Isocyanate reactive and isocyanate-bended phosphoalkylcarboxamides and the production thereof and use for the production of phosphorus-containing

Abstract

The present invention relates to isocyanate-reactive and isocyanate-terminated phosphoalkylcarboxamides as novel monomers and prepolymers for the production of plastics, which can be used, for example, for the production of polyurethanes or polyurethane / polyisocyanurate polymers.

Description

[0001] The present invention relates to novel monomers and prepolymers for producing plastics, which can be used, for example, to produce flame-retardant polyurethanes or polyurethane / polyisocyanurate polymers (hereinafter referred to as PUR / PIR, alone or in combination).

[0002] Many plastics, like most organic substances, are flammable. Therefore, for many applications, they must be provided with flame retardants. This also applies to PUR / PIR polymers, particularly those used in the construction industry or in certain coatings. PUR / PIR foams are frequently used as insulation materials, and their use as foams often increases the risk of fire due to their high surface area per unit mass. Therefore, providing flame resistance through the addition of flame retardants is essential in many PUR / PIR foam applications.

[0003] Preferred flame retardants include halogen-containing compounds, as well as nitrogen and phosphorus compounds. Halogen-containing compounds and low-valent phosphorus compounds are typical examples of flame retardants that smother flames. High-valent phosphorus compounds are intended to catalyze the cracking of polyurethane to form a solid, charred surface containing polyphosphate. This intumescent layer prevents further combustion of the material.

[0004] Low molecular weight flame retardant additives, such as tris(2-chloroisopropyl)phosphate (TCPP) or triethyl phosphate (TEP), are present in chemically unbound form in the polymer matrix and, acting as plasticizers, can affect the product and leach out over time.

[0005] An interesting alternative to phosphorus-containing flame retardant additives is the use of phosphorus-containing reactive units such as monomers and prepolymers to produce inherently flame-retardant polymers. OP560 or The hydroxyl-terminated organic phosphonates or phosphates obtained with OL1000 can be used to produce, for example, phosphorus-containing polyurethanes and polyurethane / polyisocyanurates. Phosphonate- or phosphate-containing monomers or prepolymers are incorporated into the polyurethane via polyaddition reactions, thereby influencing the characteristic structure and, consequently, the properties of the polyurethane.

[0006] Therefore, the increasing demands on safety, cost and sustainability of organic polymers in general and PUR / PIR in particular necessitate the development of new flame retardants.

[0007] One class of organic phosphorus-containing compounds that has not yet been commercially applied is the phosphoalkylcarboxamides (Figure 1, I) and phosphorus(III)carboxamides (Figure 1, II). These groups show strong structural similarities to the urea, carbamate, biuret, and isocyanurate motifs found in polyurethanes and polyisocyanurates.

[0008]

[0009] FIG1 : General structure of phosphoalkylcarboxamides (I) and phospho(III) acidcarboxamides (II); wherein R=is independently selected from (optionally heteroatom-substituted) organic radicals and hydrogen radicals.

[0010] Certain phosphoalkylformamides and phospho(III) acidformamides, each having a phosphoalkyl or phospho(III) acid function and an amide function as shown in FIG1 , are known.

[0011] The production of compounds of structure I can be carried out from the corresponding starting compounds by known synthetic methods. These include the direct reaction of primary or secondary phosphines or phosphine oxides with monofunctional isocyanates and cyanates (e.g., US 3,116,316 A). The reaction of phosphines and phosphine oxides with difunctional isocyanates to provide polymer structures has also been described (US 3,213,042 A). The reaction of primary amines with Na(OCP)(1,4-dioxane) with different 1,4-dioxane contents (e.g., x=2.5) has also been described. x However, Na(OCP)(1,4-dioxane) x The synthesis and isolation of is inconvenient because several organic solvents (DME, 1,4-dioxane, THF) must be used simultaneously, the organic solvents used require energy-intensive removal under vacuum, and time-consuming (6-12 hours) filtration and recrystallization processes with 1,4-dioxane are necessary. The resulting 1,4-dioxane adduct Na(OCP)(1,4-dioxane) x It also contains irreproducible amounts of 1,4-dioxane, so the 1,4-dioxane content of each batch of product must be quantified by NMR spectroscopy. These disadvantages led to the use of Na(OCP)(1,4-dioxane) x The synthetic routes to the constituent adducts are not suitable for producing larger quantities of compounds of structure I or II, and simplified production methods are of great interest.

[0012] Two examples of difunctional primary bis(phosphoalkylcarboxamides) of structure III are also described in the literature ( FIG. 2 , structure III, R = ethylene and R = 1,2-cyclohexylene, Y.-H. Wu, Z.-F. Li, W.-P. Wang, X.-C. Wang, Z.-J. Quan, Eur. J. Org. Chem. 2017, 2017, 5546-5553; ENFaria, AR Jupp, JM Goicoechea, Dalton Trans. 2021, 50, 6991-6996). Difunctional hydroxy(phosphoalkylcarboxamides) (IV, where X = OH) and bis(phospho(III) acid carboxamides) (V) are not disclosed in the literature.

[0013]

[0014] Figure 2: Bis(phosphoalkylcarboxamide) (III); structures of difunctional phosphoalkylcarboxamides (IV) and bis(phospho(III) acid carboxamide) (V) wherein X = NCO reactive group; wherein R = organic radicals independently selected from (optionally substituted by heteroatoms)

[0015] The use of phosphorus-containing alkylformamides or phosphorus(III) acidformamide structures as reactive phosphorus-containing units, for example for incorporation into polyurethanes or polyisocyanurates, has not yet been disclosed.

[0016] Reactive monomer units (monomers) of interest for the production of plastics, for example as reactants for polyaddition reactions with the NCO functions of isocyanate compounds in the formation of polyurethanes or polyisocyanurates, include, in particular, compounds having, firstly, one or more phosphoalkylcarboxamide structures and / or phosphorus(III) acidcarboxamide structures and, secondly, at least two isocyanate-reactive functional groups ("NCO-reactive groups"). These compounds are hereinafter referred to individually or collectively as "PCA").

[0017] The present invention relates to compounds PCA of general structure VI or VII (see FIG3 ), which have at least two NCO-reactive groups and can therefore be used, for example, as monomers for polyaddition to polyisocyanates, with the proviso that compounds having structure III with R=ethylene or R=1,2-cyclohexylene are excluded.

[0018] The invention also relates to the use of PCA as a monomer for producing phosphorus-containing prepolymers and polymers, such as PUR / PIR.

[0019] The invention further relates to prepolymers, polymers and NCO-terminated compounds which can be produced using the compound PCA and polyfunctional isocyanates.

[0020] The present invention further relates to a novel method for producing PCA, wherein

[0021] a) reacting a Na(OCP) reaction solution with an amine in the presence of a Brønsted acid and optionally an oxidizing agent in a multistage synthesis ( FIG. 4 a ), or alternatively

[0022] b) Red phosphorus, sodium, an organic carbonate, tert-butanol, and an amine are reacted in a one-pot reaction in the presence of a Bronsted acid and optionally an oxidizing agent ( FIG4 b ).

[0023] Compound PCA

[0024] The novel compound PCA is selected from organophosphorus compounds having structure VI or structure VII and having at least two isocyanate-reactive groups, with the proviso that compounds of structure III in which R=ethylene or R=1,2-cyclohexylene are excluded.

[0025]

[0026] Figure 3: Structures of phosphoalkylcarboxamides (VI) and phosphoric acid carboxamides (VII)

[0027] In the phosphoalkylcarboxamide VI or phosphoric acid (III) carboxamide VII, X represents an NCO reactive group, m=0-3, n=1-4, m+n≥2; and R is an organic group (optionally substituted by a heteroatom).

