EA043569B1 - POLYMER COMPOSITION WITH PHOSPHONATE FIRE RETARDANT - Google Patents

Description

Field of technology to which the invention relates

The invention relates to a composition containing a polymer material and a phosphorus-containing fire-retardant composition based on aminomethyl bisphosphonate, a method for producing the composition, the use of a fire-retardant composition, as well as selected structures of the fire-retardant composition.

State of the art

Numerous substances are known to impart fire resistance to polymeric materials, which can be added alone or in combination with additional substances that exhibit similar or complementary fire retardant properties. The most well-known fire retardants include halogenated organic compounds, metal hydroxides, organic or inorganic phosphates, phosphonates or phosphinates, as well as derivatives of 1,3,5-triazine compounds, and mixtures thereof. Among these flame retardants, a distinction can be made between low molecular weight and high molecular weight substances. Although high molecular weight, i.e. polymeric flame retardant compounds, such as the halogenated polyol Exolit OP 550 from Clariant, in contrast to low molecular weight flame retardant additives, favorably exhibit only a slight plasticizing effect and have a slight tendency to migrate in the polymer material; however, during technical processing they can often mix less well with the protected material polymer material, especially with low fusibility. In addition, the addition of high molecular weight flame retardant may have a negative effect on the curing of the polymer material.

Therefore, most of the flame retardants used are low molecular weight compounds. In this area, among others, phosphorus-containing compounds are known to be particularly effective. In the event of a fire, they can inflate in polymeric materials into voluminous protective layers, which is called an intumescent fire retardant coating. As a result, an insulating layer that impedes the access of oxygen is formed, which prevents further combustion of the polymer material. In addition, the combustion-preventing effect in the solid phase may be based on increasing the rate of charring of the polymer material or the formation of inorganic glasses. The combustion interruption activity is also contributed by the gas-phase mechanism, in which the combustion process of the polymer material is greatly slowed down by the recombination of radicals with PO radicals that are formed during the combustion of a phosphorus compound. The most important phosphorus-containing compounds are the halogenated phosphates tris(2-chloroethyl)phosphate (TCEP) and tris(2-chloroisopropyl)phosphate (TCPP). However, their use is increasingly limited due to the potential toxicity and environmental problems associated with their use, particularly since such phosphates can accumulate in ecosystems but are difficult to remove from wastewater in municipal wastewater treatment plants. In addition, they contain halogens, which in the event of a fire leads to the formation and release of HX gases and other toxic compounds. In particular, in the field of electronics, such corrosive combustion gases pose a particular danger.

An alternative to phosphate-containing flame retardants are halogenated and halogen-free phosphonates. Compared to phosphates, they exhibit particularly pronounced activity in preventing combustion in the gas phase. Patent document DE 2128060 describes the use of aminomethanephosphonic acid esters with a phosphorus content of up to 23.2% by weight as a flame retardant in polyurethanes. Aminomethanephosphonic acid esters are prepared from hexamethylenetetramine and dialkyl or diarylphosphonates. To use these phosphonates, they, along with other additives necessary under the circumstances, are dissolved in the polyol component of the mixture to form the polyurethane, and the polyisocyanate is added to it. Esters containing NH groups are introduced into the polymer material by addition to isocyanate groups.

Patent document EP 0001996 relates to the preparation of dimethyl esters of N,N-6uc(2-hydroxyalkyl)aminomethanephosphonic acid, which are used mainly as flame retardant additives in polymeric materials, in particular in polyurethanes. To synthesize them, an H-acid compound is added to a mixture of dimethylphosphite and oxazolidine as a catalyst. The products have a terminal secondary hydroxyl group and thus can be incorporated into the polymeric material when added to the polyol component of the mixture to form a polyurethane. However, in this case, the added H-acid substances remain in the polymer material, which can lead to deterioration of properties. Alternatively, they must be converted to their corresponding alkali metal salts before being added to the polyol component so that they can be separated from the phosphonic acid esters.

Patent document CA 2027078 relates to aryl esters of aminomethane phosphonic acid, which can be used as a flame retardant in foams, thermoplastics and duroplasts. The corresponding compounds are prepared by reacting the amine with trialkyl or triaryl phosphites and paraformaldehyde. The products either can be used in the extrusion process of the polymer material being processed, or can serve as an additive to the condensation co-component in a polycondensation reaction.

From the work of the authors Liu et al., Ind. Eng. Chem. Res. (2017), volume 56, p. 8789-8696, DOPO derivatives with flame retardant action are known, which are formed from DOPO (9,10-dihydro-9-oxa-10phosphaphenanthrene-10-oxide), paraformaldehyde and piperazine. They are halogen-free and exhibit flame retardant properties when used in polycarbonates. However, these compounds, as in the above documents, also have only insignificant thermal stability, which is explained by the weak P-C bond in the P-CH ₂ N group. Although the P-C bond is in principle chemically and thermally stable, the α-amino group stabilizes the carbon radical formed during homolysis so that the cleavage of the P-C bond in this fire retardant composition occurs already at relatively low temperatures. Since the tertiary amine that is formed during homolysis has a small molecular weight, it is removed as a highly volatile component and causes a corresponding weight loss. If a fire retardant composition is introduced into a polymer material, then due to the release of amine, flue gases can be intensively formed. Due to the low decomposition temperature, fire retardant compounds partially decompose during the molding process of the polymer material in which they are embedded. Another disadvantage of these fire retardant compositions is that, due to their low phosphorus content, they must be added to the polymer material in high concentrations, as a result of which the processability, flexibility and other technical characteristics of the polymer material are significantly deteriorated.

The essence of the invention

On this basis, the object of the present invention was therefore to create a composition with a polymeric material that has a halogen-free fire retardant composition with similar or even better fire protection characteristics compared to those known from the prior art, which can be used in lower concentrations in the composition while at the same time having good fire retardant properties. action, which decomposes only at higher temperatures than known fire retardant compositions, preferably much higher than the processing and/or production temperature, and slightly below the decomposition temperature of the polymer material, or at such a temperature, and when it decomposes in the polymer material, a flue gas with a low density is generated and/or flue gas with less toxicity.

Description of Embodiments of the Invention

This problem according to the invention is achieved by means of a composition which contains a polymeric material, in particular a thermoplastic or thermosetting polymeric material, and a halogen-free flame retardant contained therein and/or associated with it in an amount of from 1 to 40% by weight based on the entire composition wherein the fire retardant composition is a compound of formula (I), its corresponding ammonium salt, its corresponding phosphonate salt, or a mixture of the above:

R ²

N

O=P^P=O (!) wherein (i) R ¹ and R ² represent the same or different substituents and are selected from the group consisting of linear, branched or cyclic alkyl, alkenyl and alkynyl groups, unsubstituted and alkyl-substituted phenyl groups, monocyclic and polycyclic aromatic groups with up to 4 rings, monocyclic or polycyclic heteroaromatic groups with up to 4 rings, silyl groups, allyl, alkyl or aryl alcohols; or (ii) R ¹ and R ² together form an N-atom-containing saturated, or singly unsaturated, or multiply unsaturated heterocycle with 4-8 ring atoms, which are selected from carbon, oxygen, sulfur, phosphorus, silicon and nitrogen, and in heterocycle, when it has nitrogen atoms as ring atoms, these ring atoms have as substituents an H, alkyl, aryl or methyl bisphosphonate group with the following structure (II),

x O o o R ³ R ⁴ R ⁵ R ^S and at the same time in a heterocycle, when it has carbon, phosphorus or silicon as ring atoms, these atoms may have substituents selected from the group consisting of H, alkyl, aryl, - NH2, -NHR, -NR2, -OH, -OR, =O, -I, -Cl, -Br, with R=alkyl, aryl, and where -X- represents an oxygen atom, -O-, or -X- represents a simple connection, and where

