Polymer compounds containing phosphonate flame retardants

Abstract

The present invention relates to a compound containing a polymeric material and an aminomethylbisphosphonate-based phosphorus flame retardant, a method for making the compound, the use of the flame retardant and a selected flame retardant structure.

Description

[0001] Subject matter of the invention

[0002] The present invention relates to a compound containing a polymeric material and an aminomethylbisphosphonate-based phosphorus flame retardant, a method for making the compound, the use of the flame retardant and a selected flame retardant structure. Background of the Invention

[0004] A wide variety of substances are known for equipping polymer materials with flame retardancy; these substances can be used alone or in combination with other substances that provide similar or complementary flame retardancy. 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 their mixtures. Flame retardants can be divided into low-molecular and high-molecular types. Although high-molecular or polymer flame retardants (such as Clariant's halogenated polyol Exolit OP 550) advantageously have only a small softening effect and a low migration capacity in polymer materials, unlike low-molecular flame retardant additives, they are generally not easily mixed with the polymer material to be protected during technical processing, especially at low melting capacities. In addition, the addition of high-molecular flame retardants can have a negative impact on the curing of polymer materials.

[0005] Therefore, most of the flame retardants used are low molecular weight compounds. Among them, phosphorus compounds are known to be particularly effective in this regard. In a fire, these substances will expand into a large amount of protective layer in the polymer material, which is called expansion. This process forms a barrier layer, which blocks the oxygen supply and prevents the polymer material from continuing to burn. In the solid phase, the flame retardant effect can also be based on an increase in the carbonization rate of the polymer material or the formation of inorganic glass. The flame retardant activity is also promoted by a gas phase mechanism, which involves a radical combination (radical combination) of PO radicals generated by the combustion of phosphorus compounds, which significantly slows down the combustion process of the polymer material. Halogenated phosphates / esters such as tris (2-chloroethyl) phosphate (TCEP) and tris (2-chloroisopropyl) phosphate (TCPP) are the most important phosphorus compounds. However, due to its potential toxicity and the ecological problems associated with its use, its use is increasingly limited, especially because the phosphates / esters are bioaccumulated and it is difficult for urban water treatment plants to remove these phosphates / esters from wastewater. In addition, it contains halogens, which will produce and release HX gas and other toxic compounds in a fire. This corrosive fire atmosphere represents an elevated risk, especially in electronic applications.

[0006] Halogenated and halogen-free phosphates are alternatives to phosphorus flame retardants. Compared to phosphates, they have a particularly pronounced flame-retardant activity in the gas phase. DE 2 128 060 describes the use of aminomethanephosphonates with phosphorus concentrations of up to 23.2% by weight as flame retardants in polyurethanes. Aminomethanephosphonates are produced from hexamethylenetetramine and dialkyl or diarylphosphonates. The use of these phosphonates involves dissolving them together with other additives that may be required in the polyol component of the polyurethane-forming mixture and then adding the polyisocyanate thereto. Esters containing NH groups are incorporated into the polymer material by addition to the isocyanate groups.

[0007] EP 0 001 996 relates to the production of N,N-bis-(2-hydroxyalkyl) aminomethanephosphonic acid dimethyl esters, which are mainly used as flame retardant additives in polymeric materials, especially polyurethanes. It is synthesized as a catalyst by adding an H-acidic compound in a mixture of dimethyl phosphite and oxazolidine. The product has a terminal secondary hydroxyl group, and when adding the polymer component of the polyurethane to form a mixture, it can be incorporated into the polymeric material. However, the H-acidic substance added still remains in the polymeric material and may impair its characteristics. Alternatively, before adding a polyol component to separate it from the phosphonic acid ester, it is necessary to be converted into a corresponding alkaline salt.

[0008] CA 2 027 078 relates to aminomethanephosphonic acid aryl esters which can be used as flame retardants in foams, thermoplastics and duroplasts. The corresponding compounds are produced by reacting amines with trialkyl or triaryl phosphites and paraformaldehyde. The products can be added to processed polymer materials during extrusion or can be used as additives for cocondensation components in polymer condensation reactions.

[0009] Liu et al. discussed flame retardant DOPO derivatives in Industrial Engineering Chemistry Research (Ind. Eng. Chem. Res.) (2017), 56, 8789-8696. These derivatives are made of DOPO (9,10-dihydro-9-oxa-10-phosphophanol-10-oxide), polyformaldehyde and piperazine. These materials are halogen-free and have flame retardant effects when used in polycarbonate. However, as in the above literature, the thermal stability of these compounds is also very low, which is due to the P-CH 2The PC bonds of these flame retardants are caused by the weak PC bonds of the N group. Although the PC bonds are theoretically chemically and thermally stable, the α-amino group stabilizes the carbon radicals produced by homolysis; therefore, the PC bonds in these flame retardants are already broken at relatively low temperatures. Due to the low molar mass of the tertiary amines formed by homolysis, the latter dissipate as volatile components and cause corresponding mass losses. When the flame retardants are embedded in polymer materials, the release of amines may lead to elevated smoke. Due to the low decomposition temperature, the flame retardants are already partially decomposed during the molding process of the polymer materials in which they are embedded. Another disadvantage of these flame retardants is that, due to their low phosphorus concentration, they must be added to the polymer materials in high concentrations, which significantly impairs the processability, flexibility and other product properties of the polymer materials.

[0010] Task

[0011] Against this background, the object of the present invention is to provide a composition containing a polymer material, wherein the flame retardant has similar or even better flame retardant properties than those known in the prior art, can be used in the composition at lower concentrations while still providing good flame retardancy, decomposes only at temperatures higher than those of known flame retardants, preferably decomposes at a temperature far higher than the processing and / or production temperature and slightly lower than or at the decomposition temperature of the polymer material, and when the flame retardant decomposes in the polymer material, a lower smoke density and / or reduced smoke toxicity is generated.

[0012] plan

[0013] The present invention solves this problem by specifying a composition comprising a polymer material, in particular a thermosetting polymer material, and containing and / or combining therein a flame retardant in an amount of 1% to 40% by weight relative to the entire composition, characterized in that the flame retardant is a compound of formula (I), its corresponding ammonium salt, its corresponding phosphonate or a mixture of the above compounds:

[0014]

[0015] in,

[0016] (Ni)R 1 and R 2 are identical or different substituents and are selected from the group consisting of linear, branched or cyclic alkyl, alkenyl and alkynyl groups, unsubstituted and alkyl-substituted phenyl groups, mononuclear aromatic hydrocarbons and polynuclear aromatic hydrocarbons with up to 4 nuclei, mononuclear heteroaromatic hydrocarbons and polynuclear heteroaromatic hydrocarbons with up to 4 nuclei, silyl, allyl, alkyl or aromatic alcohol, or

[0017] (N-ii)R 1 and R 2Together with the N atom, it forms a saturated or monounsaturated or polyunsaturated heterocyclic ring having 4 to 8 ring atoms selected from carbon, oxygen, sulfur, phosphorus, silicon and nitrogen, wherein, if it has nitrogen atoms as ring atoms, these nitrogen atoms on the heterocyclic ring are preferably substituted by H, alkyl, aryl or methyldiphosphonate groups having the following structure (II),

[0018]

[0019] Furthermore, if there are carbon, phosphorus or silicon as ring atoms, these atoms on the heterocyclic ring may preferably have substituents selected from the group consisting of H, alkyl, aryl, -NH 2 , -NHR, -NR 2 ,-OH,-OR,=O,-I,-Cl,-Br,F,-N 3 , -SH, -SR, -OCN, epoxy, lactam, lactone, aziridine, glycolide, oxazoline, ether, alkenylene and alkynylene, -SiR x H y , wherein R = alkyl, alkenyl, alkynyl or aryl, and x + y = 3,

[0020] and, wherein -X- is an oxygen atom -O-, or -X- is a single bond, and

[0021] in,

[0022] (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 alkyl, alkenyl and alkynyl, unsubstituted and alkyl-substituted phenyl, polynuclear aromatic hydrocarbons with up to 4 nuclei, mononuclear heteroaromatic hydrocarbons and polynuclear heteroaromatic hydrocarbons with up to 4 nuclei, silyl, allyl, alkyl or aromatic alcohol, the following structures (III) and (IV), wherein n=0 to 100,

[0023]

[0024] and a cation, wherein the cation is Na + , K + Mg 2+ , Ca 2+ , B 3+ 、Al 3+ 、Zn 2+ NH 4 + or an ammonium ion of an amine compound selected from the group consisting of melamine or its condensation products, preferably melam, melem, melon, urea, guanidine, morpholine and piperazine,

[0025] and / or

[0026] (P-ii) When -X- is an oxygen atom -O-, -OR 3 AND-OR 4 and / or-OR 5 AND-OR 6 and / or-OR 3 AND-OR 5 and / or-OR 4 AND-OR 6 together with the P atom of the phosphonate group, forms a cyclic phosphonate or anhydride having a ring size of 4 to 10 atoms,

[0027] and / or

[0028] (P-iii) When -X- is a single bond, -R 3 AND-OR 4 and / or -R 3 AND-OR 5 Together with the P atom of the phosphinate group, it forms a cyclic phosphonate or anhydride having a ring size of 4 to 10 atoms, and / or -OR 5 AND-OR 6 and / or-OR 4 AND-OR 6 together with the P atom of the phosphonate group, forms a cyclic phosphonate or anhydride having a ring size of 4 to 10 atoms,

[0029] in,

[0030] A.) Substituent R 1 To R 6 One of or

[0031] B.) When

[0032] 1) Substituent R 3 -R 6 When a cyclic phosphinate or cyclic phosphonate is formed according to (P-ii) or (P-iii), or

[0033] 2) Substituent R 3 -R 6 When a cyclic phosphinic anhydride or a cyclic phosphonic anhydride is formed according to (P-ii) or (P-iii), or

[0034] 3) Substituent R 1 and R 2 When a heterocyclic ring is formed according to (N-ii),

[0035] One of the rings formed

[0036] Having an uncharged or negatively charged first functional group, the uncharged or negatively charged first functional group having:

[0037] a) heteroatoms selected from the group consisting of P, O, N, S, I, Cl, Br, F; and / or

[0038] b) an alkene or alkynyl group,

[0039] where the functional group is not -OH, and

[0040] In the case where one of the rings of 1) to 3) has a functional group, the ring atoms of the ring are substituted with the functional group or a substituent having a functional group.

[0041] The present invention defines a functional group as a group of atoms in a bond which substantially determines the physical properties and the reaction behavior of the compound, for example because it influences the polarity of the molecule and / or because it can react with other compounds. However, the functional groups defined in the present invention do not include those groups of atoms in which one of the heteroatoms cited under a) or the olefin or alkyne group is part of a ring of an aromatic hydrocarbon system (e.g. arenes and heteroaromatic hydrocarbons).

[0042] For the purposes of the present invention, the fact that the uncharged or negatively charged functional group is not -OH does not mean that the substituent R 1 To R 6 Or when the substituent R 3 -R 6 According to (P-ii) or (P-iii), a cyclic phosphinate or cyclic phosphonate or substituent R is formed 3 -R 6 According to (P-ii) or (P-iii), a cyclic phosphinic anhydride or a cyclic phosphonic anhydride or a substituent R is formed 1 and R 2 When forming a heterocycle according to (N-ii), one of the rings formed must not have an OH group. However, for the purposes of the present invention, it must additionally have an uncharged or negatively charged first functional group as described above.