[0028] The isocyanate-reactive groups of compound PCA are, in particular, at least two groups selected from -PH2, -PHR, -P(O)H2, -P(O)HR, -P(O)(H)OH, -P(OH)H, -P(OH)R (wherein R = an organic radical optionally substituted by a heteroatom), -OH, -NH2, -NHR' (wherein R' = an organic radical optionally substituted by a heteroatom, with the exception of a para-substituted anilino radical), -SH and ethylene oxide.

[0029] Particularly preferred compounds PCA are those selected from the group consisting of compounds having structures VI and VII and wherein the organic radical R is preferably selected from the group consisting of trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, cyclohexylene optionally containing heteroatoms, phenylene, biphenylene, dimethylphenylene, 2-methylpentamethylene, 2,2,4-trimethylhexamethylene, dodecamethylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, 5-(1-methylene-(1,3,3-trimethylcyclohexane)), all regioisomers of methylenebiscyclohexylene, all regioisomers of methylenebisphenylene, methylenebis(3,3′-dimethylcyclohexane-1,4-diyl), propane-2,2-diyl)bis(cyclohexane-4,1-diyl), propane-2,2-diyl -bis-4,1-phenylene, polyhexamethylene, tolylene, poly(propylene glycol)tolylene, poly(ethylene adipate)tolylene, 2,4,6-trimethyl-1,3-phenylene, 4-chloro-6-methyl-1,3-phenylene, poly[1,4-phenylene], co-[poly(1,4-butylene glycol)], poly(tetrafluoroethylene oxide-co-difluoroformaldehyde), 1,3-bis(1-methylethyl)benzene, 3,3'-dimethyl-4,4' -biphenylene, naphthalene, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 2,4- or 2,5- or 2,6-tolylene and isomer mixtures thereof, methylene-4,4'- or 2,4'- or 2,2'-bisphenylene and isomer mixtures thereof, 4,4'-, 2,4'- or 2,2'-diphenylpropane-p-xylylene and α,α,α',α'-tetramethyl-m- or p-xylylene. The organic radical R is very particularly preferably selected from trimethylene, tetramethylene, pentamethylene, hexamethylene, methylene-4,4'- or 2,4'- or 2,2'-bisphenylene and isomer mixtures thereof.

[0030] The NCO-reactive group X is especially selected from -PH2, -PHR', -P(O)H2, -P(O)HR', -P(O)(H)OH, -OH, -NH2, -NHR', -NHC(O)PH2, -NHC(O)PHR', -NHC(O)P(O)H2, -NHC(O)P(O)HR', -NHCOOH, -NHC(O)NH2, -NHC(O)NHR' (wherein R' = an organic radical optionally substituted by heteroatoms).

[0031] Particularly preferred are compounds of structure VI or VII, characterized in that

[0032] m=0, 1, n=1, 2, m+n=2;

[0033] R is selected from trimethylene, tetramethylene, pentamethylene, hexamethylene, methylene-4,4'- or -2,4'- or -2,2'-bisphenylene and isomeric mixtures thereof, and

[0034] X=OH.

[0035] Method for producing isocyanate-reactive compound PCA

[0036] The production of the compound PCA can be carried out as described above from the corresponding starting compounds by known synthesis methods, but these are not suitable, in particular, for the synthesis of larger quantities.

[0037] The present invention further relates to a novel method for producing PCA, wherein

[0038] a) reacting a Na(OCP) reaction solution with an amine in the presence of a Brønsted acid and optionally an oxidizing agent in a multistage synthesis ( FIG. 4 a ), or

[0039] b) Alternatively, red phosphorus, sodium, organic carbonate, tert-butanol, naphthalene and amine can be reacted in a one-pot reaction in the presence of a Bronsted acid and optionally an oxidizing agent ( FIG. 4 b ).

[0040] Regarding a), compounds VI and VII can be produced using a newly developed method via a Na(OCP) ("sodium phosphaethynol") reaction solution according to the following reaction scheme:

[0041]

[0042] Figure 4a: Reaction scheme for the production of PCA VI and VII via Na(OCP) reaction solution

[0043] The synthesis comprises the following steps:

[0044] (i) A 1,4-dioxane-free, storage-stable Na(OCP) reaction solution is produced from elemental phosphorus, elemental sodium, tert-butyl alcohol (tBuOH), naphthalene, and an organic carbonate in a solvent ( FIG4 a ). The solution contains sodium tert-butyl alcohol (tBuONa) and an alcohol as a non-interfering byproduct. Due to the tBuONa byproduct, the Na(OCP) reaction solution is strongly alkaline, thus facilitating storage stability. Multiple filtration steps and solvent changes are not required. Alternatively, the Na(OCP) reaction solution can be directly subjected to further reactions without further post-treatment.

[0045] The solvent used is preferably an ether, particularly preferably ethylene glycol dimethyl ether. Preferably, no dioxane is used as a solvent, so that the Na(OCP) remains dissolved and, contrary to previously known methods, does not precipitate. The OCP anion content is quantified during and / or after the reaction by infrared spectroscopy.

[0046] (ii) In the next step, the Na(OCP) reaction solution is then reacted with a suitable amine (X) m -R-(NH2) n The reaction is carried out in the presence of a suitable Bronsted acid to provide PCA of structure VI. The Bronsted acid is added in excess. Instead of amine (X) m -R-(NH2) n In combination with Bronsted acids, the corresponding hydrochlorides of the amines can also be used.

[0047] (iii) When an additional oxidizing agent is used during or after step (ii), a PCA of structure VII is obtained.

[0048] Regarding b), the production of PCA is alternatively achieved by direct reaction of red phosphorus, sodium, organic carbonate, tert-butanol, naphthalene, amine, Bronsted acid and optionally an oxidant in a one-pot reaction ( FIG. 4 b ).

[0049]

[0050] Figure 4b: Reaction scheme for the production of PCA VI and VII in a one-pot reaction

[0051] The amine used in methods a) and b) is selected from the group consisting of: m -R-(NH2) nThe compound group composed of an organic amine, wherein the substituent R is selected from an organic group (optionally substituted by a heteroatom), preferably selected from trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, cyclohexylene optionally containing a heteroatom, phenylene, biphenylene, dimethylphenylene, 2-methylpentamethylene, 2,2,4-trimethylhexamethylene, dodecamethylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1 ,4-cyclohexylene, 5-(1-methylene-(1,3,3-trimethylcyclohexane)), all regioisomers of methylenebiscyclohexylene, all regioisomers of methylenebisphenylene, methylenebis(3,3'-dimethylcyclohexane-1,4-diyl), propane-2,2-diyl)bis(cyclohexane-4,1-diyl), propane-2,2-diyl-bis-4,1-phenylene, polyhexamethylene, tolylene, poly(propylene glycol)tolylene, poly(ethylene adipate) Tolylene, 2,4,6-trimethyl-1,3-phenylene, 4-chloro-6-methyl-1,3-phenylene, poly[1,4-phenylene], co-[poly(1,4-butylene glycol)], poly(tetrafluoroethylene oxide-co-difluoroformaldehyde), 1,3-bis(1-methylethyl)benzene, 3,3'-dimethyl-4,4'-biphenylene, naphthalene, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 2,4- or 2,5- or 2,6-tolylene and mixtures of isomers thereof and R is very particularly preferably selected from trimethylene, tetramethylene, pentamethylene, hexamethylene, methylene-4,4'- or -2,4'- or -2,2'-bisphenylene and isomer mixtures thereof;

[0052] and wherein X is selected from -PH2, -PHR', -P(O)H2, -P(O)HR', -P(O)(H)OH, -OH, -NH2, -NHR', -NHC(O)PH2, -NHC(O)PHR', -NHC(O)P(O)H2, -NHC(O)P(O)HR', -NHCOOH, -NHC(O)NH2, -NHC(O)NHR' (wherein R' = organic optionally substituted with heteroatom).