- 2 043569 (i) R ³ , R ⁴ , R ⁵ and R ⁶ represent the same or different substituents and are selected from the group consisting of H, linear, branched or cyclic alkyl, alkenyl and alkynyl groups, unsubstituted and alkyl-substituted phenyl groups, polycyclic aromatic groups with the number of rings up to 4, monocyclic or polycyclic heteroaromatic groups with the number of rings up to 4, silyl groups, allyl, alkyl or aryl alcohols, cations, where the cation is Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , B ³⁺ , Al ³⁺ , Zn ²⁺ , NH ₄ ⁺ , or an ammonium ion of an amino compound selected from the group consisting of melamine or its condensation products, preferably melam, melem, melon, urea, guanidine, morpholine and piperazine; wherein (ia) when R ¹ and R ² are equally methyl, R ³ , R ⁴ , R ⁵ and R ⁶ represent the same or different substituents, and are selected from the group consisting of linear, branched or cyclic alkyl, alkenyl and alkynyl groups , unsubstituted and alkyl substituted phenyl groups, polycyclic aromatic groups with the number of rings up to 4, monocyclic or polycyclic heteroaromatic groups with the number of rings up to 4, silyl groups, allyl, alkyl or aryl alcohols, cations, where the cation is Mg ²⁺ , Ca ^{2 +} , B ³⁺ , Al ³⁺ , Zn ²⁺ , or an ammonium ion amino compound selected from the group consisting of melamine or its condensation products, preferably melam, melem, melon, urea, guanidine, morpholine and piperazine; and/or (ii) when -X- represents an oxygen atom, -O-, -OR ³ and -OR ⁴ together and/or -OR ⁵ and -OR ⁶ together, including the P-atom of the phosphonate group, form a cyclic phosphonic ester acids with a cycle size of 4-10 atoms; and/or (iii) when -X- is a single bond, R ³ and -OR ⁴ together form a cyclic phosphinic acid ester containing the P-atom of the phosphinate group with a ring size of 4-10 atoms, and/or -OR ⁵ and -OR ⁶ , including the P-atom of the phosphonate group, together form a cyclic phosphonic acid ester with a ring size of 4-10 atoms.

The fire retardant compositions according to the invention can be produced by the method described in patent document DE 3133308 A1. According to this, alkylaminomethane diphosphonic acids and, accordingly, their acrylic derivatives can be obtained in very good yields when the reaction products of acetic anhydride or acetyl chloride and phosphorous acid are reacted with alkylformamides in stoichiometric ratios. To achieve the highest possible yields, the reaction temperature in the first stage of transformation, i.e. the reaction of acetic anhydride or acetyl chloride with phosphorous acid is maintained between 40-60°C.

Instead of the starting acetic anhydride or, respectively, acetyl chloride and phosphorous acid, a mixture of phosphorus trichloride and acetic acid can also be used in the first stage of the reaction.

Suitable alkylformamides include, among others, mono- and dialkylformamides, for example methyl and dimethylformamide, ethyl and diethylformamide, as well as formyl derivatives of morpholine, piperidine, pyrrolidine, oxazolidine, alkanolamines.

In one preferred embodiment, R ¹ and R ² together form an N-atom-containing morpholine or piperidine ring, particularly preferably structures according to formula (II) and (III).

In these structures, preferably X=-O-, and R ³ , R ⁴ , R ⁵ and R ⁶ are H, Na ⁺ , NH ₄ ⁺ , Zn ²⁺ or Al ³⁺ . In one particularly preferred embodiment, all of the residues ^R3 , ^R4 , ^R5 and ^R6 are H. In a further preferred embodiment, three of the residues ^R3 , ^R4 , ^R5 and ^R6 are sodium and one residue is H.

In a further preferred embodiment, R ¹ and R ² together form an N-atom containing 1,3,5-triazacyclohexane ring, particularly preferably with the structure according to formula (IV).

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R ³

R ³ R ⁴ R ⁵ R ⁶ (IV)

In a further preferred embodiment, R ¹ and R ² together form an N-atom containing 1,3,5-triaza-2,4,6-trioxocyclohexane ring, particularly preferably with the structure according to formula (V).

.3%

I 3 I 4 I 5 1 6

R R R R (V)

In a further preferred embodiment, R ¹ and R ² are the same or different substituents, wherein at least one of the substituents is melamine, wherein the nitrogen atom of the amino groups is replaced by an H atom, an alkyl, aryl or methyl bisphosphonate group with the following structure (II).

(II)

Particularly preferred on each of the nitrogen atoms of the amino groups of one of the substituents is H and the other is a methyl bisphosphonate group with structure (II). In another preferred embodiment, on each of the nitrogen atoms of both substituents there is a methyl bisphosphonate group with structure (II).

The fire retardant compositions corresponding to the invention have higher heat resistance than the phosphonates known from the prototype, in which the carbon atom in the α-position to the nitrogen atom is replaced by only one phosphonate group. This means that the decomposition temperature is higher than that of comparable known phosphonates. In the composition according to the invention, the decomposition temperature is understood as the temperature at which the weight loss of a dry sample of the fire retardant composition reaches 2 wt.%. For example, aminotrimethylenephosphonic acid (ATMP, CAS: 6419-19-8) achieves a weight loss of 2 wt.% already at 176.4°C (see Fig. 5). The corresponding weight loss in the case of the phosphonates according to the invention is only achieved at clearly higher temperatures (see FIGS. 2 and 4). The weight loss of a sample as a function of temperature can be measured by thermogravimetry. Dry in this case means that the water content of the fire retardant composition is <0.5 wt.%. The water content of the fire retardant composition can be determined by methods known to those skilled in the art, such as, for example, colorimetric Karl Fischer titration or near-infrared spectroscopy (NIR). The fire retardant composition according to the invention is particularly suitable for incorporation into a polymeric material which is to be processed by extrusion, since it does not decompose at processing temperatures usual for extrusion, but only at higher temperatures occurring in fires, and then exhibits its flame retardant effect.

In addition, the fire retardant composition according to the invention preferably also ensures less flue gas formation. This manifests itself in a large mass of residue after decomposition.

The authors of the present invention proceeded from the fact that the increased heat resistance of the fire retardant compositions corresponding to the invention can be explained by their special structure. In principle, during the thermal decomposition of aminomethanephosphonates, the weak P-C bond of the P-CH2N group is first broken. Although the P-C bond is, in principle, chemically and thermally stable, the α-amino group stabilizes the carbon radical formed during homolysis so that the cleavage of the P-C bond into amino

- 4 043569 nomethanephosphonates occurs already at relatively low temperatures. Since in the compounds according to the prototype the α-amino group has a relatively small molecular weight, the corresponding amine evaporates as a gaseous product after homolysis. The release of the amine is the thermodynamic driving force for the reaction, so that's what mostly happens. In the case of the flame retardant compositions of the present invention, an additional phosphonate group is linked to the carbon radical at the a-position to the amino group. As a result, the amine has a higher molecular weight, so that in principle it only volatilizes in much smaller quantities. In order for the amine to volatilize at lower temperatures, it must have a lower mass, which can only be achieved by the P-C bond with the second phosphonate group also being homolytically cleaved. However, since this would result in the formation of a particularly unstable carbanion, this reaction does not occur or hardly occurs. Accordingly, during the decomposition of the polymer material, a clearly lower release of amine is observed and thus also a lower formation of flue gases. In addition, due to the fact that the amine does not volatilize immediately after bond cleavage, the possibility of a reverse reaction also arises, i.e. recombination of both radicals to form the parent compound. The above effects contribute to the fact that the cleavage of the P-C bond is not as favorable as for the compounds according to the prototype, so that the aminomethanephosphonates corresponding to the invention have a clearly higher thermal stability.

In one preferred embodiment of the invention, the decomposition temperature, i.e. weight loss of dry fire retardant composition at the level of 2 wt.% is achieved only at a temperature of 200°C, especially preferably 220°C and most preferably at a temperature of 245°C.

Since the carbon atom in the a-position to the amino group is doubly replaced by a phosphonate group, the fire retardant compositions corresponding to the invention have a higher phosphorus content than the known phosphonates according to the prototype. The fire retardant effect of phosphorus-containing fire retardants has been found to increase with increasing phosphorus content. Therefore, the efficiency is particularly high, i.e. fire-preventing effect per unit mass of the fire-retardant composition used, corresponding to the invention of fire-retardant compositions. Even with lower concentrations of the flame retardant in the polymer material, a good fire-preventive effect can thereby be achieved. At the same time, it has almost no effect on the properties of the polymer material, in particular, on workability and elongation at break. In one preferred embodiment, the phosphorus content of the fire retardant composition is at least 19.5 wt%, preferably at least 20 wt%, particularly preferably at least 21.5 wt%, most preferably at least 23.5 weight.%. Due to the high phosphorus content of the fire retardant composition according to the invention, the residues R1 to R ⁶ advantageously have as low a mass as possible.