[0043] Substituent R 1 To R 6 Or when the substituent R 3 -R 6 According to (P-ii) or (P-iii), a cyclic phosphinate or cyclic phosphonate or substituent R is formed 3 -R 6 According to (P-ii) or (P-iii), a cyclic phosphinic anhydride or a cyclic phosphonic anhydride or a substituent R is formed 1 and R 2 One of the rings formed when forming a heterocycle according to (N-ii) preferably has no OH groups. This may be advantageous, for example, when the OH groups react with other additives in the polymer material.

[0044] When the substituent R 1 To R 6 When a ring is formed according to 1) to 3), the functional group may only be arranged on a substituent of a ring atom and may therefore not be part of the ring itself. Thus, the functional group is not arranged in the ring but on a substituent of a ring atom of the ring. For example, R 1 To R 2 A morpholine ring can be formed, and thus a ring is formed according to 3); however, the ether groups contained in the ring do not represent functional groups as defined in the present invention. However, the ring atoms of morpholine may additionally be substituted with a functional group according to the present invention or with a substituent having a functional group according to the present invention.

[0045] In a preferred embodiment, -X- is an oxygen atom -O-, and -OR 3 AND-OR 4 Together with the P atom of the phosphonate group, it forms a cyclic phosphonate or cyclic phosphonic anhydride having a ring size of 4 to 10 atoms, and -OR 5 AND-OR 6 Together with the P atom of the phosphonate group, a cyclic phosphonate or anhydride having a ring size of 4 to 10 atoms is formed.

[0046] In a preferred embodiment, -X- is an oxygen atom -O-, and -OR 3 AND-OR 5 Together with the P atom of the phosphonate group, it forms a cyclic phosphonate or cyclic phosphonic anhydride having a ring size of 4 to 10 atoms, and -OR 4 AND-OR 6 Together with the P atom of the phosphonate group, a cyclic phosphonate or anhydride having a ring size of 4 to 10 atoms is formed.

[0047] In other preferred embodiments, -X- is a single bond, and -R 3 AND-OR 4 Together with the P atom of the phosphinate group, it forms a cyclic phosphinate or cyclic phosphinate anhydride having a ring size of 4 to 10 atoms, and -OR 5 AND-OR 6 Together with the P atom of the phosphonate group, a cyclic phosphonate or anhydride having a ring size of 4 to 10 atoms is formed.

[0048] In other preferred embodiments, -X- is a single bond, and -R 3 AND-OR 5 Together with the P atom of the phosphinate group, it forms a cyclic phosphinate or cyclic phosphinate anhydride having a ring size of 4 to 10 atoms, and -OR 4 AND-OR 6Together with the P atom of the phosphonate group, a cyclic phosphonate or anhydride having a ring size of 4 to 10 atoms is formed.

[0049] Particularly preferably, R 1 and R 2 Together with the nitrogen atom, it forms a morpholine ring or a piperidine ring.

[0050] In a preferred embodiment of the present invention, the substituent R 3 To R 6 Or the ring formed by the latter has the first functional group.

[0051] In a preferred embodiment of the present invention, R 1 and R 2 Together with the nitrogen atom, a heterocyclic ring is formed according to (N-ii), wherein, if carbon, phosphorus or silicon is present as a ring atom, the atoms of the heterocyclic ring have substituents preferably selected from the group consisting of H, alkyl, aryl, -NH 2 , -NH R , -NR 2 ,-OH,-OR,=O,-I,-Cl,-Br,F,-N 3 , -SH, -SR, -OCN, epoxy, lactam, lactone, aziridine, glycolide, oxazoline, ether, alkenylene and alkynylene, -SiR x H y , wherein R=alkyl, alkenyl, alkynyl or aryl, and x+y=3.

[0052] In a preferred embodiment of the invention, the first and / or second further functional group has a heteroatom from the group consisting of P, O, N, S, Si or an alkenyl or alkynyl group. Since halogen-based substituents generate elevated smoke when the flame retardant decomposes in a fire, smoke volume can be minimized by avoiding halogen substituents.

[0053] Particularly preferably, the total halogen content of the composition is <1000 ppm by weight, preferably <850 ppm by weight. The halogen content can be determined by conventional methods known to those skilled in the art, for example, combustion ion chromatography (CIC). Compared with the flame retardants of the prior art, a particularly low halogen content is advantageous, since known flame retardants have an undesirably high amount of halogen in the form of inorganic and organically bound halogens. The term "halogen-free" as defined herein allows for small amounts of halogen contaminants within the above-mentioned maximum values. However, the amount of halogen must generally be limited to avoid the adverse effects of halogen.

[0054] In a preferred embodiment of the present invention, the substituent R 3 , R 4 , R 5 and R 6At least one of the moieties is an organic group, wherein each of these organic groups has more than two, preferably more than three, carbon atoms.

[0055] The flame retardant according to the invention can be produced using a method as described in DE 31 33 308 A1. According to the latter, when the reaction product of acetic anhydride or acetyl chloride and phosphoric acid is converted in a stoichiometric ratio using an alkyl formamide, alkylaminomethane-diphosphonic acid or its acrylic derivatives are obtained in very good yields. By keeping the reaction temperature of the first conversion stage (e.g., the conversion of acetic anhydride or acetyl chloride with phosphoric acid) at 40° C. to 60° C., a yield as high as possible can be obtained. The first reaction step can also be carried out with a mixture of phosphorus trichloride and acetic acid instead of the reactants acetic anhydride or acetyl chloride and phosphoric acid. Monoalkyl and dialkyl formamides (e.g., methyl and dimethyl formamide, ethyl and diethyl formamide) as well as formyl compounds of morpholine, piperidine, pyrolidine, oxazolidine, alkanolamines are described as suitable alkyl formamides.

[0056] 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 alpha position to the nitrogen is substituted with only one phosphonate group. This means that the decomposition temperature is higher than that of comparable known phosphonates. In the context of the present invention, the decomposition temperature is defined as the temperature at which a mass loss of 2% by weight of a dried sample of the flame retardant is reached. For example, aminotrimethylenephosphonic acid (ATMP, CAS: 6419-19-8) already reaches a mass loss of 2% by weight at 176.4°C (cf. Figure 5 For the phosphonates according to the invention, a corresponding mass loss is only achieved at significantly higher temperatures (see Figure 2 and Figure 4 ).

[0057] The mass loss of the sample can be measured by thermogravimetric analysis as a function of temperature. In this case, "dry / dry" means that the water content of the flame retardant is less than 0.5 wt %. The water content of the flame retardant can be measured by methods known to those skilled in the art, such as colorimetric Karl Fischer titration or near infrared spectroscopy. The flame retardant according to the present invention is particularly suitable for incorporation into polymer materials that will be processed by extrusion, because it will not decompose at processing temperatures typically used for extrusion, but only at higher temperatures occurring during a fire, and then exerts its flame retardant effect.

[0058] The flame retardants according to the invention are also characterized by a lower smoke generation rate. This is also reflected in a higher residual mass after decomposition.

[0059] The inventors assume that the enhanced thermal stability of the flame retardant according to the present invention is based on its special structure. The thermal decomposition of aminomethanephosphonate first leads to P-CH 2 The weak PC bond of the N group is broken. Although the PC bond is theoretically chemically and thermally stable, the α-amino group stabilizes the carbon radical produced by homolysis; therefore, the PC bond in these flame retardants is already broken at relatively low temperatures. Since the α-amino group on the compounds known from the prior art has a relatively low molar weight, the corresponding amine can dissipate as a gas product after homolysis. The dissipation of the amine represents the thermodynamic driving force of the reaction, so the reaction occurs preferentially. In the flame retardant of the present invention, another phosphonate group is combined with the carbon radical in the α position of the amine group. Therefore, the molar weight of the amine is higher and, therefore, in principle, it can only dissipate in a much lower proportion. In order for the amine to dissipate at a lower temperature, it must have a lower mass; this can only be achieved by uniformly breaking the PC bond to the second phosphonate group. But because this produces a particularly unstable carbon anion, this reaction either does not occur or does not occur at all. Therefore, any decomposition in the polymer material leads to a significantly reduced release of amines, thereby reducing the incidence of smoke. In addition, since the amine does not dissipate immediately after the bond is broken, reverse reactions may occur, for example, two radicals combine to form the original bond. As a result of the above-mentioned effects, rupturing the PC bond is not as favorable as in the case of the compounds of the prior art; the aminomethanephosphonates according to the invention therefore have a significantly higher thermal stability.

[0060] At least one heteroatom and / or at least one alkenyl or alkynyl group having the first functional group and any other functional groups also leads to enhanced flame retardancy. The inventors assume that the heteroatom and / or alkenyl or alkynyl group can form free radicals with its highly excited free electron pair and / or π-bonded electron pair. The combination of these free radicals with other free radicals produced during the combustion process slows down the decomposition reaction. Since the flame retardant according to the present invention is very uniformly distributed in the polymer material, particularly good flame retardant properties are achieved.

[0061] In a preferred embodiment of the present invention, the substituent R 1 To R 6 Or the ring formed by it has at least one other functional group, and the at least one other functional group is a heteroatom selected from the following group: P, O, N, S, Si, I, Cl, Br, F and / or alkenyl or alkynyl. This further improves the above-mentioned effect of slowing down the decomposition process driven by free radicals, thereby enhancing the flame retardant effect.

[0062] In a preferred embodiment of the present invention, the substituent R 1 To R 6 Or the ring formed therefrom has at least two, preferably at least three, more preferably at least four, most preferably at least five other functional groups.

[0063] In a preferred embodiment of the present invention, the substituent R 1 To R 6 or the ring formed by the latter each has at least one functional group. In a particularly preferred embodiment of the present invention, the substituent R 3 To R 6 or the ring formed by the latter each has at least one functional group. Particularly preferably, the number of functional groups matches that of all substituents or the ring formed thereby. Most preferably, R 3 To R 6 The compounds of the general formula (I) are particularly easy to obtain, for example, by esterification of the corresponding phosphonic acid.

[0064] In a preferred embodiment of the invention, the first and / or further functional groups are used to match the polarity of the flame retardant to the polarity of the polymer material. When the flame retardant and the polymer material have comparable polarity, the flame retardant may be more easily incorporated into the polymer material, thus resulting in better distribution. It is then more difficult for the flame retardant to migrate from the polymer material.

[0065] In a preferred embodiment of the present invention, the first functional group and / or other functional groups of the flame retardant are selected from the following group: -NH 2 , -NHR, -NR 2 , -OH, -OR, =O, -SH, -SR, -COOH, -COOR, -OCN, -SCN, -SiR x H y , -I, -Cl, -Br, -F, -N 3 , and epoxy, lactam, lactone, aziridine, glycolide, oxazoline, wherein R=alkyl, alkenyl, alkynyl or aryl, and x+y=3.

[0066] The selection of these functional groups has the advantage that the polarity of the substituents is increased compared to alkyl and / or aryl substituents without functional groups. Therefore, the corresponding flame retardants can be more easily incorporated into polar polymer materials (e.g., polyacrylates, polyurethanes or polyamides) and are more difficult to migrate from the polymer materials.

[0067] In other preferred embodiments of the present invention, the first functional group and / or other functional groups of the flame retardant are selected from the following group: -SiR x H y , alkenylenes and alkinylenes, where R=alkyl, alkenyl, alkynyl or aryl, and x+y=3.

[0068] The selection of these functional groups has the advantage that the polarity of the substituents is reduced compared to alkyl and / or aryl substituents without functional groups. Therefore, the corresponding flame retardants can be more easily incorporated into non-polar polymer materials such as polyolefins (e.g. polyethylene, polypropylene) and are more difficult to migrate from polymer materials.