[0053] The organic carbonate ( FIG. 4 a / 4 b : “organic carbonate”) is preferably selected from the following compounds: dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, propylene carbonate, glycerol carbonate and mixtures thereof.

[0054] Brønsted acid (Fig. 4a / 4b: "Brønsted acid") is one or more acids, in particular selected from

[0055] - organic carboxylic acids, in particular acetic acid and / or formic acid,

[0056] - dihydrogen carbonate, sodium bicarbonate, phosphoric acid, sodium dihydrogen phosphate,

[0057] - hydrochloric acid, sulfuric acid, sodium bisulfate,

[0058] -ammonium hydrohalides, wherein the halogen is selected from Cl - Br - , I - , especially ammonium chloride (NH4)Cl, triethylammonium chloride (Et3NH)Cl or amine (X) m -R-(NH2) n The corresponding hydrochloride.

[0059] Oxidant is an oxygen transfer reagent capable of converting phosphoalkylformamide VI into phosphorus (III) acid formamide VII. Suitable examples include hydrogen peroxide (H O ), oxygen (O ), ozone (O ), peracetic acid, persulfuric acid, laughing gas (N O), nitrogen dioxide (NO ), organic peroxides such as tert-butyl peroxide, perbenzoic acid, chloroperbenzoic acid, pyridine N-oxide. Particularly preferably, hydrogen peroxide (H O ) or oxygen (O ) are used.

[0060] Compound PCA can be obtained as a pure substance after post-processing. Isolation is achieved, for example, by removing all volatile components of the reaction mixture under vacuum, optionally followed by extraction of the residue. Alternatively, the residue can be washed with water beforehand.

[0061] Isocyanate-terminated compounds VIII, IX and X:

[0062] PCA can be used to produce NCO-terminated phosphoalkylcarboxamides of structures VIII, IX, and X (Figure 5) or their equivalents with phosphorus oxide.

[0063]

[0064] Figure 5: NCO-terminated phosphoalkylformamides VIII, IX, and X

[0065] In NCO-terminated phosphoalkylformamides VIII, IX and X,

[0066] m=1, 2; n=2-4; o=1-3;

[0067] Substituent R 1is an (optionally heteroatom-substituted) organic group selected from the substituents hydrogen, methyl, ethyl, butyl, propyl, pentyl, hexyl, heptyl, octyl, phenyl, tolyl, cyclohexyl and cyclopentyl,

[0068] and the substituents R are organic groups (optionally substituted with heteroatoms) selected independently of one another and are preferably selected from the substituents methylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, cyclohexylene optionally containing heteroatoms, phenylene, biphenylene, dimethylphenylene, 2-methylpentamethylene, 2,2,4-trimethylhexamethylene, dodecamethylene, 1,2-cyclohexylene, 1,3 -cyclohexylene, 1,4-cyclohexylene, 5-(1-methylene-(1,3,3-trimethylcyclohexane)), all regioisomers of methylenebiscyclohexylene, all regioisomers of methylenebisphenylene, methylenebis(3,3'-dimethylcyclohexane-1,4-diyl), propane-2,2-diyl)bis(cyclohexane-4,1-diyl), propane-2,2-diyl-bis-4,1-phenylene, polyhexamethylene, tolylene, poly(propylene glycol)tolylene, poly(hexanediol) 1,3-phenylene, 2,4,6-trimethyl-1,3-phenylene, 4-chloro-6-methyl-1,3-phenylene, poly[1,4-phenylene], co-[poly(1,4-butylene glycol)], poly(tetrafluoroethylene oxide-co-difluoroformaldehyde), 1,3-bis(1-methylethyl)benzene, 3,3'-dimethyl-4,4'-biphenylene, naphthalene, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 2,4- or 2,5- or 2,6-tolylene and isomer mixtures thereof, methylene-4,4'- or -2,4'- or -2,2'-bisphenylene and isomer mixtures thereof, 4,4'-, 2,4'- or 2,2'-diphenylpropane-p-xylylene and α,α,α',α'-tetramethyl-m- or p-xylylene; very particularly preferably selected from trimethylene, tetramethylene, pentamethylene, hexamethylene, methylene-4,4'- or -2,4'- or -2,2'-bisphenylene and isomer mixtures thereof.

[0069] Particularly preferably further used for the production of polymers are compounds of the structures VIII, IX and / or X, wherein m=2; n=1, 2; o=1,

[0070] where R 1 is selected from hydrogen, phenyl and tolyl,

[0071] And wherein R is selected from trimethylene, tetramethylene, pentamethylene, hexamethylene, methylene-4,4'- or -2,4'- or -2,2'-bisphenylene and isomeric mixtures thereof.

[0072] Preferably, the isocyanate-terminated phosphoalkylcarboxamides of the formulae VIII, IX and X 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 at least 300 g / mol and at most 2,000 g / mol.

[0073] It is particularly preferred that the isocyanate-terminated phosphoalkylcarboxamide of the formula VIII, IX or X according to the invention is liquid and has a dynamic viscosity at 23° C. of at most 30,000 mPa*s, particularly preferably at most 20,000 mPa*s, measured with a cone and plate viscometer.

[0074] Production method of isocyanate-terminated phosphoalkylformamide VIII, IX or X:

[0075] The phosphoalkylformamide VI or phosphoric acid (III) formamide VII can be reacted with a (molar) excess of at least one diisocyanate or polyisocyanate, optionally in the presence of a catalyst, to provide isocyanate-terminated phosphoalkylformamides VIII, IX or X and compounds equivalent to VIII, IX or X containing phosphorus oxide. Preferably, at least a two-fold excess of at least one diisocyanate or polyisocyanate relative to the phosphoalkylformamide or phosphoric acid (III) formamide is used. The reaction can be carried out in a solvent or in the absence of a solvent (e.g., with an excess of diisocyanate or polyisocyanate as a (reactive) diluent). The product is obtained after distillation to remove the solvent or excess diisocyanate or polyisocyanate.

[0076] To produce the isocyanate-terminated phosphoalkylcarboxamides of structure VIII, IX or X, it is preferred to use the phosphoalkylcarboxamides of structure VI,

[0077] Where m = 0-3, n = 1-4, m + n ≥ 2;

[0078] and wherein the substituent R is selected from an organic group (optionally substituted with heteroatoms), preferably selected from trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, cyclohexylene optionally containing heteroatoms, phenylene, biphenylene, dimethylphenylene, 2-methylpentamethylene, 2,2,4-trimethylhexamethylene, dodecamethylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, 5-(1-methylene-(1,3,3-trimethylcyclohexane)), all regioisomers of methylenebiscyclohexylene, all regioisomers of methylenebisphenylene, methylenebis(3,3'-dimethylcyclohexane-1,4-diyl), propane-2,2-diyl)bis(cyclohexane-4,1-diyl), propane-2,2-diyl-bis-4,1-phenylene, polyhexane Methyl, tolylene, poly(propylene glycol)tolylene, poly(ethylene adipate)tolylene, 2,4,6-trimethyl-1,3-phenylene, 4-chloro-6-methyl-1,3-phenylene, poly[1,4-phenylene], co-[poly(1,4-butylene glycol)], poly(tetrafluoroethylene oxide-co-difluoroformaldehyde), 1,3-bis(1-methylethyl)benzene, 3,3'-dimethyl-4,4'-biphenylene, naphthalene , 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 2,4- or 2,5- or 2,6-tolylene and isomeric mixtures thereof, methylene-4,4'- or -2,4'- or 2,2'-bisphenylene and isomeric mixtures thereof, 4,4'-, 2,4'- or 2,2'-2,2'-diphenylpropane-p-xylylene and α,α,α',α'-tetramethyl-m- or p-xylylene;

[0079] Very particularly preferably selected from trimethylene, tetramethylene, pentamethylene, hexamethylene, methylene-4,4′- or -2,4′- or -2,2′-bisphenylene and isomer mixtures thereof;

[0080] and wherein X is selected from -PH2, -PHR', -P(O)H2, -P(O)HR', -P(O)(H)OH, -OH, -NH2, -NHR', -NHC(O)PH2, -NHC(O)PHR', -NHC(O)P(O)H2, -NHC(O)P(O)HR', -NHCOOH, -NHC(O)NH2, -NHC(O)NHR' (wherein R' = organic optionally substituted with heteroatom).

