EP4013817A1

EP4013817A1 - Polymer composition comprising phosphonate flame retardant

Info

Publication number: EP4013817A1
Application number: EP20754256.4A
Authority: EP
Inventors: Birgit Fassbender; Christian Dippel; Christian LITTERSCHEID; Christian KUDLA; Tobias Moss; Sebastian MOSCHEL; Sebastian FEIDNER
Original assignee: Chemische Fabrik Budenhiem KG
Current assignee: Chemische Fabrik Budenhiem KG
Priority date: 2018-08-15
Filing date: 2020-08-12
Publication date: 2022-06-22
Also published as: JP7481323B2; BR112021026877A2; CN112805323A; TW202018070A; WO2021028496A1; PT3837311T; JP2021534279A; EP3837311A1; CN114258415A; KR20220047271A; BR112021000559A2; TWI844555B; US20210309831A1; US20220389191A1; EP3837311B1; DE102018119835A1; ES2926251T3; KR102702442B1; EA202190520A1; PL3837311T3

Abstract

The invention relates to a composition containing a polymer material and a phosphorus-containing flame retardant on the basis of an aminomethyl bisphosphonate, to a process for preparing the composition, to the use of the flame retardant and to selected structures of the flame retardant.

Description

Polymer composition with phosphonate flame retardant

OBJECT OF THE INVENTION

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

BACKGROUND OF THE INVENTION

Numerous substances are known for the flame retardant finishing of polymer materials, which can be used alone or in combination with other substances which provide similar or complementary flame retardant properties. The best-known flame retardants include halogenated organic compounds, metal hydroxides, organic or inorganic phosphates, phosphonates or phosphinates and 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. High molecular, ie polymeric, flame retardants such as the halogenated polyol Exolit OP 550 from Clariant advantageously have only slight plasticizer effects and low migration capacity in the polymer material, but in contrast to the low molecular weight flame retardant additives, they are often used in technical processing less miscible with the polymer material to be protected, especially if the meltability is poor. Furthermore, the curing of the polymer material can be negatively influenced by adding the high molecular weight flame retardant.

The majority of the flame retardants used are therefore low-molecular compounds. In this field, among other things, phosphorus-containing compounds are known to be particularly efficient. In the event of a fire, these can expand into voluminous protective layers in polymer materials, which is known as intumescence. This forms an insulating layer that inhibits the supply of oxygen and prevents the polymer material from burning further. Furthermore, the flame-retardant effect in the solid phase can be based on an increase in the charring rate of the polymer material or the formation of inorganic glasses. A gas phase mechanism also contributes to the flame-retardant activity, in which the combustion process of the polymer material is caused by radical combinations with PO radicals that result from the combustion. formation of the phosphorus compound is greatly slowed down. The most important phosphorus-containing compounds are the halogenated phosphates tris (2-chloroethyl) phosphate (TCEP) and tris (2-chloroisopropyl) phosphate (TCPP). Their use is, however, due to their potential toxicity and the ecological problems associated with their use go hand in hand, increasingly restricted, in particular because such phosphates are subject to bioaccumulation, but municipal sewage treatment plants can only separate them from the wastewater with difficulty. They also contain halogen, which in the event of fire leads to the formation and release of HX gases and other toxic compounds. Corrosive combustion gases of this kind represent a high risk, particularly in the electronics sector.

An alternative to phosphate-containing flame retardants are halogenated and halogen-free phosphonates. Compared to the phosphates, these show a particularly pronounced flame-retardant gas phase activity. DE 2 128 060 describes the use of aminomethane phosphonic acid esters with a phosphorus content of up to 23.2% by weight as flame retardants in polyurethanes. The aminomethane phosphonic acid esters are made from hexamethylenetetramine and dialkyl or diaryl phosphonates. To use these phosphonates, they are dissolved together with other additives that may be required in the polyol component of a polyurethane-forming mixture and a polyisocyanate is added to this. The esters containing NH groups are incorporated into the polymer material by addition to the isoyanate group.

EP 0 001 996 relates to the production of N, N-bis (2-hydroxylalkyl) aminomethane-phosphonic acid dimethyl esters, which are mainly used as flame-retardant additives in polymer materials, especially in polyurethanes. For their synthesis, an H-acidic compound is added as a catalyst to a mixture of dimethyl phosphite and oxazolidine. The products have a terminal secondary hydroxyl group and can thus be incorporated into the polymer material when added to the polyol component of a polyurethane-forming mixture. The added H-acidic substances then remain in the polymer material, which can lead to an impairment of the properties. Alternatively, they have to be converted into their corresponding alkali metal salts before they are added to the polyol component so that they can be separated from the phosphonic acid esters.

CA 2 027 078 relates to aminomethanephosphonic acid aryl esters, which can be used as flame retardants in foams, thermoplastics and thermosets. The corresponding compounds are produced by reacting an amine with trialkyl or triaryl phosphites and paraformaldehyde. The products can either be added to the polymer material to be processed in the extrusion process or serve as an additive for the co-condensation component in a polycondensation reaction. From Liu et al., Ind. Eng. Chem. Res. (2017), 56, 8789-8696, DOPO derivatives with a flame retardant effect are known, which are derived from DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), paraformaldehyde and Piperazine can be produced. These are halogen-free and have a flame-retardant effect when used in polycarbonates. However, like those of the aforementioned documents, these compounds also have only a low thermal stability, which is due to the weak PC bond of the P-CH ₂ N group. Although the PC bond is basically chemically and thermally stable, the α-amino group stabilizes the carbon radical produced by homolysis, so that the PC bond cleavage in these flame retardants takes place at relatively low temperatures. Since the tertiary amine that is formed by homolysis has a low molar mass, it escapes as a volatile component and causes a corresponding loss of mass. If the flame retardant is embedded in a polymer material, the release of the amine can increase the formation of smoke gases. Due to the low decomposition temperature, some of the flame retardants are already degraded during the molding process of the polymer material into which they are incorporated. Another disadvantage of these flame retardants is that, due to their low phosphorus content, they have to be added to the polymer material in high concentrations, as a result of which processability, flexibility and other product properties of the polymer material are considerably impaired.

TASK

Against this background, the object of the present invention was therefore to provide a composition with a polymer material which has a flame retardant with similar or even better flame retardant properties than those known from the prior art, which has lower concentrations in the Composition can be used with a good flame-retardant effect at the same time, which only decomposes at higher temperatures than the known flame retardants, preferably well above the processing and / or production temperature and just below or at the decomposition temperature of the polymer material, and when it decomposes in the Polymer material a lower smoke density and / or a lower smoke toxicity occurs.

SOLUTION

This object is achieved according to the invention by a composition which has a polymer material, in particular a thermoset polymer material, and a flame retardant contained therein and / or bound in an amount of 1 to 40% by weight, based on the total composition , characterized in that the flame retardant is a compound of the formula (I), its corresponding ammonium salt, its corresponding phosphonate salt or a mixture of the aforementioned:

in which

(Ni) R ¹ and R ^{2 are} identical or different substituents and are selected from the group consisting of linear, branched or cyclic alkylene, alkenylene and alkynylene, unsubstituted and alkyl-substituted phenylene, mononuclear and multinuclear aromatics with up to to 4 nuclei, mononuclear or multinuclear heteroaromatics with up to 4 nuclei, silylene, allyl, alkyl or aryl alcohols, or

(N-ii) R ¹ and R ² together, including the N atom, form a saturated or monounsaturated or polyunsaturated heterocycle with 4-8 ring atoms selected from carbon, oxygen, sulfur, phosphorus, silicon and nitrogen , where on the heterocycle, if it has nitrogen atoms as ring atoms, these nitrogen atoms are preferably substituted with H, an alkyl, an aryl or a methyl bisphosphonate group of the following structure (II), and where on the heterocycle, if it has carbon, phosphorus or silicon as ring atoms, these atoms can preferably have substituents selected from the group consisting of H, alkyl, aryl, -NH ₂ , -NHR, -NR ₂ , -OH, -OR, = 0, -I, -CI, -Br, F, -N ₃ , -SH, -SR, -OCN, epoxy, lactam, lactone, aziridine, glycolide, oxazoline, ether, alkenylene and Alkynylene, -SiRxHy with R = alkyl, alkenyl, alkynyl or aryl and x + y - 3, and wherein -X- is an oxygen atom, -O-, or -X- is a single bond and wherein

(Pi) R ³ , R ⁴ , R ⁵ and R ^{6 are} identical or different substituents and are selected from the group consisting of H, linear, branched or cyclic alkylene, alkenylene and alkynylene, unsubstituted and alkyl-substituted phenylene, and multinuclear aromatic compounds with up to 4 nuclei, mononuclear or multinuclear heteroaromatics with up to 4 nuclei, silyls, allyl, alkyl or aryl alcohols, the following structures (III) and (IV) with n = 0 to 100, as well as cations wherein the cation Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , B ³⁺ , Al ³⁺ , Zn ²⁺ , NH ₄ ⁺ or the ammonium ion of an amine compound selected from the group consisting of melamine or its Condensation products, preferably melam, melem, melon, urea, guanidine, morpholine and piperazine, and / or

(P-ii) when -X- is an oxygen atom, -O-, -OR ³ and -OR ⁴ together and / or -OR ⁵ and -OR ⁶ and / or -OR ³ and -OR ⁵ together and / or -OR ⁴ and -OR ⁶ together, including the P atom of the phosphonate group, form a cyclic phosphonic acid ester or a cyclic phosphonic anhydride with a ring size of 4-10 atoms, and / or

(P-iii) when -X- is a single bond, -R ³ and -OR ⁴ and / or -R ³ and -OR ⁵ together, including the P atom of the phosphinate group, a cyclic phosphinate or a cyclic Phosphinic anhydride with a ring size of 4-10 atoms and / or -OR ⁵ and -OR ⁶ and / or -OR ⁴ and -OR ⁶ together, including the P atom of the phosphonate group, form a cyclic phosphonic acid ester or a cyclic phosphonic anhydride form a ring size of 4-10 atoms, in which

A.) one of the substituents R ¹ to R ⁶ or

B.) one of the cycles that are formed when

1) the substituents R ³ - R ^{6 form} a cyclic phosphinic or phosphonic acid ester according to (P-ii) or (P-iii) or

2) the substituents R ³ -R ^{6 form} a cyclic phosphine or phosphonic anhydride according to (P-ii) or (P-iii) or

3) the substituents R ¹ and R ^{2 form} a heterocycle according to (N-ii), having a first uncharged or negatively charged functional group, which a) a hetero atom selected from the group consisting of P, O, N, S, I, CI, Br, F and / or b) has an alkene or alkyne group, the functional group not being —OH and, in the event that one of the cycles according to 1) to 3) has the functional group, the ring atoms of the cycle with of the functional group or with a substituent which the functional group has substituted.