[0069] Furthermore, compounds having the above-mentioned functional groups can be used as comonomers for producing polymer materials, whereby the flame retardant is covalently bonded to the polymer material. This has the advantage that the flame retardant cannot migrate from the polymer material or can only migrate from the polymer material with great difficulty. A more uniform distribution of the flame retardant in the polymer material is also achieved. This leads to an improved flame retardancy.

[0070] In a preferred embodiment, the first functional group and / or other functional groups may be NH 2 -group. The flame retardant can then be added to the polymer condensation reaction and become embedded in the polymer chain by reacting with the electrophilic group of one of the monomers. An example of the formation of polyamide 6,6 is shown below.

[0071]

[0072] In a particularly preferred embodiment of the present invention, the flame retardant according to the present invention has other functional groups selected from the group consisting of: -NH 2 , -NHR, -NR 2 ,-OH,-OR,=O,-SH,-SR,-COOH,-COOR,-OCN,-SiR x H y , -I, -Cl, -Br, -F, as well as epoxy, lactam, lactone, aziridine, glycolide, oxazoline, ether, alkenylene and alkynylene, wherein R = alkyl, alkenyl, alkynyl or aryl, and x+y = 3.

[0073] This increases the possibility of embedding the flame retardant into the polymer chain and maximizes the advantages associated with embedding. In a particularly preferred embodiment of the invention, the flame retardant according to the invention has at least two functional groups that match those of the monomers of the polymer material. Thus, the flame retardant can be embedded in the polymer chain without causing chain termination.

[0074] In a particularly preferred embodiment of the invention, the flame retardant according to the invention has at least two different functional groups. Thus, the flame retardant can be embedded in different polymerization reactions. For example, one functional group can be NH 2 group, and the other can be an olefinic group. Subsequently, free radicals can be used to drive polymerization or to react with NH 2 The flame retardant is embedded in the polymer chain with olefinic groups through polycondensation reaction.

[0075] The flame retardant according to the invention has the advantage that it is liquid and / or easily soluble in polar solvents and therefore has little effect on the viscosity of the solvent. The flame retardant according to the invention is therefore easy to process and to embed in polymerization reactions. In particular, viscosity problems occurring during polyaddition and condensation reactions can be reduced by using the flame retardant according to the invention. This leads to the subsequent occurrence of the Trommsdorf-Norrish effect; therefore, a higher average molar mass of the polymer material can be obtained.

[0076] In a preferred embodiment, R 1 and R 2 form a ring, and are identical or different substituents, wherein at least one substituent is melamine, wherein the nitrogen atom of the amino group is substituted with H, an alkyl group, an aryl group or a methyl diphosphonate group of the following structure (II).

[0077]

[0078] Particularly preferably, on each nitrogen atom of the amino group, one substituent is H and the other is a methylbisphosphonate group of structure (II). In another preferred embodiment, both substituents on each nitrogen atom are methylbisphosphonate groups of structure (II).

[0079] The difference in polarity between flame retardants and polymeric materials results in polar flame retardants (such as phosphate esters) being easily migrated from non-polar polymeric materials (such as polyethylene), depending on the type.

[0080] Particularly preferably, the first functional group and / or further functional groups of the flame retardant are alkenyl or alkynyl groups. This has the advantage that the flame retardant can be bound to the non-polar polymer material (e.g. polyolefin) during polymerization, especially during free radical driven or ion driven polymerization. This prevents migration from the polymer material.

[0081] In particular, when the polymer material to be protected is not a non-polar polyolefin but a polar polymer such as a polyamide, polyurethane, or polyester, it can be advantageous to use the flame retardant of the present invention as an acid. The flame retardant is preferably an acid, especially when used as a co-condensation / addition component. In a preferred embodiment of the present invention, therefore R 3 , R 4 , R 5 and R 6At least one, preferably at least two, particularly preferably at least three, and most preferably four of the groups are H. For example, the flame retardant according to the invention can be preferably added to the polyurethane foaming process in acid form as a co-addition component. Without being bound by this theory, the inventors assume that the reaction of isocyanate and phosphonic acid groups embeds the flame retardant into the polymer by forming particularly stable POC(=O)-N groups, which favorably influences the decomposition behavior of the polyurethane. Similarly, this applies to other polymers produced by polyaddition reactions, such as polyethylene oxide, polypropylene oxide, polyethylene glycol and polyurea. Here, the phosphonic acid group also reacts with one of the components and is therefore embedded in the polymer. Therefore, when producing these polymers, it is particularly preferred to use the flame retardant in acid form as a co-addition component.

[0082] Similarly, preferred embodiments use the flame retardant of the invention in acid form as a co-condensation component in a polymerization reaction. In this case, the inventors assume that the phosphonic acid groups react with the hydroxyl or amine groups of the condensation reaction components, thereby embedding them into the polymer. Therefore, the flame retardant according to the invention is preferably used as a co-condensation component in the acid form to produce polyesters, polycarbonates, polyamides.

[0083] In a preferred embodiment of the present invention, the substituent R 3 and / or R 4 and / or R 5 and / or R 6 The organic radical has more than two carbon atoms. Phosphonates containing short-chain carbon groups, in particular methyl groups, are known from the prior art. However, since these substances have an alkylating effect under decomposition conditions, they can be very toxic. For example, human DNA can be permanently damaged. However, the alkylating effect decreases significantly as the chain length increases.

[0084] During the thermal processing method for embedding the polymer into the plastic matrix, the decomposition temperature of the polymer is preferably higher than the processing temperature of the plastic matrix. This ensures that no decomposition processes of the polymer occur when the processing temperature of the plastic matrix is ​​reached. The decomposition temperature of the polymer is preferably more than 10° C. higher than the processing temperature of the plastic matrix, particularly preferably more than 20° C. higher than the processing temperature of the plastic matrix, and most preferably more than 50° C. higher than the processing temperature of the plastic matrix.

[0085] When the decomposition temperature of the polymer is significantly higher than the decomposition temperature of the plastic matrix in which the polymer is embedded, the plastic matrix will decompose in the event of a fire, and the polymer can then partially decompose to exert its flame retardant effect. On the contrary, when the decomposition temperature of the polymer is significantly lower than the decomposition temperature of the plastic matrix, the decomposed polymer may have undergone subsequent reactions, thereby greatly reducing its flame retardant effect. Therefore, the difference between the decomposition temperature of the polymer and the decomposition temperature of the plastic matrix is ​​preferably less than 100°C, particularly preferably less than 50°C, and most preferably less than 20°C.

[0086] In a preferred embodiment of the invention, the decomposition temperature (eg mass loss of dry flame retardant of 2% by weight) is only reached starting at a temperature of 200°C, particularly preferably starting at a temperature of 220°C, most preferably starting at a temperature of 245°C.

[0087] The decomposition temperature of the polymer is determined by thermogravimetric analysis as described in the "Measurement Methods" section. If the heating rate is 10 K / min, the decomposition temperature is the temperature at which the mass loss of the dried sample reaches 2%.

[0088] Since the carbon atom at the position α to the nitrogen is replaced twice by a phosphonate group, the phosphorus content of the flame retardant according to the present invention is higher than that of the phosphonates known in the prior art. We can determine that the flame retardant effect of phosphorus-based flame retardants increases with increasing phosphorus content. Therefore, the effect of the flame retardant according to the present invention, for example, the flame retardant effect of the flame retardant used per unit mass, is particularly high. Even in the case of a low concentration of the flame retardant in the polymer material, a good flame retardant effect can be achieved. At the same time, the properties of the material (especially its processing properties 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, and most preferably at least 15% by weight. In order to ensure a high phosphorus content in the flame retardant of the present invention, the substituent R 1 -R 6 Advantageously, the mass is as low as possible.

[0089] In particular, when one or several components of the preferably catalyzed polymerization reaction are added as additives, it is advantageous to use the flame retardant of the invention as a salt or ester, particularly preferably as a salt. This avoids potential interactions of the free acid groups of the flame retardant with components such as reaction catalysts. The flame retardant according to the invention is also advantageously used as a salt or ester on pH-sensitive polymer materials, which are, for example, polymer materials whose structure changes and / or decomposes when exposed to acid. For this application, the salt form can also be dissolved in water and uniformly mixed with the polyol in some way. The water-soluble salt form can also be easily and uniformly incorporated into water-based coatings and coating systems. When the flame retardant is used as an ester, the associated hydrophobic effect can additionally promote better bonding to the matrix, resulting in improved mechanical properties and reduced migration from the polymer.

[0090] In a preferred embodiment of the present invention, the group R 3 , R 4 , R 5 and R 6 At least one, preferably at least two, even more preferably at least three, most preferably at least four of are therefore cations, wherein the cation is Na + , K + Mg 2+ , Ca2+ , B 3+ 、Al 3+ 、Zn 2+ NH 4 + or an ammonium ion of an amine compound, the amine compound being selected from melamine or its condensation products, preferably melam, melem, melonamine, urea, guanidine, morpholine and piperazine. + and Ca 2+ It is particularly preferred. Most preferably, Na + Phosphorus is used as a cation because of its low molar mass; thus, the weight share of phosphorus in the flame retardant can be kept as high as possible.

[0091] In a preferred embodiment, the polymeric material comprises a flame retardant in an amount of at least 1.5 wt%, or at least 5 wt%, or at least 10 wt%, or at least 15 wt% and / or in an amount not exceeding 35 wt%, or not exceeding 30 wt%, or not exceeding 25 wt%, relative to the total polymer composition.

[0092] In a preferred embodiment of the present invention, the overall composition comprises polymer material in an amount of at least 50% by weight, preferably at least 70% by weight, particularly preferably at least 80% by weight, most preferably at least 90% by weight.

[0093] These quantitative ratios ensure firstly good flame retardancy of the polymer composition and secondly only very little influence on the processing and material properties of the polymer material.

[0094] The flame retardants according to the present invention can be advantageously used in combination with other flame retardants, for example, those that provide flame retardancy by another mechanism. The interaction of the flame retardants according to the present invention with other flame retardants can achieve synergistic effects, for example, effects that exceed the sum of the flame retardant effects of the individual components.

[0095] The polymer material of the composition according to the invention can be an elastomeric, thermosetting or thermoplastic polymer material. The polymer material is preferably a thermosetting or thermoplastic polymer material, particularly preferably a thermosetting polymer material.

[0096] In a preferred embodiment, the polymer material comprises at least one other flame retardant component, the at least one other flame retardant component is preferably selected from: nitrogen bases, melamine derivatives, phosphates, pyrophosphates, polyphosphates, organic and inorganic phosphinates, organic and inorganic phosphonates and derivatives of the above compounds, preferably selected from: ammonium polyphosphate; and melamine; melamine resins; melamine derivatives; silanes; siloxanes; polysiloxanes; silicone or polystyrene; coated and / or uncoated and crosslinked ammonium polyphosphate particles; and 1,3,5-triazine compounds, including melamine, melam, melem, melonamine, ammelin, a ... ammelid, 2-urea melamine, acetoguanamine, benzoguanamine, diaminophenyl triazine, melamine salts and adducts, melamine cyanurate, melamine borate, melamine orthophosphate, melamine pyrophosphate, dimelamine pyrophosphate, aluminum diethylphosphinate, melamine polyphosphate, oligomers and polymers of 1,3,5-triazine compounds and polyphosphates of 1,3,5 triazine compounds; guanine; piperazine phosphate; piperazine polyphosphate; ethylenediamine phosphate; pentaerythritol; dipentaerythritol; boron phosphate; 1,3,5-trihydroxyethyl isocyanurate; 1,3,5-triglycidyl isocyanurate; triallyl isocyanurate and derivatives of the above compounds. In a preferred embodiment, the polymer material contains wax, silicone, siloxane, fat or mineral oil for improving the dispersion of other flame retardant components.