[0081] Particular preference is given to using compounds of structure VI in which:

[0082] m=0, 1, n=1, 2, m+n=2;

[0083] R is selected from trimethylene, tetramethylene, pentamethylene, hexamethylene, methylene-4,4'- or -2,4'- or -2,2'-bisphenylene and isomeric mixtures thereof; and

[0084] X=OH.

[0085] For the production of isocyanate-terminated phosphoalkylformamides VIII, IX or X, the following polyisocyanates are preferably used:

[0086] Methylene diphenyl diisocyanate (MDI), toluene diisocyanate (TDI), naphthalene diisocyanate (NDI), hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI), isophorone diisocyanate (IPDI), methylene dicyclohexyl diisocyanate (HDI), 12 MDI) and its oligomers and derivatives, such as prepolymers.

[0087] The molar ratio of isocyanate groups in the reaction mixture for producing the isocyanate-terminated phosphoalkylformamide VIII, IX or X to the isocyanate-reactive groups of the compound having structure VI or VII is >1, preferably at least 2:1 and at most 40:1, particularly preferably at least 2:1 and at most 10:1.

[0088] Excess isocyanate may remain in the product mixture after the reaction as reactive diluent or may be distilled off.

[0089] The isocyanate-terminated phosphoalkylformamides VIII, IX or X thus produced 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 at least 300 g / mol and at most 2,000 g / mol. They are very particularly preferably liquid and have a dynamic viscosity, determined at 23° C., of at most 30,000 mPa*s, particularly preferably at most 20,000 mPa*s, as determined using a cone-plate viscometer.

[0090] For the production of isocyanate-terminated phosphoalkylformamides VIII, IX or X, nitriles, such as acetonitrile, propionitrile, and ethers, such as tetrahydrofuran, diethyl ether, dioxane, are preferably used as solvents. Suitable reactive diluents include, in particular, the same polyisocyanates used for the reaction with the phosphoalkylformamide VI, such as diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), naphthalene diisocyanate (NDI), hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI), isophorone diisocyanate (IPDI), methylene dicyclohexyl diisocyanate (HDI), diisocyanate (D ... 12 MDI) and its oligomers and prepolymers.

[0091] The catalyst used is preferably a Lewis base, for example an amine base, in particular a tertiary amine, particularly preferably triethylamine. Alternatively, the reaction can also be carried out without a catalyst.

[0092] To produce compounds equivalent to VIII, IX or X with phosphorus oxide, the PCA of structure VII is used accordingly.

[0093] Polymer production

[0094] The difunctional and polyfunctional PCAs and isocyanate-terminated compounds VIII, IX or X of structures VI and VII are useful as monomers and prepolymers for producing novel phosphorus-containing polymers, especially for producing phosphorus-containing polyurethanes and polyisocyanurates.

[0095] To produce PUR / PIR from the isocyanate-reactive compounds VI or VII, these are reacted with polyisocyanates.

[0096] Isocyanate-terminated compounds VIII, IX or X and their equivalents with phosphorus oxide and their mixtures with polyisocyanates as reactive diluents can likewise be converted to PUR / PIR using corresponding isocyanate-reactive compounds, for example polyols.

[0097] The reaction can be carried out in the presence or absence of a suitable catalyst, and in the presence or absence of an additional solvent.

[0098] For the production of phosphorus-containing polyurethanes or polyisocyanurates, preference is given to using isocyanate-reactive phosphoalkylformamides VI or phosphoric acid (III) formamides VII.

[0099] Where m = 0-3, n = 1-4, m + n ≥ 2,

[0100] wherein the substituent R is selected from an organic group (optionally substituted by heteroatoms), preferably selected from trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, cyclohexylene optionally containing heteroatoms, phenylene, biphenylene, dimethylphenylene, 2-methylpentamethylene, 2,2,4-trimethylhexamethylene, dodecamethylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, 5-(1-methylene-(1,3,3-trimethylcyclohexane)), all regioisomers of methylenebiscyclohexylene, all regioisomers of methylenebisphenylene, methylenebis(3,3'-dimethylcyclohexane-1,4-diyl), propane-2,2-diyl)bis(cyclohexane-4,1-diyl), propane-2,2-diyl-bis-4,1-phenylene, polyhexamethylene tolylene, poly(propylene glycol)tolylene, poly(ethylene adipate)tolylene, 2,4,6-trimethyl-1,3-phenylene, 4-chloro-6-methyl-1,3-phenylene, poly[1,4-phenylene], co-[poly(1,4-butylene glycol)], poly(tetrafluoroethylene oxide-co-difluoroformaldehyde), 1,3-bis(1-methylethyl)benzene, 3,3'-dimethyl-4,4'-biphenylene, naphthalene, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 2,4- or 2,5- or 2,6-tolylene and isomeric mixtures thereof, methylene-4,4'- or -2,4'- or 2,2'-bisphenylene and isomeric mixtures thereof, 4,4'-, 2,4'- or 2,2'-diphenylpropane-p-xylylene and α,α,α',α'-tetramethyl-m- or p-xylylene;

[0101] and wherein X is selected from -PH2, -PHR', -P(O)H2, -P(O)HR', -P(O)(H)OH, -OH, -NH2, -NHR', -NHC(O)PH2, -NHC(O)PHR', -NHC(O)P(O)H2, -NHC(O)P(O)HR', -NHCOOH, -NHC(O)NH2, -NHC(O)NHR' (wherein R' = organic optionally substituted with heteroatom).

[0102] Particular preference is given to using compounds of structure VI or VII, which are characterized in that

[0103] m=0, 1, n=1, 2, m+n=2;

[0104] R is selected from trimethylene, tetramethylene, pentamethylene, hexamethylene, methylene-4,4'- or -2,4'- or -2,2'-bisphenylene and isomeric mixtures thereof, and

[0105] X=OH.

[0106] To produce PUR / PIR, PCA, alone or together with further isocyanate-reactive reactants and optionally with further formulation ingredients customary in polyurethane chemistry, is reacted with polyisocyanates, i.e. isocyanates having an NCO functionality of ≥ 2. Examples of such suitable polyisocyanates include 1,4-butanediisocyanate, 1,5-pentanediisocyanate, 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,2,4- and / or 2,4,4-trimethylhexamethylene diisocyanate, isomeric bis(4,4′-isocyanatocyclohexyl)methane or mixtures thereof with any desired isomer content, 1,4-cyclohexylene diisocyanate, 1,4-phenylenediisocyanate, 2,4- and / or 2,6-toluene diisocyanate (TDI), 1,5-naphthalene diisocyanate, 2,2,4- and / or 2,4,4-trimethylhexamethylene diisocyanate, isomeric bis(4,4′-isocyanatocyclohexyl)methane or mixtures thereof with any desired isomer content, 2'- and / or 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI) and / or higher homologs, 1,3- and / or 1,4-bis(2-isocyanatoprop-2-yl)benzene (TMXDI), 1,3-bis(isocyanatomethyl)benzene (XDI) and 2,6-diisocyanatohexanoic acid alkyl esters with C1- to C6-alkyl radicals (lysine diisocyanate); in a preferred embodiment, a mixture of isomers of diphenylmethane diisocyanate ("monomeric MDI", abbreviated to "mMDI") and oligomers thereof ("oligomeric MDI") is used. Mixtures of monomeric MDI and oligomeric MDI are usually referred to by the term "polymeric MDI" (pMDI). Oligomers of MDI are higher-nuclear polyphenylpolymethylene polyisocyanates, i.e., with an NCO functionality f>2 and can be represented by the following general molecular formula: C 15 H 10 N2O2[C8H5NO] n Mixtures of higher nuclear homologues of diphenylmethylene diisocyanate are described (where n = an integer > 0, preferably n = 1, 2, 3 and 4). Higher nuclear homologues C 15 H 10 N2O2[C8H5NO] m (m=integer ≥ 4) can likewise be present in mixtures of organic polyisocyanates. Further preferred as polyisocyanate component A) are mixtures of mMDI and / or pMDI containing up to 20% by weight, more preferably up to 10% by weight, of other aliphatic, cycloaliphatic and, in particular, aromatic polyisocyanates known for the production of polyurethanes, very particularly TDI.