According to the invention, a functional group is understood to mean a group of atoms in a compound which decisively determines the material properties and the reaction behavior of the compound, for example because it influences the polarity of the molecule and / or can react with other compounds. However, the functional groups according to the invention do not include those atomic groups in which one of the heteroatoms mentioned under a) or an alkene or alkyne group is part of the ring of an aromatic system, i.e. aromatics and heteroaromatics.

The fact that the first uncharged or negatively charged functional group is not —OH, however, does not mean in the context of the invention that the substituents R ¹ to R ⁶ or one of the cycles which are formed when the substituents R ³ -R ^{6 are} a cyclic phosphine - Or phosphonic acid esters according to (P-ii) or (P-iii) or the substituents R ³ -R ^{6 form} a cyclic phosphinic or phosphonic anhydride according to (P-ii) or (P-iii) or the substituents R ¹ and R ² one Form heterocycle according to (N-ii), cannot have an OH group. In the context of the invention, however, these must additionally have a first uncharged or negatively charged functional group as defined in claim 1.

The substituents R ¹ to R ⁶ or one of the cycles which are formed when the substituents R ³ -R ^{6 form} a cyclic phosphinic or phosphonic acid ester according to (P-ii) or (P-iii) or the substituents R ³ preferably have -R ^{6 form} a cyclic phosphinic or phosphonic anhydride according to (P-ii) or (P-iii) or the substituents R ¹ and R ^{2 form} a heterocycle according to (N-ii), no OH group. This can be advantageous, for example, if the OH group would react with other additives in the polymer material.

If the substituents R ¹ to R ^{6 form} a cycle according to 1) to 3), the functional group can only be arranged on the substituents of the ring atoms, ie it cannot itself be part of the ring. The functional group is therefore not arranged in the cycle but on the substituents on the ring atoms of the cycle. For example, R ¹ to R ^{2 can form} a morpholine ring and thus a cycle according to 3), but the ether group contained in the ring is not a functional group for the purposes of the present invention. The ring atoms of the morpholine can, however, additionally be substituted with a functional group according to the invention be or with a substituent which has the functional group according to the invention.

In a preferred embodiment -X- is an oxygen atom, -O- and -OR ³ and -OR ⁴ together, including the P atom of the phosphonate group, form a cyclic phosphonic acid ester or a cyclic phosphonic anhydride with a ring size of 4-10 Atoms and - OR ⁵ and -OR ⁶ together form, including the P atom of the phosphonate group, a cyclic phosphonic acid ester or a cyclic phosphonic anhydride with a ring size of 4-10 atoms.

In a preferred embodiment -X- is an oxygen atom, -O- and -OR ³ and -OR ⁵ together, including the P atom of the phosphonate group, form a cyclic phosphonic acid ester or a cyclic phosphonic anhydride with a ring size of 4-10 Atoms and - OR ⁴ and -OR ⁶ together form, including the P atom of the phosphonate group, a cyclic phosphonic acid ester or a cyclic phosphonic anhydride with a ring size of 4-10 atoms.

In a further preferred embodiment, -X- is a single bond and -R ³ and -OR ⁴ together form the P atom of the phosphinate group, including a cyclic phosphinic acid ester or a cyclic phosphinic anhydride with a ring size of 4-10 atoms and -OR ⁵ and -OR ⁶ together, including the P atom of the phosphonate group, form one cyclic phosphonic acid ester or a cyclic phosphonic acid anhydride with a ring size of 4-10 atoms.

In a further preferred embodiment -X- is a single bond and -R ³ and -OR ⁵ together form the P atom of the phosphinate group, including a cyclic phosphinic acid ester or a cyclic phosphinic anhydride with a ring size of 4-10 atoms and -OR ⁴ and -OR ⁶ together, including the P atom of the phosphonate group, form a cyclic phosphonic acid ester or a cyclic phosphonic acid anhydride with a ring size of 4-10 atoms,

Particularly preferably, R ¹ and R ² together, including the N atom, form a morpholine or piperidine ring.

In a preferred embodiment of the invention, the substituents R ³ to R ⁶ or the cycles formed by them have the first functional group.

In a preferred embodiment of the invention, R ¹ and R ² together, including the N atom, form a heterocycle according to (N-ii), these atoms having substituents on the heterocycle if it has carbon, phosphorus or silicon as ring atoms which are preferably selected from the group consisting of H, alkyl, aryl, -NH ₂ , -NHR, -NR ₂ , -OH, -OR, = 0, -I, -CI, -Br, F, -N ₃ , -SH, -SR, -OCN, epoxy, lactam, lactone, aziridine, glycolide, Oxazoline, ether, alkenylene and alkynylene, -SiRxHy with R = alkyl, alkenyl, alkynyl or aryl and x + y = 3.

In a preferred embodiment of the invention, the first and / or further functional group has a heteroatom from the group consisting of P, O, N, S, Si or an alkene or alkyne group. Since, with halogen-containing substituents, there is increased smoke gas formation when the flame retardant decomposes in the event of a fire, the amount of smoke gas can be kept low by avoiding halogen substituents.

The composition particularly preferably has a total halogen content of <1000 ppm by weight, preferably <850 ppm by weight. The halogen content can be determined by the analysis methods common to those skilled in the art, such as combustion ion chromatography (CIC). The particularly low halogen content is advantageous over the flame retardants from the prior art, since the known flame retardants introduced an undesirably large amount of halogen in the form of inorganically and organically bound halogens. The term “halogen-free” in the context of the invention allows low levels of halogen contamination in the aforementioned Maximum quantities. However, halogen should generally be kept low in order to avoid the disadvantageous effects of the halogens.

In a preferred embodiment of the invention, at least one of the substituents R ³ , R ⁴ , R ⁵ and R ^{6 is} an organic radical, each of these organic radicals having more than two, preferably more than three carbon atoms.

The flame retardants according to the invention can be produced by the method described in DE 31 33 308 A1. According to this, alkylaminomethane-diphosphonic acids or their acrylic derivatives can be obtained in very good yields if the reaction products of acetic anhydride or acetyl chloride and phosphorous acid are reacted with alkylformamides in stoichiometric ratios. To achieve the highest possible yield, the reaction temperature of the first reaction stage, i.e. the reaction of acetic anhydride or acetyl chloride with phosphorous acid, should be kept between 40-60 ° C. Instead of the educts acetic anhydride or acetyl chloride and phosphorous acid, a mixture of phosphorus trichloride and acetic acid can also be used in the first reaction step. Suitable alkylformamides include mono- and dialkylformamides such as methyl and dimethylformamide, ethyl and diethylformamide and the formyl compounds of morpholine, piperidine, pyrolidine, oxazolidine and alkanolamines.

The flame retardants according to the invention have a higher thermal stability than the phosphonates known from the prior art, in which the carbon in the α-position to the nitrogen is only substituted with one phosphonate group. This means that the decomposition temperature is higher than that of comparable known phosphonates. In the context of the invention, the decomposition temperature is understood as the temperature at which a weight loss of 2% by weight of a dry sample of the flame retardant is achieved. For example, aminotrimethylene phosphonic acid (ATMP, CAS: 6419-19-8) already achieves a mass loss of 2% by weight at 176.4 ° C. (see FIG. 5). A corresponding loss of mass is only achieved with the phosphonates according to the invention at significantly higher temperatures (see FIGS. 2 and 4).

The loss of mass of the sample as a function of the temperature can be determined by thermogravimetry. In this case, “dry” means that the water content of the flame retardant is <0.5% by weight. The water content of the flame retardant can be determined by methods known to the person skilled in the art, such as, for example, colorimetric Kari-Fischer titration or NIR spectroscopy. The flame retardant according to the invention is particularly suitable for incorporation into a polymer material which is to be processed by extrusion, since it does not decompose at the processing temperatures customary for extrusion, but only at the higher temperatures occurring in fires and then its flame retardant effect unfolds.

In addition, the flame retardant according to the invention advantageously also has a lower level of development of smoke gases. This manifests itself in a higher residual mass after decomposition.

The inventors assume that the increased thermal stability of the flame retardants according to the invention is due to their special structure. In principle, during the thermal decomposition of aminomethane phosphonates, a bond cleavage occurs first at the weak P-C bond of the P-CH ₂ N group. Although the PC bond is basically chemically and thermally stable, the α-amino group stabilizes the carbon radical produced by the homolysis, so that the PC bond cleavage with aminomethane phosphonates takes place at a lower temperature. Since the α-amino group has a relatively low molecular weight in the compounds from the prior art, the corresponding amine can escape as a gaseous product after homolysis. The escape of the amine is a thermodynamic driving force for the reaction, so that it takes place preferentially. In the flame retardants of the present invention, a further phosphonate group is bonded to the carbon radical in a position relative to the amine group. As a result, the amine has a higher molecular weight, which means that, in principle, only a much smaller proportion of it escapes. So that the amine can escape at lower temperatures, it would have to have a lower mass, which can only be achieved if the PC bond to the second phosphonate group is also cleaved homolytically. However, since this would result in a particularly unstable carbanion, this reaction does not take place or hardly takes place at all. Correspondingly, during the decomposition in a polymer material, a significantly lower amine release and thus also less smoke gas development can be observed. Furthermore, the fact that the amine does not escape immediately after the bond has been cleaved also enables the reverse reaction, ie the combination of the two radicals to form the starting compound. The abovementioned effects contribute to the fact that the cleavage of the PC bond is not as advantageous as in the case of the compounds from the prior art, so that the aminomethane phosphonates according to the invention have a significantly increased thermal stability.

In addition, the at least one heteroatom or the at least one alkene or alkene group which the first functional group and optionally the further functional group has, contributes to an increased flame retardant effect. The inventors assume that the heteroatoms or the alkene or alkyne group can form radicals with their energetically high free electron pairs or p -bonding electron pairs. By combining these radicals with the other radicals that occur during combustion processes, the degradation reactions can be slowed down. Since the flame retardants according to the invention are very uniform Can be distributed in the polymer material, a particularly good flame retardant behavior is guaranteed.