In particular, the product of adding one or more components as an additive can advantageously be made favorable by a catalyzed polymerization reaction in which the flame retardant composition according to the invention is used in the form of a salt or ester, particularly preferably in the form of a salt. Due to this, possible interaction of free acid groups of the fire retardant composition with components, for example, with a reaction catalyst, is prevented. Also in the case of pH-sensitive polymer materials, i.e. polymeric materials, the structures of which change and/or are destroyed by the action of acids, the fire retardant composition according to the invention is preferably used in the form of a salt or ester. Additionally, for such applications, the salt form can be dissolved in water and thereby mixed homogeneously with the polyol. When the flame retardant is used in ester form, it, due to hydrophobization, further promotes better binding to the matrix, which again leads to improved mechanical properties and reduced migration from the polymer.

In one preferred embodiment of the invention, at least one, preferably at least two, especially preferably at least three, most preferably four groups R ³ , R ⁴ , R ⁵ and R ⁶ represent a cation, the cation being Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , B ³⁺ , Al ³⁺ , Zn ²⁺ , NH ₄ ⁺ , or an ammonium ion of an amino compound selected from the group consisting of melamine or its condensation products, preferably melamine, melem, melon, urea, guanidine, morpholine and piperazine. Particularly preferred are Na ⁺ and Ca ²⁺ . The most preferred is the use of Na ⁺ as a cation, since it has a low molecular weight and thereby can maintain the highest possible weight fraction of phosphorus in the fire retardant composition.

In particular, when the polymer to be protected is not a non-polar polyolefin, but a polar polymer such as a polyamide, polyurethane, polyurea or polyester, it may be preferable that the flame retardant composition according to the invention is used in the form of an acid. The flame retardant composition is preferably an acid, particularly when used as condensation/addition co-components. Therefore, in one preferred embodiment of the invention at least one, preferably at least two, especially preferably at least three, most preferably four groups R ³ , R ⁴ , R ⁵ and R ⁶ represent H. For example, the fire retardant composition according to the invention is preferably mo

- 5 043569 can be added in acid form during the polyurethane foaming process as a co-component of the addition reaction. Without intending to go into theory, the authors of the present invention proceed from the fact that as a result of the reaction of the isocyanate and the phosphonic acid group, the flame retardant is incorporated into the polymer with the formation of particularly stable P-O-C(=O)-N-groups, which has a positive effect on polyurethane decomposition characteristics. The same is true for other polymers that are obtained by polyaddition, for example, polyethylene oxide, polypropylene oxide, polyethylene glycol and polyurea. Here, too, the phosphonic acid group reacts with one of the components and is thereby incorporated into the polymer. It is therefore particularly preferred to use the flame retardant composition according to the invention in acid form as a co-component of the addition reaction in the preparation of these polymers.

Likewise, in one preferred embodiment, the flame retardant composition according to the invention is used in acid form as a condensation co-component in a polycondensation reaction. Here, the authors of the present invention proceed from the fact that phosphonic acid groups react with hydroxyl or amino groups of the components of the condensation reaction, and as a result are incorporated into the polymer. Therefore, the flame retardant compositions according to the invention are preferably used in acid form as co-components of the condensation reaction in the production of polyesters, polycarbonates and polyamides.

In one preferred embodiment of the invention, the radicals R ³ and/or R ⁴ and/or R ⁵ and/or R ⁶ are organic radicals with more than two carbon atoms, for example with more than three carbon atoms. Phosphonic acid esters with short-chain carbon residues, in particular methyl groups, are known from the prototype. Since they exhibit an alkylating effect under decomposition conditions, they are still highly toxic. For example, there may be long-term damage to human DNA. However, as the chain length increases, the alkylating effect decreases greatly.

The polymeric materials into which the flame retardant composition may be incorporated are preferably selected from polyvinyl butyral (PVB), polypropylene (PP), polyethylene (PE), polyamide (PA), polyesters such as polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyurethane (PU), thermoplastic polyurethanes (TPU), polyurea, polyphenylene oxide, polyacetal, polyacrylate, polymethacrylate, polyoxymethylene, polyvinyl acetal, polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene-acrylic acid ester copolymer (ASA), polycarbonate , polyethersulfone, polysulfonate, polytetrafluoroethylene, polyurea, formaldehyde resins, melamine resins, polyetheretherketone, polyvinyl chloride, polylactide, polysiloxane, phenolic resins, epoxy resins, polyimide, bismaleimide-triazine, thermoplastic polyurethane, ethylene-vinyl acetate copolymer ( EVA), polylactide ( PLA), polyhydroxybutyric acid (PHB), copolymers and/or mixtures of the above polymers. Particularly preferred is the use of the fire retardant composition according to the invention in foams based on the above polymeric materials, particularly preferably in polyurethane foams. In this case, the fire retardant composition is preferably added as an additive or co-component of the condensation/attachment of the polyol component. When the flame retardant is added as an additive, it is preferably a salt or ester. When the fire retardant is added as a condensation/addition co-component, it is preferably an acid.

When flame retardant compositions are used for this purpose, it is particularly preferable that R ¹ and R ² together form an N-atom-containing morpholine ring so that a flame retardant composition with a structure according to formula (II) is obtained.

(AND)

It was discovered that this phosphonate not only exhibits a fire retardant effect, but that it can also catalyze the foaming of polyurethane.

In one preferred embodiment, the polymeric material contains a flame retardant composition in an amount of at least 1.5 wt.%, or at least 3 wt.%, or at least 5 wt.%, or at least 10 wt.%, or at least 15 wt.%, and/or in an amount not higher than 35 wt.%, not higher than 30 wt.%, or not higher than 25 wt.% based on the entire polymer composition.

With such quantitative ratios, on the one hand, a good fire-retardant effect of the polymer composition is ensured and, on the other hand, there is only a slight effect on the workability characteristics and properties of the polymer material.

The flame retardant composition according to the invention can advantageously be used in combination with other flame retardants, for example those which provide combustion protection according to other mechanisms of action. As a result of the interaction of the fire retardant composition according to the invention with other fire retardants, a synergistic effect can be achieved, i.e. an effect that exceeds the simple sum of the combustion-preventing effects of the individual components.

In one preferred embodiment, the polymeric material contains at least one additional flame retardant, which is preferably selected from nitrogenous bases, melamine derivatives, phosphates, pyrophosphates, polyphosphates, organic and inorganic phosphinates, organic and inorganic phosphonates, and derivatives of the above compounds, preferably selected from polyphosphate ammonium coated melamine, melamine resin, melamine derivatives, silanes, siloxanes, polysiloxanes, silicones or polystyrenes, and/or coated and cross-linked ammonium polyphosphate particles, as well as 1,3,5-triazine compounds, including melamine, melam, melem , melon, ammeline, ammelide, 2-ureidomelamine, acetoguanamine, benzoguanamine, diaminophenyltriazine, melamine salts and adducts, melamine cyanurate, melamine borate, melamine orthophosphate, melamine pyrophosphate, dimelamine pyrophosphate, aluminum diethylphosphinate, melamine polyphosphate, oligomeric and polymer derivatives 1.3 ,5-triazine and polyphosphates of derivatives of 1,3,5-triazine, guanine, piperazine phosphate, piperazine polyphosphate, ethylenediamine phosphate, pentaerythritol, dipentaerythritol, boron phosphate, 1,3,5-trihydroxyethyl isocyanurate, 1,3,5-triglycidylisocyanurate, triallyl isocyanurate , and derivatives of the above compounds. In one preferred embodiment, the polymeric material contains waxes, siloxanes, fats or mineral oils for better dispersibility of additional fire retardant components.

The polymer material, along with the fire retardant composition according to the invention, preferably contains phosphate, in particular ammonium polyphosphate, as additional flame retardants. Since the activity of phosphates in the solid phase generally exceeds that of phosphonates, and phosphonates, on the contrary, have a higher activity in the gas phase, a particularly pronounced combustion-preventive effect can be achieved by the combination.

In one preferred embodiment, the ratio of the flame retardant composition according to the invention to the at least one additional flame retardant in the polymeric material is from 1:18 to 1:1, preferably from 1:9 to 1:4, and particularly preferably from 1:6 to 1: 4. These relationships also apply to the use of ammonium polyphosphate as an additional fire retardant component.