[0107] In a further embodiment, the production of phosphorus-containing polyurethanes (PUR) / polyisocyanurates (PIR) uses isocyanate-terminated compounds of structures VIII, IX and / or X or their equivalents with phosphorus oxide,

[0108] Where m = 1, 2; n = 1-4; o = 1-3, and

[0109] R is selected from (optionally heteroatom-substituted) organic radicals, preferably from ethyl, butyl, propyl, pentyl, hexyl, isosorbide, methylenediphenyl, tolyl, lignin-based aromatic radicals, such as dimethoxyphenyl, furan-based organic radicals, very particularly preferably from propyl, butyl and pentyl, hexyl, methylenediphenyl, tolyl,

[0110] To fully or partially replace the isocyanate component commonly used in PUR / PIR reaction mixtures.

[0111] Particular preference is given to using compounds VIII, IX or X for the production of PUR / PIR

[0112] Where m = 2; n = 1, 2; n = 1, and

[0113] Wherein R is selected from propyl, butyl, pentyl, hexyl, methylenediphenyl, tolyl.

[0114] Due to the incorporated phosphorus, the new polymer exhibits inherent flame retardancy and is therefore particularly suitable for applications requiring good and durable flame retardancy, such as PUR / PIR rigid foam applications in the construction industry.

[0115] The compound PCA and the polymers produced therefrom can also be used as additives for polymers, in particular as flame retardant additives. Particularly advantageous for this are compounds having a decomposition temperature of >150°C, in particular >155°C and <250°C. Example

[0116] Starting Materials:

[0117] Red phosphorus (99%, amorphous powder), sodium (99%, rods in paraffin oil), ethylene carbonate (99%), diethyl carbonate (99%), tert-butyl alcohol (99.5%), triethylammonium hydrochloride (99+%), hexamethylene diisocyanate (HDI) (99%), 6-aminohexanol (98%), 1,6-diaminohexane dihydrochloride (99%), 5-aminopentanol (92%), 1,5-diaminopentane (9%) were used without further purification. 9%), 1,4-diaminobutane dihydrochloride (99+%), 1,3-diaminopropane (99%), ethanolamine hydrochloride (99+%), diethylamine (99.5%), 4,4′-diaminodiphenylmethane (97%), m-chloroperbenzoic acid (m-CPBA, 77+%), 1,4-diazabicyclo[2.2.2]octane (DABCO, 99+%), 1,4-butanediol (99%), and hydrogen peroxide (aqueous solution, 30%). Naphthalene (99%) was sublimed before use. 1,6-Diaminohexane dihydrochloride was synthesized according to the literature method (Neumann, J.; Bornschein, C.; Jiao, H.; Junge, K.; Beller, M. Hydrogenation of Aliphatic and Aromatic Nitriles Using a Defined Ruthenium PNP Pincer Catalyst. European J. Org. Chem. 2015, 2015(27), 5944–5948 (https: / / doi.org / 10.1002 / ejoc.201501007); Armarego, WLF; Perrin, DD Purification of Laboratory Chemicals Eighth Edition; 2017). 6-Aminohexanol hydrochloride, 5-aminopentanol hydrochloride, 1,5-diaminopentane dihydrochloride, 1,3-diaminopropane dihydrochloride, ethylenediamine dihydrochloride, and 4,4′-diaminophenylmethane dihydrochloride were similarly produced by reacting the corresponding amino alcohols or amines with ethereal or aqueous HCl in a suitable solvent. The solvents 1,2-dimethoxyethane (DME), tetrahydrofuran (THF), 1,4-dioxane, diethyl ether (Et2O), dichloromethane (CH2Cl2), and acetonitrile (CH3CN) were distilled before use and stored under protective gas over molecular sieves ( CH3CN, DME, THF, 1,4-dioxane, Et2O, CH2Cl2). NaOCP (1,4-dioxane) x (X = 2–3) were produced according to the literature method (Heift, D.; Z.; Grützmacher, H. Coulomb Repulsion versus Cycloaddition: Formation of Anionic Four-Membered Rings from Sodium Phosphaethynolate, Na(OCP). Dalt. Trans. 2014, 43(2), 831–840. https: / / doi.org / 10.1039 / C3DT52359D). The dioxane content of each batch was determined by NMR and elemental analysis. Sodium sand was produced by melting bare sodium flakes in xylene under protective gas and performing fine analysis using a KPG stirrer.

[0118] Measurement method:

[0119] Nuclear magnetic resonance experiments were performed in an AVANCE III HD Nanobay 400 MHz Ultrashield instrument from Bruker. Infrared (IR) spectra were acquired at room temperature using a Bruker Vertex 70 spectrometer with a RAM II module (d-YAG laser, 1064 nm). Elemental analysis was performed using a Vario MICRO cube elemental analyzer (Elementar Analysator systeme GmbH) in CHNS mode. TGA measurements were performed in a ceramic crucible in a TG 50 from Mettler Toledo. Viscosity measurements: Dynamic viscosity was determined at 23° C. using an MCR501-Rehometer (Anton Paar) according to DIN EN ISO 3219:1994-10. Measurements at different shear rates ensured that Newtonian flow behavior could be assumed. Details about the shear rate can therefore be omitted.

[0120] Production of Phosphoalkylcarboxamides (PCA) (VI, VII)

[0121] Method 1: Salts of amines and amino alcohols and NaOCP (1,4-dioxane) 2.4 start

[0122] The reactants diamine dihydrochloride (1 equivalent) or amino alcohol hydrochloride (2 equivalents) (see Table 1) and Na(OCP)(dioxane) 2.4 (2.1 equivalents) were suspended in acetonitrile (CH3CN) and stirred at room temperature overnight. Depending on the diamine dihydrochloride or amino alcohol hydrochloride used, the workup was performed accordingly:

[0123] Example 1-4: The resulting beige suspension is filtered and the filter residue is washed with CH3CN or warm CH3CN. The product is crystallized from the concentrated filtrate at a reduced temperature (e.g., -30°C) or by adding a suitable solvent such as diethyl ether (Et2O). After one or more recrystallizations, filtration, and vacuum drying, a solid product is obtained.

[0124] Example 5a, Example 8: The resulting beige suspension was filtered, and the product was obtained in the form of a white solid by Soxhlet extraction of the filter residue with CH2Cl2 and subsequent vacuum drying.

[0125] 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 in the form of a yellow oil.

[0126] The structures, melting points and 31 The P NMR signals are reported in Table 1.