In a preferred embodiment of the invention, the substituents R ¹ to R ⁶ or the cycles formed by them have at least one further functional group which is a heteroatom selected from the group consisting of P, O, N, S, Si, I, CI, Br, F and / or an alkene or alkyne group. As a result, the above-described effect of slowing down the radical breakdown processes and thus the flame-retardant effect is further enhanced.

In a preferred embodiment of the invention, the substituents R ¹ to R ⁶ or the cycles formed by them have at least two further functional groups, more preferably at least three, even more preferably at least four and most preferably at least five.

In a preferred embodiment of the invention, the substituents R ¹ to R ⁶ or the cycles formed by them each have at least one functional group. In a particularly preferred embodiment of the invention, the substituents R ³ to R ⁶ or the cycles formed by them each have at least one functional group. The number of functional groups in all substituents or the cycles formed by them is particularly preferably the same. Most preferably, R ³ to R ^{6 are} the same substituents. Such compounds of the general formula (I) are particularly readily accessible synthetically, for example by esterification of the corresponding phosphonic acids.

In a preferred embodiment of the invention, the first and / or further functional group is used to match the polarity of the flame retardant to the polarity of the polymer material. If the flame retardant and the polymer material have a comparable polarity, the flame retardant can be better incorporated into the polymer material and, as a result, better distribution can be achieved. In addition, the flame retardant then migrates more difficultly from the polymer material.

In a preferred embodiment of the invention, the first and / or further functional group of the flame retardant is selected from the group consisting of -NH ₂ , -NHR, -NR ₂ , -OH, -OR, = 0, -SH, -SR, -COOH, -COOR, -OCN, -SCN, -SiR _x H _y, -I, -CI, -Br, -F, -N ₃ and epoxy, lactam, lactone, aziridine, glycolide, oxazoline, where R = alkyl , Alkenyl, alkynyl or aryl and x + y = 3.

A selection of these functional groups is associated with the advantage that the polarity of the substituents is increased compared to alkyl and / or aryl substituents without functional groups and corresponding flame retardants can therefore be better incorporated into polar polymer materials (such as, for example, polyacrylates, polyurethanes or polyamides) and are more difficult to migrate out of the polymer material.

In a further preferred embodiment of the invention, the first and / or further functional group of the flame retardant are selected from the group consisting of -SiR _x H _y, alkenylene and alkynylene, where R = alkyl, alkenyl, alkynyl or aryl and x + y = 3.

A selection of these functional groups has the advantage that the polarity of the substituents is lower than that of alkyl and / or aryl substituents without functional groups and corresponding flame retardants are therefore better incorporated into non-polar polymer materials such as polyalkylenes (e.g. polyethylene, polypropylene) can and more difficult to migrate out of the polymer material.

In addition, compounds with the above-mentioned functional groups can be used as comonomers in the production of the polymer material, as a result of which the flame retardant is covalently bonded to the polymer material. This is associated with the advantage that the flame retardant cannot migrate out of the polymer material, or only with great difficulty. In addition, a more even distribution of the flame retardant within the polymer material is achieved. This results in an increased flame retardant effect.

In a preferred embodiment, the first and / or further functional group can be an NH ₂ group. The flame retardant can then be added to a polycondensation reaction and incorporated into the polymer chain by reacting with an electrophilic group of one of the monomers. This is shown below as an example for the formation of polyamide 6,6. In a particularly preferred embodiment of the invention, the flame retardant according to the invention has at least one further functional group which is selected from the group consisting of -NH ₂ , -NHR, -NR ₂ , -OH, -OR, = 0, -SH, - SR, -COOH, -COOR, -OCN, - SiRxHy, -l, -Cl, -Br, -F and epoxy, lactam, lactone, aziridine, glycolide, oxazoline, ether, alkenylene and alkynylene, where R = alkyl, alkenyl , Alkynyl or aryl and x + y = 3.

This increases the likelihood of incorporation of the flame retardant into the polymer chain and maximizes the advantages associated with incorporation. In a particularly preferred embodiment of the invention, the flame retardant according to the invention has at least two functional groups which correspond to those of a monomer of the polymer material. In this way, the flame retardant can be incorporated into the polymer chain without the chain breaking off.

In a particularly preferred embodiment of the invention, the flame retardant according to the invention has at least two different functional groups. This allows the flame retardant to be incorporated in various polymerization reactions. For example, one functional group can be an NH ₂ group and another an alkene group. The flame retardant can then either be incorporated into a polymer chain via the alkene group by means of radical polymerization or by means of a polycondensation reaction via the NH ₂ group.

The flame retardants according to the invention have the advantage that they are liquid and / or dissolve very easily in polar solvents and therefore only influence the viscosity of the solvent to a small extent. The flame retardants according to the invention can therefore be easily processed and used in polymerization reactions. In particular, the viscosity problems that occur in polyaddition and condensation reactions can be reduced by using the flame retardants according to the invention. As a result, the Trommsdorf-Norrish effect occurs later, so that higher mean molar masses of the polymer material can be achieved. In a preferred embodiment, R ¹ and R ² do not form a cycle and are identical or different substituents, with at least one of the substituents being melamine, the nitrogen atoms of the amino groups with H, an alkyl, an aryl or a methyl bisphosphonate group of the following structure (II) are substituted.

Particular preference is given to one of the substituents H on each of the nitrogen atoms of the amino groups and a methyl bisphosphonate group of structure (II) on the other. In another preferred embodiment, both substituents on each of the nitrogen atoms are a methyl bisphosphonate group of structure (II).

Because of the polarity difference between flame retardants and polymer material, polar flame retardants such as the generic phosphonates normally migrate very easily from non-polar polymer materials such as polyethylene.

The first and / or further functional group of the flame retardant is particularly preferably an alkene or alkyne group. This is associated with the advantage that the flame retardant can be bound to a non-polar polymer material such as a polyolefin in the course of a polymerization reaction, in particular a free radical or ionic polymerization reaction. This prevents migration from the polymer material.

In particular if the polymer material to be protected is not a non-polar polyolefin but a polar polymer such as a polyamide, a polyurethane, a polyurea or a polyester, it can be advantageous to use the flame retardant according to the invention as an acid. Especially when used as a co-condensation / addition component, the flame retardant is preferably an acid; in a preferred embodiment of the invention, at least one, preferably at least two, particularly preferably at least three, most preferably four of the groups R ³ , R are ⁴ , R ⁵ and R ⁶ H. For example, the flame retardant according to the invention can be added, preferably in the form of the acid, to a polyurethane foaming process as a co-addition component. Without being bound by this theory, the inventors assume that the reaction of isocyanate and phosphonic acid group causes the flame retardant to be incorporated into the polymer with the formation of a particularly stable POC (= O) -N group, which is positive affects the decomposition behavior of the polyurethane. The same applies to other polymers, which are produced by polyaddition, for example polyethylene oxides, polypropylene oxides, polyethylene glycols and polyureas. 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 retardants according to the invention in the form of the acid as a co-addition component in the production of these polymers.

Analogously, in a preferred embodiment, the flame retardant according to the invention is used in the form of the acid as a co-condensation component in a polycondensation reaction. The inventors assume here that the phosphonic acid groups react with the hydroxyl or amine groups of the components of the condensation reaction and are thereby incorporated into the polymer. The flame retardants according to the invention are therefore preferably used in the form of the acid as a co-condensation component in the production of polyesters, polycarbonates and polyamides.

In a preferred embodiment of the invention, the substituents R ³ and / or R ⁴ and / or R ⁵ and / or R ^{8 are} organic radicals with more than two carbon atoms. Phosphonic acid esters with short-chain carbon radicals, in particular methyl, are known from the prior art. Since these have an alkylating effect under decomposition conditions, they can, however, be highly toxic. For example, human DNA can be permanently damaged. With increasing chain length, however, the alkylation effect decreases sharply.

The decomposition temperature of the polymer is preferably higher than the processing temperature of the plastic matrix in the thermal processing method by which the polymer is to be incorporated into the plastic matrix. This ensures that the polymer does not undergo any decomposition processes when the processing temperature of the plastic matrix is reached. The decomposition temperature of the polymer is preferably over 10 ° C. above the processing temperature of the plastic matrix, particularly preferably over 20 ° C. above the processing temperature of the plastic matrix, most preferably over 50 ° C. above the processing temperature of the plastic matrix.

If the decomposition temperature of the polymer is well above that of the plastic matrix into which the polymer is incorporated, the plastic matrix will decompose in the event of a fire before the polymer can develop a flame-retardant effect due to its partial decomposition. In the opposite case, i.e. if the decomposition temperature of the polymer is significantly below that of the plastic matrix, the decomposed polymer may already have entered into secondary reactions, so that its flame-retardant effect is considerably reduced. The difference between the decomposition temperatures of the polymer and the plastic matrix is therefore preferably less than 100.degree. C., particularly preferably less than 50.degree. C., most preferably less than 20.degree. In a preferred embodiment of the invention, the decomposition temperature, ie a mass loss of the dry flame retardant of 2% by weight, is only reached from a temperature of 200 ° C., particularly preferably 220 ° C., most preferably from a temperature of 245 ° C.

The decomposition temperature of the polymer is determined using the thermogravimetric analysis method described in the section on measurement methods. The decomposition temperature is the temperature at which a weight loss of 2% in the dry sample is achieved at a heating rate of 10 K / min.

Since the carbon atom in position a to the amino group is twice substituted with a phosphonate group, the flame retardants according to the invention have a higher phosphorus content than the known phosphonates from the prior art. It was found that the flame retardant effect of phosphorus-containing flame retardants increases with increasing phosphorus content. The effectiveness, ie the flame-retardant effect per unit mass of flame retardant used, of the flame retardants according to the invention is therefore particularly high. A good flame-retardant effect can therefore be achieved even with low concentrations of flame retardants in the polymer material. At the same time, the properties of the polymer material, in particular the processability and elongation at break, are hardly affected. In a preferred embodiment, the phosphorus content of the flame retardant is at least 10% by weight, preferably at least 12% by weight, particularly preferably at least 14% by weight, most preferably at least 15% by weight. So that the phosphorus content of the flame retardant according to the invention is high, the substituents R ¹ -R ⁶ advantageously have the lowest possible mass.