In addition, the polymeric material, along with the fire retardant composition according to the invention, preferably contains additional fillers, which are selected from calcium carbonate, silicates such as talc, clay or mica, kaolin or wollastonite, silica, calcium and barium sulfate, aluminum hydroxide, glass fibers and glass balls, as well as wood flour, cellulose powder, and various types of carbon black and graphite. These fillers can impart additional desirable properties to the polymeric material. In particular, the cost of the polymer material can thereby be reduced, the polymer material can be colored, or its mechanical properties can be improved, for example due to glass fiber reinforcement.

In a further embodiment of the invention, the polymeric material as a whole has a halogen content by weight of <1500 ^ppm , preferably <900 ^ppm by weight. The halogen content can be determined by analysis methods familiar to those skilled in the art, such as combustion ion chromatography (CIC). A particularly low halogen content is advantageous in comparison with the flame retardant compositions according to the prototype, since in known fire retardant compositions an undesirably large amount of halogen is introduced in the form of halogens bound in inorganic and organic compounds. The term halogen-free in the sense of the invention implies minor halogen contaminants in the above-mentioned largest quantities. It is true that halogen must generally be kept at low levels to prevent the harmful effects of halogens.

If the fire retardant composition is introduced into the polymeric material to be protected during the molding process, then a dispersant is preferably used when introducing the fire retardant composition. Therefore, in a further embodiment of the invention, in the polymeric material according to the invention, the dispersant is contained in an amount of from 0.01 to 10% by weight, preferably in an amount from 0.1 to 5.0% by weight, based on the weight of the fire retardant composition according to the invention, wherein the dispersant is preferably selected from fatty acid amides, including fatty acid monoamides, fatty acid bisamides and fatty acid alkanolamides, such as oleoamides and erucamides, from fatty acid esters, including glycerol esters and wax esters, from C16- fatty acids C18 acids, from derivatives of fatty acids and alcohols, including derivatives of fatty acids and cetyl and stearyl alcohols, from natural and synthetic waxes, polyethylene waxes and oxidized polyethylene waxes, and from metal stearates, preferably Ca-, Zn-, Mg- , Ba-, Al-, Cd- and Pb-stearates. The addition of the above dispersants increases the accuracy of dosing of the fire retardant composition, improves the suitability of the polymer material for extrusion and the uniformity of the fire retardant composition dispersed inside the polymer material.

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In a further embodiment of the invention, the fire retardant composition according to the invention has a free water content (moisture content) of <0.6 wt.%, preferably <0.4 wt.%. The low water content also improves the dosage accuracy of the flame retardant, the extrudability of the polymer material and the uniformity of the flame retardant dispersed within the composition and prevents hydrolysis-induced degradation.

The fire retardant composition can be introduced into the polymer material in various ways. Primarily, the flame retardant compound may be incorporated into the polymer material during the molding process. If the polymeric material is, for example, processed by extrusion, then the flame retardant composition can be added during the extrusion process, for example, as part of a masterbatch. A masterbatch in the sense of the present invention is a polymeric material in granulate or powder form, which contains a fire retardant composition and, if necessary, additional additives, in concentrations that are higher than those in the final application. The masterbatch or various masterbatches to produce the polymeric material according to the invention are combined with additional polymeric material without the flame retardant contained in the masterbatch in such quantities and accordingly ratios that correspond to the desired concentrations of the flame retardant in the final product. Masterbatches, compared to the addition of various substances in the form of pastes, powders or liquids, have the advantage that they provide high process reliability and can be processed and dosed very well. As a result of extrusion, the fire retardant composition is uniformly distributed in the polymer material.

In another embodiment, the flame retardant composition is a condensation reaction cocomponent or an addition reaction cocomponent in a polymeric material that is used to produce a polymeric material by polycondensation or polyaddition. The fire retardant composition can thereby be bonded to the polymeric material. The incorporation of the flame retardant into the polymer can be confirmed by suitable analytical methods, in particular ³¹ P-NMR spectroscopy. In one particularly preferred embodiment, the polymeric material is a polyester or polyurethane. The corresponding operating principle has the advantage that the flame retardant composition is firmly bound to the polymer material and can therefore hardly or not be removed from the polymer material, i.e. washout is correspondingly negligible.

The invention also includes a fire retardant composition which is a compound of formula I, its corresponding ammonium salt, its corresponding phosphonate salt, or a mixture of the foregoing, characterized in that at least one of the groups R ³ , R ⁴ , R ⁵ and R ⁶ represents H or a cation, wherein the cation is Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , B ³⁺ , Al ³⁺ , Zn ²⁺ , NH ₄ ⁺ , or an ammonium ion of an amino compound selected from the group consisting of melamine or its condensation products, preferably melam, melem, melon, urea, guanidine, morpholine and piperazine.

The invention also includes the use of a compound of Formula I, its corresponding ammonium salt, its corresponding phosphonate salt, or a mixture of the foregoing, as a flame retardant composition for imparting fire resistance to a polymeric material, in particular a thermoplastic polymer.

Examples

The invention is now further explained by way of specific embodiments of the inventive flame retardant compositions, examples of the preparation of the inventive fire retardant compositions, and also by means of flame retardant examples and accompanying figures.

Specific embodiments of fire retardant compositions corresponding to the invention.

Options with dimethyl group

No. λ/L-o X R ³ R ⁴ R ⁵ R ⁶ 1 -ABOUT- n N N N 2 -ABOUT- ethyl ethyl ethyl ethyl 3 -ABOUT- butyl butyl butyl butyl 4 -ABOUT- N Na Na Na

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Options with diethyl group

No. X R ³ R ⁴ R ⁵ R ⁶ 5 -ABOUT- N N N N 6 -ABOUT- ethyl ethyl ethyl ethyl 7 -O- butyl butyl butyl butyl 8 -O- n Na Na Na

Options with morpholine, MOMP

No. X R ³ R ⁴ R ⁵ R ⁶ 9 -ABOUT- n N N N 10 -ABOUT- ethyl ethyl ethyl ethyl eleven -ABOUT- butyl butyl butyl butyl 12 0 -ABOUT- N Na Na Na

Options with piperazine, PIMP

No. X R ³ R ⁴ R ⁵ R ⁶ 13 0 -ABOUT- n N N N 14 -ABOUT- ethyl ethyl ethyl ethyl 15 -- 0 -ABOUT- butyl butyl butyl butyl 16 0 -ABOUT- N Na Na Na

- 9 043569

Options with 1,3,5-triazacyclohexane ring

No. X R ³ R ⁴ R ⁵ R ⁶ 17 -ABOUT- n N N N 18 ' ^and p' -ABOUT- ethyl ethyl ethyl ethyl 19 -ABOUT- butyl butyl butyl butyl 20 ' ^and p -ABOUT- N Na Na Na

Cyclic Phosphonic Ester Options

No. R ¹ R ² X ^R R ⁴ R ⁵ R ⁶ 21 ethyl ethyl simple connection HP Η Η 22 ethyl ethyl simple connection nr/ HP Na Na 23 ethyl ethyl simple connection nrU HP ethyl ethyl 24 ethyl ethyl simple connection i-X po ⁵ HP butyl butyl

- 10 043569

Cyclic Phosphinic Ester Options

No. R ¹ R ² X b? R^4 R ⁵ R ⁶ 25 ethyl ethyl simple connection and, 1 l*o /k o (d N N 26 ethyl ethyl simple connection STORAGE T 1*0 Na Na 27 ethyl ethyl simple connection P, | 1*0 cx ethyl ethyl 28 ethyl ethyl simple connection A , 1*0 Eh^o sx butyl butyl

Options with morpholine and cyclic phosphonic ester

No. X X ⁴ ° R ⁵ R ⁶ 29 0 simple connection Η N thirty 0 simple connection ntsskg ^Х^'° H^C Na Na 31 0 simple connection nr ethyl ethyl 32 0 simple connection ^ιΧ^· ⁰ Η£ butyl butyl 33 0 simple connection HyC R ³ R ⁴

- 11 043569

Options with morpholine and cyclic phosphinic acid ester

No. ± X VA 13? ^R R ⁵ R ⁶ 34 0 simple connection Qx A Go from N N 35 0 simple connection Qx A G° FROM Na Na 36 0 simple connection Oh ah Г° /k .O From ethyl ethyl 37 7 simple connection P A Go χλ .o From butyl butyl 38 0 simple connection η a Go From R ³ R ⁴