[0097] In addition to the flame retardant according to the invention, the polymer material preferably comprises phosphates, in particular ammonium polyphosphate, as further flame retardant components. The ammonium polyphosphate is particularly preferably ammonium polyphosphate of crystalline modification I, II or V or a mixture thereof, the latter being particularly preferably coated.

[0098] Ammonium polyphosphate in form II (which is substantially insoluble in water compared to other forms) is particularly preferred. This is a powdery substance that has a good flame retardant effect even without coating and has a low solubility in water. The advantage of using coated ammonium polyphosphate in form II is that it has a higher thermal stability and a higher compatibility with polymers. This leads to better dispersion of the flame retardant in the polymer, improved processing properties of the polymer, and more efficient fire protection.

[0099] Since the solid phase activity of phosphates is generally greater than that of phosphonates, which in contrast have a higher gas phase activity, the combination can produce a particularly pronounced flame retardant effect.

[0100] In a preferred embodiment, the ratio of the flame retardant according to the invention to at least one other flame retardant component in the polymer material is 1:18 to 1:1, preferably 1:9 to 1:4, particularly preferably 1:6 to 1:4. These ratios also apply when ammonium polyphosphate is used as the other flame retardant component.

[0101] In addition to the flame retardant of the present invention, the polymer material also contains other fillers selected from the group consisting of calcium carbonate, silicates (such as talc, clay or shimmer), kaolin or wollastonite, diatomaceous earth, calcium sulfate and barium sulfate, aluminum hydroxide, glass fibers and glass balls, as well as wood flour, cellulose powder and lamp black and graphite. These fillers can produce other desired properties of the polymer material. In particular, this can reduce the price of the polymer material, color the polymer material, or improve its mechanical properties, for example by reinforcing with glass fibers.

[0102] If the flame retardant is incorporated into the protected polymer material using a molding process, a dispersant is advantageously used when the flame retardant is incorporated. Therefore, in other embodiments of the present invention, relative to the weight of the flame retardant according to the present invention, the polymer material according to the present invention contains an amount of 0.01 to 10% by weight of a dispersant, preferably an amount of 0.1 to 5.0% by weight of a dispersant, wherein the dispersant is preferably selected from: fatty acids (including fatty acid amides, including fatty acid monoamides, fatty acid bisamides and fatty acid alkanolamides, such as oleamide and erucamide), fatty acid esters (including glycerides and wax esters), C16 to C18 fatty acids, fatty acid alcohols (including hexadecyl fatty acid alcohols and stearyl fatty acid alcohols), natural waxes and synthetic waxes, polyethylene waxes and oxidized polyethylene waxes, and metal stearates (preferably calcium stearate, zinc stearate, magnesium stearate, barium stearate, aluminum stearate, cadmium stearate and lead stearate). Adding the above-mentioned dispersant improves the ability to add flame retardants, the extrusion ability of polymer materials, and the uniformity of flame retardants dispersed in polymer materials.

[0103] In other embodiments of the present invention, the free water content (water content) of the flame retardant according to the present invention is <0.6% by weight, preferably <0.4% by weight. Low water content also improves the ability to add flame retardants, the ability to extrude polymer materials, and the uniformity of the flame retardant dispersion in the composition, and prevents decomposition caused by hydrolysis.

[0104] Flame retardants can be incorporated into polymer materials by various methods. Flame retardants can first be embedded in polymer materials during the molding process. If the polymer material is processed, for example, by extrusion, the flame retardant can be added during the extrusion process, for example, by using a masterbatch. The masterbatch defined in the present invention is a polymer material in the form of particles or powders, which contains a flame retardant and any other additives in a concentration higher than that of the final application. In order to produce a polymer material according to the present invention, a masterbatch or different masterbatches are combined with other polymer materials (without the flame retardant contained in the masterbatch) in an amount or ratio corresponding to the desired flame retardant concentration in the final product. Compared with adding various substances in the form of pastes, powders or liquids, masterbatches have the advantages of ensuring high processing reliability, easy processing and addition. The flame retardant is uniformly dispersed in the polymer material by extrusion.

[0105] The polymer material into which the flame retardant can be incorporated is preferably selected from the group consisting of polyvinyl butyral (PVB); polypropylene (PP); polyethylene (PE); polyamide (PA); polyesters, for example, polybutylene terephthalate (PBT), polyethylene terephthalate (PET); polyurethane (PU); thermoplastic polyurethane (TPU); polyurea; polyphenylene ether; polyacetal; polyacrylate; polymethacrylate; polyoxymethylene; polyvinyl acetal; polystyrene; acrylic-butadiene-benzene Ethylene (ABS); acrylonitrile-styrene-acrylate (ASA); polycarbonate; polyethersulfone; polysulfonate; polytetrafluoroethylene; polyurea; formaldehyde resin; melamine resin; polyetherketone; polyvinyl chloride; polylactide; polysiloxane; phenolic resin; epoxy resin; polyimide; bismaleimide-triazine; thermoplastic polyurethane; ethylene-vinyl acetate copolymer (EVA); polylactide (PLA); polyhydroxybutyric acid (PHB); copolymers and / or mixtures of the above polymers. The flame retardant of the present invention is particularly preferably used in foams of the above polymer materials, especially preferably in polyurethane foams. In this case, the flame retardant is preferably added as an additive or a co-condensation / addition component of a polyol component. When the flame retardant is added as an additive, the latter is preferably a salt or ester. When the flame retardant is added as a co-condensation / addition component, the latter is preferably an acid.

[0106] We can observe that these phosphonates not only have flame retardant effects, but also catalyze polyurethane foaming.

[0107] The present invention also includes a flame retardant, which is a compound of formula I, its corresponding ammonium salt, its corresponding phosphonate, or a mixture thereof, wherein the substituent R 3 To R 6 or the ring formed therefrom preferably has a first functional group, and / or is a substituent R 3 To R 6 No more than three of them are H.

[0108] The present invention also includes a method for producing a flame retardant, the method comprising the steps of:

[0109] ■Provide a mixture of the following substances:

[0110] a) at least one phosphonic acid or phosphinic acid in a reaction vessel selected from the group consisting of compounds of formula (V) and (VI)

[0111]

[0112] wherein -X- is an oxygen atom -O-, or -X- is a single bond, and

[0113] in,

[0114] (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 alkyl, alkenyl and alkynyl, unsubstituted and alkyl-substituted phenyl, polynuclear aromatic hydrocarbons with up to 4 nuclei, mononuclear heteroaromatic hydrocarbons or polynuclear heteroaromatic hydrocarbons with up to 4 nuclei, silyl, allyl, alkyl or aromatic alcohol, the following structures (III) and (IV, wherein n=0 to 100,

[0115]

[0116] and a cation, wherein the cation is Na + , K + Mg 2+ , Ca 2+ , B 3+ 、Al 3+ 、Zn 2+ NH 4 + or an ammonium ion of an amine bond, the amine bond being selected from the group consisting of melamine or its condensation products, preferably melam, melem, melonamine, urea, guanidine, morpholine and piperazine,

[0117] and / or

[0118] (P-ii) When -X- is an oxygen atom -O-, -OR 3 AND-OR 4 and / or-OR 5 AND-OR 6 and / or-OR 3 AND-OR 5 and / or-OR 4 AND-OR 6 together with the P atom of the phosphonate group, forms a cyclic phosphonate or anhydride having a ring size of 4 to 10 atoms,

[0119] and / or

[0120] (P-iii) When -X- is a single bond, -R 3 AND-OR 4 and / or -R 3 AND-OR 5 Together with the P atom of the phosphinate group, it forms a cyclic phosphonate or anhydride having a ring size of 4 to 10 atoms, and / or -OR 5 AND-OR 6 and / or-OR 4 AND-OR 6 together with the P atom of the phosphonate group, forms a cyclic phosphonate or anhydride having a ring size of 4 to 10 atoms,

[0121] b) HC(OR 7 ) 3 , where R 7 = alkyl, aryl or alkenyl, preferably triethoxymethane,

[0122] c) an amino compound of the formula (VII),

[0123]

[0124] in,

[0125] (Ni)R 1 and R 2 are identical or different substituents and are selected from the group consisting of linear, branched or cyclic alkyl, alkenyl and alkynyl groups, unsubstituted and alkyl-substituted phenyl groups, mononuclear aromatic hydrocarbons and polynuclear aromatic hydrocarbons with up to 4 nuclei, mononuclear heteroaromatic hydrocarbons and polynuclear heteroaromatic hydrocarbons with up to 4 nuclei, silyl, allyl, alkyl or aromatic alcohol, or

[0126] (N-ii)R 1 and R 2 Together with the N atom, it forms a saturated or monounsaturated or polyunsaturated heterocyclic ring having 4 to 8 ring atoms selected from carbon, oxygen, sulfur, phosphorus, silicon and nitrogen, wherein, if it has nitrogen atoms as ring atoms, these nitrogen atoms are preferably substituted on the heterocyclic ring by H, alkyl, aryl or methyldiphosphonate groups having the following structure (II),

[0127]

[0128] And, if it has carbon, phosphorus or silicon as ring atoms, these atoms on the heterocyclic ring may preferably have substituents selected from the group consisting of H, alkyl, aryl, -NH 2 , -NHR, -NR 2 ,-OH,-OR,=O,-I,-Cl,-Br,F,-N 3, -SH, -SR, -OCN, epoxy, lactam, lactone, aziridine, glycolide, oxazoline, alkenyl and alkynyl, -SiR x H y , wherein R = alkyl, alkenyl, alkynyl or aryl, and x + y = 3,

[0129] Among them,

[0130] A.) Substituent R 1 To R 6 One of, or

[0131] B.) When

[0132] 1) Substituent R 3 -R 6 When a cyclic phosphinate or cyclic phosphonate is formed according to (P-ii) or (P-iii), or

[0133] 2) Substituent R 3 -R 6 When a cyclic phosphinic anhydride or a cyclic phosphonic anhydride is formed according to (P-ii) or (P-iii), or

[0134] 3) Substituent R 1 and R 2 When a heterocyclic ring is formed according to (N-ii),

[0135] One of the rings formed

[0136] Having an uncharged or negatively charged first functional group, the uncharged or negatively charged first functional group having:

[0137] a) heteroatoms selected from the group consisting of P, O, N, S, I, Cl, Br, F; and / or

[0138] b) alkenyl or alkynyl,

[0139] where the functional group is not -OH, and

[0140] In the case where one of the rings of 1) to 3) has a functional group, the ring atoms of the ring are substituted with the functional group or a substituent having a functional group.

[0141] ■ Heat the mixture to a temperature of 40-150°C.

[0142] The heating of the mixture may be followed by a purification step. The latter preferably comprises: distillation or chromatographic purification of the mixture.

[0143] During the conversion, the amino compound of formula (VII) or the phosphonic acid or phosphinic acid reacts with the orthoester HC (OR 7 ) 3This will generate a compound of formula (I) and release three equivalents of alcohol HOR 7 .