In particular when one or more components of a preferably catalyzed polymerization reaction are added as an additive, it can be advantageous to use the flame retardant according to the invention as a salt or ester, particularly preferably as a salt. This avoids possible interaction of free acid groups of the flame retardant with the components, for example with the catalyst of the reaction. The flame retardant according to the invention can also be used advantageously as a salt or ester in the case of pH-sensitive polymer materials, ie polymer materials which change their structure and / or are decomposed under the action of acids. Furthermore, for such applications, the salt form can be dissolved in water and mixed homogeneously with the polyol in one way. The salt form dissolved in water can also be incorporated very easily and homogeneously in water-based paints and coating systems. If the flame retardant is used as an ester, the hydrophobization can also contribute to better binding to the matrix, which in turn leads to better mechanics and less migration from the polymer. In a preferred embodiment of the invention, at least one, preferably at least two, particularly preferably at least three, most preferably four of the groups R ³ , R ⁴ , R ⁵ and R ^{6 are} a cation, the cation being Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , B ³⁺ , Al ³⁺ , Zn ²⁺ , NH ₄ ⁺ or the ammonium ion of an amine compound selected from the group consisting of melamine or its condensation products, preferably melam, melem, melon, Urea, guanidine, morpholine and piperazine. Na ⁺ and Ca ²⁺ are particularly preferred. Most preferred is the use of Na ⁺ as a cation, since this has a low molar mass and the weight fraction of phosphorus in the flame retardant can be kept as high as possible.

In a preferred embodiment, the polymer material contains the flame retardant in an amount of at least 1.5% by weight or at least 5% by weight or at least 10% by weight or at least 15% by weight and / or in an amount of at most 35% by weight or at most 30% by weight or at most 25% by weight, based on the total polymer composition.

In a preferred embodiment of the invention, the entire composition contains polymer material in an amount of at least 50% by weight, preferably at least 70% by weight, particularly preferably at least 80% by weight and most preferably at least 90% by weight.

With these proportions, on the one hand, a good flame retardant effect of the polymer composition is guaranteed and, on the other hand, the processing and material properties of the polymer material are only slightly influenced.

The flame retardant according to the invention can advantageously be used in combination with other flame retardants, for example with those which bring about flame retardancy by a different mechanism. The interaction of the flame retardant according to the invention with other flame retardants can achieve a synergistic effect, i.e. an effect that goes beyond the mere sum of the flame-retardant effect of the individual components.

The polymer material of the composition according to the invention can be an elastomer, thermoset or thermoplastic polymer material. The polymer material is preferably a thermoset or thermoplastic polymer material, particularly preferably a thermoset polymer material.

In a preferred embodiment, the polymer material contains at least one further flame-retardant component, which is preferably selected from nitrogen bases, melamine derivatives, phosphates, pyrophosphates, polyphosphates, organic and inorganic phosphates Phinates, organic and inorganic phosphonates and derivatives of the aforementioned compounds, preferably selected from ammonium polyphosphate, with melamine, melamine resin, melamine derivatives, silanes, siloxanes, polysiloxanes, silicones or polystyrenes coated and / or coated and crosslinked ammonium polyphosphate particles, and 1, 3 , 5-triazine compounds, including melamine, melam, melem, melon, ammeiin, ammelide, 2-ureidomelamine, acetoguanamine, benzoguanamine, diaminphenyltriazine, melamine salts and adducts, melamine cyanurate, melamine borate, melamine orthophosphate, melamine phosphine phosphate, aluminum phosphate phosphate, melamine pyrophosphate , Melamine polyphosphate, oligomers 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 3,5-T riglycidyl isocyanurate, triallyl isocyanurate and d derivatives of the aforementioned compounds. In a preferred embodiment, the polymer material contains waxes, silicones, siloxanes, fats or mineral oils for better dispersibility of the further flame retardant component.

In addition to the flame retardant according to the invention, the polymer material preferably contains a phosphate, in particular ammonium polyphosphate, as a further flame retardant component. The ammonium polyphosphate is particularly preferably an ammonium polyphosphate of crystal forms I, II or V or a mixture thereof; it is particularly preferably coated.

Particularly preferred is ammonium polyphosphate of crystal form II, which is almost insoluble in water compared to the other crystal forms. It is a powdery substance which, even without a coating, has a good flame-retardant effect with low water solubility at the same time. The advantage of using coated ammonium polyphosphate of crystal form II is that it has a higher thermal stability and higher compatibility with polymers, so that an improved dispersion of the flame retardant in the polymer, an improved processing profile of the polymer and a more efficient fire protection achieved becomes.

Since the solid phase activity of phosphates generally exceeds that of phosphonates, whereas phosphonates have a higher gas phase activity, a particularly pronounced flame-retardant effect can be achieved through the combination.

In a preferred embodiment, the ratio of flame retardant according to the invention to the at least one further flame retardant component in the polymer material is 1:18 to 1: 1, preferably 1: 9 to 1: 4 and particularly preferably 1: 6 to 1: 4. These ratios also apply to the use of ammonium polyphosphate as a further flame retardant component. In addition to the flame retardant according to the invention, the polymer material also preferably contains other fillers, which include calcium carbonate, silicates such as talc, clay or mica, kaolin or wolastonite, silica, calcium and barium sulphate, aluminum hydroxide, glass fibers and glass balls, and wood flour, cellulose powder and Carbon blacks and graphites are selected. These fillers can bring about further desired properties of the polymer material. In particular, the price of the polymer material can be reduced, the polymer material can be colored or its mechanical properties can be improved, for example by reinforcement with glass fibers.

If the flame retardant is incorporated into the polymer material to be protected in a reshaping process, a dispersing aid is advantageously used when incorporating the flame retardant. In a further embodiment of the invention, the polymer material according to the invention therefore contains a dispersing aid in an amount of 0.01 to 10% by weight, preferably in an amount of 0.1 to 5.0% by weight, based on weight of the flame retardant according to the invention, the dispersant preferably from fatty acid amides, including fatty acid monoamides, fatty acid bisamides and fatty acid alkanolamides, such as oleamides and erucamides, from fatty acid esters, including glycerol esters and wax esters, from C16 to C18 fatty acids, including fatty acid alcohols -Fatty acid alcohols, is selected 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 aforementioned dispersing auxiliaries improves the meterability of the flame retardant, the extrudability of the polymer material and the homogeneity of the dispersed flame retardant within the polymer material.

In a further embodiment of the invention, the flame retardant according to the invention has a content of free water (moisture content) of <0.6% by weight, preferably <0.4% by weight. A low water content also improves the dosability of the flame retardant, the extrudability of the polymer material and the homogeneity of the dispersed flame retardant within the composition and prevents hydrolysis-related decomposition.

The flame retardant can be incorporated into the polymer material by various methods. First of all, the flame retardant can be incorporated into the polymer material during the molding process. If the polymer material is processed, for example, by extrusion, the flame retardant can be added in the extrusion process, for example by means of a masterbatch. For the purposes of the present invention, a masterbatch is a polymer material in the form of granules or powder, which contains the flame retardant and any other additives in concentrations that are higher than in the end use. The masterbatch or To produce the polymer material according to the invention, various masterbatches are combined with further polymer material without the flame retardant contained in the masterbatch in such amounts or proportions which correspond to the desired concentrations of the flame retardant in the end product. Compared to the addition of various substances in the form of pastes, powders or liquids, masterbatches have the advantage that they ensure a high level of process reliability and are very easy to process and dose. The extrusion distributes the flame retardant evenly in the polymer material.

Polymer materials into which the flame retardant can be incorporated are preferably 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), thermoplastic polyurethanes (TPU), polyurea, polyphenylene oxide, polyacetal, polyacrylate, polymethacrylate, polyoxymethylene, polyvinyl acetal, polystyrene, acryl-butadiene-styrene (ABS), acrylonitrile-styrene-acrylic ester (ASA), polycarbonate, Polyether sulfone, polysulfonate, polytetrafluoroethylene, polyurea, formaldehyde resins, melamine resins, polyether ketone, polyvinyl chloride, polylactide, polysiloxane, phenolic resins, epoxy resins, poly (imide), bismaleimide triazine, thermoplastic polyurethane (EVA-vinyl acetate), thermoplastic polyurethane, ethylene-vinyl acetate ), Polyhydric butyric acid (PHB), copolymers and / or mixtures of the aforementioned polymers. It is particularly preferred to use the flame retardant according to the invention in foams of the aforementioned polymer materials, particularly preferably in polyurethane foams. The flame retardant is preferably added to the polyol component as an additive or co-condensation / addition component. If the flame retardant is added as an additive, this is preferably a salt or an ester. If the flame retardant is added as a co-condensation / addition component, it is preferably an acid.

It was observed that these phosphonates not only have a flame-retardant effect, but that they can also catalyze the polyurethane foaming.

The invention also encompasses a flame retardant which is a compound of the formula I, its corresponding ammonium salt, its corresponding phosphonate salt or a mixture of the aforementioned, with the substituents R ³ to R ⁶ or the cycles formed by them preferably having the first functional group and / or at most three of the substituents R ³ to R ^{6 are} H.

The invention also comprises a method for producing a flame retardant, which comprises the following steps: Providing a mixture of a) at least one phosphonic or phosphinic acid selected from the group consisting of the compounds of the formulas (V) and (VI) in a reaction container where -X- is an oxygen atom, -O-, or -X- is a single bond and where

(Pi) R ³ , R ⁴ , R ⁵ and R ^{6 are} identical or different substituents and are selected from the group consisting of H, linear, branched or cyclic alkylene, alkenylene and alkynylene, unsubstituted and alkyl-substituted phenylene, multinuclear aromatics with up to 4 nuclei, mononuclear or multinuclear heteroaromatics with up to 4 nuclei, silyls, allyl, alkyl or aryl alcohols, the following structures (III) and (IV) with n = 0 to 100, as well as cations wherein the cation Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , B ³⁺ , Al ³⁺ , Zn ²⁺ , NH ₄ * or the ammonium ion of an amine compound selected from the group consisting of melamine or its Condensation products, preferably melam, melem, melon, urea, guanidine, morpholine and piperazine, and / or

(P-ii) when -X- is an oxygen atom, -O-, -OR ³ and -OR ⁴ together and / or -OR ⁵ and -OR ⁶ and / or -OR ³ and -OR ⁵ together, and / or -OR ⁴ and -OR ⁶ together, including the P atom of the phosphonate group, form a cyclic phosphonic acid ester or a cyclic phosphonic acid anhydride with a ring size of 4-10 atoms, and or