[0127] Method 2: Starting from the salts of amines and amino alcohols and dioxane-free NaOCP reaction solution

[0128] a) Production and quantification of NaOCP reaction solution

[0129] Red phosphorus (3g, 97mmol, 1eq.), naphthalene (620mg, 5mmol, 0.05eq.) and sodium sand (6.68g, 291mmol, 3eq.) are suspended in 420mlDME and stirred at room temperature for 4 hours with a KPG stirrer. The gained black suspension is cooled to 0°C and slowly added with warm tert-butyl alcohol (18.53ml, 194mmol, 2eq.) at 30°C. The grey suspension is stirred at room temperature for another 1 hour and is cooled to 0°C, then a solution of ethylene carbonate (8.53g, 97mmol, 1eq.) in 90mlDME is added dropwise over 1 hour. The yellow-green suspension is stirred at room temperature overnight, then filtered through a Schlenk glass frit, and the green filter residue is washed with DME (3x 30ml) to obtain a clear yellow NaOCP solution. The NaOCP content of this solution is determined by infrared spectroscopy using a standard curve. The NaOCP solution was stable for at least 6 weeks when stored under refrigeration and protective gas and could be used to prepare PCA without further processing.

[0130] B) Generation of a calibration curve for quantifying the NaOCP content of the NaOCP reaction solution

[0131] To generate the calibration curve, a NaOCP standard solution was prepared in DME / CH3CN (70 / 30) (the NaOCP (1,4-dioxane) used was determined by NMR spectroscopy and elemental analysis). 2.23The absorbance of the CO stretching vibration of NaOCP (1760 cm -1 ). The method was verified by the standard addition method. For additional samples, aliquots of the reaction solution were collected, diluted and measured in the same manner.

[0132] Example 5b: Synthesis Example Using N,N′-(hexane-1,6-diyl)bis(phosphoalkylcarboxamide) to Produce PCA-5 Starting from NaOCP Reaction Solution

[0133] To the NaOCP reaction solution (0.105M, 80ml, 8.34mmol, 2eq.) from a) was first quickly added 1,6-diaminohexane dihydrochloride (0.78g, 4.17mmol, 1eq.) at room temperature under vigorous stirring, followed by the rapid addition of triethylammonium hydrochloride (2.02g, 7.30mmol, 1.75eq.). The initially yellow suspension turned light brown when stirred overnight. The suspension was filtered, and the light brown filter residue was washed with CHCN (3x 5ml) and vacuum dried. The product was obtained as a colorless solid by Soxhlet extraction of the filter residue with CHCl and subsequent vacuum drying.

[0134] Method 3: Preparation of NaOCP reaction solution without filtration (one-pot reaction)

[0135] Example 8b: Synthesis Example Using (N-(6-hydroxyhexyl)phosphoalkylformamide) to Produce PCA-8 Starting from NaOCP Reaction Solution

[0136] Red phosphorus (0.5 g, 16 mmol, 1 eq.), naphthalene (103 mg, 1 mmol, 0.05 eq.), and sodium sulfate (1.14 g, 48 mmol, 3 eq.) were suspended in 200 ml of dimethylbenzene (DME) and stirred at room temperature for 12 hours. The resulting black suspension was cooled to 0°C, and warm tert-butanol (3.1 ml, 32 mmol, 2 eq.) was slowly added. The gray suspension was stirred at room temperature for 1 hour, cooled to 0°C, and a solution of ethylene carbonate (1.421 g, 16 mmol, 1 eq.) in 10 ml of DME was added dropwise over 1 hour. The yellow-green suspension was stirred at room temperature overnight. To a suspension of NaOCP (0.038 M, 215 ml, 8.3 mmol, 1.04 eq.) was first quickly added 6-aminohexanol (0.96 ml, 8 mmol, 1 eq.), followed by triethylammonium hydrochloride (6.7 g, 48 mmol, 6 eq.) at room temperature. The suspension turned light brown when stirred overnight. The suspension was filtered and the light brown filter residue was washed with CH3CN (3 x 5 ml). The product precipitated from the filtrate as a colorless solid at -30°C.

[0137] Example 5c: Synthesis Example of One-Step Production of PCA-5 Using N,N′-(Hexane-1,6-diyl)bis(phosphoalkylformamide) (Workup by Soxhlet Extraction)

[0138] Red phosphorus (250 mg, 8 mmol, 1 eq.), naphthalene (52 mg, 0.4 mmol, 0.05 eq.), and sodium nitrite (557 mg, 24 mmol, 3 eq.) were suspended in 15 mL of dimethylbenzene (DME) and stirred vigorously at room temperature for 12 hours. The resulting black suspension was cooled to 0°C, and a solution of tert-butyl alcohol (1.55 mL, 16 mmol, 2 eq.) and diethyl carbonate (0.98 mL, 8 mmol, 1 eq.) in 15 mL of DME was added dropwise. The yellow-green suspension was stirred at room temperature for 16 hours. The NaOCP content of the yellow supernatant was determined by infrared spectroscopy using a standard curve. The required amounts of 1,6-diaminohexane dihydrochloride and triethylammonium hydrochloride were specified based on the NaOCP concentration. To the suspension was first added 1,6-diaminohexane dihydrochloride (565 mg, 2.98 mmol, 0.37 eq.) rapidly under vigorous stirring, followed by the rapid addition of triethylammonium hydrochloride (2.51 g, 18.25 mmol, 2.26 eq.). After the addition of triethylammonium hydrochloride, the suspension quickly turned black and changed color to brown-orange in just a few seconds after the addition was complete. The suspension was stirred at room temperature overnight and then vacuum-dried to obtain a brown solid. The product was obtained as a light yellow solid by Soxhlet extraction with CH2Cl2 and subsequent vacuum drying.

[0139] Example 5d: One-step production of PCA-5 using the synthetic example of N,N′-(hexane-1,6-diyl)bis(phosphoalkylcarboxamide)

[0140] 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 of dimethylbenzene (DME) and stirred vigorously at room temperature for 16 hours. The resulting black suspension was cooled to 0°C, and a solution of tert-butyl alcohol (43.43 ml, 0.46 mol, 2 eq.) and diethyl carbonate (27.5 ml, 0.23 mol, 1 eq.) in 120 mL of DME was added dropwise. The yellow-green suspension was stirred at room temperature for 16 hours. The NaOCP content of the yellow supernatant was determined by infrared spectroscopy using a standard curve. The required amounts of 1,6-diaminohexane dihydrochloride and triethylammonium hydrochloride were specified based on the NaOCP concentration. To a NaOCP suspension (0.538M, 310ml, 0.167mol, 0.74eq.) was first added 1,6-diaminohexane dihydrochloride (15.8g, 0.084mol, 0.37eq.) with vigorous stirring, followed by the rapid addition of triethylammonium hydrochloride (70.7g, 0.51mmol, 2.26eq.). After the addition of triethylammonium hydrochloride, the suspension quickly turned black and changed color to brown-orange in just a few seconds after the addition was completed. The suspension was stirred at room temperature overnight and then vacuum dried to obtain a brown solid. The dried suspension was washed with water and Soxhlet extracted with CH2Cl2 to obtain the product PCA-5.

[0141] Table 1: Compound PCA (Structure VI) prepared

[0142]

[0143]

[0144] Production method of bis(phospho(III)formamide)(VII)

[0145] Bis(phosphoalkylformamide) (1 equivalent) or hydroxy-R-phosphoalkylformamide (2 equivalents) is dissolved or suspended in CHCl (for m-chloroperbenzoic acid (m-CPBA) only), CHCN or water, and an oxidizing agent, such as m-CPBA or aqueous hydrogen peroxide (HO; 2 or 4 equivalents) is added. The product is obtained as a colorless oil by filtering the colorless precipitate (when m-CPBA is used) and removing the solvent and water under vacuum.

[0146] Production of N,N′-(hexane-1,6-diyl)bis(phospho(III)carboxamide (PCA-9)

[0147] Example 9a: By oxidizing PCA-5 with m-chloroperbenzoic acid (m-CPBA):

[0148] To a suspension of PCA-5 (100 mg, 0.42 mmol, 1 eq.) in CH2Cl2 (5 ml) was added m-chloroperbenzoic acid (m-CPBA; 146 mg, 0.84 mmol, 2 eq.). The white suspension was stirred at room temperature for 12 hours. The reaction solution was filtered, and the filtrate was dried under vacuum to obtain the product as a colorless oil.