[0144]

[0145] In order to achieve higher conversion rates, a preferred embodiment of the present invention involves separating HOR during the conversion 7 , preferably by distillation, particularly preferably by distillation under reduced pressure.

[0146] The present invention also includes methods for producing compounds of formula (V) and (VI).

[0147]

[0148] These can be prepared by reacting phosphinic acid or phosphonic acid with the formula HC(OR 3 / 4 / 5 / 6 ) 3 In a preferred embodiment of the method, HC(OR 3 / 4 / 5 / 6 ) 3 For the purpose of the process according to the invention, the phosphinic acid or phosphonic acid is reacted with the formula HC(OR 3 / 4 / 5 / 6 ) 3 The compounds are mixed and heated to a temperature of 40°C to 140°C, preferably 80°C to 120°C, more preferably 90°C to 120°C, most preferably 100°C to 120°C. The mixture is particularly preferably heated to boiling. The reaction mixture is stirred at these temperatures for 10 minutes to 10 hours, preferably 1 hour to 5 hours, more preferably 1 hour to 3 hours, most preferably 1 hour to 2 hours. After this reaction time, the reaction solution used for fractionation will contain HOR as the main component 3 / 4 / 5 / 6 and another fraction containing the compound of formula (V) or (VI).

[0149] The above process is particularly preferably used for the production of diethylphosphite.

[0150] The present invention also comprises the use of the compound of formula (I), its corresponding ammonium salt, its corresponding phosphonate or a mixture thereof for surface treatment, preferably in the form of a coating,

[0151]

[0152] in,

[0153] (Ni)R 1 and R 2are identical or different substituents and are selected from the group consisting of linear, branched or cyclic alkyl, alkenyl and alkynyl groups, unsubstituted and alkyl-substituted phenyl groups, mononuclear aromatic hydrocarbons and polynuclear aromatic hydrocarbons with up to 4 nuclei, mononuclear heteroaromatic hydrocarbons and polynuclear heteroaromatic hydrocarbons with up to 4 nuclei, silyl, allyl, alkyl or aromatic alcohol, or

[0154] (N-ii)R 1 and R 2 Together with the N atom, it forms a saturated or monounsaturated or polyunsaturated heterocyclic ring having 4 to 8 ring atoms selected from carbon, oxygen, sulfur, phosphorus, silicon and nitrogen, wherein, if it has nitrogen atoms as ring atoms, these nitrogen atoms are preferably substituted on the heterocyclic ring by H, alkyl, aryl or methyldiphosphonate groups having the following structure (II),

[0155]

[0156] And, if it has carbon, phosphorus or silicon as ring atoms, these atoms on the heterocyclic ring may preferably have substituents selected from the group consisting of H, alkyl, aryl, -NH 2 , -NHR, -NR 2 ,-OH,-OR,=O,-I,-Cl,-Br,F,-N 3 , -SH, -SR, -OCN, epoxy, lactam, lactone, aziridine, glycolide, oxazoline, alkenylene and alkynylene, -SiR x H y , wherein R = alkyl, alkenyl, alkynyl or aryl, and x + y = 3,

[0157] and, wherein -X- is an oxygen atom -O-, or -X- is a single bond, and

[0158] in,

[0159] (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 alkyl, alkenyl and alkynyl, unsubstituted and alkyl-substituted phenyl, polynuclear aromatic hydrocarbons with up to 4 nuclei, mononuclear heteroaromatic hydrocarbons and polynuclear heteroaromatic hydrocarbons with up to 4 nuclei, silyl, allyl, alkyl or aromatic alcohol, the following structures (III) and (IV), wherein n=0 to 100,

[0160]

[0161] and a cation, wherein the cation is Na + , K + Mg 2+ , Ca 2+ , B3+ 、Al 3+ 、Zn 2+ NH 4 + or an ammonium ion of an amine bond, the amine bond being selected from the group consisting of melamine or its condensation products, preferably melam, melem, melonamine, urea, guanidine, morpholine and piperazine,

[0162] and / or

[0163] (P-ii) When -X- is an oxygen atom -O-, -OR 3 AND-OR 4 and / or-OR 5 AND-OR 6 and / or-OR 3 AND-OR 5 and / or-OR 4 AND-OR 6 together with the P atom of the phosphonate group, forms a cyclic phosphonate or anhydride having a ring size of 4 to 10 atoms,

[0164] and / or

[0165] (P-iii) When -X- is a single bond, -R 3 AND-OR 4 and / or -R 3 AND-OR 5 Together with the P atom of the phosphinate group, it forms a cyclic phosphonate or anhydride having a ring size of 4 to 10 atoms, and / or -OR 5 AND-OR 6 and / or-OR 4 AND-OR 6 together with the P atom of the phosphonate group, forms a cyclic phosphonate or anhydride having a ring size of 4 to 10 atoms,

[0166] Among them,

[0167] A.) Substituent R 1 To R 6 One of or

[0168] B.) When

[0169] 1) Substituent R 3 -R 6 When a cyclic phosphinate or cyclic phosphonate is formed according to (P-ii) or (P-iii), or

[0170] 2) Substituent R 3 -R 6 When a cyclic phosphinic anhydride or a cyclic phosphonic anhydride is formed according to (P-ii) or (P-iii), or

[0171] 3) Substituent R 1 and R 2 When a heterocyclic ring is formed according to (N-ii),

[0172] One of the rings formed

[0173] Having an uncharged or negatively charged first functional group, the uncharged or negatively charged first functional group having:

[0174] a) heteroatoms selected from the group consisting of P, O, N, S, I, Cl, Br, F; and / or

[0175] b) alkenyl or alkynyl,

[0176] where the functional group is not -OH, and

[0177] In the case where one of the rings of 1) to 3) has a functional group, the ring atoms of the ring are substituted with the functional group or a substituent having a functional group.

[0178] In a preferred embodiment, the coating acts as a flame retardant for objects, particularly preferably as a flame retardant for polymeric materials.

[0179] This embodiment is particularly preferably used for the surface treatment of metal or polymer materials, especially for thermosetting polymers. For example, it is particularly preferably used in composite materials. In this case, the above-mentioned phosphonate can be applied to the polymer matrix and / or reinforcing material (such as glass fiber) in liquid form, for example as a solution or a liquid pure substance. The advantage in this case is that the flame retardant according to the present invention is liquid, or only causes a slight change in viscosity in the suspension. Therefore, the flame retardant can be evenly distributed in the composite. In contrast, the flame retardants known in the prior art are generally solid or require a large amount of solvent to obtain a low-viscosity solution. Therefore, these flame retardants can only be incorporated into composite materials with great difficulty. Woven composite materials will also produce a filtering effect of the flame retardant. Therefore, protection is only provided on one side. The use of the flame retardant of the present invention can overcome the above-mentioned shortcomings.

[0180] In a particularly preferred embodiment of the invention, the compounds of formula (I) are used to form a coating, for example a gel coating. This has the advantage that the compounds according to the invention have good solubility in a variety of polar solvents. Thus, a uniform distribution in the solvent and ultimately on the treated surface can be achieved. Due to the good solubility, the viscosity of the solution is either not affected or only slightly affected.

[0181] The compound of formula (I) is preferably used in an amount of 1 to 40 wt. %, more preferably 2 to 30 wt. %, even more preferably 3 to 20 wt. %, most preferably 4 to 10 wt. % of the coating relative to the total coating composition.

[0182] For example, solutions of compounds of the formula (I) can be used to coat textiles, paper, ceramics or composite materials or mesophases thereof, such as prepregs.

[0183] Due to the low absorption and the homogeneous miscibility with the other components of the coating system, in particular with the binder, the compounds of formula (I) are preferably suitable for so-called "clear coats" or clear coatings. Such clear coats are particularly advantageous when structures located under the coating are not to be concealed, for example, for clear coatings on wood. Example

[0184] The present invention will now be discussed in detail based on specific embodiments of the flame retardant according to the present invention, on production examples of the composition according to the present invention, on flame retardant examples and on the basis of the accompanying drawings.

[0185] Specific embodiments of the flame retardant according to the present invention

[0186] Embodiments having the first functional group on the amino group

[0187]

[0188] Embodiments having first and second functional groups on the amino group

[0189]

[0190] Embodiments having a first functional group on one of the phosphonic acid groups

[0191]

[0192] Embodiments having a first functional group on one of the phosphonic acid groups

[0193]

[0194] Embodiments having a first functional group on one of the phosphonic acid groups

[0195]

[0196] Embodiments having a first functional group on one of the phosphonic acid groups

[0197]

[0198] Embodiments having first and second functional groups on the phosphonic acid group

[0199]

[0200] Embodiments having a first functional group on one of the phosphonic acid groups

[0201]

[0202] Embodiments with a first cyclic functional group

[0203]

[0204] Embodiments with a first cyclic functional group

[0205]

[0206] Embodiments with a first cyclic functional group

[0207]

[0208] Embodiments with Morpholine MOMP

[0209]

[0210] Embodiments with piperazine PIMPs

[0211]

[0212] Production Examples of the Compositions of the Invention Input Materials:

[0213]

[0214]

[0215] Other flame retardants:

[0216] Budit 240: Phosphorus-based partially crosslinked polyacrylate, produced according to Example 1 of WO 2014 / 124933

[0217] Budit 315: Melamine cyanurate from Chemische Fabrik Budenheim KG

[0218] Budit 342: Melamine polyphosphate from Chemische Fabrik Budenheim KG

[0219] Budit 667: Intumescent flame retardant system based on ammonium polyphosphate from Chemische Fabrik Budenheim KG

[0220] TCPP: Tris(2-chloroisopropyl)phosphate TCPP (CAS: 13674-84-5) from Sigma-Aldrich

[0221] OP 550: Phosphorus-based polyol Exolit OP 550 from Clariant AG (CAS: 184538-58-7)

[0222] Measurement method:

[0223] Dynamic Differential Calorimetry (DSC) - The measurement was carried out using a simultaneous thermogravimetry-dynamic differential calorimetry (STA / TG-DSC) apparatus, in a nitrogen atmosphere from 25 to 500°C, at a heating rate of 10 K / min, the apparatus model being STA409 PC / 3 / H Luxx, Netzsch Gatteburg GmbH GmbH). The initial sample weight was about 15 mg. The analysis was performed using the software NETZSCH Proteus.

[0224] Thermogravimetric analysis (TAG) The measurements were performed using a simultaneous thermogravimetry-dynamic differential calorimetry (STA / TG-DSC) apparatus from 25 to 800 °C in a nitrogen atmosphere at a heating rate of 10 K / min. The apparatus model was STA409 PC / 3 / H Luxx, Netzsch Gatteburg GmbH. GmbH). The initial sample weight was about 12-15 mg. The TGA curves were analyzed using the software NETZSCH Proteus.

[0225] Production Example for the Composition of the Present Invention

[0226] Example 1 :Morpholine-methylaminobisphosphonic acid (MOMP-H 4 )

[0227] 0.1 mol of 4-formylmorpholine was placed in a 500 ml round 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. Then, under a reduced pressure of about 30 mbar, the produced acetic acid and excess water were removed on a rotary evaporator. The residue was then removed from the remaining solvent in a drying cabinet at 85 ° C for 4 hours.

[0228] Example 2 :Piperazine-bis(methylaminobisphosphonic acid) (PIMP-H 4 )

[0229] While stirring, 0.28mol phosphonic acid was dissolved in 31ml of complete deionized water in a 250ml round flask. 0.07mol diformylpiperazine solution was dripped into 30ml of complete deionized water, lasting 15 minutes. During the interpolation, it was observed that the temperature had increased by several degrees. After the interpolation was completed, the reaction mixture was stirred for 3 hours under reflux. After the solution was cooled, unnecessary water was removed on a rotary evaporator. Saturated piperazine solution was dripped into the liquid distillation residue. White amorphous precipitation was formed during the heating period.