(P-iii) when -X- is a single bond, -R ³ and -OR ⁴ and / or -R ³ and -OR ⁵ together, including the P atom of the phosphinate group, a cyclic phosphinate or a cyclic Phosphinic anhydride with a ring size of 4-10 atoms and / or -OR ⁵ and -OR ⁶ and / or -OR ⁴ and -OR ⁶ together, including the P atom of the phosphonate group, form a cyclic phosphonic acid ester or a cyclic phosphonic anhydride a ring size of 4-10 atoms, b) HC (OR ⁷ ) ₃ with R ⁷ = alkyl, aryl or alkenyl, preferably triethoxymethane, c) an amino compound of the formula (VII) in which

(N-ii) R ¹ and R ² together, including the N atom, form a saturated or monounsaturated or polyunsaturated heterocycle with 4-8 ring atoms selected from carbon, oxygen, sulfur, phosphorus, silicon and

Nitrogen, where on the heterocycle, if it has nitrogen atoms as ring atoms, these nitrogen atoms are preferably substituted with H, an alkyl, an aryl or a methyl bisphosphonate group of the following structure (II), and where on the heterocycle, if it has carbon, phosphorus or silicon as ring atoms, these atoms can preferably have substituents selected from the group consisting of H, alkyl, aryl, -NH ₂ , -NHR, -NR ₂ , -OH, -OR, = 0, -I, -CI, -Br, F, -N ₃ , -SH, -SR, -OCN, epoxy, lactam, lactone, aziridine, glycolide, oxazoline, alkenylene and alkynylene, - SiRxHy with R- alkyl, alkenyl, alkynyl or aryl and x + y = 3, with preferably

A.) one of the substituents R ¹ to R ⁶ or

B.) one of the cycles that are formed when

1) the substituents R ³ -R ^{6 form} a cyclic phosphinic or phosphonic acid ester according to (P-ii) or (P-iii) or

3) the substituents R ¹ and R ^{2 form} a heterocycle according to (N-ii), having a first uncharged or negatively charged functional group which a) a hetero atom selected from the group consisting of P, O, N, S, I , CI, Br, F and / or b) has an alkene or alkyne group, the functional group not being —OH and, in the event that one of the cycles according to 1) to 3) has the functional group, the ring atoms of the cycle are substituted with the functional group or with a substituent which has the functional group Heat the mixture to a temperature in the range of 40-150 ° C.

A purification step can follow after the mixture has been heated. This preferably comprises a distillative or chromatographic purification of the mixture.

During the reaction, the phosphonic or phosphinic acids or the amino compounds of the formula (VII) attack nucleophilically on the central carbon atom of the orthoester HC (OR ⁷ ) ₃ via the lone pairs of electrons of the PH or NH groups, so that under Release of three equivalents of the alcohol HÖR ⁷ creates a compound of the formula (I).

In order to achieve higher conversions, in a preferred embodiment of the invention, HÖR ⁷ can be separated off during the reaction, preferably by distillation, particularly preferably by distillation under reduced pressure.

The invention also includes a process for the preparation of the compounds of the general formulas (V) and (VI).

These can be obtained by esterifying the phosphinic or phosphonic acids with a compound of the formula HC (OR ^3/4/5/6 ) ₃ . In a preferred embodiment of this process, HC (OR ^3/4/5/6 ) _{3 is} triethoxymethane. For the process according to the invention, phosphinic or phosphonic acids are mixed with a compound of the formula HC (OR ^{3 / 4.5 / 6} ) ₃ and heated to a temperature in the range of 40-140 ° C, preferably 80-120 ° C, more preferably 90-120 ° C and most preferred Heated 100-120 ° C. The mixture is particularly preferably heated to boiling. The reaction mixture is stirred for a period of 10 minutes to 10 hours at these temperatures, preferably for a period of 1 hour to 5 hours, more preferably 1 hour to 3 hours and most preferably 1 hour to 2 hours. After this reaction time, fractional distillation of the reaction solution ^gives one fraction with the main constituent HOR ^3/4/5/6 and another with the compound of the formula (V) or (VI).

The abovementioned process for the preparation of diethyl phosphite is particularly preferably used.

The invention also comprises the use of a compound of the formula (I), its corresponding ammonium salt, its corresponding phosphonate salt or a mixture for surface treatment, preferably in the form of a coating, in which

(N-ii) R ¹ and R ² together, including the N atom, form a saturated or monounsaturated or polyunsaturated heterocycle with 4-8 ring atoms selected from carbon, oxygen, sulfur, phosphorus, silicon and Nitrogen, where on the heterocycle, if it has nitrogen atoms as ring atoms, these nitrogen atoms are preferably substituted with H, an alkyl, an aryl or a methyl bisphosphonate group of the following structure (II), and where on the heterocycle, if it has carbon, phosphorus or silicon as ring atoms, these atoms can preferably have substituents selected from the group consisting of H, alkyl, aryl, -NH ₂ , -NHR, -NR ₂ , - OH, -OR, = 0, -I, -CI, -Br, F, -N ₃ , -SH, -SR, -OCN, epoxy, lactam, lactone, aziridine, glycolide, oxazoline, alkenylene and alkynylene, -SiR _x H _y with R = alkyl, alkenyl, alkynyl or aryl and x + y = 3, and where -X- is an oxygen atom, -O-, or -X- is a single bond and where

(Pi) R ³ , R ⁴ , R ⁵ and R ^{6 are} identical or different substituents and are selected from the group consisting of H, linear, branched or cyclic alkylene, alkenylene and alkynylene, unsubstituted and alkyl-substituted phenylene, multinuclear aromatics with up to 4 nuclei, mononuclear or multinuclear heteroaromatics with up to 4 nuclei, silyls, allyl, alkyl or aryl alcohols, the following structures (III) and (IV) with n = 0 to 100, as well as cations where the cation Na *, K ⁺ , Mg ² *, Ca ² *, B ³ *, Al ³ *, Zn ² *, NH ₄ * or the ammonium ion of an amine compound selected from the group consisting of made of melamine or its condensation products, preferably melam, meters,

Melon, urea, guanidine, morpholine and piperazine, and / or

(P-ii) when -X- is an oxygen atom, -O-, -OR ³ and -OR ⁴ together and / or -OR ⁵ and -OR ⁶ and / or -OR ³ and -OR ⁵ together, and / or -OR ⁴ and -OR ⁶ together, including the P atom of the phosphonate group, form a cyclic phosphonic acid ester or a cyclic phosphonic anhydride with a ring size of 4-10 atoms, and / or

(P-iii) when -X- is a single bond, -R ³ and -OR ⁴ and / or -R ³ and -OR ⁵ together, including the P atom of the phosphinate group, a cyclic phosphinate or a cyclic Phosphinic anhydride with a ring size of 4-10 atoms and / or -OR ⁵ and -OR ⁶ and / or -OR ⁴ and -OR ⁶ together, including the P atom of the phosphonate group, form a cyclic phosphonic acid ester or a cyclic phosphonic anhydride a ring size of 4-10 atoms, preferably

A.) one of the substituents R ¹ to R ⁶ or

B.) one of the cycles that are formed when

3) the substituents R ¹ and R ^{2 form} a heterocycle according to (N-ii), having a first uncharged or negatively charged functional group, which a) a hetero atom selected from the group consisting of P, O, N, S, I, CI, Br, F and / or b) has an alkene or alkyne group, the functional group not being —OH and, in the event that one of the cycles according to 1) to 3) has the functional group, the ring atoms of the cycle with of the functional group or with a substituent which the functional group has substituted In a preferred embodiment, the coating serves to give an object a flame retardant finish, particularly preferably to give a polymer material a flame retardant finish.

The use for the surface treatment of metals or polymer materials, in particular of thermoset polymers, is particularly preferred. Use in composites, for example, is particularly preferred. The above-mentioned phosphonates can be applied to the polymer matrix and / or the reinforcement material (e.g. glass fibers) in liquid form, for example as a solution or as a liquid pure substance. The advantage here is that the flame retardants according to the invention are liquid or cause only a slight change in the viscosity in solution. This allows the flame retardant to be distributed evenly in the composite. The flame retardants known from the prior art, on the other hand, are usually solids or require large amounts of solvents in order to obtain a low-viscosity solution, so that it is very difficult for them to be incorporated into the composite material. In addition, a fabric-like composite material ensures that the flame retardant is filtered and thus protection can only be guaranteed on one side. The above-mentioned disadvantages can be overcome with the flame retardants according to the invention.

In a particularly preferred embodiment of the invention, the compound of the formula (I) is used to form a coating, for example a gelcoat. The advantage here is that the compounds according to the invention have good solubility in a large number of polar solvents. In this way, a uniform distribution in the solvent and thus ultimately on the surface to be treated can be achieved. Due to the good solubility, the viscosity of the solution is not influenced at all or only to a small extent.

The compound of the formula (I) is preferred with 1 to 40% by weight, more preferably 2 to 30% by weight, even more preferably 3 to 20% by weight, most preferably 4 to 10% by weight, based on the entire composition of the coating is used.

Solutions of the compounds of the formula (I) can be used, for example, for coating textiles, paper, ceramics or composites or their intermediate stages, such as prepregs.

Due to the low absorption and the homogeneous miscibility with the other components of coating systems, in particular with the binder, the compounds of formula (I) are preferably suitable for so-called “clear coatings”, ie transparent coatings. Clear coatings of this kind are particularly advantageous when the structure under the coating is not to be covered, for example in the case of clear coatings for wood. EXAMPLES

The invention will now be explained further on the basis of specific embodiments of flame retardants according to the invention, production examples for compositions according to the invention and on the basis of flame retardant examples and the attached figures.

Concrete embodiments of inventive flame retardants

Embodiments with a first functional group on the amino group

Embodiments with first and second functional groups on the amino group Embodiments with a first functional group on one of the PhoDhonsäurearuDDen Embodiments with a first functional group on one of the PhoDhonsäureoruppen Embodiments with a first functional group on one of the PhoDhonsäureoruppen

Embodiments with a first functional group on one of the PhoDhonsäurearuDDen

Embodiments with first and second functional groups on the phosphonic acid groups

Embodiments with a first functional reason on one of the phosphonic acid groups Embodiments with a first cyclic functional group

Embodiments with a first cyclic functional group

Embodiments with morpholine, MOMP

Versions with PiDerazin. PIMP

Production board for compositions according to the invention

Ingredients:

Other flame retardants:

Budit 240: partially crosslinked polyacrylate containing phosphorus, produced according to example 1 of WO 2014/124933

Budit 315: Melamine cyanurate from Chemischen Fabrik Budenheim KG

Budit 342: Melamine polyphosphate from Chemischen Fabrik Budenheim KG

Budit 667: intumescent flame protection system from Chemische Fabrik Budenheim KG

Based on ammonium polyphosphate

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

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

Measurement methods:

Dynamic differential calorimetry (DSC) measurements were made using a device for simultaneous thermogravimetry - dynamic differential calorimetry (STA / TG-DSC), model STA409 PC / 3 / H Luxx, from Netzsch Gerätebau GmbH, in the range from 25 to 500 ° C Nitrogen atmosphere carried out with a heating rate of 10K / min. The weight of the samples was around 15 mg. The NETZSCH Proteus software was used for the evaluation. Then moaravimetric analyzes (TG A were carried out with a device for simultaneous thermogravimetry - dynamic differential calorimetry (STA / TG-DSC), model STA409 PC / 3 / H Luxx, Netzsch Gerätebau GmbH, in the range from 25 to 800 ° C under a nitrogen atmosphere with a heating rate of 10 K / min. The weight of the samples was 12-15 mg. The NETZSCH Proteus software was used to evaluate the TGA curves.