- 12 043569

Options with melamine and cyclic phosphonic ester

No. R ¹ R ² X %A £? R L. R ⁵ R ⁶ 39 G N^N b^M^G^U H simple connection gb \ .ABOUT N N 40 N^N H simple connection nr G ^G y^..o nr Na Na 41 hH, N^N НХ^г/~У H simple connection hucn Г ⁵ уУ^О Нр ethyl ethyl 42 N^N H simple connection 1^0 y o butyl butyl

Options with melamine and cyclic phosphonic ester

No. R ¹ R ² X %L th ? R L, R ⁵ R ⁶ 43 N^N i-y^N^y Η simple connection η. 1*0 (y N N 44 N^N nx^gIu Η simple connection ^|ϊο ug Na Na 45 y h^lN^N^y Η simple connection CXv [ g° y ethyl ethyl 46 N^N NfY^G^U Η simple connection Oh oh oh butyl butyl

- 13 043569

Options with melamine and cyclic phosphonic ester

No. R ¹ R ² X γ\ th ? R L, R ⁵ R ⁶ 47 4 O F^X^ -.4 o Η simple connection HpjT ³ ^tk-O HP N N 48 4 O R-%' .4 o N^N Η simple connection ύΥ nr Na Na 49 4 O _4 about Ν^Ν Η simple connection xX 1-bs ethyl ethyl 50 F^v ⁰ _4 _ about νΧν Η simple connection CHU butyl butyl Cyclic Ester Options 1 I with melamine and > ohm phosphonic acid No. R ¹ R ² X F o R R ⁵ R ⁶ 51 <4 O R-^4/ _4 o Η simple connection | 1*o (U N N 52 fAq /° F^xS 4_ O N^N Η simple connection 1 ko (U Na Na 53 0 ^У ⁿⁱ X Ή Η simple connection ko (U ethyl ethyl 54 4 _L O R-Q'A f^A 4 O ΙΜ^Ν Η simple connection to Χγ^^У butyl butyl

- 14 043569

Examples of obtaining compositions corresponding to the invention.

Starting materials

Name Manufacturer Purity/M _p CAS 4-Formylmorpholine Alfa Aesar 99% 4394-85-8 N, A-Dimethylformamide Merck KGaA >99% 68-12-2 Phosphonic acid Alfa Aesar 99+% 4394-85-8 Acetic anhydride Merck KGaA >98% 108-24-7 Methylene diphenyl isocyanate (MDI) Sigma Aldrich _Mn ~340 9016-87-9 Polyol Sigma Aldrich _Mn ~4000 9082-00-2 Pentane Sigma Aldrich anhydrous, >99 109-66-0 Ethylene glycol Sigma Aldrich anhydrous, 99.8 107-21-1

Additional fire retardants.

Budit 240: phosphorus-containing, partially cross-linked polyacrylate, obtained according to example 1 of patent document WO 2014/124933.

Budit 315: Melamine cyanurate from Chemischen Fabrik Budenheim KG.

Budit 342: melamine polyphosphate from Chemischen Fabrik Budenheim KG.

Budit 667: intumescent fire protection system from Chemischen Fabrik.

Budenheim KG based on ammonium polyphosphate.

TCPP: TCPP tris(2-chloroisopropyl)phosphate from Sigma Aldrich (CAS: 13674-84-5).

OP 550: phosphorus-containing polyol Exolit OP 550 from Clariant AG (CAS: 184538-58-7).

Measurement methods.

Dynamic differential calorimetry (DSC) measurements were carried out using a simultaneous thermogravimetry - dynamic differential calorimetry (STA/TG-DSC) instrument, model STA409 PC/3/H Luxx from Netzsch Geratebau GmbH, in the range from 25 to 500°C, in nitrogen atmosphere, with a heating rate of 10 K/min. The sample weight was about 15 mg. The NETZSCH Proteus software package was used to process the results.

Thermogravimetric analyzes (TGA) were carried out using a device for simultaneous thermogravimetry - dynamic differential calorimetry (STA/TG-DSC), model STA409 PC/3/H Luxx from Netzsch Geratebau GmbH, in the range from 25 to 800°C, in a nitrogen atmosphere, with a heating rate of 10 K/min. The sample weight was 12-15 mg. The NETZSCH Proteus software package was used to evaluate TGA curves.

Example 1. Synthesis of morpholine-methylaminodiphosphonic acid (MOMP-H4).

0.1 mol of 4-formylmorpholine was placed in a 500 ml round bottom flask and mixed with 0.2 mol of phosphonic acid and 30 ml of acetic anhydride. The reaction solution was stirred at 65°C for 90 minutes. Finally, the acetic acid formed was removed as well as excess water in a rotary evaporator under reduced pressure of ~30 mbar (3 kPa) and the residue was freed from residual solvent at 85°C for 4 h in an oven.

Example 2. Synthesis of piperazine-di(methylaminodiphosphonic acid) (PIMP-H ₄ ).

0.28 mol of phosphonic acid in a 250 ml round-bottom flask was dissolved with stirring in 31 ml of completely demineralized water. A solution of 0.07 mol of diformylpiperazine in 30 ml of completely desalted water was added dropwise to them over 15 minutes. During the addition, a temperature increase of several degrees was observed. After addition was complete, the reaction mixture was stirred for another 3 hours at reflux. After cooling the solution, excess water was removed in a rotary evaporator. A saturated solution of piperazine was added dropwise to the liquid residue after distillation. With the release of heat, a white amorphous precipitate formed.

Example 3. Synthesis of dimethyl-methylaminodiphosphonic acid (DAMP-H4).

0.9 mol of dimethylformamide was placed in a 500 ml round bottom flask and mixed with 1.8 mol of phosphonic acid and 225 ml of acetic anhydride. The reaction solution was stirred at 90°C for 90 minutes. Finally, the acetic acid formed was removed as well as excess water in a rotary evaporator under reduced pressure of ~300 mbar (30 kPa) and the residue was freed from residual solvent at 85°C for 4 h in an oven.

Example 4. Synthesis of an aqueous solution of sodium salt of morpholine-methylaminodiphosphonic acid (MOMP-H-Na3).

0.289 mmol of morpholine-methylaminodiphosphonic acid (MOMP-H4) was dissolved in 50 ml of completely demineralized water and 0.867 mmol of NaOH was added. A solution with a pH value of ~9 was obtained.

Example 5 Synthesis of morpholine-methylaminodiphosphonic acid tetraethyl ester (MOMP-Et ₄ ).

- 15 043569

To prepare MOMP-Et4, 0.1 mol of morpholine was placed in a reactor and stirred. Additionally, 0.1 mol of triethoxymethane was added dropwise. Then 0.2 mol of diethyl phosphite was added. The mixture was heated to 120°C and stirred at this temperature for 4 hours. After completion of the reaction, the product was purified by vacuum distillation at a pressure of 50 mbar (5 kPa) and 150°C.

Name Manufacturer Purity CAS Molecular mass Morpholine Merck >99.0% 110-91-8 87.12 g/mol Triethoxymethane Alfa Aesar 98% 122-51-0 148.20 g/mol Diethylphosphite Acros Organics 98% 762-04-9 138.10 g/mol

In one preferred embodiment of the invention, the radicals R ³ , R ⁴ , R ⁵ and R ⁶ are all cations or organic radicals, particularly preferably ethyl, since suitably substituted compounds can act as a catalyst in the synthesis of polyurethane foam. The use of such compounds is particularly advantageous since they not only accelerate the synthesis of polyurethane, but also improve the fire retardant properties of the resulting polymer. Compounds with a P-OH group, such as MOMP-H ₄ , do not exhibit a corresponding catalytic effect, probably because they are in the zwitterion form (POTNH+), the quaternary amino group of which has no catalytic properties.

The so-called reaction time before foam formation is significantly reduced when using suitably substituted compounds compared to compounds with a P-OH group, such as MOMP-H ₄ , as shown by the following experiments.