[0230] Example 3:Dimethyl-methylaminobisphosphonic acid (DAMP-H 4 )

[0231] 0.9 mol of dimethylformamide was placed in a 500 ml round 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. Then, the produced acetic acid and excess water were removed on a rotary evaporator under a reduced pressure of about 300 mbar. The residue was then removed from the remaining solvent in a drying cabinet at 85°C for 4 hours.

[0232] Example 4 :Morpholine-methylaminobisphosphonic acid (MOMP-H-Na 3 )Synthesis of trisodium salt aqueous solution

[0233] 0.289 mmol of morpholine methylaminobisphosphonic acid (MOMP-H 4 ) was dissolved in 50 ml of completely deionized water, and then 0.867 mmol of NaOH was added. The pH value of the solution was ~9.

[0234] Example 5 : Morpholine-methylaminobisphosphonic acid tetraethyl ester (MOMP-H 4 )

[0235] MOMP-Et 4 Provided in the following manner: 0.1 mol of morpholine is weighed into the reactor while stirring. Then 0.1 mol of triethoxymethane is added dropwise. Then 0.2 mol of diethylphosphite is added. The mixture is heated to 120° C. and stirred at this temperature for 4 hours. After the reaction is finished, the product is cleaned by vacuum distillation at 50 mbar and 150° C.

[0236] In a preferred embodiment, all substituents R 3 , R 4 , R 5 and R 6 The substituted ethyl group is a cation or an organic group, and the ethyl group is particularly preferred because the corresponding substituted compound can be used as a catalyst for polyurethane foam synthesis. It is particularly advantageous to use this mixture because it accelerates the synthesis and also improves the flame retardant properties of the final polymer. Compounds with P-OH groups (e.g., MOMP-H 4 ) did not show the corresponding catalytic effect, probably because its dipolar ion (PO - / NH + ) form, and its quaternary amino group does have catalytic properties.

[0237] With compounds having a P-OH group (e.g. MOMP- 4), the so-called start time until foaming is significantly shortened when correspondingly substituted compounds are used, as will be shown on the basis of the following tests.

[0238] Conventional method: polyol (22.5 g) was mixed with catalyst (ethylene glycol, 1.05 g), pentane (4.5 g) and the corresponding flame retardant at 1000 R / min. Isocyanate (MDI, 60.0 g) was added with the disperser closed; the mixture was then stirred at 1500 R / min for 10 seconds and then immediately refilled.

[0239]

[0240] *PHP - parts per hundred of polyol

[0241] Example 6 :Morpholine-methylaminodi-DOPO (MOM-DOPO 2 )

[0242]

[0243]

[0244] The reaction is a condensation reaction, which generates the product MOM-DOPO through the formyl functional group on 4-formylmorpholine (4-FM) and the PH group of the DOPO molecule. 2 , accompanied by H 2 O split. 40g DOPO was dissolved in 100ml acetic anhydride (Ac 2 O) while stirring in a 250 ml beaker and then heating the mixture to 120° C. When temperature is reached, 10 g of 4-FM are added. After 5 hours, the solution is neutralized with 80 ml of water and then external tempering is set. After cooling, a white solid precipitates, which is filtered and washed with water. Acetic acid is produced as a further by-product.

[0245] Example 7 : Morpholine-methylaminobisphosphonic acid Zn salt (MOMP-H 2 )

[0246] Zinc salt (1:1) was prepared by dispersing 50.0 g (0.191 mol) MOMP in 500 g H 2 O and then mixed with 14.6 g ZnO (0.191 mol). The reaction mixture was heated to 95° C. and stirred at this temperature for 4 hours. The batch was then cooled to below 50° C. and the solid and mother liquor were separated. The filter cake was dried in circulating air at 120° C.

[0247]

[0248] Example 8: Piperazine-bis(methylaminobisphosphonic acid) (PIMP-H 4 )

[0249]

[0250] 0.1mol 1,4-diformylpiperazine and 0.1mol acetic anhydride are filled into the reactor and mixed. The mixture is heated to 120°C. 0.4mol phosphoric acid is dissolved in 0.3mol acetic anhydride respectively. The solution is then dripped into the reactor. Finally, another 0.5mol acetic anhydride is added, and the batch is then heated to 135°C. After 30 minutes of reaction time, 2.1mol water is dripped in. After an additional 40 minutes of reaction time, the batch is cooled to room temperature. Then 70ml sodium hydroxide solution is added. The product is separated from the mother liquor and dissolved in water. The solution is then reprecipitated in sulfuric acid, and then filtered, washed and the product is dried.

[0251] Example 9 :Synthesis of diethyl phosphite

[0252] Phosphonic acid (29.7 g, 0.36 mol) and triethoxymethane (107.3 g, 0.72 mol) were mixed in a 500 ml three-necked flask with a distillation apparatus and then heated to 90° C. while stirring. After 45 minutes, the temperature was raised to 135° C., boiling began (gas phase temperature 73° C.), and a first fraction of ethanol and ethyl formate was obtained. After boiling stopped, a vacuum (30 mbar) was applied to obtain a second fraction. The relevant product was diethyl phosphite. 35.0 g of a colorless, low-odor liquid was obtained.

[0253] Example 10 :4-Hydroxy-1-(methylaminodiphosphonic acid)piperidinium ("OH-PIDMP-H 4 ”)

[0254]

[0255] “OH-PIDMP-Et 4 " is obtained by adding 4-hydroxypiperidine (0.1 mol) to a 250 ml flask and stirring. Triethoxymethane (0.1 mol) is added dropwise. Then 0.2 mol of diethyl phosphite is added. The mixture is heated to 120°C and stirred at this temperature for 4 hours, and then the product "OH-PIDMP-Et 4 ” for cleaning.

[0256]

[0257] The product was then mixed with a 5-fold excess of 1N HCl, where a small amount of heating was observed. The ethanol produced was distilled off, thereby obtaining the product "OH-PIDMP-H 4 ". The melting point is 250℃.

[0258] Embodiment 11 :4-methylene-1-(tetraethyl methylaminodiphosphonate)-piperidine ("4-methylene-PIDMP-Et 4 ”)

[0259]

[0260] "4-Methylene-PIDMP-Et 4 "It is obtained by injecting 4-methylenepiperidine hydrochloride (0.05 mol) and triethylamine (0.1 mol) into a 250 ml flask and stirring. Triethoxymethane (0.12 mol) is added dropwise. Diethylphosphite (0.31 mol) is then added. The mixture is heated to 140°C and stirred at this temperature for 6 hours. After cooling to room temperature, diethyl ether (125 ml) is added, the mixture is neutralized with sodium hydroxide solution (0.5N, 50 ml), phase separation is performed, and the organic phase is washed with 250 ml of water. The organic phase is processed by distillation, wherein the product has a boiling point of 180°C at 2 mmbar. The yield is 58%.

[0261] Example 12 :4-Hydroxy-4-vinyl-1-(tetraethyl methylaminodiphosphonate)-piperidine ("OH-vinyl-PIDMP-Et 4 ”)

[0262]

[0263] "OH-vinyl-PIDMP-Et 4 " was obtained by adding 4-piperidone ethylene acetal (0.1 mol) to a 250 flask and stirring. Triethoxymethane (0.1 mol) was added dropwise. Then 0.2 mol of diethyl phosphite was added. The mixture was heated to 120°C and stirred for 4 hours, and then the product "Ketal-PIDMP-Et" was distilled under vacuum at 50 mbar and 150°C. 4 ” for cleaning.

[0264]

[0265] "Ketal-PIDMP-Et 4" was mixed with 5-fold molar excess of 80% acetic acid and stirred at 80°C for 2 hours. The generated ethylene glycol was distilled off and the intermediate product "Keton-PIDMP-Et 4 "Cleaning was carried out by vacuum distillation at 50 mbar and 150°C.

[0266]

[0267] "OH-vinyl-PIDMP-Et 4 " was obtained by filling THF (absolute) as solvent into an anhydrous apparatus and then generating a Grignard reagent (c = 1.5 mol) therein. Magnesium chips were then added to THF while vinyl bromide (1.2 mmol) was continuously dripped. "Keton-PIDMP-Et 4 "(1 mmol). After the reaction was complete (confirmed by boiling point depression, total reaction time was about 2 hours), the reaction mixture was hydrolyzed with cooled 1N HCl (aqueous). The mixture was worked up by separating the aqueous phase and removing the solvent from the organic phase by distillation. The obtained OH-vinyl-PIDMP-Et 4 The melting point of " is 239°C. The reaction yield is 85%.

[0268] Examples of flame retardants:

[0269] Composition

[0270] The UL94 test was carried out on test specimens in accordance with the IEC / DIN EN 60695-11-10 standard to verify the flame retardant properties and to classify the flame retardant composition according to the invention into various polymers.

[0271] UL94-V test

[0272] For each measurement, 5 test specimens were clamped in a vertical position and then fixed to the open end of a Bunsen burner flame. The burning time and the fall of burning particles were evaluated with a cotton pad placed under the test specimen. The test was carried out precisely as specified in the Underwriters Laboratory standard UL94 and exposed to a 2 cm high Bunsen burner flame.

[0273] The classification of fire protection classes V-0 to V-2 is cited as the result. In this case, V-0 means that the total burning time of the 5 tested test specimens is less than 50 seconds and the cotton pad does not catch fire due to flashes or burning drops of the test specimens. The classification V-1 means that the total burning time of the 5 tested test specimens exceeds 50 seconds but is less than 250 seconds and the cotton pad does not catch fire similarly. In this case, V-2 means that the total burning time of the 5 tested test specimens is less than 250 seconds, but the cotton pad catches fire by flashes or burning drops in at least one of the 5 tests. The abbreviation NC means "not classifiable" and means that the total burning time measured exceeds 250 seconds. In many unclassifiable cases, the test specimens burn completely.

[0274] UL94-HB test

[0275] For each measurement, at least 3 test specimens are clamped in a horizontal position and then fixed at the open end of a Bunsen burner flame. This includes the evaluation of the burning rate and the total burning distance. The test is carried out precisely as specified in the Underwriters Laboratories standard UL94 and is exposed to a 2 cm high Bunsen burner flame.

[0276] The classification of fire class HB is quoted as the result. The "HB" classification means that the burning rate between two marks is less than 40 mm / min, the first mark is 25 mm from the flame end and the second mark is 100 mm from the flame end. The flame front also does not exceed the 100 mm mark. The "NC" classification means "not classifiable" and means that the burning rate at a distance of 75 mm is >40 mm / min or the total burning distance is >100 mm.

[0277] L*a*b* value

[0278] The L*a*b* values ​​were determined by an UltraScan VIS-2 spectrophotometer from HunterLab equipped with an UltraScan VIS sensor. To this end, the sample was filled into a glass cuvette and then the cuvette was impacted or densified to form a uniform surface on the side of the cuvette facing the measurement opening. The associated Easy Match QC 4.64b software used the "USVIS1145" sensor and the "RSIN mode" setting to calculate the L*a*b* values.

[0279] This method complies with the requirements of the currently valid version of EN ISO 11664-4.