Preparation examples for compositions according to the invention

Example 1: Synthesis of morpholine methylaminodiphosphonic acid (MOMP-H ₄ )

0.1 mol of 4-formylmorpholine were 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. The acetic acid formed and excess water were then removed on a rotary evaporator under reduced pressure of -30 mbar and the residue was freed from residual solvent in a drying cabinet at 85 ° C. for 4 hours.

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

0.28 mol of phosphonic acid was dissolved in 31 ml of deionized water in a 250 ml round bottom flask with stirring. To this end, a solution of 0.07 mol of diformylpiperazine in 30 ml of deionized water was added dropwise over a period of 15 minutes. A temperature increase of a few degrees was observed during the addition. After the addition had ended, the reaction mixture was stirred under reflux for a further 3 h. After the solution had cooled, excess water was removed on a rotary evaporator. A saturated piperazine solution was added dropwise to the liquid distillation residue. A white-amorphous precipitate formed with development of heat.

Example 3: Synthesis of dimethyl-methylaminodiphosphonic acid (DAMP-H ₄ )

0.9 mol of dimethylformamide were 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. The acetic acid formed and excess water were then removed on a rotary evaporator under reduced pressure of ~ 300 mbar and the residue was freed from residual solvent in a drying cabinet at 85 ° C. for 4 hours.

Example 4: Synthesis of an aqueous solution of the sodium salt of morpholine-methyl-aminodiphosphonic acid (MOMP-H-Na3)

0.289 mmol of morpholine methylaminodiphosphonic acid (MOMP-H ₄ ) were dissolved in 50 ml of deionized water and 0.867 mmol of NaOH were added. A pH of ~ 9 was obtained for the solution. Example 5: Synthesis of morpholine methylaminodiphosphonic acid tetraethyl ester (MOMP-Et ₄ )

For the preparation of the MOMP-Et ₄ , 0.1 mol of morpholine are placed in the reactor and stirred. A further 0.1 mol of triethoxymethane is added dropwise. Then 0.2 mol of diethyl phosphite are added. The mixture is heated to 120 ° C. and stirred at this temperature for 4 h. After the reaction has ended, the product is purified by vacuum distillation at 50 mbar and 150 ° C.

In a preferred embodiment of the invention, all the substituents R ³ , R ⁴ , R ⁵ and R ^{6 are} cations or organic radicals, particularly preferably ethyl, since correspondingly substituted compounds can act as catalysts in polyurethane foam synthesis. The use of such compounds is particularly advantageous since they both accelerate the synthesis of the polyurethane and improve the flame retardant properties of the finished polymer. Compounds with a P-OH group such as MOMP-H ₄ do not show a corresponding catalytic effect, probably for the reason that they are in the form of a zwitterion (PO- / NH ⁺ ), the quaternary amino group of which has no catalytic properties.

The so-called start time until foam formation is significantly shortened when using appropriately substituted compounds compared to compounds with a P-OH group such as MOMP-H ₄ , as shown on the basis of the following experiments.

General method: Polyol (22.5 g) is mixed with the catalyst (ethylene glycol, 1.05 g) pentane (4.5 g) and the respective flame retardant at 1000 rpm. The isocyanate (MDI, 60.0 g) is added with the disperser switched off, and the mixture is stirred for 10 seconds at 1500 rpm and then transferred without hesitation.

* php - parts per hundred parts of polyol, part per 100 parts of polyol Example 6: Synthesis of morpholine-methylaminodi-DOPO (MOM-DOPO ₂ ) The reaction is a condensation reaction in which the formyl function on 4-formylmorpholine (4-FM) and the PH groups of the DOPO molecules form the product MOM-DOPO ₂ with elimination of H ₂ O. For this purpose, 40 g of DOPO are dissolved in 100 ml of acetylic anhydride (AC ₂ O) in a 250 ml flask with stirring and the mixture is heated to 120 ° C. When the temperature is reached, 10 g of 4-FM are added. After 5 hours, it is neutralized with 80 ml of water and the external temperature is adjusted. After cooling, a white solid precipitates, which is filtered off and washed with water. Acetic acid is a further by-product.

Example 7: Synthesis of morpholine methylaminodiphosphonic acid Zn salt (MOMP-H ₂ Zn) For the preparation of the Zn salt (1: 1), 50.0 g (0.191 mol) of MOMP are dispersed in 500 g of H ₂ O and mixed with 14.6 g of ZnO (0.191 mol) were added. The reaction mixture is heated to 95 ° C. and stirred at this temperature for 4 h. The batch is then cooled to below 50 ° C. and the solid is separated from the mother liquor. The filter cake is dried in the circulating air at 120 ° C. Example 8: Synthesis of Piperazine-dimethylaminodiphosphonic acid (PIMP-H ₄ )

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, 0.4 mol of phosphorous acid are dissolved in 0.3 mol of acetic anhydride. This solution is then added dropwise to the reactor. Finally, a further 0.5 mol of acetic anhydride is added and the batch is heated to 135.degree. After a reaction time of 30 minutes, 2.1 mol of water are added dropwise. After a further 40 minutes' reaction time, the batch is cooled to room temperature. Then 70 ml of sodium hydroxide solution are added. The product is separated from the mother liquor and dissolved in water. The solution is then reprecipitated with sulfuric acid and the product is filtered off, washed and dried.

Example 9: Synthesis of Diethyl Phosphite

Phosphonic acid (29.7 g, 0.36 mol) and triethoxymethane (107.3 g, 0.72 mol) are mixed in a 500 ml three-necked flask with a distillation bridge and heated to 90 ° C. with stirring. After 45 minutes the temperature is increased to 135 ° C, whereby the boiling process begins (gas phase temperature 73 ° C) and a first fraction of ethanol and ethyl formate is obtained. After the boiling process has subsided, negative pressure (30 mbar) is applied and a second fraction is thereby obtained. This is the product diethyl phosphite. 35.0 g of the colorless, slightly smelling liquid are obtained. Example 10: Synthesis of 4-hydroxy-1- (methylaminodiphosphonic acid) piperidine ("OH- PIDMP-H ₄ )

To prepare the “OH-PIDMP-Et ₄ ”, 4-hydroxypiperidine (0.1 mol) is placed in a 250 ml flask and stirred. Triethoxymethane (0.1 mol) is added dropwise. Diethyl phosphite (0.2 mol) is then added. The mixture is heated to 120.degree. C., stirred at this temperature for 4 hours and the product “OH-PIDMP-EW *” is purified by means of vacuum distillation at 50 mbar and 150.degree.

A 5-fold excess of 1N HCl is added to this, and slight warming can be observed. The resulting ethanol is distilled off and the product “OH-PIDMP-H ₄ ” is obtained in a yield of 89%. The melting point is 250 ° C. Example 11: Synthesis of 4-methylene-1- (methylaminodiphosphonic acid tetraethyl ester) - piperidine ("4-methylene-PIDMP Et ₄ ")

To prepare “4-methylene-PIDMP-Et ₄ ”, 4-methylidenepiperidine hydrochloride (0.05 mol) and triethylamine (0.1 mol) are placed in a 250 ml flask and stirred. Triethoxymethane (0.12 mol) is added dropwise. Diethyl phosphite (0.31 mol) is then added. The mixture is heated to 140 ° C. and stirred at this temperature for 6 h. After cooling to room temperature, diethyl ether (125 ml) is added, the mixture is neutralized with sodium hydroxide solution (0.5 N, 50 ml), the phases are separated and the organic phase is washed with 250 ml of water. The organic phase is worked up by distillation, the product having a boiling point of 180 ° C. at 2 mmbar. The yield is 58%.

Example 12: Synthesis of 4-hydroxy-4-vinyl-1- (methylaminodiphosphonic acid tetraethyl ester) -piperidine ("OH-Vinyl-PIDMP-Et ₄ ")

For the preparation of the “OH-Vinyl-PIDMP-Et ₄ ” 4-piperidone-ethylene ketal (0.1 mol) is placed in a 250 ml flask and stirred. Triethoxymethane (0.1 mol) is added dropwise. Diethyl phosphite (0.2 mol) is then added. The mixture is heated to 120 ° C for 4 hours and the product “Ketal-PIDMP-Et ₄ ” is purified by vacuum distillation at 50 mbar and 150 ° C.

“Ketal-PIDMP-Et ₄ ” is mixed with a 5-fold molar excess of 80% acetic acid and stirred at 80 ° C. for 2 h. The ethylene glycol formed is distilled off and the intermediate product “Ketone-PIDMP-Et ₄ ” is purified by vacuum distillation at 50 mbar and 150 ° C.

For the preparation of the “OH-Vinyl-PIDMP-Et ₄ , THF (absolute) is placed in an anhydrous apparatus as the solvent and the Grignard reagent is prepared in it (c = 1.5 molar). To this end, magnesium shavings are added to the THF and vinyl bromide (1.2 mmol) is continuously added dropwise. The “ketone-PIDMP-Et ₄ ” (1 mmol) is continuously added dropwise. After the reaction has ended (to be recognized by the subsidence of the boiling process, total reaction time ~ 2 hours), the reaction mixture is hydrolyzed with cooled 1N HCl (aq). Work-up is carried out by separating off the aqueous phase and removing the solvent from the organic phases by distillation. The melting point of the “OH-Vinyl-PIDMP-Et ₄ ” obtained is 239 ° C. The reaction yield is 85%. Examples of flame protection:

Compositions

To check the flame retardant properties and to classify the flame retardant compositions according to the invention in different polymers, the UL94 test was carried out on test specimens conforming to IEC / DIN EN 60695-11-10 standards.