[0149] Example 9b: By oxidizing PCA-5 with H2O2 aqueous solution:

[0150] The H O aqueous solution (0.4 ml, 4.31 M, 1.68 mmol, 4 eq.) was added dropwise to a suspension of PCA-5 (100 mg, 0.42 mmol, 1 eq.) in deionized water (5 ml) under stirring. The pH value of the reaction mixture was maintained between pH 8 and pH 10 by the addition of NEt. The suspension was stirred at room temperature for 12 hours and excess H O was quenched by the addition of manganese (IV) oxide. The clarified reaction solution was filtered and the filtrate was vacuum dried at 60° C. to obtain the product as a colorless oil.

[0151] Embodiment 10: (N-(6-Hydroxyhexyl)phospho(III)carboxamide (PCA-10) was produced by oxidation of PCA-8 with aqueous H2O2:

[0152] Aqueous H2O2 (106 μL, 4.31 M, 0.46 mmol, 2 eq.) was added dropwise to a solution of PCA-8 (40.5 mg, 0.23 mmol, 1 eq.) in deionized water (4 ml) under stirring. The reaction mixture was stirred at room temperature for 12 hours. Excess H2O2 was quenched by adding manganese (IV) oxide, and the reaction solution was filtered. The product was obtained from the filtrate as a colorless oil after vacuum drying at 60°C.

[0153] Production of isocyanate-terminated bis(phosphoalkylformamides) and hydroxyphosphoalkylformamides (IX,X)

[0154] Example 11: Isocyanate-terminated NCO-PCA-5 (Structure IX):

[0155] A suspension of PCA-5 (12.36 g, 0.05 mol, 1 eq.) and NEt (0.3 ml) in 400 ml of CHCN was very slowly added dropwise to an excess of hexamethylene diisocyanate (HDI) (528.2 g, 503 ml, 3.08 mol, 60 eq.) while vigorously stirring with a KPG stirrer. The colorless suspension was stirred at room temperature for 16 hours, and a very small amount (<20 mg) of solid was removed by filtration. The solvent and excess HDI were removed from the filtrate by distillation. A liquid product was obtained. NCO value: 18.6%, viscosity: 3600 mPas; refractive index (nD20): 1.5299; 31 P NMR (CD3CN, 300K, in ppm): δ = -46.6.

[0156] Example 12: Isocyanate-terminated NCO-PCA-8 (Structure X):

[0157] A solution of PCA-8 (12.85 g, 0.07 mol, 1 eq.) and NEt (0.3 ml) in 200 ml of CHCN was very slowly added dropwise to an excess of HDI (365.9 g, 348.6 ml, 2.18 mol, 30 eq.) while vigorously stirring with a KPG stirrer. The colorless, clear solution was stirred for 16 hours. The solvent and excess HDI were removed by distillation. A liquid product was obtained. NCO value: 17.3%, viscosity: 2350 mPas; refractive index (nD20): 1.5113; 31 P NMR (CD3CN, 300K, in ppm): δ = -45.8.

[0158] Example 13: Production of polyurethane thermosets using NCOPCA

[0159] A mixture of 1,4-butanediol (2 ml), NCO-PCA-8 (0.3 ml), and water (0.02 ml) was heated to 70°C, followed by the addition of a catalytic amount of DABCO (1,4-diazabicyclo[2.2.2]octane). The reaction mixture solidified into a white polyurethane-containing solid. The formation of urethane bonds was confirmed by infrared spectroscopy.

[0160] TGA analysis (decomposition temperature)

[0161] TGA analysis was performed under protective gas. The decomposition temperatures of PCA-5 and PCA-8 at about 160°C were lower than those of NCO-PCA-5 (T d =180°C) and NCO-PCA-8 (190°C). HDI was measured for comparison and has a decomposition temperature of 180°C.

[0162] Table 2: Decomposition temperatures (T) of selected PCAs and NCO PCAs d )

[0163] substance <![CDATA[T d (℃)]]> HDI 180 PCA-5 160 PCA-8 160 NCO-PCA-5 180 NCO-PCA-8 190

[0164] Report T at 5% mass loss d (±5%)

[0165] Flame retardancy test

[0166] Tested according to DIN EN ISO 15025 (vertical flame test). For this reason, prepare 20cm x 8cm strips of cotton fabric test strips (Cotton Lawn Rubbing Fabric (BS EN ISO 105-109)). In order to impregnate, cotton strips are immersed in the CH3CN solution of sample. Before and after impregnation, the cotton sample is dried at 60 ℃ for 1 hour and conditioned under atmospheric conditions for 24 hours. Samples and loads are summarized in Table 3. The blank sample is processed with pure CH3CN. Other samples use HDI (about 4.00g), NCO-PCA-8 (about 4.00g) and NCO-PCA-5 (about 2.00g) in 30-50mlCH3CN solution. HDI seems to evaporate completely during sample treatment. Table 3 shows the mass ratio of phosphorus and the mass of selected samples before and after combustion.

[0167] Table 3: Summary of samples

[0168]

[0169]

[0170] *Mass of impregnated and dried samples

[0171] **The mass ratio of P in the total mass of the sample.

[0172] The samples were flamed according to DIN standards for 10 seconds. Both the HDI and blank samples ignited quickly and burned completely within approximately 30 seconds. Once the flame had consumed the entire surface of the sample and subsided again, the shrunken residue remained luminous for approximately 15 seconds. The sample left a small amount of very light gray ash, which could not be collected.

[0173] Samples impregnated with NCO-PCA-5 and NCO-PCA-8 also ignited quickly, with the flame spreading across the entire surface in approximately 20 seconds. However, the samples did not burn completely. The flames quickly extinguished with no afterglow, leaving behind a blackened sample with a recognizable (rectangular) shape. The residual mass of the charred samples averaged 30 mg.

[0174] Production of translucent foam

[0175] Components used:

[0176] Trimerization catalyst: 30HB14 (36 wt% potassium formate, 64 wt% ethylene glycol)

[0177] Catalyst: Dimethyltin neodecanoate (Formrez UL-28)

[0178] Polyol / Alcohol A used): Ethylene glycol

[0179] Foam stabilizer (polyether-polydimethylsiloxane copolymer): B8490

[0180] Isocyanates and polyisocyanates B used): N3600 (polyisocyanate containing isocyanurate groups based on 1,6-hexane diisocyanate (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 max. 0.2% by weight and a viscosity of 1200 mPas (23° C.)), 3100 (a hydrophilic polyisocyanate containing isocyanurate groups based on 1,6-hexane diisocyanate (HDI) with an NCO content of 17.4 wt.-%, an average NCO functionality of 3.2 (according to GPC), a monomeric HDI content of max. 0.1 wt.-% and a viscosity of 2800 mPa*s (23°C)), NCO-PCA-5 (viscosity of 3600 mPa*s (23°C)).

[0181] Example 14: Translucent foam containing NCO-PCA-5

[0182] 0.18g ethylene glycol, 0.22g water, 0.18g foam stabilizer Tegostab B8490 and 0.38g catalyst An isocyanate reactive composition consisting of 30HB14 and 0.13g Formrez UL-28 was mixed with 10.76g ultra N3600, 2.39g An isocyanate mixture of 3100 and 10.76 g of NCO-PCA-5 was mixed virtually bubble-free in a Speedmixer at 3540 rpm for 15 seconds and carefully poured into a mold. The mold was then placed in an oven at 74°C. The foam solidified after 240 seconds. The foam was then heat-treated in an oven at 74°C for an additional 120 minutes.

[0183] The cell size is approximately 1 to 3 mm.