[0280] Embodiment 13 :MOMP-H in polypropylene 4 Flame retardant properties

[0281] polymer

[0282] The following polymer materials were used to produce flame retardant compositions in the following examples:

[0283] Polypropylene (PP) HD120 MO from Borealis AG

[0284] Under typical polypropylene extrusion conditions, a twin screw extruder (model Process 11) produced by Thermo Fisher Scientific Inc. was used to produce particles with a particle size of about 3x1x1 mm. The extrusion process was operated with an output of about 5-7 kg / h, a screw speed of 450-500 rpm and an extrusion zone temperature of 190-220° C. High-quality specimens that meet the UL94 standard were then obtained by hot pressing. The thickness of the test specimens was 1.6 mm and 3.2 mm, respectively. The phosphonate produced according to Example 1 was then incorporated into the polymer material during the extrusion process.

[0285] Table 1:

[0286]

[0287] Embodiment 14 :MOMP-H in polyurethane (PU) 4 Flame retardant properties

[0288] The flame retardant composition is prepared by converting the following components together in a foaming reaction:

[0289] Polyol: 22.5g

[0290] Catalyst (ethylene glycol): 1.05 g

[0291] Pentane: 4.5 g

[0292] Isocyanate (MDI): 60g

[0293] Before the reaction, the flame retardant according to the present invention is added to the polyol component. The mass ratio of the flame retardant quoted in the following table refers to the sum of the mass of the polyol, catalyst, flame retardant and isocyanate.

[0294]

[0295] # MOMP-H 4 Dipotassium salt

[0296] **w / o catalyst

[0297] Embodiment 15 :MOMP-H in thermoplastic polyurethane (PU) 4 Flame retardant properties

[0298] The following polymer materials were used to produce flame retardant compositions in the following examples:

[0299] Thermoplastic polyurethane (TPU) Elastollan 1185 A from BASF SE

[0300] Under typical TPU extrusion conditions, a twin screw extruder (model Process 11) produced by Thermo Fisher Scientific Inc. was used to produce particles with a particle size of about 3x1x1 mm. The extrusion process was operated with an output of about 5 kg / h, a screw speed of 300 rpm and an extrusion zone temperature of 205°C. High-quality specimens that meet the UL94 standard were then obtained by hot pressing. The thickness of the test specimen was 0.8 mm. The phosphonate produced according to Example 1 was then incorporated into the polymer material during the extrusion process.

[0301]

[0302] * butc = test sample burns down to the fixture

[0303] # ditc = droplets falling and igniting cotton

[0304] ~ A second flame exposure cannot be performed because the test specimen has already burned out after the first flame exposure

[0305] Example 16 :MOMP-H in thermoplastic polyamide (PA) 2 Flame retardant properties of Zn

[0306] The following materials were used to produce the flame retardant compositions in the following examples:

[0307] Polyamide 6: Ultramid B3S (BASF)

[0308] Glass fiber (GF) of PA: CS7928 (Lanxess)

[0309] Under typical PA6 extrusion conditions, the twin screw extruder (model Process 11) produced by Thermo Fisher Scientific Inc. is used to produce particles with a particle size of about 3x1x1mm. The extrusion process is operated with an output of about 5kg / h, a screw speed of 300rpm and an extrusion zone temperature of 280°C. The high-quality specimens that meet the UL94 standard are then obtained by hot pressing. The thickness of the test specimen is 0.8 millimeter. Then during the extrusion process, according to Example 7 (MOMP-H 2 The phosphonates produced by Zn) are incorporated into polymeric materials.

[0310]

[0311] * butc = test sample burns down to the fixture

[0312] **Exolit OP 1230

[0313] ~ A second flame exposure cannot be performed because the test specimen has already burned out after the first flame exposure

[0314] Embodiment 17 :MOMP-Et in thermoplastic polyurethane coatings 4 Flame retardant and transparent properties

[0315] Polyurethane resin topcoat Goylake A-1219-9 from Irurena Group and MOMP-Et 4 Mix and combine while stirring vigorously. MOMP-Et 4 In the MOMP-Et 4 The ratio of the total mass (250 g) consisting of the mass of the polyurethane resin was 5 wt % (Formula A) or 10 wt % (Formula B). Relative to the total mass, 10 wt % of the curing catalyst C-212 from Irurena Group was added, and then the mixture was mixed while vigorously stirring.

[0316] The clear mixture was then applied to a commercially available particle board using a 500 μm doctor blade and the panel was then dried at 80°C.

[0317] In the subsequent Epiradiator fire test according to NF P 92-501, both Formulation A and Formulation B obtained the M3 classification.

[0318] Transparency measurement

[0319] In order to verify the transparency of formulations A and B, each formulation was applied as a coating onto a white and black substrate using a 500 μm doctor blade in each case. The L*a*b values ​​of each substrate were then determined for two samples with coating (Test Nos. 1 and 2) and two control samples without coating (Test Nos. 3 and 4).

[0320] As shown in the table below, the coatings of formulations A and B only cause negligible value changes in the L*a*b color space, for example, the coatings have high transparency and have no effect or only an insubstantial effect on the appearance of the substrate. Therefore, the flame retardant according to the present invention is particularly suitable for use in transparent coatings.

[0321] Recipe A

[0322] Black substrate

[0323] # coating L* a* b* 1 + 10.2 -0.5 -1.3 2 + 9.1 -0.5 -1.3 3 - 8.2 -0.3 -1.4 4 - 8.1 -0.4 -1.2

[0324] White substrate

[0325] # coating L* a* b* 1 + 90.8 -0.5 1.6 2 + 90.6 -0.5 1.7 3 - 91.2 -0.8 1.5 4 - 91.1 -0.9 1.5

[0326] Recipe B

[0327] Black substrate

[0328] # coating L* a* b* 1 + 9.0 -0.4 -1.4 2 + 9.0 -0.4 -1.5 3 - 8.6 -0.4 -1.3 4 - 8.4 -0.3 -1.3

[0329] White substrate

[0330] # coating L* a* b* 1 + 90.8 -0.6 2 2 + 90.7 -0.4 1.9 3 - 91.1 -0.9 1.6 4 - 91.2 -0.8 1.4 BRIEF DESCRIPTION OF THE DRAWINGS

[0331] The attached figure shows the thermogravimetric measurement; it shows:

[0332] Figure 1 :Differential calorimetry measurement of DAMP-H4

[0333] Figure 2 :Thermogravimetric measurement of DAMP-H4

[0334] Figure 3 :Differential calorimetry measurement of MOMP-H4

[0335] Figure 4 :Thermogravimetric measurement of MOMP-H4

[0336] Figure 5 : Differential calorimetry of ATMP

[0337] Figure 6 :Thermogravimetric measurement of ATMP

[0338] Figure 7:Differential calorimetry measurement of MOMP-Et4

[0339] Figure 8 :Thermogravimetric measurement of MOMP-Et4

[0340] Fig. 9 :Differential calorimetry measurements of MOMP-DOPO2

[0341] Fig.10 :Thermogravimetric measurement of MOM-DOPO2

[0342] Fig.11 :Differential calorimetry measurement of MOMP-H2Zn

[0343] Fig.12 :Thermogravimetric measurement of MOMP-H2Zn

[0344] Fig.13 :Differential calorimetry measurement of PIMP

[0345] Fig.14 :Thermogravimetric measurement of PIMP

[0346] <![CDATA[ Material ]]> <![CDATA[ 1% weight loss ]]> <![CDATA[ 2% weight loss ]]> <![CDATA[ Residual mass at 500°C ]]> <![CDATA[MOMP-H 4 ]]> 251.7℃ 276.9℃ 64.29％ <![CDATA[DAMP-H 4 ]]> 244.5℃ 273.1℃ 71.41％ <![CDATA[ATMP-H 4 ]]> 176.4℃ 193.9℃ 72.43％ <![CDATA[MOMP-Et 4 ]]> 101.7℃ 117.1℃ 19.58％ <![CDATA[MOM-DOPO 2 ]]> 305.5℃ 318.9℃ 7.50％ <![CDATA[MOMP-H 2 Zn]]> 375.0℃ 382.3℃ 78.75％ <![CDATA[PIMP-H 4 ]]> 199.3℃ 245.4℃ 71.63％

Claims

1. A composition comprising a polymer material and containing and / or combining a halogen-free flame retardant in an amount of 1% to 40% by weight relative to the entire composition, characterized in that: The flame retardant is a compound of formula (I), its corresponding ammonium salt, its corresponding phosphonate or a mixture of the above compounds: in, (Ni)R 1 and R 2 are identical or different substituents and are selected from the group consisting of linear, branched or cyclic alkyl, alkenyl and alkynyl groups, unsubstituted and alkyl-substituted phenyl groups, mononuclear aromatic hydrocarbons and polynuclear aromatic hydrocarbons with up to 4 nuclei, mononuclear heteroaromatic hydrocarbons and polynuclear heteroaromatic hydrocarbons with up to 4 nuclei, silyl, allyl, alkyl or aromatic alcohol, or (N-ii)R 1 and R 2 Together with the N atom, it forms a saturated or monounsaturated or polyunsaturated heterocyclic ring having 4 to 8 ring atoms selected from carbon, oxygen, sulfur, phosphorus, silicon and nitrogen, wherein If it has nitrogen atoms as ring atoms, these nitrogen atoms in the heterocyclic ring are substituted by H, alkyl, aryl or methylbisphosphonate groups having the following structure (II), And, if there are carbon, phosphorus or silicon as ring atoms, these atoms on the heterocyclic ring have substituents selected from the group consisting of H, alkyl, aryl, -NH2, -NHR, -NR2, -OH, -OR, =O, -N3, -SH, -SR, -OCN, epoxy, lactam, lactone, aziridine, Glycolide, oxazoline, ether, alkenylene and alkynylene, -SiR x H y , wherein 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 in, (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 alkyl, alkenyl and alkynyl, unsubstituted and alkyl-substituted phenyl, polynuclear aromatic hydrocarbons with up to 4 nuclei, mononuclear heteroaromatic hydrocarbons or polynuclear heteroaromatic hydrocarbons with up to 4 nuclei, silyl, allyl, alkyl or aromatic alcohol, the following structures (III) and (IV), wherein n=0 to 100, and a cation, wherein the cation is Na + , K + Mg 2+ , Ca 2+ , B 3+ 、Al 3+ 、Zn 2+ NH4 + or an ammonium ion of an amine compound selected from melamine or its condensation products, urea, guanidine, morpholine and piperazine, and (P-ii) When -X- is an oxygen atom -O-, -OR 3 AND-OR 4 and / or-OR 5 AND-OR 6 and / or-OR 3 AND-OR 5 and / or-OR 4 AND-OR 6 together with the P atom of the phosphonate group forms a cyclic phosphonate or anhydride having a ring size of 4 to 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 with the P atom of the phosphinate group, it forms a cyclic phosphinate or anhydride having a ring size of 4 to 10 atoms, and / or -OR 5 AND-OR 6 and / or-OR 4 AND-OR 6 together with the P atom of the phosphonate group, forms a cyclic phosphonate or anhydride having a ring size of 4 to 10 atoms, in, A.) Substituent R 1 To R 6 One of or B.) When 1) Substituent R 3 -R 6 When a cyclic phosphinate or cyclic phosphonate is formed according to (P-ii) or (P-iii), or 2) Substituent R 3 -R 6 When a cyclic phosphinic anhydride or a cyclic phosphonic anhydride is formed according to (P-ii) or (P-iii), or 3) Substituent R 1 and R 2 When a heterocyclic ring is formed according to (N-ii), One of the rings formed Having an uncharged or negatively charged first functional group, the uncharged or negatively charged first functional group having: a) heteroatoms selected from the group consisting of P, O, N, S; and / or b) an alkenyl or alkynyl group, where the functional group is not -OH, and In the case where one of the rings of 1) to 3) has a functional group, the ring atoms of the ring are substituted with the functional group or a substituent having a functional group.