UL94-V test

For each measurement, 5 test specimens were clamped in a vertical position and held at the free end of a Bunsen burner flame. The burning time and the falling off of burning parts were evaluated with the aid of a cotton swab placed under the test specimen. The exact implementation of the tests and the flame application with a 2 cm high Bunsen burner flame was carried out according to the specifications of the Underwriter Laboratories, Standard UL94.

The results are the classifications in fire protection classes V-0 to V-2. V-0 means that the total burning time of 5 tested specimens was less than 50 seconds and the cotton ball was not ignited by dripping glowing or burning components of the test specimen. The classification V-1 means that the total burning time of 5 tested specimens was more than 50 seconds but less than 250 seconds and that the cotton ball was also not ignited. V-2 means that the total burning time of 5 tested specimens was less than 250 seconds, but the cotton ball was ignited by dripping test specimen components in at least one of the 5 tests. The abbreviation NC stands for "non-classifiable" and means that a total burning time of more than 250 seconds was measured. In many cases of non-classifiability, the test specimen burned completely.

UL94-HB test

For each measurement, at least 3 test specimens were clamped in a horizontal position and held at the free end of a Bunsen burner flame. The burn rate and the total burn distance were evaluated. The exact implementation of the tests and the flame exposure with a 2 cm high Bunsen burner flame was carried out according to the specifications of the Underwriter Laboratories, Standard UL94.

The results are the classification in fire protection class HB. The “HB” classification means that the burning rate between two markings, the first 25 mm away from the end of the flame and the second 100 mm away from the end exposed to the flame, was less than 40 mm / min. In addition, the flame front did not exceed the 100 mm mark. The abbreviation NC stands for “not classifiable” and means that over a distance of 75mm the burn rate was> 40 mm / min or the total burn distance was> 100 mm. L * a * b * values

The L * a * b * values were determined using an UltraScan VIS-2 spectrophotometer equipped with the UltraScanVIS sensor from HunterLab. For this purpose, the samples were filled into a glass cuvette and a homogeneous surface was created on the cuvette side facing the measurement opening by bumping the cuvette or compressing the sample. The associated software Easy Match QC 4.64 uses the settings "USVIS 1145" Sensor and "RSIN Mode" and calculates the L * a * b * values.

The method is based on the currently valid version of EN ISO 11664-4.

Example 13: Flame Retardant Properties of MOMP-H ₄ in Polypropylene Polymers

The following polymer materials were used to produce the flame-retardant compositions in the following examples:

Polypropylene (PP) HD120 MO from Borealis AG

With the aid of a twin-screw extruder, model Process 11, from Thermo Fisher Scientific Inc., granules with a grain size of about 3x1x1 mm were produced under the extrusion conditions customary for polypropylene. The extrusion process was carried out with a throughput of about 5-7 kg / h and a screw speed of 450-500 rpm and a temperature of the extrusion zone of 190-220 ° C. Subsequent hot pressing resulted in good quality test specimens conforming to UL94. The thickness of the test specimens was 1.6 and 3.2 mm, respectively. In the extrusion process, the phosphonate produced according to Example 1 was incorporated into the polymer material.

Example 14: Flame retardant properties of MOMP-H ₄ in polyurethane (PU)

To produce the flame-retardant compositions, the following components were reacted with one another 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 according to the invention was added to the polyol component before the reaction. The mass fractions of flame retardants listed in the table below relate to the sum of the masses of polyol, catalyst, flame retardant and isocyanate.

* double potassium salt of MOMP-H ₄ ** without catalyst

Example 15: Flame retardant properties of MOMP-H ₄ in thermoplastic polyurethane

(TPU)

The following polymer materials were used to produce the flame-retardant compositions in the following examples: Thermoplastic polyurethane (TPU) Elastollan 1185 A from BASF SE

With the aid of a twin-screw extruder, model Process 11, from Thermo Fisher Scientific Inc., granules with a grain size of about 3 × 1 × 1 mm were produced under the extrusion conditions customary for TPU. The extrusion process was carried out with a throughput of about 5 kg / h and a screw speed of 300 rpm and a temperature of the extrusion zone of about 205 ° C. Subsequent hot pressing resulted in good quality test specimens conforming to UL94. The thickness of the test specimens was 0.8 mm. During the extrusion process, the phosphonate produced according to Example 1 was incorporated into the polymer material.

^* butc = test body burns down to the clamp

^# ditc = falling drops ignite cotton

~ no second flame exposure possible, as the test specimen has already burned off after the first flame exposure

Example 16: Flame retardant properties of MOMP-H ₂ Zn in thermoplastic polyamide (PA)

The following materials were used to produce the flame-retardant compositions in the following examples:

Polyamide 6: Ultramid B3S (BASF)

Glass fibers (GF) for PA: CS7928 (Lanxess)

With the aid of a twin-screw extruder, model Process 11, from Thermo Fisher Scientific Inc., granules with a grain size of about 3 × 1 × 1 mm were produced under the extrusion conditions customary for PA6. The extrusion process was carried out with a throughput of about 5 kg / h and a screw speed of 300 rpm and a temperature of the extrusion zone of about 280 ° C. Subsequent hot pressing made UL94-compliant test specimens good Get quality. The thickness of the test specimens was 0.8 mm. During the extrusion process, the phosphonate produced according to Example 7 (MOMP-H ₂ Zn) was incorporated into the polymer material.

^* butc = test body burns up to the clamp ** Exolit OP 1230

“A second flame application is not possible because the test specimen has already burned down after the first flame exposure

Example 17: Flame retardant and door saving properties of MOMP-Et «in a thermoplastic polyurethane coating

A polyurethane resin Top-Coat Goylake A-1219-9 from the Irurena Group was mixed with MOMP-Et «and mixed intensively by stirring. The proportion of MOMP-Et ₄ in the total mass (250 g) consisting of the mass of MOMP-Et ”and the mass of the polyurethane resin was 5% by weight (formulation A) and 10% by weight (formulation B). Based on this total mass, 10% by weight of the curing catalyst C-212 from the Irurena Group were added and the mixture was intensively mixed by stirring.

The transparent mixtures were then applied to a commercially available pressboard using a 500 μm doctor blade, and the board was then dried at 80.degree.

In the subsequent Epiradiateur fire test according to NF P 92-501, both formulation A and formulation B achieved an M3 rating.

Measurement of transparency

In order to demonstrate the transparency of formulations A and B, the formulations were each applied as a coating to a white and a black background using a 500 μm doctor blade. The L * a * b values were determined for each substrate for two samples with a coating (tests no. 1 and 2) and for two control samples (tests no. 3 and 4) without a coating. As can be seen from the tables below, coatings with the formulations A and B only lead to negligible changes in the values in the L * a * b color space, ie the coatings have a high degree of transparency and do not or only insignificantly influence the appearance of the substrate. The flame retardants according to the invention are therefore particularly suitable for use in transparent coatings.

Formulation A black background

White background

Formulation B black background White background

Character description:

The attached figures represent thermogravimetric measurements, showing:

Figure 1: Differential calorimetric measurement of DAMP-H ₄ Figure 2: Thermogravimetric measurement of DAMP-H ₄ Figure 3: Differential calorimetric measurement of MOMP-H ₄ Figure 4: Thermogravimetric measurement of MOMP-H ₄ Figure 5: Differential calorimetric measurement of ATMP Figure 6: Thermogravimetric measurement of ATMP Figure 7: Differential calorimetric measurement of MOMP-Et ₄ Figure 8: Thermogravimetric measurement of MOMP-Et ₄ Figure 9: Differential calorimetric measurement of MOMP-DOPO2 Figure 10: Thermogravimetric measurement of MOM-DOPO2 Figure 11: Differential calorimetric measurement of MOMP- H ₂ Zn Figure 12: Thermogravimetric measurement of MOMP-H ₂ Zn Figure 13: Differential calorimetric measurement of PIMP Figure 14: Thermogravimetric measurement of PIMP

Claims

Patent claims

1. Composition which contains a polymer material, in particular a duromer polymer material, and contains and / or bound a halogen-free flame retardant in an amount of 1 to 40% by weight, based on the total composition, characterized in that the Flame retardant is a compound of the formula (I), its corresponding ammonium salt, its corresponding phosphonate salt or a mixture of the above: in which

Nitrogen, where on the heterocycle, if it has nitrogen atoms as ring atoms, these nitrogen atoms are preferably substituted with H, an alkyl, an aryl or a methyl bisphosphonate group of the following structure (II), and where on the heterocycle, if it has carbon, phosphorus or silicon as ring atoms, these atoms can preferably have substituents selected from the group consisting of H, alkyl, aryl, -NH ₂ , -NHR, -NR ₂ , -OH, -OR, = 0, -I, -CI, -Br, F, -N ₃ , -SH, -SR, -OCN, epoxy, lactam, lactone, aziridine, glycolide, oxazoline, alkenylene and alkynylene, -SiR _x H _y with R = alkyl, alkenyl, alkynyl or aryl and x + y = 3, and where -X- is an oxygen atom, -O-, or -X- is a single biodiesel and where

(Pi) R ³ , R ⁴ , R ⁵ and R ^{6 are} identical or different substituents and are selected from the group consisting of H, linear, branched or cyclic alkylene, alkenylene and alkynylene, unsubstituted and alkyl-substituted phenylene, multinuclear aromatics with up to 4 nuclei, mononuclear or multinuclear heteroaromatics with up to 4 nuclei, silyls, allyl, alkyl or aryl alcohols, the following structures (III) and (IV) with n = 0 to 100, as well as cations, the cation Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , B ³⁺ , Al ³⁺ , Zn ²⁺ , NH ₄ ⁺ or the ammonium ion of an amine compound selected from the group consisting from melamine or its condensation products, preferably melam, melem,

Melon, urea, guanidine, morpholine and piperazine, and / or

(P-ii) when -X- is an oxygen atom, -O-, -OR ³ and -OR ⁴ together and / or -OR ⁵ and -OR ⁶ together and / or -OR ³ and -OR ⁵ together and / or —OR ⁴ and —OR ⁶ together, including the P atom of the phosphonate group, form a cyclic phosphonic acid ester or a cyclic phosphonic anhydride with a ring size of 4-10 atoms, and / or

(P-iii) when -X- is a single bond, -R ³ and -OR ⁴ and / or -R ³ and -OR ⁵ together, including the P atom of the phosphinate group, a cyclic phosphinate or a cyclic Phosphinic anhydride with a ring size of 4-10 atoms and / or -OR ⁵ and -OR ⁶ and / or -OR ⁴ and -OR ⁶ together, including the P atom of the phosphonate group, form a cyclic phosphonic acid ester or a cyclic phosphonic anhydride a ring size of 4-10 atoms, where

A.) one of the substituents R ¹ to R ⁶ or

B.) one of the cycles that are formed when

3) the substituents R ¹ and R ^{2 form} a heterocycle according to (N-ii), having a first uncharged or negatively charged functional group, which a) a hetero atom selected from the group consisting of P, O, N, S, I, CI, Br, F and / or b) has an alkene or alkyne group, the functional group not being —OH, and in the event that one of the cycles according to 1) to 3) has the functional group, the ring atoms of the cycle are substituted with the functional group or with a substituent which the functional group has.