[0184] Example 15 (comparative example): Translucent foam without NCO-PCA-5

[0185] 0.34g ethylene glycol, 0.22g water, 0.18g foam stabilizer Tegostab B8490 and 0.38g catalyst An isocyanate reactive composition consisting of 30HB14 and 0.13g Formrez UL-28 was mixed with 21.38g Ultra N3600 and 2.38g The 3100% isocyanate mixture was mixed using a Speedmixer at 3540 rpm for 15 seconds, virtually free of bubbles, and carefully poured into the mold. The mold was then placed in an oven at 73°C. The foam solidified after 540 seconds. The foam was then heat-treated in the oven at 74°C for a further 120 minutes.

[0186] The cell size is approximately 1 to 3 mm.

[0187] Fire testing / determination of heat release according to ISO 5660-1

[0188] The heat release rate of the product to be tested is determined in a "Cone Calorimeter" test apparatus in accordance with ISO 5660-1.

[0189] Table 3: Fire test results

[0190]

[0191]

[0192] Heat flux: irradiance irradiating the respective sample

[0193] HRR (Heat Release Rate): Heat Release

[0194] HRR 峰值 : Maximum heat release

[0195] HRR 平均 :Average heat release

[0196] THR (Total Heat Release): Total Heat Release

[0197] The data show that NCO-PCA-5, acting as a flame retardant, was inactive at the start of the experiment in Example 1: compared to the comparative example without NCO-PCA-5, the autoignition time was identical, and the heat of the first flare was even slightly greater. However, NCO-PCA-5, acting as a flame retardant in Example 1, self-extinguished surprisingly quickly. This was achieved not by improved charring (with comparable mass loss), but rather by very effectively interrupting the oxidation reaction in the flame. This corresponds to a lower effective heat release.

[0198] NCO-PCA-5, which acts as flame retardant in Example 1, thus ensures an improvement in the overall heat release, which is one of the important criteria for the approval of building materials.

Claims

1. Organophosphorus compound PCA, characterized in that It comprises one of structures VI or VII containing an isocyanate-reactive group in X is an NCO reactive group, m=0, 1, 2 or 3, n = 1, 2, 3 or 4, and m+n≥2 and R is an (optionally heteroatom-substituted) organic group, Provided that compounds having structure III with R = ethylene or R = 1,2-cyclohexylene are excluded 2. The organophosphorus compound according to claim 1, characterized in that The isocyanate-reactive groups of the compound PCA are at least two groups selected from -PH2, -PHR, -P(O)H2, -P(O)HR, -P(O)(H)OH, -P(OH)H, -P(OH)R (wherein R = an organic group optionally substituted by a heteroatom), -OH, -NH2, -NHR' (wherein R' = an organic group optionally substituted by a heteroatom, except for a para-substituted aniline group), -SH and ethylene oxide.

3. The organophosphorus compound according to claim 1 or 2, characterized in that m=0 or 1 and n=1 or 2, where in each case m+n=2, and R is selected from trimethylene, tetramethylene, pentamethylene, hexamethylene, methylene-4,4'- or -2,4'- or -2,2'-bisphenylene and isomeric mixtures thereof, and X=OH.

4. A method for producing an organophosphorus compound according to claims 1 to 3, characterized in that Red phosphorus, sodium, an organic carbonate, tert-butanol and an amine are reacted with one another in a one-pot reaction in the presence of a Bronsted acid and optionally an oxidizing agent.

5. Method for producing an organophosphorus compound PCA comprising any one of structures VI or VII Where X is an NCO reactive group, m=0, 1, 2 or 3, n = 1, 2, 3 or 4, and m+n≥2 and R is an (optionally heteroatom-substituted) organic group, The method comprises the steps (i) producing a 1,4-dioxane-free, storage-stable Na(OCP) reaction solution from elemental phosphorus, elemental sodium, tert-butyl alcohol (tBuOH), naphthalene, and an organic carbonate in a solvent, and (ii) which is reacted in a further step with an amine or an amine hydrochloride in the presence of a suitable Bronsted acid, and (iii) optionally oxidizing with an oxidizing agent.

6. The method according to claim 5, comprising quantifying the OCP anion content in the Na(OCP) solution by infrared spectroscopy during or after step (i).

7. A process for producing isocyanate-terminated compounds by reacting an organophosphorus compound according to any one of claims 1 to 3 with a molar excess of at least one diisocyanate or polyisocyanate, wherein the diisocyanate or polyisocyanate can remain in the product mixture as a reactive diluent after the reaction or can be distilled off.

8. An isocyanate-terminated compound obtainable by the process according to claim 7.

9. An isocyanate-terminated compound comprising any one of structures VIII, IX, and X, or one of the equivalent structures of VIII, IX, or X containing phosphorus oxide: in m=1, 2; n=2-4; o=1-3; R 1 =(optionally heteroatom-substituted) organic radical, preferably selected from the substituents hydrogen, methyl, ethyl, butyl, propyl, pentyl, hexyl, heptyl, octyl, phenyl, tolyl, cyclohexyl and cyclopentyl; and R = organic radicals (optionally substituted by heteroatoms) selected independently of one another, preferably selected from the group consisting of the substituents methylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, cyclohexylene optionally containing heteroatoms, phenylene, biphenylene, dimethylphenylene, 2-methylpentamethylene, 2,2,4-trimethylhexamethylene, dodecamethylene, 1,2-cyclohexylene, 1,3-cyclohexylene , 1,4-cyclohexylene, 5-(1-methylene-(1,3,3-trimethylcyclohexane)), all regioisomers of methylenebiscyclohexylene, all regioisomers of methylenebisphenylene, methylenebis(3,3'-dimethylcyclohexane-1,4-diyl), propane-2,2-diyl)bis(cyclohexane-4,1-diyl), propane-2,2-diyl-bis-4,1-phenylene, polyhexamethylene, tolylene, poly(propylene glycol)tolylene, poly(ethylene adipate) esters)tolylene, 2,4,6-trimethyl-1,3-phenylene, 4-chloro-6-methyl-1,3-phenylene, poly[1,4-phenylene], co-[poly(1,4-butylene glycol)], poly(tetrafluoroethylene oxide-co-difluoroformaldehyde), 1,3-bis(1-methylethyl)benzene, 3,3'-dimethyl-4,4'-biphenylene, naphthalene, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 2,4- or 2,5- or 2,6-tolylene and isomers thereof R is preferably selected from trimethylene, tetramethylene, pentamethylene, hexamethylene, methylene-4,4'- or -2,4'- or -2,2'-bisphenylene and isomer mixtures thereof, 4,4'-, 2,4'- or 2,2'-2,2'-diphenylpropane-p-xylylene and α,α,α',α'-tetramethyl-m- or p-xylylene, very particularly preferably R being selected from trimethylene, tetramethylene, pentamethylene, hexamethylene, methylene-4,4'- or -2,4'- or -2,2'-bisphenylene and isomer mixtures thereof.

10. Use of the phosphoalkylformamides and phospho(III)formyls according to any one of claims 1 to 3 as monomers for producing polymers, in particular polymers having a phosphorus content >1%.

11. Process for producing polymers, preferably polyurethanes (PUR) or polyurethane / polyisocyanurate (PUR / PIR), particularly preferably PUR / PIR rigid foams, by reacting an isocyanate-terminated compound according to any one of claims 8 and 9 with an isocyanate-reactive compound, such as a polyol.

12. The method according to claim 11, characterized in that The reaction is carried out in the presence of diisocyanates and / or polyisocyanates.

13. A polymer obtainable using the phosphoalkylformamide and phosphoric acid (III) formamide according to any one of claims 1 to 4 and / or using the isocyanate-terminated compound according to claim 8 or 9.

14. The polymer according to claim 12, characterized in that It is a polyurethane (PUR) or polyurethane / polyisocyanurate (PUR / PIR), in particular a PUR / PIR rigid foam.

15. Use of a compound according to any one of claims 1 to 4, 8 and 9 and / or a polymer according to any one of claims 13-14 as a flame retardant additive.

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