2. The composition according to claim 1, characterized in that The polymer material is a thermosetting polymer material.

3. The composition according to claim 1, characterized in that The amine compound is selected from the group consisting of melam, melem, melonamine, urea, guanidine, morpholine and piperazine.

4. The composition according to claim 1, characterized in that Substituent R 1 To R 6 At least one of or by a substituent R 1 To R 6 Any of the formed rings has at least one further functional group having a heteroatom and / or an alkenyl or alkynyl group selected from the group consisting of N, S, O, Si.

5. The composition according to claim 1, characterized in that The first functional group and / or other functional groups are selected from the following group: -NH2, -NHR, -NR2, -OH, -OR, =O, -SH, -SR, -COOH, -COOR, -OCN, -SiR x H y , -N3, epoxy, lactam, lactone, aziridine, glycolide, oxazoline, ether, alkenylene and alkynylene, wherein R = alkyl, alkenyl, alkynyl or aryl, and x+y = 3.

6. The composition according to claim 1, characterized in that The flame retardant has a covalent bond with the polymeric material by using the flame retardant as a co-monomer in a polymer forming reaction of the polymeric material.

7. The composition according to claim 1, characterized in that R 1 and R 2 are the same substituents.

8. The composition according to claim 1, characterized in that The first functional group and / or the other functional groups are alkenyl or epoxy groups.

9. The composition according to claim 1, characterized in that The dry flame retardant starts to lose 10% by weight of mass at a temperature of 180°C.

10. The composition according to claim 9, characterized in that The dry flame retardant starts to lose 10% by weight of mass at a temperature of 190°C.

11. The composition according to claim 9, characterized in that The dry flame retardant starts to lose 10% by weight of mass at a temperature of 200°C.

12. The composition according to claim 1, characterized in that The flame retardant has a phosphorus content of at least 10.0% by weight.

13. The composition according to claim 12, characterized in that The flame retardant has a phosphorus content of at least 12.5% ​​by weight.

14. The composition according to claim 12, characterized in that The flame retardant has a phosphorus content of at least 21.5% by weight.

15. The composition according to claim 12, characterized in that The flame retardant has a phosphorus content of at least 15.0 wt%.

16. The composition according to claim 1, characterized in that Group R 3 , R 4 , R 5 and R 6 At least one of them is a cation or H, wherein the cation is Na + , K + Mg 2+ , Ca 2+ , B 3+ 、Al 3+ 、Zn 2+ NH4 + or an ammonium ion of an amine compound selected from melamine or a condensation product thereof, urea, guanidine, morpholine and piperazine.

17. The composition according to claim 16, characterized in that The amine compound is selected from the group consisting of melam, melem, melonamine, urea, guanidine, morpholine and piperazine.

18. The composition according to claim 1, characterized in that The polymeric material comprises a flame retardant in an amount of at least 3 wt%, or at least 5 wt%, or at least 10 wt%, or at least 15 wt% and / or in an amount not exceeding 35 wt%, or not exceeding 30 wt%, or not exceeding 25 wt%, relative to the total composition.

19. The composition according to claim 1, characterized in that The at least one other flame retardant component is selected from the group consisting of nitrogen bases, melamine, phosphates, pyrophosphates, polyphosphates, organic and inorganic phosphinates, organic and inorganic phosphonates.

20. The composition of claim 1, wherein The at least one other flame retardant component is selected from: ammonium polyphosphate; and melamine; melamine resins; silanes; siloxanes; polysiloxanes; polystyrene; coated and / or uncoated and crosslinked ammonium polyphosphate particles; and 1,3,5-triazine compounds.

21. The composition of claim 1, wherein The at least one other flame retardant component includes melamine, melam, melem, melonamine, amelin, amelide, 2-ureidomelamine, acetoguanamine, benzoguanamine, diaminophenyl triazine, melamine salts and adducts, melamine cyanurate, melamine borate, melamine orthophosphate, melamine pyrophosphate, dimelamine pyrophosphate, aluminum diethylphosphinate, melamine polyphosphate, oligomers and polymers of 1,3,5 triazine compounds and polyphosphates of 1,3,5 triazine compounds; guanine; piperazine phosphate; piperazine polyphosphate; ethylenediamine phosphate; pentaerythritol; dipentaerythritol; boron phosphate; 1,3,5-trihydroxyethyl isocyanurate; 1,3,5-triglycidyl isocyanurate; triallyl isocyanurate.

22. A method for producing a composition as claimed in any one of claims 1 to 21, characterized in that The flame retardant is a cocondensation component or coaddition component of the polymer material, which is added to the polymer material during production by polycondensation or polyaddition, wherein the polymer material is a polyester or a polyurethane.

23. A flame retardant contained in a composition as claimed in any one of the preceding claims 1 to 21, characterized in that Substituent R 3 To R 6 Or the ring formed by these substituents has the first functional group.

24. A method for producing a flame retardant, comprising the steps of: ·●Provide a mixture of the following substances: a) at least one phosphonic acid or phosphinic acid in a reaction vessel selected from the group consisting of compounds of formula (V) and (VI) wherein -X- is an oxygen atom -O-, or -X- is a single bond, and in, (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 alkyl, alkenyl and alkynyl, unsubstituted and alkyl-substituted phenyl, polynuclear aromatic hydrocarbons with up to 4 nuclei, mononuclear heteroaromatic hydrocarbons or polynuclear heteroaromatic hydrocarbons with up to 4 nuclei, silyl, allyl, alkyl or aromatic alcohol, the following structures (III) and (IV), wherein n=0 to 100, and a cation, wherein the cation is Na + , K + Mg 2+ , Ca 2+ , B 3+ 、Al 3+ 、Zn 2+ NH4 + or an ammonium ion of an amine bond selected from melamine or its condensation products, urea, guanidine, morpholine and piperazine, and (P-ii) When -X- is an oxygen atom -O-, -OR 3 AND-OR 4 and / or-OR 5 AND-OR 6 and / or-OR 3 AND-OR 5 and / or-OR 4 AND-OR 6 together with the P atom of the phosphonate group, forms a cyclic phosphonate or anhydride having a ring size of 4 to 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 with the P atom of the phosphinate group, it forms a cyclic phosphonate or anhydride having a ring size of 4 to 10 atoms, and / or -OR 5 AND-OR 6 and / or-OR 4 AND-OR 6 together with the P atom of the phosphonate group, forms a cyclic phosphonate or anhydride having a ring size of 4 to 10 atoms, b) HC(OR 7 )3, where R 7 = alkyl, aryl or alkenyl, c) an amino compound of the formula (VII), in, (Ni)R 1 and R 2 are identical or different substituents and are selected from the group consisting of linear, branched or cyclic alkyl, alkenyl and alkynyl groups, unsubstituted and alkyl-substituted phenyl, mononuclear aromatic hydrocarbons and polynuclear aromatic hydrocarbons with up to 4 nuclei, mononuclear heteroaromatic hydrocarbons or polynuclear heteroaromatic hydrocarbons with up to 4 nuclei, silyl, allyl, alkyl or aromatic alcohol, or (N-ii)R 1 and R 2 Together with the N atom, it forms a saturated or monounsaturated or polyunsaturated heterocyclic ring having 4 to 8 ring atoms selected from carbon, oxygen, sulfur, phosphorus, silicon and nitrogen, wherein, if it has nitrogen atoms as ring atoms, these nitrogen atoms on the heterocyclic ring are substituted by H, alkyl, aryl or methyldiphosphonate groups having the following structure (II), Furthermore, if there are carbon, phosphorus or silicon as ring atoms, these atoms on the heterocyclic ring have substituents selected from the group consisting of H, alkyl, aryl, -NH2, -NHR, -NR2, -OH, -OR, =O, -N3, -SH, -SR, -OCN, epoxy, lactam, lactone, aziridine, glycolide, oxazoline, alkenylene and alkynylene, -SiR x H y , wherein R = alkyl, alkenyl, alkynyl or aryl, and x + y = 3, • Heat the mixture to a temperature of 40-150°C.

25. The method of claim 24, wherein: The amine bond is selected from the group consisting of melam, melem, melonamine, urea, guanidine, morpholine and piperazine.

26. The method of claim 24, wherein: R 7 =Triethoxymethyl.

27. Use of a compound of formula (I), its corresponding ammonium salt, its corresponding phosphonate or a mixture thereof for surface treatment, in, (Ni)R 1 and R 2 are identical or different substituents and are selected from the group consisting of linear, branched or cyclic alkyl, alkenyl and alkynyl groups, unsubstituted and alkyl-substituted phenyl, mononuclear aromatic hydrocarbons and polynuclear aromatic hydrocarbons with up to 4 nuclei, mononuclear heteroaromatic hydrocarbons or polynuclear heteroaromatic hydrocarbons with up to 4 nuclei, silyl, allyl, alkyl or aromatic alcohol, or (N-ii)R 1 and R 2 Together with the N atom, it forms a saturated or monounsaturated or polyunsaturated heterocyclic ring having 4 to 8 ring atoms selected from carbon, oxygen, sulfur, phosphorus, silicon and nitrogen, wherein, if it has nitrogen atoms as ring atoms, these nitrogen atoms on the heterocyclic ring are substituted by H, alkyl, aryl or methyldiphosphonate groups having the following structure (II), Furthermore, if there are carbon, phosphorus or silicon as ring atoms, these atoms on the heterocyclic ring have substituents selected from the group consisting of H, alkyl, aryl, -NH2, -NHR, -NR2, -OH, -OR, =O, -N3, -SH, -SR, -OCN, epoxy, lactam, lactone, aziridine, glycolide, oxazoline, alkenylene and alkynylene, -SiR x H y , wherein 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 in, (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 alkyl, alkenyl and alkynyl, unsubstituted and alkyl-substituted phenyl, polynuclear aromatic hydrocarbons with up to 4 nuclei, mononuclear heteroaromatic hydrocarbons or polynuclear heteroaromatic hydrocarbons with up to 4 nuclei, silyl, allyl, alkyl or aromatic alcohol, the following structures (III) and (IV), wherein n=0 to 100, and a cation, wherein the cation is Na + , K + Mg 2+ , Ca 2+ , B 3+ 、Al 3+ 、Zn 2+ NH4 + or an ammonium ion of an amine compound selected from melamine or its condensation products, urea, guanidine, morpholine and piperazine, and (P-ii) When -X- is an oxygen atom -O-, -OR 3 AND-OR 4 and / or-OR 5 AND-OR 6 and / or-OR 3 AND-OR 5 and / or-OR 4 AND-OR 6 together with the P atom of the phosphonate group, forms a cyclic phosphonate or anhydride having a ring size of 4 to 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 with the P atom of the phosphinate group, it forms a cyclic phosphinate or anhydride having a ring size of 4 to 10 atoms, and / or -OR 5 AND-OR 6 and / or-OR 4 AND-OR 6 Together with the P atom of the phosphonate group, a cyclic phosphonate or anhydride having a ring size of 4 to 10 atoms is formed.

28. The use according to claim 27, characterized in that The amine compound is selected from the group consisting of melam, melem, melonamine, urea, guanidine, morpholine and piperazine.

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