2. Composition according to claim 1, characterized in that at least one of the substituents R ¹ to R ⁶ or one of those formed by the substituents R ¹ to R ⁶ Cycles has at least one further functional group which has a heteroatom selected from the group consisting of N, S, O, Si, I, CI, Br, F and / or an alkene or alkyne group.

3. Composition according to claim 1 or 2, characterized in that the first and / or further functional groups are selected from the group consisting of - NH ₂ , -NHR, -NR ₂ , -OH, -OR, = 0, -SH , -SR, -COOH, -COOR, -OCN, -SiR _x H _y, -l, -CI, -Br, -F, -N ₃ , epoxy, lactam, lactone, aziridine, glycolide, oxazoline, ether, alkenylene and alkynylene, where R = alkyl, alkenyl, alkynyl or aryl and x + y = 3.

4. Composition according to one of the preceding claims, characterized in that the flame retardant is covalently bonded to the polymer material, preferably by using the flame retardant as a co-monomer in the polymer formation reaction of the polymer material.

5. Composition according to one of the preceding claims, characterized in that R ¹ and R ^{2 are} identical substituents.

6. Composition according to one of the preceding claims, characterized in that the first and / or further functional group is an alkenyl or epoxy group.

7. Composition according to one of the preceding claims, characterized in that the dry flame retardant has a mass loss of 10% by weight from a temperature of 180 ° C, preferably from a temperature of 190 ° C, particularly preferably from a temperature of 200 ° C reached.

8. Composition according to one of the preceding claims, characterized in that the phosphorus content of the flame retardant is at least 10.0% by weight, preferably at least 12.5% by weight, particularly preferably at least 21.5% by weight, am - most preferably at least 15.0% by weight.

9. Composition according to one of the preceding claims, characterized in that at least one, preferably two, even more preferably at least three, most preferably four of the groups R ³ , R ⁴ , R ⁵ and R ^{6 are} a cation or H, preferably H. , wherein the cation Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , B ³⁺ , Al ³⁺ , Zn ²⁺ , NH ₄ ⁺ or the ammonium ion of an amine compound selected from the group consisting of melamine or its Condensation products, preferably melam, melem, metene, urea, guanidine, morpholine and piperazine.

10. Composition according to one of the preceding claims, characterized in that the polymer material contains the flame retardant in an amount of at least 3% by weight or at least 5% by weight or at least 10% by weight or at least 15% by weight and / or in an amount of at most 35% by weight or at most 30% by weight or at most 25% by weight, based on the total composition.

11. Composition according to one of the preceding claims, characterized in that it has at least one further flame-retardant component, which is preferably selected from nitrogen bases, melamine derivatives, phosphates, pyrophosphates, polyphosphates, organic and inorganic phosphinates, organic and inorganic Phosphonates and derivatives of the aforementioned compounds, preferably selected from ammonium polyphosphate, with melamine, melamine resin, melamine derivatives, silanes, siloxanes, silicones or polystyrenes coated and / or coated and crosslinked ammonium polyphosphate particles, and 1,3,5-triazine compounds compounds, including melamine, melam, meter, melon, ammeiin, ammelid, 2-ureidomelamin, acetoguanamine, benzoguanamine, diaminphenyltriazine, melamine salts and adducts, melamine cyanurate, melamine borate, melamine orthophosphate, melamine phosphine pyrophosphate, melamine phosphine phosphate, aliphosphine pyrophosphate, di-miethylamine Oligomers un d polymer 1,3,5-triazine compounds and polyphosphates of 1,3,5-triazine compounds, guanine, piperazine phosphate, piperazine polyphosphate, ethylenediamine phosphate, pentaerythritol, dipen-taerythritol, boron phosphate, 1,3,5-trihydroxyethyl isocyanurate, 1, 3,5-triglycidyl isocyanurate, trially isocyanurate and derivatives of the aforementioned compounds.

12. A method for producing a composition according to any one of the preceding claims, characterized in that the flame retardant is a co-condensation component or a co-addition component of the polymer material which is formed into the polymer material during the production of the polymer material by polycondensation or polyaddition - Material is introduced, wherein the polymer material is preferably a polyester or a polyurethane.

13. Flame retardant which is defined as in one of the preceding claims, characterized in that the substituents R ³ to R ⁶ or the cycles formed by them have the first functional group.

14. A method of manufacturing a flame retardant comprising the following steps: ^■ providing a mixture of a) at least one phosphonic or phosphinic acid selected from the group con- sisting of the compounds of formulas (V) and (VI) in a Reaktionsbehält- nis where -X- is an oxygen atom, -O-, or -X- is a single bond and where

(Pi) R ³ , R ⁴ , R ⁵ and R ^{6 are} identical or different substituents and are selected from the group consisting of H, linear, branched or cyclic alkylene, alkenylene and alkynylene, unsubstituted and alkyl-substituted phenylene, multinuclear aromatics with up to 4 nuclei, mononuclear or multinuclear heteroaromatics with up to 4 nuclei, silyls, allyl, alkyl or aryl alcohols, the following structures (III) and (IV) with n = 0 to 100, as well as cations where the cation Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , B ³⁺ , Al ³⁺ , Zn ²⁺ , NhV or the ammonium ion of an amine compound selected from the group consisting of melamine or its condensation products, preferably melam, melem, melon, urea, guanidine, morpholine and piperazine, and / or

(P-ii) when -X- is an oxygen atom, -O-, -OR ³ and -OR ⁴ together and / or -OR ⁵ and -OR ⁶ and / or -OR ³ and -OR ⁵ together, and / or -OR ⁴ and -OR ^{6 in} common- sam, including the P atom of the phosphonate group, form a cyclic phosphonic acid ester or a cyclic phosphonic anhydride with a ring size of 4-10 atoms, and / or

(N-ii) R ¹ and R ² together, including the N atom, form a saturated or monounsaturated or polyunsaturated heterocycle with 4-8 ring atoms selected from carbon, oxygen, sulfur, phosphorus, silicon and Nitrogen, where on the heterocycle, if it has nitrogen atoms as ring atoms, these nitrogen atoms are preferably substituted with H, an alkyl, an aryl or a methyl bisphosphonate group of the following structure (II), and where on the heterocycle, if it has carbon, phosphorus or silicon as ring atoms, these atoms can preferably have substituents which are preferably selected from the group consisting of H, alkyl, aryl, -NH ₂ , -NHR, -NR ₂ , -OH, -OR, = 0, -I, -CI, -Br, F, -N ₃ , -SH, -SR, -OCN, epoxy, lactam, lactone, aziridine, glycolide, oxazoline, alkenylene and alkynylene , -SiRxHy with R- alkyl, alkenyl, alkynyl or aryl and x + y = 3,

^■ Heating the mixture to a temperature in the range of 40-150 ° C.

15. Use of a compound of the formula (I), its corresponding ammonium salt, its corresponding phosphonate salt or a mixture for surface treatment, preferably in the form of a coating, in which

(Ni) R ¹ and R ^{2 are the} same or different substituents and are selected from the group consisting of linear, branched or cyclic alkylene, alkylene and alkynylene, unsubstituted and alkyl-substituted phenylene, mononuclear arene and multinuclear aromatics with up to 4 nuclei, mononuclear or multinuclear heteroaromatics with up to 4 nuclei, silylene, allyl, alkyl or aryl alcohols, or

(N-ii) R ¹ and R ² together, including the N atom, form a saturated or monounsaturated or polyunsaturated heterocycle with 4-8 ring atoms selected from carbon, oxygen, sulfur, phosphorus, silicon and nitrogen , where on the heterocycle, if it has nitrogen atoms as ring atoms, these nitrogen atoms are preferably substituted with H, an alkyl, an aryl or a methyl bisphosphonate group of the following structure (II), and where on the heterocycle, if it has carbon, phosphorus or silicon as ring atoms, these atoms can preferably have substituents selected from the group consisting of H, alkyl, aryl, -NH ₂ , -NHR, -NR ₂ , - OH, -OR, = 0, -I, -CI, -Br, F, -N ₃ , -SH, -SR, -OCN, epoxy, lactam, lactone, aziridine, glycolide, oxazoline, alkenylene and alkynylene, -SiR _x H _y with R = alkyl, alkenyl, alkynyl or aryl and x + y = 3, and where -X- is an oxygen atom, -O-, or -X- is a single bond and where

(Pi) R ³ , R ⁴ , R ⁵ and R ^{6 are} identical or different substituents and are selected from the group consisting of H, linear, branched or cyclic alkylene, alkenylene and alkynylene, unsubstituted and alkyl-substituted phenylene, multinuclear aromatics with up to 4 nuclei, mononuclear or multinuclear heteroaromatics with up to 4 nuclei, silyls, allyl, alkyl or aryl alcohols, the following structures (III) and (IV) with n = 0 to 100,

and cations where the cation is Na *, K *. Mg ² *, Ca ² *, B ³ *, Al ³ *, Zn ² *, NH ₄ * or the ammonium ion of an amine compound, selected from the group consisting of melamine or its condensation products, preferably melam, melem, melon, urea, Guanidine, morpholine and piperazine, is, and / or

(P-iii) when -X- is a single bond, -R ³ and -OR ⁴ and / or -R ³ and -OR ⁵ together, including the P atom of the phosphinate group, a cyclic phosphinate or a cyclic Phosphinic anhydride with a ring size of 4-10 atoms and / or -OR ⁵ and -OR ⁶ and / or -OR ⁴ and -OR ⁶ together, including the P atom of the phosphonate group, form a cyclic phosphonic acid ester or a cyclic phosphonic anhydride form a ring size of 4-10 atoms,