General procedure: Polyol (22.5 g) is mixed with catalyst (ethylene glycol, 1.05 g), pentane (4.5 g) and this flame retardant at 1000 rpm. Add isocyanate (methylene diphenyl diisocyanate (MDI), 60.0 g) with the dispersant off and the mixture is stirred for 10 s at 1500 rpm and then poured without delay. _______________________

Fire retardant composition Loading [php]* Time [sec] to foaming absent 0 15 MOMR-N ₄ 7.5 15 MOMR-N4 5.0 10 MOMR-N4 2.5 5 MOMP-Et ₄ 10 0-1 Exolit OR 550 7.5 15 Exolit OR 550 2.5 15 TSRR 7.5 10 TSRR 2.5 10

* php - parts per hundred parts of polyol, part per 100 parts of polyol. Example 6. Synthesis of morpholine-methylaminodi-DOPO (MOM-DOPO2).

Name Melting temperature Boiling temperature Molecular mass DOPO (Metadynea DOP11 S25) ~120°С ~400°С 216.18 g/mol 4-FM (AlfaAesar >98%)) 20°С 240°C 115.13 g/mol Ac ₂ O (Merck >98%) -73°С 139°C 102.09 g/mol MOM-DOPO2 no data no data 529.47 g/mol Water 0°C 100°С 18.02 g/mol Acetic acid 17°С 118°C 60.05 g/mol

- 16 043569

In terms of the reaction, we are talking about a condensation reaction in which the product MOM-DOPO2 is formed from the formyl functional group in 4-formylmorpholine (4-FM) and the P-H groups of the DOPO molecule with the elimination of H2O. To do this, 40 g of DOPO are dissolved with stirring in 100 ml of acetic anhydride (Ac2O) in a 250 ml flask and the mixture is heated to 120°C. When this temperature is reached, 10 g of 4-FM is added. After 5 hours, the mixture is neutralized by adding 80 ml of water and external thermostating is stopped. After cooling, a white solid precipitates, which is filtered and washed again with water. Acetic acid is formed as an additional by-product.

Example 7. Synthesis of the Zn salt of morpholine-methylaminodiphosphonic acid (MOMP-H ₂ Zn).

To obtain the Zn salt (1:1), 50.0 g (0.191 mol) of MOMP is dispersed in 500 g of H2O and reacted with 14.6 g of ZnO (0.191 mol). The reaction mixture is heated to 95°C and stirred for 4 hours at this temperature. The mixture is then cooled to below 50° C. and the solid is separated from the mother liquor. The filter cake is dried in ambient air at 120°C.

Name Manufacturer Purity CAS MOMR see Example 1 ZnO Alfa Aesar minimum 99.0% 1314-13-2 H ₂ O, distilled

Example 8. Synthesis of piperazine-dimethylaminodiphosphonic acid. (Р1МР-Н4).

Name Manufacturer Purity CAS Molecular mass 1,4-Diformylpiperazine Alfa Aesar 98+% 4164-39-0 142.16 g/mol Acetic anhydride VWR AnalaR NORMAP UR 108-24-7 102.09 g/mol Phosphorous acid Alfa Aesar 97% 13598-3-2 82.0 g/mol H ₂ O, distilled NaOH, 50% solution 1310-73-2 39.997 g/mol Sulfuric acid Merck 95-97% 7664-93-9 98.08 g/mol

0.1 mol of 1,4-diformylpiperazine and 0.1 mol of acetic anhydride are placed in the reactor and stirred. The mixture is heated to 120°C. Separately dissolve 0.4 mol of phosphorous acid in 0.3 mol of acetic anhydride. This solution is then added dropwise to the reactor. An additional 0.5 mol of acetic anhydride is then added and the mixture is heated to 135°C. After 30 minutes of reaction time, 2.1 moles of water are added dropwise. After an additional 40 minutes of reaction time, the mixture is cooled to room temperature. Then add 70 ml of sodium hydroxide solution. The product is separated from the mother liquor and dissolved in water. Then the precipitate is again separated from the solution by adding sulfuric acid, the product is filtered, washed and dried.

Examples of fire protection.

Compositions.

To verify the fire protection properties and to classify the flame retardant compositions according to the invention in various polymers, a UL94 test was carried out on the test samples prescribed by the IEC/DIN EN 60695-11-10 standard.

UL94-V test.

For each test in each case, 5 test pieces were secured in a vertical position and the free end was inserted into the flame of a Bunsen burner. In this case, using one of the test samples, the burning time and also the falling off of the burning part were assessed. Testing and treatment with a 2 cm Bunsen burner flame was carried out exactly as specified by Underwriter Laboratories, UL94 standard.

The results show gradations according to fire protection classes from V-0 to V-2. V-0 means that the total burning time of the 5 test pieces tested was less than 50 seconds and the cotton swab was not ignited by falling drops of hot or burning components of the test piece. Class V-1 means 5 total burning time tested

- 17 043569 test samples was more than 50 s but less than 250 s, and the cotton swab also did not ignite. V-2 means that the total burning time of the 5 test samples tested was less than 250 seconds, but the cotton swab was ignited by falling drops of the test sample in at least one of the 5 tests. The abbreviation NC means cannot be classified and implies that a total combustion duration of more than 250 s was measured. In many cases where classification was not possible, the test samples burned completely.

UL94-NV-test.

For each measurement in each case, at least 3 test pieces were secured in a horizontal position and the free end was inserted into the flame of a Bunsen burner. At the same time, the burnout rate and the total length of the burned area were assessed. Testing and treatment with a 2 cm Bunsen burner flame was carried out exactly as specified by Underwriter Laboratories, UL94 standard.

The results show gradations according to NV fire protection classes.

The NV classification means that the burnout rate between two markings, the first of which was 25 mm from the burning end, the second 100 mm from the burning end, was less than 40 mm/min. In addition, the flame front did not cross the 100 mm marking. The abbreviation NC means cannot be classified and implies that over a 75 mm long section the burn rate was >40 mm/min or the total length of the burnt section was >100 mm.

Example 9. Characteristics of fire protection MOMP-N ₄ in polypropylene.

Polymers.

To obtain flame retardant compositions in the following examples, the following polymeric materials were used.

Polypropylene (PP) HD120 MO from Borealis AG.

Using a Process 11 twin-screw extruder from Thermo Fisher Scientific Inc., granulates with a grain size of approximately 3x1x1 mm were formed under normal conditions for polypropylene extrusion. The extrusion process was carried out with a productivity of 5-7 kg/h and a screw rotation speed of 450-500 rpm and at an extrusion zone temperature of 190-220°C. Subsequent hot pressing produced UL94-compliant test pieces with good quality. The thickness of the test samples was 1.6 and, respectively, 3.2 mm. During the extrusion process, the phosphonate obtained according to Example 1 was introduced into the polymer material.

No. RR [%] Thickness [mm] PTO R [%] Budit 667 Budit 240 UL94 ti C tges 0 100 1.6 0 - - N.C. 376* _* 376 1 75 1.6 25 - - N.C. 95 70 165 2 72.5 1.6 27.5 - - V-2 9 54 63 3 75 3.2 25 - - v-o. 4 6 10 4 72.5 3.2 27.5 - - V-0 4 4 8 5 75 3.2 - 25 - V-0 5 5 10 6 75 1.6 - - 25 N.C. 231 34 265 7 72.5 1.6 - - 27.5 N.C. 227 28 255

Example 10. Combustion protection characteristics of MOMP-N4 in polyurethane (PU).

To obtain fire-protective compositions, the following components were introduced into the reaction in a foaming reaction:

polyol: 22.5 g;

catalyst (ethylene glycol): 1.05 g;

pentane: 4.5 g;

isocyanate (MDI): 60 g.

The flame retardant composition according to the invention was added to the polyol component before the reaction. The mass fractions of fire retardant listed in the following table correspond to the sum of the masses of polyol, catalyst, fire retardant and isocyanate.

- 18 043569

No. P.U. [%] Fire retardant composition [%] Loading [%] UL94-HB tges 0 100 - - N.C. 50 1 98.2 MOMR-N ₄ 1.8 NV 7 2 98.2 MOMR-2K ^# 1.8 N.C. thirty 3 91.8 MOMP-2K7 8.2 N.C. 20 4 98.2 DAMP-H ₄ 1.8 NV 4 54 98.2 TSRR 1.8 N.C. 26 6 97.1 OR 550 2.9 NV 32 7 97.4 MOMP-Et ₄ 2.6 NV 4 8** 97.4 MOMP-Et ₄ 2.6 NV 6

* Double potassium salt MOMP-H4;

* * without catalyst.

