolymères pour la production de plastiques, qui peuvent, par exemple, être utilisés pour la production de polyuréthanes ou de polymères polyuréthane/polyisocyanurate.
EP24702155.3A 2023-01-31 2024-01-26 Phosphanylcarboxamides à terminaison isocyanate et réactifs vis-à-vis des isocyanates ainsi que leur production et leur utilisation pour la production de polyisocyanurates et polyuréthanes phosphoreux Pending EP4658695A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP23154150.9A EP4410856A1 (fr) 2023-01-31 2023-01-31 Phosphanylcarboxamides réactifs à l'isocyanate et terminés par des isocyanates, leur préparation et leur utilisation pour la préparation de polyuréthanes et de polyisocyanurates contenant du phosphore
PCT/EP2024/051851 WO2024160659A1 (fr) 2023-01-31 2024-01-26 Phosphanylcarboxamides à terminaison isocyanate et réactifs vis-à-vis des isocyanates ainsi que leur production et leur utilisation pour la production de polyisocyanurates et polyuréthanes phosphoreux

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EP23154150.9A Withdrawn EP4410856A1 (fr) 2023-01-31 2023-01-31 Phosphanylcarboxamides réactifs à l'isocyanate et terminés par des isocyanates, leur préparation et leur utilisation pour la préparation de polyuréthanes et de polyisocyanurates contenant du phosphore
EP24702155.3A Pending EP4658695A1 (fr) 2023-01-31 2024-01-26 Phosphanylcarboxamides à terminaison isocyanate et réactifs vis-à-vis des isocyanates ainsi que leur production et leur utilisation pour la production de polyisocyanurates et polyuréthanes phosphoreux

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Publication number Priority date Publication date Assignee Title
US3213042A (en) 1960-12-07 1965-10-19 American Cyanamid Co Reaction product of an organic diisocyanate with a primary phosphine or primary phosphine oxide
US3116316A (en) 1961-07-21 1963-12-31 American Cyanamid Co Tertiary phosphines and methods of preparing same
DD242812A1 (de) * 1985-11-21 1987-02-11 Univ Halle Wittenberg Verfahren zur herstellung von phosphonigformyl-aminosaeuren und deren derivaten
CN112442073A (zh) * 2019-08-28 2021-03-05 广东广山新材料股份有限公司 一种含磷的反应型阻燃剂及其制备方法和应用

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