Example 11. Flame retardant properties of MOMP-N4 in thermoplastic polyurethane (TPU).

To obtain flame retardant compositions in the following examples, the following polymeric materials were used: thermoplastic polyurethane (TPU) Elastollan 1185 A from BASF SE.

Using a Process 11 twin-screw extruder from Thermo Fisher Scientific Inc., granulates with a grain size of approximately 3x1x1 mm were formed under normal TPU extrusion conditions. The extrusion process was carried out with a productivity of 5 kg/h and a screw rotation speed of 300 rpm and at an extrusion zone temperature of about 205°C. Subsequent hot pressing produced UL94-compliant test pieces with good quality. The thickness of the test samples was 0.8 mm. During the extrusion process, the phosphonate obtained according to Example 1 was introduced into the polymer material.

No. TPU [%1 Budit 315 [%1 Budit 342 [%1 Budit 240 [%] M.O.M. P [%] Loading [%] UL94 tl t ₂ tges Notes 0 100 - - - - 0 N.C. 323~ -~ 323 butc* 1 90 - 5 - 5 10 V-2 4 2 6 4/5 ditc ^# 2 90 5 - - 5 10 V-0 2 4 6 - 3 90 - - - 10 10 V-0 9 5 14 - 4 90 10 - - - 10 V-0 3 5 8 - 5 90 - 10 - - 10 V-2 eleven 5 16 5/5 ditc ^# 6 90 5 - 5 - 10 V-2 3 1 4 5/5 ditc ^#

* butc=test sample burned to clamp;

# ditc=falling drops set the cotton on fire;

~ the second ignition is impossible, since the test sample has already burned out after the first ignition.

Example 12 Flame retardant performance of MOMP-H ₄ Zn in thermoplastic polyamide (PA).

To obtain flame retardant compositions in the following Examples, the following polymeric materials were used:

polyamide 6: Ultramid B3S (BASF);

glass fibers (GF) for PA: CS7928 (Lanxess).

Using a Process 11 twin-screw extruder from Thermo Fisher Scientific Inc., granulates with a grain size of approximately 3x1x1 mm were formed under normal PA6 extrusion conditions. The extrusion process was carried out with a productivity of 5 kg/h and a screw rotation speed of 300 rpm and at an extrusion zone temperature of about 280°C. Subsequent hot pressing produced UL94-compliant test pieces with good quality. The thickness of the test samples was 0.8 mm. During the extrusion process, the phosphonate obtained according to example 7 (MOMP-H ₂ Zn) was introduced into the polymer material.

- 19 043569

No. PA6 [%] GF [%] Budit 611 [%] Exolit* * [%] MOMP-H ₂ Zn Budit 341 [%] UL94-V tl [s] _t2 [s] tges [s] Notes 0 44.8 thirty 23 2.2 V.O. 8 10 18 1 55 thirty 15 N.C. 243 butc 2 50 thirty 20 V.O. 12 5 17 3 45 thirty 25 V.O. 6 2 8 4 45 thirty 17.5 7.5 V.O. 9 9 18

* butc=test sample burned to clamp;

** Exolit OP 1230;

~ the second ignition is impossible, since the test sample has already burned out after the first ignition.

Description of the figures

The accompanying figures present the results of thermogravimetric measurements, with FIG. 1 - measurement of DAMP-H4 by differential calorimetry;

in fig. 2 - thermogravimetric measurement DAMP-H ₄ ;

in fig. 3 - measurement of MOMP-H4 by differential calorimetry;

in fig. 4 - thermogravimetric measurement of MOMR-N4;

in fig. 5 - ATMR measurement using differential calorimetry;

in fig. 6 - thermogravimetric ATMR measurement;

in fig. 7 - measurement of MOMP-Et ₄ by differential calorimetry;

in fig. 8 - thermogravimetric measurement MOMP-Et ₄ ;

in fig. 9 - measurement of MOMP-DOPO2 by differential calorimetry;

in fig. 10 - thermogravimetric measurement of MOM-DOPO2;

in fig. 11 - measurement of MOMP-H ₂ Zn by differential calorimetry;

in fig. 12 - thermogravimetric measurement of MOMP-H ₂ Zn;

in fig. 13 - PIMP measurement using differential calorimetry;

in fig. 14 - thermogravimetric measurement PIMP.

Material 1% loss weight 2% weight loss Residual mass at 500°C MOMP-H ₄ 251.7°C 276.9°C 64.29% DAMP-H ₄ 244.5°C 273.1°C 71.41% ATMP-H4 176.4°C 193.9°C 72.43% MOMP-Et ₄ 101.7°C 117.1°C 19.58% MOM-dopo ₂ 305.5°C 318.9°C 7.50% MOMP-H ₂ Zn 375.0°C 382.3°C 78.75% PIMP-H ₄ 199.3 245.4 71.63%

Claims (15)

1. A fire-retardant composition that contains a polymeric material and a halogen-free fire-retardant composition contained therein and/or associated with it in an amount of 1 to 40 wt.% based on the entire composition, characterized in that the fire-retardant composition is a compound of the formula (I), its corresponding ammonium salt, its corresponding phosphonate salt, or a mixture of the above: 1 2 r' to Ν О=Р _> ^/ ^Р=О x ^z b о о R ³ R ⁴ R ⁵ R ⁶ (!) where (i) R ¹ and R ² represent the same or different substituents and are selected from the group consisting of linear, branched or cyclic alkyl, alkenyl and alkynyl groups, unsubstituted and alkyl-substituted phenyl groups , monocyclic and polycyclic aromatic groups with a number of rings up to 4, monocyclic or polycyclic heteroaromatic groups with a number of rings up to 4, silyl groups, allyl, alkyl or aryl alcohols; or - 20 043569 (ii) R ¹ and R ² together form an N-atom containing saturated, or singly unsaturated, or multiply unsaturated heterocycle with 4-8 atoms in the ring, which are selected from carbon, oxygen, sulfur, phosphorus, silicon and nitrogen, moreover, in a heterocycle, when it has nitrogen atoms as ring atoms, these ring atoms have as substituents H, an alkyl, aryl or methyl bisphosphonate group with the following structure (II): Moreover, in a heterocycle, when it has carbon, phosphorus or silicon as ring atoms, these atoms may have substituents selected from the group consisting of H, alkyl, aryl, -NH ₂ , -NHR, -NR2, -OH, - OR, =O, -I, -Cl, -Br, with R=alkyl, aryl, where -X- represents an oxygen atom -O- or -X- represents a single bond, and where (i) R ³ , R ⁴ , R ⁵ and R ⁶ represent the same or different substituents and are selected from the group consisting of H, linear, branched or cyclic alkyl, alkenyl and alkynyl groups, unsubstituted and alkyl-substituted phenyl groups, polycyclic aromatic groups with up to 4 rings, monocyclic or polycyclic heteroaromatic groups with the number of rings up to 4, silyl groups, allyl, alkyl or aryl alcohols, cations, where the cation is Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , B ³⁺ , Al ³⁺ , Zn ²⁺ , NH4 ⁺ or ammonium ion of an amino compound selected from the group consisting of melamine or its condensation products; wherein (ia) when R ¹ and R ² represent methyl, R ³ , R ⁴ , R ⁵ and R ⁶ represent the same or different substituents and are selected from the group consisting of linear, branched or cyclic alkyl, alkenyl and alkynyl groups, unsubstituted and alkyl-substituted phenyl groups, polycyclic aromatic groups with a number of rings up to 4, monocyclic or polycyclic heteroaromatic groups with a number of rings up to 4, silyl groups, allyl, alkyl or aryl alcohols, cations, where the cation is Mg ²⁺ , Ca ²⁺ , B ³⁺ , Al ³⁺ , Zn ²⁺ or ammonium ion of an amino compound selected from the group consisting of melamine or its condensation products; and/or (ii) when -X- represents an oxygen atom, -O-, -OR ³ and -OR ⁴ together and/or -OR ⁵ and -OR ⁶ together, including the P-atom of the phosphonate group, form a cyclic phosphonic acid ester with a cycle size of 4-10 atoms; and/or (iii) when -X- is a single bond, R ³ and -OR ⁴ together form a cyclic phosphinic acid ester containing the P-atom of the phosphinate group with a ring size of 4-10 atoms and/or -OR ⁵ and -OR ⁶ together form a cyclic phosphonic acid ester containing the P-atom of the phosphonate group with a ring size of 4-10 atoms, wherein in the case where the composition contains a polymeric material to which a halogen-free flame retardant composition is associated, said halogen-free flame retardant composition is is a co-component of a condensation reaction or a co-component of an addition reaction in a polymer material, which is used to obtain a polymer material by polycondensation or polyaddition. 2. The composition according to claim 1, characterized in that R ¹ and R ² together form an N-atom-containing morpholine or piperidine ring. 3. The composition according to claim 1, characterized in that R ¹ and R ² represent the same or different substituents, and at least one of the substituents is melamine, where the nitrogen atoms of the amino group are replaced by an H atom, an alkyl, aryl or methyl bisphosphonate group with the following structure (II): 4. The composition according to one of the preceding claims, characterized in that the dry fire retardant composition achieves a mass loss of 10 wt.% at a temperature of 320°C, where dry means that the water content in the fire retardant composition is <0.5 wt.%, while weight loss is determined by thermogravimetric analysis in a nitrogen atmosphere at a heating rate of 10 K/min. 5. The composition according to one of the preceding claims, characterized in that the phosphorus content in the fire retardant composition is at least 19.5 wt.%. 6. Composition according to one of the preceding claims, characterized in that at least one, preferably two, even more preferably at least three, most preferably - 21 043569 four groups R ³ , R ⁴ , R ⁵ and R ⁶ represent a cation or H, preferably H, the cation being Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , B ³⁺ , Al ³⁺ , Zn ²⁺ , NH ₄ ⁺ , or an ammonium ion amino compound selected from the group consisting of melamine or its condensation products, preferably melamine, melem, melon, urea, guanidine, morpholine and piperazine. 7. The composition according to one of the preceding claims, characterized in that at least one of the groups R ³ , R ⁴ , R ⁵ and R ⁶ represents an organic residue, each organic residue having more than two carbon atoms. 8. The composition according to one of the preceding claims, characterized in that the polymeric material is a thermoplastic selected from the group consisting of polyvinyl butyral (PVB), polypropylene (PP), polyethylene (PE), polyamide (PA), polyesters such as polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyurethane (PU), polyurea, polyphenylene oxide, polyacetal, polyacrylate, polymethacrylate, polyoxymethylene, polyvinyl acetal, polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene-acrylic acid ester copolymer (ASA), polycarbonate, polyethersulfone, polysulfonate, polytetrafluoroethylene, formaldehyde resins, melamine resins, polyetherketone, polyvinyl chloride, polylactide, polysiloxane, phenolic resins, epoxy resins, polyimide, bismaleimide triazine, thermoplastic polyurethane, ethylene vinyl acetate copolymer (EVA), copolymers and/or mixtures of the above polymers. 9. The composition according to one of the preceding claims, characterized in that the polymer material contains a fire retardant composition in an amount of at least 3 wt.%, or at least 5 wt.%, or at least 10 wt.%, or at least 15 wt.%, and/or in an amount not exceeding 35 wt.%, or not exceeding 30 wt.%, or not exceeding 25 wt.% based on the entire composition. 10. The composition according to one of the preceding claims, characterized in that it contains at least one additional flame retardant, which is preferably selected from nitrogenous bases, melamine derivatives, phosphates, pyrophosphates, polyphosphates, organic and inorganic phosphinates, organic and inorganic phosphonates and derivatives of the above compounds preferably selected from ammonium polyphosphate coated with melamine, melamine resin, melamine derivatives, silanes, siloxanes, polysiloxanes, silicones or polystyrenes and/or ammonium polyphosphate particles coated and cross-linked therewith, as well as 1,3,5-triazine compounds , including melamine, melam, melem, melon, ammeline, ammelide, 2-ureidomelamine, acetoguanamine, benzoguanamine, diaminophenyltriazine, melamine salts and adducts, melamine cyanurate, melamine borate, melamine orthophosphate, melamine pyrophosphate, dimelamine pyrophosphate, aluminum diethylphosphinate, polyphosphate melamine, oligomeric and polymeric 1,3,5-triazine compounds and polyphosphates of 1,3,5-triazine compounds, guanine, piperazine phosphate, piperazine polyphosphate, ethylenediamine phosphate, pentaerythritol, dipentaerythritol, boron phosphate, 1,3,5-trihydroxyethyl isocyanurate, 1,3,5-triglycidyl isocyanurate and triallyl isocyanurate. 11. The composition according to one of the preceding claims, characterized in that it contains at least one filler which is selected from calcium carbonate, silicates such as talc, clay or mica, silica, calcium and barium sulfate, aluminum hydroxide, glass fibers and glass beads, as well as wood flour, cellulose powder and various types of carbon black and graphite. 12. The composition according to one of the preceding claims, characterized in that it contains a polymeric material in an amount of at least 50 wt.%, preferably at least 70 wt.%, especially preferably at least 80 wt.% and most preferably at least at least 90 wt.%. 13. A method for producing a fire retardant composition according to one of the preceding paragraphs, characterized in that the fire retardant composition is a co-component of the condensation reaction or a co-component of the addition reaction of the polymer material, which, upon production of the polymer material, is introduced into the polymer material by polycondensation or polyaddition. 14. A fire retardant composition as defined in one of claims 1 to 12, characterized in that at least one of the groups R ³ , R ⁴ , R ⁵ and R ⁶ is H or a cation, wherein the cation is Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , B ³⁺ , Al ³⁺ , Zn ²⁺ , NH ₄ ⁺ , or an ammonium ion of an amino compound selected from the group consisting of melamine or its condensation products. 15. Use of a compound of formula (I), its corresponding ammonium salt, its corresponding phosphonate salt or a mixture of the above components as a fire retardant composition for imparting fire resistance to a polymeric material: - 22 043569 O=P P=O wherein (i) R ¹ and R ² represent the same or different substituents and are selected from the group consisting of linear, branched or cyclic alkyl, alkenyl and alkynyl groups, unsubstituted and alkyl-substituted phenyl groups, monocyclic and polycyclic aromatic groups with the number rings up to 4, monocyclic or polycyclic heteroaromatic groups with the number of rings up to 4, silyl groups, allyl, alkyl or aryl alcohols; or (ii) R ¹ and R ² together form an N-atom-containing saturated or singly unsaturated or multiply unsaturated heterocycle with 4-8 ring atoms selected from carbon, oxygen, sulfur, phosphorus, silicon and nitrogen, wherein heterocycle, when it has nitrogen atoms as ring atoms, these ring atoms have as substituents an H, alkyl, aryl or methyl bisphosphonate group with the following structure (II): (II) where in a heterocycle, when it has carbon, phosphorus or silicon as ring atoms, these atoms may have substituents selected from the group consisting of H, alkyl, aryl, -NH ₂ , -NHR, -NR ₂ , - OH, -OR, =O, -I, -Cl, -Br, with R=alkyl, aryl, and where -X- represents an oxygen atom, -O- or -X- represents a single bond, and where (i) R ³ , R ⁴ , R ⁵ and R ⁶ represent the same or different substituents and are selected from the group consisting of H, linear, branched or cyclic alkyl, alkenyl and alkynyl groups, unsubstituted and alkyl-substituted phenyl groups, polycyclic aromatic groups with up to 4 rings , monocyclic or polycyclic heteroaromatic groups with the number of rings up to 4, silyl groups, allyl, alkyl or aryl alcohols, cations, where the cation is Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , B ³⁺ , Al ³⁺ , Zn ²⁺ , NH ₄ ⁺ or ammonium ion of an amino compound selected from the group consisting of melamine or its condensation products; and/or (ii) when -X- represents an oxygen atom, -O-, -OR ³ and -OR ⁴ together and/or -OR ⁵ and -OR ⁶ together, including the P-atom of the phosphonate group, form a cyclic phosphonic acid ester with a cycle size of 4-10 atoms; and/or (iii) when -X- is a single bond, R ³ and -OR ⁴ together form a cyclic phosphinic acid ester containing the P-atom of the phosphinate group with a ring size of 4-10 atoms and/or -OR ⁵ and -OR ⁶ together they form a cyclic ester of phosphonic acid containing the P-atom of the phosphonate group with a ring size of 4-10 atoms.